JPH02152977A - Substituted pyrazolecarboxylic acid derivative, its production and agricultural and horticultural fungicide containing the derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R1 is CH3 or CF3; R2 is halogen; R3 and R4 are CH3 or C2H5; R5 is C2H5, n-propyl, n-butyl or H). EXAMPLE:N-(1,3-dimethyl-1-n-propyl-2-oxa-4-indanyl)-5-chloro-1,8- dimethylpyrazole-4-carboxylic acid amide. USE:An active component of agricultural and horticultural fungicide. It exhibits excellent effect against various plant blights caused by various phytopathogens, especially by microorganisms belonging to basidiomycetes. It can be used as a fungicide in paddy field, plowed land, orchard, pasture land, lawn, etc. PREPARATION:The compound of formula I can be produced by reacting a substituted pyrazolecarboxylic acid of formula II or its reactive derivative with a substituted aminoxaindane derivative of formula III in a solvent (e.g. tetrahydrofuran) in the presence of a reaction assistant such as triethylamine.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a substituted pyrazole carboxylic acid derivative, a method for producing the same, and an agricultural and horticultural fungicide containing the same as an active ingredient.

<Prior art> The fact that bactericidal activity is observed in pyrazolecarboxylic acid anilide derivatives consisting of
P-4184987) Publication, JP-A-60-84949
It is stated in the publication number etc.

<Problems to be Solved by the Invention> However, the compounds exemplified in these documents are insufficient in terms of efficacy, etc., and cannot be said to be necessarily satisfactory, and it is desired to develop drugs with fewer such drawbacks. ing.

Means for Solving the Problems In view of the above circumstances, the present inventors conducted various studies to develop a compound with excellent bactericidal activity, and as a result, the substituted pyrazole carbon represented by the following general formula (1) It has been discovered that acid derivatives have excellent bactericidal activity with few of the above-mentioned drawbacks, and the present invention has been achieved.

That is, the present invention relates to the general formula [wherein R1 represents a methyl group or a trifluoromethyl group, R8 represents a halogen atom, R, and R4
are the same or different and each represents a methyl group or an ethyl group, and R5 represents an ethyl group, n-propyl group, n-butyl group or a hydrogen atom. The present invention provides a substituted pyrazole carboxylic acid derivative represented by (hereinafter referred to as the compound of the present invention), a method for producing the same, and an agricultural and horticultural fungicide containing the same as an active ingredient.

Plant diseases for which the compound of the present invention has excellent efficacy include:
For example, rice sheath blight (Rhizoctoniaso)
lani), pseudosheath blight (Rhizoctonia o
ryzae, R.

5olani ] I [type B], wheat rust (Puc
ciniastriiformis, P. grami
nis, P. recondita, P.

horde i), snow rot (Typhula 1n)
carnata, T. 1shi-kariensis
), naked smut (Ustilago tritici,
U.

nuda), damping-off disease of various crops (Rhizoctoni
a 5olani) - Corticium r.
Rhizoctonia 5olani), Rhizoctonia 5olani, Gymnosporangiurn hara
eanum),.

Apple fishmonger disease (Venturia 1naequa)
Rhizocton ria), leaf rot diseases of grasses, lawns, etc.
ia 5olani), Corticium
rolfsii), leaf rust (Uromycestri
folii), snow rot (Typhula 1ncarn)
ata, T.

1shikariensis) and the like.

Next, the method for producing the compound of the present invention will be explained in detail.

The compound of the present invention has, for example, the general formula [wherein R1 and R8 represent the same meanings as above]. ] Pyrazolecarboxylic acid or its reactive derivative represented by the general formula [wherein R,, R4 and R have the same meanings as above. ] It can be produced by reacting with the substituted aminooxindane derivative shown below.

In the above reaction, a solvent is not necessarily required, but examples of solvents that can be used include hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as chlorobenzene, methylene chloride, chloroform, and carbon tetrachloride. , diisopropyl ether, tetrahydrofuran, dioxane, and other ketones; acetone, methyl ethyl ketone, and other ketones; ethyl acetate, and other esters; acetonitrile and other nitrites; dimethyl sulfoxide, dimethyl formamide, water, etc., with preference given to tetrahydrofuran. It will be done.

