CN109836391B - Isoxazoline derivatives and their use in agriculture - Google Patents

Isoxazoline derivatives and their use in agriculture Download PDF

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CN109836391B
CN109836391B CN201711190272.2A CN201711190272A CN109836391B CN 109836391 B CN109836391 B CN 109836391B CN 201711190272 A CN201711190272 A CN 201711190272A CN 109836391 B CN109836391 B CN 109836391B
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methyl
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CN109836391A (en
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李义涛
张虎
刘倩
池伟林
曾水明
林健
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Ningxia Jianpai Agrochemical Technology Co.,Ltd.
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Dongguan Dongyangguang Pesticide R & D Co Ltd
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Abstract

The invention provides isoxazoline derivatives and their use in agriculture; specifically, the present invention provides a novel isoxazoline derivative and a preparation method thereof; compositions containing these compounds and their use in agriculture, in particular as herbicidal active ingredients for controlling unwanted vegetation.

Description

Isoxazoline derivatives and their use in agriculture
Technical Field
The invention provides a novel isoxazoline derivative and a preparation method thereof; compositions containing these compounds and their use in agriculture.
Background
Isoxazolines are a class of compounds with excellent biological activity, and their herbicidal activity is reported, for example, in WO 2002062770, WO 2003000686 and WO 2003010165. However, the compounds of the present invention described in detail hereinafter are not described in these documents.
Disclosure of Invention
The invention provides a novel isoxazoline compound with herbicidal activity, which shows better herbicidal activity on broadleaf weeds and grassy weeds.
In one aspect, the invention provides compounds of formula (I) or stereoisomers, N-oxides, and salts thereof of compounds of formula (I):
wherein:
R1and R2Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, alkyl, cycloalkyl, or cycloalkylalkyl; or R1、R2And the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms;
R3and R4Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, alkyl, cycloalkyl, or cycloalkylalkyl; or R3、R4And the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms;
n is 0, 1 or 2;
R5and R6Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, or alkyl;
R7is hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylamino, haloalkylamino, alkylthio or haloalkylthio;
m is 1,2 or 3;
each R8Independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylamino, haloalkylamino, alkylthio, haloalkylthio, -NRaRb-C (═ O) -alkyl or-S (═ O)2-an alkyl group;
each RaAnd RbIndependently hydrogen, alkyl, haloalkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, -C (═ O) -Rc、-C(＝O)-NRc1Rc2、-C(＝O)-ORd、-S(＝O)2-Re、-S(＝O)2-NRe1Re2or-S (═ O)2-ORf；
Each RcAnd ReIndependently hydrogen, fluoro, chloro, bromo, iodo, alkyl, haloalkyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl;
each RdAnd RfIndependently hydrogen, alkyl, haloalkyl, amino-substituted alkyl, cyano-substituted alkyl, or hydroxy-substituted alkyl;
each Rc1、Rc2、Re1And Re2Independently hydrogen, alkyl, haloalkyl, cycloalkyl, heterocyclyl, aryl or heteroaryl;
or Ra、RbAnd the nitrogen atom to which they are attached form a ring consisting of 3 to 12 atoms;
wherein R is1、R2、R3、R4、R5、R6、R7、R8、Ra、Rb、Rc、Re、Rd、Rf、Rc1、Rc2、Re1、Re23-8 and 3-12 rings optionally substituted with one or more groups selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, halo C1-6Alkyl, halo C2-6Alkenyl, halo C2-6Alkynyl, hydroxy-substituted C1-6Alkyl, amino substituted C1-6Alkyl, cyano-substituted C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkoxy, hydroxy-substituted C1-6Alkoxy, amino substituted C1-6Alkoxy, cyano-substituted C1-6Alkoxy radical, C1-6Alkylamino radical, C3-8Cycloalkyl radical, C6-10Aryl or C1-9Heteroaryl group is substituted.
In some of these embodiments, the present invention provides a compound of formula (II) or stereoisomers, N-oxides, and salts thereof of a compound of formula (II):
wherein: n, R1、R2、R3、R4、R5、R6、R7And R8Have the meaning as described in the present invention.
In some of these embodiments, the present invention provides a compound of formula (II '), stereoisomers, N-oxides, and salts thereof, of a compound of formula (II'):
wherein: n, R1、R2、R3、R4、R5、R6、R7And R8Have the meaning as described in the present invention.
In some of these embodiments, the present invention provides a compound of formula (IIa), (IIb), or (IIc) or a stereoisomer, N-oxide, or salt thereof, of a compound of formula (IIa), (IIb), or (IIc):
wherein: r1、R2、R3、R4、R5、R6、R7And R8Have the meaning as described in the present invention.
In some of these embodiments, R1And R2Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-6Alkyl radical, C3-6Cycloalkyl or C3-6Cycloalkyl radical C1-6An alkyl group; or R1、R2And together with the carbon atoms to which they are attached form a ring consisting of 3 to 6 atoms.
In some of these embodiments, R3And R4Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-6Alkyl radical, C3-6Cycloalkyl or C3-6Cycloalkyl radical C1-6An alkyl group; or R3、R4And together with the carbon atoms to which they are attached form a ring consisting of 3 to 6 atoms.
In some of these embodiments, R5And R6Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxy or C1-6An alkyl group.
In some of these embodiments, R7Is hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkoxy radical, C1-6Alkylamino, halogeno C1-6Alkylamino radical, C1-6Alkylthio or halogeno C1-6An alkylthio group.
In some of these embodiments, each R is8Independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, carboxyl, C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkoxy radical, C1-6Alkylamino, halogeno C1-6Alkylamino radical, C1-6Alkylthio, halo C1-6Alkylthio, -NRaRb、-C(＝O)-C1-6Alkyl or-S (═ O)2-C1-6An alkyl group;
wherein R isaAnd RbHave the meaning as described in the present invention.
In some of these embodiments, each R isaAnd RbIndependently of one another is hydrogen, C1-6Alkyl, halo C1-6Alkyl radical, C3-8Cycloalkyl radical, C2-12Heterocyclic group, C6-10Aryl radical, C1-9Heteroaryl, -C (═ O) -Rc、-C(＝O)-NRc1Rc2、-C(＝O)-ORd、-S(＝O)2-Re、-S(＝O)2-NRe1Re2or-S (═ O)2-ORf(ii) a Or Ra、RbAnd the nitrogen atom to which they are attached form a ring consisting of 3 to 12 atoms;
wherein R isc、Rc1、Rc2、Rd、Re、Re1、Re2And RfHave the meaning as described in the present invention.
In some of these embodiments, each R iscAnd ReIndependently hydrogen, fluorine, chlorine, bromine, iodine, C1-8Alkyl, halo C1-8Alkyl radical, C3-8Cycloalkyl radical, C2-12Heterocyclic group, C6-10Aryl or C1-9A heteroaryl group.
In some of these embodiments, each R isdAnd RfIndependently of one another is hydrogen, C1-8Alkyl, halo C1-8Alkyl, amino substituted C1-8Alkyl, cyano-substituted C1-8Alkyl or hydroxy substituted C1-8An alkyl group.
In some of these embodiments, each R isc1、Rc2、Re1And Re2Independently of one another is hydrogen, C1-6Alkyl, halo C1-6Alkyl radical, C3-8Cycloalkyl radical, C2-12Heterocyclic group, C6-10Aryl or C1-9A heteroaryl group.
In some of these embodiments, R1、R2、R3、R4、R5、R6、R7、R8、Ra、Rb、Rc、Re、Rd、Rf、Rc1、Rc2、Re1、Re23-6 atoms and 3-12 atoms optionally substituted with one or more groups selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C1-4Alkyl, halo C2-4Alkenyl, halo C2-4Alkynyl, hydroxy-substituted C1-4Alkyl, amino substituted C1-4Alkyl, cyano-substituted C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkoxy, hydroxy-substituted C1-4Alkoxy, amino substituted C1-4Alkoxy, cyano-substituted C1-4Alkoxy radical, C1-4Alkylamino radical, C3-6Cycloalkyl radical, C6-10Aryl or C1-5Heteroaryl group is substituted.
In other embodiments, R1And R2Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl or cyclohexylethyl.
In other embodiments, R3And R4Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl or cyclohexylethyl.
In other embodiments, R5And R6Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, methyl, ethyl, n-propyl or isopropyl.
In other embodiments, R7Is hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, isopropoxy or trifluoromethoxy.
In other embodiments, each R is8Independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, carboxyl, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkoxy radical, C1-4Alkylamino, halogeno C1-4Alkylamino radical, C1-4Alkylthio, halo C1-4Alkylthio, -NRaRb、-C(＝O)-C1-4Alkyl or-S (═ O)2-C1-4An alkyl group;
wherein R isaAnd RbHave the meaning as described in the present invention.
In other embodiments, each R isaAnd RbIndependently of one another is hydrogen, C1-4Alkyl, halo C1-4Alkyl radical, C3-6Cycloalkyl radical, C3-8Heterocyclic group, C6-10Aryl radical, C1-5Heteroaryl, -C (═ O) -Rc、-C(＝O)-NRc1Rc2、-C(＝O)-ORd、-S(＝O)2-Re、-S(＝O)2-NRe1Re2or-S (═ O)2-ORf(ii) a Or Ra、RbAnd the nitrogen atom to which they are attached form a ring consisting of 4 to 10 atoms;
wherein R isc、Rc1、Rc2、Rd、Re、Re1、Re2And RfHave the meaning as described in the present invention.
In other embodiments, each R iscAnd ReIndependently hydrogen, fluorine, chlorine, bromine, iodine, C1-6Alkyl, halo C1-6Alkyl radical, C3-6Cycloalkyl radical, C3-8Heterocyclic group, C6-10Aryl or C1-5A heteroaryl group.
In other embodiments, each R isdAnd RfIndependently of one another is hydrogen, C1-6Alkyl, halo C1-6Alkyl, amino substituted C1-6Alkyl, cyano-substituted C1-6Alkyl or hydroxy substituted C1-6An alkyl group.
In other embodiments, each R isc1、Rc2、Re1And Re2Independently of one another is hydrogen, C1-4Alkyl, halo C1-4Alkyl radical, C3-6Cycloalkyl radical, C3-8Heterocyclic group, C6-10Aryl or C1-5A heteroaryl group.
In other embodiments, each R is8Independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, carboxyl, methyl, ethyl, n-propyl, isopropyl, halogenated C1-3Alkyl, methoxy, ethoxy, n-propoxy, isopropoxy, halo C1-3Alkoxy, methylamino, ethylamino, methylthio, ethylthio or-NRaRb；
Wherein R isaAnd RbHave the meaning as described in the present invention.
