CN111303062B - Benzamide compound and application thereof as herbicide - Google Patents
Benzamide compound and application thereof as herbicide Download PDFInfo
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- CN111303062B CN111303062B CN201811516182.2A CN201811516182A CN111303062B CN 111303062 B CN111303062 B CN 111303062B CN 201811516182 A CN201811516182 A CN 201811516182A CN 111303062 B CN111303062 B CN 111303062B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
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- 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
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Abstract
The invention discloses a benzamide compound and application thereof as a herbicide, wherein the compound is shown as a general formula (I):
Description
Technical Field
The invention belongs to the field of herbicides. In particular to a benzamide compound and application thereof as a herbicide.
Background
Due to succession and transition of weed populations and generation and rapid development of drug resistance of chemical pesticides, people continuously strengthen the awareness of ecological environment protection, and continuously increase the awareness of chemical pesticide pollution, the influence of pesticides on non-target organisms and the problem of homing in the pesticide ecological environment. With the diminishing area of cultivated land in the world, the increasing population and the increasing demand for food, people are forced to rapidly develop agricultural production techniques, improve the complete cultivation system, and need to continuously invent novel and improved herbicidal compounds and compositions.
CN108290846A reports that certain benzamide compounds have herbicidal activity, such as compound No. 1-28 (KC1) and compound No. 1-9 (KC2) among them:
the benzamide compounds shown in the present invention are not disclosed.
Disclosure of Invention
The invention aims to provide a benzamide compound which is novel in structure and safe to crops and application thereof as a herbicide.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a benzamide compound is shown as a general formula I:
in the formula:
X 1 and X 3 Are the same or different and are respectively selected from cyano, nitro, halogen and C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Haloalkylsulfonyl group, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Halogenoalkylsulfinyl, C 1 -C 6 Alkylthio radical, C 1 -C 6 Halogenoalkylthio, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 3 Alkoxy radical C 1 -C 3 Alkyl radical, C 1 -C 6 Alkoxy radical C 1 -C 3 Alkoxy radical, C 1 -C 6 Alkoxy radical C 1 -C 3 Alkoxy radical C 1 -C 3 Alkyl radical, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Cycloalkyl radical C 1 -C 3 Alkyl radical, C 3 -C 6 Cycloalkyl radical C 1 -C 3 Alkoxy or C 3 -C 6 A cycloalkyloxy group;
X 2 selected from hydrogen, cyano, nitro, halogen, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Haloalkylsulfonyl group, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Haloalkylsulfinyl radical, C 1 -C 6 Alkylthio radical, C 1 -C 6 Haloalkylthio, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Cycloalkyl radical C 1 -C 6 Alkyl radical, C 3 -C 6 Halocycloalkyl radical C 1 -C 6 Alkyl radical, R 1 Oxy, R 1 Oxy radical C 1 -C 6 Alkyl, R 1 Thio radical C 1 -C 6 Alkyl radical, R 1 Sulfoxide group C 1 -C 6 Alkyl radical, R 1 Sulfone group C 1 -C 6 Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C 1 -C 6 Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms 1 -C 6 Alkyl, the following substituents are selected from nitro, halogen and C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 A cycloalkoxy group;
R 1 is selected from C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl radical C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C 1 -C 6 Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms 1 -C 6 Alkyl, the following substituents are selected from nitro, halogen and C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 A cycloalkoxy group;
Y 1 and Y 2 Are selected from cyano, nitro, halogen, C, which may be the same or different 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Haloalkylsulfonyl group, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Haloalkylsulfinyl radical, C 1 -C 6 Alkylthio radical, C 1 -C 6 Haloalkylthio, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 3 Alkoxy radical C 1 -C 3 Alkyl radical, C 1 -C 6 Alkoxy radical C 1 -C 3 Alkoxy radical, C 1 -C 6 Alkoxy radical C 1 -C 3 Alkoxy radical C 1 -C 3 Alkyl radical, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Cycloalkyl radical C 1 -C 3 Alkyl radical, C 3 -C 6 Cycloalkyl radical C 1 -C 3 Alkoxy or C 3 -C 6 A cycloalkoxy group;
when X is present 1 And Y 1 Are identical and X 3 And Y 2 When same, X 2 Is not hydrogen.
