CN115701430A

CN115701430A - Isoxazoline-containing phenylpyridine compound and application thereof

Info

Publication number: CN115701430A
Application number: CN202110870040.1A
Authority: CN
Inventors: 请求不公布姓名
Original assignee: Shenyang Xiyuanfeng Biotechnology Co ltd
Current assignee: Shenyang Xiyuanfeng Biotechnology Co ltd
Priority date: 2021-08-02
Filing date: 2021-08-02
Publication date: 2023-02-10

Abstract

The invention belongs to the field of agricultural herbicides, and particularly relates to a substituted phenylisoxazoline compound or a salt thereof. The compound has good herbicidal activity, can effectively control weeds such as cockspur grass, green bristlegrass herb, sedge heterotype, large crabgrass, piemarker, zinnia elegans and the like, has good herbicidal effect under low dosage, and can be used as herbicide in agriculture.

Description

Isoxazoline-containing phenylpyridine compound and application thereof

Technical Field

The invention belongs to the field of agricultural herbicides, and relates to a substituted phenyl isoxazoline compound and application thereof.

Background

For substituted biaryl benzenesulfonamide compounds, many patents are reported, such as WO9842700, WO2001070736, WO2006065646, WO20081224614, WO2009148052, WO2009103440, FR2727413, FR2749584, JP61050975, and the like, and are mainly applied to the research of medicines.

US5783522 mentions that 2-phenylpyridine compounds have certain herbicidal activity, and WO2004056785 discloses benzoxazole compounds having certain herbicidal activity. However, the herbicidal action of these known compounds on weeds is not always entirely satisfactory. The compounds of the invention are distinguished from the prior art by a significant difference and all have good herbicidal activity.

Disclosure of Invention

The object of the present invention is to provide novel herbicidal compounds which have an excellent herbicidal activity compared with the herbicidal compounds provided in the prior art and can be used for the targeted control of harmful plants.

In order to achieve the purpose, the invention adopts the technical scheme that:

the invention provides a substituted phenyl isoxazoline compound or a salt thereof, which is shown as a general formula (I):

in the formula:

R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ are respectively selected from hydrogen, halogen, CN, NO ₂ C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

R ₅ 、R ₆ 、R ₇ 、R ₈ are independently selected from hydrogen, halogen or C1-C4 alkyl;

R ₉ 、R ₁₀ are independently selected from hydrogen or C1-C4 alkyl;

R ₁₁ selected from hydrogen, C1-C4 alkyl or C-C4 haloalkyl;

R ₁₂ selected from CO ₂ R ₁₃ 、CONHR ₁₄ Or CH ₂ OR ₁₅ ；

R ₁₃ 、R ₁₄ Are independently selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, allyl, propargyl, C1-C4 alkoxyC 1-C3 alkyl, C1-C4 alkylcarbonyloxy C1-C4 alkyl, benzyl, furylmethyl or tetrahydrofurylmethyl;

R ₁₅ selected from C1-C4 alkylcarbonyl, C1-C4 haloalkylcarbonyl, C3-C6 cycloalkylcarbonyl, C1-C4 alkylcarbonyl or C1-C4 haloalkylsulfonyl.

Or a sodium, potassium or copper salt thereof.

The more preferred compounds of the present invention are those of the general formula (I)

R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ Are independently selected from hydrogen, halogen, C1-C4 alkyl or C1-C4 haloalkyl;

R ₅ 、R ₇ are respectively selected from hydrogen, chlorine, fluorine or methyl;

R ₆ 、R ₈ are each selected from hydrogen;

R ₉ 、R ₁₀ are respectively selected from hydrogen or methyl;

R ₁₁ selected from hydrogen, methyl, ethyl, trifluoromethyl or difluoromethyl;

R ₁₂ selected from CO ₂ R ₁₃ 、CONHR ₁₄ Or CH ₂ OR ₁₅ ；

R ₁₃ 、R ₁₄ Are each selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, trifluoroethyl, allyl, propargyl, methoxyethyl, ethoxyethyl, methylcarbonyloxyethyl or tetrahydrofurylmethyl;

R ₁₅ selected from C1-C4 alkylcarbonyl, C3-C6 cycloalkylcarbonyl or C1-C4 alkylsulfonyl.

Or a sodium or potassium salt thereof.

Further preferred compounds of the invention are those of the formula (I)

R ₅ 、R ₇ are independently selected from hydrogen, chlorine or fluorine;

R ₆ 、R ₈ are respectively selected from hydrogen;

R ₉ 、R ₁₀ are respectively selected from hydrogen or methyl;

R ₁₁ selected from hydrogen, methyl or ethyl;

R ₁₂ selected from CO ₂ R ₁₃ 、CONHR ₁₄ Or CH ₂ OR ₁₅ ；

R ₁₃ 、R ₁₄ Are each selected from methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, trifluoroethyl, allyl, propargyl, methoxyethyl, ethoxyethyl, methylcarbonyloxyethyl or tetrahydrofurylmethyl;

Or a sodium or potassium salt thereof.

