JPS61260065A - Pyrazole derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 is alkyl, alkenyl, alkynyl or halogen; n is integer 0-3; R2 is H, alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, cyanoalkyl, alkylsulfonyl, phenylsulfonyl, etc.; X and Y are halogen). EXAMPLE:1-( 2-Fluoro-4-chloro-5-methylsulfonyloxyphenyl )-3,4,5-trimethylpyrazo le. USE:A herbicide capable of extending the applicability by using the above- mentioned compound with the known herbicides, insecticides or plant growth regulators, etc. PREPARATION:For example, a substituted phenylhydrazine compound expressed by formula II (R2 is a group other than H) is reacted and cyclized with a dicarbonyl compound expressed by formula III (R1 is group other than halogen), e.g. 3-methylpentane-2,4-dione, to afford the corresponding compound expressed by formula I.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel pyrazole derivative, and more specifically, a novel N-arylpyrazole derivative represented by the general formula (1) below, and a herbicide containing the derivative. It is related to drugs. It is useful in the chemical industry and agriculture, especially in the field of pesticide manufacturing. (Prior Art) It has been known that certain pyrazole derivatives have physiological activity as agricultural chemicals. For example, Tokko Sho+t
O-/Tata JT publication describes the linear formula (in the formula, - is a hydrogen atom, 9 is a phenyl group, R= is a hydrogen atom or a lower alkyl group, R3 is a hydrogen atom, a nitro group, i or a cyano group, R4
is a lower alkyl group. (represents an amino group or lower alkoxy group)
- It has been stated that phenylpyrazole derivatives have herbicidal activity. In addition, N-toro-substituted phenyl) pyrazole derivatives or N-(chloro-nitro-substituted phenylnhirazole derivatives) represented by Tokko Shozanko (wherein X is OL or HK) have bactericidal activity. However, a specific N-phenylpyrazole as seen in the present invention has a -logen atom at the 1st and 3rd positions of the phenyl nucleus and an oxy-derived group at the 3rd position as a substituent.
-Phenylpyrazole derivatives have not been known at all. (Problems to be Solved by the Invention) Conventionally known pyrazole derivatives, namely Tokko Sho go-
The specific pyrazole compounds described in ttyzr publication and 4t2-/8113 publication have extremely weak herbicide activity and are not practical. Therefore, the object of the present invention is to develop a new pyrazole derivative which is practical as a pyrazole herbicide and a field herbicide, compared to these conventional pyrazole derivatives. ′ (Means for solving the problem) In order to achieve the above object, the present inventors. We have synthesized many pyrazole derivatives and investigated their usefulness.

[After careful consideration.] As a result, it was discovered that the pyrazole derivatives represented by the general formula (1) below are new compounds that have not been described in literature, and that these compounds have high herbicidal activity that can be put to practical use. Therefore, the gist of the first invention is as follows. (t61). (In the formula, R1 represents a lower alkynyl group or a lower alkenyl group. It represents a lower alkynyl group or a halogen atom, and n
' represents an integer from 0 to 3, and R2 is a hydrogen atom, a lower □ alkyl group, a lower alkenyl group, a lower arginyl □ group, a lower alkyl group, a lower alkyl group, a lower alkyl group, a lower alkyl group, a lower alkyl group, and a lower alkyl group. Calzenyl lower alkyl group, lower alkoxycarzenyl lower alkyl group, lower alkylthiocarzenyl lower alkyl group, cyano lower alkyl group, lower alkyl sulfonyl group, phenylsulfonyl group, halogen substituted phenyl A pyrazole derivative represented by a sulfonyl group or a lower alkyl-substituted phenylsulfonyl group, where X and Y represent the same or different halogen atoms. The gist of the second invention resides in a herbicide characterized by containing the pyrazole derivative of the above general formula (I) as an active ingredient. In the general formula (I) representing the compound of the present invention, a lower alkyl group, a lower alkylthio lower alkyl group. Examples of "lower alkyl groups" in cyanogen lower alkyl groups include methyl, ethyl, propyl, isopropyl,
Butyl, isobutyl, secondary butyl. Examples include tertiary butyl, pentyl, hexyl, and isohexyl groups. In addition, as a lower alk 1″ group, ♂
Examples include nyl, allyl, /-propenyl, -1-methyl-co-propenyl, l-methyl-co-prohe, nyl, a-butenyl, J-i-tenyl, cohendenyl, co-, and 4cm hexagenyl groups. Examples of the lower alkyl group include ethynyl, coprovinyl, 1-methyl-coprovinyl, corbutynyl, and 1-methyl-cobutchel groups. Further, the halogen atom is at. 8r, F, I can be used. Therefore, each of the substituents of al, n, R2, X, and Y in general formula (1) can be any combination of the above-mentioned various groups. Next, typical specific examples of the compounds of the present invention in the general formula are shown in Section 7.
