Pyridyloxadiazolone compounds and uses thereof

Abstract

The application provides a pyridine oxadiazole ketone compound and application thereof; in particular, the application provides a compound shown in formula (I), a preparation method and application thereof as a herbicide; wherein R 1 is hydrogen, C 1‑6 alkyl, halogenated C 1‑6 alkyl, C 1‑6 alkoxy C 1‑6 alkyl, C 2‑8 alkenyl, C 2‑6 alkynyl, C 3‑6 cycloalkyl C 1‑6 alkyl, C 3‑6 heterocyclyl C 1‑6 alkyl, C 3‑6 heterocyclyl C 1‑6 alkylthio, C 1‑5 heteroaryl C 1‑6 alkyl or C 6‑10 aryl C 1‑6 alkyl; R 2 is hydrogen, fluorine, chlorine or bromine.

Description

Technical Field

[0001] This invention provides a pyridine oxadiazolone compound and its preparation method; compositions containing these compounds and their applications in agriculture. Background Technology

[0002] Pyridine-2-carboxylic acid and its herbicidal properties have been described in the art. WO2003011853A1 and WO2007082098A2 disclose a class of 4-amino-6-arylpyridine-2-carboxylic acids and their derivatives, and their use as selective herbicides. WO2005063721A1 discloses 6-amino-2-substituted pyrimidine-4-carboxylic acids and their derivatives, and their use as herbicides. WO2007082076A1 discloses 2-(polysubstituted aryl)-6-amino-5-halo-4-pyrimidinecarboxylic acids and their derivatives, and their use as herbicides. WO2009029735A1 discloses 2-(substituted phenyl)-6-amino-5-alkoxy (haloalkoxy, alkylthio, haloalkylthio, or alkylamino)-4-pyrimidine carboxylic acid and its derivatives and their use as herbicides. WO2009046090A1 discloses 2-(substituted)-6-amino-5-(alkyl, alkenyl, or alkynyl)-4-pyrimidine carboxylic acid and 6-(substituted)-4-amino-3-(alkyl, alkenyl, or alkynyl))pyridinecarboxylic acid and their derivatives and their use as herbicides.

[0003] The disadvantages of the active ingredients known from the literature cited above in their use include, for example, (a) having no or insufficient herbicidal effect on weeds, (b) having a narrow spectrum of weeds to be controlled, or (c) having low selectivity in useful plant crops.

[0004] 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

[0005] This invention provides a novel pyridine diazonone compound with excellent herbicidal activity, high safety, and excellent selectivity between crops and weeds.

[0006] On the one hand, the present invention provides a compound of formula (I) or a stereoisomer, nitride, or salt thereof:

[0007]

[0008] in:

[0009] R 1 For hydrogen, C 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 1-6Alkoxy C 1-6 Alkyl, C 2-8 alkenyl, C 2-6 alkynyl group, C 3-6 cycloalkyl C 1-6 Alkyl, C 3-6 Heterocyclic C 1-6 Alkyl, C 3-6 Heterocyclic C 1-6 Alkylthio, C 1-5 heteroaryl C 1-6 Alkyl or C 6-10 Aryl C 1-6 alkyl;

[0010] Among them, R 1 Optionally selected from 1, 2, 3, 4 or 5 elements chosen by R 3 Substituents of the substituents;

[0011] R 2 It can be hydrogen, fluorine, chlorine, or bromine;

[0012] R 3 Selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, amino, C 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkoxy, C 1-6 alkylthio or halogenated C 1-6 Alkylthio group.

[0013] In some implementation schemes, R 1 For hydrogen, C 1-4 Alkyl, Halogenated C 1-4 Alkyl, C 1-4 Alkoxy C 1-4 Alkyl, C 2-6 alkenyl, C 2-4 alkynyl group, C 3-6 cycloalkyl C 1-4 Alkyl, C 3-6 Heterocyclic C 1-4 Alkyl, C 3-6 Heterocyclic C 1-4 Alkylthio, C 1-5 heteroaryl C 1-4 Alkyl or phenyl C 1-4 alkyl;

[0014] Among them, R 1 Optionally selected from 1, 2, 3, 4 or 5 elements chosen by R 3 Substituents of the substituents;

[0015] R 3 Selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, amino, C 1-4 Alkyl, Halogenated C1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkoxy, C 1-4 alkylthio or halogenated C 1-4 Alkylthio group.

[0016] In other implementations, R 1 is hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH(CH3)2, -CHF2, -CH2CHF2, -CH2CH2 CHF2, -CF3, -CH2CF3, -CH2CH2CF3, -CH2OCH3, -CH2OCH2CH3, -CH2CH2OCH3, -CH2CH2CH2OCH3, -CH2CH2OC H2CH3, -CH=CH2, -CH2CH=CH2, -CH2CH2CH=CH2, -CH2C(CH3)=CH2, -CH2CH=C(CH3)2, -C≡CH, -C≡CCH3, -CH2-C≡CH, -CH2-C≡CCH3, -CH2CH2-C≡CH, cyclopropylmethyl, cyclobutylmethyl, tetrahydrofuranylmethyl, thiazolylmethyl, 5,5-dimethyl-4,5-dihydroisoxazol-3-yl-thio or benzyl;

[0017] Among them, R 1 Optionally selected from 1, 2, 3, 4 or 5 elements chosen by R 3 Substituents of the substituents;

[0018] R 3 Selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, amino, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CHF2, -CH2CHF2, -CH2CH2CHF2, -CF3, -CH2CF3, -CH2CH2CF3, -OCH3, -OCH2CH3, -OCF3, -OCHF2, -OCH2CF3 or -OCH2CHF2.

[0019] The structural formula of the cyclopropylmethyl group is as follows: The structural formula of cyclobutylmethyl is: The structural formula of tetrahydrofuranylmethyl is: The structural formula of thiazolylmethyl is: The structural formula of 5,5-dimethyl-4,5-dihydroisoxazol-3-yl-thio is: The structural formula of benzyl is The cyclopropylmethyl, cyclobutylmethyl, tetrahydrofuranylmethyl, thiazolylmethyl, 5,5-dimethyl-4,5-dihydroisoxazol-3-yl-thio or benzyl group may optionally be represented by 1, 2, 3, 4 or 5 groups selected from R 3 Substituents, wherein R 3 Selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, amino, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CHF2, -CH2CHF2, -CH2CH2CHF2, -CF3, -CH2CF3, -CH2CH2CF3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCF3, -OCHF2, -OCH2CF3 or -OCH2CHF2.

