CN111559965A - Substituted benzoyl compounds and application thereof in agriculture - Google Patents

Abstract

The present invention provides a substituted benzoyl compound and its application in agriculture; specifically, the present invention provides a compound represented by formula (I) and a preparation method thereof; compositions and preparations containing these compounds and their use as Use of herbicides; wherein Q is oxocyclohexenyl or substituted pyrazolyl; R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen, halogen, cyano, hydroxyl and the like.

Description

Substituted benzoyl compounds and their applications in agriculture

technical field

The present invention provides a new substituted benzoyl compound and its preparation method; a composition containing these compounds and its application in agriculture.

Background technique

Substituted benzoyl compounds are a class of compounds with excellent biological activity, the herbicidal activities of which are reported in eg CN 107674025, CN 108264484 and EP 137963. However, the compounds of the present invention described in detail hereinafter are not described in these documents.

The active ingredients known from the documents cited above have disadvantages in use in that, for example, (a) there is no or only insufficient herbicidal action on weed plants, (b) the weed plants to be controlled are overused narrow or (c) too low selectivity in crops of useful plants.

Therefore, there is a need to provide chemically active ingredients that can be advantageously used as herbicides or plant growth regulators.

SUMMARY OF THE INVENTION

The present invention provides a novel substituted benzoyl compound with excellent herbicidal action and excellent selectivity between crops and weeds.

In one aspect, the present invention provides compounds represented by formula (I) or stereoisomers, tautomers, nitrogen oxides and salts of compounds represented by formula (I):

in:

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen, halogen, cyano, hydroxy, nitro, amino, carboxyl, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl , haloalkynyl, alkoxy, haloalkoxy, alkylthio, alkylamino, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkylalkyl, heterocyclylalkyl, aryl alkyl, heteroarylalkyl, cycloalkyloxy, heterocyclyloxy, aryloxy or heteroaryloxy;

Q is the following substructure formula:

wherein R ^a and R ^b are each independently hydrogen, alkyl or cycloalkyl;

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^b and ^Ra are each independently optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^c ;

Each R ^c is independently fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxyl, C _1-8 alkyl, haloC _1-8 alkyl, C _2-8 alkenyl, halo Substituted C _2-8 alkenyl, C _2-8 alkynyl, halogenated C _2-8 alkynyl, C _1-8 alkoxy, halogenated C _1-8 alkoxy, C _1-8 alkylamino, C _1-8 alkylthio, halogenated C _1-8 alkylamino, halogenated C _1-8 alkylthio, C _6-10 aryl, C _6-10 aryloxy, C _1-9 heteroaryl or C _1-9 Heteroaryloxy.

In some of these embodiments, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen, halogen, cyano, hydroxyl, nitro, amino, carboxyl, C _1-8 alkyl, C _{2- 8} alkenyl, C _2-8 alkynyl, halo C _1-8 alkyl, halo C _2-8 alkenyl, halo C _2-8 alkynyl, C _1-8 alkoxy, halo C _{1 -8} alkoxy, C _1-8 alkylthio, C _1-8 alkylamino, C _3-10 cycloalkyl, C _2-12 heterocyclyl, C _6-14 aryl, C _1-9 heteroaryl base, C _3-10 cycloalkyl C _1-8 alkyl, C _2-12 heterocyclyl C _1-8 alkyl, C _6-14 aryl C _1-8 alkyl, C _1-9 heteroaryl C _1-8 alkyl, C _3-10 cycloalkyloxy, C _2-12 heterocyclyloxy, C _6-14 aryloxy or C _1-9 heteroaryloxy;

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^c ;

Each R ^c is independently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C _1-6 alkyl, haloC _1-6 alkyl, C _2-6 alkenyl, halo Substituted C _2-6 alkenyl, C _2-6 alkynyl, halogenated C _2-6 alkynyl, C _1-6 alkoxy, halogenated C _1-6 alkoxy, C _1-6 alkylamino, C _1-6 alkylthio, halogenated C _1-6 alkylamino, halogenated C _1-6 alkylthio, C _6-10 aryl, C _6-10 aryloxy, C _1-6 heteroaryl or C _1-6 Heteroaryloxy.

In other embodiments, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each independently hydrogen, halogen, cyano, hydroxy, nitro, amino, carboxyl, C _1-6 alkyl, C _{2- 6} alkenyl, C _2-6 alkynyl, halo C _1-6 alkyl, halo C _2-6 alkenyl, halo C _2-6 alkynyl, C _1-6 alkoxy, halo C _{1 -6} alkoxy, C _1-6 alkylthio, C _1-6 alkylamino, C _3-8 cycloalkyl, C _2-8 heterocyclyl, C _6-10 aryl, C _1-6 heteroaryl base, C _3-8 cycloalkyl C _1-6 alkyl, C _2-8 heterocyclyl C _1-6 alkyl, C _6-10 aryl C _1-6 alkyl, C _1-6 heteroaryl C _1-6 alkyl, C _3-8 cycloalkyloxy, C _2-8 heterocyclyloxy, C _6-10 aryloxy or C _1-6 heteroaryloxy;

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^c ;

Each R ^c is independently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C _1-4 alkyl, haloC _1-4 alkyl, C _2-4 alkenyl, halo Substituted C _2-4 alkenyl, C _2-4 alkynyl, halogenated C _2-4 alkynyl, C _1-4 alkoxy, halogenated C _1-4 alkoxy, C _1-4 alkylamino, C _1-4 alkylthio, halogenated C _1-4 alkylamino, halogenated C _1-4 alkylthio, C _6-10 aryl, C _6-10 aryloxy, C _1-6 heteroaryl or C _1-6 Heteroaryloxy.

In other embodiments, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each independently hydrogen, halogen, cyano, hydroxyl, nitro, amino, carboxyl, C _1-4 alkyl, C _{2- 4} alkenyl, C _2-4 alkynyl, halo C _1-4 alkyl, halo C _2-4 alkenyl, halo C _2-4 alkynyl, C _1-4 alkoxy, halo C _{1 -4} alkoxy, C _1-4 alkylthio, C _1-4 alkylamino, C _3-6 cycloalkyl, C _2-6 heterocyclyl, C _6-10 aryl, C _1-5 heteroaryl base, C _3-6 cycloalkyl C _1-3 alkyl, C _2-6 heterocyclyl C _1-3 alkyl, C _6-10 aryl C _1-3 alkyl, C _1-5 heteroaryl C _1-3 alkyl, C _3-6 cycloalkyloxy, C _2-6 heterocyclyloxy, C _6-10 aryloxy or C _1-5 heteroaryloxy;

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^c ;

Each R ^is independently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, methyl, ethyl, n-propyl, isopropyl, difluoromethyl, trifluoromethyl, Methoxy or trifluoromethoxy.

In some of these embodiments, R ^a and R ^b are each independently hydrogen, C _1-6 alkyl, or C _3-8 cycloalkyl.

In other embodiments, R ^a and R ^b are each independently hydrogen, C _1-4 alkyl, or C _3-6 cycloalkyl.

In some of these embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound of formula (Ia):

wherein Q, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the meanings as described in the present invention.

In some of these embodiments, the present invention provides a compound that is a compound of formula (Ib) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound of formula (Ib):

wherein Q, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the meanings as described in the present invention.

In some of these embodiments, the present invention provides a compound that is a compound of formula (Ic) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound of formula (Ic):

wherein Q, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the meanings as described in the present invention.

In other embodiments, Q is the following substructural formula:

wherein R ^a and R ^b are each independently hydrogen, methyl, ethyl or cyclopropyl;

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen, halogen, cyano, hydroxyl, nitro, amino, carboxyl, methyl, ethyl, n-propyl, isopropyl, difluoro Methyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy or trifluoromethoxy.

In another aspect, the present invention provides a composition comprising a compound described herein, further optionally comprising at least one additional component.

In another aspect, the present invention provides the use in agriculture of a composition comprising the compound of the present invention.

Further, the present invention provides the application of the composition comprising the compound of the present invention in the control of plant diseases.

In some of these embodiments, the present invention provides the use of a composition comprising a compound of the present invention for controlling unwanted plants.

In another aspect, the present invention provides a method of controlling unwanted plants, characterized in that an effective amount of the compound of the present invention is applied to plants, plant seeds, soil in which or on which plants grow, or cultivated areas.

Compounds of formula (I), formula (Ia), formula (Ib) or formula (Ic) may exist in different stereoisomeric or optical isomers or tautomeric forms. The present invention includes all such isomers and tautomers and mixtures thereof in various ratios, as well as isotopic forms such as deuterium containing compounds.

Isotopically enriched compounds have the structures depicted by the general formulae given herein, except that one or more atoms are replaced by atoms having a selected atomic weight or mass number. Exemplary isotopes that can be incorporated into the compounds of the present invention include isotopes of ^hydrogen , carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine, and chlorine, such as 2H, ^3H , ^11C , ^13C , ^14C , ^15N , ^17O , ¹⁸ O, ¹⁸ F, ³¹ P, ³² P, ³⁵ S, ³⁶ Cl and ¹²⁵ I.

Any asymmetric atom (eg, carbon, etc.) of the compounds disclosed herein may exist in racemic or enantiomerically enriched forms, such as (R)-, (S)- or (R,S)-configurations exist.

The foregoing merely outlines certain aspects of the present invention, but is not limited to these and other aspects, which will be described in greater detail below.

Detailed Description of the Invention

Definitions and General Terms

Certain embodiments of the invention will now be described in detail, examples of which are illustrated by the accompanying structural and chemical formulae. The present invention is intended to cover all alternatives, modifications and equivalents, which are included within the scope of the present invention as defined by the claims. One skilled in the art will recognize that many methods and materials similar or equivalent to those described herein could 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 literature, patents, and similar materials differs from or contradicts this application (including, but not limited to, terms defined, uses of terms, techniques described, etc.), this Application shall prevail.