The most preferred compounds of the invention are those of the formula (I)

R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ Are respectively selected from hydrogen, chlorine, fluorine, methyl or trifluoromethyl;

R ₅ 、R ₇ are respectively selected from hydrogen, chlorine or fluorine;

R ₆ 、R ₈ are each selected from hydrogen;

R ₉ 、R ₁₀ are respectively selected from hydrogen;

R ₁₁ selected from hydrogen, methyl or ethyl;

R ₁₂ selected from CO ₂ R ₁₃ 、CONHR ₁₄ Or CH ₂ OR ₁₅ ；

R ₁₃ 、R ₁₄ Are respectively selected from methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, trifluoroethyl, allyl, propargyl, methoxyethyl, ethoxyethyl, methylcarbonyloxyethyl or tetrahydrofurylmethyl;

R ₁₅ selected from C1-C4 alkylcarbonyl, cyclopropylformyl or C1-C4 alkylsulfonyl.

Or a sodium salt thereof.

In the definitions given above for compounds of the general formula (I), the collective terms used generally represent the following substituents:

halogen: refers to fluorine, chlorine, bromine or iodine. Alkyl groups: refers to straight or branched chain alkyl groups. A haloalkyl group: straight-chain or branched alkyl groups in which some or all of the hydrogen atoms are replaced by halogen atoms. Alkoxy groups: a linear or branched alkyl group attached to the structure via an oxygen atom bond. A haloalkoxy group: the hydrogen atoms of the straight-chain or branched alkoxy groups are partially or wholly substituted by halogen atoms. Alkenyl: straight or branched chain and may have at least one carbon-carbon double bond in any position. Haloalkenyl groups: the hydrogen atoms of the straight-chain or branched alkenyl group are partially or wholly substituted by halogen atoms. Alkynyl: straight or branched chain and may have at least one carbon-carbon triple bond at any position. Halogenated alkynyl group: straight or branched chain alkynylThe hydrogen atoms are partially or completely substituted by halogen atoms. Cycloalkyl groups: cyclic alkanes having three or more carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and the like. An alkylcarbonyl group: the alkyl radical being bound to the structure via a carbonyl group, e.g. CH ₃ CO-，CH ₃ CH ₂ CO-. A halogenated alkylcarbonyl group: the hydrogen atoms of the alkyl group of the alkylcarbonyl group may be partially or fully substituted by halogen atoms, e.g. CF ₃ CO-. Alkoxycarbonyl group: the alkoxy group is attached to the structure via a carbonyl group. Such as CH ₃ OCO-，CH ₃ CH ₂ OCO-. Halogenated alkoxycarbonyl group: the hydrogen atoms on the alkyl group of the alkoxycarbonyl group may be partially or completely substituted by halogen atoms. Such as ClCH ₂ CH ₂ OCO-. An alkylsulfonyl group: straight or branched alkyl via sulfonyl (-SO) ₂ -) is attached to a structure, such as a methylsulfonyl group. Haloalkylsulfinyl group: straight-chain or branched alkylsulfinyl groups in which the hydrogen atoms of the alkyl group may be partially or fully substituted by halogen atoms. Haloalkylsulfonyl group: a straight-chain or branched alkylsulfonyl group in which the hydrogen atoms of the alkyl group may be partially or wholly replaced by halogen atoms. An alkylamino group: straight or branched chain alkyl, linked to the structure via a nitrogen atom. Alkyl acylamino: such as CH ₃ CONH-,CH ₃ CH ₂ CONH-. Alkylsulfonylamino group: such as CH ₃ SO ₂ NH-,CH ₃ CH ₂ SO ₂ NH-。

Some of the compounds of the present invention can be illustrated by the specific compounds listed in the following table, but the present invention is not limited to these compounds. When the compound R ₁ ＝H、R ₂ ＝H、R ₃ ＝CF ₃ 、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、R ₉ ＝H、R ₁₀ ＝H、 R ₁₁ ＝CH ₃ Other groups are shown in Table 1, and the compounds are numbered 1.001-1.148.

TABLE 1

A compound of the general formula (I), wherein R is a compound ₁ ＝CF ₃ 、R ₂ ＝H、R ₃ ＝H、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、 R ₉ ＝H、R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The radicals correspond in turn to 1.001 to 1.148 in Table 1 and represent the compounds numbered 2.001 to 2.148.

A compound of the general formula (I), wherein R is a compound ₁ ＝H、R ₂ ＝CF ₃ 、R ₃ ＝H、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、 R ₉ ＝H、R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The radicals correspond in turn to 1.001 to 1.148 in Table 1 and represent the compounds numbered 3.001 to 3.148.

