CN112939958B - Condensed ring acyl compound and application thereof - Google Patents

Condensed ring acyl compound and application thereof Download PDF

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CN112939958B
CN112939958B CN201911260893.2A CN201911260893A CN112939958B CN 112939958 B CN112939958 B CN 112939958B CN 201911260893 A CN201911260893 A CN 201911260893A CN 112939958 B CN112939958 B CN 112939958B
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alkyl
compound
alkoxy
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cycloalkyl
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CN112939958A (en
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程岩
杨辉斌
马宏娟
王明欣
崔东亮
英君伍
秦博
王刚
陈霖
孙冰
梁爽
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
    • 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
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
    • 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
    • C07D409/06—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 carbon chain containing only aliphatic carbon atoms
    • 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
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention discloses a condensed ring acyl compound and application thereof, wherein the compound is shown as a general formula (I):

Description

Condensed ring acyl compound and application thereof
Technical Field
The invention belongs to the field of herbicides. In particular to a condensed ring acyl 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.
CN103282354B reports that certain benzamide compounds have herbicidal activity, for example, compound KC1:
condensed ring acyl compounds as shown in the present invention are not disclosed.
Disclosure of Invention
The invention aims to provide a condensed ring acyl compound which has a novel structure and is safe for crops and application of the condensed ring acyl compound as herbicide.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
A fused ring acyl compound, characterized in that: the compound is shown in a general formula I:
wherein:
X is selected from the group consisting of hydrogen, halogen, cyano, nitro, thiocyanato, 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, C 3-C6 cycloalkyloxy, C 3-C6 halocycloalkyl, C 3-C6 halocycloalkyl-C 1-C6 alkyl, C 2-C6 alkenyl, C 2-C6 haloalkenyl, C 2-C6 alkynyl or C 2-C6 haloalkynyl;
n represents 0,1, 2;
q is selected from the group consisting of Q1, Q2, Q3, Q4, Q5, Q6, or Q7;
R 1 is selected from hydrogen, Y, YCO, YOCO or Y sulfonyl;
y is selected from the group consisting of C alkyl, C haloalkyl, C cycloalkyl, C halocycloalkyl, C cycloalkyl-C alkyl, C halocycloalkyl-C alkyl, C alkenyl, C haloalkenyl, C alkynyl, C haloalkynyl, phenyl-C alkyl, heteroaryl-C alkyl, heterocyclylcycloalkyl, phenyl, heteroaryl or heterocyclyl, each of which hydrogen on the phenyl, heteroaryl, heterocyclyl may be substituted with one or more substituents, the substituent is selected from the group consisting of halogen, cyano, nitro, thiocyanato, C alkyl, C haloalkyl, C alkoxy, C haloalkoxy, C alkoxy-C alkyl, C alkylsulfonyl, C haloalkylsulfonyl, C alkylsulfinyl, C haloalkylsulfinyl, C alkylthio, C haloalkylthio, C alkoxy-C alkoxy, C alkoxy-C alkyl, C cycloalkyl-C alkyl, C cycloalkyl-C alkoxy, C halocycloalkyl-C alkyl, C haloalkoxy-C alkyl, heterocyclyl-C alkoxy-C alkyl, C alkenyl, C haloalkenyl, C alkynyl, C haloalkynyl, C alkenyloxy-C alkyl, C alkynyloxy-C alkyl, phenyl, heteroaryl, heterocyclyl, heteroaryl C 1-C6 alkyl or heterocyclyl C 1-C6 alkyl, each of the hydrogens on the phenyl, heteroaryl, heterocyclyl may be substituted with one or more substituents selected from halogen, cyano, nitro, C 1-C6 alkyl or C 1-C6 haloalkyl;
R 2 is selected from hydrogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C6 alkyl, C 3-C6 halocycloalkyl, C 3-C6 halocycloalkyl C 1-C6 alkyl, C 2-C6 alkenyl, C 2-C6 haloalkenyl, C 2-C6 alkynyl, C 2-C6 haloalkynyl, heterocyclyl, heteroaryl, phenyl or benzyl, optionally substituted with at least one substituent selected from: halogen, nitro, cyano, thiocyanato, C 1-C6 alkyl or C 1-C6 haloalkyl;
R 3 is selected from hydrogen, halogen, cyano, nitro, 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 alkylsulfonyl, C 1-C6 haloalkylsulfonyl, C 1-C6 alkylsulfinyl, C 1-C6 haloalkylsulfinyl, C 1-C6 alkylthio, C 1-C6 haloalkylthio, 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, C 3-C6 cycloalkyloxy, C 3-C6 halocycloalkyl, C 3-C6 halocycloalkyl C 1-C6 alkyl, C 2-C6 alkenyl, C 2-C6 haloalkenyl, C 2-C6 alkynyl or C 3-C6 haloalkynyl.
