JPS6351305A - Synergistic fungicidal composition - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides substituted carboxyamidothiazoles consisting of (^) and (B) imidazoles, triazoles, guanadines, halonitrobenzenes, manganese and zinc salts of ethylene-bis(dithiocarbamate), A synergistic fungicidal composition comprising one or more compounds selected from the group consisting of pyrimidines, dicarboxamides, pyrrolidines and thiurams. In another aspect, the present invention relates to a method of protecting plants from fungal diseases, comprising treating the plants with a fungicide-effective amount of the composition.

The need for effective protection of plants against fungal diseases does not need to be discussed in detail, as the consequences of such fungal attacks are
Well proven. However, in the past, many effective disinfectants were mercury-based and therefore toxic to warm-blooded animals.

Accordingly, several non-mercury-based fungicides have been developed. Thus, for example, the phono Schmeling (
Von Schmeling et al. U.S. Patent No. 3.5
No. 05.055 describes carboxyamidothiazoles which are effective fungicides.

Similarly, U.S. Pat. No. 3,658,813 to Godefroy et al. describes bactericidal 1-[betaaryl-beta(R-oxy)-ethylcoimidazoles, while British Patent No. 1,522. No. 657 discloses dioxolane-substituted triazoles that exhibit fungicidal activity. Sarrett et al.
No. 3,017,415 discloses thiazolylbenzimidazoles that act as anthelmintics.

The above compounds, when used alone, act admirably as fungicides; U.S. Patent No. 3,505.
No. 055 and others are closely similar compounds), surprisingly, the effect of such a combination is greater than that expected from the simple addition of the compounds alone. It turns out.

In one aspect, the present invention provides compounds of the formula: (A) wherein R and R are the same or different and are hydrogen or C-C alkyl; and (B) imidazoles. , triazoles, guanadines, halonitrobenzenes, manganese and zinc salts of ethylene-bis(dithiocarbamate), pyrimidines,
The present invention relates to a disinfectant composition containing one or more compounds selected from the group consisting of dicarboxamides, pyrrolidines, and thiurams.

In another aspect, the invention provides a fungicidally effective amount of a compound of the formula: (A) wherein R and R are the same or different and are hydrogen or C-C alkyl. , and (B) imidazoles, triazoles, guanadines, halonitrobenzenes, manganese and zinc salts of ethylene-bis(dithiocarbamate), pyrimidines,
The present invention relates to a method for protecting plants from fungal diseases, which comprises applying to plants a composition containing one or more compounds selected from the group consisting of dicarboxamides, pyrrolidines, and thiurams.

The carboxyamidothiazoles used in the present invention are:
as described in or similar to U.S. Pat. No. 3,505,055 and of the formula: ) is a compound.

More preferably, R and R1 are each independently hydrogen or C-
It is C4 alkyl. Most preferably R and R1 are both methyl.

imidazoles constituting component (8) of the composition of the present invention,
Triazoles, guanadines, halonitrobenzenes, manganese and zinc salts of ethylene-bis(dithiocarbamate), pyrimidines, dicarboxamides, or thiurams are all known compounds with fungicidal activity.

Typical imidazoles used are 1-C
2-<2.4-dichlorophenyl)-2-(2=propenyloxy)ethyl E-1H-imidazole, 1-N-
Propyl-N-[2-(2゜4.6-drichlorophenoxy)ethyl]carbamoylimidazole, 1-[(
2-[4-<4-promophenoxy)phenyl]-1,
3-oxadiolan-2-yl)methyl]-1H-imidazole, 1-[(2-[4-fluorophenyl]-1゜3-oxathiolan-2-yl〉methyl J-1) 1-imidazole, and 2- (4-thiazolyl)-1-benzimidazole. Typical triazoles used include 1-[[2-(2,4-dichlorophenyl)-4-ethyl-1°3-dioxolan-2-ylcomethyl]-1H-1,2,4-triazole; 1-
[[2-<1゜1'-biphenyl-4-yl)-1,3
-oxathiolane-2-ylcomethyl]-11-1-1
,2゜4-triazole, 1-[[2-(4-fluorophenyl)-1,3-oxathiolan-2-ylcomethyl]-1H-1,2,4-triazole, 1-[2-(
4-Phenoxyphenylcin-1,3-dithiolane-2
-ylcomethyl]-11-1-1゜2.4-1-lyazole, 1-[(2-[[(1゜1'-biphenyl)-
4-ylco1,3-1,3-dithian-2-yl]methyl]-1H-1,2,4-triazole, 1-[[2
-[2-(1-,methylethoxy)phenyl]-1,3
-oxathiolane~2-yl1methyl] -1H-1,
2,4-triazole, 4-chloro-benzyl N-(2
,4-dichlorophenyl)-'2-(1,2,4-triazol-1-yl)ethanethioimidate and 2.
4'-difluoro-alpha-(1-1,2°4-triazol-1-ylmethyl)benzdihydryl alcohol.

