Agricultural and horticultural fungicidal composition

The present invention provides an agricultural and horticultural fungicidal composition including a compound A which is at least one selected from a nitrogen-containing heterocyclic compound having a specific structure including a compound represented by the formula (1), and a salt thereof, and a compound B which is at least one selected from the group of specific pesticidally active compounds:

TECHNICAL FIELD

The present invention relates to an agricultural and horticultural fungicidal composition. More particularly, the present invention relates to an agricultural and horticultural fungicidal composition which exhibits excellent controlling effect on plant diseases even at low doses and does not pose concern for harmful effects on useful plants.

Priority is claimed on Japanese Patent Application No. 2011-209969, filed on Sep. 26, 2011, the content of which is incorporated herein by reference.

BACKGROUND ART

In the related art, a number of controlling drugs were used to control crop diseases in the cultivation of agricultural and horticultural crops. However, since the controlling effects are insufficient or the uses of the drugs are limited due to the emergence of pathogens with drug resistance, or since harmful effects or contaminations occur in plants or the toxicity to humans, animals, fish, or the like is strong, the drugs in the related art have often been insufficient to control crop diseases. Therefore, there is a demand for development of the fungicidal composition which can be safely used with a reduction in the aforementioned drawbacks. For example, it is described that a nitrogen-containing heterocyclic compound and/or a salt thereof are useful as an active ingredient in a fungicidal composition in PTLs 1 and 2.

CITATION LIST

Patent Literature

SUMMARY OF INVENTION

Technical Problem

An object of the present invention is to provide an agricultural and horticultural fungicidal composition which exhibits an excellent controlling effect on plant diseases even at low doses and does not pose a concern for harmful effects on useful plants.

Solution to Problem

In order to attain the object, the present inventors have made more extensive studies on fungicidal composition including the nitrogen-containing heterocyclic compound and/or a salt thereof described in PTLs 1 and 2 as an active ingredient. As a result, they have found that by using a combination of the nitrogen-containing heterocyclic compound and/or a salt thereof with a specific pesticidally active compound, an excellent controlling effect on plant diseases even at low doses are exhibited and there is no concern about harmful effects on useful plants. The present invention has been completed by further conducting repeated investigations based on the aforementioned finding.

That is, the present invention relates to the followings.

[1] An agricultural and horticultural fungicidal composition including:

at least one selected from the group consisting of a nitrogen-containing heterocyclic compound represented by the formula (1), a nitrogen-containing heterocyclic compound represented by the formula (2), and salts thereof:

in the formula (1), X each independently represents a halogeno group or a C1 to 6 alkyl group. n represents the number of X(s) and is an integer of 0 to 6. X′ represents a halogeno group. R1, R2and R3each independently represent a C1 to 6 alkyl group or a hydroxyl group.

in the formula (2), X each independently represents a halogeno group or a C1 to 6 alkyl group. n represents the number of X(s) and is an integer of 0 to 6. X′ represents a halogeno group. R4, R5, R6and R7each independently represent a hydrogen atom, a C1 to 6 alkyl group, or a hydroxyl group; and

at least one compound selected from the group consisting of an SBI agent, a benzimidazole-based agent, an acid amide-based fungicide, a dicarboximide-based fungicide, a phenylpyrrole-based fungicide, an organic (thio)phosphate-based agent, a guanidine-based fungicide, a mitochondrial electron transport chain complex II inhibitor, a mitochondrial electron transport chain complex III inhibitor, an anilinopyrimidine-based agent, a neonicotinoid-based agent, an SH inhibitor, cyflufenamid, cymoxanil, proquinazid, metrafenone, quinoxyfen, diclomezine, isoprothiolane, bupirimate, hexythiazox, tebufenozide, thiodicarb, spinosad, etofenprox, fipronil, ethiprole, pymetrozine, buprofezin, chlorfenapyr, a compound represented by the formula (3), a compound represented by the formula (4), and salts thereof

in the formula (3), W represents a C1 to 6 alkyl group, a C1 to 6 alkoxy group, a halogen atom, a nitro group, a cyano group, a C6 to 10 aryl group, or a C1 to 6 alkylsulfonyl group. Y represents a C1 to 6 alkyl group. m represents the number of W(s) and is an integer of 0 to 5. Z represents a hydrogen atom, an amino group, or a group represented by the formula: —NHC(═O)-Q, in which Q represents a hydrogen atom, a C1 to 8 alkyl group, a C1 to 6 haloalkyl group, a C3 to 6 cycloalkyl group, a C1 to 8 alkoxy group, a C3 to 6 cycloalkyloxy group, a C7 to 20 aralkyloxy group, a C1 to 4 alkylthio-C1 to 8 alkyl group, a C1 to 4 alkoxy-C1 to 2 alkyl group, a C1 to 4 acylamino-C1 to 6 alkyl group, a C1 to 4 acylamino-C1 to 6 alkoxy group, a C1 to 8 alkylamino group, a C2 to 6 alkenyl group, an aralkyl group, or a phenyl group. R represents a halogen atom. n represents the number of R(s) and is an integer of 0 to 3.

in the formula (4), Y represents a group represented by O or NR1, in which R1represents a hydrogen atom or a methyl group. Z represents a group represented by CR2R3or NR2, in which R2and R3independently represent a hydrogen atom or a methyl group. R represents a hydroxyl group, a halogen atom, a C1 to 4 alkyl group, a C1 to 4 haloalkyl group, a C1 to 4 alkoxy group, or a C1 to 4 haloalkoxy group. m represents the number of R(s) and is an integer of 0 to 3. R′ and R″ independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a C1 to 4 alkyl group, a C1 to 4 haloalkyl group, a C1 to 4 alkoxy group, or a C1 to 4 haloalkoxy group. R′″ represents a hydroxyl group, a halogen atom, a C1 to 4 alkyl group, a C1 to 4 haloalkyl group, a C1 to 4 alkoxy group, or a C1 to 4 haloalkoxy group. n represents the number of R′″ and is an integer of 0 to 4. And, ═Y and R′ may be combined to represent a group represented by ═N—O—, and R′ and R″ may be combined to represent a C2 to 3 alkylene group.