It should further be appreciated that certain features of the invention, which are, for clarity, described in the context of multiple separate embodiments, can 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, can also be provided separately or in any suitable subcombination.

Unless otherwise defined, 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.

Unless otherwise stated, the following definitions used herein shall apply. For the purposes of the present invention, chemical elements are in accordance with the Periodic Table of the Elements, CAS Edition, and Handbook of Chemistry and Physics, 75th Edition, 1994. In addition, general principles of organic chemistry may be referred to as described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausalito: 1999, and "March's Advanced Organic Chemistry" by Michael B. Smith and Jerry March, John Wiley & Sons, New York: 2007, Its entire contents are incorporated herein by reference.

As used herein, the articles "a", "an" and "the" are intended to include "at least one" or "one or more" unless stated otherwise or otherwise clearly contradicted by context. Thus, as used herein, these articles refer to one or more than one (ie, at least one) object of the article. For example, "a component" refers to one or more components, ie, there may be more than one component contemplated for use or use in the implementation of the described embodiments.

The term "comprising" is an open-ended expression, that is, it includes the contents specified in the present invention, but does not exclude other aspects.

"Stereoisomers" refer to compounds that have the same chemical structure, but differ in the arrangement of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis/trans), atropisomers, etc. .

"Enantiomer" refers to two nonsuperimposable, but mirror-image isomers of a compound.

"Diastereomer" refers to a stereoisomer that has two or more chiral neutralities and whose molecules are not mirror images of each other. Diastereomers have different physical properties such as melting point, boiling point, spectral properties and reactivity. Diastereomeric mixtures can be separated by high resolution analytical procedures such as electrophoresis and chromatography, eg HPLC.

Stereochemical definitions and rules used in the present invention generally follow S.P. Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; and Eliel, E. and Wilen, S., "Stereochemistry of Organic Compounds", definitions and rules for stereochemistry as described in John Wiley & Sons, Inc., New York, 1994.

Many organic compounds exist in optically active forms, that is, 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 the molecule about one or more of its chiral centers. The prefixes d and 1 or (+) and (-) are symbols used to designate the rotation of plane polarized light by the compound, where (-) or 1 indicates that the compound is levorotatory. Compounds prefixed with (+) or d are dextrorotatory. A specific stereoisomer is an enantiomer, and a mixture of such isomers is called an enantiomeric mixture. A 50:50 mixture of enantiomers is called a racemic mixture or racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.

The term "tautomer" or "tautomeric form" refers to structural isomers of different energies that are interconvertible through a low energy barrier. A chemical equilibrium of tautomers can be achieved if tautomerism is possible (eg, in solution). For example, protontautomers (also known as prototropic tautomers) include interconversions by migration of protons, such as keto-enol isomerization and imine-ene Amine isomerization. Valence tautomers include interconversions by recombination of some of the bonding electrons. Specific examples of keto-enol tautomers are pentane-2,4-dione, hexane-1,3-dione and 4-hydroxypent-3-en-2-one tautomers Mutual transformation. Another example of tautomerism is phenol-ketone tautomerism. A specific example of phenol-ketone tautomerism is the interconversion of pyridin-4-ol and pyridin-4(lH)-one tautomers. Unless otherwise indicated, all tautomeric forms of the compounds of the present invention are within the scope of the present invention.

In the present invention, depending on external conditions (such as solvent, pH, etc.), there is a keto-enol interconversion:

As described herein, the compounds of the present invention may be optionally substituted with one or more substituents, such as the compounds of the general formula above, or as in the Examples, subclasses, and subclasses encompassed by the present invention. a class of compounds. It is to be understood that the term "optionally substituted" is used interchangeably with the term "substituted or unsubstituted". In general, the term "substituted" means that one or more hydrogen atoms in a given structure have been replaced with a specified 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 can be substituted identically or differently at each position. The substituents mentioned therein can be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkane Oxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkane Alkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl, hydroxy-substituted alkane Amino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkylacyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkane radical, heterocyclyl, heterocyclylalkyl, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, amino Sulfonyl, etc.

In addition, it should be noted that, unless clearly stated otherwise, the description modes "each independently" and "...independently" and "...independently" used in the present invention can be interchanged, and both are interchangeable. It should be understood in a broad sense. It can either mean that in different groups, the specific options expressed between the same symbols do not affect each other, or it can mean that in the same group, the specific options expressed between the same symbols do not affect each other.

In various parts of this specification, the substituents of the compounds disclosed in the present invention are disclosed in terms of group type or scope. Specifically, the present invention includes each and every independent subcombination of each member of these group species and ranges. For example, the term " _{C1 - C6} alkyl" or " _C1-6 alkyl" specifically refers to the independently disclosed methyl, ethyl, C3 alkyl, _C4 alkyl, _C5 alkyl and _C6 alkanes base.

As used herein, the term "alkyl" or "alkyl group" refers to a saturated straight or branched chain monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted with one or more of the substituents described herein. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1-12 carbon atoms; in one embodiment, the alkyl group contains 1-10 carbon atoms; in one embodiment, the alkyl group contains 1-8 carbon atoms; in another embodiment, the alkyl group contains 1-6 carbon atoms; in yet another embodiment, the alkyl group contains 1-4 carbon atoms; in yet another embodiment, the alkane group Radical groups contain 1-3 carbon atoms.

Examples of alkyl groups include, but are not limited to, methyl (Me, _-CH3 ), ethyl (Et, -CH2CH3), n _{- propyl} (n _- Pr, _{-CH2CH2CH3 )} ), isopropyl (i-Pr, -CH(CH ₃ ) ₂ ), n-butyl (n-Bu, -CH ₂ CH ₂ CH ₂ CH ₃ ), isobutyl (i-Bu, -CH ₂ CH ) (CH ₃ ) ₂ ), sec-butyl (s-Bu, -CH(CH ₃ )CH ₂ CH ₃ ), tert-butyl (t-Bu, -C(CH ₃ ) ₃ ), n-pentyl (-CH 2CH2CH2CH2CH3), ₂ -pentyl (-CH( _{CH3 ) CH2CH2CH3 )} , _{3 -} pentyl (-CH( _{CH2CH3 ) 2 )} , ₂ -methyl -2-butyl(-C(CH3)2CH2CH3), ₃ -methyl- _{2-butyl(-CH(CH3)CH(CH3)2 ) , 3 - methyl} -1- Butyl ( _-CH2CH2CH ( _CH3 ) ₂ ), ₂ -methyl- ₁ -butyl (-CH2CH( _CH3 ) _{CH2CH3 )} , n _- hexyl _{( -CH2CH2CH2 CH2CH2CH3} ), ₂ -hexyl (-CH( _CH3 ) _{CH2CH2CH2CH3 )} , _{3 -} hexyl (-CH( _{CH2CH3 ) ( CH2CH2CH3 ) )} , 2-methyl-2-pentyl(-C( _CH3 )2CH2CH2CH3), ₃ -methyl- ₂ -pentyl(-CH( _{CH3 ) CH} ( _{CH3 ) CH2CH3} ), 4-methyl-2-pentyl (-CH(CH ₃ )CH ₂ CH(CH ₃ ) ₂ ), 3-methyl-3-pentyl (-C(CH ₃ )(CH ₂ CH ₃ ) ₂ ), 2-methyl-3-pentyl (-CH(CH ₂ CH ₃ )CH(CH ₃ ) ₂ ), 2,3-dimethyl-2-butyl (-C(CH ₃ ) ₂ CH (CH ₃ ) ₂ ), 3,3-dimethyl-2-butyl (-CH(CH ₃ )C(CH ₃ ) ₃ ), n-heptyl, n-octyl, and the like.

The term "alkenyl" refers to a linear or branched monovalent hydrocarbon group containing 2 to 12 carbon atoms, wherein there is at least one site of unsaturation, i.e., a carbon-carbon sp ² double bond, wherein the alkenyl group A group can be optionally substituted with one or more substituents described herein, including the "cis" and "tans" positions, or the "E" and "Z" positions. In one embodiment, an alkenyl group contains 2-10 carbon atoms; in one embodiment, an alkenyl group contains 2-8 carbon atoms; in another embodiment, an alkenyl group contains 2- 6 carbon atoms; in yet another embodiment, the alkenyl group contains 2-4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH= _CH2 ), allyl (-CH2CH= _CH2 ), propenyl ( _{CH3 -} CH=CH-), -CH ₂ CH ₂ CH = CH ₂ , -CH ₂ CH = CHCH ₃ , -CH ₂ CH ₂ CH ₂ CH = CH ₂ , -CH ₂ CH ₂ CH = CHCH ₃ , -CH ₂ CH ₂ CH ₂ CH = CHCH ₃ , etc. Wait.

The term "alkynyl" refers to a straight or branched chain monovalent hydrocarbon group containing 2 to 12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond, wherein the alkynyl group may be optionally combined with one or more substituted with one of the substituents described in the present invention. In one embodiment, the alkynyl group contains 2-10 carbon atoms; in one embodiment, the alkynyl group contains 2-8 carbon atoms; in another embodiment, the alkynyl group contains 2- 6 carbon atoms; in yet another embodiment, the alkynyl group contains 2-4 carbon atoms. Examples of alkynyl groups include, but are not limited to, -C≡CH, _-C≡CCH3 , _-CH2 -C≡CH, _{-CH2 - C≡CCH3} , -CH2CH2 _- C≡CH , -CH ₂ -C≡CCH ₂ CH ₃ , -CH ₂ CH ₂ -C≡C-CH ₂ CH ₃ and so on.

