Isoxazole safeners and use thereof

Abstract

The present application provides a kind of formula I compound its stereoisomer and salt, formula I structure as follows: Wherein R is selected from hydrogen, optionally substituted C1-C6 Alkyl, optionally substituted phenyl or optionally substituted benzyl.The present application compound and herbicide composition use show good plant safety, with better application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of pesticides, and particularly relates to a kind of isoxazole safeners and application thereof. BACKGROUND

[0002] The extensive use of herbicides has made a great contribution to agricultural production in China and even the world, but the subsequent phytotoxicity phenomenon is also increasingly serious, which affects the yield and quality of crops to different extents, causes symptoms such as growth stagnation, plant metamorphosis and even death of crops, and brings losses to agricultural production and the pesticide industry.

[0003] One of the important means to reduce or eliminate herbicide phytotoxicity is to add herbicide safeners, the use of herbicide safeners not only can improve the drug resistance of crops and reduce phytotoxicity, but also can enhance the selectivity of herbicides to crops and weeds, and at the same time can solve the problem of difficult-to-control weeds, the use of herbicide safeners expands the application range and efficacy of herbicides.

[0004] Since the discovery of safeners in 1947, only more than thirty varieties have been commercialized, mainly including carboxylic acid derivatives, dichloroacetamide, oxime ether, growth regulator and heterocyclic compound, etc., a new type of heterocyclic isoxazole herbicide safener is developed by the company, which has the advantages of less dosage and better effect compared with existing isoxazole safeners. SUMMARY

[0005] The present application provides a new type of isoxazole herbicide safener, which has better effect than existing safeners.

[0006] Specifically, the present application provides a compound of formula I, stereoisomers and salts thereof, characterized in that the structure of formula I is as follows:

[0007]

[0008] wherein R is selected from hydrogen, optionally substituted C1-C6 alkyl, optionally substituted phenyl or optionally substituted benzyl.

[0009] The present application also provides a preparation method of the compound of formula I, and the synthetic route is as follows:

[0010]

[0011] The present application also provides a preparation method of a compound of formula I'', and the synthetic route is as follows:

[0012]

[0013] The present application also provides a preparation method of a compound of formula I''', and the synthetic route is as follows:

[0014]

[0015] wherein R is selected from hydrogen, optionally substituted C1-C6 alkyl, optionally substituted phenyl or optionally substituted benzyl, R' is selected from methyl or ethyl; R" is selected from optionally substituted phenyl; R'" is selected from optionally substituted benzyl, R'" is in particular X is selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkyl, cyano, amino, hydroxy, nitro and halogen, n is selected from an integer from 0 to 5.

[0016] The present application also discloses a herbicidal composition comprising the compound of formula I, stereoisomers and salts thereof and a herbicide.

[0017] Advantages

[0018] The compound of formula I disclosed in the present application has better effect than the existing safener, has lower production cost, and has better alleviating effect on the criticality of the herbicide when used in combination with the herbicide, and has good application prospect. DETAILED DESCRIPTION

[0019] The specific embodiments of the present application will be further described below in conjunction with the examples. To make the objectives, technical schemes and advantages of the embodiments of the present application clearer, the technical schemes in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application. Unless otherwise explicitly indicated, in the entire specification and claims, the term "comprise" or its variants such as "include" or "contain" and the like will be understood to include the stated components and steps, and not exclude the presence of other material components or steps.

[0020] In addition, in order to better illustrate the present application, numerous specific details are given in the specific embodiments below.

[0021] Those skilled in the art should understand that the present application can also be implemented without certain specific details. In some embodiments, the raw materials, methods, means and the like which are well known to those skilled in the art are not described in detail, in order to highlight the main idea of the present application.

[0022] In the following, the embodiments of the present application are described in detail. However, these embodiments are exemplary, the present application is not limited thereto, and the present application is defined by the scope of the claims.

[0023] As used herein, when no specific definition is provided otherwise, the following terms used in the specification and claims have the following meanings.

[0024] Halogen in the present invention means fluorine, chlorine, bromine or iodine.

[0025] The term "stereoisomer" as used in the present invention refers to configurational stereoisomers, which include geometric isomers and optical isomers, as well as conformational isomers.

[0026] Geometric isomers (also referred to as E / Z isomers or cis / trans isomers) are caused by different positions of substituents on a C=C double bond, which can have a Z or E configuration, also referred to as cis or trans configuration.