Compounds of the general formula (I), wherein R is ₁ ＝H、R ₂ ＝H、R ₃ ＝H、R ₄ ＝CF ₃ 、R ₆ ＝H、R ₈ ＝H、 R ₉ ＝H、R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The groups in turn correspond to 1.001-1.1 in table 148, numbers of the representative compounds are 4.001-4.148.

A compound of the general formula (I), wherein R is a compound ₁ ＝CH ₃ 、R ₂ ＝H、R ₃ ＝H、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、 R ₉ ＝H、R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The radicals correspond in turn to 1.001 to 1.148 in Table 1 and represent the compounds numbered 5.001 to 5.148.

A compound of the general formula (I), wherein R is a compound ₁ ＝H、R ₂ ＝CH ₃ 、R ₃ ＝H、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、 R ₉ ＝H、R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The radicals correspond in turn to 1.001 to 1.148 in Table 1 and represent the compounds numbered 6.001 to 6.148.

Compounds of the general formula (I), wherein R is ₁ ＝H、R ₂ ＝H、R ₃ ＝CH ₃ 、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、 R ₉ ＝H、R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The radicals correspond in turn to 1.001 to 1.148 in Table 1 and represent the compounds with the numbers 7.001 to 7.148.

A compound of the general formula (I), wherein R is a compound ₁ ＝H、R ₂ ＝H、R ₃ ＝H、R ₄ ＝CH ₃ 、R ₆ ＝H、R ₈ ＝H、 R ₉ ＝H、R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The radicals correspond in turn to 1.001 to 1.148 in Table 1 and represent the compounds numbered 8.001 to 8.148.

Compounds of the general formula (I), wherein R is ₁ ＝H、R ₂ ＝H、R ₃ ＝H、R ₄ ＝Cl、R ₆ ＝H、R ₈ ＝H、R ₉ ＝H、 R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The radicals correspond in turn to 1.001 to 1.148 in Table 1 and represent compounds numbered 9.001 to 9.148.

A compound of the general formula (I), wherein R is a compound ₁ ＝Cl、R ₂ ＝H、R ₃ ＝H、R ₄ ＝Cl、R ₆ ＝H、R ₈ ＝H、R ₉ ＝H、 R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The groups correspond to 1.001-1.148 in sequence in Table 1 and represent compounds numbered 10.001-10.148.

A compound of the general formula (I), wherein R is a compound ₁ ＝H、R ₂ ＝H、R ₃ ＝Cl、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、R ₉ ＝H、 R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The groups correspond to 1.001-1.148 in Table 1 in turn, and represent compounds with numbers of 10.001-10.148.

Compounds of the general formula (I), wherein R is ₁ ＝Cl、R ₂ ＝H、R ₃ ＝Cl、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、R ₉ ＝H、 R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The groups correspond in turn to 1.001 to 1.148 in Table 1, representing compounds numbered 11.001 to 11.148.

Compounds of the general formula (I), wherein R is ₁ ＝H、R ₂ ＝H、R ₃ ＝NO ₂ 、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、 R ₉ ＝H、R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The radicals correspond in turn to 1.001 to 1.148 in Table 1 and represent the compounds numbered 12.001 to 12.148.

Compounds of the general formula (I), wherein R is ₁ ＝H、R ₂ ＝H、R ₃ ＝CN、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、 R ₉ ＝H、R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The groups correspond to 1.001-1.148 in sequence in table 1 and represent the compounds with the numbers of 13.001-13.148.

Compounds of the general formula (I), wherein R is ₁ ＝Cl、R ₂ ＝H、R ₃ ＝CF ₃ 、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、 R ₉ ＝H、R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The groups correspond to 1.001-1.148 in sequence in table 1 and represent the compounds with the numbers of 14.001-14.148.

Compounds of the general formula (I), wherein R is ₁ ＝H、R ₂ ＝H、R ₃ ＝F、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、R ₉ ＝H、 R ₁₀ ＝H、R ₁₁ ＝CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The groups correspond in turn to 1.001 to 1.148 in Table 1, representing compounds numbered 15.001 to 15.148.

A compound of the general formula (I), wherein R is a compound ₁ ＝H、R ₂ ＝H、R ₃ ＝CF ₃ 、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、 R ₉ ＝H、R ₁₀ ＝H、R ₁₁ ＝H，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The radicals correspond in turn to 1.001 to 1.148 in Table 1 and represent the compounds numbered 16.001 to 16.148.

Compounds of the general formula (I), wherein R is ₁ ＝H、R ₂ ＝H、R ₃ ＝CF ₃ 、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、 R ₉ ＝H、R ₁₀ ＝H、R ₁₁ ＝CF ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The groups correspond to 1.001-1.148 in sequence in Table 1 and represent the compounds with the numbers of 17.001-17.148.

