USH811H - Biocidal composition - Google Patents
Biocidal composition Download PDFInfo
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- USH811H USH811H US07/322,460 US32246089A USH811H US H811 H USH811 H US H811H US 32246089 A US32246089 A US 32246089A US H811 H USH811 H US H811H
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
Definitions
- This invention relates to a biocidal composition containing as active ingredients at least one imidazole compound of formula (I) shown below and at least one other specific compound.
- imidazole compounds of formula (I) shown below are useful as a biocide for controlling harmful organisms, which were found by the inventors of the present invention as described in European Patent 298,196A.
- the present invention relates to a biocidal composition for controlling harmful organisms containing, as active ingredients, at least one imidazole compound represented by formula (I): ##STR2## wherein R 1 represents a phenyl group, a halogen-substituted phenyl group, an alkyl group, or a halogen-substituted alkyl group; and Rz represents a halogen atom, and at least one compound selected from the group consisting of azole compounds, quinoxaline compounds, dithiocarbamate compounds, organic chlorine compounds, benzimidazole compounds, pyridinamine compounds, cyanoacetamide compounds, phenylamide compounds, sulfenic acid compounds, copper compounds, isoxazole compounds, organophosphorus compounds, N-halogenothioalkyl compounds, dicarboximide compounds, benzanilide compounds, benzamide compounds, piperazine compounds, pyridine compounds, pyrimidine compounds, piperidine compounds, morpho
- the halogen atom includes fluorine, chlorine, bromine, and iodine atoms.
- the alkyl group contains from 1 to 4 carbon atoms and mention may be made of, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, etc.
- a biocidal composition wherein the compound which is used in admixture with the imidazole compounds represented by formula (I) is at least one compound selected from the group consisting of azole compounds, quinoxaline compounds, dithiocarbamate compounds, organic chlorine compounds, benzimidazole compounds, pyridinamine compounds, cyanoacetamide compounds, phenylamide compounds, sulfenic acid compounds, copper compounds, isoxazole compounds, organophosphorus compounds, dicarboximide compounds, benzanilide compounds, and benzamide compounds.
- a biocidal composition wherein the imidazole compound is represented by formula (I'): ##STR3## wherein R 1 ' represents a phenyl group or a halogen-substituted alkyl group; and R 2 ' represents a chlorine atom.
- a biocidal composition whose main use is for a fungicide.
- the imidazole compounds represented by formula (I) include compounds represented by formula (I-a) and/or compounds represented by formula (I-b): ##STR4##
- JP-A as used herein means a "published unexamined patent application”.
- the imidazole compounds represented by formula (I) can be prepared, for example, by the following reaction schemes. ##STR6## wherein Z represents a hydrogen atom, a chlorine atom, or a bromine atom; Y represents a chlorine atom, a fluorine atom, a bromine atom, or an iodine atom; Y' represents a chlorine atom, a bromine atom, or an iodine atom; and R 1 is as defined above. ##STR7## wherein Y, R 1 , and R 2 are as defined above.
- Step 1 of process A and Process B are carried out, if desired, in the presence of a solvent and an acid acceptor.
- the solvent which can be used includes aromatic hydrocarbons, e.g., benzene, toluene, xylene, chlorobenzene, etc.; cyclic or acyclic aliphatic hydrocarbons, e.g., chloroform, carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, n-hexane, cyclohexane, etc.; ethers, e.g., diethyl ether, dioxane, tetrahydrofuran, etc.; ketones, e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; nitriles, e.g., acetonitrile, propionitrile, etc.; and aprotic polar solvents, e.g., dimethylformamide, N-methylpyrrolidone, dimethyl sul
- the acid acceptor which can be used includes inorganic bases such as alkali metal hydroxides, e.g., sodium hydroxide and potassium hydroxide, alkali metal or alkaline earth metal carbonates, e.g., anhydrous potassium carbonate and anhydrous calcium carbonate, alkali metal hydrides, e.g., sodium hydride, and alkali metals, e.g., metallic sodium; and organic basis, e.g., triethylamine.
- inorganic bases such as alkali metal hydroxides, e.g., sodium hydroxide and potassium hydroxide, alkali metal or alkaline earth metal carbonates, e.g., anhydrous potassium carbonate and anhydrous calcium carbonate, alkali metal hydrides, e.g., sodium hydride, and alkali metals, e.g., metallic sodium; and organic basis, e.g., triethylamine.
- Step 1 of Process A and Process B can be effected in the presence of an appropriate catalyst, such as a phase transfer catalyst (e.g., quaternary ammonium salt derivatives).
- a phase transfer catalyst e.g., quaternary ammonium salt derivatives
- the compound of formula (II) includes tautomers represented by the following formulae: ##STR9## wherein R 1 and R 2 are as defined above.
- reaction mixture was poured into water and extracted with methylene chloride.
- the extract was washed with water and dried over anhydrous sodium sulfate.
- the solvent was removed by distillation, and the residue was purified by silica gel column chromatography using methylene chloride as a developing solvent to obtain 28.0 g of 2-cyano-1-dimethylsulfamoylimidazole having a melting point of from 74 to 76° C.
- reaction mixture was poured into water and extracted with 500 ml of ethyl acetate.
- the ethyl acetate layer was washed with water and dried over anhydrous sodium sulfate.
- the ethyl acetate was removed by distillation, and the residue was purified by silica gel column chromatography using methylene chloride as a developing solvent and separated to give 4.8 g of 2-cyano-1-dimethylsulfamoyl-5-n-propylimidazole having a melting point of from 51 to 52° C.
- the acetonitrile was removed by distillation from the reaction mixture. After pouring 100 ml of water into the residue, the resulting mixture was extracted with 50 ml of methylene chloride. The extract was washed with water and dried over anhydrous sodium sulfate. The methylene chloride was removed by distillation, and the residue was allowed to stand overnight at room temperature. The analysis of the residue revealed that one of the two isomers in the mixture decomposed and returned to the starting 4(5)-chloro-2-cyano-5(4)-n-propylimidazole.
- reaction mixture was poured into water and extracted with chloroform. After washing with water, the extracted layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: methylene chloride) to give 1.28 g of 4(5)-chloro-2-cyano-5(4)-phenylimidazole having a melting point of from 149° to 151° C.
- reaction mixture was poured into water and extracted with ethyl acetate. After washing with water, the extracted layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was then purified by silica gel column chromatography (developing solvent: methylene chloride) to give 0.5 g of 4(5)-chloro-2-cyano-1-dimethylsulfamoyl-5(4)phenylimidazole having a melting point of from 106° to 109° C.
- the compound described above was found to be an isomeric mixture of 4-chloro-2-cyano-1-dimethylsulfamoyl-5-phenylimidazole and 5-chloro-2-cyano-1-dimethylsulfa- moyl-4-phenylimidazole in almost equal ratios.
- biocidal compositions according to the present invention comprising the imidazole compound of formula (I) in combination with other specific compound, are particularly useful as agricultural fungicides. Specifically, they exhibit excellent effects of controlling diseases of crop plants such as rice blast caused by Pyricularia oryzae, rice sheath blight caused by Rhizoctonia solani, cucumber anthracnose caused by Colletotrichum lagenarium, cucumber powdery mildew caused by Sphaerotheca fuliginea, cucumber downy mildew caused by Pseudoperonospora cubensis, tomato late blight caused by Phytophthora infestans, tomato early blight caused by Alternaria solani, citrus melanose caused by Diaporthe citri, citrus common green mold caused by Penicillium digitatum, pear scab caused by Venturia nashicola, apple alternaria blotch caused by Alternaria mali, grape downy mildew caused by Plasmopara viticola,
- biocidal compositions of the present invention exhibit excellent effects of controlling diseases such as potato or tomato late blight caused by Phytophthora infestans, cucumber downy mildew caused by Pseudoperonospora cubensis, grape downy mildew caused by Plasmopara viticola, tobacco blue mold caused by Peronospora tabacina; and various soil diseases caused by phycomycetes such as Plasmodiophora, Aphanomyces, Pythium, etc.
- diseases such as potato or tomato late blight caused by Phytophthora infestans, cucumber downy mildew caused by Pseudoperonospora cubensis, grape downy mildew caused by Plasmopara viticola, tobacco blue mold caused by Peronospora tabacina
- various soil diseases caused by phycomycetes such as Plasmodiophora, Aphanomyces, Pythium, etc.
- biocidal compositions of the present invention have a prolonged residual effect so that they exhibit an excellent preventive effect, and also exhibit an excellent curative effect as well. It is therefore possible to control diseases by treatment after infection. In addition, since they possess a systemic activity, it is also possible to control diseases of the stem and leaf by soil treatment.
- biocidal compositions of the present invention show an excellent controlling effect against agriculturally and horticulturally harmful insects such as planthoppers, diamondback moth (Plutella xylostella), green rice leafhopper (Nephotettix cincticeps), adzuki bean weevil (Callosobruchus chinensis), common cutworm (Spodoptera litura), green peach aphid (Myzus persicae), etc.; mites such as twospotted spider mite (Tetranychus urticae), carmine spider mite (Tetranychus cinnabarinus), citrus red mite (Panonychus citri), etc.; and nematodes such as southern root-knot nematode (Meloidogyne incognita), etc.
- the compounds constituting the biocidal composition of the present invention can be formulated into a variety of forms, such as emulsifiable concentrates, dusts, wettable powders, aqueous solutions, granules, suspension concentrates, etc., together with various adjuvants, as in conventional agricultural preparations.
