CN112430220A - Substituted benzoyl compound and application thereof - Google Patents

Substituted benzoyl compound and application thereof Download PDF

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CN112430220A
CN112430220A CN201910791866.1A CN201910791866A CN112430220A CN 112430220 A CN112430220 A CN 112430220A CN 201910791866 A CN201910791866 A CN 201910791866A CN 112430220 A CN112430220 A CN 112430220A
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compound
formula
hydrogen
tautomer
stereoisomer
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CN112430220B (en
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李义涛
林健
张虎
黄敏
刘鹏飞
康维明
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Dongguan Hec Pesticides R&d Co ltd
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    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
    • C07D271/113—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
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    • A—HUMAN NECESSITIES
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
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    • 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
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
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    • 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
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    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
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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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
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    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D211/84—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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 directly attached to ring carbon atoms
    • C07D211/86—Oxygen atoms
    • C07D211/88—Oxygen atoms attached in positions 2 and 6, e.g. glutarimide
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    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
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    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
    • C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
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    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
    • C07D249/12—Oxygen or sulfur atoms
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    • C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
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    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
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    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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  • Chemical & Material Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)
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Abstract

The invention provides a substituted benzoyl compound and application thereof; specifically, the invention provides a compound shown as a formula (I), a preparation method and application thereof as a herbicide; wherein Q is optionally substituted oxocyclohexenyl or substituted pyrazolyl, or the like; x is chlorine or-SO2CH3(ii) a Hy is optionally substituted indazolyl, piperidinyl, and the like.

Description

Substituted benzoyl compound and application thereof
Technical Field
The invention provides a new substituted benzoyl compound and a preparation method thereof; compositions containing these compounds and their use in agriculture.
Background
Substituted benzoyl compounds are a class of compounds with excellent biological activity, and their herbicidal activity is reported in, for example, CN1310714A, WO2001010850, DE19962923, WO2002010155, etc. However, the compounds of the present invention described in detail hereinafter are not described in these documents.
The active ingredients known from the documents cited above have disadvantages in use, for example, (a) no or only insufficient herbicidal action on the weed plants, (b) too narrow a spectrum of weed plants to be controlled or (c) too low a selectivity in crops of useful plants.
Accordingly, there is a need to provide chemically active ingredients that can be advantageously used as herbicides or plant growth regulators.
Disclosure of Invention
The present invention provides a novel substituted benzoyl compound having excellent herbicidal action, a broad weed control spectrum and excellent selectivity between crops and weeds.
In one aspect, the invention provides a compound of formula (I) or a stereoisomer, tautomer, nitroxide or salt thereof:
Figure BDA0002179760620000011
wherein:
hy is indazolyl; or Hy is the following sub-structural formula:
Figure BDA0002179760620000012
wherein
G is-CH2-, -O-, -S-or-NR1j-；
m is 0, 1 or 2;
M1is-O-or-S-;
M2is-O-or-S-;
M3is-N-, -NR1k-, -O-or-S-;
t is-O-, -S-or-NR1m-；
Figure BDA0002179760620000021
Represents a single bond or a double bond;
R1a、R1b、R1c、R1d、R1e、R1f、R1g、R1h、R1j、R1kand R1mEach independently is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical、C2-6Alkynyl, halo C1-6Alkyl radical, C1-6Alkoxy or halo C1-6An alkoxy group;
or R1a、R1bAnd the carbon atoms to which they are attached form a 3-8 membered cycloalkyl group;
or R1c、R1dAnd the carbon atoms to which they are attached form a 3-8 membered cycloalkyl group;
x is chlorine or-SO2CH3；
Q is the following subformula:
Figure BDA0002179760620000022
R2and R2aEach independently is hydrogen or C1-6An alkyl group;
R3is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-8A cycloalkyl group;
R4is hydrogen or-CH2-CO-C6-10An aryl group; wherein said-CH2-CO-C6-10Aryl is optionally substituted by 1, 2 or 3 substituents selected from halogen or C1-6Alkyl substituents.
In some of these embodiments, Hy is 1H-indazol-1-yl or 2H-indazol-2-yl; or Hy is the following sub-structural formula:
Figure BDA0002179760620000023
wherein
G is-O-or-S-;
M1is-O-or-S-;
M2is-O-or-S-;
M3is-N-;
t is-O-, -S-or-NR1m-；
R1m、R1a、R1b、R1c、R1d、R1e、R1f、R1gAnd R1hEach independently is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4An alkoxy group;
or R1a、R1bAnd the carbon atoms to which they are attached form a 3-6 membered cycloalkyl group;
or R1c、R1dAnd the carbon atoms to which they are attached form a 3-to 6-membered cycloalkyl group.
In other embodiments, R1m、R1a、R1b、R1c、R1d、R1e、R1f、R1gAnd R1hEach independently hydrogen, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy or isopropoxy;
or R1a、R1bAnd the carbon atom to which it is attached, together form a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group;
or R1c、R1dAnd the carbon atom to which it is attached, together form a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group.
In other embodiments, Hy is the following subformula:
Figure BDA0002179760620000031
in some of these embodiments, R2And R2aEach independently is hydrogen or C1-4An alkyl group.
In other embodiments, R2And R2aEach independently hydrogen, methyl or ethyl.
