CN112300092A - Heterocyclic alkyl substituted dichlorobenzoyl compound and application thereof - Google Patents

Heterocyclic alkyl substituted dichlorobenzoyl compound and application thereof Download PDF

Info

Publication number
CN112300092A
CN112300092A CN202010739115.8A CN202010739115A CN112300092A CN 112300092 A CN112300092 A CN 112300092A CN 202010739115 A CN202010739115 A CN 202010739115A CN 112300092 A CN112300092 A CN 112300092A
Authority
CN
China
Prior art keywords
compound
hydrogen
alkyl
methyl
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010739115.8A
Other languages
Chinese (zh)
Other versions
CN112300092B (en
Inventor
李义涛
林健
吴庆国
张虎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan Hec Pesticides R&d Co ltd
Original Assignee
Dongguan Hec Pesticides R&d Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongguan Hec Pesticides R&d Co ltd filed Critical Dongguan Hec Pesticides R&d Co ltd
Publication of CN112300092A publication Critical patent/CN112300092A/en
Application granted granted Critical
Publication of CN112300092B publication Critical patent/CN112300092B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
    • C07D295/112—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C07D295/116—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings with the doubly bound oxygen or sulfur atoms directly attached to a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • A01N43/84—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 six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
    • 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
    • C07D413/10—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 carbon chain containing aromatic rings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention provides a heterocyclic alkyl substituted dichlorobenzoyl compound and application thereof; specifically, the invention provides a compound shown as a formula (I) and a preparation method thereof; compositions containing these compounds and their use as herbicides; wherein Q is optionally substituted oxocyclohexenyl or substituted pyrazolyl, or the like; r1Is hydroxy, C1‑6Alkyl, etc.; m is 0, 1, 2, etc.; x is-O-, -S (═ O)n-and the like; n is 0, 1 or 2.