[0020] In other implementations, R 1 It is hydrogen or has the following substructure:

[0021]

[0022] In some embodiments, the present invention provides a compound having one of the following structures, or a stereoisomer, nitride, or salt thereof having one of the following structures:

[0023]

[0024]

[0025]

[0026]

[0027] On the other hand, the present invention provides a composition comprising the compound described in the present invention or a stereoisomer of the compound described in the present invention, a nitrogen oxide or a salt.

[0028] In some embodiments, the composition of the present invention optionally comprises at least one pesticide-acceptable adjuvant.

[0029] In other embodiments, the adjuvant is pesticide-acceptable, including but not limited to surfactants, solid diluents, liquid diluents, buffers, defoamers, thickeners, antifreeze agents, antimicrobial agents, and / or film-forming agents.

[0030] On the other hand, the present invention provides the use of the compounds of the present invention or compositions containing the compounds of the present invention in agriculture.

[0031] On the other hand, the present invention provides the use of the compounds described in the present invention or compositions containing the compounds described in the present invention in the control of weeds.

[0032] In some implementations, the weeds are one or more of the following: garland chrysanthemum, purslane, zinnia, barnyard grass, or foxtail grass.

[0033] On the other hand, the present invention provides the use of the compounds described in the present invention or compositions containing the compounds described in the present invention in the control of grass weeds.

[0034] On the other hand, the present invention provides the use of the compounds described in the present invention or compositions containing the compounds described in the present invention in the control of broadleaf weeds.

[0035] On the other hand, the present invention provides the use of the compounds described in the present invention or compositions containing the compounds described in the present invention in the control of garland chrysanthemum, purslane, zinnia, barnyard grass or foxtail grass.

[0036] In some embodiments, the present invention provides the use of the compounds of the present invention or compositions comprising the compounds of the present invention for the control of unwanted plants.

[0037] On the other hand, the present invention provides the use of the compounds described herein or compositions containing the compounds described herein as herbicides.

[0038] On the other hand, the present invention provides the use of the compounds described herein or compositions containing the compounds described herein as pre-emergence herbicides.

[0039] On the other hand, the present invention provides the use of the compounds described herein or compositions containing the compounds described herein as post-emergence herbicides.

[0040] On the other hand, the present invention provides a method for controlling unwanted plants, characterized in that an effective amount of the compound of the present invention or a composition containing the compound of the present invention is applied to a plant, plant seeds, soil in which or on which plants grow, or a cultivation area.

[0041] In another aspect, the present invention provides a method for controlling the growth of weeds in useful plants, comprising applying an effective amount of the compound of the present invention or a composition comprising the compound of the present invention to the location of the weeds.

[0042] In some implementations, the useful plants are wheat and corn; the weeds are velvetleaf.

[0043] The compound provided by this invention is a novel compound that is more effective against weeds, lower in cost, less toxic, and safe for the environment and crops.

[0044] The compounds represented by formula (I) may exist in different stereoisomers, optical isomers, or tautomers. This invention includes all such isomers and mixtures thereof in various proportions, as well as isotopic forms such as compounds containing deuterium.

[0045] The isotope-enriched compounds have the structures described by the general formulas given in this invention, except that one or more atoms are replaced by atoms having a selected atomic weight or mass number. Exemplary isotopes that can be introduced into the compounds of this 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 O, 18 O, 18 F, 31 P, 32 P, 35 S, 36 Cl and 125 I.

[0046] Any asymmetric atom (e.g., carbon, etc.) in the compounds disclosed in this invention can exist in racemic or enantiomerically enriched forms, such as (R)-, (S)-, or (R,S)- configurations.

[0047] The foregoing description only outlines certain aspects of the invention, but is not limited to these aspects. Other aspects will be described in more detail and in full below.

[0048] Detailed Description of the Invention

[0049] Definitions and general terms

[0050] Certain embodiments of the invention will now be described in detail, examples of which are illustrated by the accompanying structural and chemical formulas. The invention is intended to cover all alternatives, modifications, and equivalents, all of which are included within the scope of the invention as defined in the claims. Those skilled in the art will recognize that many similar or equivalent methods and materials can be used to practice the invention. The invention is by no means limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ from or contradict this application (including, but not limited to, defined terminology, application of terminology, described techniques, etc.), this application shall prevail.

[0051] It should be further appreciated that certain features of the invention, for clarity, have been described in multiple independent embodiments, but may also be provided in combination in a single embodiment. Conversely, various features of the invention, for brevity, have been described in a single embodiment, but may also be provided individually or in any suitable sub-combination.

[0052] Unless otherwise stated, all technical terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. All patents and publications related to this invention are incorporated herein by reference in their entirety.

[0053] Unless otherwise stated, the following definitions as used in this invention shall apply. For the purposes of this invention, chemical elements are consistent with the periodic table (CAS edition) and the Handbook of Chemistry and Physics, 75th edition, 1994. Furthermore, 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.

[0054] Unless otherwise stated or there is an obvious conflict in the context, the articles “a,” “an,” and “described” as used in this invention are intended to include “at least one” or “one or more.” Therefore, these articles as used in this invention refer to articles for one or more (i.e., at least one) objects. For example, “a component” refers to one or more components, meaning that more than one component may be considered for use or employed in the embodiments described.

[0055] The term "comprising" is an open-ended expression, meaning it includes the contents specified in this invention, but does not exclude other aspects.

[0056] "Stereoisomers" are compounds that have the same chemical structure but whose atoms or groups are arranged differently in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotational isomers), geometric isomers (cis / trans) isomers, and hindered isomers, etc.

[0057] "Enantiomers" refer to two non-overlapping but mirror-image isomers of a compound.