In some of these embodiments, R3Is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl or C3-6A cycloalkyl group.
In other embodiments, R3Is hydrogen, methyl, ethyl, n-propyl, isopropyl, cycloPropyl, cyclobutyl, cyclopentyl or cyclohexyl.
In some of these embodiments, R4Is hydrogen or-CH2-CO-phenyl; wherein said-CH2-CO-phenyl optionally substituted by 1, 2 or 3 substituents selected from halogen or C1-4Alkyl substituents.
In other embodiments, R4Is hydrogen or-CH2-CO-phenyl; wherein said-CH2-CO-phenyl is optionally substituted with 1, 2 or 3 substituents selected from chloro or methyl.
In some of these embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, tautomer, nitroxide or salt thereof of a compound of formula (Ia):
Figure BDA0002179760620000032
wherein: q, X, R1aAnd R1bHave the meaning as described in the present invention.
In still other embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, tautomer, nitroxide or salt thereof, of a compound of formula (Ia), wherein R is1aAnd R1bEach independently is hydrogen or C1-3An alkyl group; or R1a、R1bTogether with the carbon atom to which they are attached form C3-6A cycloalkyl group.
In still other embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, tautomer, nitroxide or salt thereof, of a compound of formula (Ia), wherein R is1aAnd R1bEach independently hydrogen or methyl; or R1a、R1bAnd the carbon atom to which it is attached, together form a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group.
In some of these embodiments, the present invention provides a compound that is a compound of formula (Ib) or a stereoisomer, tautomer, nitroxide or salt thereof of a compound of formula (Ib):
Figure BDA0002179760620000041
wherein: q, X, G, R1aAnd R1bHave the meaning as described in the present invention.
In still other embodiments, the invention provides a compound that is a compound of formula (Ib) or a stereoisomer, tautomer, nitroxide or salt thereof, wherein
G is-O-or-S-;
R1aand R1bEach independently is hydrogen or C1-3An alkyl group.
In still other embodiments, the invention provides a compound that is a compound of formula (Ib) or a stereoisomer, tautomer, nitroxide or salt thereof, wherein
G is-O-or-S-;
R1aand R1bEach independently hydrogen or methyl.
In some embodiments, the present invention provides a compound that is a compound of formula (Ic) or a stereoisomer, tautomer, nitroxide or salt thereof of a compound of formula (Ic):
Figure BDA0002179760620000042
wherein: q, X, M1、R1c、R1dAnd R1eHave the meaning as described in the present invention.
In still other embodiments, the invention provides a compound that is a compound of formula (Ic) or a stereoisomer, tautomer, nitroxide or salt thereof of a compound of formula (Ic), wherein
M1is-O-or-S-;
R1c、R1dand R1eEach independently is hydrogen or C1-3An alkyl group.
In still other embodiments, the invention provides a compound that is a compound of formula (Ic) or a stereoisomer, tautomer, nitroxide or salt thereof of a compound of formula (Ic), wherein
M1is-O-or-S-;
R1c、R1dand R1eEach independently hydrogen or methyl.
In some of these embodiments, the invention provides a compound that is a compound of formula (Id) or a stereoisomer, tautomer, nitroxide or salt thereof of a compound of formula (Id):
Figure BDA0002179760620000043
wherein: q, X, M2、R1fAnd R1gHave the meaning as described in the present invention.
In still other embodiments, the invention provides a compound that is a compound of formula (Id) or a stereoisomer, tautomer, nitroxide or salt thereof, of a compound of formula (Id), wherein
M2is-O-or-S-;
R1fand R1gEach independently is hydrogen or C1-3An alkyl group.
In still other embodiments, the invention provides a compound that is a compound of formula (Id) or a stereoisomer, tautomer, nitroxide or salt thereof, of a compound of formula (Id), wherein
M2is-O-or-S-;
R1fand R1gEach independently hydrogen or methyl.
In some of these embodiments, the present invention provides a compound that is a compound of formula (Ie) or a stereoisomer, tautomer, nitroxide or salt thereof of a compound of formula (Ie):
Figure BDA0002179760620000051
wherein: q, X, M3T and R1hHave the meaning as described in the present invention.
In still other embodiments, the invention provides a compound that is a compound of formula (Ie) or a stereoisomer, tautomer, nitroxide or salt thereof, of a compound of formula (Ie), wherein
M3is-N-;
t is-O-, -S-or-NR1m-；
R1mAnd R1hEach independently is hydrogen, C1-4Alkyl or C1-4An alkoxy group.
In still other embodiments, the invention provides a compound that is a compound of formula (Ie) or a stereoisomer, tautomer, nitroxide or salt thereof, of a compound of formula (Ie), wherein
M3is-N-;
t is-O-, -S-or-NR1m-；
R1mAnd R1hEach independently is hydrogen, C1-3Alkyl or C1-3An alkoxy group.
In still other embodiments, the invention provides a compound that is a compound of formula (Ie) or a stereoisomer, tautomer, nitroxide or salt thereof, of a compound of formula (Ie), wherein
M3is-N-;
t is-O-, -S-or-NR1m-；
R1mAnd R1hEach independently hydrogen, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy or isopropoxy.
In some of these embodiments, the present invention provides a compound that is a compound of formula (If) or a stereoisomer, tautomer, nitroxide or salt thereof of a compound of formula (If):
Figure BDA0002179760620000052
wherein: q and X have the meanings as described in the invention.