The amount of the reagent used in the above reaction is 0.4 of the substituted pyrazole carboxylic acid represented by the general formula (4) or its reactive derivative per 1 equivalent of the substituted aminooxindane 8 conductor represented by the general formula (4). ~1.5 equivalents, preferably
It is in the range of 0.5 to 1.1 equivalents.

The above reaction temperature can be set arbitrarily, but it is generally preferred to range from OC to the reflux temperature of the reaction solution.

The substituted pyrazole carboxylic acid represented by the general formula (6) or its reactive derivative to be used includes the corresponding carboxylic acid, acid anhydride, acid chloride, acid bromide, carboxylic acid ester, etc. The reaction can be carried out in the presence of a suitable reaction aid depending on the substituted pyrazole carboxylic acid represented by the general formula (4) or its reactive derivative. For example, when a carboxylic acid is used, 1-(8-dimethylaminoprobyl)-8-ethylcarboxylic acid tomethiodite, dicyclohexylcarbodiimide, etc. can be used, and when a carboxylic acid ester is used, Sodium hydride, sodium methylate, sodium ethylate, etc. can be used. Furthermore, when using acid halides or acid anhydrides, sodium hydroxide, potassium hydroxide, triethylamine, N-methylmorpholine, pyridine, etc. can be used.

These reaction aids are usually used in an amount ranging from a catalytic amount to 2 equivalents, but preferably 0.95 to 1.1 equivalents.

After the reaction is completed, the reaction aid or its reaction product is removed by filtration or washing with water, etc., and the solvent m is distilled off to obtain a substituted pyrazole carboxylic acid derivative represented by the general formula CI]. Depending on the situation, further purification can be achieved by subjecting the product to operations such as chromatography and recrystallization.

Incidentally, among the substituted aminooxindane derivatives represented by the general formula which are raw materials for the compounds of the present invention, the following general formula (wherein R8 represents a methyl group or an ethyl group) is used. ] For example, the compound represented by Jean Venea
nd Jaan Tirouflet Compt r
(C) (d) [In the formula, R8 is the same as above. Q represents meaning. ] That is, 4-
7 Cetaminophthalide is reacted with 4 to 12 equivalents of an ethyl Grignard reagent such as ethylmagnesium bromide in an ether solvent such as diethyl ether or tetrahydrofuran at a temperature from -10°C to room temperature to obtain diol compound (a). . Next, the diol body (a) is reacted with 6 to 20 equivalents of activated manganese dioxide in an ether solvent such as dioxane or tetrahydrofuran or a halogenated hydrocarbon solvent such as chloroform or dichloroethane at reflux temperature,
A lactone body (6) is obtained.

Next, the lactone body (b) is reacted with 2 to 4 equivalents of methyllithium or ethyllithium in an ether solvent such as diethyl ether or tetrahydrofuran at -80°C to room temperature to obtain the acetal body (C).

Next, the acetal form (C) is reacted with hydrogen at room temperature in an alcohol medium such as methanol or ethanol in the presence of a catalytic amount of palladium on carbon and concentrated hydrochloric acid to obtain the anilide form (d).

Further, the anilide (ψ) is reacted with 6 to 20 equivalents of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide in ethylene glycol and a water bath medium at reflux temperature to obtain a substituted aminooxindane σ■.

Further, among the a-substituted aminooxindane derivatives represented by the general formula (4), the general formula 戊 [wherein R1 represents a methyl group or an ethyl group,
2 represents a methyl group, ethyl group, n-propyl group or n-butyl group. ] For example, the compound represented by Organic Synthetic Chemistry 685 (
Starting from 8-acetaminophthalic anhydride described in 196g), it can be synthesized by the following route.

Φ) c In the formula, R6 and R2 represent the same meanings as above, and R
, represents a hydrogen atom, methyl group, ethyl group or n-propyl group, and R1 represents a lower alkyl group. ] That is, 8-acetaminophthalic anhydride is reacted with 1 to 5 equivalents of 2-alkylmalonic acid in a pyridine solvent under heating to obtain carboxylic acid form (e). Next, the carboxylic acid form (e) is heated and reacted with i to 2 equivalents of alkyl halide or dialkyl sulfate in the presence of i to 2 equivalents of a base such as potassium carbonate to obtain the ester form (0).

Next, the ester form (0) is reacted with 4 to 10 equivalents of methylmagnesium bromide or ethylmagnesium bromide in an ether solvent such as diethyl ether or tetrahydrofuran at -10°C to 10°C to form the acetal form <1>. obtain.