The preferred compounds, in formula I:
x is selected from halogen, cyano, nitro, thiocyanato, 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;
n represents 0,1, 2;
q is selected from the group consisting of Q1, Q2, Q3, Q4, Q5, Q6, or Q7;
R 1 is selected from hydrogen, Y, YCO, YOCO or Y sulfonyl;
y is selected from the group consisting of C alkyl, C haloalkyl, C cycloalkyl, C halocycloalkyl, C cycloalkyl-C alkyl, C halocycloalkyl-C alkyl, C alkenyl, C haloalkenyl, C alkynyl, C haloalkynyl, phenyl-C alkyl, heteroaryl-C alkyl, heterocyclylcycloalkyl, phenyl, heteroaryl or heterocyclyl, each of which hydrogen on the phenyl, heteroaryl, heterocyclyl may be substituted with one or more substituents, the substituent is selected from the group consisting of halogen, cyano, nitro, thiocyanato, C alkyl, C haloalkyl, C alkoxy, C haloalkoxy, C alkoxy-C alkyl, C alkylsulfonyl, C haloalkylsulfonyl, C alkylsulfinyl, C haloalkylsulfinyl, C alkylthio, C haloalkylthio, C alkoxy-C alkoxy, C alkoxy-C alkyl, C cycloalkyl-C alkyl, C cycloalkyl-C alkoxy, C halocycloalkyl-C alkyl, C haloalkoxy-C alkyl, heterocyclyl-C alkoxy-C alkyl, C alkenyl, C haloalkenyl, C alkynyl, C haloalkynyl, C alkenyloxy-C alkyl, C alkynyloxy-C alkyl, phenyl, heteroaryl, heterocyclyl, heteroaryl C 1-C6 alkyl or heterocyclyl C 1-C6 alkyl, each of the hydrogens on the phenyl, heteroaryl, heterocyclyl may be substituted with one or more substituents selected from halogen, cyano, nitro, C 1-C6 alkyl or C 1-C6 haloalkyl;
R 2 is selected from hydrogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C6 alkyl, C 3-C6 halocycloalkyl, C 3-C6 halocycloalkyl C 1-C6 alkyl, C 2-C6 alkenyl, C 2-C6 haloalkenyl, C 2-C6 alkynyl or C 2-C6 haloalkynyl;
R 3 is selected from hydrogen, halogen, cyano, nitro, 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 alkylsulfonyl, C 1-C6 haloalkylsulfonyl, C 1-C6 alkylsulfinyl, C 1-C6 haloalkylsulfinyl, C 1-C6 alkylthio, C 1-C6 haloalkylthio, 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, C 3-C6 cycloalkyloxy, C 3-C6 halocycloalkyl, C 3-C6 halocycloalkyl C 1-C6 alkyl, C 2-C6 alkenyl, C 2-C6 haloalkenyl, C 2-C6 alkynyl or C 3-C6 haloalkynyl.