In some of these embodiments, the present invention provides a compound that is a compound of formula (Ig) or a stereoisomer, tautomer, nitroxide or salt thereof of a compound of formula (Ig):
Figure BDA0002179760620000053
wherein: q and X have the meanings as described in the invention.
In still other embodiments, X is chlorine.
In still other embodiments, X is-SO2CH3。
In still other embodiments, Q is of the sub-formula:
Figure BDA0002179760620000061
in some of these embodiments, the present invention provides a compound that is a compound having one of the following structures or a stereoisomer, tautomer, nitroxide or salt thereof of a compound having one of the following structures:
Figure BDA0002179760620000062
Figure BDA0002179760620000071
Figure BDA0002179760620000081
in another aspect, the invention provides a composition comprising a compound of the invention.
In some of these embodiments, the compositions of the present invention further optionally comprise at least one additional component.
In another aspect, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention in agriculture.
In another aspect, the present invention provides the use of a compound of the present invention or a composition comprising a compound of the present invention for controlling grassy weeds.
In another aspect, the present invention provides the use of a compound of the present invention or a composition comprising a compound of the present invention for controlling broadleaf weeds.
In another aspect, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention for controlling abutilon, purslane, barnyard grass or zinnia.
In some of these embodiments, the present invention provides the use of a compound described herein or a composition comprising a compound described herein for controlling unwanted vegetation.
In another aspect, the present invention provides the use of a compound of the invention or a composition comprising a compound of the invention as a herbicide.
In another aspect, the present invention provides the use of a compound of the present invention or a composition comprising a compound of the present invention as a post-emergence herbicide.
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.
In a further aspect, the present invention provides a method of controlling the growth of weeds in useful plants, which comprises applying to the locus of the weeds an effective amount of a compound of the present invention or a composition comprising a compound of the present invention.
The compound provided by the invention is a novel compound which is more effective to weeds, lower in cost, lower in toxicity and safe to environment.
The compounds of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), formula (If) or formula (Ig) 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 referred to as described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and Jerry March, 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-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; stereochemical definitions and rules as described in 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 l 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 term "tautomer" or "tautomeric form" refers to structural isomers having different energies that can interconvert by a low energy barrier (low energy barrier). If tautomerism is possible (e.g., in solution), then the chemical equilibrium of the tautomer can be reached. For example, proton tautomers (also known as proton transfer tautomers) include interconversions by proton migration, such as keto-enol isomerization and imine-enamine isomerization. Valence tautomers (valenctautomers) include interconversion by recombination of some of the bonding electrons. Specific examples of keto-enol tautomerism are the tautomerism of the pentan-2, 4-dione, hexane-1, 3-dione, and 4-hydroxypent-3-en-2-one tautomers. Another example of tautomerism is phenol-ketone tautomerism. One specific example of phenol-ketone tautomerism is the tautomerism of pyridin-4-ol and pyridin-4 (1H) -one tautomers. Unless otherwise indicated, all tautomeric forms of the compounds of the invention are within the scope of the invention.
In the present invention, depending on the external conditions (such as solvent, pH, etc.), keto-enol tautomerism exists:
Figure BDA0002179760620000101
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 10 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) N-hexyl (-CH)2CH2CH2CH2CH2CH3) 2-hexyl (-CH (CH)3)CH2CH2CH2CH3) 3-hexyl (-CH (CH)2CH3)(CH2CH2CH3) 2-methyl-2-pentyl (-C (CH))3)2CH2CH2CH3) 3-methyl-2-pentyl (-CH (CH)3)CH(CH3)CH2CH3) 4-methyl-2-pentyl (-CH (CH)3)CH2CH(CH3)2) 3-methyl-3-pentyl (-C (CH)3)(CH2CH3)2) 2-methyl-3-pentyl (-CH (CH)2CH3)CH(CH3)2) 2, 3-dimethyl-2-butyl (-C (CH)3)2CH(CH3)2) 3, 3-dimethyl-2-butyl (-CH (CH)3)C(CH3)3) N-heptyl, n-octyl, and the like.
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 10 carbon atoms; 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-)，-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH2CH2CH2CH＝CH2、-CH2CH2CH＝CHCH3、-CH2CH2CH2CH＝CHCH3And so on.
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, wherein the alkynyl radical may be optionally substituted with one or more substituents as described herein. In one embodiment, alkynyl groups contain 2-10 carbon atoms; in one embodiment, alkynyl groups contain 2-8 carbon atoms; in another embodiment, alkynyl groups contain 2-6 carbon atoms; in yet another embodiment, alkynyl groups contain 2-4 carbon atoms. Examples of alkynyl groups include, but are not limited to, -C.ident.CH, -C.ident.CCH3、-CH2-C≡CH、-CH2-C≡CCH3、-CH2CH2-C≡CH、-CH2-C≡CCH2CH3、-CH2CH2-C≡CH2CH3And so on.