Next, the acetal compound (r) is reacted with hydrogen at room temperature in an alcohol medium such as methanol or ethanol in the presence of a catalytic amount of palladium carbon and concentrated hydrochloric acid to obtain the anilide compound (h).

Furthermore, the anilide compound (b) was dissolved in ethylene glycol and 6 to 20 equivalents of sodium hydroxide at reflux temperature in a water bath medium.
Reaction with an alkali metal hydroxide such as potassium hydroxide yields a substituted aminooxindane.

Also, among the substituted akinoxindane derivatives represented by the general formula, compounds represented by the general formula: For example, Department of Organic Synthetic Chemistry, 685 (196g)
It can be synthesized by the following route starting from 8-7 cetaminophthalic anhydride described in .

[In the formula, R1° and R11 represent the same meanings as above, and R1! represents a methyl group or a hydrogen atom, and Rla represents a lower alkyl group. ] That is, 8-acetaminophthalic anhydride is heated and reacted with 1 to 6 equivalents of 2-alkylmalonic acid in a pyridine solvent to obtain carboxylic acid compound (i).

Next, the carboxylic acid form (i) is heated and reacted with 1 to 2 equivalents of furkyl halide or dialkyl sulfate in the presence of 1 to 2 equivalents of a base such as potassium carbonate to obtain the ester form (D).

Next, the ester (j) was dissolved in a hydroalcoholic bath medium for 1
It is reacted with ~4 equivalents of sodium borohydride at 0°C to room temperature to obtain the lactone (g).

Next, the lactone body (3) is reacted with 2 to 4 equivalents of methyllithium or ethyllithium in an ether solvent such as diethyl ether or tetrahydrofuran at -80°C to room temperature to obtain an acetal body (2).

Next, the acetal form (j) is reacted with hydrogen in an alcoholic solvent such as methanol or ethanol in the presence of a catalytic amount of palladium carbon and concentrated hydrochloric acid at room temperature to obtain an anilide form.

Furthermore, the anilide compound is reacted with 5 to 20 equivalents of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide in ethylene glycol and water at reflux temperature to obtain substituted aminooxindane (b).

When using the compound of the present invention as an active ingredient of a fungicide,
Although it may be used as is without adding any other ingredients, it is usually mixed with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries to form emulsions, wettable powders, suspensions, and granules. It is used in formulations such as tablets, powders, and liquids.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 99.9%, preferably 0.2 to 8096%.
contains.

Solid carriers include fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene;
Examples include alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, acetonitrile, and water.

Surfactants used for emulsification, dispersion, wet carbonization, etc. include alkyl sulfate salts, alkyl (aryl)
Anionic surfactants such as sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers Sorbikun Examples include nonionic surfactants such as fatty acid esters and polyoxyethylene sorbitan fatty acid esters.

As formulation adjuvants, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(Carboxymethyl cellulose PAP (isopropyl acid phosphate) etc. will cause irritation.

These preparations are applied undiluted or, for example, diluted with water, directly to plants or to soil.

More specifically, the above-mentioned preparation can be used in various forms, such as by being sprayed or powdered on plants, sprayed, powdered or granulated on the soil surface, or further mixed with soil if necessary.

In addition, when used as a seed treatment agent, it can be used after seed coating treatment, seed soaking treatment, etc. Furthermore, by mixing it with other disinfectants, it can be expected to increase the bactericidal efficacy. In addition, insecticides, acaricides, nematicides,
It can also be used in combination with herbicides, plant growth regulators, fertilizers, and soil conditioners.

The compound of the present invention can be used in rice fields, fields, orchards, pastures,
It can be used as an active ingredient in fungicides for lawns, etc.

When the compound of the present invention is used as an active ingredient of a fungicide, the application amount varies depending on weather conditions, formulation form, application timing, method, location, target disease, target crop, etc., but usually 1.
0.6f~1oor per are, preferably 1t~
50f, and when applying emulsions, wettable powders, suspensions, solutions, etc. diluted with water, the application concentration is 0.001 to 1.
%, preferably 0.005 to 0.596, and granules, powders, etc. are applied as they are without any dilution.

<Effects of the Invention> The compound of the present invention is highly effective against plant diseases caused by various plant pathogens, especially microorganisms belonging to Basidiomycetes, and therefore can be used for various purposes as an active ingredient of a pesticide. .