Typical guanadines used are 1゜1'-
Iminobis(octamethylene)diguanadine, and a representative of the halonitrobenzenes used is pentachloronitrobenzene.

Component (B) of the composition of the invention comprises a manganese, zinc or mixed manganese-zinc salt of ethylene-bis(dithiocarbamate).

Typical pyrimidines used are 5-butyl-2-ethylamino-6-methyl-4-(3H)-pyrimidinone and alpha-(2-chlorophenyl)-alpha-(4-fluorophenyl)-5. -pyrimidine methanol. A typical dicarboxamide used is 3-(3,5-dichlorophenyl)-N-
(1-methylethyl)-2,4-dioxo-1-imidazolidinecarboxamide, while tetramethylthiuram is a typical example of the thiurams used.

Typical pyrrolidines used are 1-(3
,5-dichlorophenyl)-3-methoxymethyl-2,
5-pyrrolidinedione.

In general, component (A) present in the compositions of the invention (i.e.
The weight ratio of carboxyamidothiazole) to component (B) is preferably between about 1:5 and about 500:1. Typically, the weighting is generally more preferably from about 1:2 to
It is between about 200:1.

When component (8) is 1-[2-<2.4-dichlorophenyl)-2-(propenyloxy)ethyl]-1-imidazole or 2-(4-thiazolyl)-1-benzimidazole, Most preferably, the weight ratio of component (A) to component (B) is from about 5=1 to about 75:1. Component (8) is 1-[[2-(2,4-dichlorophenyl)
-4-ethyl-1゜3-dioxolan-2-ylcomethyl]-1H-1,2,4-triazole,
Most preferably, the weight ratio of component (A) to component (B) is from about 25:1 to about 375:1. Component (8) is 4-chlorobenzyl N-(2,4-dichlorophenyl)-2-
When (1,2,4-triazol-1-yl)ethanethioimidate, most preferably the weight ratio of component (A) to component (B) is from about 1:2 to about 10:1. . The most preferred weight ratios for a particular combination of components (8) and (8) are readily determined by one skilled in the art using routine experimentation.

The compositions of the invention may further comprise one or more carrier materials such as talc, kaolin, bentonite and baryters, as well as binders such as spindle oil, ethylene glycol and polyvinyl acetate. The composition may also include commonly used pigments such as iron oxide, lupine toner, titanium dioxide, and the like.

The compositions of the present invention are formulated as a powder by mixing together all dry ingredients, including the carrier and additives, until a homogeneous mixture is formed.

The fixing agent is then added and the whole is mixed again until the mixture is essentially homogeneous.

In the case of liquid formulations, organic solvents such as xylene, dimethylformamide, ethylene glycol, methanol and cyclohexane can be used as diluents, and surfactants such as calcium dodecylbenzenesulfonate, polyglycol ethers and acrylic (such as polyether alcohols) and dyes (such as rhodamine, methylviolet and the like).

Additionally, the compositions of the present invention may contain insecticides such as linguine (Li).
fenced chlorine compounds, such as diazinon, isazophos,
fos), Thiophanox (Th1oranox)
and one or more additional compounds, such as organophosphate esters, such as Carbofuran, Hercaptodimethar, Bendiocarb, and the like.
a, as well as anthraquinone, thioanthraquinone, Bcnzathrone, Chiram (
2iram) and diphenylguanidine.