A compound of the general formula (I), wherein R is a compound ₁ ＝H、R ₂ ＝H、R ₃ ＝CF ₃ 、R ₄ ＝H、R ₆ ＝H、R ₈ ＝H、 R ₉ ＝H、R ₁₀ ＝H、R ₁₁ ＝CH ₂ CH ₃ ，R ₅ 、R ₇ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ The groups correspond in turn to 1.001 to 1.148 in table 1, representing compounds numbered 18.001 to 18.148.

The compounds of the formula (I) according to the invention can be prepared by the following processes (the radicals are as defined above, unless otherwise stated), but the invention is not restricted to these processes.

Firstly, in the presence of a transition metal catalyst, reacting a halogenated aromatic compound (VI) with an aromatic boric acid or ester (V) in an inert solvent to obtain a compound (IV):

in the formula: hal is chlorine, bromine or iodine, R ₉ And R ₁₀ Independently is hydrogen or C ₁ -C ₄ An alkyl group. The transition metal catalyst may be a palladium catalyst such as tetrakis (triphenylphosphine) -palladium (0) or the like. The solvent can be selected from inert solvents such as toluene, 1, 2-dichloroethane, or dioxane. The reaction temperature is 80-120 ℃.

The halogenated aromatic compound represented by the general formula (VI) is commercially available.

The aromatic boronic acid or ester compound of the formula (V) is partially commercially available and can also be prepared by known methods, see for example U.S. Pat. No. 5,5783522.

Compound IV is subjected to redox reaction in the presence of pyridinium chlorochromate and the like to obtain compound III, and the target compound I can be obtained from compound III by using the method described in J.Agric.food chem.2005,53,8639-8643 or WO 200609234.

The above preparation process can obtain isomer mixture of the compound of formula (I), and if pure isomer is required, the separation can be carried out by conventional method such as crystallization or chromatography.

The compound with the general formula (I) can effectively control weeds such as cockspur grass, green bristlegrass, cyperus heterophyllus, cyperus hydropiper, crabgrass, piemarker, zinnia elegans, amaranthus retroflexus, purslane, cocklebur, cassia tora and the like, has certain safety to crops such as wheat, rice, corn, soybean and cotton, and can be used as a herbicide in agriculture. The invention therefore also encompasses the use of the compounds of the general formula (I) or their salts as herbicides.

The invention also provides a weeding composition, which contains the compound of the general formula (I) or the salt thereof as an active component and an agriculturally acceptable carrier, wherein the weight percentage of the compound of the general formula (I) in the composition is 0.1-99%. The invention also relates to the use of said compositions as herbicides.

The compositions of the invention can be prepared according to conventional methods: mixing the compound of formula (I) with a carrier. The active ingredient in such compositions may comprise a single compound or a mixture of several compounds according to the invention.

The carrier in the composition of the present invention is a substance satisfying the following conditions: it is formulated with the active ingredient so as to be conveniently applied to the locus to be treated, which may be, for example, a plant, seed or soil; or to facilitate storage, transport or handling. The carrier may be a solid or liquid, including those which are normally gaseous but which have been compressed to form a liquid, and may be those which are normally used in formulating herbicidal compositions.

Suitable solid carriers include natural and synthetic clays and silicates, such as diatomaceous earth, talc, attapulgite, aluminum silicate (kaolin), montmorillonite and mica; calcium carbonate; calcium sulfate; ammonium sulfate; synthetic silica and synthetic calcium or aluminum silicates; elements such as carbon and sulfur; natural and synthetic resins such as benzofuran resins, polyvinyl chloride and styrene polymers and copolymers; solid polychlorophenol; asphalt; waxes such as beeswax, paraffin wax.

Suitable liquid carriers include water; alcohols such as isopropyl alcohol and ethyl alcohol; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexyl ketone; an ether; aromatic hydrocarbons such as benzene, toluene, xylene; petroleum fractions such as kerosene and mineral oil; chlorinated hydrocarbons such as carbon tetrachloride, perchloroethylene and trichloroethylene. In general, mixtures of these liquids are also suitable.

Herbicidal compositions are typically processed into concentrate form and are thus ready for shipment, which is diluted by the user prior to application. The presence of a small amount of surfactant carrier aids the dilution process. Thus, at least one carrier in the composition according to the invention is preferably a surfactant. For example, the composition may contain at least two carriers, at least one of which is a surfactant.

The surfactant can be an emulsifier, dispersant or wetting agent; it may be a nonionic or ionic surfactant. Examples of suitable surfactants include sodium or calcium salts of polyacrylic acid and lignosulfonic acid; condensates of fatty acids or fatty amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide. Glycol, sorbitol, sucrose or pentaerythritol fatty acid esters and condensates of these esters with ethylene oxide and/or propylene oxide; condensates of aliphatic alcohols or alkylphenols, such as p-octylphenol or p-octylcresol, with ethylene oxide and/or propylene oxide; sulfates and sulfonates of these condensation products; alkali metal or alkaline earth metal salts of sulfuric acid or sulfonic acid esters having at least 10 carbon atoms in the molecule, preferably sodium salts, for example sodium laurate sulfate, sodium secondary alkyl sulfate, sodium sulfonated castor oil, sodium alkyl aryl sulfonate, such as sodium dodecyl benzene sulfonate.

