Cyclohexanedione-benzothiadiazine compounds and their applications

Abstract

The present invention provides a cyclohexanedione-benzothiadiazine compound and its application; specifically, the present invention provides a compound represented by formula (I) or a stereoisomer, a tautomer, a nitrogen oxide or a salt thereof of the compound represented by formula (I), a preparation method, and a composition containing these compounds and its application in agriculture, especially as an active ingredient of a herbicide for preventing and controlling unwanted plants; wherein A, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and Q have the meanings as defined in the present invention.

Description

Technical Field

[0001] The invention provides a novel cyclohexanedione-benzothiadiazine compound and a preparation method thereof; a composition containing the compound and application thereof in agriculture. Background Art

[0002] Cyclohexanedione compounds are a class of compounds with excellent biological activity, and their herbicidal activity is reported in, for example, WO2015058519, etc. However, the compounds of the present invention described in detail below are not described in these documents.

[0003] The active ingredients known from the documents cited above have disadvantages in use, for example, in that (a) no or only an insufficient herbicidal action is achieved against weed plants, (b) the spectrum of weed plants to be controlled is too narrow or (c) the selectivity in crops of useful plants is too low.

[0004] Therefore, there is a continuing need to provide active chemical ingredients that can be used advantageously as herbicides. Summary of the invention

[0005] The invention provides a novel cyclohexanedione-benzothiadiazine compound, which has excellent herbicidal effect, a wide weed control spectrum and excellent selectivity between crops and weeds.

[0006] In one aspect, the present invention provides a compound represented by formula (I) or a stereoisomer, a tautomer, a nitrogen oxide or a salt thereof of the compound represented by formula (I):

[0007]

[0008] in:

[0009] A is a hydroxyl group;

[0010] R 1 H, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl or halogenated C 1-6 Alkoxy;

[0011] R 2 H, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, -C(=O)NH-C 1-6 Alkyl, -S(=O)2NH-C 1-6 Alkyl, -C(=O)OC 1-6 Alkyl or -S(=O)2O-C1-6 alkyl;

[0012] R 3 , R 4 , R 5 , R 6 , R 7 or R 8 are each independently H, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C 1-6 Alkyl, halogenated C 1-6 Alkyl, C 1-6 Alkoxy or halogenated C 1-6 Alkoxy;

[0013] Or, R 3 , R 4 Together with the carbon atoms to which they are attached, they form a ring of 3-8 atoms; or, R 5 , R 6 Together with the carbon atoms to which they are attached, they form a ring of 3-8 atoms; or, R 7 , R 8 Together with the carbon atoms to which they are attached, they form rings consisting of 3-8 atoms;

[0014] Or, R 4 , R 5 Together with the carbon atoms to which they are attached, they form a ring of 3-8 atoms; or, R 6 , R 7 Together with the carbon atoms to which they are attached, they form rings consisting of 3-8 atoms;

[0015] Or, R 4 , R 7 Together with the carbon atoms to which they are attached, they form rings consisting of 3-8 atoms;

[0016] Q is C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 2-6 Alkenyl, halogenated C 2-6 Alkenyl, C 2-6 Alkynyl, halo C 2-6 Alkynyl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylthio C 1-6 Alkyl, -C(=O)NH-C 1-6 Alkyl, -S(=O)2NH-C 1-6 Alkyl, -C(=O)OC 1-6 Alkyl, -S(=O)2O-C 1-6Alkyl, C 3-8 Cycloalkyl, C 6-10 Aryl, C 1-9 Heteroaryl, C 2-10 Heterocyclic group, C 3-8 Cycloalkyl C 1-6 Alkyl, C 6-10 Aryl C 1-6 Alkyl, C 1-9 Heteroaryl C 1-6 Alkyl or C 2-10 Heterocyclyl C 1-6 alkyl;

[0017] wherein Q is optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C 1-6 Alkyl, halogenated C 1-6 Alkyl, C 1-6 Alkoxy or halogenated C 1-6 The substituents of the alkoxy group are substituted.

[0018] In some embodiments, R 1 H, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C 1-4 Alkoxy;

[0019] R 2 H, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl, halogenated C 1-4 Alkoxy, -C(=O)NH-C 1-4 Alkyl, -S(=O)2NH-C 1-4 Alkyl, -C(=O)OC 1-4 Alkyl or -S(=O)2O-C 1-4 alkyl;

[0020] R 3 , R 4 , R 5 , R 6 , R 7 or R 8 are each independently H, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C 1-4 Alkyl, halogenated C 1-4 Alkyl, C 1-4 Alkoxy or halogenated C 1-4 Alkoxy;

[0021] Or, R 3 , R4 Together with the carbon atoms to which they are attached, they form a ring of 3-6 atoms; or, R 5 , R 6 Together with the carbon atoms to which they are attached, they form a ring of 3-6 atoms; or, R 7 , R 8 Together with the carbon atoms to which they are attached, they form rings consisting of 3-6 atoms;

[0022] Or, R 4 , R 5 Together with the carbon atoms to which they are attached, they form a ring of 3-6 atoms; or, R 6 , R 7 Together with the carbon atoms to which they are attached, they form rings consisting of 3-6 atoms;

[0023] Or, R 4 , R 7 Together with the carbon atoms to which they are attached, they form a ring consisting of 3-6 atoms.

[0024] In some embodiments, Q is C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl, halogenated C 1-4 Alkoxy, C 2-4 Alkenyl, halogenated C 2-4 Alkenyl, C 2-4 Alkynyl, halo C 2-4 Alkynyl, C 1-4 Alkoxy C 1-4 Alkyl, C 1-4 Alkylthio C 1-4 Alkyl, -C(=O)NH-C 1-4 Alkyl, -S(=O)2NH-C 1-4 Alkyl, -C(=O)OC 1-4 Alkyl, -S(=O)2O-C 1-4 Alkyl, C 3-8 Cycloalkyl, C 6-10 Aryl, C 1-5 Heteroaryl, C 2-8 Heterocyclic group, C 3-8 Cycloalkyl C 1-4 Alkyl, C 6-10 Aryl C 1-4 Alkyl, C 1-5 Heteroaryl C 1-4 Alkyl or C 2-8 Heterocyclyl C 1-4 alkyl;

[0025] wherein Q is optionally replaced by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C 1-4 Alkyl, halogenated C 1-4 Alkyl, C 1-4 Alkoxy or halogenated C 1-4 The substituents of the alkoxy group are substituted.

[0026] In some embodiments, R 2 is H, -CH3, -CH2CH3, -CH(CH3)2, -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH(CH3)2, -CHF2, -CF3, -CH2CHF2, -OCHF2, -OCF3 or -OCH2CHF2.

[0027] Preferably, R 2 It is -CH3.