Description

Heterocyclic alkyl substituted dichlorobenzoyl compound and application thereof
Technical Field
The invention relates to the field of agriculture, in particular to a novel heterocyclic alkyl substituted dichlorobenzoyl compound and a preparation method thereof; compositions containing these compounds and their use in agriculture.
Background
Substituted benzoyl compounds are a class of compounds with excellent biological activity, the herbicidal activity of which is described in, for example, CN105766944, CN102464630, WO2004024687, CN 103025718. However, the active ingredients known from the documents cited above have disadvantages in use, for example (a) no or only insufficient herbicidal action on the weed plants, (b) too narrow a spectrum of weed plants to be controlled or (c) too low a selectivity in crops of useful plants.
Therefore, further development and improvement of benzoyl compounds are still needed to obtain a series of benzoyl compounds with better herbicidal activity and/or selectivity.
Disclosure of Invention
The invention provides a novel heterocyclic alkyl substituted dichlorobenzoyl compound which has excellent weeding effect, wide weed control spectrum and excellent selectivity between crops and weeds.
In one aspect, the invention provides a compound of formula (I) or a stereoisomer, tautomer, nitroxide or salt of a compound of formula (I):
Figure BDA0002606171070000011
wherein:
R1is hydroxy, cyano, amino, nitro, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C1-6Alkoxy, halo C1-6Alkyl, halo C2-6Alkenyl, halo C2-6Alkynyl, halo C1-6Alkoxy or C3-8A cycloalkyl group;
m is 0, 1, 2,3, 4, 5, 6, 7, 8, 9 or 10;
x is-CH2-、-O-、-S(＝O)n-or-NH-;
n is 0, 1 or 2;
q is the following subformula:
Figure BDA0002606171070000021
R2and R2aEach independently is hydrogen or C1-6An alkyl group;
R3is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-8A cycloalkyl group;
R4is hydrogen or-CH2-CO-C6-10An aryl group; wherein said-CH2-CO-C6-10Aryl is optionally substituted by 1, 2 or 3 substituents selected from halogen or C1-6Alkyl substituents.
In some of these embodiments, R1Is hydroxy, cyano, amino, nitro, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C1-4Alkoxy, halo C1-4Alkyl, halo C2-4Alkenyl, halo C2-4Alkynyl, halo C1-4Alkoxy or C3-6A cycloalkyl group.
In other embodiments, R1Is hydroxy, cyano, amino, nitro, methyl, ethyl, n-propyl, isopropyl, -CHF2、-CF3、-CH2CHF2、-CH2CF3Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
In some of these embodiments, R2And R2aEach independently is hydrogen or C1-4An alkyl group.
In other embodiments, R2And R2aEach independently is hydrogen or C1-3An alkyl group.
In other embodiments, R2And R2aEach independently hydrogen or methyl.
In some of these embodiments, R3Is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl or C3-6A cycloalkyl group.
In other embodiments, R3Is hydrogen, C1-3Alkyl radical, C2-3Alkenyl radical, C2-3Alkynyl or C3-6A cycloalkyl group.
In other embodiments, R3Hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
In some of these embodiments, R4Is hydrogen or-CH2-CO-phenyl; wherein said-CH2-CO-phenyl optionally substituted by 1, 2 or 3 substituents selected from halogen or C1-4Alkyl substituents.
In other embodiments, R4Is hydrogen or-CH2-CO-phenyl; wherein said-CH2-CO-phenyl is optionally substituted with 1, 2 or 3 substituents selected from chloro or methyl.
In some embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, tautomer, nitroxide, or salt of a compound of formula (Ia):
Figure BDA0002606171070000022
wherein:
q has the meaning as described herein;
R1aand R1bEach independently is hydrogen or C1-3An alkyl group.
In some embodiments, the present invention provides a compound of formula (Ib), or a stereoisomer, tautomer, nitroxide, or salt of a compound of formula (Ib):
Figure BDA0002606171070000031
wherein: q and n have the meanings as described in the invention.
In other embodiments, Q is of the subformula:
Figure BDA0002606171070000032
in other embodiments, R1aAnd R1bEach independently hydrogen or methyl.
In other embodiments, n is 0, 1, or 2.
In some of these embodiments, the present invention provides a compound that is a compound of formula (Ia-1) or a stereoisomer, tautomer, nitroxide or salt of a compound of formula (Ia-1):
Figure BDA0002606171070000041
wherein:
R1aand R1bEach independently is hydrogen or C1-6An alkyl group;
R2and R2aEach independently is hydrogen or C1-6An alkyl group.
In other embodiments, R1aAnd R1bEach independently is hydrogen or C1-3An alkyl group; r2And R2aEach independently is hydrogen or C1-3An alkyl group.
In other embodiments, R1aAnd R1bEach independently hydrogen or methyl; r2And R2aEach independently hydrogen or methyl.
In some of these embodiments, the present invention provides a compound that is a compound of formula (Ia-2) or a stereoisomer, tautomer, nitroxide or salt of a compound of formula (Ia-2):
Figure BDA0002606171070000042
wherein:
R1aand R1bEach independently is hydrogen or C1-6An alkyl group.
In other embodiments, R1aAnd R1bEach independently is hydrogen or C1-3An alkyl group.
In other embodiments, R1aAnd R1bEach independently hydrogen or methyl.
In some of these embodiments, the present invention provides a compound that is a compound having one of the following structures or a stereoisomer, tautomer, nitroxide or salt thereof of a compound having one of the following structures:
Figure BDA0002606171070000043
Figure BDA0002606171070000051
Figure BDA0002606171070000061
Figure BDA0002606171070000071
in some of these embodiments, the present invention provides a compound, most preferably a compound having the specific structure:
Figure BDA0002606171070000072
Figure BDA0002606171070000081
or a stereoisomer, tautomer, nitroxide or salt thereof of said structure.
Biological activity tests show that the compound shown in the formula (I) has good herbicidal activity, and the herbicidal activity is more excellent compared with a compound with a 4-substituent of a benzene ring as a methylsulfonyl group. Taking purslane control as an example, according to the indoor weeding activity record in CN103025718A, spraying treatment is carried out on post-emergence weeds, and the control effect of the compound I-1-1 in example 1 on purslane at 60g/ha and 90g/ha is 0; the control effect of the compound on the purslane at 37.5g/ha and 75g/ha is at least more than 82%.
Example 1 (Compound I-1-1) in CN103025718A, having the following compound structure:
Figure BDA0002606171070000082
the compound of the invention can effectively control abutilon, purslane, cockspur grass or zinnia and other weeds, and can obtain good effect under low dosage. The compounds of the present invention have excellent safety to peanuts, corn, rice and wheat, and are preferably used for controlling weeds in peanut fields, corn fields, paddy fields and wheat fields.
In another aspect, the invention provides a composition comprising a compound of the invention.
In some of these embodiments, the compositions of the present invention further optionally comprise at least one additional component.
In particular, the additional component is a surfactant, a solid diluent, a liquid diluent, a buffer, a defoamer, a thickener, a cryoprotectant, a biocide and/or a film former.
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 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 herbicide to control weeds in useful plants.
In other embodiments, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention for controlling grassy weeds.
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 for controlling broadleaf weeds.
In other embodiments, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention for controlling abutilon, purslane, echinochloa and/or zinnia.
In another aspect, the present invention provides the use of a compound according to the invention or a composition comprising a compound according to the invention for controlling undesired vegetation.
In another aspect, the present invention provides the use of a compound of the invention or a composition comprising a compound of the invention as a herbicide.
In another aspect, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention as a pre-emergence herbicide.
In another aspect, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention as a post-emergence herbicide.
In another aspect, the present invention provides a method for controlling unwanted vegetation, characterized in that an effective amount of a compound according to the invention is applied to the plants, to the plant seeds, to the soil in or on which the plants are grown, or to the cultivation area.
In a further aspect, the present invention provides a method of controlling the growth of weeds in useful plants, which comprises applying to the locus of the weeds an effective amount of a compound of the present invention or a composition comprising a compound of the present invention.
Specifically, the weeds are one or more of piemarker, purslane, cockspur grass or zinnia.
Specifically, the useful plant is at least one of peanut, corn, rice or wheat.
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.
In the compound shown in the formula (I), the formula (Ia-1), the formula (Ia-2) or the formula (Ib), stereoisomers can be formed due to different configurations (R and S represent different configurations respectively), and the invention comprises an R-type isomer, an S-type isomer and a mixture of the R-type isomer and the S-type isomer in any proportion; since keto/enol tautomerism can exist in a variety of tautomers, the present invention includes all tautomers and mixtures thereof in any proportion.
Isotopically enriched compounds have the structure depicted by the formulae given herein, except that one or more atoms are replaced by an atom having a selected atomic mass or mass number. Exemplary isotopes that can be incorporated into compounds of the invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine and chlorine, such as2H，3H，11C，13C，14C，15N，17O，18O，18F，31P，32P， 35S，36Cl and125I。