[0058] A diastereomer is a stereoisomer that has two or more chiral neutral molecules that are not mirror images of each other. Diastereomers possess different physical properties, such as melting point, boiling point, spectral properties, and reactivity. Mixtures of diastereomers can be separated using high-resolution analytical techniques such as electrophoresis and chromatography, for example, HPLC.

[0059] The stereochemical definitions and rules used in this invention generally follow those described in 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”, John Wiley & Sons, Inc., New York, 1994.

[0060] Many organic compounds exist in an optically active form, meaning they possess 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 indicate the absolute configuration of the molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are symbols used to specify the plane-polarized light rotation caused by the compound, where (-) or l indicates that the compound is levorotatory. Compounds with the prefix (+) 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 the chemical reaction or process.

[0061] As described in this invention, the compounds of this invention may optionally be substituted with one or more substituents, such as the general formula compounds above, or the specific examples, subclasses, and classes of compounds included in this invention, as described in the embodiments. It should be understood that the term "optionally substituted" is used interchangeably with the term "substituted or unsubstituted." Generally, the term "substituted" means that one or more hydrogen atoms in the given structure are substituted by a specific substituent. Unless otherwise indicated, an optional substituent group may be substituted at each substituted position of the group. When more than one position in the given structural formula can be substituted by one or more substituents selected from a specific group, the substituents may be substituted at the same or different positions. The substituents described therein can be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclic alkoxy, arylalkoxy, heteroarylalkoxy, heterocyclic alkoxy, cycloalkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, 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, heterocyclic, heterocyclic alkyl, heterocyclic acyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amide, sulfonyl, aminosulfonyl, etc.

[0062] Additionally, it should be noted that, unless otherwise explicitly stated, the descriptive terms “each…independently is”, “…each independently is”, and “…independently is” used in this invention are interchangeable and should be interpreted broadly. They can mean that the specific options expressed by the same symbols in different groups do not affect each other, or that the specific options expressed by the same symbols in the same group do not affect each other.

[0063] In various parts of this specification, the substituents of the compounds disclosed herein are disclosed according to the type or scope of the groups. In particular, this invention includes every independent secondary combination of the various members of these group types and scopes. For example, the terms "C1-C6 alkyl" or "C..." 1-6 "Alkyl" specifically refers to independently disclosed methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl.

[0064] As used in this invention, the term "alkyl" or "alkyl group" refers to a saturated straight-chain or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted by one or more substituents described in this invention. Unless otherwise specified, the alkyl group contains 1 to 20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in another embodiment, the alkyl group contains 1 to 10 carbon atoms; in another embodiment, the alkyl group contains 1 to 8 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 6 carbon atoms; in still another embodiment, the alkyl group contains 1 to 4 carbon atoms; and in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms.

[0065] 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), and tert-butyl (t-B). 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, etc.

[0066] The term "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group containing 2-12 carbon atoms, with at least one unsaturated site, i.e., one carbon-carbon sp.2 The double bond, wherein the alkenyl group may optionally be substituted by one or more substituents described in this invention, including the orientation of "cis" and "tans", or the orientation of "E" and "Z". In one embodiment, the alkenyl group comprises 2-10 carbon atoms; in another embodiment, the alkenyl group comprises 2-8 carbon atoms; in yet another embodiment, the alkenyl group comprises 2-6 carbon atoms; and in still another embodiment, the alkenyl group comprises 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, etc.

[0067] The term "alkynyl" refers to a straight-chain or branched monovalent hydrocarbon group containing 2-12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond, wherein the alkynyl group may optionally be substituted by one or more substituents described in this invention. In one embodiment, the alkynyl group contains 2-10 carbon atoms; in another embodiment, the alkynyl group contains 2-8 carbon atoms; in yet another embodiment, the alkynyl group contains 2-6 carbon atoms; and in still 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, -CH2-C≡CCH2CH3, -CH2CH2-C≡CCH3, etc.

[0068] The term "alkoxy group" indicates that an alkyl group is attached to the remainder of the molecule by an oxygen atom, wherein the alkyl group has the meaning as described in this invention. Unless otherwise specified, the alkoxy group contains 1-12 carbon atoms. In one embodiment, the alkoxy group contains 1-10 carbon atoms; in another 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; and in yet another embodiment, the alkoxy group contains 1-3 carbon atoms. The alkoxy group may optionally be substituted by one or more substituents described in this invention.

[0069] 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-l-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-pentoxy (n-pentoxy, -OCH2CH2CH2CH2CH3), 2-pentoxy (-OCH(CH3)CH2CH2CH3), 3-pentoxy (-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), etc.

[0070] The term "alkylthio" indicates that an alkyl group is attached to the rest of the molecule via a sulfur atom, wherein the alkyl group has the meaning as described in this invention. Examples of alkylthio groups include, but are not limited to, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH(CH3)2, etc.

[0071] The term "alkoxyalkyl" means that an alkyl group is replaced by one or more alkoxy groups, wherein the alkyl and alkoxy groups have the meanings as described in this invention. Examples of alkoxyalkyl groups include, but are not limited to, -CH2OCH3, -CH2OCH2CH3, -CH2OCH2CH2CH3, -CH2CH2OCH3, -CH2CH2OCH2CH3, -CH2CH2CH2OCH3, etc.

[0072] The term "haloalkyl" indicates that an alkyl group is replaced by one or more halogen atoms. Examples of haloalkyl groups include, but are not limited to, -CH2F, -CHF2, -CH2Cl, -CH2Br, -CF3, -CH2CF3, -CH2CH2F, -CH2CH2Cl, -CH2CH2Br, -CH2CHF2, -CH2CH2CF3, -CH2CH2CH2F, -CH2CH2CH2Cl, -CH2CH2CH2Br, -CHFCH2CH3, -CHClCH2CH3, etc.

[0073] The term "cycloalkyl" refers to a monovalent or polyvalent saturated monocyclic, bicyclic, or tricyclic system containing 3-12 carbon atoms. In one embodiment, the cycloalkyl group comprises 3-12 carbon atoms; in another embodiment, it comprises 3-10 carbon atoms; in yet another embodiment, it comprises 3-8 carbon atoms; and in still another embodiment, it comprises 3-6 carbon atoms. The cycloalkyl group may optionally be substituted by one or more substituents described in this invention. Examples of such substituents include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, adamantyl, etc.