[0028] In some embodiments, R 3 , R 4 , R 5 , R 6 , R 7 or R 8 Each is independently H, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, -CH3, -CH2CH3, -CH(CH3)2, -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH(CH3)2, -CHF2, -CF3, -CH2CHF2, -OCHF2, -OCF3 or -OCH2CHF2.

[0029] Preferably, R 3 , R 4 , R 5 , R 6 , R 7 or R 8 Each is independently H.

[0030] In some embodiments, the present invention provides a compound, which is a compound represented by formula (Ia) or a stereoisomer, tautomer, nitrogen oxide or salt thereof of the compound represented by formula (Ia):

[0031]

[0032] Among them, R 1 and Q have the meanings as defined in the present invention.

[0033] In some embodiments, R 1It is H, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -CHF2, -CF3, -CH2CHF2, -CH2CF3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH(CH3)2, -OC(CH3)3, -OCHF2, -OCF3, -OCH2CHF2 or -OCH2CF3.

[0034] Preferably, R 1 It is H or -CH3.

[0035] In other embodiments, Q is -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -OCH(CH3)2, -OCH2CH2CH2CH3, -OCH2CH(CH3)2, -OC(CH3)3, -CHF2, -CF3, -CH2CHF2, -CH2CF3, -OCHF2, -OCF3, -OCH2CHF2, -OCH2CF3, -CH2CH=CH2, -CH2CH2CH=CH2, -CH2CH=CHCH3, -CH2-C≡C H, -CH2-C≡CCH3, -CH2CH2-C≡CH, -CH2OCH3, -CH2CH2OCH3, -CH2OCH2CH3, -CH2CH2OCH2CH3, -CH2SCH3, -CH2CH2SCH3, -CH2CH2SCH2CH3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, phenyl, 3-methylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, benzyl, 4-fluorophenethyl, 2-chlorophenethyl or 2-thienylethyl.

[0036] In some embodiments, Q is the following sub-structure:

[0037]

[0038] In some embodiments, the present invention provides 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:

[0039]

[0040] In another aspect, the present invention provides a composition comprising the compound of the present invention.

[0041] In some embodiments, the composition of the present invention further comprises at least one pesticidally acceptable adjuvant.

[0042] In another aspect, the present invention provides use of the compound of the present invention or a composition comprising the compound of the present invention in agriculture.

[0043] Furthermore, the present invention provides use of the compound of the present invention or a composition comprising the compound of the present invention as a herbicide in agriculture.

[0044] In another aspect, the present invention provides use of the compound of the present invention or a composition comprising the compound of the present invention in controlling grass weeds.

[0045] In another aspect, the present invention provides use of the compound of the present invention or a composition comprising the compound of the present invention in controlling broadleaf weeds.

[0046] In another aspect, the present invention provides use of the compound of the present invention or a composition comprising the compound of the present invention in controlling velvetleaf, purslane or barnyard grass.

[0047] In some embodiments, the present invention provides use of the compounds of the present invention or compositions comprising the compounds of the present invention for controlling unwanted vegetation.

[0048] In another aspect, the present invention provides use of the compound of the present invention or a composition comprising the compound of the present invention as a herbicide.

[0049] In another aspect, the present invention provides use of the compound of the present invention or a composition comprising the compound of the present invention as a post-emergence herbicide.

[0050] 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, plant seeds, the soil in or on which the plants grow, or the area under cultivation.

[0051] In yet another aspect, the present invention provides a method for 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.

[0052] The compound provided by the invention is a novel compound which is more effective against weeds, has lower cost, lower toxicity and is safe for the environment.

[0053] The compound represented by formula (I) or formula (Ia) may exist in different stereoisomers 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 compounds containing deuterium.

[0054] An isotopically enriched compound has a structure depicted by the formula 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 the compounds of the invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine, and chlorine, such as 2 H, 3 H, 11 C, 13 C, 14 C, 15 N, 17 Oh, 18 Oh, 18 F, 31 P, 32 P, 35 S, 36 Cl and 125 I.

[0055] Any asymmetric atom (eg, carbon, etc.) in the compounds disclosed herein may exist in a racemic or enantiomerically enriched form, such as the (R)-, (S)- or (R,S)-configuration.

[0056] The foregoing only summarizes certain aspects of the present invention, but is not limited to these aspects and other aspects will be described in more detail and fully below.

[0057] Detailed description of the invention

[0058] Definitions and general terms

[0059] Certain embodiments of the present invention are now described in detail, examples of which are illustrated by the accompanying structural formula and chemical formula. The present invention is intended to cover all substitutions, modifications and equivalent technical solutions, which are all included in the scope of the present invention as defined in the claims. It should be appreciated by those skilled in the art that many methods and materials similar or equivalent to those described in the present invention can be used to practice the present invention. The present invention is by no means limited to the methods and materials described in the present invention. In the event that one or more of the combined documents, patents and similar materials are different from or contradictory to the present application (including but not limited to defined terms, term applications, described technologies, etc.), the present application shall prevail.

[0060] It should be further appreciated that certain features of the invention, which for clarity are described in multiple separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which for brevity are described in a single embodiment, may also be provided separately or in any suitable sub-combination.

[0061] Unless otherwise specified, all technical terms used in the present invention have the same meaning as commonly understood by those skilled in the art to which the present invention belongs. All patents and publications related to the present invention are incorporated herein by reference in their entirety.

[0062] Unless otherwise indicated, the following definitions used in the present invention shall apply. For purposes of the present invention, chemical elements are consistent with the Periodic Table of the Elements, CAS version, and Handbook of Chemistry and Physics, 75th edition, 1994. In addition, general principles of organic chemistry can be found 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, the entire contents of which are incorporated herein by reference.

[0063] Unless otherwise specified or there is a clear conflict in context, the articles "a", "an", and "the" as used herein are intended to include "at least one" or "one or more". Therefore, these articles as used herein refer to articles that refer to one or more than one (i.e., at least one) of the objects. 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 the implementation of the described embodiment.

[0064] The term "comprising" is an open expression, that is, including the contents specified in the present invention but not excluding other contents.

[0065] "Stereoisomers" refer to compounds that have the same chemical constitution but differ in the way the atoms or groups are arranged in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis / trans) isomers, atropisomers, and the like.

[0066] "Enantiomers" refer to two non-superimposable isomers of a compound that are mirror images of each other.

[0067] "Diastereoisomers" refer to stereoisomers that have two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereoisomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivity. Diastereomeric mixtures can be separated by high-resolution analytical procedures such as electrophoresis and chromatography, for example HPLC.

[0068] The stereochemical definitions and conventions used in the present invention generally follow those described in SP 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", John Wiley & Sons, Inc., New York, 1994.