[2] The agricultural and horticultural fungicidal composition as described in [1], in which the SBI agent is at least one selected from the group consisting of triflumizole, difenoconazole, and tebuconazole.

[3] The agricultural and horticultural fungicidal composition as described in [1] or [2], in which the benzimidazole-based agent is thiophanate-methyl.

[4] The agricultural and horticultural fungicidal composition as described in any one of [1] to [3], in which the acid amide-based fungicide is at least one selected from the group consisting of metalaxyl, benthiavalicarb-isopropyl, fluopicolide, fluopyram, zoxamide, flutolanil, carboxin, thifluzamide, and boscalid.

[5] The agricultural and horticultural fungicidal composition as described in any one of [1] to [4], in which the dicarboxylmide-based fungicide is iprodione.

[6] The agricultural and horticultural fungicidal composition as described in any one of [1] to [5], in which the phenylpyrrole-based fungicide is fludioxonil.

[7] The agricultural and horticultural fungicidal composition as described in any one of [1] to [6], in which the organic (thio)phosphate-based agent is at least one selected from the group consisting of compounds represented by the formula (5):

in the formula (5), R′ and R2represent a methyl group or an ethyl group. Ar represents a phenyl group or a 6-membered heteroaromatic ring group. R3represents a halogen atom or a methyl group. n represents the number of R3and is an integer of 0 to 5.

[8] The agricultural and horticultural fungicidal composition as described in any one of [1] to [7], in which the organic (thio)phosphate-based agent is at least one selected from the group consisting of fosetyl, tolclofos-methyl, and chlorpyrifos.

[9] The agricultural and horticultural fungicidal composition as described in any one of [1] to [8], in which the guanidine-based fungicide is iminoctadine.

[10] The agricultural and horticultural fungicidal composition as described in any one of [1] to [9], in which the mitochondrial electron transport chain complex II inhibitor is at least one including an anilide-based fungicide.

[11] The agricultural and horticultural fungicidal composition as described in any one of [1] to [10], in which the mitochondrial electron transport chain complex III inhibitor is at least one selected from the group consisting of a QoI agent, a QiI agent, and ametoctradin.

[12] The agricultural and horticultural fungicidal composition as described in [11], in which the QoI agent is at least one selected from the group consisting of trifloxystrobin, azoxystrobin, kresoxim-methyl, orysastrobin, famoxadone, and pyribencarb.

[13] The agricultural and horticultural fungicidal composition as described in [11] or [12], in which the QiI agent is cyazofamid.

[14] The agricultural and horticultural fungicidal composition as described in any one of [1] to [13], in which the anilinopyrimidine-based agent is cyprodinil.

[15] The agricultural and horticultural fungicidal composition as described in any one of [1] to [14], in which the neonicotinoid-based agent is at least one selected from the group consisting of compounds represented by the formula (6):

in the formula (6), A represents N or CH. B represents a methyl group or a group represented by —NR21R22, wherein R21represents a hydrogen atom or a methyl group, and R22represents a methyl group or is combined with R3to form a 5- to 6-membered ring. R1represents a cyano group or a nitro group. R2represents an unsubstituted or substituted 5- to 6-membered heterocyclic group. R3represents a hydrogen atom, a methyl group, or an ethyl group or is combined with R22to form a 5- to 6-membered ring.

[16] The agricultural and horticultural fungicidal composition as described in any one of [1] to [15], in which the neonicotinoid-based agent is at least one selected from the group consisting of acetamiprid, imidacloprid, thiamethoxam, clothianidin, and dinotefuran.

[17] The agricultural and horticultural fungicidal composition as described in any one of [1] to [16], in which the SH inhibitor is at least one selected from the group consisting of manzeb, thiram, chlorothalonil, captan, folpet, and fluazinam.

[18] The agricultural and horticultural fungicidal composition as described in any one of [1] to [17], in which the compound represented by the formula (3) is a compound represented by the formula (7):

[19] The agricultural and horticultural fungicidal composition as described in any one of [1] to [18], in which the compound represented by the formula (4) is a compound represented by the formula (8) or the formula (9):

Advantageous Effects of Invention

The agricultural and horticultural fungicidal composition of the present invention exhibits an excellent controlling effect on plant diseases even at very low doses and does not pose a concern about harmful effects on useful plants.

DESCRIPTION OF EMBODIMENTS

The agricultural and horticultural fungicidal composition of the present invention includes at least one selected from the group consisting of a nitrogen-containing heterocyclic compound having a specific structure and a salt thereof (which may be hereinafter sometimes referred to a compound A), and at least one selected from the group of specific pesticidally active compounds (which may be hereinafter sometimes referred to a compound B). The agricultural and horticultural fungicidal composition of the present invention exhibits a remarkably synergistic controlling effect on plant diseases, which could not be predicted from controlling effect on plant diseases obtained from the use of the compound A alone or the compound B alone.