[0074] The term "cycloalkylalkyl" indicates that an alkyl group is replaced by a cycloalkyl group, wherein the alkyl group and the cycloalkyl group have the meaning as described in this invention. Examples of such groups include, but are not limited to, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, etc.

[0075] The term "unsaturated" as used in this invention means that the group contains one or more degrees of unsaturation.

[0076] The terms "heterocyclic group" and "heterocycle" are used interchangeably herein, referring to a saturated or partially unsaturated monocyclic, bicyclic, or tricyclic ring comprising 3 to 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 stated, the heterocyclic group can be carbocyclic or nitrogen-based, and the -CH2- group may optionally be replaced by -C(=O)-. The sulfur atom of the ring may optionally be oxidized to an S-oxide. The nitrogen atom of the ring may optionally be oxidized to an N-oxide. Examples of heterocyclic groups include, but are not limited to, ethylene oxide, azirrobutyl, oxoheterobutyl, thioheterobutyl, pyrrolidinyl (such as 2-pyrrolidinyl), 2-pyrrolinyl, 3-pyrrolinyl, pyrazolyl, imidazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, dihydrothiophenyl, 1,3-dioxocyclopentyl, dithiocyclopentyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl Dynanoyl, tetrahydrothiaranyl, piperidinyl (2-piperidinyl, 3-piperidinyl, 4-piperidinyl), morpholinyl, thiomorpholinyl, (1-oxo)-thiomorpholinyl, (1,1-dioxo)-thiomorpholinyl, piperazineyl, dioxaneyl, dithiaalkyl, thiaalkyl, homopiperidinyl, homopiperidinyl, oxeheptyl, thioheptyl, 2-oxa-5-azabicyclo[2.2.1]hept-5-yl, tetrahydropyridinyl. Examples of heterocyclic groups in which the -CH2- group is substituted by -C(=O)- include, but are not limited to, 2-oxopyrrolyl, oxo-1,3-thiazolyl, 2-piperidinoneyl, 3,5-dioxopyridinyl. Examples of heterocyclic groups in which the sulfur atom is oxidized include, but are not limited to, sulfolane, 1,1-dioxothiomorpholinyl. The heterocyclic group is optionally replaced by one or more substituents described in this invention.

[0077] The term "heterocyclic alkyl" refers to a heterocyclic substituted alkyl group; wherein the heterocyclic group and alkyl group have the meanings as described in this invention. Examples of such groups include, but are not limited to, tetrahydrofuranylmethyl, etc.

[0078] The term "heterocyclic alkylthio" refers to a heterocyclic substituted alkylthio group; wherein the heterocyclic and alkylthio groups have the meanings as described in this invention. Examples of such groups include, but are not limited to, 5,5-dimethyl-4,5-dihydroisoxazol-3-yl-thio, etc.

[0079] The term "heteroatom" refers to O, S, N, P, and Si, including any oxidation state of N, S, and P; primary, secondary, tertiary amines, and quaternary ammonium salts; or forms in which the hydrogen atom on the nitrogen atom in the heterocycle is substituted, for example, N (like N in 3,4-dihydro-2H-pyrrole), NH (like NH in pyrroleyl), or NR (like NR in N-substituted pyrroleyl).

[0080] The term "aryl" refers to a monocyclic, bicyclic, or tricyclic carbocyclic system containing 6-14, 6-12, or 6-10 ring atoms, wherein at least one ring system is aromatic, and each ring system comprises a ring of 3-7 atoms with one or more attachment sites connected to the remainder of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring." Examples of aryl groups may include phenyl, indenyl, naphthyl, and anthraceneyl. The aryl group may optionally be substituted by one or more substituents described in this invention.

[0081] The term "arylalkyl" refers to an aryl-substituted alkyl group; wherein the aryl group and the alkyl group have the meanings as described in this invention. Examples of such groups include, but are not limited to, benzyl, etc.

[0082] The term "heteroaryl" refers to a monocyclic, bicyclic, or tricyclic system containing 5-12, 5-10, 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 attachment sites connected to the remainder of the molecule. The term "heteroaryl" may be used interchangeably with the terms "heteroaromatic ring" or "heteroaromatic compound." The heteroaryl group may optionally be substituted by one or more substituents described in this invention. In one embodiment, the 5-10 atom heteroaryl group comprises 1, 2, 3, or 4 heteroatoms independently selected from O, S, and N.

[0083] Examples of heteroaryl groups include, but are not limited to, 2-furanyl, 3-furanyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isooxazolyl, 4-isooxazolyl, 5-isooxazolyl, 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), and 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, pyrimidinoneyl, pyridinoneyl; also including, but not limited to, the following bicyclic groups: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (such as 2-indolyl), benzopiperidinyl, etc.

[0084] The terms "5-12-membered heteroaryl", "5-10-membered heteroaryl", or "5-6-membered heteroaryl" typically describe the number of ring atoms in a molecule. For example, pyrrole, pyrazolyl, imidazolyl, thiophene, isothiazolyl, thiazolyl, furanyl, isoxazolyl, and oxazolyl are 5-membered heteroaryl groups, while pyridinyl, pyrimidinyl, pyrazinyl, and pyridazinyl are 6-membered heteroaryl groups.

[0085] The term "heteroarylalkyl" means that a heteroaryl group is attached to the rest of the molecule by an alkyl group, wherein the alkyl and heteroaryl groups have the meanings as described in this invention.

[0086] When the compounds of the present invention contain an acid moiety, the salts of the compounds of the present invention include those derived from alkali metals or alkaline earth metals, as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and those having the chemical formula N. + (R 19 R 20 R 21 R 22 The ammonium cation of ) where R 19 R 20 R 21 and R 22 The compounds are independently selected from hydrogen, C1-C6 alkyl, and C1-C6 hydroxyalkyl. Salts of compounds having formula (I) can be prepared by treating compounds having formula (I) with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine).

[0087] When the compounds of the present invention contain a base moiety, the acceptable salts can 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.