- the imidazole compound of formula (I) and the other specific compound may be mixed and formulated, or each of the compounds may be separately formulated and then mixed together.
- the preparation may be used as such or as diluted with an appropriate diluent, e.g., water, to a predetermined concentration.
- adjuvants examples include carriers, emulsifying agents, suspending agents, dispersing agents, spreaders, penetrating agents, wetting agents, thickeners, stabilizers, etc. These adjuvants can be added appropriately according to necessity.
- the carriers are classified into solid carriers and liquid carriers.
- the solid carriers include animal and vegetable powders, e.g., starch, sugar, cellulose powders, cyclodextrin, activated charcoal, soybean powders, wheat powders, chaff powders, wood powders, fish powders, powdery milk, etc., and mineral powders, e.g., talc, kaolin, bentonite, bentonite-alkylamine complexes, calcium carbonate, calcium sulfate, sodium bicarbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, silica, sulfur powders, etc.
- animal and vegetable powders e.g., starch, sugar, cellulose powders, cyclodextrin, activated charcoal, soybean powders, wheat powders, chaff powders, wood powders, fish powders, powdery milk, etc.
- mineral powders e.g., talc, kaolin, bentonite, bentonite
- the liquid carriers include water, animal and vegetable oils, e.g., soybean oil, cotton seed oil, etc., alcohols, e.g., ethyl alcohol, ethylene glycol, etc., ketones, e.g., acetone, methyl ethyl ketone, etc., ethers, e.g., dioxane, tetrahydrofuran, etc., aliphatic hydrocarbons, e.g., kerosene, lamp oil, liquid paraffin, etc., aromatic hydrocarbons, e.g., xylene, trimethylbenzene, tetramethylbenzene, cyclohexane, solvent naphtha, etc., halogenated hydrocarbons, e.g., chloroform, chlorobenzene, etc., acid amides, e.g., dimethylformamide, etc., esters, e.g., ethyl acetate, fatty acid gly
- a suitable mixing ratio of the imidazole compound of formula (I) and other specific compound usually ranges from 1:300 to 300:1, preferably from 1:100 to 100:1, and more preferably from 1:50 to 5:1, by weight.
- concentration of the biocidal composition of the present invention is hard to specify as it varies depending on the crop to which the composition is applied, the method of application, the preparation form, the dose to be applied, and the like.
- concentrations of the imidazole compound of formula (I) and the specific compound to be combined are from 1 to 1,000 ppm and from 1 to 5,000 ppm, respectively, in the case of foliar treatment, and those in the case of soil treatment are from 10 to 10,000 g/ha and from 10 to 50,000 g/ha, respectively.
- biocidal compositions according to the present invention are hereinafter given for illustrative purposes only but not for limitation.
- Tomato (cultivars: Ponderosa) was cultivated in a polyethylene pot having a diameter of 7.5 cm.
- 10 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration was sprayed over tomato using a spray gun.
- a zoosporangium suspension of fungi of late blight (Phytophthora infestans) was inoculated by spraying.
- Five days after the inoculation an area of lesion on the leaves was investigated, and an index of control was determined according to the following standard. The results obtained are shown in Tables 2-1 through 2-6.
- the controlling effect was determined by visually observing a degree of disease of a test plant and expressed by the following 5 grades of the index of control.
- Test Example 1 A test similar to Test Example 1 was carried out. The degree of disease has visually observed to determine the index of control according to the following standard for evaluation. The results obtained are shown in Tables 3-1 through 3-3.
- Cucumber (cultivars: Suyo) was cultivated in a polyethylene pot having a diameter of 7.5 cm.
- a spore suspension of fungi of downy mildew (Pseudoperonospora cubensis) was inoculated by spraying.
- 10 ml of a solution of each of test compounds adjusted to a predetermined concentration was sprayed over cucumber using a spray gun.
- an area of lesion on the first leaf was visually observed to determine the index of control according to the standard of Test Example 2. The results obtained are shown in Tables 5-1 through 5-3.
- Cucumber (cultivars: Suyo) was cultivated in a polyethylene pot having a diameter of 7.5 cm.
- 10 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration has sprayed over cucumber using a spray gun.
- a mycelial disc having a diameter of 5 mm of fungi of gray mold (Botrytis cinerea) was inoculated on the first leaf.
- Three days after the inoculation a length of lesion was investigated, and an index of control was determined according to the standard of Test Example 2. The results shown in Table 6 were obtained.
- Rice plant (cultivars: Chukyo Asahi) was cultivated in a polyethylene pot having a diameter of 7.5 cm.
- 20 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration was sprayed over rice plant using a spray gun.
- rice straw in which fungi of sheath blight (Rhizoctonia solani) had been previously incubated was set between leaf sheath portions to inoculate.
- a length of lesion was investigated, and an index of control was determined according to the standard of Test Example 2. The results shown in Table 7 were obtained.
- Mycelial disc (agar punching) of preincubated Pythium aphanidermatum was transplanted on potato-dextrose agar medium (PDA medium) containing 100 ppm of streptomycin and a predetermined concentration of each of test compounds. After incubation at 22° C. for 48 hours, a diameter of mycellium was measured. Inhibition of hyphal growth (%) was determined by the following equation. The results shown in Table 8 were obtained. ##EQU1##
- the above components are uniformly mixed to prepare a wettable powder.
- a wettable powder can be prepared in the same manner as in Formulation Example 1, except for replacing Compound No. A-1b with 25 parts by weight of Compound No. A-12b and replacing Compound No. D-3 with 25 parts by weight of Compound No. I-1.
- a wettable powder can be prepared in the same manner as in Formulation Example 1, except for replacing Compound No. D-3 with Compound No. K-1.
- the above components are uniformly mixed to prepare a wettable powder.
- a wettable powder can be prepared in the same manner as in Formulation Example 4, except for replacing Compound No. G-1 with Compound No. F-1.
- a wettable powder can be prepared in the same manner as in Formulation Example 4, except for replacing Compound No. G-1 with Compound No. O1.
- the above components are uniformly mixed to prepare a wettable powder.
- a mixture consisting of the above components is mixed with Compound No. A-1b and Compound No. I-1 at a weight mixing ratio of 8:1:1 to prepare a wettable powder.
- the above components are uniformly mixed to prepare a dust.
- the above components are mixed and finely pulverized to prepare a suspension concentrate.
- a suspension concentrate can be prepared in the same manner as in Formulation Example 14, except for replacing Compound No. D-3 with Compound No. E-2.
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Abstract
A biocidal composition containing, as active ingredients, at least one imidazole compound represented by formula (I): <CHEM> wherein R<1> represents a phenyl group, a halogen-substituted phenyl group, an alkyl group, or a halogen-substituted alkyl group; and R<2> represents a halogen atom, and at least one other specific compound. The combination of the compound represented by formula (I) and other specific compound can produce an unexpected effect in amount required and biocidal spectrum.
Description
This invention relates to a biocidal composition containing as active ingredients at least one imidazole compound of formula (I) shown below and at least one other specific compound.
The imidazole compounds of formula (I) shown below are useful as a biocide for controlling harmful organisms, which were found by the inventors of the present invention as described in European Patent 298,196A.
On the other hand, most of the compounds which are to be combined with the imidazole compounds of formula (I) have already been known to be effective as a fungicide, an insecticide, etc.
The imidazole compounds of formula (I) and many other biocides so far proposed each produces the respective characteristic biocidal effects on the respective objects. Some of them exert insufficient biocidal effects on specific harmful organisms, or some of them produce slightly inferior curative effects as compared with their preventive effects, or some of them are relatively short in their residual effect. Hence, the biocidal effects exhibited by these biocides on harmful organisms are sometimes unsatisfactory for practical utility depending on the occasion of application.
In the light of the above-described problem, the inventors of the present invention have conducted extensive investigations and, as a result, it has now been found that a combination of the imidazole compound represented by formula (I) shown below and other specific biocidal compound brings about unexpected results such as reduced amount of each compound to be used and enlarged biocidal spectrum of each compound as compared with the use of each compound alone.
The present invention relates to a biocidal composition for controlling harmful organisms containing, as active ingredients, at least one imidazole compound represented by formula (I): ##STR2## wherein R1 represents a phenyl group, a halogen-substituted phenyl group, an alkyl group, or a halogen-substituted alkyl group; and Rz represents a halogen atom, and at least one compound selected from the group consisting of azole compounds, quinoxaline compounds, dithiocarbamate compounds, organic chlorine compounds, benzimidazole compounds, pyridinamine compounds, cyanoacetamide compounds, phenylamide compounds, sulfenic acid compounds, copper compounds, isoxazole compounds, organophosphorus compounds, N-halogenothioalkyl compounds, dicarboximide compounds, benzanilide compounds, benzamide compounds, piperazine compounds, pyridine compounds, pyrimidine compounds, piperidine compounds, morpholine compounds, organotin compounds, urea compounds, cinnamic acid compounds, carbamate compounds, pyrethroid compounds, benzoylurea compounds, thiazolidine compounds, thiadiazine compounds, nereistoxin derivatives, pyridazinone compounds, and spores of Bacillus thurinqiensis and crystalline toxin produced thereby.
In formula (I), the halogen atom includes fluorine, chlorine, bromine, and iodine atoms.
Further, in formula (I), the alkyl group contains from 1 to 4 carbon atoms and mention may be made of, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, etc.
As to the present invention, preferred embodiments are illustrated below.
