JPH05509103A - Substituted arylalkylsulfonylpyrazole herbicide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Substituted arylalkylsulfonylpyrazole herbicides Field of the invention The field of the invention described herein is broadly defined by the heading Weed Control. The present invention relates to an agent compound, a composition containing the compound, and a method for producing the compound.

Background of the invention A variety of substituted 3- and 5-arylpyrazole compounds are known in the literature. Ru. Such compounds have various uses such as chemical intermediates, pharmaceutical agents and herbicides. have a way.

Among conventional substituted aryl pyrazole compounds, the aryl and/or Some have various substituents on the pyrazole moiety. For example, when the aryl moiety is , Substituted [substituent is alkyl, cycloalkyl, alkaryl, halogen, triflu] oromethyl, heterocycle or substituted heterocycle, such as chenyl or alkyl-substituted ranyl, pyridyl, pyrimidinyl urea, etc.] or unsubstituted phenyl group. , the pyrazolyl group is present at various positions on the nitrogen or carbon atom, alkyl, halogen , alkoxy, heterocycle, 5(0)ゎR group [where n is 0 to 2, R is or pyrazole radicals can be substituted with various groups. Compounds of this type are known.

Conventional compounds of the above type that have use as herbicides typically have sufficient 5 or 10 kg per hectare or more to achieve weed control. Take advantage of the high dispersion rate above. Therefore, the object of the present invention is to f) and broadleaf! Particularly high drug against a wide range of weeds including grasses has harmful unit activity and is effective against a large number of crops, especially wheat, barley, corn, type, high safety in small grain crops such as groundnuts and/or short plants. To provide a new class of aryl pyrazole compounds that maintain the Ru.

Summary of the invention The present invention relates to herbicidally active compounds, compositions containing such compounds, and methods for producing them. , and methods of using such compounds in weed control.

[In the formula, -R is hydrogen, CI-, alkyl, optionally substituted with R1 group, or C1-, cycloalkyl optionally substituted with cl, 1 alkyl or cycloalkenyl, R7 is C1-, alkyl optionally substituted with R4 group, R1 is hydrogen or halogen, R1 is hydrogen, C+-S alkyl, haloalkyl, alkyl 1,000, alkoxy alkyl or polyalkoxyalkyl, CZ-S cycloalkyl, cycloalkyl Kenyl, cycloalkyalkyl or cycloalkyalkyl; C, -.

alkenyl or alkynyl, carbamyl, halogen, amino, nitro, sia hydroxy, 1 to 4 0.5(0), and/or N heteroatoms C1-1゜heterocycle, CS-+Z aryl, aralkyl or alkaryl, -C XYR,, -CXR,, CH20COR+. , -YR, , -NR', 2R,3 or any two R4 groups are When two R1 groups are bonded via a heteroatom -C-N- bond, a complex saturated and/or unsaturated, provided that the ring has at least 6 ring members. Up to 9 rings linked via carbon, -C- and 7' or heteroatom bonds forming a heterocyclic ring having members, and this ring is substituted with any of the above R4 groups. self-inclusive or not self-inclusive If so, it is substituted with R@-13 or R4 which is substituted with any of the above RI groups. It is okay to be :( is 0.5(0), NR, or CRls R+s; Y is O,5 (0), or N with R11: R8 to R17 are one of the above R groups: m is O~2, n is 0 to 5].

A preferred subspecies of substituted arylpyrazolyl compounds of the invention is of formula II [wherein R1, R2 and R1 are as defined in formula 1: R1 is independently one of said R3 groups, and R2 and R7 are independently one of said R4 groups. or such two groups R6 and R2 have a heteroatom -C-N- bond. the condition that the heterocycle has at least 6 ring members when bonded through to form a heterocycle with up to 9 ring members containing OlN and/or S atoms and the ring is alkyl, each having up to 4 carbon atoms, Even if monosubstituted with a haloalkyl, alkoxy, alknyl or alkynyl group good〕 It has the following.

Particularly preferred compounds of the invention have the formula ITI: [wherein R1 and R2 are C+-s is alkyl: R3 and R9 are hydrogen, bromo, chloro or fluoro .

R6 is an R1 group or nitro.

R7 is an R4 group, or R6 and R1 are bonded via a 0CH2(C=O)-N-(R,)- bond and condensed. together forming a six-membered ring.

More preferred compounds of the present invention are: R1 and R2 are methyl; R5 is hydrogen, bromo or chloro; R3 is chloro or fluoro ; R6 is chloro, fluoro or nitro; R7 is Y as defined in formula I R+ + group, or R6 and R7 are -○CH2(C=O)-N-(pro- (pinyl) bond to form a fused 6-membered ring.

Preferred species of the invention include: 4-chloro-3-(2-fluoro-4-chloro-5-(2-propynyloxy) phenyl)-1-methyl-5-(methylsulfonyl)-IH-pyrazole; 4-bromo-3-(2-fluoro-4-chloro-5-(2-provinyloxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazole; 4-chloro-3-(2-fluoro-4-chloro-5-(2-methoxyethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazole; 4-bromo-3-(2-fluoro-4-chloro-5-(2-methoxyethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-IH-pyrazole; 6-(4-ri-4-1-methyl-5-(methylsulfonyl)-LH-pyrazole -3-yl)-7-fluoro-4-(2-propynyl)-28-1,4-benzo Oxazin-3-(4H)-one; (5-(4-bromo-1-methyl-5-(methylsulfonyl)-1H-pyrazo (3-yl)-2-chloro-4-fluorophenoxy)acetic acid, 1-methylethyl ester (5-(4-chloro-1-methyl-5-(methylsulfonylluorof) enoxy)acetic acid, 1-methylethyl ester; 2-(5-(4-bromo) -1-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl)-2 -chloro-4-fluorophenoxy)propanoic acid. Ethyl ester 2-(5-(4-chloro-1-methyl-5-(methylsulfonyl) -fluorophenoxy)propanoic acid, ethyl ester.

Another aspect of the present invention is a method for producing compounds 2-11 and their precursors. bodies and intermediate starting materials. The method of separation will be explained in detail later.

Another aspect of the invention provides herbicidal compositions comprising compounds of formulas 1-III and The present invention relates to a weed control method using a weed composition for controlling weeds.

Additionally, substituted arylpyrazole compounds of formulas I-III can be substituted, for example with acetanilide. , thiocarbamates, ureas, sulfonylureas, imidazolinones, benzoic acids and These derivatives, diphenyl ether, glyphosa t 6) Formulated into a composition containing other herbicide compounds such as salts as auxiliary herbicides. It is also within the scope of the invention.

Such herbicidal preparations may optionally and appropriately contain, for example, antidotes for herbicides. Plant disease control such as (toxicity relievers), antibacterial agents, insecticides, nematicides and other pesticides It can be included with other additives such as agents.

As used herein alone or, for example, haloalkyl, haloalkenyl, alkoxy "Alkyl", "alkyl" when used in a compound form such as , alkoxyalkyl, etc. The terms "kenyl" and "alkynyl" include straight-chain or branched groups. Ru. Preferred alkyl groups are lower alkyl having 1 to 4 carbon atoms. , preferred alkenyl and alkynyl groups are those having 2 to 4 carbon atoms. Ru.

The term "haloalkyl" refers to one or more halogens (chloro, bromo, iodo or or a fluoro atom), and this class is preferred. The subgroups are those having 1 to 4 carbon atoms, especially halomethyl groups, such as trifluor It is oromethyl. In polyhaloalkyl groups, all halogens are the same. or a mixture.

Representative but non-limiting alkyl, alkenyl, alkynyl, cycloalkyl , cycloalkylalkyl, cycloalkenyl and cycloalkenylalkyl groups The following can be mentioned: Methyl, ethyl, propyl isomers, butyl, pentyl, hexyl, heptyl, oxyisomer Cutyl, nonyl, decyl, etc.; vinyl, allyl, crotyl, methallyl, butenyl Isomers, pentyl, hexenyl, heptenyl, octenyl; ethynyl.

Propynyl isomers, butynyl, pentynyl, hexynyl, etc.: alkoxy, poly Alkoxy, alkoxyalkyl and polyalkoxyalkyl of the above alkyl group Analogs such as methoxy, ethoxy, propoxy, butoxy, pentoxy and xoxy and the corresponding polyalkoxy and alkoxyalkyl, such as methoxy Cymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, methoxy Dimethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, propoxymethythyl , impropoxymethyl, butoxymethyl, isobutoxymethyl, tert- Butoxymethyl, pentoxymethyl, hexoxymethyl, etc., cyclopropyl, Cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylene Pyrmethyl, cyclobutylmethyl, cyclopentylmethyl, etc. Isomers of cyclopentene, cyclohexane and cycloheptene with the sum: representative As typical aryl, aralkyl and alkaryl groups, phenyl, tolyl isomers and xylyl, benzyl, naphthyl, etc.

Representative mono-, di- and trihaloalkyl groups include chloromethyl, chloromethyl, loethyl, bromomethyl, bromoethyl, iodomethyl, iodoethyl, chloro Propyl, bromopropyl, iodopropyl, 1,1-dichloromethyl, 1,1 -dibromomethyl, 1,1-dichloropropyl.

1,2-dibromopropyl, 2,3-dibromopropyl, 1-chloro-2-bro Moethyl, 2-chloro-3-bromopropyl, trifluoromethyl, trichloro Examples include methyl.

Typical heterocyclic members include alkylthiodiazolyl; piperidyl; piperidyl; dylalkyl; dioxolanylalkyl; thiazolyl; alkylthiazolyl; nzothiazolyl; halobenzothiazolyl; furyl; alkyl-substituted furyl: furyl Alkyl; Pyridyl; Alkylpyridyl; Alkyloxasilyl; Tetrahydro Furyl alkyl; 3-cyanochenyl; chenyl alkyl; alkyl-substituted chenyl 4,5-polyalkylene-chenyl; biverizinyl: alkyl biveridinyl ;pyridyl; di- or tetrahydropyridinyl; alkyltetrahydromorpho; Lyle: alkylmorpholyl; azabicyclononyl; diazacycloalkanyl; alkylpyrrolidinyl; oxazolidinyl; perhydroxazolidinyl; Alkyloxazolidyl;furyloxazolidinyl;thenyloxazolidinyl ;pyridyloxazolidinyl;pyrimidinyloxazolidinyl;benzoxazo Lysinyl; C, -, spirocycloalkyloxazolidinyl: alkylaminoa Lukenyrunimino: Virolidinyl: Biberidonyl: Perhydroazevinyl; Per Hydroazocinyl; Pyrazolyl; Dihydrobirazolyl: Viperazinyl; Berhyde rho-1,4-diazevinyl; quinolinyl; inquinolinyl; di-, tetra- and Verhydroxylyl or isoquinolyl; indolyl and di and perhydro Indolyl and heterocyclic structures substituted with groups as defined in formula 1 Members can be mentioned.

As used herein, "agriculturally acceptable salts" (of compounds defined by the above formula) terms that readily ionize in aqueous media to form cations or anions of said compound. a salt that forms a corresponding anion or cation with a given herbicide. It does not adversely affect the herbicidal properties of the agent, and is easy to mix, suspend, stabilize, use a sprayer, and package. It means a salt that enables the production of herbicidal compositions without problems such as herbicides.

The expression "herbicidally effective" means that the expression "herbicidally effective" means Have a minute! means the amount of herbicide necessary to cause significant damage or destruction. Scattered There are no hard and fast rules, but there are far more Weed growth can be significantly suppressed commercially at low levels; Preferably, 0-85% or more is destroyed.

Details of the invention Compounds of this description may be suitably prepared by a variety of processes, such as those described below.

Broadly speaking, preferred overall processes for preparing compounds of formulas I-III include intermediates, immediate precursors, and the separate processes necessary to obtain the final products of these formulas. This can be best examined in From this point on, at least 13 major steps are involved. and they are described below. Products of formulas I to HI can be prepared using the general "process" described below. I to XIII", but with various modifications obvious to those skilled in the art. It is understood that this can be done. Specific implementations in+ are described below in Examples 1-27 do.

In the series of processes described below, various symbols defining substituents, e.g. R1~R,,,X. Unless otherwise specified or limited, Y and the like are represented by the formulas I to I11. has the same meaning as defined for compound.

Process ■ The second process is a heavy compound useful in the process of producing compounds of formula Ii11. The production of the necessary intermediate compounds will be explained.

The intermediate compound 2B below, where R, is H, is prepared by this process.

The process for preparing the compound of 2B is based on the (un)substituted atom of 2A known in the art. A good place to start is setophenone. The process can be carried out using any anhydrous solvent or Although the solvent can be carried out in a mixture of solvents, the preferred solvent is dimethyl sulfoxy These include hydrogen, toluene, and benzene. (un)substituted acetophenone, alkaline water with a strong base such as an alkali alkoxide or alkali alkoxide, preferably a Potassium is also an alkali alkoxide, such as -butoxide.

Treat the base mixture with carbon disulfide. The reaction temperature is -100°C to 100°C, preferably The temperature should be within the range of -78"C to 50°C. After adding carbon disulfide, add the reactant. quality, halogen f hyalkyl, alkyl dihalide, alkyl sulfate, sulfone Although treatment with nialkyl acid or other suitable alkylating agents is preferred, the preferred reagent is iodine. It is methyl uride. The reaction time varies from a few minutes to several minutes depending on the amount of reagents, reaction temperature, etc. You can choose within a week. Once the reaction is complete, the reaction mixture is diluted with water. From, the intermediate 1-(substituted)-3.3-bis(alkylthio)-2-propene-1 -one and isolate the product by methods such as crystallization or solvent extraction. ．． If necessary, purify the product using standard methods. Crystallize this intermediate to obtain a compound of formula B, in which hydrazine or substituted hydrazine, Preferably, this can be carried out by treatment with an alkylhydrazine. The reaction temperature is one The temperature is within the range of 78°C to 150°C, preferably 10°C to 100°C. The reaction time is The duration can be selected from several minutes to several weeks depending on the amount of reagents, reaction temperature, etc. The reaction Once complete, isolate the product by filtering and/or concentrating the reaction mixture. Ru. If necessary, standard methods such as extraction, crystallization, and column chromatography Purify the product by a method.

Intermediate 1-(substituted)-3,3-bis(alkylthio)-2-propen-1-one When hydrazine is added to Upon treatment with an alkyl sulfonate or other suitable alkylating agent, a compound of formula B can be obtained. In this case, the above compound may be methyl iodide, benzyl bromide, By treating with alkylating agents such as allyl bromide and dimethyl sulfate, the production of NiB can be reduced. Product 3 can be obtained. Preferred solvents are dimethyl sulfoxide, acetone, Dimethylformamide, dioxane, etc. 1 reaction temperature is -78℃~150℃ , preferably within the range of 10°C to 100°C, the reaction time depends on the amount of reagents, the reaction Two reactions can be completed within a range of several minutes to several weeks depending on temperature, etc. Once done, the product is isolated by filtering and/or concentrating the reaction mixture.

If necessary, use standard methods such as extraction, crystallization, and column chromatography. The product is thus purified.

Used to produce compounds numbered 4.9.10 and 11 in Table 1 by the above method. 2-fluoro-4-chloro-5-methoxyacetophenone is known in the art. This is a known method CC, A, Buehler and D, E, Pearson, 5urvey of Organic 5ynthes is, pp, 285- 382. WiIey-Interscience, New York, 197 2-chloro- obtained from 2-chloro-4-fluoro-phenol by It was produced from 4-fluoroanisole. 2-chloro-4-fluoroanisole When treated at room temperature with titanium chloride and dichloromethyl methyl ether, 2-Fluoro-4-chloro-5-methoxybenzaldehyde is obtained. First of all, treatment with Chir Grignard and then using standard methods known in the art. 2-Fluoro-4-chloro-5-methoxybenzal Convert the dehyde to 2-fluoro-4-chloro-5-methoxyacetophenone.