In other embodiments, each R isaAnd RbIndependently hydrogen, methyl, ethyl, n-propyl, isopropyl, halogeno C1-3Alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, -C (═ O) -Cl, -C (═ O) -Br, -C (═ O) -CH3、-C(＝O)-CH2CH3、-C(＝O)-CH2CH2CH3、-C(＝O)-CH(CH3)2、-C(＝O)-C(CH3)3、-C(＝O)-CH2F、-C(＝O)-CH2Cl、-C(＝O)-CH2Br、-C(＝O)-CF3、-C(＝O)-CH2CF3、-C(＝O)-CH2CH2CF3-C (═ O) -phenyl, -C (═ O) -pyridyl, -C (═ O) -pyrimidinyl, -C (═ O) -pyridazinyl, -C (═ O) -NH-phenyl, -C (═ O) -NH-pyridyl, -C (═ O) -NH-pyrimidinyl, -C (═ O) -NH-pyridazinyl, -C (═ O) -OCH3、-C(＝O)-OCH2CH3、-C(＝O)-OCH2CH2CH3、-C(＝O)-OCH(CH3)2、-C(＝O)-OC(CH3)3、-C(＝O)-OCH2F、-C(＝O)-OCH2Cl、-C(＝O)-OCH2Br、-S(＝O)2-CH3、-S(＝O)2-CH2CH3、-S(＝O)2-phenyl, -S (═ O)2-pyridyl, -S (═ O)2-pyrimidinyl, -S (═ O)2-pyridazinyl or-S (═ O)2-NH-phenyl;
Raand RbOptionally substituted with one or more substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, methyl, ethyl, methoxy or ethoxy;
or Ra、RbAnd the nitrogen atom to which they are attached form the following subformula:
in some of these embodiments, the present invention provides a compound of formula (III), stereoisomers, N-oxides, and salts thereof, of the compound of formula (III):
wherein: n is 0, 1 or 2;
each RaAnd RbIndependently hydrogen, methyl, ethyl, n-propyl, isopropyl, halogeno C1-3Alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclohexyl,Cyclopentyl, cyclohexyl, -C (═ O) -Cl, -C (═ O) -Br, -C (═ O) -CH3、-C(＝O)-CH2CH3、-C(＝O)-CH2CH2CH3、-C(＝O)-CH(CH3)2、-C(＝O)-C(CH3)3、-C(＝O)-CH2F、-C(＝O)-CH2Cl、-C(＝O)-CH2Br、-C(＝O)-CF3、-C(＝O)-CH2CF3、-C(＝O)-CH2CH2CF3-C (═ O) -phenyl, -C (═ O) -pyridyl, -C (═ O) -pyrimidinyl, -C (═ O) -pyridazinyl, -C (═ O) -NH-phenyl, -C (═ O) -NH-pyridyl, -C (═ O) -NH-pyrimidinyl, -C (═ O) -NH-pyridazinyl, -C (═ O) -OCH3、-C(＝O)-OCH2CH3、-C(＝O)-OCH2CH2CH3、-C(＝O)-OCH(CH3)2、-C(＝O)-OC(CH3)3、-C(＝O)-OCH2F、-C(＝O)-OCH2Cl、-C(＝O)-OCH2Br、-S(＝O)2-CH3、-S(＝O)2-CH2CH3、-S(＝O)2-phenyl, -S (═ O)2-pyridyl, -S (═ O)2-pyrimidinyl, -S (═ O)2-pyridazinyl or-S (═ O)2-NH-phenyl;
Raand RbOptionally substituted with one or more substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, methyl, ethyl, methoxy or ethoxy;
or Ra、RbAnd the nitrogen atom to which they are attached form the following subformula:
in some of these embodiments, the present invention provides a compound of formula (IIIa), (IIIb), or (IIIc), or stereoisomers, N-oxides, and salts thereof, of a compound of formula (IIIa), (IIIb), or (IIIc):
wherein: each RaAnd RbIndependently hydrogen, methyl, ethyl, n-propyl, isopropyl, halogeno C1-3Alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, -C (═ O) -Cl, -C (═ O) -Br, -C (═ O) -CH3、-C(＝O)-CH2CH3、-C(＝O)-CH2CH2CH3、-C(＝O)-CH(CH3)2、-C(＝O)-C(CH3)3、-C(＝O)-CH2F、-C(＝O)-CH2Cl、-C(＝O)-CH2Br、-C(＝O)-CF3、-C(＝O)-CH2CF3、-C(＝O)-CH2CH2CF3-C (═ O) -phenyl, -C (═ O) -pyridyl, -C (═ O) -pyrimidinyl, -C (═ O) -pyridazinyl, -C (═ O) -NH-phenyl, -C (═ O) -NH-pyridyl, -C (═ O) -NH-pyrimidinyl, -C (═ O) -NH-pyridazinyl, -C (═ O) -OCH3、-C(＝O)-OCH2CH3、-C(＝O)-OCH2CH2CH3、-C(＝O)-OCH(CH3)2、-C(＝O)-OC(CH3)3、-C(＝O)-OCH2F、-C(＝O)-OCH2Cl、-C(＝O)-OCH2Br、-S(＝O)2-CH3、-S(＝O)2-CH2CH3、-S(＝O)2-phenyl, -S (═ O)2-pyridyl, -S (═ O)2-pyrimidinyl, -S (═ O)2-pyridazinyl or-S (═ O)2-NH-phenyl;
Raand RbOptionally substituted with one or more substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, methyl, ethyl, methoxy or ethoxy;
or Ra、RbAnd the nitrogen atom to which they are attached form the following subformula:
in some of these embodiments, the present invention provides compounds having one of the following structures or stereoisomers, nitroxides and salts of compounds having one of the following structures:
in another aspect, the invention provides a composition comprising a compound of the invention, further comprising an agriculturally acceptable surfactant and a carrier.
In some of these embodiments, the compositions of the present invention comprise at least one additional pesticidally active substance selected from the group consisting of insecticides, acaricides, herbicides, fungicides, safeners and growth regulators.
In another aspect, the present invention provides the use of a composition comprising a compound of the present invention for the control of plant diseases.
In some of these embodiments, the present invention provides the use of compositions comprising the compounds described herein for controlling unwanted vegetation.
In another aspect, the present invention provides a method for controlling unwanted vegetation, characterized in that an effective amount of a compound according to the invention is applied to the plants, to the plant seeds, to the soil in or on which the plants are grown, or to the cultivation area.
The compounds of formula (I) may exist in different stereoisomers or optical isomers or tautomeric forms. The invention encompasses all such isomers and tautomers and mixtures thereof in various ratios, as well as isotopic forms such as heavy hydrogen-containing compounds.
Isotopically enriched compounds have the structure depicted by the formulae given herein, except that one or more atoms are replaced by an atom having a selected atomic mass or mass number. Exemplary isotopes that can be incorporated into compounds of the invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine and chlorine, such as2H，3H，11C，13C，14C，15N，17O，18O，18F，31P，32P，35S，36Cl and125I。
any asymmetric atom (e.g., carbon, etc.) of a compound disclosed herein can exist in racemic or enantiomerically enriched forms, such as the (R) -, (S) -or (R, S) -configuration.
The foregoing has outlined only certain aspects of the present invention and is not intended to be limited in these or other respects to the details described herein.
Detailed description of the invention
Definitions and general terms
Reference will now be made in detail to certain embodiments of the invention, examples of which are illustrated by the accompanying structural and chemical formulas. The invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. One skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ or contradict this application (including but not limited to defined terminology, application of terminology, described techniques, and the like), this application controls.
It will be further appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.
The following definitions, as used herein, should be applied unless otherwise indicated. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the periodic Table of the elements, and the handbook of chemistry and Physics, 75 th edition, 1994. In addition, general principles of Organic Chemistry can be found in the descriptions of "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and JerryMarch, John Wiley & Sons, New York:2007, the entire contents of which are incorporated herein by reference.
The articles "a," "an," and "the" as used herein are intended to include "at least one" or "one or more" unless otherwise indicated or clearly contradicted by context. Thus, as used herein, the articles refer to articles of one or more than one (i.e., at least one) object. For example, "a component" refers to one or more components, i.e., there may be more than one component contemplated for use or use in embodiments of the described embodiments.
The term "comprising" is open-ended, i.e. includes the elements indicated in the present invention, but does not exclude other elements.
"stereoisomers" refers to compounds having the same chemical structure but differing in the arrangement of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.
"enantiomer" refers to two isomers of a compound that are not overlapping but are in mirror image relationship to each other.
"diastereomer" refers to a stereoisomer that has two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivities. Mixtures of diastereomers may be separated by high resolution analytical procedures such as electrophoresis and chromatography, e.g., HPLC.
The stereochemical definitions and rules used in the present invention generally follow the general definitions of S.P. Parker, Ed., McGraw-Hilldictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; and Eliel, E.and Wilen, S., "Stereochemistry of Organic Compounds", John Wiley & Sons, Inc., New York, 1994.
Many organic compounds exist in an optically active form, i.e., they have the ability to rotate the plane of plane polarized light. In describing optically active compounds, the prefixes D and L or R and S are used to denote the absolute configuration of a molecule with respect to one or more of its chiral centers. The prefixes d and 1 or (+) and (-) are the symbols used to specify the rotation of plane polarized light by the compound, where (-) or l indicates that the compound is left-handed. Compounds prefixed with (+) or d are dextrorotatory. A particular stereoisomer is an enantiomer and a mixture of such isomers is referred to as an enantiomeric mixture. A50: 50 mixture of enantiomers is referred to as a racemic mixture or racemate, which may occur when there is no stereoselectivity or stereospecificity in the chemical reaction or process.
The compounds of the invention may be optionally substituted with one or more substituents, as described herein, in compounds of the general formula above, or as specifically exemplified, sub-classes, and classes of compounds encompassed by the invention. It is understood that the term "optionally substituted" may be used interchangeably with the term "substituted or unsubstituted". In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced with a particular substituent. Unless otherwise indicated, an optional substituent group may be substituted at each substitutable position of the group. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, the substituents may be substituted at each position, identically or differently. Wherein said substituent may be, but is not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxyl-substituted alkyl, hydroxyl-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkanoyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, aminosulfonyl, and the like.