(1) A biocidal composition wherein the compound which is used in admixture with the imidazole compounds represented by formula (I) is at least one compound selected from the group consisting of azole compounds, quinoxaline compounds, dithiocarbamate compounds, organic chlorine compounds, benzimidazole compounds, pyridinamine compounds, cyanoacetamide compounds, phenylamide compounds, sulfenic acid compounds, copper compounds, isoxazole compounds, organophosphorus compounds, dicarboximide compounds, benzanilide compounds, and benzamide compounds.
(2) A biocidal composition wherein the compound which is used in admixture with the imidazole compounds represented by formula (I) is at least one compound selected from the group consisting of 1-[N-(4-chloro-2-trifluoromethylphenyl)-2-propoxyacetimidoyl]imidazale [triflumizole], 6-methyl-1,3-dithiolo[4,5-b]quinoxalin-2-one [chinomethionate], a complex of zinc and manganese ethylenebis(dithiocarbamate) [mancozeb], tetrachloroisophthalonitrile [chlorothalonil], methyl 1-(butyl-carbamoyl)benzimidazol-2-yl carbamate [benomyl], 3-chloro-N-(3-chloro-2,6-dinitro-4-α,α,α-trifluorotolyl)-5-trifluoromethyl-2-pyridinamine [fluazinam], 1-(2- cyano-2-methoxyiminoacetyl)-3-ethylurea [cymoxanil], methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate [metalaxyl], 2-methoxy-N-(2-oxo-1,3-oxazolidin-3-yl)- acet-2',6'-xylidide [oxadixyl], N-dichlorofluoro- methylthio-N',N'-dimethyl-N-phenylsulphamide [dichlofluanid], copper hydroxide [copper hydroxide], 5-methyl- isoxazol-3-ol [hydroxyisoxazole], aluminum tris(ethyl phosphonate) [fosetyl-Al], N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide [procymidone], α,α,α-trifluoro-3'-isopropoxy-o-toluanilide [flutolanil], and (RS)-4-chloro-N-[cyano(ethoxy)methyl]benzamide.
(3) A biocidal composition wherein the imidazole compound is represented by formula (I'): ##STR3## wherein R1 ' represents a phenyl group or a halogen-substituted alkyl group; and R2 ' represents a chlorine atom.
(4) A biocidal composition whose main use is for a fungicide.
The imidazole compounds represented by formula (I) include compounds represented by formula (I-a) and/or compounds represented by formula (I-b): ##STR4##
Typical examples of the imidazole compounds of formula (I) are shown in Table 1 below.
TABLE 1
______________________________________
##STR5## (I)
Compound Physical
No.* R.sup.1 R.sup.2
Property
______________________________________
A-lb phenyl C1 m.p. 109-112° C.
A-2b 2-chlorophenyl
Cl m.p. 113-117° C.
A-3 2-fluorophenyl
Cl m.p. 96-101° C.
A-4 4-chlorophenyl
Cl m.p. 108° C.
A-5b ethyl Cl m.p. 95-97° C.
A-6b n-propyl Cl m.p. 64-66° C.
A-7b n-butyl Cl m.p. 48-49° C.
A-8b n-propyl Br m.p. 93-94° C.
A-9b 3-fluroropropyl
Cl m.p. 75-79° C.
A-10b 3-brompropyl Cl m.p. 79-84° C.
A-11b 4-chlorobutyl
Cl n.sub.D.sup.22.1 1.5382
A-12b 3-chloropropyl
Cl m.p. 102-105° C.
A-13b 2-chloroethyl
Cl m.p. 92-94° C.
______________________________________
Note:
*The compounds having compound numbers with a mark "b" are included under
the formula (Ib) and those with no mark are mixtures of compounds under
the formulae (Ia) and (Ib).
Examples of the compounds which can be used in combination with the imidazole compounds of formula (I) are tabulated below.
______________________________________
Compound Common
No. Compound Name Name
______________________________________
Azole Compounds:
B-1 1-(4-Chlorophenoxy)-3,3-di-
Triadimefon
methyl-1-(1H-1,2,4-triazol-1-
yl)butanone
B-2 1-(Biphenyl-4-yloxy)-3,3-di-
Bitertanol
methyl-1-(1H-1,2,4-triazol-1-yl)-
butan-2-ol
B-3 1-[N-(4-Chloro-2-trifluoromethyl-
Triflumizole
phenyl)-2-propoxyacetimidoyl]-
imidazole
B-4 1-[2-(2,4-Dichlorophenyl)-4-
Etaconazole
ethyl-1,3-dioxolan-2-ylmethyl]-
1H-1,2,4-triazole
B-5 1-[2-(2,4-Dichlorophenyl)-4-
Propiconazole
propyl-1,3-dioxolan-2-ylmethyl]-
1H-1,2,4-triazole
B-6 1-[2-(2,4-Dichlorophenyl)pentyl]-
Penconazole
1H-1,2,4-triazole
B-7 Bis(4-fluorophenyl)(methyl)(1H-
Flusilazole
1,2,4-triazol-1-ylmethyl)silane
B-8 2-(4-Chlorophenyl)-2-(1H-1,2,4-
Myclobutanil
triazol-1-ylmethyl)hexanenitrile
B-9 (2RS, 3RS)-2-(4-Chlorophenyl)-3-
Cyproconazole
cyclopropyl-1-(1H-1,2,4-triazol-
1-yl)butan-2-ol
B-10 (RS)-1-(4-Chlorophenyl)-4,4-
Terbuconazole
dimethyl-3-(1H-1,2,4-triazol-
1-ylmethyl)pentan-3-ol
B-11 (RS)-2-(2,4-Dichlorophenyl)-1-
Hexaconazole
(1H-1,2,4-triazol-1-yl)hexan-
2-ol
B-12 (2RS, 5RS)-5-(2,4-Dichloro-
Furconazole-
phenyl)tetrahydro-5-(1H-1,2,4-
cis
triazol-1-ylmethyl)-2-furyl
2,2,2-trifluoroethyl ether
B-13 N-Propyl-N-[2-(2,4,6-trichloro-
Prochloraz
phenoxy)ethyl]imidazole-1-
carboxamide
Quinoxaline Compounds:
C-1 6-Methyl-1,3-dithiolo[4,5-b]-
Chinomethio-
quinoxalin-2-one nate
Dithiocarbamate Compounds:
D-1 Manganese ethylenebis(dithio-
Maneb
carbamate) polymer
D-2 Zinc ethylenebis(dithiocarbamate)
Zineb
polymer
D-3 Complex of zinc and manganese
Mancozeb
ethylenebis(dithiocarbamate)
(Maneb)
D-4 Dizinc bis(dimethyldithio)-
Polycarbamate
carbamate) ethylenebis-
(dithiocarbamate)
D-5 Zinc propylenebis(dithio-
Propineb
carbamate) polymer
Organic Chlorine Compounds:
E-1 4,5,6,7-Tetrachlorophthalide
Fthalide
E-2 Tetrachloroisophthalonitrile
Chlorothalo-
nil
E-3 Pentachloronitrobenzene
Quintozene
E-4 2,2,2-Trichloro-1,1-bis(4-
Dicofol
chlorophenyl)ethanol
Benzimidazole Compounds:
F-1 Methyl 1-(butylcarbamoyl)benz-
Benomyl
imidazol-2-yl carbamate
F-2 Dimethyl 4,4'-(o-phenylene)-bis-
Thiophanate-
(3-thioallophanate) methyl
F-3 Methyl benzimidazol-2-
Carbendazim
ylcarbamate
Pyridinamine Compounds:
G-1 3-Chloro-N-(3-chloro-2,6-dinitro-
Fluazinam
4-α,α,α-trifluorotolyl)-5-tri-
fluoromethyl-2-pyridinamine
Cyanoacetamide Compounds:
H-1 1-(2-Cyano-2-methoxyiminoacetyl)-
Cymoxanil
3-ethylurea
Phenylamide Compounds:
I-1 Methyl N-(2-methoxyacetyl)-N-
Metalaxyl
(2,6-xylyl)-DL-alaninate
I-2 2-Methoxy-N-(2-oxo-1,3-oxa-
Oxadixyl
zolidin-3-yl)acet-2',6'-xylidide
I-3 (±)-α-2-Chloro-N-(2,6-xylylacet-
Ofurace
amide)-γ-butyrolactone
I-4 Methyl N-phenylacetyl-N-(2,6-
Benalaxyl
xylyl)-DL-alaninate
I-5 Methyl N-(2-furoyl)-N-(2,6-
Furalaxyl
xylyl)-DL-alaninate
I-6 (±)-α-[N-(3-Chlorophenyl)cyclo-
Cyprofuram
propane-carboxamide]-γ-butyro-
lactone
Sulfenic Acid Compounds:
J-1 N-Dichlorofluoromethylthio-N',N'-
Dichlo-
dimethyl-N-phenylsulphamide
fluanid
Copper Compounds:
K-1 Copper hydroxide Copper
Hydroxide
K-2 Copper-8-quinolinolate
Oxine-copper
Isoxazole Compounds:
L-1 5-Methylisoxazol-3-ol
Hydroxy-
isoxazole
Organophosphorus Compounds:
M-1 Aluminum tris(ethyl phosphonate)
Fosetyl-Al
M-2 O-2,6-Dichloro-p-tolyl-
Tolclofos-
O,O-dimethyl phosphorothioate
methyl
M-3 (RS)-S-(RS)-Sec-butyl-O-ethyl-
disclosed in
2-oxo-2-thiazolidinyl-
U.S. Pat. No.