[0069] Many organic compounds exist in optically active forms, i.e. they have the ability to rotate the plane of plane polarized light. When describing an optically active compound, the prefixes D and L or R and S are used to indicate the absolute configuration of the molecule about its chiral center(s). The prefixes d and l or (+) and (-) are the symbols used to designate the rotation of plane polarized light caused by the compound, where (-) or l indicates that the compound is left-handed. Compounds prefixed with (+) or d are right-handed. A specific stereoisomer is an enantiomer, and a mixture of such isomers is called a mixture of enantiomers. 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.

[0070] The term "tautomer" or "tautomeric form" refers to structural isomers with different energies that can be mutually converted through a low energy barrier. If tautomerism is possible (such as in solution), the chemical equilibrium of the tautomers can be reached. For example, proton tautomers (protontautomers) (also known as prototropic tautomers) include mutual conversions by proton migration, such as keto-enol isomerization and imine-enamine isomerization. Valence tautomers include mutual conversions by the reorganization of some bonding electrons. A specific example of keto-enol tautomerism is the interconversion of pentane-2,4-dione, hexane-1,3-dione and 4-hydroxypent-3-ene-2-one tautomers. Another example of tautomerism is phenol-keto tautomerism. A specific example of phenol-keto tautomerism is the interconversion of pyridine-4-ol and pyridine-4 (1H)-one tautomers. Unless otherwise stated, all tautomeric forms of the compounds of the invention are within the scope of the invention.

[0071] In the present invention, depending on external conditions (such as solvent, pH, etc.), there is keto-enol interconversion:

[0072]

[0073] As described herein, the compounds of the present invention may be optionally substituted with one or more substituents, such as the general formula compounds above, or as specific examples in the embodiments, subclasses, and classes of compounds encompassed by the present invention. It should 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 are replaced by a specific 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 structural formula can be substituted by one or more substituents selected from a specific group, the substituents may be substituted at each position in the same or different manner. The substituents may be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl, hydroxy-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkylacyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amide, sulfonyl, aminosulfonyl and the like.

[0074] In addition, it should be noted that, unless explicitly stated otherwise, the description methods used in the present invention, "each... is independently" and "... are each independently" and "... are independently" can be interchanged and should be understood in a broad sense, which can mean that in different groups, the specific options expressed by the same symbols do not affect each other, or that in the same group, the specific options expressed by the same symbols do not affect each other.

[0075] In various parts of this specification, substituents of compounds disclosed in the present invention are disclosed according to group types or ranges. It is particularly noted that the present invention includes each independent subcombination of the individual members of these group types and ranges. For example, the term "C1-C6 alkyl" or "C 1-6 "Alkyl" specifically refers to methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl and C6 alkyl as disclosed independently.

[0076] The term "alkyl" or "alkyl group" as used herein refers to a saturated straight or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise specified, the alkyl group contains 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 another embodiment, the alkyl group contains 1-4 carbon atoms; in another embodiment, the alkyl group contains 1-3 carbon atoms.

[0077] 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(CH3)2), n-butyl (n-Bu, -CH2CH2CH2CH3), isobutyl (i-Bu, -CH2CH(CH3)2), sec-butyl (s-Bu, -CH(CH3)CH2CH3), tert-butyl (t-Bu, -CH(CH3)CH2CH3), u, -C(CH3)3), n-pentyl (-CH2CH2CH2CH2CH3), 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 (-CH2CH2CH2CH2CH2CH3), 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(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3), n-heptyl, n-octyl, and the like.

[0078] The term "alkenyl" refers to a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms and having at least one site of unsaturation, i.e., a carbon-carbon sp2 Double bond, wherein the alkenyl group may be optionally substituted with one or more substituents described herein, including "cis" and "tans" orientations, or "E" and "Z" orientations. In one embodiment, the alkenyl group contains 2-10 carbon atoms; in one embodiment, the alkenyl group contains 2-8 carbon atoms; in another embodiment, the 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-), -CH2CH2CH=CH2, -CH2CH=CHCH3, -CH2CH2CH2CH=CH2, -CH2CH2CH=CHCH3, -CH2CH2CH2CH=CHCH3, and the like.

[0079] The term "alkynyl" refers to a straight or branched monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein at least one carbon-carbon sp triple bond exists, wherein the alkynyl group may be optionally substituted with one or more substituents described herein. In one embodiment, the alkynyl group contains 2 to 10 carbon atoms; in one embodiment, the alkynyl group contains 2 to 8 carbon atoms; in another embodiment, the alkynyl group contains 2 to 6 carbon atoms; in yet another embodiment, the alkynyl group contains 2 to 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, -CH2-C≡CCH2CH3, -CH2CH2-C≡CCH3, and the like.

[0080] The term "alkoxy" means an alkyl group attached to the rest of the molecule via an oxygen atom, wherein the alkyl group has the meaning as described herein. Unless otherwise specified, the alkoxy group contains 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 group may be optionally substituted with one or more substituents as described herein.

[0081] Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH3), ethoxy (EtO, -OCH2CH3), 1-propoxy (n-PrO, n-propoxy, -OCH2CH2CH3), 2-propoxy (i-PrO, i-propoxy, -OCH(CH3)2), 1-butoxy (n-BuO, n-butoxy, -OCH2CH2CH2CH3), 2-methyl-1-propoxy (i-BuO, i-butoxy, -OCH2CH(CH3)2), 2-butoxy (s-BuO, s-butoxy, -OCH(CH3)CH2CH3), 2-methyl-2- Propoxy (t-BuO, t-butoxy, -OC(CH3)3), 1-pentyloxy (n-pentyloxy, -OCH2CH2CH2CH2CH3), 2-pentyloxy (-OCH(CH3)CH2CH2CH3), 3-pentyloxy (-OCH(CH2CH3)2), 2-methyl-2-butoxy (-OC(CH3)2CH2CH3), 3-methyl-2-butoxy (-OCH(CH3)CH(CH3)2), 3-methyl-l-butoxy (-OCH2CH2CH(CH3)2), 2-methyl-l-butoxy (-OCH2CH(CH3)CH2CH3), and the like.

[0082] The term "haloalkyl" means that an alkyl group is 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, -CHClCH2CH3, and the like.

[0083] The term "haloalkoxy" means that an alkoxy group is 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, -OCHClCH2CH3, and the like.

[0084] The term "haloalkenyl" means an alkenyl group substituted with one or more halogen atoms.

[0085] The term "haloalkynyl" means that an alkynyl group is substituted with one or more halogen atoms.