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 elements, and with 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 Jerry March, John Wiley & Sons, New York:2007, the entire contents of which are incorporated herein by reference.
The articles "a," "an," and "the" as used herein are intended to include "at least one" or "one or more" unless otherwise indicated or clearly contradicted by context. Thus, as used herein, the articles refer to articles of one or more than one (i.e., at least one) object. For example, "a component" refers to one or more components, i.e., there may be more than one component contemplated for use or use in embodiments of the described embodiments.
The term "comprising" is open-ended, i.e. includes the elements indicated in the present invention, but does not exclude other elements.
"stereoisomers" refers to compounds having the same chemical structure but differing in the arrangement of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.
"enantiomer" refers to two isomers of a compound that are not overlapping but are in mirror image relationship to each other.
"diastereomer" refers to a stereoisomer that has two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivities. Mixtures of diastereomers may be separated by high resolution analytical procedures such as electrophoresis and chromatography, e.g., HPLC.
The stereochemical definitions and rules used in the present invention generally follow the general definitions of S.P. Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; stereochemical definitions and rules as described in and Eliel, e.and Wilen, s, "Stereochemistry of Organic Compounds", John Wiley & Sons, inc, New York, 1994.
Many organic compounds exist in an optically active form, i.e., they have the ability to rotate the plane of plane polarized light. In describing optically active compounds, the prefixes D and L or R and S are used to denote the absolute configuration of a molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are the symbols used to specify the rotation of plane polarized light by the compound, where (-) or l indicates that the compound is left-handed. Compounds prefixed with (+) or d are dextrorotatory. One particular stereoisomer is an enantiomer, and mixtures of such isomers are referred to as enantiomeric mixtures. A50: 50 mixture of enantiomers is referred to as a racemic mixture or racemate, which may occur when there is no stereoselectivity or stereospecificity in the chemical reaction or process.
The term "tautomer" or "tautomeric form" refers to structural isomers having different energies that can interconvert by a low energy barrier (low energy barrier). If tautomerism is possible (e.g., in solution), then the chemical equilibrium of the tautomer can be reached. For example, proton tautomers (also known as proton transfer tautomers) include interconversions by proton migration, such as keto-enol isomerization and imine-enamine isomerization. Valence tautomers (valenctautomers) include interconversion by recombination of some of the bonding electrons. Specific examples of keto-enol tautomerism are the tautomerism of the pentan-2, 4-dione, hexane-1, 3-dione, and 4-hydroxypent-3-en-2-one tautomers. Another example of tautomerism is phenol-ketone tautomerism. One specific example of phenol-ketone tautomerism is the tautomerism of pyridin-4-ol and pyridin-4 (1H) -one tautomers. Unless otherwise indicated, all tautomeric forms of the compounds of the invention are within the scope of the invention.
In the present invention, depending on the external conditions (such as solvent, pH, etc.), keto-enol tautomerism exists:
Figure BDA0002606171070000111
"nitroxide" in the context of the present invention means that when a compound contains several amine functional groups, 1 or more than 1 nitrogen atom can be oxidized to form an N-oxide. Specific examples of N-oxides are N-oxides of tertiary amines or N-oxides of nitrogen-containing heterocyclic nitrogen atoms. The corresponding amines can be treated with an oxidizing agent such as hydrogen peroxide or a peracid (e.g., peroxycarboxylic acid) to form the N-oxide (see Advanced Organic Chemistry, Wiley Interscience, 4 th edition, Jerry March, pages). In particular, the N-oxide may be prepared by the method of L.W.Deady (Syn.Comm.1977,7,509-514) in which an amine compound is reacted with m-chloroperoxybenzoic acid (MCPBA), for example, in an inert solvent such as dichloromethane.
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, 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, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amidino, 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 include all such individual members of the group classes and rangesEach independent sub-combination. For example, the term "C1-C6Alkyl "or" C1-6Alkyl "means in particular independently disclosed methyl, ethyl, C3Alkyl radical, C4Alkyl radical, C5Alkyl and C6An alkyl group.
The term "alkyl" or "alkyl group" as used herein, denotes a saturated, straight or branched chain, monovalent hydrocarbon group containing from 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in one embodiment, the alkyl group contains 1 to 10 carbon atoms; in one embodiment, the alkyl group contains 1 to 8 carbon atoms; in another embodiment, the alkyl group contains 1 to 6 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 4 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms.
Examples of alkyl groups include, but are not limited to, methyl (Me, -CH)3) Ethyl group (Et, -CH)2CH3) N-propyl (n-Pr, -CH)2CH2CH3) Isopropyl group (i-Pr, -CH (CH)3)2) N-butyl (n-Bu, -CH)2CH2CH2CH3) Isobutyl (i-Bu, -CH)2CH(CH3)2) Sec-butyl (s-Bu, -CH (CH)3)CH2CH3) Tert-butyl (t-Bu, -C (CH)3)3) N-pentyl (-CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH)3)CH2CH2CH3) 3-pentyl (-CH (CH)2CH3)2) 2-methyl-2-butyl (-C (CH)3)2CH2CH3) 3-methyl-2-butyl (-CH (CH)3)CH(CH3)2) 3-methyl-1-butyl (-CH)2CH2CH(CH3)2) 2-methyl-1-butyl (-CH)2CH(CH3)CH2CH3) N-hexyl (-CH)2CH2CH2CH2CH2CH3) 2-hexyl (-CH (CH)3)CH2CH2CH2CH3) 3-hexyl (-CH (CH)2CH3)(CH2CH2CH3) 2-methyl-2-pentyl (-C (CH))3)2CH2CH2CH3) 3-methyl-2-pentyl (-CH (CH)3)CH(CH3)CH2CH3) 4-methyl-2-pentyl (-CH (CH)3)CH2CH(CH3)2) 3-methyl-3-pentyl (-C (CH)3)(CH2CH3)2) 2-methyl-3-pentyl (-CH (CH)2CH3)CH(CH3)2) 2, 3-dimethyl-2-butyl (-C (CH)3)2CH(CH3)2) 3, 3-dimethyl-2-butyl (-CH (CH)3)C(CH3)3) N-heptyl, n-octyl, and the like.
The term "alkenyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one site of unsaturation, i.e. one carbon-carbon sp2A double bond, wherein the alkenyl group may be optionally substituted with one or more substituents described herein, including the positioning of "cis" and "tans", or the positioning of "E" and "Z". In one embodiment, the alkenyl group contains 2 to 10 carbon atoms; in one embodiment, the alkenyl group contains 2 to 8 carbon atoms; in another embodiment, the alkenyl group contains 2 to 6 carbon atoms; in yet another embodiment, the alkenyl group contains 2 to 4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH ═ CH)2) Allyl (-CH)2CH＝CH2) Allyl (CH)3-CH＝CH-)， -CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH2CH2CH2CH＝CH2、-CH2CH2CH＝CHCH3、 -CH2CH2CH2CH＝CHCH3And so on.
The term "alkynyl" denotes radicals containing 2-12 carbon atomsWherein there is at least one carbon-carbon sp triple bond, wherein said alkynyl group 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≡CCH3And so on.
The term "alkoxy" means an alkyl group attached to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Unless otherwise specified, the alkoxy group contains 1 to 12 carbon atoms. In one embodiment, the alkoxy group contains 1 to 10 carbon atoms; in one embodiment, the alkoxy group contains 1 to 8 carbon atoms; in one embodiment, the alkoxy group contains 1 to 6 carbon atoms; in another embodiment, the alkoxy group contains 1 to 4 carbon atoms; in yet another embodiment, the alkoxy group contains 1 to 3 carbon atoms. The alkoxy group may be optionally substituted with one or more substituents described herein.
Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH)3) Ethoxy (EtO, -OCH)2CH3) 1-propoxy (n-PrO, n-propoxy, -OCH)2CH2CH3) 2-propoxy (i-PrO, i-propoxy, -OCH (CH)3)2) 1-butoxy (n-BuO, n-butoxy, -OCH)2CH2CH2CH3) 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH)2CH(CH3)2) 2-butoxy (s-BuO, s-butoxy, -OCH (CH)3)CH2CH3) 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC (CH)3)3) 1-pentyloxy (n-pentyloxy, -OCH)2CH2CH2CH2CH3) 2-pentyloxy (-OCH (CH)3)CH2CH2CH3) 3-pentyloxy (-OCH (CH))2CH3)2) 2-methyl-2-butoxy (-OC (CH))3)2CH2CH3) 3-methyl-2-butoxy (-OCH (CH)3)CH(CH3)2) 3-methyl-l-butoxy (-OCH)2CH2CH(CH3)2) 2-methyl-l-butoxy (-OCH)2CH(CH3)CH2CH3) And so on.
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The term "haloalkyl" denotes an alkyl group substituted with one or more halogen atoms. 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 "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 "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, cyclododecyl, adamantyl, 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 term "aryl" denotes monocyclic, bicyclic and tricyclic carbon ring systems containing 6 to 14 ring atoms, or 6 to 12 ring atoms, or 6 to 10 ring atoms, wherein at least one ring system is aromatic, wherein each ring system comprises a ring of 3 to 7 atoms with one or more attachment points to the rest of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring". Examples of the aryl group may include phenyl, indenyl, naphthyl and anthryl. The aryl group is optionally substituted with one or more substituents described herein.
