JP2019031442A - Quinoxalyl isoquinoline compounds - Google Patents

Abstract

A quinoxalylisoquinoline compound having excellent fungicidal activity or a salt thereof, and an agricultural and horticultural fungicide containing the same are provided. A quinoxalylisoquinoline compound represented by the following formula (I) or a salt thereof, and an agricultural and horticultural fungicide containing the same. (Wherein R1 and R2 are each independently a hydrogen atom or a methyl group, R3 and R4 are each independently a hydrogen atom, a fluorine atom, or a methyl group, and X is a fluorine atom or the like) Yes, n is an integer from 0 to 4, Y is a halogen atom, etc., m is an integer from 0 to 5.) [Selection] None

Description

  The present invention relates to a quinoxalylisoquinoline compound or a salt thereof and an agricultural and horticultural fungicide containing the same.

Patent Document 1 and Patent Document 2 describe quinolylisoquinoline compounds as agricultural and horticultural fungicides.
Patent Document 3 describes a quinoxanyl pyrazolyl isoquinoline compound as an inhibitor of NFkB-induced kinase (NIK).

International Publication No. 2005/070917 International Publication No. 2007/011022 International Publication No. 2005/012301

However, Patent Document 1 and Patent Document 2 do not describe a quinoxalylisoquinoline compound. Further, the compound described in Patent Document 3 is a pyrazoloisoquinoline derivative, and there is no description of an isoquinoline compound in which other rings are not condensed, and the invention is an invention for pharmaceutical use such as rheumatoid arthritis. No mention of agricultural or horticultural use.
On the other hand, various compounds have been developed as agricultural and horticultural fungicides, but due to the occurrence of low-sensitivity bacteria, a sufficient control effect cannot be expected. Therefore, agricultural and horticultural fungicides having an excellent bactericidal activity against various plant diseases in a wide spectrum are desired.

As a result of intensive research on quinoxaline compounds, the present inventors have found that certain quinoxalylisoquinoline compounds have excellent bactericidal activity against various plant diseases and are useful as active ingredients of agricultural chemicals. The present invention has been completed.
That is, the present invention includes the following aspects.

<1> The following formula (I)

Wherein R ¹ and R ² are each independently a hydrogen atom or an optionally substituted C _{1 to} C ₆ alkyl group, and R ³ and R ⁴ are each independently a hydrogen atom, fluorine atom, or a an optionally substituted _C 1 -C ₆ alkyl group, X is a halogen atom, or a _C 1 -C ₆ alkyl group, n is an integer from 0 4, Y is A quinoxalylisoquinoline compound or a salt thereof, which is a halogen atom or a C ₁ -C ₆ alkyl group, and m represents an integer of 0 to 5.

<2> The quinoxalylisoquinoline compound or a salt thereof according to <1>, wherein R ¹ and R ² in the formula (I) are both methyl groups, or one is a methyl group and the other is an ethyl group.
<3> The quinoxalylisoquinoline compound or a salt thereof according to <1>, wherein R ¹ and R ² in the formula (I) are both methyl groups.
<4> The quinoxalylisoquinoline compound or a salt thereof according to any one of <1> to <3>, wherein R ³ and R ⁴ in the formula (I) are both a fluorine atom, a hydrogen atom, or a methyl group. .
<5> The quinoxalylisoquinoline compound or a salt thereof according to <4>, wherein R ³ and R ⁴ in the formula (I) are both fluorine atoms.
<6> The quinoxalylisoquinoline according to any one of <1> to <5>, wherein n in the formula (I) is 1 and X is a chlorine atom or a fluorine atom, or n is 0. Compound or salt thereof.
<7> The quinoxalylisoquinoline compound or a salt thereof according to <1>, wherein m in the formula (I) is 1 and Y is a fluorine atom, or m is 0.

<8> An agricultural and horticultural fungicide containing the quinoxalylisoquinoline compound or a salt thereof according to any one of <1> to <7> as an active ingredient.

According to the present invention, a quinoxalylisoquinoline compound having excellent fungicidal activity or a salt thereof, and an agricultural and horticultural fungicide containing this as an active ingredient are provided.
The agricultural and horticultural fungicide containing the quinoxalylisoquinoline compound or a salt thereof according to the present invention as an active ingredient is also useful as an agricultural and horticultural fungicide showing an excellent control effect against various plant diseases.

In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. .
In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In this specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
The terms used herein have the meanings set forth below in their definitions.
The “halogen atom” is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The halogen atom in the substituents X and Y is preferably a fluorine atom.