Further preferred are compounds of formula I:
x is selected from halogen, cyano, nitro, thiocyanato, 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;
n represents 0,1, 2;
Q is selected from the group consisting of Q1, Q3, Q6, or Q7;
R 1 is selected from hydrogen, Y, YCO, YOCO or Y sulfonyl;
Y is selected from the group consisting of C alkyl, C haloalkyl, C cycloalkyl, C halocycloalkyl, C cycloalkyl-C alkyl, C halocycloalkyl-C alkyl, C alkenyl, C haloalkenyl, C alkynyl, C haloalkynyl, phenyl-C alkyl, heteroaryl-C alkyl, heterocyclylcycloalkyl, phenyl, heteroaryl or heterocyclyl, each of which hydrogen on the phenyl, heteroaryl, heterocyclyl may be substituted with one or more substituents, the substituent is selected from the group consisting of halogen, cyano, nitro, thiocyanato, C alkyl, C haloalkyl, C alkoxy, C haloalkoxy, C alkoxy-C alkyl, C alkylsulfonyl, C haloalkylsulfonyl, C alkylsulfinyl, C haloalkylsulfinyl, C alkylthio, C haloalkylthio, C alkoxy-C alkoxy, C alkoxy-C alkyl, C cycloalkyl-C alkyl, C cycloalkyl-C alkoxy, C halocycloalkyl-C alkyl, C haloalkoxy-C alkyl, heterocyclyl-C alkoxy-C alkyl, C alkenyl, C haloalkenyl, C alkynyl, C haloalkynyl, C alkenyloxy-C alkyl, C alkynyloxy-C alkyl, phenyl, heteroaryl, heterocyclyl, heteroaryl C 1-C6 alkyl or heterocyclyl C 1-C6 alkyl, each of the hydrogens on the phenyl, heteroaryl, heterocyclyl may be substituted with one or more substituents selected from halogen, cyano, nitro, C 1-C6 alkyl or C 1-C6 haloalkyl;
R 2 is selected from hydrogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C6 alkyl, C 3-C6 halocycloalkyl, C 3-C6 halocycloalkyl C 1-C6 alkyl, C 2-C6 alkenyl, C 2-C6 haloalkenyl, C 2-C6 alkynyl or C 2-C6 haloalkynyl;
R 3 is selected from hydrogen, halogen, cyano, nitro, 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.
Still further preferred compounds are those of formula I:
x is selected from halogen, cyano, nitro, thiocyanato, 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;
n represents 0,1, 2;
Q is selected from the group consisting of Q1, Q3, Q6, or Q7;
r 1 is selected from YCO;
Y is selected from the group consisting of C alkyl, C haloalkyl, C cycloalkyl, phenyl C alkyl, heteroaryl C alkyl, heterocyclylC alkyl, phenyl, heteroaryl or heterocyclyl, each of which hydrogen on the phenyl, heteroaryl, heterocyclyl may be substituted with one or more substituents, the substituent is selected from halogen, cyano, nitro, thiocyanato, C alkyl, C haloalkyl, C alkoxy, C haloalkoxy, C alkoxy-C alkyl, C alkylsulfonyl, C haloalkylsulfonyl, C alkylsulfinyl, C haloalkylsulfinyl, C alkylthio, C haloalkylthio, C alkoxy-C alkoxy, C alkoxy-C alkyl, C cycloalkyl-C alkyl, C cycloalkyl-C alkoxy, C halocycloalkyl-C alkyl, C haloalkoxy-C alkyl, heterocyclyl-C alkoxy-C alkyl, C alkenyl, C haloalkenyl, C alkynyl, C haloalkynyl, C alkenyloxy-C alkyl, C alkynyloxy-C alkyl, phenyl, heteroaryl, heterocyclyl, heteroaryl-C alkyl or heterocyclyl-C alkyl, each hydrogen on the phenyl, heteroaryl, heterocyclyl may be substituted with one or more substituents selected from halogen, cyano, nitro, C 1-C6 alkyl or C 1-C6 haloalkyl;
R 2 is selected from C 1-C6 alkyl;
R 3 is selected from C 1-C6 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. 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. Heterocyclyl refers to 3-7 membered heterocyclic compounds containing 1-4 heteroatoms without aromatic character, such as ethylene oxide, tetrahydrofuran, imidazolidinone, caprolactam, etc. Heteroaryl means a 5-7 membered heterocyclic compound having an aromatic character containing 1 to 4 heteroatoms, 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:
reacting the compound of formula Ia in a suitable solvent in the presence of an oxidizing agent at a temperature of-10deg.C to the boiling point of the suitable solvent for 0.5-48 hours to obtain 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.