[0088] Compositions and formulations of the compounds of the present invention

[0089] The compounds of this invention can generally be used as herbicide active ingredients in compositions or formulations having at least one adjuvant selected from surfactants, solid diluents, liquid diluents, buffers, defoamers, thickeners, antifreeze agents, antimicrobial agents, film-forming agents, etc. Components that meet the requirements for pesticide use are all within the scope of this invention. The formulation or composition components are selected to be consistent with the physical properties, application method, and environmental factors (such as soil type, humidity, and temperature) of the active ingredient.

[0090] Useful formulations include liquid compositions and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and / or suspensions), etc., which can optionally be thickened into gels. Common types of aqueous liquid compositions include soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, and suspensions. Common types of non-aqueous liquid compositions include emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates, and oil dispersions.

[0091] Solid compositions are generally available in the form of powders, granules, pellets, pellets, pellets, lozenges, tablets, and filled films (including seed coatings), and can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredients can be encapsulated (micro)capsules and further formed into suspensions or solid formulations; 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 concentrates and dry granule formulations. High-concentration compositions are primarily used as intermediates for other formulations.

[0092] Sprayable formulations are typically dispersed in a suitable medium before spraying. These liquid and solid formulations are formulated to be easily diluted in the spraying medium (usually water). Spray volumes can range from about one liter to several thousand liters per hectare, but more typically from about ten liters to several hundred liters per hectare. Sprayable formulations can be mixed in a trough with water or another suitable medium for foliar application via air or ground application, or applied to the plant's growing medium. Liquid and dry formulations can be added directly to drip irrigation systems or added in measured amounts to furrows during planting.

[0093] The formulation will typically contain effective amounts of active ingredients, diluents, and surfactants, totaling 100% by weight.

[0094] Solid diluents include, for example, clays such as bentonite, montmorillonite, palygorskite, 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, sodium bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd ed., Dorland Books, Caldwell, New Jersey.

[0095] Liquid diluents include, for example, water, N,N-dimethylalkanamide (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidone (e.g., N-methylpyrrolidone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffin (e.g., white mineral oil, n-alkanes, isoalkanes), alkylbenzenes, alkylnaphthalenes, glycerol, triacetylglycerol, sorbitol, aromatics, dearomatized aliphatic compounds, alkylbenzenes, alkylnaphthalenes, ketones (e.g., 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 alkyl lactates, diesters, and γ-butyrolactone), and may be straight-chain, branched, saturated, or unsaturated alcohols (such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecanol, isoctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, and benzyl alcohol). Liquid diluents also include saturated and unsaturated fatty acids (typically C6-C). 22 Liquid diluents include glycerides of plant seeds and fruits (e.g., olive oil, castor oil, flaxseed oil, sesame oil, corn oil, peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), animal fats (e.g., beef tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, which can be obtained by hydrolysis of glycerides derived from plants and animals and purified by distillation. Typical liquid diluents are described in Marsden's Solvents Guide, 2nd edition, Interscience, New York, 1950.

[0096] The solid and liquid compositions of the present invention typically contain one or more surfactants. When added to a liquid, the surfactant (also referred to as a "surface-active agent") typically alters, most commonly by reducing 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 defoamer.

[0097] Surfactants can be classified as nonionic surfactants, anionic surfactants, or cationic surfactants. Nonionic surfactants that can be used in the compositions of this 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, butane 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 ethoxylation, and dodecylphenol ethoxylation (prepared from phenol and ethylene oxide, propylene oxide, butane 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... Alkylated fatty acids; ethoxylated aliphatic esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including those prepared from ethylene oxide, propylene oxide, butane oxide, or mixtures thereof); fatty acid esters, glycerides, lanolin-based derivatives, polyethoxylated esters, such as polyethoxylated sorbitol fatty acid esters, polyethoxylated sorbitan fatty acid esters, and polyethoxylated glycerol fatty acid esters; other sorbitol derivatives, such as sorbitol esters; polymeric surfactants such as random copolymers, block copolymers, alkyd PEG (polyethylene glycol) resins, grafted or combed 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.

[0098] Available anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohols or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives, such as lignin sulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonates; phosphate esters, such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters 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-alkyl taurine; sulfonates of benzene, isopropylbenzene, toluene, xylene, and dodecylbenzene and tridecylbenzene; sulfonates of condensed naphthalene; sulfonates of naphthalene and alkylnaphthalene; sulfonates of petroleum fractions; sulfosuccinates; and sulfosuccinates and their derivatives, such as dialkylsulfosuccinates.

[0099] Available cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines, such as N-alkylpropylenediamine, tripropylenetriamine and dipropylenetetraamine, as well as ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butyl oxide or mixtures thereof); amine salts, such as amine acetates and diamine salts; quaternary ammonium salts, such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides, such as alkyldimethylamine oxides and di-(2-hydroxyethyl)-alkylamine oxides.

[0100] Also usable 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 several published references, including McCutcheon's Emulsifiers and Detergents, North American and International Yearbook editions, published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisley and Wood's Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A.S. Davidson and B. Milwidsky's Synthetic Detergents, 7th edition, John Wiley and Sons, New York, 1987.

[0101] The compositions of this invention may also contain formulation adjuvants and additives known to those skilled in the art as auxiliary formulations (some of which may also be considered as solid diluents, liquid diluents, or surfactants). Such formulation adjuvants and additives can control: pH (buffers), foaming during processing (defoamers such as polysiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth within the container (antimicrobial agents), product freezing (antifreeze agents), color (dye / pigment dispersions), elution (film-forming agents or binders), evaporation (anti-evaporation agents), and other formulation properties. Film-forming agents include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation adjuvants 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 those listed in PCT Publication WO03 / 024222.

