JPH11322513A - Plant disease damage controlling agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition showing synergistically enhanced effects on plant disease damage, especially late bright, downy mildew, etc., by including a substituted thiophene derivative and a dithiocarbamate-based compound as active ingredients. SOLUTION: This composition comprises (A) a substituted thiophene derivative of formula I [R is a 3-12C alkyl, a 3-12C halogenoalkyl or the like; Ar is a group of formula II (R1 is a trifluoromethyl or the like) or the like] e.g. N-[2-(1,3-dimethylbutyl)-3-thienyl]-5-chloro-3-trifluoromethylpyrazole -4-carboxylic acid amide or the like} and (B) a dithiocarbamate-based compound (e.g. zinc dimethyldithiocarbamate or the like) as active ingredients. Preferably the composition comprises 0.1-100 pts.wt. of the component B based on 1 pt.wt. of the component A1. The composition is effective for blast of rice plant, powdery mildew of wheat and barley, early blight of potato, powdery mildew of Pisum sativum, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a plant protection composition having at least two active ingredients and having a synergistically enhanced effect on disease infection. More specifically,
The present invention relates to a composition in which one of the active ingredients is a substituted thiophene derivative having a plant disease controlling action, and the other is a dithiocarbamate compound.

[0002]

2. Description of the Related Art Conventionally, many chemicals have been put to practical use for controlling plant diseases. That is, JP-A-9
JP-A-235282 (EP-A-737682) discloses that various substituted thiophene derivatives have a bactericidal effect. This compound has a high control effect on various diseases, but has a low effect on diseases such as plague and downy mildew at a low concentration. Further, this patent does not describe a compound having the structure of the present invention.

On the other hand, component II is a known dithiocarbamate compound selected from the following group,
["Product name (English name)", page], and the page means [The Pesticide M.
anual), 11th edition, The British C
rop Protection Council, 19
1997]. 1. 1. Zinc ethylenebisdithiocarbamate [“Zineb (I)”, pp. 1276-1277] Manganese ethylene bisdithiocarbamate ["maneb (I)", No. 764-76
6 pages] 3. Zinc ion coordination manganese ethylenebisdithiocarbamate ["manzezeb (mancozeb)
(I) ”), pp. 761-763] 4. diammonium ethylenebisdithiocarbamate [“ amobam ”] 5. bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate [“ polycarbamate (poly)
carbamate) "] 6. Zinc propylene bisdithiocarbamate [" propineb (I) ", 1032-103
Page 4] 7. Zinc dimethyldithiocarbamate ["Jiram (z
iram (I)) ", pp. 1277-1279] 8. Bis (dimethylthiocarbamoyl) disulfide
["Thiuram", 1203-120
Page 5] These have a prophylactic effect against a relatively wide range of pathogenic bacteria including plague and downy mildew, but have a high drug dose and a large burden on the environment.

[0004]

Accordingly, the present invention comprises at least two active ingredients, one of the thiophene derivatives of component I and one of the dithiocarbamate compounds of component II, which are synergistically enhanced. It is an object of the present invention to provide a composition for controlling plant diseases having an improved action.

[0005]

The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, surprisingly, at least one of the dithiocarbamate compounds of the component II and the thiophene derivative of the component I It has been found that a composition which is a mixture of any one of the above shows an enhanced synergistic effect against the infection of a wide range of plant diseases, particularly diseases such as plague and downy mildew, and thus meets the above-mentioned problem. ,
The present invention has been completed.

[0006] That is, the present invention is a plant protection composition having at least two kinds of active ingredients and having a synergistic effect against disease infection.

