CN115417791B - Oxime ether 1, 3-cyclohexanedione compound and synthetic method and application thereof - Google Patents

Oxime ether 1, 3-cyclohexanedione compound and synthetic method and application thereof Download PDF

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CN115417791B
CN115417791B CN202211162176.8A CN202211162176A CN115417791B CN 115417791 B CN115417791 B CN 115417791B CN 202211162176 A CN202211162176 A CN 202211162176A CN 115417791 B CN115417791 B CN 115417791B
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formula
reaction
methyl
compounds
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CN115417791A (en
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邓照西
郭少雄
胡合伟
岑金
谭宾
贾云飞
杜兵兵
李志军
李君沛
杨莉娜
吴世凡
曹展
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Zhengzhou Institute Of Chiral Drugs Research Co ltd
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Zhengzhou Institute Of Chiral Drugs Research Co ltd
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Abstract

Oxime ether 1, 3-cyclohexanedione compound and a synthesis method and application thereof. The invention provides a 1, 3-cyclohexanedione compound shown in a formula I and a stereoisomer and a pesticide acceptable salt thereof, wherein R 1 、R 2 、R 3 、R 4 As defined in the specification. The invention also discloses a preparation method of the compound shown in the formula I and application of the compound as herbicide. The structure of the compound of formula I is as follows:

Description

Oxime ether 1, 3-cyclohexanedione compound and synthetic method and application thereof
Technical Field
The invention relates to an oxime ether type 1, 3-cyclohexanedione compound, a synthesis method and application thereof. In particular to oxime ether type 1, 3-cyclohexanedione compounds, the use thereof for controlling undesired weeds in plants, and a preparation method of the compounds.
Background
Cyclohexanediones are a large class of substances having a wide range of biological activities such as herbicidal, bactericidal, insecticidal, etc., among which herbicidal activity is the most interesting. Cyclohexanedione herbicides are mainly divided into two classes, one of which is a 2-acyl-1, 3-cyclohexanedione compound, which is an HPPD inhibitor, and has broad-spectrum herbicidal activity; the second is oxime ether 1, 3-cyclohexanedione compound which is ACCase inhibitor and is used for preventing and killing annual or perennial grassy weeds.
Compounds comprising cyclohexanedione structures are known to be clethodim, sethoxydim, graminezide, thioxanthone, butoxycyclic ketone, triclopyr, pyrone and fenpropion. But develops resistance on many weeds due to long-term use. Those skilled in the art are continually looking for suitable alternative pesticide herbicides.
The prior patent document 1 (CN 105884665B) discloses a cyclohexenone compound and a preparation method and application thereof, wherein the disclosed compound has the following structure:the compound is found to have better control effect on barnyard grass and stephania, and has higher safety on rice.
The patent (CN 1120528A) published by the applicant discloses a cyclohexane-1, 3-dione compound and a synthetic method and application thereof, wherein the structure of the compound is as follows:the compound e1 disclosed therein:the weeding composition has good weeding effect and safety to crops.
The patent (CN 114105842A) published by the applicant discloses a cyclohexadiene oxime ether compound and application thereof, wherein the compound 5 shows a relatively excellent weeding effect. The structure of compound 5 is as follows:
in addition, the pretilachlor proposed by domestic companies,
it has poor control effect on resistant barnyard grass.
At present, the herbicidal properties of these known compounds against harmful plants, in particular against resistant weeds, are not entirely satisfactory, and at the same time the safety against crops is also to be improved.
It is therefore an object of the present invention to provide oxime ether 1, 3-cyclohexanedione compounds having improved herbicidal action. In particular, it is intended to provide oxime ether type 1, 3-cyclohexanedione compounds which have high herbicidal activity, particularly at low application rates, are excellent in herbicidal effect against resistant weeds, and are highly safe for crops.
Disclosure of Invention
The invention aims to provide a novel oxime ether type 1, 3-cyclohexanedione compound, which has higher herbicidal activity when applied in small dosage compared with the existing known research and development compounds, has high selectivity and compatibility to plant crops, shows better safety, and has better control effect on weeds with resistance to the existing oxime ether type 1, 3-cyclohexanedione compound herbicides, such as the benpropenone, clethodim and the like. Can be widely applied to weed control in agriculture, forestry and orchards.
The invention provides an oxime ether type 1, 3-cyclohexanedione compound shown in a formula I,
Wherein:
R 1 is H, optionally substituted C 1 -C 6 Alkyl, optionally substituted C 1 -C 6 Alkoxy, optionally substituted C 1 -C 6 Thio, optionally substituted C 1 -C 6 alkoxy-C 1 -C 6 Alkyl, optionally substituted C 1 -C 6 alkylthio-C 1 -C 6 Alkyl, optionally substituted C 3 -C 6 Cycloalkyl, optionally substituted C 3 -C 6 Cycloalkyloxy-C 1 -C 6 Alkyl, optionally substituted C 3 -C 6 Cycloalkylthio-C 1 -C 6 Alkyl, optionally substituted heterocyclyl;
R 2 is optionally substituted C 1 -C 6 Alkyl, optionally substituted C 3 -C 6 Cycloalkyl;
R 3 is optionally substituted C 1 -C 6 Alkyl, optionally substituted C 2 -C 6 Alkenyl, optionally substituted C 3 -C 6 Cycloalkyl;
R 4 is H, optionally substituted phenyl, optionally substituted heterocyclyl, optionally substituted C 2 -C 6 Alkenyl groups;
diastereoisomers, enantiomers and rotamers of the compounds of formula I and their agriculturally acceptable salts are also included.
The invention also provides a preparation method of the compound shown in the formula I.
The invention also provides a weeding composition which comprises the compound shown in the formula I.
The invention also provides the use of the compounds of the formula I as herbicides for controlling undesired plants.
Furthermore, the present invention provides a method for controlling undesired plant growth, wherein a herbicidally effective amount of at least one compound of the formula I is allowed to act on plants, their seeds and/or their habitat. Application may be performed before, during and/or after emergence of the undesirable plants.
Furthermore, the present invention relates to processes and intermediates for preparing formula I.
The beneficial effects of the invention are that
The compound has higher efficient weeding activity and safety to crops, simultaneously shows excellent weeding effect on resistant weeds, and has wide application prospect.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated elements or steps without excluding other material elements or steps.
In addition, numerous specific details are set forth in the following description in order to provide a better illustration of the invention.
It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, methods, means, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present invention.
The terms "control" and "control" as used herein are synonymous.
The terms "undesired vegetation" and "pest plants" as used herein are synonymous.
If the compounds of the formula I according to the invention are capable of forming geometric isomers, for example E/Z isomers, both pure isomers and mixtures thereof can be applied in the compositions according to the invention.
If the compounds of the formula I according to the invention have one or more chiral centers and are therefore present as enantiomers or diastereomers, pure enantiomers, racemates, diastereomers may be used in the compositions according to the invention.
If the compounds of the formula I according to the invention have functional groups which can be ionized, they can also be used in the form of their agriculturally acceptable salts or mixtures thereof.
Suitable are generally salts of those cations whose cations do not adversely affect the action of the active compound ("agriculturally acceptable"). Preferred cations are ions of alkali metals, preferably lithium, sodium and potassium ions, alkaline earth metals, preferably calcium and magnesium ions, and transition metals, preferably manganese, copper, zinc and iron ions.
Anions of useful acid addition salts are mainly chloride, bromide, fluoride, iodide, hydrogen sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate.
In the definition of the variables according to the invention, R is in particular 1 -R 4 The organic junction mentionedWhich, like the term halogen, is a collective term for a separate enumeration of each group member.