phosphonothioate 4,590,182
M-4 O,S-Dimethyl acetylphosphor-
Acephate
amidothioate
M-5 2,2-Dichlorovinyl dimethyl
Dichlorvos
phosphate
M-6 O-2,4-Dichlorophenyl O-ethyl
Prothiofos
S-propyl phosphorodithioate
N-Halogenothioalkyl Compounds:
N-1 N-(Trichloromethylthio)cyclohex-
Captan
4-ene-1,2-dicarboximide
N-2 N-(1,1,2,2-Tetrachloroethyl-
Captafol
thio)cyclohex-4-ene-1,2-di-
carboximide
N-3 N-(Trichloromethylthio)phthal-
Folpet
imide
Dicarboximide Compounds:
O-1 N-(3,5-Dichlorophenyl)-1,2-di-
Procymidone
methylcyclopropane-1,2-di-
carboximide
O-2 3-(3,5-Dichlorophenyl)-N-iso-
Iprodione
propyl-2,4-dioxoimidazolidine-1-
carboxamide
O-3 (RS)-3-(3,5-Dichlorophenyl)-5-
Vinclozolin
methyl-5-vinyl-1,3-oxazolidine-
2,4-dione
Benzanilide Compounds:
P-1 α,α,α-Trifluoro-3'-isopropoxy-
Flutolanil
o-toluanilide
P-2 3'-Isopropoxy-o-toluanilide
Mepronil
Benzamide Compounds:
Q-1 (RS)-4-Chloro-N-[cyano(ethoxy)-
disclosed in
methyl]benzamide U.S. Pat. No.
4,447,446
Q-2 2-(1,3-Dimethylpyrazol-4-yl-
disclosed in
carbonylamino)-4-methyl-3-
British
pentenenitrile Patent
2,190,375
Q-3 α-(Nicotinylamino)-(3-fluoro-
disclosed in
phenyl)acetonitrile JP-A-63-
135364
______________________________________
(The term "JP-A" as used herein means a "published unexamined patent application".)
______________________________________
Compound Common
No. Compound Name Name
______________________________________
Piperazine Compounds:
R-1 N,N'-[Piperazine-1,4-diylbis-
Triforine
[(trichloromethyl)methylene]]-
diformamide
Pyridine Compounds:
S-1 2',4'-Dichloro-2-(3-pyridyl)-
Pyrifenox
acetophenone O-methyloxime
Pyrimidine Compounds:
T-1 (±)-2,4'-Dichloro-α-(pyrimidin-
Fenarimol
5-yl)benzhydryl alcohol
Piperidine Compounds:
U-1 (RS)-1-[3-(4-Tert-butylphenyl)-
Fenpropidin
2-methylpropyl]piperidine
Morpholine Compounds:
V-1 (±)-Cis-4-[3-(4-tert-butyl-
Fenpropimorph
phenyl)-2-methylpropyl]-2,6-
dimethylmorpholine
Organotin Compounds:
W-1 Triphenyltin hydroxide Fentin
hydroxide
W-2 Triphenyltin acetate Fentin
acetate
Urea Compounds:
X-1 1-(4-Chlorobenzyl)-1-cyclo-
Pencycuron
pentyl-3-phenylure
Cinnamic Acid Compounds:
Y-1 (E,Z)4-[3-(4-Chlorophenyl)-3-
Dimethomorph
(3,4-dimethoxyphenyl)acryloyl]
morpholine
Carbamate Compounds:
Za-1 1-Naphthyl methylcarbamate
Carbaryl
Za-2 S-Methyl N-(methylcarbamoyloxy)-
Methomyl
thioacetimidate
Za-3 2-Ethylthiomethylphenyl
Ethiofencarb
methylcarbamate
Za-4 Ethyl N-benzyl-N-[[methyl-
ORION ®
[[(Z)-1-methylthioethylidene]-
(trade name)
aminooxycarbonyl]amino]thio]-
β-alaninate
Pyrethroid Compounds:
Zb-1 (RS)-α-Cyano-3-phenoxybenzyl
Cyhalothrin
(Z)-(1RS, 3RS)-(2-chloro-3,3,3-
trifluoropropenyl)-2,2-dimethyl-
cyclopropanecarboxylate
Zb-2 2,3,5,6-Tetrafluoro-4-methyl-
Tefluthrin
benzyl (Z)-(1RS, 3RS)-3-(2-
chloro-3,3,3-trifluoroprop-1-
enyl)-2,2-dimethylcyclopropane-
carboxylate
Zb-3 2-(4-Ethoxyphenyl)-2-methyl-
Ethofenprox
propyl-3-phenoxybenzyl ether
Zb-4 (RS)-α-Cyano-3-phenoxybenzyl
Cypermethrin
(1RS, 3RS; 1RS, 3SR)-3-(2,2-
dichlorovinyl)-2,2-dimethylcyclo-
propanecarboxylate
Benzoylurea Compounds:
Zc-1 1-(4-Chlorophenyl)-3-(2,6-
Diflubenzuron
difluorobenzoyl)urea
Zc-2 1-(3,5-Dichloro-2,4-difluoro-
Teflubenzuron
phenyl)-3-(2,6-difluorobenzoyl)-
urea
Zc-3 1-[3,5-Dichloro-4-(3-chloro-5-
Chlorfluaz-
trifluoromethyl-2-pyridyloxy)-
uron
phenyl]-3-(2,6-difluorobenzoyl)-
urea
Thiazolidine Compounds:
Zd-1 (4RS, 5RS)-5-(4-Chlorophenyl)-
Hexythiazox
N-cyclohexyl-4-methyl-2-oxo-
1,3-thiazolidine-3 carboxamide
Thiadiazine Compounds:
Ze-1 2-Tert-butylimino-3-isopropyl-
Buprofezin
5-phenyl-1,3,5-thiadiazinan-4-one
Nereistoxin Derivatives
Zf-1 N,N-Dimethyl-1,2,3-trithian-
Thiocyclam
5-ylamine
Zf-2 S,S'-2-Dimethylaminotri-
Cartap
methylene bis(thiocarbamate)
Pyridazinone Compounds:
Zg-1 2-Tert-butyl-5-(4-tert-butyl-
disclosed in
benzylthio)-4-chloropyridazin-
European
3(2H)-one Patent
134,439
Spores of Bacillus thuringiensis and crystalline toxin
produced thereby:
Name of Pathogen
Zh-1 Bacillus thuringiensis
THURI-
subsp, Kurstaki, HD-1
CIDE ® (trade
name)
______________________________________
The imidazole compounds represented by formula (I) can be prepared, for example, by the following reaction schemes. ##STR6## wherein Z represents a hydrogen atom, a chlorine atom, or a bromine atom; Y represents a chlorine atom, a fluorine atom, a bromine atom, or an iodine atom; Y' represents a chlorine atom, a bromine atom, or an iodine atom; and R1 is as defined above. ##STR7## wherein Y, R1, and R2 are as defined above.
Step 1 of process A and Process B are carried out, if desired, in the presence of a solvent and an acid acceptor.
The solvent which can be used includes aromatic hydrocarbons, e.g., benzene, toluene, xylene, chlorobenzene, etc.; cyclic or acyclic aliphatic hydrocarbons, e.g., chloroform, carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, n-hexane, cyclohexane, etc.; ethers, e.g., diethyl ether, dioxane, tetrahydrofuran, etc.; ketones, e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; nitriles, e.g., acetonitrile, propionitrile, etc.; and aprotic polar solvents, e.g., dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, etc.
The acid acceptor which can be used includes inorganic bases such as alkali metal hydroxides, e.g., sodium hydroxide and potassium hydroxide, alkali metal or alkaline earth metal carbonates, e.g., anhydrous potassium carbonate and anhydrous calcium carbonate, alkali metal hydrides, e.g., sodium hydride, and alkali metals, e.g., metallic sodium; and organic basis, e.g., triethylamine.
The reactions of Step 1 of Process A and Process B can be effected in the presence of an appropriate catalyst, such as a phase transfer catalyst (e.g., quaternary ammonium salt derivatives).
The compound represented by formula (II), the starting compounds of Process B, can be prepared according to the following process or processes similar thereto. ##STR8## wherein R3 represents a hydrogen atom or a halogen atom; and R1 is as defined above.
The compound of formula (II) includes tautomers represented by the following formulae: ##STR9## wherein R1 and R2 are as defined above.
Accordingly, in cases where the compound of formula (I) is prepared by starting with the compound of formula (II), the compounds having formulae (I-a) and/or (I-b) can be obtained.
Thus, the reaction of introducing --SO2 N(CH3)2 group to the starting compound including tautomers yields either one of the two isomers or a mixture thereof. Whether a mixture of tautomers or either one of the tautomers is obtained depends on the starting compound, the reaction process of from the starting compound through the product, the reaction conditions, and the like. In the case where a mixture is obtained, the mixing ratio is also determined by these factors.
Synthesis Examples of the imidazole compounds of formula (I) are exemplified below.
(1) 2-Formyl-1-diethoxymethylimidazole was obtained as an oily substance from 1-diethoxymethylimidazole in accordance with the method described in J. Org. Chem., Vol. 45, 4038-4040 (1980). The resulting compound was reacted with hydroxylamine hydrochloride-sodium acetate in water to obtain imidazole-2-aldoxime, which was then dehydrated with acetic anhydride to obtain 2-cyanoimidazole having a melting point of 176° C.