The above 2-fluoro-4-chloro-5-methoxyacetophenone and related precursors thereof 2-fluoro-4-chloro-5-methoxybenzaldehyde and their products The manufacturing method was developed by other inventors employed by the applicant (Bruce C., Hampe et al. It is an invention of R and Kindrick L, Leschinsky).

Table 1 shows examples of typical compounds produced by Process I.

Compounds such as those shown in Table I are intermediates in the preparation of compounds of formula II. is useful as a starting material for the production of a variety of other compounds that are useful as 6 For example, the compounds in Table 1 can be halogenated at the 3-position of the pyrazole to form the compounds shown in Table II. It is possible to produce novel compounds represented by

Process ■ This process involves oxidizing the compound of formula It describes important steps. An important feature of this process is that Conversion of ruphide derivatives to obtain S,S-dioxide derivatives of compounds of formula I It is. Therefore, the oxidation systems described below are merely representative and are conceptually intended. The sulfide derivative of formula I is converted into the S,S-dioxide derivative of formula I. Any suitable means are contemplated.

2B's:! Oxidation of mono-substituted thiopyrazole gives the corresponding sulfonylpyrazole of formula I You can get it with This reaction requires Any inert solvent may be used. Such solvents include, but are not limited to, l! Acids, inorganic acids, hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, ethers or or sulfone.

Suitable oxidizing agents include, but are not limited to, molecular oxygen, organic and inorganic peroxides, Examples include organic peracids and inorganic oxides. Preferred l1 is hydrogen peroxide, hydrogen peroxide, Rest 1! Fvi, alkaline periodate, alkaline permanganate, etc. The reaction temperature is within the range of -78°C to 150°C, preferably 10°C to 100°C. The reaction time can be selected from a few minutes to several weeks depending on the amount of reagents, reaction temperature, etc. Once the reaction is complete, the reaction mixture can be diluted with water. monolayer of the product and further isolation of the product by methods such as crystallization or solvent extraction. do. If necessary, the product is purified by standard methods.

Process III In this process, the product of the class of formulas in which R1 is halogen is converted to R2 is hydrogen and p is O or 2. Manufactured by.

For the above reaction, use any inert solvent that does not significantly inhibit the progress of the reaction. It is possible. Examples of caustic solvents include, but are not limited to, organic acids, sideless hydrocarbons, and halide solvents. Logenated hydrocarbons, aromatic hydrocarbons, ethers and sulfides, sulfoxides or sulfone. Halogenating agents suitable for the above reaction include: Bromine, chlorine, N-bromosuccinimide, N-talolosuccinimide, sulfuri chloride, 1,3-dichloro-5,5-dimethylhydantoin, etc. I can do it. With some halogenating agents, organic peroxides or light catalyzes It is preferable to use it as The amount of halogenating agent ranges from an equimolar amount to an excess amount. It can be done. The reaction temperature ranges from -100°C to 150°C, preferably from 10°C to 100°C. The reaction time ranges from several minutes to several weeks depending on the amount of reagents, reaction temperature, etc. or more. Once the reaction is complete, dilute the reaction mixture with water The product can be isolated by further isolation by methods such as crystallization or solvent extraction. The product is isolated. If necessary, purify the product by standard methods. .

process tv In this section, starting from compounds of formula I, one of the R4 residues is a nitro group. A method for producing the compound of formula 1 (compound of formula E) will be described.

For the above reaction, 1feT! 4 acids, fuming nitric acid, mixtures of nitric acid and concentrated sulfuric acid, alkyl nitrates Nitrating agents such as acetate and acetyl nitrate are suitable. Mineral acids, acetic anhydride or salts organic solvents such as methylene chloride, and solvents such as water or mixtures of these solvents. can be used. The nitrating agent may be used in equimolar amounts or in excess. The reaction temperature is within the range of -100°C to 150°C, preferably -10°C to 100°C. 0 Reaction time can be selected from a few minutes to several days depending on the amount of reagents, reaction temperature, etc. Once the reaction is complete, isolate the product by diluting the reaction mixture with water. The product may then be monolayered by methods such as crystallization or solvent extraction. need If so, purify the product by standard methods.

Sue Otomi In this process, the corresponding One class of products of 2G (formula 11 compounds) are produced.

Compound No. 2F is added to the alkoxide, thioalcohol, etc. in the presence of a base in any suitable solvent. using lucoxides, amines, etc. or alcohols, mercaptans, amines, etc. The product of formula G can be formed by treatment. The preferred solvent is dimethyls These include sulfoxide, acetone, dimethylformamide, dioxane, and water. salt The group can be an organic base (e.g. a trialkylamine or another organic amine) or an inorganic salt. as a group (e.g. an alkali carbonate such as potassium carbonate or mono-lium carbonate) The obtained zero reaction temperature ranges from -100°C to 150°C, preferably from -10°C to 100°C. The zero reaction time ranges from several minutes to several weeks depending on the amount of reagents, reaction temperature, etc. Once the reaction is complete, the reaction mixture can be filtered and/or concentrated. The product is isolated by If necessary, perform extraction, crystallization, and column chromatography. Purify the product by standard methods such as filtration.

Process Vl In this process, each of the formulas I (exemplified by formula J below) The compound is prepared from a compound of formula H (R, a compound of formula I in which one of the groups is a nitro residue) Build.

A. In the first step of this two-step process, a compound of formula H is reduced to give an amine derivative of formula J in which one of the R4 groups is an amine group. acidic medium Suitable reducing agents include, but are not limited to, metals such as iron, zinc or tin. As reaction solvents, mention may be made of organic or inorganic acids, such as acetic acid. or hydrochloric acid; these acids can be used as concentrated acid solutions or dilute aqueous solutions. The usable reaction temperature is within the range of 0°C to 150°C, preferably 10°C to 100°C. The reaction time ranges from a few minutes to several weeks depending on the amount of reagents, reaction temperature, etc. can be selected.

Once the reaction is complete, the product is isolated by diluting the reaction mixture with water and further The product is isolated by methods such as , crystallization or solvent extraction. If necessary , purify the product by standard methods.

Alternatively, compounds of formula H can be reduced by catalytic hydrogenation. normal pressure or A catalyst suitable for catalytic hydrogenation that can be carried out at pressures higher than normal pressure is Raneni 7-ke. palladium on charcoal, palladium black, palladium on any suitable support, oxidized Examples include palladium, platinum, and platinum black. Alcohol is used as a solvent. List any inert solvent that does not significantly inhibit the reaction, such as solvents, ethers, etc. Once the reaction is complete, the reaction mixture can be filtered and concentrated. isolate the product. If necessary, extract, crystallize, column chroma 1 ~ graph (-) Any standard method (by which the product is purified).

B. The amine group of the product of step A can be modified with various functional groups, such as halogen (preferred). ), cyano, hydroxyl groups, etc. by subsequent steps of the process. koto power (can be done)

Any suitable solvent may be used in this reaction, such as anhydrous acetonitrile. The solution or slurry of the product of step A, preferably in an anhydrous solvent such as Cupric halides, cupric halides, mixtures of cupric halides and cuprous halides, or others and mixtures thereof, as well as nitrites such as Wtit-butyl nitrite. 9 Reaction temperature for treatment with alkyl acid or other organic nitrates is 0-150°C; The zero reaction time, which is preferably within the range of 10°C to 100°C, depends on the amount of reagent and the reaction temperature. After the reaction is completed, which can take anywhere from a few minutes to several weeks, mix the reaction mixture. The product is isolated by passing and/or concentrating the compound. If necessary, The product is isolated by standard methods such as extraction, crystallization, and column chromatography. refine.

Another method for converting amine groups into various functional groups, including those listed above, is to For example, using diazonium salt as an intermediate for Sandmeyer reaction, Meerwein reaction, etc. Mention may be made of the use of various conventional procedures used as

Process’/11 In this process, a compound of formula I in which one of the R1 groups is YH is One is YR, , prepared from a compound of formula I in which R11 is not hydrogen.

The reaction may be carried out as a solution or suspension in any suitable solvent or as a pure substance. It can be implemented. Although not limited to, Br3, AlCl3, etc. Use Lewis acids or inorganic acids such as concentrated or dilute hydrochloric, sulfuric, or hydrobromic acids The possible reaction temperature is within the range of 0 to 150°C, preferably 10°C to 100°C. 1. Reaction time can be selected from a few minutes to several weeks depending on the amount of reagents, reaction temperature, etc. Once the reaction is complete, the reaction mixture can be quenched by passing and/or concentrating the reaction mixture. Isolate the product. If necessary, perform extraction, crystallization, and column chromatography. Purify the product by any standard method.

Process VI11 In this process, one of the R4 groups is Y　R+　+ and R1 is hydrogen. Compounds of formula I in which one of the R4 groups is Y)() are prepared from compounds of formula I in which one of the R4 groups is Y)(.

In a typical embodiment of this process, the starting material is an alkyl halide. or alkyl sulfonates, such as methyl iodide, allyl bromide, propaldi bromide treatment with alkylating or acylating agents such as The reaction which can form the above products by carried out in a mixture, with or without a catalyst, in the presence or absence of a base. obtain. Preferred solvents are dimethylsulfoxide, acetone, dimethylformamide , dioxane, etc. The base is an organic base (e.g. trialkylamine or another organic amines) or inorganic bases (e.g. potassium carbonate or sodium carbonate). The reaction temperature can be 0°C to 150°C, preferably 10°C. The reaction time, which should be within the range of ~100℃, is several minutes depending on the amount of reagents, reaction temperature, etc. Once the reaction is complete, which can take anywhere from a few weeks to a few weeks, the reaction mixture is filtered and/or Alternatively, the product is isolated by concentration.

If necessary, use standard methods such as extraction, crystallization, and column chromatography. The product is thus purified.

Process IX In this process, a compound of formula M (R? is YCHt-(R+s), , C0YR 2, (compounds of formula IN) are prepared from compounds of the corresponding formula. base RIM ~R7° is as defined for the R1 group above.

A. In the first step of this two-step process, The reaction that converts a compound into a compound of formula by hydrolyzing the YR, group is , in any suitable solvent or solvent mixture, with or without a catalyst. Alternatively, it can be carried out in the presence of an acid. The preferred solvent is water.

Alcohol, dioxane, dimethyl sulfoxide, acetone, dimethyl formua Mido etc. In the case of basic hydrolysis, inorganic salts such as alkali hydroxides Groups are preferred.

In acidic hydrolysis, hydrochloric acid or concentrated sulfuric acid may be used. acid Alternatively, the reaction temperature at which mixtures of such acids may be used is from 0°C to 150°C, preferably The temperature should be within the range of 10°C to 100°C.The reaction time may vary depending on the amount of reagents, reaction temperature, etc. Therefore, once a reaction is complete, which can take anywhere from a few minutes to a few weeks, the reaction mixture is dilution with water and/or (in case of basic hydrolysis) treatment of the solution with acid. The product can be isolated by methods such as crystallization or solvent extraction. isolate the product. If necessary, the product is purified by standard methods.

B. The product of step A is converted into 2M by esterification or amide formation reaction. Convert to compound. This can be done directly from the compound or with alkali metals in the compound. This can be done through salt. Esterification involves adding an excess amount of alcohol corresponding to the desired ester. This can be done by using coal in the presence of a mineral acid (eg sulfuric acid). Amide Derivatives can be obtained by treating the compound with the desired amine, neat or in a suitable solvent. It can be manufactured by Esterification or amide formation reactions are carried out using inert solvents and dehydration. 6 can be carried out in the presence of agents.

Alternatively, the product of step A can be converted to an acid halide or anhydride and an alcohol Non-limiting acid halides can also be treated with alcohols or amines. In the presence of a halogenating agent such as thionyl chloride, phosphorus pentachloride, or oxalyl chloride, It may be prepared with or without inert solvents.

Any inert solvent that does not interfere with the reaction may be used. In order to promote this reaction, When used with amine bases such as triethylamine, pyridine or dimethylformamide, The reaction temperature that can be added per amount of solvent is from -20℃ to the boiling point of the solvent used. One reaction time within the range is several minutes depending on the amount of reactants used and the reaction temperature. The period is 48 hours.

Once the reaction is complete, excess halogenating agent and solvent can be removed by evaporation or distillation. removed from the reaction product. The obtained acid halide is treated with amine or alcohol. or by conventional means.

Treatment of acid halide with alcohol or amine yields compound 2M. . Any inert solvent can be used; triethyl Add a catalytic amount of an amine base such as amine, pyridine or dimethylformamide The reaction temperature is within the range from -20°C to the boiling point of the solvent used. The reaction time varies from a few minutes to 48 hours depending on the amount of reactants used and the reaction temperature. Once the reaction is complete, the reaction mixture can be filtered and/or concentrated. The product is isolated by If necessary, perform extraction, crystallization, and column chromatography. Purify the product by standard methods such as filtration.

process In this process, compounds of the formula O, P, Q, R, S or T (where the R? substituent is an alkyl Kyl, substituted alkyl, haloalkyl.

Carboxaldehyde, carboxylic acid or previously defined CXYR, or CX A compound of formula TI which is a carboxylic acid derivative such as R*) is prepared from a compound of formula N do. The groups R2 and R22 are as already defined for the R1 group, and xl and X2 is halogen.The reaction formula is as follows.

In the first step of this process, a compound of formula N is converted into a compound of formula 0 or Q. compound or mixture thereof. This reaction requires Any inert solvent that does not have to be used can be used. Such solvents are limited to However, there are no blind side hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, Mention may be made of esters and sulfides, sulfoxides or sulfones. the above Halogenating agents suitable for the reaction include bromine, chlorine, N-bromosuccinimide, Examples include N-chlorosuccinimide and sulfuryl chloride. a For some types of halogenating agents, organic peroxides or light are used as catalysts. is preferred, and the amount of halogenating agent can range from equimolar to excess. The reaction temperature is within the range of -100°C to 150°C, preferably 10°C to 100°C. Reaction times range from a few minutes to several weeks, depending on the amount of reagents, reaction temperature, etc. Once the reaction is complete, isolate the product by diluting the reaction mixture with water. , further isolating the product by methods such as crystallization or solvent extraction. necessary Purify the product, if any, by standard methods.

Compounds of formula O can be prepared from compounds of formula P by replacing the halogen group X1 with a suitable nuclear material. It can be converted into a compound. 2P's raw ff1N converts the compound of formula 0 into an alkoxide, thi oalkoxides, amines, alkyl or aryl anions, or mercaptans, amines, etc. in the presence of a base in any suitable solvent. It can be formed by processing. Preferred solvents are dimethyl sulfoxide, acetic ton, dimethylformamide, dioxane, etc. Bases are organic bases (e.g. trialkylamine or another organic amine) or no 81@ group (e.g. potassium carbonate). alkaline charcoal such as sodium carbonate or sodium carbonate! ! The possible reaction temperature is The temperature is within the range of 0°C to 150°C, preferably 10°C to 100°C.

Reaction times range from a few minutes to several weeks, depending on the amount of reagents, reaction temperature, etc. Once the reaction is complete, the reaction mixture can be purified by passing and/or concentrating the reaction mixture. isolate the product. If necessary, extraction, crystallization, column chromatography, etc. The product is purified by black rate method.

Acidic hydrolysis of a compound of formula Q may form a product of formula R. acidic To carry out the hydrolysis, a compound of formula Q 3 is treated with an excess of a mineral acid, such as hydrochloric acid or sulfuric acid. Exposure to acid, but a significant excess of sulfuric acid is preferred. Reaction temperatures range from 0°C to inert solution. The reaction time is within the range up to the boiling point of the reagent, preferably 10°C to 100°C. The reaction time can be selected from a few minutes to several weeks depending on the reaction temperature etc. Once obtained, the product is isolated by diluting the reaction mixture with water and further crystallized or isolate the product by methods such as solvent extraction. If necessary, standard Purify the product by a method.