The term halogen denotes in each case fluorine, chlorine, bromine and iodine.
Integers from 0 to 3 in the present invention, preferably 0, 1,2 and 3.
In the present invention all hydrocarbon chains, i.e. all alkyl groups, may be straight or branched, C n ～C m The subscripts of (2) in each case denote the number of carbon atoms in the group. The term "alkyl" (as well as in alkyl moieties that contain other groups of alkyl groups, such as alkoxy groups) as used herein. C (C) 1 ～C 6 Examples of alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl), 1-dimethylethyl (tert-butyl), n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1, 2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl.
The term "optionally substituted" means that the relevant group may or may not be substituted with a substituent.
When the relevant group (e.g., alkyl) is substituted with a substituent, the substituent may include hydroxy, cyano, nitro, halogen, and alkyl. When the alkyl group is substituted with halogen, a haloalkyl group is formed.
The term "ring" or "cycloalkyl" according to the invention denotes in each case a radical having generally from 3 to 6 carbon atoms ("C 3 ～C 6 Cycloalkyl ") and a mono-or bicyclic cycloaliphatic radical. Examples of the monocyclic group having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
C 2 -C 6 Alkenyl groups, e.g. vinyl, 1-propenyl, 2-propenyl, 1-methylethenyl1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-2-butenyl, 3-methyl-3-butenyl, 3-methyl-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-3-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 1-methyl-2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1-dimethyl-2-butenyl, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dimethyl-2-butenyl 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 2-dimethyl-3-butenyl, 2, 3-dimethyl-1-butenyl, 2, 3-dimethyl-2-butenyl, 2, 3-dimethyl-3-butenyl, 3-dimethyl-1-butenyl, 3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl.
C 3 -C 6 Halogenated alkenyl: c as described above, which is partially or completely substituted by fluorine, chlorine, bromine and/or iodine 3 -C 6 Alkenyl groups, such as 2-chloropropyl-2-en-1-yl, 3-chloropropyl-1-enyl, 2, 3-dichloroprop-2-en-1-yl, 3-dichloroprop-2-en-1-yl, 2, 3-trichloroprop-2-en-1-yl, 2, 3-dichlorobut-2-en-1-yl,2-bromoprop-2-en-1-yl, 3-bromoprop-2-en-1-yl, 2, 3-dibromoprop-2-en-1-yl, 3-dibromoprop-2-en-1-yl, 2, 3-tribromoprop-2-en-1-yl or 2, 3-dibromobut-2-en-1-yl.
C 1 -C 6 alkoxy-C 1 -C 6 Alkyl, C 1 -C 6 alkylthio-C 1 -C 6 C of alkyl groups 1 -C 6 Alkyl moiety: for example methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl), 1-dimethylethyl (tert-butyl), n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, hexyl, 1-methylpentyl 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1, 2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl.
A heterocyclic group: a monocyclic or bicyclic saturated, partially unsaturated or aromatic heterocycle having 3 or more, for example 3 to 10, ring atoms, for example a 3, 4, 5, 6, 7 membered heterocycle containing 1 to 4 identical or different heteroatoms selected from oxygen, sulfur and nitrogen, for example:
wherein P is selected from H, -CH 3 、-C 2 H 5 、-C 3 H 7 、-Cl、-F、-Br、-I、-CN、-NO 2 or-CF 3 X is oxygen, sulfur and nitrogen, Y is C 1 -C 3 Alkyl, n is an integer from 0 to 3.
The following descriptions of the variables and preferred embodiments of the variables of the compounds of formula (I), the features of the uses and methods according to the invention and the features of the compositions according to the invention are valid both on their own and preferably in combination with one another.
The invention provides an oxime ether type 1, 3-cyclohexanedione compound shown in a formula I,
wherein:
R 1 is H, optionally substituted C 1 -C 6 Alkyl, optionally substituted C 1 -C 6 Alkoxy, optionally substituted C 1 -C 6 Thio, optionally substituted C 1 -C 6 alkoxy-C 1 -C 6 Alkyl, optionally substituted C 1 -C 6 alkylthio-C 1 -C 6 Alkyl, optionally substituted C 3 -C 6 Cycloalkyl, optionally substituted C 3 -C 6 Cycloalkyloxy-C 1 -C 6 Alkyl, optionally substituted C 3 -C 6 Cycloalkylthio-C 1 -C 6 Alkyl, optionally substituted heterocyclyl;
R 2 is optionally substituted C 1 -C 6 Alkyl, optionally substituted C 3 -C 6 Cycloalkyl;
R 3 is optionally substituted C 1 -C 6 Alkyl, optionally substituted C 2 -C 6 Alkenyl, optionally C 3 -C 6 Cycloalkyl;
R 4 is H, optionally substituted C 2 -C 6 Alkenyl, optionally substituted phenyl, optionally substituted heterocyclyl;
diastereoisomers, enantiomers and rotamers of the compounds of formula I and their agriculturally acceptable salts are also included.
According to one embodiment of the invention, R in the compounds of formula I 1 is-H, -CH 3 、-C 2 H 5 、-C 3 H 7 、-C 4 H 9 、-C 5 H 11 、-C 6 H 13 、-Q-CH 3 、-Q-C 2 H 5 、-CH 2 -Q-CH 3 、-Q-C 3 H 7 、-C 2 H 4 -Q-CH 3 、-CH 2 -Q-C 2 H 5 、-Q-C 4 H 9 、-CH 2 -Q-C 3 H 7 、-C 2 H 4 -Q-C 2 H 5 、-C 3 H 6 -Q-CH 3 、-Q-C 5 H 11 、-CH 2 -Q-C 4 H 9 、-CH 2 -Q-C 4 H 9 、-C 2 H 4 -Q-C 3 H 7 、-C 3 H 6 -Q-C 2 H 5 、-C 4 H 8 -Q-CH 3 、-Q-C 6 H 13 、-CH 2 -Q-C 5 H 11 、-C 2 H 4 -Q-C 4 H 9 、-C 3 H 6 -Q-C 3 H 7 、-C 4 H 8 -Q-C 2 H 5 、-C 5 H 10
-Q-CH 3 、Wherein X is C, O or S; q is O or S.
According to one embodiment of the invention, R in the compounds of formula I 1 is-CH 3 、-CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 3 、-CH 2 -O-CH 2 CH 3 、-CH 2 CH 2 -S-CH 3 、-CH 2 -O-CH(CH 3 ) 2 、-CH 2 CH(CH 3 )SCH 2 CH 3 、
According to one embodiment of the invention, R in the compounds of formula I 2 is-CH 3 、-C 2 H 5 、-C 3 H 7 、-C 4 H 9 、-C 5 H 11 、-C 6 H 13 、Wherein n is selected from integers from 0 to 3 and Y is C 1 -C 3 Is a hydrocarbon group.
According to one embodiment of the invention, R in the compounds of formula I 2 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 )CH 2 CH 3 、-CH(CH 3 ) 2 、-CH(CH 3 )CH(CH 3 )CH 3 、-CH 2 CH 2 CH(CH 3 ) 2 。
According to one embodiment of the invention, R in the compounds of formula (I) 3 Selected from-CH 3 、-C 2 H 5 、-C 3 H 7 、-C 4 H 9 、-C 5 H 11 、-C 6 H 13 、-CH＝CHCH 3 、-CH 2 CH＝CH 2 、-CH 2 CH＝CHZ、-CH＝CHCH 2 Z、Wherein Z is selected from F, cl, br, I, n is selected from integers from 0 to 3, Y is C 1 -C 3 Is a hydrocarbon group.