The compound A is at least one selected from the group consisting of the nitrogen-containing heterocyclic compound represented by the formula (1), the nitrogen-containing heterocyclic compound represented by the formula (2), and salts thereof.

X in the formula (1) or the formula (2) each independently represents a halogeno group or a C1 to 6 alkyl group. n represents the number of X(s) and is an integer of 0 to 6.

Examples of the C1 to 6 alkyl group in X include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group. In the C1 to 6 alkyl group, a part or all of the hydrogen atoms may be substituted with other group(s) within a range not interfering with the effect of the present invention. Examples of the substituent include a halogeno group and a hydroxyl group.

Examples of the halogeno group in X include a fluoro group, a chloro group, a bromo group, and an iodo group.

X′ in the formula (1) or the formula (2) represents a halogeno group. The halogeno group in X′ has the same meaning as in X.

R1, R2and R3in the formula (1) each independently represent a C1 to 6 alkyl group or a hydroxyl group. The C1 to 6 alkyl group in R′ R2and R3have the same meanings as in X.

R4, R5, R6and R7in the formula (2) each independently represent a hydrogen atom, a C1 to 6 alkyl group, or a hydroxyl group. The C1 to 6 alkyl group in R4, R5, R6and R7have the same meanings as in X.

The salt of the nitrogen-containing heterocyclic compound represented by the formula (1) or the formula (2) is not particularly limited as long as it is agriculturally and horticulturally acceptable salt, and examples thereof include salts of inorganic acids, such as hydrochloride, nitrate, sulfate, and phosphate; and salts of organic acids, such as acetate, lactate, propionate, and benzoate.

The nitrogen-containing heterocyclic compound represented by the formula (1) used in the present invention is a known material and specific examples thereof include the compounds described in the pamphlet of PCT International Publication No. WO2011/081174. Further, the nitrogen-containing heterocyclic compound represented by the formula (1) and a salt thereof can be prepared by a known method. Specific examples of the preparation method therefor include the methods described in the pamphlet of PCT International Publication No. WO2011/081174.

The nitrogen-containing heterocyclic compound represented by the formula (2) used in the present invention is a known material and specific examples thereof include the compounds described in the pamphlet of PCT International Publication No. WO2010/018686. Further, the nitrogen-containing heterocyclic compound represented by the formula (2) and a salt thereof can be prepared by a known method. Specific examples of the preparation method therefor include the methods described in the pamphlet of PCT International Publication No. WO2010/018686.

The compound B is at least one compound selected from the group consisting of:

in the formula (10), W represents a C1 to 6 alkyl group, a C1 to 6 alkoxy group, a halogen atom, a nitro group, a cyano group, a C6 to 10 aryl group, or a C1 to 6 alkylsulfonyl group. Y represents a C1 to 6 alkyl group. m represents the number of W(s) and is an integer of 0 to 5. Z represents a hydrogen atom, an amino group, or a group represented by the formula: —NHC(═O)-Q, in which Q represents a hydrogen atom, a C1 to 8 alkyl group, a C1 to 6 haloalkyl group, a C3 to 6 cycloalkyl group, a C1 to 8 alkoxy group, a C3 to 6 cycloalkyloxy group, a C7 to 20 aralkyloxy group, a C1 to 4 alkylthio-C1 to 8 alkyl group, a C1 to 4 alkoxy-C1 to 2 alkyl group, a C1 to 4 acylamino-C1 to 6 alkyl group, a C1 to 4 acylamino-C1 to 6 alkoxy group, a C1 to 8 alkylamino group, a C2 to 6 alkenyl group, an aralkyl group, or a phenyl group. R represents a halogen atom. n represents the number of R(s) and is an integer of 0 to 3.

in the formula (11), Y represents a group represented by O or NR1, in which R1represents a hydrogen atom or a methyl group. Z represents a group represented by CR2R3or NR2, in which R2and R3independently represent a hydrogen atom or a methyl group. R represents a hydroxyl group, a halogen atom, a C1 to 4 alkyl group, a C1 to 4 haloalkyl group, a C1 to 4 alkoxy group, or a C1 to 4 haloalkoxy group. m represents the number of R(s) and is an integer of 0 to 3. R′ and R″ independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a C1 to 4 alkyl group, a C1 to 4 haloalkyl group, a C1 to 4 alkoxy group, or a C1 to 4 haloalkoxy group. R′″ represents a hydroxyl group, a halogen atom, a C1 to 4 alkyl group, a C1 to 4 haloalkyl group, a C1 to 4 alkoxy group, or a C1 to 4 haloalkoxy group. n represents the number of R′″ and is an integer of 0 to 4. And, ═Y and R′ may be combined with each other to represent a group represented by ═N—O—, and R′ and R″ may be combined to represent a C2 to 3 alkylene group.

The compound represented by the formula (11) is preferably a compound represented by the formula (12).

in the formula (12), Y, Z, R′, R″, R′″, and n have the same meanings as Y, Z, R′, R″, R′″, and n described in the formula (11).

Additionally, the compound B further includes an optically active compound thereof. For example, it is in the same case as metalaxyl M with respect to metalaxyl. The compound B includes known materials and these may be available according to known preparation methods or by purchasing from manufacturers.

Among these, particularly preferred examples of the compound include triflumizole, difenoconazole, and tebuconazole.