The term "alkoxy" means that an alkyl group is attached to the remainder of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Unless otherwise specified, the alkoxy groups contain 1-12 carbon atoms. In one embodiment, the alkoxy group contains 1-10 carbon atoms; in one embodiment, the alkoxy group contains 1-8 carbon atoms; in one embodiment, the alkoxy group contains 1-6 carbon atoms; in another embodiment, the alkoxy group contains 1-4 carbon atoms; in yet another embodiment, the alkoxy group contains 1-3 carbon atoms. The alkoxy groups 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 ₂ CH ₃ ), 1-propoxy (n-PrO, n- Propoxy, -OCH ₂ CH ₂ CH ₃ ), 2-propoxy (i-PrO, i-propoxy, -OCH(CH ₃ ) ₂ ), 1-butoxy (n-BuO, n- Butoxy, -OCH ₂ CH ₂ CH ₂ CH ₃ ), 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH ₂ CH(CH ₃ ) ₂ ), 2-butanyl Oxy (s-BuO, s-butoxy, -OCH(CH ₃ )CH ₂ CH ₃ ), 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC(CH ₃ ) ₃ ), ₁ -pentyloxy (n _- pentyloxy, -OCH2CH2CH2CH2CH3), _{2 -} pentyloxy (-OCH _{( CH3 ) CH2CH2CH3 )} , 3-pentyloxy (-OCH(CH ₂ CH ₃ ) ₂ ), 2-methyl-2-butoxy (-OC(CH ₃ ) ₂ CH ₂ CH ₃ ), 3-methyl-2-butoxy group (-OCH(CH ₃ )CH(CH ₃ ) ₂ ), 3-methyl-1-butoxy (-OCH ₂ CH ₂ CH(CH ₃ ) ₂ ), 2-methyl-1-butoxy (-OCH ₂ CH(CH ₃ )CH ₂ CH ₃ ), etc.

The term "alkylamino" or "alkylamino" includes "N-alkylamino" and "N,N-dialkylamino" wherein the amino group is independently substituted with one or two alkyl groups, respectively. In some embodiments, alkylamino is a lower alkylamino group with one or two _C1-6 alkyl groups attached to a nitrogen atom. In other embodiments, the alkylamino group is a _C1-3 lower alkylamino group. Suitable alkylamino groups may be monoalkylamino or dialkylamino, examples of which include, but are not limited to, N-methylamino, N-ethylamino, N,N-dimethylamino, N,N -Diethylamino, etc.

The term "alkylthio" refers to a straight or branched chain alkyl group attached to a divalent sulfur atom, wherein the alkyl group has the meaning as described herein. Examples _of alkylthio groups include, but are not limited to, _{-SCH3 , -SCH2CH3 , -SCH2CH2CH3} , and the like.

The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

The term "haloalkyl" means an alkyl group substituted with one or more halogen atoms. Examples of haloalkyl groups include, but are not limited to, _-CH2F , _-CHF2 , _-CH2Cl , _-CH2Br , _-CF3 , _{-CH2CF3 , -CH2CH2F , -CH2 CH2Cl , -CH2CH2Br , -CH2CHF2 , -CH2CH2CF3 , -CH2CH2CH2F , -CH2CH2CH2Cl , -CH2CH2CH2 _ _ _ _ Br} , _-CHFCH2CH3 , _-CHClCH2CH3 , _etc.

The term "haloalkoxy" refers to an alkoxy group substituted with one or more halogen atoms. Examples _of haloalkoxy groups include, but are not limited to, _-OCH2F , _-OCHF2 , _-OCH2Cl , _-OCH2Br , _-OCF3 , _-OCH2CF3 , _-OCH2CH2F , _{-OCH 2CH2Cl , -OCH2CH2Br , -OCH2CHF2 , -OCH2CH2CF3 , -OCH2CH2CH2F , -OCH2CH2CH2Cl , -OCH2CH2CH _ _ _ _ 2Br} , _-OCHFCH2CH3 , _{-OCHClCH2CH3 , etc.}

The term "haloalkylamino" refers to an alkylamino group substituted with one or more halogen atoms.

The term "haloalkylthio" means an alkylthio group substituted with one or more halogen atoms.

The term "haloalkenyl" means an alkenyl group substituted with one or more halogen atoms.

The term "haloalkynyl" means an alkynyl group substituted with one or more halogen atoms.

The term "cycloalkyl" denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing 3 to 12 carbon atoms. In one embodiment, the cycloalkyl group contains 3-12 carbon atoms; in one embodiment, the cycloalkyl group contains 3-10 carbon atoms; in another embodiment, the cycloalkyl group contains 3-8 carbon atoms atom; in yet another embodiment, the cycloalkyl group contains 3-6 carbon atoms. The cycloalkyl group is optionally substituted with one or more substituents described herein. Such examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl Alkyl, adamantyl, etc.

The term "cycloalkylalkyl" means that an alkyl group is substituted with a cycloalkyl group, wherein the alkyl group and the cycloalkyl group have the meanings as described herein.

The term "cycloalkyloxy" refers to a cycloalkyl group, as defined herein, attached to an oxygen atom and by the oxygen atom to the rest of the molecule, wherein the cycloalkyl group has the meaning as defined herein .

The term "unsaturated" as used herein means that the group contains one or more degrees of unsaturation.

The term "heteroatom" refers to O, S, N, P, and Si, including N, S, and P in any oxidation state; in the form of primary, secondary, tertiary amines, and quaternary ammonium salts; or on a nitrogen atom in a heterocyclic ring. Hydrogen substituted form, for example, N (like N in 3,4-dihydro-2H-pyrrolidinyl), NH (like NH in pyrrolidinyl) or NR (like in N-substituted pyrrolidinyl) NR).

The terms "heterocyclyl" and "heterocycle" are used interchangeably herein, and both refer to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring containing 3 to 15 ring atoms, wherein a monocyclic, bicyclic or tricyclic ring The ring contains no aromatic rings and at least one ring atom is selected from nitrogen, sulfur and oxygen atoms. Unless otherwise specified, heterocyclyl can be carbon or nitrogen, and _-CH2- groups can be optionally replaced by -C(=O)-. Ring sulfur atoms can optionally be oxidized to S-oxides. The nitrogen atoms of the rings can be optionally oxidized to N-oxygen compounds. Examples of heterocyclyl groups include, but are not limited to, oxiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (eg 2-pyrrolidinyl), 2-pyrrole Linyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, 1,3-dioxocyclopentyl, Dithiocyclopentyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidine base, 4-piperidinyl), morpholinyl, thiomorpholinyl, (1-oxo)-thiomorpholinyl, (1,1-dioxo)-thiomorpholinyl, piperazine base, dioxanyl, dithianyl, thioxanyl, homopiperazinyl, homopiperidinyl, oxepanyl, thiepanyl, 2-oxa-5-aza Bicyclo[2.2.1]hept-5-yl, tetrahydropyridyl. Examples of heterocyclyl groups where the _-CH2- group is substituted with -C(=O)- include, but are not limited to, 2-oxopyrrolidinyl, oxo-1,3-thiazolidinyl, 2-piperidine Keto, 3,5-dioxopiperidinyl. Examples of oxidized sulfur atoms in a heterocyclyl group include, but are not limited to, sulfolanyl, 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 the heterocyclyl and alkyl groups have the meanings as described herein.

The term "heterocyclyloxy" includes an optionally substituted heterocyclyl group, as defined herein, attached to an oxygen atom and connected to the remainder of the molecule by the oxygen atom, wherein the heterocyclyl group has as defined herein said meaning.

The term "aryl" refers to monocyclic, bicyclic and tricyclic carbocyclic ring systems containing 6-14 ring atoms, or 6-12 ring atoms, or 6-10 ring atoms, wherein at least one ring system is aromatic A family of rings in which each ring system contains a ring of 3-7 atoms with one or more points of attachment to the rest of the molecule. The term "aryl" is used interchangeably with the term "aromatic ring". Examples of aryl groups may include phenyl, indenyl, naphthyl, and anthracenyl. The aryl group is optionally substituted with one or more substituents described herein.

The term "arylalkyl" or "aralkyl" means that an alkyl group is substituted with one or more aryl groups, wherein the alkyl and aryl groups have the meanings as described herein.

The term "aryloxy" or "aryloxy" includes an optionally substituted aryl group, as defined herein, attached to an oxygen atom and through the oxygen atom to the remainder of the molecule, wherein the aryl group has meaning as described in the present invention.

The term "heteroaryl" refers to monocyclic, bicyclic and tricyclic ring systems containing 5-12 ring atoms, or 5-10 ring atoms, or 5-6 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 5-7 atoms and has one or more points of attachment to the rest of the molecule. The term "heteroaryl" may be used interchangeably with the terms "heteroaromatic ring" or "heteroaromatic". 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 contain 1-9 carbon atoms and 1-4 heteroatoms selected from N, O, or S; in another embodiment, the ring atoms of the heteroaryl group contain 1-5 carbon atoms and 1-4 heteroatoms selected from N, O or S.

In yet another embodiment, heteroaryl represents a 5- or 6-membered heteroaryl group containing 1-4 N heteroatoms; in yet another embodiment, heteroaryl represents a group containing 1-3 N, O or a 5-membered heteroaryl of a heteroatom of S; in yet another embodiment, heteroaryl represents a 5-membered heteroaryl containing 1-3 heteroatoms selected from N or O; in yet another embodiment, Heteroaryl means 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 (such as 3-pyridazinyl), 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, tetrazolyl (such as 5-tetrazolyl), triazolyl (such as 2-triazolyl and 5-triazolyl), 2-thienyl, 3-thienyl, pyrazolyl, iso Thiazolyl, 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,3-triazolyl, 1,2, 3-thioadiazolyl, 1,3,4-thiodiazolyl, 1,2,5-thiodiazolyl, pyrazinyl, 1,3,5-triazinyl, pyrimidinone, Pyridonyl; also including, but in no way limited to, the following bicyclic rings: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (eg 2-indolyl), etc. Wait.

The term "heteroarylalkyl" means that an alkyl group is substituted with one or more heteroaryl groups, wherein the alkyl group and the heteroaryl group have the meanings as described herein.