“C ₁ -C ₆ alkyl group” means, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, 2- Methylbutyl group, neopentyl group, 1-ethylpropyl group, hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2, 1-6 carbon atoms such as 2-dimethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, etc. Straight or branched alkyl groups.
Substituents _R 1 _{to R} 4, X, and as the _C 1 -C ₆ alkyl group in Y, preferably a 1-3 straight-chain or branched-chain alkyl group with a carbon number, more preferably methyl It is a group.

Examples of the substituent substituted on the C ₁ -C ₆ alkyl group include a halogen atom, a C ₃ -C ₆ cycloalkyl group, and an aryl group.
Examples of the C ₁ -C ₆ alkyl group substituted with a halogen atom include a linear or branched alkyl group having 1 to 6 carbon atoms such as a difluoromethyl group, a trifluoromethyl group, and a perfluoroisopropyl group. A straight-chain or branched alkyl group having 1 to 3 carbon atoms to which a fluorine atom is bonded is preferable, and a difluoromethyl group or a trifluoromethyl group is more preferable.
Examples of the C _{1 to} C ₆ alkyl group substituted by the C _{3 to} C ₆ cycloalkyl group include ₁ to ₆ carbon atoms to which a cycloalkyl group such as a cyclohexylmethyl group, a cyclobutylmethyl group, and a cyclopropylmethyl group is bonded. A straight-chain or branched-chain alkyl group, preferably a cyclohexylmethyl group or a cyclobutylmethyl group.
The C ₁ -C ₆ alkyl group substituted with an aryl group is, for example, a linear or branched alkyl group having 1 to 6 carbon atoms to which an aryl group such as a benzyl group, a phenethyl group, or a phenylethyl group is bonded. . Preferred is a linear or branched alkyl group having 1 to 2 carbon atoms to which an aryl group is bonded, and more preferred is a benzyl group.
The substituted C _{1 to} C ₆ alkyl group in the substituents R ¹ to R ⁴ is preferably a C _{1 to} C ₆ alkyl group to which a halogen atom is bonded, and more preferably a chloromethyl group or trifluoro It is a methyl group.

The quinoxalylisoquinoline compound according to this embodiment is represented by the following formula (I).

In the formula, R ¹ and R ² are each independently a hydrogen atom or an optionally substituted C _{1 to} C ₆ alkyl group, and R ³ and R ⁴ are each independently a fluorine atom or a substituted atom. An optionally substituted C ₁ -C ₆ alkyl group, X is a halogen atom or a C ₁ -C ₆ alkyl group, n is an integer of 0 to 4, Y is a hydrogen atom, a halogen atom, or a _C 1 -C ₆ alkyl group, m represents an integer of from 0 5.

The quinoxalylisoquinoline compound represented by the formula (I) can be made into a salt such as sulfate, hydrochloride, nitrate, phosphate and the like. These salts are included in the present invention as long as they can be used as agricultural chemicals.
The quinoxalylisoquinoline compound represented by the formula (I) and a salt thereof can be solvated, and these solvates are also encompassed in the present invention. The solvate is preferably a hydrate.

  The quinoxalylisoquinoline compound represented by the formula (I) may contain an asymmetric atom. Any isomer derived from an asymmetric atom is encompassed by the present invention. In this case, the isomer ratio is a single or an arbitrary mixing ratio, and is not particularly limited.

  Representative compounds of the quinoxalylisoquinoline compound represented by the formula (I) are exemplified below, but the present invention is not limited to these compounds.

In the following table, “Me” represents a methyl group, “Et” represents an ethyl group, “Pr” represents a propyl group (n-propyl group), “Bu” represents a butyl group, and “Pen” represents a pentyl group. , “IPr” represents an isopropyl group (i-propyl group), “iBu” represents an isobutyl group (i-butyl group), “cHexCH ₂ ” represents a cyclohexylmethyl group, “Bn” represents a benzyl group, “CF ₃ "Is a trifluoromethyl group," ClCH ₂ "is a chloromethyl group," F "is a fluorine atom," Cl "is a chlorine atom," Br "is a bromine atom," I "is an iodine atom, Each is shown. In “Xn”, “H” indicates n = 0, and in “Ym”, “H” indicates m = 0. An expression such as “5,6-F ₂ ” in “Xn” indicates that n is 2, and 5 and 6 are substituted positions, that is, fluorine atoms are substituted at the 5th and 6th positions. Similarly, “F ₃ ” represents 3-substitution where n is 3, and “F ₄ ” represents 4-substitution where n is 4, and the other descriptions are also the same.
Hereinafter, the compounds represented by the following formula (I) are exemplified in Table 1 (1) to Table 1 (7).

  The quinoxalylisoquinoline compound represented by the formula (I) can be produced, for example, by Method A described below.

