CN111574509A - Isoxazoline derivatives and their use in agriculture - Google Patents

Isoxazoline derivatives and their use in agriculture Download PDF

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Publication number
CN111574509A
CN111574509A CN202010097088.9A CN202010097088A CN111574509A CN 111574509 A CN111574509 A CN 111574509A CN 202010097088 A CN202010097088 A CN 202010097088A CN 111574509 A CN111574509 A CN 111574509A
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radical
alkyl
halo
compound
cycloalkyl
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CN111574509B (en
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李义涛
林健
池伟林
曾水明
吴双志
刘新烁
张兵兵
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Ningxia Jianpai Agrochemical Technology Co.,Ltd.
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Dongguan Hec Pesticides R&d Co ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • A01P13/02—Herbicides; Algicides selective
    • 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
    • A01N43/80—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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Organic Chemistry (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention provides isoxazoline derivatives and their use in agriculture; specifically, the invention provides a compound shown in a formula (I) or a stereoisomer, a nitrogen oxide or a salt of the compound shown in the formula (I), and a preparation method thereof; wherein R is1、R2、R3、R4、n、R5、R6Y and R7Have the meaning as described in the present invention. Further, the present invention provides compositions containing these compounds and their use in agriculture, particularly 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 WO2002062770, WO 2003000686 and WO 2003010165. The isoxazolines known from the documents cited above, however, have disadvantages in use, such as (a) no or only an inadequate herbicidal action on the weed plants, (b) a too narrow spectrum of weed plants to be controlled or (c) too low 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 isoxazoline compound having excellent herbicidal action and excellent selectivity between crops and weeds.
In one aspect, the invention provides a compound of formula (I) or a stereoisomer, a nitroxide or a salt of a compound of formula (I):
Figure BDA0002385464920000011
wherein:
y is alkoxy, alkoxyalkoxy, alkenyloxy, alkynyloxy, haloalkoxy, haloalkenyloxy or haloalkynyloxy;
R1and R2Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, alkyl, haloalkyl, cycloalkyl, or cycloalkylalkyl; or R1、R2And the carbon atoms to which they are attached form a ring consisting of 3 to 12 atoms;
R3and R4Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, alkyl, haloalkyl, cycloalkyl, or cycloalkylalkyl; or R3、R4And the carbon atoms to which they are attached form a ring consisting of 3 to 12 atoms;
R5and R6Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, alkyl, alkenyl, or alkynyl; or R5、R6And the carbon atoms to which they are attached form a ring consisting of 3 to 12 atoms;
n is 0, 1 or 2;
R7is alkyl, haloalkyl, aryl, arylalkyl, aryl-C (═ O) -, aryl-S (═ O)m-, heteroaryl, heteroarylalkyl, heteroaryl-C (═ O) -, heteroaryl-S (═ O)m-, cycloalkyl, cycloalkylalkyl, cycloalkyl-C (═ O) -, cycloalkyl-S (═ O)m-, heterocyclyl, heterocyclylalkyl, heterocyclyl-C (═ O) -or heterocyclyl-S (═ O)m-; wherein R is7Optionally substituted by 1,2,3, 4,5 or 6 substituents selected from RaSubstituted with the substituent(s);
each m is independently 0, 1 or 2;
each RaIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-8Alkyl, halo C1-8Alkyl radical, C1-8alkyl-C (═ O) -, halo-C1-8alkyl-C (═ O) -, C2-8Alkenyl, halo C2-8Alkenyl radical, C2-8Alkynyl, halo C2-8Alkynyl, C1-8Alkoxy, halo C1-8Alkoxy radical, C1-8Alkylamino radical, C1-8Alkylthio, halo C1-8Alkylamino, halogeno C1-8Alkylthio radical, C6-14Aryl radical, C6-14Aryloxy radical, C1-9Heteroaryl or C1-9A heteroaryloxy group;
with the following conditions:
when Y is methoxy or difluoromethoxy, R7Is ethyl or isopropyl, R5And R6Is hydrogen, n is 0 or 2, R3And R4Is hydrogen, R1When it is methyl, R2Is not chloromethyl;
or when Y is methoxy or difluoromethoxy, R7Is ethyl or isopropyl, R5And R6Is hydrogen, n is 0 or 2, R3And R4Is hydrogen, R2When it is methyl, R1Is not chloromethyl.
In some of these embodiments, Y is C1-6Alkoxy radical, C1-6Alkoxy radical C1-6Alkoxy radical, C2-6Alkenyloxy radical, C2-6Alkynyloxy, halo C1-6Alkoxy, halo C2-6Alkenyloxy or halogeno C2-6An alkynyloxy group;
R1and R2Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-6Alkyl, halo C1-6Alkyl radical, C3-6Cycloalkyl or C3-6Cycloalkyl radical C1-6An alkyl group; 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, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-6Alkyl, halo C1-6Alkyl radical, C3-6Cycloalkyl or C3-6Cycloalkyl radical C1-6An alkyl group; or R3、R4And the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms;
R5and R6Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-6Alkyl radical, C2-6Alkenyl or C2-6An alkynyl group; orR5、R6And the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms;
R7is C1-6Alkyl, halo C1-6Alkyl radical, C6-14Aryl radical, C6-14Aryl radical C1-6Alkyl radical, C6-14aryl-C (═ O) -, C6-14aryl-S (═ O)m-、C1-9Heteroaryl group, C1-9Heteroaryl C1-6Alkyl radical, C1-9heteroaryl-C (═ O) -, C1-9heteroaryl-S (═ O)m-、C3-8Cycloalkyl radical, C3-8Cycloalkyl radical C1-6Alkyl radical, C3-8cycloalkyl-C (═ O) -, C3-8cycloalkyl-S (═ O)m-、C2-10Heterocyclic group, C2-10Heterocyclyl radical C1-6Alkyl radical, C2-10heterocyclyl-C (═ O) -or C2-10heterocyclyl-S (═ O)m-; wherein R is7Optionally substituted by 1,2,3, 4,5 or 6 substituents selected from RaSubstituted with the substituent(s);
each RaIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-6Alkyl, halo C1-6Alkyl radical, C1-6alkyl-C (═ O) -, halo-C1-6alkyl-C (═ O) -, C2-6Alkenyl, halo C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkynyl, C1-6Alkoxy, halo C1-6Alkoxy radical, C1-6Alkylamino radical, C1-6Alkylthio, halo C1-6Alkylamino, halogeno C1-6Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-6Heteroaryl or C1-6A heteroaryloxy group.
In other embodiments, R1And R2Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-4Alkyl, halo C1-4Alkyl radical, C3-6Cycloalkyl or C3-6Cycloalkyl radical C1-3An alkyl group; or R1、R2And the carbon atoms to which they are attached form a ring consisting of 3 to 6 atoms;
R3and R4Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-3Alkyl, halo C1-3Alkyl radical, C3-6Cycloalkyl or C3-6Cycloalkyl radical C1-3An alkyl group; or R3、R4And the carbon atoms to which they are attached form a ring consisting of 3 to 6 atoms;
R5and R6Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-4Alkyl radical, C2-4Alkenyl or C2-4An alkynyl group; or R5、R6And together with the carbon atoms to which they are attached form a ring consisting of 3 to 6 atoms.
In some of these embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, a nitroxide, or a salt of a compound of formula (Ia):
Figure BDA0002385464920000021
wherein:
y and R7Have the meaning as described in the present invention.
In some of these embodiments, Y is C1-4Alkoxy radical, C1-4Alkoxy radical C1-4Alkoxy radical, C2-4Alkenyloxy radical, C2-4Alkynyloxy, halo C1-4Alkoxy, halo C2-4Alkenyloxy or halogeno C2-4An alkynyloxy group.
In still other embodiments, Y is-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2OCH3、-OCH2CH2OCH3、-OCH2CH2CH2OCH3、-OCH2OCH2CH3、-OCH2CH2OCH2CH3、-OCH2F、-OCHF2、-OCF3、-OCH2CHF2、-OCH2CF3、-OCF2CH3、-OCH2CH2CF3、-O-CH＝CH2、-O-CH2CH＝CH2、-O-C≡CH、-OC≡CCH3or-O-CH2-C≡CH。
In some of these embodiments, R7Is C1-4Alkyl, halo C1-4Alkyl radical, C6-10Aryl radical, C6-10Aryl radical C1-4Alkyl radical, C6-10aryl-C (═ O) -, C6-10aryl-S (═ O)m-、C1-6Heteroaryl group, C1-6Heteroaryl C1-4Alkyl radical, C1-6heteroaryl-C (═ O) -, C1-6heteroaryl-S (═ O)m-、C3-6Cycloalkyl radical, C3-6Cycloalkyl radical C1-4Alkyl radical, C3-6cycloalkyl-C (═ O) -, C3-6cycloalkyl-S (═ O)m-、C2-6Heterocyclic group, C2-6Heterocyclyl radical C1-4Alkyl radical, C2-6heterocyclyl-C (═ O) -or C2-6heterocyclyl-S (═ O)m-; wherein R is7Optionally substituted by 1,2,3, 4,5 or 6 substituents selected from RaSubstituted with the substituent(s);
each RaIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-4Alkyl, halo C1-4Alkyl radical, C1-4alkyl-C (═ O) -, halo-C1-4alkyl-C (═ O) -, C2-4Alkenyl, halo C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkynyl, C1-4Alkoxy, halo C1-4Alkoxy radical, C1-4Alkylamino radical, C1-4Alkylthio, halo C1-4Alkylamino, halogeno C1-4Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-6Heteroaryl or C1-6A heteroaryloxy group.