The benzimidazole-based agent as mentioned in the present invention refers to a group of the compounds having a benzimidazole skeleton and binding to a tubulin constituting microtubules to inhibit nuclear division, and a precursor thereof, and a group of the compounds that are transformed to forms having benzimidazole skeletons to exert the same inhibitory effect. Preferred examples of the benzimidazole-based agent include benomyl, carbendazim, fuberidazole, chlorfenazole, and thiabendazole, and examples of the precursor include thiophanate and thiophanate-methyl.

Among these, particularly preferred examples of the compound include thiophanate-methyl.

The acid amide-based fungicide as mentioned in the present invention is a group of the compounds having a fungicidal effect, which has a carboxyl acid amide structure. Preferred examples of the acid amide-based fungicide include fluopyram, flutolanil, carboxin, oxycarboxin, thifluzamide, boscalid, penthiopyrad, mepronil, furametpyr, isofetamid, penflufen, metalaxyl, benthiavalicarb-isopropyl, fluopicolide, zoxamide, pencycuron, tiadinil, zarilamid, dimethomorph, flumorph, iprovalicarb, mandipropamid, and valifenalate.

As a representative group of the compounds included in the acid amide-based fungicides, there is a group of the compounds which are called anilide-based fungicides. These generally have structures of the formula (13).

in the formula (13), Cy1and Cy2independently represent an unsubstituted or substituted phenyl group, or an unsubstituted or substituted 5- to 6-membered heterocyclic group, and R represents a single bond, a methylene group, or an ethylene group.

Furthermore, the mitochondrial electron transport chain complex II inhibitor as mentioned in the present invention is a group of the compounds having a property of binding to a mitochondrial electron transport chain complex II (succinic acid dehydrogenase complex) to inhibit respiration.

Representative Examples of the group of the compounds included in the mitochondrial electron transport chain complex II inhibitor include the anilide fungicides as described above.

Particularly preferred examples of the compound out of the group of the compounds listed as the acid amide-based fungicide or the mitochondrial electron transport chain complex II inhibitor include fluopyram, flutolanil, carboxin, thifluzamide, boscalid, metalaxyl, benthiavalicarb-isopropyl, fluopicolide, and zoxamide.

The dicarboxylmide-based fungicide as mentioned in the present invention is a group of the compounds having 5-membered rings including dicarboxylmide structures, and targets a signal transduction system protein OS-1 with respect to the osmotic pressure control in fungi. Preferred examples of the dicarboxylmide-based fungicide include iprodione, procymidone, vinclozolin, chlozolinate, and fluoroimide.

Among these, particularly preferred examples of the compound include iprodione.

The phenylpyrrole-based fungicide as mentioned in the present invention is a group of the compounds having 3-phenylpyrrole structures, and targets a signal transduction system protein OS-2 with respect to the osmotic pressure control in fungi. Preferred examples of the phenylpyrrole-based fungicide include fludioxonil and fenpiclonil.

Among these, particularly preferred examples of the compound include fludioxonil.

Among these, a preferred compound is a compound represented by the formula (14).

in the formula (14), R1and R2represent a methyl group or an ethyl group. Ar represents a phenyl group or a 6-membered heteroaromatic ring group. R3represents a halogen atom or a methyl group. n represents the number of R3and is an integer of 0 to 5.

Among the organic (thio)phosphate-based agents, more preferred examples of the compound include fosetyl, tolclofos-methyl, and chlorpyrifos.

The guanidine-based fungicide as mentioned in the present invention refers to a group of the compounds having guanidine partial structures. Preferred examples of the guanidine-based fungicide include iminoctadine acetate, iminoctadine albesilate, dodine, and guazatine.

The mitochondrial electron transport chain complex III inhibitor as mentioned in the present invention refers to a group of compound having a property of binding to a mitochondrial electron transport chain complex III (bcl complex) to inhibit the respiration, and is used in the applications of fungicides, acaricides, or the like. These can be divided into Qo site inhibitors (QoI agents), Qi site inhibitors (QiI agents), and other compounds according to the binding sites in the complex III.

Representative examples of the group of the compounds that are QoI agents include strobilurin-based agents, as well as famoxadone and pyribencarb. Examples of the QiI agent include cyazofamid, amisulbrom, fenamidone, and furmecyclox, and cyazofamid is particularly preferred. Other examples of the compound include ametoctradin and tebufloquin, and ametoctradin is particularly preferable.

The strobilurin-based agent refers to a group of the compounds having partial structures of a 3-methoxyacrylic ester (methoxyacrylate-based), an N-methoxycarbamic ester (methoxycarbamate-based), an methoxyiminoacetic ester (methoxyiminoacetate-based), a 2-methoxyiminoacetamide (methoxyiminoacetamide-based), or the like, and binding to a Qo site of a respiration chain complex III to inhibit the respiration. Examples of the strobilurin-based agent include methoxyacrylate-based azoxystrobin, picoxystrobin, pyraoxystrobin, enestroburin, and phenoxystrobin; methoxycarbamate-based pyraclostrobin, pyrametostrobin, and triclopyricarb; methoxyiminoacetate-based kresoxim-methyl, and trifloxystrobin; methoxyiminoacetamide-based orysastrobin, metominostrobin, metominofen, and dimoxystrobin; as well as fluoxastrobin.

A preferred compound as the strobilurin-based agent is a compound represented by the formula (15).

in the formula (15), A represents a CH or N. B represents O or NH. Ar—R— represents a group represented by any one of Ar—O—, Ar—CH2—, Ar—CH2O—, Ar—OCH2—, and Ar—C(CH3)═NOCH2—, and Ar represents an unsubstituted or substituted phenyl group or an unsubstituted or substituted 6-membered heteroaromatic ring group.

