JP2001055304A - Pyridylpyridine compound, production and agricultural and horticultural fungicide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject new compound useful as an active ingredient of safely usable agricultural and horticultural fungicides capable of exhibiting excellent fungicidal power for a wide range and various kinds of mold fungi and providing sure effects thereon and having slight phytotoxicity. SOLUTION: This pyridylpyridine compound is represented by formula I (R1 and R2 are each H, a halogen, a 1-6C alkyl or a 1-6C alkoxy; R3 is methyl or ethyl; R4 is cyano, hydroxy, a halogen, a 1-6C alkyl or the like; n is 0 or 1-4), e.g. methyl N-methoxy-N- 2-[6-(6-methyl-2-pyridyl)pyridin-2- yloxymethyl]phenyl)carbamate. The compound represented by formula I can be produced by reacting, e.g. a compound represented by formula II (L is a leaving group) with a compound represented by formula III in the presence of a base in an inert solvent at -50 to +150 deg.C for 1-48 h. The agricultutral and horticultural fungicide comprising, the compound represented by formula I as an active, ingredient can be used for seed treatment, foliage spraying, soil application, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel pyridylpyridine compound, a method for producing the same, and a fungicide for agricultural and horticultural use containing the same as an active ingredient.

[0002]

2. Description of the Related Art In the cultivation of agricultural and horticultural crops, a large number of control agents are used for controlling pests and diseases of crops. However, its control efficacy is insufficient, the emergence of drug-resistant pathogens, its use is restricted by drug-resistant pests, etc., or it causes phytotoxicity or contamination of plants, toxicity to humans, fish, and the environment. Due to the effects of harmful effects, etc., it is not always possible to say that it is a satisfactory control drug.
Therefore, there is a demand for the development of a drug that can be used safely with few such disadvantages.

As a compound similar to the compound of the present invention, for example, EP033775 describes that pyridyloxymethylphenylacrylic acid compounds are useful as a fungicide for agricultural and horticultural use.

However, there is no description of a compound having an optionally substituted pyridyl group as a substituent of the pyridyl group as in the compound of the present invention.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a novel pyridylpyridine compound which can be used as an agricultural and horticultural fungicide which is reliable and can be used safely, a method for producing the same, and an agricultural and horticultural fungicide containing these as an active ingredient. It is intended to provide an agent.

[0006]

According to the present invention, there is provided a compound represented by the general formula (1):

[0007]

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(Wherein R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group. R ³ represents a methyl group or an ethyl group R ⁴ represents a cyano group, a hydroxy group, a halogen atom, a C _1-6 alkyl group, a C _1-6 alkenyl group,
_1-6 alkynyl group, C _1-6 alkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 haloalkyl group, C _3-8 cycloalkyl group , C _1-6 alkylcarbonyl group, C _1-6 alkylcarbonyloxy group, C _1-6 alkoxycarbonyl group, hydroxyimino C _1-6 alkyl group, C _1-6 alkoxyimino C _1-6 alkyl group, (C Carbamoyl group, which may be substituted with _1-6 alkyl group, phenyl group which may have a substituent, benzyl group which may have a substituent, and It represents a good phenoxy group or a benzyloxy group which may have a substituent. n represents 0 or an integer of 1 to 5, and when n is 2 or more, R ⁴ may be the same or different. ), A method for producing the same, and a fungicide for agricultural and horticultural use containing these as an active ingredient.

In the general formula (1), R ¹ , R
² is each independently a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine or iodine, a C _1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl or hexyl group, or a methoxy group; represents ethoxy, propyloxy, isopropyloxy, butoxy, t-butoxy, a C _1-6 alkoxy group such as hexyl group.