(Method A)

^R 1 ^{to R} 4 in the formula (II), and (III), X, Y, n and m, ^R 1 ^{to R} 4 in Formula (I), X, a Y, respectively n and m synonymous The preferred embodiment is also the same.

In the method A, the nitrile compound represented by the formula (II) and the alcohol compound represented by the formula (III) are reacted in a solvent or in a non-solvent in the presence of an acid. It is a method of manufacturing the compound represented by these.
The amount of the compound (III) used is usually 1 to 6 mol, preferably 1 to 3 mol, per 1 mol of compound (II).

The acid used in Method A is not particularly limited as long as it is used as an acid in a normal liter reaction. For example, inorganic acids such as sulfuric acid, formic acid, phosphoric acid and perchloric acid; sulfonic acids such as benzenesulfonic acid, toluenesulfonic acid and trifluoromethanesulfonic acid; or Lewis such as tin tetrachloride and trifluoroboric acid An acid etc. can be mentioned. Preferred is an inorganic acid or sulfonic acid, and more preferred is sulfuric acid or trifluoromethanesulfonic acid.
The amount of the acid used is usually 1 mol to 20 mol, preferably 1 mol to 15 mol, per 1 mol of compound (II).

  When a solvent is used in Method A, the solvent used is not particularly limited as long as it does not inhibit the reaction. For example, hydrocarbon solvents such as hexane, cyclohexane, benzene, toluene; halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, tetrachloroethane; ether solvents such as dioxane, diethyl ether, tetrahydrofuran (THF), ethylene glycol dimethyl ether, etc. Can be mentioned. A hydrocarbon solvent or a halogenated hydrocarbon solvent is preferable, and benzene or dichloroethane is more preferable.

While the reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, it is usually −20 ° C. to 100 ° C., preferably 0 ° C. to 80 ° C.
While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 15 minutes to 120 hours, preferably 30 minutes to 72 hours.

  The 3-quinoxaline carbonitrile compound (II) which is a starting material of the method A may be a known compound, or a known method {eg, tetrahedron Tetrahedron, 62, 4705 (2006), European Journal, etc.・ Of Organic Chemistry J. et al. Org. Chem. , Page 436 (2014), etc.}.

  As the alcohol compound (III) used in the method A, a known compound may be used, or according to a known method {for example, a method described in Tetrahedron Tetrahedron, 55, 4595 (1999), etc.} Can be manufactured.

In the above method A, after completion of each reaction, the target compound of each reaction can be collected from the reaction mixture according to a conventional method. For example, the reaction mixture is appropriately neutralized, and if insoluble matter is present, it is removed by filtration, water and an organic solvent immiscible with water such as ethyl acetate are added, and the target compound is washed with water. The organic layer is separated and dried over anhydrous magnesium sulfate, and then the solvent is distilled off.
If necessary, the obtained target compound can be further purified by a conventional method such as recrystallization, reprecipitation, chromatography or the like.

  The step of producing a salt of the quinoxalylisoquinoline compound represented by the formula (I) comprises an extract concentrate of a reaction mixture containing the quinoxalylisoquinoline compound represented by the formula (I) produced by each method, or It is carried out by adding an acid to a solution in which the quinoxalylisoquinoline compound represented by the formula (I) is dissolved in a suitable solvent.

Acids used in the step of producing the salt include hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and inorganic acids such as nitric acid, perchloric acid, sulfuric acid, phosphoric acid, etc. A lower alkyl sulfonic acid such as methane sulfonic acid, trifluoromethane sulfonic acid, and ethane sulfonic acid, an aryl sulfonic acid such as benzene sulfonic acid and p-toluene sulfonic acid, an organic acid salt such as succinic acid and oxalic acid; an organic acid such as saccharin; Examples thereof include acid amide compounds.
The acid is usually used in an amount of 1 equivalent to 10 equivalents, preferably 1 equivalent to 5 equivalents.

  The solvent used for the reaction is not particularly limited as long as the reaction is not inhibited. Preferable examples include ethers such as ether, diisopropyl ether, tetrahydrofuran (THF) and dioxane, and alcohols such as methanol and ethanol.

The reaction temperature is −20 ° C. to 50 ° C., and preferably −10 ° C. to 30 ° C.
The reaction time varies depending on the type of solvent used, temperature, and the like, but is usually 10 minutes to 1 hour.

  The resulting salt is isolated by conventional methods. That is, when it precipitates as a crystal, it is isolated as a crystal by filtration, and when it is water-soluble, it is isolated as an aqueous solution by separating an organic solvent and water.

  The quinoxalylisoquinoline compound represented by the formula (I) or a salt thereof is useful as an active ingredient of an agricultural and horticultural fungicide. That is, the quinoxalylisoquinoline compound represented by the formula (I) or a salt thereof has an excellent effect as an active ingredient of an agricultural and horticultural fungicide.