When the compounds of the present invention contain an acid moiety, 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 represented by formula (I), formula (Ia) or formula (Ib) can be prepared by treating the compound represented by formula (I), formula (Ia) or formula (Ib) with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine).
When a compound of the invention comprises a base moiety, acceptable salts can be formed from organic and inorganic acids, such as acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, napthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids.
Compositions and formulations of the compounds of the invention
The compounds of the present invention are generally useful as herbicidal active ingredients in compositions or formulations having at least one additional component selected from the group consisting of surfactants, solid diluents, liquid diluents, buffers, antifoams, thickeners, antifreeze agents, antimicrobial agents, film forming agents and the like, all of which meet the requirements of use as pesticides, and are within the scope of the present invention. The formulation or composition ingredients are selected to be compatible with the physical characteristics of the active ingredient, the mode of application, and environmental factors such as soil type, moisture and temperature.
Useful formulations include liquid compositions and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions), and the like, which may optionally be thickened into gels. Common types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions and suspoemulsions. Typical 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 composition is mainly used as an intermediate 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 dosed 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 sulphate. Typical solid Diluents are described in Handbook of Instrument Dust Diluents and Cariers, 2 nd edition, Dorland Books, Caldwell, N.J. by Watkins et al.
Liquid diluents include, for example, water, N-dimethyl alkanamides (e.g., N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oil, N-paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones (e.g., cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone), acetates (e.g., isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate, and isobornyl acetate), Other esters (such as alkylated lactates, dibasic esters and gamma-butyrolactones), and may be straight chain, branched chain, saturated or unsaturated alcohols (such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecanol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzyl alcohol). Liquid diluents also include saturated and unsaturated fatty acids (typically C)6-C22) Such as vegetable seed and fruit oils (e.g., olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), animal-derived fats (e.g., tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, which can be obtained by hydrolysis of glycerides derived from plants and animals 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 alcohol alkoxylate phosphate esters, alkylphenol alkoxylate phosphate esters, and styrylphenol ethoxylate phosphate esters; 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, isopropyl benzene, toluene, xylene, and sulfonates of dodecyl benzene and tridecyl benzene; a sulfonate of condensed polynaphthalene; sulfonates of naphthalene and alkylnaphthalenes; sulfonates of petroleum fractions; sulfosuccinamates; and sulfosuccinates and their derivatives, such as dialkyl sulfosuccinates.
Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propylene diamine, tripropylene triamine and dipropylene tetramine, and ethoxylated, ethoxylated and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts, such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxide and bis- (2-hydroxyethyl) -alkylamine oxide.
Also useful in the compositions of the present invention are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their proposed uses are disclosed in a number of published references, including McCutcheon's Emulsifiers and Detergents, north american and international yearbook versions, published by McCutcheon's Division, The Manufacturing conditioner Publishing co; the Encyclopdia of Surface Active Agents by Sisely and Wood, Chemical Publ.Co., Inc., New York, 1964; and Synthetic Detergents, seventh edition, John Wiley and Sons, New York, 1987, by a.s.davidson and b.milwidsky.
The compositions of the present invention may also contain formulation adjuvants and additives known to those skilled in the art as co-formulations (some of which may also be considered to act as solid diluents, liquid diluents or surfactants). Such formulation aids and additives may control: pH (buffer), foaming during processing (antifoam such as polyorganosiloxane), sedimentation of the active ingredient (suspending agent), viscosity (thixotropic thickener), microbial growth in the container (biocide), product freezing (antifreeze), color (dye/pigment dispersion), elution (film former or binder), evaporation (anti-evaporation agent), and other formulation attributes. Film formers include, for example, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include McCutcheon's Volume 2 published by McCutcheon's Division, The Manufacturing conditioner Publishing co: functional Materials, north american and international yearbook versions; and those listed in PCT publication WO 03/024222.
The compounds of the invention and any other active ingredients are incorporated into the compositions of the invention, typically 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 emulsifying agent is typically 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). Granules and pellets can be prepared by spraying the active on preformed particulate carriers or by agglomeration techniques. See Browning "agglomerization" (Chemical Engineering, 12.4.1967, pages 147-48; Perry's Chemical Engineering' Handbook, 4 th edition, McGraw-Hill, New York, 1963, pages 8-57 and later and WO 91/13546. the pellets can be prepared as described in u.s.4,172,714. the water dispersible and water soluble particles can be prepared as set forth in u.s.4,144,050, u.s.3,920,442 and de.3,246,493. the tablets can be prepared as set forth in u.s.5,180,587, u.s.5,232,701 and u.s.5,208,030. the films can be prepared as set forth in GB2,095,558 and u.s.3,299,566.
For additional information regarding The field of formulation, see "The formulations's Toolbox-Product Forms for model Agriculture" by T.S. woods, The Food-Environment Challenge, T.Brooks and T.R. Roberts eds, Proceedings of The 9th International conformation on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, p.120. 133. See also U.S.3,235,361, column 6, line 16 to column 7, line 19 and examples 10-41; U.S. Pat. No. 3,309,192, column 5, column 43 to column 7, column 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138, 162, 164, 166, 167 and 169, 182; U.S.2,891,855 at column 3, line 66 to column 5, line 17 and examples 1-4; wed Control as a Science by Klingman, John Wiley and Sons, Inc., New York, 1961, pages 81-96; weed Control Handbook, 8 th edition, Blackwell Scientific Publications, Oxford, 1989, by Hance et al; and development in simulation technology, PJB Publications, Richmond, UK, 2000.
Use of the Compounds of the invention
The herbicides of the present invention can be used by spraying plants, applying to soil, applying to the surface of water. The amount of the active ingredient is appropriately determined to meet the purpose of use. The content of the active ingredient is appropriately determined depending on the purpose.
The amount of the compound of the present invention to be used depends on the kind of the compound to be used, the target weed, the tendency of weed to appear, environmental conditions, the kind of herbicide, and the like. When the herbicides of the invention are used as such, for example in the form of powders or granules, the amount is suitably selected from 1g to 50kg, preferably 10g to 10kg, of active ingredient per hectare. 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 the formula (I), formula (Ia-1), formula (Ia-2) or formula (Ib).
The term "herbicide" means a compound that controls or modifies the growth of plants. The term "effective amount" means the amount of such a compound or composition of such compounds that is capable of producing an effect of controlling or modifying the growth of a plant. The effects of control or modification include all deviations from natural development, e.g., kills, delays, leaf burns, albinism, dwarfing, etc. The term "plant" refers to all physical 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 useful plant crops. "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 (e.g., barley and wheat), cotton, oilseed rape, corn, rice, soybeans, sugar beet, sugar cane, sunflowers, ornamentals, switchgrass, turf and vegetables, especially cereals, corn and soybeans.
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, ryegrass, monocrotopsis, panicum, poa, cymaroma, arrowhead, scirpus, setaria, sida and sorghum, and dicotyledonous species, such as kenaf, amaranthus, chenopodium, chrysanthemum, euphorbia, labra, ipomoea, kochia, eclipta, polygonum, sida, 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 crop plants 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., poa pratensis, saint augustane grass (st. augustine grass), Kentucky boehne grass and bermudagrass).
If desired, the compounds according to the invention having the formula (I), formula (Ia-1), formula (Ia-2) or formula (Ib) 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, mixtures of the invention also include mixtures of two or more different compounds having formula (I), formula (Ia-1), formula (Ia-2) or formula (Ib). In particular, the present invention also relates to a composition of the invention comprising at least one further herbicide in addition to the compound of formula (I), formula (Ia-1), formula (Ia-2) or formula (Ib).