Examples of the composition of the invention are solid preparations and liquid preparations described in GB/T19378-2017, such as powder, wettable powder, water dispersible granules, missible oil, emulsion in water, suspending agent, oil suspending agent and the like. Wettable powders usually contain 25%,50% or 75% by weight of active ingredient and usually contain, in addition to the solid inert carrier, from 3 to 10% by weight of dispersing agent and, if desired, from 0 to 10% by weight of stabilizers and/or other additives such as penetrating agents or sticking agents. Dusts may generally be formed as dust concentrates having a similar composition to the wettable powders but without the dispersing agent, and may be further diluted with a solid carrier to give a composition which typically contains from 0.5 to 10% by weight of the active ingredient. Granules are typically prepared to have a size of 10 to 100 mesh (1.676-0.152 mm) and may be prepared using agglomeration or injection techniques. Granules generally contain 0.5 to 75% by weight of active ingredient and 0 to 10% by weight of additives such as stabilisers, surfactants, sustained release modifiers. So-called "flowable dry powders" consist of relatively small particles having a relatively high concentration of active ingredient. Emulsifiable concentrates usually contain, in addition to the solvent, a co-solvent, 1-50% w/V of the active ingredient, 2-20% w/V of the emulsifier and 0-20% w/V of other additives such as stabilizers, penetrants and corrosion inhibitors, as required. Suspending agents generally contain 10 to 75% by weight of active ingredient, 0.5 to 15% by weight of dispersing agent, 0.1 to 10% by weight of other additives such as antifoams, corrosion inhibitors, stabilizers, penetrants and adhesives.

Aqueous dispersions and emulsions, for example compositions obtained by diluting the wettable powders or concentrates according to the invention with water, are also included in the scope of the invention. The emulsion may be of the two types water-in-oil or oil-in-water.

By adding one or more additional herbicides to the composition, a broader spectrum of activity is achieved than with the compound of formula (I) alone. In addition, other herbicides can have a synergistic effect on the herbicidal activity of the compounds of the general formula (I).

Detailed Description

The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are only for purposes of illustration and explanation and are not intended to be limiting. (all materials used were commercially available, unless otherwise noted)

Preparation examples

EXAMPLE 1 preparation of Compound 1.004

(1) Preparation of intermediate 1.004-A

Adding 2, 3-dichloro-5-trifluoromethylpyridine, palladium carbon, potassium carbonate, triphenylphosphine and DMF (dimethyl formamide) into a three-necked bottle, heating to 80 ℃, dropwise adding a DMF solution of 4-chloro-2-fluoro-5-methylphenylboronic acid, and detecting by TLC (thin layer chromatography) dot plate. When the raw materials are not transformed, filtering the system while the raw materials are hot, removing the catalyst, adding water into the system to precipitate a product, washing a solid, and recrystallizing by using ethanol to obtain an intermediate 1.004-A.

(2) Preparation of intermediate 1.004-B

The intermediate 1.004A, PCC, etc. were added to acetonitrile in amounts of substance and refluxed for 3 hours, and the reaction was monitored by TLC. After the reaction is finished, PCC is removed through filtration, and after column chromatography, a target product, namely a light-colored solid, can be obtained.

(3) Preparation of intermediate 1.004-C

Dissolving the intermediate 1.004-B in ethanol, cooling to 0 ℃, dropwise adding a hydroxylamine hydrochloride aqueous solution while stirring, heating to room temperature for reacting for 2h, detecting by TLC, pouring the system into water after the reaction is completed to obtain a solid, and filtering to obtain a white solid.

(4) Preparation of object 1.004

Dissolving the intermediate 1.004-C in dichloromethane, cooling to 0-5 ℃, adding methyl methacrylate and triethylamine, and keeping the reaction at 0-5 ℃ for 1 hour. Washed with hydrochloric acid and saturated brine in this order, and dried over anhydrous sodium sulfate. Vacuum distillation, silica gel column purification of the crude product, and vacuum distillation to obtain the target product. ¹ H NMR(300MHz，TMS， CDCl ₃ ) δ ppm 1.30 (t, 3H), 1.71 (s, 3H), 3.34 (d, 1H), 3.89 (d, 1H), 4.27 (q, 2H), 7.36 (d, 1H), 7.38 (s, 1H), 7.82 (d, 1H), 8.41 (s, 1H), 8.86 (s, 1H). Elemental analysis results: c,52.99; h is 3.52; n,6.48 (theoretical C, 52.98H, 3.51N, 6.50.