  Examples of plant diseases that can be controlled using the quinoxalylisoquinoline compound represented by the formula (I) or a salt thereof include, for example, rice blast (Pyricularia oryzae), blight (Thanatephorus cucumeris), sesame leaf blight ( Cochliobolus miyabeanus), idiot seedling disease (Gibberella fujikuroi), seedling blight (Pythium spp., Fusarium spp., Trichoderma spp., Rhizopus spp., Rhizoctonia solani, etc.), rice rot (Claviceps virens), smut (Tilletia) barelayana); wheat powdery mildew (Erysiphe graminis f.sp.hordei; f.sp.tritici), rust (Puccinia striiformis; Puccinia graminis, Puccinia recondita, Puccinia hordei), leafy disease (Pyrenophora graminea), net Spot disease (Pyrenophora teres), Red mold disease (Fusarium graminearum, Fusarium culmorum, Fusarium avenaceum, Microdochium nivale), Snow rot (Typhula incarnata, Typhula ishikariensis, Micronectriella nivalis), Bare smut (Ustilago tritic) i, Ustilago nigra, Ustilago avenae), Tuna scab (Tilletia caries, Tilletia pancicii), eye disease (Pseudocercosporella herpotrichoides), strain rot (Rhizoctonia cerealis), cloud disease (Rhynchosporium secalis), triatosis (Triticus) , Dry blight (Leptosphaeria nodorum), seedling blight (Fusarium spp., Pythium spp., Rhizoctonia spp., Septoria nodorum, Pyrenophora spp.), Blight (Gaeumannomyces graminis), anthrax (Colletotrichum gramaminicola) Disease (Claviceps purpurea), spot disease (Cochliobolus sativus); corn leaf mold (Fusarium graminearum, etc.), seedling blight (Fusarium avenaceum, Penicillium spp, Pythium spp., Rhizoctonia spp), rust (Puccinia sorghi), Sesame leaf blight (Cochliobolus heterostrophus), smut (Ustilago maydis), anthrax (Colletotrichum gramaminicola), northern spot (Cochliobolus carbonum);

  Grape downy mildew (Plasmopora viticola), rust (Phakopsora ampelopsidis), powdery mildew (Uncinula necator), black mildew (Elsinoe ampelina), late rot (Glomerella cingulata), black rot (Guignardia bidwellii), vine Of split disease (Phomopsis viticola), soot spot disease (Zygophiala jamaicensis), gray mold disease (Botrytis cinerea), bud blight disease (Diaporthe medusaea), purple gate feather disease (Helicobasidium mompa), white crest feather disease (Rosellinia necatrix); Powdery mildew (Podosphaera leucotricha), black spot disease (Venturia inaequalis), spotted leaf disease (Alternaria alternata (apple pathotype)), red star disease (Gymnosporangium yamadae), monilia disease (Monillia mali), rot disease (Valsa ceratosperma), ring crest Disease (Botryosphaeria berengeriana), anthracnose (Colletotrichum acutatum), soot spot (Zygophiala jamaicensis), soot spot (Gloeodes pomigena), black spot (Mycosphaerella pomi), purple coat (Helicobasidium mom) pa), White Rose (Rosellinia necatrix), Blight (Phomopsis mali, Diaporthe tanakae), Brown Spot (Diplocarpon mali); Pear Black Spot (Alternaria alternate (Japanese pear pathotype)), Black Star Disease (Venturia) nashicola), red scab (Gymnosporangium haraeanum), ring rot (Physalospora piricola), blight (Diaporthe medusaea, Diaporthe eres), pear plague (Phytophthora cactorum); peach black rot (Cladosporium carpophilum) (Phomopsis sp.), Plague (Phytophthora sp.), Anthracnose (Gloeosporium laeticolor); sweet potato anthracnose (Glomerella cingulata), larvae sclerotia (Monilinia kusanoi), ash scab (Monilinia fructicola); Diseases (Gloeosporium kaki), deciduous disease (Cercospora kaki; Mycosphaerella nawae), powdery mildew (Phyllactinia kakikora); citrus black spot (Diaporthe citri), green mold (Penicillium digitatum), blue mold (Penicillium) italicum), common scab (Elsinoe fawcettii);