The term "heteroaryloxy" or "heteroaryloxy" includes an optionally substituted heteroaryl group, as defined herein, attached to an oxygen atom and through the oxygen atom to the remainder of the molecule, wherein heteroaryl The radical group has the meaning as described in the present invention.

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 and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and ammonium cations of formula N ⁺ (R ¹⁹ R ²⁰ R ²¹ R ²² ), wherein R ¹⁹ , R ²⁰ , R ²¹ and R ²² are independently selected from hydrogen, C ₁ -C ₆ alkyl and C ₁ -C ₆ hydroxyalkyl. Salts of compounds of formula (I), formula (Ia), formula (Ib) or formula (Ic) can be prepared by using metal hydroxides (eg sodium hydroxide) or amines (eg ammonia, trimethylamine, diethanolamine) , 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine) for formula (I), formula (Ia), formula (Ib) or The compound represented by formula (Ic) is processed to prepare.

When the compounds of the present invention contain a base moiety, acceptable salts can be formed with organic and inorganic acids, such as acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid and similarly known Accepted acid.

DETAILED DESCRIPTION OF THE COMPOUNDS OF THE INVENTION

The purpose of the present invention is to provide a novel substituted benzoyl compound, herbicidal compositions and formulations containing the compound, and applications thereof.

In one aspect, the present invention provides a compound, which is a compound represented by formula (I) or a stereoisomer, tautomer, nitrogen oxide and salt of the compound represented by formula (I):

in:

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen, halogen, cyano, hydroxy, nitro, amino, carboxyl, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl , haloalkynyl, alkoxy, haloalkoxy, alkylthio, alkylamino, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkylalkyl, heterocyclylalkyl, aryl alkyl, heteroarylalkyl, cycloalkyloxy, heterocyclyloxy, aryloxy or heteroaryloxy;

Q is the following substructure formula:

wherein R ^a and R ^b are each independently hydrogen, alkyl or cycloalkyl;

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^b and ^Ra are each independently optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^c ;

Each R ^c is independently fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxyl, C _1-8 alkyl, haloC _1-8 alkyl, C _2-8 alkenyl, halo Substituted C _2-8 alkenyl, C _2-8 alkynyl, halogenated C _2-8 alkynyl, C _1-8 alkoxy, halogenated C _1-8 alkoxy, C _1-8 alkylamino, C _1-8 alkylthio, halogenated C _1-8 alkylamino, halogenated C _1-8 alkylthio, C _6-10 aryl, C _6-10 aryloxy, C _1-9 heteroaryl or C _1-9 Heteroaryloxy.

In some of these embodiments, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen, halogen, cyano, hydroxyl, nitro, amino, carboxyl, C _1-8 alkyl, C _{2- 8} alkenyl, C _2-8 alkynyl, halo C _1-8 alkyl, halo C _2-8 alkenyl, halo C _2-8 alkynyl, C _1-8 alkoxy, halo C _{1 -8} alkoxy, C _1-8 alkylthio, C _1-8 alkylamino, C _3-10 cycloalkyl, C _2-12 heterocyclyl, C _6-14 aryl, C _1-9 heteroaryl base, C _3-10 cycloalkyl C _1-8 alkyl, C _2-12 heterocyclyl C _1-8 alkyl, C _6-14 aryl C _1-8 alkyl, C _1-9 heteroaryl C _1-8 alkyl, C _3-10 cycloalkyloxy, C _2-12 heterocyclyloxy, C _6-14 aryloxy or C _1-9 heteroaryloxy;

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^c ;

wherein each R ^c has the meaning described in the present invention.

In other embodiments, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each independently hydrogen, halogen, cyano, hydroxy, nitro, amino, carboxyl, C _1-6 alkyl, C _{2- 6} alkenyl, C _2-6 alkynyl, halo C _1-6 alkyl, halo C _2-6 alkenyl, halo C _2-6 alkynyl, C _1-6 alkoxy, halo C _{1 -6} alkoxy, C _1-6 alkylthio, C _1-6 alkylamino, C _3-8 cycloalkyl, C _2-8 heterocyclyl, C _6-10 aryl, C _1-6 heteroaryl base, C _3-8 cycloalkyl C _1-6 alkyl, C _2-8 heterocyclyl C _1-6 alkyl, C _6-10 aryl C _1-6 alkyl, C _1-6 heteroaryl C _1-6 alkyl, C _3-8 cycloalkyloxy, C _2-8 heterocyclyloxy, C _6-10 aryloxy or C _1-6 heteroaryloxy;

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^c ;

wherein each R ^c has the meaning described in the present invention.

In other embodiments, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each independently hydrogen, halogen, cyano, hydroxyl, nitro, amino, carboxyl, C _1-4 alkyl, C _{2- 4} alkenyl, C _2-4 alkynyl, halo C _1-4 alkyl, halo C _2-4 alkenyl, halo C _2-4 alkynyl, C _1-4 alkoxy, halo C _{1 -4} alkoxy, C _1-4 alkylthio, C _1-4 alkylamino, C _3-6 cycloalkyl, C _2-6 heterocyclyl, C _6-10 aryl, C _1-5 heteroaryl base, C _3-6 cycloalkyl C _1-3 alkyl, C _2-6 heterocyclyl C _1-3 alkyl, C _6-10 aryl C _1-3 alkyl, C _1-5 heteroaryl C _1-3 alkyl, C _3-6 cycloalkyloxy, C _2-6 heterocyclyloxy, C _6-10 aryloxy or C _1-5 heteroaryloxy;

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^c ;

wherein each R ^c has the meaning described in the present invention.

In other embodiments, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each independently hydrogen, halogen, cyano, hydroxyl, nitro, amino, carboxyl, methyl, ethyl, n-propyl, isopropyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy or trifluoromethoxy.

In some of these embodiments, each R is independently fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, ^C _1-6 alkyl, haloC _1-6 alkyl, C _{2 -6} alkenyl, haloC _2-6 alkenyl, C _2-6 alkynyl, halo C _2-6 alkynyl, C _1-6 alkoxy, halo C _1-6 alkoxy, C _{1 -6} alkylamino, C _1-6 alkylthio, halogenated C _1-6 alkylamino, halogenated C _1-6 alkylthio, C _6-10 aryl, C _6-10 aryloxy, C _{1- 6heteroaryl} or _{C1-6heteroaryloxy} .

In other embodiments, each ^Rc is independently fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, _C1-4alkyl , _{haloC1-4alkyl} , _{C2 -4} alkenyl, halogenated C _2-4 alkenyl, C _2-4 alkynyl, halogenated C _2-4 alkynyl, C _1-4 alkoxy, halogenated C _1-4 alkoxy, C _{1 -4} alkylamino, C _1-4 alkylthio, halogenated C _1-4 alkylamino, halogenated C _1-4 alkylthio, C _6-10 aryl, C _6-10 aryloxy, C _{1- 6heteroaryl} or _{C1-6heteroaryloxy} .

In other embodiments, each R is independently ^fluoro , chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, methyl, ethyl, n-propyl, isopropyl, difluoromethyl , trifluoromethyl, methoxy or trifluoromethoxy.

In some of these embodiments, R ^a and R ^b are each independently hydrogen, C _1-8 alkyl, or C _3-12 cycloalkyl.

In other embodiments, R ^a and R ^b are each independently hydrogen, C _1-6 alkyl, or C _3-8 cycloalkyl.

In other embodiments, R ^a and R ^b are each independently hydrogen, C _1-4 alkyl, or C _3-6 cycloalkyl.

In other embodiments, R ^a and R ^b are each independently hydrogen, methyl, ethyl, or cyclopropyl.

In some of these embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound of formula (Ia):

wherein Q, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the meanings as described in the present invention.

In some of these embodiments, the present invention provides a compound that is a compound of formula (Ib) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound of formula (Ib):

wherein Q, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the meanings as described in the present invention.

In some of these embodiments, the present invention provides a compound that is a compound of formula (Ic) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound of formula (Ic):

wherein Q, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the meanings as described in the present invention.

In other embodiments, Q is the following substructural formula:

wherein R ^a and R ^b are each independently hydrogen, methyl, ethyl or cyclopropyl;

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen, halogen, cyano, hydroxyl, nitro, amino, carboxyl, methyl, ethyl, n-propyl, isopropyl, difluoro Methyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy or trifluoromethoxy.

The present invention is preferably the compound represented by the formula (Ia) or the stereoisomer, tautomer, nitrogen oxide or salt of the compound represented by the formula (Ia), for example, the dosage is 150g a.i./ha, such compounds The post-emergence control effect on purslane can reach 89-100%, and compared with other types of formula (Ib) or formula (Ic) of the present invention, it has more excellent control effect.

In some of these embodiments, the present invention provides a compound, which is a compound having one of the following structures or a stereoisomer, tautomer, nitrogen oxide or salt thereof of a compound having one of the following structures:

或者

or

In another aspect, the present invention provides a composition comprising the compound of the present invention.

In some of these embodiments, the compositions described herein optionally further comprise at least one additional component.

In other embodiments, the compositions of the present invention are herbicidal compositions.

In another aspect, the present invention provides the use of a compound of the present invention or a composition comprising the compound of the present invention in agriculture.

In another aspect, the present invention provides the use of a compound of the present invention or a composition comprising the compound of the present 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 the compound of the present invention as a pre-emergence 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 the application of the compound of the present invention or the composition comprising the compound of the present invention in the control of plant diseases.

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 controlling unwanted plants.

In another aspect, the present invention provides a method for controlling unwanted plants, characterized in that an effective amount of a compound according to the invention or a composition comprising a compound according to the invention is applied to plants, plant seeds, plants growing therein or thereon soil, or cultivation area.

In yet another aspect, the present invention provides a method of controlling the growth of weeds in useful plants, comprising applying an effective amount of a compound of the present invention or a composition comprising the compound of the present invention to a pre-emergence locus of the weed.

In some of these embodiments, the weeds include broadleaf weeds and grass weeds.

In other embodiments, the broadleaf weed is abalone, amaranth, purslane or snakehead.

