JPH02268165A - Pyrazole amide derivative and fungicide for agricultural and horticultural use - Google Patents

Abstract

NEW MATERIAL:The pyrazole amide derivative of formula I (R<1> is 3-10C substituted or unsubstituted aliphatic cyclic substituent which may contain 0 or S atom in the ring; R<2> is H, lower alkyl, halogen or halogenated alkyl: B is furyl, thienyl, pyrazolyl. phenyl. 2-8C alkenyl, 2-8C alkynyl, etc.; D is cyano or thiocarbamoyl) and its optically active isomer. EXAMPLE:N-[3-furyl(thiocarbamoyl)methyl]-l-cyclobutyl-3-methyl-1Hpyraz ole-5- carboxamide. USE:A fungicide for agricultural and horticultural use. It exhibits preventive and remedying effect against blights caused by phytipathogens belonging to Phycomycetes, e.g. downy mildew and late blight. PREPARATION:The compound of formula I can be produced e.g. by reacting a compound of formula II with a compound of formula III (A is group of formula IV) and reacting the resultant compound of formula V with hydrogen sulfide.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel pyrazolamide derivative, a method for producing the same, and an agricultural and horticultural fungicide containing the derivative as an active ingredient. [Prior art and problems] One of the important problems in agricultural production, especially in the cultivation of fruit trees and sulfur vegetables, is the problem of diseases caused by plant pathogenic bacteria (e.g., downy mildew, late blight, etc.). be. Diseases caused by these bacteria are difficult to control due to the physiological and ecological special characteristics of the bacteria, and the development of excellent control agents is desired. Many crops are affected by downy mildew and late blight, and the damage caused is extremely large. Currently, for diseases caused by plant disease genus countries that belong to the same circle, cabtan (common name), capterhor (-ship name),
Dithiocarbamate fungicides such as zineb (generic name) and chlorothalonil (generic name) are widely used. However, these fungicides mainly have a preventive effect and can hardly be expected to have a curative effect, so they have the major drawback that if they are used only when a disease outbreak is observed, sufficient effects cannot be expected. There is. Antibacterial agents containing acylalanine compounds that have recently been developed and put into practical use, such as metalaxyl (-ship name), have both preventive and curative effects, but resistant bacteria have already emerged. However, its control effect has been considerably reduced. Conventionally, regarding amide-substituted acetonitrile derivatives that are chemically structurally similar to the compounds of the present invention, Japanese Patent Application Laid-Open No. 57-16797
No. 8, JP-A-58-69866, JP-A-60-255759, etc., but this prior art is not sufficient as a practical agricultural and horticultural fungicide. In particular, there is phytotoxicity of useful crops due to drugs, and this is a major unresolved problem. [Problems to be Solved by the Invention] The present invention has a preventive effect and a curative effect against diseases caused by plant pathogenic bacteria (for example, downy mildew, late blight, etc.) belonging to the above-mentioned category, and also has a useful effect. The aim is to provide a fungicide that does not harm crops. [Means and effects for solving the problems] As a result of intensive research on the above-mentioned pyrazolamide derivatives in order to solve the above-mentioned problems, the following compound group of general formula (1) has been found to be effective against various plant diseases and downy mildew. We have completed the present invention by discovering that it has both preventive and curative effects against diseases, etc., and exhibits the characteristics of little phytotoxicity to crops. The compound of the present invention is a new compound that has not been described in any literature. (Hereinafter, blank space) That is, the present invention is based on the general formula [1]: [In the formula, R- represents an unsubstituted or substituted aliphatic cyclic substituent having 3 to 10 carbon atoms, and an oxygen atom is present in the ring. Alternatively, it may contain a sulfur atom. R2 represents a hydrogen atom, a lower alkyl group, a halogen atom or a halogenated alkyl group. B is a furyl group, a thienyl group, a pyrazolyl group, a phenyl group, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, and 2 to 10 carbon atoms;