  Gray mold (Botrytis cinerea) such as tomatoes, cucumbers, beans, strawberries, potatoes, cabbage, eggplant, lettuce; Sclerotinia sclerotiorum such as tomatoes, cucumbers, beans, strawberries, potatoes, rapeseed, cabbage, eggplant, lettuce ); Seedling blight of various vegetables such as tomato, cucumber, beans, radish, watermelon, eggplant, rapeseed, pepper, spinach, sugar beet (Rhizoctonia spp., Pythium spp., Fusarium spp., Phythophthora spp., Sclerotinia sclerotiorum, etc.) Cucumber downy mildew (Pseudoperonospora cubensis), powdery mildew (Sphaerotheca fuliginea), anthrax (Colletotrichum lagenarium), vine blight (Mycosphaerella melonis), vine split disease (Fusarium oxysporum), plague (Phythythophhala) , Phytophthora nicotianae, Phytophthora drechsleri, Phytophthora capsici); Tomato ring-rot (Alternaria solani), leaf mold Cladosporium fulvam), plague (Phytophthora infestans), wilt (Fusarium oxysporum), root rot (Pythium myriotylum, Pythium dissotocum), anthracnose (Colletotrichum phomoides); eggplant powdery mildew (Sphaerotheca fuliginea) Mycovellosiella nattrassii), plague (Phytophthora infestans), brown rot (Phytophthora capsici); rape black spot (Alternaria brassicae), cruciferous vegetable black spot (Alternaria brassicae, etc.), white spot (Cercosporella brassicae), root decay Disease (Leptospheria maculans), clubroot (Plasmodiophora brassicae), downy mildew (Peronospora brassicae); cabbage stock rot (Rhizoctonia solani), yellow rot (Fusarium oxysporum); Verticillium dahlie; green onion rust (Puccinia allii), black spot (Alternaria porri), silkworm (Sclerotium rolfsii. Sclerotium rolfsii), white plague (Phytophthora) porri); Soybean purpura (Cercospora kikuchii), black scab (Elsinoe glycinnes), black spot (Diaporthe phaseololum), rhizoctonia solani, stem rot (Phytophthora megasperma), downy mildew (Peronospora manshurica) , Rust (Phakopsora pachyrhizi), anthracnose (Colletotrichum truncatum); bean anthracnose (Colletotrichum lindemuthianum); peanut black astringency (Mycosphaerella personatum); brown spot (Cercospora arachidicola); pisi), downy mildew (Peronospora pisi); broad bean downy mildew (Peronospora viciae), plague (Phytophthora nicotianae); potato summer plague (Alternaria solani), black rot (Rhizoctonia solani), plague (Phytophthora infestans), Silver scab (Spondylocladium atrovirens), dry rot (Fusarium oxysporum, Fusarium solani), powdery scab (Spongospora subterranea); sugar beet brown spot (C ercospora beticola), downy mildew (Peronospora schachtii), black root disease (Aphanomyces cochioides), potato disease (Phoma batae); carrot black leaf blight (Alternaria dauci); strawberry powdery mildew (Sphaerotheca humuli), plague (Phytophthora nicotianae), anthrax (Gromerella cingulata), fruit rot (Pythium ultimum Trow var.ultimum);

  Tea net blast (Exobasidium reticulatum), white scab (Elsinoe leucospila), anthracnose (Colletotrichum theaesinensis), ring rot (Pestalotiopsis longiseta); tobacco scab (Alternaria alternate (Tobacco pathotype)), powdery mildew (Erysiphe) cichoracearum), anthrax (Colletotrichum tabacum), plague (Phytophthora parasitica); cotton wilt (Fusarium oxysporum);

  Sunflower sclerotia (Sclerotinia sclerotiorum); rose black spot (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa), plague (Phytophthora megasperma), downy mildew (Peronospora sparsa); chrysanthemum leaf spot (Septoria chrysanthemi-) indici), white rust (Puccinia horiana), plague (Phytophthora cactorum);

  Brown patch disease (Rhizoctonia solani), dollar spot disease (Sclerotinia homoeocarpa), curvularia leaf blight disease (Curvularia geniculata), rust disease (Puccinia zoysiae), hermitosporum leaf blight (Cochliobolus sp.), Cloud disease ( Rhynchosporium secalis), wilt (Gaeumannomyces graminis), anthracnose (Colletotrichum graminicola), snow rot brown granule nuclei (Typhula incarnata), snow rot black sclerotia nuclei (Typhula ishikariensis), Sclerotinia borealis), fairy rings (Marasmius oreades, etc.), pisium diseases (Pythium aphanidermatum, etc.), and rice blasts (Pyricularia grisea), but the present invention is not limited thereto.

  The quinoxalylisoquinoline compound represented by the formula (I) or a salt thereof exhibits an excellent control effect particularly against various diseases such as rice blast and tomato gray mold.