Compounds of formula S are obtained by oxidizing compounds of formula R. This reaction has Any suitable material including hydrocarbons, aromatic hydrocarbons, pyridine and its derivatives, water, etc. Any inert solvent may be used. Oxidizing agents used include, but are not limited to, permanent Peroxides such as potassium ganate or potassium dichromate may be mentioned. The reaction temperature ranges from 0°C to the boiling point of the inert solvent, preferably from 10°C to The zero reaction time at 100℃ varies from several minutes to several weeks depending on the amount of reagents, reaction temperature, etc. Once the reaction is complete, the reaction mixture can be diluted with water. Isolate the product! -7, further produced by methods such as crystallization or solvent extraction isolate something If necessary, the product is purified by standard methods.

The most important step in this process is to produce various standard derivatives of carboxylic acids. converting a compound of formula S into a compound of 2T by any of the following methods: It will be.

This step is an esterification or amide forming reaction.

This can be done directly from compound S or via an alkali metal salt of compound S. obtain. Esterification involves converting an excess amount of alcohol corresponding to the desired ester into a mineral acid (e.g. For example, sulfuric acid) may be used in the presence of sulfuric acid. Amide derivatives are compounds S may be prepared by treating S with the desired amine, neat or in a suitable solvent. Ru. Esterification or amide formation reactions can also be carried out in the presence of inert solvents and dehydrating agents. It can be implemented.

Alternatively, a compound of formula S can be converted to an acid halide or anhydride and added to an alcohol or anhydride. can also be treated with amines.

Acid halides include, but are not limited to, thionyl chloride, phosphorous pentachloride, and oxalichloride. may be prepared with or without inert solvents in the presence of halogenating agents such as Any inert solvent that does not interfere with the reaction may be used. The purpose of promoting this reaction with triethylamine, and amine bases such as lysine or dimethylformamide 6 The reaction temperature at which a catalytic amount of can be added is from -20"C to the boiling point of the solvent used. The reaction time, which should be within the range up to 9 Once the reaction is complete, which can range from a few minutes to 48 hours, remove excess halogenating agent and The solvent and solvent are removed from the reaction product by evaporation or distillation. the resulting acid Halides can also be exposed directly to amines or alcohols and are usually It can also be purified by the following means.

Treatment of acid halide with alcohol or amine yields compound 2T. . Any inert solvent can be used, including triethyl alcohol to accelerate the reaction. Addition of catalytic amounts of amine bases such as amines, pyridine or dimethylformamide The reaction temperature that can be increased is within the range from -20°C to the boiling point of the solvent used. 3 The reaction time varies from a few minutes to 48 minutes, depending on the amounts of reactants used and the reaction temperature. Once one reaction is complete within a certain time range, the reaction mixture can be strained and/or concentrated. The product is isolated by. Extraction, crystallization, column chromatography if necessary The product is purified by standard methods such as graphy.

Process X [ In this section, starting from a compound of formula 1, we will discuss the formula A method for making compounds of formula I (formula U) is described.

In this process, a halosulfonyl intermediate is prepared and then reduced to the formula U The desired compound is obtained by obtaining the compound. Halogen〉′carbonized hydrocarbon, ether Use any solvent that does not inhibit the progress of the reaction, such as alkyl nitriles, mineral acids, etc. obtain. Excess amount of chlorosulfonic acid forms the chlorosulfonyl intermediate. 9 The preferred reaction temperature as both a reagent and a solvent is from 25°C to the boiling point of the solvent used. 3. Reaction time should be within the range of several minutes depending on the amount of reagents, 1. reaction temperature, etc. After the reaction is complete, the reaction mixture can be diluted with water. to isolate the product and further produce it by methods such as crystallization or solvent extraction. isolate something If necessary, the product is purified by standard methods.

Reduction of the halosulfonyl intermediate can be carried out with an organic acid such as acetic acid or hydrochloric acid or without tRa. These acids can be carried out in inert cutting containing either 2! I acid solution or Can be used as a dilute aqueous solution. Reducing agents suitable for U-based media include, but are not limited to: However, metals such as iron, zinc or silk can be mentioned.The reaction temperature is between 0°C and 1°C. The reaction time is 50°C, preferably within the range of 10°C to 100°C, depending on the amount of reagent, The time period can be selected from several minutes to several weeks depending on the reaction temperature and the like.

Once the reaction is complete, the product is isolated by diluting the reaction mixture with water and further The product is isolated by methods such as , crystallization or solvent extraction. If necessary, Purify the product by standard methods.

Process Xll In this process, a compound of formula (1) (R2 is CH2R*, (where R22 is a compound of formula I], wherein R1 is one of the R groups defined above, is methyl. prepared from a compound of formula I.

The condition is that it is a water-based product, does not react with water, and does not interfere with the progress of the reaction. Any solvent may be used. Preferably tetrahydrofuran, diethyl ether or using anhydrous ethers such as polyesters, the reaction temperature is usually -10 The range is from 0°C to the boiling point of the solvent used, but preferably from -78°C to 25°C. It is ℃. First, a compound of formula I is converted into a metal alkyl, metal hydrate, metal amide, etc. treatment with a strong base and then alkyl halides, alkyl sulfonates, etc. The reaction time for treatment with a killing agent varies from several minutes depending on the amount of reagent, reaction temperature, etc. You can choose between several weeks.

Once the reaction is complete, the product is monolayered by diluting the reaction mixture with water and further The product is isolated by methods such as , crystallization or solvent extraction. If necessary , purify the product by standard methods.

Process XIII This process describes the conversion of a compound of formula W to a compound of formula X or Y.

The group R24 is as defined above for one of the R1 groups, and n is 0 or 1. is an integer.

In this process, the nitro group of a compound of formula W is reduced to obtain an amine intermediate. , which can be isolated or crystallized directly into formulas X or X according to the characteristics of the R24 group. or Y product is obtained. In some cases, to facilitate crystallization of the amine intermediate, Therefore, it may be necessary to carry out the above reaction at a temperature higher than room temperature. in acidic medium Suitable reducing agents include, but are not limited to, metals such as iron, zinc or tin. The reaction solvent that can be removed is an organic acid such as acetic acid or hydrochloric acid or an organic acid such as acetic acid or hydrochloric acid. acid These acids can be used as concentrated acid solutions or dilute aqueous solutions. 5. The reaction temperature that can be used is 0°C to 150°C, preferably 10°C to 100°C. The reaction time ranges from several minutes to several weeks depending on the amount of reagents, reaction temperature, etc. You can choose between.

Once the reaction is complete, the product is isolated by diluting the reaction mixture with water and further The product is isolated by methods such as , crystallization or solvent extraction. If necessary, Purify the raw material by standard methods.

Alternatively, compounds of formula W can be reduced by catalytic hydrogenation. normal pressure or Raney nickel is a catalyst for catalytic hydrogenation that can be carried out at pressures higher than normal pressure. , palladium on charcoal, palladium black, palladium on any suitable support, oxidized buffer Examples include radium, platinum, and platinum black. Alcohol is used as a solvent. Any inert solvent that does not significantly inhibit the reaction, such as alcohol, ether, etc. Once the reaction is complete, the reaction mixture can be filtered and/or concentrated. The product is isolated by If necessary, perform extraction, crystallization, and column chromatography. Purify the product by standard methods such as filtration.

Examples 1-27 below describe specific embodiments of the preparation of representative compounds of the invention. This is what is described. In the following examples, chromatographic purification was performed. In some cases, the adsorbent material was silica.

Examples 1-3 illustrate the preparation of intermediate compounds for making the final products of the invention. 1 describes a specific implementation of Process I, as used in the following.

Example 1 (A,) All equipment was flame dried under nitrogen, 15 5.4 g (0°18 mol) of 80% sodium dispersion in 0 ml of dry DMSO 14.04g (0.09mol) of 2.5-difluoro was added to the slurry containing H. Acetophenone (commercially available) was added over 10 minutes. Gas generation was observed 0. Cool the reaction solution to 15°C, maintaining the temperature at 15°C and controlling gas evolution. , 5.4 ml (0.09 mol>) of C82 was added over 15 minutes. Immediately after finishing the process, 11.1 m1 (0,018 mo1) of methyl iodide was added at 20°C. The 9-reaction mixture obtained by stirring the 1-reaction solution added in step 1 at room temperature for 2 hours was poured into 500 ml of water. and stirred for 1 hour.

The solid was washed with water and air dried. The residue was dissolved in hexane as eluent. Purification by chromatography using 20% ethyl acetate gave a yellow solid. 1-<2,5-difluorophenyl)-3,3-bis(methylthio)-2-pro 19.8 g (85%) of pen-1-one was obtained. Melting point: 105°5°C.

Alternatively, in the procedure described in step (A), a mixture of anhydrous solvents, e.g. It is also possible to use a mixture of DMSO and THF.

C+ + H+ o Fz OIS 2 +’) Elemental analysis’ calculated value C, 5 0,75,H,3,87,S,24.63 Actual value C,50,85,H,3,8 6, S, 24.75 (B,) 4.0 g (0,01 1°65 ml ( 0,031 mol) of methylhydrazine was added over 15 minutes at 24°C. solution was refluxed for 6 hours. The solution was stripped under vacuum. Use the residue as the eluent. and purified by chromatography using 10% ethyl acetate in hexane. 3-<2.5-difluorophenyl)-1-methyl-5- as a pale yellow oil. 3.05 g (82%) of (methylthio)-1H-pyrazole was obtained.

Elemental analysis of C11H1°F 2 N 2 S 1: Calculated value C, 54, 99; H, 4, 20; N, 11.66°S, 13.34° Actual measurement value C, 55,03; H, 4,26, N, 11.55; S, 13.38° Thick II2 This example shows 3-(2,5-difluorophenyl)-1-methyl-5-methyl Thio-IH-pyrazole and 5-(2゜5-difluorophenyl)-1-methyl- Describes the preparation of an isomer mixture of 3-methylthio-IH-pyrazole .

A, 5.2 g of 1-(2,5-difluorophenyl) in 50 ml of acetonitrile 24°C solution containing To the solution, 1.3 ml of anhydrous hydrazine was added over 3 minutes and the 0 reaction solution was added over 1 hour. The six reactions heated to 95° C. were concentrated under vacuum. Residue in diethyl ether The solution was washed with water, dried over anhydrous MgSO4, and concentrated under vacuum. Hex the residue 3-(2,5-difluorophenyl)-5-(methylene) as a white solid. 4.14 g (94%) of ruthio)-1H-pyrazole were obtained. Melting point: 88°C.

Elemental analysis two calculated values of C+ o Ht F 2 N 2S + C, 53, 09, H, 3,56; N, 12.38; S, 14.17° Actual measurement value C, 53, 12; H, 3, 55; N, 12.40°S, 14.15° 3.44 g of step A product in 8.75 ml of acetone, 2.2 g of A slurry containing , CO2 and 1.0 ml of methyl iodide was stirred overnight at 25 °C. . The solution was diluted with 300ml of cold water and extracted three times with ethyl acetate. Ethyl acetate extraction The output was washed with brine, dried over anhydrous MgS04 and concentrated under vacuum.

The residue was chromatographed using 10% ethyl acetate in hexane as the eluent. 3-(2,5-difluorophenyl) as a pale yellow oil =1-methyl-5-methylthio-IH-pyrazole (elemental analysis given in Example 1) 2.97 g (85%) and 5-(2,5-difluorophenyl) 1-Methyl-3-(methylthio)-1H-pyrazole 0.35g (10%) Obtained.

no2s1.5731.

CIIHI. Elemental analysis of F2N, S: Calculated value C, 54,99; H, 4 , 20; N, 11.66° Actual measurement C, 54, 83; H, 4, 19; N, 11. 85゜Leaving JLfiyu This example shows that 3-(2,4-difluoro)-1-methyl=5-(methylthio) -LH-pyrazole preparation is described.

All glassware was flame dried. in anhydrous tetrahydrofuran (600 ml) Potassium t-butoxide (43g).

2,4-difluoroacetate was added to a mechanically stirred solution containing 0.38 mo 1). Phenone (30g, 0.192mol) was added. This solution heats up to 40℃ and stirred at this temperature for 30 minutes. The solution was then cooled to 0°C and the carbon disulfide solution The reaction solution (11.6 ml, 0.192 mol) was heated to a temperature of 1℃. I added it at such a speed that I couldn't exceed it. Once the addition is complete, stir the reaction mixture at 0°C for 15 minutes. Then, methyl iodide ( 23.6 g, 0.38 mol) was added. Allow the solution to reach 10°C without cooling. The mixture was stirred at a temperature of 100 mL, and at this temperature the reaction solution was poured into 1 liter of ice water. ? acceptable yellow The colored solid was collected twice to give a total yield of 48.1 g (96% yield) of dithioketal. Obtained. dithioketal <47g, 0.180mol) in acetonitrile (500g, 0.180mol) ml) and methylhydrazine (21 g, 0.45 mol) was dissolved in 1 Added in the episode. The solution was brought to reflux for 24 hours, then most of the acetonitrile was removed under vacuum. It was stripped and removed. Pour the remaining liquid into ice water and dilute with diethyl ether. Extracted. The organics were washed three times with brine, dried over anhydrous magnesium sulfate, and all 3-(2,4-difluoride) is extracted as an amber oil. lophenyl)-]-methyl-5-(methylthio)-1H-pyrazole 37.7 7 g (yield 87%) was obtained. 'HNMR (CDCI*) ppm: 7.82 ( q, J=6.6. LH＞.

6.78 (m, 2H), 6.55 (d, J=3.6.IH), 3°83 (s, 3 H), 2.34 (s, 3H).

CzH+. Elemental analysis of F2N2S+: Calculated value C, 54,99; H, 4,20,N,11.66゜Actual measurement C,55,06,H,4,23,N,11 ．． 60° Examples 4.5 and 6 describe specific implementations of Process II It is.

K-seed 41 This example shows 3-(2,5-difluorophenyl)-1-methyl-5-(methyl 1 describes the preparation of (1H-pyrazole)-1H-pyrazole.

2.66 g (0.11 mol) of the step of Example 1 in 50 ml of methylene chloride The solution containing the product of step (B) was cooled to -5°C. 100ml methylene chloride Contains 7.6 g (0,022 mol) of 50-60% m-chloro-perbenzoic acid. The solution was added to the reaction mixture and stirred at room temperature overnight. The solution was diluted with 5% sodium thiosulfate. Wash with saturated sodium bicarbonate solution containing Mg, then with water, anhydrous Mg Dried over S04 and concentrated under vacuum. Recrystallize the residue with methylcyclohexane 3-(2,5-difluorophenyl)-1-methyl-5-(methyl) as a white solid. 2.8 g (93%) of (tylsulfonyl)-1H-pyrazole were obtained. Melting point 126~ 127℃.

Elemental analysis of C+ + H+ o Fz Ox S I: Calculated value C, 48, 5 3; H, '3.70; N, 10.29; S, 11.78° Actual measurement: C, 48,61, H, 3,70; N, 10.26°S, 11.71° K-凰■5 This example shows 5-(4-chloro-2-fluoro-5-methoxyphenyl)-3 Describes the preparation of -(methylsulfonyl)-LH-pyrazole.