Shown in the table. (Action 2 of the Invention The compound of the present invention of the general formula (1) has superior f'L & herbicidal activity compared to known similar compounds. That is, the compound of the present invention has a superior f'L and herbicidal activity compared to known similar compounds. That is, the compound of the present invention has It has a wide range of effects on paddy field weeds such as
Weeds can be completely killed by applying f or less. Also, depending on the particular example of the compound of the present invention, 4. Complete pressure weeding can be achieved by applying a dosage of J j f or less. SaraK is also effective against various upland weeds such as crabgrass, whiteweed, dogweed, and knotweed. 70 are (If)! Weeds can be completely killed by applying the following treatments. Further, depending on the compound, it is possible to completely kill weeds by applying a dosage of 1, 1, or less. Moreover, it does not cause any chemical damage to useful crops such as paddy rice, soybeans, beets, radish, wheat, and corn. Furthermore, it is not toxic to humans, animals, or fish. Therefore, it can be used safely. Production of the compound of general formula (1) according to the first invention is as follows. The following μ methods are explained below:
B], method [0], or method CD). Method (A) Compound of the present invention (1-47 is a substitution of the following formula (II-A) when R1 is a group other than norogen and - is a group other than a hydrogen atom in the general formula (I)) It can be produced by reacting a phenylhydrazine compound with a sicarunyl compound of the following formula [phase], such as 3-methylpenta-2,4L-dione or μ-ethyl with buta-3,!-dione, and cyclizing it. (l-1 This condensation and cyclization reaction can usually be carried out in various organic solvents. Hydrocarbons, ethers, alcohols, water, etc. are used as the solvent. The reaction proceeds even at room temperature, but depending on the solvent used, It is preferable to heat up to the boiling point.After the reaction, the desired compound can be obtained by distilling off the solvent from the reaction solution.React water with an organic solvent such as benzene, toluene, tetrahydrofuran, or chloroform. The compound of the present invention (Li
Kill by getting t. Example/Example of production by method ['A]. and 10f/C are also shown.゛Method [8] 2. The compound (1-8) of the present invention in which R2 is a hydrogen atom in general formula (1) according to the present invention can be produced from K by hydrolyzing R2. This hydrolysis reaction can be carried out by simply heating compound CI-k) with water, but it is usually carried out in the presence of an equivalent or more amount of base. As a base. Sodium hydroxide, potassium hydroxide, sodium carbonate,
The reaction in which sodium hydrogen carbonate or the like can be used may be carried out at room temperature or under heating. Alcohol in t'fic aqueous solution,
The reaction rate can be increased by adding ethers such as dioxane to allow the reaction to proceed in a homogeneous solution. After the reaction is complete, the reaction solution is made acidic with hydrochloric acid or sulfuric acid, and the desired product is extracted with an organic solvent such as benzene, toluene, tetrahydrochloride, or chloroform, and the solvent is distilled off to obtain the compound (1- 8) can be obtained. Examples 3 to 4 I--show examples of backing by method [8]. Method (0) Ni Compound of the present invention (1-0) when R2 is a group other than a hydrogen atom in the general formula (1) Fi, a corresponding compound of the present invention in which R2 is a hydrogen atom (f-87 is a group other than a hydrogen atom) (IV
Halide compound 1 of J can be produced by reacting, for example, alkyl chloride, alkenyl chloride, alkyl sulfonyl chloride, etc. This substitution reaction is carried out in an organic solvent in the presence of an acid binding agent. Examples of the organic solvent include hydrocarbons such as benzene toluene, and ethyl ether. Ethers such as tetrahydrofuran, esters such as methyl acetate and ethyl acetate, ketones such as acetone and methyl isobutyl ketone, nitriles such as acetonitrile and zolobionitrile, alides such as dimethylformamide and dimethylacetamide, and dimethyl Sulfo-Naka-shito etc. can be used. As the acid binder, inorganic bases such as sodium hydroxide, sodium hydroxide, potassium carbonate, etc., or organic bases such as triethylamine and pyridine can be used.6 The reaction proceeds even at room temperature, but only up to the boiling point of the solvent. You can also warm it up. After the reaction is complete, salts of the acid binder and the like are separated by F, and the desired product can be obtained by distilling off the first solvent, and an organic solvent such as aqueous tobenzene, toluene, tetrahydro7rane, or chloroform is added. The compound of the present invention (X-O) can also be obtained by fractionating the target product and distilling off the solvent. An example of production using this method [0]! - shown below. Method CD] In the general formula (1), the compound CI-D) of the present invention containing a halogen atom as B corresponds to a compound CI-D) that does not contain a halogen atom as B, or that is different from the halogen atom to be introduced or Compound Cl-1 of the present invention, which contains only a small number of atoms as R4! It can be produced by reacting J) with a halogenating agent having a halogen pentad (Z, ) to be introduced. However, R1, R2, X, and Y are the same as above, and L is Ol.
or a halogen atom introduced into ZFi,
m is 3.2 or l, and (trm) is an integer from 1 to J. This halogenation reaction can usually be carried out in an organic solvent, and examples of the solvent that can be used include genated hydrocarbons, amides, and water. As the halogenating agent, elemental halogens such as chlorine and bromine, sul7lylhalite, and halogenated phosphorus can be used. The reaction temperature is appropriately selected within the range from room temperature to the boiling point of the solvent. After the reaction, the target product can often be obtained by distilling off the solvent, but if necessary, add a large amount of water and an organic solvent to disperse the target product, and then distilling off the solvent to obtain the compound CI-DJ. . Examples of production by method (CD) are shown in Examples 1/-/JK. The substituted phenylhydra-dine compound of formula (U-A) used in method (A) above is a new compound. , R
When 2 is a sulfonyl group or a substituted sulfonyl group, ffEm7t' can be prepared by the following reaction scheme starting from the substituted phenol of formula (2). (V) (Vln
(■n(■)
(II-A) However, in the above reaction formula, R is a substituted or unsubstituted alkyl group or aryl group,
Intermediate products (VI), (■), (■) are also new compounds. In method [E] according to the above reaction formula, f! IIt
The formula R8O20 is also tiBr
When the sulfonyl halide is reacted with K, and the phenolic hydroxyl group is sulfonylated, a sulfonyloxy compound (Vl) is obtained. This sulfonylation reaction is preferably carried out using pyridine f which also serves as an acid binding agent: a solvent. Usually, when a sulfonyl halide is added dropwise to a mixture of dihalophenol and pyridine under ice water and stirred at room temperature after one drop, the zero reaction that takes place from K takes a long time. By heating, one reaction time can be shortened. After the reaction is complete, the precipitated pyridine salt fi-F is separated and pyridine is removed to obtain a disulfonyloxy compound (V
T) is obtained, but water, benzene, and toluene. An organic solvent such as tetrahydrofuran or chloroform is added, the target compound (Vl) is separated, washed with hydrochloric acid water to remove pyridine, and the solvent II is distilled off to obtain the sulfonyloxy compound (VI). The obtained sulfonyloxy compound (Vl) is nitrated with nitric acid to obtain a dinitro compound (■). The nitration reaction is carried out under mixed acid conditions in a conventional manner. Add an equivalent amount of concentrated nitric acid to a mixture of sulfuric acid and a sulfonyloxy compound.