(2) Thirty grams of 2-cyanoimidazole as obtained in (1) above, 53.4 g of anhydrous potassium carbonate, and 600 ml of acetonitrile were mixed at room temperature, and the mixture was allowed to react at reflux for 2 hours. After cooling, 55.6 g of dimethylsulfamoyl chloride was added thereto, and the reaction at reflux was continued for an additional period of 2 hours.
After completion of the reaction, the reaction mixture was poured into water and extracted with methylene chloride. The extract was washed with water and dried over anhydrous sodium sulfate. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using methylene chloride as a developing solvent to obtain 28.0 g of 2-cyano-1-dimethylsulfamoylimidazole having a melting point of from 74 to 76° C.
(3) In a four-necked flask were charged in a nitrogen atmosphere 12.0 g of 2-cyano-1-dimethylsulfamoylimidazole as obtained in (2) above and 240 ml of anhydrous tetrahydrofuran, and 41.3 ml of a 1.6M n-butyl lithium-hexane solution (produced by Aldrich) was gradually added dropwise to the mixture while maintaining at a temperature of -75° C. or lower with dry ice-acetone. After the dropwise addition, the mixture was kept at that temperature for 15 minutes, and 30 ml of a tetrahydrofuran solution of 15.3 g of n-propyl iodide was added dropwise thereto at -70° C. or lower. After the dropwise addition, the reaction mixture was stirred overnight to gradually elevate the temperature to room temperature.
After completion of the reaction, the reaction mixture was poured into water and extracted with 500 ml of ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous sodium sulfate. The ethyl acetate was removed by distillation, and the residue was purified by silica gel column chromatography using methylene chloride as a developing solvent and separated to give 4.8 g of 2-cyano-1-dimethylsulfamoyl-5-n-propylimidazole having a melting point of from 51 to 52° C.
(4) 4.8 g of 2-cyano-1-dimethylsulfamoyl-5-n-propylimidazole as obtained in (3) above, 40 ml of pyridine, and 11.4 g of pyridinium chloride were mixed, and the mixture was stirred at 90° C. for 4 hours.
After completion of the reaction, the pyridine was removed by distillation from the reaction mixture, and the residue was extracted with ethyl acetate. The extract was washed with water and then dried over anhydrous sodium sulfate. Thereafter, the ethyl acetate was removed by distillation, and the residue was purified by silica gel column chromatography (developing solvent: a mixture of ethyl acetate and n-hexane) and separated to give 2.46 g of 2-cyano-4(5)-n-propylimidazole having a melting point of from 52 to 54° C.
(5) 2.35 g of 2-cyano-4(5)-n-propylimidazole as obtained in (4) above, 80 ml of chloroform, and 2.6 g of N-chlorosuccinimide were mixed, and the mixture was reacted at the reflux temperature for 4 hours.
After completion of the reaction, 200 ml of water was added to the reaction mixture. The resulting organic layer was washed with water and then dried over anhydrous sodium sulfate. The chloroform was removed by distillation, and the residue was purified by silica gel column chromatography (developing solvent: a 1:1 mixture of ethyl acetate and n-hexane) and separated to give 2.2 g of 4(5)-chloro-2-cyano-5(4) n-propylimidazole having a melting point of from 107 to 109° C.
(6) 2.0 g of 4(5)-chloro-2-cyano-5(4)-n-propylimidazole as obtained in (5) above, 30 ml of acetonitrile, 1.95 g of anhydrous potassium carbonate, and 1.86 g of dimethylsulfamoyl chloride were mixed, and after gradually elevating the temperature, the mixture was reacted at the reflux temperature for 1 hour.
After completion of the reaction, the acetonitrile was removed by distillation from the reaction mixture. After pouring 100 ml of water into the residue, the resulting mixture was extracted with 50 ml of methylene chloride. The extract was washed with water and dried over anhydrous sodium sulfate. The methylene chloride was removed by distillation, and the residue was allowed to stand overnight at room temperature. The analysis of the residue revealed that one of the two isomers in the mixture decomposed and returned to the starting 4(5)-chloro-2-cyano-5(4)-n-propylimidazole. The residue containing the other isomer was purified by silica gel column chromatography (developing solvent: methylene chloride) and separated to give 1.1 g of 4-chloro-2-cyano-1-dimethylsulfamoyl-5-n-propylimidazole (Compound No. A-6b) having a melting point of from 64° to 66° C.
(1) In 100 ml of chloroform was dissolved 1.352 g of 2-cyano-4(5)-phenylimidazole, and 1.175 g of N-chlorosuccinimide was added to the solution. The mixture was reacted upon heating at the reflux temperature for 4 hours.
After completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. After washing with water, the extracted layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: methylene chloride) to give 1.28 g of 4(5)-chloro-2-cyano-5(4)-phenylimidazole having a melting point of from 149° to 151° C.
(2) In 6 ml of acetone was dissolved 0.43 g of 4(5)- chloro-2-cyano-5(4)-phenylimidazole as obtained in (1) above, and 0.29 g of anhydrous potassium carbonate and 0.36 g of dimethylsulfamoyl chloride were added to the solution. The mixture was reacted upon heating at the reflux temperature for 30 minutes.
After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. After washing with water, the extracted layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was then purified by silica gel column chromatography (developing solvent: methylene chloride) to give 0.5 g of 4(5)-chloro-2-cyano-1-dimethylsulfamoyl-5(4)phenylimidazole having a melting point of from 106° to 109° C.
As a result of analysis by means of NMR spectra, the compound described above was found to be an isomeric mixture of 4-chloro-2-cyano-1-dimethylsulfamoyl-5-phenylimidazole and 5-chloro-2-cyano-1-dimethylsulfa- moyl-4-phenylimidazole in almost equal ratios.
(3) After allowing to stand for 24 hours at room temperature, 2.9 g of the mixture of these isomers as obtained in a manner similar to (2) above was purified by silica gel column chromatography (developing solvent: methylene chloride) to give 1.15 g of 4-chloro-2-cyano-1-dimethylsulfamoyl-5-phenylimidazole (Compound No. A-1b) having a melting point of from 109° to 112° C. Further, by purification of and isolation from this compound, 0.7 g of 4(5)-chloro-2-cyano-5(4)-phenylimidazole was also obtained.
(1) In a four-necked flask were charged in a nitrogen atmosphere 9.4 g of 2-cyano-4,5-dichloro-1-dimethylsulfamoylimidazole and 152 ml of anhydrous tetrahydrofuran, and 28.6 ml of a 1.6 M n-butyl lithiumhexane solution was slowly added thereto while maintaining at a temperature of -75° C. or lower by cooling with dry ice-acetone. After the dropwise addition, the mixture was kept at that temperature for 15 minutes. Then, 31 ml of a tetrahydrofuran solution of 14.3 g of 1-chloro-3-iodopropane was added dropwise to the mixture at -70° C. or lower, followed by stirring at room temperature overnight to gradually elevate the temperature to room temperature.
After completion of the reaction, the reaction mixture was poured into water and extracted with methylene chloride. The extract was washed with water and dried over anhydrous sodium sulfate. The methylene chloride was removed by distillation, and the residue was purified by silica gel column chromatography once using methylene chloride and then using a mixture of n-hexane and ethyl acetate as developing solvents to obtain 4.1 g of 4-chloro-5-(3-chloropropyl)-2-cyano-1-dimethylsulfamoylimidazole (Compound No. A-12b) having a melting point of from 102° to 105° C.
The biocidal compositions according to the present invention, comprising the imidazole compound of formula (I) in combination with other specific compound, are particularly useful as agricultural fungicides. Specifically, they exhibit excellent effects of controlling diseases of crop plants such as rice blast caused by Pyricularia oryzae, rice sheath blight caused by Rhizoctonia solani, cucumber anthracnose caused by Colletotrichum lagenarium, cucumber powdery mildew caused by Sphaerotheca fuliginea, cucumber downy mildew caused by Pseudoperonospora cubensis, tomato late blight caused by Phytophthora infestans, tomato early blight caused by Alternaria solani, citrus melanose caused by Diaporthe citri, citrus common green mold caused by Penicillium digitatum, pear scab caused by Venturia nashicola, apple alternaria blotch caused by Alternaria mali, grape downy mildew caused by Plasmopara viticola, gray mold caused by Botrytis cinerea, sclerotinia rot caused by Sclerotinia sclerotiorum, rust, etc.; and soil diseases caused by phytopathogenic fungi such as Fusarium, Pythium, Rhizoctonia, Verticillium, Plasmodiophora, etc. In particular, the biocidal compositions of the present invention exhibit excellent effects of controlling diseases such as potato or tomato late blight caused by Phytophthora infestans, cucumber downy mildew caused by Pseudoperonospora cubensis, grape downy mildew caused by Plasmopara viticola, tobacco blue mold caused by Peronospora tabacina; and various soil diseases caused by phycomycetes such as Plasmodiophora, Aphanomyces, Pythium, etc.
The biocidal compositions of the present invention have a prolonged residual effect so that they exhibit an excellent preventive effect, and also exhibit an excellent curative effect as well. It is therefore possible to control diseases by treatment after infection. In addition, since they possess a systemic activity, it is also possible to control diseases of the stem and leaf by soil treatment.