R ⁴ is a cyano group, a hydroxy group, a halogen atom such as fluorine, chlorine, bromine, etc., a C _1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl group, vinyl, 1-propenyl, 2
- propenyl, 1-butenyl, 2-butenyl, 3-butenyl, C _1-6 alkenyl groups such as butadienyl group, ethynyl, 1-propynyl, 1-butynyl, C _1-6 alkynyl groups such as 2-butynyl group,

C _1-6 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy and butoxy groups, methylthio, ethylthio, propylthio, isopropylthio,
C _1-6 alkylthio group such as butylthio group, methylsulfinyl, ethylsulfinyl, propylsulfinyl,
C _1-6 alkylsulfinyl groups such as isopropylsulfinyl and butylsulfinyl groups,

C _1-6 alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl and butylsulfonyl groups, fluoromethyl, 1-fluoroethyl, 2-fluoroethyl, difluoromethyl, trifluoromethyl, difluorochloro C _1-6 haloalkyl groups such as methyl and pentafluoroethyl groups; C _3-8 cycloalkyl groups such as cyclopropyl, cyclopentyl and cyclohexyl groups; C _1-6 alkylcarbonyl groups such as acetyl and propionyl groups; acetoxy and propionyloxy C _1-6 alkylcarbonyloxy group such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, C _1-6 alkoxycarbonyl group such as a t- butoxycarbonyl group,

Hydroxyimino C _1-6 alkyl groups such as hydroxyiminomethyl and 1-hydroxyiminoethyl groups, and C _1-6 alkoxyimino C ₁ groups such as methoxyiminomethyl, 1-methoxyiminoethyl and 2-ethoxyiminoethyl groups. _-6 alkyl group, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-
A carbamoyl group which may be substituted with a C _1-6 alkyl group such as a diethylcarbamoyl group;

The benzene ring may have a substituent at any position (benzyl, α-methylbenzyl, α, α-
A substituted benzyl group such as dimethylbenzyl), a phenoxy group which may have a substituent at any position of the benzene ring,
And a substituent at any position of the benzene ring (benzyloxy, α-methylbenzyloxy,
α, α-dimethylbenzyloxy) and the like.

The above substituents may be substituted (phenyl group, benzyl group, phenoxy group and benzyloxy group)
As the substituent for, a nitro group, a cyano group, chlorine, bromine,
Halogen atom such as fluorine, C _1-6 such as methyl or ethyl group
Alkyl group, methoxy, C _1-6 alkoxy group such as ethoxy group, triflupromazine Rollo C _1-6 haloalkyl group such as a methyl group, methylthio, C _1-6 alkylthio group such as an ethylthio group, such as methylsulfonyl group C _{1- 6} C such as alkylsulfonyl group, methoxycarbonyl, ethoxycarbonyl group, etc.
Examples thereof _{include a 1-6} alkoxycarbonyl group.
Further, the phenyl group, benzyl group, phenoxy group and benzyloxy group may have the same or different plural substituents.

The salt of the compound of the present invention is not particularly limited as long as it is acceptable in agriculture and horticulture. For example, salts of alkali metals such as sodium, potassium and lithium, salts of alkaline earth metals such as calcium and magnesium, metal salts such as transition metals such as nickel, cobalt, manganese, copper and zinc, and minerals such as hydrochloric acid and sulfuric acid Acid salts and methanesulfonic acid, p
-Salts of organic acids such as toluenesulfonic acid and oxalic acid can be exemplified.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention can be produced by the following method.

[0018]

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[Wherein R ¹ , R ² , R ³ , R ⁴ and n
Represents the same meaning as described above, and L represents chlorine, bromine, OSO
₂ represents a leaving group such as a CH ₃ group or an OTs group (Ts: tosyl group). ]

In this method, the compound represented by the general formula (2) and the compound represented by the general formula (3) are reacted in an inert solvent in the presence of a base at a reaction temperature of -50 to 150 ° C., preferably Is for producing a compound represented by the general formula (1) by reacting at 0 to 100 ° C. for 1 to 48 hours.

Solvents that can be used in this reaction include aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether and tetrahydrofuran (THF), acetonitrile, N, N-dimethylformamide (DMF), dimethyl Sulfoxide (DMSO) and the like can be mentioned, and preferably, DMF and acetonitrile can be exemplified.

Examples of the base that can be used in the reaction include inorganic bases such as sodium hydride, potassium carbonate, potassium hydroxide, and sodium hydroxide, and triethylamine, 1,8-diazabicyclo [5.4.0] undecene-. Amines such as 7 (DBU); metal salts such as silver oxide (Ag ₂ O) and silver carbonate;

After completion of the reaction, the desired product can be obtained by performing ordinary post-treatment. The structure of the compound of the present invention is
It was determined from IR, NMR, Mass spectrum and the like.