The preferred compounds, of formula I:
X 1 and X 3 Are the same or different and are respectively selected from cyano, nitro, halogen and C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Haloalkylsulfonyl group, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Haloalkylsulfinyl radical, C 1 -C 6 Alkylthio radical, C 1 -C 6 Haloalkylthio, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 3 Alkoxy radical, C 1 -C 3 Haloalkoxy, C 1 -C 3 Alkoxy radical C 1 -C 3 Alkyl radical, C 1 -C 6 Alkoxy radical C 1 -C 3 Alkoxy radical, C 1 -C 6 Alkoxy radical C 1 -C 3 Alkoxy radical C 1 -C 3 Alkyl radical, C 3 -C 6 Cycloalkyl or C 3 -C 6 A cycloalkyloxy group;
X 2 selected from hydrogen, halogen, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Haloalkylsulfonyl group, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Haloalkylsulfinyl radical, C 1 -C 6 Alkylthio radical, C 1 -C 6 Haloalkylthio, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Cycloalkyl radical C 1 -C 6 Alkyl radical, C 3 -C 6 Halogenocycloalkyl C 1 -C 6 Alkyl radical, R 1 Oxy, R 1 Oxy radical C 1 -C 6 Alkyl radical, R 1 Thio radical C 1 -C 6 Alkyl radical, R 1 Sulfoxide group C 1 -C 6 Alkyl, R 1 Sulfone group C 1 -C 6 Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C 1 -C 6 Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms 1 -C 6 Alkyl, the following substituents are selected from nitro, halogen,C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 A cycloalkoxy group;
R 1 is selected from C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Cycloalkyl radical C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C 1 -C 6 Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms 1 -C 6 Alkyl, the following substituent is selected from nitro, halogen and C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 A cycloalkoxy group;
Y 1 and Y 2 Are selected from cyano, nitro, halogen, C, which may be the same or different 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Haloalkylsulfonyl, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Haloalkylsulfinyl radical, C 1 -C 6 Alkylthio radical, C 1 -C 6 Halogenoalkylthio, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 3 Alkoxy radical C 1 -C 3 Alkyl radical, C 1 -C 6 Alkoxy radical C 1 -C 3 Alkoxy radical, C 1 -C 6 Alkoxy radical C 1 -C 3 Alkoxy radical C 1 -C 3 Alkyl radical, C 3 -C 6 Cycloalkyl radical C 1 -C 3 Alkoxy or C 3 -C 6 A cycloalkoxy group;
when X is present 1 And Y 1 Are identical and X 3 And Y 2 When same, X 2 Is not hydrogen.
Further preferred are compounds of formula I:
X 1 and X 3 Can be the same or different and are respectively selected from nitro, halogen and C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Haloalkylsulfonyl group, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Haloalkylsulfinyl radical, C 1 -C 6 Alkylthio radical, C 1 -C 6 Halogenoalkylthio, C 1 -C 6 Alkyl or C 1 -C 6 A haloalkyl group;
X 2 selected from hydrogen, halogen, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Haloalkylsulfonyl group, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Haloalkylsulfinyl radical, C 1 -C 6 Alkylthio radical, C 1 -C 6 Haloalkylthio, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl radical C 1 -C 6 Alkyl radical, C 3 -C 6 Halogenocycloalkyl C 1 -C 6 Alkyl radical, R 1 Oxy, R 1 Oxy radical C 1 -C 6 Alkyl radical, R 1 Thio radical C 1 -C 6 Alkyl, R 1 Sulfoxide group C 1 -C 6 Alkyl, R 1 Sulfone group C 1 -C 6 Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocycle having 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocycle having 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocycle having 1 to 4 hetero atoms C 1 -C 6 Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms 1 -C 6 Alkyl, the following substituent is selected from nitro, halogen and C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 A cycloalkoxy group;
R 1 is selected from C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Cycloalkyl radical C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms, 5-to 7-membered heteroaryl containing 1 to 4 heteroatoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms C 1 -C 6 Alkyl, 5-7 membered heteroaryl C containing 1-4 heteroatoms 1 -C 6 Alkyl, the following substituents are selected from nitro, halogen and C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 A cycloalkoxy group;
Y 1 and Y 2 Can be the same or different and are respectively selected from nitro, halogen and C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Haloalkylsulfonyl group, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Haloalkylsulfinyl radical, C 1 -C 6 Alkylthio radical, C 1 -C 6 Haloalkylthio, C 1 -C 6 Alkyl or C 1 -C 6 A haloalkyl group;
when X is 1 And Y 1 Are identical and X 3 And Y 2 Same as each other, X 2 Is not hydrogen.