In other embodiments, the grass weed is crabgrass, barnyardgrass, ryegrass, or foxtail.

In other embodiments, the useful plants include corn, rice, cotton, canola, soybean, or peanut.

The compound provided by the invention is a novel compound which is more effective to weeds, has lower cost, less toxicity and is safe to crops.

Compositions and Formulations of 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 and liquid diluents Agents, wetting agents, dispersing agents, emulsifiers, thickening agents, disintegrating agents, antifreeze agents, defoaming agents, preservatives, stabilizers, etc., the components that meet the requirements of pesticide use all belong to the scope of the present invention. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, the mode of application and environmental factors such as soil type, humidity and temperature.

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. The general types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions and suspoemulsions. The general types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.

The general types of solid compositions are powders, powders, granules, granules, pellets, lozenges, tablets, filled films (including seed coatings), etc., 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 can be (micro)encapsulated and further formed into a suspension or solid formulation; or the entire active ingredient formulation can be encapsulated (or "coated"). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granule formulations. High concentration compositions are mainly used as intermediates for other formulations.

Sprayable formulations are usually dispersed in a suitable medium before spraying. Such liquid and solid formulations are formulated for ease of dilution in a spray medium, usually water. Spray volumes can range from about one to several thousand liters per hectare, but are more typically in the range of about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by air or ground application, or applied to the growing medium of plants. Liquid and dry formulations can be dosed directly into drip irrigation systems or into furrows during planting.

The formulations will generally contain effective amounts of active ingredient, diluent and surfactant, which add up to 100% by weight.

Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (eg lactose, sucrose), silica, talc, mica, diatoms Soil, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Edition, Dorland Books, Caldwell, New Jersey.

Liquid diluents include, for example, water, N,N-dimethylalkaneamides (eg, N,N-dimethylformamide), limonene, dimethylsulfoxide, N-alkylpyrrolidones (eg, N-methylpyrrolidone) , ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (such as white mineral oil, n-paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, Glycerin, triacetin, sorbitol, aromatic hydrocarbons, dearomatized aliphatic compounds, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4 - methyl-2-pentanone), acetates (such as 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-butyrolactone), and may be linear, branched, saturated or unsaturated alcohols (such as methanol, ethanol, n-propanol, isopropyl alcohol) Propanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decyl alcohol, isodecyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oil alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzyl alcohol). Liquid diluents also include glycerides of saturated and unsaturated fatty acids (usually _C6 - _C22 ), such as oils of plant seeds and fruits (eg olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil , sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), fats of animal origin (such as tallow, lard, lard, cod liver oil, fish oil), and their mixture. Liquid diluents also include alkylated (eg, methylated, ethylated, butylated) fatty acids, which fatty acids can be obtained by hydrolysis of glycerides derived from plants and animals, and can be purified by distillation. Typical liquid diluents are described in Marsden's Solvents Guide, 2nd Edition, Interscience, New York, 1950.

The solid and liquid compositions of the present invention typically contain one or more surfactants. When added to a liquid, surfactants (also referred to as "surface-active agents") typically change, most typically lower the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, surfactants can be used as wetting agents, dispersing agents, emulsifiers or defoaming agents.

Surfactants can be classified as nonionic surfactants, anionic surfactants or cationic surfactants. Nonionic surfactants useful in the compositions of the present invention include, but are not limited to, alcohol alkoxylates, such as those based on natural alcohols and synthetic alcohols (which are branched or linear) and composed of alcohols and ethylene oxide, Alcohol alkoxylates prepared from propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate and ten Dialkylphenol ethoxylates (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); prepared from ethylene oxide or propylene oxide and reverse block polymers Block polymers wherein the end blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated triglycerides Styryl phenols (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 sorbitan fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan Alcohol esters; polymeric surfactants such as random copolymers, block copolymers, alkyd PEG (polyethylene glycol) resins, graft or cosmetic polymers and star polymers; polyethylene glycol (PEG); poly Glycol fatty acid esters; silicone-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglucosides, and alkyl polysaccharides.

Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenylsulfonate derivatives; lignin and lignin derivatives sulfonates, such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphates, such as phosphates of alcohol alkoxylates, phosphates of alkylphenol alkoxylates, and benzene Phosphate esters of vinylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol ether sulfates; sulfates and sulfonates of oils and fatty acids; ethoxylated alkylphenols Sulfates and sulfonates of alcohols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides, such as N,N-alkyl taurates; benzene, cumene, toluene , xylene and sulfonates of dodecylbenzene and tridecylbenzene; sulfonates of polycondensed naphthalenes; 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-alkylpropylenediamines, tripropylenetriamines, and dipropylenetetramines, and ethoxylated amines, Ethoxylated diamines and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetate and diamine salts; quaternary Ammonium salts, such as quaternary, ethoxylated, and diquaternary salts; and amine oxides, such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

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 suggested uses are disclosed in various published references, including McCutcheon's Emulsifiers and Detergents, North American and International Yearbook editions, published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co. ; Sisely and Wood, Encyclopedia of Surface ActiveAgents, Chemical Publ. Co., Inc., New York, 1964; and A.S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.

The compositions of the present invention may also contain formulation aids and additives known to those skilled in the art as adjuvants (some of which may also be considered to function as solid diluents, liquid diluents or surfactants). Such formulation aids and additives control: pH (buffers), foaming during processing (defoamers such as polyorganosiloxanes), settling of active ingredients (suspending agents), viscosity (thixotropic thickeners) ), microbial growth in containers (anti-microbial agents), product freezing (anti-freeze agents), color (dye/pigment dispersions), elution (film formers or binders), evaporation (anti-evaporation agents), and others Formulation properties. Film formers include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include those listed in McCutcheon's Volume 2: Functional Materials, North American and International Yearbook Editions, published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO03/024222.

The compounds of the present invention and any other active ingredients are generally 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 or 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 immiscible with water, an emulsifier is usually added to emulsify the solvent containing the active ingredient upon dilution with water. A media mill can be used to wet-mill active ingredient slurries having a particle size of up to 2,000 μm to obtain particles with an average diameter of less than 3 μm. Aqueous slurries can be prepared as finished suspension concentrates (see, eg, U.S. 3,060,084) or further processed by spray drying to form water-dispersible particles. Dry formulations typically require a dry milling step, which yields an average particle size in the range of 2 μm to 10 μm. Dusts and powders can be prepared by mixing, and usually by grinding (eg, with a hammer mill or fluid energy mill). Granules and pellets can be prepared by spraying the active material onto preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration" (Chemical Engineering, December 4, 1967, pp. 147-48; Perry's Chemical Engineer's Handbook, 4th edition, McGraw-Hill, New York, 1963, pp. 8-57 et seq. and WO91/13546. Granules can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as proposed in U.S. 4,144,050, U.S. 3,920,442 and DE.3,246,493. Tablets can be prepared as described in U.S. 5,180,587 , U.S. 5,232,701 and U.S. 5,208,030. Membranes can be prepared as proposed in GB 2,095,558 and U.S. 3,299,566.

For additional information related to the formulation field, see "The Formulator's Toolbox-Product Forms for Modern Agriculture" by T.S. Woods, Pesticide Chemistry and Bioscience, The Food-Environment Challenge, edited by T. Brooks and T.R. Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361 column 6, lines 16 to 7, line 19 and Examples 10-41; U.S. 3,309,192 column 5, lines 43 to 7, line 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; U.S. 2,891,855 col. 3, lines 66-5, col. 17 Rows and Examples 1-4; Klingman's Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp. 81-96; Hance et al., Weed Control Handbook, 8th Edition, Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

Use of the compounds of the present invention

The herbicides of the present invention can be used by spraying plants, applying to soil, to water surfaces. The amount of active ingredient is appropriately determined to suit the purpose of application. The content of the active ingredient is appropriately determined according to the purpose.

The amount of the compound of the present invention depends on the type of the compound used, the target weed, the tendency of weed emergence, the environmental conditions, the type of herbicide, and the like. When the herbicide of the present invention is used in its own form, eg, in the form of powder or granules, the amount thereof is appropriately selected to be 1 g to 50 kg, preferably 10 g to 10 kg per 1 hectare of active ingredient. When the herbicide of the present invention is used in a liquid form such as an emulsifiable concentrate, a wettable powder or a flowable formulation, the amount thereof is appropriately selected to be 0.1-50,000 ppm, preferably 10-10,000 ppm.

The present invention provides a method for controlling weeds in crops of useful plants, the method comprising directing the weeds or to the locus of the weeds or to the useful plants or to the locus of the useful plants A compound or composition of the present invention is administered.

The present invention also provides a method for selectively controlling grasses and/or weeds in crops of useful plants, the method comprising applying to the useful plants or their locus or to a cultivation area a herbicidally effective amount of a herbicide having formula (I), A compound represented by formula (Ia), formula (Ib) or formula (Ic).

The term "herbicide" means a compound that controls or alters the growth of plants. The term "herbicidally effective amount" means an amount of such a compound or a combination of such compounds capable of producing the effect of controlling or altering plant growth. Controlling or altering effects include all deviations from natural development, eg, killing, delaying, leaf burn, albinism, dwarfism, and the like. The term "plant" refers to all tangible parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stalks, leaves, and fruits. The term "locus" is intended to include soil, seeds and seedlings, as well as established vegetation and includes not only areas where weeds may have grown, but also areas where weeds have not yet emerged, and also includes information on crops of useful plants planting area. "Cultivated area" includes land on which crop plants have grown, as well as land intended to be used to grow such crop plants. The term "weed" as used herein means any unwanted plant, and thus includes not only important agronomic weeds as described below, but also volunteer crop plants.

Useful plant crops for which the compositions according to the present invention may be used include, but are not limited to, perennial crops such as citrus fruits, vines, nuts, oil palm, olives, pome fruits, stone fruits and rubber, and annual crops, For example cereals (eg barley and wheat), cotton, canola, corn, rice, soybeans, sugar beets, sugar cane, sunflowers, ornamentals, switchgrass, turf and vegetables, especially cereals, corn and soybeans.

