CN112939953B - Benzamide compound and application thereof as herbicide - Google Patents

Benzamide compound and application thereof as herbicide Download PDF

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CN112939953B
CN112939953B CN201911259251.0A CN201911259251A CN112939953B CN 112939953 B CN112939953 B CN 112939953B CN 201911259251 A CN201911259251 A CN 201911259251A CN 112939953 B CN112939953 B CN 112939953B
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alkyl
compound
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alkoxy
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CN112939953A (en
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英君伍
秦博
马宏娟
杨辉斌
商璐
王刚
孙冰
陈霖
张帆
梁爽
王明欣
李斌
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Jiangsu Yangnong Chemical Co Ltd
Shenyang Sinochem Agrochemicals R&D Co Ltd
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Jiangsu Yangnong Chemical Co Ltd
Shenyang Sinochem Agrochemicals R&D Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Abstract

The invention discloses a benzamide compound and application thereof as herbicide, wherein the compound is shown in a general formula (I):

Description

Benzamide compound and application thereof as herbicide
Technical Field
The invention belongs to the field of herbicides. In particular to a benzamide compound and application thereof as herbicide.
Background
Due to succession and transition of weed populations and generation and rapid development of drug resistance to chemical pesticides, people continuously strengthen awareness of ecological environment protection, awareness of chemical pesticide pollution and pesticide influence on non-target organisms and importance of homing problems in pesticide ecological environments are continuously improved. With the progressive decrease in the area of cultivated land, the increasing population and the increasing demand for foodstuffs, people are forced to rapidly develop agricultural production technologies, improve and perfect cultivation systems, and there is a continuing need to invent new and improved herbicidal compounds and compositions.
CN108290846a reports that certain benzamide compounds have herbicidal activity, such as compounds 1-28 (KC 1) and 1-9 (KC 2) among them:
benzamide compounds as shown in the present invention are not disclosed.
Disclosure of Invention
The invention aims to provide a benzamide compound with novel structure and safety to crops and application of the benzamide compound as herbicide.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a benzamide compound is shown as a general formula I:
Wherein:
X 1 and X 3 may be the same or different and are selected from the group consisting of hydrogen, cyano, nitro, halogen, C 1-C6 alkylsulfonyl, C 1-C6 haloalkylsulfonyl, C 1-C6 alkylsulfinyl, C 1-C6 haloalkylsulfinyl, C 1-C6 alkylthio, C 1-C6 haloalkylthio, C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkoxy, C 1-C6 haloalkoxy, C 1-C3 alkoxy C 1-C3 alkyl, C 1-C6 alkoxy C 1-C3 alkoxy, C 1-C6 alkoxy C 1-C3 alkoxy C 1-C3 alkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C3 alkyl, C 3-C6 cycloalkyl C 1-C3 alkoxy, or C 3-C6 cycloalkyloxy, respectively;