1.12 g of 5-(4- Chloro-2-fluoro-5-methoxyphenyl)-3-(methylthio)-1H- 3.2 g of Oxone® was added to the solution containing the pyrazole. Heterogeneous mixture The combined solution was heated to 85°C and after 2 hours poured into ice water. Chloride the resulting mixture Extracted three times with methylene and concentrated the organic extracts to give an oily residue. This oily residue Dissolved in 10% NaOH aqueous solution and neutralized with concentrated hydrochloric acid to obtain a solid precipitate, which was recycled. 0.60 g (48%) of 5-(4-chloro-2-fluoro- 5-methoxyphenyl)-3-(methylsulfonyl)-1H-pyrazole was obtained. . The yellow crystalline solid was obtained as an analytical sample by recrystallization with methanol/water. Obtained 0M points 213-216 (dec).

CI+H+. N20. Elemental analysis calculation value of Fl C, 43, 36; H, 3, 31 , N, 9.19°S, 10.52° Actual measurement: C, 43,51; H, 3,33; N, 9.10°S, 10.44° Sorry to hear that This example shows 4-chloro-3-(2-fluoro-4-methoxyphenyl)-1 -Describes the production of methyl-5-(methylsulfonyl)-LH-pyrazole It is.

4-chloro-3-(2-fluoro-4-methoxy) in methylene chloride (150 ml) Cyphenyl)-1-methyl-5-(methylthio)-1H-pyrazole (3.5g , 0.0122m.

m-chlorobenzoic acid was added little by little to a solution at 0°C containing Stir for 20 minutes at Extracted twice with diluted sodium bicarbonate solution. Dehydrate organic matter with anhydrous magnesium sulfate The volatiles were removed under vacuum to give a yellow solid.

Melting point: 75°C.

C12H12F IN 203S Ic l +) Elemental analysis: Calculated value C, 45 , 22; H, 3,79; N, 8.79° Actual measurement value C, 45, 49, H, 3, 77 , N, 8.69° Examples 7 and 8 describe specific implementations of Process III. It is something that

1 liter of milk This example shows 4-chloro-3-(2,5-difluoro);nyl)-1-methyl Describes the preparation of -5-(methylsulfonyl)-1H-pyrazole.

At 25° C., 2.25 g (8.2 mmol) of the product of Example 4 was added to 40 m 1.1g (16.4mmol) of chlorine gas was dissolved in glacial acetic acid for 50 minutes. The 0 reaction solution was stirred for 45 minutes and then poured into 300 ml of ice water. and extracted with diethyl ether. Wash the ether with saturated sodium bicarbonate solution. Cleaned, dried over anhydrous MgS04 and concentrated under vacuum. Use the residue as the eluent. and purified by chromatography using 30% ethyl acetate in hexane. , white solid 4-chloro-3-(2,5-difluorophenyl)-1-methyl- 1.35 g (84%) of 5-(methylsulfonyl)-1H-pyrazole was obtained.

Melting point: 77°C.

Elemental analysis and calculated value of C,,H,CI　,F2N202S,C,43,08,H , 2,96, N, 9.13°S, 10.45; C1, 11,56° Actual measurement value C, 43,16; H, 2,97; N, 9.12°S-10,':! Q: C1, 11, 49° 1st eye 1st child This example shows 4-chloro-3-(2-fluoro-4-methoxyphenyl)-1 -Describes the production of methyl-5-(methylthio)-1H-pyrazole .

3-(2-fluoro-4- methoxyphenyl)-1-methyl-5-(methylthio)-IH-pyrazole (4 g, 0.015m.

1,3-dichloro-5,5-dimethylhydantoin ( 1.77 g, 0.009 mol> was added.

The reaction was stirred at room temperature for 1 hour, then poured onto ice, and the organics were dissolved in diethyl ether. extracted with water, washed with brine, dried over anhydrous magnesium sulfate, and strung under vacuum. A yellow oil was obtained. n at 25°C. ” = 1.5943.

Elemental analysis of CI2Hl 2F + N20 + S + CI +: Calculated value C, 50, 26; H, 4, 22; N, 9.77° Actual value C, 49, 84, H , 4, 13; N, 9.61° Examples 9 and 10 are specific implementations of process TV. It describes the situation.

E1 Yuyu This example shows 4-chloro-3-(2,5-difluoro-4-nitrophenyl) -1-Methyl-5-(methylsulfonyl)-LH-pyrazole is described. It is something that

At 24°C, 1.5 g (4,9 mmo 1) of 4-chloro-'3-(2,5 -difluorophenyl)-1-methyl-5-(methylsulfonyl)-1H-pyra 6 The reaction mixture, in which Sol was slowly added to 25 ml of fuming nitric acid, was stirred at 30°C for 30 minutes. The stirred reaction solution was poured into 300 ml of water. Strain the slurry and make a cake. Wash thoroughly with water and air dry. The solid was recrystallized from methylcyclohexane and 4-chloro-3-<2.5-difluoro-4-nitrophenyl) as a brown solid -1-Methyl-5-(methylsulfonyl)-IH-pyrazole 1.1.3g ( 66%). 11 points 147℃.

Elemental analysis and calculated values of C,, H, CI, F, N, O, S, C, 37, 56: H, 2, 29, N, 11.95°S, 9.12° Actual measurement: C, 37, 60, H, 2, 29, N, 11.98°S, 9.10° K1 Todohiki This example shows 4-chloro-3-<4-chloro-2-fluoro-5-nitrophe describes the production of 1-methyl-5-(methylsulfonyl)-1H-pyrazole. This is what is described.

3 g (0,0093 mo1) of 4-chloro-3-(4-chloride) in 3 ml of concentrated sulfuric acid Lolo-2-fluorophenyl)-1-methyl-5-(methylsulfonyl)-1H -To a solution containing pyrazole, add a mixture of 1 ml of concentrated nitric acid in 3 ml of concentrated sulfuric acid. The reaction mixture was then stirred at 25°C for 2 hours. The organic extract was poured into water and extracted with ether. 1 aqueous solution three times, dried (MgSOn), filtered and concentrated to give a yellow solid. 4-chloro-3-(4-chloro-2-fluoro-5-nitrophenyl)-1-mer 2.3 g (67%) of thyl-5-(methylsulfonyl)-1H-pyrazole was obtained. . Analytical samples were analyzed by chromatography (10% EtOAC/CH, Ctz). Obtained 0M point 111-115°C.

CIIHIN) 04C12FISl+1/4EtOAC elemental analysis: Calculated value C , 36, 45, H, 2, 60; N, 10.85° Actual value C, 36, 39; H, 2,26,N,10.91. .

Examples 11 and 12 describe specific implementations of Process V.

Large 111 Yu” 2 This example shows 4-chloro-3-(2-fluoro-5-methoxy-4-nitroph Production of phenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazole It is something to describe.

4.8 g (0.013 mo I) of the product of Example 9 and 1.9 g (0.014 mo I) of the product of Example 9 A mixture of mol) of K2C03 and 5ml of methanol was heated at 50°C at 25°C. 1 reaction mixture slurried in 1 m of DMSO and stirred at 45°C for 8 hours. was cooled, diluted with 100 ml of ice water and extracted four times with ethyl acetate. Ethyl acetate The extracts were washed with brine, dried over anhydrous MgO, and stripped under vacuum. did. The residue was recrystallized from ethyl acetate 2/hexane to give a yellow solid of 4-chloro-3. -(2-fluoro-5-methoxy-4-nitrophenyl)-1-methyl-5-( 4.21 g (84%) of methylsulfonyl)-1H-pyrazole were obtained. Melting point 17 8.5-180°C.

Elemental analysis of CI28 IIc 11F IN 305S l: Calculated value C, 39 , 62, H, 3, 05, N, 11.55°S, 8.81° Actual measurement value C, 39,58; H, 2,98; N, 11.54; S, 8.59° 夾m This example shows 5-[4-chloro-1-methyl-5-(methylsulfonyl)-1 H-pyrazol-3-yl]-4-fluoro-N-(1-methylethyl)-2- This describes the production of nitrobenzeneamine.

4-chloro-3-(2,5-difluoro) in n-methylpyrrolidone (50 ml) -4-nitrophenyl)-1-methyl-5-(methylsulfonyl)-IH-pyra Sol (7.6g.

Isopropylamine (1.94 g, 0.0218 mo 1) was added to a solution containing 0.0218 mo 1). 328mol 1), potassium carbonate <4.5g, 0°0328mol) and catalyst amount The reaction solution to which fluorinated steel (I) was added was heated to 60°C for 2 hours and analyzed by TLC. After confirming the completion of the reaction, the reaction solution was diluted with ethyl acetate, and the organic matter was removed with brine. Wash twice, dry with anhydrous magnesium sulfate, remove volatiles under vacuum, and evaporate with evaporator. Recrystallization from alcohol/methylcyclohexane gave an orange solid of 5-[4-chloride. lolo-1-methyl-5-(methylsulfonyl)-1H-virazol-3-yl] -4-Fluoro-N-(1-methylethyl)-2-nitrobenzeneamine 8- 4g (98%) was obtained.

Melting point: 152°C.

Elemental analysis of CI4H+*Cl + F IN 40, S l: Calculated value C, 43 ,03:H,4,13;N,14.34°Actual measurement value c,43.09;H,4, 09;N, 14.36°K seed and ↓yu This example shows that 4-chloro to 3-(4-chloro-2-fluoro-5-methoxyph) Production of phenyl)-1-methyl-5-(methylsulfonyl)-18-pyrazole This is a particular implementation of process Vl.

(A, 3.3 g (9,1 mmo I) of 4-chloro-3 in >100 ml of acetic acid -(2-fluoro-5-methoxy-4-nitrophenyl)-1-methyl-5-( The slurry containing methylsulfonyl)-1H-pyrazole was heated to 80°C under nitrogen. Then, it was treated little by little with 1.5 g (27 mmol) of iron powder. 20 minutes at 85℃ After that, the mixture was cooled and filtered through Celite (registered trademark). The liquid was diluted with 250ml of water and extracted three times with ethyl acetate. Boil the organic extract in water until saturated. NaHCO3 aqueous solution, washed with water, dried over MgSO4 and concentrated to give 3.1 g A tan solid was obtained.

(B,) 3.0 g (9.0 mmol) of Ste in 70 ml of dry acetonitrile. The solution containing the product of step (A,) was added to 0.9 g (9.0 mmol) of CuC1 and and 1-8g (13,1mm.

It was treated with Cu C12 of 1). Add 2.4 ml (18 mmol) to this reaction mixture. >90% t-butyl nitrite was added over 5 minutes. After 1 hour at 28°C, the reaction mixture The combined solution was concentrated in vacuo.The reaction residue was taken up in ethyl acetate and diluted with 10% HCI solution. Washed three times, twice with brine, dried over anhydrous MgSO and concentrated under vacuum. Ta. The residue was chromatographed using 50% ethyl acetate in hexane as the eluent. Purified by roughy to give a white solid, 4-chloro-3-(4-chloro-2-fluoride). fluoro-5-methoxyphenyl)-1-methyl-5-(methylsulfonyl)-1 2.64 g (83%) of H-pyrazole was obtained. Melting point: 175.5°C.

Cl281IC12F+Nzois+(') Elemental analysis: Calculated value C, 40, 81 , H, 3, 14, N, 7.93° S, 9.08; C1, 10, 08° actual measurement value C, 40,94, H, 3,14, N, 7.88°S, 8.97. CI, 19. 95° Examples 14-16 describe specific implementations of process Vll.

Egokatsu 1 This example shows that 2-chloro-'5-[4-chloro-1-methyl-5-(methylsulphate) ruphonyl)-1H-pyrazol-3-yl-4-fluoroN-2-propenylate This describes the production of rubenzenamine.

1 g (0,0023 mo I) of N-[2-chloro-5-[4-chloro-1- Methyl-5-(methylsulfonyl)-LH-pyrazol-3-yl]-4-flu orophenyl]-2,2゜2-trifluoroacetamide and 0.97 g (0 ,007 mo of potassium carbonate, 25 ml of anhydrous DMF, and 0.85 g (0 ,007 mol) of allyl bromide was stirred at 70°C for 24 hours. this The solution was diluted with EtOAc, washed three times with 100 ml of 5% MCI, and dried (Mg SO,), filtered and concentrated to give 0.9 g of a red oil. 2 of this oil Dissolved in 0ml methanol and added 3ml 10% NaOH. This mixture The reaction mixture, stirred at 25°C for 8 h, was diluted with EtOAc and added with 100 ml of N Washed three times with aqueous acl solution, dried (MgSO,), filtered, and concentrated to 0.8 g of red oil was obtained. By chromatography (CH2C1□), a yellow ozone 2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl) )-1H-pyrazol-3-yl]-4-fluoroN-2-propenylbenze Obtained 0.6 g (69%) of amine. snD"' = 1.5956.

Elemental analysis of CI4H14N xo□Cl2F, S+: Calculated value C, 44, 46, H, 3,73, N, 11.11° Actual measurement C, 44,66; H, 3,68, N, 10.85° erect ■ Yuj This example shows N-[2-chloro-5-[4-chloro-1=methyl-5-(methyl (sulfonyl)-1H-pyrazol-3-yl]-4-fluorophenyl]-mer 1 describes the production of tansulfonamide.

0.5 g (0,001 mo I> of N-[2-chloro -5-[4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazo -3-yl]-4-fluorophenyl]-N-(methylsulfonyl)-meth A mixture of 2 ml of 10% NaOH was added to the solution containing sulfonamide. The reaction mixture, which was stirred at 25°C for 4 hours, was diluted with EtOAc and 100ml of Washed three times with 5% HCI, dried (MgSO4), concentrated to yellow to yellow. Brown solid N-[2-chloro-5-[4-chloro-1-methyl-5-(methyls) ruphonyl)-1H-pyrazol-3-yl]-4-fluorophenylcomethanes 0.2 g (48%) of sulfonamide was obtained, and then chromatography (EtOA An analytical sample was obtained by e>. Melting point 165-166°C.

Elemental analysis calculation value of C12812N304Cl2Fls2+1/4EtOAc C , 35, 18; H, 3, 24: N, 9.65° Actual value C335, 09; H, 2,97: N, 9.90゜to 3 Jl Examples include 4-chloro-3-(4-chloro-2-fluoro-5-hydroxyphenyl) Production of phenyl)-1-methyl-5-(methylsulfonyl)-18-pyrazole It is something to describe.

1.15 g (3.25 mm) in 30 ml of methylene chloride.

I) 4-chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl) A solution containing -1-methyl-5-(methylsulfonyl)-LH-pyrazole was heated to 0°C. Cooled to nOl) was slowly added over 5 minutes. The solution was stirred at room temperature overnight. solution was washed twice with water, dried over anhydrous Mg5O, and concentrated under vacuum. Hex the residue 4-chloro-3-(4-chloro-2-fluoro) as a beige solid. lo-5-hydroxyphenyl)-1-methyl-5-(methylsulfonyl)-1H -Pyrazole 1.1 g (1,00%) was obtained.

Melting point: 190.5°C.

C11HsCl 2F, N, 03S, elemental analysis calculation value C, 38,95; H, 2,67; N, 8.26° Actual measurement C, 38,93, H, 2,67; N, 8.43° Examples 17, 18, 19 and 20 are 7O-1 = S VITI (71 special It describes certain implementations.

E5 Jyu This example shows 2-chloro-5-[4-chloro-1-methyl-5-(methylsulfur) (honyl)-1H-pyrazol-3-yl]-4-fluoro-N-(1-methylethyl) 1 describes the preparation of (chill)-benzenamine.

0.5 g (0,0015 mo1) of 2-chloro-5 in 5 ml of anhydrous DMF -[4-chloro-1-methyl-5-(methylsulfonyl)-IH-pyrazole- containing 3-ylco-4-fluorobenzenamine and 2 ml of 2-iodopropane. The solution was stirred at 75°C for 6 hours and then at 25°C for 2.5 days. The solution was diluted with EtOAc, washed twice with 50 ml of 5% HCI, and dried (MgSO , ) L, P and concentrated to obtain 0.5 g of red oil. chromatography (methylene chloride) to form a red solid, 2-chloro-5-[4-chloro-1-methyl Thyl-5-(methylsulfonyl)-11(-pyrazol-3-yl]-4-fluor Obtained 0.25 g (44%) of oro-N-(1-methylethyl)-benzenamine. Ta.