General synthetic procedure
In this specification, a structure is dominant if there is any difference between the chemical name and the chemical structure. In general, the compounds of the invention may be prepared by the methods described herein, unless otherwise indicated.
The test conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: brookfield (Bruker) nuclear magnetic instrument at 400MHz or 600MHz in CDC1 at room temperature3，d6-DMSO，CD3OD or d6Acetone as solvent (reported in ppm) with TMS (0ppm) or chloroform (7.26ppm) as reference standard. When multiple peaks occur, the following abbreviations will be used: s (singleton), d (doublet), t (triplet), q (quatet, quartet), m (multiplet ), br (broadpeded, broad), dd (doublet of doublets), dt (doublet of triplets, doublet). Coupling constants are expressed in hertz (Hz).
The mass spectrometry method used in the invention comprises the following steps: agilent 1260HPLC was used; agilent 6120 ESI.
Phase A: water (0.1% formic acid); phase B: acetonitrile (0.1% formic acid).
Gradient elution: 0-3min, 5-100% B; 3-6min, 100% B.
Flow rate: 0.6 mL/min.
Detection wavelength: 254 nm.
MS parameters: ESI positive scan, collision induced ionization: 70V.
Drying nitrogen gas: 12L/min, atomizing gas pressure: 40psi, gas temperature: at 350 ℃.
Taking a proper amount of sample, dissolving in 0.5mL of methanol, injecting a sample, and performing primary MS full scanning in a positive ESI mode to obtain an excimer peak [ M + H ]]+And (6) reading.
The following abbreviations are used throughout the present invention:
AIBN: azobisisobutyronitrile
DCM: methylene dichloride
DMF: n, N-dimethylformamide, dimethylformamide
MeOH: methanol
NBS: n-bromosuccinimide
EtOH: ethanol
EtOAc: ethyl acetate
PE or Petroleum ether: petroleum ether
THF: tetrahydrofuran (THF)
TLC: thin layer chromatography
SOCl2: thionyl chloride
Na2SO4: sodium sulfate
K2CO3: potassium carbonate
DMSO, DMSO: dimethyl sulfoxide
The following synthetic schemes and examples 1-38 serve to further illustrate the context of the present invention.
Synthetic schemes
Synthesis scheme I
Figure BDA0002606171070000211
Figure BDA0002606171070000221
Compound (E) can be prepared by synthetic scheme one, wherein R1M and X have the meanings given in the description of the invention. Reacting 2, 4-dichloro-3- (bromomethyl) methyl benzoate with a nitrogen-containing heterocyclic compound (M1) under an alkaline condition (such as sodium carbonate and potassium carbonate) at 0-35 ℃ to obtain a compound (A); hydrolyzing the compound (A) under alkaline conditions (such as lithium hydroxide) to obtain a compound (B); halogenating the compound (B) with acyl chloride (such as oxalyl chloride) at 0-100 ℃ to obtain a compound (C); carrying out esterification reaction on the compound (C) and cyclohexanedione at 0-35 ℃ to obtain a compound (D); the compound (D) is subjected to Fries rearrangement reaction at 10-40 ℃ under the action of a catalyst (such as trimethyl cyanide silane and acetone cyanohydrin) to obtain a target compound (E).
Synthesis scheme two
Figure BDA0002606171070000222
Compound (G) can be prepared by synthesis scheme two, wherein R1M, X and R3Have the meaning as described in the present invention. Carrying out esterification reaction on the compound (C) and substituted pyrazole (F1) at 0-35 ℃ to obtain a compound (F); the compound (F) is subjected to Fries rearrangement reaction at 10-40 ℃ under the action of a catalyst (such as trimethyl cyanide silane and acetone cyanohydrin) to obtain a target compound (G).
Synthesis scheme three
Figure BDA0002606171070000223
Compound (H) can be prepared by synthesis scheme III, wherein R1M, X and R3Have the meaning as described herein; wherein R is5Is hydrogen, C1-6Alkyl or halogen; y is halogen. Reacting compound (G) with compound (H1) under basic conditions (e.g. Cs)2CO3、K2CO3Etc.) to generate nucleophilic substitution reaction at 25-50 ℃ to obtain the target compound (H).
Synthesis scheme four
Figure BDA0002606171070000231
Compound (K) can be prepared by synthesis scheme IV, wherein R1M and X have the meanings given in the description of the invention. Compounds (C) and bicyclo [3.2.1]Carrying out esterification reaction on octane-2, 4-diketone at the temperature of 0-35 ℃ to obtain a compound (J); the compound (J) is subjected to Fries rearrangement reaction at 10-40 ℃ under the action of a catalyst (such as trimethyl cyanide silane and acetone cyanohydrin) to obtain a target compound (K).
Examples
Example 1: preparation of 2- (2, 4-dichloro-3- (morpholinomethyl) benzoyl) -3-hydroxycyclohexa-2-enone
Figure BDA0002606171070000232
Step 1: preparation of 2, 4-dichloro-3-methylacetophenone
Figure BDA0002606171070000233
To a single neck flask was added aluminum chloride (49.68g, 372.6mmol) and 2, 6-dichlorotoluene (50g, 310.5mmol), stirred at room temperature, then acetyl chloride (26.81g, 341.6mmol) was slowly added dropwise, heated to 40 ℃ for 2h, and TLC monitored for completion of the starting material reaction. The system was poured slowly into ice water (500mL), acidified with dilute hydrochloric acid solution (1M, 30mL), extracted with dichloromethane (150mL x 3), dried over anhydrous sodium sulfate, and concentrated to give 60g of a colorless oil in 95% yield.
Step 2: preparation of 2, 4-dichloro-3-methylbenzoic acid
Figure BDA0002606171070000241
2, 4-dichloro-3-methylacetophenone (30g, 147.7mmol) and 1, 4-dioxane (100mL) were added to a single vial, the temperature was raised to 80 deg.C, sodium hypochlorite solution (5% available chlorine 300mL) was added dropwise, the temperature was maintained and stirred for 5h, and TLC monitored for completion of the starting material reaction. After returning to room temperature, the mixture was separated into two phases, the lower solution was separated, acidified to pH 2 with concentrated hydrochloric acid, filtered, the filter cake washed with water (100mL x 3), and dried at 50 ℃ to give 22g of a white solid with a yield of 74%.
And step 3: preparation of methyl 2, 4-dichloro-3-methylbenzoate
Figure BDA0002606171070000242
2, 4-dichloro-3-methylbenzoic acid (20g, 97.54mmol) and methanol (80mL) were added to a single-neck flask, the temperature was reduced to 0 ℃ and SOCl was slowly added dropwise2(13.85mL, 195.0mmol), after the addition, the temperature was raised to 60 ℃ for reaction for 10 h. The major part of the methanol was distilled off under reduced pressure, the remaining material was slowly added to ice water (200mL) and the pH was adjusted to 8 with saturated sodium bicarbonate solution, extracted with dichloromethane (50mL x 3), dried over anhydrous sodium sulfate, the organic phase was concentrated and recrystallized to give 16.3g of white solid in 76% yield.
And 4, step 4: preparation of methyl 2, 4-dichloro-3- (bromomethyl) benzoate
Figure BDA0002606171070000243
To a single neck flask was added methyl 2, 4-dichloro-3-methylbenzoate (12g, 54.78mmol), NBS (13.65g, 76.69 mmol), carbon tetrachloride (60mL) and AIBN (1.8g, 10.92mmol), protected with nitrogen, the reaction was stirred at 78 ℃ for 3.5h and monitored by TLC for completion. After cooling and suction filtration, the filter cake was washed with carbon tetrachloride (20mL x 3), the carbon tetrachloride was distilled off under reduced pressure, and recrystallization (petroleum ether/ethyl acetate (V/V) ═ 5/1) gave 15g of a white solid with a yield of 92%.
And 5: preparation of methyl 2, 4-dichloro-3- (morpholinomethyl) benzoate
Figure BDA0002606171070000244
Morpholine (2.66g, 30.54mmol) and potassium carbonate (4.22g, 30.54mmol) were dissolved in acetonitrile (50mL), stirred at room temperature for 30min, then a solution of methyl 2, 4-dichloro-3- (bromomethyl) benzoate (7g, 23.49mmol) in acetonitrile (30mL) was slowly added dropwise, the reaction was carried out at room temperature, and the completion of the reaction was monitored by TLC. The reaction was filtered, the filter cake was washed with acetonitrile (10mL x 3), the filtrate was recovered and concentrated to give the crude product as a pale yellow oil 6.55g, which was used directly in the next reaction.
Step 6: preparation of 2, 4-dichloro-3- (morpholinomethyl) benzoic acid
Figure BDA0002606171070000251
Methyl 2, 4-dichloro-3- (morpholinomethyl) benzoate (6.4g, 21.04mmol), lithium hydroxide monohydrate (1.77g, 42.08mmol) was dissolved in THF (30mL), EtOH (30mL) and H2O (30mL) in a mixed solvent, and the reaction is carried out for 2h at room temperature, and the completion of the reaction is monitored by TLC. The organic solvent was distilled off under reduced pressure, diluted with water (50mL), extracted with ethyl acetate (30mL × 2), the aqueous phase was recovered, acidified to pH 5 by adding dilute hydrochloric acid (1M) dropwise with stirring, the aqueous phase was extracted with dichloromethane (30mL × 3), and the organic phase was concentrated to give 5.2g of a yellow solid, yield 86%.
And 7: preparation of 2, 4-dichloro-3- (morpholinomethyl) benzoyl chloride
Figure BDA0002606171070000252
The compound 2, 4-dichloro-3- (morpholinomethyl) benzoic acid (1.0g, 3.45mmol) was dissolved in ultra-dry dichloromethane (30mL), cooled to 0 deg.C, oxalyl chloride (874.9mg, 6.89mmol) was added to the reaction solution, and finally N, N-dimethylformamide (7.24mg, 0.34mmol) was added, reacted at room temperature for 3h, and then the solvent was distilled off under reduced pressure to give 848mg of a pale yellow viscous liquid, in 80% yield.
And 8: preparation of 3-oxocyclohex-1-en-1-yl 2, 4-dichloro-3- (morpholinomethyl) benzoate
Figure BDA0002606171070000253