[0007]

Embedded image [Wherein, R represents a straight-chain or branched alkyl group having 3 to 12 carbon atoms, a straight-chain or branched halogenoalkyl group having 3 to 12 carbon atoms, a straight-chain or branched alkenyl group having 3 to 10 carbon atoms, A linear or branched halogenoalkenyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, A halogeno-substituted cycloalkyl group having 3 to 10 carbon atoms, or a phenyl group optionally substituted by 1 to 3 substituents, wherein the substituent of the phenyl group is a hydrogen atom, An alkyl group of 4,
C2-4 alkenyl group, C2-4 alkynyl group, C3-6 cycloalkyl group, C1-4
An alkoxy group, a C1-4 halogenoalkoxy group, a C1-4 alkylthio group, a C1-4 alkylsulfoxy group, a C1-4 alkylsulfonyl group, a halogen atom, a cyano group, An acyl group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, an amino group, or an amino group substituted with an alkyl group having 1 to 3 carbon atoms, wherein R and -NHCOAr are adjacent to each other; , Ar represents the following (A1) to (A6)

[0008]

Embedded image (Wherein R1 is a trifluoromethyl group, a difluoromethyl group, a methyl group, an ethyl group or a halogen atom;
R2 is a halogen atom, a methyl group or a methoxy group, and n is an integer of 0 to 2),
However, Ar is (A2), (A3), (A4), (A6)
Excluding the case where R1 is a halogen atom when the above is the case), and Component II relates to a composition containing at least one of dithiocarbamate compounds.

By using the composition of the present invention, disease can be effectively controlled with an unexpectedly small amount of the active ingredient as compared with a conventional method. In addition to the synergistic effect on plague and mildew, it also has an effect on gray mold and powdery mildew, which is a major feature of this drug.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Among the compounds represented by Component I of the present invention, preferred are those wherein Ar is (A1) and R1 is C
An F ₃ or CHF ₂ group, wherein R 2 is a chlorine atom;
Ar is (A2) and R1 is a Me group, while
R is a compound represented by a linear or branched alkyl group having 5 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms.
Particularly preferred are compounds wherein Ar is (A2), R2 is Me, and R is a straight or branched alkyl group having 5 to 8 carbon atoms.

The following are some specific examples of the compound represented by the component I. Compound No. 1: N- {2- (1,3-dimethylbutyl) -3-thienyl} -5-chloro-3-trifluoromethylpyrazole-4-carboxylic acid amide [R is 1,3
A dimethylbutyl group and Ar is A1 (R1 = CF
₃ , R2 = Cl)] Compound No. 2: N- {2- (1,3-dimethylbutyl) -3-thienyl} -6-methyl-3,4-dihydro-2H-pyran-5-carboxylic acid Amide [R is 1,3-
A dimethylbutyl group and Ar is A2 (R1 = Me)] Compound No. 3: N- {2- (1,3-dimethylbutyl) -3-thienyl} -6-methyl-2,3-dihydro-1 , 4-oxathiin-5-carboxylic acid amide [wherein R is a 1,3-dimethylbutyl group and Ar is A3 (R1 =
Me, n = 0)