The method of the invention consists of applying the fungicidal efficacy of the composition of the invention to plants.

Although the composition may be applied to any part of the plant to be protected, the composition is particularly effective when used as a seed dressing.

When used as a seed dressing, preferably from about 5 grams to about 100 grams of the composition is applied to each 100 kilograms of seed. More preferably, the composition is applied at a rate of about 10 grams to about 50 grams per 100 kilograms of seed.

The synergistic fungicidal control exhibited by the compositions of the present invention is demonstrated only when a limited number of fungicides are used; It should be understood that it is not possible to have a synergistic effect when used in a culm where essentially complete control can be expected. The essence of the invention is that less fungicide is required to obtain a given control.

As shown in the Examples below, the compositions of the invention exhibit unexpectedly enhanced, ie synergistic, activity over a mere cumulative effect.

The compositions and methods of the invention may be used, for example, with Calonect cari.
es), Ustilag.

graminis) and similar species, and are useful for controlling a broad spectrum of fungi such as (C.
It shows a high degree of activity against any seed pathogens such as Ochliobolus 5avitus) and similar ones.

Furthermore, the compositions of the present invention are well suited for agricultural, horticultural and forestry applications because they are much less toxic to phlebotomy animals than mercury-based fungicides.

EXAMPLE 1 The following examples are intended to further illustrate the invention and are not intended to limit the scope of the invention.

Examples 1-9 In these examples, the seed treatment method was
H, ), Frohbeyer,
P.

F,), Reinhard (Re1nhard, If,
) and Roder (1974)
“Preliminary Guidelines for Testing Seed Dressings against Cereal Diseases”
guide 1ines f'or thetesti
ng of 5eed dressings agai
'39
March 1974, BBA, Hessevegl 1 /
12, 3300 B published by Braunschweig.
It was performed according to BA Guideline 4-1.1 (March 1974). In this example, the following abbreviations represent the compounds shown below.

DMCI=2.4-dimethyl-5-carboxyanilidethiazole DCPI=1-[2-(2,4-dichlorophenyl)
-2-(2-propenyloxy)ethyl]-1-imidazoleTBIA=2-(4-thiazolyl)-1-benzimidazoleDCDT=1-[[2-(2,4-dichlorophenyl)
A wettable powder formulation was prepared using the following ingredients (all parts by weight: -4-ethyl-1,3-dioxolan-2-yl]methyl]-1dan-1,2,4-triazole).

DM (175,0 Surfactant (-14,1 0-Damine dye 3500 0.5 Ethylene glycol 3.0 Dixy-clay 17.4 (Umbrella) Alkylnaphthalene sulfone potassium gold salt:
A combination of poly(ethylene oxide and propylene oxide).

Additional formulations were made by dissolving component (8) fungicide in dimethylformamide at various concentrations shown below. (Each formulation similarly contains 058% rhodamine dye 3
Contains 500. ) Fungicide 81 degrees DCPI 0.5 TBIA 0.5 DCDT 0.1 Spring wheat (cv. Timmo) was applied to wheat seeds at 2 g/g.
Tilleti at the rate of spores of g
acaries) was artificially infected with dried spores. The infected wheat seeds were treated with various formulations as summarized in Table 1 below. This treatment consists of diluting the above formulation with water and deVilbiss
[Trademark] Consists of spraying a fine mist of the specific dilution formulation used on the infected seeds using a compressed air-driven spray gun, followed by shaking the seeds and drug in a bottle for 5 minutes.

Seed infected and treated as described above was harvested using a tractor-mounted Oyjord seed drill.
Seecl Drill) was used to drill holes in open ground on clay loam soil types. The size of the ground was quadrupled to 1.6 meters x 5 meters, and all treatments were completely irregular.

Evaluation of fungicidal efficacy was carried out by taking 100 randomly selected heads per field and examining them for disease, thus determining the % control of infection.

The results of such tests are summarized in the schedule below.

Using the treatment recipes and methods described in Experiments A-I above, several experiments were conducted using mixtures of compounds as summarized in Table 1 below. Colpy (S, R, C
``Calculating Synergistic and Reciprocal Responses of Herbicide Combinations''
stic and antagonistic Re5
ponces ortlerbicide C0Ill
binatiOnS″)” WeedS 1
5, pp. 20-22 (1967), the expected control percentage was calculated for each experiment using the results of experiments A-I using the formula developed by Mt.
Introduce it to i.