[0027] Optical isomers are caused by different positions of substituents or lone pairs in space on an atom (such as a carbon atom or a sulfur atom) which contains four different substituents (potentially including lone pairs). This atom thus represents a chiral or asymmetric center. Optical isomers which are not mirror images of each other are referred to as "diastereoisomers", while optical isomers which are non-superimposable mirror images of each other are referred to as "enantiomers".

[0028] The term "alkyl" (as well as the alkyl moiety in other groups comprising alkyl, such as alkoxy, haloalkyl, alkylthio) as used herein denotes in each occurrence an alkyl group typically having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms (C1-C6), examples of which are methyl, ethyl, n-propyl, i-propyl, n-butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (i-butyl), 1,1-dimethylethyl (tert-butyl), n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl, but not limited thereto.

[0029] The term "optionally substituted" means that the relevant group can be substituted with a substituent or can not be substituted.

[0030] When a group is substituted, the substituents can be alkyl, alkoxy, alkylthio, cyano, nitro, halogen, etc., but not limited thereto, for example, when an alkyl group is substituted with halogen, a haloalkyl group is formed, but not limited thereto.

[0031] The term "halogenated C1-C6-alkyl" according to the application means a C1-C6-alkyl group which is partially or completely halogenated, where the halogen atoms are fluorine, chlorine and / or bromine, i.e. for example chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloro-2-fluoroethyl and the like, especially halogenated methyl, more preferably CH(F)2 and CF3.

[0032] The term "C1-C6-alkoxy" according to the application means methoxy, ethoxy, n-propyloxy and the like, but is not limited thereto.

[0033] The term "C1-C6-alkylthio" according to the application means methylthio, ethylthio, n-propylthio and the like, but is not limited thereto.

[0034] The present application provides, first of all, a compound of the formula I, the stereoisomers and salts thereof, the structure of which is as follows:

[0035]

[0036] where R is selected from the group consisting of hydrogen, optionally substituted C1-C6-alkyl, optionally substituted phenyl or optionally substituted benzyl.

[0037] Preferably, in some embodiments, R is H, C1-C6-alkyl, halogenated C1-C6-alkyl, phenyl substituted by C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, halogenated C1-C6-alkyl, cyano, amino, hydroxy, nitro and halogen.

[0038] Further, preferably, in some embodiments, R is H, methyl, ethyl, isopropyl, phenyl, p-chlorophenyl, 2,4-dichlorophenyl, benzyl.

[0039] Preferably, the compound of the formula I is a compound of the formula I" and a compound of the formula I'", the structures of which are as follows:

[0040]

[0041] Particularly preferably, the compound of the formula I according to the application is selected from the following compounds:

[0042]

[0043] The compounds of the formula I according to the application can be obtained by the following synthesis routes:

[0044]

[0045] where R is selected from the group consisting of hydrogen, optionally substituted C1-C6-alkyl, optionally substituted phenyl or optionally substituted benzyl.

[0046] The present application also provides a preparation method of the compound of formula I", the synthetic route of which is as follows:

[0047]

[0048] wherein R' is selected from methyl or ethyl; and R" is selected from optionally substituted phenyl.

[0049] The present application also provides a preparation method of the compound of formula I", the synthetic route of which is as follows:

[0050]

[0051] wherein R'" is selected from optionally substituted benzyl, and R'" is specifically X is selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkyl, cyano, amino, hydroxyl, nitro and halogen, and n is an integer from 0 to 5.

[0052] The preparation method of each route above specifically comprises the following steps:

[0053] Preparation of the compound of formula I

[0054] First step: synthesis of 9-fluorenone hydrazone

[0055] 9-fluorenone is reacted with hydrazine hydrate in a solvent, and after the reaction is completed, 9-fluorenone hydrazone is obtained by cooling and crystallization, and filtration.

[0056] Preferably, the reaction of 9-fluorenone with hydrazine hydrate in a solvent is carried out under reflux conditions, and the reaction is heated under reflux for 1-10 h, preferably 1-5 h, and after the reaction is completed, the reaction is cooled to 0-25 °C, and 9-fluorenone hydrazone is obtained by filtration, and the solvent is selected from one or more of ethyl acetate, methanol, ethanol, petroleum ether, acetonitrile, cyclohexane and tetrahydrofuran.