Melting point: 118°C to 121°C.

Elemental analysis of C1, HI, N, 0□C12F + S l + 1 / 2 H20 : Weight value C, 43, 20; H, 4, 40; N, 10.79° Actual measurement value C, 42 , 88, H, 4, 02; N, 10.70° This example shows N-[2-chloro-5-[4-chloro-1-methyl-5-(methyl rusulfonyl)-1H-pyrazol-3-yl]-4-fluorophenyl core This describes the production of lanine ethyl ether.

Alanine, N-[2-chloro-5-[4-chloro-2-methyl- 5-(Methylsulfonyl)-IH-pyrazol-3-ylco-4-fluorophe A solution containing acetyl chloride]- and a catalytic amount of acetyl chloride was stirred at 25°C for 18 hours.

This solution was diluted with EtOAc, once with water and once with 100 ml of potassium carbonate aqueous solution. Washed twice, dried (MgSO4), filtered and concentrated to 0.5 g yellow oil. I got it. By chromatography (CH2C) a), a yellow oily N- [2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-I H-pyrazol-3-yl]-4-fluorophenyl]-alanine, ethyl ether 0.17 g (20%) of teral was obtained. 'HNMR (400MHz, CDC13) dl, 2 (5, 3H), 1.48 (d, 3H), 3.23 (s, 3H), 3.8 (q, IH), 4.15 (q, 2H), 4.18 (s.

3H), 4.7 (bs, LH), 6.6 (d, IH), 7.1 (d.

LH) Ppm:;”FNMR (360MHz, CDCl5) d-128( S, IP) ppm.

Elemental analysis calculation value of C+sHIIN 30-C1zF + S+ C, 43, 8 5; H, 4, 14, N, 9.59° Actual measurement value C, 43, 90, H, 4, 11, N ,9.52゜衷JLfLLSae This example shows N-[2-di-4-5-[4-chloro-1=methyl-5- rusulfonyl)-IH-pyrazol-3-yl]-4-fluorophenyl]-N Describes the preparation of ~(methylsulfonyl)methanesulfonamide.

0.5g<0.0015m in 20ml methylene chloride.

l) 2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl) -1H-pyrazol-3-yl]-4-fluorobenzenamine in a solution containing First, add 0.33 g (0°0033 mo I) of triethylamine, then add 0.3 g (0°0033 mo I) of triethylamine. 7 g (0,0033 mol) of methanesulfonyl chloride was added. This mixture One reaction mixture was stirred at 25°C for 18 hours, diluted with EtOAc, and diluted with 100 ml of Washed three times with 5% HCI, dried (MgSO, ), filtered and concentrated to give a yellow-white color ( Of f-wh itt e) Solid N-[2-chloro-5-[4-chloro-1 -Methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl]-4-ph [fluorophenyl]-N-(methylsulfonyl)methanesulfonamide 0.7 g (94%) was obtained. Analytical samples were obtained by chromatography (EtOAc). Ta. Melting point 234-237°C.

CI3HlaN 30 sCI 2F I S y+ 1. /4 E t O A　C elemental analysis calculation value C, 32, 17, H13, 14; N, 8.18゜Actual Measured values: C, 32,05, H, 2,86, N, 8.48° 1" 11 days This example shows that 4-chloro-3-(4-chloro-2-fluoro-5-(2-propylene) pinyloxy)phenyl)-1-methyl-5-(methylsulfonyl)-18-py This describes the production of lazole. ′ 0.87 g (2,5 mmol) of 4-chloro-3-(4-chloro-2-fluoro lo-5-hydroxyphenyl)-1-methyl-5-(methylsulfonyl)-IH - pyrazole, 0°4 g (3,0 mmol) of K2COs, and 0.3 ml (3, Ommol) of the mixture with propargyl bromide was added to 10 ml of the mixture at 25°C. The 0 reaction slurried in DMSO was stirred at 45°C for 16 h. The 0 reaction was cooled. The mixture was cooled, diluted with 100 ml of cold water, and extracted four times with ethyl acetate. Ethyl acetate extraction Wash the items with brine, dehydrate with anhydrous MgS O4, and strip under vacuum. I clicked. The residue was chromatographed using 50% ethyl acetate in hexane as the eluent. Purification by chromatography yielded 4-chloro-3-(4) as a tan solid. -chloro-2=fluoro-5-(2-propynyloxy)phenyl)-1-methy 0.93 g (96%) of Ru-5-(methylsulfonyl)-IH-pyrazole was obtained. . Melting point: 135°C.

Elemental analysis of CI 4 H1 + CI 2 F + N 20 y S +: Calculation Value C, 44, 58; H, 2, 94; N, 7.43 Actual value C, 44, 75, H , 3,08, N, 7.36° Examples 21 and 22 are specific implementations of Process IX. It describes the aspect.

【Left】U outside 21 This example shows that 2-(2-chloro-5-(4-chloro-1-methyl-5-(methyl) rusulfonyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)- This describes the production of propanoic acid.

3°77 g (8,6 mm) in 20 ml of water and 20 ml of 1,4-dioxane o l) of 2-(2-chloro-5-(4-chloro-1-methyl-5-(methyls) sulfonyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)-pro 3.5 ml (8.6 mm 01) of slurry containing panic acid, ethyl ester 0% NaOH aqueous solution was added. After 30 minutes, the reaction solution became clear, and TLC showed that the reaction was complete. indicated that it was completed.

The solution was cooled, the pH was adjusted to 3 using concentrated hydrochloric acid, and the 0 reaction solution was diluted with ethyl acetate. Extracted. The extracts were washed with water, dried over anhydrous Mg5o, and concentrated under vacuum.

The residue was recrystallized from hexane to give a white image of 2-(2-chloro-5-(4-chloro). -1-methyl-5-(methylsulfonyl)-18-pyrazol-3-yl)-4 2.9 g (83%) of -fluorophenoxy)-propanoic acid were obtained. Melting point: 56°C.

Elemental analysis of CI4H+sCl□F, N, ○SS+: Calculated values C, 40, 80, H 13, 19; N, 6.81° Actual value C, 40, 87, H, 3, 24, N, 6. 69゜K1 Yu 11 This example shows that 2-(2-chloro-5-(4-chloro-1-methyl-5-(methyl) (sulfonyl)-1H-pyrazol-3-yl)-4-fluorophenoxy-N - describes the production of methylpropanamide.

1.17 g (5.9 mmo 1) of 2-(2-chloride) in 10 ml of methylene chloride rho-5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazo 08 m 1 (9°6 mmol) of oxalyl chloride was added over 3 minutes to generate gas. . When gas evolution stopped, 1 drop of DMF was added and the solution was stirred until gas evolution stopped. . The solution was stripped to dryness under vacuum. Dissolve the residue in 5ml THF Then, at 0°C, 10ml of 40% methylamine aqueous solution was added over 5 minutes. 7 The reaction mixture was stirred at room temperature for 30 minutes. Pour the solution into 150ml of cold water , extracted with ethyl acetate. Wash the ethyl acetate extract several times with brine and anhydrous M g S O4 and stripped under vacuum. Convert the solid to methylcyclohexyl 2-(2-chloro-5-(4-chloro Rho-1-methyl-5-(methylsulfonyl)-]H-pyrazol-3-yl)- 0.96 g (80%) of 4-fluorophenoxy-N-methylpropanamide Obtained. Melting point: 178°C.

'HNMR (CDCI *) ppm: 1.55 (d, 3H), 2.81 (d, 3H), 3.23 (s, 3H), 4.17 (s, 3H).

4.64 (q, 3H), 6.65 (br, LH), 6.97 (d.

LH), 7.22(d, IH).

Elemental analysis of C+sH+aC12F IN xo 4S l: Calculated value C, 42, 46, H, 3,80; N, 9.90, actual value C, 42,60; H, 3,68 , N, 9.86° Examples 23 and 24 describe specific implementations of process It is something that

K1 and 23 This example rusulfonyl)-1H-pyrazol-3-yl)-4-fluorophenyl)methy This paper describes the production of ethyl)thio)acetic acid, ethyl ester.

At 25°C, 1.25 g (3,0 mmol) of 3-(5-bromomethyl) -4-chloro-2-fluorophenyl)-4-chloro-1-methyl-5-(methyl rusulfonyl)-1H-pyrazole and 0.5 g (3,3 mrno 1) of K z　CO! and 0.4 ml (3.3 mmo 1) of ethyl bromoacetate in 15 m The 1 reaction solution slurried in 1 acetone was stirred at 20°C for 8 hours. Pour into 150ml of water, filter and air dry. Methylcyclohexa solid A white solid ((2-chloro-5-(4-chloro-1-methyl =5-(methylsulfonyl)-1H-pyrazol-3-yl)-4-fluoroph 1.2 g (93%) of acetic acid, ethyl ester (1.2 g (93%)) was obtained. Melt Point 110℃.

Elemental analysis of C, sHl, CI 2F, N 20, S 2: Calculated value C, 42 ,20;H,3,76;N,6.15゜Actual measurement C,42,25;H,3,72 ;N, 6.18°Tuesday 1st Iノ''.

This example shows that 2-chloro-5-(4-chloro-1-methyl-5-(methylsulfur) Honyl)-1H-pyrazol-3-yl)-4-fluoro-N-methylbenzaa This describes the production of mido.

1.34 g (3.7 mmo 1) of 2-chloro-5 in 25 ml of methylene chloride -(4-chloro-1-methyl-5-(methylsulfonyl)-IH-pyrazole- 3-yl)-4-fluorobenzoic acid to a solution containing 1.0 ml (11,1 m Mo 1) oxalyl chloride was added over 3 minutes to generate gas.

When gas evolution stopped, one drop of DMF was added and the solution was stirred until gas evolution stopped.

The solution was stripped to dryness under vacuum. The residue was dissolved in 5 ml THF and 0 6 reactions in which 10 ml of 40% methylamine aqueous solution was added over 5 minutes at °C. The mixture was stirred at room temperature for 30 minutes. Pour the solution into 150ml of cold water and filter and air dried. The solid was recrystallized from methylcyclohexane/ethyl acetate to give a white Color solid 2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl) )-IH-pyrazol-3-yl)-4-fluoro-N-methylbenzamide 0.95g (69%) was obtained. Melting point: 187°C.

CI3H12c 12F IN so) S + Elemental analysis calculated value C, 41, 07, H, 3, 18; N, 11.05° Actual value C, 41, 12: H, 3, 13 , N, 11.03° 11 spots n This example shows 2-chloro-5-(4-di-4-1-methyl-5-(methylsulf Preparation of (honyl)-1H-pyrazol-3-yl)-4-fluorobenzenethiol This is a specific implementation of Process XI.

9.3 g (0,022 mo 1> of 2-chloro-5-( 4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazole-3- yl)-4-fluorobenzenesulfonyl chloride and 29 g (0,44 mo A slurry containing zinc powder of +> was stirred at 90° C. for 4 hours.

The slurry was cooled and filtered through Celite®.

The r solution was poured into 1 liter of water and the slurry was filtered and air dried. solid Recrystallization from ethanol/water gave a white solid of 2-chloro-5-(4-chloro-1- Methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl)-4-fur 5.8 g (74%) of orobenzenethiol was obtained. Melting point: 111°C.

Elemental analysis calculation value of CzHlC12F IN 202S 2 C, 37, 19, H , 2, 55: N, 7.86°S, 18.05° Actual measurement: C, 37,29; H, 2,44; N, 7.86°S, 1.7.95° large 111j This example shows 4-chloro-3-(4-chloro-2-fluoro-5-methoxyph Production of phenyl)-1-methyl-5-(ethylsulfonyl)-1H-pyrazole This is a particular implementation W of process XII.

All equipment was flame dried under nitrogen. 4 in 50ml dry tetrahydrofuran -chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-meth Chil-5-(methylsulfonyl)-1H-pyrazole (1,25g, 3.5mm o Into the solution containing I) at -78°C, be sure to never let the temperature rise above -60°C. Add 1M n-butyllithium solution (3.5 ml, 3.5 mmol 1) to 0 incubation. The reaction solution was stirred at -78°C for 30 minutes, and methyl iodide (0.49 g, 3.5 mmo 1) was added to the reaction solution. The reaction solution was warmed to room temperature, then poured onto ice, and added with ethyl acetate. Extracted with. The organics were washed twice with brine, dried over anhydrous magnesium sulfate, Concentrated under vacuum.

The residue was chromatographed using a 1=1 hexane to ethyl acetate elution system. Purification gave 0.5 g (39% yield) of a yellow solid. Melting point: 65°C.

CI3H13N 20 ss lC12 elemental analysis calculation value C, 42, 52, H , 3,57, N, 7.63°Actual measurement C, 42,53; H, 3,80, N, 7. 71゜e seed and lyu This example shows 7-[4-chloro-1-methyl-5-(methylsulfonyl)-1 H-pyrazol-3-yl]-6-fluoro-2H-1,4-benzothiazine- 4(3H)-one, which is specific to Process XIII. This is an embodiment of

((5-(4-chloro-1-methyl-5-(methylsulphate)) in glacial acetic acid (150 ml) ruphonyl)-L H-pyrazol-3-yl)-4-fluoro-2-nitrophe A solution containing (nyl)thio)acetic acid, ethyl ether (3.0g, 6.6mol) Heat to 80℃ and add iron <1.5g, 0.0268mol) all at once. Ta. The solution was heated at 80 °C to 100 °C for 1 h, then cooled and e (registration plane 1) and washed with water until the solids came out of solution. solid Separation gave 1.7 g (68%) of the title compound of this example as a white solid. Melt Point 245°C, 'HNMR (CDCI Ppm near, 28 (d.

J=7.2. IH), 6.79 (d, J=10.8.IH), 4°1 (s, 3H ), 3.27 (s, 2H), 3.22 (s, 3H).

Elemental analysis calculation value of C1s H+ lCI lF IN 30s S+ C, 41,55,H,2,95,N,11.18゜Actual measurement value C,41,72,H,3 , 09, N, 10.81° Tables 3 and 4 show that the manufactured by processes II to X1ll and/or any combination of these processes. Examples of compounds produced are shown below.

Emergence weeding test As mentioned above, the compounds of the present invention were found to be surprisingly effective as herbicides. did.

A pre-emergence herbicidal activity test was conducted as follows.

Place the topsoil in a flat pot made of aluminum ram, and place it at a distance of 0°95 to 1.27 cm from the upper edge of the pot. A predetermined number of monocotyledonous and dicotyledonous annual plants, each on top of the soil, packed to a depth of Seeds of species and/or vegetative propagules of various perennial plant species (active propagules) such as acetone Seed with a known amount of active ingredient dissolved or suspended in water as a solvent or carrier. Sprayed directly onto the floor, which was then covered with a layer of untreated topsoil that evenly filled the pot.

After treatment, the flat pots should be moved to a bench in the greenhouse to provide sufficient moisture for germination and growth. Depending on the situation, water was supplied from below.

Approximately 10/14 days after sowing and treatment (usually after 11 days), observe the flat pots and check the results (% inhibition) was recorded.

Table 5 below summarizes the results of the pre-emergence herbicidal activity of the compounds of the invention against weeds. The herbicidal rates shown in Table 5 are the % inhibition of each plant species.

The plant species normally considered weeds used in the tests and whose data are shown in Table 5 are: The abbreviations on each shelf of the table are identified according to the description below.