Examples of the compounds included in the present invention are shown in Table 1. The abbreviations in the table have the following meanings. M
e: methyl group Et: ethyl group Pr: propyl group B
u: butyl group Pen: pentyl group Ph: phenyl group Ac: acetyl group n: normal i: iso se
c: Secondary t: Tertiary c: Cyclo

The compounds shown in Table 1 are compounds represented by the following structural formulas.

[0026]

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[0027]

[Table 101]

[0028]

[Table 102]

[0029]

[Table 103]

[0030]

[Table 104]

[0031]

[Table 105]

[0032]

[Table 106]

[0033]

[Table 107]

[0034]

[Table 108]

(Agricultural and Horticultural Fungicide) When the compound of the present invention thus obtained is actually used as an agricultural and horticultural fungicide, it can be used in a pure form without adding other components. In addition, forms that can be taken by general agrochemicals for the purpose of using as agrochemicals and medicaments, ie, granules, solid preparations such as powders,
It can also be formulated into liquid preparations such as wettable powders, emulsions, aqueous solvents, suspensions, and flowables, and used.

When a solid preparation is used, plant powders such as soybean grains and flour, mineral fine powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite and clay, sodium benzoate, urea, Additives and carriers such as organic and inorganic compounds such as sodium sulfate can be used.

When a liquid preparation is used, petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, DMF, DMSO, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water, etc. Can be used as a solvent.

Further, in order to make the preparations more uniform and stable, a surfactant may be added to these preparations, if necessary. Examples of the surfactant include, but are not particularly limited to, alkyl phenyl ether to which polyoxyethylene is added, alkyl ether to which polyoxyethylene is added, higher fatty acid ester to which polyoxyethylene is added, and sorbitan to which polyoxyethylene is added. Nonionic surfactants such as higher fatty acid esters, tristyryl phenyl ether added with polyoxyethylene, sulfates of alkyl phenyl ethers added with polyoxyethylene, alkyl benzene sulfonates, sulfates of higher alcohols, alkyls A naphthalene sulfonate, a polycarboxylate, a lignin sulfonate, a formaldehyde condensate of an alkyl naphthalene sulfonate, a copolymer of isobutylene-maleic anhydride and the like can be used.

In the case of the obtained liquid preparations such as wettable powders, emulsions, suspensions and flowables, the suspensions are diluted to a predetermined concentration with water to obtain suspensions or emulsions such as powders and granules. In the case of a solid preparation, it can be used as it is. In any of the above-mentioned preparations, the content of the compound (1) of the present invention, which is an active ingredient, in the composition is preferably 0.1%.
It is from 0.01 to 90% by weight, more preferably from 0.05 to 85% by weight.

(Agricultural and horticultural fungicides) The compounds of the present invention can be used for a wide variety of fungi, for example, algal fungi.
s), ascomycetes (Ascomycetes),
It has excellent bactericidal activity against bacteria belonging to Deuteromycetes and Basidiomycetes. The composition containing the compound of the present invention as an active ingredient is used for controlling various diseases that occur during cultivation of agricultural and horticultural crops including flowers, turf, grass, seed treatment, foliage spraying,
It can be used by soil application or water surface application.