In other embodiments R7is-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH(CH3)2、-CH2F、-CHF2、-CH2Cl、-CH2Br、-CF3、-CH2CF3、-CH2CH2F、-CH2CH2Cl、-CH2CH2Br、-CH2CHF2、-CH2CH2CF3、-CH2CH2CH2F、-CH2CH2CH2Cl、-CH2CH2CH2Br、-CHFCH2CH3、-CHClCH2CH3Cyclopropylmethyl, phenyl, 3-fluorophenyl, 2, 4-difluorophenyl or phenylsulfonyl.
In another aspect, the present invention provides a composition comprising a compound of the present invention, further comprising at least one additional component required for formulation.
In some of these embodiments, the compositions of the present invention are herbicidal compositions.
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.
Further, the present invention provides use of the compound of the present invention or a composition containing the compound of the present invention for controlling a plant disease.
In some of these embodiments, the present invention provides the use of a compound of the present invention or a composition comprising a compound of the present invention for agricultural weeding.
In other embodiments, 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 herbicide.
In other embodiments, 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 pre-emergent herbicide.
In other embodiments, 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 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 a method for controlling unwanted vegetation, characterized in that an effective amount of a compound according to the invention or of a composition comprising a compound according to the invention is applied to the plants, to the seeds of the plants, to the soil in which or on which the plants grow, or to the cultivated area.
In yet another aspect, the present invention provides a method of controlling weed development in useful plants comprising applying an effective amount of a compound of the present invention or a composition comprising a compound of the present invention to the plant, the plant seed, the soil in or on which the plant is growing, or the area of cultivation.
Further, the weeds include broadleaf weeds and grass weeds.
Further, the broadleaf weeds are piemarker, Amaranthus retroflexus or snakehead intestine; the grassy weeds are large crabgrass, barnyard grass or green bristlegrass.
Still further, the useful plants include cotton, canola, soybean or peanut.
The compounds of formula (I) or (Ia) may exist in different stereoisomers or optical isomers or tautomeric forms. The present invention encompasses all such isomers and tautomers and mixtures thereof in various ratios.
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 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 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-first of allRadical-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≡CCH2CH3And so on.
The term "alkenyloxy" means an alkenyl group attached to the rest of the molecule through an oxygen atom, wherein the alkenyl group has the meaning as described herein.
The term "alkynyloxy" denotes an alkynyl group attached to the rest of the molecule through an oxygen atom, wherein the alkynyl group has the meaning as described herein. Examples of alkynyloxy groups include, but are not limited to, -O-C.ident.CH, -O-C.ident.CCH3、-O-CH2-C ≡ CH etc.
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 "alkylamino" or "alkylamino" includes "N-alkylamino" and "N, N-dialkylamino" in which the amino groups are each independently substituted with one or two alkyl groups. In some of these embodiments, the alkylamino group is one or two C1-6Lower alkylamino groups in which the alkyl group is attached to the nitrogen atom. In other embodiments, the alkylamino group is C1-3Lower alkylamino groups of (a). Suitable alkylamino groups can be monoalkylamino or dialkylamino, and such examples include, but are not limited to, N-methylamino, N-ethylamino, N-dimethylamino, N-diethylamino, and the like.
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. Alkylthio groupsExamples of (2) 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. Examples of haloalkyl 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 "haloalkoxy" denotes an alkoxy group substituted with one or more halogen atoms. Examples of haloalkoxy include, but are not limited to, -OCH2F，-OCHF2，-OCH2Cl，-OCH2Br，-OCF3，-OCH2CF3，-OCH2CH2F，-OCH2CH2Cl，-OCH2CH2Br，-OCH2CHF2，-OCH2CH2CF3，-OCH2CH2CH2F，-OCH2CH2CH2Cl，-OCH2CH2CH2Br，-OCHFCH2CH3，-OCHClCH2CH3And so on.
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 "haloalkenyl" denotes an alkenyl group substituted with one or more halogen atoms.
The term "haloalkynyl" denotes an alkynyl group substituted by one or more halogen atoms.
The term "haloalkenyloxy" denotes an alkenyloxy group substituted with one or more halogen atoms.
The term "haloalkynyloxy" denotes an alkynyloxy group substituted with one or more halogen atoms.
The term "ring of x atoms", 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 "ring of 3 to 12 atoms" refers to a carbocyclic, heterocyclic or aromatic ring system of 3 to 12 atoms, i.e. a saturated, partially unsaturated or fully unsaturated ring system optionally containing one or more heteroatoms.
The term "ring of 3 to 10 atoms" refers to a carbocyclic, heterocyclic or aromatic ring system of 3 to 10 atoms, i.e. a saturated, partially unsaturated or fully unsaturated ring system optionally containing one or more heteroatoms.
The term "ring of 3 to 8 atoms" refers to a carbocyclic, heterocyclic or aromatic ring system of 3 to 8 atoms, i.e. a saturated, partially unsaturated or fully unsaturated ring system optionally containing one or more heteroatoms.
The term "ring of 3 to 6 atoms" refers to a carbocyclic, heterocyclic or aromatic ring system of 3 to 6 atoms, i.e. a saturated, partially unsaturated or fully unsaturated ring system optionally containing one or more heteroatoms.
The term "carbocyclyl" or "carbocycle" denotes a monovalent or multivalent, non-aromatic, saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring system containing 3 to 12 carbon atoms. Carbobicyclic groups include spirocarbocyclic and fused carbocyclic groups, and suitable carbocyclic groups include, but are not limited to, cycloalkyl, cycloalkenyl and cycloalkynyl groups. Examples of carbocyclyl groups further include cyclopropyl, cyclobutyl, cyclopentyl, 1-cyclopentyl-1-alkenyl, 1-cyclopentyl-2-alkenyl, 1-cyclopentyl-3-alkenyl, cyclohexyl, 1-cyclohexyl-1-alkenyl, 1-cyclohexyl-2-alkenyl, 1-cyclohexyl-3-alkenyl, cyclohexadienyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and the like.
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 "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 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 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, thioxanyl, 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 "heterocyclylalkyl" refers to a heterocyclyl-substituted alkyl group; wherein heterocyclyl and alkyl groups have the meaning as indicated in the present invention.
The term "heterocyclyloxy" includes optionally substituted heterocyclyl groups, as defined herein, attached to an oxygen atom and linked to the rest of the molecule by an oxygen atom, wherein the heterocyclyl group has the meaning as described herein.
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 "arylalkyl" or "aralkyl" means that the alkyl group is substituted with one or more aryl groups and is attached to the rest of the molecule by an alkyl group, wherein the alkyl and aryl groups have the meaning as described herein.
The term "aryloxy" or "aryloxy" includes optionally substituted aryl groups, as defined herein, attached to and linked from an oxygen atom to the rest of the molecule, wherein the aryl group has the meaning as 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.
In another embodiment, the ring atoms of the heteroaryl group comprise 1 to 9 carbon atoms and 1 to 4 heteroatoms selected from N, O or S; in another embodiment, the ring atoms of the heteroaryl group comprise 1 to 5 carbon atoms and 1 to 4 heteroatoms selected from N, O or S.
In yet another embodiment, heteroaryl represents a 5-or 6-membered heteroaryl group containing 1-4N heteroatoms; in yet another embodiment, heteroaryl represents a 5 membered heteroaryl group containing 1-3 heteroatoms selected from N, O or S; in yet another embodiment, heteroaryl represents a 5 membered heteroaryl group containing 1-3 heteroatoms selected from N or O; in yet another embodiment, heteroaryl represents a 5 membered heteroaryl group containing 1-3 heteroatoms selected from N or S.
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.
The term "heteroarylalkyl" means that the alkyl group is substituted with one or more heteroaryl groups and is attached to the rest of the molecule by an alkyl group, wherein the alkyl group and heteroaryl groups have the meaning as described herein.
The term "heteroaryloxy" includes optionally substituted heteroaryl groups, as defined herein, attached to and linked by an oxygen atom to the rest of the molecule, wherein the heteroaryl group has the meaning as described herein.
The term "alkoxyalkoxy" denotes an alkoxy group substituted by one or more alkoxy groups, wherein the alkoxy groups have the meaning as described herein.
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. The salt of the compound having formula (I) or formula (Ia) can be prepared by treating the compound having formula (I) or formula (Ia) 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.
Detailed description of the Compounds of the invention
The invention aims to provide a novel isoxazoline compound, a herbicide composition containing the compound, a preparation and application of the compound.