Even further preferred are compounds of formula I wherein:
X 1 and X 3 Can be the same or different and are respectively selected from nitro, halogen and C 1 -C 3 Alkylsulfonyl radical, C 1 -C 3 Alkyl or C 1 -C 3 A haloalkyl group;
X 2 selected from hydrogen, halogen, C 1 -C 6 Alkyl, aryl, heteroaryl, and heteroaryl,C 1 -C 6 Haloalkyl, C 1 -C 6 Alkylsulfonyl radical, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Cycloalkyl radical C 1 -C 6 Alkyl radical, R 1 Oxy, R 1 Oxy radical C 1 -C 3 Alkyl, R 1 Thio radical C 1 -C 3 Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C 1 -C 6 Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms 1 -C 6 Alkyl, the following substituents are selected from halogen and C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 A cycloalkoxy group;
R 1 is selected from C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Cycloalkyl radical C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C 1 -C 6 Alkyl, 5-to 7-membered heteroaromatic ring C containing 1-4 heteroatoms 1 -C 6 Alkyl, the following substituent is selected from nitro, halogen and C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 A cycloalkoxy group;
Y 1 and Y 2 Can be the same or different and are respectively selected from nitro, halogen and C 1 -C 3 Alkylsulfonyl radical, C 1 -C 3 Alkyl or C 1 -C 3 A haloalkyl group;
when X is present 1 And Y 1 Are identical and X 3 And Y 2 When same, X 2 Is not hydrogen.
In the definitions of the compounds of the general formula I given above, the terms used are collectively defined as follows:
alkyl means 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 cyclic chain forms such as cyclopropyl, methylcyclopropyl, cyclopropylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. Alkoxy means a group having an oxygen atom attached to the terminal of an alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, and the like. The 5-7 membered aliphatic heterocyclic ring containing 1-4 hetero atoms means a 5-7 membered heterocyclic compound containing 1-4 hetero atoms and having no aromatic character, such as ethylene oxide, tetrahydrofuran, imidazolidinone, caprolactam, etc. The 5-7 membered aromatic heterocyclic ring containing 1-4 hetero atoms refers to a 5-7 membered heterocyclic compound containing 1-4 hetero atoms and having aromatic characteristics, such as furan, thiophene, pyrazole, pyridine and the like.
The compound I with the general formula can be prepared by the following method:
the method comprises the following steps:
the compound of the general formula II and the compound of the general formula III react in a proper solvent at a temperature of between 10 ℃ below zero and 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 addition of suitable alkali substances in the reaction system can be beneficial to 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 III can be prepared from the corresponding acids (commercially available).
The second method comprises the following steps:
the compound of the general formula IV and the compound of the general formula V react in a proper solvent at the temperature of-10 ℃ to the boiling point of the proper solvent for 0.5-48 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 addition of suitable alkali substances in the reaction system can be beneficial to 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 V can be prepared from the corresponding acids (commercially available).
The preparation of the compounds of formula II is as follows:
reacting a compound of formula VI (commercially available) with a compound of formula VII (commercially available) in a suitable base and solvent with a suitable activating agent at a temperature of-10 ℃ to the boiling point of the suitable solvent for 0.5 to 48 hours to produce a compound of 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 or 4-methylpyridine, and the like. Suitable activating agents are selected from phosgene, triphosgene, CDI, DCC, thionyl chloride, oxalyl chloride, phosphorus oxychloride or phosphorus pentachloride, etc. Suitable bases are selected from N-methylimidazole, DMAP, or the like.
The preparation of the compounds of the formula IV can be referred 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 in the prior art, the benzamide compound disclosed by the invention not only has excellent herbicidal activity, but also is safe to crops.