According to one embodiment of the invention, R in the compounds of formula I 3 Selected from-CH 2 CH＝CH 2 、-CH 2 CH＝CHCl、-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH＝CHCH 3 、-CH＝CHCH 2 Cl、-CH 2 CH 2 CH 2 CH 3 。
According to one embodiment of the invention, R in the compounds of formula I 4 Selected from-H, -CH 2 CH＝CH 2 、-CH 2 CH＝CHZ、
Wherein P is selected from H, -CH 3 、-C 2 H 5 、-C 3 H 7 、-Cl、-F、-Br、-I、-CN、-NO 2 or-CF 3 N=0-3, z is F, cl, br, I.
Particularly preferred compounds of the invention are as follows:
compound 1:compound 2: />Compound 3:compound 4: / >Compound 5: />Compound 6: />Compound 7: />Compound 8:compound 9: />Compound 10: />Compound 11: />Compound 12: />
In another aspect, the present invention provides a method for preparing a compound of formula I, comprising the steps of: the compounds of the formula II and the formula III are prepared under the acidic condition to obtain the compound of the formula I, wherein R is 2 、R 3 、R 4 As defined above;
preferably the above reaction is carried out in an organic solvent selected from one of dichloromethane, dichloroethane, acetone, toluene, DMF, petroleum ether and methanol, and the acid is selected from organic acids, preferably formic acid and acetic acid. The reaction temperature of the reaction is in the range of 0-100 ℃, and the reaction time is in the range of 1-10h, preferably 1-3 h;
further, the compound shown in the formula III is obtained by reacting the compound shown in the formula IV with hydrazine hydrate, the reaction is carried out in an organic solvent, the organic solvent is selected from one of dichloromethane and dichloroethane, the reaction is carried out at 0-80 ℃ for 1-3 h, water is added for extraction after the reaction is finished, and an organic layer is taken for concentration to obtain the compound III;
further, the synthesis of the compound of the formula IV comprises the following steps:
step 1: preparing a compound of a formula VI to obtain a compound of a formula V;
step 2: the compound of formula V is prepared to obtain a compound of formula IV, and the reaction route is as follows:
Wherein step 1 comprises adding VI compound and base into organic solvent, and dripping methylsulfonyl chloride at-20-40deg.C to obtain compound V. Wherein the organic solvent is selected from one of dichloromethane, dichloroethane, petroleum ether, ethyl acetate, acetone and toluene, and the alkali is selected from one of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, sodium hydroxide and potassium hydroxide.
Step 2 comprises adding the compound V and N-hydroxyphthalimide into an organic solvent, adding alkali after dissolving, and reacting at 40-100 ℃ to prepare the compound IV. The organic solvent is selected from one of DMF, acetonitrile, 1, 4-dioxane, N-methylpyrrolidone and N, N-dimethylacetamide, and the alkali is selected from one of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide and potassium hydroxide.
The compounds of the formula I according to the invention are suitable for plant protection and control of undesired plants in agriculture, forestry, horticulture, since they have excellent herbicidal activity and crop safety.
The compounds of formula I according to the invention can be used for controlling weeds by means of an effective weed-controlling amount of the active compounds.
The herbicidal compositions according to the invention generally comprise from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of compounds of the formula (I). When the agents containing the compounds according to the invention are used for combating undesired vegetation and weeds, the application rate of the compounds according to the invention of the formula I is generally selected to be from 0.01 to 1000g per hectare, preferably an effective amount of from 0.01 to 500g per hectare. Preferred compounds of formula I according to the invention, for example, compounds 1 to 12, have a good weed killing effect at a dosage of 0.5 g/mu, and particularly preferred compounds have a good weed killing effect at a dosage of 0.01 g/mu. When the pesticidal composition containing the compound of formula I is used for weed control in the form of emulsifiable concentrates, wettable powders or microemulsions or the like, it is usually applied by diluting the formulation containing the compound of formula I of the present invention with water at a concentration of active ingredient in the range of 0.01 to 5000 ppm. The granule, powder, etc. may be administered without dilution. The results of the study show that the compounds of formula (I) according to the invention have a killing effect of at least 90% on certain weeds and resistant weeds in a concentration range of 0.01 to 100ppm (0.01 mg/L to 100 mg/L). Preferred compounds have at least 90% killing effect on certain weeds and resistance in the range of 0.1ppm to 100 ppm.
The compounds of formula (I) may be formulated into conventional formulations by conventional formulation methods, such as emulsifiable concentrates, oil solutions, powders, granules, wettable powders, flowable formulations, microcapsules, aerosols, fumigants, baits and the like. The form of use depends on the particular purpose of use.
The formulations are prepared in a manner known per se, for example by mixing the active compounds with solvents and/or carriers, if appropriate with the addition of suitable emulsifiers and dispersants or other customary auxiliaries.
The agent for controlling harmful plants of the present invention comprises the compound of the present invention and an inert carrier. Inert carriers as used herein mean extenders, diluents and formulations used in the agricultural field. The agent for controlling harmful plants of the present invention is usually prepared by mixing the compound of the present invention with an inert carrier such as a solid carrier, a liquid carrier or a gaseous carrier, and if necessary, surfactants and other adjuvants for formulation to be formulated into emulsifiable concentrates, oil solutions, powders, granules, wettable powders, flowable agents, microcapsules, aerosols, fumigants, poison baits and the like.
Examples of solid carriers used in the pesticide composition support formulation include: fine powder or particles of clay (e.g., kaolin clay, diatomaceous earth, bentonite), synthetic hydrous silica, talc, ceramics, other inorganic materials (e.g., quartz, sulfur, activated carbon, calcium carbonate, or hydrous silica), chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, or ammonium chloride), and synthetic resins (e.g., polyester resins such as polypropylene, polyacrylonitrile, polymethyl methacrylate, and polyethylene terephthalate, nylon resins, polyamide resins, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-propylene copolymers), and the like.
Examples of the above-mentioned liquid carrier include: water, alcohols (e.g., methanol, ethanol, isopropanol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, or phenoxyethanol), ketones (e.g., acetone, methyl ethyl ketone, or cyclohexanone), aromatic hydrocarbons (e.g., toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylylethane, or methylnaphthalene); aliphatic hydrocarbons (e.g., hexane, cyclohexane, kerosene or light oil), esters (e.g., ethyl acetate, butyl acetate, isopropyl myristate, ethyl oleate, diisopropyl adipate, diisobutyl adipate or propylene glycol monomethyl ether acetate, propylene carbonate), nitriles (e.g., acetonitrile or isobutyronitrile), ethers (e.g., diisopropyl ether, 1, 4-dioxane, ethylene glycol dimethyl ether, diglyme, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether or 3-methoxy-3-methyl-1-butanol), amides (e.g., N-dimethylformamide or N, N-dimethylacetamide), halogenated hydrocarbons (e.g., dichloromethane, trichloroethane or carbon tetrachloride), sulfoxides (e.g., dimethyl sulfoxide) and vegetable oils (e.g., soybean oil or cottonseed oil).
The surfactant used in the invention comprises: nonionic surfactants such as polyoxyethylated alkyl ethers, polyoxyethylated alkylaryl ethers, polyethylene glycol fatty acid esters, anionic surfactants such as alkyl sulfonate/benzene sulfonate/sulfate, and also include commercial surfactants such as agro-milk 500, agro-milk 100, agro-milk 300, agro-milk 400, agro-milk 600, agro-milk 700, agro-milk 0204, agro-milk 1600, ning-milk 32, ning-milk 36.