Suitable oxidizing agents are selected from hydrogen peroxide, m-chloroperoxybenzoic acid, nitric acid, magnesium monoperoxyphthalate, and the like.
The second method is as follows:
When Q is Q1, the compound is selected from the group consisting of,
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 Ib.
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 the formula III are commercially available or are prepared with reference to CN 103282354B.
The compounds of the formula II are prepared by the process of WO2018052967A 1.
When Q is Q2, Q3, Q4 and Q5, the preparation method refers to the synthesis method when Q is Q1.
When Q is Q6, the number of times,
L is selected from leaving groups.
The compound of formula Id is reacted with the compound of formula IV in a suitable solvent at a temperature of-10℃to the boiling point of the suitable solvent for 0.5 to 48 hours to produce the desired compound Ic. 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 addition of a suitable base is advantageous for the reaction. 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 IV can be prepared from the corresponding acids, which are commercially available.
The preparation method of the compound of the general formula Id is as follows:
The compound of the general formula V reacts in a proper solvent at the temperature of minus 10 ℃ to the boiling point of the proper solvent for 0.5 to 48 hours under the action of alkali and catalyst to prepare the compound of the general formula Id. 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. Suitable bases are selected from sodium carbonate, potassium carbonate or triethylamine, etc. Suitable catalysts are selected from sodium carbonate, potassium carbonate, acetone cyanohydrin, azide, quaternary ammonium azide, metal cyanide, DMAP, and the like.
The preparation method of the compound of the general formula V comprises the following steps:
The compounds of formula VI are reacted with compounds of formula VII (prepared by methods described in commercial or reference EP 0240001) in a suitable solvent at a temperature of-10℃to the boiling point of the suitable solvent for 0.5 to 24 hours to give compounds of formula V. 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 addition of a suitable base is advantageous for the reaction. 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 corresponding starting carboxylic acid (commercially available) of the compound of formula VI is reacted with an acyl halide reagent in a suitable solvent at a temperature of-10℃to the boiling point of the suitable solvent for 0.5 to 48 hours to produce the compound of formula V. The acyl halogenating agent is selected from oxalyl chloride, sulfoxide chloride, phosphorus oxychloride, phosphorus trichloride or phosphorus pentachloride. Suitable solvents are selected from dichloromethane, 1, 2-dichloroethane, hexane, benzene, toluene, acetonitrile, acetic acid or dioxane and the like.
When Q is Q7, reference is made to the synthetic method when Q is Q6.
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 condensed ring acyl compounds not only have excellent herbicidal activity, but also are safe to 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 1g 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 condensed ring acyl compounds, the compound of the general formula of the invention contains two different benzoyl substitutions, has novel structure, and the condensed ring acyl compounds of the invention have unexpected high herbicidal activity and high herbicidal activity at lower dosage, thus not only being efficient, but also reducing the use 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 3-trifluoromethyl-6- (2-carboxyethylthio) benzoic acid
Reaction system a: to a 100ml single-necked flask was added 2-amino-4-trifluoromethylbenzoic acid (10 g, 48.7 mmol), followed by addition of 20 ml of water and stirring at room temperature. Sodium hydroxide (1.92 g, 48.0 mmol) was weighed into a small beaker and dissolved in 30 ml of water. Sodium hydroxide solution was added to reaction system a, stirred at room temperature until the reactants were completely dissolved, sodium nitrite (4.03 g, 58.4 mmol) was added and stirred at room temperature for use.
Reaction system B: to a 1000 ml four-necked flask was added concentrated hydrochloric acid (17.5 g, 175.5 mmol), an ice bath (0 ℃ C.), 17.5 g of water, and the ice bath (0 ℃ C.) was mechanically stirred. The reaction system A was added dropwise to the reaction system B, and stirred in an ice bath (0 ℃ C.) for about 3 hours. And (3) taking a drop of the reaction liquid onto starch potassium iodide test paper, wherein the starch potassium iodide test paper turns blue and does not fade for 5 minutes, and the reaction is finished. Potassium acetate was added and water was made up to ph=6-7. The four-mouth bottle is placed in an ice bath for standby.