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. Unless otherwise specified, the alkoxy group contains 1 to 12 carbon atoms. In one embodiment, the alkoxy group contains 1 to 10 carbon atoms; in one embodiment, the alkoxy group contains 1 to 8 carbon atoms; in one embodiment, the alkoxy group contains 1 to 6 carbon atoms; in another embodiment, the alkoxy group contains 1 to 4 carbon atoms; in yet another embodiment, the alkoxy group contains 1 to 3 carbon atoms. The alkoxy group may be optionally substituted with one or more substituents 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) 1-butoxy (n-BuO, n-butoxy, -OCH)2CH2CH2CH3) 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH)2CH(CH3)2) 2-butoxy (s-BuO, s-butoxy, -OCH (CH)3)CH2CH3) 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC (CH)3)3) 1-pentyloxy (n-pentyloxy, -OCH)2CH2CH2CH2CH3) 2-pentyloxy (-OCH (CH)3)CH2CH2CH3) 3-pentyloxy (-OCH (CH))2CH3)2) 2-methyl-2-butoxy (-OC (CH))3)2CH2CH3) 3-methyl-2-butoxy (-OCH (CH)3)CH(CH3)2) 3-methyl-l-butoxy (-OCH)2CH2CH(CH3)2) 2-methyl-l-butoxy (-OCH)2CH(CH3)CH2CH3) And 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. HalogenatedExamples of alkyl groups include, but are not limited to, -CH2F，-CHF2，-CH2Cl，-CH2Br，-CF3，-CH2CF3，-CH2CH2F，-CH2CH2Cl，-CH2CH2Br，-CH2CHF2，-CH2CH2CF3，-CH2CH2CH2F，-CH2CH2CH2Cl，-CH2CH2CH2Br，-CHFCH2CH3，-CHClCH2CH3And so on.
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 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, adamantyl, and the like.
The term "unsaturated" as used herein means that the group contains one or more unsaturations.
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.
When the compounds of the present invention contain an acid moiety, the compounds of the present inventionSalts of (i) include those derived from alkali or alkaline earth metals and 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. The salt of the compound having formula (I), formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), formula (If), or formula (Ig) can be prepared by treating the compound having formula (I), formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), formula (If), or formula (Ig) 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 or formulations having at least one additional component selected from the group consisting of surfactants, solid diluents, liquid diluents and the like, all of which meet the requirements of use as pesticides, and are within the scope of the present invention. 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 Instrument Dust Diluents and Cariers, 2 nd edition, Dorland Books, Caldwell, N.J. by 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 saturated and unsaturated fatty acids (typically C)6-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 Encyclopdia of Surface Active Agents by Sisely and Wood, Chemical Publ.Co., Inc., New York, 1964; 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 field of formulation, see "The formulations's Toolbox-Product Forms for model Agriculture" by T.S. woods, The Food-Environment Challenge, T.Brooks and T.R. Roberts eds, Proceedings of The 9th International conformation on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, p.120. 133. 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 simulation 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 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 cultivated area a herbicidally effective amount of a compound having the formula (I), formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), formula (If) or formula (Ig).
The term "herbicide" means a compound that controls or modifies the growth of plants. The term "effective amount" means the amount of such a compound or composition of such compounds that is capable of producing an effect of controlling or modifying the growth of a plant. 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 according to the invention having formula (I), formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), formula (If) or formula (Ig) may 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, mixtures of the invention also include mixtures of two or more different compounds having formula (I), formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), formula (If) or formula (Ig). In particular, the present invention also relates to a composition of the invention comprising at least one further herbicide in addition to the compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), formula (If) or formula (Ig).
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 test conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: brookfield (Bruker) nuclear magnetic instrument at 400MHz or 600MHz in CDC1 at room temperature3，d6-DMSO，CD3OD or d6Acetone as solvent (reported in ppm) with TMS (0ppm) or chloroform (7.26ppm) as reference standard. When multiple peaks occur, the following abbreviations will be used: s (singleton), d (doublet), t (triplet), q (quatet, quartet), m (multiplet ), br (broadpeded, broad), dd (doublet of doublets), dt (doublet of triplets). Coupling constants are expressed in hertz (Hz).
The mass spectrometry method used in the invention comprises the following steps: agilent 1260HPLC was used; agilent 6120 ESI.
Phase A: water (0.1% formic acid); phase B: acetonitrile (0.1% formic acid).
Gradient elution: 0-3min, 5-100% B; 3-6min, 100% B.
Flow rate: 0.6 mL/min.
Detection wavelength: 254 nm.
MS parameters: ESI positive scan, collision induced ionization: 70V.
Drying nitrogen gas: 12L/min, atomizing gas pressure: 40psi, gas temperature: at 350 ℃.
Taking a proper amount of sample, dissolving in 0.5mL of methanol, injecting a sample, and performing primary MS full scanning in a positive ESI mode to obtain an excimer peak [ M + H ]]+And (6) reading.
The following abbreviations are used throughout the present invention:
DMF: n, N-dimethylformamide, dimethylformamide; TLC: thin layer chromatography; DMSO, DMSO: dimethyl sulfoxide;
g: g; mg: mg; mol: molar ratio; mmol: millimole; m: mol/L, mol/L; mL: and (4) milliliters.
The following synthetic schemes and examples 1-30 serve to further illustrate the context of the present invention.