! A mixture of thiosulfuric acid was added dropwise under ice-water cooling. This is carried out by stirring at room temperature after the dropwise addition. After the reaction is complete, add one reaction solution to ice, dilute it, and add an organic solvent such as benzene, toluene, tetrahydrofuran, or chloroform.
A dinitro compound is obtained by extracting the target product and distilling off the solvent. The obtained nitro compound (■) is reduced with t-iron to obtain a diamino compound (■). Reduction reactions are normal. Water is used as a solvent, and a small amount of water is used to accelerate the reaction.
□It is preferable to add hydrochloric acid and heat the reaction to 30 to 100°C to shorten the reaction time. After the reaction, benzene,
A disulfonyloxyamino compound is obtained by extracting with an organic solvent such as toluene, tetrahydromifuran, or chloroform, and distilling off the solvent. Next, the t/c, amine compound (■) is diazotized and then reduced with stannous chloride and hydrochloric acid to obtain a cyhydrazino compound (III-A). The above diazotization is carried out by adding the amino compound (2) to an aqueous hydrochloric acid solution and dropping an equivalent amount of an aqueous sodium nitrite solution at around -20°C.For the subsequent reduction, the diazonium salt solution obtained is After the completion of the zero reaction, which is carried out by adding 7th tin to an aqueous solution of hydrochloric acid under ice-water cooling and stirring at room temperature, it is made weakly alkaline with an aqueous solution of sodium chloride, and then a solution of benzene, toluene, tetrahedral t=r7 run, chloroform, etc. By extracting with a solvent and distilling off the solvent, the desired hydrazino compound (II-A) is obtained. An example of the preparation of a hydrazino compound (...-) by the above method Cm) is shown in Reference Example 1 below. Further, using the compound (lI-A') of the present invention produced by this method [E) in which f'L7'cR2 is a sulfonyl group dust as a raw material, the method [8] and/or method [ 0], the compound of the present invention having other desired substituents as R1 and R2 can be produced.In addition, the first herbicide of the present invention can be prepared by adding the compound of general formula (I) to a conventional formulation. It can be prepared in any suitable form such as milk powder, emulsion, aqueous solution, liquid, flowable (sol), powder, Driftless (DL) powder (1 grain), fine granule (1 tablet), etc.The carrier used here is Any solid or liquid carrier commonly used in agricultural and horticultural chemicals can be used, and is not limited to any particular carrier.For example, solid carriers include mineral powders (kaolin, bentonite, clay, montmorillonite, Talc, diatomaceous earth, g.) 9-miculite 1 gypsum, calcium carbonate, apatite, white karne, slaked lime, silica sand, ammonium sulfate, urea, etc.], vegetable powder (soybean flour, wheat flour, wood flour. Tobacco flour, Starch, crystalline cellulose carbon, polymer/molecular compounds (petroleum resin, polyvinyl chloride, ketone resin, dammar gum, etc.), alumina, silicates. Sugar polymers, highly dispersed silicic acid, waxes, etc. Examples of liquid carriers include water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, l5o-furobyl alcohol, phthanol, ethylene glycol, benzyl alcohol, etc.), and aromatic hydrocarbons. (toluene, benzene, xylene, ethylbenzene, methylnaphthalene, etc.), halogenated hydrocarbons (roform, carbon tetrachloride, dichloromethane,
(dichloroethylene, monocoolbenzene, trichlorofluoromethane, dichlorodifluoromethane, etc.). Ethers WR (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone, etc.), esters (
ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc.]. Amides (dimethylformamide, dimethylacetamiton, etc.), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfonate II (dimethyl sulfoxide, etc.), alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, etc.) Ethyl ether, aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), industrial gasoline (petroleum ether, norpent naphtha, etc.), petroleum distillates (nosorafuin, kerosene, light oil, etc.) 11 When preparing formulations such as emulsions, aquariums, flowable agents, etc.
Emulsification 1 Various surfactants (or emulsifiers) are used for purposes such as dispersion, solubilization, wetting, foaming, lubrication, and spreading. , phosphoryoxyethylene alkyl ester. ?Lyoxyethylene sorbitan alkyl ester. Sorbitan alkyl ester, etc.), anionic products (alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate% polyoxyethylene alkyl 7ate, aryl sulfonate, etc.), cationic Examples include ionic type [alkylamines (laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, etc.), polyoxyethylene alkylamines], amphoteric type [caloo/acid (betaine IJ1), sulfur ester salt, etc.] Ranruga,
Of course, the present invention is not limited to these examples. In addition to these, various adjuvants such as polyvinyl alcohol, calxoxymethylcellulose, gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate, and tragacantom can be used. In the present invention, when producing the various formulations described above, the formulations contain the compound of the present invention at a concentration of 0.00/IIs to
The formulation can be formulated so that the weight ratio is the same hereafter, λ, preferably in the range of o, oi - Ots.