The invention also comprises a weeding composition taking the compound in the general formula I as an active component. 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 compositions of the present invention can be applied in the form of various formulations. The compounds of the present invention are typically formulated to be more easily dispersed for use as herbicides by dissolving or dispersing the compounds in a carrier. For example: the chemical preparation can be prepared into wettable powder or missible oil and the like. Thus, in these compositions, at least one liquid or solid carrier is added, and it is generally necessary to add a suitable surfactant.
The present invention also provides an implementation method for controlling weeds, which comprises applying a herbicidally effective amount of the herbicidal composition of the present invention to the weeds or to a site where the weeds grow or to a surface of a growth medium thereof. Preferably, the effective dose is from 1 to 1000 grams per hectare, preferably from 10 to 500 grams per hectare. For certain applications, one or more additional herbicides may be added to the herbicidal compositions of the present invention, thereby providing additional advantages and benefits.
The compounds of the present invention can be used alone or in combination with other known insecticides, fungicides, plant growth regulators or fertilizers.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims.
The invention has the advantages that:
compared with the known benzamide compounds, the compound of the general formula contains two different benzoyl substitutions, has a novel structure, has unexpected high herbicidal activity, has high herbicidal activity under a lower dosage, is high in efficiency, reduces the using amount of pesticides, reduces the cost and reduces the pollution to the environment.
Detailed Description
The following examples and biological test results are provided to further illustrate the invention and are not meant to limit the invention.
Synthesis examples
Example 1, synthesis of compound 7:
(1) synthesis of N- (1-methyl-tetrazole-5-yl) -2-chloro-3-methyl-4-methylsulfonyl benzamide
To a reaction flask were added 2-chloro-3-methyl-4-methylsulfonylbenzoic acid (1 g, 4.0 mmol), 1-methyl-5-amino-tetrazole (0.44 g, 4.4 mmol), and N-methylimidazole (0.66 g, 8.0 mmol), and 6ml of 3-methylpyridine was added and stirred at room temperature for 30 minutes. After gradually cooling to 10 ℃, thionyl chloride (0.65 g, 6.4 mmol) was slowly added dropwise and stirred at room temperature for 24 hours. Water (5 ml) was slowly added dropwise to the reaction mixture cooled in an ice bath, and after completion of the dropwise addition, the mixture was stirred for 30 minutes and filtered to obtain 1.0 g of a white solid in a yield of 75%.
(2) Synthesis of 2, 4-dichlorobenzoyl chloride
2, 4-Dichlorobenzoic acid (0.31 g, 1.6 mmol) and toluene (20 ml) were added to a reaction flask, thionyl chloride (0.77 g, 6.4 mmol) was slowly added, and the mixture was heated under reflux for 4 hours, and the solvent was evaporated off under reduced pressure to directly proceed to the next step. (3) Synthesis of Compound 7
Adding N- (1-methyl-tetrazol-5-yl) -2-chloro-3-methyl-4-methylsulfonyl benzamide (0.3 g, 0.9 mmol), dichloromethane (5 ml) and triethylamine (0.18 g, 1.8 mmol) into a reaction bottle, cooling to below 10 ℃ in an ice bath, dissolving 2, 4-dichlorobenzoyl chloride in 5 ml dichloromethane, dropwise adding into the reaction bottle, and reacting at room temperature for 30 minutes. Column chromatography of the reaction mixture directly gave 0.28g of a white solid, 76% pure and 46% yield.
Example 2 Synthesis of Compound 18
(1) Synthesis of N- (1-methyl-tetrazole-5-yl) -2-chloro-4-methylsulfonyl benzamide
To a reaction flask were added 2-chloro-4-methylsulfonylbenzoic acid (20 g, 85 mmol), 1-methyl-5-amino-tetrazole (9.3 g, 94 mmol), N-methylimidazole (14 g, 170 mmol), and 3-methylpyridine (130 ml), and stirred at room temperature for 30 minutes. The temperature was reduced to 10 ℃ in an ice bath, thionyl chloride (16.2 g, 136 mmol) was added dropwise with internal temperature controlled to less than 20 ℃. After the dropwise addition, the temperature is raised to 30 ℃ and the reaction is stirred for 18 hours. And dropwise adding water (200 ml) into the system in an ice bath, controlling the internal temperature to be less than 30 ℃, stirring at room temperature for 30 minutes after the dropwise adding is finished, dropwise adding concentrated hydrochloric acid (20 ml), and stirring for 1 hour after the dropwise adding is finished to precipitate a solid. Filtration, washing of the filter cake 2 times (200 ml x 2), natural air drying, gave 20.7 g of a pale yellow solid, 98.8% purity, 76% yield.