The grasses and weeds to be controlled can be either monocotyledonous species, such as Prunus, Avena, Avena, Brachiaria, Brome, Tribulus, Cyperus, Crabata, Barnyardgrass, Mimia, Ryegrass, Plumbago, Milletium, Poa, Cylindrica, Cinnamon, Thorngrass, Setaria, Phyllostachys, and Sorghum, and may also be dicotyledonous Species such as Acanthus, Amaranth, Chenopodium, Chrysanthemum, Euphorbia, Lara, Ipomoea, Kochia, Nasturtium, Polygonum, Rhizoma, Mustard, Solanum Genus, chickweed, mother-in-law, violet and cocklebur.

The compounds of the present invention may show tolerance to important crops including, but not limited to, alfalfa, barley, cotton, wheat, canola, sugar beet, corn (maize), sorghum, soybean, rice, oat, peanut, Vegetables, tomatoes, potatoes, perennial crops including coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, bananas, plantains, pineapples, hops, tea and forests such as arbor and conifers (e.g. loblolly pine), and turf species (eg, bluegrass, St. Augustine grass, Kentucky oxhair, and bermudagrass).

If desired, the compounds of formula (I), formula (Ia), formula (Ib) or formula (Ic) according to the present invention may also be combined with other active ingredients such as other herbicides and/or insecticides and/or acaricides and/or nematicides and/or molluscicides and/or fungicides and/or plant growth regulators. These mixtures, and the use of these mixtures to control the growth of weeds and/or unwanted plants, form yet other aspects of the present invention. For the avoidance of doubt, mixtures of the present invention also include mixtures of two or more different compounds of formula (I), formula (Ia), formula (Ib) or formula (Ic). In particular, the present invention also relates to a composition of the present invention comprising, in addition to a compound represented by formula (I), formula (Ia), formula (Ib) or formula (Ic), at least one additional of herbicides.

General synthetic procedure

In this specification, if there is any difference between chemical name and chemical structure, the structure will prevail. In general, the compounds of the present invention can be prepared by the methods described herein unless otherwise indicated.

The test conditions of the hydrogen nuclear magnetic resonance spectrum of the present invention are: under room temperature conditions, Bruker (Bruker) 400MHz or 600MHz nuclear magnetic instrument, with CDC1 ₃ , d ⁶ -DMSO, CD ₃ OD or d ⁶ -acetone as solvent (reported in ppm as units), with TMS (0 ppm) or chloroform (7.26 ppm) as the reference standard. When multiplets are present, the following abbreviations are used: s (singlet, singlet), d (doublet, doublet), t (triplet, triplet), q (quartet, quartet), m (multiplet, multiplet), br (broadened, broad peak), dd (doublet of doublets, double doublet), dt (doublet of triplets, double triplet). Coupling constant, expressed in Hertz (Hz).

The mass spectrometry analysis method used in the present invention is: using Agilent 1260HPLC; Agilent 6120ESI.

Phase A: water (containing 0.1% formic acid); phase B: acetonitrile (containing 0.1% formic acid).

Gradient elution: 0-3 min, 5-100% B; 3-6 min, 100% B.

Flow rate: 0.6 mL/min.

Detection wavelength: 254nm.

MS parameters: ESI positive scan, collision induced ionization: 70V.

Dry nitrogen: 12 L/min, atomizing gas pressure: 40 psi, gas temperature: 350°C.

Take an appropriate amount of sample, dissolve it in 0.5 mL of methanol, inject the sample, and perform a first-level MS full scan in positive ESI mode to obtain the quasi-molecular ion peak [M+H] ⁺ reading.

The following abbreviations are defined throughout this invention:

DMF: N,N-Dimethylformamide, Dimethylformamide

MeOH: methanol

Et ₃ N: triethylamine

EtOAc: ethyl acetate

PE or Petroleum ether: Petroleum ether

TEA: Triethanolamine

The following synthetic schemes and examples serve to further illustrate the content of the present invention.

Synthetic scheme

Synthesis scheme one

Compound D can be prepared by Synthetic Scheme 1, wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the meanings as described in the present invention. Compound A undergoes halogenation reaction with acid chloride (such as oxalyl chloride) at 60°C-100°C to obtain compound B; compound B undergoes esterification reaction with 1,3-cyclohexanedione at 0°C-35°C to obtain compound C; Compound C and trimethylsilyl cyanide undergo Fries rearrangement reaction at 10°C-40°C to obtain target compound D.

Synthesis scheme two

Compound F can be prepared by synthetic scheme II, wherein R ^a , R ^b , R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the meanings as described in the present invention. Compound B undergoes esterification reaction with optionally substituted hydroxypyrazole at 0°C-35°C to obtain compound E; compound E undergoes Fries rearrangement reaction with trimethylsilyl cyanide at 10°C-40°C to obtain target compound F.

Example

Example 1 2-(5-(2-Chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoyl)-3-hydroxycyclohex-2-enone

Step 1: Synthesis of 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoyl chloride

Acifluorfen (600 mg, 1.66 mmol) was dissolved in ultra-dry dichloromethane (10 mL), cooled at -5 °C, after 10 min, oxalyl chloride (2.11 g, 16.59 mmol) was added to the reaction solution, and finally added 5 drops of N,N-dimethylformamide were reacted at room temperature for 3 hours, and then the solvent was distilled off under reduced pressure to obtain 600 mg of a light yellow viscous liquid with a yield of 95%.

Step 2: Synthesis of 3-oxocyclohex-1-en-1-yl 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate

Dissolve 1,3-cyclohexanedione (212mg, 1.89mmol) in ultra-dry dichloromethane (20mL), then add triethylamine (319mg, 3.16mmol) to the reaction solution, cool at -5°C, after 10min , a solution of 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoyl chloride (600 mg, 1.58 mmol) in dichloromethane (10 mL) was added to the reaction solution at room temperature. The reaction was completed for 4h, and the reaction of the raw materials was monitored by TLC. Saturated sodium bicarbonate solution (100 mL) was added to the reaction solution, extracted with dichloromethane (50 mL×3), the organic phases were combined, dried over anhydrous Na ₂ SO ₄ , filtered, washed with dichloromethane, and separated by column chromatography (eluting Agent: PE/EtOAc (v/v)=20/3) to obtain 560 mg of brown oily liquid, yield 78%.

MS-ESI: m/z 478.0[M+Na] ⁺ .

Step 3: Synthesis of 2-(5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoyl)-3-hydroxycyclohex-2-enone

3-Oxocyclohex-1-en-1-yl 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate (560 mg, 1.23 mmol) was dissolved In ultra-dry acetonitrile (20 mL), triethylamine (249 mg, 2.46 mmol) was added to the reaction solution, and trimethylsilyl cyanide (12 mg, 0.12 mmol) was finally added to the reaction solution, and the reaction was carried out at room temperature. After 6h, the reaction of the raw materials was monitored by TLC. The reaction was evaporated under reduced pressure to remove the solvent, extracted with dichloromethane (50 mL×3), washed with water (50 mL), combined the organic phases, dried over anhydrous Na ₂ SO ₄ , filtered, washed with dichloromethane (10 mL), and separated by column chromatography (eluent: DCM/MeOH (v/v)=100/1) to obtain 248 mg of a yellow solid, yield 44%.

MS-ESI: m/z 456.0[M+H] ⁺ ;

¹ H NMR (400 MHz, CDCl ₃ ) δ 16.33 (s, 1H), 8.22 (d, J=9.1 Hz, 1H), 7.79 (s, 1H), 7.58 (d, J=8.2 Hz, 1H), 7.23 (d, J=8.5Hz, 1H), 7.01 (dd, J=9.0, 2.3Hz, 1H), 6.74 (d, J=2.3Hz, 1H), 2.78 (t, J=6.2Hz, 2H), 2.38 (t, J=6.4Hz, 2H), 2.09–1.98 (m, 2H).

Example 2 (5-(2-Chloro-4-(trifluoromethyl)phenoxy)-2-nitrophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazole-4 -yl) ketone

Step 1: Synthesis of 1,3-Dimethyl-1H-pyrazol-5-yl 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate

Dissolve 1,3-dimethyl-5-hydroxypyrazole (425 mg, 3.78 mmol) in ultra-dry dichloromethane (20 mL), then add triethylamine (639 mg, 6.31 mmol) to the reaction solution, at -5°C After 10 min, 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoyl chloride (1200 mg, 3.16 mmol) in dichloromethane ( 20mL) solution, reacted at room temperature for 4h, and TLC monitored the reaction of the raw materials. Saturated sodium bicarbonate solution (100 mL) was added to the reaction solution, extracted with dichloromethane (50 mL×3), the organic phases were combined, dried over anhydrous Na ₂ SO ₄ , filtered, the filter cake was washed with dichloromethane (20 mL), and the column layer was Separation (eluent: PE/EtOAc (v/v)=20/4) gave 1.19 g of a yellow oily liquid with a yield of 83%.

MS-ESI: m/z 456.0[M+H] ⁺ .

Step 2: (5-(2-Chloro-4-(trifluoromethyl)phenoxy)-2-nitrophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazole-4 Synthesis of -yl)methanone

1,3-Dimethyl-1H-pyrazol-5-yl 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate (1190 mg, 2.61 mmol) ) was dissolved in ultra-dry acetonitrile (30 mL), then triethylamine (528 mg, 5.22 mmol) was added to the reaction solution, and finally trimethylsilyl cyanide (24 mg, 0.24 mmol) was added to the reaction solution, and the reaction was carried out at room temperature. After 12h, the reaction of the starting materials was monitored by TLC. The reaction was evaporated under reduced pressure to remove the solvent, extracted with dichloromethane (50 mL×3), washed with water (50 mL), combined the organic phases, dried over anhydrous Na ₂ SO ₄ , filtered, washed with dichloromethane (10 mL), and separated by column chromatography (eluent: DCM/MeOH (v/v)=100/1) to obtain 180 mg of a pink solid in a yield of 15%.