[0057] Second step: synthesis of 9-fluorenyl diazomethane

[0058] An appropriate amount of solvent is taken, 9-fluorenone hydrazone and an oxidizing agent are added, and the reaction is carried out at 0-100 °C for 1-5 h, preferably 1-3 h, and after the reaction is completed, the reaction is filtered, and the filtrate is directly used in the next step or the solvent is removed by distillation under reduced pressure to obtain 9-fluorenyl diazomethane, wherein the solvent is one or more of ethyl acetate, cyclohexane, petroleum ether, acetonitrile and tetrahydrofuran, and the oxidizing agent is one or more of manganese oxide, manganese dioxide, mercury oxide, nickel peroxide, potassium permanganate and manganese dioxide.

[0059] Third step: synthesis of the compound of formula II

[0060] Suitable amount of solvent, 9-fluorenyl diazomethane and acrylic acid or acrylate ester are added, and the reaction is carried out at 0-100℃ for 1-6h, preferably 1-3h. After the reaction is completed, the solvent is removed by distillation under reduced pressure to obtain the target product. The solvent is one or more of ethyl acetate, methanol, ethanol, acetone, petroleum ether, acetonitrile, cyclohexane and tetrahydrofuran.

[0061] Step 4: Synthesis of the compound of formula I

[0062] Suitable amount of solvent, the compound of formula II, acid and sodium nitrite are added, and the reaction is carried out at 0-100℃ for 1-8h, preferably 1-4h. After the reaction is completed, the compound of formula I is obtained by purification. The solvent is one or more of ethyl acetate, acetone, acetic acid, petroleum ether, acetonitrile, cyclohexane and tetrahydrofuran. The acid is an inorganic acid or an organic acid. Preferably, the acid is one or more of hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, methanesulfonic acid and trifluoroacetic acid.

[0063] Preparation of the compound of formula I"

[0064] The compound of formula I' is added to a suitable amount of solvent, R"-OH and a catalyst are added, and the reaction is carried out at 0-100℃ for 1-5h. After the reaction is completed, the compound of formula I" is obtained by purification. The solvent is one or more of acetone, toluene, petroleum ether and tetrahydrofuran. The catalyst is one or more of sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, potassium tert-butoxide, sodium tert-butoxide and tetrabutyl titanate.

[0065] Preparation of the compound of formula I"

[0066] The compound of formula I-1 and a benzyl bromide compound are added to a solvent, and then a base is added. The reaction is carried out at 0-100℃ for 1-3h. After the reaction is completed, the compound of formula I" is obtained by purification. The solvent is one or more of ethyl acetate, methanol, ethanol, petroleum ether, acetonitrile, cyclohexane, tetrahydrofuran, DMF and dichloroethane. The base is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide.

[0067] The present application also discloses a herbicidal composition containing the compound of formula I, its stereoisomers and salts, and a herbicide. The herbicide in the composition is preferably one or more of the following herbicides:

[0068] A) sulfonylurea herbicides: one or more of pyrazosulfuron-ethyl, bensulfuron-methyl, halosulfuron-methyl, nicosulfuron, sulfometuron-methyl, mesosulfuron-methyl, foramsulfuron, chlorsulfuron, monosulfuron-ethyl, triflusulfuron-methyl and flazasulfuron, but not limited to.

[0069] B) aryloxyphenoxypropionic herbicides: one or more of cyhalofop-butyl, quizalofop-P, fenoxaprop-P, fenoxaprop-R and fenclorim; the cyclohexenone / triketone herbicides are one or more of allelchlor, alloxydim, butroxydim, clethodim, clodinafop-propargyl, cycloxydim, profoxydim, sethoxydim, tralkoxydim, sulcotrion, mesotrion, and benzobicyclon, but not limited thereto.

[0070] C) isoxazole herbicides: one or more of isoxaflutole and isoxachlortole; the aryl carboxylic acid herbicides are one or more of 2,4-D, 2-methyl-4-chloro, 2,4,5-T, 2-methyl-4-chloropropionic acid, 2,4-D butyric acid, 2,4-D butyl ester, dicamba, dichlorprop, dichlorprop-P, triclopyr, but not limited thereto.

[0071] Particularly preferably, the safeners of the present application are combined with one or more of nicosulfuron, rimsulfuron, mesosulfuron, foramsulfuron, fenoxaprop-P, sulcotrion, isoxaflutole and dicamba.