Yens-Yellow nutsedge＾nbg-＾nnual blue grassSejg-Seedling johnsor+grassDobr -Downy Brome Bygr - Barnyardgrass Hog! -Morning glory yCobu-Cocklebur Vele - Velvetleaf In+5u-Indian mustardNibw-Mild buckwh In the table below, the code “C” represents 100% control, and the code “N” represents 100% control. This indicates that the seeds were planted, but data could not be obtained for various reasons.

Post-emergence weeding test The post-emergence herbicidal activity of some of the various compounds of the present invention was determined as follows: Shown by greenhouse test. Fill an aluminum flat well with holes in the bottom with topsoil. Each of seeds of several monocotyledonous and dicotyledonous annual plant species and/or perennial plants; 0-seed and/or vegetative propagation by placing vegetative propagules of species and pushing them into the soil surface layer After covering the body with soil and leveling it, place the Hirai on a bench in the greenhouse and lower it as necessary. Water was supplied from Once the plants have reached the desired growth stage (2-3 weeks), separate each hirai individually. Move to the spray chamber/< and operate at a spray pressure of 170.3 kPa (Lops i g). The indicated application rate was applied using a sprayer. Approximately 0.4% by volume of An amount of the emulsifier mixture was introduced to give a spray solution or suspension containing the emulsifier. Spraying The total amount of liquid or spray suspension is 3870 liters/ha (200 gallons/ha). When spraying equivalent solutions or suspensions on contained a sufficient amount of the candidate chemical to deliver the corresponding amount of active ingredient. Hirai Return to the greenhouse and water as before, approximately 10-14 days after application (usually 11 days later). , sometimes after 24-28 days (usually after 25 days) of the plants compared to the control. The post-emergence herbicidal activity shown in Table 6G is the % inhibition of each plant species when damage was observed.

Herbicidal compositions of the invention, including concentrates that need to be diluted before application, contain at least It may contain an IN active ingredient and a liquid or solid adjuvant. The composition includes: In the form of finely divided granular solids, particles, pellets, solutions, dispersions or emulsions The active ingredient may be combined with diluents, fillers, carriers and condensers to give a composition of It is prepared by mixing with an adjuvant containing a dispersion agent. i.e. active Ingredients include finely divided solids, organic liquids, water, wetting agents, dispersing agents, and emulsifying agents. It is contemplated that it may be used with adjuvants or any suitable combination of these. It will be done.

Suitable wetting agents include alkylbenzenes, alkylnaphthalyl sulfonates, Long chains of sulfated fatty alcohols, amines or acid amides, sodium inthionate Acid ester, ester of sodium sulfosuccinate, sulfated or sulfonated Fatty acid ester, petroleum sulfonate, sulfonated vegetable oil, ditertiary acetylene Glycols, polyoxyethylene derivatives of alkylphenols (especially in-octyl) mono-higher fats such as phenol and nonylphenol), and anhydrous hexitol. Polyoxyethylene derivatives of acid esters (e.g. sorbitan) may be mentioned. Wear. Preferred dispersants are methylcellulose, polyvinyl alcohol, lignin. Sodium Sulfonate, Polymeric Alkylnaphthalene Sulfonate, Sodium Munaphthalene sulfonate and polymethylene bisnaphthalene sulfonate . Wettable powders (i.e. wettable powders) contain one or more active ingredients, an inert solid filler and one A water-dispersible composition containing one or more wetting and dispersing agents. Inert solid fillers are natural of mineral origin, such as synthetic minerals derived from ray, diatomaceous earth, and silica. It is.

Examples of such fillers include carolinite, attapulgite clay and composites. The wettable powder compositions of the present invention typically include magnesium silicate. contains 0.5 to 60 parts or more (preferably 5 to 20 parts) of active ingredient and about 0.25 to 2 5 parts (preferably 1-15 parts) of wetting agent and about 0.25-25 parts (preferably 1 ．． 0 to 15 parts) of a dispersant and about 5 to about 95 parts (preferably 5 to 50 parts) of an inert solid fillers, provided that all such parts are by weight based on the weight of the entire composition. It depends on the quantity. If necessary, about 0.1 to 2.0 parts of a solid inert filler. , corrosion inhibitors or antifoaming agents or both.

Other formulations may contain from 0.1 to 60% by weight of active ingredient based on a suitable filler. Powder concentrates (du, stc.

ncecentrates). Such powders are suitable for dispersion at approx. It can be diluted to a concentration within the range of 0.1-10% by weight.

Aqueous suspensions and emulsions consist of non-aqueous solutions of water-insoluble active ingredients and emulsifiers in water. Stir until homogeneous and then homogenize to obtain a stable solution of extremely fine particles. It can be produced by providing a emulsion. The resulting concentrated aqueous suspension has a particle size of It is quite small and has excellent drug coverage when diluted and sprayed. It is characterized by being uniform. Suitable concentrates of such formulations are about 0.1 to 60 wt. % by weight of active ingredient, preferably from 5 to 50% by weight, but the upper limit is the activity in the solvent. determined by the solubility range of the chemical components.

Concentrates typically contain water-immiscible or partially water-immiscible active ingredients, including surfactants. Suitable solvents for the active ingredients of the present invention which are solutions of sterile solvents include dimethylform. Amides, dimethyl sulfoxide, N-methylpyrrolidone, hydrocarbons, and water immiscible Mention may be made of compatible ethers, esters or ketones. However, The active ingredients are dissolved in a solvent and the concentrate is then diluted with e.g. kerosene for spraying. Other strong liquid concentrates can also be prepared by

Concentrated compositions of the present invention typically contain about 0.1 to 95 parts (preferably 5 to 60 parts) of active about 0.25 to 50 parts (preferably 1 to 25 parts) of a surfactant; 5 to 94 parts of solvent, provided that all of these parts are the emulsifying oil. The weight is based on the total weight.

Granules are made by adhering to or containing a base matrix of inert, finely divided particulate filler. A physically stable particulate composition comprising an active ingredient distributed within. bulking agent particles Surfactants, such as those described above, are included in the composition to facilitate leaching of the active ingredient from the can be made to exist. Natural clay, pyrophyllite, illite, vermiculite are examples of the types of particulate mineral fillers that can be used. Preferred fillers have porosity and and adsorbent preformed particles 1 such as preformed and sieved attapulgite. particles or thermally expanded vermiculite particles, and fine particles such as kaolin clay. Ground clay, hydrated attapulgite or bentonite clay. these The bulking agent may be sprayed or mixed with the active ingredient to form the herbicidal granule. can be done.

The granule composition of the present invention contains from about 0.1 to about 30 parts by weight of active per 100 parts by weight of clay. and a surfactant in an amount of O to about 5 parts by weight per 100 parts by weight of clay particles. obtain.

Furthermore, the compositions of the invention may contain other additives, such as fertilizers, other herbicides, other pesticides, toxic used in combination with emollients and adjuvants or adjuvants mentioned above. Chemicals that may be useful in combination with the active ingredients of the present invention may include substances such as contains triazines, ureas, sulfonylureas, carbamates, acetamides, and toanilide, uracil, acetic acid or phenol derivatives, thiol carbamates, Triazoles, benzoic acid derivatives, nitriles, heterophenyl ethers, nitrophs phenyl ether, diphenyl ether, pyridine, etc., such as the following: can be given.

, -1 2-Chloro-4-ethylamino-6-itupropylamino≦-triazine: 2-chloro-4,6-bis(isopropylamino)-≦-triazine: 2-chloro-4,6-bis(ethylamino)-≦-triazine; 3-isopropyl-IH-2,1,3-benzothiadiazine-4-(3H)-o 2.2-dioxide.

3-amino-1,2,4-triazole.

6.7-Sihydrodiviride (1,2-:2',1'-c)-biradidiinium salt.

5-Bromo-3-isopropyl-6-methyluracil; 1.1°-dimethyl-4 ,4”-bipyridinium; 2-(4-isopropyl-4-methyl-5-oxo- 2-imidacylin-2-yl)-3-quinolinecarboxylic acid; 2-(4-isopropropyl) pyl-4-methyl-5-oxo-2-imidacillin-2-yl) nicotinic acid Sopropylamine salt; Methyl 6-(4-isopropyl-4-methyl-5-oxo-2-imidacyline -2-yl)-m-toluate, and methyl 2-(4-isopropyl-4-methyl) Chil-5-oxo-2-imidacylin-2-yl)-p-toluate 5-k trifluoromethyl)-4-chloro-3-(3'-[1-ethoxycarbonyl] -ethoxy-4°-nitrophenoxy)-1-methylpyrazole; 5-(trifluoromethyl)-4-chloro-3-<3'-methoxy-4'-ditho lophenoxy)-1-methylpyrazole 5-(trifluoromethyl)-4-chloro rho-3-(3°-[1-butoxycarbonyl]-ethoxy-4'-nitropheno xy)-4-methylpyrazole: 5-(trifluoromethyl)-4-chloro-3-(3'-methylsulfamoyl Carbonyl propoxy-4°-nitrophenoxy)-4-methylpyrazole; 5-(trifluoromethyl)-4-chloro-3-(3°-propoxycarbonyl Methyloxime-4'-nitrophenoxy)-1-methylpyrazole: (±)-2-[4-[[5-()lifluoromethyl)-2-pyridinyl]oxy cophenoxy]-propanoic acid (9CI); S,S-dimethyl-2-(difluoro methyl)-4-isobutyl-6-trifluoromethyl-3,5-pyridine dihydryl Pothioate; 3-Pyridinecarboxylic acid, 2-(Shiffleolomethyl)-5-(4,5-Dihydromethyl) Dro-2-thiazolyl)-4-<2-methylpropyl)-6-()rifluorome methyl)-, methyl ester 3,5-pyridinedicarboxylic acid, 2-(difluoromethane)-, methyl ester methyl)-4-(2-methylpropyl)-6-()lifluoromethyl)-, dimethyl Luester; 3.5-pyridine dirubothionic acid 54-(cyclopropylmethyl)-2-(di fluoromethyl)-6-()lifluoromethyl)-,S,S-dimethyl ester ; Sulfoximine, N-(jethoxyphosphinyl)-8-methyl-8-phenylene Lou Sulfonylurea N-(4-chlorophenoxy)phenyl-N,N-dimethylurea; N,N-dimethyl-N'-(3-chloro-4-methylphenyl)urea; 3-(3,4-dichlorophenyl)-1,1-dimethylurea.

1.3-dimethyl-3-(2-benzothiazolyl)urea 3-(p-chlorophene) 1-butyl-3-(3,4-dichlorophenylene)-1,1-dimethylurea; )-1-methylurea; 2-chloro-N[(4-methoxy-6-methyl-1,3,5-triazine-2- yl) aminocarbonyllow benzene sulfonamide; Methyl 2-(<(((4,6-dimethyl-2-pyrimidinyl)amino)car (bonyl)amino)sulfonyl)benzoate; ethyl 1-[methyl 2-( ((((4,6-cymethyl-2-pyrimidinyl)amino)carbonyl)amino) sulfonyl)] benzoate; Methyl 2-((((4,6-dimethoxy-pyrimidin-2-yl)amino ) carbonyl)amino)sulfonylmethyl)benzoate; Methyl 2-(((((4-methoxy-6-methyl-1,3゜5-triazine -2-yl)amino)carbonyl)amine)sulfonyl)benzoate: N-[3-(N,N-dimethylcarbamoyl)-2-pyridin-2-ylcosul Honyl-N'-<4.6-cymethoxypyrimidin-2-yl)urea; N-[(3-ethylsulfonyl)-2-pyridin-2-yl]-sulfonyl-N '-(4,6-cymethoxypyrimidin-2-yl)urea; N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-bis- difluoromethoxypyrimidin-2-yl)urea.

Rubamate Rubamate 2-chloroallyl-diethyldithiocarbamate; 5-(4-chlorobenzyl) -N, N-diethylthiol carbamate: Isopropyl N-(3-chlorophenyl)carbamate S-2,3-dichloro Allyl-N,N-diisopropylthiol carbamate; S -N, N-dipropylthiol carbamate: S - propyl-N, N-di Propylthiol carbamate; S-2,3,3-)dichloroallyl-N. N-diisopropylthiol carba Mate.

Otsu (ΣL main Zl cetanilito A Sanami no 11 U 2-chloro-N, N-diary Ruacetamide; N,N-dimethyl-2,2-diphenylacetamide; N- (2,4-dimethylcheno-3-yl)-N-(1-methoxyprop-2-yl )-2-chloroacetamide; N-(IH-pyrazol-1-ylmethyl-N~ (2,4-dimethylcheno-3-yl)-2-chloroacetamide N-(1-pi lazol-1-ylmethyl)-N-(4,6-cymethoxypyrimidin-5-yl )-2-chloroacetamide; N-(2,4-dimethyl-5-[[()-lifluoromethyl)sulfonyl]a Mino]phenyl]acetamide; N-isopropyl-2-chloroacetanilide ;N-isopropyl-1-<3.5.5-)tumethylcyclobexen-1-yl )-2-chloroacetamide; 2°,6°-diethyl-N-(butoxymethyl) -2-chloroacetanilide; 2',6'-diethyl-N(2-n-propoxyethyl)-2-chloroacetoa Nirid; 2',6"-dimethyl-N-(1-pyrazol-1-ylmethyl)-2-chloro Acetanilide: 2',6'-diethyl-N-methoxymethyl-2-chloroacetanilide; 2′-Methyl-6′-dithyl-N-(2-methoxyprop-2-yl)-2-k Loroacetanilide; 2'-methyl-6'-ethyl-N-2-ethoxymethyl )-2-chloroacetanilide; α,α,α-trifluoro-2,6-sinitro-N,N-dipropyl-p-tolu Yijin N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamide.

esul alcohol 2.2-dichloropropionic acid; 2-Methyl-4-chlorophenoxyacetic acid: 2.4-dichlorophenoxyacetic acid; Methyl-2-[4-(2,4-dichlorophenoxy)phenoxy]propione to; 3-amino-2,5-dichlorobenzoic acid; 2-methoxy-3,6-dichlorobenzoic acid Fragrant acid: 2.3.6-) dichlorophenylacetic acid; N-1-naphthylphthalamic acid ; 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitroben Sodium fragrant; 4,6-sinitro-o-5ec-butylphenol; sulfonomethyl)glycine and its salt; butyl (R)-2-[4-[(5-() (lifluoromethyl)-2-pyridinyl)oxy]phenoxy]propanoate.

Twenty-two oxen 2.4-dichlorophenol-4-nitrophenyl ether; 2-chloro-δ,δ,δ-trifluoroP-)dyl-3-ethoxy-4-nito Rodiphenyl ether; 5-(2-chloro-4-trifluoromethylphenoxy )-N-methylsulfonyl-2-nitropenzamide: 1°-(carboethoxy )-ethyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2 -Nitrobenzoate.

tΩ Emperor 2.6-cyclobenzonitrile; Sodium methanarsonate; Disodium methanarsonate; 2-(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidino hmm; 7-oxabicyclo(2,2,1)hebutane, 1-methyl-4-(1-methylethyl) methyl)-2-(2-methylphenylmethoxy)-1-exo-glyphosate and its These salts.

Fertilizers that are effective in combination with active ingredients include, for example, ammonium nitrate, urea, potassium carbonate, and and lime perphosphate. Other effective additives include mixed soil, Materials that allow plants to take root and grow, such as organic fertilizer, humus, and sand, can be mentioned. Wear.

Herbicidal formulations of the type described above are illustrated in the following embodiments for illustrative purposes. .