Synthetic schemes
Synthesis scheme I
Figure BDA0002179760620000181
Compound (Ia) can be prepared by scheme one, wherein Q, R1a、R1bAnd X has the meaning as described in the present invention. Reacting the compound (A1) with the compound (M-1) under alkaline conditions (such as potassium carbonate, sodium bicarbonate and the like) to obtain a compound (A); halogenating compound (A) with acyl chloride (such as oxalyl chloride) at 0-100 deg.C to obtain compound (B); the compound (B) and Q-H are subjected to esterification reaction at 0-35 ℃, and then further subjected to Fries rearrangement reaction with trimethylsilyl cyanide at 10-40 ℃ to obtain the target compound (Ia).
Synthesis scheme two
Figure BDA0002179760620000182
Compound (Ie) can be prepared by synthesis scheme two, wherein Q, M3、T、R1hAnd X has the formulaThe meaning is stated. Reacting the compound (A1) with the compound (M-2) under alkaline conditions (such as potassium carbonate, sodium bicarbonate and the like) to obtain a compound (C); halogenating compound (C) with acyl chloride (such as oxalyl chloride) at 0-100 deg.C to obtain compound (D); the compound (D) and Q-H are subjected to esterification reaction at 0-35 ℃, and then further subjected to Fries rearrangement reaction with trimethylsilyl cyanide at 10-40 ℃ to obtain the target compound (Ie).
Synthesis scheme three
Figure BDA0002179760620000191
The compound (I-1) can be prepared by the third synthesis scheme, wherein Q and X have the meanings as described in the present invention. Reacting the compound (A1) with 4, 4-dimethylisoxazolin-3-one under alkaline conditions (such as potassium carbonate, sodium bicarbonate and the like) to obtain a compound (F); halogenating compound (F) with acyl chloride (such as oxalyl chloride) at 0-100 deg.C to obtain compound (G); the compound (G) and Q-H are subjected to esterification reaction at 0-35 ℃, and then further subjected to Fries rearrangement reaction with trimethylsilyl cyanide at 10-40 ℃ to obtain the target compound (I-1).
Synthesis scheme four
Figure BDA0002179760620000192
Compound (I-2) can be prepared by synthesis scheme IV, wherein R2、R2aAnd X has the meaning as described in the present invention. Reacting the compound (A1) with 1H-indazole under basic conditions (such as potassium carbonate, sodium bicarbonate and the like) to obtain a compound (J); halogenating compound (J) with acyl chloride (such as oxalyl chloride) at 0-100 deg.C to obtain compound (K); carrying out esterification reaction on the compound (K) and optionally substituted cyclohexanedione at 0-35 ℃ to obtain a compound (L); the compound (L) and trimethylsilyl cyanide undergo Fries rearrangement reaction at 10-40 ℃ to obtain the target compound (I-2).
Synthesis scheme five
Figure BDA0002179760620000201
Compound (I-4) can be prepared by synthesis scheme five, wherein R3Hy and X have the meanings as described in the invention; wherein R is5Is alkyl or halogen; y is halogen. Nucleophilic substitution reaction is carried out on the compound (I-3) and the compound (N-1) under alkaline conditions (such as cesium carbonate, potassium carbonate and the like) at 25-50 ℃ to obtain the target compound (I-4).
Examples
Example 1: 3- (2, 6-dichloro-3- (2-hydroxy-6-oxocyclohex-1-enecarbonyl) benzyl) -5-methyl-1, 3, 4-oxadiazol-2 (3H) -one
Figure BDA0002179760620000202
Step 1: preparation of 2, 4-dichloro-3-methylacetophenone
Figure BDA0002179760620000203
To a single neck flask was added aluminum chloride (49.68g, 372.60mmol) and 2, 6-dichlorotoluene (50.00g, 310.50mmol), stirred at room temperature, then acetyl chloride (26.81g, 341.60mmol) was slowly added dropwise, heated to 40 ℃ for 2h, and TLC monitored for completion of the starting material reaction. The system was poured slowly into ice water (500mL), acidified with dilute hydrochloric acid solution (1M, 30mL), extracted with dichloromethane (150mL x 3), dried over anhydrous sodium sulfate, and concentrated to give 60g of a colorless oil in 95% yield.
Step 2: preparation of 2, 4-dichloro-3-methylbenzoic acid
Figure BDA0002179760620000204
2, 4-dichloro-3-methylacetophenone (30.00g, 147.70mmol) and 1, 4-dioxane (100mL) were added to a single vial, the temperature was raised to 80 deg.C, sodium hypochlorite solution (5% available chlorine 300mL) was added dropwise, the temperature was maintained and stirred for 5h, and TLC monitored that the starting material was completely reacted. After returning to room temperature, the phases were separated and the lower solution was separated, acidified to pH 2 with concentrated hydrochloric acid, filtered, the filter cake washed with water (100mL x 3) and dried at 50 ℃ to give 22g of a white solid in 74% yield.
And step 3: preparation of 3- (bromomethyl) -2, 4-dichlorobenzoic acid
Figure BDA0002179760620000211
2, 4-dichloro-3-methylbenzoic acid (20.00g, 97.54mmol), carbon tetrachloride (250mL), N-bromosuccinimide (26.04g, 97.54mmol) and azobisisobutyronitrile (3.20g, 19.51mmol) were added to a single-neck flask, which was then placed in an oil bath at 78 ℃ for 5 hours. After the reaction was stopped, the reaction solvent carbon tetrachloride was dried off, ethyl acetate (100mL) was added to dissolve the residue, which was washed with water (100mL × 3), and the organic phase was dried over anhydrous sodium sulfate, concentrated, and recrystallized (petroleum ether/ethyl acetate (v/v) ═ 20/1) to give 20.77g of a white solid in 75% yield.
MS(ES-API,pos.ion)m/z:284.9[M+H]+.
And 4, step 4: preparation of 2, 4-dichloro-3- ((5-methyl-2-oxo-1, 3, 4-oxadiazol-3 (2H) -yl) methyl) benzoic acid
Figure BDA0002179760620000212
To a single neck flask were added 3- (bromomethyl) -2, 4-dichlorobenzoic acid (4.00g, 14.09mmoL), 5-methyl-1, 3, 4-oxadiazol-2 (3H) -one (1.69g, 16.91mmoL), potassium carbonate (3.89g, 28.18mmoL), tetrabutylammonium bromide (0.45g,1.41mmoL) and water (50mL), and the reaction was stirred at room temperature for 24H. After the reaction had stopped, it was extracted with ethyl acetate (50 mL. times.2), the aqueous phase was acidified to pH 3 with dilute hydrochloric acid (1mol/L) to precipitate a white solid, which was filtered off with suction, the filter cake was washed with a small amount of water and dried to give 2.99g of a white solid in 70% yield.
MS(ES-API,pos.ion)m/z:303.9[M+H]+.
And 5: preparation of 2, 4-dichloro-3- ((5-methyl-2-oxo-1, 3, 4-oxadiazol-3 (2H) -yl) methyl) benzoyl chloride
Figure BDA0002179760620000213
2, 4-dichloro-3- ((5-methyl-2-oxo-1, 3, 4-oxadiazol-3 (2H) -yl) methyl) benzoic acid (800mg,2.64mmol) and ultra-dry dichloromethane (30mL) were added to a single vial, oxalyl chloride (1010mg,7.92mmol) and DMF (12mg, 0.17mmol) were added under ice bath, and the reaction was carried out at room temperature for 3 hours. The system was drained and ultra-dry dichloromethane (10mL) was added to give a solution of 2, 4-dichloro-3- ((5-methyl-2-oxo-1, 3, 4-oxadiazol-3 (2H) -yl) methyl) benzoyl chloride.
Step 6: preparation of 3-oxocyclohex-1-en-1-yl 2, 4-dichloro-3- ((5-methyl-2-oxo-1, 3, 4-oxadiazol-3 (2H) -yl) methyl) benzoate
Figure BDA0002179760620000214
To a single neck flask was added 1, 3-cyclohexanedione (356mg,3.17mmol), dried dichloromethane (20mL) and triethylamine (535mg,5.29mmol), stirred at 0 deg.C, then added the solution of 2, 4-dichloro-3- ((5-methyl-2-oxo-1, 3, 4-oxadiazol-3 (2H) -yl) methyl) benzoyl chloride obtained in step 5. The reaction was allowed to warm to room temperature for 3 hours, and after completion of the TLC monitoring, the reaction was washed with a saturated sodium bicarbonate solution (20mL), a saturated brine (20mL), the organic phase was concentrated, and column chromatography was performed (eluent: n-hexane/ethyl acetate (v/v) ═ 5/2) to give 630mg of a white solid with a yield of 60%.
And 7: synthesis of 3- (2, 6-dichloro-3- (2-hydroxy-6-oxocyclohex-1-enecarbonyl) benzyl) -5-methyl-1, 3, 4-oxadiazol-2 (3H) -one
Figure BDA0002179760620000221
To a single-necked flask was added 3-oxocyclohex-1-en-1-yl 2, 4-dichloro-3- ((5-methyl-2-oxo-1, 3, 4-oxadiazol-3 (2H) -yl) methyl) benzoate (630mg,1.59mmol), acetonitrile (30mL) and triethylamine (321mg,3.17mmol), stirred at room temperature, and then trimethylsilyl cyanide (25mg,0.26mmol) was added. The reaction was carried out at room temperature for 24h and the completion of the reaction was monitored by TLC. The reaction mixture was acidified with glacial acetic acid (1mL), stirred at room temperature for 30min, the organic solvent was removed from the reaction mixture, dissolved in water (20mL), extracted with dichloromethane (20mL × 2), and purified by column chromatography (eluent: dichloromethane/methanol (v/v) ═ 50/1) to give 440mg of a white solid in 70% yield.
MS(ES-API,pos.ion)m/z:397.0[M+H]+；
1H NMR(400MHz,CDCl3)δ7.43(d,J＝8.3Hz,1H),7.13(d,J＝8.3Hz,1H),5.15(s,2H),2.80(t,J＝6.3Hz,2H),2.44(t,J＝6.5Hz,2H),2.19(s,3H),2.09–2.02(m,2H).