EXAMPLE 2 preparation of Compound 1.001

Compound 1 was added.004 was dissolved in the ethanol solution, and an excess amount of an aqueous sodium hydroxide solution was added thereto, followed by stirring at room temperature for 4 hours. And after TLC monitoring reaction, pouring into water, adjusting the pH to 3 by using hydrochloric acid, filtering, drying to obtain a solid, and washing by using ether for a plurality of times to obtain the product. ¹ H NMR(300MHz，TMS，CDCl ₃ ) δ ppm 1.71 (s, 3H), 3.34 (d, 1H), 3.89 (d, 1H), 7.36 (d, 1H), 7.38 (s, 1H), 7.82 (d, 1H), 8.86 (s, 1H), 9.18 (s, 1H). Elemental analysis results: c,50.72; h is 2.75; n,6.94 (theoretical C,50.70; H, 2.75N, 6.96).

EXAMPLE 3 preparation of Compound 1.002

(1) Preparation of intermediate 1.001-A

The compound 1.001 was dissolved in dichloromethane, 3 times the amount of oxalyl chloride was added dropwise, stirred at room temperature for 4 hours, the reaction was monitored by TLC and the solvent was removed under reduced pressure to give an oil 1.001-a, which was used in the next step without purification.

(2) Preparation of object 1.002

1.001-A was dissolved in methylene chloride, a mixture of 1.5 times the amount of dehydrated alcohol and 3 times the amount of triethylamine was carefully added, the reaction was stirred at room temperature for 1 hour, and the completion of the reaction was monitored by TLC. Reducing pressure, removing solvent, and separating by column chromatography to obtain light-colored solid, i.e. the target product. ¹ H NMR(300MHz，TMS，CDCl ₃ ) δ ppm 1.71 (s, 3H), 3.39 (d, 1H), 3.60 (s, 1H), 3.90 (d, 1H), 7.36 (d, 1H), 7.38 (s, 1H), 7.82 (d, 1H), 8.41 (s, 1H), 8.86 (s, 1H). C,54.12; h is 4.10; n,9.47 (theoretical C, 54.12H, 4.09N, 9.47).

By this method, compounds 1.003-1.026 were also prepared, and characterization data are shown in the table below.

EXAMPLE 4 preparation of Compound 1.034

Dissolving intermediate 1.001-A in dichloromethaneA mixture of 1.5-fold amount of isopropylamine and 3-fold amount of triethylamine was added to the reaction flask, and the mixture was stirred at room temperature for 1 hour, followed by TLC to monitor completion of the reaction. Reducing pressure, removing solvent, and separating by column chromatography to obtain light-colored solid, i.e. the target product. ¹ H NMR(300MHz，TMS，CDCl ₃ ) δ ppm 1.18 (m, 6H), 1.71 (s, 3H), 3.39 (d, 1H), 3.90 (d, 1H), 4.05 (m, 1H), 7.36 (d, 1H), 7.38 (s, 1H), 7.82 (d, 1H), 8.41 (s, 1H), 8.86 (s, 1H). Elemental analysis results: c,54.12; h is 4.10; n,9.47 (theoretical C,54.12 h, 4.09N, 9.47.

By this method, compounds 1.027-1.052 can also be prepared, with characterization data in the tables below.

EXAMPLE 5 preparation of Compound 1.053

Intermediate 1.004-C was dissolved in DMF, warmed to 30 ℃ and 1.5 times the amount of NCS added in portions at that temperature to form a pale yellow solution, which was kept at that temperature for 1 hour. After cooling to room temperature, methylene chloride was added, followed by washing with 1N hydrochloric acid 2 times, washing with saturated brine 2 times, drying over anhydrous magnesium sulfate, suction filtration, cooling the methylene chloride solution to 0 ℃, dropwise adding a mixed solution of 1.5 times of methallyl alcohol and 3 times of triethylamine, and reacting at that temperature for 1 hour. Washed with 1N hydrochloric acid and brine in sequence, and the organic phase is dried over anhydrous magnesium sulfate, concentrated and separated by column chromatography to obtain a yellow solid. ¹ H NMR(300MHz，TMS，CDCl ₃ ) δ ppm 1.69 (s, 3H), 3.39 (d, 1H), 3.62 (s, 2H), 3.90 (d, 1H), 4.01 (s, 1H), 7.36 (d, 1H), 7.38 (s, 1H), 7.82 (d, 1H), 8.41 (s, 1H), 8.86 (s, 1H). Elemental analysis results: c,52.52; h is 3.39; n,7.21 (theoretical C, 52.52H, 3.37N, 7.21).