Reaction system C: to a three-necked flask, potassium ethylxanthate (16.8 g, 107.2 mmol) was added, 8.6 g of water was added, and the mixture was stirred at 85 ℃. Slowly dropwise adding the reaction system B into the reaction system C, stirring at 85 ℃ for about 2.5h after the dropwise adding is finished, and cooling to room temperature. Adding concentrated hydrochloric acid to adjust pH to be 3, stirring, and separating out sticky oily solid. The supernatant was poured, a small amount of water was added, the solid was washed twice, and the supernatant was poured. 80g of 10% sodium hydroxide solution is added, stirred for 2 hours at 80 ℃, 6-8 g of sodium hydrosulfite is added, stirred for 10 minutes, and cooled to room temperature. 3-bromopropionic acid (8.2 g, 53.6 mmol) was added thereto, and stirred at room temperature.
Adding concentrated hydrochloric acid into a reaction bottle to adjust the pH to 1-2, precipitating a large amount of yellow solid, and filtering to obtain 11.81 g of target product, wherein the content is 95.5%, and the yield is 78.7%.
(2) Synthesis of 5-trifluoromethyl-4-thiochromanone-8-carboxylic acid
To a 100ml three-necked flask was added 3-trifluoromethyl-6- (2-carboxyethylthio) benzoic acid (10 g, 34.0 mmol), polyphosphoric acid (100 g), and the solution was mechanically stirred at 120℃for 4h to change from yellow to red. Adding water into a three-mouth bottle under ice bath, releasing heat, separating out solid, filtering, washing a filter cake twice, dissolving with ethyl acetate, extracting an aqueous phase with ethyl acetate, combining an organic phase with the solid obtained by filtering, performing rotary evaporation/extraction with ethyl acetate, drying and rotary evaporation of the organic phase, and performing column chromatography to obtain 3.6 g of mixture.
(3) Synthesis of Compound 1
5-Trifluoromethyl-4-thiochromanone-8-carboxylic acid (1.2 g, 4.2 mmol), 1-methyl-5-aminotetrazole (0.6 g, 6.4 mmol), 3-methylpyridine (0.4 g, 4.2 mmol), N-methylimidazole (0.7 g, 8.5 mmol) were added to the flask, stirred at room temperature for half an hour, cooled to below 10℃in an ice water bath, thionyl chloride (1.0 g, 8.5 mmol) was slowly added dropwise, stirred at room temperature, and the reaction monitored by TLC. Extracting with ethyl acetate and water, and rotary evaporating to remove solvent. The compound 1 was isolated by column chromatography as an orange solid 0.2 g with a purity of 94% in 12.42%.
Example 2 synthesis of compound 3:
(1) Synthesis of Compound 3
To the reaction flask was added compound 1 (0.1 g, 0.3 mmol, see example 1 step 3), 5 ml acetic acid as solvent, sodium tungstate (0.008 g, 0.03 mmol), stirred at 60 ℃, hydrogen peroxide (0.03 g, 0.8 mmol) dropwise, and stirring at 60 ℃ for about 4 hours, followed by TLC monitoring the reaction. Cooling to room temperature, adding a large amount of water, precipitating solid, and filtering to obtain 0.04 g of compound 3 as yellow solid with purity of 90% and yield of 33%.
Example 3 synthesis of compound 266:
(1) Synthesis of 5-trifluoromethyl-4-thiochromanone-8-carbonyl chloride
To the reaction flask was added 5-trifluoromethyl-4-thiochromanone-8-carboxylic acid (1.5 g, 5.43 mmol, see example 1 step 2), toluene (10 ml), thionyl chloride (2.6 g, 21.7 mmol), and reflux reacted for 4 hours, and the 5-trifluoromethyl-4-thiochromanone-8-carbonyl chloride was desolventized under reduced pressure and used directly in the next step.