[0086] The term "alkoxyalkyl" refers to an alkyl group substituted by one or more alkoxy groups, wherein the alkyl group and the alkoxy group have the meanings as described herein. The alkoxyalkyl group is C 1-8 Alkoxy C 1-8 Alkyl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-4 Alkoxy C 1-4 Alkyl, C 1-4 Alkoxy C 1-3 Alkyl or C 1-3 Alkoxy C 1-3 Alkyl. Such examples include, but are not limited to, -CH2OCH3, -CH2CH2OCH3, -CH2OCH2CH3, -CH2CH2OCH2CH3, -CH2OCH2CH2CH3, -CH2CH2CH2OCH3, and the like.

[0087] The term "alkylthio" means an alkyl group attached to the rest of the molecule via a sulfur atom, wherein the alkyl group has the meaning as described herein.

[0088] The term "alkylthioalkyl" refers to an alkyl group substituted by one or more alkylthio groups, wherein the alkyl group and the alkylthio group have the meanings as described in the present invention. The alkylthioalkyl is C 1-8 Alkylthio C 1-8 Alkyl, C 1-6 Alkylthio C 1-6 Alkyl, C 1-4 Alkylthio C 1-4 Alkyl, C 1-4 Alkylthio C 1-3 Alkyl or C 1-3 Alkylthio C 1-3 Alkyl. Such examples include, but are not limited to, -CH2SCH3, -CH2CH2SCH3, -CH2SCH2CH3, -CH2CH2SCH2CH3, -CH2SCH2CH2CH3, -CH2CH2CH2CH3, -CH2CH2CH2SCH3, and the like.

[0089] The term "cycloalkyl" refers to a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing 3-12 carbon atoms. In one embodiment, the cycloalkyl contains 3-12 carbon atoms; in one embodiment, the cycloalkyl contains 3-10 carbon atoms; in another embodiment, the cycloalkyl contains 3-8 carbon atoms; in yet another embodiment, the cycloalkyl 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, adamantyl, and the like.

[0090] As used herein, the term "unsaturated" means that the group contains one or more degrees of unsaturation.

[0091] The term "cycloalkylalkyl" means an alkyl group substituted by a cycloalkyl group, wherein the alkyl group and the cycloalkyl group have the meanings as described herein. The cycloalkylalkyl is C 3-12 Cycloalkyl C 1-8 Alkyl, C 3-8 Cycloalkyl C 1-6 Alkyl, C 3-6 Cycloalkyl C 1-4 Alkyl or C 3-6 Cycloalkyl C 1-3 Alkyl. Such examples include, but are not limited to, etc.

[0092] The terms "heterocyclyl" and "heterocycle" are used interchangeably herein and refer to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring containing 3-15 ring atoms, wherein the monocyclic, bicyclic or tricyclic ring does not contain an aromatic ring and at least one ring atom is selected from nitrogen, sulfur and oxygen atoms. Unless otherwise specified, the heterocyclyl group can be a carbon group or a nitrogen group, and the -CH2- group can be optionally replaced by -C(=O)-. The sulfur atom of the ring can be optionally oxidized to S-oxide. The nitrogen atom of the ring can be optionally oxidized to N-oxide. Examples of heterocyclic groups include, but are not limited to, oxirane, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (e.g., 2-pyrrolidinyl), 2-pyrrolinyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, dihydrothiophenyl, 1,3-dioxolane, dithiolanyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidinyl, 4-piperidinyl), morpholinyl, thiomorpholinyl, (1-oxo)-thiomorpholinyl, (1,1-dioxo)-thiomorpholinyl, piperazinyl, dioxanyl, dithianyl, thioxanyl, homopiperazinyl, homopiperidinyl, oxepanyl, thiepanyl, 2-oxa-5-azabicyclo[2.2.1]hept-5-yl, tetrahydropyridinyl. Examples of heterocyclic groups in which the -CH2- group is replaced by -C(=O)- include, but are not limited to, 2-oxopyrrolidinyl, oxo-1,3-thiazolidinyl, 2-piperidonyl, 3,5-dioxopiperidinyl. Examples of heterocyclic groups in which the sulfur atom is oxidized include, but are not limited to, sulfolane, 1,1-dioxothiomorpholinyl. The heterocyclyl group is optionally substituted with one or more substituents described herein.

[0093] The term "heterocyclylalkyl" refers to an alkyl group substituted with a heterocyclyl group; wherein the heterocyclyl and alkyl groups have the meanings as described herein.

[0094] The term "aryl" refers to monocyclic, bicyclic and tricyclic carbon 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, wherein each ring system contains a ring consisting of 3-7 atoms and has one or more points of attachment to the rest of the molecule. The term "aryl" can be used interchangeably with the term "aromatic ring". Examples of aryl groups can include phenyl, indenyl, naphthyl and anthracenyl. The aryl group is optionally substituted with one or more substituents described herein.

[0095] The term "arylalkyl" or "aralkyl" means an alkyl group substituted with one or more aryl groups, wherein the alkyl and aryl groups have the meanings as described herein.

[0096] 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 5-7 atoms to form a ring and has one or more points of attachment to the rest of the molecule. The term "heteroaryl" can be used interchangeably with the term "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein.

[0097] 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 in the form of a nitrogen atom in a heterocyclic ring in which the hydrogen is substituted, for example, N (such as N in 3,4-dihydro-2H-pyrrolyl), NH (such as NH in pyrrolidinyl) or NR (such as NR in N-substituted pyrrolidinyl).

[0098] In one embodiment, the 5-10 atom heteroaryl group contains 1, 2, 3 or 4 heteroatoms independently selected from O, S and N.

[0099] 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.

[0100] In another embodiment, heteroaryl represents a 5-membered or 6-membered heteroaryl containing 1-4 N heteroatoms; in another embodiment, heteroaryl represents a 5-membered heteroaryl containing 1-3 heteroatoms selected from N, O or S; in another embodiment, heteroaryl represents a 5-membered heteroaryl containing 1-3 heteroatoms selected from N or O; in another embodiment, heteroaryl represents a 5-membered heteroaryl containing 1-3 heteroatoms selected from N or S.

[0101] Examples of heteroaryl groups include, but are not limited to, 2-furanyl, 3-furanyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyridazinyl (e.g., 3-pyridazinyl), 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, tetrazolyl (e.g., 5-tetrazolyl), triazolyl (e.g., 2- triazolyl and 5-triazolyl), 2-thienyl, 3-thienyl, pyrazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,3-triazolyl, 1,2,3-thiodiazolyl, 1,3,4-thiodiazolyl, 1,2,5-thiodiazolyl, pyrazinyl, 1,3,5-triazinyl, pyrimidinone, pyridone; also including the following bicyclic rings, but in no way limited to these bicyclic rings: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (such as 2-indolyl), and the like.

[0102] The term "heteroarylalkyl" means an alkyl group substituted by one or more heteroaryl groups, wherein the alkyl group and the heteroaryl group have the meanings described herein.