<Examples> The present invention will be explained in more detail below using production examples, reference examples, formulation examples, and test examples.

First, a manufacturing example will be shown.

Production Example 1 (Synthesis of compound (8)) 1.8-dimethyl-1-n-propyl-2-oxa-4
-Aki Twindan 80mF and Triethylamine 48
mF was dissolved in 5 mJ of tetrahydrofuran, and under water cooling,
A solution prepared by dissolving 76 ml of 5-chloro-1,8-dimethylpyrazole-4-carboxylic acid chloride in 2 ml of tetrahydrofuran was added dropwise while stirring at an internal temperature of 5° C. or lower. After the dropwise addition, the mixture was stirred at room temperature overnight, and then extracted with water and chloroform. The organic layer was washed with water, then dried and concentrated. N-(1,8-dimethyl-1-
121 mF of n-propyl-2-oxa-4-indanyl)-5-chloro-1,8-dimethylpyrazole-4-carboxylic acid amide was obtained.

Table 1 shows some of the compounds of the present invention that can be produced by the above production method.

Reference Example 1 Synthesis of α,α-diethyl-2- and droxymethyl-8-acetaminobenzyl alcohol Metallic magnesium 9.52 mj and diethyl ether 60 mj
A solution prepared by dissolving ethyl bromide 48F in diethyl ether 120mj was slowly added dropwise to the mixture with stirring. After the dropwise addition was completed, the mixture was heated under reflux for 15 minutes,
It was left to cool. The ether solution of ethylmagnesium bromide thus prepared was added to 4-acetaminophthalide 7.
．． 62 was slowly added dropwise to a solution of 120 ml of tetrahydrofuran at 10° C. or below while stirring. After the dropwise addition was completed, the mixture was further stirred at room temperature overnight.

After the reaction was completed, the reaction mixture was poured into saturated ammonium chloride water under water cooling, and extracted twice with 400 mj of ethyl acetate.

After drying and concentrating the extract, the obtained oil was purified by silica gel column chromatography to obtain α,α-diethyl-2-hydroxymethyl-
Colorless oil of 8-acetaminobenzyl alcohol 8,
I got Of.

/H-NMR (CDCj, )δppm1.6(6
H%t, J 閤6. OH, 2.1 (8H1s), 8.
6 (2Hs brls ), 5.0 (2H,S
), 7.2-7.8 (8H1m), 8.7 (IH%
br, 8) Reference Example 28. Synthesis of 8-diethyl-7-1cetaminophthalide α,α-diethyl-2-hydroxymethyl-8-acedo [no-benzyl alcohol 8. Of was dissolved in 800mj of tetrahydrofuran, 82f of activated manganese dioxide was added, and the mixture was heated under reflux for 6 hours. After the reaction was completed, the reaction mixture was left to cool and filtered through a glass filter lined with Celite.
The residue was washed with 100 mJ of tetrahydrofuran.

The F solution and the washing solution were combined and condensed, and the resulting oil was purified by silica gel column chromatography to obtain 4.92% of a colorless oil of 8,8-diethyl-7-acetaminophthalide. . n, :I°61.58
76'H-NMRJ ppm o, 75 (6H, t, J frequency 6.0Hz), 1.8
~2.8 (4H, m), 2.8 (8H%B), 7.
0 (IHld, J-8,0Hz), 7.6 (IH,
t, J-8,0Hz), 8.5 (IH, dl J-
8,0Hz), 9.7 (tHsbrl g) Reference Example 8 Synthesis of 1,1-diethyl-8-methyl-8-hydroxy-2-oxa-4-acetaminoindan 8.8-diethyl-7-acetaminophtha ride 4.9
In a solution of v in 80 mJ of tetrahydrofuran, -
20C? Trowel, ether solution of methyllithium (1,4
M) 48 mJ was slowly dropped. After the dropwise addition was completed, the mixture was further stirred at the same temperature for 20 minutes. After the reaction was completed, the reaction mixture was poured into saturated ammonium chloride water under water cooling, and ethyl acetate 2
Extracted twice at 00 mJ. The extract was dried and then concentrated to obtain 5.82 g of an oily product of 1,1-diethyl-8-methyl-8-hydroxy-2-oxa-4-acetaminoindan.