Compound 1, 3-cyclohexanedione (338.94mg, 3.02mmol) was dissolved in ultra-dry dichloromethane (20mL), triethylamine (556.14mg, 5.50mmol) was added to the reaction mixture, the mixture was cooled to 0 ℃ or lower, and a solution of 2, 4-dichloro-3- (morpholinomethyl) benzoyl chloride (848mg, 2.75mmol) in dichloromethane (20mL) was added to the reaction mixture, and the mixture was reacted at room temperature for 4 hours. The reaction was diluted with dichloromethane (50mL) and washed with saturated sodium bicarbonate solution (50 mL. times.2) and the organic phase recovered as anhydrous Na2SO4Drying, filtration, washing with dichloromethane (10mL x 2), column chromatography (eluent: PE/EtOAc (V/V) ═ 20/3) afforded 900mg of yellow oily liquid in 85% yield.
And step 9: preparation of 2- (2, 4-dichloro-3- (morpholinomethyl) benzoyl) -3-hydroxycyclohexa-2-enone
Figure BDA0002606171070000254
The compound 3-oxocyclohex-1-en-1-yl 2, 4-dichloro-3- (morpholinomethyl) benzoate (900mg, 2.34mmol) was dissolved in ultra-dry acetonitrile (30mL), triethylamine (474mg, 4.68mmol) was added to the reaction solution, and finally trimethylsilyl cyanide (34.85mg, 0.35mmol) was added to the reaction solution, reacted at room temperature for 6h, and the completion of the starting material reaction was monitored by TLC. Distilling under reduced pressure to remove organic solvent, dissolving the system with water (50mL), acidifying with dilute hydrochloric acid solution (1M) to pH 5, extracting with dichloromethane (40mL x 3), combining organic phases, anhydrous Na2SO4Drying, filtration, concentration and column chromatography (eluent: DCM/MeOH (V/V) ═ 100/1) gave 400mg of a white solid in 46% yield.
MS(ES-API,pos.ion)m/z:384.1[M+H]+；
1H NMR(400MHz,CDCl3)δ7.37(d,J＝8.2Hz,1H),7.02(d,J＝8.2Hz,1H),3.76(s,2H), 3.68–3.63(m,4H),2.79(t,J＝6.2Hz,2H),2.59–2.52(m,4H),2.43(t,J＝6.4Hz,2H),2.08– 2.01(m,2H).
Example 2: preparation of 2- ((3-cyclopropyl-4- (2, 4-dichloro-3- (morpholinomethyl) benzoyl) -1-methyl-1H-pyrazol-5-yl) oxy) -1-phenylethanone
Figure BDA0002606171070000261
Step 1: preparation of 3-cyclopropyl-1-methyl-1H-pyrazol-5-yl 2, 4-dichloro-3- (morpholinomethyl) benzoate
Figure BDA0002606171070000262
3-cyclopropyl-1-methyl-5-hydroxypyrazole (290mg, 2.10mmol) was dissolved in ultra-dry dichloromethane (20mL), triethylamine (360mg, 3.57mmol) was added to the reaction mixture, the mixture was cooled to 0 ℃ and a solution of 2, 4-dichloro-3- (morpholinomethyl) benzoyl chloride (549mg, 1.78mmol) in dichloromethane (10mL) was added to the reaction mixture, the mixture was reacted at room temperature for 3 hours, and the completion of the reaction of the starting materials was monitored by TLC. Saturated sodium bicarbonate solution (100mL) was added to the reaction, extracted with dichloromethane (50mL x 3), and the organic phases combined, anhydrous Na2SO4Drying, filtration, washing with dichloromethane and column chromatography (eluent: PE/EtOAc (V/V) ═ 100/30) afforded 642mg of a yellow solid in 88% yield.
MS-ESI:m/z 411.10[M+H]+.
Step 2: preparation of (3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl) (2, 4-dichloro-3- (morpholinomethyl) phenyl) methanone
Figure BDA0002606171070000271
3-cyclopropyl-1-methyl-1H-pyrazol-5-yl 2, 4-dichloro-3- (morpholinomethyl) benzoate (642mg, 1.56mmol) was dissolved in ultra-dry acetonitrile (20mL), triethylamine (314mg, 3.10mmol) was then added to the reaction solution, and finally trimethylsilyl cyanide (25mg, 0.25mmol) was added to the reaction solution, followed by reaction at room temperature for 5H, and completion of the raw material reaction was monitored by TLC. Using the reaction solutionAcidifying acetic acid to pH 5, stirring for 30min, distilling under reduced pressure to remove solvent, adding water (50mL), extracting with dichloromethane (50mL x 3), combining organic phases, anhydrous Na2SO4Drying, filtration, concentration and column chromatography (eluent: DCM/MeOH (V/V) ═ 100/1) gave 320mg of a yellow solid in 50% yield.
MS(ES-API,pos.ion)m/z:410.1[M+H]+.
1H NMR(400MHz,CDCl3)δ7.37(d,J＝8.2Hz,1H),7.19(d,J＝8.2Hz,1H),3.78(s,2H), 3.65–3.61(m,4H),3.50(s,3H),2.59–2.53(m,4H),0.94(d,J＝4.8Hz,1H),0.71(s,2H),0.36 (d,J＝7.6Hz,2H).
And step 3: preparation of 2- ((3-cyclopropyl-4- (2, 4-dichloro-3- (morpholinomethyl) benzoyl) -1-methyl-1H-pyrazol-5-yl) oxy) -1-phenylethanone
Figure BDA0002606171070000272
The compound (3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl) (2, 4-dichloro-3- (morpholinomethyl) phenyl) methanone (150mg, 0.366mmol) and K2CO3(75.8mg, 0.548mmol) was dissolved in DMF (10mL), stirred at room temperature for 10min, then bromoacetophenone (80.0mg, 0.402mmol) was added to the reaction solution, reacted at room temperature for 4h, and TLC monitored that the starting material was completely reacted. Diluting the system with water (50mL), extracting with ethyl acetate (50mL x 3), combining the organic phases, washing the organic phases once with saturated brine solution (50mL), anhydrous Na2SO4Drying, filtration, concentration and column chromatography (eluent: PE/EtOAc (V/V) ═ 20/4) gave 86mg of an off-white solid in 45% yield.
MS(ES-API,pos.ion)m/z:528.1[M+H]+；
1H NMR(400MHz,CDCl3)δ7.89(d,J＝7.4Hz,2H),7.61(t,J＝7.4Hz,1H),7.49(t,J＝ 7.7Hz,2H),7.36(d,J＝8.2Hz,1H),7.19(d,J＝8.2Hz,1H),5.87(s,2H),3.82(s,3H),3.74(s, 2H),3.61(s,4H),2.53(s,4H),1.10–1.04(m,1H),0.78–0.73(m,2H),0.42–0.36(m,2H).
With reference to the first to fourth synthesis schemes of the present invention, the target compounds of table 1 can be obtained by combining the synthesis methods of specific examples 1-2 and using the corresponding raw materials and conditions.
TABLE 1
Figure BDA0002606171070000281
Figure BDA0002606171070000291
Figure BDA0002606171070000301
Figure BDA0002606171070000311
Figure BDA0002606171070000321
Figure BDA0002606171070000331
Figure BDA0002606171070000341
Figure BDA0002606171070000351
Figure BDA0002606171070000361
Figure BDA0002606171070000371
Figure BDA0002606171070000381
Figure BDA0002606171070000391
Figure BDA0002606171070000401
Figure BDA0002606171070000411
Biological examples
Weighing a certain mass of original medicine by an analytical balance (0.0001g), dissolving the original medicine by a proper amount of DMF (dimethyl formamide), and then diluting the original medicine by a certain volume of distilled water containing 1 per mill of Tween-80 emulsifier for later use.
Taking flowerpots with the length and the width of 7.0cm, filling soil to 3/4, directly sowing pretreated weed target seeds, covering soil about 0.5cm, performing spray treatment when seedlings are grown to a proper age stage, transferring the seedlings to a greenhouse for conventional culture after the application of the herbicide after the pesticide is naturally dried in the air, and investigating the activity (%) of weeds after 21 days; where 0 indicates no damage or normal growth process and 100 indicates at least complete aboveground death.
TABLE 2 Activity of the Compounds of the invention on weeds at 300g/ha
Figure BDA0002606171070000412
Figure BDA0002606171070000421
TABLE 3 Activity of the compounds of the invention against Abutilon and Portulaca oleracea at 150g/ha, 75g/ha, 37.5g/ha and 18.75g/ha
Figure BDA0002606171070000422
Figure BDA0002606171070000431
Figure BDA0002606171070000441
TABLE 4 Activity of the compounds of the invention on barnyard grass at 150g/ha
Examples Barnyard grass Examples Barnyard grass
Example 2 90 Example 3 85
Example 4 90 Example 6 90
Example 7 80 Example 8 85
Example 14 85 Example 25 87
Example 26 80 Example 32 93
TABLE 5 Activity of the compounds of the invention on zinnia at 150g/ha, 75g/ha and 37.5g/ha
Figure BDA0002606171070000442
Where ND means not tested.
The results in tables 2 to 5 show that the compounds of the present invention have excellent controlling effects on abutilon, purslane, zinnia, barnyard grass at 300g/ha, 150g/ha, 75g/ha, 37.5g/ha and 18.75 g/ha.
Peanut safety test
Weighing a certain mass of compound by using an analytical balance (0.0001g), dissolving the compound by using a proper amount of DMF (dimethyl formamide), and then diluting the compound by using a certain volume of distilled water containing 1 per mill of Tween-80 emulsifier for later use.
Loading soil in pots with the length and width of 7.0cm to 3/4 points, directly sowing pretreated crop seeds, covering soil about 0.5cm, performing spray treatment when seedlings grow to a proper age stage, transferring the liquid medicine into a greenhouse for conventional culture after the liquid medicine is naturally dried, and checking the phytotoxicity (%) of peanuts after 21 days; where 0 indicates no harm or normal growth process and 100 indicates complete death of at least the aerial part.
TABLE 6 peanut safety test for compounds of the invention
Figure BDA0002606171070000451
The results in Table 6 show that the compounds of the invention are peanut safe at 75-600g/ha, and are more safe at the same dosage compared to the prior art. The compound of the invention still shows excellent safety to peanuts at high dose.
Table 7 safety testing of the compounds of the invention on corn
Figure BDA0002606171070000452
Figure BDA0002606171070000461
The results in Table 7 show that the compounds of the invention are corn safe at 75-300g/ha, yet still show excellent safety at high doses.
In addition, the compound of the invention also has certain safety to rice and wheat, for example, the phytotoxicity of example 1 to wheat is below 15% at 75-300 g/ha; in example 20, the damage to wheat at 75-300g/ha is less than 10%, and the damage to rice is less than 5%.
The compound has good control effect on broadleaf weeds (such as abutilon, amaranthus retroflexus, zinnia elegans, snakehead intestine and purslane) and grassy weeds (such as crab grass, cockspur grass, ryegrass and green bristlegrass). The herbicide composition is safe to peanuts, corns, rice and wheat, has quick drug effect, has better weed control effect than commercial herbicides and benzoyl compounds with similar structures, and has good application prospect.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (14)