8 thioalkoxy group or a cycloalkyl group having 3 to 8 carbon atoms. D represents a cyano group or a thiocarbamoyl group. The present invention provides a pyrazolamide derivative represented by the following formula, an optically active substance thereof, and an agricultural and horticultural fungicide containing one or more of these as an active ingredient. More desirable compounds are general formula [1] in which R1 is an unsubstituted or substituted cycloalkyl group having 3 to 10 carbon atoms, an unsubstituted or substituted cycloalkenyl group having 5 to 10 carbon atoms, or a cycloalkenyl group having 3 to 10 carbon atoms. -1O unsubstituted or substituted halogenated cycloalkyl group, having 2 to 1 carbon atoms
0 unsubstituted or substituted oxiranyl group, unsubstituted or substituted oxiranyl group having 3 to 10 carbon atoms,
An unsubstituted or substituted tetrahydrofuryl group having 4 to 10 carbon atoms, an unsubstituted or substituted tetrahydrothienyl group having 4 to 10 carbon atoms, an unsubstituted or substituted pyranyl group having 5 to 10 carbon atoms, or an unsubstituted or substituted pyranyl group having 5 to 10 carbon atoms. These are pyrazoleamide derivatives and optically active substances thereof, which are 5 to 10 unsubstituted or substituted thiopyranyl groups, B is a furyl group or a thienyl group, and D is a cyano group or a thiocarbamoyl group. Next, the production method of the present invention is shown in a reaction scheme and explained below. Synthesis of tolyl derivatives in neem) [Production method
] [4] [Production method 2] [8] [5] [7] [Production method 3] A-CONH! +

[9] 0HCCOOR3 [10] C0N)IcHcOOR' H [11] [Production method 4] -COX + H,NCHICN -> A-CONHCH,CN [6] [14] [14] + halogenation Agent-> ^-CONHCHCN [15] Synthesis of thioamide derivatives [2] [6] [16] [7] [16] (However, R1 and R2 represent the same meanings as above. R'I represents an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom. Method a-1 is a method in which the starting material aldehyde [3] is synthesized with aqueous ammonia and/or ammonium chloride and an alkali cyanide such as sodium cyanide or potassium cyanide in ethyl ether. The reaction is carried out in a binary solvent system of water and ethers such as tetrahydrofuran, aromatic hydrocarbons such as benzene and toluene, and water.The reaction temperature is usually preferably around 0 to 100°C. a-2 In the method, the starting material aldehyde [3] and a trialkylsilyl nitrile represented by trimethylsilyl nitrile are reacted, if necessary, in the presence of a catalytic amount of a Lewis acid such as zinc iodide to obtain an intermediate [4]. The aminoacetonitrile derivative [5] is obtained by reacting with ammonia dissolved in a solvent such as methanol or ethanol.The obtained aminoacetonitrile derivative [5] is reacted with hydrogen chloride in an ether solvent such as diethyl ether. It can also be purified and isolated by forming a salt with a hydrogen halide such as ] is reacted in the presence of an acid acceptor. Examples of acid acceptors include organic bases such as triethylamine, dimethylaniline, and pyridine, ammonia, potassium carbonate, sodium carbonate, ammonium hydrogen carbonate, and water. Examples include inorganic bases typified by sodium oxide, ammonium carbonate, etc. Also, this reaction is preferably carried out in the presence of a solvent, such as ethers typified by diethyl ether, tetrahydrofuran, diisopropyl ether, etc., acetic acid, etc. methyl,
Esters such as ethyl acetate, halogenated hydrocarbons such as methylene chloride, chloroform, l,2-dichloroethane, and acetonitrile can be used. Since the reaction is an exothermic reaction, the reaction temperature is preferably carried out under cooling, and is preferably from around -30°C to around 50°C.
Practically speaking, a temperature around -20 to 30°C is desirable. In this way, nitrile derivative [7] is obtained. This is a method of dehydrating and condensing the starting material carboxylic acid derivative [8] and the aminoacetonitrile derivative [5] obtained in [Production method 1] in the presence of a dehydrating agent to obtain an amide-substituted acetonitrile derivative. . As a dehydrating agent, dicyclohexylcarbodiimide (D
Particularly preferred are carbodiimides such as CC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and inorganic dehydrating agents such as silicon tetrachloride. JJjllcmouth'λ1 absorption amide derivative

The reaction between [9] and glyoxylic acid ester is carried out in an ester solvent such as ethyl acetate or isobutyl acetate or in an acetone solvent at a reaction time of 50 to 100 ml.