Examples of other formulation aids that may be added as needed include: binders, dispersants, colorants and stabilizers. Specific examples thereof include starch, gum arabic, cellulose derivatives and alginic acid, lignin derivatives, bentonite, polyvinyl alcohol, polyvinylpyrrolidone and polyacrylic acid, 2, 6-di-tert-butyl-4-cresol, 2-tert-butyl-4-methoxyphenol and a mixture of 3-tert-butyl-4-methoxyphenol.
The preparations produced generally contain 0.01 to 95% by weight, preferably 0.1 to 90% by weight, of active compound.
The pesticidal agent for controlling undesired plants of the present invention can be used in agricultural fields of the following crops. The crop comprises: corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, beet, canola, sunflower, sugarcane, tobacco, eggplant, tomato, sweet pepper, chilli, potato, cucumber, pumpkin, zucchini, watermelon, melon, japanese radish, white radish, horseradish, kohlrabi, cabbage, broccoli, cauliflower, crowndaisy, artichoke, lettuce, onion, garlic or asparagus, carrot, parsley, celery, parsnip, spinach, swiss beet, apple, pear, papaya, peach, plum, nectarine, plum, cherry, apricot, prune, citrus unshiu, orange, lemon, lime, grapefruit, chestnut, walnut, hazelnut, almond, pistachio, cashew or macadamia nut, grape, persimmon, olive, loquat, banana, coffee, date, coconut, oil palm, etc. The undesirable plants include annual or perennial weeds and weeds that develop resistance, preferably annual grasses and weeds that develop resistance, particularly preferably barnyard grass, crab grass, goosegrass, moleplant seed, resistant barnyard grass. The resistant weeds of the invention are opposite to sensitive weeds, for example, the sensitive weeds can have better control effect when the application amount is lower, and the application amount of the resistant weeds is required to be larger, which can be ten times, even hundreds times, that of the sensitive weeds. The test data of the invention show that the compound has better effect of preventing and controlling the resistant weed targets under the condition that the application amounts of the corresponding sensitive targets and the resistant targets are the same.
The compound of the invention has better safety for farmland crops compared with the prior disclosed compound, in particular to corn, wheat, rice, soybean and rape.
Preparation example
The preparation and use of the active ingredients of formula (I) of the present invention are illustrated by, but not limited to, the following examples. The raw materials in the preparation example of the invention can be purchased in the market or synthesized by referring to the method disclosed by the prior art.
EXAMPLE 1 Compound 12- {1- [1- (4-methyl-phenoxymethyl) -but-3-enyloxyimino ] -ethyl } -3-hydroxy-5-methyl-cyclohex-2-enone
1.1 Synthesis of 1- (4-methyl-phenoxymethyl) -but-3-enyl methylsulfonate
11.5g of 1- (4-methyl-phenoxy) -pent-4-en-2-ol and 9.5g of sodium carbonate are added into dichloromethane, 8.3g of methylsulfonyl chloride is added dropwise at the temperature of minus 15 ℃, the reaction is carried out for 3 hours after the dropwise addition, suction filtration is carried out after the reaction is finished, the filtrate is extracted by hydrochloric acid aqueous solution, and the organic layer is concentrated to obtain 15.9g of target product;
1.2 Synthesis of O- [1- (4-methyl-phenoxymethyl) -but-3-enyl ] -hydroxylamine
Adding 15.9g of the product obtained in the previous step and 9.8. 9.8g N-hydroxyphthalimide into DMF, dissolving, adding 7.6g of sodium carbonate, reacting for 2 hours at 40 ℃, then adding dichloromethane into the system, dropwise adding 10.8g of 50% hydrazine hydrate, reacting for 3 hours at 5 ℃ after the dropwise adding is finished, extracting by adding water after the reaction is finished, and concentrating an organic layer to obtain 11.2g of target product;
1.3 Synthesis of 2- {1- [1- (4-methyl-phenoxymethyl) -but-3-enyloxyimino ] -ethyl } -3-hydroxy-5-methyl-cyclohex-2-enone
11.2g of the product obtained in the previous step and 9.3g of 2-acetyl-3-hydroxy-5-methyl-cyclohex-2-enone are dissolved by methylene dichloride, 5.4g of acetic acid is added for catalysis, the reaction is carried out for 2 hours at the temperature of 35 ℃, and 18.6g of target product is obtained after the reaction is finished and the solvent is removed, wherein the total yield is 87%.
1HNMR(300MHz，CDCl3)：δ14.68(br,1H),δ6.95-7.10(d,2H),δ6.68-6.74(d，2H),δ5.06-5.54(m,3H),δ4.51-4.58(m,1H),δ4.01-4.06(d,2H),δ2.39-2.96(m,4H),δ2.17-2.35(m,6H),δ1.81-1.92(s,3H),δ0.98-1.02(d,3H)
EXAMPLE 2 Compound 2 (Z) -2- {1- [ 4-chloro-1- (3-chloro-5-fluoro-phenoxymethyl) -but-3-enyloxyimino ] -propyl } -3-hydroxy-5-propyl-cyclohex-2-enone
2.1 Synthesis of methanesulfonic acid (Z) -4-chloro-1- (3-chloro-5-fluoro-phenoxymethyl) -but-3-enyl ester
15.9g of (Z) -5-chloro-1- (3-chloro-5-fluoro-phenoxy) -pent-4-en-2-ol and 16.6g of potassium carbonate are added into dichloroethane, 7.6g of methylsulfonyl chloride is added dropwise at 10 ℃, the reaction is carried out for 2 hours after the dropwise addition, the filtrate is filtered by suction after the reaction is finished, the filtrate is extracted by hydrochloric acid aqueous solution, and the organic layer is concentrated to obtain 19.9g of target product;
2.2 Synthesis of (Z) -O- [ 4-chloro-1- (3-chloro-5-fluoro-phenoxymethyl) -but-3-enyl ] -hydroxylamine
Adding 19.9g of the product obtained in the previous step and 9.8. 9.8g N-hydroxyphthalimide into acetonitrile, dissolving, adding 8.3g of potassium carbonate, reacting for 3 hours at 60 ℃, cooling to room temperature, adding dichloroethane into a reaction system, then dropwise adding 7.5g of 80% hydrazine hydrate, reacting for 3 hours at 20 ℃ after the dropwise adding is finished, extracting by adding water after the reaction is finished, and concentrating an organic layer to obtain 15.1g of target product;
2.3 Synthesis of (Z) -2- {1- [ 4-chloro-1- (3-chloro-5-fluoro-phenoxymethyl) -but-3-enyloxyimino ] -propyl } -3-hydroxy-5-propyl-cyclohex-2-enone
15.1g of the product obtained in the previous step and 12.6g of 3-hydroxy-2-propionyl-5-propyl-cyclohex-2-enone are dissolved by dichloroethane, 2.8g of formic acid is added for catalysis, the reaction is carried out for 2 hours at 70 ℃, and after the reaction is finished, 23.6g of target product is obtained by removing the solvent, and the total yield is 83%.