For example, rice blast ( Pyricularia oryzae ), blight blight ( Rhizoctonia solani ), stupid seedling blight ( Gibberella fujikuroi), sesame leaf blight ( Cochliobolus miyabeanus ), barley, naked smut ( Ustilago nuda ), wheat blight ( Gibberella ze ) leaf rust (Puccinia recondita) Memonbyo (Pseudocercosporella herpotrichoides) glume blotch (Leptosphaeria nodorum) powdery mildew (Erysiphe gaminis f. sp. tritici ) pink snow mold disease (Monographella nivalis) potato late blight (Phytophthora infestans) peanut brown spot disease (Mycosphaerella arachidis) sugar beet brown spot disease (Cercospora beticola) bean gray mold (Botritis cinerea) cucumber powdery mildew (Sphaerotheca fuliginea) rot (Sclerotinia sclerotiorum) gray mold (Botrytis cinerea) downy mildew (Pseudoperonospora cubensis) tomatoes leaf blight (Cladosporium fulvum) late blight (Phytophthora infestans) eggplant black blight (Corynespora melongenae) onion gray rot (Botrytis allii) strawberry powdery mildew (Sphaerotheca humuli) apple powdery mildew (Podosphaera leucotricha) scab (Venturia inaequalis) blossom disease (Monilinia mali) persimmon anthracnose (Gloeosporium kaki) Peach Haihoshibyo (Monilinia fructicola) Grapes Udon Downy mildew ( Uncinula necator) Downy mildew ( Plasmopara viticola ) Pear Red scab ( Gymnosporangium asiaticum) Black spot ( Alternaria kikuchiana ) Tea Ring spot ( Pestalotia theae) Anthrax ( Colletotrichum theae-sinensis ) Citrus scab ( Elisinoe ) fawcetti ) Blue mold ( Penicillium italicum ) It can be used to control western grass, snow rot and Sclerotinia borealis .

Further, in recent years, various pathogens have developed resistance to benzimidazole agents, dicarboximide agents, and the like, resulting in insufficiency of the efficacy of these agents, and there is a need for an agent that is also effective against resistant pathogens. The compound of the present invention is not only sensitive but also has an excellent bactericidal effect against pathogenic bacteria resistant to benzimidazole agents and dicarboximide agents. In addition, the compound of the present invention shows an excellent control effect on gray mold which is generally inferior in the control effect of acrylic acid compounds.

Diseases that are more preferably applied include brown spot of sugar beet, powdery mildew of wheat, rice blast, apple scab, gray mold of bean, gray mold of cucumber, brown spot of peanut, Tomato plague, grape downy mildew and the like.

Further, the compound of the present invention is a highly safe drug having little phytotoxicity, low toxicity to fish poisons and warm-blooded animals.

In addition, the compounds of the present invention can be used in aquatic organisms,
It can also be used as an antifouling agent for preventing it from adhering to underwater contacts such as fish nets.

The compound of the present invention can be used as an antibacterial and fungicide for walls and bathtubs, shoes and clothes by mixing it with paints and fibers.

When the compound of the present invention is used as a fungicide for agricultural and horticultural use, it exhibits sufficient efficacy even when used alone, but is used in combination with at least one of various fungicides, insecticides, acaricides or synergists. You can also.

The fungicides, insecticides, acaricides, nematicides, and plant growth regulators which can be used by mixing with the compound of the present invention include the following.

Fungicides: captan, folpet, thiuram, ziram, zineb, maneb. Mancozeb, propineb, polycarbamate, chlorothalonil, quintosen, captaphor, iprodione, prosamide, vinclozolin, fluoroimide, thymoxanil, mepronil, flutolanil, pencyclon, oxycarboxyne, fosetyl aluminum, propamocarb, triazimefone, triazimenol, propiconazole, dicicon Robutrazole, bitertanol, hexaconazole,
Microbutanil, fursilazole, etaconazole,
Fluotrimazole, flutriafen, benconazole, diconazole, cyproconazoles, fenarimol, triflumizole, prochloraz, imazalil,
Perfurazoate, tridemorph, fenpropimorph,
Triforine, butiobate, pyrifenox, anilazine, polyoxin, metalaxyl, oxadixyl,
Furalaxyl, isoprothiolane, probenazole, pyrrolnitrin, blasticidin S, kasugamycin, validamycin, dihydrostreptomycin sulfate, benomyl, carbendazim, thiophanate methyl, himexazole, basic copper chloride, basic copper sulfate, fentin acetate, triphenyl hydroxide Tin, dietofencarb, metasulfocarb, quinomethionate, binapacryl, lecithin, baking soda, dithianone, dinocap, phenaminosulf, diclomedine, guazatine, dozine, IBP, edifenphos, mepanipyrim, fermzone, triclamide, metasulfocarb, fluazinam, ethinolac, etorazinome Pyroquilon, Teclophthalam, Fusalide, Phenazine oxide, Thiabendazole, Tricycla Lumpur, vinclozolin, cymoxanil, cyclobutanyl, guazatine, propamocarb hydrochloride, oxolinic acid, Fenamoriru, cyproconazole, epoxiconazole, metconazole, hydroxy isoxazole, iminoctadine acetate, and the like.