It is preferable to carry out heating at around °C. Subsequently, the hydroxy compound [11] is reacted with an excess amount of thionyl chloride at below room temperature to around room temperature to obtain the chlor compound. After the reaction, excess thionyl chloride is distilled off, and then the ester compound [13] is obtained by reacting with a compound represented by General 2BZ (12) in a solvent, optionally in the presence of a base. Examples of solvents used here include ester solvents such as ethyl acetate and isobutyl acetate, as well as ether and acetonitrile.As for bases, organic bases such as triethylamine and pyridine, and inorganic bases such as sodium carbonate and ammonium carbonate are used. Then, this ester (13) is reacted with ammonia to form an amide.This reaction is carried out using a solvent such as an alcohol such as methanol or ethanol or an ether such as diethyl ether or tetrahydrofuran.
It is preferable to carry out the reaction at around 50°C to room temperature. The amide form is
Furthermore, a dehydrating agent such as trifluoroacetic anhydride in an organic amine such as pyridine is used, a dehydrating agent such as phosphorus oxychloride in an amide solvent such as N,N-dimethylformamide (Ko F) is used, or a dehydrating agent such as phosphorus oxychloride in an amide solvent such as N,N-dimethylformamide (Ko F) is used. The nitrile derivative [7] can be obtained by reacting with a dehydrating agent such as PPA), polyphosphoric acid alkyl ester (PPE), or polyphosphoric acid alkylsilyl ester (PPSE). +j4cλ [Skin] The reaction between aminoacetonitrile and acid chloride [6] can easily yield the acylaminoacetonitrile derivative [14] under commonly used condensation reaction conditions. In this reaction, the presence of a base is generally preferred, and inorganic bases such as sodium carbonate and ammonium carbonate, and organic bases such as triethylamine and pyridine are preferred. Acylaminoacetonitrile derivative [14] can be converted to halide (15) using a halogenating agent. The halogenating agents used here include chlorine, bromine,
N-chlorosuccinimide, N-bromosuccimide and the like are preferred. Since this halogenated intermediate has poor thermal stability, it is directly carried to the next step without being isolated and purified. That is, after halogenation, this halogenated intermediate [15] is converted to BZ(
12) by reacting with nitrile derivatives [7]
is obtained. The reaction conditions are the same as those in (Production method 3). (Hereinafter, blank) Nitomameda (a) From the aminoacetonitrile derivative [5] obtained in [Production method 1] and hydrogen sulfide, the desired thioamide is produced. Derivatives are easily obtained. The base used is preferably an organic base such as triethylamine, pyridine, dimethylaniline, etc., and the amount added is 0.01 to 1 mol per 1 mol of raw material [5]. The reaction proceeds satisfactorily within this range.The reaction may proceed even without the use of a solvent, but
Generally, it is preferable to use them, and the types thereof are not particularly limited, but examples include hydrocarbons such as benzene and toluene, ethers such as tetrahydrofuran and dioxane, and aromatic amines such as pyridine and dimethylaniline. The following are preferred. Further, two or more of these may be used as a mixed solvent. As hydrogen sulfide, one of the raw materials, commercially available gaseous hydrogen sulfide can be used as is, and the amount of feed is determined by the raw material [
5], the reaction temperature at which the reaction can be carried out in an equimolar amount or a slight excess amount is -20 to 100.
℃ is desirable, and 0 to 50°C is particularly preferable. When the reaction is carried out at room temperature, the reaction is usually completed in 5 to 6 hours. Intermediate [2] thus obtained can be easily isolated and purified by recrystallization. (b) The reaction between the intermediate [2] obtained in (a) and the acid halide [6] can be carried out under the same conditions as in [Production method 1] (°C). The reaction to obtain the desired thioamide derivative [16] from the nitrile derivative [7] and hydrogen sulfide is [Production method 5].
It can be carried out under the same conditions as in (a). The pyrazolamide derivative thus obtained can be recrystallized,
A pure product can be obtained by conventional purification methods such as column chromatography. Next, the method for producing the compound of the present invention will be explained using specific examples, but the present invention is not limited to these. Example 1 (Synthesis of compound No. 117) α-(3-furyl)aminoacetothioamide (3.1 g
) (0.02 mol) in tetrahydrofuran (THF)
50mj! followed by triethylamine (2,
4g) (0,024 mol) is added. While stirring this mixture under water cooling, 1-cyclobutyl-3-methyl-IH-pyrazole-5-carboxylic acid chloride (4.0 g) (0.02 mol) was added to 6.2 ml of tetrahydrofuran (THF). The dissolved solution was added dropwise. Thereafter, stirring was continued for 5 hours at room temperature to complete the reaction. Subsequently, the reaction solution was concentrated, and the residue was washed with water. The obtained crystals were further recrystallized from toluene-ethyl acetate to obtain crystals (4.5 g) (liquid chromatography purity 99%). This crystal can be used for mass spectrometry and 'H-NMR purposes.