7H-NMR (CDCj,) δppm 0.75 (8H,t, J-6,0H1), 0.8(
81(.

tlJ-6,0Hz), 1.8 (8H,s), 1.
4-11 (4H, m), 2.15 (8H%g), 4.5
(IH% brss), 6.8 (IH
%d, J-8,0Hz), 7.8(IHltlJ
-8,0Hz), 7,96(IH,d, J-8,0H
z), 8.0 (IH,s) Reference Example 41. Synthesis of 1-diethyl-8-methyl-2-oxa-4-acetaminoindan 1.1-diethyl-8-methyl-8-hydroxy-2-
6.82 oxa-4-acetaminoindan was bathed in 120 mJ of ethanol, concentrated hydrochloric acid and 1096 palladium carbon were added in catalytic amounts, and the mixture was vigorously stirred at room temperature in a hydrogen atmosphere for 6 hours.

After the reaction was completed, the reaction mixture was filtered through a glass filter lined with Celite, and the residue was washed with 60 ml of ethyl acetate. By combining and concentrating the F solution and the washing solution, 1.
4.82 g of 1-diethyl-8-methyl-2-oxa-4-7cetaminoindan oil was obtained.

'H-NMR (CDCJ,) δppm 0.7 (8H, t, J=6.0Hz), 0.8 (8H
.

j%J=6.0Hz),X,5(8H,d,J=
6.0Hz), 1.8-2.0 (4H%m'), 2
゜1can.

S), 5.4 (IH, q% Jx6.0Hz), 6
．． 7-7.4 (8H, m), 8.1 (IH, S
) Reference Example 5 Synthesis of 1,1-diethyl-8-methyl-2-oxa-4-aminoindan 1. 4.82% of 1-diethyl-8-methyl-2-oxa-4-acetaminoindan was dissolved in 60ml of ethylene glycol.
j and water 80mj) Cm oak, potassium hydroxide IIF
was added, and the mixture was heated under reflux for 8 hours under a nitrogen atmosphere. After the reaction is completed, the reaction mixture is allowed to cool and water is poured into 60ml of water. and extracted four times with 60 mJ of chloroform. The extracts were combined and washed 8 times with water, then dried and concentrated. The obtained oil was purified by silica gel thin layer chromatography to obtain 1,1-diethyl-8-methyl-2-oxa-4-
2.8 f of a colorless oil of 7 mm was obtained. n:
"1.5884'H-NMR (CDCj,) δppm 0.7 (8H, t, J=6.0Hz), 0.8 (
8H.

t, J=6,0H2), 1.55 (8H,d, J-
6,0H2), 1.5-2.1 (4Hlm), 8.
6 (2H%br%8), 5.85(IH,Q
, J=6.0Hz), 6.8-6.7 (2H,m)
, 7.1 (IH, dd, each at J-6.0 Hz) Next, a production example of a substituted aminooxindane derivative represented by general formula X will be shown as a reference example.

Reference example 6 8-acedo history nophthalic anhydride 6. Of, malonic acid 6. Of, a mixture of 5 ml of pyridine was heated to 90-100°C.
After heating and stirring for 8 hours, the mixture was added to hydrochloric acid under water cooling, and extracted with ethyl acetate. After concentrating the obtained extract, water was added to the residue, the crystals were filtered and dried to obtain 6.6
2-acetyl-6-acetaminobenzoic acid of f was obtained.

Yield 86%, mp 180.8°C IH-NMR (CDCJ, ) δppm 1.85 (8)), $), 2.16 (8H, s), 4.
8-5.1 (1) (1broad s ), 7.2
0 (IH.

d, J-7,8Hz), 7.55 (IH, dd, J=+
7.8.8.0Hz), 8.17 (LH, d, J-
8,0Hz), 9.2-9.6(IH, broad
s) Reference Example 7 2-Acetyl-6-acetaminamine Q Hetav1 Diethyl sulfate 8.1f1 Potassium carbonate 2.8F was dissolved in 40 mj of 7 setone and stirred under reflux for 5 hours. After the reaction, the reaction solution was poured into ice water and extracted with ethyl acetate. By washing the extract with water and concentrating it, 4. IF 2-acetyl-6
-Ethyl acetaminobenzoate was obtained.

Yield 91%, mp 88.0°C 'H/-NMR (CDCJ, ) δ ppm 1.
84 (8H%t, I-7,9Hz), 2.20
(8H.