The agricultural and horticultural fungicide containing the quinoxalylisoquinoline compound represented by the formula (I) or a salt thereof as an active ingredient refers to the conventional quinoxalylisoquinoline compound represented by the formula (I) or a salt thereof. As in the case of agricultural chemical preparations, it refers to those formulated into various forms such as emulsions, powders, wettable powders, liquids, granules, suspension preparations, etc., together with adjuvants, but represented by the formula (I) An embodiment in which the quinoxalylisoquinoline compound or a salt thereof is used as it is is also included in the agricultural and horticultural fungicide of the present invention.
The formulated agricultural and horticultural fungicide can be used as it is or diluted to a predetermined concentration with a diluent such as water.

  Examples of the adjuvant used in formulating the quinoxalylisoquinoline compound represented by the formula (I) or a salt thereof include carriers, emulsifiers, suspending agents, dispersing agents, spreading agents, penetrating agents, wetting agents. , Thickeners, stabilizers and the like. These adjuvants can be appropriately added as necessary.

  The carrier is divided into a solid carrier and a liquid carrier. Solid carriers include starch, sugar, cellulose powder, cyclodextrin, activated carbon, soybean powder, wheat flour, rice bran powder, wood powder, fish powder, powdered milk and other animal and vegetable powders; talc, kaolin, bentonite, organic bentonite, calcium carbonate, Examples thereof include mineral powders such as calcium sulfate, sodium bicarbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, silica, and sulfur powder. These solid carriers can be used singly or in combination of two or more at an appropriate ratio.

  As liquid carrier, water; animal and vegetable oils such as soybean oil, nut oil, corn oil; alcohol solvents such as ethyl alcohol and ethylene glycol; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as dioxane and tetrahydrofuran; kerosene and kerosene Aliphatic / aromatic hydrocarbon solvents such as liquid paraffin, xylene, trimethylbenzene, tetramethylbenzene, cyclohexane and solvent naphtha; halogenated hydrocarbon solvents such as chloroform and chlorobenzene; acid amides such as dimethylformamide and N-methylpyrrolidone Solvents; ester solvents such as ethyl acetate and glycerin esters of fatty acids; nitrile solvents such as acetonitrile; and sulfur-containing compound solvents such as dimethyl sulfoxide. These liquid carriers can be used alone or in admixture of two or more at an appropriate ratio.

  A surfactant is usually used as the emulsifier, suspending agent, dispersing agent, spreading agent, penetrating agent, or wetting agent. Examples of surfactants include anions such as alkyl sulfate ester salts, alkyl aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphate esters, lignin sulfonates, and naphthalene sulfonate formaldehyde polycondensates. Nonionic surfactants such as surfactants and polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters and the like can be mentioned. These surfactants can be used singly or in combination of two or more at an appropriate ratio.

  Examples of the thickener or stabilizer include dextrin, sodium salt of carboxymethyl cellulose, polycarboxylic acid polymer compound, polyvinyl pyrrolidone, polyvinyl alcohol, sodium lignin sulfonate, calcium lignin sulfonate, sodium polyacrylate, gum arabic, Xanthan gum, sodium alginate, mannitol, sorbitol, bentonite mineral, white carbon and the like can be mentioned.

The compounding mass ratio of the quinoxalylisoquinoline compound represented by the formula (I) or a salt thereof and the adjuvant is usually 0.05: 99.95 to 90:10, preferably 0.2: 99.8-80: 20.
The “mixed mass of the quinoxalylisoquinoline compound or a salt thereof” as used herein means a quinoxalylisoquinoline compound equivalent value.

  The concentration of the quinoxalylisoquinoline compound represented by formula (I) or a salt thereof in the preparation varies depending on the target crop, method of use, formulation form, application rate, etc. In terms of quinoxalylisoquinoline compound, it is usually 0.1 ppm to 10000 ppm, preferably 1 ppm to 1000 ppm, and the amount of the quinoxalylisoquinoline compound of the present invention or a salt thereof used in the case of soil treatment In terms of the quinoxalylisoquinoline compound, it is usually 10 g / ha to 100,000 g / ha, preferably 100 g / ha to 10,000 g / ha.

  The quinoxalylisoquinoline compound represented by the formula (I) or a salt thereof may contain other agricultural chemicals such as insecticides, acaricides, attractants, nematicides, fungicides, antiviral agents, if necessary. It can be mixed or used in combination with herbicides, plant growth regulators, etc., and is preferably used in combination or in combination with at least one selected from the group consisting of insecticides, acaricides, nematicides and fungicides.

  Examples of insecticides include organophosphate compounds; carbamate compounds; pyrethroid compounds; benzoyl urea compounds; neonicotinoid compounds; pyrazole compounds.