The compositions of the present invention are effective against the following types of plant diseases: Pyricularia ory
zae ), sheath blight ( Rhizoctonia solani ), sesame leaf blight ( Cochl
iobolus miyabeanus ), idiot disease ( Gibberella fujikuro)
i ); Powdery mildew of wheat ( Erysiphe graminis f.sp. hord)
ei; f.sp. tritici), rust (Puccinia striiformis; P.
graminis ; P. recondita ; P. hordei) , leaf spot disease ( Pyrenoph
ora graminea ), net spot disease (Pyrenophora teres ), Fusarium head blight
( Gibberella zeae ), snow rot ( Typhula sp .; Micronectri
ella nivalis ), nude smut ( Ustilago tritic i; U. nud)
a ), black smut ( Tilletia caries ), eye spot disease ( Pseudo
cercosporella herpotrichoides ), strain rot ( Rhizoctonia
cerealis), scald (Rhynchosporium secalis), leaf blight
( Septoria tritici ), blight ( Leptosphaeria nodoru)
m); beans, cucumber, tomato, strawberry, grape, potato, soybean, cabbage, eggplant, lettuce gray mold disease (Botrytis cinerea); grape downy mildew (Plasmopora
viticola), rust (Phakopsora ampelopsidis), powdery mildew (Uncinula necator), sphaceloma disease (Elsinoe ampelin
a ), late rot ( Glomerella cingulata ); powdery mildew on apples ( Podosphaera leucotricha ), scab ( Venturia inaeq)
ualis ), spot leaf rot ( Alternaria mali ), scab ( Gymnos )
porangium yamadae ), Monilia disease ( Sclerotinia mali ),
Rot rot ( Valsa mali ); Black spot of pear ( Alternaria kiku)
chiana), scab (Venturia nashicola), gymnosporangium (Gymnos
porangium haraeanum ), ring spot disease ( Physalospora piricol )
a ); Peach ash disease ( Sclerotinia cinerea ), scab ( Clad )
osporium carpophilum), Phomopsis rot (Phomopsi
s sp.); oyster anthracnose ( Gloeosporium kaki ), leaf blight ( Ce )
rcospora kaki ; Mycosphaerella nawae ), powdery mildew ( P
hyllactinia kakikora ); downy mildew of cucumber ( Pseudopero
nospora cubensis ), powdery mildew of cucumber ( Sphaerotheca
fuliginea ), Anthracnose ( Colletotrichum lagenarium ), Vine blight ( Mycosphaerella melonis ); Tomato ring spot ( Alt
ernaria solani ), leaf mold ( Cladosporium fulvam ), plague ( Phytophthora infestans ); eggplant powdery mildew ( Erysi
phe cichoracorum), Susukabi disease (Mycovellosiella natt
rassii ); Black spot of cruciferous vegetables ( Alternaria japoni
ca ), white spot disease ( Cercosporella brassicae );
(Puccinia allii), black spot disease (Alternaria porri); soybean purpura (Cercospora kikukuchii), sphaceloma disease (Elsino
e glycinnes ), black spot ( Diaporthe phaseololum ); kidney anthracnose ( Colletotrichum lindemuthianum ); peanut black spot ( Mycosphaerella personatum ), brown spot ( C
ercospora arachidicola ); powdery mildew of pea ( Erys
iphe pisi ), downy mildew ( Peronospora pisi ); potato summer plague ( Alternaria solani ), black bruise ( Rhizoctonia so
lani ), plague ( Phytophthora infestans ); broad bean downy mildew ( Peronospora viciae ), plague ( Phytophthora nicoti )
anae ); Tea blast ( Exobasidium reticulatum ), white scab ( Elsinoe leucospila ), anthracnose ( Colletotrichum t
heae-sinensis); Tobacco scab ( Alternaria longipe)
s ), powdery mildew ( Erysiphe cichoracearum ), anthracnose ( Co
lletotrichum tabacum ), plague ( Phytophthora parasitic )
a ); Brown spot of sugar beet ( Cercospora beticola ); Rose scab ( Diplocarpon rosae ), powdery mildew ( Sphaerotheca )
pannosa ), plague ( Phytophthora megasperma ); chrysanthemum leaf spot ( Septoria chrysanthemi - indici ), white rust ( Puc
cinia horiana ); strawberry powdery mildew ( Sphaerotheca hu)
muli ), plague ( Phytophthora nicotianae ); sclerotium disease (S clerotinia s
clerotiorum ); citrus black spot ( diaporthe citri );
Bacterial leaf blight of carrots ( Alternaria dauci ) and the like. Above all,
It has a synergistically enhanced effect on plague, downy mildew and the like. Such a potentiating effect was not to be expected from the sum of the effects of the individual active ingredients.

In the fungicide composition of the present invention, the mixing ratio of the substituted thiophene derivative of the component I and the dithiocarbamate compound of the component II is not particularly limited. Compound is 0.1
To 100 parts by weight, preferably 0.5 to 50 parts by weight, more preferably 0.5 to 20 parts by weight.