(2) Synthesis of 5-trifluoromethyl-4-thiochromanone-8-methanesulfonyl (1, 3-dimethylpyrazol-5-yl) ester
To the reaction flask was added 1, 3-dimethyl-5-hydroxypyrazole (0.7 g, 6.5 mmol), dichloromethane (5 ml), triethylamine (0.9 g, 7.8 mmol) was added, 5-trifluoromethyl-4-thiochromanone-8-carbonyl chloride was dissolved in dichloromethane (5 ml) and added dropwise to the reaction flask, and the mixture was stirred at room temperature. Water and ethyl acetate were added to extract, and the organic phase was dried and desolventized, followed by column chromatography to give 0.5 g of 5-trifluoromethyl-4-thiochromanone-8-methanesulfonyl (1, 3-dimethylpyrazol-5-yl) ester in 57% yield.
(3) Synthesis of Compound 266
To the reaction flask was added 5-trifluoromethyl-4-thiochromanone-8-methanesulfonyl (1, 3-dimethylpyrazol-5-yl) ester (0.5 g, 1.4 mmol), dichloromethane (5 ml), triethylamine (0.27 g, 2.7 mmol) and acetone cyanohydrin (0.5 g, 5.4 mmol) and reacted for 4 hours. Water and ethyl acetate are added for extraction, and organic phase is dried and desolventized to obtain 0.4 g of 1, 3-dimethyl-4- (5-trifluoromethyl-4-thiochromanone-8-methylsulfonyl) -5-hydroxypyrazole with the yield of 80 percent.
Example 4 synthesis of compound 301:
(1) Synthesis of 1-ethyl-5-methyl-1H-pyrazole-3-carbonyl chloride
To the reaction flask was added 1-ethyl-5-methyl-1H-pyrazole-3-carboxylic acid (0.25 g, 1.6 mmol), toluene (5 ml), thionyl chloride (0.8 g, 6.5 mmol), and the mixture was refluxed for 4 hours, and then desolventized under reduced pressure to give 1-ethyl-5-methyl-1H-pyrazole-3-carbonyl chloride, which was used directly in the next step.
(2) Synthesis of Compound 301
To the reaction flask was added 1, 3-dimethyl-4- (5-trifluoromethyl-4-thiochromanone-8-methanesulfonyl) -5-hydroxypyrazole (0.4 g, 1.1 mmol, see example 3, step 3), dichloromethane (10 ml), triethylamine (0.13 g, 1.3 mmol) was added, 1-ethyl-5-methyl-1H-pyrazole-3-carbonyl chloride was dissolved in dichloromethane (10 ml) and added dropwise to the reaction flask, followed by stirring at room temperature. Water and ethyl acetate are added for extraction, the organic phase is dried and desolventized, and the target product is obtained by column chromatography separation, wherein the yield is 33%.
Example 5 synthesis of compound 303:
To the reaction flask was added compound 301 (0.2 g, 0.395 mmol, see example 4 step 2), acetic acid (5 ml), hydrogen peroxide (0.04 g, 1.2 mmol) and sodium tungstate (0.02 g, 0.07 mmol). The oil bath was warmed to 60℃and stirred for 4 hours. Extracting with water and ethyl acetate, washing with water for three times, and separating by column chromatography to obtain compound 0.05 g with purity of 97% and yield of 23%.
Example 6 synthesis of compound 324:
(1) Synthesis of 5-trifluoromethyl-4-thiochromanone-8-carbonyl chloride
To the reaction flask was added 5-trifluoromethyl-4-thiochromanone-8-carboxylic acid (0.2 g, 0.7 mmol, see example 1 step 2), toluene (10 ml), thionyl chloride (0.09 g, 0.7 mmol), and reflux reacted for 4 hours, and the 5-trifluoromethyl-4-thiochromanone-8-carbonyl chloride was desolventized under reduced pressure and used directly in the next step.