1HNMR(300MHz，CDCl3)：δ14.81(br,1H),δ6.46-7.79(m，3H),δ5.84-6.14(m，2H),δ4.48-4.51(m,1H),δ3.96-4.15(d,2H),δ2.64-2.99(m,4H),δ2.12-2.41(m,3H),δ1.21-1.71(m,6H),δ0.94-1.06(m,6H)
EXAMPLE 3 Compound 3 (R) -4- {2- [1- (4-butyl-2-hydroxy-6-oxo-cyclohex-1-enyl) -butyrylaminooxy ] -propoxy } -benzonitrile
3.1 Synthesis of (R) -methylsulfonic acid 2- (4-cyanophenoxy) -1-methylethyl ester
Adding 10.6g of (R) -4- (2-hydroxy propoxy) -benzonitrile and 15.1g of sodium bicarbonate into petroleum ether, dropwise adding 6.9g of methylsulfonyl chloride at 35 ℃, reacting for 3 hours after the dropwise adding is finished, suction filtering to obtain filtrate after the reaction is finished, extracting with sulfuric acid aqueous solution, and concentrating an organic layer to obtain 15.0g of target product;
3.2 Synthesis of (R) -4- (2-aminooxy-propoxy) -benzonitrile
Adding 15.0g of the product obtained in the previous step and 11.7g of N-hydroxyphthalimide into 1, 4-dioxane, adding 14.1g of sodium bicarbonate after dissolution, reacting for 2 hours at 95 ℃, cooling to room temperature after the reaction is finished, adding dichloroethane into a reaction system, then dropwise adding 12.5g of 60% hydrazine hydrate, reacting for 1 hour at 80 ℃ after the dropwise adding is finished, extracting with water after the reaction is finished, and concentrating an organic layer to obtain 10.6g of target product;
3.3 Synthesis of (R) -4- {2- [1- (4-butyl-2-hydroxy-6-oxo-cyclohex-1-enyl) -butyrylaminooxy ] -propoxy } -benzonitrile
10.6g of the product obtained in the previous step and 15.7g of 5-butyl-2-butyl-3-hydroxy-cyclohex-2-enone are dissolved by toluene, 4.3g of acetic acid is added for catalysis, the reaction is carried out for 1h at 90 ℃, and after the reaction is finished, 22.3g of target product is obtained by removing the solvent, and the total yield is 90%.
1HNMR(300MHz，CDCl3)：δ14.67(br,1H),δ7.45-7.52(d，2H),δ6.88-6.94(d，2H),δ4.45-4.52(m,1H),δ3.90-4.07(d,2H),δ2.58-2.97(m,4H),δ2.20-2.39(m,1H),δ1.23-1.62(m,13H),δ0.98-1.02(m,6H)
EXAMPLE 4 Compound 4 (S) -5-ethoxymethyl-3-hydroxy-2- { 2-methyl-1- [1- (3-trifluoromethyl-phenoxymethyl) -propoxyimino ] -butyl } -cyclohex-2-enone
4.1 Synthesis of (S) -methylsulfonic acid 1- (3-trifluoromethyl-phenoxymethyl) -propyl ester
14.1g of (S) -1- (3-trifluoromethyl-phenoxy) -butanol and 7.2g of potassium bicarbonate are added into ethyl acetate, 6.9g of methylsulfonyl chloride is added dropwise at 15 ℃, the mixture is reacted for 3 hours after the dripping is finished, the filtrate is filtered after the reaction is finished, the filtrate is extracted by hydrochloric acid aqueous solution, and the organic layer is concentrated to obtain 18.4g of target product;
4.2 Synthesis of (S) -O- [1- (3-trifluoromethyl-phenoxymethyl) -propyl ] -hydroxylamine
Adding 18.4g of the product obtained in the previous step and 9.8. 9.8g N-hydroxyphthalimide into N-methylpyrrolidone, adding 6.6g of potassium bicarbonate after dissolution, reacting for 5 hours at 50 ℃, cooling to room temperature after the reaction is finished, adding solvent dichloroethane into a reaction system, then dropwise adding 5.7g of 85% hydrazine hydrate, reacting for 3 hours at 60 ℃ after the dropwise adding is finished, extracting with water after the reaction is finished, and concentrating an organic layer to obtain 13.5g of target product;
4.3 Synthesis of (S) -5-ethoxymethyl-3-hydroxy-2- { 2-methyl-1- [1- (3-trifluoromethyl-phenoxymethyl) -propoxyimino ] -butyl } -cyclohex-2-enone
13.5g of the product obtained in the previous step and 15.2g of 5-ethoxymethyl-3-hydroxy-2- (2-methyl-butyl) -cyclohex-2-enone are dissolved by acetone, 3.6g of acetic acid is added for catalysis, the reaction is carried out for 3 hours at 50 ℃, and after the reaction is finished, 24.7g of target product is obtained by removing the solvent, and the total yield is 85%.
1H NMR(300MHz，CDCl3)：δ14.53(br,1H),δ6.77-7.12(m，4H),δ4.42-4.49(m,1H),δ3.93-4.01(d,2H),δ3.31-3.50(m，4H),δ2.54-2.93(m,4H),δ2.11-2.19(m,1H),δ1.11-1.71(m,11H),δ0.96-1.04(m,6H)
Example 5 Compound 52- { [1- (4-chloro-pyridin-2-oxymethyl) -butoxyimino ] -cyclopropylmethyl } -3-hydroxy-5- (2-methylsulfonaminoethyl) -cyclohex-2-enone
5.1 Synthesis of 1- (4-chloro-pyridin-2-oxymethyl) butyl methanesulfonate
Adding 12.9g of 1- (4-chloro-pyridine-2-oxy) -pentane-2-ol and 6.7g of triethylamine into acetone, dropwise adding 7.8g of methylsulfonyl chloride at the temperature of 0 ℃, reacting for 3 hours after the dropwise adding is finished, suction-filtering to obtain filtrate after the reaction is finished, extracting with hydrochloric acid aqueous solution, and concentrating an organic layer to obtain 17.3g of target product;
5.2 Synthesis of O- [1- (4-chloro-pyridin-2-oxymethyl) -butyl ] -hydroxylamine
17.3g of the product obtained in the previous step and 11.7g of N-hydroxyphthalimide are added into N, N-dimethylacetamide, 3.1g of sodium hydroxide is added after dissolution, reaction is carried out for 3 hours at 40 ℃, dichloroethane is added into a reaction system after the reaction is finished, 9.4g of 80% hydrazine hydrate is then dropwise added, reaction is carried out for 2.5 hours at 60 ℃ after the dropwise addition is finished, water is added for extraction after the reaction is finished, and 13.0g of target product is obtained by concentrating an organic layer;
5.3 Synthesis of 2- { [1- (4-chloro-pyridin-2-oxymethyl) -butoxyimino ] -cyclopropylmethyl } -3-hydroxy-5- (2-methylsulfanylethyl) -cyclohex-2-enone
13.0g of the product obtained in the previous step and 19.5g of 2-cyclopropanecarbonyl-3-hydroxy-5- (2-methylsulfanylethyl) -cyclohex-2-enone are dissolved by using a solvent DMF, 5.4g of acetic acid is added for catalysis, the reaction is carried out for 2 hours at 70 ℃, and after the reaction is finished, the solvent is removed to obtain 25.7g of target product, and the total yield is 92%.