In one aspect, the invention provides a compound that is a compound of formula (I) or a stereoisomer, a nitroxide, or a salt of a compound of formula (I):
Figure BDA0002385464920000091
wherein:
y is alkoxy, alkoxyalkoxy, alkenyloxy, alkynyloxy, haloalkoxy, haloalkenyloxy or haloalkynyloxy;
R1and R2Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, alkyl, haloalkyl, cycloalkyl, or cycloalkylalkyl; or R1、R2And the carbon atoms to which they are attached form a ring consisting of 3 to 12 atoms;
R3and R4Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, alkyl, haloalkyl, cycloalkyl, or cycloalkylalkyl; or R3、R4And the carbon atoms to which they are attached form a ring consisting of 3 to 12 atoms;
R5and R6Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, alkyl, alkenyl, or alkynyl; or R5、R6And the carbon atoms to which they are attached form a ring consisting of 3 to 12 atoms;
n is 0, 1 or 2;
R7is alkyl, haloalkyl, aryl, arylalkyl, aryl-C (═ O) -, aryl-S (═ O)m-, heteroaryl, heteroarylalkyl, heteroaryl-C (═ O) -, heteroaryl-S (═ O)m-, cycloalkyl, cycloalkylalkyl, cycloalkyl-C (═ O) -, cycloalkyl-S (═ O)m-, heterocyclyl, heterocyclylalkyl, heterocyclyl-C (═ O) -or heterocyclyl-S (═ O)m-; wherein R is7Optionally substituted by 1,2,3, 4,5 or 6 substituents selected from RaSubstituted with the substituent(s);
each m is independently 0, 1 or 2;
each RaIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-8Alkyl, halo C1-8Alkyl radical, C1-8alkyl-C (═ O) -, halo-C1-8alkyl-C (═ O) -, C2-8Alkenyl, halo C2-8Alkenyl radical, C2-8Alkynyl, halo C2-8Alkynyl, C1-8Alkoxy, halo C1-8Alkoxy radical, C1-8Alkylamino radical, C1-8Alkylthio, halo C1-8Alkylamino, halogeno C1-8Alkylthio radical, C6-14Aryl radical, C6-14Aryloxy radical, C1-9Heteroaryl or C1-9A heteroaryloxy group;
with the following conditions:
when Y is methoxy or difluoromethoxy, R7Is ethyl or isopropyl, R5And R6Is hydrogen, n is 0 or 2, R3And R4Is hydrogen, R1When it is methyl, R2Is not chloromethyl; or when Y is methoxy or difluoromethoxy, R7Is ethyl or isopropyl, R5And R6Is hydrogen, n is 0 or 2, R3And R4Is hydrogen, R2When it is methyl, R1Is not chloromethyl.
In some of these embodiments, Y is C1-6Alkoxy radical, C1-6Alkoxy radical C1-6Alkoxy radical, C2-6Alkenyloxy radical, C2-6Alkynyloxy, halo C1-6Alkoxy, halo C2-6Alkenyloxy or halogeno C2-6An alkynyloxy group.
In some of these embodiments, R1And R2Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-6Alkyl, halo 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 8 atoms.
In some of these embodiments, R3And R4Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-6Alkyl, halo 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 8 atoms.
In some of these embodiments, R5And R6Each independently of the others is hydrogen, fluorine, chlorineBromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-6Alkyl radical, C2-6Alkenyl or C2-6An alkynyl group; or R5、R6And together with the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms.
In some of these embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, a nitroxide, or a salt of a compound of formula (Ia):
Figure BDA0002385464920000101
wherein:
y and R7Have the meaning as described in the present invention.
In some of these embodiments, R7Is C1-6Alkyl, halo C1-6Alkyl radical, C6-14Aryl radical, C6-14Aryl radical C1-6Alkyl radical, C6-14aryl-C (═ O) -, C6-14aryl-S (═ O)m-、C1-9Heteroaryl group, C1-9Heteroaryl C1-6Alkyl radical, C1-9heteroaryl-C (═ O) -, C1-9heteroaryl-S (═ O)m-、C3-8Cycloalkyl radical, C3-8Cycloalkyl radical C1-6Alkyl radical, C3-8cycloalkyl-C (═ O) -, C3-8cycloalkyl-S (═ O)m-、C2-10Heterocyclic group, C2-10Heterocyclyl radical C1-6Alkyl radical, C2-10heterocyclyl-C (═ O) -or C2-10heterocyclyl-S (═ O)m-; wherein R is7Optionally substituted by 1,2,3, 4,5 or 6 substituents selected from RaSubstituted with the substituent(s); each RaHave the meaning as described in the present invention.
In some of these embodiments, each R isaIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-6Alkyl, halo C1-6Alkyl radical, C1-6alkyl-C (═ O) -, halo-C1-6alkyl-C (═ O) -, C2-6Alkenyl, halo C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkynyl, C1-6Alkoxy, halo C1-6Alkoxy radical, C1-6Alkylamino radical, C1-6Alkylthio, halo C1-6Alkylamino, halogeno C1-6Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-6Heteroaryl or C1-6A heteroaryloxy group.
In other embodiments, R1And R2Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-4Alkyl, halo C1-4Alkyl radical, C3-6Cycloalkyl or C3-6Cycloalkyl radical C1-3An 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 other embodiments, R3And R4Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-3Alkyl, halo C1-3Alkyl radical, C3-6Cycloalkyl or C3-6Cycloalkyl radical C1-3An 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 other embodiments, R5And R6Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-4Alkyl radical, C2-4Alkenyl or C2-4An alkynyl group; or R5、R6And together with the carbon atoms to which they are attached form a ring consisting of 3 to 6 atoms.
In other embodiments, Y is C1-4Alkoxy radical, C1-4Alkoxy radical C1-4Alkoxy radical, C2-4Alkenyloxy radical, C2-4Alkynyloxy, halo C1-4Alkoxy, halo C2-4Alkenyloxy or halogeno C2-4An alkynyloxy group.
In still other embodiments, Y is-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2OCH3、-OCH2CH2OCH3、-OCH2CH2CH2OCH3、-OCH2OCH2CH3、-OCH2CH2OCH2CH3、-OCH2F、-OCHF2、-OCF3、-OCH2CHF2、-OCH2CF3、-OCF2CH3、-OCH2CH2CF3、-O-CH＝CH2、-O-CH2CH＝CH2、-O-C≡CH、-OC≡CCH3or-O-CH2-C≡CH。
In other embodiments, R7Is C1-4Alkyl, halo C1-4Alkyl radical, C6-10Aryl radical, C6-10Aryl radical C1-4Alkyl radical, C6-10aryl-C (═ O) -, C6-10aryl-S (═ O)m-、C1-6Heteroaryl group, C1-6Heteroaryl C1-4Alkyl radical, C1-6heteroaryl-C (═ O) -, C1-6heteroaryl-S (═ O)m-、C3-6Cycloalkyl radical, C3-6Cycloalkyl radical C1-4Alkyl radical, C3-6cycloalkyl-C (═ O) -, C3-6cycloalkyl-S (═ O)m-、C2-6Heterocyclic group, C2-6Heterocyclyl radical C1-4Alkyl radical, C2-6heterocyclyl-C (═ O) -or C2-6heterocyclyl-S (═ O)m-; wherein R is7Optionally substituted by 1,2,3, 4,5 or 6 substituents selected from RaSubstituted with the substituent(s); each RaHave the meaning as described in the present invention.
In other embodiments, each R isaIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-4Alkyl, halo C1-4Alkyl radical, C1-4alkyl-C (═ O) -, halo-C1-4alkyl-C (═ O) -, C2-4Alkenyl, halo C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkynyl, C1-4Alkoxy, halo C1-4Alkoxy radical, C1-4Alkylamino radical, C1-4Alkylthio, halo C1-4Alkylamino, halogeno C1-4Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-6Heteroaryl or C1-6A heteroaryloxy group.
In other embodiments, R7is-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2F、-CHF2、-CH2Cl、-CH2Br、-CF3、-CH2CF3、-CH2CH2F、-CH2CH2Cl、-CH2CH2Br、-CH2CHF2、-CH2CH2CF3、-CH2CH2CH2F、-CH2CH2CH2Cl、-CH2CH2CH2Br、-CHFCH2CH3、-CHClCH2CH3Phenyl, 3-fluorophenyl, 2, 4-difluorophenyl or phenylsulfonyl.
In some of these embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, a nitroxide, or a salt of a compound of formula (Ia); wherein:
y is halogeno C1-4An alkoxy group;
R7is C1-4Alkyl or halo C1-4An alkyl group.
In still other embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, a nitroxide, or a salt of a compound of formula (Ia); wherein:
y is halogeno C1-2An alkoxy group;
R7is C1-2Alkyl or halo C1-2An alkyl group.
In still other embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, a nitroxide, or a salt of a compound of formula (Ia); wherein:
y is-OCH2F、-OCHF2、-OCF3、-OCH2CHF2or-OCH2CF3；
R7is-CH3、-CH2CH3、-CF3、-CH2CH2F、-CH2CHF2or-CH2CF3。
In still other embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, a nitroxide, or a salt of a compound of formula (Ia); wherein:
y is-OCHF2、-OCH2CHF2or-OCH2CF3；
R7is-CH3、-CH2CH3or-CH2CF3。
In some embodiments, the present invention provides a compound that is a compound having one of the following structures or a stereoisomer, a nitroxide, or a salt of a compound having one of the following structures:
Figure BDA0002385464920000121
Figure BDA0002385464920000131
Figure BDA0002385464920000141
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 required for formulation.
In some of these embodiments, the compositions of the present invention are herbicidal compositions.
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 invention or a composition comprising a compound of the invention as a herbicide.
In some of these embodiments, 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 pre-emergent herbicide.
In other embodiments, 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.
Further, the present invention provides use of the compound of the present invention or a composition containing the compound of the present invention for controlling a plant disease.
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 a method for controlling unwanted vegetation, characterized in that an effective amount of a compound according to the invention or of a composition comprising a compound according to the invention is applied to the plants, to the seeds of the plants, to the soil in which or on which the plants grow, or to the cultivated area.
In a further aspect, the present invention provides a method of controlling weed growth in useful plants, which comprises pre-emergence application to the locus of the weeds of an effective amount of a compound of the invention, or a composition comprising a compound of the invention.
In some embodiments, the weeds comprise broadleaf weeds and grasses.
In other embodiments, the broadleaf weed is piemarker, amaranthus retroflexus, or snakehead gut.
In still other embodiments, the grass weed is large crabgrass, barnyard grass, or green bristlegrass.
In still other embodiments, the useful plants include cotton, canola, soybean, or peanut.
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 crops.
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 and liquid diluents, wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze, antifoam agents, preservatives, stabilizers, and the like, all of which meet the requirements for 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 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 emulsions and Detergents published by McCutcheon's Division, The Manufacturing meeting Publishing co, north american and international yearbook versions; 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 field of formulation, see "The formulations's Toolbox-Product Forms for model Agriculture" in T.S. woods, The food-environmental 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-. 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 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 to the locus thereof or to the area of cultivation a herbicidally effective amount of a compound having formula (I) or formula (Ia).