For example, in the case of 2 regular powders, DL powders, and fine granules (to), Fi
o, b i tip -z % h Granule O field ea O
, 0/1 to 1 ozb, /9 for wettable powders, emulsions, and liquids
It can be contained in a range of 6 to 71%. For example, in the case of a single granule, the preparation prepared in this way is directly added to the soil surface, in the soil, or in the water in an amount of 0.3 to 50 ml of active ingredient.
A hydrating agent that only needs to be sprayed within a range of about 100 ml. In the case of emulsions and sol formulations, dilute one ounce of water with an appropriate solvent to give an active ingredient amount of 0. It is sufficient to spray within a range of about JP-700P. Furthermore, when the compound of the present invention is used as a herbicide, it can be mixed with known herbicides, insecticides, plant regulators, etc. to expand its applicability. In some cases, synergistic effects can also be expected. Especially for such mixed herbicides. Examples include the following. Triazine herbicide t-chloro-N-ethyl-Nl-isozorovir-1,3
゜! -triazinediylruco, f-diamine t-chloro-N, N'-diethyl-! ,J,! -1-Riazine-2. l-diyldiamine N-ethyl-N'-isozorobyl-6-methylthio-/
. J, j-triazine-2,4cm diyldiamine N,
N'-diisopropyl-t-methylthio-l, 3゜7
-) riazine-2,4A-diyldiamine N, N'
-diethyl-t-methylthio-/,J,'-triazine-2.4cmdiyldiamine N-(/,codimethylpropylJ-Nl-ethyl-methylthio-/,J,j-)riazine-coj4A
-diyldiamine J- (≠-chloro to monoethylamino/ , J sj
-triazine-choylamine-comethylzolopionitrile J-cyclohexyl-4-dimethylamino-1-methyl-/, J,! r-triazine-J, 4! (/H, JH)
-dionehiro-amino-6-tert-butyl-3-methylthio-1,co,4C-)riazine-J'(uH)-one-
Amino-3-methyl-6-phenyl-/, co, μ-triazin-j(μH)-one (1), and the like. Amide herbicide 2-chloro 2', dimethylacetanilide in t'-diethyl-N-metho, Coke 4'-ethyl-N-
Methylethyl-N-(2-propoxyethylnoacetanilide) λ-chloro-N- Impropylacetanilide 3/,
l-dichlorozo is pionanilide N-/-su7thyl7
Talamitsukuamidoethyl N-Hensyl-N-(3,1A-J chlorpher)-DL-alaninate N, N-dimethyldiphenylacetamide S, Z-dichloro-N-(/,/-dimethylpropynyl)benzamide 11-() Refluoromethanesulfonate ξdofacet
λ', daI-xylidide N-(α, a-J methylpenzylnocozolomo-3゜3-dimethylbutamide N-methylurea (penzthiazole-co-yloyl)acetanilide, etc. Carbamate remover B- a-Chlorobenzyl diethyl (thiocarpamate no 8-ethyl azenozone/-calzethioate B-f lopyl diprovir (thiocarpamate no S-ethyl dipropyl (thiocarpamay)) S-ethyl diisobutyl (thiocarbamate) 8-P Award Vylbutyl (ethylnotiocarpamate 8-ethyl N-cyclohexyl-N-ethyl) Methyl carpanilate sulfanilyl carpamate methyl 3-(3-methylcarpaniloyloxyf carpanilate 8-isozolovir hexahydro-/1-1-azepine-7-car-thioate 8-J-rialoprovir 3.t-dimethylhexahydro-1H-azepine-7-car-thioate B-a,a
-,) methylbenzyl piperidine-/-car-thioate, etc. Urea herbicide s-<a-p lorophenyl>-tri--) methylurea J-(J,e-dichlorophenyl)-/-methoxy-
l-methylurea J-(J,4A--)chlorotetraphenylfu1. /-dimethylurea/, /-dimethyl-J-(α, (f, (f-) refluoro-meth-tolyl) urea j-(#-bromo-3-chloroc17.enyl)-7-medium- Methylurea 3-(3-chloro-l-methoxyphenyl no/,/-
Dimethylurea
-(#-(Hiro-/rolophenoxy]phenyl)-/ .l-dimethylurea I-(comethylcyclohenoxyl)-J-phenylurea 7-penzothiazol-2-yl-3-methylurea/
-Henzothiazole-Koylhu/, J-dimethylurea ゛/-(j-tert-butyl-1,J,e-thiadiazole-Koylhu/,!-dimethylurea 3-(♂
-tert-butyl-i, s,
Methoxy-4-methyl-/, J,! -triazine--irunureamethyl no [[(French, t-dimethoxy-pyrimidine-
Noyl]aminocarzenyl]aminesulfonylmethyl]benzoate/-(a,a-dimethylbenzylnoJ-(para-tolyl)urea, etc.Toluidine herbicide a,a,a-trifluoro-2,t-dini )I:1-N
IN-dipropyl-para-toluidine N-(/-ethylpropylnorco, t-dinitro-3゜e-xylidine N, N-diethyl-co, t-dinitro-trifluoromethyl-meta-phenylenediamine N-(λ-chloro Ethylin-a,a,a-trifluoro-p-2,1-dini)0-N-zolopyl-paratoluidine-methylsulfonyl-, A-J nido μmN, N-dibu-shobiruaniline, etc. Diazine herbicides !-tert-butyl-3-(co,≠-cyclo-isoproxyphenyl)-/,J,u-oxadiazole-,2(JH)-on-no(J,4A--)chlorophenylf≠-methyl −
l,co,daroxadiazolidine-3,! -Zion 3-
Isopropyl-(/H)-2,/, J-penzothiacazin-4t(31()-one) -Paratoluene sulfonate/!