[0072] In the herbicidal compositions of the present application, the weight ratio of the herbicide to the compound of formula I of the present application is 1:99 to 99:1, preferably 1:1 to 25:1.

[0073] The herbicidal compositions of the present application containing the compound of formula I can be prepared into various dosage forms, for example, one of a suspension concentrate, a microcapsule suspension concentrate, an emulsifiable concentrate, an oil suspension concentrate, a microemulsion, an aqueous emulsion, an aqueous agent, a wettable powder, a tablet, a soluble powder, and a water dispersible granule. The above-mentioned various dosage forms can be prepared by using the preparation methods known in the art, which will not be described here.

[0074] Specifically, different auxiliary ingredients can be selected according to different dosage forms.

[0075] The auxiliary ingredients can include one or more of water, an emulsifier, a wetting agent, a dispersing agent, a thickening agent, an antifreezing agent, an antifoaming agent, a binder, a disintegrant, an organic solvent, a solid inert carrier / filler, and a stabilizer, and more specifically two, three, four or five kinds.

[0076] The organic solvent is selected from one or more of benzene, toluene, xylene, naphthalene, heavy benzene, methanol, ethanol, cyclohexanone, acetone, vegetable oil, dichloromethane, trichloromethane, acetonitrile, methyl phenol, ethylene glycol, n-butanol, sorbitol, dimethylformamide, ethyl acetate, and methyl oleate;

[0077] The emulsifier is selected from one or more of octylphenol polyoxyethylene (polyoxypropylene) ether, nonylphenol polyoxyethylene ether, benzylphenol polyoxyethylene ether, phenylethylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, fatty amine polyoxyethylene ether, polyhydric alcohol fatty acid ester, alkylbenzene sulfonate, alkyl sulfonate, agricultural emulsifier series, and Tween series. For example: one or more of calcium dodecylbenzenesulfonate, styrylphenol polyoxyethylene ether phosphate, benzylphenol polyoxyethylene ether phosphate, sorbitan trioleate, glycerol monostearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene monopalmitate, sorbitan polyoxyethylene ether, polyoxyethylene sorbitan monooleate, and castor oil polyoxyethylene ether;

[0078] The dispersant is selected from one or more of alkyl naphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, aralkyl naphthalene sulfonate formaldehyde condensate, naphthol sulfonate formaldehyde condensate, alkyl benzene sulfonate, alkyl phosphate ester, alkyl phenol polyoxyethylene ether, lignin sulfonate, fatty acid polyoxyethylene ester, fatty amine polyoxyethylene ether, vegetable oil ethylene oxide adduct, ethylene oxide-propylene oxide block copolymer, and ethylenediamine polyoxyethylene polyoxypropylene ether;

[0079] The wetting agent / penetrant mainly includes one or more of fatty alcohol sulfate, alkyl benzene sulfonate, alpha-olefin sulfonate, dialkyl succinate sulfonate, fatty amide N-methyl taurine sodium salt, and sodium alkyl naphthalene sulfonate;

[0080] The thickening agent is selected from one or more of starch, xanthan gum, agar, methyl cellulose, hydroxypropyl methyl cellulose, organic bentonite, diatomite, polyvinyl alcohol, magnesium aluminum silicate, clay, and white carbon black;

[0081] The organic suspending medium is selected from one or more of soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, palm oil, peanut oil, castor oil, and transesterification products thereof;

[0082] The antifreeze agent is selected from one or more of ethylene glycol, propylene glycol, glycerol, urea, polyethylene glycol, and sodium chloride;

[0083] The defoaming agent is selected from polyether defoaming agent and / or silicone defoaming agent;

[0084] The binder is selected from one or more of sucrose, maltose, dextrin, and starch;

[0085] The disintegrant is selected from one or more of corn starch, dextrose, hydroxypropyl starch, carboxypropyl cellulose, and urea;

[0086] The solid inert carrier / filler can include one or more of diatomite, attapulgite, bentonite, sepiolite, kaolin, pottery clay, white carbon black, talcum powder, and light calcium;

[0087] The preservative is selected from one or more of benzoic acid, sorbic acid, p-hydroxybenzoic acid, hydroquinone, and the like.