[0102] The compounds of the present invention and any other active ingredients are typically incorporated into the compositions of the present invention by dissolving the active ingredient in a solvent or by grinding the active ingredient in a liquid 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 typically added to emulsify the solvent containing the active ingredient when diluted with water. Active ingredient slurries with a particle size of up to 2,000 μm can be wet-milled using a media mill to obtain particles with an average diameter of less than 3 μm. Aqueous slurries can be prepared as finished suspension concentrates (see, for example, US 3,060,084) or further processed by spray drying to form water-dispersible particles. Dry formulations typically require a dry milling step, which produces an average particle size in the range of 2 μm to 10 μm. Powders and granules can be prepared by mixing and typically by milling (e.g., using a hammer mill or kinetic mill). Particles and granules can be prepared by spraying the active material onto a pre-formed particle carrier or by agglomeration techniques. See Browning's "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 and following pages, and WO91 / 13546). Granules can be prepared as described in US4,172,714. Water-dispersible and water-soluble granules can be prepared as described in US4,144,050, US3,920,442, and DE.3,246,493. Tablets can be prepared as described in US5,180,587, US5,232,701, and US5,208,030. Films can be prepared as described in GB2,095,558 and US3,299,566.

[0103] For further information related to formulation, see T.S. Woods, “The Formulator’s Toolbox – Product Forms for Modern Agriculture,” 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 US 3,235,361, column 6, lines 16-7, line 19 and Examples 10-41; U.S. 3,309,192, column 5, lines 43-7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; US 2,891,855, column 3, lines 66-5, line 17 and Examples 1-4; Klingman, 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.

[0104] Application of the compounds of this invention

[0105] The herbicide of this invention can be used by spraying plants, applying it to soil, or applying it to water surfaces. The amount of active ingredient is appropriately determined to meet the application objective. The content of the active ingredient is appropriately determined according to this objective.

[0106] The dosage of the compounds of this invention depends on the type of compound used, the target weed, the trend of weed emergence, environmental conditions, and the type of herbicide. When the herbicide of this invention is used in its own form, such as in powder or granule form, the dosage is appropriately selected as 1 g-50 kg, preferably 10 g-10 kg / ha of active ingredient. When the herbicide of this invention is used in liquid form, such as in the form of an emulsifiable concentrate, wettable powder, or flowable formulation, the dosage is appropriately selected as 0.1-50,000 ppm, preferably 10-10,000 ppm.

[0107] The present invention provides a method for controlling weeds in a crop containing useful plants, the method comprising applying the compound or composition of the present invention to the weed or to the site of the weed or to the useful plant or to the site of the useful plant.

[0108] The present invention also provides a method for selectively controlling grasses and / or weeds in crops containing useful plants, the method comprising applying a herbicidally effective amount of a compound having the formula (I) to the useful plant or its location or to the cultivation area.

[0109] The term "herbicide" refers to a compound that controls or alters plant growth. The term "effective amount" refers to the amount of such a compound or a combination of such compounds that produces an effect of controlling or altering plant growth. Controlled or altered effects include all deviations from natural development, such as killing, delaying, leaf burn, albinism, dwarfing, etc. The term "plant" refers to all tangible parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, culms, leaves, and fruits. The term "site" is intended to include soil, seeds, and seedlings, along with established vegetation, and includes not only areas where weeds may have grown but also areas where weeds have not yet appeared, and also areas where useful plant crops are planted. "Planted area" includes land on which crop plants have already grown, and land intended for planting such crop plants. The term "weed," as used herein, means any unwanted plant, and therefore includes not only the important agronomic weeds described below but also free-growing crop plants.

[0110] Useful plant crops that may use the compositions according to the invention include, but are not limited to, perennial crops such as citrus fruits, grapevines, nuts, oil palms, olives, pome fruits, stone fruits and rubber, and annual arable crops such as cereals (such as barley and wheat), cotton, rapeseed, corn, rice, soybeans, sugar beets, sugarcane, sunflowers, ornamental plants, switchgrass, turf and vegetables, especially cereals, corn and soybeans.

[0111] The grasses and weeds to be controlled can be monocotyledonous species, such as *Agrostis*, *Alopecurus*, *Oat*, *Gnaphalium*, *Brassica*, *Tribulus*, *Sedge*, *Digitaria*, *Barnyardgrass*, *Wild Millet*, *Lolium*, *Lysimachia*, *Sorghum*, *Poa*, *Eriocaulon*, *Sagittaria*, *Scirpus*, *Setaria*, *Rhodomyrtus tomentosa*, and *Sorghum*, or dicotyledonous species, such as *Hemp*, *Amaranthus*, *Chenopodium*, *Chrysanthemum*, *Euphorbia*, *Gnaphalium*, *Ipomoea*, *Kochia*, *Tropaeolum*, *Polygonum*, *Rhodomyrtus tomentosa*, *Sinapis*, *Solanum*, *Stellaria*, *Stellaria*, *Veronica*, *Viola*, and *Xanthium*.

[0112] The compounds of this invention can exhibit tolerance to important crops, including but not limited to alfalfa, barley, cotton, wheat, rapeseed, sugar beets, corn, sorghum, soybean, rice, oats, peanuts, vegetables, tomatoes, potatoes, perennial crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, bananas, plantain, pineapple, hops, tea, and forestry such as eucalyptus and conifers (e.g., slash pine), as well as turfgrasses (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky bluegrass, and bermudagrass).

[0113] If desired, the compounds according to the invention having the form shown in formula (I) can also be used in combination 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 their use in controlling the growth of weeds and / or unwanted plants, constitute other aspects of the invention. For the avoidance of doubt, the mixtures of the invention also include mixtures of two or more different compounds having the form shown in formula (I). Specifically, the invention also relates to a composition of the invention comprising at least one additional herbicide in addition to the compound shown in formula (I).

[0114] General Synthesis Process

[0115] In this specification, if there are any differences between chemical names and chemical structures, the structure is preferred. Generally, the compounds of this invention can be prepared by the methods described herein, unless further specified.

[0116] The testing conditions for the proton NMR spectrum of this invention are: room temperature, a Bruker 400MHz or 600MHz NMR spectrometer, with CD13, d 6 -DMSO, CD3OD or d 6- Acetone is used as the solvent (reported in ppm), with TMS (0 ppm) or chloroform (7.26 ppm) as reference standards. When multiplets are observed, the following abbreviations will be used: s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet), br (broadened), dd (doublet of doublets), dt (doublet of triplets). The coupling constant is expressed in Hertz (Hz).

[0117] The mass spectrometry analysis methods used in this invention are: Agilent 1260 HPLC; Agilent 6120 ESI.

[0118] Phase A: Water (containing 0.1% formic acid); Phase B: Acetonitrile (containing 0.1% formic acid).