[0103] When the compounds of the present invention contain an acid moiety, salts of the compounds of the present invention include those derived from alkali metals or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and those having the formula N + (R 19 R 20 R 21 R 22 ) of an ammonium cation, wherein R 19 , R 20 , R 21 and R 22 Independently selected from hydrogen, C1-C6 alkyl and C1-C6 hydroxyalkyl. The salt of the compound shown in formula (I) or formula (Ia) can be prepared by processing the compound shown in formula (I) or formula (Ia) with a metal hydroxide (such as sodium hydroxide) or an amine (such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine).

[0104] When the compounds of the present invention contain a basic moiety, acceptable salts may be formed from organic and inorganic acids such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, 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 acceptable acids.

[0105] Compositions and preparations of the compounds of the present invention

[0106] The compounds of the present invention are generally useful as herbicide active ingredients in compositions or formulations having at least one pesticide-acceptable adjuvant selected from surfactants, solid diluents, and liquid diluents, etc., and components that meet the requirements for pesticide use are within 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).

[0107] Useful formulations include liquid compositions and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and / or suspoemulsions), etc., which may optionally be thickened into gels. General types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, and suspoemulsions. General types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates, and oil dispersions.

[0108] General types of solid compositions are dusts, powders, granules, pellets, pellets, pastilles, 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 may be (micro)encapsulated and further formed into a suspension or solid formulation; or the entire active ingredient formulation may be encapsulated (or "coated"). Encapsulation may control or delay the release of the active ingredient. Emulsifiable particles combine the advantages of both emulsifiable concentrates and dry granular formulations. High concentration compositions are primarily used as intermediates for other formulations.

[0109] Sprayable preparations are usually dispersed in suitable media before spraying. Such liquid preparations and solid preparations are formulated into preparations that are easy to dilute in spray media (normally water). The spray volume can be in the range of about one liter per hectare to several thousand liters, but more typically in the range of about ten liters per hectare to several hundred liters. Sprayable preparations can be mixed with water or another suitable medium in a tank, for processing leaves by air or ground application, or are applied to the growth medium of plants. Liquid and dry preparations can be directly quantitatively added to the drip irrigation system, or quantitatively added to the furrow during planting.

[0110] The formulation will generally contain effective amounts of active ingredient, diluent and surfactant, the total being 100% by weight.

[0111] Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Edition, Dorland Books, Caldwell, New Jersey.

[0112] Liquid diluents include, for example, water, N,N-dimethylalkaneamides (e.g., N,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, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerol, triacetin, sorbitol, aromatic hydrocarbons, dearomatized aliphatic compounds, alkylbenzenes, alkylnaphthalenes, ketones (e.g., cyclohexanone, 2-heptanone, isophorone and 4-hydroxy- The liquid diluent may also include saturated and unsaturated fatty acids (usually C6-C8 fatty acids). The liquid diluent may also include saturated and unsaturated fatty acids (usually C6-C8 fatty acids). 22 ) glycerides, such as oils of plant seeds and fruits (e.g., olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil, sunflower oil, grape seed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil and palm kernel oil), animal fats (e.g., beef tallow, lard, 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 purified by distillation. Typical liquid diluents are described in Marsden's Solvents Guide, 2nd Edition, Interscience, New York, 1950.

[0113] The solid compositions and liquid compositions of the present invention generally contain one or more surfactants. When added to a liquid, a surfactant (also referred to as a "surface-active agent") generally changes, most often reduces, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, the surfactant can be used as a wetting agent, dispersant, emulsifier or defoaming agent.

[0114] Surfactants can be classified as nonionic surfactants, anionic surfactants or cationic surfactants. Nonionic surfactants that can be used as the composition of the present invention include, but are not limited to, alcohol alkoxylates, such as alcohol alkoxylates based on natural alcohols 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 oils; alkylphenol alkoxylates, such as octylphenol ethoxylation, nonylphenol ethoxylation, dinonylphenol ethoxylate and dodecylphenol ethoxylate (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers, wherein the terminal blocks are prepared from propylene oxide; ethoxylated phenols; 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 sorbitan 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; silicone-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglucosides and alkyl polysaccharides.

[0115] Useful anionic surfactants include, but are not limited to, alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives, such as lignin sulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonates; phosphates, such as phosphates of alcohol alkoxylates, phosphates of alkylphenol alkoxylates, and phosphates of styrylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol ether sulfates; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides, such as N,N-alkyltaurates; sulfonates of benzene, isopropylbenzene, toluene, xylene, and dodecylbenzene and tridecylbenzene; sulfonates of polycondensed naphthalene; sulfonates of naphthalene and alkylnaphthalene; sulfonates of petroleum fractions; sulfosuccinamates; and sulfosuccinates and their derivatives, such as dialkyl sulfosuccinates.

[0116] Useful cationic surfactants include, but are not limited to, amides and ethoxylated amides; amines, such as N-alkylpropylenediamine, tripropylenetriamine, and dipropylenetetramine, as well as 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 acetates and diamine salts; quaternary ammonium salts, such as quaternary ammonium salts, ethoxylated quaternary ammonium salts, and diquaternary ammonium salts; and amine oxides, such as alkyldimethylamine oxides and di-(2-hydroxyethyl)-alkylamine oxides.

[0117] 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 recommended uses are disclosed in a number of published references, including McCutcheon's Emulsifiers and Detergents, North American and International Annual Editions, published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood's Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and AS Davidson and B. Milwidsky's Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.

[0118] The compositions of the present invention may also contain formulation aids and additives known to those skilled in the art as formulation aids (some of which may also be considered to function as solid diluents, liquid diluents, or surfactants). Such formulation aids and additives may control: pH (buffers), foaming during processing (defoamers such as polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth in containers (antimicrobial agents), product freezing (antifreeze agents), color (dye / pigment dispersions), elution (film formers or adhesives), evaporation (evaporation inhibitors), and other formulation attributes. Film formers include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinyl pyrrolidone-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 Edition, published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co., and PCT Publication WO03 / 024222.

[0119] The compounds of the present invention and any other active ingredients are usually incorporated into the compositions of the present invention by dissolving the active ingredient in a solvent or by grinding the active ingredient in a liquid diluent or a dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of the liquid composition used as an emulsifiable concentrate is immiscible with water, an emulsifier is usually added to emulsify the solvent containing the active ingredient when it is diluted with water. A medium mill can be used to wet grind a slurry of active ingredients with 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, for example, US3,060,084) or further processed by spray drying to form water-dispersible particles. Dry preparations usually require a dry grinding step, which produces 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 (e.g., with a hammer mill or fluid energy mill). Granules and granules can be prepared by spraying the active substance on a preformed granular carrier or by agglomeration techniques. See Browning, "Agglomeration" (Chemical Engineering, December 4, 1967, pages 147-48; Perry, Chemical Engineer's Handbook, 4th edition, McGraw-Hill, New York, 1963, pages 8-57 and following pages and WO91 / 13546. Granules can be prepared as described in US 4,172,714. Water-dispersible and water-soluble granules can be prepared as proposed in US 4,144,050, US 3,920,442 and DE. 3,246,493. Tablets can be prepared as proposed in US 5,180,587, US 5,232,701 and US 5,208,030. Films can be prepared as proposed in GB 2,095,558 and US 3,299,566.