--) Methyl-F-(co, p-dichloropenzoylno!-phenacyloxy-pyrazole, etc.) Diphenyl ether herbicide!-(Co-chloro-a, a, a-trifluoro-para-
Tolyloxyno-2-nitrobenzoic agitoko
Chloro-no (3-ethoxy-μ-nitrophenoxyno μm (trifluoromethyl)) (Nzen J, 4C-,
, ff chlorophenyl 3-methoxy-hiro'-nitrophenyl ether-z*5e4-)'J/lorphenylene'-nidotetraphenyl ether methyl j-(J, 4L-dichlorophenoxyno 2-
2-tube benzoate, etc. Phenoxy herbicide no methyl - chlorophenol cyacetic acid or its salt, ester or amide derivative 2, IA - dichlorophenol cyacetic acid or its salt, ester or amide derivative ±-No (Hiro-Kurozono--Methyl) phenoxy]propionic acid or its salts, esters or amide derivatives (4L-chloro-O-tributyloxybutyric acid or its salts, esters or amide derivatives 8-ethyl μm
Chloro-O-tolyloxythioacetate 2-(29μm dichloro-3-methylphenoxy)propionanilide a-(λ-tolyloxythioacetate (R8
)-N,N-diethyl-2-(/-naphthyloxine zolopionamide (R8J-2-[ku(j,4t-dichlorophenokidinephenoxy)profonic acid or its ester derivative (R8)-no[μm (!-Trifluorotetramethyl-nobiridyloxy) phenoΦshicopropionic acid or its ester derivative (R8) -2-[μm(3-chloro-3-trifluoromethyl-2-pyridyloxy)phenoxy] pion Acid or its ester derivative (R8)-No[μm(3I!-di-pyridyloxy]phenoxy]propionic acid or its salt. -Chloroquinoxalinyloxy) phenoxyfupropionic acid or its ester derivatives, etc. DL-Homoalanine-μmyl(methyl)phosphinic acid or its derivatives no-amino-gu [(hydroxyno(methylnophosphionyl)butylene) Lylalanylalanine or its salt derivative O-ethyl 0-6-nitro-meta-tolyl Secondary-butyl phosphoramidothioate S-rulyrollo N-isozolobyl carpanyl dimethyl 01O-dimethyl phosphorodithioate S-Nomethylpiperidinocarzenylmethyl 0゜0-dipropyl phosphorodithioate 5-2-benzenesulfonamidoethyl 0
．． O-di-isopropyl phosphorodithioate, etc. 3, 4-7 chloropenzonitrile, A-dichloro(thiobenzamide) 3,! -dibromo μm hydroxybenzonitrile μm Hydrogysy J
, J-G iodopenzonitrile, etc. ! - Zolomo 3-Secondary Butyl-4-Methyluracil 3-Cyclohexyroot,! , t,7-titrahydrosic gastric pentabilimidine, μ(JH)-dione! -Tasha leaf chiroo! -Chloro-t-methyluracil
Such. Benzoic acid herbicide J-aminoco, j-dichlorobenzoic acid or its salt derivative J, t--)chloro-ortho-anisic acid 4L<fl
(Salt derivatives of J, J, J, t-tetrachloroterephthalic acid or its salts, esters and amide derivatives, etc.) Phenolic herbicides such as secondary phenol, t-dinitocphenol or its Salts and carboxylic acid ester derivatives≠, t
-dinitro-orthocresol or a salt thereof and carzenate ester derivatives, etc. φ-class ammonium herbicides/, 7'-dimethyl-μ4c/-bipyridinium dichloride 7, 7'-ethyleneco, 2'-bipyridylium dibromide, etc. Pyridazine herbicide! -Aminogu Chloronophenylpyridazine-3
(H)-one l-chloro-! -MethylaminoJ-((1,(1,(
f-trifluorometholylnoviridazin-3(coH)-one, and the like. Pyridine herbicide≠-amino J, J”, 4-trichloropyridine-2-
Carzenic acid or its salt derivative J, j, but-trichloronobilidyloxyacetic acid or its salt or ester derivative I-Methyl-3-phenyl-7-((1, (!, +!-
) Refluorometholyl λ-darviridone 1, etc. 3-(chloronoamino/, 4A-naphthoquinonemethyl J-(/-(aryloxyiminobutyl)-μ-human or its salt derivative ω-2-(l-ethoxyiminobutyl-!-[no(
Ethylthione furovir-3-hydroxycyclohexacol-eno. l・Korg Methyl-3,! -diphenylpyrazolium methyl sulfate, etc. ``ulIL' -(No fluoro-μm 4-ru!-
methylsulfonyloxyphenyl)-3, μ. ! -Production of trimethylpyrazole (compound Nl j J) 1 # - 0 Ru! -Methylsulfonyloxyphenylhydrazine 2! ,! F,! -Methylpentaco. Reference-dione (0H3000H (OH, JOOOH3)/
Hehiro? , 100 yd of ethanol and 100 yd of water was refluxed for 1 hour. After cooling, toluene was added and the toluene layer was separated. After washing with water, the solvent was distilled off under reduced pressure. Then, it became a white crystal with a melting point of 2J-/2°C. Example K/-(J-fluoro-pi-chloro-y-phenylsulfoyloxyphenyl)-3゜#,j-)Production of limethylpyrazole (compound part 1j) 11 Fluoro-chloro-7-phenylsulfonyl A mixture of oxyphenylhydrazine J/, 7t, J-methylpent-2, dardion//, J f and water/jOdl was stirred at 70°C for /aj'. After cooling, add toluene, separate on the toluene layer, and wash with water. When the solvent was distilled off under reduced pressure, the title compound was obtained as pale brown crystals as J7. j f got f'. When recrystallized with carbon tetrachloride, white crystals are formed, and the refractive index is n F /, j
4'? − was shown. Practical example 3 /-(No fluoro-chloro-!-diphenyl in hydro)-J+"*t") Preparation of limethylpyrazole (compound NILλ7) l-(No fluoro-chloro-!-methylsulfonyl-Φdiphenyl ) −
J −e a * z −) +3 methyl pituzol J
J, j f, 2N-Water WRf Hysodium 1OO-
and ethanol! Mix O-. The mixture was stirred at μ0°C for 30 minutes. After cooling, the reaction solution was made acidic with an aqueous hydrochloric acid solution and extracted with toluene. After washing the toluene layer with water, the solvent was distilled off under reduced pressure to obtain the title compound as pale yellow crystals. Recrystallization with hexane/ethyl acetate mixed solvent gives white crystals, melting point/sr