■、Emaru 2nd ”b A, compound number 22 4.0 Free acid of complex organic phosphate 3.5 or an aromatic or aliphatic hydrophobic base (For example, AFACRE-610 (f; registered trademark of AF Company)) Contains butanol Polyoxyethylene/polyoxy 1.5 propylene buculo copolymer (For example, Tergitol X1l (registered trademark of Union Carbide) )) Xylene 5.34 Monochlorobenzene 100.00 8. Compound No. 36 3.0 Free acid of complex organic phosphate 4.0 or an aromatic or aliphatic hydrophobic base (e.g. GAFACRE-610) Polyoxyethylene/polyoxy 1.60 propylene book containing butanol copolymer (e.g. Tergitol XH) Xylene 4.75 Monochlorobenzene 1 100.00 Compound No. 0.43 2.5 Free acid of complex organic phosphate 4.0 or an aromatic or aliphatic hydrophobic base (e.g. CAFACRE-610 (registered trademark of GAF)) containing butanol. Lioxyethylene/polyoxy 1.5 propylene bucullo copolymer (For example, Tergitol XI (registered trademark of Union Carbide) ) Cyclohexanone 5.5 Aromatic 200 8 roasted j 100.00 D, compound number 52 5.0 Free acid of complex organic phosphate 3.00 or an aromatic or aliphatic hydrophobic base (e.g. GAFACRE-610) Polyoxyethylene/polyoxy 2.0 propylene book containing butanol locopolymer (e.g. Tergitol XH) Water 45.9 100.0 0.102 compound! IIj30.0 Sodium naphthalene sulfonate formaldehyde 10.0 Hardware Propylene glycol 7,0 Agility (snelling grade) bentonite 0.5 antifoaming agent 0.5 Water 52. .

100, O Vl My Lobusel is turned into Bo1mer A, Compound No. 69 4. 0 Polyurea shell wall> 0.4Reax (registered trademark) 88B (Dispersant) 1.0 NaCl (electrolyte) 5.0 Water” Dan J 100, O B, compound number 81 0.5 Polyurea shell wall 6.82 Reax <registered trademark) C-21 (dispersant) 1.0 Nano, (electrolyte) 5.0 ^romatie 200 (solvent) 45.0 water 41.68 Too,.

C, compound number 130 1.0 Polyurea shell wall 7.0 Reax (registered trademark) C-212,0 NaCI 10.0 Xylene 40.0 Water 40.0 100, O D, compound number 63 48.0 Polyurea shell wall 4.8 Reax (registered trademark) 88B 3.0 NaCI 15.0 Kerosene 29.2 100.0 E, compound number 74 40.0 Polyurea shell wall 6.5 Reax (registered trader 51I) 88B 2.0NaNO310,5 Solvent 25.0 Water” 1st theory 100.0 F, compound number 157 10.0 Polyurea shell wall 8.5 Reax (registered trader II) C-211,5NaC16,0 Solvent 20.0 Water” 1 side 100.0 When working in accordance with the invention, an effective amount of a compound of the invention may be administered to seeds or vegetative plants. Sprayed on the soil containing the propagules or incorporated into the soil medium by any convenient method. can do. Application of liquid compositions and granular solid compositions to soil is by powder application. machines, booms, and conventional equipment such as manual sprayers and spray spreaders. It can be done by law. Additionally, the compositions of the present invention are effective at low doses, so that finely powdered Or it can be applied from an airplane as a spray. Exactly which active ingredients to use The appropriate amount depends on the plant species and its growth stage, soil type and condition, rainfall amount, and the amount used. With the choice of pre-emergence, post-emergence and soil application depending on a variety of factors including the specific compound. So, usually about 0.0005kg/ha (0.5g/ha) to about 11.2kg/ha used in a dose of ha. Preferably about 0.001 kg/ha (1.0 g/ha ) to about 0.50 kg/ha (500 g/ha). Depending on the situation Smaller or larger amounts may be required. A person skilled in the art will understand that in any particular case The optimum amount to be applied can be legally determined from this specification, including the above examples. Ru.

The term “soil” is from Webster’s New International tional Dictionary, 2nd edition, Unabridged (1961 ) is used in the broadest sense, including all ordinary "soil" as defined in . That is, for this purpose The term means any substance or medium in which vegetation can take root and grow, including only in the ground. Mixed soil, fertilizer, black mud, humus, and loam that are designed to support plant growth Also includes silt, mud, clay, sand, etc.

Although the invention has been described with reference to particular embodiments, the details of these embodiments are not limiting. Various modifications and changes may be made without departing from the spirit and scope of the present invention. And variations are possible and implementation of such equality! Mr. IIi also forms part of the present invention. I want to be understood.

summary The present invention provides certain substituted arylpyrazole compounds, herbicide compositions containing the compounds, , as well as a method for using the composition as a herbicide and a method for producing the composition.

The scope of the claims 1. Formula: [In the formula, R1 is hydrogen, optionally substituted with hydrogen or R1 or an Rt group] substituted with C1-, alkyl, or optionally C1-4 alkyl C is S-*cycloalkyl, R2 is optionally hydrogen or C3-5 atom substituted with Ro or R2 group; It is Lukiru, R1 is hydrogen or halogen, R1 is halogen, R6 and R2 are C1-, alkyl, haloalkyl, alkylthio, alkoxy Alkyl or polyalkoxyalkyl, C1-8 cycloalkyl, cycloa alkenyl, cycloalkyalkyl or cycloalkenylalkyl; C2-, Alkenyl or alkynyl; carbamyl, halogen, amino, nitro, sia , hydroxy, containing 1 to 4 0, S(0), and/or N heteroatoms C4-1゜Heterocycle, C,-, aryl, aralkyl or alkaryl, -C XY Ra, -CX Rs, CHz OCOR+ o, -YR,, -NR1 2R13 or any two R1-R7 groups are such two R7- When the R2 group is bonded via a heteroatom -C-N- bond, there are fewer heterocycles. Saturated and/or unsaturated carbon atoms, provided that they have at least 6 ring members. a compound having up to 9 ring members linked through mono- and/or heteroatom bonds; It forms a bare ring, and even if this ring is substituted with any of the above R3-R1 groups, may be substituted with any of the above R9-R7 groups if not self-inclusive. may be substituted with R1-R11 group or R1-R1 group; χ is 0.5 (0), N R+ h or CR+ s R+ i; Y is 0 ．． 5 (0), or N R + 7;

R8-R1 is one of the above R2-R1 groups; m is 0 to 2; compound.

2. Formula 111: [Wherein, R1 and R2 are C+-S alkyl; R1 is hydrogen, bromo, chloro or fluoro; Rs is halogen; R5 is halogen or nitro; R2 is as defined in claim 1 is a group of, or R, and R2 are bonded via a 10CH2(C=O)-N-(propynyl)-bond and forming a fused 6-membered ring.

3, R1 and R2 are methyl; R1 is hydrogen, bromo or chloro; R3 is chloro or fluoro; R, is chloro, fluoro or nitro; R2 is defined in formula 1; YB2 group, or R1 and R2 are 10CH2(C=O)-N-(propylene) ropinyl)-bond to form a fused 6-membered ring. Compound.

4.4-chloro-3-(2-fluoro-4-chloro-5-(2-propynyloxy) c) phenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazole; 4-bromo-3-(2-fluoro-4-chloro-5-(2-10 vinyloxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazole; 4-chloro-3-(2-fluoro-4-ly-4-5-(2-methoxyethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazole; 4-bromo-3-(2-fluoro-4-chloro-5-(2-methoxyethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazole; 6-(4-chloro-1-methyl-5-(methylsulfonyl)-IH-pyrazole -3-yl)-7-fluoro-4-(2-propynyl)-2)I-1,4-ben Zooxazin-3-(4H)-one; (5-(4-bromo-1-methyl-5-(methylsulfonyl)-1H-pyrazo (3-yl)-2-chloro-4-fluorophenoxy)acetic acid, 1-methylethyl (5-(4-chloro-1-methyl-5-(methylsulfonyl)-1 H-pyrazol-3-yl)-2-chloro-4-fluorophenoxy)acetic acid, 1 -Methyl ethyl ester; 2-(5-(4-bromo-1-methyl-5-(methythyl) rusulfonyl)-IH-pyrazol-3-yl)-2-chloro-4-fluorophore (enoxy)propanoic acid, ethyl ester; and 2-(5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-pi razol-3-yl)-2-chloro-4-fluorophenoxy)propanoic acid, A compound according to claim 1 selected from the group consisting of methyl esters.

5.4-chloro-3-(2-fluoro-4-chloro-5-(2-provinyloxy) c) phenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazole.

6.4-Bromo-3-(2-fluoro-4-chloro-5-(2-propynyloxy) c)phenyl)-1-methyl-5-(methylsulfonyl)-IH-pyrazole.

7.2-(5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H- pyrazol-3-yl)-2-chloro-4-2fluorophenoxy)propanoic acid 1 ethyl ester.

8. <5-(4-hechloro-1-methyl-5-(methylsulfonyl)-iH -pyrazol-3-yl)-2-chloro-4-fluorophenoxy)acetic acid 11- Methyl ethyl ester.

9. an adjuvant and a herbicidally effective amount of the compound according to any one of claims 1 to 8; A herbicide composition comprising a compound.

10. Apply a herbicidally effective amount of the insecticides of claims 1 to 8 to the vegetation area of plants that are undesirable for crops. The removal of undesirable plants from crops by spraying a compound as defined in any one of the preceding paragraphs. How to process.

11. Reaction formula: [In the formula, R1 is hydrogen, c1-s alkyl optionally substituted with R4 group , or C1-8 cycloalkyl optionally substituted with C, -, alkyl or cycloalkenyl, R2 is cI-s alkyl optionally substituted with R1 group, R3 is hydrogen or halogen, R6 is hydrogen C+-e alkyl, haloalkyl, alkylthio, alkoxy alkyl or polyalkoxyalkyl, c i-s cycloalkyl, cycloa C, -.

Alkenyl or alkynyl; carbamyl, halogen, amino, nitro, sia , hydroxy, containing 1 to 4 ○, 5(O)8 and/or N heteroatoms C4-tO heterocycle, C&-1 aryl, aralkyl or alkaryl, -CX YR,, -CXR,, CH20COR,. , -YR, , -NR12Rl 3 or any two R1 groups are such that two such R4 groups are heteroatoms and the heterocycle has at least 6 ring members when linked through -N- bonds saturated and/or unsaturated carbon, -C- and/or hetero bonded through the bond of the ro atoms to form a heterocycle having up to 9 ring members, This ring may be substituted with any of the R1 groups above or be self-inclusive. If not, R rho 1. substituted with any of the above R1 groups. group or R4 group May be substituted; , , Y is 0.5(0), or NRI; R1-R1, is the above R 1 group; m is 0 to 2; n is 0 to 5] preparing a compound of formula I by reacting a compound of formula B with an oxidizing agent according to how to.

12. The compound of formula I has the formula ■■: [wherein R1, R2 and R1 are as defined in formula 1: R1 is independently one of said R3 groups, and R6 and R1 are independently one of said R1 groups. or such two groups R6 and R2 have a heteroatom -C-N- bond. the condition that the heterocycle has at least 6 ring members when bonded through to form a heterocycle with up to 9 ring members containing ○, N and/or S atoms and the ring is alkyl, each having up to 4 carbon atoms, Even if substituted with haloalkyl, alkoxy, alkenyl or alkynyl groups good〕 12. The method according to claim 11, wherein the compound is a compound of

13, the compound of formula I has the formula III: [wherein R2 and R2 are C3-, Al] R and R are hydrogen, bromo, chloro or fluoro; R5 is an R3 group or nitro; R2 is an R1 group, or Rs and R7 are bonded via a 0CH2(C=O)-N-(R4)- bond and condensed. 12. The method according to claim 11, wherein the compound is a 6-membered ring.

14, R+ and R2 are methyl, R is hydrogen, bromo or chloro; Rs is chloro or fluoro; R; is chloro, fluoro or nitro; R7 is defined in the formula 14. The method according to claim 13, wherein YR, , is a group.

15, consisting of reacting a compound of formula 1 in which R3 is hydrogen with a halogenating agent 12. The method according to claim 11, for producing a compound of formula (2), wherein R1 is halogen.

16. The compound of formula (1) produced by the halogenation process is 17. The method of claim 16, wherein said compound is a compound defined by formula III.

17, R, and R2 are methyl, R1 is fluoro, and R6 is 17. The method according to claim 16, which is chloro, fluoro or nitro.

18, where R, is hydrogen, using an acylating agent or an alkylating agent. One of the R4 groups is -YR,, and R11 is 12. A method according to claim 11, wherein the compound of formula 1 is prepared which is not hydrogen.

19, the compound of formula 1 before acylation or alkylation, R7 is -YH 19. The method of claim 18, wherein the compound is defined by formula I11.

Claims (33)