EXAMPLE 6 preparation of Compound 1.056

Compound 1.053 was dissolved in dichloromethane, a mixture of 1.5 times the amount of propionyl chloride and 3 times the amount of triethylamine was carefully added, the reaction was stirred at room temperature for 1 hour, and the completion of the reaction was monitored by TLC. Reducing pressure, removing solvent, and separating by column chromatography to obtain light-colored solid, i.e. the target product. ¹ H NMR(300MHz，TMS，CDCl ₃ ) δ ppm 1.21 (q, 3H), 1.69 (s, 3H), 2.65 (m, 2H), 3.39 (d, 1H), 3.60 (s, 2H), 3.90 (d, 1H), 7.36 (d, 1H), 7.38 (s, 1H), 7.82 (d, 1H), 8.41 (s, 1H), 8.86 (s, 1H). Elemental analysis results: c,52.98; h is 3.50; n,6.51 (theoretical C,52.98 h, 3.51N, 6.50.

By this method, compounds 1.054-1.074 can also be prepared, with the characterization data shown in the table below.

Other compounds were prepared according to the methods described above, and some of the compounds were characterized as shown in Table 19.

Table 19:

preparation examples

(in the formula, the active components are weighed after being folded in hundred percent, and the percentages are weight percentage)

Example 7:60% wettable powder

60% of compound 1.004 (content of 97.2%), 2% of sodium dodecyl naphthalene sulfonate, 9% of sodium lignosulfonate and kaolin, wherein the balance is 100%;

compound 1.004, sodium dodecylnaphthalenesulfonate, sodium lignosulfonate and kaolin (all solids) were mixed together and pulverized in a pulverizer until the particles reached the standard.

Example 8:35% emulsifiable concentrate

Compound 14.004 (content 98.4%) 35%, phosphorous acid 10%, ethoxylated triglyceride 15%, cyclohexanone to 100%;

the phosphorous acid is dissolved in cyclohexanone, then compound 14.004 and ethoxylated triglyceride are added to obtain a transparent solution.

Example 9:30% suspension

14.067 (96.4 percent) of compound, 30 percent of sodium dodecyl naphthalene sulfonate, 2 percent of hemicellulose, 8 percent of propylene oxide and water which are complemented to 100 percent;

compound 14.067 was pulverized together with 80% of the amount of water to be added and sodium dodecylnaphthalenesulfonate in a ball mill (1 mm beads). Hemicellulose and propylene oxide were dissolved in the remaining 20% water, and then the above components were added with stirring.

Example 10:25% aqueous emulsion

25% of compound 1.132 (content 96.2%), 4% of lauryl alcohol polyethylene glycol phosphate, 2% of ethoxylated glycerol triester, 1.5% of calcium dodecylbenzene sulfonate, 2.5% of ethylene oxide propylene oxide copolymer, 30% of cyclohexanone and alkyl aryl fraction to 100%;

compound 1.132 was dissolved in 80% of the amount of solvent to be added (cyclohexanone and alkylaryl fraction), then emulsifier (lauryl alcohol polyethylene glycol phosphate, ethoxylated triglyceride and calcium dodecylbenzene sulfonate) and dispersant (2.5 parts of ethylene oxide propylene oxide copolymer) were added and the mixture was thoroughly stirred. The mixture was pulverized in a ball mill (1 mm beads) and then the remaining 20% of the solvent was added.

Examples of biological Activity test

Example 11 indoor herbicidal Activity assay

Sowing quantitative weed seeds in paper cups with the diameter of 7cm and containing nutrient soil respectively, covering soil with the thickness of 1cm after sowing, performing compaction and water spraying, culturing in a greenhouse, and performing pretreatment on seedlings 24 hours after sowing; after seedling treatment, thinning and planting (10-20 grass weeds/cup, 2-4 broad leaf weeds/cup) after seedling emergence, spraying stem and leaf with a crop sprayer according to the experimental design dosage when the 2-3 leaf stage of the gramineous weeds and the 2 true leaf stage of the broad leaf weeds are grown (the spraying pressure is 1.95 kg/cm) ² The amount of the sprayed liquid is 50ml/m ² And the track speed is 1.48 km/h). The experiment was repeated 3 times. After the liquid medicine is naturally dried, the liquid medicine is placed in a greenhouse to be managed according to a conventional method, and the growth and development conditions of the test material are regularly observedAnd according to the actual situation, the weed control effect of the test agent is periodically checked visually after the treatment.

Grading standard of control effect: 0 is ineffective and 100% is complete killing or severe inhibition of weeds.

Part of the postemergence test results are as follows (all mass concentrations are calculated by effective components): at 1000g a.i./hm ² At the dose, the compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.013, 1.014, 1.019, 1.022, 1.025, 1.026, 1.030, 1.034, 1.053, 1.056, 1.068, 1.078, 1.082, 1.087, 1.106, 1.108, 1.112, 1.131, 1.142, 1.144, 2.004, 3.022, 4.056, 5.004, 6.004, 7.004, 8.099, 10.004, 10.032, 11.012, 12.004, 13.004, 14.004, 14.005, 14.030, 14.034, 14.056, 14.067, 15.011, 16.120, 17.004, etc., the compounds have better herbicidal activity on pennywort, such as cuckoo grass, and the like than that of cuckoo grass after the treatment, and the compounds have higher herbicidal activity on pennywort plants such as cuckoo grass.