, it o°C. -! Solid≦Llnni粁 /=(ko,pi-dichloro-ohydroxyphenyl)-3,! --) Production of methyl-chloropyrazole (compound wnyr)/-(, Z, 4
C--,? / Lolu! -methylsulfonyloxyphenyl)-3,! -Dimethyl-μm chlorpyrazole! 7
．． A mixture of Of and CoN-sodium hydroxide was heated at 30°C with S
The mixture was stirred for 0 minutes. After cooling. The reaction solution was acidified with an aqueous t-salt solution and extracted with toluene. After washing the toluene layer with water, the solvent was distilled off under reduced pressure to obtain the title compound as pale yellow crystals. Recrystallization from a hexane/ethyl acetate mixed solvent gave white crystals] with a melting point of 17/74A'C. Example j /-(λ-fluoro-l-chloro-!-isopropyloxyphenyl) -j s 4' @Yoichi Preparation of trimethylpyrazole (compound NaJ4A)/-(no-fluoro-≠-chloro-!-hydroxyphenyl)-3, μe j−)'Limethylpyrazolco! ,
! ? , isopropyl iodide 71.7 f, anhydrous potassium carbonate l≠, J t and dimethyl sulfoxytoko O0-
The mixture was stirred at 10°C for 1 hour. After cooling, water and toluene were added to the first reaction solution, and the toluene layer was separated. After washing with water, the solvent was distilled off under reduced pressure to obtain the title compound as a pale yellow oil. When purified by silica gel column chromatography, it becomes a colorless oil.
9, ni'/, 10-041-shown. Example 4/-(No fluoro-chloro-!-al-1-noroxyphenyl-J,u,!-Production of trimethylpyrazole (compound *ai)/-(J-fluoro-chloro-j-hydroxyphenyl)" J e 4'
# j −) Limethylpyrazoleco! J f , allyl bromide/J, J f , anhydrous potassium carbonate t a, z
t > and acetonitrile l! The mixture of 0- was stirred at reflux for 3 hours. After cooling, inorganic salt t-F in the reaction solution is separated,
P solution t - When concentrated, the title compound was obtained as light brown crystals.
t, 7F was obtained. Recrystallization from cyclohexane gave white crystals with a melting point of 27-22°C. Example 7 /-(no fluoro-chloro-!-ethoxycarzenylmethyloxyphenyl)-3,!-dimethyl-μm-p-ruvirazole (preparation of dimethyl chloride turn/-(no 2 fluoro-chloro-!-ethoxycarzenylmethyloxyphenyl) Phenyl)-J,J--dimethyl-Hiro-chlorvirazole 7.3? was dissolved in tetrahydro7ran 200-, and sodium amide U and Ot were added. After the generation of ammonia gas had finished, monochloroacetic acid Ethyl ester/J, JP was added dropwise. After the addition, the mixture was refluxed and stirred for 3 hours. After cooling, toluene and water were added to the reaction mixture to separate the organic layer, which was washed with water and dried over anhydrous sodium sulfate. Reduced pressure. When the solvent and medium were distilled off, the title compound was obtained as pale brown crystals. Recrystallization from cyclohexane gave white crystals with a melting point of 10 to 10 IA°C.Example r/ -(ko, dichlororu!-inzoropodiphenyl) -J,u,!-trimethylpyrazole (
Preparation of compound NIL37)/-(J, $-diku4!-hydro diphenyl)-
3,4c,j-trimethylpyrazole J 7. A mixture of /f, isopropyl bromide, Jf, sodium hydroxide, cof and dimethylformamide/10- was stirred at 70°C for 2 hours. After cooling, water and toluene were added, and the toluene layer was separated and washed with water. Toluene was distilled off under reduced pressure to obtain the title compound as a pale yellow oil. Purification by silica gel chromatography gave white crystals with a melting point of 74-J-1'ct-. Example: Preparation of /-(J,4I-dichloro-!-zolonoldyloxyfer)-S,Z--)methyl-da-chlorpyrazole (compound N144j)/-(J,4A-dichloro-!- and dolo middle diphenyl)
-J,z-J methyl-darklorpyrasolkota,kot
Oyohifuronogludyl bromide l, 0ttsh, metal sodium J, j f and methanol 200gd
The mixture was added to a well-adjusted sodium methane solution and stirred under reflux for 3 hours. After cooling, add water and toluene, separate the toluene layer, and wash thoroughly with water. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain the title compound, JO0/f, as light brown crystals. Recrystallization from a cyclohexane/acetone mixed solvent gave white crystals, with a melting point of /j 47~/jt°C. Example 10/-Preparation of (no-fluoro-chloro-!-zoronoryloxyphenyl)-S,a,Z-triethylpyrazole (compound N17J) 2-fluoro-≠-chloro-! -Flopardyloxyphenylhydrazine 1. Yot, 4! -Ethyl hebutar J
,! -React dione/t, af in the same manner as in Example 1,
Upon treatment, the title compound, JO6/f, was obtained as a pale yellow oil. Purification by silica gel chromatography gave white crystals with a melting point of ~47°C. Example///-(Nofluor-goochloro-!-methylsulfonyloxyphenyl)-J,z-Dimethyl-Hiro-Chlorpyrazole (fhi-product mya) Preparation l-(Nofluoro-goochloro-3-methyl) Dissolve sulfonyloxyphenyl no J e j-dimethylpyrazole J /, 5' f in chloroform co□0-,
After introducing 7,000 chlorine gas/l for 10 minutes under water cooling,