[Claims] 1. Formula I: I▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R1 is hydrogen, C1-9 alkyl optionally substituted with R4 group, Or C3-6 cycloalkyl optionally substituted with C1-4 alkyl or cycloalkenyl, R2 is C1-5 alkyl optionally substituted with an R4 group, R3 is hydrogen or halogen, R4 is hydrogen, C1-6 alkyl, haloalkyl, alkylthio, alkoxy C3-6 cycloalkyl or polyalkoxyalkyl, C3-6 cycloalkyl, cycloalkyl Kenyl, cycloalkyalkyl or cycloalkenylalkyl; C2-3 a rukenyl or alkynyl; carbamyl, halogen, amino, nitro, cyano , hydroxy, C containing 1 to 4 O, S(O)m and/or N heteroatoms 4-10 heterocycle, C6-12 aryl, aralkyl or alkaryl, -CX YR8, -CXR9, -CH2OCOR10, -YR11, -NR12R13 or any two R4 groups, such two R4 groups have ▲number of heteroatoms. There are formulas, chemical formulas, tables, etc.▼If they are bonded through a bond, there are fewer heterocycles. saturated and/or unsaturated carbon, ▲, provided that it has at least 6 ring members; Contains mathematical formulas, chemical formulas, tables, etc. ▼ and/or bonds via heteroatom bonds to form a heterocycle having up to 9 ring members, and this ring is It may be substituted with any of the above R4 groups, or if it is not self-inclusive, the R4 group may be substituted with May be substituted with R3-13 group or R4 substituted with any; O, S(O)m, NR14 or CR15R16; Y is O, S(O)m or or NR17; R5 to R17 are one of the above R4 groups; m is 0 to 2; the law of nature, n is 0 to 5] compound. 2. Formula II: II▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R1, R2 and R3 are defined in Formula I. As defined: R5 is independently one of said R3 groups, and R6 and R7 are independently one of said R4 groups. or such two groups R6 and R7 are heteroatoms ▲ mathematical formula, chemical formula, There are tables, etc. ▼If the heterocycle is connected through a bond, there are at least 6 heterocycles. up to 9 ring members including O, N and/or S atoms; are joined to form heterocycles having up to four carbon atoms, each ring containing up to four carbon atoms. alkyl, haloalkyl, alkoxy, alkenyl or alkynyl with atoms may be substituted with a group] compound. 3. Formula III: III▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R1 and R2 are C1-5 alkyl R3 and R5 are hydrogen, bromo, chloro or fluoro; R6 is R5 group or nitro: R7 is an R4 group, or R6 and R7 are bonded via -OCH2(C=O)-N-(R4)- and condensed A compound that forms a 6-membered ring. 4. R1 and R2 are methyl; R3 is hydrogen, bromo or chloro; R5 is chloro or fluoro; R6 is chloro, fluoro or nitro; R7 is defined in formula I; or R6 and R7 are -OCH2(C=O)-N-( brovinyl)-bond to form a fused 6-membered ring. compound. 5.4-chloro-3-(2-fluoro-4-chloro-5-(2-brovinyloxy) c) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole; 4-bromo-3-(2-fluoro-4-chloro-5-(2-brovinyloxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole; 4-chloro-3-(2-fluoro-4-chloro-5-(2-methoxyethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole; 4-bromo-3-(2-fluoro-4-chloro-5-(2-methoxyethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole; 6-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-virazole -3-yl)-7-fluoro-4-(2-brovinyl)-2H-1,4-benzo Oxazin-3-(4H)-one; (5-(4-bromo-1-methyl-5-(methylsulfonyl)-1H-virazo (3-yl)-2-chloro-4-fluorophenoxy)acetic acid, 1-methylethyl (5-(4-chloro-1-methyl-5-(methylsulfonyl)-1 H-virazol-3-yl)-2-chloro-4-fluorophenoxy)acetic acid, 1 -Methyl ethyl ester; 2-(5-(4-bromo-1-methyl-5-(methyl sulfonyl)-1H-virazol-3-yl)-2-chloro-4-fluorophe (oxy)propanoic acid, ethyl ester; and 2-(5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-bira sol-3-yl)-2-chloro-4-fluorophenoxy)propanoic acid, ethyl 2. A compound according to claim 1 selected from the group consisting of esters. 6.4-chloro-3-(2-fluoro-4-chloro-5-(2-brovinyloxy) c) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole. 7.4-Bromo-3-(2-fluoro-4-chloro-5-(2-brovinyloxy) c) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole. 8.2-(5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H- pyrazol-3-yl)-2-chloro-4-fluorophenoxy)propanoic acid, ethyl ester. 9. (5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-bira sol-3-yl)-2-chloro-4-fluorophenoxy)acetic acid, 1-methyl ethyl ester. 10. Adjuvant and herbicidal effective amount formula I:I▲Mathematical formula, chemical formula, table, etc. S▼ [In the formula, R1 is hydrogen, C1-5 alkyl optionally substituted with R4 group, Or C3-6 cycloalkyl optionally substituted with C1-4 alkyl or cycloalkenyl, R2 is C1-5 alkyl optionally substituted with an R4 group, R3 is hydrogen or halogen, R4 is hydrogen, C1-6 alkyl, haloalkyl, alkylthio, alkoxy C3-8 cycloalkyl or polyalkoxyalkyl, C3-8 cycloalkyl, cycloalkyl Kenyl, cycloalkyalkyl or cycloalkenylalkyl; C2-6 a Lukenyl or alkynyl: carbamyl, halogen, amino, nitro, cyano , hydroxy, C combining 1 to 4 O, S(O)m and/or N heteroatoms 4-10 heterocycle, C6-12 aryl, aralkyl or alkaryl, -CX YR8, -CXR9, -CH2OCOR10, -YR11, -NR12R13 or any two R4 groups, such two R4 groups have ▲number of heteroatoms. There are formulas, chemical formulas, tables, etc.▼If they are bonded through a bond, there are fewer heterocycles. saturated and/or unsaturated carbon, ▲, provided that it has at least 6 ring members; Contains mathematical formulas, chemical formulas, tables, etc. ▼ and/or bonds via heteroatom bonds to form a heterocycle having up to 9 ring members, and this ring is or, if not self-inclusive, the R4 group may be substituted with any of the above R4 groups. May be substituted with R5-13 group or R4 substituted with any; O, S(O)m, NR14 or CR15R16; Y is O, S(O)m or or NR17; R5 to R17 are one of the above R4 groups; m is 0 to 2; the law of nature, n is 0 to 5] A herbicide composition comprising a compound of 11. Formula II of adjuvant and herbicidal effective amount: II▲ Numerical formula, chemical formula, table, etc. ▼ [wherein R1, R2 and R3 are as defined in formula I: R5 is independently one of said R3 groups, and R6 and R7 are independently one of said R4 groups. or such two groups R6 and R7 are heteroatoms ▲ mathematical formula, chemical formula, There are tables, etc. ▼If the heterocycle is connected through a bond, there are at least 6 heterocycles. up to 9 ring members including O, N and/or S atoms; are joined to form heterocycles having up to four carbon atoms, each ring containing up to four carbon atoms. alkyl, haloalkyl, alkoxy, alkenyl or alkynyl with atoms may be substituted with a group] A herbicide composition comprising a compound of 12. Adjuvant and herbicidally effective amount formula III:III▲Mathematical formula, chemical formula, table, etc. ▼ [In the formula, R1 and R2 are C1-5 alkyl; R3 and R5 are hydrogen, bromo, chloro or fluoro; R6 is R5 group or nitro: R7 is an R4 group, or R6 and R7 are bonded via -OCH2(C=O)-N-(R4)- bond and condensed. A herbicidal composition comprising a compound which forms a 6-membered ring. 13. In the compound, R1 and R2 are methyl; R3 is hydrogen, bromo or chloro; R5 is chloro or fluoro; R: R6 is chloro, fluoro or nitro; R7 is defined in formula I; or R6 and R7 are -OCH2(C=0)-N-( brovinyl)-bond to form a fused 6-membered ring. composition. 14. The compound is 4-chloro-3-(2-fluoro-4-chloro-5-(2-brovinyloxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole; 4-bromo-3-(2-fluoro-4-chloro-5-(2-brovinyloxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole; 4-chloro-3-(2-fluoro-4-chloro-5-(2-methoxyethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole; 4-bromo-3-(2-fluoro-4-chloro-5-(2-methoxyethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole: 6-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-virazole -3-yl)-7-fluoro-4-(2-brovinyl)-2H-1,4-benzo Oxazin-3-(4H)-one: (5-(4-bromo-1-methyl-5-(methylsulfonyl)-1H-virazo (3-yl)-2-chloro-4-fluorophenoxy)acetic acid, 1-methylethyl (5-(4-chloro-1-methyl-5-(methylsulfonyl)-1 H-virazol-3-yl)-2-chloro-4-fluorophenoxy)acetic acid, 1 -Methyl ethyl ester; 2-(5-(4-bromo-1-methyl-5-(methyl sulfonyl)-1H-virazol-3-yl)-2-chloro-4-fluorophe (oxy)propanoic acid, ethyl ester; and 2-(5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-bira sol-3-yl)-2-chloro-4-fluorophenoxy)propanoic acid, ethyl 11. The composition of claim 10, wherein the composition is selected from the group consisting of polyesters. 15. an adjuvant and a herbicidally effective amount of 4-chloro-3-[1-fluoro-4- Chloro-5-(2-brovinyloxy)phenyl)-1-methyl-5-(methyl sulfonyl)-1H-virazole. 16. an adjuvant and a herbicidally effective amount of 4-bromo-3-(2-fluoro-4- Chloro-5-(2-brovinyloxy)phenyl)-1-methyl-5-(methyl sulfonyl)-1H-virazole. 17. an adjuvant and a herbicidally effective amount of 2-(5-(4-chloro-1-methyl- 5-(methylsulfonyl)-1H-virazol-3-yl)-2-chloro-4- A herbicide composition containing fluorophenoxy)propanoic acid and ethyl ester. 18. an adjuvant and a herbicidally effective amount of (5-(4-chloro-1-methyl-5- (methylsulfonyl)-1H-virazol-3-yl)-2-chloro-4-fur A herbicide composition comprising (orophenoxy)acetic acid, 1-methylethyl ester. 19. A herbicidally effective amount of Formula I: I▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R1 is hydrogen, C1-5 alkyl optionally substituted with R4 group, Or C3-8 cycloalkyl optionally substituted with C1-4 alkyl or cycloalkenyl, R2 is C1-5 alkyl optionally substituted with an R4 group, R3 is hydrogen or halogen, R4 is hydrogen, C1-6 alkyl, haloalkyl, alkylthio, alkoxy C3-6 cycloalkyl or polyalkoxyalkyl, C3-6 cycloalkyl, cycloalkyl Kenyl, cycloalkyalkyl or cycloalkenylalkyl; C2-8a rukenyl or alkynyl; carbamyl, halogen, amino, nitro, cyano , hydroxy, C containing 1 to 4 O, S(O)m and/or N heteroatoms 4-10 heterocycle, C6-12 aryl, aralkyl or alkaryl, -CX YR6, -CXR9, -CH2OCOR10, -YR11, -NR12R13 or any two R4 groups, such two R4 groups have ▲number of heteroatoms. There are formulas, chemical formulas, tables, etc.▼If they are bonded through a bond, there are fewer heterocycles. saturated and/or unsaturated carbon, ▲, provided that it has at least 6 ring members; Contains mathematical formulas, chemical formulas, tables, etc. ▼ and/or bonds via heteroatom bonds to form a heterocycle having up to 9 ring members, and this ring is The above R4 group may be substituted with any of the above, or if it is not self-inclusive, It may be substituted with R2-13 group or R4 which is substituted with any of: X is O, S(O)m, NR14 or CR15R16; Y is O, S(O) m or NR17; R6 to R17 are one of the R4 groups; m is 0 to 2; and n is 0 to 5] A method of treating undesirable plants in crops, consisting of spraying compounds of 20. A herbicidally effective amount of formula II: II▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R1, R2 and R3 are defined in Formula I. As defined: R5 is independently one of said R3 groups, and R6 and R7 are independently one of said R4 groups. or such two groups R6 and R7 are heteroatoms ▲ mathematical formula, chemical formula, There are tables, etc. ▼If the heterocycle is connected through a bond, there are at least 6 heterocycles. up to 9 ring members including O, N and/or S atoms; are joined to form heterocycles having up to four carbon atoms, each ring containing up to four carbon atoms. alkyl, haloalkyl, alkoxy, alkenyl or alkynyl with atoms may be substituted with a group] A method of treating undesirable plants in crops, consisting of spraying compounds of 21. A herbicidally effective amount of formula III: III▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R1 and R2 are C1-5 alkyl R3 and R5 are hydrogen, bromo, chloro or fluoro; R6 is R5 group or nitro: R7 is an R4 group, or R6 and R7 are bonded via -OCH2(C=O)-N-(R4)- bond and condensed. chemical compounds which are undesirable for crops, and which consist of spraying compounds that form 6-membered rings together. How to treat ugly plants. 22. In the compound, R1 and R2 are methyl; R3 is hydrogen, bromo or chloro; R5 is chloro or fluoro; R6 is chloro, fluoro or nitro; R7 is defined in formula I; or R6 and R7 are -OCH2(C=O)-N-( brovinyl)-bond to form a fused 6-membered ring. How to put it on. 23. The compound is 4-chloro-3-(2-fluoro-4-chloro-5-(2-brovinyloxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole; 4-bromo-3-(2-fluoro-4-chloro-5-(2-brovinyloxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole; 4-chloro-3-(2-fluoro-4-chloro-5-(2-methoxyethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole; 4-bromo-3-(2-fluoro-4-chloro-5-(2-methoxyethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-1H-virazole; 6-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-virazole -3-yl)-7-fluoro-4-(2-brovinyl)-2H-1,4-benzo Oxazin-3-(4H)-one; (5-(4-bromo-1-methyl-5-(methylsulfonyl)-1H-virazo (3-yl)-2-chloro-4-fluorophenoxy)acetic acid, 1-methylethyl (5-(4-chloro-1-methyl-5-(methylsulfonyl)-1 H-virazol-3-yl)-2-chloro-4-fluorophenoxy)acetic acid, 1 -Methyl ethyl ester: 2-(5-(4-bromo-1-methyl-5-(methyl sulfonyl)-1H-virazol-3-yl)-2-chloro-4-fluorophe (oxy)propanoic acid, ethyl ester: and 2-(5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-bira sol-3-yl)-2-chloro-4-fluorophenoxy)propanoic acid, ethyl 20. The method of claim 19, wherein the method is selected from the group consisting of esters. 24. A herbicidally effective amount of 4-chloro-3-[ 2-Fluoro-4-chloro-5-(2-brovinyloxy)phenyl]-1-mer consisting of spraying thyl-5-(methylsulfonyl)-1H-virazole, How to treat undesirable plants in your crops. 25. Reaction formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼B Oxidation▲There are mathematical formulas, chemical formulas, tables, etc. ▼I [In the formula, R1 is hydrogen, optionally C1-5 alkyl substituted with R4 group] or C3-8 cycloalkyl optionally substituted with C1-4 alkyl. kyl or cycloalkenyl, R2 is C1-5 alkyl optionally substituted with an R4 group, R3 is hydrogen or halogen, R4 is hydrogen, C1-6 alkyl, haloalkyl, alkylthio, alkoxy C3-8 cycloalkyl or polyalkoxyalkyl, C3-8 cycloalkyl, cycloalkyl Kenyl, cycloalkyalkyl or cycloalkenylalkyl; C2-8a rukenyl or alkynyl; carbamyl, halogen, amino, nitro, cyano , hydroxy, C containing 1 to 4 O, S(O)m and/or N heteroatoms 4-10 heterocycle, C6-12 aryl, aralkyl or alkaryl, -CX YR8, -CXR9, -CH2OCOR10, -YR11, -NR12R13 or any two R4 groups, such two R4 groups have ▲number of heteroatoms. There are formulas, chemical formulas, tables, etc.▼If they are bonded through a bond, there are fewer heterocycles. saturated and/or unsaturated carbon, ▲, provided that it has at least 6 ring members; Contains mathematical formulas, chemical formulas, tables, etc. ▼ and/or bonds via heteroatom bonds to form a heterocycle having up to 9 ring members, and this ring is It may be substituted with any of the above R4 groups, or if it is not self-inclusive, the R4 group may be substituted with It may be substituted with R3-13 group or R4 substituted with either: X is O, S(O)m, NR14 or CR15R16: Y is O, S(O)m or or NR17; R6 to R17 are one of the above R4 groups; m is 0 to 2; the law of nature, n is 0 to 5] A compound of formula I is prepared by reacting a compound of formula B with an oxidizing agent according to Method. 26. The compound of formula I has the formula II: II▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R1, R2 and R3 are defined in Formula I. As defined: R5 is independently one of said R3 groups, and R6 and R7 are independently one of said R4 groups. or such two groups R6 and R7 are heteroatoms ▲ mathematical formula, chemical formula, There are tables, etc. ▼If the heterocycle is connected through a bond, there are at least 6 heterocycles. up to 9 ring members including O, N and/or S atoms; are joined to form heterocycles having up to four carbon atoms, each ring containing up to four carbon atoms. alkyl, haloalkyl, alkoxy, alkenyl or alkynyl with atoms may be substituted with a group] 26. The method according to claim 25, wherein the compound is a compound of 27. The compound of formula I above has formula III: III▲ mathematical formula, chemical formula, table, etc. ▼ [In the formula, R1 and R2 are C1-5 alkyl; R3 and R5 are hydrogen, bromine mo, chloro or fluoro; R6 is an R5 group or nitro; R7 is an R4 group, or R6 and R7 are bonded via -OCH2(C=O)-N-(R4)- bond and condensed. 26. The method according to claim 25, wherein the compound is a 6-membered ring. 28. R1 and R2 are methyl, R3 is hydrogen, bromo or chloro; R5 is chloro or fluoro; R6 is chloro, fluoro or nitro; R7 is defined in formula I; 28. The method according to claim 27, which is a YR11 group. 29. consisting of reacting a compound of formula I in which R3 is hydrogen with a halogenating agent , R3 is halogen. 30. Compounds of formula I, prepared by a halogenation process, wherein R3 is halo 30. The method according to claim 29, wherein the compound is a compound defined by formula III, which is gen. 31. R1 and R2 are methyl, R5 is chloro or fluoro, R6 31. The method of claim 30, wherein is chloro, fluoro or nitro. 32. The corresponding compound of formula I, where R11 is hydrogen, with an acylating agent or an alkylating agent One of the R4 groups is -YR11, and R11 is A method of making a compound of formula I that is not hydrogen. 33. In the compound of formula I before acylation or alkylation, R7 is -YH. 33. The method of claim 32, wherein the compound is defined by formula III.