[0120] For additional information related to the formulation field, see "The Formulator's Toolbox - Product Forms for Modern Agriculture" by TS Woods, in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, edited by T. Brooks and TR Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, column 6, lines 16 to column 7, line 19, and Examples 10-41; U.S. Pat. No. 3,309,192, column 5, lines 43 to column 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. Pat. No. 2,891,855, column 3, lines 66 to column 5, line 17, and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pages 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.

[0121] Application of the compounds of the present invention

[0122] The herbicide of the present invention can be used by spraying plants, applying to soil, or applying to water surfaces. The amount of the active ingredient is appropriately determined to meet the application purpose. The content of the active ingredient is appropriately determined according to the purpose.

[0123] The amount of the compound of the present invention to be used depends on the type of compound used, target weeds, tendency of weed emergence, environmental conditions and type of herbicide, etc. When the herbicide of the present invention is used in the form of itself, such as powder or granules, its amount is appropriately selected as 1g-50kg / hectare, preferably 10g-10kg / hectare of active ingredient. When the herbicide of the present invention is used in the form of a liquid, such as an emulsifiable concentrate, a wettable powder or a flowable formulation, its amount is appropriately selected as 0.1-50,000ppm, preferably 10-10,000ppm.

[0124] The present invention provides a method for controlling weeds in crops of useful plants, which method comprises applying to 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.

[0125] The present invention also provides a method for selectively controlling grass and / or weeds in crops of useful plants, which comprises applying a herbicidally effective amount of a compound of formula (I) or (Ia) to the useful plants or their loci or to the cultivation area.

[0126] The term "herbicide" means a compound that controls or changes plant growth. The term "effective amount" means the amount of such a compound or a composition of such compounds that can produce a control or change plant growth effect. The effect of control or change includes all deviations from natural development, for example, killing, delaying, leaf burns, albinism, dwarfing, etc. 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 "location" is intended to include soil, seeds and seedlings, together with established plants (established vegetation) and not only include areas where weeds may have grown, but also include areas where weeds have not yet appeared, and also include areas about the planting of useful plant crops."Planted areas" include land where crop plants have grown thereon, and land intended to be used to plant such crop plants. The term "weeds" as used herein means any undesirable plant, and therefore not only includes important agronomic weeds as described below, but also includes volunteer crop plants.

[0127] Useful plant crops 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 palm, olives, pome fruits, stone fruits and rubber, and annual arable crops such as cereals (e.g. barley and wheat), cotton, rapeseed, corn, rice, soybeans, sugar beets, sugar cane, sunflowers, ornamentals, switchgrass, turf and vegetables, especially cereals, corn and soybeans.

[0128] The grasses and weeds to be controlled may be both monocotyledonous species, such as bentgrass, alopecuroides, avena, brachiaria, brome, tricholoma, sedge, crabgrass, barnyard grass, wild millet, ryegrass, longleaf, panicum, bluegrass, cyperus, sagittaria, scabrous grass, setaria, rhubarb and sorghum, and dicotyledonous species, such as aconite, amaranth, quinoa, chrysanthemum, euphorbia, larvae, ipomoea, kochia, nasturtium, polygonum, rhubarb, mustard, solanum, chickweed, veronica, violet and xanthium.

[0129] The compounds of the invention may show tolerance to important agricultural crops including, but not limited to, alfalfa, barley, cotton, wheat, canola, sugar beet, corn (maize), sorghum, soybean, rice, oats, peanuts, vegetables, tomatoes, potatoes, perennial plantations including coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, bananas, plantain, pineapple, hops, tea, and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., bluegrass, St. Augustine grass, Kentucky fescue, and bermudagrass).

[0130] If necessary, the compound according to the present invention as shown in formula (I) or formula (Ia) can also be used in combination with other active ingredients, for example other herbicides and / or insecticides and / or miticides and / or nematicides and / or molluscicides and / or fungicides and / or plant growth regulators. These mixtures and the purposes of these mixtures in order to control the growth of weeds and / or undesirable plants have formed other aspects of the present invention. For the avoidance of doubt, mixture of the present invention also includes two or more different mixtures with compounds as shown in formula (I) or formula (Ia). Specifically, the invention further relates to a composition of the present invention, which comprises at least one other herbicide except the compound as shown in formula (I) or formula (Ia).

[0131] General synthesis process

[0132] In this specification, if there is any difference between the chemical name and the chemical structure, the structure prevails. Generally, the compounds of the present invention can be prepared by the methods described in the present invention, unless otherwise specified.

[0133] The test conditions of the nuclear magnetic resonance hydrogen spectrum of the present invention are: at room temperature, a Bruker 400MHz or 600MHz nuclear magnetic spectrometer is used, with CDC13, d 6 -DMSO, CD3OD or d 6- Acetone is the solvent (reported in ppm), TMS (0 ppm) or chloroform (7.26 ppm) is used as the reference standard. When multiple peaks appear, the following abbreviations are used: s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet), br (broadened), dd (doublet of doublets), dt (doublet of triplets). Coupling constants are expressed in Hertz (Hz).

[0134] The mass spectrometry analysis method used in the present invention is: using Agilent 1260HPLC; Agilent 6120ESI.

[0135] Phase A: water (containing 0.1% formic acid); Phase B: acetonitrile (containing 0.1% formic acid).

[0136] Gradient elution: 0-3 min, 5-100% B; 3-6 min, 100% B.

[0137] Flow rate: 0.6mL / min.

[0138] Detection wavelength: 254nm.

[0139] MS parameters: ESI positive scan, collision induced ionization: 70V.

[0140] Dry nitrogen: 12 L / min, nebulizing gas pressure: 40 psi, gas temperature: 350°C.

[0141] Take an appropriate amount of sample, dissolve it in 0.5 mL of methanol, inject it, and perform a first-level MS full scan in positive ESI mode to obtain the quasi-molecular ion peak [M+H] + reading.

[0142] The following abbreviations are used throughout this invention:

[0143] DMSO: dimethyl sulfoxide;

[0144] g: gram; mg: milligram; mol: mole; mmol: millimole; μmol: micromole; M: mol / L, mole / liter; mL: milliliter.

[0145] The following synthetic schemes and Examples 1-8 are provided to further illustrate the present invention.