Insecticides and miticides: Organophosphorus and carbamate insecticides: phenthion, fenitrothion, diazinon, chlorpyrifos, ES
P, bamidothion, fentoate, dimethoate, formotion, marathon, trichlorfon, thiometon,
Hosmet, Dichlorvos, Acephate, EPBP,
Methyl parathion, oxydimetone methyl, ethion,
Salithion, cyanophos, isoxathion, pyridafenthion, phosalon, methidathion, sulprophos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, ethylthiometon, profenophos, pyraclophos, monocrotophos, azinphosmethyl, aldicarb, mesomil, thiodicarb, Carbofuran, carbosulfan, benfracarb, fratiothiocarb, propoxur, BPMC,
MTMC, MIPC, carbaryl, pirimicarb, ethiophencarb, phenoxycarb, EDDP and the like. Pyrethroid insecticides: permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propasulin, phenothrin, prothrin, fulvalinate, cyfluthrin, cyhalothrin, flucitrinate, etofenprox, Cycloprothrin, trolametrin, silafluofen,
Profenprox, acrinatrine and the like.

Benzoylurea and other insecticides: diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, benzoepin, diafenthiu Ron, acetamiprid, imidacloprid, nitenpyram, fipronil, cartap, thiocyclam, bensultap, nicotine sulfate, rotenone, methaldehyde, machine oil, microbial pesticides such as BT and insect pathogenic virus, and the like.

Nematicides: fenamiphos, phosthiazate and the like. Acaricides: chlorbenzylate, phenisobromolate, dicofol, amitraz, BPPS, benzomate,
Hexitiazox, fenbutatin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentezin, cyhexatin, pyridaben, fenpyroximate, tebufenpyrad, pyrimidifen, phenothiocarb, dienochlor and the like. Plant growth regulators: gibberellins (eg, gibberellin A ₃ , gibberellin A ₄ , gibberellin A ₇ ), IAA, N
AA etc.

[0053]

The compounds of the present invention are described in more detail with reference to the following examples.

Example 1 Preparation of methyl N-methoxy-N- {2- [6- (6-methyl-2-pyridyl) pyridin-2-yloxymethyl] phenyl} carbamate (Compound No. 5)

[0055]

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2-hydroxy-6- (6-methyl-2-
Pyridyl) pyridine (0.21 g) was dissolved in DMF (3 ml), potassium carbonate (0.17 g) and methyl N- [2-
(Bromomethyl) phenyl] -N-methoxycarbamate (0.31 g) was added, and the mixture was stirred at room temperature for 24 hours. Water was added, extracted with ethyl acetate, washed with saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (developing solvent: chloroform) to obtain 0.31 g (yield 74%) of the desired product.

Example 2 Preparation of methyl N-methoxy-N- {2- [6- (2-chloro-4-pyridyl) pyridin-2-yloxymethyl] phenyl} carbamate (Compound No. 15)

[0058]

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2-hydroxy-6- (2-chloro-4-
0.33 g of (pyridyl) pyridine was dissolved in 10 ml of DMF, and 0.18 g of potassium carbonate and 0.3 g of methyl N- [2- (bromomethyl) phenyl] -N-methoxycarbamate were added, followed by stirring at room temperature for 24 hours. Water was added, extracted with ethyl acetate, washed with saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (developing solvent: chloroform) to obtain 0.31 g (yield 74%) of the desired product.