(2) Synthesis of 3- (5-trifluoromethyl-4-thiochromanone-8-acyl) oxy-2-cyclohexen-1-one
To the reaction flask were added 1, 3-cyclohexanedione (0.09 g, 0.8 mmol) and triethylamine (0.09 g, 0.9 mmol) in dichloromethane (5 ml), and a dichloromethane solution of 5-trifluoromethyl-4-thiochromanone-8-carbonyl chloride was added dropwise and reacted at room temperature for 1 hour. Washing with water, desolventizing the organic phase, separating by column chromatography to obtain 0.13 g, purity 61%, yield 30%.
(3) Synthesis of Compound 324
To the reaction flask was added 3- (5-trifluoromethyl-4-thiochroman-8-oyl) oxy-2-cyclohexen-1-one (0.4 g, 1.1 mmol), dichloromethane (10 ml), triethylamine (0.1 g, 1.1 mmol) and acetone cyanohydrin (0.1 g, 1.1 mmol) and the mixture was refluxed for 3 hours. Water and ethyl acetate are added for extraction, the organic phase is dried and desolventized, and the brown solid is separated by column chromatography to obtain 0.15 g, the purity is 70%, and the yield is 26%.
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
1H NMR(600MHz,CDCl3) Data for a portion of the compounds are as follows:
compounds 1:8.13-8.15 (d, 1H), 8.76-8.77 (d, 1H), 4.13 (s, 3H), 3.18-3.20 (m, 2H), 3.14-3.16 (m, 2H).
Compound 266:8.26-8.27 (d, 1H), 7.67-7.69 (d, 1H), 3.73 (s, 3H), 3.20-3.23 (m, 2H), 3.14-3.17 (m, 2H), 2.27 (s, 3H).
Compounds of formula (I) 301:7.33-7.34(d,1H),7.35-7.36(d,1H),6.21(s,1H),4.10-4.14(m,2H),3.63(s,3H),3.17-3.20(t,2H),3.01-3.03(t,2H),2.56(s,3H),3.28(s,3H),1.23-1.25(t,3H).
Compounds of formula (I) 303:7.77-7.79(d,1H),7.56-7.57(d,1H),6.24(s,1H),4.09-4.13(m,2H),3.72-3.74(t,2H),3.60(s,3H),3.30-3.32(t,2H),2.60(s,3H),2.31(s,3H),1.40-1.42(t,3H).
Compounds of formula (I) 324:8.19-8.20(d,1H),7.60-7.62(m,1H),3.16-3.18(m,2H),3.09-3.13(m,2H),2.60-2.62(t,2H),2.06-2.10(m,2H),1.98-2.04(m,2H).
Biological measurement example
Example 7 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 of the compounds tested, such as compounds 1, 3, 266, 303, 324, had better control over zinnia, abutilon, setaria, or barnyard grass at a dose of 600g a.i./hm2, with control greater than 80%.
According to the test method, compound 3 and KC1 were selected for parallel comparison of the control abutilon, and the results are shown in Table 2.
Table 2: compound 3 and control compound KC1 for controlling abutilon activity
(After seedling, control effect%)
"/" Represents: not tested, the same as
The compound of the general formula has herbicidal activity and can be used for preventing and controlling various weeds in agriculture. Meanwhile, the condensed ring acyl compound not only has excellent herbicidal activity, but also is safe to crops.

Claims (5)

1. A fused ring acyl compound, characterized in that: the compound is shown in a general formula I:；
wherein:
x is selected from C 1-C6 haloalkyl;
n represents 2;
Q is selected from the group consisting of Q1; ；
R 1 is selected from hydrogen;
R 2 is selected from C 1-C6 alkyl.
2. The compound according to claim 1, wherein formula I is selected from the group consisting of
。
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 (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103282354A (en) * 2010-09-01 2013-09-04 拜耳知识产权有限责任公司 N-(tetrazol-5-l)- and n-(triazol-5-yl)arylcarboxamides and use thereof as herbicides

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Publication number Priority date Publication date Assignee Title
JPH07291970A (en) * 1994-04-22 1995-11-07 Idemitsu Kosan Co Ltd Pyrazole derivative and herbicide using the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103282354A (en) * 2010-09-01 2013-09-04 拜耳知识产权有限责任公司 N-(tetrazol-5-l)- and n-(triazol-5-yl)arylcarboxamides and use thereof as herbicides

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