x is selected from hydrogen, cyano, nitro, halogen, C alkyl, C haloalkyl, C alkylsulfonyl, C haloalkylsulfonyl, C alkylsulfinyl, C haloalkylsulfinyl, C alkylthio, C haloalkylthio, C cycloalkyl, C cycloalkylC alkyl, C halocycloalkylC alkyl, Y oxo C alkyl, Y thioC alkyl, Y sulfoxyC alkyl, Y aminoalkyl-CH=alkyl-O-N=CY, or phenyl which is unsubstituted or substituted with 1 to 5 substituents selected from nitro, halogen, C alkyl, C haloalkyl, C alkoxy, C haloalkoxy, C cycloalkyl or C cycloalkoxy, a 5 to 7 membered alicyclic ring containing 1 to 4 heteroatoms, or a 5 to 7 membered aromatic heterocyclic ring containing 1 to 4 heteroatoms;
y 1、Y2 is independently selected from C 1-C6 alkyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C6 alkyl, C 1-C6 alkoxyC 1-C6 alkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, or phenyl unsubstituted or substituted with 1-5 substituents selected from nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkoxy, C 1-C6 haloalkoxy, C 3-C6 cycloalkyl, or C 3-C6 cycloalkoxy, a 5-7 membered alicyclic ring containing 1-4 heteroatoms, a 5-7 membered alicyclic C 1-C6 alkyl containing 1-4 heteroatoms, or a 5-7 membered aromatic C 1-C6 alkyl containing 1-4 heteroatoms;
Q is a 5-6 membered heteroaromatic ring containing 1-4 heteroatoms, unsubstituted or substituted with 1-4 identical or different R substituents, which heteroaromatic ring does not contain a pyrazole or pyridine ring;
R is selected from halogen, nitro, cyano, C 1-C6 alkyl, C 1-C6 alkoxy, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 halocycloalkyl, C 3-C6 cycloalkylC 1-C3 alkyl, C 2-C6 alkenyl, C 2-C6 haloalkenyl, C 2-C6 alkynyl, C 2-C6 haloalkynyl, C 1-C6 alkylsulfonyl, C 1-C6 haloalkylsulfonyl, C 1-C6 alkoxyC 1-C3 alkyl, C 1-C6 haloalkoxy C 1-C3 alkyl, C 1-C6 alkoxyC 1-C3 alkoxyC 1-C3 alkyl, C 1-C6 alkylthio C 1-C3 alkyl, C 1-C6 haloalkylthio C 1-C3 alkyl, C 1-C6 alkylsulfoxide C 1-C3 alkyl, C 1-C6 haloalkylsulfanyl C 1-C3 alkyl, C 1-C6 alkylsulfonyl C 1-C3 alkyl, C 1-C6 haloalkylsulfonyl C 1-C3 alkyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents selected from cyano, nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 3-C6, C 1-C6 alkoxy or C 1-C6 haloalkoxy.
The preferred compounds, in formula I:
X 1 and X 3 may be the same or different and are each selected from cyano, nitro, halogen, C 1-C6 alkylsulfonyl, C 1-C6 haloalkylsulfonyl, C 1-C6 alkylsulfinyl, C 1-C6 haloalkylsulfinyl, C 1-C6 alkylthio, C 1-C6 haloalkylthio, C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C3 alkoxy, C 1-C3 haloalkoxy, C 1-C3 alkoxy C 1-C3 alkyl, C 1-C6 alkoxy C 1-C3 alkoxy, C 1-C6 alkoxy C 1-C3 alkoxy C 1-C3 alkyl, C 3-C6 cycloalkyl or C 3-C6 cycloalkyloxy;
X is selected from hydrogen, halogen, C alkyl, C haloalkyl, C alkylsulfonyl, C haloalkylsulfonyl, C alkylsulfinyl, C haloalkylsulfanyl, C haloalkylthio, C cycloalkyl, C cycloalkylC alkyl, C halocycloalkylC alkyl, Y oxo C alkyl, Y thioC alkyl, Y sulfoxyC alkyl, Y aminoalkylC alkyl-CH=alkyl-O-N=CY, or phenyl which is unsubstituted or substituted with 1 to 5 substituents selected from nitro, halogen, C alkyl, C haloalkyl, C alkoxy, C haloalkoxy, C cycloalkyl or C cycloalkoxy, a 5 to 7 membered alicyclic ring containing 1 to 4 heteroatoms, or a 5 to 7 membered aromatic heterocyclic ring containing 1 to 4 heteroatoms;