This Colby equation can be summarized as follows.

If X = % growth inhibition by herbicide A at pbond/Δ, and Y = % growth inhibition by herbicide A at Qbond/A, and E = % growth by herbicide A+8 at p+Qbond/A. When it is suppression, E = X + Y - XY/100.

When the observed response is greater than expected, the combination is synergistic; when it is less than expected, it is reciprocal. If the observed response is equal to the expected one, the combination is cumulative.

The predicted and actual control % for each experiment are
Display in table.

3456- DMCI 37.5 37.5 75 75 3
7.5 37.5DCPI i 5 1
5TBIA -13 DCDT -- Control: Expected % 60.5 62.4 95.3 95.5 5
9.5 60.5 Actual measurement% 69 g5.7 100
97.6 81 7L4 Example NQ Cor Top
- DCMI 37.5 37.5 37.5DCPI
- TBIA 5 DCDT -0,20,6 Control i1: Expected % 74.9 88.4 97.1 Actual % 92.
9 100 100 The data in Table 1 are clear indicators of the synergistic fungicidal effect exhibited by the compositions of the present invention in which component (8) is an imidazole or triazole.

The effectiveness of some of the compositions of the present invention in controlling was measured in the following manner. F. Wheat seeds infected with n1vale were treated with chemicals at dose 1 shown in Table 1 for seed treatment. For each treatment, 100 seeds were placed between two sheets of water-soaked absorbent paper to provide moisture for seed germination. Absorbent paper was then wrapped loosely to keep the seeds in the wet paper.

The rolled absorbent paper was then placed in a sealable plastic bag with a 5 cm space at the top for proper air exchange.

All treatments were placed in separate bags and placed in a cold room at 5°C for 7 days. The same was done for the untreated control bag. This temperature promoted the development of Fusarium disease. These bags were then removed and transferred to a lighted incubator at 20° C. for an additional 7 hours for further development of Fusarium disease. At the end of this period, by counting the number of infected seedlings from each treatment and tabulating the % diseased seedlings,
Control effectiveness was measured. These data were compared to those from untreated controls and the % reduction in disease (
% rs> was estimated for each treatment.

Additionally, the theoretical control for each combination was determined using the Colby equation. The results of such tests are summarized in Table II.

Examples 16-19 Using the Fusarium nib test used in Examples 10-17, 2,4-dimethyl-5-carboxyanilide thiazole (DMCI) and 4-chlorobenzyl N
-(2,4-dichlorophenyl)-2-(1,2,4-
triazol-1-yl)ethanethioimidate (CB
DT) were evaluated for their bactericidal efficacy.

The results of such tests are summarized in Table II.

1tll III observed with DMCI alone is as follows.

Gram DMCI/10 (ly seeds % control 20
71.1 40 94.2 The control observed with CBDT alone is as follows.

Gram CBDT/100 to 9 seeds % control 20
28.8 Table ■16 20 10 71.10
86.517 20 20 7
9.42 94.2+8 40
10 94.20 10019
40 20 95.88 10
0 The above results demonstrate the synergistic effect of the composition comprising DMCI and CBDT.

The above data demonstrate the very superior control exhibited by the compositions of the present invention compared to the control exhibited by either component alone.

Claims (23)