In addition, unless otherwise explicitly indicated, the descriptions of the terms "… independently" and "… independently" and "… independently" used in the present invention are interchangeable and should be understood in a broad sense to mean that the specific items expressed between the same symbols do not affect each other in different groups or that the specific items expressed between the same symbols in the same groups do not affect each other.
In the various parts of this specification, substituents of the disclosed compounds are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C1-C6Alkyl "or" C1-6Alkyl "means in particular independently disclosed methyl, ethyl, C3Alkyl radical, C4Alkyl radical, C5Alkyl and C6An alkyl group.
The term "alkyl" or "alkyl group" as used herein, denotes a saturated, straight or branched chain, monovalent hydrocarbon group containing from 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in one embodiment, the alkyl group contains 1 to 8 carbon atoms; in another embodiment, the alkyl group contains 1 to 6 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 4 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms.
Examples of alkyl groups include, but are not limited to, methyl (Me, -CH)3) Ethyl group (Et, -CH)2CH3) N-propyl (n-Pr, -CH)2CH2CH3) Isopropyl group (i-Pr, -CH (CH)3)2) N-butyl (n-Bu, -CH)2CH2CH2CH3) Isobutyl (i-Bu, -CH)2CH(CH3)2) Sec-butyl (s-Bu, -CH (CH)3)CH2CH3) Tert-butyl (t-Bu, -C (CH)3)3) N-pentyl (-CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH)3)CH2CH2CH3) 3-pentyl (-CH (CH)2CH3)2) 2-methyl-2-butyl (-C (CH)3)2CH2CH3) 3-methyl-2-butyl (-CH (CH)3)CH(CH3)2) 3-methyl-1-butyl (-CH)2CH2CH(CH3)2) 2-methyl-1-butyl (-CH)2CH(CH3)CH2CH3) And so on.
The term "alkenyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one site of unsaturation, i.e. one carbon-carbon sp2A double bond, wherein the alkenyl group may be optionally substituted with one or more substituents described herein, including the positioning of "cis" and "tans", or the positioning of "E" and "Z". In one embodiment, the alkenyl group contains 2 to 8 carbon atoms; in another embodiment, the alkenyl group contains 2 to 6 carbon atoms; in yet another embodiment, the alkenyl group contains 2 to 4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH ═ CH)2) Allyl (-CH)2CH＝CH2) Allyl (CH)3-CH ═ CH-), oxo butenyl (CH)3-C (═ O) -CH ═ CH-) and the like.
The term "alkynyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond.
The term "alkoxy" means an alkyl group attached to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH)3) Ethoxy (EtO, -OCH)2CH3) 1-propoxy (n-PrO, n-propoxy, -OCH)2CH2CH3) 2-propoxy (i-PrO, i-propoxy, -OCH (CH)3)2) And so on.
The term "alkylthio" refers to a straight or branched chain alkyl group attached to a divalent sulfur atom, wherein the alkyl group has the meaning as described herein. Examples of alkylthio groups include, but are not limited to, -SCH3、-SCH2CH3、-SCH2CH2CH3And so on.
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The term "haloalkyl" denotes an alkyl group substituted with one or more halogen atoms.
The term "haloalkoxy" denotes an alkoxy group substituted with one or more halogen atoms.
The term "haloalkylamino" denotes an alkylamino group substituted with one or more halogen atoms.
The term "haloalkylthio" denotes an alkylthio group substituted by one or more halogen atoms.
The term "cycloalkyl" denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing from 3 to 12 carbon atoms. In one embodiment, the cycloalkyl group contains 3 to 10 carbon atoms; in another embodiment, cycloalkyl contains 3 to 8 carbon atoms; in yet another embodiment, the cycloalkyl group contains 3 to 6 carbon atoms. The cycloalkyl group is optionally substituted with one or more substituents described herein. Examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and the like.
The term "cycloalkylalkyl" denotes an alkyl group substituted by a cycloalkyl group, wherein the alkyl group and the cycloalkyl group have the meaning as described herein.
The term "cycloalkenyl" denotes mono-, bi-or tricyclic ring systems containing 3 to 12 carbon atoms, mono-or polyvalent, comprising at least one carbon-carbon double bond, said ring systems being non-aromatic. In one embodiment, cycloalkenyl groups contain 3 to 10 carbon atoms; in another embodiment, cycloalkenyl groups contain 3 to 8 carbon atoms; in yet another embodiment, cycloalkenyl groups contain 3 to 6 carbon atoms. The cycloalkenyl group is optionally substituted with one or more substituents described herein. Examples include, but are not limited to, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, and the like.
The terms "heterocyclyl" and "heterocycle" are used interchangeably herein and refer to a saturated or partially unsaturated monocyclic, bicyclic, or tricyclic ring containing 3 to 15 ring atoms, wherein no aromatic ring is included in the monocyclic, bicyclic, or tricyclic ring, and at least one ring atom is selected from the group consisting of nitrogen, sulfur, and oxygen atoms. Unless otherwise specified, heterocyclyl may be carbon-or nitrogen-based, and-CH2-the group may optionally be replaced by-C (═ O) -. The sulfur atom of the ring may optionally be oxidized to the S-oxide. The nitrogen atom of the ring may optionally be oxidized to an N-oxygen compound. Examples of heterocyclyl groups include, but are not limited to, oxiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (e.g., 2-pyrrolidinyl), 2-pyrrolinyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, 1, 3-dioxocyclopentyl, dithiocyclopentyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidinyl, 4-piperidinyl), morpholinyl, thiomorpholinyl,(1-oxo) -thiomorpholinyl, (1, 1-dioxo) -thiomorpholinyl, piperazinyl, dioxanyl, dithianyl, thiaxalyl, homopiperazinyl, homopiperidinyl, oxepanyl, thiepanyl, 2-oxa-5-azabicyclo [2.2.1]Hept-5-yl, tetrahydropyridinyl. In heterocyclic radicals of-CH2Examples of-groups substituted by-C (═ O) -include, but are not limited to, 2-oxopyrrolidinyl, oxo-1, 3-thiazolidinyl, 2-piperidinonyl, 3, 5-dioxopiperidinyl. Examples of sulfur atoms in heterocyclic groups that are oxidized include, but are not limited to, sulfolane, 1, 1-dioxothiomorpholinyl. The heterocyclyl group is optionally substituted with one or more substituents described herein.
The term "x-atomic," where x is an integer, typically describes the number of ring-forming atoms in a molecule in which the number of ring-forming atoms is x. For example, piperidinyl is a heterocyclic group consisting of 6 atoms.
The term "unsaturated" as used herein means that the group contains one or more unsaturations.
The term "heteroatom" refers to O, S, N, P and Si, including N, S and any oxidation state form of P; primary, secondary, tertiary amines and quaternary ammonium salt forms; or a form in which a hydrogen on a nitrogen atom in the heterocycle is substituted, for example, N (like N in 3, 4-dihydro-2H-pyrrolyl), NH (like NH in pyrrolidinyl) or NR (like NR in N-substituted pyrrolidinyl).
The term "aryl" denotes monocyclic, bicyclic and tricyclic carbon ring systems containing 6 to 14 ring atoms, or 6 to 12 ring atoms, or 6 to 10 ring atoms, wherein at least one ring system is aromatic, wherein each ring system comprises a ring of 3 to 7 atoms with one or more attachment points to the rest of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring". Examples of the aryl group may include phenyl, indenyl, naphthyl and anthryl. The aryl group is optionally substituted with one or more substituents described herein.
The term "heteroaryl" denotes monocyclic, bicyclic and tricyclic ring systems containing 5 to 12 ring atoms, or 5 to 10 ring atoms, or 5 to 6 ring atoms, wherein at least one ring system is aromatic and at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring of 5 to 7 atoms with one or more attachment points to the rest of the molecule. The term "heteroaryl" may be used interchangeably with the terms "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein. In one embodiment, a heteroaryl group of 5-10 atoms contains 1,2,3, or 4 heteroatoms independently selected from O, S, and N.
Examples of heteroaryl groups include, but are not limited to, 2-furyl, 3-furyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyridazinyl (e.g., 3-pyridazinyl), 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, tetrazolyl (e.g., 5-tetrazolyl), triazolyl (e.g., 2-triazolyl and 5-triazolyl), 2-thienyl, 3-thienyl, pyrazolyl, isothiazolyl, 1,2, 3-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 3-triazolyl, 1,2, 3-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, pyrazinyl, 1,3, 5-triazinyl, pyrimidinonyl, pyridonyl; the following bicyclic rings are also included, but are in no way limited to these: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (e.g., 2-indolyl), and the like.
In one embodiment, the heteroaryl group is of the following sub-formula:
and so on.
As described herein, the attachment point may be attached to the rest of the molecule at any point on the ring that is attachable; in formula a, one attachment point can be attached to the rest of the molecule, as shown in formula b, formula c, formula d and formula e.
When the compounds of the present invention contain an acid moiety, salts of the compounds of the present invention include those derived from alkali or alkaline earth metals as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and those of formula N+(R19R20R21R22) Ammonium cation of (2), wherein R is19、R20、R21And R22Independently selected from hydrogen, C1-C6Alkyl and C1-C6A hydroxyalkyl group. Salts of compounds of formula (I) may be prepared by treating a compound of formula (I) with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine).
When a compound of the invention comprises a base moiety, acceptable salts can be formed from organic and inorganic acids, such as acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, napthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids.
Compositions and formulations of the compounds of the invention
The compounds of the present invention are generally useful as herbicidal active ingredients in compositions, i.e., formulations, having at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, used as a carrier. The formulation or composition ingredients are selected to be compatible with the physical characteristics of the active ingredient, the mode of application, and environmental factors such as soil type, moisture and temperature.
Useful formulations include liquid compositions and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions), and the like, which may optionally be thickened into gels. Common types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions and suspoemulsions. Common types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.
The general types of solid compositions are powders, granules, pellets, prills, lozenges, tablets, filled films (including seed coatings), and the like, which may be water dispersible ("wettable") or water soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. The active ingredient may be (micro) encapsulated and further formed into a suspension or solid formulation; alternatively, the entire active ingredient formulation may be encapsulated (or "coated"). Encapsulation may control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granular formulations. The high concentration compositions are mainly used as intermediates for other formulations.