Further, the biocidal compositions of the present invention show an excellent controlling effect against agriculturally and horticulturally harmful insects such as planthoppers, diamondback moth (Plutella xylostella), green rice leafhopper (Nephotettix cincticeps), adzuki bean weevil (Callosobruchus chinensis), common cutworm (Spodoptera litura), green peach aphid (Myzus persicae), etc.; mites such as twospotted spider mite (Tetranychus urticae), carmine spider mite (Tetranychus cinnabarinus), citrus red mite (Panonychus citri), etc.; and nematodes such as southern root-knot nematode (Meloidogyne incognita), etc.
The compounds constituting the biocidal composition of the present invention can be formulated into a variety of forms, such as emulsifiable concentrates, dusts, wettable powders, aqueous solutions, granules, suspension concentrates, etc., together with various adjuvants, as in conventional agricultural preparations. The imidazole compound of formula (I) and the other specific compound may be mixed and formulated, or each of the compounds may be separately formulated and then mixed together. Upon use, the preparation may be used as such or as diluted with an appropriate diluent, e.g., water, to a predetermined concentration.
Examples of the adjuvants which can be used include carriers, emulsifying agents, suspending agents, dispersing agents, spreaders, penetrating agents, wetting agents, thickeners, stabilizers, etc. These adjuvants can be added appropriately according to necessity.
The carriers are classified into solid carriers and liquid carriers. The solid carriers include animal and vegetable powders, e.g., starch, sugar, cellulose powders, cyclodextrin, activated charcoal, soybean powders, wheat powders, chaff powders, wood powders, fish powders, powdery milk, etc., and mineral powders, e.g., talc, kaolin, bentonite, bentonite-alkylamine complexes, calcium carbonate, calcium sulfate, sodium bicarbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, silica, sulfur powders, etc. The liquid carriers include water, animal and vegetable oils, e.g., soybean oil, cotton seed oil, etc., alcohols, e.g., ethyl alcohol, ethylene glycol, etc., ketones, e.g., acetone, methyl ethyl ketone, etc., ethers, e.g., dioxane, tetrahydrofuran, etc., aliphatic hydrocarbons, e.g., kerosene, lamp oil, liquid paraffin, etc., aromatic hydrocarbons, e.g., xylene, trimethylbenzene, tetramethylbenzene, cyclohexane, solvent naphtha, etc., halogenated hydrocarbons, e.g., chloroform, chlorobenzene, etc., acid amides, e.g., dimethylformamide, etc., esters, e.g., ethyl acetate, fatty acid glycerine esters, etc., nitriles,, e.g., acetonitrile, etc., sulfur-containing compounds, e.g., dimethyl sulfoxide, etc., N-methylpyrrolidone, and so on.
A suitable mixing ratio of the imidazole compound of formula (I) and other specific compound usually ranges from 1:300 to 300:1, preferably from 1:100 to 100:1, and more preferably from 1:50 to 5:1, by weight.
The concentration of the biocidal composition of the present invention is hard to specify as it varies depending on the crop to which the composition is applied, the method of application, the preparation form, the dose to be applied, and the like. Generally speaking, the concentrations of the imidazole compound of formula (I) and the specific compound to be combined are from 1 to 1,000 ppm and from 1 to 5,000 ppm, respectively, in the case of foliar treatment, and those in the case of soil treatment are from 10 to 10,000 g/ha and from 10 to 50,000 g/ha, respectively.
Examples of testing of the biocidal compositions according to the present invention as agricultural and horticultural fungicides are hereinafter given for illustrative purposes only but not for limitation.
Tomato (cultivars: Ponderosa) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When - tomato reached the four-leaf stage, 10 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration was sprayed over tomato using a spray gun. After keeping the pots in a constant temperature chamber of 22° to 24° C. over one day and one night, a zoosporangium suspension of fungi of late blight (Phytophthora infestans) was inoculated by spraying. Five days after the inoculation, an area of lesion on the leaves was investigated, and an index of control was determined according to the following standard. The results obtained are shown in Tables 2-1 through 2-6.
The controlling effect was determined by visually observing a degree of disease of a test plant and expressed by the following 5 grades of the index of control.
______________________________________
[Index of Control]
[Degree of Disease]
______________________________________
5 No lesion is noted at all.
4 Area of lesions is less than 10% as
compared to the non-treated plot.
3 Area of lesions is less than 40% as
compared to the non-treated plot.
2 Area of lesions is less than 70% as
compared to the non-treated plot.
1 Area of lesions is 70% or more as
compared to the non-treated plot.
______________________________________
TABLE 2-1
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-6b 0.5 3
0.125 1
B-3 31 2
8 2
A-6b + B-3 0.5 + 31 4
0.5 + 8 4
0.125 + 31 3
0.125 + 8 4
C-1 31 1
8 1
A-6b + C-1 0.5 + 31 5
0.5 + 8 5
0.125 + 31 2
0.125 + 8 2
______________________________________
TABLE 2-2
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-6b 0.5 5
0.125 3
D-3 31 3
8 1
A-6b + D-3 0.5 + 31 5
0.5 + 8 4
0.125 + 31 5
0.125 + 8 3
E-2 31 2
8 1
A-6b + E-2 0.5 + 31 5
0.5 + 8 5
0.125 + 31 5
0.125 + 8 3
______________________________________
TABLE 2-3
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-1b 8 5
2 1
0.5 1
F-1 31 2
8 1
A-1b + F-1 8 + 31 5
8 + 8 5
2 + 31 5
2 + 8 3
0.5 + 31 1
0.5 + 8 1
______________________________________
TABLE 2-4
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-1b 8 5
2 3
0.5 2
G-1 8 3
2 1
A-1b + G-1 8 + 8 5
8 + 2 5
2 + 8 5
2 + 2 4
0.5 + 8 5
0.5 + 2 3
______________________________________
TABLE 2-5
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-1b 0.5 4
0.125 1
D-3 31 1
8 1
A-1b + D-3 0.5 + 31 5
0.5 + 8 5
0.125 + 31 4
0.125 + 8 4
______________________________________
TABLE 2-6
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-1b 0.5 4
0.125 3
H-1 8 3
2 3
A-1b + H-1 0.5 + 8 5
0.5 + 2 5
0.125 + 8 3
0.125 + 2 4
______________________________________
A test similar to Test Example 1 was carried out. The degree of disease has visually observed to determine the index of control according to the following standard for evaluation. The results obtained are shown in Tables 3-1 through 3-3.
______________________________________
Standard for Evaluation:
[Index of Control]
[Degree of Disease]
______________________________________
7 No lesion is observed at all.
6 Area or length of lesions is less
than 5% of that of the non-treated
plot.
5 Area or length of lesions is from 5
to less than 10% of that of the non-
treated plot.
4 Area or length of lesions is from 10
to less than 25% of that of the non-
treated plot.
3 Area or length of lesions is from 25
to less than 40% of that of the non-
treated plot.
2 Area or length of lesions is from 40
to less than 70% of that of the non-
treated plot.
1 Area or length of lesions is 70% or
more of that of the non-treated
plot.
______________________________________
TABLE 3-1
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-1b 0.125 4
A-12b 0.125 2
I-1 2 2
0.5 1
A-1b + I-1 0.125 + 2 5
0.125 + 0.5 7
A-12b + I-1 0.125 + 2 7
0.125 + 0.5 6
______________________________________
TABLE 3-2
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-1b 0.5 4
I-2 31 5
H-1 31 4
Q-1 8 1
A-1b + I-2 0.5 + 31 7
A-1b + H-1 0.5 + 31 7
A-1b + Q-1 0.5 + 8 7
______________________________________
TABLE 3-3
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-12b 0.5 4
K-1 500 2
I-2 8 3
2 1
A-12b + K-1 0.5 + 500 7
A-12b + I-2 0.5 + 8 7
0.5 + 2 7
______________________________________
Tomato (cultivars: Ponderosa) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When tomato reached the four-leaf stage, a zoosporangium suspension of fungi of late blight (Phytophthora infestans) was inoculated by spraying. Six hours later, 10 ml of a solution of each of test compounds at a predetermined concentration has sprayed onto the tomato plant using a spray gun. After keeping the pots in a constant temperature chamber of 22° to 24° C. for 5 days, an area of lesions was examined to obtain the index of control according to the standard of Test Example 2. The results obtained are shown in Tables 4-1 through 4-3.
TABLE 4-1
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-1b 500 4
125 4
I-1 8 3
2 1
A-1b + I-1 500 + 8 7
500 + 2 7
125 + 8 7
125 + 2 5
______________________________________
TABLE 4-2
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-1b 500 3
125 1
I-2 31 4
H-1 8 3
Q-1 8 4
A-1b + I-2 500 + 31 6
125 + 31 6
A-1b + H-1 500 + 8 5
125 + 8 6
A-1b + Q-1 500 + 8 6
______________________________________
TABLE 4-3
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-12b 8 2
2 1
I-2 31 2
H-1 31 5
8 1
Q-1 31 2
A-12b + I-2 8 + 31 6
2 + 31 5
A-12b + H-1 8 + 31 7
8 + 8 4
A-12b + Q-1 8 + 31 6
2 + 31 6
______________________________________
Cucumber (cultivars: Suyo) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When cucumber reached the two-leaf stage, a spore suspension of fungi of downy mildew (Pseudoperonospora cubensis) was inoculated by spraying. Twenty-four hours after the inoculation, 10 ml of a solution of each of test compounds adjusted to a predetermined concentration was sprayed over cucumber using a spray gun. After keeping the pots in a constant temperature chamber of 22° to 24° C. for 6 days, an area of lesion on the first leaf was visually observed to determine the index of control according to the standard of Test Example 2. The results obtained are shown in Tables 5-1 through 5-3.