1HNMR(300MHz，CDCl3)：δ14.59(br,1H),δ8.21-8.24(d,1H),δ6.90-6.94(m,2H),δ3.76-4.25(m,3H),δ2.44-2.84(m,6H),δ2.09-2.13(m,1H),δ1.33-1.89(m,9H),δ0.88-1.01(m,8H)
EXAMPLE 6 Compound 62- [ (1-allyloxymethyl-2-methylpropoxyimino) - (2-methylcyclopropyl) -methyl ] -3-hydroxy-5-isopropoxymethyl-cyclohex-2-enone
6.1 Synthesis of 1-allyloxymethyl-2-methylpropyl sulfamate
Adding 8.7g of 1-allyloxy-3-methyl-butane-2-alcohol and 7.3g of triethylamine into toluene, dropwise adding 8.4g of methylsulfonyl chloride at the temperature of minus 10 ℃, reacting for 3 hours after the dropwise adding is finished, suction filtering to obtain filtrate after the reaction is finished, extracting with hydrochloric acid aqueous solution, and concentrating an organic layer to obtain 12.7g of target product;
6.2 Synthesis of O- (1-allyloxymethyl-2-methylpropyl) -hydroxylamine
Adding 12.7g of the product obtained in the previous step and 9.8g of N-hydroxyphthalimide into a solvent N, N-dimethylacetamide, dissolving, adding 4.0g of potassium hydroxide, reacting for 1h at 50 ℃, cooling to room temperature after the reaction is finished, adding dichloromethane into a reaction system, then dropwise adding 9.8g of 40% hydrazine hydrate, reacting for 1.5h at 30 ℃ after the dropwise adding is finished, extracting with water after the reaction is finished, and concentrating an organic layer to obtain 7.8g of target product.
6.3 Synthesis of 2- [ (1-allyloxymethyl-2-methylpropyloxyimino) - (2-methylcyclopropyl) -methyl ] -3-hydroxy-5-isopropoxymethyl-cyclohex-2-enone
7.8g of the product obtained in the previous step and 13.1g of 3-hydroxy-5-isopropoxymethyl-2- (2-methyl-cyclopropylmethyl) -cyclohex-2-enone are dissolved by petroleum ether, 2.8g of formic acid is added for catalysis, the reaction is carried out for 1.5 hours at the temperature of 60 ℃, and after the reaction is finished, the solvent is removed to obtain 19.1g of the target product, and the total yield is 78%.
1H NMR(300MHz，CDCl3)：δ14.43(br,1H),δ5.23-5.69(m,3H),δ4.21-4.28(m,3H),δ3.98-4.04(d,2H),δ3.33(d,2H),δ2.35-2.96(m,5H),δ2.05-2.18(m,1H),δ1.01-1.78(m,16H),δ0.84-0.99(m,4H)
EXAMPLE 7 Compound 72- {1- [2- (4-chloro-phenoxy) -1-methyl-ethoxyimino ] -propyl } -5- (2-ethylsulfanyl-propyl) -3-hydroxy-cyclohex-2-enone
7.1 Synthesis of 2- (4-chloro-phenoxy) -1-methylethyl methylsulfonate
22.4g of 1- (4-chloro-phenoxy) -propane-2-ol and 18.2g of triethylamine are added into acetone, 15.3g of methylsulfonyl chloride is added dropwise at 15 ℃, the mixture reacts for 3 hours after the dripping is finished, filtrate is filtered after the reaction is finished, the filtrate is extracted by hydrochloric acid aqueous solution, and an organic layer is concentrated to obtain 31.1g of target product;
7.2 Synthesis of O- [2- (4-chloro-phenoxy) -1-methylethyl ] -hydroxylamine
Adding 31.1g of the product obtained in the previous step and 21.5g of N-hydroxyphthalimide into DMF solvent, dissolving, adding 14.4g of sodium hydroxide, reacting at 60 ℃ for 1h, cooling to room temperature after the reaction is finished, adding dichloroethane into a reaction system, then dropwise adding 15.4g of 70% hydrazine hydrate, reacting at 50 ℃ for 2h after the dropwise adding is finished, extracting with water after the reaction is finished, and concentrating an organic layer to obtain 21.9g of target product;
7.3 Synthesis of 2- {1- [2- (4-chloro-phenoxy) -1-methyl-ethoxyimino ] -propyl } -5- (2-ethylsulfanyl-propyl) -3-hydroxy-cyclohex-2-enone
11.0g of the product obtained in the previous step and 17.8g of 5- (2-ethylthio-propyl) -3-hydroxy-2-propionyl-cyclohex-2-enone are dissolved by dichloroethane, 7.2g of acetic acid is added for catalysis, the reaction is carried out for 2 hours at 80 ℃, and after the reaction is finished, the solvent is removed to obtain 24.2g of the target product, and the total yield is 89%.
1HNMR(300MHz，CDCl3)：δ14.52(br,1H),δ7.28-7.32(d,2H),δ6.88-6.91(d，2H),δ4.51-4.58(m,1H),δ3.99-4.06(d,2H),δ2.38-2.89(m,7H),δ2.07-2.15(m,1H),δ1.20-1.58(m,13H),δ0.99-1.04(t,3H)
EXAMPLE 8 Compound 82- {1- [2- (4-chloro-phenoxy) -1-methyl-ethoxyimino ] -butyl } -5- (2-ethylsulfanyl-propyl) -3-hydroxy-cyclohex-2-enone
8.1 Synthesis of 2- {1- [2- (4-chloro-phenoxy) -1-methyl-ethoxyimino ] -butyl } -5- (2-ethylsulfanyl-propyl) -3-hydroxy-cyclohex-2-enone
Petroleum ether is used for dissolving 10.9g O- [2- (4-chlorine-phenoxy) -1-methyl ethyl ] -hydroxylamine and 17.6g of 2-butyl-5- (2-ethylthio-propyl) -3-hydroxy-cyclohex-2-enone, 4g of acetic acid is added for catalysis, the reaction is carried out for 3 hours at 80 ℃, and after the reaction is finished, the solvent is removed to obtain 24.8g of target product, and the yield is 98%.
1HNMR(300MHz，CDCl3)：δ14.51(br,1H),δ7.22-7.26(d,2H),δ6.85-6.87(d，2H),δ4.49-4.54(m,1H),δ3.98-4.03(d,2H),δ2.33-2.86(m,7H),δ2.07-2.15(m,1H),δ1.23-1.59(m,15H),δ0.91-0.96(t,3H)
EXAMPLE 9 Compound 94- {2- [1- (2-hydroxy-4-oxiranyl-6-oxo-cyclohex-1-enyl) -butyrylaminooxy ] -pent-3-enoxy } -benzonitrile
9.1 Synthesis of 1- (4-cyano-phenoxymethyl) -but-2-enyl methanesulfonate
Adding 12.2g of 4- (2-hydroxy-pent-3-alkenyloxy) -benzonitrile and 5.4g of potassium hydroxide into a solvent dichloroethane, dropwise adding 7.6g of methylsulfonyl chloride at 35 ℃, reacting for 1.5h after the dropwise adding is finished, suction-filtering to obtain filtrate after the reaction is finished, extracting with a hydrochloric acid aqueous solution, and concentrating an organic layer to obtain 16.0g of target product;
9.2 Synthesis of 4- (2-aminooxy-pent-3-enoxy) -benzonitrile
Adding 16.0g of the product obtained in the previous step and 9.8. 9.8g N-hydroxyphthalimide into DMF, dissolving, adding 4.0g of potassium hydroxide, reacting for 3 hours at 45 ℃, adding dichloroethane into a reaction system after the reaction is finished, then dropwise adding 9.0g of 50% hydrazine hydrate, reacting for 2 hours at 50 ℃ after the dropwise adding is finished, extracting with water after the reaction is finished, and concentrating an organic layer to obtain 11.1g of target product;
9.3 Synthesis of 4- {2- [1- (2-hydroxy-4-oxiranyl-6-oxo-cyclohex-1-enyl) -butyrylaminooxy ] -pent-3-enoxy } -benzonitrile
11.1g of the product obtained in the previous step and 13.4g of 2-butyl-3-hydroxy-5-oxiranyl-cyclohex-2-enone are dissolved by methanol, 3.9g of acetic acid is added for catalysis, the reaction is carried out for 1.5h at 60 ℃, and after the reaction is finished, 20.6g of target product is obtained by removing the solvent, and the total yield is 81%.