Sprayable formulations are typically dispersed in a suitable medium prior to spraying. Such liquid and solid formulations are formulated to be readily diluted in a spray medium, typically water. The spray volume may be in the range of about one to several thousand liters per hectare, but more typically in the range of about ten to several hundred liters per hectare. The sprayable formulation may be mixed with water or another suitable medium in a water tank for treatment of the foliage by air or ground application, or applied to the growing medium of the plant. The liquid and dry formulations can be dosed directly into the drip irrigation system or into the furrow during planting.
The formulation will typically comprise effective amounts of active ingredient, diluent and surfactant, the sum being 100% by weight.
Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starches, dextrins, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate and sodium sulfate. Typical solid Diluents are described in Handbook of the instruments Dust Diluents and Carriers, 2 nd edition, Dorland Books, Caldwell, new jersey, Watkins et al.
Liquid diluents include, for example, water, N-dimethyl alkanamides (e.g., N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oil, N-paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerol, triacetin, sorbitol, aromatic hydrocarbons, dealkylated aliphatics, alkylbenzenes, alkylnaphthalenes, ketones (e.g., cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone), acetates (e.g., isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate, and isobornyl acetate), Other esters (such as alkylated lactates, dibasic esters and gamma-butyrolactones), and may be straight chain, branched chain, saturated or unsaturated alcohols (such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecanol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzyl alcohol). Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C22), such as vegetable seed and fruit oils (e.g., 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), animal derived fats (e.g., tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, which can be obtained by hydrolysis of vegetable and animal derived glycerides and can be purified by distillation. Typical liquid diluents are described in Marsden's Solvents Guide, 2 nd edition, Interscience, New York, 1950.
The solid and liquid compositions of the present invention typically comprise one or more surfactants. Surfactants (also known as "surface active agents") generally change when added to a liquid, most often lowering the surface tension of the liquid. Surfactants can be used as wetting agents, dispersing agents, emulsifying agents, or defoaming agents, depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule.
Surfactants can be classified as nonionic, anionic, or cationic surfactants. Nonionic surfactants useful as compositions of the present invention include, but are not limited to: alcohol alkoxylates, such as alcohol alkoxylates based on natural and synthetic alcohols (which are branched or linear) and prepared from alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylation, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean, castor and rapeseed oil; alkylphenol alkoxylates such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate and dodecylphenol ethoxylate (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); a block polymer prepared from ethylene oxide or propylene oxide and a reverse block polymer, wherein the end block is prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including those prepared from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); fatty acid esters, glycerides, lanolin-based derivatives, polyethoxylated esters, such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives, such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd PEG (polyethylene glycol) resins, graft or comb polymers, and star polymers; polyethylene glycol (PEG); polyethylene glycol fatty acid esters; a silicone-based surfactant; and sugar derivatives such as sucrose esters, alkyl polyglucosides, and alkyl polysaccharides.
Useful anionic surfactants include, but are not limited to: alkyl aryl sulfonic acids and their salts; carboxylated alcohols or alkylphenol ethoxylates; a diphenyl sulfonate derivative; lignin and lignin derivatives, such as lignosulfonates; maleic or succinic acid or anhydrides thereof; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrylphenol ethoxylates; a protein-based surfactant; a sarcosine derivative; styrylphenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; amine and amide sulfonates, such as N, N-alkyl taurates; benzene, cumene, toluene, xylene, and sulfonates of dodecylbenzene and tridecylbenzene; a sulfonate of condensed polynaphthalene; sulfonates of naphthalene and alkylnaphthalenes; sulfonates of petroleum fractions; sulfosuccinamates; and sulfosuccinates and their derivatives, such as dialkyl sulfosuccinates.
Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propylene diamine, tripropylene triamine and dipropylene tetramine, and ethoxylated, ethoxylated and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts, such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxide and bis- (2-hydroxyethyl) -alkylamine oxide.
Also useful in the compositions of the present invention are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their proposed uses are disclosed in a number of published references, including McCutcheon's Emulsifiers and Detergents, north american and international yearbook versions, published by McCutcheon's Division, The Manufacturing conditioner Publishing co; the Encyclopedia of Surface active Agents, Chemical Publ.Co., Inc., New York, 1964, by Sisely and Wood; and Synthetic Detergents, seventh edition, John Wiley and Sons, New York, 1987, by a.s.davidson and b.milwidsky.
The compositions of the present invention may also contain formulation adjuvants and additives known to those skilled in the art as co-formulations (some of which may also be considered to act as solid diluents, liquid diluents or surfactants). Such formulation aids and additives may control: pH (buffer), foaming during processing (antifoam such as polyorganosiloxane), sedimentation of the active ingredient (suspending agent), viscosity (thixotropic thickener), microbial growth in the container (biocide), product freezing (antifreeze), color (dye/pigment dispersion), elution (film former or binder), evaporation (anti-evaporation agent), and other formulation attributes. Film formers include, for example, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include McCutcheon's volume 2 published by McCutcheon's division, The Manufacturing conditioner Publishing co: functional Materials, north american and international yearbook versions; and those listed in PCT publication WO 03/024222.
The compounds of the present invention and any other active ingredients are typically incorporated into the compositions of the present invention by dissolving the active ingredient in a solvent or by grinding the active ingredient in a liquid diluent or a dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of the liquid composition used as an emulsifiable concentrate is water-immiscible, an emulsifier is usually added to emulsify the solvent containing the active ingredient upon dilution with water. A media mill may be used to wet grind an active ingredient slurry having a particle size of up to 2,000 μm to obtain particles having an average diameter of less than 3 μm. The aqueous slurry can be prepared as a finished suspension concentrate (see, e.g., U.S.3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations typically require a dry milling step, which results in an average particle size in the range of 2 to 10 μm. Powders and dusts can be prepared by mixing, and usually by grinding (e.g., with a hammer mill or fluid energy mill). Particles and granules can be prepared by spraying the active substance onto preformed particle carriers or by agglomeration techniques. See Browning "agglomerization" (Chemical Engineering, 12.4.1967, pages 147-48; Perry's Chemical Engineering' Handbook, 4 th edition, McGraw-Hill, New York, 1963, pages 8-57 and later and WO 91/13546. the pellets can be prepared as described in u.s.4,172,714. the water dispersible and water soluble particles can be prepared as set forth in u.s.4,144,050, u.s.3,920,442 and de.3,246,493. the tablets can be prepared as set forth in u.s.5,180,587, u.s.5,232,701 and u.s.5,208,030. the films can be prepared as set forth in GB2,095,558 and u.s.3,299,566.
For additional information regarding The formulation area, see "The formulations's Toolbox-Product Forms for model Agriculture" by T.S. woods, The food-environmental Challenge, T.Brooks and T.R. Roberts eds, Proceedings ofhe 9th International conformation on Pesticide Chemistry, The Royal society of Chemistry, Cambridge, 1999, p.120-. See also U.S.3,235,361, column 6, line 16 to column 7, line 19 and examples 10-41; U.S. Pat. No. 3,309,192, column 5, column 43 to column 7, column 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138, 162, 164, 166, 167 and 169, 182; U.S.2,891,855 at column 3, line 66 to column 5, line 17 and examples 1-4; wed Control as a Science by Klingman, John Wiley and Sons, Inc., New York, 1961, pages 81-96; weed Control Handbook, 8 th edition, Blackwell scientific Publications, Oxford, 1989, by Hance et al; and Developments in relational technology, PJB Publications, Richmond, UK, 2000.
Use of the Compounds of the invention
The herbicides of the present invention can be used by spraying plants, applying to soil, applying to the surface of water. The amount of the active ingredient is appropriately determined to meet the purpose of use. The content of the active ingredient is appropriately determined depending on the purpose.
The amount of the compound of the present invention to be used depends on the kind of the compound to be used, the target weed, the tendency of weed to appear, environmental conditions, the kind of herbicide, and the like. When the herbicides of the invention are used as such, for example in the form of powders or granules, the amount is suitably selected from 1g to 50kg, preferably 10g to 10kg, per 1 hectare of active ingredient. When the herbicide of the present invention is used in a liquid form, for example, in the form of an emulsifiable concentrate, a wettable powder or a flowable formulation, the amount thereof is suitably selected from 0.1 to 50,000ppm, preferably from 10 to 10,000 ppm.
The present invention provides a method for controlling weeds in a crop of useful plants, comprising applying to said weeds or to the locus of said weeds, or to said useful plants or to the locus of said useful plants, a compound or composition of the invention.
The present invention also provides a method of selectively controlling grasses and/or weeds in crops of useful plants, which comprises applying to the useful plants or the locus thereof or to the area of cultivation a herbicidally effective amount of a compound of formula (I).
The term "herbicide" means a compound that controls or modifies the growth of plants. The term "herbicidally effective amount" means the amount of such a compound or combination of such compounds that is capable of producing a control or modification of the growth of plants. The effects of control or modification include all deviations from natural development, e.g., kills, delays, leaf burns, albinism, dwarfing, etc. The term "plant" refers to all tangible parts of a plant, including seeds, seedlings, plantlets, roots, tubers, stems, stalks, leaves, and fruits. The term "locus" is intended to include soil, seeds and seedlings, as well as established plants (grassed habitat) and includes not only areas where weeds may have grown, but also areas where weeds have not yet emerged, and also areas for the planting of crops of useful plants. "planted area" includes the land on which crop plants have grown, as well as the land intended for planting such crop plants. The term "weeds" as used herein means any undesirable vegetation and thus includes not only important agronomic weeds as described below, but also volunteer crop plants.
Crops of useful plants in which the compositions according to the invention may be used include, but are not limited to, perennial crops such as citrus fruits, grapevines, nuts, oil palms, olives, pome fruits, stone fruits and rubber, and annual arable crops such as cereals (such as barley and wheat), cotton, oilseed rape, maize, rice, soya, sugar beet, sugar cane, sunflowers, ornamentals, switchgrass, turf and vegetables, especially cereals, maize and soya.
The grasses and weeds to be controlled can be both monocotyledonous species, such as agrostis, alopecurus, avena, brachiaria, bromus, tribulus, cyperus, digitaria, barnyard grass, kojima, lolium, monocrotonia, panicum, poa, cylindron, arrowhead, scirpus, setaria, sida and sorghum, and dicotyledonous species, such as kenaf, amaranthus, chenopodium, chrysanthemum, euphorbia, labra, ipomoea, kochia, eclipta, polygonum, rhodomyrtus, sinapis, solanum, chickweed, veronica, viola and xanthium.