Among the strobilurin-based agents, more preferred examples of the compound include trifloxystrobin, kresoxim-methyl, azoxystrobin, and orysastrobin.

The anilinopyrimidine-based agent as mentioned in the present invention is a fungicide which has a 2-phenylaminopyrimidine skeleton and has an action of inhibiting methionine biosynthesis and an action of inhibiting the secretion of cell wall degrading enzymes. Preferred examples of the anilinopyrimidine-based agent include andoprim, cyprodinil, mepanipyrim, and pyrimethanil. Among these, cyprodinil is particularly preferable.

The neonicotinoid-based agent as mentioned in the present invention is an insecticide which functions as a blocking agent for a nicotinic acetylcholine receptor. Examples of the neonicotinoid-based agent include acetamiprid, imidacloprid, thiamethoxam, clothianidin, dinotefuran, nitenpyram, and thiacloprid. A preferred compound as the neonicotinoid-based agent is a compound represented by the formula (16).

in the formula (16), A represents N or CH. B represents a methyl group or a group represented by —NR21R22, wherein R21represents a hydrogen atom or a methyl group, and R22represents a methyl group or is combined with R3to form a 5- to 6-membered ring. R1represents a cyano group or a nitro group. R2represents an unsubstituted or substituted 5- to 6-membered heterocyclic group. R3represents a hydrogen atom, a methyl group, or an ethyl group or is combined with R22to form a 5- to 6-membered ring.

Among these, particularly preferred examples of the compound include acetamiprid, imidacloprid, thiamethoxam, clothianidin, and dinotefuran.

The SH inhibitor as mentioned in the present invention refers to a protective fungicide that inhibits mainly enzymes in the respiratory system, having an SH group, and has a spore germination inhibitory activity, and thus, has no therapeutic activity. Preferred examples of the SH inhibitor include inorganic copper, organic copper, zineb, maneb, manzeb, ziram, polycarbamate, thiram, chlorothalonil, fluazinam, captan, captafol, folpet, methyl bromide, dazomet, pyridinitrile, anilazine, dichlofluanid, dichlone, fluoroimide, and dithianon.

Among these, particularly preferred examples of the compound include manzeb, thiram, chlorothalonil, fluazinam, captan, and folpet.

The compound represented by the formula (10) is not particularly limited, but is particularly preferably a compound represented by the formula (17).

The compound represented by the formula (12) is not particularly limited, but is particularly preferably a compound represented by the formula (18) or the formula (19).

Additionally, the meanings of “unsubstituted” and “substituted” in the description above are as follows.

The term “unsubstituted” means that there is only a group which is a scaffold. A description in which there is no description of “substituted” with only the names of the groups which are scaffolds has the same meaning as “unsubstituted” unless otherwise mentioned.

On the other hand, the term “substituted” means that any hydrogen atom of the groups which are scaffolds is substituted with a group having a structure of the same as or different from the scaffold. Accordingly, the “substituent” is another group binding to a group which is a scaffold. The number of the substituent(s) may be one, or two or more. The two or more substituents may be the same as or different from each other.

The term “C1-6” or the like denotes that the number of carbon atoms of a group to be a scaffold is 1 to 6, or the like. For the number of carbon atoms, the number of the carbon atoms in the substituent is not counted. For example, the butyl group having an ethoxy group as a substituent is classified as a C2 alkoxy-C4 alkyl group.

The “substituent” is chemically allowed and is not particularly limited as long as it has the effect of the present invention.

C1-6 alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an s-butoxy group, an i-butoxy group, and a t-butoxy group; C2-6 alkenyloxy groups such as a vinyloxy group, an allyloxy group, a propenyloxy group, and a butenyloxy group; C2-6 alkynyloxy groups such as an ethynyloxy group and a propargyloxy group; C6-10 aryl groups such as a phenyl group and a naphthyl group; C6-10 aryloxy groups such as a phenoxy group and a 1-naphthoxy group; C7-11 aralkyl groups such as a benzyl group and a phenethyl group; C7-11 aralkyloxy groups such as a benzyloxy group and a phenethyloxy group; C1-7 acyl groups such as a formyl group, an acetyl group, a propionyl group, a benzoyl group, and a cyclohexylcarbonyl group; C1-7 acyloxy groups such as a formyloxy group, an acetyloxy group, a propionyloxy group, a benzoyloxy group, and a cyclohexylcarbonyloxy group; C1-6 alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group; a carboxyl group;

a hydroxyl group; an oxo group; C1-6 haloalkyl groups such as a chloromethyl group, a chloroethyl group, a trifluoromethyl group, a 1,2-dichloro-n-propyl group, a 1-fluoro-n-butyl group, and a perfluoro-n-pentyl group; C2-6 haloalkenyl groups such as a 2-chloro-1-propenyl group and a 2-fluoro-1-butenyl group; C2-6 haloalkynyl groups such as a 4,4-dichloro-1-butynyl group, a 4-fluoro-1-pentynyl group, and a 5-bromo-2-pentynyl group; C1-6 haloalkoxy groups such as a 2-chloro-n-propoxy group and a 2,3-dichlorobutoxy group; C2-6 haloalkenyloxy groups such as a 2-chloropropenyloxy group and a 3-bromobutenyloxy group; C6-10 haloaryl groups such as a 4-chlorophenyl group, a 4-fluorophenyl group, and a 2,4-dichlorophenyl group; C6-10 haloaryloxy groups such as a 4-fluorophenyloxy group and a 4-chloro-1-naphthoxy group; C1-7 haloacyl groups such as a chloroacetyl group, a trifluoroacetyl group, a trichloroacetyl group, and a 4-chlorobenzoyl group;