[0119] Gradient elution: 0-3 min, 5-100% B; 3-6 min, 100% B.

[0120] Flow rate: 0.6 mL / min.

[0121] Detection wavelength: 254nm.

[0122] MS parameters: ESI positive scan, collision-induced ionization: 70V.

[0123] Dry nitrogen: 12 L / min, atomizing gas pressure: 40 psi, gas temperature: 350 °C.

[0124] Take an appropriate amount of sample, dissolve it in 0.5 mL of methanol, inject the sample, and perform a single-stage MS full scan in positive ESI mode to obtain the quasi-molecular ion peak [M+H]. + reading.

[0125] The following abbreviations are explained throughout this invention:

[0126] DMF: N,N-dimethylformamide, dimethylformamide

[0127] EtOAc: Ethyl acetate

[0128] PE or Petroleum ether: petroleum ether

[0129] DMSO: Dimethyl sulfoxide

[0130] The following synthesis schemes and Examples 1-27 are used to further illustrate the content of the present invention.

[0131] Synthesis Scheme 1

[0132]

[0133] The target compound shown in formula (I) can be prepared by synthetic scheme one. The compound shown in formula (A) reacts with (4-chloro-2-fluoro-3-methoxyphenyl)boronic acid to give the compound shown in formula (B), and then reacts the compound shown in formula (B) with hydrazine hydrate to give the compound shown in formula (C). The compound shown in formula (C) undergoes cyclization and then a substitution reaction to give the target compound shown in formula (I).

[0134] Among them, R 1 and R 2 It has the meaning described in this invention. Example

[0135] Example 1: Synthesis of 5-(4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridin-2-yl)-1,3,4-oxadiazol-2-(3H)-one

[0136]

[0137] Step 1: Synthesis of methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridinecarboxylate

[0138]

[0139] Methyl 4-amino-3,6-dichloropyridinecarboxylate (5.00 g, 22.6 mmol) was added to a mixed solution of dioxane (40 mL) and water (10 mL). Potassium fluoride (3.94 g, 67.9 mmol) and (4-chloro-2-fluoro-3-methoxyphenyl)boronic acid (6.01 g, 29.4 mmol) were added to the system at room temperature. Then, under nitrogen protection, palladium dichloride bis(triphenylphosphine) chloride (0.79 g, 1.13 mmol) was added to the system. The mixture was heated to 100 °C and reacted at 100 °C for 16 h. After the reaction was complete, the mixture was cooled to room temperature, and water (50 mL) was added. The mixture was extracted with ethyl acetate (50 mL × 2). The organic phases were combined, and the solvent was removed under reduced pressure. The residue was purified by column chromatography (eluent: PE / EtOAc (v / v) = 5 / 1) to give 4.00 g of a white solid product, yield: 51.2%.

[0140] MS-ESI: m / z 345.0 [M+H] + .

[0141] Step 2: Synthesis of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridinecarboxyhydrazide

[0142]

[0143] Methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridinecarboxylate (5.00 g, 14.50 mmol) was dissolved in anhydrous methanol (75 mL), and then hydrazine hydrate (3.63 g, 72.40 mmol) was added to the mixture. The mixture was heated to 80 °C and stirred for 24 h. After the reaction was completed, a solid precipitated out. The mixture was cooled to room temperature and stirred for 2 h. After filtration under reduced pressure and drying, 4.50 g of a white solid product was obtained, with a yield of 90.0%.

[0144] MS-ESI: m / z 345.0 [M+H] + .

[0145] Step 3: Synthesis of 5-(4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridin-2-yl)-1,3,4-oxadiazol-2-(3H)-one

[0146]

[0147] 4-Amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridinecarboxylhydrazine (500 mg, 1.45 mmol) was added to water (10 mL). Then, triphosgene dissolved in toluene (447 mg, 1.45 mmol, 5 mL) was added dropwise to the mixture under ice bath conditions. After the addition was complete, the mixture was transferred to room temperature and stirred for 1 h. The pH was then adjusted to 8-9 with sodium hydroxide solution (2 mol / L), water (10 mL) was added, and the mixture was extracted with ethyl acetate (20 mL × 2). The organic phases were combined, the solvent was removed under reduced pressure, and the residue was purified by column chromatography (eluent: PE / EtOAc (v / v) = 1 / 1) to give 0.30 g of white solid product, yield: 55.8%.

[0148] MS-ESI: m / z 371.0 [M+H] + .

[0149] 1 H NMR (400MHz, DMSO-d) 6 )δ12.77(s,1H),8.02(t,J=8.4Hz,1H),7.43(d,J=8.5Hz,1H),7.38(s,1H),7.01(s,2H),3.94(s,3H).

[0150] Example 2: Synthesis of 3-allyl-5-(4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridin-2-yl)-1,3,4-oxadiazol-2-(3H)-one

[0151]

[0152] 5-(4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridin-2-yl)-1,3,4-oxadiazol-2-(3H)-one (200 mg, 0.54 mmol) was dissolved in DMF (10 mL). Sodium hydride (24 mg, 0.59 mmol, 60%) was added to the reaction flask at room temperature and the mixture was reacted at room temperature for 1 h. Then, 3-bromopropene (78 mg, 0.65 mmol) was added dropwise to the mixture. After the addition was complete, the mixture was reacted overnight at room temperature. After the reaction was completed, water (20 mL) was added, and the mixture was extracted with ethyl acetate (20 mL × 2). The organic phases were combined, the solvent was removed under reduced pressure, and the residue was purified by column chromatography (eluent: PE / EtOAc (v / v) = 2 / 1) to give 140 mg of white solid, yield: 63.2%.

[0153] MS-ESI: m / z 411.0 [M+H] + .

[0154] 1 H NMR (400MHz, DMSO-d) 6 )δ7.66(t,J=8.2Hz,1H),7.45(dd,J=8.7,1.2Hz,1H),7.31(d,J=1.2Hz,1H),6.96(s,2H),5 .98(ddd,J=22.5,10.6,5.4Hz,1H),5.35-5.24(m,2H),4.44(d,J=5.4Hz,2H),3.94(s,3H).