-(3-Furyl(thiocarbamoyl)methyl-1-cyclobutyl-3-methyl-IH-pyrazole-5-carboxamide. (Hereafter, blank) Example 2 (Synthesis of compound No.) α-( 3-Furyl) aminoacetonitrile (2.5g)
and triethylamine (2.1 g) to a7tonitrile 50
l-Cyclobutyl-3-methyl-LH-pyrazole-5-carboxylic acid chloride (2
,0g) was added thereto, and after stirring for 1 hour, the mixture was stirred in the chamber for 5 hours. After filtering off the resulting solid, the solvent was distilled off, and the resulting oil was purified by column chromatography to obtain N-(cyano-3-furanylmethyl)-1-cyclobutyl-3-
Methyl-IH-pyrazole-5-carboxamide (3,
42g) of crystals were obtained. Table 1 below shows compounds of the present invention that can be synthesized in the same manner. (Hereinafter, blank space) In the compound represented by, the compound R. 5NHI 5NHt C5NII□ 5Not C5NH. 5NHx 5NHx C3NII. SNL 5NHt 5NHz C5NH. 5NHI 5NHz SNL 5NHz 5NHt 5NHx 5NIII 5NHx 5NHt 5NHI 5NHt 5NHt C5NH□ C3N)I. 5NHz 5NHz Compound R. C3NH. C3NII. C3NH. 5NHz Compound CH,F CS N H□ 5NHI 5NIII 5NHt 5NHt SNHg SNHt Compound Nα CH2F C1l□F C1,F IIzF CH2F C1,F Hip CH2F CH,F C1l□F C H2F HJ ut CHl Hz JIs CH3 CH3 CHツCl. Hff CH. C.I. C.I. C.I. CH3 L CHl CH3 CH3 CH3 CHl Hs C1(. CI3 5NHz 5NHz C3NII□ 5NHz 5NIII 5NIII 5Nlh C3NI(. 5NHz 5NH2 5NHz 5NH2 5NH z 5NHz C5NH. 5NH2 5NHt 5NI12 5NHz 5Nl12 5NH2 5NHz CS N 11□ 5NHz 5NHz C5N) Iz 5NHz 5NHz 5NH2 5Nl12 C3NH. 5NIII 5NHz 5NHz CSNH! Compound Nα R. 5NHt 5NH2 5NH2 5NH2 5NHI 5NHz C3NII□ 5Noz CS N II□ C3NI(z 5NH2 5N lh C5NII. C3NII□ C3N)l I C5NH. C5NII□ 5NHI 5NHz 5NHz 5NHt 5NHz 5NHz C5NH. C3NII. 5NHz C3NII□ C3NH. 5NHz C5NH. 5NHt 5NHt CS N II□ 5NHz 5NHI 5NH2 C3NII□ 5NHI 5NHt C5NH. 5NHI 5NHz 5NIh 5NHz C5NI (t 5NFIz 5NHz C3NT. SNHg C5NII. 5NHI 5NHz 5NHz 5NHz 5NHz 5NHI 5NHz C5NII□ 5NHI 5NHI 5NH2 5NHz C3NI(I C5NH! 5snz 5NH1 5NHz 5NHt C5NH! Compound R2 z (hereinafter, blank) CIl□F ozp C■. C11゜HI C11゜L N N Q in Table 1 above 1~Q46 and B1~ B6 shows the following structural formula. FuJ layer Jl pu'1 1 ballfu Jdanfu'1 S eye A J1 澹'2 1'5 1 Sat'yut'-1 1 Sat LL Dani Next, the physical property values of the compounds of the present invention are shown in Table 2. (Hereinafter, blank space) Table Compound No. Solvent CDCj!j + DMSOd-6 CDCf. rJC13 CDCf3 'H-NMR6ppIll (Standard material TMS) 1.4 (
) J, 78 (+*, 611), 2.64 (s, 311
). 5.48 (quint, IH, J, 7.8Hz). 5.80 (d, IH, J=8.411z), 6.2
1-6.64 (m, 28). 7.12-7.37 (rm, II(), 7.3
7-7.61 (m, IH). 7.98 (d, IH, J-8, 4Hz), 9.18 (
brs, IH). 9.37 (brs, 18) 1.50-2.84 (11,68), 2.17 (s,
31). 5.43 (quint, LH, J-7, 8Hz). 6.12 (d, IH, J=8.4Hz), 6.2M+
, 35 (m, 2) 1). 6.35-6.50 (m, IH), 7.13 (d, I
H, J-8, 4Hz). ? , 20,7.35(-9IH) 1.46-2.98(m, 6M), 2.17(s, 3
8). 5.44 (quint, IH, J-7, 8Hz). 6.27 (d, IH, J-7, 8Hz), 6.29 (
s, lH). 6.74-7.01 (m, l1l), 7.05-7
．． 37 (m, 2H). 7.62 (d, IH, J-7,8Hz) 1.56-2.
92 (m, 6H), 2.25 (s, 311). 5.53 (qaint, 1) 1. J-7,8Hz). 6.02(d,lH,J-7,8Hz), 6.25(
s, 18). 6.32-6.48 (m, IH), 6.50
(d, 18. J-7, 8&). 7.35-7. ．． 48 (m, 110.7.54-7.6
6 (s, IK) Melting point (''C) 193~195 114~116 115~117 138~!39 Compound No. H-NMRδppII (I quasi-substance TMS) Melting point ('
C) CDCj! s 1.52-2.88 (-6H), 2.22 (s, 31
1). 5.49 (quint, IH, J-7, 811z). 6.13(d, 11(, J-8,411z), 6.2
4 (s, IH). 6.78 (d, LH, J=8.4Hz), 6.94~
7.15 (m, IH). 7.1% 7.52 (m, 211) 135-136 CDCj! 3 1.25=2.15 (a+, 8H), 2.17 (s,
311). 5, (B-5, 68 (m, IH), 6.23 (s, I
H). 6.30 (d, IH, J-8, 4Hz). 6.89 (d, IH, J=8.4Hz), 6.77~
7.03(m, II(). 7.03-7.346w, 21() 122-123 ocis 1.26-2.16(s+, 8), 2.21(s, 3
H). 5.13=5.76 (m, 1■), 6.16 (d,
IH, J = 8.4Hz). 6.26 (s, 111), 6.84 (d, LH, J=
8.4Hz). 6.96-7.17 (m, 111), 7.23=7
．． 52(m, 2H) 146-147 (hereinafter referred to as blank space) The present invention is further characterized in that it contains as an active ingredient a pyrazole amide derivative represented by the general formula (1) according to the present invention and an optically active substance thereof. The present invention provides a fungicide for agricultural and horticultural use. The agricultural and horticultural fungicide of the present invention is not only effective against downy mildew and late blight of various crops, but also effective against other diseases. The main diseases include cucumber downy mildew, grape downy mildew, lettuce downy mildew, Chinese cabbage downy mildew, hoppe downy blight, potato late blight, tomato late blight, cucumber gray late blight, green pepper late blight, tomatoes caused by Vicinium blight,
Examples include seedling damping-off of cucumbers and rice, and seedling damping-off of beets caused by Aphanomyces bacteria. Application methods for the agricultural and horticultural fungicide of the present invention include seed treatment, foliage spraying, soil application, and the like. Application 1! The application concentration varies depending on the target crop, target disease, degree of disease occurrence, application method, etc., but when spraying, the amount of active ingredient is 2.
~2000g is applicable, preferably 10-1000g. It can be applied at a spraying concentration of 1 to 11,000 pp.
5 to 500 pp- is desirable. In addition, since the agricultural and horticultural fungicide of the present invention has both preventive and curative effects, it can be applied both preventively and after the onset of disease, and there is a wide range of suitable times for its application. have. The agricultural and horticultural fungicides of the present invention may optionally contain other biologically active compounds, such as similar or complementary fungicides, or agricultural chemicals such as insecticides, herbicides, plant growth regulators, and fertilizers. Not only can it be used in combination with effective substances, soil conditioners, etc., but also mixed formulations with these are also possible. The agricultural and horticultural fungicide of the present invention can be carried out using a suitable carrier, such as a solid carrier such as clay, talc, bentonand, diatomaceous earth, or water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.). ), chlorinated hydrocarbons, ethers, ketones, esters M (
ethyl acetate, etc.). It can be applied by mixing with a liquid carrier such as acid amides (dimethylformamide, etc.), and if desired, an emulsifier, a dispersant, a suspending agent, a penetrating agent, a spreading agent, a stabilizer, etc. are added.
Emulsions, oils, hydrating agents, powders. It can be put to practical use in any desired dosage form such as granules and fluffy preparations. Next, the range of each component and the type of each component in formulation examples of these compositions will be shown, but the agricultural and horticultural fungicide of the present invention is not limited to these. In addition, in the following formulation examples, "parts" mean parts by weight. (1) Wettable powder Compound of the present invention: 5 to 75 parts Solid portion: 9 to 86 parts Surfactant: 5 to 10 parts Others
.... Calcium carbonate, kaolinite, ziecrite A, ziecrite PFP as the 1- to 5-hedral carrier. Examples include diatomaceous earth and talc. As the surfactant, Lunox 1oooc, Tsurupol 5039, Tsurupol 5050. Crane pole oo
So. Examples include Trupol 5029-0, calcium sulfonate, sodium dodecyl sulfonate, and the like. Other components include Carplex #80. (2) Emulsion Compound of the present invention: 5 to 50 parts Liquid carrier: 35 to 90 parts Surfactant
・・・・・・ 5 to 15 parts As a liquid carrier,
xylene, dimethylformamide, methylnaphthalene,
Examples include isophorone. Examples of the surfactant include Tsurupol 2680, Tsurupol 3005X, and Tsurupol 3346. (3) Flowable agent Compound of the present invention: 5 to 75 parts Liquid carrier: 14.5 to 68 parts Surfactant: 5 to 10 parts Others
... 5 to 10 parts Water is used as the liquid carrier. Examples of the surfactant include Lunox 100OC, Trupol 3353, Sorbohol PL, Nippol, Agrisol S-710, sodium ligninsulfonate, and the like. Other ingredients include ethylene glycol, propylene glycol, xanthan gum, and the like. (4) Powder Compound of the present invention: 0.03 to 3-hedral carrier: 94-98.97 parts Others: 1- to 3-hedral carrier: carbonic acid; Calcium, kaolinite, gicrite,
Examples include talc. Other ingredients include diisopropyl phosphate,
Examples include Carplex 1180. (5) Granules Compound of the present invention: 0.3 to 10 parts Solid part: 92 to 98.7 parts Others: 1 to 5 parts As a hedral carrier: , calcium carbonate, kaolinite, bentonite, talc, etc. Other ingredients include calcium lignin sulfonate, polyvinyl alcohol, and the like. Next, specific formulation examples of the agricultural and horticultural fungicide containing the thioamide derivative represented by the general formula (1) according to the present invention as an active ingredient will be shown.
It should be noted that in the following formulation examples, "1 part" means parts by weight. ! IJI Gojo Wettable powder Compound of the present invention 5 parts Sieglite PPP 85
Part (Mixture of kaolinite and sericite: Sieglite Industries ■Product name) Tsurupol 5039 5039
Part Carplex #80 ・・・・・・
Three or more parts (white carbon: Shionogi & Co., Ltd. trade name) or more are mixed and pulverized uniformly to make a wettable powder. When used, the above-mentioned hydrating agent is diluted 100 to 10,000 times and sprayed so that the amount of active ingredient is 10 to 1000 g per hectare. Type 1 Example D Wettable powder Compound of the present invention 25 parts Sieglite PPP 69
(Mixture of kaolinite and sericite: Sieglite Industries ■Product name) Tsurupol 5039 3
1 part (mixture of anionic surfactant and white carbon: Toho Chemical ■trade name) Carplex #80 ... 3 parts (white carbon: Shionogi & Co., Ltd. ■trade name) or more are uniformly mixed and pulverized. Use as a hydrating agent. When using, add the above hydrating agent to 500~
Dilute to 50.0 ( ) 0 times and spray so that the amount of active ingredient is 10 to 1000 g per hectare. Type 1 example - Wettable powder Compound of the present invention 75 parts Calcium carbonate (powder) 69 parts (Kaolinite and sericite Tsurupol 5050 10
Part (mixture of anionic surfactant and white carbon: Toho Chemical ■trade name) Carplex #80... 1 part (white carbon; Shionogi & Co., Ltd. ■trade name) or more are mixed and pulverized uniformly. Use as a hydrating agent. When using, add 1500% of the above hydrating agent.
~150,000 times Ni5ilR, the amount of active ingredient is
Spray at 10-1000g per hectare. ■Compound of the present invention Xylene N, N-dimethylformamide Tsurpol 2680 (Mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■Product name) The above are mixed uniformly to form an emulsion. . When using the above emulsion,
It is diluted 0 to 10,000 times and applied so that the amount of active ingredient is 10 to 1000 g per hectare. ■ Anal emulsion Compound of the present invention 5 parts 70 parts 20 parts 5 parts 50 parts Xylene ・Old ◆ ・ 25 parts N,
N-dimethylformamide... 10 parts Tsurpol 3346... River 15
(Mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■trade name) The above is mixed uniformly to form an emulsion. When used, the emulsion is diluted 1,000 to 100,000 times and spread so that the amount of active ingredient is 10 to 1,000 g per hectare. Flowable agent Compound of the present invention 5 parts Tsurupol 3353 ・・・・・・
5 parts (Nonionic surfactant: Toho Chemical ■Product name) Lunox 1oooc...
3 parts (Anionic surfactant: Toho Chemical ■Product name) 1% aqueous solution of xanthan gum 20 parts (
natural polymer) water...
・57 parts ethylene glycol ・・・・
... 100 parts The above components except for the active ingredient (the compound of the present invention) are uniformly dissolved, and then the compound of the present invention is added, stirred thoroughly, and then wet-pulverized in a sand mill to obtain a flowable agent. When using, add the above flowable agent to 100~
It is diluted 10,000 times and applied so that the amount of active ingredient is 10 to 1000 g per hectare. Flowable agent Compound of the present invention 75 parts Tsurupol 3353 ・・・・・・
5 parts (nonionic surfactant: Toho Chemical ■trade name) Lunox 100OC...0.5 parts (anionic surfactant: Toho Chemical ■trade name) 1% of xanthan gum
Aqueous solution: 10 parts (natural polymer) Water:
・4.5 parts・Propylene glycol...
... The above components except for 5 parts of the active ingredient (the compound of the present invention) are uniformly dissolved, and then the compound of the present invention is added, stirred well, and then wet-pulverized in a sand mill to obtain a flowable agent. When using, add 150% of the above flowable agent.
It is diluted 0 to 150,000 times and applied so that the amount of active ingredient is 10 to 1000 g per hectare. U...Powder Compound of the present invention 10 parts Clay 90 parts or more are mixed uniformly to obtain a powder. When used, the above-mentioned powder is sprayed as is at an amount of active ingredient of 10 to 1000 g per hectare. ... Granules Compound of the present invention ... 5 parts Bentonite ... 25 parts Tarri
・・・・・・ After uniformly mixing and pulverizing 70 parts or more,
Add a small amount of water, stir and mix, granulate using an extrusion granulator, and dry to form granules. When used, the above-mentioned granules are sprayed as is at an amount of active ingredient of 10 to 1000 g per hectare. Next, the effects of the compounds of the present invention in biological tests will be specifically described. On an armpit plate Cucumber and disease prevention effect test 1 to 2 cucumbers (variety: Sumo Hanshiro) grown in a 7C11 diameter pot
When the leaves reached the leaf stage, the test compound in emulsion form prepared according to Formulation Example 2 was diluted with water to adjust to 1100 pp, and 20 mff1 per pot was sprayed using a spray gun. The day after spraying, cucumbers and diseased bacteria (Pseudopero)
spore suspension (2
Spray x l O' individual m1, temperature 25℃, humidity 9
They were placed in a 5% or higher inoculation box overnight. Thereafter, the plants were placed in a greenhouse, and the proportion of lesions formed on the inoculated leaves 7 days after inoculation was measured, and the control value was calculated according to the following formula. The results of this test are shown in Table 3. (Hereafter, in the margins) Table (Treatment concentration: 20 ppm) Compound inhibition and prevention of chemical damage (hereinafter, in the margins) M Cucumbers and disease cure efficacy test Cucumbers (variety: Sumo Hanshiro) grown in pots with a diameter of 1 as ~When the two-leaf stage is reached, cucumbers and diseased fungi (P
seudoperonospora cuber+5i
A spore suspension (2 x 10' spores/m 1 ) of s) was sprayed and placed in an inoculation box at a temperature of 25° C. and a humidity of 95% or higher overnight for inoculation. The next day, the test compound in the form of an emulsion prepared according to Formulation Example 2 was diluted with water to give 100 ppp.