  Examples of the disinfectant include dithiocarbamate compounds; N-halogenoalkylthioimide compounds; benzimidazole compounds; azole compounds; pyridineamine compounds; cyanoacetamide compounds; phenylamide compounds; Examples thereof include copper compounds; isoxazole compounds; organophosphorus compounds; carboxylic acid anilide compounds; morpholine compounds; iminotadine compounds; melanin biosynthesis inhibitors; resistance inducers;

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In the examples, the quinoxalylisoquinoline compound represented by the formula (I) or a salt thereof is also collectively referred to as “the compound of the present invention”. The chemical shift value of ¹ H-NMR is a value using tetramethylsilane as an internal reference material unless otherwise specified.

[Example 1 (Method A)]
2- (3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) quinoxaline (compound number: 41)
In a 200 mL eggplant-shaped flask, concentrated sulfuric acid (3.5 mL) was added to 3-cyanoquinoxaline (500 mg, 3.2 mmol) and 2-methyl-3-phenylpropan-2-ol (775 mg, 5.2 mmol) under ice-cooling. Was added dropwise, stirred at room temperature for 1 hour, the reaction solution was poured into ice water, the aqueous layer washed with ethyl acetate was made alkaline with aqueous sodium hydrogen carbonate, extracted with ethyl acetate, dried over magnesium sulfate, filtered and concentrated. . The obtained residue was purified by silica gel column chromatography to obtain the target compound of the present invention (Compound No. 41) (684 mg) in a yield of 74%. The property of the obtained compound and the chemical shift value of ¹ H-NMR are shown below.

Properties: Gummy.
¹ H-NMR (CDCl ₃ ) δ: 9.42 (1H, s), 8.23-8.15 (2H, m), 7.84-7.82 (2H, m), 7.64 (1H, dd, J = 7.6, 0.9 Hz), 7.44 (1H, td, J = 7.5, 1.3 Hz), 7.31 (1H, dd, J = 7.6, 1.2 Hz), 7.27 (1H, d, J = 7.3 Hz), 2.90 (2H, s), 1.39 (6H, s).

  In the same manner as in Example 1, the compounds of the present invention shown in Table 2 below were synthesized.

[Formulation Example 1]
(Powder)
Compound obtained in Example 1 (1.0 part by mass), Doreless A (alkyl ether phosphate ester, Mitsui Chemicals Agro Co., Ltd., 0.4 part by mass), Carplex 80-D (white carbon, Evonik Japan Co., Ltd., 1.5 parts by mass), calcium carbonate (Adachi Lime Co., Ltd., 0.5 parts by mass) and Keiwa clay-style HI (Keiwa Furnace Co., Ltd., 32.1 parts by mass) are mixed. After that, the obtained mixture was pulverized with a sample mill KII-1 type (hammer mill, manufactured by Fuji Powder Co., Ltd.). To the obtained pulverized product, 1.5 times the amount of DL clay Keiwa (manufactured by Keiwa Furnace Co., Ltd.) was added to and mixed with the pulverized product to obtain a powder DL (Low Drift Dust). .

[Formulation Example 2]
(emulsion)
The compound (10 parts by mass) obtained in Example 1 was dissolved in a mixed solution of xylene (Wako Pure Chemical Industries, Ltd., 40 parts by mass) and DMSO (Wako Pure Chemical Industries, Ltd., 25 parts by mass). did. Paracol KPS (a mixture of an anionic surfactant and a nonionic surfactant, manufactured by Nippon Emulsifier Co., Ltd., 25 parts by mass) was added to the resulting solution and mixed to obtain an emulsion.

[Formulation Example 3]
(Wettable powder)
Compound obtained in Example 1 (1 part by mass), Carplex 80-D (10 parts by mass), Gohsenol GL-05S (polyvinyl alcohol, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., 2 parts by mass), Neogen powder ( Linear alkylbenzene sulfonic acid sodium salt, Daiichi Kogyo Seiyaku Co., Ltd., 5 parts by mass), Radiolite # 200 (calcined diatomaceous earth, Showa Chemical Industry Co., Ltd., 10 parts by mass) and H fine powder (Kaolinite clay, Keiwa Furnace material Co., Ltd., 72 parts by mass) was sufficiently mixed, and the obtained mixture was pulverized with a sample mill KII-1 type to obtain a wettable powder.