y 1、Y2 is independently selected from C 1-C6 alkyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C6 alkyl, C 1-C6 alkoxyC 1-C6 alkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, or phenyl unsubstituted or substituted with 1-5 substituents selected from nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkoxy, C 1-C6 haloalkoxy, C 3-C6 cycloalkyl, or C 3-C6 cycloalkoxy, a 5-7 membered alicyclic ring containing 1-4 heteroatoms, a 5-7 membered alicyclic C 1-C6 alkyl containing 1-4 heteroatoms, or a 5-7 membered aromatic C 1-C6 alkyl containing 1-4 heteroatoms;
Q is a 5-6 membered heteroaromatic ring containing 1-4 heteroatoms, unsubstituted or substituted with 1-4 identical or different R substituents, which heteroaromatic ring does not contain a pyrazole or pyridine ring;
R is selected from halogen, nitro, cyano, C 1-C6 alkyl, C 1-C6 alkoxy, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 halocycloalkyl, C 3-C6 cycloalkyl C 1-C3 alkyl, C 2-C6 alkenyl, C 2-C6 haloalkenyl, C 2-C6 alkynyl, C 2-C6 haloalkynyl, C 1-C6 alkylsulfonyl, C 1-C6 alkoxy C 1-C3 alkyl, C 1-C6 haloalkoxy C 1-C3 alkyl, C 1-C6 alkylsulfonyl C 1-C3 alkyl, C 1-C6 haloalkylsulfonyl C 1-C3 alkyl, or phenyl which is unsubstituted or substituted with 1 to 5 substituents selected from cyano, nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkoxy, or C 1-C6 haloalkoxy.
The further preferred compounds are of the formula I:
X 1 and X 3 may be the same or different and are each selected from nitro, halogen, C 1-C6 alkylsulfonyl, C 1-C6 haloalkylsulfonyl, C 1-C6 alkylsulfinyl, C 1-C6 haloalkylsulfinyl, C 1-C6 alkylthio, C 1-C6 haloalkylthio, C 1-C6 alkyl or C 1-C6 haloalkyl;
x is selected from hydrogen, halogen, C alkyl, C haloalkyl, C alkylsulfonyl, C haloalkylsulfonyl, C alkylsulfinyl, C haloalkylsulfinyl, C alkylthio, C haloalkylthio, C cycloalkyl, C cycloalkylC alkyl, C halocycloalkylC alkyl, Y oxo C alkyl, Y thioC alkyl, Y sulfoxyC alkyl, Y aminoC alkyl, COOY alkyl-CH=alkyl-O-N=CY, or phenyl which is unsubstituted or substituted with 1 to 5 substituents selected from nitro, halogen, C alkyl, C haloalkyl, C alkoxy, C haloalkoxy, C cycloalkyl or C cycloalkoxy, a 5 to 7 membered alicyclic ring containing 1 to 4 heteroatoms, or a 5 to 7 membered aromatic heterocyclic ring containing 1 to 4 heteroatoms;
Y 1、Y2 is independently selected from C 1-C6 alkyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C6 alkyl, C 1-C6 alkoxyC 1-C6 alkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, or phenyl which is unsubstituted or substituted with 1 to 5 substituents selected from nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkoxy, C 1-C6 haloalkoxy, C 3-C6 cycloalkyl or C 3-C6 cycloalkoxy, 5-7 membered alicyclic ring containing 1 to 4 heteroatoms, 5-7 membered alicyclic C 1-C6 alkyl containing 1 to 4 heteroatoms, 5-7 membered aromatic heterocyclic C 1-C6 alkyl containing 1 to 4 heteroatoms;
q is selected from the following groups:
n is 0-4;
R is selected from halogen, nitro, cyano, C 1-C3 alkyl, C 1-C3 haloalkyl, C 3-C6 cycloalkyl, C 1-C3 alkylsulfonyl, C 1-C6 alkoxyC 1-C3 alkyl or C 1-C6 alkylsulfonyl C 1-C3 alkyl.