1HNMR(300MHz，CDCl3)：δ14.66(br,1H),δ7.42-7.56(d,2H),δ6.95-7.02(d，2H),δ5.52-5.69(m,2H),δ4.75-4.89(m,1H),δ4.02-4.13(d,2H),δ2.53-2.96(m,8H),δ1.47-1.72(m,7H),δ0.99(t,3H)
EXAMPLE 10 Compound 102- {1- [ 4-chloro-1- (4-nitro-phenoxymethyl) -but-2-enyloxyimino ] -2-methylpropyl } -3-hydroxy-5- (2-methyl-cyclopropylsulfamomethyl) -cyclohex-2-enone
10.1 Synthesis of 4-chloro-1- (4-nitrophenoxymethyl) -but-2-enyl methanesulfonate
15.5g of 5-chloro-1- (4-nitrophenoxy) -pent-3-en-2-ol and 7.2g of potassium bicarbonate are added into dichloromethane, 7.6g of methylsulfonyl chloride is added dropwise at the temperature of minus 5 ℃, the reaction is carried out for 2 hours after the dropwise addition, the filtrate is filtered after the reaction is finished, the filtrate is extracted by sulfuric acid aqueous solution, and the organic layer is concentrated to obtain 19.7g of target product;
10.2 Synthesis of O- [ 4-chloro-1- (4-nitro-phenoxymethyl) -but-2-enyl ] -hydroxylamine
Adding 19.7g of the product obtained in the previous step and 10.8g of N-hydroxyphthalimide into 1, 4-dioxane, adding 10.2g of sodium carbonate after dissolution, reacting for 4 hours at 60 ℃, cooling to room temperature after the reaction is finished, adding dichloroethane into a reaction system, then dropwise adding 6.5g of 60% hydrazine hydrate, reacting for 3 hours at 70 ℃ after the dropwise adding is finished, extracting with water after the reaction is finished, and concentrating an organic layer to obtain 14.8g of target product;
10.3 Synthesis of 2- {1- [ 4-chloro-1- (4-nitro-phenoxymethyl) -but-2-enyloxyimino ] -2-methylpropyl } -3-hydroxy-5- (2-methyl-cyclopropylsulfamomethyl) -cyclohex-2-enone
14.8g of the product obtained in the previous step and 17.0g of 3-hydroxy-2-isobutyl-5- (2-methyl-cyclopropylsulfanylmethyl) -cyclohex-2-enone are dissolved by petroleum ether, 7.2g of acetic acid is added for catalysis, the reaction is carried out for 2 hours at 70 ℃, and after the reaction is finished, the solvent is removed to obtain 28.5g of the target product, and the total yield is 88%.
1HNMR(300MHz，CDCl3)：δ14.49(br,1H),δ8.02-8.13(d,2H),δ7.11-7.24(d，2H),δ5.84-5.96(m,2H),δ4.65-4.93(m,3H),δ4.09-4.15(d,2H),δ2.63-2.87(m,7H),δ1.26-1.42(m,2H),δ1.02-1.09(m,9H),δ0.87-0.92(m,3H)
EXAMPLE 11 Compound 112- {1- [1- (furan-2-oxymethyl) -pentoxyimino ] -2, 3-dimethylbutyl } -3-hydroxy-5- (tetrahydrothiopyran-3-yl) -cyclohex-2-enone
11.1 Synthesis of 1- (furan-2-oxymethyl) -pentyl methylsulfonate
Adding 11.1g of 1- (furan-2-oxy) -hexane-2-ol and 8.1g of sodium bicarbonate into dichloromethane, dropwise adding 7.6g of methylsulfonyl chloride at the temperature of 0 ℃, reacting for 3 hours after the dropwise adding is finished, suction-filtering to obtain filtrate after the reaction is finished, extracting with hydrochloric acid aqueous solution, and concentrating an organic layer to obtain 14.8g of target product;
11.2 Synthesis of 2- [1- (furan-2-oxymethyl) -pentoxy ] -isoindole-1, 3-dione
Adding 14.8g of the product obtained in the previous step and 9.8g of g N-hydroxyphthalimide into acetonitrile, dissolving, adding 10.8g of potassium carbonate, reacting for 2 hours at 60 ℃, adding a large amount of water and toluene for extraction after the reaction is finished, and collecting an organic layer to remove a solvent to obtain 18.5g of a target product;
11.3 Synthesis of O- [1- (furan-2-oxymethyl) -pentyl ] -hydroxylamine
Adding 18.5g of the product obtained in the previous step into dichloromethane, then dropwise adding 4.2g of 85% hydrazine hydrate, reacting for 3 hours at 20 ℃ after the dropwise adding is finished, adding water for extraction after the reaction is finished, and concentrating an organic layer to obtain 11.0g of target product;
11.4 Synthesis of 2- {1- [1- (furan-2-oxymethyl) -pentoxyimino ] -2, 3-dimethylbutyl } -3-hydroxy-5- (tetrahydrothiopyran-3-yl) -cyclohex-2-enone
11.0g of the product obtained in the previous step and 17.4g of 2- (2, 3-dimethyl-butyl) -3-hydroxy-5- (tetrahydro-thiopyran-3-yl) -cyclohex-2-enone are dissolved by dichloroethane, 4.8g of formic acid is added for catalysis, reaction is carried out for 3 hours at 80 ℃, and after the reaction is finished, the solvent is removed to obtain 23.8g of target product, and the total yield is 80%.
1H NMR(300MHz，CDCl3)：δ14.71(br,1H),δ6.04-6.73(m,3H),δ4.24-4.36(m,1H),δ4.01 -4.06(d,2H),δ2.07-2.85(m,9H),δ1.31-1.79(m,11H),δ1.03-1.21(m,14H)
EXAMPLE 12 Compound 125- (2-ethylthiopropyl) -3-hydroxy-2- { 4-methyl-1- [1- (4-methyl-1H-pyrrole-2-oxymethyl) -propoxyimine ] -pentyl } -cyclohex-2-enone
12.1 Synthesis of 1- (4-methyl-1H-pyrrole-2-propoxymethyl) -propyl methylsulfonate
10.2g of 1- (4-methyl-1H-pyrrole-2-propoxy) -butanol and 7.3g of triethylamine are added into toluene, 8.3g of methylsulfonyl chloride is added dropwise at the temperature of 10 ℃, the mixture is reacted for 2 hours after the dripping is finished, the filtrate is filtered by suction after the reaction is finished, the filtrate is extracted by hydrochloric acid aqueous solution, and the organic layer is concentrated to obtain 13.9g of target product;
12.2 Synthesis of O- [1- (4-methyl-1H-pyrrole-2-oxymethyl) -propyl ] -hydroxylamine
13.9g of the product obtained in the previous step and 9.8. 9.8g N-hydroxyphthalimide are added into DMF, 3.4g of potassium hydroxide is added after dissolution, the reaction is carried out for 6 hours at 30 ℃, dichloroethane is added into a reaction system after the reaction is finished, 7.4g of 65% hydrazine hydrate is then added dropwise, the reaction is carried out for 3 hours at 60 ℃ after the dropwise addition is finished, water is added for extraction after the reaction is finished, and 9.3g of target product is obtained by concentrating an organic layer;
12.3 Synthesis of 5- (2-ethylthiopropyl) -3-hydroxy-2- { 4-methyl-1- [1- (4-methyl-1H-pyrrole-2-oxymethyl) -propoxyimine ] -pentyl } -cyclohex-2-enone
9.3g of the product obtained in the previous step and 18.8g of 5- (2-ethylthiopropyl) -3-hydroxy-2- (4-methylpentyl) -cyclohex-2-enone are dissolved by dichloroethane, 7.2g of acetic acid is added for catalysis, the reaction is carried out for 2 hours at 80 ℃, and after the reaction is finished, the solvent is removed to obtain 23.6g of the target product, and the total yield is 82%.