In 200g a.i./hm ² Under the dosage, the compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.013, 1.014, 1.019, 1.022, 1.025, 1.026, 1.030, 1.034, 1.053, 1.056, 1.087, 1.106, 1.108, 1.142, 1.144, 2.004, 5.004, 6.004, 7.004, 8.099, 10.004, 10.032, 11.012, 12.004, 13.004, 14.004, 14.005, 14.030, 14.034, 14.056, 14.067, 15.011, 16.120, 17.004 and the like have high herbicidal activity on Abutilon, setaria, zinnia eleuthica, zinnia eleocharis, zinnia japonica and the like, and the effect of preventing cockspur grass is more than 70 percent.

Example 12 herbicidal Spectrum test

The compound 14.004 of the invention is subjected to a weed control spectrum test, and is compared with commercial varieties of saflufenacil and 41% glyphosate isopropylamine salt, the result is shown in the following table, and the determination method is the same as that described above.

Example 13: test for preventing and controlling weeds in field

The method is carried out in a Guangxi Nanning orange test base, and the field weeds are in a 2-4 leaf stage during the test. The manual sprayer has the liquid spraying amount of 45 kilograms per mu. After 15 days of treatment, the control effect and the total control effect on broadleaf weeds and grassy weeds were visually investigated.

The field test drug effect calculation method comprises the following steps:

the results are as follows:

compound (I)	Dosage g (a.i./ha)	Broad-leaved weed control	Preventing and controlling effect of gramineous weeds	General control effect
					14.004	300	90	85	86
Saflufenacil WG	100	45	85	65

Claims

1. A substituted phenyl isoxazoline compound or a salt thereof has a structure shown as a general formula (I):

in the formula:

R ₉ 、R ₁₀ are independently selected from hydrogen or C1-C4 alkyl;

R ₁₁ selected from hydrogen, C1-C4 alkyl or C-C4 haloalkyl;

R ₁₂ selected from CO ₂ R ₁₃ 、CONHR ₁₄ Or CH ₂ OR ₁₅ ；

R ₁₅ selected from hydrogen, C1-C4 alkylcarbonyl, C1-C4 haloalkylcarbonyl, C3-C6 cycloalkylcarbonyl, C1-C4 alkylcarbonyl or C1-C4 haloalkylsulfonyl.

Or a sodium, potassium or copper salt thereof.

2. The compound of claim 1, wherein: in the general formula (I)

R ₆ 、R ₈ are respectively selected from hydrogen;

R ₉ 、R ₁₀ are each selected from hydrogen or methyl;

R ₁₂ selected from CO ₂ R ₁₃ 、CONHR ₁₄ Or CH ₂ OR ₁₅ ；

R ₁₅ selected from hydrogen, C1-C4 alkylcarbonyl, C3-C6 cycloalkylcarbonyl or C1-C4 alkylsulfonyl.

Or a sodium or potassium salt thereof.

3. A compound according to claim 2, wherein: in the general formula (I)

R ₅ 、R ₇ are respectively selected from hydrogen, chlorine or fluorine;

R ₆ 、R ₈ are respectively selected from hydrogen;

R ₉ 、R ₁₀ are respectively selected from hydrogen or methyl;

R ₁₁ selected from hydrogen, methyl or ethyl;

R ₁₂ selected from CO ₂ R ₁₃ 、CONHR ₁₄ Or CH ₂ OR ₁₅ ；

R ₁₃ 、R ₁₄ Are respectively selected from methyl, ethyl, n-propyl, n-butyl, isopropyl,Isobutyl, tert-butyl, trifluoroethyl, allyl, propargyl, methoxyethyl, ethoxyethyl, methylcarbonyloxyethyl or tetrahydrofurylmethyl;

Or a sodium or potassium salt thereof.

4. A compound according to claim 3, wherein: in the general formula (I)

R ₅ 、R ₇ are respectively selected from hydrogen, chlorine or fluorine;

R ₆ 、R ₈ are respectively selected from hydrogen;

R ₉ 、R ₁₀ are respectively selected from hydrogen;

R ₁₁ selected from hydrogen, methyl or ethyl;

R ₁₂ selected from CO ₂ R ₁₃ 、CONHR ₁₄ Or CH ₂ OR ₁₅ ；

Or a sodium salt thereof.

5. Use of a compound of the general formula (I) or a salt thereof according to claim 1 for controlling weeds.

6. A herbicidal composition characterized by: the compound of the general formula (I) or a salt thereof according to claim 1 is used as an active ingredient, wherein the weight percentage of the active ingredient in the composition is 0.1-99%.

7. Use of the herbicidal composition according to claim 6 for controlling weeds.