In the definition of compounds of the general formula I given above, the terms used in the collection are defined as follows:
Alkyl refers to straight or branched chain forms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and the like. Cycloalkyl is meant to include groups in the form of cyclic chains such as cyclopropyl, methylcyclopropyl, cyclopropylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Alkenyl refers to straight or branched alkenyl groups such as 1-propenyl, 2-propenyl, butenyl, pentenyl, hexenyl and the like. Alkynyl refers to straight or branched chain alkynyl groups such as 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl and the like. Alkoxy refers to a group having an oxygen atom attached to the end of the alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, and the like. By 5-7 membered alicyclic ring containing 1-4 hetero atoms is meant a 5-7 membered heterocyclic ring containing 1-4 hetero atoms without aromatic character, such as tetrahydrofuran, imidazolinone, caprolactam, etc. The 5-7 membered aromatic heterocycle having 1 to 4 hetero atoms means a 5-7 membered heterocyclic compound having 1 to 4 hetero atoms and having an aromatic character, such as furan, thiophene, pyrazole, pyridine, etc.
The compounds of the general formula I according to the invention can be prepared by the following process:
The method comprises the following steps:
the compound of the general formula II and the compound of the general formula III are reacted in a proper solvent at the temperature of minus 10 ℃ to the boiling point of the proper solvent for 0.5 to 48 hours to prepare the target compound I.
Suitable solvents are selected from dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N-dimethylformamide or dimethyl sulfoxide, and the like.
The reaction can be facilitated by adding a suitable alkali substance to the reaction system. Suitable bases are selected from organic bases such as triethylamine, N-dimethylaniline or pyridine, etc., or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide, etc.
The preparation method of the compound of the general formula II comprises the following steps:
Reacting a compound of the general formula VI (commercially available) with a compound of the general formula VII (commercially available) in a suitable base and a solvent with a suitable activator at a temperature of-10 ℃ to the boiling point of the suitable solvent for 0.5 to 48 hours to obtain a compound of the general formula II; suitable solvents are selected from petroleum ether, hexane, benzene, toluene, chlorobenzene, ethyl acetate, acetonitrile, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, and the like. Suitable activators are selected from phosgene, triphosgene, CDI, DCC, thionyl chloride, oxalyl chloride, phosphorus oxychloride or phosphorus pentachloride, etc. Suitable bases are selected from N-methylimidazole or DMAP, and the like.
The compounds of formula III can be prepared from the corresponding acids (commercially available).
The second method is as follows:
The compound of the general formula IV and the compound of the general formula V are reacted in a proper solvent at the temperature of minus 10 ℃ to the boiling point of the proper solvent for 0.5 to 48 hours to prepare the target compound I.
Suitable solvents are selected from dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N-dimethylformamide or dimethyl sulfoxide, and the like.
The reaction can be facilitated by adding a suitable alkali substance to the reaction system. Suitable bases are selected from organic bases such as triethylamine, N-dimethylaniline or pyridine, etc., or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide, etc.
The compounds of formula V may be prepared from the corresponding acids (commercially available).
The preparation of the compounds of the formula IV can be carried out by reference to the preparation of the formula II.
The compound of the general formula I has herbicidal activity and can be used for preventing and controlling various weeds in agriculture. Compared with the compounds disclosed by the prior art, the benzamide compound disclosed by the invention not only has excellent weeding activity, but also is safe for crops.
The invention also includes herbicidal compositions comprising compounds of formula I as active ingredients. The weight percentage of the active components in the weeding composition is 1-99%. The herbicidal composition also includes an agriculturally acceptable carrier.
The herbicidal composition of the present invention can be applied in the form of various formulations. The compounds of the present invention are typically formulated in a formulation dissolved or dispersed in a carrier for easier dispersion when used as herbicides. For example: these chemicals can be formulated as wettable powders or emulsifiable concentrates and the like. Thus, in these compositions, at least one liquid or solid carrier is added, and it is often necessary to add an appropriate surfactant.
The present invention also provides a method of effecting weed control which comprises applying a herbicidally effective amount of the herbicidal composition of the present invention to the weeds or to the locus where the weeds are growing or to the surface of the growth medium thereof. Preferably, the effective dosage is 1 g to 1000 g per hectare, preferably 10 g to 500 g per hectare. For certain applications, one or more other herbicides may be added to the herbicidal compositions of the present invention, thereby producing additional advantages and effects.