[0155] Example 3: Synthesis of 5-(4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridin-2-yl)-3-(2,2-difluoroethyl)-1,3,4-oxadiazol-2-(3H)-one

[0156]

[0157] 5-(4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridin-2-yl)-1,3,4-oxadiazol-2-(3H)-one (300 mg, 0.81 mmol) was dissolved in DMF (10 mL). Sodium hydride (36 mg, 0.90 mmol, 60%) was added to the reaction flask at room temperature and reacted for 1 h at room temperature. Then, 1,1-difluoro-2-iodoethane (186 mg, 0.97 mmol) was added dropwise to the mixture. After the addition was complete, the mixture was reacted overnight at room temperature. After the reaction was completed, water (20 mL) was added, and the mixture was extracted with ethyl acetate (20 mL × 2). The organic phases were combined, the solvent was removed under reduced pressure, and the mixture was purified by column chromatography (eluent: PE / EtOAc (v / v) = 2 / 1) to give 120 mg of white solid. Yield: 34.1%.

[0158] MS-ESI: m / z 435.0 [M+H] + .

[0159] 1 H NMR (400MHz, DMSO-d) 6 )δ7.66(t,J=8.3Hz,1H),7.46(dd,J=8.7,1.5Hz,1H),7.32(d,J=1.4Hz,1H),6.99 (s,2H),6.40(tt,J=54.2,3.2Hz,1H),4.31(td,J=15.4,3.1Hz,2H),3.94(s,3H).

[0160] Referring to the synthesis methods in Examples 1-3, and using the corresponding raw materials and conditions, the target compounds in Table 1 can be obtained.

[0161] Table 1

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170] Biological Examples

[0171] Weigh a certain amount of the technical grade pesticide using an analytical balance (0.0001 g), dissolve it in an appropriate amount of DMF, and then dilute it with a certain volume of distilled water containing 1‰ Tween-80 emulsifier. Take flowerpots with a length and width of 7.0 cm, fill them with soil to 3 / 4 full, directly sow the pre-treated weed target seeds, and cover with about 0.5 cm of soil. When the seedlings reach the appropriate age, spray them. After application, allow the pesticide solution to air dry naturally, then transfer them to a greenhouse for conventional cultivation. Investigate the activity (%) against weeds after 21 days; where 0 indicates no damage or normal growth, and 100 indicates at least complete death of the above-ground parts. The experimental results are shown in Table 2.

[0172] Table 2. Post-emergence herbicidal activity of the compounds of this invention (150g ai / ha)

[0173]

[0174]

[0175] Table 2 shows that the compounds of this invention exhibit excellent herbicidal activity against garland chrysanthemum at a concentration of 150 g ai / ha.

[0176] Crop safety testing

[0177] Weigh a certain mass of the technical grade pesticide using an analytical balance (0.0001 g), dissolve it in an appropriate amount of DMF, and then dilute it with a certain volume of distilled water containing 1‰ Tween-80 emulsifier. Take flowerpots with a length and width of 7.0 cm, fill them with soil to 3 / 4 full, directly sow the pre-treated crop seeds, and cover with about 0.5 cm of soil. When the seedlings reach the appropriate age, spray them with the pesticide. After the pesticide solution has air-dried naturally, transplant them into a greenhouse for conventional cultivation. Investigate the phytotoxicity (%) on the crops after 21 days; where 0 indicates no damage or normal growth, and 100 indicates at least complete death of the above-ground parts. The experimental results are shown in Table 3.

[0178] Chloropyridine ester is a compound described in patent WO2007082098 and is prepared according to the method described therein. The structure of chloropyridine ester is as follows:

[0179] Fluorochloropyridine ester is a compound described in patent WO2012103042 and prepared according to the method described therein. The structure of fluorochloropyridine ester is as follows:

[0180] Table 3. Post-emergence crop safety of the compounds of this invention (150g ai / ha)

[0181] Example wheat corn Example 2 0 0 Example 8 0 0 Example 11 0 0 Example 26 0 0 Fluorochloropyridine ester 10 60 chloropyridine ester 5 40

[0182] Table 3 shows that the compounds of the present invention exhibit zero phytotoxicity to both wheat and corn at 150 g ai / ha, indicating that the compounds of the present invention have excellent safety for wheat and corn.

[0183] The compounds of this invention exhibit excellent control efficacy against the tested broadleaf weed *Abutilon theophrasti*, and their safety against wheat and corn is significantly superior to that of commercially available comparative compounds.

[0184] The compounds of this invention have excellent control effects on weeds (such as garland chrysanthemum) and excellent safety against wheat and corn, showing great promise for application.

Claims

1. A compound, characterized in that, It is a compound or salt as shown in formula (I): Where: R 1 For hydrogen, C 1-4 Alkyl, Halogenated C 1-4 Alkyl, C 2-6 alkenyl, C 2-4 alkynyl, cyclopropylmethyl or benzyl; R 2 It is either hydrogen or fluorine.

2. The compound according to claim 1, wherein... R 1 It is hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH(CH3)2, -CHF2, -CH2CHF2, -CH2CH2CHF2, -CF3, -CH2CF3, -CH2CH2CF3, -CH=CH2, -CH2CH=CH2, -CH2CH2CH=CH2, -CH2C(CH3)=CH2, -CH2CH=C(CH3)2, -C≡CH, -C≡CCH3, -CH2-C≡CH, -CH2-C≡CCH3, -CH2CH2-C≡CH, cyclopropylmethyl or benzyl.

3. The compound according to claim 2, wherein... R 1 It is hydrogen or has the following substructure:

4. The compound according to claim 1, characterized in that, It is a compound or a salt thereof having one of the following structures:

5. A composition comprising the compound of any one of claims 1-4; optionally comprising at least one pesticide-acceptable adjuvant.

6. The use of the compound according to any one of claims 1-4 or the composition according to claim 5 as a herbicide in agriculture.

7. A method for controlling the growth of weeds in useful plants, comprising applying an effective amount of the compound of any one of claims 1-4 or the composition of claim 5 to the location of the weeds.

8. The method according to claim 7, wherein the weed is velvetleaf; and the useful plants are wheat and corn.

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