a cyano group; an isocyano group; a nitro group; an isocyanato group; a cyanato group; an azide group; an amino group; C1-6 alkylamino groups such as a methylamino group, a dimethylamino group, and a diethylamino group; C6-10 arylamino groups such as an anilino group and a naphthylamino group; C7-11 aralkylamino groups such as a benzylamino group and a phenylethylamino group; C1-7 acylamino groups such as a formylamino group, an acetylamino group, a propanoylamino group, a butyrylamino group, an i-propylcarbonylamino group, and a benzoylamino group; C1-6 alkoxycarbonylamino groups such as a methoxycarbonylamino group, an ethoxycarbonylamino group, an n-propoxycarbonylamino group, and an i-propoxycarbonylamino group; a carbamoyl group; substituted carbamoyl groups such as a dimethylcarbamoyl group, a phenylcarbamoyl group, and an N-phenyl-N-methylcarbamoyl group; imino-C1-6 alkyl groups such as an iminomethyl group, a (1-imino)ethyl group, and a (1-imino)-n-propyl group; hydroxyimino-C1-6 alkyl groups such as a hydroxyiminomethyl group, a (1-hydroxyimino)ethyl group, and a (1-hydroxyimino)propyl group; C1-6 alkoxyimino-C1-6 alkyl groups such as a methoxyiminomethyl group and a (1-methoxyimino)ethyl group;

a mercapto group; an isothiocyanato group; a thiocyanato group; C1-6 alkylthio groups such as a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, an i-butylthio group, an s-butylthio group, and a t-butylthio group; C2-6 alkenylthio groups such as a vinylthio group and an allylthio group; C2-6 alkynylthio groups such as an ethynylthio group and a propargylthio group; C6-10 arylthio groups such as a phenylthio group and a naphthylthio group; heteroarylthio groups such as a thiazolylthio group and a pyridylthio group; C7-11 aralkylthio groups such as a benzylthio group and a phenethylthio group; (C1-6 alkylthio)carbonyl groups such as a (methylthio)carbonyl group, an (ethylthio)carbonyl group, an (n-propylthio)carbonyl group, an (i-propylthio)carbonyl group, an (n-butylthio)carbonyl group, an (i-butylthio)carbonyl group, an (s-butylthio)carbonyl group, and a (t-butylthio)carbonyl group;

C1-6 alkylsulfinyl groups such as a methylsulfinyl group, an ethylsulfinyl group, and a t-butylsulfinyl group; C2-6 alkenylsulfinyl groups such as an allylsulfinyl group; C2-6 alkynylsulfinyl groups such as a propargylsulfinyl group; C6-10 arylsulfinyl groups such as a phenylsulfinyl group; heteroarylsulfinyl groups such as a thiazolylsulfinyl group and a pyridylsulfinyl group; C7-11 aralkylsulfinyl groups such as a benzylsulfinyl group and a phenethylsulfinyl group; C1-6 alkylsulfonyl groups such as a methylsulfonyl group, an ethylsulfonyl group, and a t-butylsulfonyl group; C2-6 alkenylsulfonyl groups such as an allylsulfonyl group; C2-6 alkynylsulfonyl groups such as a propargylsulfonyl group; C6-10 arylsulfonyl groups such as a phenylsulfonyl group; heteroarylsulfonyl groups such as a thiazolylsulfonyl group and a pyridylsulfonyl group; C7-11 aralkylsulfonyl groups such as a benzylsulfonyl group and a phenethylsulfonyl group;

5-membered heteroaryl groups such as a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, an oxadiazolyl group, a thiadiazolyl group, and a tetrazolyl group; 6-membered heteroaryl groups such as a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, and a triazinyl group; saturated heterocyclic groups such as a an aziridinyl group, an epoxy group, a pyrrolidinyl group, a tetrahydrofuranyl group, a piperidyl group, a piperazinyl group, and a morpholinyl group; tri-C1-6 alkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group; and a triphenylsilyl group.

Furthermore, these “substituents” may have other “substituent(s)” therein. For example, a butyl group as a substituent may have an ethoxy group as another substituent, that is, an ethoxybutyl group.

In the agricultural and horticultural fungicidal composition of the present invention, the weight ratio of the compound A to the compound B, (compound A):(compound B), is usually 1:10,000,000 to 10,000,000:1, is preferably 1:1,000,000 to 1,000,000:1, is more preferably 1:100,000 to 100,000:1, and is particularly preferably 1:10,000 to 10,000:1.

For the agricultural and horticultural fungicidal composition of the present invention, known insecticide, acaricides, herbicides, plant growth regulators, or the like may be used in mixture, in addition to the compound A and the compound B, leading to a labor-saving effect in some cases.

Examples of the method for preparing the fungicidal composition of the present invention include (a) a method including formulating a compound A and a compound B as separate preparations, and mixing the preparations together, (b) a method including formulating a compound A as a preparation and mixing the preparation with a compound B, (c) a method including formulating a compound B as a preparation and mixing the preparation with a compound A, and (d) a method including mixing a compound A and a compound B, and if desired, formulating the mixture as a preparation.

The fungicidal composition of the present invention may include a fertilizer, a solid carrier, a thickener, a surfactant, a spreading agent, an additive, a solvent, or the like, within a range not interfering with the effect of the present invention.