TABLE 5-1
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-1b 0.5 3
0.125 1
A-12b 0.5 3
0.125 1
I-1 8 3
2 1
A-1b + I-1 0.5 + 8 6
0.5 + 2 4
0.125 + 8 4
0.125 + 2 1
A-12b + I-1 0.5 + 8 5
0.5 + 2 4
0.125 + 8 4
0.125 + 2 1
______________________________________
TABLE 5-2
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-1b 0.5 1
0.125 1
M-1 125 1
Q-1 31 5
8 2
A-1b + M-1 0.5 + 125 5
0.125 + 125 3
A-1b + Q-1 0.5 + 31 7
0.5 + 8 4
______________________________________
TABLE 5-3
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-12b 0.5 3
M-1 500 1
125 1
I-2 8 2
2 1
H-1 8 3
2 1
Q-1 31 3
8 2
A-12b + M-1 0.5 + 500 6
0.5 + 125 6
A-12b + I-2 0.5 + 8 5
0.5 + 2 5
A-12b + H-1 0.5 + 8 6
0.5 + 2 6
A-12b + Q-1 0.5 + 31 6
0.5 + 8 6
______________________________________
Cucumber (cultivars: Suyo) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When cucumber reached the two-leaf stage, 10 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration has sprayed over cucumber using a spray gun. After keeping the pots in a constant temperature chamber of 22° to 24° C. over one day and one night, a mycelial disc having a diameter of 5 mm of fungi of gray mold (Botrytis cinerea) was inoculated on the first leaf. Three days after the inoculation, a length of lesion was investigated, and an index of control was determined according to the standard of Test Example 2. The results shown in Table 6 were obtained.
TABLE 6
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-1b 500 1
125 1
J-1 8 2
2 1
O-1 31 3
A-1b + J-1 500 + 8 6
500 + 2 4
A-1b + O-1 500 + 31 5
125 + 31 5
______________________________________
Rice plant (cultivars: Chukyo Asahi) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When rice plant reached the five-leaf stage, 20 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration was sprayed over rice plant using a spray gun. After keeping the pots in a constant temperature chamber of 22° to 24° C. over one day and one night, rice straw in which fungi of sheath blight (Rhizoctonia solani) had been previously incubated was set between leaf sheath portions to inoculate. After keeping the pots in an inoculation room having a temperature of 28° C. and humidity of 100% for 5 days, a length of lesion was investigated, and an index of control was determined according to the standard of Test Example 2. The results shown in Table 7 were obtained.
TABLE 7
______________________________________
Concentration
Compound No. (ppm) Index of Control
______________________________________
A-1b 500 1
125 1
A-12b 500 1
125 1
P-1 31 4
A-1b + P-1 500 + 31 7
125 + 31 7
A-12b + P-1 500 + 31 7
125 + 31 7
______________________________________
Mycelial disc (agar punching) of preincubated Pythium aphanidermatum was transplanted on potato-dextrose agar medium (PDA medium) containing 100 ppm of streptomycin and a predetermined concentration of each of test compounds. After incubation at 22° C. for 48 hours, a diameter of mycellium was measured. Inhibition of hyphal growth (%) was determined by the following equation. The results shown in Table 8 were obtained. ##EQU1##
TABLE 8
______________________________________
Inhibition of
Concentration
Hyphal Growth
Compound No. (ppm) (%)
______________________________________
A-1b 1 91
0.1 85
A-12b 1 85
0.1 88
L-1 100 54
A-1b + L-1 1 + 100 100
0.1 + 100 100
A-12b + L-1 1 + 100 100
0.1 + 100 100
______________________________________
Formulation Examples of the biocidal composition according to the present invention are described below, but the present invention is not deemed to be limited thereto.
______________________________________
Compound No. A-1b 5 parts by weight
Compound No. D-3 45 parts by weight
Kaolin 40 parts by weight
Calcium lignin sulfonate
7 parts by weight
Dialkylsulfosuccinate
3 parts by weight
______________________________________
The above components are uniformly mixed to prepare a wettable powder.
A wettable powder can be prepared in the same manner as in Formulation Example 1, except for replacing Compound No. A-1b with 25 parts by weight of Compound No. A-12b and replacing Compound No. D-3 with 25 parts by weight of Compound No. I-1.
A wettable powder can be prepared in the same manner as in Formulation Example 1, except for replacing Compound No. D-3 with Compound No. K-1.
______________________________________
Compound No. A-1b 5 parts by weight
Compound No. G-1 15 parts by weight
Calcium carbonate 20 parts by weight
Kaolin 52 parts by weight
Calcium lignin sulfonate
4 parts by weight
Polyoxyethylene alkylaryl ether
4 parts by weight
______________________________________
The above components are uniformly mixed to prepare a wettable powder.
A wettable powder can be prepared in the same manner as in Formulation Example 4, except for replacing Compound No. G-1 with Compound No. F-1.
A wettable powder can be prepared in the same manner as in Formulation Example 4, except for replacing Compound No. G-1 with Compound No. O1.
______________________________________
Compound No. A-6b 5 parts by weight
Compound No. B-3 5 parts by weight
Diatomaceous earth 84 parts by weight
Dialkylsulfosuccinate
2 parts by weight
Polyoxyethylene alkylphenyl
4 parts by weight
ether sulfate
______________________________________
The above components are uniformly mixed to prepare a wettable powder.
A wettable powder can be prepared in the same manner as in Formulation Example 7, except for replacing Compound No. B-3 with Compound No. M-1.
______________________________________
Kaolin 78 parts by weight
Sodium β-naphthalenesulfonate-
2 parts by weight
formaldehyde condensate
Polyoxyethylene alkylaryl
5 parts by weight
sulfate
Hydrated amorphous silicon
15 parts by weight
dioxide
______________________________________
A mixture consisting of the above components is mixed with Compound No. A-1b and Compound No. I-1 at a weight mixing ratio of 8:1:1 to prepare a wettable powder.
A wettable powder can be prepared in the same manner as in Formulation Example 9, except for replacing Compound No. I-1 with Compound No. I-7.
______________________________________
Compound No. A-12b 0.25 parts by weight
Compound No. I-1 0.25 parts by weight
Calcium carbonate 99.0 parts by weight
Lower alcohol phosphate
0.5 parts by weight
______________________________________
The above components are uniformly mixed to prepare a dust.
______________________________________
Compound No. A-6b 2.5 parts by weight
Compound No. H-1 2.5 parts by weight
Xylene 75 parts by weight
Polyoxyethylene alkylaryl ether
20 parts by weight
______________________________________
The above components are mixed and dissolved to prepare an emulsifiable concentrate.
______________________________________
Compound No. A-1b 0.5 parts by weight
Compound No. I-1 0.5 parts by weight
Bentonite 20 parts by weight
Kaolin 74 parts by weight
Sodium lignin sulfonate
5 parts by weight
______________________________________
To the above components is added an adequate amount of water for granulation, and the mixture is mixed and granulated to prepare granules.
______________________________________
Compound No. A-1b 2.5 parts by weight
Compound No. D-3 22.5 parts by weight
Kerosene 63 parts by weight
A mixture of polyoxyethylene
12 parts by weight
phenylphenol derivative and
polyoxyethylene sorbitan
alkylate
______________________________________
The above components are mixed and finely pulverized to prepare a suspension concentrate.
A suspension concentrate can be prepared in the same manner as in Formulation Example 14, except for replacing Compound No. D-3 with Compound No. E-2.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (3)
1. A biocidal composition containing, as active ingredients, at least one imidazole compound represented by formula (I): ##STR10## wherein R1 represents a phenyl group, a halogen-substituted phenyl group, an alkyl group, or a halogen-substituted alkyl group; and R2 represents a halogen atom, and at least one compound selected from the group consisting of azole compounds, quinoxaline compounds, dithiocarbamate compounds, organic chlorine compounds, benzimidazole compounds, pyridinamine compounds, cyanoacetamide compounds, phenylamide compounds, sulfenic acid compounds, copper compounds, isoxazole compounds, organophosphorus compounds, N-halogenothioalkyl compounds, dicarboximide compounds, benzanilide compounds, benzamide compounds, piperazine compounds, pyridine compounds, pyrimidine compounds, piperidine compounds, morpholine compounds, organotin compounds, urea compounds, cinnamic acid compounds, carbamate compounds, pyrethroid compounds, benzoylurea compounds, thiazolidine compounds, thiadiazine compounds, nereistoxin derivatives, pyridazinone compounds, and spores of Bacillus thuringiensis and crystalline toxin produced thereby.
2. A biocidal composition as claimed in claim 1, wherein the imidazole compound is represented by formula (I'): ##STR11## wherein R1 ' represents a phenyl group or a halogen-substituted alkyl group; and R2 ' represents a chlorine atom.