1. A compound which is a compound of formula (I) or a stereoisomer, tautomer, nitroxide or salt of a compound of formula (I):
Figure FDA0002606171060000011
wherein:
R1is hydroxy, cyano, amino, nitro, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C1-6Alkoxy, halo C1-6Alkyl, halo C2-6Alkenyl, halo C2-6Alkynyl, halo C1-6Alkoxy or C3-8A cycloalkyl group;
m is 0, 1, 2,3, 4, 5, 6, 7, 8, 9 or 10;
x is-CH2-、-O-、-S(＝O)n-or-NH-;
n is 0, 1 or 2;
q is the following subformula:
Figure FDA0002606171060000012
R2and R2aEach independently is hydrogen or C1-6An alkyl group;
R3is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-8A cycloalkyl group;
R4is hydrogen or-CH2-CO-C6-10An aryl group; wherein said-CH2-CO-C6-10Aryl is optionally substituted by 1, 2 or 3 substituents selected from halogen or C1-6Alkyl substituents.
2. The compound of claim 1, wherein,
R1is hydroxy, cyanoRadical, amino, nitro, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C1-4Alkoxy, halo C1-4Alkyl, halo C2-4Alkenyl, halo C2-4Alkynyl, halo C1-4Alkoxy or C3-6A cycloalkyl group;
R2and R2aEach independently is hydrogen or C1-4An alkyl group.
3. The compound of claim 2, wherein,
R1is hydroxy, cyano, amino, nitro, methyl, ethyl, n-propyl, isopropyl, -CHF2、-CF3、-CH2CHF2、-CH2CF3Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
R2and R2aEach independently hydrogen or methyl.
4. The compound of claim 1, wherein,
R3is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl or C3-6A cycloalkyl group;
R4is hydrogen or-CH2-CO-phenyl; wherein said-CH2-CO-phenyl optionally substituted by 1, 2 or 3 substituents selected from halogen or C1-4Alkyl substituents.
5. The compound of claim 4, wherein,
R3is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
R4is hydrogen or-CH2-CO-phenyl; wherein said-CH2-CO-phenyl is optionally substituted with 1, 2 or 3 substituents selected from chloro or methyl.
6. The compound of any one of claims 1-5, which is a compound of formula (Ia) or a stereoisomer, tautomer, nitroxide, or salt of a compound of formula (Ia); or a stereoisomer, a tautomer, a nitroxide, or a salt of a compound of formula (Ib):
Figure FDA0002606171060000021
wherein:
R1aand R1bEach independently is hydrogen or C1-3An alkyl group.
7. The compound of claim 6, wherein,
q is the following subformula:
Figure FDA0002606171060000022
Figure FDA0002606171060000031
R1aand R1bEach independently hydrogen or methyl;
n is 0, 1 or 2.
8. The compound according to any one of claims 1 to 7, which is a compound having one of the following structures or a stereoisomer, a tautomer, a nitroxide or a salt thereof of a compound having one of the following structures:
Figure FDA0002606171060000032
Figure FDA0002606171060000041
Figure FDA0002606171060000051
Figure FDA0002606171060000061
9. a composition comprising a compound of any one of claims 1-8.
10. The composition of claim 9, wherein the composition further comprises at least one additional component that is a surfactant, a solid diluent, a liquid diluent, a buffer, an anti-foaming agent, a thickener, an anti-freeze agent, an antimicrobial agent, a film-forming agent.
11. Use of a compound according to any one of claims 1 to 8 or a composition according to claim 9 or 10 as a herbicide for controlling weeds in useful plants.
12. The use according to claim 11, wherein the useful plant is at least one of peanut, corn, rice or wheat; the weeds are one or more of abutilon, purslane, cockspur grass or zinnia.
13. A method of controlling weed development in useful plants comprising applying to the locus of the weeds an effective amount of a compound according to any one of claims 1 to 8 or a composition according to claim 9 or 10.
14. The method of claim 13, wherein the useful plant is at least one of peanut, corn, rice, or wheat; the weeds are one or more of abutilon, purslane, cockspur grass or zinnia.
CN202010739115.8A 2019-07-31 2020-07-28 Heterocyclylalkyl-substituted dichlorobenzoyl compounds and application thereof Active CN112300092B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNPCT/CN2019/098492 2019-07-31
CN2019098492 2019-07-31