[0088] The herbicidal composition of the present application can be provided in a finished form, i.e., the components of the composition have been mixed, or in the form of separate preparations of each component, which are mixed just prior to use.

[0089] The herbicidal composition containing the compound of formula I of the present application can be used in the field of agricultural crops. The agricultural crops include corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, sugar beet, oilseed rape, sunflower, sugarcane, tobacco, eggplant, tomato, sweet pepper, hot pepper, potato, cucumber, pumpkin, zucchini, watermelon, melon, Japanese radish, white radish, horseradish, kohlrabi, Chinese cabbage, cabbage, mustard, broccoli, cauliflower, artichoke, lettuce, onion, garlic or asparagus, carrot, parsley, celery, parsnip, spinach, Swiss chard, apple, pear, papaya, peach, plum, nectarine, prune, cherry, apricot, prune, orange, lemon, lime, grapefruit, chestnut, walnut, hazel, almond, pistachio or macadamia nut, grape, persimmon, olive, loquat, banana, coffee, date palm, coconut, oil palm, and the like. The herbicidal composition containing the compound of formula I of the present application exhibits excellent safety to the above-mentioned plants.

[0090] The preparation and use of the compound of formula I of the present application are exemplified by, but not limited to, the following examples. The starting materials in the preparation examples of the present application can be purchased in the market or synthesized according to the methods disclosed in the prior art.

[0091] Preparation Example

[0092] Example 19 - Synthesis of fluorenyl diazomethane

[0093] Example 19 - Synthesis of fluorenyl diazomethane

[0094] Example 29 - Synthesis of fluorenyl diazomethane

[0095] Take 9.01 g of 9-fluorenone and 12.52 g of hydrazine hydrate (mass fraction 30%) into ethyl acetate, heat to reflux for 1 h, cool to 20°C after the reaction is completed, crystallize, filter to obtain 9.52 g of 9-fluorenone hydrazone, take 9.52 g of 9-fluorenone hydrazone and 16.25 g of mercuric oxide into acetonitrile, react at 20°C for 3 h, filter after the reaction is completed, take the filtrate to remove the solvent by distillation under reduced pressure to obtain 8.95 g of 9-fluorenyl diazomethane, with a yield of 93%.

[0096] Example 39-fluorenyl diazomethane synthesis

[0097] Take 9.01 g of 9-fluorenone and 4.59 g of hydrazine hydrate (mass fraction 60%) into tetrahydrofuran, heat to reflux for 3 h, cool to 5°C after the reaction is completed, crystallize, filter to obtain 9.56 g of 9-fluorenone hydrazone, take 9.56 g of 9-fluorenone hydrazone and 4.53 g of nickel peroxide into petroleum ether, react at 80°C for 1 h, filter after the reaction is completed, take the filtrate to remove the solvent by distillation under reduced pressure to obtain 9.08 g of 9-fluorenyl diazomethane, with a yield of 94%.

[0098] Example 4 Synthesis of compound of formula I-1

[0099]

[0100] Take 5.77 g of 9-fluorenyl diazomethane and 2.38 g of acrylic acid into ethyl acetate, react at 40°C for 2 h, remove the solvent by distillation under reduced pressure after the reaction is completed to obtain 6.95 g of compound of formula II-1, take 6.95 g of compound of formula II-1, 0.3 g of concentrated sulfuric acid and 2.28 g of sodium nitrite into acetonitrile, react at 50°C for 2 h, concentrate after the reaction is completed, wash with water and dry to obtain 7.64 g of compound of formula I-1, with a yield of 96%.

[0101] Nuclear magnetic resonance: 1H NMR (300 MHz, CDCl3) δ 7.76-7.78 (d, 2H), δ 7.58-7.60 (d, 2H), δ 7.42-7.46 (t, 2H), δ 7.31-7.35 (t, 2H), δ 3.74 (s, 2H)

[0102] Example 5 Synthesis of compound of formula I-2

[0103]

[0104] To 5.77 g of 9-fluorene diazomethane and 3.30 g of ethyl acrylate in acetonitrile, 80°C for 1 h, after the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain 7.77 g of the compound of formula II-2. To 7.77 g of the compound of formula II-2, 0.86 g of methanesulfonic acid and 2.48 g of sodium nitrite in acetic acid, 70°C for 1 h, after the reaction was completed, the organic layer was extracted with water and concentrated to obtain 8.45 g of the compound of formula I-2, with a yield of 96%.