The compounds of the present invention may be used alone or in combination with other known pesticides, fungicides, plant growth regulators or fertilizers.
It should be understood that various changes and modifications can be made within the scope of the invention as defined in the appended claims.
The invention has the advantages that:
Compared with the known benzamide compounds, the compound of the general formula of the invention contains one benzoyl group and one heterocyclic acyl group for substitution, has novel structure, and the benzamide compound of the invention has unexpected high herbicidal activity and high herbicidal activity at lower dosage, thus not only being efficient, but also reducing the using amount of pesticides, lowering the cost and reducing the environmental pollution.
Detailed Description
The following examples and green test results are provided to further illustrate the invention and are not meant to limit the invention.
Synthesis example
Example 1, synthesis of compound 1:
(1) Synthesis of N- (1-methyl-tetrazol-5-yl) -2-methanesulfonyl-4-trifluoromethylbenzoic acid amide
2-Methanesulfonyl-4-trifluoromethylbenzoic acid (19.1 g, 71.2 mmol), 1-methyl-5-aminotetrazole (8.5 g, 85.4 mmol), 3-methylpyridine (80 g, 855 mmol), N-methylimidazole (11.7 g, 142 mmol) were added to the flask, stirred at room temperature for half an hour, cooled to 10℃in an ice water bath, thionyl chloride (13.6 g, 114 mmol) was slowly added dropwise, stirred at room temperature for 2 hours, warmed to 50℃for 2 hours, cooled to 10℃in an ice water bath, slowly added dropwise in cold water, solid was precipitated, filtered, the filter cake was washed twice with 100 ml water, and dried to give a white solid, 17.5 g, yield 70%.
(2) Synthesis of 2-furoyl chloride
2-Furanoic acid (0.64 g, 5.7 mmol) and methylene chloride (20 ml) were added to the flask, thionyl chloride (1.8 g, 14.3 mmol) was slowly added, and 1 drop of DMF was reacted at room temperature for 4 hours, and the solvent was distilled off under reduced pressure to give 0.74 g of yellow oil which was directly used in the next step.
(3) Synthesis of Compound 1
To the reaction flask was added N- (1-methyl-tetrazol-5-yl) -2-methanesulfonyl-4-trifluoromethylbenzamide (1 g, 2.8 mmol), dichloromethane (20 ml), triethylamine (0.58 g, 5.7 mmol) and a dichloromethane solution of step 2-furoyl chloride (10 ml) was added dropwise. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure, ethyl acetate (100 ml) was added to the residue, water (50 ml) was extracted by liquid-separation, the organic phase was washed with saturated brine (20 ml) in this order, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to give 0.39 g of compound 1 as a white solid with a purity of 92% and a yield of 28%.
Example 2 synthesis of compound 62:
(1) Synthesis of 2-thiophenecarboxyl chloride
2-Thiophenecarboxylic acid (0.73 g, 5.7 mmol) and toluene (20 ml) were added to the reaction flask, thionyl chloride (1.8 g, 14.3 mmol) was slowly added, and 1 drop of DMF was reacted at room temperature for 4 hours, and the solvent was distilled off under reduced pressure to obtain 0.83 g of a yellow oil which was directly used in the next step.
(2) Synthesis of Compound 62
To the reaction flask was added N- (1-methyl-tetrazol-5-yl) -2-methanesulfonyl-4-trifluoromethylbenzamide (1 g, 2.8 mmol), dichloromethane (20 ml), triethylamine (0.58 g, 5.7 mmol) and a dichloromethane solution of step 2-thiophenecarboxchloride (10 ml) was added dropwise. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure, ethyl acetate (100 ml) was added to the residue, water (50 ml) was extracted by liquid-separation, the organic phase was washed with saturated brine (20 ml) in this order, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to give 0.78 g of compound 2 as a white solid with a purity of 83% and a yield of 49%.