[Formulation Example 4]
(Granule)
The compound obtained in Example 1 (2 parts by mass), sodium tripolyphosphate (manufactured by Mitsui Chemicals, 2 parts by mass), Amicol NO. 1 (dextrin, manufactured by Nissho Chemical Co., Ltd., 1.5 parts by mass), bentonite (manufactured by Hojun Co., Ltd., 25 parts by mass) and Calfin 600 (calcium carbonate, manufactured by Adachi Lime Co., Ltd., 69.5 parts by mass) Then, the obtained mixture was extruded and granulated using Dome Gran (Fuji Paudal Co., Ltd., screen 0.9 mmφ). The obtained granulated product was dried with a shelf dryer (manufactured by Tabai Co., Ltd., PERFECT OVEN PS-222 type, 60 ° C.) and then sieved to 600 μm to 1180 μm to obtain granules.

[Test Example 1]
(Rice blast control trial)
A spray liquid containing 250 ppm of the compound of the present invention shown in Table 1 above was uniformly sprayed onto a pot cultivation test plant (rice: Kofu) at the third to fourth leaf stages with a spray gun. On the day of spraying, the bacterial spore suspension was spray-inoculated and placed in an inoculation room at 23-25 ° C. and a greenhouse at 20-25 ° C. to promote disease. The control value was calculated based on the results of disease investigation 6 days after the inoculation. This test was carried out in two consecutive systems.

Disease investigation: The disease area ratio was investigated, and the average disease area ratio was calculated for each section.
Control value: The control value was calculated from the average disease area ratio shown above using the following formula.

Formula: Control value = 100 × {1- (n / N)}
N = average disease area rate of untreated area, n = average disease area ratio of each area

  As a result of conducting this test on the compounds of the present invention shown in Table 1 above, the compounds Nos. 1, 41, 42, 50, and 75 had a controlling value of 90 or more.

[Test Example 2]
(Tomato gray mold control test)
A spray liquid containing 250 ppm of the compound of the present invention shown in Table 1 above was uniformly sprayed with a spray gun on a pot cultivation test plant (tomato: the world's best or the largest Fuju in the third to fourth leaf stages). On the day of spraying, the spore suspension of the pathogen was spray-inoculated and placed in an inoculation room at 23 to 25 ° C. to promote disease. The control value was calculated based on the results of disease investigation 2 days after the inoculation. This test was carried out in two consecutive ways.

Disease investigation: The disease area ratio was investigated, and the average disease area ratio was calculated for each section.
Control value: The control value was calculated from the average disease area ratio shown above using the following formula.

Formula: Control value = 100 × {1- (n / N)}
N = average disease area rate of untreated area, n = average disease area ratio of each area

  As a result of conducting this test on the compounds of the present invention shown in Table 1 above, the compounds Nos. 1, 41, 42, 50, and 75 had a controlling value of 90 or more.

The quinoxalylisoquinoline compound or a salt thereof of the present invention exhibits a remarkable effect against various plant pathogenic fungi such as rice blast and tomato gray mold without causing damage to the host plant. Or the agrochemical which contains the salt as an active ingredient is excellent as an agricultural and horticultural fungicide.
The spectrum of plant diseases in which the quinoxalyl isoquinoline compound or salt thereof of the present invention exhibits excellent efficacy is not limited to these.

Claims (8)

Following formula (1):

Wherein R ¹ and R ² are each independently a hydrogen atom or an optionally substituted C _{1 to} C ₆ alkyl group, and R ³ and R ⁴ are each independently a hydrogen atom, fluorine atom, or a an optionally substituted _C 1 -C ₆ alkyl group, X is a halogen atom, or a _C 1 -C ₆ alkyl group, n is an integer from 0 4, Y is A quinoxalylisoquinoline compound or a salt thereof, which is a halogen atom or a C ₁ -C ₆ alkyl group, and m represents an integer of 0 to 5. The quinoxalylisoquinoline compound or a salt thereof according to claim 1, wherein R ¹ and R ² in the formula (I) are both a methyl group, or one is a methyl group and the other is an ethyl group. The quinoxalylisoquinoline compound or a salt thereof according to claim 1, wherein R ¹ and R ² in the formula (I) are both methyl groups. The quinoxalylisoquinoline compound or a salt thereof according to any one of claims 1 to 3, wherein R ³ and R ⁴ in the formula (I) are both a fluorine atom, a hydrogen atom, or a methyl group. The quinoxalylisoquinoline compound or a salt thereof according to claim 4, wherein R ³ and R ⁴ in the formula (I) are both fluorine atoms.   6. In the formula (I), n is 1, and X is a chlorine atom or a fluorine atom, or n is 0. The quinoxalylisoquinoline compound or a salt thereof according to any one of claims 1 to 5. .   The quinoxalylisoquinoline compound or a salt thereof according to any one of claims 1 to 6, wherein m in the formula (I) is 1 and Y is a fluorine atom or m is 0.   An agricultural and horticultural fungicide containing the quinoxalylisoquinoline compound according to any one of claims 1 to 7 or a salt thereof as an active ingredient.