The compounds of the invention may show tolerance to important crops including, but not limited to, alfalfa, barley, cotton, wheat, canola, sugar beet, corn (maize), sorghum, soybean, rice, oats, peanut, vegetables, tomato, potato, perennial plant crops including coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, bananas, plantains, pineapple, hops, tea and forests such as eucalyptus and conifer (e.g., loblolly pine), and turf varieties (e.g., prairie grass, san augustine grass (st. augustine grass), Kentucky grass and bermudagrass).
If desired, the compounds of the formula (I) according to the invention can also be used in combination with other active ingredients, for example other herbicides and/or insecticides and/or acaricides and/or nematicides and/or molluscicides and/or fungicides and/or plant growth regulators. These mixtures, and the use of these mixtures for controlling the growth of weeds and/or undesired vegetation, form yet further aspects of the invention. For the avoidance of doubt, inventive mixtures also include mixtures of two or more different compounds of formula (I). In particular, the present invention also relates to a composition according to the invention comprising, in addition to the compound of formula (I), at least one further herbicide.
When a compound of formula (I) is combined with at least one additional herbicide, the following mixtures of compounds of formula (I) are preferred. Compound of formula (I) + acetochlor, compound of formula (I) + acifluorfen-sodium, compound of formula (I) + aclonifen, compound of formula (I) + acrolein, compound of formula (I) + larvas, compound of formula (I) + diclofop-methyl, compound of formula (I) + allyl alcohol, compound of formula (I) + ametryn, compound of formula (I) + amicarbazone, compound of formula (I) + amidosulfuron, compound of formula (I) + aminocyclopyrachlor, compound of formula (I) + aminopyralid, compound of formula (I) + clomazone, compound of formula (I) + aminopyralid, compound of formula (I) + sulfamate, ammonium sulfamate, sodium sulfamate, bromacil, Compound of formula (I) + anilofos, compound of formula (I) + asulam, compound of formula (I) + atrazine, compound of formula (I) + ivermectin (aviglycine), compound of formula (I) + oxadiazon, compound of formula (I) + tetrazolium, compound of formula (I) + BCPC, compound of formula (I) + beflubutamid, compound of formula (I) + benazolin, compound of formula (I) + benzofenamate (bencambazone), compound of formula (I) + flumioxazin, compound of formula (I) + furazan, compound of formula (I) + bensulfuron-methyl, compound of formula (I) + bensulam, compound of formula (I) + bensulap, compound of formula (I) + bensulide, compound of formula (I) + bentazon, compound of formula (I) + bentazofamid, compound of formula (I) + bensultap bensulam-methyl, Compound of formula (I) + mesotrione, compound of formula (I) + bicyclopyrone, compound of formula (I) + dicyclopyrone, compound of formula (I) + bifenox, compound of formula (I) + bialaphos, compound of formula (I) + bispyribac-sodium, compound of formula (I) + borax, compound of formula (I) + herbicidal, compound of formula (I) + butyryl-chloramide, compound of formula (I) + bromophenol oxime (bromophenoxim), compound of formula (I) + bromoxynil, compound of formula (I) + butachlor, compound of formula (I) + butafenacil, compound of formula (I) + fluoropyrimidoyl flurazone, compound of formula (I) + butafenacet, Compound of formula (I) + glufosinate, compound of formula (I) + butralin, compound of formula (I) + butroxylon, compound of formula (I) + dichloflufen, compound of formula (I) + dimethylarsinic acid, compound of formula (I) + calcium chlorate, compound of formula (I) + cafenstrole, compound of formula (I) + carpronium, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + CDEA, compound of formula (I) + CEPC, compound of formula (I) + shaping alcohol-methyl, compound of formula (I) + chlorphenamine, compound of formula (I) + chlorimuron (chlorimuron), compound of formula (I) + chlorimuron-ethyl, compound of formula (I) + chloroacetic acid, compound of formula (I) + chlortoluron, compound of formula (I) + chlorpropham, compound of formula (I) + chlorsulfuron, compound of formula (I) + dichlorthal (chlorothal), compound of formula (I) + dichlorthal-dimethyl, compound of formula (I) + indolodon-ethyl, compound of formula (I) + cinmethylin, compound of formula (I) + sulfoethermethyl, compound of formula (I) + pyroxene, compound of formula (I) + clethodim, compound of formula (I) + clodinafop, Compound of formula (I) + clodinafop propargyl (clodinafoproparyl), compound of formula (I) + clomazone, compound of formula (I) + clofenamid, compound of formula (I) + clofenamido (cloransulam), compound of formula (I) + clofenamido-methyl (cloransulam-methyl), compound of formula (I) + CMA, compound of formula (I) +4-CPB, compound of formula (I) + CPMF, compound of formula (I) +4-CPP, compound of formula (I) + CPPC, compound of formula (I) + cresol, compound of formula (I) + benzosulfuron, compound of formula (I) + cyanamide (cyanamide) + cyanamide (I) +, Compound of formula (I) + cyanazine, compound of formula (I) + bentazone, compound of formula (I) + cyclosulfamuron, compound of formula (I) + thiopyran, compound of formula (I) + cyhalofop-butyl (cyhalofop-butyl), compound of formula (I) +2,4-D, compound of formula (I) +3,4-DA, compound of formula (I) + fururon, compound of formula (I) + dalapon, compound of formula (I) + dazomet, compound of formula (I) +2,4-DB, compound of formula (I) +3,4-DB, compound of formula (I +2,4-DEB, compound of formula (I + betalain, compound of formula (I) + dimethoate, compound of formula (I + dicamba), compound of formula (I + dichlobenil, compound of formula (I + o-dichlorobenzene), compound of formula (I + P-dichlorobenzene), compound of formula (I + dichloropropionic acid-P), compound of formula (I + diclofop), compound of formula (I) + diclofop-methyl, compound of formula (I) + diclosulam, compound of formula (I) + difenzoquat, compound of formula (I) +, Compound of formula (I) + diflufenican, compound of formula (I) + diflufenzopyr, compound of formula (I) + oxazolone, compound of formula (I) + pyroxsulam, compound of formula (I) + dimethenamid, compound of formula (I) + isoacetochlor, compound of formula (I) + dimethenamid-P, compound of formula (I) + thionine, compound of formula (I) + dimethylarsinic acid, compound of formula (I) + fluanid, compound of formula (I) + tebucol, compound of formula (I) + metaldehyde, compound of formula (I) + ipropyn), compound of formula (I) + benoxaden, compound of formula (I) + flurazote, flurazone, compound of formula (I) +, Compound of formula (I) + diquat dibromide, compound of formula (I) + dithiopyr, compound of formula (I) + diuron, compound of formula (I) + DNOC, compound of formula (I) +3,4-DP, compound of formula (I) + DSMA, compound of formula (I) + EBEP, compound of formula (I) + endothal, compound of formula (I) + EPTC, compound of formula (I) + penetrol, compound of formula (I) + ethylbutenfluanid, compound of formula (I) + aminobenzsulfuron-methyl, formula (I) + ethephon, compound of formula (I) +) carbendazim, compound of formula (I) + ethephon, compound of formula (I) + furoxan, compound of formula (I) + benfurazone, dithiopyr, compound of formula (I) +, dithiopyr, Compound of formula (I) + fluroxypyr ether, compound of formula (I) + ethoxysulfuron, compound of formula (I) + phenetole, compound of formula (I) + fenoxaprop-P, fenoxaprop-P, compound of formula (I) + fenoxaprop-ethyl, fenoxaprop-ethyl of formula (I) + fenoxaprop-penthyl), compound of formula (I) + tetrazolamide, compound of formula (I) + ferrous sulfate, compound of formula (I) + mevinolin-M, compound of formula (I) + flazasulfuron, compound of formula (I) + diflufenican, florasulam, Compound of formula (I) + fluazifop, compound of formula (I) + fluazifop-butyl, compound of formula (I) + fluazifop-P-butyl, compound of formula (I) + isopyrazate (fluazolate), compound of formula (I) + fluoroketosulfuron-sodium, compound of formula (I) + fluazifop-ethyl, compound of formula (I) + flufenacet, compound of formula (I) + flupyridazine (flufenpyr), compound of formula (I) + flupyridazone-ethyl, compound of formula (I) + fluflurazoxylin, Compound of formula (I) + flumetsulam, compound of formula (I) + flumiclorac-pentyl, compound of formula (I) + flumetsulam, compound of formula (I) + flumetop, compound of formula (I) + fluometuron, compound of formula (I) + fluoroglycofen (fluoroglycofurofen), compound of formula (I) + fluoroglycofen-ethyl (fluoroglycofuron-ethyl), compound of formula (I) + fluoroprop (fluorooxaprot), compound of formula (I) + fluxofenazole (fluxofam), compound of formula (I) + flupropaferol), compound of formula (I) + flupropaferon + flufenamate, compound of formula (I) + flufenamidopropyl, compound of formula (I) + flufenamate, compound of formula (I) + flufenacetrimsulfuron, compound of formula (I) +, Compound of formula (I) + butadine, compound of formula (I) + fluridone (fluridone), compound of formula (I) + fludioxolone, compound of formula (I) + fluroxypyr, compound of formula (I) + flurtamone, compound of formula (I) + oxazinoxalic acid, compound of formula (I) + oxazino-methyl, compound of formula (I) + fomesafen, compound of formula (I) + foramsulfuron, compound of formula (I) + conditioning phosphine, compound of formula (I) + glufosinate, compound of formula (I) + glyphosate, compound of formula (I) + halauxifen, methyl ester, fluroxypyr, compound of formula (I) + fluroxypyr, compound of formula (I) + halosulfuron-methyl, compound of formula (I) + haloxyfop-ethyl, compound of formula (I) + haloxyfop-P, compound of formula (I) + HC-252, compound of formula (I) + hexazinone, compound of formula (I) + imazamox methyl, compound of formula (I) + imazethapyr, compound of formula (I) + imazapyr, compound of formula (I) + imazamox, compound of formula (I) + imazaquin, compound of formula (I) + imazethapyr, compound of formula (I) + imazasulfuron, compound of formula (I) + pyrazosulfuron-methyl, Compound of formula (I) + indandim, compound of formula (I) and triazinediamine (indaziflam), compound of formula (I) + methyl iodide, compound of formula (I) + iodometsulfuron-methyl-sodium, compound of formula (I) + iodobenzonitrile, compound of formula (I) and ebazone (ipfencarbazone), compound of formula (I) + isoproturon, compound of formula (I) + isoxoron, compound of formula (I) + isoxon, compound of formula (I) + isoxaben, compound of formula (I) + isoxaflutole, compound of formula (I) + tetramisoxaflutole, compound of formula (I) +, Compound of formula (I) + lactofen, compound of formula (I) + cyhalofop-butyl, compound of formula (I) + lenacil, compound of formula (I) + linuron, compound of formula (I) + MAA, compound of formula (I) + MAMA, compound of formula (I) + MCPA-thioethyl, compound of formula (I) + MCPB, compound of formula (I) + chlorophenoxypropionic acid (mecoprop), compound of formula (I) + chlorophenoxypropionic acid-P, compound of formula (I) + mefenacet, compound of formula (I) + flufenide, compound of formula (I) + disulfuron-methyl, thiuron-methyl, thidiazuron, Compound of formula (I) + mesotrione, compound of formula (I) + metam, compound of formula (I) + metamifop, compound of formula (I) + metamitron, compound of formula (I) + pyrazoxazole, compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) and diethofenchloropyrazosulfuron (methazosulfuron), compound of formula (I) + mefenathiuron, formula (I) + mefenazole (methazole), compound of formula (I) and methicillin (methiozolin), compound of formula (I) + methylarsinic acid, compound of formula (I) + mefenacetron, compound of formula (I) + metoxuron, compound of formula (I) + bromogluron, compound of formula (I) + metosulam + metolachlor, Compound of formula (I) + metolachlor, compound of formula (I) + sulfentrazone, compound of formula (I) + metoxuron, compound of formula (I) + metribuzin, compound of formula (I) + metsulfuron), compound of formula (I) + metsulfuron-methyl, compound of formula (I) + MK-616, compound of formula (I) + diclofop-methyl, compound of formula (I) + chlorsulfuron, compound of formula (I) + bensulfuron, compound of formula (I) + glusulfuron and monosulfuron (monosulfuron), compound of formula (I) + monosulfuron-ester, compound of formula (I) + MSMA, compound of formula (I) + napropamide, compound of formula (I) + alachlor-methyl, compound of formula (I) + napropamide, compound of formula (I) + metolachlor, Compound of formula (I) + naproxen, formula (I) + NDA-402989, compound of formula (I) + fenflururon, compound of formula (I) + nicosulfuron, formula (I) + fluorochlormid (nipyraclofen), formula (I) + n-methyl glyphosate, compound of formula (I) + nonanoic acid, compound of formula (I) + norflurazon, compound of formula (I) + oleic acid (fatty acids), compound of formula (I) + prosulfocarb, compound of formula (I) + pyribencarb, compound of formula (I) + pyribensulfuron, compound of formula (I) + amosulalin, compound of formula (I) + oxadiargyl, compound of formula (I) + bensulfuron, compound of formula (I) + oxadiargyl of formula (I), compound of formula (I) + oxadiargyl, compound of formula (I) +, Compound of formula (I) + cloxazoline, compound of formula (I) + oxyfluorfen, compound of formula (I) + paraquat dihydrochloride, compound of formula (I) + dichlormate, compound of formula (I) + pendimethalin, compound of formula (I) + penoxsulam, compound of formula (I) + pentachlorophenol, compound of formula (I) + mechlorethamine, compound of formula (I) + cyclopentadiol, compound of formula (I) + dimethoxamine, compound of formula (I) + petroleum oils, compound of formula (I) + phenmedipham, compound of formula (I) + phenmedim, compound of formula (I) + phenmedipham-ethyl, phenmedim, phen, Compound of formula (I) + picloram, compound of formula (I) + flupyrazamide, compound of formula (I) + pinoxaden, compound of formula (I) + piperaphos, compound of formula (I) + arsenite, compound of formula (I) + potassium azide, compound of formula (I) + pretilachlor, compound of formula (I) + primisulfuron-methyl, compound of formula (I) + flumeturon-methyl, compound of formula (I) + aminotrifluralin, compound of formula (I) + flutolanil, compound of formula (I) + cycloxadim, formula (I) + proxadione-calceium), compound of formula (I) + prometon, compound of formula (I) + flunixol, compound of formula (I) + flunipagin, fluquine, compound of formula (I), fluquine, compound of formula (I) +, Compound of formula (I) + prometryn, compound of formula (I) + propaquizamide, compound of formula (I) + propanil, compound of formula (I) + propaquizafop, compound of formula (I) + anilazine, compound of formula (I) + propisochlor, compound of formula (I) + albenuron, compound of formula (I) + albendan-sodium, compound of formula (I) + propyzamide, compound of formula (I) + prosulfocarb, compound of formula (I) + pyraclonil, compound of formula (I) + pyraflufen-ethyl, Compound of formula (I) + sulfonatopyrazole (pyrasulfotole), compound of formula (I) + pyrazolate, compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) + benzoxazole, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyributea-ethyl, compound of formula (I) + chlorobenzotriol (pyridafol), compound of formula (I) + pyridate, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyriminobac-methyl, compound of formula (I) + pyrithiobac-n, compound of formula (I) + pyrithiobac-methyl, Compound of formula (I) + pyrithiobac-sodium, formula (I) + pyrosulfuron (pyroxasulfone), formula (I) + pyrimethanil (pyroxualm), compound of formula (I) + quinconazole (pyroxulam), compound of formula (I) + quinclorac, compound of formula (I) + chloroquinolinic acid, compound of formula (I) + fucoxanthin, compound of formula (I) + quizalofop), compound of formula (I) + quizalofop-ethyl, compound of formula (I) + zalofop-P-ethyl), compound of formula (I) + rimsulfuron, compound of formula (I) + bensulfuron, compound of formula (I) + saflufenacil, compound of formula (I) + fluazifop-P-ethyl, Compound of formula (I) + cycluron, compound of formula (I) + simazine, compound of formula (I) + simetryn, compound of formula (I) + SMA, compound of formula (I) + sodium arsenite, compound of formula (I) + sodium azide, compound of formula (I) + sodium chloride, compound of formula (I) + sulcotrione, compound of formula (I) + sulfentrazone, compound of formula (I) + sulfosulfuron, compound of formula (I) + sulfuric acid, compound of formula (I) + pyrone, pyroxylin, sodium chloride, compound of formula (I) +2,3,6-TBA, compound of formula (I) + TCA-sodium, formula (I) + gramidil (tebutam), compound of formula (I) + buthiuron, formula (I) + bicyclosulfonate, compound of formula 1) + Tembotrione, compound of formula (I) + dinetofenuron, compound of formula (I) + terbutazone, compound of formula (I) + terbutaline, compound of formula (I) + terbutazone, compound of formula (I) + desmetryn, compound of formula (I) + methoxythiachlor, compound of formula (I) + thiafluazuron (thiazafluron), compound of formula (I) + thiazopyr, thiazop, Compound of formula (I) + thifensulfuron-methyl, compound of formula (I) + dithianesulfonyl (thiencarbazone), compound of formula (I) + thifensulfuron-methyl, compound of formula (I) + prosulfocarb, compound of formula (I) + topramezone, compound of formula (I) + tralkoxydim, compound of formula (I) and triafamone (triafamone), compound of formula (I) + triallate, compound of formula (I) + triasulfuron-methyl, compound of formula (I) + triallate-herbicidal, Compound of formula (I) + triclopyr, compound of formula (I) + atrazine, compound of formula (I) + trifloxysulfuron-sodium, compound of formula (I) + trifluralin, compound of formula (I) + triflusulfuron-methyl, compound of formula (I) + triflusoxypropionic acid (trifop), compound of formula (I) + trifloxysopropionic acid-methyl (trifop-methyl), compound of formula (I) + trihydroxy triazine, compound of formula (I) + trinexapac-ethyl), compound of formula (I) + triflusulfuron, compound of formula (I) + 3- [ 2-chloro-4-fluoro-5- Ethyl (1-methyl-6-trifluoromethyl-2, 4-dioxo-1, 2,3, 4-tetrahydropyrimidin-3-yl) phenoxy ] -2-pyridyloxy ] acetate (CAS RN 353292-31-6), compounds of formula (I) +2- [ [ 8-chloro-3, 4-dihydro-4- (4-methoxyphenyl) -3-oxo-2-quinoxalinyl ] carbonyl ] -1, 3-cyclohexanedione and compounds of formula (I) + VX-573.
The compounds of formula (I) according to the invention can also be used in combination with one or more safeners. Likewise, mixtures of the compounds of formula (I) according to the invention with one or more further active ingredients, in particular with one or more further herbicides, can also be used in combination with one or more safeners. The term "safener" as used herein means a chemical that, when used in combination with a herbicide, reduces the undesirable effects of the herbicide on non-target organisms, e.g., a safener protects crops from damage by the herbicide, but does not prevent the herbicide from killing weeds. When a compound of formula (I) is combined with a safener, the following combinations of a compound of formula (I) with a safener are particularly preferred. Compound of formula (I) + AD 67(MON4660), compound of formula (I) + benoxacor, compound of formula (I) + mequindox, compound of formula (I) + mefenacet and the (Z) isomer of compound of formula (I) + corresponding mefenacet, compound of formula (I) + cyprosulfamide (CAS RN221667-31-8), compound of formula (I) + dichloracrylamide, compound of formula (I) and dicyclonone (dicyclonon), compound of formula (I) and diethanolate (diethoxylate), compound of formula (I) + mefenpyr, compound of formula (I) +), compound of formula (I) + mefenpyr, compound of formula (I) + furazolazole and a compound of formula (I) + the corresponding R isomer or methylfumazone, compound of formula (I) + ethylbisbenzoxazole acid, compound of formula (I) + mefenpyr-diethyl ester, compound of formula (I) and cresylate (mephenate), compound of formula (I) + oxabetrinil, compound of formula (I) + naphthalic anhydride (CAS RN 81-84-5), compound of formula (I) and TI-35, compound of formula (I) + N-isopropyl-4- (2-methoxy-benzoyl sulfamoyl) -benzamide (CAS RN221668-34-4) and compound of formula (I) + N- (2-methoxybenzoyl) -4- [ (methylamino-carbamoyl) -4- [ (methylamino) ethyl-methyl-ethyl-propyl-4- (2-methoxy-benzoyl sulfamoyl) -benzamide (CAS RN221668-34-4) Alkylcarbonyl) amino ] benzenesulfonamide. Particularly preferred are mixtures of compounds of formula (I) with cloquintocet-mexyl, compounds of formula (I) with mefenpyr-diethyl, compounds of formula (I) with cyprosulfamide and mixtures of compounds of formula (I) with N- (2-methoxybenzoyl) -4- [ (methylaminocarbonyl) amino ] benzenesulfonamide.