Examples of the fertilizer include compost, oil cake, fish meal, cow feces, poultry feces, or the like, or organic materials formed by processing them; nitrogen fertilizers such as ammonium sulfate, ammonium nitrate, lime nitrate, and urea; phosphoric acid fertilizers such as lime superphosphate, monoammonium phosphate, and a fused phosphorus fertilizer; potassium fertilizers such as potassium chloride, potassium sulfate, and potassium nitrate; magnesia fertilizers such as magnesia lime; lime fertilizers such as slaked lime; silicic acid fertilizers such as potassium silicate; boron fertilizers such as borate; and chemical fertilizers formed of various inorganic fertilizers.

Examples of the solid carrier include vegetable powder such as soybean flour and wheat flour; and mineral fine powder such as silicon dioxide, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay, and soil.

Example of the additive include organic and inorganic compounds such as sodium benzoate, urea, and mirabilite; and rapeseed oil, soybean oil, sunflower oil, castor oil, pine oil, cottonseed oil, and derivatives of these oils, and oil concentrates thereof.

One kind or two or more kinds of other fungicides or insecticides/acaricides, and synergists may be mixed with the agricultural and horticultural fungicidal composition of the present invention so long as they do not interfere with the effects of the present invention.

Representative examples of the fungicides, insecticides, acaricides, and plant growth regulators that can be mixed and used above are shown below.

METI II and III compounds: acequinocyl, fluacrypyrim, and rotenone;

Plant Growth Regulators:

The formulation obtained by formulating the compound A, the compound B, or a mixture thereof into a preparation is not particularly limited, and may adopt a form able to be adopted by ordinary agricultural and horticultural chemicals, for example, powder, a wettable powder, a soluble powder, an emulsifiable concentrate, a flowable agent, wettable granules, granules, or the like.

The concentration of the active ingredient (the total concentration of the compound A and the compound B) in the fungicidal composition of the present invention, which has been formulated into a preparation, is not particularly limited and various concentrations can be adopted according to the forms of the preparations above. For example, for wettable powders, the concentration of the active ingredient may be usually 5% by weight to 90% by weight, and preferably 10% by weight to 85% by weight; for emulsifiable concentrates, the concentration of the active ingredient may be usually 3% by weight to 70% by weight, and preferably 5% by weight to 60% by weight; and for granules, the concentration of the active ingredient may be usually 0.01% by weight to 50% by weight, and preferably 0.05% by weight to 40% by weight.

The fungicidal composition of the present invention, which has been formulated into a preparation, is diluted as it is or at a predetermined concentration with water, and thus, it is used by spraying to plants, or irrigating, incorporating, or spraying to soil, in the form of a solution, a suspension, or an emulsion. When the fungicidal composition of the present invention is subjected to an agricultural field, a suitable amount of 0.1 g or more (as a compound total amount with the compound A and the B) of an active ingredient per hectare is usually used.

Examples of useful plants to be treated in the fungicidal composition of the present invention include cereals, vegetables, root vegetables, potatoes, trees, grasses, and lawn. In this case, each part of these plants may be subjected to the treatment. Examples of the part of the plants include leaves, stems, florals, flowers, buds, fruits, seeds, sprouts, roots, tubers, tuberous roots, shoots, and cuttings. It is also possible to subject the improved varieties/variants of these plants, and cultivars, mutants, hybrid bodies, or genetically modified bodies (GMO) to the treatment.

An example of the useful plants is shown below.

The fungicidal composition of the present invention has an excellent fungicidal power for a wide variety of filamentous fungi, for example, fungi belong to algae fungi (Oomycetes), sac fungi (Ascomycetes), imperfect fungi (Deuteromycetes), or Basidiomycete fungi (Basidiomycetes).

The fungicidal composition of the present invention can be in control of various diseases generated upon cultivation of agricultural and horticultural crops, including flowers, lawn, and glasses by seed treatment, foliar spray, soil application, water application, or the like.

The fungicidal composition of the present invention can be used for the control of problems with:

Furthermore, the fungicidal composition of the present invention has an excellent fungicidal effect even on resistant fungi. Further, since the fungicidal composition exhibits the effect even when used at very low doses, it has an effect of preventing the emergence of new resistant fungi.

Examples of diseases for which the application of the fungicidal composition of the present invention is more preferable include scab of apples, gray mold disease of cucumbers, powdery mildew of wheat, late blight of tomato, leaf rust of wheat, rice blast, and vine wilt of cucumbers.

EXAMPLES

Next, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to Examples in any way.

Example 1 and Comparative Example 1

The drug I and the drug II were dissolved in dimethyl sulfoxide separately at the concentrations shown in Tables 1 to 5. The solutions thus obtained were mixed to prepare fungicidal compositions.

Additionally, in Tables, the symbol A indicating the drug I represents a nitrogen-containing heterocyclic compound represented by the formula (A), the symbol B indicating the drug I represents a nitrogen-containing heterocyclic compound represented by the formula (B), and the symbol C indicating the drug I represents a nitrogen-containing heterocyclic compound represented by the formula (C). Further, in Tables, the number indicating the drug II represents each of the compounds [1] to [61] described below. Additionally, “-” in Tables represents that the drug was not used.

[38] Compound represented by the formula (20)

[39] Compound represented by the formula (21)

[61] Compound represented by the formula (22)

Conidia ofBotrytis cinereawere added to and dispersed in a potato dextrose culture medium. A fungicidal composition was added thereto and mixed. This was dispensed in a 96-well microplate and cultured at 20° C. for 3 days in a dark setting. Then, the turbidity was measured at a wavelength of 405 nm in a microplate reader. From comparison with the measured value of turbidity in the case of non-treatment (without the addition of the fungicidal composition), the growth inhibition rate ofBotrytis cinerea(%) was calculated. The test was carried out in duplicate. Further, the expected value of the growth inhibition was calculated based on Colby's equation. The results thereof are shown in Tables 1 to 5.