[0105] NMR:1H NMR (300 MHz, CDCl3) δ 7.78-7.80 (d, 2H), δ 7.58-7.61 (d, 2H), δ 7.42-7.47 (t, 2H), δ 7.32-7.36 (t, 2H), δ 4.29-4.37 (q, 2H), δ 3.75 (s, 2H), δ 1.32-1.36 (t, 3H)

[0106] Example 6 Synthesis of the compound of formula I-3

[0107]

[0108] To 5.77 g of 9-fluorene diazomethane and 3.30 g of ethyl acrylate in acetonitrile, 80°C for 1 h, after the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain 7.77 g of the compound of formula II-2. To 7.77 g of the compound of formula II-2, 0.86 g of methanesulfonic acid and 2.48 g of sodium nitrite in acetic acid, 70°C for 1 h, after the reaction was completed, the organic layer was extracted with water and concentrated to obtain 8.45 g of the compound of formula I-2, with a yield of 96%.

[0109] NMR:1H NMR (300 MHz, CDCl3) δ 7.78-7.80 (d, 2H), δ 7.58-7.61 (d, 2H), δ 7.42-7.47 (t, 2H), δ 7.32-7.36 (t, 2H), δ 4.29-4.37 (q, 2H), δ 3.75 (s, 2H), δ 1.32-1.36 (t, 3H)

[0110] Example 7 Synthesis of the compound of formula I-4

[0111]

[0112] To 5.87 g of the compound of formula I-2 in toluene, 2.82 g of phenol and 1.52 g of potassium carbonate were added, and the mixture was reacted at 90°C for 2 h. After the reaction was completed, the solvent was removed, and the residue was washed with water and dried to obtain 6.55 g of the compound of formula I-4, with a yield of 96%.

[0113] NMR: 1H NMR (300 MHz, DMSO) δ7.82-7.84 (d, 2H), δ7.71-7.73 (d, 2H), δ7.33-7.52 (m, 9H), δ3.89 (s, 2H)

[0114] Example 8 Synthesis of Compound of Formula I-5

[0115]

[0116] Take 5.87g of the compound of formula I-2 and add it to toluene. Then add 3.86g of p-chlorophenol and 3.6g of sodium methoxide methanol solution (mass fraction 30%). React at 80°C for 3h. After the reaction is completed, cool and add a large amount of ice water. Take the organic layer and remove the solvent to obtain 7.22g of the compound of formula I-5, with a yield of 96%.

[0117] NMR: 1H NMR (300 MHz, DMSO) δ7.81-7.84 (d, 2H), δ7.70-7.72 (d, 2H), δ7.32-7.54 (m, 8H), δ3.86 (s, 2H)

[0118] Example 9 Synthesis of Compound of Formula I-6

[0119]

[0120] 5.87 g of the compound of formula I-2 was added to tetrahydrofuran, and then 4.89 g of 2,4-dichlorochlorophenol and 0.80 g of sodium hydroxide were added. The mixture was reacted at 60° C. for 3 h. After the reaction, the solvent was removed, and the mixture was washed with water and dried to obtain 7.79 g of the compound of formula I-6 with a yield of 95%.

[0121] NMR: 1H NMR (300MHz, DMSO) δ7.82-7.85 (d, 2H), δ7.71-7.74 (d, 2H), δ7.15-7.54 (m, 7H), δ3.82 (s, 2H)

[0122] Example 10 Synthesis of Compound of Formula I-7

[0123]

[0124] 5.31 g of the compound of formula I-1 and 3.42 g of benzyl bromide were added to DMF, and then 1.38 g of potassium carbonate was added. The mixture was reacted at 70° C. for 2 h. After reaction, the mixture was filtered, concentrated to remove the solvent, washed with water, and dried to obtain 6.96 g of the compound of formula I-7 with a yield of 98%.

[0125] NMR:1H NMR (300 MHz, DMSO) δ 7.79-7.81 (d, 2H), δ 7.61-7.63 (d, 2H), δ 7.32-7.51 (m, 9H), δ 5.37 (s, 2H), δ 3.80 (s, 2H)

[0126] Formulation Examples

[0127] The percentages stated in the formulation examples are percentages by weight, unless otherwise stated.