The composition may be applied directly as a mixture containing the two active ingredients, separately or simultaneously with the individual active ingredients, or applied one after the other. Furthermore,
For the mixture containing the active ingredients, the concentrated composition containing the two active ingredients may be diluted with water, or a mixture may be prepared at the time of use from the two concentrates containing the individual active ingredients, and this may be used. It may be diluted with water (tank mix method). When the composition of the present invention is used as a plant disease controlling agent, the drug substance may be used as it is for the plant to be treated, but it is generally mixed with an inert liquid carrier, a solid carrier, a surfactant, It is used in the form of powders, wettable powders, flowables, emulsions, granules and other commonly used forms which are commonly used. If necessary for the preparation, an auxiliary agent can be added.

[0015] The carrier as used herein refers to a synthetic or natural inorganic or organic substance incorporated to assist in reaching the active ingredient to the site to be treated and to facilitate storage, transportation and handling of the active ingredient compound. Means As the carrier, any solid or liquid carrier can be used as long as it is generally used for agricultural and horticultural medicines, and it is not limited to a specific one.

For example, solid carriers include clays such as montmorillonite and kaolinite; inorganic substances such as diatomaceous earth, terra alba, talc, vermiculite, gypsum, calcium carbonate, silica gel, and ammonium sulfate; and soybean powder, sawdust, flour and the like. Plant organic substances and urea. In order to improve the physical properties, it is also possible to add a highly dispersed silicic acid or a highly dispersed absorbent polymer.

As the liquid carrier, toluene, xylene,
Aromatic hydrocarbons such as cumene; paraffinic hydrocarbons such as kerosene and mineral oil; ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as dioxane and diethylene glycol dimethyl ether; alcohols such as methanol, ethanol, propanol and ethylene glycol Aprotic solvents such as dimethylformamide and dimethylsulfoxide, and water.

Further, the following adjuvants can be added singly or in combination according to the purpose, taking into account the dosage form of the preparation, the application scene, and the like. As auxiliary agents,
Commonly used surfactants, binders (eg, ligninsulfonic acid, alginic acid, polyvinyl alcohol, gum arabic, sodium CMC, etc.), stabilizers (eg, phenolic compounds, thiol compounds, or higher fatty acid esters for antioxidation) Etc., a phosphate as a pH adjuster, and sometimes a light stabilizer) can be used alone or in combination as necessary. Further, depending on the case, an industrial bactericide, a bactericidal / antifungal agent or the like may be added for bactericidal / fungicidal purposes.

The adjuvant will be described in more detail. Auxiliaries include lignin sulfonate, alkylbenzene sulfonate, alkyl sulfate, polyoxyalkylene alkyl sulfate, polyoxyalkylene alkyl phosphate for the purpose of emulsification, dispersion, spreading, wetting, bonding, stabilization, etc. Anionic surfactants such as salts; polyoxyalkylene alkyl ethers, polyoxyalkylene alkylaryl ethers, polyoxyalkylene alkylamines, polyoxyalkylene alkylamides, polyoxyalkylene alkylamides, polyoxyalkylene alkylthioethers, polyoxyalkylene fatty acids Ester, glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxypropylene polyoxyethylene block polymer Nonionic surfactants; Lubricants such as calcium stearate and wax; Stabilizers such as isopropylhydrodiene phosphate; Natural or synthetic phospholipids of cephalin or lecithin series such as phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, and lysolecithin; Methyl cellulose,
Carboxymethyl cellulose, casein, gum arabic and the like can be mentioned. However, these components are not limited to those described above.

The content of the active ingredient composition in the composition of the present invention varies depending on the form of preparation, but is usually 0.1 to 30% by weight for powders and 0.1 to 80% by weight for wettable powders.
It is 0.5 to 20% by weight for granules, 2 to 50% by weight for emulsions, 1 to 50% by weight for flowable preparations, 1 to 80% by weight for dry flowable preparations, preferably 0.5 to 20% by weight for powders. 10% by weight, 5-60% by weight for wettable powder,
5 to 20% by weight for emulsions, 5 to 50 for flowable formulations
% By weight and 5 to 50% by weight for dry flowable preparations
It is.

The content of the adjuvant is from 0 to 80% by weight,
The content of the carrier is an amount obtained by subtracting the content of the active ingredient compound and the content of the auxiliary from 100% by weight.

The method of applying the composition of the present invention includes seed disinfection, foliage application, soil irrigation, and the like, and any method generally used by those skilled in the art will exert sufficient efficacy. The application rate and application concentration vary depending on the target crop, the target disease, the degree of occurrence of the disease, the dosage form of the compound, the application method and various environmental conditions, etc., but when sprayed, the active ingredient amount is 50 to 1,000 g per hectare. Is suitable, desirably from 100 to 500 g per hectare. When a wettable powder, a flowable or an emulsion is diluted with water and sprayed, the dilution ratio is 200 to 20,000.
A factor of 2 is appropriate, preferably a factor of 500 to 5,000. In the case of seed disinfection, the amount of fungicide mixture used is
0.001 to 50 g, preferably 0.1 to 0.1 g per kg of seed.
01 to 10 g.

The composition of the present invention can be used not only in combination with other fungicides, insecticides, herbicides, plant growth regulators and other pesticides, soil improvers or fertilizers, but also in mixed preparations with these. It is possible.

Next, the present invention will be described in more detail with reference to formulation examples and test examples. The parts in the preparation examples represent parts by weight.

[0025]

Examples Formulation Example 1 (Wettable powder) Compound No. 2: 10 parts, Maneb: 30 parts, sodium ligninsulfonate: 10 parts, sodium alkylnaphthalenesulfonate: 5 parts, white carbon: 10 parts and diatomaceous earth : 35 parts were uniformly ground and mixed to obtain a wettable powder.

Formulation Example 2 (Wettable powder) Compound No .: 1:10 parts, Manzeb: 50 parts, sodium ligninsulfonate: 1 part, sodium alkylbenzenesulfonate: 2 parts and diatomaceous earth: 37 parts are pulverized and mixed. A sum was obtained.

Formulation Example 3 (Wettable powder) Compound No .: 1:10 parts, Manzeb: 50 parts, calcium ligninsulfonate: 3 parts, sodium lauryl sulfate:
2 parts and 35 parts of diatomaceous earth were pulverized and mixed to obtain a wettable powder.

Formulation Example 4 (Flowable formulation) Compound No. 3: 10 parts, polycarbamate compound: 10
Part, propylene glycol: 3 parts, sodium lignin sulfonate: 2 parts, dioctyl sulfosuccinate sodium salt: 1 part, and water: 74 parts were wet-pulverized with a sand grinder to obtain a flowable agent.

Formulation Example 5 (floatable) Compound No. 2: 5 parts, Manzeb: 25 parts, polyoxyethylene sorbitan monooleate: 3 parts, carboxymethyl cellulose: 3 parts, and water: 64 parts with a sand grinder. The wet pulverization was performed to obtain a flowable agent.

Test Example 1 Tomato Blight Preventive Effect Test Tomato (variety: world's best) grown in a greenhouse in a 7.5 cm-diameter plastic pot until the 5th leaf stage was treated with a wettable powder prepared according to Formulation Example 2. After dilution to a predetermined concentration, 50 ml was sprayed per 4 pots. After the medicinal solution dries, the zoospores are washed off with water from the tomato blight fungus cultured on the potato section, and the zoospores are exposed after cooling on ice (1 × 10 5).
⁵ cells / ml). Temperature 18 ° C, Humidity 95%
After keeping in the above greenhouse for 5 days, the area occupied by the disease spot of the plague was investigated according to the following index to determine the degree of onset, and the control value was calculated according to the following formula. The results are shown in Table 1 (Table 1).

Severity 0: No disease 1: Lesion area 5% or less 2: Lesion area 5 to 25% 3: Lesion area 25 to 50% 4: Lesion area 50% The average value of each treatment section and the non-treatment section was defined as the disease severity.

Control value (%) = (1−degree of disease in treated group / degree of disease in untreated group) × 100

[0033]

[Table 1]

Test Example 2 Test for Preventive Effect of Cucumber Downy Mildew
To a cucumber (cultivar: Sagami Hanjiro) grown to the leaf stage, a wettable powder prepared according to Formulation Example 2 was diluted to a predetermined concentration,
50 ml was sprayed per 4 pots. After the drug solution was dried, a spore suspension of cucumber downy mildew was sprayed and inoculated. After being kept in a greenhouse for 7 days, the area occupied by the mildew spots was investigated according to the following index to determine the degree of onset, and the control value was calculated according to the following formula. The results are shown in Table 2 (Table 2).

Severity 0: No disease 1: Lesion area 5% or less 2: Lesion area 5 to 25% 3: Lesion area 25 to 50% 4: Lesion area 50% The average value of each treatment section and the non-treatment section was defined as the disease severity.

Control value (%) = (1−degree of disease in treated group / degree of disease in untreated group) × 100

[0037]

[Table 2]

[0038]

Industrial Applicability The present invention is a fungicidal composition containing at least two kinds of active ingredients, and has a synergistically enhanced effect on a wide range of plant diseases, especially plague and downy mildew. It is useful as a plant disease controlling agent composition. By using such a composition of the present invention, it is possible to control a disease with an unexpectedly small amount of an active ingredient as compared with a conventional method. In addition, since the activity and the disinfection spectrum of the component I and the component II are different and the component I also has a therapeutic effect, the present composition is also advantageous in that it can control a wide range of plant diseases therapeutically.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI A01N 43/32 A01N 43/32 43/40 101 43/40 101B 43/56 43/56 B 43/80 102 43/80 102 47 / 26 47/26 55/02 55/02 BG (72) Inventor Hideo Kawashima 1144, Togo, Mobara-shi, Chiba Mitsui Chemicals Co., Ltd. Inside

Claims (6)

[Claims] 1. A plant protection composition having at least two kinds of active ingredients and having a synergistic effect against infection of a disease, wherein the component I is represented by the following formula. [Wherein, R represents a straight-chain or branched alkyl group having 3 to 12 carbon atoms, a straight-chain or branched halogenoalkyl group having 3 to 12 carbon atoms, a straight-chain or branched alkenyl group having 3 to 10 carbon atoms, A linear or branched halogenoalkenyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, A halogeno-substituted cycloalkyl group having 3 to 10 carbon atoms, or a phenyl group optionally substituted by 1 to 3 substituents, wherein the substituent of the phenyl group is a hydrogen atom, An alkyl group of 4,
C2-4 alkenyl group, C2-4 alkynyl group, C3-6 cycloalkyl group, C1-4
An alkoxy group, a C1-4 halogenoalkoxy group, a C1-4 alkylthio group, a C1-4 alkylsulfoxy group, a C1-4 alkylsulfonyl group, a halogen atom, a cyano group, An acyl group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, an amino group, or an amino group substituted with an alkyl group having 1 to 3 carbon atoms, wherein R and -NHCOAr are adjacent to each other; , Ar are represented by the following formulas (A1) to (A6). (Wherein R1 is a trifluoromethyl group, a difluoromethyl group, a methyl group, an ethyl group or a halogen atom;
R2 is a halogen atom, a methyl group or a methoxy group, and n is an integer of 0 to 2),
However, Ar is (A2), (A3), (A4), (A6)
Excluding the case where R1 is a halogen atom in the above formula), and the component II is a dithiocarbamate compound. 2. In the component I, R represents a linear or branched alkyl group having 5 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms. The composition according to claim 1, which is: 3. The composition according to claim 2, wherein in component I, Ar is (A1), R1 is a trifluoromethyl group or a difluoromethyl group, and R2 is a halogen atom. 4. The composition according to claim 2, wherein in component I, Ar is (A2) and R1 is a methyl group or an ethyl group. 5. The composition according to claim 2, wherein the dithiocarbamate compound of the component II is at least one selected from the group consisting of zineb, maneb, manzeb, and ambam. 6. The composition according to claim 2, wherein the dithiocarbamate compound of the component II is at least one selected from the group consisting of polycarbamate, propineb, ziram, and thiuram.