In addition, the Colby's equation is E=M+N−MN/100. Here, E is the expected value of a growth inhibition rate (%), M is the growth inhibition rate (%) calculated from the measurement with the use of the drug I alone, and N is the growth inhibition rate (%) calculated from the measurement with the use of the drug II alone. Additionally, in Tables, the expected values with the use of the drug alone were not shown, because they were the same as the values calculated from the measurement.

Example 2 and Comparative Example 2

At the concentrations shown in Tables 6 to 8, the drug I and the drug II were dissolved separately in dimethyl sulfoxide. The obtained solution was mixed to prepare a fungicidal composition.

Using the same methods as in Example 1 and Comparative Example 1, the sterilization test was carried out. The results thereof are shown in Tables 6 to 8. Additionally, in Tables, the expected values with the use of the drug alone were not shown, because they were the same as the values calculated from the measurement.

From these results, it can be seen that values of the growth inhibition rates measured when using the fungicidal composition according to the present invention are greater than the expected values of the growth inhibition rates calculated according to the above Colby's equation, and all the compositions exhibit a synergistic sterilization effect.

(Control Test for Cucumber Gray Mold Disease)

The drug I and the drug II were dissolved in an organic solvent and a surfactant, and the prepared mixed emulsifiable concentrate was diluted with water to a predetermined concentration, and sprayed to cucumber seedlings that had been cultivated in unglazed pots (cultivar “Sagamihanjiro” cotyledon stage). Additionally, in Tables, the symbol A indicating the drug I represents a nitrogen-containing heterocyclic compound represented by the formula (A), the symbol B indicating the drug I represents a nitrogen-containing heterocyclic compound represented by the formula (B), and the symbol C indicating the drug I represents a nitrogen-containing heterocyclic compound represented by the formula (C). Further, the number indicating the drug II represents each of the compounds described in the numbers described above. Additionally, “-” in Tables represents that the drug was not used.

After air-drying at room temperature, a suspension of the conidia of cucumber gray mold disease pathogens (Botrytis cinerea) was inoculated by dropwise addition and held in a dark room at 20° C. with a high humidity for 3, 4, or 5 days. By investigation on the state of lesion appearance in leaves with comparison with a non-treatment case, the controlling effect was determined. The test was carried out in duplicate. In addition, the expected value of the controlling effect was calculated based on Colby's equation.

At the same time, in Comparative Example, in the case of using the drug I only and the case of using the drug II only, the test was carried out by the same method.

The results thereof are shown in Tables 9 to 14.

Additionally, the Colby's equation is E=M+N−MN/100. Here, E is the expected value of the controlling effect (%), M is the controlling effect (%) calculated from the measurement with the use of the drug I alone, and N is the controlling effect (%) calculated from the measurement with the use of the drug II alone. Additionally, in Tables, the expected values with the use of the drug alone were the same as the values calculated from the measurement, and were thus not shown.

(Control Test for Cucumber Powdery Mildew Disease)

The drug I and the drug II were dissolved in an organic solvent and a surfactant, and the prepared mixed emulsifiable concentrate was diluted with water to a predetermined concentration, and sprayed to cucumber seedlings that had been cultivated in unglazed pots (cultivar “Sagamihanjiro”, cotyledon stage). Additionally, in Tables, the symbol A indicating the drug I represents a nitrogen-containing heterocyclic compound represented by the formula (A), the symbol B indicating the drug I represents a nitrogen-containing heterocyclic compound represented by the formula (B), and the symbol C indicating the drug I represents a nitrogen-containing heterocyclic compound represented by the formula (C). Further, in Tables, the number indicating the drug II represents each of the compounds described in the numbers described above. Additionally, “-” in Tables represents that the drug was not used.

After air-drying at room temperature, the conidia of cucumber powdery mildew disease pathogens (Sphaerotheca fuliginea) was inoculated by shaking off and held in a warm room for 7 days. By investigation on the state of lesion appearance in leaves with comparison with a non-treatment case, the controlling effect was determined. The test was carried out in duplicate. In addition, the expected value of the controlling effect was calculated based on Colby's equation.

At the same time, in Comparative Example, in the case of using the drug I only and the case of using the drug II only, the test was carried out by the same method.

The results thereof are shown in Table 15.

Additionally, the Colby's equation is E=M+N−MN/100. Here, E is the expected value of the controlling effect (%), M is the controlling effect (%) calculated from the measurement with the use of the drug I alone, and N is the controlling effect (%) calculated from the measurement with the use of the drug II alone. Additionally, in Tables, the expected values with the use of the drug alone were the same as the values calculated from the measurement, and were thus not shown.

From these results, it can be seen that the value of the controlling effect measured in the case of using the fungicidal compositions according to the present invention exceeded the expected value of the controlling effect calculated according to the above Colby's equation, and all the compositions exhibit a synergistic sterilization effect.

INDUSTRIAL APPLICABILITY

The agricultural and horticultural fungicidal composition of the present invention exhibits an excellent controlling effect on plant diseases even at very low doses and does not pose a concern for harmful effects on useful plants. Therefore, the present invention can be suitably used in agricultural and horticultural fungicidal compositions, and thus, the present invention is extremely useful industrially.