(2) Synthesis of 2-chloro-3-methoxymethyl-4-methylsulfonylbenzoyl chloride
2-chloro-3-methoxymethyl-4-methylsulfonylbenzoic acid (1 g, 3.6 mmol), oxalyl chloride (2.3 g, 17.9 mmol) and dichloromethane (20 ml) were added to a reaction flask and stirred at room temperature for 20 minutes, 2 drops of N, N-dimethylformamide were added dropwise to the system and then stirred at room temperature for 40 minutes, and the mixture was evaporated under reduced pressure to remove the solvent and used in the next step.
(3) Synthesis of Compound 18
N- (1-methyl-tetrazol-5-yl) -2-chloro-4-methanesulfonylbenzamide (0.57 g, 1.8 mmol), triethylamine (0.36 g, 3.6 mmol) and dichloromethane (20 ml) were added to a reaction flask, the solid was dissolved by stirring at room temperature for 10 minutes, and a dichloromethane solution of the step 2-chloro-3-methoxymethyl-4-methanesulfonylbenzoyl chloride (15 ml) was added dropwise under ice bath. After stirring at room temperature for 30 minutes, the solvent was evaporated off under reduced pressure, ethyl acetate (50 ml) was added to the residue to dissolve it, the residue was washed 3 times with saturated sodium bicarbonate solution (50 ml x 3), the organic phase was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, the solvent was evaporated off under reduced pressure, and the residue was separated by column chromatography to give 0.38 g of a white solid with a purity of 89% and a yield of 33%.
Example 3, synthesis of compound 20:
(1) synthesis of compound N- (1-methyl-tetrazole-5-yl) -2-methylsulfonyl-4-trifluoromethyl benzamide
Adding 2-methylsulfonyl-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), and N-methylimidazole (11.7 g, 142 mmol) into a reaction flask, stirring at room temperature for half an hour, cooling in an ice-water bath to below 10 ℃, slowly dropping thionyl chloride (13.6 g, 114 mmol), stirring at room temperature for 2 hours, heating to 50 ℃, keeping the temperature for reaction for 2 hours, cooling in an ice-water bath to below 10 ℃, slowly dropping cold water, precipitating solids, filtering, washing a filter cake twice with 100 ml water, and drying to obtain 17.5 g of white solids with a yield of 70%.
(2) Synthesis of 2-chloro-4-methylsulfonyl-3- (2,2, 2-trifluoroethoxy-methyl) benzoyl chloride
2-chloro-4-methylsulfonyl-3- (2,2, 2-trifluoroethoxy-methyl) benzoic acid (0.8 g, 2.3 mmol), toluene (10 ml) and thionyl chloride (0.62 g, 5.2 mmol) were added slowly to the reaction flask, the mixture was heated under reflux for 4 hours, and the solvent was evaporated off under reduced pressure to give 0.8 g of a yellow oil which was used directly in the next step.
(3) Synthesis of Compound 20
N- (1-methyl-tetrazol-5-yl) -2-methylsulfonyl-4-trifluoromethylbenzamide (0.35 g, 1 mmol), dichloromethane (10 ml), triethylamine (0.2 g, 2 mmol) were added to the reaction flask, and the above dichloromethane solution (10 ml) of 2-chloro-4-methylsulfonyl-3- (2,2, 2-trifluoroethoxy-methyl) benzoyl chloride was added dropwise. After stirring at room temperature for 1 hour, the solvent was evaporated off under reduced pressure and the residue was subjected to column chromatography to give 0.16 g of a yellow oil with a purity of 91% and a yield of 20%.