Perform chlorination by stirring for a minute. The solvent was distilled off under reduced pressure to obtain the title compounds J j and J f as pale yellow oils. When purified by silica gel column chromatography, it became a white oil with nAs/, j da of 31. Example/J/-(No fluoro-ruchlor-3-diphenyl in dichloromethoxychloride) Preparation of !t-dil-glucol-3-diphenyl in dichloromethane (compound part 10) )-3et--) Methyl pyrazole t, 2t was dissolved in chloroform-200d, and sulfur 7lyl/J, J''f was added dropwise in io minutes under water cooling, and the mixture was stirred for 30 minutes to perform chlorination. When the solvent was distilled off under reduced pressure, the title compound was obtained as pale yellow crystals. Recrystallization from n-hexane/ethyl acetate mixed solvent gave white crystals with a melting point of 10 to 0.7°C. Reference Example 1 0) Preparation of C, -R-fluorophenyl methyl sulfonate 2-R-ruder-fluorophenol/4C,7f and methylsulfonyl chloride//, Ift: Mixed. Pyridine 301 under water cooling. After dropping 0 drops, leave at room temperature for 30 minutes.
Methylsulfonylation was carried out by stirring for several minutes. Thereafter, pyridine is distilled off under reduced pressure. Toluene and water were added to the residue, washed first with diluted hydrochloric acid and then with water, and the toluene layer was dried over anhydrous sodium sulfate. When toluene was distilled off under reduced pressure, the title f metal compound was obtained as a pale yellow oil -
2o,r was obtained. When purified by silica gel chromatography, it becomes a colorless oil, n23=/,! //7t
-Show L[. ←) No Chlor-4L-Fluororu! - Manufacture of ditrophenylmethylsulfonate Coke Crew μm Fluorophenylmethylsulfonate coco, t f K f ! Sulfuric acid 3! Add - to this! Polysulfuric acid7. ! - and 4/nitric acid/0. A mixture of Jf was added dropwise to ice water to carry out a nitration reaction. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and then the reaction mixture was added with ice and extracted with toluene. The toluene layer was washed with a /N aqueous sodium chloride solution and then with water, and then dried over anhydrous sodium sulfate. When toluene was distilled off under reduced pressure, the title compound appeared as pale yellow crystals. , I got it. It showed a melting point ia'-tz, zC. f3 co-chlor-4t-fluor-! -Manufacture of anξnophenylmethylsulfonateCochlororu≠-Fluororu! -Nitro7-Dylmethylsulfone) J 7. Of and iron J J,! f to water l
When the reaction solution reached 10°C, the Jj-hydrochloric acid 3
．． Added 2f. After cooling, add sodium chloride to reduce the p of the reaction solution.
After making it u'ly, toluene and tetrahydrofuran were added for extraction. After washing the organic layer with water. Dried with anhydrous sulfuric acid (IJ) and distilled off under reduced pressure. The title compound was obtained as a pale yellow oil. Purification by silica gel column chromatography revealed white crystals with a melting point of 72-0°C. 2) Preparation of Cochrochlore-Fluor-3-Hydrazinophenylmethylsulfonate Cochrochlore-a-Fluor-! - Akino 7 engineering dimethyl sulfonate λhiro, Of, J! A mixture of % hydrochloric acid t3t and Mizuhiro tdl was stirred at 60°C for 30 minutes, and then added sodium nitrite and water! ! A diazotization reaction was carried out by dropping a solution dissolved in - at -2θ°C. This reaction solution was mixed with Jj% hydrochloric acid JJsd and water 100Il11 in advance.
1! and stannous hydrate 111] and added to the solution which had been cooled to -10°C. After stirring for 30 minutes under cooling, the reaction solution was brought to room temperature and adjusted to pH with aqueous sodium hydroxide solution.
Toluene and tetrahydrofuran were added for extraction. After washing with water, drying with 17 um of anhydrous sodium sulfate, and distilling off the solvent under reduced pressure, primary yellow crystals were obtained. I got it f'. Cyclohexane recrystallizes as pale yellow crystals), melting point 7! ~77℃
showed that. A method for formulating the compound of the present invention represented by the general formula (1) as a herbicide will be explained with reference to Example 19-here. The combined moving parts are shown in the wI1 table above. The second invention is not limited to these examples, and can be mixed with other various additives in any proportion, and may be mixed with other herbicides such as those mentioned above in any proportion. It can also be formulated. In the Examples, all parts refer to parts by weight. Example/P (granules) Compound f part of compound magnetodynamic 3 da, lauryl sulfate)/f
fi, 1 part calcium ligninsulfonate. After adding iz parts of water to 3o parts of bentonite and 47 parts of clay and kneading them in an S kneader, they are granulated in a granulator and dried in a fluidized fluid dryer to obtain granules containing 1 part of the active ingredient. Example 0 (Irrigation agent) Compound Ij part of compound part @3, white carzen/! N
, I)/3 parts of calcium ninsulfonate. polyoxyethylene nonylphenyl ether 21B,
'Keiso±! and clay to parts were uniformly mixed with a grinding mixer to obtain a hydrate containing 1 jqbt of the active ingredient.
□ Obtain the agent. Example 1 (Emulsion) Mixing ○ parts of compound m4At, 20 parts of Tulpol 700H emulsifier (product of Toho Chemical Industry Co., Ltd.), and 0 parts of xylene to obtain an emulsion containing the active ingredient CotlI. Example Coco (Powder) Compound OJ part of compound mrr, anhydrous silica fine powder O0j part, calcium stearate O0ta part, clay JO part, and talc 4Ar,! vi5t - Uniformly mixed and pulverized with 0.0% active ingredient. A powder containing J-% is obtained. (Effects of the Invention) Test Example 1 is shown in order to illustrate the herbicidal activity of the inventive ornament of general formula (1). Test Example 1 Herbicidal effect on paddy field weeds and drug damage test on transplanted paddy rice. A 17zoo Aarwagener pot was filled with rice paddy soil (alluvial loam), and 30 seeds each of Japanese barnyard grass, bulrush, Japanese azalea, Japanese azalea, and Japanese cypress were uniformly sown on the surface layer. After 18 days of sowing, the soil was flooded and the water depth was maintained at 21 degrees. 3 days after sowing. One μ-leaf stage seedling of paddy rice was planted, and three Todoroki seedlings were transplanted. One day after transplanting paddy rice, dilute the emulsion prepared according to Example 1 with water, and apply it by dropping 10 ares of Pottodo 9 treatment chemical solution tows (calculated as the amount of active ingredient applied). The test was conducted in a series of 7 plots, and 30 days after the chemical treatment, the herbicidal effect and phytochemical damage of paddy rice were investigated based on the evaluation indicators shown below.The results are shown in Table 2. Evaluation value of herbicidal effect Weeding rate (4)!
/QOq4! to～to
Less than ots J60-JO# Ko 440-40 z/
20 ~ Buddha OIOλOz! Dead μ Large chemical damage J z Medium λ l Small l I Slight OI No Ro Ro Ro Threshold Example Herbicidal effect on paddy field weeds and phytotoxicity test on transplanted paddy rice (low concentration treatment). ζ Using the same test method as Test Example 1, a low concentration treatment was conducted to examine the herbicidal effect of Tomoi on paddy field weeds and the chemical damage to transplanted paddy rice. The results are shown in Table 3. Test Example 3 Test for herbicidal effect on field-grown weeds and chemical damage to crops The herbicidal effect on weeds was tested as follows. That is, field soil (alluvial loam) was packed in a clay pot of 1700 m area, and soil of 1 surface layer/cWI and crabgrass,
Seeds of weeds such as Shiroza, Japanese knotweed, and Japanese knotweed.
Mix the O grains evenly and press lightly on the surface layer. Two days after sowing, the emulsion prepared according to Example 4C was diluted with water,
The treatment was carried out by spraying 1001 of the treatment chemical solution per 10 ares (equivalent to 100 f per 10 ares in terms of the amount of active ingredient applied) on the soil surface. The test was conducted in a series of 1 area, and the herbicidal effect was tested 30 days after the chemical treatment. The investigation was conducted based on the same evaluation index as in Example 1. The phytotoxicity test on crops was conducted as follows:
/ / Filled with 0.000 are unglazed pot) K field soil (alluvial loam), seeds of each crop (radish grains, heat) / t) grains, 10 radish grains, 410 comb grains, and corn grains! Seeds (grains) were sown in nine different pots, and the surface layer of one was lightly pressed. One day after sowing, the emulsion prepared according to Example 1 was diluted with water to give a concentration of 10%.
A treatment chemical solution (active ingredient amount equivalent to 100f per area) was sprayed onto the soil surface. The test was conducted in a 1-section continuous system, and 30 days after the chemical treatment, the chemical damage to each crop was investigated based on the same evaluation index □ as in Test Example 1. The results are shown in Table μ. Test Example 4 Test for herbicidal effects on field-grown weeds and phytotoxicity on crops (low 11 degree treatment). The herbicidal effects on field-grown weeds and phytotoxicity on transplanted paddy rice were investigated when low-concentration treatment was performed using the same test method as in Test Example 4. Results. are shown in Table 3. Procedural amendment (voluntary) August 15, 1986.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1 represents a lower alkyl group, a lower alkynyl group of a lower alkenyl group, or a halogen atom, and n is from 0 to Indicates an integer up to 3, R_2 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy lower alkyl group, a lower alkylthio lower alkyl group, a lower alkylcarbonyl lower alkyl group, a lower alkoxycarbonyl lower alkyl group, lower alkylthiocarbonyl lower alkyl group, cyano lower alkyl group, lower alkylsulfonyl group, phenylsulfonyl group, halogen-substituted phenylsulfonyl group, or lower alkyl-substituted phenylsulfonyl group, where X and Y represent the same or different halogen atoms) A pyrazole derivative represented by 2. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1 is a lower alkyl group, a lower alkenyl group,
Represents a lower alkynyl group or a halogen atom, n represents an integer from 0 to 3, and R_2 is a hydrogen atom, lower alkyl group, lower alkenyl group, lower alkynyl group, lower alkoxy lower alkyl group, lower alkylthio lower alkyl group, lower Indicates an alkylcarbonyl lower alkyl group, a lower alkoxycarbonyl lower alkyl group, a lower alkylthiocarbonyl lower alkyl group, a cyano lower alkyl group, a lower alkylsulfonyl group or a phenylsulfonyl group, a halogen-substituted phenylsulfonyl group, a lower alkyl-substituted phenylsulfonyl group, and Y represents a halogen atom) as an active ingredient.