Reference Example 1 Production of 2-hydroxy-6- (6-methyl-2-pyridyl) pyridine

[0061]

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25 g of 2,2′-bipyridyl was dissolved in 100 ml of chloroform, 57 g of 30% peracetic acid was added dropwise at room temperature, and the mixture was stirred at room temperature for 7 hours. An aqueous solution obtained by mixing 10 g of sodium sulfite with 200 ml of a 20% aqueous sodium hydroxide solution was added to the reaction mixture, and the mixture was stirred at room temperature for 30 minutes. The chloroform layer and the aqueous layer were separated, and the chloroform layer was extracted again from the aqueous layer. The resultant was dried over magnesium sulfate and concentrated under reduced pressure to obtain 21 g of 2- (2-pyridyl) pyridine-N-oxide (yield: 76%). 2
21 g of-(2-pyridyl) pyridine-N-oxide was added to 30 ml of phosphorus oxychloride, and the mixture was heated under reflux for 30 minutes. After cooling and concentration under reduced pressure, the residue was neutralized with an aqueous solution of sodium hydrogen carbonate, extracted with ethyl acetate, washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. Column chromatography of the residue (hexane: ethyl acetate = 10: 1)
The desired 2- (6-chloro-2-pyridyl) pyridine was obtained in an amount of 4.45 g (yield of 19%), and the desired 2- (4-chloro-2-pyridyl) pyridine was obtained in an amount of 6.5 g (yield of 28%). )Obtained. 3. 2- (6-chloro-2-pyridyl) pyridine
45 g was dissolved in 100 ml of chloroform, 8.6 g of metachloroperbenzoic acid was added, and the mixture was stirred at room temperature for 24 hours. To this, 20 ml of a 2N aqueous solution of sodium hydroxide was added, and 30
After stirring for two minutes, the chloroform layer and the aqueous layer were separated, and the chloroform layer was extracted again from the aqueous layer. The combined chloroform layers were dried over magnesium sulfate and concentrated under reduced pressure to give 2- (6-
3. Chloro-2-pyridyl) pyridine-N-oxide.
45 g (92% yield) were obtained. Next, 2.56 g of benzyl alcohol was added to a suspension of 0.95 g of sodium hydride in 15 ml of DMF, and the mixture was stirred at room temperature. After the generation of hydrogen had ceased, 4.45 g of the obtained 2- (6-chloro-2-pyridyl) pyridine-N-oxide was added, and
Stirred at C for 3 hours. After cooling, water was added, the mixture was extracted with ethyl acetate, washed with saturated saline, dried over magnesium sulfate, concentrated under reduced pressure, and the obtained crystals were washed with ether, and 2- (6-
3.44 g (yield 57%) of benzyloxy-2-pyridyl) pyridine-N-oxide was obtained. Next, 1.78 g of Meldrum's acid was dissolved in 6 ml of acetic anhydride to obtain 2-
(6-benzyloxy-2-pyridyl) pyridine-N-
3.44 g of the oxide was added under ice cooling. After stirring at room temperature for 24 hours, the precipitated crystals were collected by filtration and the crude product was purified by silica gel column chromatography (chloroform → chloroform: methanol = 50: 1) to give 2,2-dimethyl-5- [2- (6- Benzyloxy-2-pyridyl)
[Pyridin-6yl] -1,3-dioxane-4,6-dione was obtained in an amount of 1.2 g (yield: 24%). The resulting 2,2-
Dimethyl-5- [2- (6-benzyloxy-2-pyridyl) pyridin-6yl] -1,3-dioxane-4,
30 ml of concentrated hydrochloric acid was added to 1.03 g of 6-dione, and the mixture was heated under reflux for one day. After cooling, the mixture was concentrated under reduced pressure, neutralized with a saturated aqueous solution of sodium bicarbonate, extracted with ethyl acetate, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 0.21 g of the desired product (44% yield).