1H NMR(300MHz，CDCl3)：δ14.58(br,1H),δ5.96-6.34(m,2H),δ4.31-4.39(m,1H),δ4.06-4.11(d,2H),δ2.37-2.89(m,7H),δ1.98-2.19(m,2H),δ1.25-1.62(m,17H),δ0.91-1.02(m,9H)
Biological Activity assay
The weeding experiments were performed using the 12 oxime ether 1, 3-cyclohexanedione compounds provided in examples 1 to 12, respectively.
The specific experimental conditions are as follows:
sowing weed seeds in a greenhouse, wherein the growth conditions are as follows: the pH of the soil is approximately equal to 6.8, the organic matter content of the soil is approximately equal to 30%, the temperature is 22-25 ℃, and the illumination time is 14 hours of photoperiod; timely supplementing water and nutrition, enabling weeds to grow to 3-4 leaf stages, diluting with 450L/ha water, spraying the diluted water onto the weeds, and observing and calculating plant prevention effect after 10 days.
Weed species: barnyard grass, crab grass, gooseberry, moleplant seed and resistant barnyard grass
The plant prevention effect calculation formula: plant control= (number of plants before treatment-plant tree after treatment)/plant tree before treatment 100.
Medicament: the 12 oxime ether type 1, 3-cyclohexanedione compounds provided in examples 1 to 12 are used for preparing 5 weight percent emulsifiable concentrates, and the specific components are as follows: 5% of compound (1 to 12) +6% of agro-milk 0204+4% ethanol+85% of naphtha.
Control sample 1:5 wt.% Compound e1 (CN 11205208A) +6% Nongru 0204+4% ethanol+85% naphtha
Control sample 2:5 wt.% Compound 5 (patent CN 114105842A) +6% Nongru 0204+4% ethanol+85% naphtha
Control sample 3:30% quinclorac suspending agent, which is purchased from the fine chemical company of Lvba, texas, and the dosage is 45-85 ml/mu.
Control sample 4:25 g/L penoxsulam dispersible oil suspension is purchased from Kedi Hua agricultural technology Co., ltd, and used at a dosage of 40-80 ml/mu.
Control sample 5:15% bispyribac-sodium suspending agent is purchased from Anhui Shang Hewo to biotechnology limited company, and the dosage is 10-18 ml/mu.
Control sample 6:5 wt.% of pretilachlor+6% of agro-emulsion 0204+4% of ethanol+85% of naphtha, the synthesis of pretilachlor from which CN11205208A is referred.
Control sample 7: the 24% clethodim emulsifiable concentrate is purchased from Shandong Jinan Corp sea limited company, and the dosage is 15-20 ml/mu.
/>
TABLE 2 control effect of oxime ether 1, 3-cyclohexanedione Compounds on resistant barnyard grass
/>
Compound safety test
Sowing crop seeds in a greenhouse for cultivation (the pH of soil is approximately equal to 6.8, the content of soil organic matters is approximately equal to 30%, the temperature is 22-25 ℃, the illumination is 14h photoperiod, water and nutrition are timely supplemented), applying the emulsifiable concentrate with the effective mass of the active ingredients of 5% when the crop seeds grow to 2-3 leaf periods, and evaluating the damage condition of plants after 5-7 days. The evaluation criteria for the plant damage condition were as follows:
5, damage 100%;
4, damage is more than 80%;
3, damage is more than 50%;
2, damage is more than 20%;
1, damage 0-20%;
0, no damage to plants; has no effect.
/>
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a plurality of simple variants of the technical proposal of the invention can be carried out, including that each technical feature is combined in any other suitable way and that the combination sequence is included, and the simple variants and the combination are also considered as the disclosure of the invention, and all the simple variants and the combination belong to the protection scope of the invention.

Claims (10)

1. A compound of the formula I,
diastereomers, enantiomers and rotamers of the compounds of formula I and their agriculturally suitable salts, wherein the compounds of formula I are selected fromFrom the following compounds, compound 1: />The method comprises the steps of carrying out a first treatment on the surface of the Compound 2: />；
Compound 3:the method comprises the steps of carrying out a first treatment on the surface of the Compound 4: />；
Compound 5:the method comprises the steps of carrying out a first treatment on the surface of the Compound 6: />；
Compound 7:the method comprises the steps of carrying out a first treatment on the surface of the Compound 8: />；
Compound 9:the method comprises the steps of carrying out a first treatment on the surface of the Compound 10: />；
Compound 12:。
2. a process for the preparation of a compound of formula I according to claim 1, comprising the steps of: compounds of formula II and formula III Preparing the compound of the formula I under an acidic condition,，/>，wherein R is 1 、R 2 、R 3 、R 4 As defined in claim 1.
3. The preparation method according to claim 2, wherein the reaction is carried out in an organic solvent selected from one of dichloromethane, dichloroethane, acetone, toluene, DMF, petroleum ether and methanol, and the acid is selected from organic acids, the reaction temperature is in the range of 0 to 100 ℃, and the reaction time is 1 to 10 hours.
4. The method according to claim 3, wherein the acid is selected from the group consisting of formic acid and acetic acid, and the reaction time is 1 to 3. 3 h.
5. The preparation method according to claim 4, wherein the compound of formula III is obtained by reacting the compound of formula IV with hydrazine hydrate, the reaction is carried out in an organic solvent, the organic solvent is selected from one of dichloromethane and dichloroethane, the reaction is carried out at 0-80 ℃ for 1-3 h, water is added for extraction after the reaction is finished, and the organic layer is taken for concentration to obtain the compound III;，/>。
6. the method of claim 5, wherein the synthesis of the compound of formula IV comprises the steps of:
step 1: preparing a compound of a formula VI to obtain a compound of a formula V;
step 2: the compound of formula V is prepared to obtain a compound of formula IV, and the reaction route is as follows:
。
7. The method according to claim 6, wherein,
step 1, adding a VI compound and alkali into an organic solvent, and dropwise adding methylsulfonyl chloride at the temperature of-20-40 ℃ to prepare a compound V; wherein the organic solvent is selected from one of dichloromethane, dichloroethane, petroleum ether, ethyl acetate, acetone and toluene, and the alkali is selected from one of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, sodium hydroxide and potassium hydroxide;
the step 2 comprises the steps of adding the compound V and N-hydroxyphthalimide into an organic solvent, dissolving, adding alkali, and reacting at 40-100 ℃ to prepare the compound IV, wherein the organic solvent is selected from one of DMF, acetonitrile, 1, 4-dioxane, N-methylpyrrolidone and N, N-dimethylacetamide, and the alkali is selected from one of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide and potassium hydroxide.
8. A herbicidal composition comprising a compound of claim 1 and a pesticidally acceptable carrier.
9. The herbicidal composition of claim 8, further comprising other herbicidally active compounds.
10. A method of controlling undesired vegetation, which is barnyard grass, crab grass, gooseberry and moleplant seed, comprising treating a farmland in need of control with a herbicidally effective amount of the compound of claim 1 or the composition of claim 8.
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