[0128] Example 1: 18% nicosulfuron dispersible oil suspension

[0129] Nicosulfuron 18%

[0130] Compound of formula I-2 3%

[0131] Calcium dodecylbenzenesulfonate 4%

[0132] Organobentonite 2.5%

[0133] Methyl oleate to 100%

[0134] Example 2: 10% fenoxaprop-ethyl emulsion

[0135] Fenoxaprop-ethyl 10%

[0136] Compound of formula I-7 2%

[0137] Castor oil polyoxyethylene ether 2%

[0138] Farmal 601# 3%

[0139] Glycerol 2%

[0140] Naphtha to 100%

[0141] Example 3: 40% dicamba soluble concentrate

[0142] Dicamba 40%

[0143] Compound of formula I-6 1.6%

[0144] Tween-20 4%

[0145] Ethylene glycol 1%

[0146] Ethanol to 100%

[0147] Example 4: 20% sulfometuron-methyl water dispersible granules

[0148] Sulfometuron-methyl 20%

[0149] Compound of formula I-2 4%

[0150] Calcium dodecylbenzenesulfonate 5%

[0151] Diatomaceous earth 1%

[0152] Carboxypropyl cellulose 1%

[0153] Starch to 100%

[0154] Example 5 53% mesosulfuron dispersible oil suspension Mesosulfuron 3%

[0155] Compound of formula I-3 1%

[0156] Calcium dodecylbenzenesulfonate 2%

[0157] Polyoxyethylene sorbitan monooleate 2% Methyl oleate to 100%

[0158] Example 6 66% carfentrazone ethyl dispersible oil suspension Carfentrazone ethyl 6%

[0159] Compound of formula I-4 1%

[0160] Tween-205%

[0161] White carbon black 1%

[0162] Naphtha to 100%

[0163] Example 7 18% isoxaflutole suspension Isoxaflutole 18%

[0164] Compound of formula I-5 6%

[0165] Agro- 1601 # 5%

[0166] Methyl cellulose 1%

[0167] Propylene glycol 1%

[0168] Water to 100%

[0169] Example 8 81% mesosulfuron

[0170] Mesosulfuron 1%

[0171] Compound of formula I-2 1%

[0172] Castor oil polyoxyethylene ether 5%

[0173] Magnesium aluminum silicate 2%

[0174] Methyl oleate to 100%

[0175] Biological activity test

[0176] 1.1 Test agents: Safeners Formula I compound and isoxadiazine ethyl were synthesized by our company, and herbicides nicosulfuron, sulfamethoxam, mesosulfuron, foramsulfuron, fenoxaprop-P-ethyl, tembotrione, isoxadiazol-1-methyl, and dicamba were purchased from the market. A certain amount of herbicide and safener was weighed, dissolved in acetone, and diluted with 0.1% Tween 80 aqueous solution. Specific dosages and ratios are shown in Table 1-3. Unless otherwise specified, the dosage data in Table 1-3 represent the dosage of the herbicide active ingredient or safener compound.

[0177] 1.2 Experimental method: Take sieved air-dried soil with good permeability (organic matter content 2.5%, pH 7), fill the soil to 4 / 5 of the pot, water from the top to make the soil completely moist, take 30 crop seeds and evenly sow them on the soil surface, cover with about 1.0 cm of soil, move to a greenhouse, and cultivate at 20±2℃. Corn, wheat and other dryland crops are watered by infiltration irrigation at the bottom of the pot, and rice and other paddy field crops are watered to saturation by irrigation at the top of the pot. After the seedlings emerge, thinning and transplanting are carried out. Spray the pesticide when the crop has 3-4 leaves, and the spray volume is calculated according to 450L / ha. There are 4 replicates for each treatment, and a clean water treatment is set as a blank control. The pesticide damage is observed and recorded after 14 days.

[0178] Phytotoxicity effect: 0 means safe, no phytotoxicity; 1-10 means no obvious phytotoxicity; 11-30 means slight phytotoxicity; 31-50 means moderate phytotoxicity; >50 means severe phytotoxicity (reference standard NY / T 1155.8-2007).

[0179] Table 1. Effect of compounds of formula I as safeners on reducing herbicide damage in corn fields

[0180]

[0181]

[0182] From the results in Table 1, it can be seen that the compound of the present invention can effectively reduce the herbicide damage to corn during application in corn fields.