The compounds of formula I were obtained by substituting the starting materials during the reaction according to the preparation method described above, and are shown in Table 1.
TABLE 1 Structure and physical Properties of part of the Compounds of formula I
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1H NMR(300MHz,CDCl3) Data for a portion of the compounds are as follows:
compound 1:8.30 (s, 1H), 8.02 (d, 1H), 7.83 (d, 1H), 7.36 (s, 1H), 7.14 (d, 1H), 6.48 (d, 1H), 4.16 (s, 3H), 3.20 (s, 3H).
Compound 62:8.33 (s, 1H), 7.99 (d, 1H), 7.83 (d, 1H), 7.67 (d, 1H), 7.30 (d, 1H), 7.01 (d, 1H), 4.06 (s, 3H), 3.22 (s, 3H).
Compound 123:8.30 (s, 1H), 8.03 (d, 1H), 7.87 (d, 1H), 4.14 (s, 3H), 3.20 (s, 3H), 2.60 (s, 3H), 2.56 (s, 3H).
Compound 184:8.29 (s, 1H), 8.04 (d, 1H), 7.85 (d, 1H), 4.20 (s, 3H), 3.20 (s, 3H), 2.34 (s, 3H), 2.23 (s, 3H).
Biological measurement example
Example 3 determination of herbicidal Activity
Sowing broadleaf weeds (zinnia, abutilon) or grassy weeds (green bristlegrass and barnyard grass) seeds into paper cups with 7cm diameter and containing nutrient soil, covering 1cm after sowing, compacting, watering, culturing in a greenhouse according to a conventional method, and carrying out stem and leaf spraying treatment after 2-3 leaf periods of weeds.
After the raw material is dissolved in acetone, the solution to be tested with the required concentration is prepared by using 1 per mill of Tween 80 to stand tap water according to the test requirement. According to the test design dose, spraying treatment (spraying pressure 1.95kg/cm 2, spraying amount 500L/hm 2, track speed 1.48 km/h) was performed on a track type crop sprayer (manufactured by British ENGINEER RESEARCH Ltd. Design). The test was repeated 3 times. After the test materials are treated, the test materials are placed in an operation hall, after the liquid medicine is naturally dried in the shade, the test materials are placed in a greenhouse for management according to a conventional method, the reaction condition of weeds to the chemical agents is observed and recorded, after the test materials are treated, the control effect of the test materials to the weeds is visually detected at regular intervals, the test materials are expressed by 0-100%, and 0 represents no control effect and 100 represents complete killing.
The test results show that the compound of the general formula I has higher control effect on broadleaf weeds and grassy weeds. Some tested compounds, such as compound 1,62, 123, 184, all had better control over zinnia, abutilon, setaria and barnyard grass at 600g a.i./hm 2, with control over greater than 90%.
According to the test method, partial compounds of the general formula I, KC1 and KC2 are selected for performing an activity test of preventing and killing off the zinnia, and the results are shown in Table 2.
Table 2: partial compound of general formula I and control compound KC1, KC2 for preventing and killing off zinnia (post-emergence, preventing effect%)
According to the test method, partial compounds with the general formula I, KC1 and KC2 are selected for an activity test of preventing and killing abutilon, and the results are shown in Table 3.
Table 3: partial compound of general formula I and control compound KC1, KC2 for preventing and killing abutilon activity (post-emergence, preventing effect%)
According to the test method, part of compounds of the general formula I, KC1 and KC2 are selected for carrying out an activity test of preventing and killing barnyard grass, and the results are shown in Table 4.
Table 4: part of the compounds of the general formula I and the control compounds KC1 and KC2 prevent and remove barnyard grass activity (post-emergence, control effect%)
According to the test method, partial compounds of the general formula I, KC1 and KC2 are selected for activity test of preventing and killing off green bristlegrass, and the results are shown in Table 5.