Example 4, synthesis of compound 24:
(1) synthesis of 2-chloro-4-methylsulfonyl-3- (tetrahydrofuran-2-yl-methoxy-methyl) benzoyl chloride
2-chloro-4-methylsulfonyl-3- (tetrahydrofuran-2-yl-methoxy-methyl) benzoic acid (1.2 g, 2.4 mmol) and toluene (10 ml) were added to a reaction flask, thionyl chloride (0.65 g, 5.5 mmol) was slowly added, the mixture was heated under reflux for 4 hours, and the solvent was evaporated off under reduced pressure to give 1.3 g of a yellow oil which was used directly in the next step.
(2) Synthesis of Compound 24
To a reaction flask were added N- (1-methyl-tetrazol-5-yl) -2-methylsulfonyl-4-trifluoromethylbenzamide (0.38 g, 1.1 mmol), dichloromethane (10 ml), and triethylamine (0.22 g, 2.2 mmol), and a dichloromethane solution (10 ml) of the above-obtained 2-chloro-4-methylsulfonyl-3- (tetrahydrofuran-2-yl-methoxy-methyl) benzoyl chloride was added dropwise. After stirring at room temperature for 1 hour, the solvent was evaporated off under reduced pressure and the residue was subjected to column chromatography to give 0.4 g of a yellow oil with a purity of 94% and a yield of 50%.
The compounds represented by general formula I can be obtained by substituting the starting materials during the reaction as described in the above preparation method, and the compounds are described in table 1.
Table 1 structural and physical properties of some compounds of formula I
Of partial compounds 1 H NMR(600MHz,CDCl 3 ) The data are as follows:
compound 5(600MHz, DMSO-d) 6 ):8.12(d,1H),8.08(d,1H),7.96-7.98(m,2H),7.91(d,1H),4.25(s,3H),3.33(s,3H),3.32(s,3H),2.68(s,3H)。
Compounds 6:8.25(s,1H),8.08(d,1H),8.03(d,1H),7.98(d,1H),7.50(d,1H),4.16(s,3H),3.18(s,3H),3.11(s,3H),2.77(s, 3H).
Compounds 7:8.11(d,1H),7.57(d,1H),7.50(d,1H),7.36(s,1H),7.33(d,1H),4.11(s,3H),3.12(s,3H),2.78(s, 3H).
Compounds 8:8.77(d,1H),8.56-8.55(m,1H),8.37-8.36(m,1H),7.98-7.97(m,1H),7.73-7.72(m,1H),4.27(s,3H),3.46(s,3H),3.30(s,3H),2.76(s, 3H).
Compounds 18:8.11(d,1H),7.87-7.91(m,2H),7.74(d,1H),7.67(d,1H),5.00(s,2H),4.12(s,3H),3.47(s,3H),3.22(s,3H),3.06(s, 3H).
Compound 19(600MHz, DMSO-d) 6 ):8.76(d,1H),8.54-8.53(m,1H),8.36(d,1H),8.03-8.02(m,1H),7.96-7.95(m,1H),4.90(s,2H),4.26(s,3H),3.45(s,3H),3.36(s,3H),3.31(s,3H)。
Compounds 20:8.23(s,1H),8.15(d,1H),7.96-8.02(m,2H),7.69(d,1H),5.32(s,2H),4.16(s,3H),4.03(q,2H),3.20(s,3H),3.16(s, 3H).
Compound 22 (DMSO-d) 6 ):8.12-8.13(m,2H),8.07-8.09(m,2H),7.96(d,1H),5.19(s,2H),4.24-4.33(m,5H),3.34-3.38(m,6H)。
Compounds 23:8.14(d,1H),7.91-7.94(m,2H),7.77(d,1H),7.67(d,1H),5.13(s,2H),4.14(s,3H),3.81-3.85(m,1H),3.73-3.77(m,1H),3.63-3.65(m,1H),3.56-3.59(m,1H),3.29(s,3H),3.09(s,1H),3.08(s,3H),1.95-2.00(m,1H),1.86-1.91(m,2H),1.58-1.59(m, 1H).
Compounds 24:8.23(s,1H),8.13(d,1H),8.02(d,1H),7.98(d,1H),7.63(d,1H),5.16(s,2H),4.16(s,3H),4.05-4.10(m,1H),3.83(q,1H),3.75(q,1H),3.65(dd,1H),3.59(dd,1H),3.30(s,3H),3.17(s,3H),1.94-2.01(m,1H),1.84-1.91(m,2H),1.56-1.61(m, 1H).