[Claims] (1) (A) Formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R and R^1 are the same or different,
and hydrogen or C_1-C_8 alkyl. ), and (B) a group consisting of imidazoles, triazoles, guanadines, halonitrobenzenes, manganese and zinc salts of ethylene-bis(dithiocarbamate), pyrimidines, dicarboxamides, pyrrolidines, and thiurams. A disinfectant composition containing one or more compounds selected from: (2) The disinfectant composition according to item 1 above, wherein R and R^1 are hydrogen or C_1-C_8 alkyl. (3) The fungicide composition according to item 2 above, wherein R and R^1 are methyl. (4) The weight ratio of compound (A) to compound (B) is about 1:
5 to about 500:1. (5) The weight ratio of compound (A) to compound (B) is about 1:
5. The fungicidal composition of paragraph 4 above, wherein the ratio is from 2 to about 200:1. (6) The fungicide composition according to item 1 above, wherein component (B) is imidazole. (7) The imidazole is 1-[2-(2,4-dichlorophenyl)-2-(2-propenyloxy)ethyl]
-1H-imidazole, 1-N-propyl-N-[2-
(2,4,6-trichlorophenoxy)ethyl]carbamoylimidazole, 1-[(2-[4-(4-promophenoxy)phenyl]-1,3-oxathiolane-2
-yl)methyl]-1H-imidazole, 1-[(2-
[4-fluorophenyl]-1,3-oxathiolane-
2-yl)methyl]-1H-imidazole and 2-(4
-thiazolyl)-1H-benzimidazole. (8) The fungicide composition according to item 1 above, wherein component (B) is a triazole. (9) The triazole is 1-[[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolane-
2-yl]methyl]-1H-1,2,4-triazole, 1-[[2-(1,1'-biphenyl-4-yl)-
1,3-oxathiolan-2-yl]methyl]-1H-
1,2,4-triazole, 1-[[2-(4-fluorophenyl)-1,3-oxathiolan-2-yl]methyl]-1H-1,2,4-triazole, 1-[[2
-(4-phenoxyphenyl)-1,3-dithiolane-
2-yl]methyl]-1H-1,2,4-triazole, 1-[2-[[(1,1'-biphenyl)-4-yl]-1,3-dithian-2-yl]methyl] -1H-1
, 2,4-triazole, 1-[[2-[2-(1-methylethoxy)phenyl]-1,3-oxathiolane-
2-yl]methyl]-1H-1,2,4-triazole, 4-chlorobenzyl N-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)ethanethioimidate and 2,4′-difluoro-alpha-(1H-1,2,4-triazol-1-ylmethyl)benzhydryl alcohol,
The fungicide composition according to item 8 above. (10) The fungicide composition according to item 1 above, wherein component (B) is guanadine. (11) The fungicide composition according to item 10 above, wherein the guanadine is 1,1'-iminobis(octamethylene)diguanazine. (12) The disinfectant composition according to item 1 above, wherein component (8) is halonitrobenzene. (13) The disinfectant composition according to item 12 above, wherein the halonitrobenzene is pentachloronitrobenzene. (14) The disinfectant composition according to item 1 above, wherein component (B) is a manganese, zinc or mixed manganese-zinc salt of ethylene-bis(dithiocarbamate). (15) The fungicide composition according to item 1 above, wherein component (B) is pyrimidine. (16) The pyrimidine is selected from 5-butyl-2-ethylamino-6-methyl-4-(3H)-pyrimidinone and alpha-(2-chlorophenyl)-alpha-(4-fluorophenyl)-5-pyrimidinemethanol. 16. The fungicide composition according to item 15 above, which is selected from the group consisting of: (17) The fungicide composition according to item 1 above, wherein component (B) is dicarboxamide. (18) The dicarboxamide is 3-(3,5-dichlorophenyl)-N-(1-methylethyl)-2,4-
The fungicide composition according to item 17 above, which is dioxo-1-imidazolidinecarboxamide. (19) The fungicide composition according to item 1 above, wherein component (B) is thiuram. (20) the thiuram is tetramethylthiuram,
The fungicide composition according to item 19 above. (21) The fungicide composition according to item 1 above, wherein component (8) is pyrrolidine. (22) The fungicide composition according to item 21 above, wherein the pyrrolidine is 1-(3,5-dichlorophenyl)-1-methoxymethyl-2,4-pyrrolidinedione. (23) Effective amount as a disinfectant, (A) Formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R and R^1 are the same or different,
and hydrogen or C_1-C_8 alkyl. ), and (B) from the group consisting of imidazoles, triazoles, guanadines, halonitrobenzenes, manganese and zinc salts of ethylene-bis(dithiocarbamate), pyrimidines, dicarboxamides, pyrrolidines and thiurams. A method of protecting plants from fungal diseases, comprising applying to the plants a composition containing one or more selected compounds.