Table 5: partial compound of general formula I and control compounds KC1 and KC2 prevent and kill off green bristlegrass activity (post-emergence, control effect%)
Example 4 corn safety test
Quantitative corn seeds are sown in paper cups with the diameter of 7cm and containing nutrient soil, the soil is covered for 1cm after sowing, and the corn seeds are pressed and sprayed with water and then are cultured in a greenhouse according to a conventional method. When corn grows to 3 leaves, selecting a crawler-type crop sprayer (ENGINEER RESEARCH Ltd. Design production in UK) for stem and leaf spraying treatment (spraying pressure is 1.95kg/cm 2, spraying liquid amount is 50mL/m 2, crawler speed is 30cm/s, nozzle is fan-shaped nozzle), placing the treated corn in an operation hall, and after the liquid medicine is naturally air-dried, placing in a greenhouse for conventional management. After the treatment, the corn was observed periodically for the response to the test compound, and visual inspection was performed 4 weeks after the treatment, with the inhibition rates being various degrees of injury compared to the control, expressed as 0 to 100%, with "0" representing no injury and "100%" representing complete death.
A parallel comparison test of corn safety was performed for compound 1 of formula I with KC2, and the results are shown in Table 6.
Table 6: mid-differentiation compounds of formula I are safe for maize (post-emergence, percent injury)
The compound of the general formula has herbicidal activity and can be used for preventing and controlling various weeds in agriculture. Meanwhile, the benzamide compound provided by the invention not only has excellent herbicidal activity, but also is safe to crops.

Claims (5)

1. A benzamide compound, characterized in that: the compound is shown in a general formula I:
Wherein:
x 1 is selected from C 1-C6 alkylsulfonyl;
X 3 is selected from C 1-C6 haloalkyl;
x 2 is selected from hydrogen; q is selected from the following groups:
n is 0-2;
R is selected from C 1-C3 alkyl.
2. A compound according to claim 1, wherein the compound of formula I is selected from:
3. Use of a compound of the general formula I according to claim 1 for controlling weeds.
4. A herbicidal composition characterized in that: the weeding composition is an active substance and an agriculturally acceptable carrier, the active component is a compound of the general formula I as described in claim 1, and the weight percentage of the active component in the composition is 1-99%.
5. A method of controlling weeds in a herbicidal composition according to claim 4, wherein: a herbicidal composition according to claim 4 in a herbicidally effective amount applied to weeds or to a growth medium or locus of weeds.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102464630A (en) * 2010-11-19 2012-05-23 中国中化股份有限公司 Nitrogen heterocyclic substituent-containing benzoyl compound and application thereof
WO2014126070A1 (en) * 2013-02-15 2014-08-21 石原産業株式会社 Triazinone carboxamide compound or salt thereof
CN108290846A (en) * 2015-09-28 2018-07-17 拜耳作物科学股份公司 Acylated N- (1,2,5- oxadiazole -3- bases) -, N- (1,3,4- oxadiazole -2- bases) -, N- (tetrazolium -5- bases)-and N- (triazole -5- bases)-aryl carboxylic acid amides and its purposes as herbicide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102464630A (en) * 2010-11-19 2012-05-23 中国中化股份有限公司 Nitrogen heterocyclic substituent-containing benzoyl compound and application thereof
WO2014126070A1 (en) * 2013-02-15 2014-08-21 石原産業株式会社 Triazinone carboxamide compound or salt thereof
CN108290846A (en) * 2015-09-28 2018-07-17 拜耳作物科学股份公司 Acylated N- (1,2,5- oxadiazole -3- bases) -, N- (1,3,4- oxadiazole -2- bases) -, N- (tetrazolium -5- bases)-and N- (triazole -5- bases)-aryl carboxylic acid amides and its purposes as herbicide

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