Publications (2)

Publication Number Publication Date
CN112300092A true CN112300092A (en) 2021-02-02
CN112300092B CN112300092B (en) 2023-06-09

Family

ID=74228561

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010739115.8A Active CN112300092B (en) 2019-07-31 2020-07-28 Heterocyclylalkyl-substituted dichlorobenzoyl compounds and application thereof

Country Status (2)

Country Link
CN (1) CN112300092B (en)
WO (1) WO2021018135A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114409524A (en) * 2021-12-31 2022-04-29 上海柏狮生物科技有限公司 Preparation method of 2, 6-dichlorophenylacetic acid

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN88101455A (en) * 1987-03-17 1988-09-28 日产化学工业株式会社 Pyrazole derivatives and herbicides containing the same
CN1310714A (en) * 1998-07-24 2001-08-29 拜尔公司 Substituted benzoylcyclohexandiones
CN1323292A (en) * 1998-10-10 2001-11-21 阿温提斯作物科学有限公司 Benzoylcyclohexandiones, method for the production and use thereof as herbicides and plant growth regulators
CN1416422A (en) * 2000-03-06 2003-05-07 拜尔公司 Substituted benzoylcyclohexenones
CN1509141A (en) * 2001-03-14 2004-06-30 �ݶ�ũ�����ѧ�ɷݹ�˾ Herbicides based on substituted aryl ketones
CN1543311A (en) * 2001-02-12 2004-11-03 拜尔农作物科学股份公司 Selective substituted aryl ketone and safener based herbicides
CN101573035A (en) * 2006-12-27 2009-11-04 石原产业株式会社 Herbicide containing benzoylpyrazole compound
WO2012065573A1 (en) * 2010-11-19 2012-05-24 中国中化股份有限公司 Nitrogen heterocyclic substituted benzoyl compound and use thereof
CN105766944A (en) * 2014-12-22 2016-07-20 沈阳中化农药化工研发有限公司 A herbicide and an application thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN88101455A (en) * 1987-03-17 1988-09-28 日产化学工业株式会社 Pyrazole derivatives and herbicides containing the same
CN1310714A (en) * 1998-07-24 2001-08-29 拜尔公司 Substituted benzoylcyclohexandiones
CN1323292A (en) * 1998-10-10 2001-11-21 阿温提斯作物科学有限公司 Benzoylcyclohexandiones, method for the production and use thereof as herbicides and plant growth regulators
CN1416422A (en) * 2000-03-06 2003-05-07 拜尔公司 Substituted benzoylcyclohexenones
CN1543311A (en) * 2001-02-12 2004-11-03 拜尔农作物科学股份公司 Selective substituted aryl ketone and safener based herbicides
CN1509141A (en) * 2001-03-14 2004-06-30 �ݶ�ũ�����ѧ�ɷݹ�˾ Herbicides based on substituted aryl ketones
CN101573035A (en) * 2006-12-27 2009-11-04 石原产业株式会社 Herbicide containing benzoylpyrazole compound
WO2012065573A1 (en) * 2010-11-19 2012-05-24 中国中化股份有限公司 Nitrogen heterocyclic substituted benzoyl compound and use thereof
CN105766944A (en) * 2014-12-22 2016-07-20 沈阳中化农药化工研发有限公司 A herbicide and an application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
R.B.西尔弗曼 编，郭宗儒 主译: "《有机药物化学[原著第二版]》", 31 January 2008, 化学工业出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114409524A (en) * 2021-12-31 2022-04-29 上海柏狮生物科技有限公司 Preparation method of 2, 6-dichlorophenylacetic acid

Also Published As

Publication number Publication date
WO2021018135A1 (en) 2021-02-04
CN112300092B (en) 2023-06-09

Similar Documents

Publication Publication Date Title
CN110878058B (en) Isoxazoline derivatives and their use in agriculture
CN110511216B (en) Isoxazoline derivatives and their use in agriculture
CN111566088B (en) Quinoline derivative and preparation method and application thereof
CN111574509B (en) Isoxazoline derivatives and their use in agriculture
CN112409226B (en) Substituted benzoyl compounds and application thereof
CN112300092B (en) Heterocyclylalkyl-substituted dichlorobenzoyl compounds and application thereof
CN112689626B (en) Substituted benzoyl-pyrazole compounds and application thereof in agriculture
CN112430220B (en) Substituted benzoyl compounds and application thereof
CN112174889B (en) Substituted benzoyl compounds and application thereof in agriculture
CN114163430A (en) Benzothiadiazine derivative and application thereof in agriculture
CN112794846B (en) Ethyl isoxazoline derivative and application thereof
CN113527224B (en) Thiazole derivative and application thereof in agriculture
CN112142671B (en) Substituted benzoyl-pyrazoles and application thereof in agriculture
CN111559965B (en) Substituted benzoyl compounds and application thereof in agriculture
CN111943900A (en) Isoxazoline derivatives and their use in agriculture
CN112409263B (en) Substituted benzoyl compounds and application thereof
CN112225707B (en) Isoxazoline derivatives and their use in agriculture
CN113620941B (en) Cyclopropyl-pyrazole derivatives and their use in agriculture
CN114075149A (en) Difluorophenyl-containing heterocyclic compound and application thereof
CN114163400A (en) Cyclohexanedione-benzothiadiazine compound and application thereof
CN114478506A (en) Pyridine oxazole compound and application thereof
CN114163394A (en) Chloromethyl-containing isoxazoline derivatives and use thereof
CN114380761A (en) Novel isoxazole derivative and application thereof in agriculture
CN111670182A (en) Quinoline derivatives, preparation method and application thereof
CN114478507A (en) Pyrimidine oxazole compound and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant