JP3435810B2 - Agricultural and horticultural sterilizing composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a fungicidal composition for agricultural and horticultural use. The present inventors have developed an excellent agricultural and horticultural fungicide.
As a result of intensive studies to develop, (a)
An amide derivative represented by the following formula:
(E) -2- {2- [6- (2-cyanophenoxy) pi
Limidin-4-yloxy] phenyl} -3-methoxy
By using in combination with acrylate,
Excellent synergistic effect against plant diseases
And found the present invention. That is,
Akira is (a) General formula 2 Embedded image(Wherein X represents a hydrogen atom or a chlorine atom, and Y represents a salt
R represents a methyl group or a bromine atom;
Represents a nyl group. An amide derivative represented by the formula (b):
Methyl (E) -2- {2- [6- (2-cyanopheno
Xy) pyrimidin-4-yloxy] phenyl} -3-
Farm containing methoxy acrylate as active ingredient
Provided is a germicidal composition for entertainment (hereinafter, referred to as the composition of the present invention).
I do. The general formula 2 used in the present invention is
Table 1 shows examples of such amide derivatives. [Table 1] An amide derivative represented by the general formula (2) is
JP-A-2-76846, JP-A-2-76845 or JP-A-2-76845
It is described in JP-A-1-156951. Methyl (E)-
2- {2- [6- (2-cyanophenoxy) pyrimidine
-4-yloxy] phenyl} -3-methoxyacryle
(Hereinafter referred to as Compound A) is Brighton Crop Prot
Section Conference-Pests and Disease 1992,435-442
European Patent Application Publication No. EP-0382375
A (Table 9, Compound 9). Plant diseases to which the composition of the present invention has control effect
As, for example, rice blast (Pyricularia oryza
e), Sheath blight (Rizoctonia solani), Pseudo blight(Helmin
thosporium sigmoideum,Sclerotium hydrophilum,S
clerotium fumigatum,Sclerotium oryzae-sativae
), Sesame leaf blight ((Cochliobolus miyabeanus)But
It is. (A) General formula which is an active ingredient of the composition of the present invention
Mixture of the amide derivative represented by 2 and (b) compound A
In the case of (a) 1 part by weight of the amide derivative, (b)
Compound A is usually 0.02 to 100 parts by weight from the viewpoint of controlling effect.
And preferably 0.2 to 20 parts by weight. The composition of the present invention is used as a fungicide for agricultural and horticultural use.
In general, the active ingredient compound is added to a solid carrier, a liquid carrier, etc.
Or mixed with a gaseous carrier, if necessary, a surfactant,
Add oils, emulsions, hydration by adding other formulation auxiliaries
Agents, granules, powders, solutions, suspensions, foams, microcaps
Formulated into cells, ULVs, pastes, etc. and used. these
In the preparations of the formula, the total amount of the active ingredient compound is
And 0.1 to 99.9%, preferably 0.2 to 80%.
These formulations, for example, develop active compound
Agent, i.e., a solid carrier, a liquid carrier,
Surfactants, fixing agents, dispersants, stabilizers, foaming agents, etc.
Or by mixing them using
Can be. As a solid carrier, for example, clay
(For example, kaolin, diatomaceous earth, synthetic hydrous silicon oxide,
Fubasami clay, bentonite, acid clay), talc
And other inorganic minerals (eg, sericite, quartz powder)
Powder, sulfur powder, activated carbon, calcium carbonate, hydrated silica)
Etc., and fine powders or granular materials such as
Is, for example, water, alcohols (for example, methanol
Water, ethanol), ketones (for example, acetone,
Butyl ethyl ketone), aromatic hydrocarbons (for example,
Benzene, toluene, xylene, ethylbenzene, methyl
Naphthalene), aliphatic hydrocarbons (eg, n-hexene)
Sun, cyclohexanone, kerosene, kerosene), ester
(Eg, ethyl acetate, butyl acetate), nitriles
(For example, acetonitrile, isobutylnitrile),
Ethers (eg, dioxane, diisopropyl
Acid amides (eg, dimethylformamide)
Dimethylacetamide), halogenated hydrocarbons
(For example, dichloroethane, trichloroethylene,
Carbon chloride) and the like. As a surfactant,
For example, alkyl sulfates, alkyl sulfonates,
Alkyl aryl sulfonate, alkyl arylate
Tells and their polyoxyethylenates, polyoxy
Ethylene glycol ethers, polyhydric alcohol esthetics
And sugar alcohol derivatives. Fixing agent and minute
Powders include, for example, casein, gelatin, polysaccharides
(For example, starch, arabic gum, cellulose
Conductor, alginic acid), lignin derivatives, bentonite,
Sugars, synthetic water-soluble polymers (eg, polyvinyl alcohol)
, Polyvinylpyrrolidone, polyacrylic acids)
Examples of the stabilizer include PAP (acidic resin).
Isopropyl), BHT (2,6-di-tert-)
Butyl-4-methylphenol), BHA (2-ter
t-butyl-4-methoxyphenol and 3-tert-
Mixture with butyl-4-methoxyphenol), plant
Oils, mineral oils, surfactants, fatty acids or their esters
Throw. The above preparation can be used as is or with water
It can be used after dilution,
Spraying or dusting on the plant body, or
Spraying, dusting or dusting on soil surface, or necessary
Depending on the condition, it can be further mixed with soil
Wear. In addition, the above formulation should be treated in a rice nursery box
Can also. Further, the composition of the present invention, other fungicides, insecticides,
Acaricides, nematicides, herbicides, plant growth regulators, fertilizers, etc.
Or with or without a soil conditioner
You can also be. The application rate of the composition of the present invention depends on the active ingredient.
Compound mixing ratio, weather conditions, formulation form, application time, application
It depends on the method, application place, target disease, target crop, etc.
However, the total amount of the active ingredient compound is 1 atm.
0.1 to 1000 g, preferably 1 to 100 g
Emulsions, wettable powders, suspensions, liquids, etc. are diluted with water
When applied, the application concentration depends on the sum of the active ingredient compounds.
The amount is usually 0.0001 to 1%, preferably 0.001 to 1%.
0.1%, granules and powders should not be diluted at all.
Apply as is. When processing rice seedling boxes,
Nursery box (30cmX60cm) per total amount of active ingredients
And usually 0.1 to 100 g, preferably 1 to 10 g
is there. [0006] The present invention will be further described in the following formulation examples and test examples.
Although described in detail, the present invention is limited to only these examples.
Not something. In addition, the part indicating the use ratio of the formulation examples and
% And% are parts by weight and% by weight unless otherwise specified.
You. The amide compound represented by the general formula 2 was tested.
Is shown by the compound numbers in Table 1. Formulation Example 1 1 part of each of compounds (1) to (5), 2 parts of compound A,
88 parts of Olinclay and 9 parts of talc are pulverized and mixed well
To obtain each 3% powder. Formulation Example 2 1.5 parts of each of compounds (1) to (5), compound A2.5
Parts, 87 parts kaolin clay and 9 parts talc
Mix to obtain each 4% powder. Formulation Example 3 10 parts of each of compounds (1) to (5), compound A 10
Part, polyoxyethylene sorbitan monooleate 3
Parts, 3 parts of CMC (carboxymethylcellulose) and
Mix 74 parts of water, wet-pulverize, each 20% suspending agent
Get. Formulation Example 4 10 parts of each of compounds (1) to (5), compound A 20
Parts, calcium lignin sulfonate 3 parts, lauryl sulfate
2 parts of sodium and 65 parts of synthetic silicon hydroxide are pulverized well
Mix to obtain each 30% wettable powder. Formulation Example 5 20 parts of each of compounds (1) to (5), compound A30
Parts, calcium lignin sulfonate 3 parts, lauryl sulfate
2 parts of sodium and 45 parts of synthetic silicon hydroxide are pulverized well
Mix to obtain each 50% wettable powder. Formulation Example 6 10 parts of each of compounds (1) to (5), compound A 20
Part, polyoxyethylene styryl phenyl ether 14
Part, calcium dodecylbenzenesulfonate 6 parts,
Mix well 50 parts of silene to obtain 30% emulsion of each.
You. Formulation Example 7 1 part of each of compounds (1) to (5), 8 parts of compound A,
1 part of hydrous silicon oxide, calcium lignin sulfonate 2
Parts, 30 parts of bentonite and 57 parts of kaolin clay
After crushing and mixing well, adding water and kneading well, granulation
Dry to obtain each 10% granule. Formulation Example 8 1.5 parts of each of compounds (1) to (5), compound A 5
Parts, synthetic hydrous silicon oxide 1.5 parts, lignin sulfonic acid
2 parts of Lucium, 30 parts of bentonite and Kaolinkure
-60 parts are crushed and mixed well, water is added and kneaded well
After that, the mixture is granulated and dried to obtain each 6.5% granule. Compound
Each of the objects (3) and (4) is, for example,
Therefore, it can be formulated. Reference preparation example 1 One part of compound (3) or (4), Khao Link
90 parts of laye and 9 parts of talc are crushed and mixed well, and
To give a 1% powder. Reference preparation example 2 10 parts of either compound (3) or (4), polyoxo
3 parts of ethylene sorbitan monooleate, 3 parts of CMC
And 84 parts of water are mixed and wet-pulverized, and 10% of each
Obtain a suspension. Reference preparation example 3 20 parts of either compound (3) or (4), lignin
3 parts calcium sulfonate, sodium lauryl sulfate 2
Parts and 75 parts of synthetic silicon hydroxide, pulverized and mixed well, and
Each 20% wettable powder is obtained. Reference preparation example 4 15 parts of compound (3) or (4),
14 parts of ethylene styryl phenyl ether, dodecyl
6 parts of calcium benzenesulfonate and 6 parts of xylene
Mix well 5 parts to obtain each 15% emulsion. Reference preparation example 5 4 parts of either compound (3) or (4), synthetic hydrous acid
1 part of silicon halide, 2 parts of calcium ligninsulfonate, ben
30 parts of tonite and 63 parts of kaolin clay are crushed well
After mixing, adding water and kneading well, granulate and dry.
To obtain each 4% granule. Other compounds (1),
Each of (2), (5) and A is also referred to
It can be formulated according to the formulation examples. Next, the composition of the present invention is represented by the following general formula (a):
Each of the amide derivative represented by
Has a synergistically superior agricultural and horticultural germicidal effect than when used.
This is shown in a test example. Test example 1 Preventive effect test for rice blast Fill plastic pots with sandy loam and rice (Kinki 33
No. 2) and cultivated in a greenhouse for 20 days. Formulation Example 4
Dilute the reagent in the form of a wettable powder with water to the specified concentration.
So that it adheres well to the leaves of the rice seedlings
Foliage was sprayed. After air-drying, the spore suspension of the blast fungus
Spray inoculated. After inoculation, keep at 24 ° C under high humidity for 10 days,
The control effect was investigated with the following control index. Table 2 shows the results. [Table 2]Test Example 2 Water Treatment for Rice Blast
Preventive effect test 1 / 10,000 are Wagner pot filled with sandy loam
After transplanting rice, transplant the rice (Kinki 33) of the 2 leaf stage,
Grow indoors for 7 days. Thereafter, the granules were prepared according to Formulation Example 7.
Each pot was treated with water on each pot. 7 days after processing
Was spray-inoculated with a spore suspension of the blast fungus. After inoculation,
Keep at 24 ° C and high humidity for 10 days, and control according to Test Example 1.
The fruits were investigated by control index. Table 3 shows the results. [Table 3][0009] Test Example 3 Water surface treatment for rice sheath blight
Protection effect test 1 / 10,000 are Wagner pot filled with sandy loam
After watering, transplant the rice (Kinki No. 33) of the 2 leaf stage, greenhouse
Grew up within 7 days. Then, according to Formulation Example 7, granules
Each of the test reagents was subjected to a water surface treatment on each pot. 7 days after processing
Then, the sclerotium of the sheath blight fungus was inoculated into the strain base. 27 after inoculation
Keep at high temperature and high humidity for 10 days.
The control index was used. Table 4 shows the results. [Table 4]Reference Production Example 1 (Production of Compound (3)) 23 g of commercially available 4-bromo-2-chlorobenzoic acid (97.7 mm
ol) in 50 ml of thionyl chloride and N, N'-dimethylform
One to two drops of muamide were added, and the mixture was heated under reflux for 4 hours. Chloride
Onyl was distilled off under reduced pressure to give 4-bromo-2-chlorobenzoyi.
There was obtained the chloride. To this is added 100 ml of anhydrous THF.
And cooled to -78 ° C.
Of a 1MTHF solution (0.1 mol) was added dropwise. reaction
The temperature was returned to room temperature, and the mixture was stirred for 3 hours. 10% hydrochloric acid 10
After adding 0 ml and stirring for 10 minutes, ethyl acetate was added,
It was washed sequentially with a sodium hydroxide solution and a saline solution. Acetic acid
The ethyl layer was dried over anhydrous magnesium sulfate and concentrated.
And the resulting crude product is chromatographed on silica gel.
(Hexane: ethyl acetate = 10: 1), 4′-bromo
19.2 g of -2'-chloroacetophenone was obtained. like this
4'-bromo-2'-chloroacetophenone obtained by
Add 1.44 g of formic acid and 14.30 g of formamide to 19.2 g
And stirred at 180 to 190 ° C. for 6 hours. Cool the reaction solution
Then, chloroform was added, and the mixture was washed with saline. Black
The roform layer was dried over anhydrous magnesium sulfate and concentrated.
And a residue was obtained. 10 ml of concentrated hydrochloric acid was added thereto, and 10
Stirred at 0 ° C. for 1 hour. The reaction solution was cooled and
The crystals were separated by filtration and washed with chloroform (chloroform layer).
Was discarded). Dissolve the crystals in the aqueous layer of the filtrate, and add
After adding sodium hydroxide solution to make it alkaline,
Extracted with loroform. Chloroform layer with anhydrous magnesium sulfate
After drying with cesium, the mixture was concentrated and 1- (4-bromo-2)
8.34 g of -chlorophenyl) ethylamine were obtained. 2-shi
1.0 g of ano-3,3-dimethylbutanoic acid was added to anhydrous
Dissolve in drofuran and carbonyl at 0 ° C under nitrogen atmosphere
1.38 g of diimidazole were added. Return the reaction temperature to room temperature
And stirred for 1 hour. There, 1- obtained as described above
(4-bromo-2-chlorophenyl) ethylamine 1.83
g of tetrahydrofuran solution at room temperature.
For 3 hours. Ethyl acetate was added to the reaction solution, and 1N
With aqueous sodium hydroxide, 1N hydrochloric acid and saturated saline
Washed sequentially. Dry the organic layer over anhydrous magnesium sulfate
After that, the mixture was concentrated and the crude product was washed with hexane to give N- [1
-(4-Bromo-2-chlorophenyl) ethyl] -2-
Cyano-3,3-dimethylbutanoic acid amide (compound
(3)) 1.40 g was obtained. mp 161.0 ° C 'H-NMR (CDCl_Three/ TMS) δ (ppm): 1.
14 and 1.18 (each s, 9H in total), 1.51 and 1.52
(D, J = 6.99 Hz, 9H in total), 3.14 and 3.
16 (each s, total 1H), 5.28-5.39 (m, 1
H), 6.37-6.49 (br, 1H), 7.20 (dd, J = 8.
31 Hz, J = 1.67 Hz, 1H), 7.40 (dd, J = 8.31)
Hz, J = 1.97 Hz, 1H), 7.54 to 7.55 (m, 1H) Reference Production Example 2 (Production of Compound (4)) 1.0 g of 2-cyano-3,3-dimethyl-4-pentenoic acid
Was dissolved in anhydrous tetrahydrofuran, and the solution was dissolved at 0 ° C. in a nitrogen atmosphere.
Then, 1.27 g of carbonyldiimidazole was added. Reaction temperature
The temperature was returned to room temperature and stirred for 1 hour. There reference production example 1
1- (4-Bromo-2-chloropheny) obtained in the first half of
L) Ethylamine 1.68 g in tetrahydrofuran solution
The mixture was added dropwise at the same temperature and stirred at the same temperature for 3 hours. Vinegar in the reaction solution
Ethyl acid, 1N aqueous sodium hydroxide, 1N salt
The extract was washed sequentially with an acid and a saturated saline solution. Organic layer is sulfuric anhydride
After drying over magnesium, and concentrating, the obtained crude product was obtained.
Was washed with hexane to give N- [1- (4-bromo-2-).
Chlorophenyl) ethyl] -2-cyano-3,3-dimethyl
1.05 g of tyl-4-pentenoic acid amide (compound (4))
Obtained. mp 158.0 ° C 'H-NMR (CDCl_Three/ TMS) δ (ppm): 1.
23-1.29 (m, 6H), 1.48 and 1.50 (d, J =
6.88Hz, 3H in total, 3.23 and 3.25 (s each, total)
  1H), 5.10 to 5.23 (m, 2H), 5.30 (q, J = 6.
00Hz, 1H), 5.88-6.00 (m, 1H), 6.22-6.35
(Br, 1H), 7.18 (d, J = 8.30 Hz, 1H), 7.
39 (dd, J = 8.30 Hz, J = 0.65 Hz, 1H), 7.53
7.57.54 (m, 1H) [0013] Industrial Applicability The composition of the present invention has excellent protection against plant diseases.
It has the effect of removing.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Tsutohiro Kato 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. (56) Reference JP-A 8-27090 (JP, A) JP JP-A-2-264765 (JP, A) JP-A-7-126112 (JP, A) JP-A-7-157404 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 37 / 34 107 A01N 37/34 108 A01N 43/54

Claims (1)

(57) [Claims] [Claim 1] (a) General formula (1) (Wherein X represents a hydrogen atom or a chlorine atom, Y represents a chlorine atom or a bromine atom, and R represents a methyl group or a vinyl group), and (b)
Methyl (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-
A fungicidal composition for agricultural and horticultural use, comprising methoxy acrylate as an active ingredient.