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 according to the invention having the formula (I) or (Ia) 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 having formula (I) or formula (Ia). 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) or formula (Ia).
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.
Synthetic schemes
Synthesis scheme I
Figure BDA0002385464920000181
Figure BDA0002385464920000191
The compound of formula (5a) may be prepared by synthetic scheme one, wherein R2aIs alkyl, alkoxyalkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl or haloalkynyl; r7Have 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'); difluoroacetoacetic acid ethyl ester and R1NHNH2Reacting to obtain a compound of formula (1a) and a compound of formula (1 b); a compound of formula (1a) with R2a-Cl to give a compound of formula (2 a); reacting the compound shown in the formula (2a) with paraformaldehyde and hydrochloric acid to obtain a compound shown in a formula (3 a); under basic conditions (e.g. K) the compounds of formula (3a)2CO3Etc.) to produce a compound of formula (4a) by condensation reaction with a compound of formula (b'); the compound of formula (4a) is further oxidized to give the compound of formula (5 a).
Synthesis scheme two
Figure BDA0002385464920000192
The compounds of formula (5b) may be prepared by synthesis scheme two, wherein R2aIs alkyl, alkoxyalkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl or haloalkynyl; r7Have the meaning as described in the present invention. A compound of formula (1b) with R2a-Cl to give a compound of formula (2 b); reacting the compound shown in the formula (2b) with paraformaldehyde and hydrochloric acid to obtain a compound shown in a formula (3 b); under basic conditions (e.g. K) the compounds of formula (3b)2CO3Etc.) to produce a compound of formula (4b) by condensation reaction with a compound of formula (b'); the compound of formula (4b) is further oxidized to give the compound of formula (5 b).
Synthesis scheme three
Figure BDA0002385464920000201
The compounds of formula (5a) may also be prepared by synthesis scheme three, wherein R2aIs alkyl, alkoxyalkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl or haloalkynyl; r7Have the meaning as described in the present invention. Difluoro ethyleneThe ethyl acetoacetate reacts with hydrazine hydrate firstly and then reacts with phosphorus oxychloride to obtain an intermediate and R7-I to give a compound of formula (1c) and a compound of formula (1 d); a compound of formula (1c) with an alcohol R2a-OH and potassium tert-butoxide to obtain the compound of formula (2 c); the compound of the formula (2c) is subjected to reduction reaction to obtain a compound of a formula (3 c); reacting the compound of formula (3c) with a bromohydrocarbon (e.g., carbon tetrabromide) to obtain a compound of formula (4 c); under basic conditions (e.g. K) the compounds of formula (4c)2CO3Etc.) to produce a compound of formula (5c) by condensation reaction with a compound of formula (b'); the compound of formula (5c) is further oxidized to give the compound of formula (5 a).
Synthesis scheme four
Figure BDA0002385464920000202
Figure BDA0002385464920000211
Compounds of formula (5b) may also be prepared by synthesis scheme IV, wherein R2aIs alkyl, alkoxyalkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl or haloalkynyl; r7Have the meaning as described in the present invention. A compound of formula (1d) with an alcohol R2a-OH and potassium tert-butoxide to obtain the compound of formula (2 d); the compound of the formula (2d) is subjected to reduction reaction to obtain a compound of a formula (3 d); reacting the compound of formula (3d) with a bromohydrocarbon (e.g., carbon tetrabromide) to obtain a compound of formula (4 d); under basic conditions (e.g. K) the compounds of formula (4d)2CO3Etc.) to produce a compound of formula (5d) by condensation reaction with a compound of formula (b'); the compound of formula (5d) is further oxidized to give the compound of formula (5 b).
Examples
Example 1: 3- (((5- (difluoromethoxy) -3- (difluoromethyl) -1- (2,2, 2-trifluoroethyl) -1H-pyrazol-4-yl) methyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazoles
Figure BDA0002385464920000212
Step 1: 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 reduced pressure, and the resulting solid was recrystallized from ethyl acetate to give 19.2g of white crystals, yield: 96.0 percent.
Step 2: synthesis of compound 3- (difluoromethyl) -1- (2,2, 2-trifluoroethyl) -1H-pyrazol-5-ol
Figure BDA0002385464920000213
Ethyl difluoroacetoacetate (3.32g,20mmol) was dissolved in acetic acid (30mL), stirred at room temperature, and then trifluoroethylhydrazine solution (65%, 3.86g,22mmol) was slowly added dropwise to the above mixture, after the dropwise addition was completed, the reaction was allowed to react for 18h at 80 ℃, the reaction was stopped, washed with water (200mL), ethyl acetate (100mL) was extracted three times, the organic phases were combined and the solvent was removed under reduced pressure, and separated by column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 2.0g of a reddish brown solid, yield: 46.3 percent.
MS-ESI:m/z 217.0[M+H]+.
And step 3: synthesis of compound 5- (difluoromethoxy) -3- (difluoromethyl) -1- (2,2, 2-trifluoroethyl) -1H-pyrazole
Figure BDA0002385464920000221
Dissolving 3- (difluoromethyl) -1- (2,2, 2-trifluoroethyl) -1H-pyrazol-5-ol (1.08g,5mmol) and potassium carbonate (2.07g,15mmol) in acetonitrile (50mL), heating to the middle temperature of 80 ℃, stirring, slowly adding chlorodifluoroacetic acid methyl ester (1.08g,15mmol) into the mixed solution, after the addition is finished, heating to 90 ℃, stirring for 8 hours, removing acetonitrile after the reaction is finished, washing with water (100mL), extracting ethyl acetate (50mL) for three times, combining organic phases, and removing the solvent under reduced pressure to obtain 1.20g of yellow liquid, wherein the yield is as follows: 90.2 percent.
MS-ESI:m/z 267.1[M+H]+.
And 4, step 4: synthesis of the compound 4- (chloromethyl) -5- (difluoromethoxy) -3- (difluoromethyl) -1- (2,2, 2-trifluoroethyl) -1H-pyrazole
Figure BDA0002385464920000222
Dissolving 5- (difluoromethoxy) -3- (difluoromethyl) -1- (2,2, 2-trifluoroethyl) -1H-pyrazole (1.20g,4.5mmol) in concentrated hydrochloric acid (36%, 15mL), adding concentrated sulfuric acid (98%, 0.5mL), stirring at room temperature for 10min, adding paraformaldehyde (0.18g,6.3mmol) into the above mixture, heating to 80 ℃ and refluxing for 12H, after the reaction is finished, washing with water (300mL), extracting with ethyl acetate (100mL) for three times, combining organic phases, and removing the solvent under reduced pressure to obtain 1.0g of brown liquid, wherein the yield is as follows: 71.3 percent.
MS-ESI:m/z 315.0[M+H]+.
And 5: synthesis of the compound 3- (((5- (difluoromethoxy) -3- (difluoromethyl) -1- (2,2, 2-trifluoroethyl) -1H-pyrazol-4-yl) methyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000223
4- (chloromethyl) -5- (difluoromethoxy) -3- (difluoromethyl) -1- (2,2, 2-trifluoroethyl) -1H-pyrazole (1.00g,3.2mmol), 5, 5-dimethyl-4, 5-dihydroisoxazol-3-ylisothiourea hydrobromide (0.97g,3.8mmol) was dissolved in acetonitrile (50mL) and after stirring at room temperature for 10min, potassium carbonate (1.77g,12.8mmol) was added to the above mixture, the reaction was stopped after 12H, then acetonitrile was removed, washed with water (100mL), ethyl acetate (50mL) was extracted three times, the organic phases were combined and the solvent was removed under reduced pressure to give 1.30g of a yellow liquid, yield: 99.0 percent.
MS-ESI:m/z 410.3[M+H]+.
Step 6: synthesis of the Compound 3- (((5- (difluoromethoxy) -3- (difluoromethyl) -1- (2,2, 2-trifluoroethyl) -1H-pyrazol-4-yl) methyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000224
3- (((5- (difluoromethoxy) -3- (difluoromethyl) -1- (2,2, 2-trifluoroethyl) -1H-pyrazol-4-yl) methyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (1.30g,3.2mmol) was dissolved in dichloromethane (50mL), stirred at room temperature, mCPBA (1.46g,6.4mmol) was added to the above mixture, the reaction was stopped after 5 hours of reaction, and then washed with a saturated aqueous solution of sodium bisulfite (100mL) and a saturated aqueous solution of sodium bicarbonate (100mL), dichloromethane (50mL) was extracted, dried over anhydrous sodium sulfate, the combined organic phases were decompressed to remove the solvent, column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 5/1), 0.50g of a yellow oily liquid was obtained, yield: 35.7 percent.
MS-ESI:m/z 442.3[M+H]+；
1H NMR(400MHz,CDCl3)7.04–6.63(m,2H),4.71(q,J＝7.9Hz,2H),4.62(s,2H),3.09(s,2H),1.51(s,6H).
Example 2: synthesis of 3- (((3- (difluoromethyl) -1-ethyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole (Compound (24)) and 3- (((3- (difluoromethyl) -1-ethyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methyl) sulfinyl) -5, 5-dimethyl-4, 5-dihydroisoxazole (Compound (25))
Figure BDA0002385464920000231
Step 1: synthesis of compound 5-chloro-3- (difluoromethyl) -1-ethyl-1H-pyrazole-4-carbaldehyde
Figure BDA0002385464920000232
5-chloro-3- (difluoromethyl) -1H-pyrazole-4-carbaldehyde (2g,3.70mmol) and potassium carbonate (4.6g,33.20mmol) were dissolved in DMF (30mL) and stirred at room temperature, iodoethane (0.70g,4.40mmol) was added to the mixture, the addition was completed, and stirred at room temperature for 24H, after the reaction was completed, the mixture was washed with water (20mL), ethyl acetate (40mL) was extracted three times, the organic phases were combined and the solvent was removed under reduced pressure, and separated by column chromatography with EtOAc (eluent: Petroleum ether/v 10/1) to give 1.64g of a colorless transparent liquid, yield: 45 percent.
MS-ESI:m/z 209.0[M+H]+.
Step 2: synthesis of compound 3- (difluoromethyl) -1-ethyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazole-4-carbaldehyde
Figure BDA0002385464920000233
After potassium tert-butoxide (0.81g,7.20mmol) was dissolved in anhydrous tetrahydrofuran (30mL) and stirred at 0 ℃, trifluoroethanol (0.72g,7.20mmol) was added to the mixture, after stirring for 2H, 5-chloro-3- (difluoromethyl) -1-ethyl-1H-pyrazole-4-carbaldehyde (1.00g,4.80mmol) was added to the mixture, stirred at room temperature for 12H, after completion of the reaction, tetrahydrofuran was removed, washed with water (20mL), ethyl acetate (40mL) was extracted three times, the organic phases were combined and the solvent was removed under reduced pressure to give 1.0g of a yellow liquid, yield: 77.6 percent.
MS-ESI:m/z 273.7[M+H]+.
And step 3: synthesis of the compound (3- (difluoromethyl) -1-ethyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methanol
Figure BDA0002385464920000234
Dissolving 3- (difluoromethyl) -1-ethyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazole-4-carbaldehyde (1.0g,3.70mmol) in absolute methanol (40mL) and stirring at 0 ℃, then gradually adding sodium borohydride (0.28g,7.40mmol) to the above mixed solution in batches, after the addition is finished, heating to room temperature and stirring for 4H, after the reaction is finished, removing the methanol, washing with water (40mL), extracting with ethyl acetate (50mL) for three times, combining organic phases and removing the solvent under reduced pressure to obtain 0.90g of colorless liquid, and obtaining the yield: 88.2 percent.
MS-ESI:m/z 275.7[M+H]+.
And 4, step 4: synthesis of the compound 4- (bromomethyl) -3- (difluoromethyl) -1-ethyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazole
Figure BDA0002385464920000241
Dissolving (3- (difluoromethyl) -1-ethyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methanol (0.90g,3.28mmol) in dichloromethane (20mL), stirring at 0 ℃, then dissolving phosphorus tribromide (1.06g,3.93mmol) in dichloromethane (10mL), slowly dropwise adding the mixture into the dichloromethane (10mL), controlling the temperature to be not higher than 5 ℃, completing dropwise adding, heating to room temperature, stirring for 3.5H, after the reaction is completed, quenching with ice water (30mL), extracting ethyl acetate (40mL) for three times, combining organic phases, removing the solvent under reduced pressure, and performing column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to obtain 1.03g of colorless liquid, wherein the yield is as follows: 91.2 percent.
MS-ESI:m/z 336.9[M+H]+.
And 5: synthesis of the Compound 3- (((3- (difluoromethyl) -1-ethyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000242
4- (bromomethyl) -3- (difluoromethyl) -1-ethyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazole (7.50g,27.4mmol) and 5, 5-dimethyl-4, 5-dihydroisoxazol-3-ylisothiourea hydrobromide (1.00g,2.96mmol) were dissolved in acetonitrile (30mL), stirred at room temperature for 10min, then potassium carbonate (1.60g,11.86mmol) was added to the above mixture and reacted for 12H before stopping the reaction, then acetonitrile was removed, washed with water (50mL), ethyl acetate (50mL) was extracted three times, the combined organic phases were decompressed to remove the solvent, yielding a yellow liquid 0.76g, yield: 71.0 percent.
MS-ESI:m/z 388.0[M+H]+.
Step 6: synthesis of the Compounds 3- (((3- (difluoromethyl) -1-ethyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole (Compound (24)) and 3- (((3- (difluoromethyl) -1-ethyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methyl) sulfinyl) -5, 5-dimethyl-4, 5-dihydroisoxazole (Compound (25)))
Figure BDA0002385464920000243
3- (((3- (difluoromethyl) -1-ethyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (0.76g,1.96mmol) was dissolved in dichloromethane (200mL), stirred at room temperature, mCPBA (1.03g,4.51mmol) was added to the above mixture, the reaction was stopped after 5 hours of reaction, and then washed with a saturated aqueous sodium bisulfite solution (200mL) and a saturated aqueous sodium bicarbonate solution (200mL) in this order, dichloromethane (30mL) was extracted, dried over anhydrous sodium sulfate, the organic phases were combined and the solvent was removed under reduced pressure, column chromatography (eluent: Petreum ether/EtOAc (v/v) ═ 5/1) was performed to obtain 0.50g of a white solid, yield: 60.9 percent; the characterization data for this compound are:
MS-ESI:m/z 420.9[M+H]+；
1H NMR(400MHz,CDCl3)6.73(t,J＝54.8Hz,1H),4.66(q,J＝8.1Hz,2H),4.58(s,2H),4.10(q,J＝7.3Hz,2H),3.10(s,2H),1.52(s,6H),1.45(t,J＝7.3Hz,3H)；
determining from the characterization data for the compound that it is compound (24);
after the column chromatography in the step 6, another white solid of 0.20g is obtained at the same time, and the yield is as follows: 25.3 percent; the characterization data for this compound are:
MS-ESI:m/z 404.1[M+H]+；
1H NMR(400MHz,CDCl3)6.61(t,J＝54.2Hz,1H),4.71(ddq,J＝84.1,11.8,8.2Hz,2H),4.29–4.13(m,2H),4.07(q,J＝7.2Hz,2H),3.10(dd,J＝42.0,17.1Hz,2H),1.51(d,J＝4.5Hz,6H),1.44(t,J＝7.3Hz,3H)；
this compound was identified as compound (25) from its characterization data.
Example 3: 3- (((5- (difluoromethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazol-4-yl) methyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000251
Step 1: synthesis of compound 3- (difluoromethyl) -1-methyl-1H-pyrazol-5-ol
Figure BDA0002385464920000252
Ethyl difluoroacetoacetate (83.06g,0.5mol) was dissolved in absolute ethanol (200mL), ice-washed, and an aqueous solution of methylhydrazine (40%, 86.25g,0.75mol) was added dropwise thereto, reacted at room temperature for 4 hours, and then heated to 80 ℃ for overnight reaction. The solvent was evaporated under reduced pressure, and the residue was dissolved in ethyl acetate (150mL) and washed with water. The organic phase was dried over anhydrous sodium sulfate, and the solvent was evaporated to dryness to give 42.90g of a pale yellow solid with a yield of 58.0%.
MS-ESI:m/z 149.0[M+H]+.
Step 2: synthesis of compound 5- (difluoromethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazole
Figure BDA0002385464920000253
3- (difluoromethyl) -1-methyl-1H-pyrazol-5-ol (0.74g,5mmol) is dissolved in acetonitrile (50mL), potassium carbonate (2.07g,15mmol) is added, the temperature is raised to 80 ℃, methyl chlorodifluoroacetate (1.08g,7.5mmol) is added dropwise, the temperature is raised to 100 ℃, the reaction is stirred for 12 hours, acetonitrile is removed, the mixture is dissolved in ethyl acetate (60mL), and the liquid is washed by water. The organic phase was dried over anhydrous sodium sulfate, and the solvent was evaporated to dryness to give a pale yellow liquid 0.50g, yield: 50.5 percent.
MS-ESI:m/z 199.0[M+H]+.
And step 3: synthesis of the compound 4- (chloromethyl) -5- (difluoromethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazole
Figure BDA0002385464920000261
5- (Difluoromethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazole (0.50g,2.5mmol) was dissolved in hydrochloric acid (36%, 15mL), concentrated sulfuric acid (98%, 0.5mL) was added dropwise, and the mixture was stirred for 5 minutes. Paraformaldehyde (0.10g,3.5mmol) was added and the temperature was raised to 80 ℃ for reaction for 8 h. Water (100mL) was added for dilution, and extraction was performed with ethyl acetate (60 mL). The organic phase was dried over anhydrous sodium sulfate, and the solvent was evaporated to dryness to give a pale yellow liquid 0.50g, yield: 81.1 percent.
MS-ESI:m/z 247.0[M+H]+.
And 4, step 4: synthesis of the Compound 3- (((5- (difluoromethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazol-4-yl) methyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000262
4- (chloromethyl) -5- (difluoromethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazole (0.50g,2.0mmol) and 5, 5-dimethyl-4, 5-dihydroisoxazol-3-ylisothiourea hydrobromide (0.62g,2.4mmol) were dissolved in acetonitrile (30mL), and potassium carbonate (1.10g,8.0mmol) was added and stirred at room temperature for 12H. Acetonitrile was removed, and the residue was dissolved in ethyl acetate (60mL) and washed with water. The organic phase was dried over anhydrous sodium sulfate, and the solvent was evaporated to dryness to give 0.38g of a yellow liquid, yield: 55.9 percent.
MS-ESI:m/z 342.0[M+H]+.
And 5: synthesis of the Compound 3- (((5- (difluoromethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazol-4-yl) methyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000263
3- (((5- (difluoromethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazol-4-yl) methyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (0.38g,1.1mmol) was dissolved in dichloromethane (30mL) and stirred at room temperature, then mCPBA (0.51g,2.2mmol) was added to the mixture and reacted for 5 hours, and then the reaction was stopped, then washed with saturated aqueous sodium bisulfite (200mL) and saturated aqueous sodium bicarbonate (200mL) in this order, extracted with dichloromethane (100mL), dried over anhydrous sodium sulfate, the combined organic phases were freed of solvent under reduced pressure, and purified by column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 5/1) to give 0.18g of a white solid, yield: 44.0 percent.
MS-ESI:m/z 374.0[M+H]+；
1H NMR(400MHz,CDCl3)7.04–6.57(m,2H),4.59(s,2H),3.83(s,3H),3.10(s,2H),1.51(s,6H).
Example 4: 3- (((3- (difluoromethyl) -1-methyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000271
Step 1: synthesis of compound 5-chloro-3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carbaldehyde
Figure BDA0002385464920000272
5-chloro-3- (difluoromethyl) -1H-pyrazole-4-carbaldehyde (1.80g,10.0mmol) and potassium carbonate (2.80g,20.00mmol) were dissolved in DMF (30mL) and stirred at room temperature, methyl iodide (1.60g,11.00mmol) was added to the mixture, the addition was completed, and stirred at room temperature for 24H, after the reaction was completed, washed with water (20mL), ethyl acetate (60mL) was extracted three times, the organic phases were combined and the solvent was removed under reduced pressure, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to obtain 0.73g of a colorless transparent liquid, yield: 38.0 percent.
MS-ESI:m/z 195.1[M+H]+.
Step 2: synthesis of compound 3- (difluoromethyl) -1-methyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazole-4-carbaldehyde
Figure BDA0002385464920000273
After potassium tert-butoxide (0.21g,1.85mmol) was dissolved in anhydrous tetrahydrofuran (20mL) and stirred at 0 ℃, trifluoroethanol (0.19g,1.85mmol) was added to the mixture, after which time 5-chloro-3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carbaldehyde (0.30g,1.54mmol) was added to the mixture, which was stirred at room temperature for 12H, after which time tetrahydrofuran was removed, washed with water (20mL), extracted with ethyl acetate (30mL) three times, the organic phases were combined and the solvent was removed under reduced pressure to give a pale yellow liquid 0.32g, yield: 89.0 percent.
MS-ESI:m/z 259.0[M+H]+.
And step 3: synthesis of the compound (3- (difluoromethyl) -1-methyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methanol
Figure BDA0002385464920000274
Dissolving 3- (difluoromethyl) -1-methyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazole-4-carbaldehyde (0.32g,1.24mmol) in absolute methanol (20mL) and stirring at 0 ℃, then gradually adding sodium borohydride (0.09g,2.48mmol) to the above mixed solution in batches, after the addition is finished, heating to room temperature and stirring for 4H, after the reaction is finished, removing the methanol, washing with water (20mL), extracting with ethyl acetate (30mL) for three times, combining organic phases and removing the solvent under reduced pressure to obtain 0.28g of light yellow liquid, and obtaining the yield: 87.0 percent.
MS-ESI:m/z 260.1[M+H]+.
And 4, step 4: synthesis of the compound 4- (bromomethyl) -3- (difluoromethyl) -1-methyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazole
Figure BDA0002385464920000281
Dissolving (3- (difluoromethyl) -1-methyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methanol (0.28g,1.07mmol) in dichloromethane (20mL), stirring at 0 ℃, then dissolving phosphorus tribromide (0.32g,1.20mmol) in dichloromethane (10mL), slowly dropwise adding the mixture into the dichloromethane (20mL), controlling the temperature to be not higher than 5 ℃, completing dropwise adding, heating to room temperature, stirring for 3.5H, after the reaction is completed, quenching with ice water (30mL), extracting ethyl acetate (40mL) for three times, combining organic phases, removing the solvent under reduced pressure, and performing column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to obtain 0.28g of colorless liquid, wherein the yield: 81.6 percent.
MS-ESI:m/z 323.9[M+H]+.
And 5: synthesis of the Compound 3- (((3- (difluoromethyl) -1-methyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000282
4- (bromomethyl) -3- (difluoromethyl) -1-methyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazole (0.28g,0.88mmol), 5, 5-dimethyl-4, 5-dihydroisoxazol-3-ylisothiourea hydrobromide (0.25g,1.05mmol) was dissolved in acetonitrile (20mL), stirred at room temperature for 10min, then potassium carbonate (0.48g,3.56mmol) was added to the above mixture to react for 12H and then the reaction was stopped, then acetonitrile was removed, washed with water (30mL), ethyl acetate (50mL) was extracted three times, the organic phases were combined and the solvent was removed under reduced pressure to give 0.33g of yellow liquid, yield: 99.0 percent.
MS-ESI:m/z 374.0[M+H]+.
Step 6: synthesis of the Compound 3- (((3- (difluoromethyl) -1-methyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000283
3- (((3- (difluoromethyl) -1-methyl-5- (2,2, 2-trifluoroethoxy) -1H-pyrazol-4-yl) methyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (0.33g,0.88mmol) was dissolved in dichloromethane (20mL), stirred at room temperature, m-CPBA (75%, 0.46g,2.20mmol) was added to the above mixture to react for 5 hours, then the reaction was stopped, and then washed with 20mL of saturated sodium bisulfite and aqueous sodium bicarbonate solution, dichloromethane (30mL) was extracted, dried over anhydrous sodium sulfate, the organic phases were combined and the solvent was removed under reduced pressure, column chromatography (eluent: Petrolum ether/EtOAc (v/v) ═ 5/1) was performed to obtain 0.12g of a white solid product, yield: 40.0 percent.
MS-ESI:m/z 406.0[M+H]+；
1H NMR(400MHz,CDCl3)6.72(t,J＝54.8Hz,1H),4.66(q,J＝8.1Hz,2H),4.58(s,2H),3.79(s,3H),3.11(s,2H),1.52(s,6H).
Example 5: 3- (((5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazol-4-yl) methyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000291
Step 1: synthesis of compound 5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carbaldehyde
Figure BDA0002385464920000292
Potassium tert-butoxide (0.35g,3.16mmol) was dissolved in anhydrous tetrahydrofuran (20mL) and stirred at 0 ℃, then 2, 2-difluoroethanol (0.26g,3.16mmol) was added to the above mixture, after stirring for 2H, 5-chloro-3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carbaldehyde (0.41g,2.10mmol) was added to the above mixture, stirred at room temperature for 12H, after completion of the reaction, tetrahydrofuran was removed, washed with water (20mL), extracted with ethyl acetate (30mL) three times, the organic phases were combined and the solvent was removed under reduced pressure to give crude yellow liquid 0.38g, yield: 75.0 percent.
MS-ESI:m/z 241.0[M+H]+.
Step 2: synthesis of the compound (5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazol-4-yl) methanol
Figure BDA0002385464920000293
Dissolving 5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carbaldehyde (0.38g,1.58mmol) in absolute methanol (10mL) and stirring at 0 ℃, then gradually adding sodium borohydride (0.12g,3.16mmol) to the above mixed solution in batches, after the addition is finished, heating to room temperature and stirring for 4H, after the reaction is finished, removing methanol, washing with water (20mL), extracting with ethyl acetate (30mL) for three times, combining organic phases and removing the solvent under reduced pressure to obtain 0.30g of a light yellow liquid crude product, wherein the yield is as follows: 78.0 percent.
MS-ESI:m/z 243.0[M+H]+.
And step 3: synthesis of compound 4- (bromomethyl) -5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazole
Figure BDA0002385464920000294
Dissolving (5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazol-4-yl) methanol (0.30g,1.23mmol) in dichloromethane (15mL), stirring at 0 ℃, then dissolving phosphorus tribromide (0.40g,1.47mmol) in dichloromethane (10mL), slowly dropwise adding the above mixed solution while controlling the temperature to be not higher than 5 ℃, completing dropwise adding, stirring at room temperature for 3.5H, after the reaction is completed, quenching with ice water (20mL), extracting ethyl acetate (30mL) for three times, combining organic phases, removing the solvent under reduced pressure, and performing column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to obtain 0.36g of a yellow liquid product, wherein the yield is as follows: 98.0 percent.
MS-ESI:m/z 305.9[M+H]+.
And 4, step 4: synthesis of the Compound 3- (((5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazol-4-yl) methyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000301
4- (bromomethyl) -5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazole (0.36g,1.23mmol), 5, 5-dimethyl-4, 5-dihydroisoxazol-3-ylisothiourea hydrobromide (0.37g,1.47mmol) was dissolved in acetonitrile (20mL), stirred at room temperature for 10min, then potassium carbonate (0.68g,4.92mmol) was added to the above mixture to react for 12H and then the reaction was stopped, then acetonitrile was removed, washed with water (30mL), ethyl acetate (30mL) was extracted three times, the organic phases were combined and the solvent was removed under reduced pressure to give 0.38g of a yellow liquid, yield: 86.0 percent.
MS-ESI:m/z 356.1[M+H]+.
And 5: synthesis of the Compound 3- (((5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazol-4-yl) methyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000302
3- (((5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-methyl-1H-pyrazol-4-yl) methyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (0.38g,1.07mmol) was dissolved in dichloromethane (20mL) and stirred at room temperature, then m-CPBA (75%, 0.56g,2.46mmol) was added to the above mixture to react for 5h and then the reaction was stopped, then washed with 30mL of saturated aqueous sodium bisulfite and sodium bicarbonate, respectively, extracted with dichloromethane (30mL), dried over anhydrous sodium sulfate, the combined organic phases are freed of solvent under reduced pressure and purified by column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 5/1) to give 0.30g of a white solid in yield: 72.3 percent.
MS-ESI:m/z 388.0[M+H]+；
1H NMR(400MHz,CDCl3)6.72(t,J＝54.8Hz,1H),6.10(tt,J＝54.5,3.6Hz,1H),4.58(s,2H),4.47(td,J＝13.5,3.6Hz,2H),3.78(s,3H),3.10(s,2H),1.51(s,6H).
Example 6: 3- (((5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-ethyl-1H-pyrazol-4-yl) methyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000303
Step 1: synthesis of compound 5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-ethyl-1H-pyrazole-4-carbaldehyde
Figure BDA0002385464920000304
Potassium tert-butoxide (0.81g,7.20mmol) was dissolved in anhydrous tetrahydrofuran (30mL) and stirred at 0 ℃, then 2, 2-difluoroethanol (0.59g,7.20mmol) was added to the above mixture, after stirring for 2H, 5-chloro-3- (difluoromethyl) -1-ethyl-1H-pyrazole-4-carbaldehyde (1.00g,4.80mmol) was added to the above mixture, stirred at room temperature for 12H, after completion of the reaction, tetrahydrofuran was removed, washed with water (20mL), extracted with ethyl acetate (40mL) three times, the organic phases were combined and the solvent was removed under reduced pressure to give crude yellow liquid 1.00g, yield: 91.6 percent.
MS-ESI:m/z 255.0[M+H]+.
Step 2: synthesis of the compound (5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-ethyl-1H-pyrazol-4-yl) methanol
Figure BDA0002385464920000311
Dissolving 5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-ethyl-1H-pyrazole-4-carbaldehyde (1.00g,4.30mmol) in anhydrous methanol (20mL) and stirring at 0 ℃, then gradually adding sodium borohydride (0.33g,8.60mmol) to the above mixed solution in batches, after the addition is finished, heating to room temperature and stirring for 4H, after the reaction is finished, removing methanol, washing with water (30mL), extracting with ethyl acetate (50mL) for three times, combining organic phases and removing the solvent under reduced pressure to obtain 1.00g of a light yellow liquid crude product, wherein the yield is as follows: 98.0 percent.
MS-ESI:m/z 257.0[M+H]+.
And step 3: synthesis of compound 4- (bromomethyl) -5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-ethyl-1H-pyrazole
Figure BDA0002385464920000312
Dissolving (5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-ethyl-1H-pyrazol-4-yl) methanol (1.00g,3.89mmol) in dichloromethane (30mL), stirring at 0 ℃, then dissolving phosphorus tribromide (1.26g,4.67mmol) in dichloromethane (10mL), slowly dropwise adding the above mixture to the mixture while controlling the temperature to be not higher than 5 ℃, completing dropwise adding, stirring at room temperature for 3.5H, after the reaction is completed, quenching with ice water (30mL), extracting ethyl acetate (60mL) for three times, combining organic phases, removing the solvent under reduced pressure, and performing column chromatography (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to obtain 1.09g of a yellow liquid product, wherein the yield: 88.0 percent.
MS-ESI:m/z 320.0[M+H]+.
And 4, step 4: synthesis of the Compound 3- (((5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-ethyl-1H-pyrazol-4-yl) methyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000313
4- (bromomethyl) -5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-ethyl-1H-pyrazole (1.00g,3.41mmol), 5, 5-dimethyl-4, 5-dihydroisoxazol-3-ylisothiourea hydrobromide (1.04g,4.10mmol) were dissolved in acetonitrile (20mL), stirred at room temperature for 10min, then potassium carbonate (1.89g,13.64mmol) was added to the above mixture to react for 12H and then the reaction was stopped, then acetonitrile was removed, washed with water (50mL), ethyl acetate (50mL) was extracted three times, the organic phases were combined and the solvent was removed under reduced pressure to give 1.00g of a yellow liquid crude product, yield: 80.0 percent.
MS-ESI:m/z 370.1[M+H]+.
And 5: synthesis of the Compound 3- (((5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-ethyl-1H-pyrazol-4-yl) methyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole
Figure BDA0002385464920000321
3- (((5- (2, 2-difluoroethoxy) -3- (difluoromethyl) -1-ethyl-1H-pyrazol-4-yl) methyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (1.00g,2.70mmol) was dissolved in dichloromethane (40mL) and stirred at room temperature, then m-CPBA (75%, 1.40g,6.22mmol) was added to the above mixture to react for 5H, then the reaction was stopped, and then washed with 30mL of saturated sodium bisulfite and aqueous sodium bicarbonate solution, dichloromethane (50mL) was extracted, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure from the combined organic phases, column chromatography (eluent: Petrolum ether/EtOAc (v/v) ═ 5/1) was carried out to obtain 0.59g of a colorless liquid product, yield: 55.0 percent.
MS-ESI:m/z 402.1[M+H]+；
1H NMR(400MHz,CDCl3)6.72(t,J＝54.8Hz,1H),6.10(tt,J＝54.4,3.6Hz,1H),4.58(s,2H),4.46(td,J＝13.5,3.6Hz,2H),4.09(q,J＝7.3Hz,2H),3.09(s,2H),1.51(s,6H),1.44(t,J＝7.3Hz,3H).
With reference to the examples of the present invention, the target compounds of Table 1 can be prepared using the corresponding starting materials.
TABLE 1
Figure BDA0002385464920000322
Figure BDA0002385464920000331
Figure BDA0002385464920000341
Figure BDA0002385464920000351
Biological examples
Compound preparation: a certain mass of the original compound of the compound is weighed by an analytical balance (0.0001g), dissolved by DMF containing 1% of Tween-80 emulsifier to prepare 1.0 wt% of mother liquor, and then diluted by distilled water for later use.
The test method comprises the following steps: the potting method comprises the test targets of piemarker, redroot amaranth, snakehead intestine, crab grass, cockspur grass and green bristlegrass. 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 six weed targets are directly sown (the germination rate is more than or equal to 85 percent), the soil is covered by 0.2cm, and water is added to keep the soil moist for 24 hours for later use. After each compound is applied to an automatic spray tower (model: 3WPSH-700E) according to the dosage of 150g a.i./ha, the soil surface liquid medicine is aired and then transferred to a greenhouse for culture, and the activity (%) of the compound on weeds is checked after 25 days; where 0 means no damage or normal growth process and 100 means no emergence or at least complete death of the aerial parts.
The inventors examined the herbicidal activities of the compounds (20) and (21), (24) and (25), (27) and (28) according to the above test methods, and found that the herbicidal activity of the compound (21) is superior to that of the compound (20), the herbicidal activity of the compound (24) is superior to that of the compound (25), and the herbicidal activity of the compound (28) is superior to that of the compound (27) at the same dose, for example, the herbicidal activities of the compound (21), the compound (24), and the compound (28) against abutilon were 95%, 100%, and 90%, respectively, and the herbicidal activities of the compound (20), the compound (25), and the compound (27) against crowndaisy hemp were 50%, 20%, and 30%, respectively, at a dose of 150g a.i./ha.
Meanwhile, the inventors compared the herbicidal activity of the compound 3-0054Pyroxasulfone in Table 13 of WO2002062770 (the inventors prepared Pyroxasulfone according to the method described in WO2002062770, and the structure of the Pyroxasulfone is shown below).
Figure BDA0002385464920000352
The test results are shown in table 2.
Pre-emergence herbicidal Activity of the Compounds of the invention at a dosage of 2150 g a.i./ha
Figure BDA0002385464920000353
Figure BDA0002385464920000361
The results in Table 2 show that the compounds of the present invention all have better herbicidal activity than pyroxasulfofone at 150g a.i./ha against abutilon, Amaranthus retroflexus, snakehead intestine, crab grass, Echinochloa crusgalli and Setaria viridis.
Crop safety testing
Compound preparation: a certain mass of the original compound of the compound is weighed by an analytical balance (0.0001g), dissolved by DMF containing 1% of Tween-80 emulsifier to prepare 1.0 wt% 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 the targets of soybean, peanut, cotton and rape. 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 crop targets are directly sown (the bud rate is more than or equal to 85 percent), the soil is covered by 0.2cm, and water is added to keep the soil moist for 24 hours for later use. After the compounds are applied to an automatic spray tower (model: 3WPSH-700E) according to the specified dosage, the liquid medicine on the surface of the soil is air-dried and then transferred to a greenhouse for culture, and the phytotoxicity (%) of the crops is checked after 25 days. Where 0 means no damage or normal growth process and 100 means no emergence or at least complete death of the aerial parts.
The test results are shown in tables 3 to 5.
TABLE 3 safety of the compounds of the invention against soybeans and peanuts
Figure BDA0002385464920000362
TABLE 4 safety of the compounds of the invention to cotton
Figure BDA0002385464920000371
TABLE 5 safety of the compounds of the invention against oilseed rape
Figure BDA0002385464920000372
The results in tables 3 to 5 show that the compounds of the present invention have very good safety to soybean, peanut, cotton and rape. Compared with pyroxasulfolane, the compound shows more excellent safety for crops under the same dosage.
The compound has good control effect on broadleaf weeds (such as piemarker, amaranthus retroflexus and snakehead gut) and grassy weeds (such as crab grass, cockspur grass and green bristlegrass). Is safe to crops, has better control effect on weeds than commercial herbicides and isoxazoline compounds with similar structures, and has excellent application prospect.