MS-ESI: m/z 456.0[M+H] ⁺ ;

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.28 (d, J=9.1 Hz, 1H), 7.81 (s, 1H), 7.63 (d, J=8.4 Hz, 1H), 7.29 (d, J=8.5 Hz ,1H),7.13(dd,J=9.1,2.6Hz,1H),6.81(d,J=2.6Hz,1H),3.63(s,3H),1.71(s,3H).

Referring to the similar preparation method of Example 2, the compounds of the following examples can be obtained.

Example 3 (5-(2-Chloro-4-(trifluoromethyl)phenoxy)-2-nitrophenyl)(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyridine oxazol-4-yl)methanone

MS-ESI: m/z 482.1[M+H] ⁺ .

¹ H NMR (400MHz, CDCl ₃ ) δ 8.26(s, 1H), 7.80(s, 1H), 7.62(d, J=7.6Hz, 1H), 7.27(s, 1H), 7.14-7.02(m, 1H), 6.91(s, 1H), 3.57(s, 3H), 0.88(s, 1H), 0.71(s, 2H), 0.45(s, 2H).

Example 4 (5-(2-Chloro-4-(trifluoromethyl)phenoxy)-2-nitrophenyl)(5-hydroxy-1-methyl-1H-pyrazol-4-yl) ketone

MS-ESI: m/z 442.0 [M+H] ⁺ ;

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.19 (d, J=9.1 Hz, 1H), 7.81 (s, 1H), 7.62 (d, J=8.5 Hz, 1H), 7.29 (d, J=8.5 Hz ,1H),7.24(s,1H),7.11(dd,J=9.1,2.7Hz,1H),6.96(d,J=2.7Hz,1H),3.70(s,3H).

Example 5 (5-(2-Chloro-4-(trifluoromethyl)phenoxy)-2-nitrophenyl)(5-hydroxy-1-ethyl-1H-pyrazol-4-yl) ketone

MS-ESI: m/z 456.0[M+H] ⁺ ;

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.19 (d, J=9.0 Hz, 1H), 7.81 (s, 1H), 7.62 (d, J=8.5 Hz, 1H), 7.28 (d, J=8.6 Hz) ,1H),7.25(s,1H),7.11(dd,J=9.0,2.7Hz,1H),6.97(d,J=2.7Hz,1H),4.06(q,J=7.3Hz,2H),1.45 (t,J=7.3Hz,3H).

Example 6 (3-(2,6-Dimethylphenoxy)-2-nitrophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone

MS-ESI: m/z 382.1 [M+H] ⁺ ;

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.39 (t, J=8.0 Hz, 1H), 7.13 (s, 3H), 7.05 (d, J=7.6 Hz, 1H), 6.66 (d, J=8.4 Hz) ,1H),3.64(s,3H),2.16(s,6H),1.92(s,3H).

Example 7 (3-(2-Chloro-4-(trifluoromethyl)phenoxy)-2-nitrophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazole-4 -yl) ketone

MS-ESI: m/z 456.1[M+H] ⁺ ;

¹ H NMR (400MHz, CDCl ₃ ) δ 7.78(s, 1H), 7.58(t, J=7.9Hz, 2H), 7.28(s, 1H), 7.20(d, J=8.5Hz, 1H), 7.04 (d, J=8.3Hz, 1H), 3.65(s, 3H), 1.94(s, 3H).

Example 8 (3-(2-Chloro-4-(trifluoromethyl)phenoxy)-2-nitrophenyl)(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyridine oxazol-4-yl)methanone

MS-ESI: m/z 482.1[M+H] ⁺ ;

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.80 (s, 1H), 7.58 (t, J=7.9 Hz, 2H), 7.47 (d, J=7.6 Hz, 1H), 7.21 (d, J=8.5 Hz ,1H),7.05(d,J=8.3Hz,1H),3.64(s,3H),1.32(dd,J=9.2,4.1Hz,1H),0.94–0.88(m,2H),0.67–0.60( m, 2H).

Example 9 (5-(2,4-Dichlorophenoxy)-2-nitrophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone

MS-ESI: m/z 422.0[M+H] ⁺ ;

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.27 (d, J=9.1 Hz, 1H), 7.55 (d, J=2.3 Hz, 1H), 7.36 (dd, J=8.6, 2.3 Hz, 1H), 7.21 –7.07(m, 2H), 6.76(d, J=2.6Hz, 1H), 3.64(s, 3H), 1.71(s, 3H).

Example 10 (5-(2,4-Dichlorophenoxy)-2-nitrophenyl)(5-hydroxy-1-methyl-1H-pyrazol-4-yl)methanone

MS-ESI: m/z 409.9 [M+H] ⁺ ;

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.18 (d, J=9.1 Hz, 1H), 7.55 (d, J=2.4 Hz, 1H), 7.36 (dd, J=8.6, 2.4 Hz, 1H), 7.28 (s, 1H), 7.16 (d, J=8.7Hz, 1H), 7.09 (dd, J=9.1, 2.7Hz, 1H), 6.91 (d, J=2.7Hz, 1H), 3.72 (s, 3H) .

Example 11 (3-(4-Chlorophenoxy)-2-nitrophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone

MS-ESI: m/z 388.0[M+H] ⁺ .

Example 12 (3-(4-Chlorophenoxy)-2-nitrophenyl)(1-ethyl-5-hydroxy-1H-pyrazol-4-yl)methanone

MS-ESI: m/z 388.0[M+H] ⁺ .

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.63-7.44 (m, 3H), 7.36 (d, J=7.2 Hz, 2H), 7.19-6.96 (m, 3H), 4.08 (d, J=7.2 Hz, 2H),1.46(t,J=6.6Hz,3H).

Example 13 (3-(2,4-Dichlorophenoxy)-2-nitrophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone

MS-ESI: m/z 422.1[M+H] ⁺ .

Example 14 (3-(2-Chloro-4-(trifluoromethyl)phenoxy)-4-nitrophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazole-4 -yl) ketone

MS-ESI: m/z 456.0[M+H] ⁺ .

Referring to the similar preparation method of Example 1, the compounds of the following examples can be obtained.

Example 15 2-(3-(2,6-dimethylphenoxy)-2-nitrobenzoyl)-3-hydroxycyclohex-2-enone

MS-ESI: m/z 382.1 [M+H] ⁺ ;

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.33 (t, J=8.0 Hz, 1H), 7.11 (s, 3H), 6.85 (d, J=7.6 Hz, 1H), 6.60 (d, J=8.4 Hz , 1H), 2.78(s, 2H), 2.45(s, 2H), 2.18(s, 6H), 2.10–2.01(m, 2H).

Example 16 3-Hydroxy-2-(3-(4-methoxyphenoxy)-2-nitrobenzoyl)cyclohex-2-enone

MS-ESI: m/z 384.1 [M+H] ⁺ ;

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.41 (t, J=8.0 Hz, 1H), 7.06 (d, J=9.2 Hz, 2H), 6.95 (d, J=8.8 Hz, 1H), 6.92 (d , J＝8.8Hz, 3H), 3.81(s, 3H), 2.78(t, J＝6.4Hz, 2H), 2.44(t, J＝6.4Hz, 2H), 2.09–2.00(m, 2H).

Example 17 2-(3-(2,4-Dichlorophenoxy)-4-nitrobenzoyl)-3-hydroxycyclohex-2-enone

MS-ESI: m/z 422.0[M+H] ⁺ ;

¹ H NMR (400 MHz, CDCl ₃ ) δ 16.49 (s, 1H), 8.00 (d, J=8.4 Hz, 1H), 7.51 (d, J=2.4 Hz, 1H), 7.28 (td, J=8.4, 2.0Hz, 2H), 7.06(d, J=8.7Hz, 1H), 6.96(d, J=1.4Hz, 1H), 2.78(s, 2H), 2.46(s, 2H), 2.24–1.98(m, 2H).

Example 18 2-(5-(2,4-Dichlorophenoxy)-2-nitrobenzoyl)3-hydroxycyclohex-2-enone

MS-ESI: m/z 422.0[M+H] ⁺ ;

¹ H NMR (400 MHz, CDCl ₃ ) δ 16.37 (s, 1H), 8.21 (d, J=9.1 Hz, 1H), 7.54 (d, J=2.4 Hz, 1H), 7.45-7.29 (m, 1H) ,7.08(t,J＝28.2Hz,1H),6.95(dt,J＝21.5,10.7Hz,1H),6.69(d,J＝2.7Hz,1H),2.80(t,J＝6.2Hz,2H) ,2.39(t,J=6.5Hz,2H),2.14–1.98(m,2H).

Example 19 2-(3-(4-Chlorophenoxy)-2-nitrobenzoyl)-3-hydroxycyclohex-2-enone

MS-ESI: m/z 388.0[M+H] ⁺ .

Example 20 2-(3-(2,4-Dichlorophenoxy)-2-nitrobenzoyl)-3-hydroxycyclohex-2-enone

MS-ESI: m/z 422.1[M+H] ⁺ .

Example 21 3-(5-(2-Chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoyl)-4-hydroxybicyclo[3.2.1]oct-3-ene- 2-keto

MS-ESI: m/z 482.1[M+H] ⁺ .

¹ H NMR (400MHz, CDCl ₃ ) δ 8.22 (d, J=9.2Hz, 1H), 7.81 (d, J=2.0Hz, 1H), 7.60 (dd, J=8.4, 2.0Hz, 1H), 7.26 (d, J=8.8Hz, 1H), 7.03 (dd, J=9.2, 2.8Hz, 1H), 6.80 (d, J=2.8Hz, 1H), 2.20 (d, J=12.0Hz, 2H), 2.10 (d, J=37.6Hz, 2H), 1.77–1.66 (m, 2H), 1.67–1.57 (m, 2H).