Example 2: 3- (2, 6-dichloro-3- (5-hydroxy-1, 3-dimethyl-1H-pyrazole-4-carbonyl) benzyl) -5-methyl-1, 3, 4-oxadiazol-2 (3H) -one
Figure BDA0002179760620000222
Step 1: preparation of 1, 3-dimethyl-1H-pyrazol-5-yl 2, 4-dichloro-3- ((5-methyl-2-oxo-1, 3, 4-oxadiazol-3 (2H) -yl) methyl) benzoate
Figure BDA0002179760620000223
To a single-necked flask was added 1, 3-dimethyl-1H-pyrazol-5-ol (491mg, 4.39mmol), dried dichloromethane (20mL) and triethylamine (592mg, 5.85mmol), stirred at 0 ℃, and then a solution of 2, 4-dichloro-3- ((5-methyl-2-oxo-1, 3, 4-oxadiazol-3 (2H) -yl) methyl) benzoyl chloride obtained in step 5 of example 1 was added. The reaction was allowed to warm to room temperature for 3 hours, and after completion of the TLC monitoring, the reaction was washed with a saturated sodium bicarbonate solution (20mL), a saturated brine (20mL), the organic phase was concentrated, and column chromatography was performed (eluent: n-hexane/ethyl acetate (v/v) ═ 5/2) to give 1000mg of a pale yellow solid with a yield of 86%.
Step 2: preparation of 3- (2, 6-dichloro-3- (5-hydroxy-1, 3-dimethyl-1H-pyrazole-4-carbonyl) benzyl) -5-methyl-1, 3, 4-oxadiazol-2 (3H) -one
Figure BDA0002179760620000224
To a single-necked flask was added 1, 3-dimethyl-1H-pyrazol-5-yl 2, 4-dichloro-3- ((5-methyl-2-oxo-1, 3, 4-oxadiazol-3 (2H) -yl) methyl) benzoate (1000mg, 2.52mmol), acetonitrile (30mL) and triethylamine (510mg, 5.04mmol), stirred at room temperature, and then trimethylsilyl cyanide (25mg,0.26mmol) was added. The reaction was carried out at room temperature for 24h and the completion of the reaction was monitored by TLC. The reaction mixture was acidified with glacial acetic acid (1mL), stirred at room temperature for 30min, the organic solvent was removed from the reaction mixture, dissolved in water (20mL), extracted with dichloromethane (20mL × 2), and subjected to column chromatography (eluent: dichloromethane/methanol (v/v) ═ 50/1) to obtain 800mg of a pale yellow solid with a yield of 80%.
MS(ES-API,pos.ion)m/z:397.0[M+H]+.
By referring to the synthesis methods of examples 1-2, and by combining the synthesis schemes one to five of the present invention, the target compounds of table 1 can be obtained by using the corresponding raw materials and conditions.
TABLE 1
Figure BDA0002179760620000231
Figure BDA0002179760620000241
Figure BDA0002179760620000251
Figure BDA0002179760620000261
Figure BDA0002179760620000271
Figure BDA0002179760620000281
Biological examples
Weighing a certain mass of original medicine by an analytical balance (0.0001g), dissolving the original medicine by a proper amount of DMF (dimethyl formamide), and then diluting the original medicine by a certain volume of distilled water containing 1 per mill of Tween-80 emulsifier for later use. Taking flowerpots with the length and the width of 7.0cm, filling soil to 3/4, directly sowing pretreated weed target seeds, covering soil for about 0.5cm, performing spray treatment when seedlings are grown to a proper age stage, transferring the seedlings to a greenhouse for conventional culture after the application of the herbicide after the pesticide is naturally dried in the air, and checking the activity (%) of weeds after 21 days; where 0 indicates no harm or normal growth process and 100 indicates complete death of at least the aerial part. The test results are shown in tables 2-4.
TABLE 2 Activity of the compounds of the invention against abutilon at 300g/ha and 150g/ha
Examples Dosage of Abutilon Examples Dosage of Abutilon
Example 1 150g/ha 96.5 Example 2 300g/ha 82
Example 3 150g/ha 98 Example 6 150g/ha 94
Example 9 300g/ha 85 Example 10 300g/ha 80
Example 12 300g/ha 98 Example 13 300g/ha 88
Example 16 150g/ha 82.5 Example 17 150g/ha 92.5
Example 18 300g/ha 98 Example 19 300g/ha 96
Example 24 300g/ha 99 Example 25 300g/ha 98
Example 27 300g/ha 83
TABLE 3 Activity of the Compounds of the invention on Portulaca oleracea at 300g/ha and 150g/ha
Examples Dosage of Herba Portulacae Examples Dosage of Herba Portulacae
Practice ofExample 3 150g/ha 91.5 Example 4 150g/ha 82.5
Example 5 150g/ha 98 Example 6 150g/ha 98
Example 7 150g/ha 91.5 Example 9 300g/ha 98
Example 10 300g/ha 98 Example 11 300g/ha 95
Example 12 300g/ha 100 Example 16 150g/ha 80
Example 18 300g/ha 98 Example 19 300g/ha 82
Example 22 300g/ha 87 Example 25 300g/ha 98
Example 27 300g/ha 83
TABLE 4 Activity of the compounds of the invention on barnyard grass at 300g/ha
Examples Barnyard grass
Example 12 98
TABLE 5 Activity of the compounds of the invention on zinnia at 150g/ha
Examples All-grass of whooping Examples All-grass of whooping
Example 1 98 Example 3 94
Example 17 85
The results in tables 2 to 5 show that the compounds of the present invention have excellent controlling effects on abutilon, purslane, cockspur grass and zinnia at 300g/ha and 150 g/ha.