Claims (16)

1. A compound which is a compound of formula (I) or a stereoisomer, a nitroxide or a salt of a compound of formula (I):
Figure FDA0002385464910000011
wherein:
y is alkoxy, alkoxyalkoxy, alkenyloxy, alkynyloxy, haloalkoxy, haloalkenyloxy or haloalkynyloxy;
R1and R2Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, alkyl, haloalkyl, cycloalkyl, or cycloalkylalkyl; or R1、R2And the carbon atoms to which they are attached form a ring consisting of 3 to 12 atoms;
R3and R4Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, alkyl, haloalkyl, cycloalkyl, or cycloalkylalkyl; or R3、R4And the carbon atoms to which they are attached form a ring consisting of 3 to 12 atoms;
R5and R6Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, alkyl, alkenyl, or alkynyl; or R5、R6And the carbon atoms to which they are attached form a ring consisting of 3 to 12 atoms;
n is 0, 1 or 2;
R7is alkyl, haloalkyl, aryl, arylalkyl, aryl-C (═ O) -, aryl-S (═ O)m-, heteroaryl, heteroarylalkyl, heteroaryl-C (═ O) -, heteroaryl-S (═ O)m-, cycloalkyl, cycloalkylalkyl, cycloalkyl-C (═ O) -, cycloalkyl-S (═ O)m-, heterocyclyl, heterocyclylalkyl, heterocyclyl-C (═ O) -or heterocyclyl-S (═ O)m-; wherein R is7Optionally substituted by 1,2,3, 4,5 or 6 substituents selected from RaSubstituted with the substituent(s);
each m is independently 0, 1 or 2;
each RaIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-8Alkyl, halo C1-8Alkyl radical, C1-8alkyl-C (═ O) -, halo-C1-8alkyl-C (═ O) -, C2-8Alkenyl, halo C2-8Alkenyl radical, C2-8Alkynyl, halo C2-8Alkynyl, C1-8Alkoxy, halo C1-8Alkoxy radical, C1-8Alkylamino radical, C1-8Alkylthio, halo C1-8Alkylamino, halogeno C1-8Alkylthio radical, C6-14Aryl radical, C6-14Aryloxy radical, C1-9Heteroaryl or C1-9A heteroaryloxy group;
with the following conditions:
when Y is methoxy or difluoromethoxy, R7Is ethyl or isopropyl, R5And R6Is hydrogen, n is 0 or 2, R3And R4Is hydrogen, R1When it is methyl, R2Is not chloromethyl;
or when Y is methoxy or difluoromethoxy, R7Is ethyl or isopropyl, R5And R6Is hydrogen, n is 0 or 2, R3And R4Is hydrogen, R2When it is methyl, R1Is not chloromethyl.
2. The compound of claim 1, wherein:
y is C1-6Alkoxy radical, C1-6Alkoxy radical C1-6Alkoxy radical, C2-6Alkenyloxy radical, C2-6Alkynyloxy, halo C1-6Alkoxy, halo C2-6Alkenyloxy or halogeno C2-6An alkynyloxy group;
R1and R2Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-6Alkyl, halo C1-6Alkyl radical, C3-6Cycloalkyl or C3-6Cycloalkyl radical C1-6An alkyl group; or R1、R2And the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms;
R3and R4Each of which isIndependently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-6Alkyl, halo C1-6Alkyl radical, C3-6Cycloalkyl or C3-6Cycloalkyl radical C1-6An alkyl group; or R3、R4And the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms;
R5and R6Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-6Alkyl radical, C2-6Alkenyl or C2-6An alkynyl group; or R5、R6And the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms;
R7is C1-6Alkyl, halo C1-6Alkyl radical, C6-14Aryl radical, C6-14Aryl radical C1-6Alkyl radical, C6-14aryl-C (═ O) -, C6-14aryl-S (═ O)m-、C1-9Heteroaryl group, C1-9Heteroaryl C1-6Alkyl radical, C1-9heteroaryl-C (═ O) -, C1-9heteroaryl-S (═ O)m-、C3-8Cycloalkyl radical, C3-8Cycloalkyl radical C1-6Alkyl radical, C3-8cycloalkyl-C (═ O) -, C3-8cycloalkyl-S (═ O)m-、C2-10Heterocyclic group, C2-10Heterocyclyl radical C1-6Alkyl radical, C2-10heterocyclyl-C (═ O) -or C2-10heterocyclyl-S (═ O)m-; wherein R is7Optionally substituted by 1,2,3, 4,5 or 6 substituents selected from RaSubstituted with the substituent(s);
each RaIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-6Alkyl, halo C1-6Alkyl radical, C1-6alkyl-C (═ O) -, halo-C1-6alkyl-C (═ O) -, C2-6Alkenyl, halo C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkynyl, C1-6Alkoxy, halo C1-6Alkoxy radical, C1-6Alkylamino radical, C1-6Alkylthio, halo C1-6Alkylamino, halogeno C1-6Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-6Heteroaryl or C1-6A heteroaryloxy group.
3. The compound of claim 1 or 2, wherein:
R1and R2Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-4Alkyl, halo C1-4Alkyl radical, C3-6Cycloalkyl or C3-6Cycloalkyl radical C1-3An alkyl group; or R1、R2And the carbon atoms to which they are attached form a ring consisting of 3 to 6 atoms;
R3and R4Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-3Alkyl, halo C1-3Alkyl radical, C3-6Cycloalkyl or C3-6Cycloalkyl radical C1-3An alkyl group; or R3、R4And the carbon atoms to which they are attached form a ring consisting of 3 to 6 atoms;
R5and R6Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-4Alkyl radical, C2-4Alkenyl or C2-4An alkynyl group; or R5、R6And together with the carbon atoms to which they are attached form a ring consisting of 3 to 6 atoms.
4. A compound according to any one of claims 1 to 3 which is a compound of formula (Ia) or a stereoisomer, a nitroxide or a salt of a compound of formula (Ia):
Figure FDA0002385464910000021
5. the compound according to any one of claims 1-4, wherein:
y is C1-4Alkoxy radical, C1-4Alkoxy radical C1-4Alkoxy radical,C2-4Alkenyloxy radical, C2-4Alkynyloxy, halo C1-4Alkoxy, halo C2-4Alkenyloxy or halogeno C2-4An alkynyloxy group.
6. The compound according to any one of claims 1-5, wherein:
y is-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2OCH3、-OCH2CH2OCH3、-OCH2CH2CH2OCH3、-OCH2OCH2CH3、-OCH2CH2OCH2CH3、-OCH2F、-OCHF2、-OCF3、-OCH2CHF2、-OCH2CF3、-OCF2CH3、-OCH2CH2CF3、-O-CH＝CH2、-O-CH2CH＝CH2、-O-C≡CH、-OC≡CCH3or-O-CH2-C≡CH。
7. The compound according to any one of claims 1-6, wherein:
R7is C1-4Alkyl, halo C1-4Alkyl radical, C6-10Aryl radical, C6-10Aryl radical C1-4Alkyl radical, C6-10aryl-C (═ O) -, C6-10aryl-S (═ O)m-、C1-6Heteroaryl group, C1-6Heteroaryl C1-4Alkyl radical, C1-6heteroaryl-C (═ O) -, C1-6heteroaryl-S (═ O)m-、C3-6Cycloalkyl radical, C3-6Cycloalkyl radical C1-4Alkyl radical, C3-6cycloalkyl-C (═ O) -, C3-6cycloalkyl-S (═ O)m-、C2-6Heterocyclic group, C2-6Heterocyclyl radical C1-4Alkyl radical, C2-6heterocyclyl-C (═ O) -or C2-6heterocyclyl-S (═ O)m-; wherein R is7Optionally substituted by 1,2,3, 4,5 or 6 substituents selected from RaSubstituted with the substituent(s);
each RaIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-4Alkyl, halo C1-4Alkyl radical, C1-4alkyl-C (═ O) -, halo-C1-4alkyl-C (═ O) -, C2-4Alkenyl, halo C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkynyl, C1-4Alkoxy, halo C1-4Alkoxy radical, C1-4Alkylamino radical, C1-4Alkylthio, halo C1-4Alkylamino, halogeno C1-4Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-6Heteroaryl or C1-6A heteroaryloxy group.
8. The compound according to any one of claims 1-7, wherein:
R7is-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH(CH3)2、-CH2F、-CHF2、-CH2Cl、-CH2Br、-CF3、-CH2CF3、-CH2CH2F、-CH2CH2Cl、-CH2CH2Br、-CH2CHF2、-CH2CH2CF3、-CH2CH2CH2F、-CH2CH2CH2Cl、-CH2CH2CH2Br、-CHFCH2CH3、-CHClCH2CH3Cyclopropylmethyl, phenyl, 3-fluorophenyl, 2, 4-difluorophenyl or phenylsulfonyl.
9. The compound according to any one of claims 1 to 8, which is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt of a compound having one of the following structures:
Figure FDA0002385464910000031
Figure FDA0002385464910000041
Figure FDA0002385464910000051
Figure FDA0002385464910000052
or
Figure FDA0002385464910000053
10. A composition comprising a compound of any one of claims 1-9.
11. The composition of claim 10, further comprising at least one additional component required for formulation.
12. Use of a compound according to any one of claims 1 to 9 or a composition according to claim 10 or 11 in agriculture.
13. Use of a compound according to any one of claims 1 to 9 or a composition according to claim 10 or 11 as a herbicide.
14. A method of controlling weed growth in useful plants comprising pre-emergence application to the locus of the weeds of an effective amount of a compound according to any one of claims 1 to 9 or a composition according to claim 10 or 11.
15. The method of claim 14, wherein the weeds comprise broadleaf weeds and grass weeds;
optionally, the broadleaf weeds are piemarker, amaranthus retroflexus or snakehead intestine;
optionally, the grass weeds are large crabgrass, barnyard grass or green bristlegrass.
16. The method of claim 14, wherein the useful plant is a crop plant;
preferably, the crop is cotton, canola, soybean or peanut.
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