[0146] Synthesis scheme

[0147] Synthesis Scheme 1

[0148]

[0149] Compound (Ia) can be prepared by synthetic scheme 1, wherein R 1 and Q have the meanings as described in the present invention. Compound (I-1) reacts with compound (I-2) to obtain compound (I-3); compound (I-3) is ring-closed at 45-80°C to obtain compound (I-4); N-methylation on compound (I-4) obtains compound (I-5), compound (I-5) undergoes esterification reaction with 1,3-cyclohexanedione at room temperature, and undergoes Fries rearrangement reaction at room temperature under the action of trimethylsilyl cyanide to obtain target compound (Ia). Example

[0150] Example 1: Synthesis of Compound 3-(2,6-dimethylphenyl)-6-(2-hydroxy-6-oxocyclohex-1-enecarbonyl)-1-methyl-1H-benzo[c][1,2,6]thiadiazin-4(3H)-one 2,2-dioxide

[0151]

[0152] Step 1: Synthesis of intermediate 4-nitroisophthalic acid

[0153]

[0154] Potassium hydroxide (12.39 g, 662 mmol), water (400 mL) and 2-nitro-5-methylbenzoic acid (40 g, 220 mmol) were added to a 1-liter reaction bottle and heated to 90°C. After the solid was completely dissolved, potassium permanganate (104.69 g, 662 mmol) was added in batches. After reacting at 90°C for 3 hours, heating was stopped. The system was filtered while hot and the filter residue was rinsed with water (50 mL × 2). After the mother liquor was cooled to room temperature, the pH was adjusted to 1, and then stirred at 0°C for 30 minutes, filtered, and the solid was dried to obtain 43 g of a white solid with a yield of 92%.

[0155] MS(ES-API,pos.ion)m / z:209.9[MH] - .

[0156] Step 2: Synthesis of intermediate 4-nitroisophthalic acid dimethyl ester

[0157]

[0158] 4-Nitroisophthalic acid (43.00 g, 203 mmol) and methanol (300 mL) were added to a 500 mL reaction bottle. After stirring at 0°C for 30 minutes, thionyl chloride (121.15 g, 1020 mmol) was added dropwise. After the addition was complete, the temperature was raised to 60°C and the reaction was continued for 8 hours. The heating was then stopped. The solvent was removed from the reaction system. Ethyl acetate (400 mL) was added. The organic phase was washed with water (200 mL × 2). The organic phase was dried over anhydrous sodium sulfate. After the solvent was removed, 38.8 g of a white solid was obtained with a yield of 79.6%.

[0159] Step 3: Synthesis of intermediate 4-aminoisophthalic acid dimethyl ester

[0160]

[0161] Add dimethyl 4-nitroisophthalate (38.80 g, 162 mmol), methanol (300 mL) and palladium on carbon (0.17 g, 1.6 mmol) into a 500 mL reaction bottle, heat to 45 °C, introduce hydrogen, and stop heating after 8 hours of reaction. After the reaction system cools to room temperature, filter, wash the filter residue with methanol (50 mL × 3), and remove the solvent from the filtrate to obtain 30.6 g of off-white solid with a yield of 90%.

[0162] MS(ES-API,pos.ion)m / z:210.1[M+H] + .

[0163] Step 4: Synthesis of intermediate (2,6-dimethylphenyl)aminosulfonic acid

[0164]

[0165] Add 2,6-dimethylaniline (11.68 g, 96 mmol), triethylamine (16.02 g, 158 mmol) and dichloromethane (80 mL) into a 250 mL reaction bottle. After cooling to 0°C, add chlorosulfonic acid (8.02 g, 68 mmol). After the addition is complete, transfer to room temperature to react for 1 hour. The reaction solution is protected with nitrogen and used directly in the next step.

[0166] Step 5: Synthesis of intermediate 4-((N-(2,6-dimethylphenyl)sulfamoyl)amino)isophthalic acid dimethyl ester

[0167]

[0168] Add dimethyl 4-aminoisophthalate (7.20 g, 34 mmol) to the reaction system of step 4, react at 40 ° C for 30 minutes, then cool to 0 ° C, add phosphorus oxychloride (9.50 g, 61 mmol) dropwise, raise the temperature to 40 ° C after the addition is complete, react for 4 hours, stop heating, cool the reaction system to room temperature, wash with water (100 mL × 2), dry the organic phase over anhydrous sodium sulfate, remove the solvent, and obtain 9.12 g of off-white solid with a yield of 67.5%.

[0169] MS(ES-API,pos.ion)m / z:414.7[M+Na] + .

[0170] Step 6: Synthesis of intermediate methyl 3-(2,6-dimethylphenyl)-4-oxo-3,4-dihydro-1H-benzo[c][1,2,6]thiadiazine-6-carboxylate 2,2-dioxide

[0171]

[0172] Add dimethyl 4-((N-(2,6-dimethylphenyl)sulfamoyl)amino)isophthalate (9.12 g, 23 mmol), sodium methoxide (3.14 g, 58 mmol) and methanol (100 mL) into a 250 mL reaction bottle. After reacting at 60 °C for 3 hours, stop heating, remove the solvent from the reaction system, add water (100 mL) to dissolve the solid, add hydrochloric acid to adjust the pH to 1, and filter to obtain 8.03 g of white solid with a yield of 85.8%.

[0173] MS(ES-API,pos.ion)m / z:361.1[M+H] + .

[0174] 1 H NMR (400MHz, DMSO-d6) δ8.55(s,1H),8.13(d,J=7.9Hz,1H),7.26(d,J=6.9Hz,1H),7.21(dd,J=19.3,12.0Hz,3H),3.86(s,3H),2.20(s,6H).

[0175] Step 7: Synthesis of intermediate methyl 3-(2,6-dimethylphenyl)-1-methyl-4-oxo-3,4-dihydro-1H-benzo[c][1,2,6]thiadiazine-6-carboxylate 2,2-dioxide

[0176]

[0177] Methyl 3-(2,6-dimethylphenyl)-4-oxo-3,4-dihydro-1H-benzo[c][1,2,6]thiadiazine-6-carboxylate 2,2-dioxide (8.03 g, 22 mmol), potassium carbonate (6.16 g, 44 mmol) and acetonitrile (80 mL) were added into a 250 mL reaction bottle, and iodomethane (9.49 g, 66 mmol) was added dropwise at 60°C. After the addition was completed, the mixture was reacted at 60°C for 4 hours, and the heating was stopped. The solvent was removed from the reaction system, and ethyl acetate (100 mL) was added. The organic phase was washed with water (100 mL×2), dried over anhydrous sodium sulfate, and the solvent was removed to obtain 6.71 g of off-white solid with a yield of 80.4%.

[0178] MS(ES-API,pos.ion)m / z:375.1[M+H] + .