Example 22 2-(3-(2-Chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoyl)-3-hydroxycyclohex-2-enone

MS-ESI: m/z 456.0[M+H] ⁺ .

¹ H NMR (400 MHz, CDCl ₃ ) δ 16.43 (s, 1H), 7.78 (s, 1H), 7.60 (d, J=8.0 Hz, 1H), 7.58–7.49 (m, 1H), 7.19–7.12 ( m, 2H), 7.09(d, J=8.4Hz, 1H), 2.81(s, 2H), 2.45(s, 2H), 2.07(p, J=6.4Hz, 2H).

Example 23 2-(3-(2-Chloro-4-(trifluoromethyl)phenoxy)-4-nitrobenzoyl)-3-hydroxycyclohex-2-enone

MS-ESI: m/z 456.0[M+H] ⁺ .

Referring to the similar preparation methods of Examples 1 and 2, respectively, the compounds of the following comparative examples can be obtained.

Comparative Example 1 3-Hydroxy-2-(3-phenoxybenzoyl)cyclohex-2-enone

MS-ESI: m/z 309.1[M+H] ⁺ .

Comparative example 2(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)(3-phenoxyphenyl)methanone

MS-ESI: m/z 309.1[M+H] ⁺ .

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.41 (t, J=7.6 Hz, 1H), 7.34 (t, J=7.6 Hz, 2H), 7.27 (d, J=4.8 Hz, 1H), 7.20-7.08 (m, 3H), 7.02(d, J=7.8Hz, 2H), 3.58(s, 3H), 1.96(s, 3H).

biological example

Compound preparation: Weigh a certain quality of the original drug with an analytical balance (0.0001g), dissolve it with an appropriate amount of DMF, and then dilute it with a certain volume of distilled water containing 1‰ Tween-80 emulsifier for use.

Test method: The test targets were Abalone, purslane, barnyardgrass and zinnia.

Stem and leaf spray method: Take a flowerpot with a length and width of 7.0cm, fill it with soil to 3/4, directly sow the pretreated weed target seeds, cover the soil with about 1.0cm, and spray the seedlings when they grow to the appropriate age. After each compound was applied at the set dose, it was transferred to the outside for cultivation, and the activity (%) against weeds was investigated after 21 days.

The test results are shown in Tables A to D.

Table A The dose is 300g a.i./ha, the control effect of the compound of the present invention on purslane

The results in Table A show that the compound of the present invention has an excellent control effect on purslane at 300 g a.i./ha. In addition, at 300 g a.i./ha, the compound of the present invention also has a good control effect on abalone, barnyardgrass and zinnia, for example, the control effect of Example 1 on abalone is 98%; The control effect is 85%; the control effect of Example 22 on barnyardgrass is 80%.

Table B The dose is 150 g a.i./ha, the control effect of the compound of the present invention on purslane

Table C The dose is 150 g a.i./ha, the control effect of the compound of the present invention on zinnia

The results in Tables B and C show that the compounds of the present invention have excellent control effects on purslane and zinnia at 150 g a.i./ha. In addition, the compound of the present invention also has a good control effect on abalone and barnyard grass at 150 g a.i./ha. For example, the control effect of Example 1 on abalone is 98%; the control effect of Example 21 on barnyard grass is 82%. ; The control effect of Example 22 on barnyardgrass is 85%.

Table D Control efficacy of compounds of the present invention against purslane at doses of 75, 37.5 or 18.75 g a.i./ha

The results in Table D show that the compounds of the present invention still have excellent control effects on purslane at low doses.

The compound of the present invention has good control effect on broad-leaved weeds (such as amaranth, amaranth, snakehead and purslane) and grass weeds (such as crabgrass, barnyardgrass, ryegrass and foxtail) . It is safe to crops, has fast drug effect, and has better control effect on weeds than commercial herbicides and benzoyl compounds with similar structures, and has a good application prospect.

Claims (10)

1. A compound which is a compound of formula (I) or a stereoisomer, tautomer, nitroxide or salt of a compound of formula (I):

wherein:

R¹、R²、R³、R⁴and R⁵Each independently is hydrogen, halogen, cyano, hydroxy, nitro, amino, carboxyl, C_1-8Alkyl radical, C_2-8Alkenyl radical, C_2-8Alkynyl, halo C_1-8Alkyl, halo C_2-8Alkenyl, halo C_2-8Alkynyl, C_1-8Alkoxy, halo C_1-8Alkoxy radical, C_1-8Alkylthio radical, C_1-8Alkylamino radical, C_3-10Cycloalkyl radical, C_2-12Heterocyclic group, C_6-14Aryl radical, C_1-9Heteroaryl group, C_3-10Cycloalkyl radical C_1-8Alkyl radical, C_2-12Heterocyclyl radical C_1-8Alkyl radical, C_6-14Aryl radical C_1-8Alkyl radical, C_1-9Heteroaryl C_1-8Alkyl radical, C_3-10Cycloalkyl oxy, C_2-12Heterocyclyloxy, C_6-14Aryloxy radical or C_1-9A heteroaryloxy group;

q is the following subformula:

R^aand R^bEach independently is hydrogen, C_1-8Alkyl or C_3-8A cycloalkyl group;

R¹、R²、R³、R⁴、R⁵、R^aand R^bEach independently is optionally selected from R by 1,2,3, 4, 5 or 6^cSubstituted with the substituent(s);

each R^cIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C_1-6Alkyl, halo C_1-6Alkyl radical, C_2-6Alkenyl, halo C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_2-6Alkynyl, C_1-6Alkoxy, halo C_1-6Alkoxy radical, C_1-6Alkylamino radical, C_1-6Alkylthio, halo C_1-6Alkylamino, halogeno C_1-6Alkylthio radical, C_6-10Aryl radical, C_6-10Aryloxy radical, C_1-6Heteroaryl or C_1-6A heteroaryloxy group.

2. The compound of claim 1, wherein

R¹、R²、R³、R⁴And R⁵Each independently is hydrogen, halogen, cyano, hydroxy, nitro, amino, carboxyl, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, C_1-6Alkoxy, halo C_1-6Alkoxy radical, C_1-6Alkylthio radical, C_1-6Alkylamino radical, C_3-8Cycloalkyl radical, C_2-8Heterocyclic group, C_6-10Aryl radical, C_1-6Heteroaryl group, C_3-8Cycloalkyl radical C_1-6Alkyl radical, C_2-8Heterocyclyl radical C_1-6Alkyl radical, C_6-10Aryl radical C_1-6Alkyl radical, C_1-6Heteroaryl C_1-6Alkyl radical, C_3-8Cycloalkyl oxy, C_2-8Heterocyclyloxy, C_6-10Aryloxy radical or C_1-6A heteroaryloxy group;

R¹、R²、R³、R⁴and R⁵Each independently is optionally selected from R by 1,2,3, 4, 5 or 6^cSubstituted with the substituent(s);

each R^cIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C_1-4Alkyl, halo C_1-4Alkyl radical, C_2-4Alkenyl, halo C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_2-4Alkynyl, C_1-4Alkoxy, halo C_1-4Alkoxy radical, C_1-4Alkylamino radical, C_1-4Alkylthio, halo C_1-4Alkylamino, halogeno C_1-4Alkylthio radical, C_6-10Aryl radical, C_6-10Aryloxy radical, C_1-6Heteroaryl or C_1-6A heteroaryloxy group.

3. The compound of claim 2, wherein

R¹、R²、R³、R⁴And R⁵Each independently is hydrogen, halogen, cyano, hydroxy, nitro, amino, carboxyl, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, C_1-4Alkoxy, halo C_1-4Alkoxy radical, C_1-4Alkylthio radical, C_1-4Alkylamino radical, C_3-6Cycloalkyl radical, C_2-6Heterocyclic group, C_6-10Aryl radical, C_1-5Heteroaryl group, C_3-6Cycloalkyl radical C_1-3Alkyl radical, C_2-6Heterocyclyl radical C_1-3Alkyl radical, C_6-10Aryl radical C_1-3Alkyl radical, C_1-5Heteroaryl C_1-3Alkyl radical, C_3-6Cycloalkyl oxy, C_2-6Heterocyclyloxy, C_6-10Aryloxy radical or C_1-5A heteroaryloxy group;

R¹、R²、R³、R⁴and R⁵Each independently is optionally selected from R by 1,2,3, 4, 5 or 6^cSubstituted with the substituent(s);

each R^cIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyCarboxy, methyl, ethyl, n-propyl, isopropyl, difluoromethyl, trifluoromethyl, methoxy or trifluoromethoxy.

4. The compound of claim 1, wherein

R^aAnd R^bEach independently is hydrogen, C_1-6Alkyl or C_3-8A cycloalkyl group.

5. The compound of claim 4, wherein

R^aAnd R^bEach independently is hydrogen, C_1-4Alkyl or C_3-6A cycloalkyl group.

6. The compound according to any one of claims 1 to 5, which is a compound of formula (Ia) or a stereoisomer, tautomer, nitroxide or salt of a compound of formula (Ia):

or, it is a compound of formula (Ib) or a stereoisomer, tautomer, nitroxide or salt of a compound of formula (Ib):

or, it is a compound of formula (Ic) or a stereoisomer, tautomer, nitroxide or salt of a compound of formula (Ic):

7. the compound of claim 6, wherein

Q is the following subformula:

wherein R is^aAnd R^bEach independently hydrogen, methyl, ethyl or cyclopropyl;

R¹、R²、R³、R⁴and R⁵Each independently hydrogen, halogen, cyano, hydroxy, nitro, amino, carboxy, methyl, ethyl, n-propyl, isopropyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy or trifluoromethoxy.

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:

9. a composition comprising a compound of any one of claims 1-8.

10. Use of a compound according to any one of claims 1 to 8 or a composition according to claim 9 in agriculture.