3. A biocidal composition as claimed in claim 1, wherein the compound which is used in admixture with the imidazole compounds represented by formula (I) is at least one compound selected from the group consisting of azole compounds, quinoxaline compounds, dithiocarbamate compounds, organic chlorine compounds, benzimidazole compounds, pyridinamine compounds, cyanoacetamide compounds, phenylamide compounds, sulfenic acid compounds, copper compounds, isoxazole compounds, organophosphorus compounds, dicarboximide compounds, benzanilide compounds, and benzamide compounds.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-57920 | 1988-03-11 | ||
| JP63057920A JP2606720B2 (en) | 1987-03-13 | 1988-03-11 | Imidazole compounds and pesticides containing them |
| JP63-229327 | 1988-09-13 | ||
| JP22932788 | 1988-09-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USH811H true USH811H (en) | 1990-08-07 |
Family
ID=26399005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/322,460 Abandoned USH811H (en) | 1988-03-11 | 1989-03-13 | Biocidal composition |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | USH811H (en) |
| EP (1) | EP0337103B1 (en) |
| KR (1) | KR890013985A (en) |
| CN (1) | CN1036879A (en) |
| AT (1) | ATE85498T1 (en) |
| AU (1) | AU609264B2 (en) |
| BR (1) | BR8901097A (en) |
| DE (2) | DE68904792T2 (en) |
| ES (1) | ES2014385T3 (en) |
| GR (2) | GR900300071T1 (en) |
| HU (1) | HU205833B (en) |
| IL (1) | IL89475A0 (en) |
| MY (1) | MY129863A (en) |
| NZ (1) | NZ228284A (en) |
| PH (1) | PH25549A (en) |
| PT (1) | PT89972B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248675A (en) * | 1990-03-15 | 1993-09-28 | Tanabe Seiyaku Co., Ltd. | Polysulfate of cyclodextrin derivative and process for preparing the same |
| US5250520A (en) * | 1990-03-15 | 1993-10-05 | Tanabe Seiyaku Co., Ltd. | Polysulfate of cyclodextrin derivative and process for preparing the same |
| US5506216A (en) * | 1993-04-23 | 1996-04-09 | Boehringer Mannheim Gmbh | Cyclodextrin-biocide complex |
| US5656281A (en) * | 1989-12-14 | 1997-08-12 | Rhone-Poulenc Agrochimie | Water-dispersible granules of phosphite fungicidal products |
| US5891918A (en) * | 1996-06-28 | 1999-04-06 | Rohm And Haas Company | Method for controlling resistant fungi |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9023082D0 (en) * | 1990-10-24 | 1990-12-05 | Schering Agrochemicals Ltd | Fungicides |
| DE4122868A1 (en) * | 1991-07-11 | 1993-01-14 | Bayer Ag | MICROBICIDAL COMBINATIONS OF ACTIVE SUBSTANCES |
| DE4139950A1 (en) * | 1991-12-04 | 1993-06-09 | Bayer Ag, 5090 Leverkusen, De | 2-CYANOBENZIMIDAZOLE, A METHOD FOR THE PRODUCTION AND THEIR USE AND NEW PRE-PRODUCTS |
| ES2140778T3 (en) * | 1994-09-08 | 2000-03-01 | Ishihara Sangyo Kaisha | PROCEDURE FOR THE PREPARATION OF 2-CIANOIMIDAZOLE 1-SUBSTITUTED COMPOUNDS. |
| FR2737085B1 (en) * | 1995-07-26 | 1997-08-22 | Rhone Poulenc Agrochimie | INSECTICIDE ASSOCIATIONS OF A CARBAMATE OXIME WITH A PYRAZOLE OR PHENYLIMIDAZOLE GROUP INSECTICIDE |
| JPH10109912A (en) * | 1996-10-04 | 1998-04-28 | Akio Suganuma | Antimicrobial composition |
| DE69811654T2 (en) * | 1997-04-25 | 2003-10-23 | Ishihara Sangyo Kaisha Ltd., Osaka | COMPOSITION AND METHOD FOR CONTROLLING HARMFUL ORGANIC ORGANISMS |
| AU6597200A (en) * | 1999-08-19 | 2001-03-19 | Ishihara Sangyo Kaisha Ltd. | Agents for controlling animal diseases caused by parasites |
| US6713500B2 (en) | 1999-08-19 | 2004-03-30 | Ishihara Sangyo Kaisha Ltd. | Agent for controlling animal diseases caused by parasites |
| US20040191289A1 (en) * | 2001-07-30 | 2004-09-30 | Shigeru Mitani | Compositions for controlling plant pathogenic bacterium and method of controlling plant pathogenic bacterium |
| US7851497B2 (en) | 2004-07-16 | 2010-12-14 | Ishihara Sangyo Kaisha, Ltd. | Bactericidal composition for agricultural or horticultural use and method of controlling plant disease |
| EP2617287A1 (en) * | 2005-11-22 | 2013-07-24 | Ishihara Sangyo Kaisha, Ltd. | Germicide composition for agricultural and gardening applications and method for controlling plant disease |
| JP5584532B2 (en) * | 2009-07-06 | 2014-09-03 | 石原産業株式会社 | Agricultural / horticultural fungicide composition and method for controlling plant diseases |
| WO2019022857A1 (en) * | 2017-07-28 | 2019-01-31 | Dow Global Technologies Llc | Use of non oxidant biocide for the selective recovery of valuable metals in a froth flotation process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0298196A1 (en) | 1987-03-13 | 1989-01-11 | Ishihara Sangyo Kaisha, Ltd. | Imidazole compounds and biocidal compositions comprising the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62142164A (en) * | 1985-12-13 | 1987-06-25 | Ishihara Sangyo Kaisha Ltd | 4,5-dichloroimidazole based compound and pest controlling agent containing said compound |
| EP0298186A1 (en) * | 1987-07-09 | 1989-01-11 | Ebner-Industrieofenbau Gesellschaft m.b.H. | Process for operating a convection bell type annealing furnace, especially for coils of steel wire or strip |
-
1989
- 1989-02-27 MY MYPI89000236A patent/MY129863A/en unknown
- 1989-03-03 IL IL89475A patent/IL89475A0/en not_active IP Right Cessation
- 1989-03-06 DE DE8989103887T patent/DE68904792T2/en not_active Expired - Fee Related
- 1989-03-06 ES ES89103887T patent/ES2014385T3/en not_active Expired - Lifetime
- 1989-03-06 EP EP89103887A patent/EP0337103B1/en not_active Expired - Lifetime
- 1989-03-06 DE DE198989103887T patent/DE337103T1/en active Pending
- 1989-03-06 AT AT89103887T patent/ATE85498T1/en active
- 1989-03-07 AU AU31093/89A patent/AU609264B2/en not_active Ceased
- 1989-03-07 PH PH38294A patent/PH25549A/en unknown
- 1989-03-09 NZ NZ228284A patent/NZ228284A/en unknown
- 1989-03-09 BR BR898901097A patent/BR8901097A/en not_active Application Discontinuation
- 1989-03-10 KR KR1019890002940A patent/KR890013985A/en not_active Application Discontinuation
- 1989-03-10 PT PT89972A patent/PT89972B/en not_active IP Right Cessation
- 1989-03-10 CN CN89101331A patent/CN1036879A/en active Pending
- 1989-03-10 HU HU891195A patent/HU205833B/en not_active IP Right Cessation
- 1989-03-13 US US07/322,460 patent/USH811H/en not_active Abandoned
-
1991
- 1991-07-31 GR GR90300071T patent/GR900300071T1/en unknown
-
1993
- 1993-03-05 GR GR930400468T patent/GR3007247T3/el unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0298196A1 (en) | 1987-03-13 | 1989-01-11 | Ishihara Sangyo Kaisha, Ltd. | Imidazole compounds and biocidal compositions comprising the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5656281A (en) * | 1989-12-14 | 1997-08-12 | Rhone-Poulenc Agrochimie | Water-dispersible granules of phosphite fungicidal products |
| US5248675A (en) * | 1990-03-15 | 1993-09-28 | Tanabe Seiyaku Co., Ltd. | Polysulfate of cyclodextrin derivative and process for preparing the same |
| US5250520A (en) * | 1990-03-15 | 1993-10-05 | Tanabe Seiyaku Co., Ltd. | Polysulfate of cyclodextrin derivative and process for preparing the same |
| US5506216A (en) * | 1993-04-23 | 1996-04-09 | Boehringer Mannheim Gmbh | Cyclodextrin-biocide complex |
| US5891918A (en) * | 1996-06-28 | 1999-04-06 | Rohm And Haas Company | Method for controlling resistant fungi |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE85498T1 (en) | 1993-02-15 |
| BR8901097A (en) | 1989-10-31 |
| DE68904792T2 (en) | 1993-07-01 |
| GR3007247T3 (en) | 1993-07-30 |
| CN1036879A (en) | 1989-11-08 |
| KR890013985A (en) | 1989-10-21 |
| GR900300071T1 (en) | 1991-07-31 |
| EP0337103A3 (en) | 1990-01-17 |
| PH25549A (en) | 1991-08-08 |
| HU205833B (en) | 1992-07-28 |
| ES2014385A4 (en) | 1990-07-16 |
| DE68904792D1 (en) | 1993-03-25 |
| AU609264B2 (en) | 1991-04-26 |
| PT89972A (en) | 1989-10-04 |
| MY129863A (en) | 2007-05-31 |
| ES2014385T3 (en) | 1994-08-01 |
| HUT54867A (en) | 1991-04-29 |
| EP0337103A2 (en) | 1989-10-18 |
| DE337103T1 (en) | 1990-06-13 |
| PT89972B (en) | 1994-01-31 |
| EP0337103B1 (en) | 1993-02-10 |
| IL89475A0 (en) | 1989-09-10 |
| NZ228284A (en) | 1991-01-29 |
| AU3109389A (en) | 1989-09-14 |
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