Reference Example 2 Production of 6- (2-chloro-4-pyridyl) -2-hydroxypyridine

[0064]

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9.6 g of 6-benzyloxy-2-bromopyridine, 2.55 g of bis (triphenylphosphine) palladium dichloride and 14.72 g of 4- (tri-n-butylstannyl) pyridine were added to 250 ml of dioxane.
The mixture was heated and refluxed all day long. After allowing to cool, water was added, the insolubles were filtered off, extracted with ethyl acetate, washed with saturated saline, dried over magnesium sulfate and concentrated under reduced pressure. The crude product is subjected to silica gel column chromatography (hexane: ethyl acetate =
8: 1) to give 7.59 g (80% yield) of 2-benzyloxy-6- (4-pyridyl) pyridine. 7.59 g of the obtained 2-benzyloxy-6- (4-pyridyl) pyridine was dissolved in 100 ml of chloroform, and 16.7 g of metachloroperbenzoic acid was added, followed by stirring at room temperature for 24 hours. After adding a saturated aqueous sodium carbonate solution and stirring, the chloroform layer and the aqueous layer were separated, the chloroform layer was washed with saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure to give 4- (6-benzyloxy-2). 8.0 g (quantitative) of -pyridyl) pyridine-N-oxide were obtained. 3.0 g of the obtained 4- (6-benzyloxy-2-pyridyl) pyridine-N-oxide was added to 5 ml of phosphorus oxychloride and stirred at 100 ° C. for 30 minutes. After cooling and concentration under reduced pressure, the residue was neutralized with an aqueous solution of sodium hydrogen carbonate, extracted with ethyl acetate, washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. The remaining crystals were washed with ethyl acetate to obtain 0.33 g (yield 15%) of the desired product.

Table 2 shows representative examples of the compounds of the present invention, including the above Examples. Table 3 shows the ¹ H-NMR data of the compound of the present invention.

The abbreviations in the table have the same meanings as in Table 1.

[0068]

[Table 201]

[0069]

[Table 301]

Next, preparation examples of the fungicide for agricultural and horticultural use of the present invention will be described. However, the additives and the addition ratio are not limited to these examples, but can be changed in a wide range. . Parts in the following formulation examples represent parts by weight. Example 3 wettable powder 40 parts of the compound of the present invention 53 parts of diatomaceous earth 4 parts of higher alcohol sulfate 4 parts of alkylnaphthalene sulfonate If the above are uniformly mixed and finely pulverized, the active ingredient 40
% Wettable powder.

Example 4 Emulsion 30 parts of the compound of the present invention 33 parts of xylene 30 parts of dimethylformamide 7 parts of polyoxyethylene alkylaryl ether 7 parts By mixing and dissolving the above, an emulsion containing 30% of the active ingredient is obtained.

Example 5 Dust 10 parts of the compound of the present invention 89 parts of talc 1 part of polyoxyethylene alkylaryl ether 1 part If the above components are uniformly mixed and finely pulverized, the active ingredient 10
% Powder.

Example 6 Granules Compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctyl sulfosuccinate sodium salt 1 part Sodium phosphate 1 part The above components were thoroughly pulverized and mixed, and water was added and kneaded well.
The granules are dried by granulation to obtain granules having an active ingredient of 5%.

Example 7 Suspension Compound of the present invention 10 parts Sodium ligninsulfonate 4 parts Sodium dodecylbenzenesulfonate 1 part Xanthan gum 0.2 parts Water 84.8 parts Mix until more than 1 micron particle size If wet milled, a 10% active ingredient suspension is obtained.

[0075]

Next, Test Examples show that the compound of the present invention is useful as an active ingredient of various plant disease controlling agents. The control effect was determined by visually observing the growth of lesions and microflora that appeared on leaves, stems, and the like at the time of the survey, and calculating the control effect.

Test Example 1 Wheat Powdery Mildew Control Test Wheat seedlings (cultivar “Norin 61”) cultivated in unglazed pots
No., 1.0-1.2 leaf stage), the emulsion of the compound of the present invention was sprayed at a concentration of 200 ppm of the active ingredient. After the leaves allowed to air dry, wheat powdery mildew (Erysiphe g ram
inis f. sp. tritici ) was shaken off, inoculated and grown in a greenhouse at 22-25 ° C. for 7 days,
The control effect was investigated. As a result, the following compound was 75%
The above excellent control value was shown. The compound numbers correspond to the compound numbers in the table (the same applies hereinafter).