Adjust to m and use a spray gun to get 20mj per pot!
It was scattered. Thereafter, the plants were placed in a greenhouse, and the ratio of lesions formed 7 days after inoculation to the inoculated leaves was measured, and the control value was calculated according to the following formula. The results of this test are shown in Table 4. (Hereafter, in the margins) Table (Treatment concentration: ppm,) Compound Nα Prevention value of chemical damage (hereinafter, in the margins) Limbs ■1 Tomato late blight preventive effect test A tomato (variety: Fukuju) grown in a pot with a diameter of 8 cm has 3 leaves. When the period is reached, the wettable powder prepared according to Formulation Examples 1 to 3 above is diluted with water to a predetermined concentration of the active ingredient,
It was sprayed at 20 ml per pot using a spray gun. The day after spraying, tomato late blight fungus (Phytophthora
1nfestans) in a spore fA suspension (2x 10'
The control value was calculated according to the formula below. . The results of this test are shown in Table 5. Table (Treatment concentration: ppn+) Compound Nα Control value of phytotoxicity (hereinafter referred to as blank space) Tomato blight curative efficacy test Tomatoes (cultivar Nifukuju) grown in pots with a diameter of 81 reached the 3-leaf stage Phytophthora 1n
festans) spore suspension (2xlO' spores/ml)
Spray it into an inoculation box at a temperature of 20°C and a humidity of 95% or higher.
I kept it day and night. Thereafter, the wettable powders prepared according to Formulation Examples 1 to 3 are diluted with water to a predetermined concentration of the active ingredient,
It was sprayed at 20 mA per pot using a spray gun. After air-drying, the pot was placed in the inoculation box described above, and the proportion of the area of lesions formed after 5 days to the inoculated leaves was measured, and the control value was calculated according to the following formula. The test results are shown in Table 6.

Claims (4)

[Claims] (1) General formula [1]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] [In the formula, R^1 represents an unsubstituted or substituted aliphatic cyclic substituent having 3 to 10 carbon atoms. may contain an oxygen atom or a sulfur atom in its ring. R^2 represents a hydrogen atom, a lower alkyl group, a halogen atom, or a halogenated alkyl group. B is a furyl group, a thienyl group, a pyrazolyl group, a phenyl group, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, and 2 to 10 carbon atoms;
8 thioalkoxy group or a cycloalkyl group having 3 to 8 carbon atoms. ] A pyrazole amide derivative and its optically active substance. (2) In the general formula [1] according to claim (1), R^
1 is an unsubstituted or substituted cycloalkyl group having 3 to 10 carbon atoms, an unsubstituted or substituted cycloalkenyl group having 5 to 10 carbon atoms, or an unsubstituted or substituted cyclohalogenated cycloalkyl group having 3 to 10 carbon atoms. Alkyl group, carbon number 2
-10 unsubstituted or substituted oxiranyl group, C3-10 unsubstituted or substituted oxetanyl group, C4-10 unsubstituted or substituted tetrahydrofuryl group, C4-10 unsubstituted or substituted oxiranyl group, Substituted or substituted tetrahydrothienyl group, unsubstituted or substituted pyranyl group having 5 to 10 carbon atoms, or 5 to 1 carbon atoms
0 unsubstituted or substituted thiopyranyl group,
A pyrazolamide derivative and an optically active substance thereof, wherein B is a furyl group or a thienyl group, and D is a cyano group or a thiocarbamoyl group. (3) A fungicide for agriculture and horticulture containing one or more of the pyrazolamide derivative and its optically active substance according to claim (1) as an active ingredient. (4) A fungicide for agriculture and horticulture, which contains one or more of the pyrazoleamide derivative and its optically active substance according to claim (2) as an active ingredient.