Compounds 25:8.15(d,1H),7.68(d,1H),7.51(d,1H),7.33(d,2H),7.32(dd,1H),5.15(d,2H),4.11(s,3H),4.07-4.11(m,1H),3.81-3.85(m,1H),3.73-3.77(m,1H),3.64-3.66(m,1H),3.57-3.60(m,1H),3.30(s,3H),1.95-2.00(m,1H),1.85-1.91(m,2H),1.56-1.60(m, 1H).
Compound 80: (DMSO-d) 6 )8.13-8.14(m,2H),7.99(d,1H),7.84(d,1H),7.79(s,1H),7.53(d,1H),4.22(s,3H),3.35(s,3H)。
Compound 81: 8.83(s,1H),8.36(d,1H),8.21(s,1H),7.92-7.90(m,2H),7.83(s,1H),4.20(s,3H),3.17(s, 6H).
Compound 82: 8.28(s,1H),8.03(d,1H),7.97(d,1H),7.44(d,1H),7.38(s,1H),7.29(d,1H),4.14(s,3H),3.20(s, 3H).
Examples of bioassay
Example 5 determination of herbicidal Activity
Sowing seeds of broad-leaved weeds (zinnia elegans and abutilon) or grassy weeds (green bristlegrass and barnyard grass) in a paper cup with the diameter of 7cm and containing nutrient soil, covering soil for 1cm after sowing, compacting, spraying water, culturing in a greenhouse according to a conventional method, and spraying stems and leaves after 2-3 leaf periods of the weeds.
After the original drug is dissolved by 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 requirements. The spray treatment (spray pressure 1.95 kg/cm) was carried out on a crawler-type crop sprayer (Engineer Research Ltd. in England) at the experimental design dose 2 The amount of the liquid spray is 500L/hm 2 And the track speed is 1.48 km/h). The experiment was repeated 3 times. After being treated, the test material is placed in an operation hall, after the liquid medicine is naturally dried in the shade, the test material is placed in a greenhouse for management according to a conventional method, the reaction condition of weeds to the agent is observed and recorded, the weed control effect of the test agent to weeds is regularly observed and visually observed after the treatment, the weed control effect is expressed by 0-100%, and the non-control effect is expressed by 0% and the complete killing is expressed by 100%.
Test results show that the compound of the general formula I has higher control effect on broad leaf weeds and grassy weeds generally. Of some of the compounds tested, compounds 6, 7, 8, 81, 82, 83 were administered at a dose of 1000g a.i./hm 2 The composition has better prevention effect on the zinnia elegans, and the prevention effect is more than 80 percent. Such as compounds 6, 7, 81, 82, at an administration dose of 1000g a.i./hm 2 The composition has good control effect on green bristlegrass, and the control effect is more than 80 percent.
Compound 6 was selected for parallel comparison with KC1 and KC2 for zinnia control according to the test methods above and the results are shown in table 2.
Table 2: zinnia control activity of compound 6 and control compounds KC1 and KC2
(post-emergence, control effect%)
"/" denotes: not tested, the following are the same
Compound 6 was selected for parallel comparison with KC2 for control of abutilon according to the test methods above and the results are shown in Table 3.
Table 3: abutilon-controlling activity of compound 6 and control compound KC2
(post-emergence, control effect%)
Compound 6 was selected for parallel comparison with KC for barnyard grass control according to the test methods above and the results are shown in table 4.
Table 4: echinochloa against cockspur grass activity of Compound 6 and control Compounds KC1 and KC2
(post-emergence, control effect%)
Compound 6 was selected for parallel comparison with KC1 and KC2 for green bristlegrass control according to the test methods above and the results are shown in table 5.