General synthetic procedure
In this specification, a structure is dominant if there is any difference between the chemical name and the chemical structure. In general, the compounds of the invention may be prepared by the methods described herein, unless otherwise indicated. The following synthetic schemes and examples serve to further illustrate the context of the invention.
Synthesis scheme I
Compounds of formula (c) and (d) may be prepared by synthetic scheme one, wherein R is8Have the meaning as described in the present invention. Reacting the compound of formula (a ') with thiourea in HBr to obtain a compound of formula (b'); carrying out bromination reaction on the compound of the formula (a) to obtain a compound of a formula (b); reacting a compound of formula (b) with a compound of formula (b') to give a compound of formula (c); the compound of formula (c) is further oxidized to give the compound of formula (d).
Examples
Example 1N-acetyl-N- (5- (((5, 5-dimethyl-4, 5-dihydroisoxazolyl-3-yl) thio) methyl) -3- (trifluoromethyl) benzisoxazol-4-yl) acetamide
Step 1: synthesis of Compound 2,2, 2-trifluoromethyl-1- (2-hydroxy-5-methylphenyl) ethan-1-one
The compound is p-toluenePhenol (43.2g,400mmol), anhydrous aluminum trichloride (130g,1.0mol) were dissolved in dry dichloromethane (400mL), trifluoroacetic anhydride (126g,600mmol) was slowly added dropwise at 10 deg.C, and the reaction was stopped after reacting at room temperature for 15 h. Water (800mL) was slowly added to the reaction mixture, followed by extraction with dichloromethane (200 mL. times.3), and the organic phases were combined and washed with saturated brine (200mL) and anhydrous Na2SO4Drying, removal of solvent, column chromatography of the concentrate (eluent: Petroleum ether/EtOAc (v/v) ═ 15/1) afforded 70.2g of a pale yellow oily liquid, yield: 86 percent.
MS-ESI:m/z 203.1[M-H]-。
Step 2: synthesis of compound 2,2, 2-trifluoromethyl-1- (2-hydroxy-5-methylphenyl) ethane-1-ketoxime
The compound 2,2, 2-trifluoromethyl-1- (2-hydroxy-5-methylphenyl) ethane-1-one (75.85g,371.5mmol), hydroxylamine hydrochloride (51.64g,743mmol), sodium acetate (60.96g,743mmol) were dissolved in methanol (500mL) and reacted at 60 ℃ in an oil bath for 5 hours, and then the reaction was stopped. Vacuum filtering to remove solid, desolventizing, concentrating, adding water (400mL), extracting with dichloromethane (150 mL. times.3), mixing organic phases, washing with saturated saline (200mL), and removing anhydrous Na2SO4Drying, removal of solvent, column chromatography of the concentrate (eluent: Petroleum ether/EtOAc (v/v) ═ 5/1) afforded 75.7g of a pale yellow oily liquid, yield: 93 percent.
And step 3: synthesis of compound 2- (1-acetohydroxyimino-2, 2, 2-trifluoromethyl) -4-methylphenol acetate
The compound 2,2, 2-trifluoromethyl-1- (2-hydroxy-5-methylphenyl) ethane-1-ketoxime (67.26g,306.8mmol) was dissolved in acetic anhydride (300mL) and reacted at 65 ℃ in an oil bath for 2 hours, and then the reaction was stopped. After the solvent was distilled off under reduced pressure, 78g of a crude product was obtained as a yellow oily liquid.
And 4, step 4: synthesis of compound 5-methyl-4-nitro-3-trifluoromethyl benzisoxazole
Dissolving the compound 2- (1-acetohydroxyimino-2, 2, 2-trifluoromethyl) -4-methylphenol acetate (35.1g,115.7mmol) in cold concentrated sulfuric acid (170mL), slowly adding nitric acid (mass fraction is 65-68%) dropwise at 20 ℃, reacting at room temperature for 12h, and stopping the reaction. The reaction was slowly added to water (510mL),dichloromethane (150 mL. times.3) extraction, combined organic phases, washed with water (200 mL. times.2), saturated brine (200mL), anhydrous Na2SO4Drying, removal of solvent, column chromatography of the concentrate (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) afforded 17.65g of a yellow solid, yield: 62 percent.
1H NMR(400MHz,CDCl3):δppm 7.82(d,J＝8.8Hz,1H),7.66(d,J＝8.8Hz,1H),2.55(s,3H)；
19F NMR(400MHz,CDCl3):δppm-61.79。
And 5: synthesis of compound 5-methyl-3-trifluoromethyl benzisoxazol-4-amine
The compound 5-methyl-4-nitro-3-trifluoromethylbenzisoxazole (14.76g,60mmol), ammonium chloride (3.85g,72mmol) and iron powder (13.44g,240mmol) were dissolved in a mixture of ethanol (162mL) and water (18mL) and reacted at 90 ℃ in an oil bath for 15 hours, whereupon the reaction was stopped. After removing the solid by suction filtration, the solution was concentrated by precipitation, and the concentrated solution was subjected to column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 10.37g of a yellow solid, yield: 80 percent.
MS-ESI:m/z 217.1[M+H]+；
1HNMR(400MHz,CDCl3):δppm 7.33(d,J＝8.4Hz,1H),6.95(d,J＝8.4Hz,1H),4.36(s,2H),2.26(s,3H)。
Step 6: synthesis of compound 5-methyl-3-trifluoromethyl benzisoxazole-4-N, N-diethylamide
The compound 5-methyl-3-trifluoromethylbenzisoxazol-4-amine (7.56g,35mmol) was dissolved in acetic anhydride (150mL) and reacted at 115 ℃ in an oil bath for 16 hours, after which the reaction was stopped. After the solvent was removed by distillation under the reduced pressure, petroleum ether and ethyl acetate were recrystallized to obtain 9.34g of a white solid, yield: 89 percent.
1HNMR(400MHz,CDCl3):δppm 7.71(d,J＝8.8Hz,1H),7.66(d,J＝8.8Hz,1H),2.31(s,3H),2.27(s,6H)。
19F NMR(400MHz,CDCl3):δppm-62.33。
And 7: synthesis of compound 5-bromomethyl-3-trifluoromethyl benzisoxazole-4-N, N-diethylamide
The compound 5-methyl-3-trifluoromethylbenzisoxazole-4-N, N-diethylamide (6.8g,22.6mmol), NBS (6.85g,38.5mmol), AIBN (1.48g,9.1mmol) was dissolved in dry carbon tetrachloride (170mL) and reacted at 75 ℃ in an oil bath for 8 hours, and then the reaction was stopped. After removing the solid by suction filtration, the solution was concentrated by precipitation, and the concentrated solution was subjected to column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 6.34g of a pale yellow solid, yield: 74 percent.
1H NMR(400MHz,CDCl3):δppm 7.92(d,J＝8.8Hz,1H),7.83(d,J＝8.8Hz,1H),4.42(s,2H),2.35(s,6H)。
And 8: synthesis of compound 5, 5-dimethyl-4, 5-dihydroisoxazol-3-ylisothiourea hydrobromide
Thiourea (6g,79mmol) was dissolved in acetonitrile (65mL) at room temperature, hydrobromic acid (48%, 10mL) was added dropwise, and the mixture was stirred at room temperature for 1 h. To the above-mentioned mixed solution was added dropwise 3-chloro-5, 5-dimethyl-4, 5-dihydroisoxazole (12.6g,95mmol), and the mixture was stirred overnight while warming to 40 ℃. The solvent was distilled off under pressure, and the obtained solid was recrystallized from ethyl acetate to obtain 19.2g of white crystals, yield: 96.0 percent.
And step 9: synthesis of the Compound N-acetyl-N- (5- (((5, 5-dimethyl-4, 5-dihydroisoxazolyl-3-yl) thio) methyl) -3- (trifluoromethyl) benzisoxazol-4-yl) acetamide
The compound 5-bromomethyl-3-trifluoromethylbenzisoxazol-4-N, N-diethylamide (10.98g,28.9mmol), potassium carbonate (14.72g,115.6mmol), 5, 5-dimethyl-4, 5-dihydroisoxazol-3-ylisothiourea hydrobromide (14.72g,57.8mmol) was dissolved in acetonitrile (230mL) and reacted at room temperature for 8h to stop the reaction. After removing the solid by suction filtration, the solution was concentrated by precipitation, and the concentrated solution was subjected to column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 5/1) to give 4.67g of a white solid, and 3.56g of the starting material was recovered, yield: 56 percent.
1H NMR(400MHz,CDCl3):δppm 8.02(d,J＝8.8Hz,1H),7.78(d,J＝8.8Hz,1H),4.26(s,2H),2.78(s,2H),2.32(s,6H),1.41(s,6H)；
19F NMR(400MHz,CDCl3):δppm-62.18。
Example 2N-acetyl-N- (5- (((5, 5-dimethyl-4, 5-dihydroisoxazolyl-3-yl) sulfonyl) methyl) -3- (trifluoromethyl) benzisoxazol-4-yl) acetamide
The compound N-acetyl-N- (5- (((5, 5-dimethyl-4, 5-dihydroisoxazolyl-3-yl) thio) methyl) -3- (trifluoromethyl) benzisoxazol-4-yl) acetamide (4.6g,10.7mmol) and m-chloroperoxybenzoic acid (6.41g,26.8mmol) were dissolved in dichloromethane (60mL) and reacted at room temperature for 4h, then the reaction was stopped. After removing the solid by suction filtration, the solution was concentrated by precipitation, and the concentrated solution was subjected to column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 5/1) to give 4.87g of a pale yellow solid, yield: 98 percent.
MS-ESI:m/z 462.2[M+H]+。
Example 3N- (5- (((5, 5-dimethyl-4, 5-dihydroisoxazolyl-3-yl) sulfonyl) methyl) -3- (trifluoromethyl) benzisoxazol-4-yl) acetamide
The compound N-acetyl-N- (5- (((5, 5-dimethyl-4, 5-dihydroisoxazolyl-3-yl) sulfonyl) methyl) -3- (trifluoromethyl) benzisoxazol-4-yl) acetamide (4.14g,8.9mmol), hydrazine hydrate (0.68g,13.4mmol) was dissolved in methanol (50mL) and reacted at room temperature for 3 hours and then stopped. After exsolution concentration, column chromatography separation (eluent: Petroleum ether/EtOAc (v/v) ═ 3/1) afforded 3.61g of a white solid, yield: 96 percent.
MS-ESI:m/z 420.1[M+H]+；
1H NMR(400MHz,CDCl3):δppm 7.80(d,J＝8.8Hz,1H),7.73(d,J＝8.8Hz,1H),7.69(s,1H),4.80(s,2H),3.03(s,2H),2.28(s,3H),1.48(s,6H)。
19F NMR(400MHz,CDCl3):δppm-61.45。
Example 4N- (5- (((5, 5-dimethyl-4, 5-dihydroisoxazolyl-3-yl) thio) methyl) -3- (trifluoromethyl) benzisoxazol-4-yl) acetamide
Prepared in a similar manner to the synthesis of example 3 to give a white solid in 97% yield.
1H NMR(600MHz,CDCl3):δppm 8.52(s,1H),7.76(d,J＝8.4Hz,1H),7.62(d,J＝8.4Hz,1H),4.24(s,2H),2.74(s,2H),2.27(s,3H),1.37(s,6H)。
Example 52- (5- (((5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl) thio) methyl) -3- (trifluoromethyl) benzisoxazol-4-yl) isoindole-1, 3-dione
Step 1: synthesis of Compound 2- (5-methyl-3- (trifluoromethyl) benzisoxazol-4-yl) isoindole-1, 3-dione
The compound 5-methyl-3- (trifluoromethyl) benzisoxazol-4-amine (5.4g,25mmol), phthalic anhydride (7.4g,50mmol) was dissolved in acetic acid (75mL) and reacted at 120 ℃ in an oil bath for 12 hours, after which the reaction was stopped. The system was concentrated by desolventizing and the concentrate was subjected to column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 5/1) to give 8.2g of a pink solid in yield: 95 percent.
MS-ESI:m/z 347.0[M+H]+；
1H NMR(400MHz,CDCl3):δppm 8.01(dd,J＝5.4,3.0Hz,2H),7.87(dd,J＝5.4,3.0Hz,2H),7.77(d,J＝8.8Hz,1H),7.70(d,J＝8.8Hz,1H),2.33(s,3H)。
Step 2: synthesis of Compound 2- (5-bromomethyl-3- (trifluoromethyl) benzisoxazol-4-yl) isoindole-1, 3-dione
The compound 2- (5-methyl-3- (trifluoromethyl) benzisoxazol-4-yl) isoindole-1, 3-dione (4.76g,13.7mmol), NBS (4.89g,27.5mmol), AIBN (0.57g,3.4mmol) was dissolved in dry carbon tetrachloride (90mL), reacted at 80 ℃ in an oil bath for 4 hours, and then the reaction was stopped. After removing the solid by suction filtration, the solution was concentrated by precipitation, and the concentrated solution was subjected to column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 5/1) to give 3.72g of a pale yellow solid, yield: and 64 percent.
1H NMR(400MHz,CDCl3):δppm 8.04(dd,J＝5.6,3.2Hz,2H),7.94–7.86(m,4H),4.45(s,2H)。
And step 3: synthesis of Compound 2- (5- (((5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl) thio) methyl) -3- (trifluoromethyl) benzisoxazol-4-yl) isoindole-1, 3-dione
The compound 2- (5-bromomethyl-3- (trifluoromethyl) benzisoxazol-4-yl) isoindole-1, 3-dione (4.25g,10.0mmol), potassium carbonate (5.53g,40.0mmol), 5, 5-dimethyl-4, 5-dihydroisoxazol-3-ylisothiourea hydrobromide (5.08g,20.0mmol) was dissolved in acetonitrile (60mL) and reacted at room temperature for 20 hours, and then the reaction was stopped. After removing the solid by suction filtration, the solution was concentrated by precipitation, and the concentrated solution was subjected to column chromatography (eluent: petroleumeher/EtOAc (v/v) ═ 5/1) to give 4.67g of a white solid, and 3.23g of the starting material was recovered, yield: 68 percent.
MS-ESI:m/z 476.1[M+H]+；
1H NMR(400MHz,CDCl3):δppm 8.03–7.99(m,3H),7.87(dd,J＝5.6,3.2Hz,2H),7.83(d,J＝8.8Hz,1H),4.31(s,2H),2.67(s,2H),1.33(s,6H)。
Example 62- (5- (((5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl) sulfonyl) methyl) -3- (trifluoromethyl) benzisoxazol-4-yl) isoindole-1, 3-dione
The compound 2- (5- (((5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl) thio) methyl) -3- (trifluoromethyl) benzisoxazol-4-yl) isoindole-1, 3-dione (5.1g,10.7mmol) and m-chloroperoxybenzoic acid (6.41g,26.8mmol) were dissolved in dichloromethane (70mL) and reacted at room temperature for 7 hours, followed by stopping the reaction. After removing the solid by suction filtration, the solution was concentrated by precipitation, and the concentrated solution was subjected to column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 3/1) to give 5.25g of a white solid, yield: 96 percent.
MS-ESI:m/z 508.1[M+H]+；
1H NMR(400MHz,CDCl3):δppm 8.03–8.00(m,3H),7.92(d,J＝8.8Hz,1H),7.87(dd,J＝5.6,3.2Hz,2H),4.77(s,2H),2.90(s,2H),1.41(s,6H)。
Example 75- (((5, 5-dimethyl-4, 5-dihydroisoxazolyl) sulfonyl) methyl) -3- (trifluoromethyl) benzisoxazol-4-amine
Compound 2- (5- (((5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl) sulfonyl) methyl) -3- (trifluoromethyl) benzisoxazol-4-yl) isoindole-1, 3-dione (5.18g,10.2mmol), hydrazine hydrate (0.95g,15.3mmol) was dissolved in a mixture of methanol (50mL) and dichloromethane (30mL) and reacted at room temperature for 10 hours, followed by stopping the reaction. After exsolution concentration, column chromatography separation (eluent: Petroleum ether/EtOAc (v/v) ═ 5/1) afforded 2.0g of a white solid, yield: 52 percent.
MS-ESI:m/z 378.0[M+H]+；
1H NMR(600MHz,CDCl3):δppm 7.46(d,J＝8.4Hz,1H),7.09(d,J＝8.4Hz,1H),5.08(s,2H),4.72(s,2H),3.00(s,2H),1.47(s,6H)。
Example 85- (((5, 5-dimethyl-4, 5-dihydroisoxazolyl) thio) methyl) -3- (trifluoromethyl) benzisoxazol-4-amine
Prepared in a similar manner to the synthesis of example 7 as a pale yellow solid in 55% yield.
1HNMR(400MHz,CDCl3):δppm 7.41(d,J＝8.0Hz,1H),6.96(d,J＝8.0Hz,1H),5.10(s,2H),4.36(s,2H),2.81(s,2H),1.43(s,6H)。
The compounds shown in table 1 were prepared by analogous synthetic methods to the examples of the invention, and by the synthetic methods described in the present invention or analogous synthetic methods, starting with the corresponding starting materials:
table 1 Compounds and characterization data thereof
Biological examples
Compound preparation: a certain mass of the original drug is weighed by an analytical balance (0.0001g), dissolved by DMF containing 1% of Tween-80 emulsifier to prepare 1.0% of mother liquor, and then diluted by distilled water for later use.
The test method comprises the following steps: the potting method is used for testing target piemarker, redroot amaranth, snakehead intestine and cockspur grass. A flowerpot with the inner diameter of 7.5cm is taken, composite soil (vegetable garden soil: seedling raising matrix, 1:2, v/v) is filled to 3/4 positions, the four weed targets are directly sown (the germination rate is more than or equal to 85 percent), the soil is covered by 0.2cm, and the weeds are kept for later use when the weeds grow to about 3-leaf stage. After each compound is applied in an automatic spray tower (model: 3WPSH-700E) according to the dosage of 300g a.i./ha or 150g a.i./ha, the weed leaves are transplanted to a greenhouse for culture after the liquid medicine on the weed leaves is dried, and the activity (%) of the weed is checked after 25 days.
And (3) test results:
example 1 herbicidal activity against abutilon at 300g ai/ha and 150g ai/ha was 100% and 80%, respectively;
the herbicidal activity of example 1, example 2, example 3 and example 8 on Amaranthus retroflexus at 300g ai/ha was 100%;
example 1, example 2 and example 3 had herbicidal activity against Amaranthus retroflexus at 150g ai/ha of 80%, 70%, 80% and 90%, respectively;
the herbicidal activity of 300g ai/ha for snakehead intestine in examples 1,2 and 3 is 100%;
both example 1 and example 2 had 100% herbicidal activity against barnyard grass at 300g ai/ha.
While at 300gai/ha, the herbicidal activity of Pyroxaufone against abutilon, Amaranthus retroflexus, snakehead gut and Echinochloa crusgalli was 50%, 60%, 75% and 75%, respectively.
While at 150gai/ha, the herbicidal activity of Pyroxaufone against abutilon, Amaranthus retroflexus and snakehead intestine was 0%, 0% and 50%, respectively.
Therefore, the herbicidal activity of the compound on piemarker, Amaranthus retroflexus and snakehead intestine is superior to that of pyroxasulfofone; and the compound of the present invention shows more excellent herbicidal activity than the prior art at a low dose.
The compound has good control effects on piemarker, Amaranthus retroflexus, snakehead intestine and cockspur grass. Is safe to crops, and has better weed control effect than the commercial herbicides and isoxazoline compounds with similar structures.

Claims (5)

1. A compound which is a compound of formula (III) or a salt of a compound of formula (III):
wherein:
n is 0, 1 or 2;
each RaAnd RbIndependently hydrogen or-C (═ O) -Rc；
Each RcIndependently is C1-6Alkyl or halo C1-6An alkyl group.
2. The compound of claim 1, wherein
Each RaAnd RbIndependently hydrogen, -C (═ O) -CH3、-C(＝O)-CH2CH3、-C(＝O)-CH2CH2CH3、-C(＝O)-CH(CH3)2、-C(＝O)-C(CH3)3、-C(＝O)-CH2F、-C(＝O)-CH2Cl、-C(＝O)-CH2Br、-C(＝O)-CF3、-C(＝O)-CH2CF3or-C (═ O) -CH2CH2CF3。
3. A compound which is a compound having one of the following structures or a salt of a compound having one of the following structures:
4. a composition comprising a compound of any one of claims 1-3, further comprising an agriculturally pharmaceutically acceptable surfactant and a carrier.
5. Use of the compound according to any one of claims 1 to 3 or the composition according to claim 4 for controlling plant diseases.
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