S), 2.50 (aH,a), 4.82 (,2H
, q, J-7, 0H2), 7.07 (IH, dlJ-
7,0Hz), 7.46 (IH, ddlJ-7,0,
8,OHZ), 8.50(IH,dSJ-8,0)
iz), 9.6-1.0.1 (IH.

broad s) Reference example 8 2-7 cetyl 6-7 cetaminobenzoa a ethyl 0.7
11 was diluted with 20 mJl of tetrahydrofuran, and 18.4 mmol of EtMttBr ether solution was added dropwise at 6°C or lower. After the dropwise addition, the mixture was gradually warmed to room temperature and stirred overnight, then poured into ammonium chloride water and extracted with ethyl acetate. After concentrating the obtained extract, the residue was dissolved in ethanol, catalytic amounts of concentrated hydrochloric acid and palladium on carbon were added, and hydrogenated under a hydrogen atmosphere. After the reaction, the palladium on carbon was separated from each other, the furnace solution was concentrated, and silica gel chromatography (developing solution; n
-hexane:ethyl acetate = 1: IV/V) to obtain 0.2Of 1.8-diethyl-1-methyl-2-oxa-4-acetaminoindan.

Yield 80% lt-NMR (CDC71s) δppm0.6-1.1
1 (6H%m), tJ4 (8H, s), 1.8-2.
1 (4H%m), 2.02 (8H, s), 5.1-5
．． 5 (IH, m), 6.7-7.5 (8H, m), 7
．． 8-8.4 (IH,brlg) Reference Example 9 1.5r of 1.8-diethyl-1-methyl-2-oxa-4-acedoamitindane, 1.72% of potassium hydroxide, 2ml of water, and ethylene glycol 6 ml was added and the reaction was carried out under reflux for 8 hours. After the reaction, the reaction solution was poured into water and extracted with ethyl acetate.

After concentrating the extract, the residue was subjected to silica gel chromatography (developing solution: n-hexane: ethyl acetate-1: IV/V)
0.882 of 1,8-diethyl-1-methyl-2-oxa-4-aminoindan was obtained.

Yield 67%, n:" 1.5459 'H" NMRc CDCJ, > δppm 1.42 (8
H1t1J聰6.4 HE), L, S4 (8H.

t,,J-7,0Hz), 1.88.1.49 (Total 8H.

S), 1.8-2.2 (4H, rn), 8.8-8 respectively
．． 8 (2H, broad s), 5.0-5.4 (I
H, m), 6.46 (IH%d, J = a7.O
Hz), 6.49 (IH.

d, J-7,4Hz), 7.56 (IH, dd,
J-7,0,7,4H2) The following compounds were produced in the same manner.

01.8-Dimethyl-1-ethyl-2-oxa-4-a[twindan n:"L, 529 B'H'-NMRCCDCJ, )δppm0.88 (
8H1ts J-7,6Hz), 1.86°1.47
(8H total, 8 each), 1.52 (8H1d.

J-6,0Hz), 1.4-2.1 (2H%m>, 8
．． 2-4.0C2H1broad s), 5J7 (IH
.

Q, J-6,0Hz), 6.48 (IH, d, J
-8,0Hz), 6.48 (IH, d%J-8,0H
z ), 7.04 (IH%dd, each 8.GHz) 01
．． 8-dimethyl-1-n-propyl-2-oxa-4-
Aminoindan nP-111,5885't-NMRccDct, ) δppm 0.5-1.1 (8H, broad t), 1.87° 1.48 (total 9H, each S), 1.58 (8H, d
.

J=6.2Hz), 1.8-2.0 (4H, m), 8
．． 1-8.8 (2H, broad s), 5J7 (I
H.

QlJ-6,2Hz), 6.45 (IH,d, J-
8,0Hz), 6.50 (IH, d%Jm8.0Hz
), 7.06 (IH, dd, J-8,0,8,0Hz
) Next, a production example of a substituted a[nooxindane derivative] represented by the general formula (capital) will be shown as a reference example.

Reference Example 10 Ethyl 2-acetyl-6-acetaminobenzoate 1.4
f was dissolved in a mixed bath medium of 10 mJ of ethanol and 2 mJ of water, and 0.72 f of sodium borohydride was added little by little at 0°C.

After stirring at room temperature for 1 hour, the reaction solution was poured into 5% aqueous hydrochloric acid and left at room temperature for 1 hour. Next, the mixture was extracted with ethyl acetate, the extract was concentrated, and the residue was purified by silica gel column chromatography to obtain 0.8Of of white crystals of 8-methyl-7-acetaminophthalide.

m-1), 112. IC'H-NMR (CDCJ,) δppm 1.65 (8H%d, J=6.0Hz), 2.2
5 (8H.