Table 5: setaria viridis activity control of compound 6 and control compounds KC1 and KC2
(post-emergence, control effect%)
Example 6 corn safety test
Sowing a certain amount of corn seeds in a paper cup with the diameter of 7cm and containing nutrient soil, covering soil of 1cm after sowing, compacting, spraying water, and culturing in a greenhouse according to a conventional method. When the corn grows to 3 leaves, selecting a test material with uniform growth, and carrying out stem and leaf spraying treatment (spraying pressure is 1.95 kg/cm) by using a crawler-type crop sprayer (designed and produced by Engineer Research Ltd. in England) 2 The amount of the sprayed liquid was 50mL/m 2 The track speed is 30cm/s, the nozzle is a fan-shaped nozzle), the test material is placed in an operation hall after being treated, and the test material is placed in a greenhouse for management according to a conventional method after the liquid medicine is naturally air-dried. After the treatment, the reaction condition of the corn to the test compound is regularly observed, visual investigation is carried out 4 weeks after the treatment, the inhibition rate is various damage degrees compared with the control, and is expressed by 0-100%, and 0 represents no damage and 100% represents complete death.
The compound 6 of formula I was tested for corn safety and the results are shown in Table 6.
Table 6: safety of Compound 6 to corn
(post-emergence injury Rate%)
The compound with the general formula has herbicidal activity and can be used for controlling various weeds in agriculture. Meanwhile, the benzamide compound has excellent herbicidal activity and is safe to crops.
Claims (6)
1. A benzamide compound characterized by: the compound is shown as a general formula I:
in the formula:
X 1 selected from halogens;
X 3 selected from halogen or C 1 -C 6 An alkylsulfonyl group;
X 2 selected from hydrogen, C 1 -C 6 Alkyl radical, C 1 -C 6 A haloalkyl group;
Y 1 is selected from C 1 -C 6 An alkylsulfonyl group;
Y 2 is selected from C 1 -C 6 A haloalkyl group.
2. A compound according to claim 1, wherein in formula I:
X 1 selected from halogens;
X 3 selected from halogen, C 1 -C 3 An alkylsulfonyl group;
X 2 selected from hydrogen or C 1 -C 3 An alkyl group;
Y 1 is selected from C 1 -C 3 An alkylsulfonyl group;
Y 2 is selected from C 1 -C 3 A haloalkyl group.
3. A compound according to claim 2, wherein in formula I:
X 1 selected from chlorine;
X 3 selected from chloro or methylsulfonyl;
X 2 selected from hydrogen or methyl;
Y 1 selected from the group consisting of methylsulfonyl;
Y 2 is selected from trifluoromethyl.
4. The use of a compound of the general formula I according to claim 1 for controlling weeds.
5. A herbicidal composition characterized by: the herbicidal composition comprises an active substance and an agriculturally acceptable carrier, wherein the active ingredient is the compound shown in the general formula I in claim 1, and the weight percentage of the active ingredient in the composition is 1-99%.
6. A method of controlling weeds, comprising: applying a herbicidally effective dose of the herbicidal composition of claim 5 to the weeds or to a growth medium or locus of the weeds.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103987701A (en) * | 2011-12-13 | 2014-08-13 | 拜耳知识产权有限责任公司 | N-(1,2,5-oxadiazol-3-yl), N-(1,3,4-oxadiazol-2-yl), N-(tetrazol-5-yl), and N-(triazol-5-yl) aryl carboxylic acid amides and use thereof as herbicides |
| CN106660951A (en) * | 2014-06-30 | 2017-05-10 | 拜耳作物科学股份公司 | Herbicidally active n-(1-methyltetrazol-5-yl)benzoic acid amides |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103987701A (en) * | 2011-12-13 | 2014-08-13 | 拜耳知识产权有限责任公司 | N-(1,2,5-oxadiazol-3-yl), N-(1,3,4-oxadiazol-2-yl), N-(tetrazol-5-yl), and N-(triazol-5-yl) aryl carboxylic acid amides and use thereof as herbicides |
| CN106660951A (en) * | 2014-06-30 | 2017-05-10 | 拜耳作物科学股份公司 | Herbicidally active n-(1-methyltetrazol-5-yl)benzoic acid amides |
| 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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| "THE TAUTOMERISM OF 5-AMINOTETRAZOLE VII. Synthesis, Structure, and Spectra of Diacyl Derivatives of 5-Amino-1-Methyltetrazole and 5-Amino-2-Methyltetrazole";V. P. Shehipanov;《KHLMIYA GETEROTSIKLICHESKIKH SOEDINENII》;19691231;第5卷(第5期);第923-926页 * |
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