The compound has good control effect on broadleaf weeds (such as abutilon, amaranthus retroflexus, zinnia elegans, snakehead intestine and purslane) and grassy weeds (such as crab grass, cockspur grass, ryegrass and green bristlegrass). The herbicide composition is safe to crops, has quick drug effect, has better weed control effect than commercial herbicides and benzoyl compounds with similar structures, and has good application prospect.

Claims (11)

1. A compound which is a compound of formula (I) or a stereoisomer, tautomer, nitroxide or salt thereof:
Figure FDA0002179760610000011
wherein:
hy is indazolyl; or Hy is the following sub-structural formula:
Figure FDA0002179760610000012
wherein
G is-CH2-, -O-, -S-or-NR1j-；
m is 0, 1 or 2;
M1is-O-or-S-;
M2is-O-or-S-;
M3is-N-, -NR1k-, -O-or-S-;
t is-O-, -S-or-NR1m-；
Figure FDA0002179760610000013
Represents a single bond or a double bond;
R1a、R1b、R1c、R1d、R1e、R1f、R1g、R1h、R1j、R1kand R1mEach independently is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, halo C1-6Alkyl radical, C1-6Alkoxy or halo C1-6An alkoxy group;
or R1a、R1bAnd the carbon atoms to which they are attached form a 3-8 membered cycloalkyl group;
or R1c、R1dAnd the carbon atoms to which they are attached form a 3-8 membered cycloalkyl group;
x is chlorine or-SO2CH3；
Q is the following subformula:
Figure FDA0002179760610000014
R2and R2aEach independently is hydrogen or C1-6An alkyl group;
R3is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-8A cycloalkyl group;
R4is hydrogen or-CH2-CO-C6-10An aryl group; wherein said-CH2-CO-C6-10Aryl is optionally substituted by 1, 2 or 3 substituents selected from halogen or C1-6Alkyl substituents.
2. The compound of claim 1, wherein
Hy is 1H-indazol-1-yl or 2H-indazol-2-yl; or Hy is the following sub-structural formula:
Figure FDA0002179760610000021
wherein
G is-O-or-S-;
M1is-O-or-S-;
M2is-O-or-S-;
M3is-N-;
t is-O-, -S-or-NR1m-；
R1m、R1a、R1b、R1c、R1d、R1e、R1f、R1gAnd R1hEach independently is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4An alkoxy group;
or R1a、R1bAnd the carbon atoms to which they are attached form a 3-6 membered cycloalkyl group;
or R1c、R1dAnd the carbon atoms to which they are attached form a 3-to 6-membered cycloalkyl group.
3. The compound of claim 2, wherein
R1m、R1a、R1b、R1c、R1d、R1e、R1f、R1gAnd R1hEach independently hydrogen, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy or isopropoxy;
or R1a、R1bAnd the carbon atom to which it is attached, together form a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group;
or R1c、R1dAnd the carbon atom to which it is attached, together form a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group.
4. The compound of claim 1, wherein
R2And R2aEach independently is hydrogen or C1-4An alkyl group;
R3is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl or C3-6A cycloalkyl group;
R4is hydrogen or-CH2-CO-phenyl; wherein said-CH2-CO-phenyl optionally substituted by 1, 2 or 3 substituents selected from halogen or C1-4Alkyl substituents.
5. The compound of claim 4, wherein
R2And R2aEach independently hydrogen, methyl or ethyl;
R3is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
R4is hydrogen or-CH2-CO-phenyl; wherein said-CH2-CO-phenyl optionally substituted with 1, 2 or 3 substituents selected from chloro or methylAnd (4) substituting.
6. The compound according to any one of claims 1 to 5, which is a compound represented by formula (Ia) or a stereoisomer, tautomer, nitroxide or salt thereof of a compound represented by formula (Ia):
Figure FDA0002179760610000022
or a stereoisomer, a tautomer, a nitroxide or a salt thereof of a compound of formula (Ib):
Figure FDA0002179760610000031
or a stereoisomer, tautomer, nitroxide or salt thereof of a compound of formula (Ic):
Figure FDA0002179760610000032
or a stereoisomer, tautomer, nitroxide or salt thereof of a compound of formula (Id):
Figure FDA0002179760610000033
or a stereoisomer, a tautomer, a nitroxide or a salt thereof of a compound of formula (Ie):
Figure FDA0002179760610000034
or a stereoisomer, a tautomer, a nitroxide or a salt thereof of a compound of formula (If):
Figure FDA0002179760610000035
or a stereoisomer, a tautomer, a nitroxide or a salt thereof of a compound of formula (Ig):
Figure FDA0002179760610000036
7. the compound of claim 6, wherein
Q is the following subformula:
Figure FDA0002179760610000041
8. the compound according to any one of claims 1 to 7, which is a compound having one of the following structures or a stereoisomer, a tautomer, a nitroxide or a salt thereof of a compound having one of the following structures:
Figure FDA0002179760610000042
Figure FDA0002179760610000051
Figure FDA0002179760610000061
Figure FDA0002179760610000062
or
Figure FDA0002179760610000063
9. A composition comprising a compound of any one of claims 1-8.
10. Use of a compound according to any one of claims 1 to 8 or a composition according to claim 9 in agriculture.
11. A method of controlling weed development in useful plants comprising applying to the locus of the weeds an effective amount of a compound according to any one of claims 1 to 8 or a composition according to claim 9.
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