S), 5.5 (IH, q%J-6,0Hz), 6
．． 96 (IH, d, Jx6.0Hz), 7.55 (I
H,t.

J-6,0Hz), 8.4 (IH, d%J-6,0H
z), 9.5 (LH, br d) Reference Example 11 0.82 of 8-methyl-7-acetaminophthalide was dissolved in 10 mJ of tetrahydrofuran, and an ether solution of methyllithium (1,19 M) 9 was prepared at -20°C. .8 mJ was dropped. After the dropwise addition, the mixture was stirred for an additional 80 minutes at the same temperature.
The mixture was poured into ammonium chloride water and extracted with ethyl acetate. After testing the obtained extract, dissolve the residue in ethanol,
A catalytic amount of concentrated hydrochloric acid and palladium on carbon were added and hydrogenated under a hydrogen atmosphere. After the reaction, the palladium on carbon is separated from P,
The F solution was subjected to IIIF chromatography (silica gel chromatography).
Developing solution; n-hexane:acetic acid ether 1:1'/
/''/) to obtain 0.72f of 1,8-dimethyl-2-oxa-4-acetaminoindan.

Yield 9096 m f //'%, /'' and 'H'-NMR (CDCJ, ) j ppm-Furuichibe silkworm 1.45 (8H%d, J-6,0Hz), 1.
5 (8H1d, Jx6.0Hz), 2.1 (8H, 8)
, 5.0-5.6 (2H, m), 6.8-7.9 (4
H, m) Reference Example 12 0.7F of 1.8-dimethyl-2-oxa-4-acetaminoindan and 1.92 of potassium hydroxide were reacted with 2 mj of water and 6 mj of ethylene glycol under reflux for 8 hours. After the reaction, the reaction solution was poured into water and extracted with ethyl acetate. After concentrating the extract, the residue was subjected to silica gel chromatography 1: n-hexane: ethyl acetate.
o, 46t of 1,
8-dimethyl-2-oxa-4-a[twindan] was obtained.

Yield 8496, m, p 94.1°C') I'-NMR (CDCJ,) δppm1.5 (8
H, d, J++6.0Hz), 1.55 (8H.

d%J=6.0Hz), 8.6 (2H, b r s
), 5.0-5.5 (2H, m), 6.55 (2H
,br d.

J-8,0Hz), 7.1 (IH%br t, J
-8,0Hz), The following compounds were produced in the same manner.

ol-ethyl-8-methyl-2-oxa-4-7 minoindan mp 54.1°C! H-NMR (CDCj, )δppm1.0 (8H
, dlJ-6,0Hz), 1.55 (8H.

d%J-6,0Hz), 1.8-2.0 (2H, m
), 8.6 (2H, br s), 4.8-5.4 (2
H, m), 6.55 (2H, b rd, Jsm
8. OHz), 7.1(l)i, br t%J x
g, QHz) Formulation Example 1 50 parts each of the compounds (1) to (9) of the present invention, 8 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 46 parts of synthetic hydrous silicon oxide were thoroughly ground and mixed to form the active ingredient 5G96. of each of the hydrating agents.

Formulation Example 2 1 part each of the compounds (1) to (9) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 70 parts of xylene were thoroughly mixed to form an emulsion containing 105% active ingredient. Get each.

Formulation Example 8 2 parts each of the compounds (1) to (9) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 80 parts of bentonite and 66 parts of kaolin clay were thoroughly ground and mixed, and water was added. After thoroughly kneading, the mixture is granulated and dried to obtain granules containing 296 active ingredients.

Formulation Example 4 26 parts each of the compounds (1) to (9) of the present invention, 8 parts polyoxyethylene sorbitan monooleate, 8 parts CMC,
Each suspension of active ingredient 2696 is obtained by mixing with 69 parts of water and wet milling until the particle size is less than 6 microns.

Formulation Example 6 2 parts each of the compounds (1) to (9) of the present invention, 88 parts of kaolin clay, and 1 G part of talc are thoroughly ground and mixed to obtain powders containing 296 active ingredients.

Formulation Example 6 10 parts of each of the compounds (1) to (9) of the present invention, 1 part of polyoxyethylene styrylphenyl ether, and 89 parts of water are mixed to obtain each liquid preparation of active ingredient 1096.

Next, test examples will show that the compounds of the present invention are useful as active ingredients of fungicides. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used as a comparative control Iζ are indicated by the compound symbols in Table 2.

Table 2 The pesticidal efficacy is determined by visually observing the degree of disease and disease on the test plants during the survey, i.e., the degree of clusters and lesions on leaves, stems, etc., and if no M clusters or lesions are observed, the rating is 6. , if about 10% is confirmed, it is "4", if about 80% is confirmed, it is "8", if about lsO% is confirmed, it is r2J, and if about 70% is confirmed, it is "1".
'', if there is no difference from the disease onset state when no compound is tested, it is evaluated as ``0'' and evaluated on a 6-point scale from 0 to 6, and is indicated as 0.1.2.8.4.6. .

Test Example 1 Rice sheath blight preventive effect test A plastic pot was filled with sandy loam, and rice (Kia No. 88) was sown and grown in a greenhouse for 20 days. A test compound prepared as an emulsion in accordance with Formulation Example 2 was diluted with water to a predetermined concentration, and sprayed on the foliage of rice seedlings with 4 to 6 leaves developed so as to sufficiently adhere to the leaf surface. Four hours after the spraying, edible agar pieces of rice sheath blight bacteria were pasted and inoculated. 28℃ after inoculation,
The plants were grown for 4 days in a humid environment and their pesticidal efficacy was investigated. The results are shown in Table 8.

Test Example 2 in Table 2 Test for penetration and transfer effect of rice sheath blight A plastic pot was filled with sandy loam, and rice plants (I & No. 88) were sown and grown in a greenhouse for 8 weeks.

A test compound made into a hydrating powder according to Formulation Example 1 was added diluted with water to rice plants with 4 to 5 leaves developed, and the specified amount was sprinkled on the soil, and the rice plants were grown in a greenhouse for 7 days. Bacillus blight agar pieces were pasted and inoculated. After collecting the liquid, the seeds were grown for 4 days at 28°C under high humidity.
The pesticidal efficacy was investigated. The results are shown in Table 4.

Table 4. A test compound made into a wettable powder according to Formulation Example 1 was diluted with water, and a predetermined amount of the solution was sprinkled onto the soil.

After irrigation, the plants were grown in an 8-hole greenhouse, and the pesticidal efficacy was investigated based on the severity of disease on the stems at the ground level. The results are shown in Table 6.

Table 6 Test Example 8 Preventive Effect Test on French Bean White Silk Disease The white silk pathogenic bacteria, which had been cultured in advance in a bran medium, was thoroughly mixed with sandy loam and packed in a plastic pot. Sweep green beans (Taisho Kintoki) on top of it. Test Example 4 Wheat Rust Treatment Efficacy Test A plastic pot was filled with sandy loam and wheat (Norin No. 78)
were sown and grown in a greenhouse for 10 days. Wheat seedlings with the second to eighth leaves developed were inoculated with spores of the wheat rust fungus. After inoculation, the test compound was grown for 1 day at 28° C. in a humid environment, made into an emulsion according to Formulation Example 2, diluted with water to a predetermined concentration, and sprayed on the foliage so that it would sufficiently adhere to the leaf surface.

After spraying 2 Grow for 7 days under 8℃ lighting, prevention The removal force was investigated.

The results are shown in Table 6.

Claims (1)

[Claims] (1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [I] [In the formula, R_1 represents a methyl group or trifluoromethyl group, R_2 represents a halogen atom, R_3 and R_4 are the same or different and each represents a methyl group or an ethyl group, and R_5 represents an ethyl group, n-propyl group, n-butyl group or a hydrogen atom. ] A substituted pyrazole carboxylic acid derivative represented by (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1 represents a methyl group or a trifluoromethyl group, and R_2 represents a halogen atom. [In the formula, R_3 and R_4 are the same or different and represent a methyl group or an ethyl group, and R_5 is Represents an ethyl group, n-propyl group, n-butyl group or a hydrogen atom. ] The method for producing a substituted pyrazole carboxylic acid derivative according to claim 1, which comprises reacting with a substituted aminooxindane derivative represented by the following. (8) A fungicide for agriculture and horticulture, which contains the substituted pyrazole carboxylic acid derivative according to claim 1 as an active ingredient.