[0179] 1 H NMR(400MHz, CDCl3) δ8.91(d,J=1.9Hz,1H),8.37(dd,J=8.6,2.0Hz,1H),7.33(d,J=8.6H z,1H),7.31-7.27(m,1H),7.20(d,J=7.5Hz,2H),3.96(s,3H),3.62(s,3H),2.30(s,6H).

[0180] Step 8: Synthesis of intermediate 3-(2,6-dimethylphenyl)-1-methyl-4-oxo-3,4-dihydro-1H-benzo[c][1,2,6]thiadiazine-6-carboxylic acid 2,2-dioxide

[0181]

[0182] The intermediate methyl 3-(2,6-dimethylphenyl)-1-methyl-4-oxo-3,4-dihydro-1H-benzo[c][1,2,6]thiadiazine-6-carboxylate 2,2-dioxide (6.71 g, 18 mmol) and lithium hydroxide monohydrate (1.50 g, 35 mmol) were dissolved in a mixed solvent of tetrahydrofuran (30 mL), methanol (30 mL) and water (30 mL). After reacting at room temperature for 4 hours, the solvent was removed under reduced pressure, and the residue was dissolved in water (50 mL). The aqueous phase was extracted with ethyl acetate (30 mL×2), and then the aqueous phase was acidified to pH=1 with hydrochloric acid. After stirring for 1 hour, solid precipitated and filtered to obtain 3.62 g of white solid. The yield was 56.0%.

[0183] MS(ES-API,pos.ion)m / z:359.0[MH] - .

[0184] Step 9: Synthesis of intermediate 3-oxocyclohex-1-en-1-yl 3-(2,6-dimethylphenyl)-1-methyl-4-oxo-3,4-dihydro-1H-benzo[c][1,2,6]thiadiazine-6-carboxylate 2,2-dioxide

[0185]

[0186] 3-(2,6-Dimethylphenyl)-1-methyl-4-oxo-3,4-dihydro-1H-benzo[c][1,2,6]thiadiazine-6-carboxylic acid 2,2-dioxide (0.50 g, 1.4 mmol), tetrahydrofuran (20 mL), triethylamine (0.28 g, 2.7 mmol) and 2-chloro-1-methylpyridinium iodide (0.46 g, 1.8 mmol) were added to a 100 mL reaction bottle, and then 1,3-cyclohexanedione (0.20 g, 1.8 mmol) was added. After stirring at room temperature for 8 hours, the solvent was removed, ethyl acetate (50 mL) was added, and the mixture was washed with saturated sodium bicarbonate solution (50 mL×2). After the organic phase was dried over anhydrous sodium sulfate, the solvent was removed to obtain 0.41 g of a brown liquid with a yield of 65.0%.

[0187] MS(ES-API,pos.ion)m / z:455.0[M+H] + .

[0188] Step 10: Synthesis of compound 3-(2,6-dimethylphenyl)-6-(2-hydroxy-6-oxocyclohex-1-enecarbonyl)-1-methyl-1H-benzo[c][1,2,6]thiadiazin-4(3H)-one 2,2-dioxide

[0189]

[0190] 3-Oxocyclohex-1-en-1-yl 3-(2,6-dimethylphenyl)-1-methyl-4-oxo-3,4-dihydro-1H-benzo[c][1,2,6]thiadiazine-6-carboxylate 2,2-dioxide (0.41 g, 0.9 mmol), acetonitrile (15 mL) and triethylamine (0.18 g, 1.8 mmol) were added to a 50 mL reaction bottle, trimethylsilyl cyanide (13 mg, 135 μmol) was added, and the reaction was carried out at room temperature. After 8 hours, the reaction solution was adjusted to pH = 6 with dilute hydrochloric acid solution (1M, 2 mL), the solvent was removed from the reaction system, dichloromethane (40 mL) was added, the organic phase was washed with water (40 mL×2), dried over anhydrous sodium sulfate, the solvent was removed, and separation was carried out by silica gel column chromatography [n-hexane / mixed solvent (v / v) = 7 / 3] (mixed solvent: ethyl acetate / dichloromethane / methanol (v / v / v) = 10 / 10 / 1) to obtain 0.24 g of a white solid with a yield of 51.2%.

[0191] MS(ES-API,pos.ion)m / z:455.1[M+H] + .

[0192] 1 H NMR(400MHz, CDCl3)δ8.43(d,J=2.0Hz,1H),7.86(dd,J=8.5,2.1Hz,1H),7.27(s,1H),7.25(s,1H),7 .22-7.15(m,2H),3.61(s,3H),2.78(s,2H),2.52(s,2H),2.29(d,J=10.5Hz,6H),2.15-2.04(m,2H).

[0193] Referring to the synthesis method of Example 1, combined with the synthesis scheme 1 of the present invention, using corresponding raw materials and conditions, the target compounds in Table 1 can be obtained.

[0194] Table 1

[0195]

[0196]

[0197]

[0198] Biological Examples

[0199] Weigh a certain mass of the original drug using an analytical balance (0.0001 g), 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 later use.

[0200] Take a flower pot with a length and width of 7.0 cm, fill it to 3 / 4 of the pot, directly sow the pretreated weed target seeds, cover it with soil about 0.5 cm, wait for the seedlings to grow to the appropriate age, spray them, wait for the liquid to dry naturally after application, and then move them to the greenhouse for routine cultivation. After 21 days, investigate the activity (%) against weeds; 0 means no damage or normal growth process, and 100 means at least the above-ground part is completely dead. The test results are shown in Table 2.

[0201] Table 2 Activity of the compounds of the present invention against weeds at 150 g / ha

[0202] Example Dosage Ramie purslane Barnyard grass Example 1 150g / ha 100 100 85

[0203] The results in Table 2 show that the compound of the present invention has a good control effect on velvetleaf, purslane and barnyard grass at 150 g / ha.

[0204] The compound of the present invention has a good control effect on broadleaf weeds (such as velvetleaf, Amaranthus retroflexus, Zinnia, Caragana and Purslane) and grass weeds (such as crabgrass, barnyard grass, ryegrass and foxtail grass). It is safe for crops, has a fast efficacy, and has a better control effect on weeds than commercial herbicides and compounds with similar structures, and has a good application prospect.

Claims

1. A compound having the following structure or a stereoisomer, tautomer or salt thereof of a compound having the following structure:

2. A composition comprising the compound of claim 1, optionally further comprising at least one pesticidally acceptable adjuvant.

3. Use of the compound according to claim 1 or the composition according to claim 2 in agriculture.

4. A method for controlling the growth of weeds in useful plants, comprising applying an effective amount of a compound according to claim 1 or a composition according to claim 2 to the locus of the weeds, wherein: The weeds are velvetleaf, purslane and / or barnyard grass.

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