[0183] Table 2. Effect of compounds of formula I as safeners on reducing herbicide damage in rice fields

[0184]

[0185]

[0186] From the results in Table 2, it can be seen that the compound of the present invention can effectively reduce the herbicide damage to rice during application in rice fields.

[0187] Table 3. Effect of Formula I compounds as safeners on reducing herbicide damage in wheat fields

[0188]

[0189] From the results of Table 3, it can be seen that the compound of the present application can reduce the phytotoxicity of herbicides to wheat during application in wheat field.

[0190] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including combination of various technical features in any other suitable manner and including combination of the sequence, and these simple modifications and combinations should also be considered as disclosed by the present application and belong to the protection scope of the present application.

Claims

1. A compound of formula I and a salt thereof, characterized in that The structure of formula I is as follows: Wherein, R is H, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, phenyl substituted by C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkyl, cyano, amino, hydroxyl, nitro and halogen, benzyl, benzyl substituted by C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkyl, cyano, amino, hydroxyl, nitro and halogen.

2. The compound of formula I and salt according to claim 1, characterized in that R is H, methyl, ethyl, isopropyl, phenyl, p-chlorophenyl, 2,4-dichlorophenyl, or benzyl.

3. The compound of formula I and salt according to any one of claims 1 or 2, characterized in that Selected from the following compounds, 4. A method for preparing the compound of formula I according to claim 1, characterized in that: The synthetic route is as follows: Wherein, R is selected from H, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, phenyl substituted by C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkyl, cyano, amino, hydroxy, nitro and halogen, benzyl, benzyl substituted by C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkyl, cyano, amino, hydroxy, nitro and halogen.

5. A method for preparing a compound of formula I, characterized in that: Its synthetic route is as follows: wherein R' is selected from methyl or ethyl; and R" is selected from phenyl, phenyl substituted by C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkyl, cyano, amino, hydroxy, nitro and halogen.

6. A method for preparing a compound of formula I'', characterized in that: Its synthetic route is as follows: Wherein, R'' is selected from benzyl, benzyl substituted by C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkyl, cyano, amino, hydroxyl, nitro and halogen, and R'' is specifically X is selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkyl, cyano, amino, hydroxy, nitro and halogen, and n is selected from an integer of 0-5.

7. A herbicidal composition, characterized in that Containing the compound of formula I and salt according to any one of claims 1 to 3 and a herbicide.

8. The herbicidal composition according to claim 7, characterized in that The herbicides are sulfonylurea, aryloxyphenoxypropionic acid, cyclohexenone / triketone, amide, isoxazole and aryl carboxylic acid herbicides.

9. The herbicidal composition according to claim 8, characterized in that The sulfonylurea herbicide is one or more of pyrazosulfuron-methyl, bensulfuron-methyl, chlorpyrazosulfuron-methyl, nicosulfuron-methyl, sulfamethoxam, mesosulfuron-methyl, amidosulfuron-methyl, chlorsulfuron-methyl, sulfamethoxam, flumethoxam and flazasulfuron-methyl; the aromatic oxyphenoxypropionic acid herbicide is one or more of cyhalofop-butyl, quizalofop-butyl, methamphetamine, fenoxaprop-butyl and cypermethrin; the cyclohexenone / triketone herbicide is trimethylol, sethoxydim, pyraclostrobin, cycloxydim, benzothiazolin , cyclohexim, clethodim, butyclotrim, chlorpyrifos, sulfotrione, mesotrione, cyclosulfone and bicyclosulfone; the isoxazole herbicide is one or more of isoxaflutole and isoxaflutole; the aromatic carboxylic acid herbicide is one or more of 2.4-D, 2-methyl-4-chloro, 2,4,5-T, 2-methyl-4-chloropropionic acid, 2.4-D butyric acid, 2,4,-D butyl ester, dicamba, diclofenac, diclofenac, cypermethrin and quick-kill barnyard grass.

10. The herbicidal composition according to claim 9, characterized in that The herbicide is one or more of nicosulfuron, sulfamethoxam, mesosulfuron, foramsulfuron, fenoxaprop-P-ethyl, cypermethrin, isoxathiapiprolin and dicamba.

11. The herbicidal composition according to claim 10, characterized in that The weight ratio of the herbicide to the compound of formula I is 1:99-99:

1.

12. The herbicidal composition according to claim 11, characterized in that The weight ratio of the herbicide to the compound of formula I is 1:1-25:1.

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