Compound number: 1, 2, 3, 4, 5, 6, 7, 9, 15

Test Example 2 Apple Scab Control Test Apple seedlings (cultivar “Kunimitsu”, 3
~ 4 leaf stage), the emulsion of the compound of the present invention
Sprayed at a concentration of pm. After spraying, air-dry at room temperature and scab of apple ( Venturia inaequali)
The conidia of s ) were inoculated and kept in a high humidity constant temperature room (20 ° C.) where light and dark were repeated every 12 hours for 2 weeks. As a result of comparing and investigating the appearance of a lesion on the leaf with no treatment, and controlling the effect, the following compounds showed an excellent control effect of 75% or more.

Compound number: 1, 2, 3, 4, 5, 6, 11, 15

Test Example 3 Grape downy mildew control test Grape seedlings (cultivar “Kaiji”, cultivated in unglazed pots)
In the 2 leaf stage), the emulsion of the compound of the present invention was mixed with the active ingredient at 200 pp.
m. After spraying, air-dry at room temperature, and the grape downy mildew ( Plasmopara viticol)
The zoosporang suspension of a ) was sprayed and inoculated, and kept in a high humidity constant temperature room (20 ° C.) where light and dark were repeated every 12 hours for 10 days. The appearance of lesions on the leaves was compared with that of no treatment, and the control effect was determined. As a result, the following compounds exhibited an excellent controlling effect of 75% or more.

Compound number: 1, 2, 3, 4, 5, 7,
8, 9, 11, 12, 13, 15

Test Example 4 Test for controlling common bean gray mold Green beans cultivated in seedling bats (variety "Naga quail")
The flower of the compound of the present invention was excised, and 200 p
It was immersed in a chemical solution prepared to a concentration of pm. After immersion, air-dry at room temperature, and bean gray mold ( Botrytis)
cinerea ). The inoculated flower was placed on an untreated kidney leaf, and kept in a high-humidity constant temperature room (20 ° C.) where light and dark were repeated every 12 hours for 7 days. The lesion diameter on the leaf was compared with that of the untreated one, and the control value was determined. As a result, the following compounds exhibited excellent control values of 75% or more.

Compound number: 1, 2, 3, 4, 5, 7,
8, 9, 10, 12, 15

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Hamamura 345 Takada, Odawara-shi, Kanagawa Japan Soda Co., Ltd.Odawara Research Laboratory Co., Ltd. Reference) 4H011 AA01 BA01 BA05 BB13 BC01 BC04 BC07 BC18 BC19 BC20 BC22 DA02 DA15 DA16 DH03

Claims (3)

[Claims] 1. A compound of the general formula (1) (Wherein, R ¹ and R ² are each independently a hydrogen atom,
Represents a halogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group. R ³ represents a methyl group or an ethyl group.
R ⁴ represents a cyano group, a hydroxy group, a halogen atom, C
_1-6 alkyl group, C _1-6 alkenyl group, C _1-6 alkynyl group, C _1-6 alkoxy group, C _1-6 alkylthio group, C
_1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl groups, C _1-6 haloalkyl group, C _3-8 cycloalkyl group, C _1-6 alkylcarbonyl group, C _1-6 alkylcarbonyloxy, C _{1- 6} alkoxycarbonyl group, hydroxyimino C _1-6 alkyl group, C _1-6 alkoxyimino C _1-6 alkyl group, carbamoyl group (which may be substituted by C _1-6 alkyl group), and substituent Represents a phenyl group which may be substituted, a benzyl group which may have a substituent, a phenoxy group which may have a substituent, or a benzyloxy group which may have a substituent. n represents 0 or an integer of 1 to 4, and when n is 2 or more, R ⁴
May be the same or different. Or a salt thereof. 2. A compound of the general formula (2) (Wherein, R ² and R ³ represent the same meaning as described above;
Represents a leaving group. And a compound represented by the general formula (3): (Wherein R ¹ , R ⁴ and n have the same meanings as described above), characterized by reacting with a compound represented by the following general formula (1): (Wherein R ¹ , R ² , R ³ , R ⁴ and n represent the same meaning as described above). 3. A compound of the general formula (1) (Wherein, R ¹ , R ² , R ³ , R ⁴ and n have the same meanings as described above), which contains one or more of a pyridylpyridine compound or a salt thereof as an active ingredient. A fungicide for agricultural and horticultural use, characterized in that: