JP2005330258A - Thiazoline compound and its use for controlling plant disease - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound having excellent plant disease controlling effect. <P>SOLUTION: The thiazoline compound expressed by formula (I) has excellent effect for the control of plant diseases. In the formula, A is phenyl group which may be substituted with a 1-5C alkyl group, a 1-5C haloalkyl group, a 1-5C alkoxy group, a 1-5C haloalkoxy group, a 2-5C alkoxyalkyl group, a 2-5C alkoxycarbonyl group, a 3-5C alkenyloxy group, a 3-5C alkynyloxy group, phenoxy group or a halogen atom, or the like. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thiazoline compound and its use for controlling plant diseases.

等のチアゾリン化合物が３−ブロモ−１，１，１−トリフルオロプロパン−２−オンとチオアミド化合物との反応生成物として知られている（非特許文献１参照。）。 4-Hydroxy-2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline

Such a thiazoline compound is known as a reaction product of 3-bromo-1,1,1-trifluoropropan-2-one and a thioamide compound (see Non-Patent Document 1).

Journal of Heterocyclic Chemistry, 1991, 28, 907 (J. Heterocyclic Chem., 28, p.907, (1991)).

  An object of the present invention is to provide a compound having an excellent plant disease control effect.

〔式中、Ａはフリル基、チエニル基、或いはＣ１−Ｃ５アルキル基、Ｃ１−Ｃ５ハロアルキル基、Ｃ１−Ｃ５アルコキシ基、Ｃ１−Ｃ５ハロアルコキシ基、Ｃ２−Ｃ５アルコキシアルキル基、Ｃ２−Ｃ５アルコキシカルボニル基、Ｃ３−Ｃ５アルケニルオキシ基、Ｃ３−Ｃ５アルキニルオキシ基、フェノキシ基若しくはハロゲン原子で置換されていてもよいフェニル基を表す。〕で示されるチアゾリン化合物（以下、本発明化合物と記す。）、本発明化合物を有効成分として含有することを特徴とする植物病害防除剤、及び本発明化合物の有効量を植物又は土壌に施用することを特徴とする植物病害の防除方法を提供する。 As a result of intensive studies to find a compound having an excellent plant disease control effect, the present inventors have found that the thiazoline compound represented by the following formula (I) has an excellent plant disease control effect, completed.
That is, the present invention relates to the formula (I)

[In the formula, A represents a furyl group, a thienyl group, or a C1-C5 alkyl group, a C1-C5 haloalkyl group, a C1-C5 alkoxy group, a C1-C5 haloalkoxy group, a C2-C5 alkoxyalkyl group, a C2-C5 alkoxycarbonyl group. A phenyl group which may be substituted with a group, a C3-C5 alkenyloxy group, a C3-C5 alkynyloxy group, a phenoxy group or a halogen atom; ] A thiazoline compound (hereinafter referred to as the compound of the present invention), a plant disease control agent characterized by containing the compound of the present invention as an active ingredient, and an effective amount of the compound of the present invention is applied to plants or soil. The present invention provides a method for controlling plant diseases.

  Since this invention compound has the outstanding plant disease control effect, it can be used as an active ingredient of a plant disease control agent.

In the present invention,
Examples of the furyl group represented by A include a 2-furyl group and a 3-furyl group.
Examples of the thienyl group include a 2-thienyl group and a 3-thienyl group.
C1-C5 alkyl group, C1-C5 haloalkyl group, C1-C5 alkoxy group, C1-C5 haloalkoxy group, C2-C5 alkoxyalkyl group, C2-C5 alkoxycarbonyl group, C3-C5 alkenyloxy group, C3-C5 alkynyl The phenyl group which may be substituted with an oxy group, a phenoxy group or a halogen atom means that one of the carbon atoms forming the phenyl group is a C1-C5 alkyl group, a C1-C5 haloalkyl group, a C1-C5 alkoxy group, C1 -C5 haloalkoxy group, C2-C5 alkoxyalkyl group, C2-C5 alkoxycarbonyl group, C3-C5 alkenyloxy group, C3-C5 alkynyloxy group, phenoxy group or phenyl group with or without a bond with a halogen atom Represents
C1-C5 alkyl group, C1-C5 haloalkyl group, C1-C5 alkoxy group, C1-C5 haloalkoxy group, C2-C5 alkoxyalkyl group, C2-C5 alkoxycarbonyl group, C3-C5 alkenyloxy group, C3-C5 alkynyl Examples of the C1-C5 alkyl group in the phenyl group optionally substituted with an oxy group, a phenoxy group, or a halogen atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tert-butyl group.
Examples of the C1-C5 haloalkyl group include a trifluoromethyl group and a difluoromethyl group,
Examples of the C1-C5 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a tert-butoxy group.
Examples of the C1-C5 haloalkoxy group include a trifluoromethoxy group and a difluoromethoxy group,
Examples of the C2-C5 alkoxyalkyl group include a methoxymethyl group and an ethoxymethyl group,
Examples of the C2-C5 alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, and a tert-butoxycarbonyl group.
Examples of the C3-C5 alkenyloxy group include an allyloxy group and a 2-butenyloxy group,
Examples of the C3-C5 alkynyloxy group include a propargyloxy group and a 2-butynyloxy group,
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As an aspect of this invention compound, the following thiazoline compounds are mentioned, for example.
In the formula (I), A represents a C1-C5 alkyl group, a C1-C5 haloalkyl group, a C1-C5 alkoxy group, a C1-C5 haloalkoxy group, a C2-C5 alkoxyalkyl group, a C2-C5 alkoxycarbonyl group, a C3-C5 A thiazoline compound which is an alkenyloxy group, a C3-C5 alkynyloxy group, a phenoxy group or a phenyl group optionally substituted by a halogen atom;
In the formula (I), A represents a C1-C5 alkyl group, a C1-C5 haloalkyl group, a C1-C5 alkoxy group, a C1-C5 haloalkoxy group, a C2-C5 alkoxyalkyl group, a C2-C5 alkoxycarbonyl group, a C3-C5 A thiazoline compound which is a phenyl group substituted with an alkenyloxy group, a C3-C5 alkynyloxy group, a phenoxy group or a halogen atom;
A thiazoline compound represented by formula (I), wherein A is a phenyl group;
In formula (I), A is a C1-C5 alkyl group, a C1-C5 haloalkyl group, a C1-C5 alkoxy group, a C1-C5 haloalkoxy group, a C2-C5 alkoxyalkyl group, a C3-C5 alkenyloxy group at the 4-position. A thiazoline compound which is a phenyl group substituted with a C3-C5 alkynyloxy group, a phenoxy group or a halogen atom;
A thiazoline compound represented by formula (I), wherein A is a phenyl group substituted with a C1-C5 alkyl group or a halogen atom at the 2-position;
A thiazoline compound represented by formula (I), wherein A is a phenyl group substituted with a C1-C5 alkyl group, a C1-C5 alkoxy group or a halogen atom at the 3-position;
In the formula (I), A is a C1-C5 haloalkyl group, C1-C5 haloalkoxy group, C2-C5 alkoxyalkyl group, C2-C5 alkoxycarbonyl group, C3-C5 alkenyloxy group, C3-C5 alkynyloxy group or phenoxy A thiazoline compound which is a phenyl group substituted by a group;
A thiazoline compound represented by formula (I), wherein A is a furyl group or a thienyl group;
A thiazoline compound represented by formula (I), wherein A is a thienyl group;
A thiazoline compound represented by formula (I), wherein A is a furyl group.

で示される化合物（４−ヒドロキシ−２−（３−ピリジル）−４−トリフルオロメチル−２−チアゾリン）と、式（III）

〔式中、Aは前記と同じ意味を表し、Yは塩素原子又は臭素原子を表す。〕
で示される化合物とを、塩基の存在下で反応させることにより製造することができる。
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばヘキサン、ヘプタン、オクタン、ノナン等の脂肪族炭化水素類、ベンゼン、トルエン、キシレン等の芳香族炭化水素類、塩化メチレン、１、２−ジクロロエタン、クロロベンゼン、ベンゾトリフルオリド等のハロゲン化炭化水素類、ジイソプロピルエーテル、テトラヒドロフラン、１、４−ジオキサン等のエーテル類及びそれらの混合物が挙げられる。
反応に用いられる塩基としては、例えばトリエチルアミン、ジイソプロピルエチルアミン等の第３級アミン化合物、ピリジン、４−ジメチルアミノピリジン等の含窒素複素環化合物が挙げられる。
該反応の反応温度は通常-２０℃から１００℃若しくは溶媒の還流温度までの範囲であり、反応時間は通常０.１〜７２時間の範囲である。
反応に用いられる試剤の量は、式（II）で示される化合物１モルに対して、式（III）で示される化合物が通常０．７〜１．５モルの割合、塩基が通常１〜５モルの割合である。
反応終了後は、反応液を水に注加した後、有機溶媒抽出、濃縮等の後処理操作を行うことにより、本発明化合物を単離することができる。単離された本発明化合物は、必要に応じて洗浄、再結晶、カラムクロマトグラフィー等によりさらに精製することもできる。 Production Method Next, the production method of the compound of the present invention will be explained.
The compound of the present invention is represented by, for example, formula (II)

(4-Hydroxy-2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline) represented by formula (III)

[Wherein, A represents the same meaning as described above, and Y represents a chlorine atom or a bromine atom. ]
It can manufacture by making the compound shown by react with presence of a base.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic hydrocarbons such as hexane, heptane, octane, and nonane, aromatic hydrocarbons such as benzene, toluene, and xylene, methylene chloride, 1,2-dichloroethane, chlorobenzene, and benzotrifluor. Halogenated hydrocarbons such as Lido, ethers such as diisopropyl ether, tetrahydrofuran, 1,4-dioxane, and mixtures thereof.
Examples of the base used in the reaction include tertiary amine compounds such as triethylamine and diisopropylethylamine, and nitrogen-containing heterocyclic compounds such as pyridine and 4-dimethylaminopyridine.
The reaction temperature of the reaction is usually in the range from −20 ° C. to 100 ° C. or the reflux temperature of the solvent, and the reaction time is usually in the range of 0.1 to 72 hours.
The amount of the reagent used in the reaction is usually 0.7 to 1.5 mol of the compound represented by the formula (III) and 1 to 5 mol of the base based on 1 mol of the compound represented by the formula (II). The molar ratio.
After completion of the reaction, the compound of the present invention can be isolated by pouring the reaction solution into water and performing post-treatment operations such as organic solvent extraction and concentration. The isolated compound of the present invention can be further purified by washing, recrystallization, column chromatography or the like, if necessary.

  The compound represented by the formula (II) can be produced, for example, by the method described in J. Heterocyclic. Chem., 28, p.907 (1991).

Examples of plant diseases that can be controlled by the compounds of the present invention include the following diseases.
Rice blast (Pyricularia oryzae), sesame leaf blight (Cochliobolus miyabeanus), blight (Rhizoctonia solani);
Wheat powdery mildew (Erysiphe graminis), red mold (Gibberella zeae), rust (Puccinia striiformis, P. graminis, P. recondita, P. hordei), snow rot (Typhula sp., Micronectriella nivalis), Bare smut (Ustilago tritici, U. nuda), Nagusa smut (Tilletia caries), eye ailment (Pseudocercosporella herpotrichoides), cloud disease (Rhynchosporium secalis), leaf blight (Septoria tritici), blight (Leptosphaeria nodorum) ;
Citrus black spot (Diaporthe citri), common scab (Elsinoe fawcetti), fruit rot (Penicillium digitatum, P. italicum);
Apple Monilia (Sclerotinia mali), rot (Valsa mali), powdery mildew (Podosphaera leucotricha), spotted leaf (Alternaria mali), scab (Venturia inaequalis);

Pear black spot (Venturia nashicola, V. pirina), black spot (Alternaria kikuchiana), red star (Gymnosporangium haraeanum);
Peach ash scab (Sclerotinia cinerea), black scab (Cladosporium carpophilum), Phomopsis sp. (Phomopsis sp.);
Grapes black rot (Elsinoe ampelina), late rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black lot disease (Guignardia bidwellii), downy mildew (Plasmopara viticola);
Oyster anthracnose (Gloeosporium kaki), deciduous leaf disease (Cercospora kaki, Mycosphaerella nawae);
Colletotrichum lagenarium, powdery mildew (Sphaerotheca fuliginea), vine blight (Mycosphaerella melonis), vine split (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), plague (Phytophthora) Seedling blight (Pythium sp.);

Tomato ring disease (Alternaria solani), leaf mold (Cladosporium fulvum), plague (Phytophthora infestans);
Eggplant brown spot (Phomopsis vexans), powdery mildew (Erysiphe cichoracearum);
Brassicaceae vegetable black spot (Alternaria japonica), white spot (Cercosporella brassicae);
Leek rust (Puccinia allii);
Soybean purpura (Cercospora kikuchii), black scab (Elsinoe glycines), sunspot (Diaporthe phaseolorum var. Sojae);
Kidney anthracnose (Colletotrichum lindemthianum);
Groundnut black rot (Cercospora personata), brown spot (Cercospora arachidicola);
Pea powdery mildew (Erysiphe pisi);

Potato summer plague (Alternaria solani), plague (Phytophthora infestans);
Strawberry powdery mildew (Sphaerotheca humuli);
Tea net blast (Exobasidium reticulatum), white scab (Elsinoe leucospila);
Tobacco red blight (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), plague (Phytophthora nicotianae);
Brown spot of sugar beet (Cercospora beticola);
Rose black spot (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa);
Chrysanthemum brown spot disease (Septoria chrysanthemi-indici), white rust disease (Puccinia horiana);
Various crops such as gray mold (Botrytis cinerea), sclerotia (Sclerotinia sclerotiorum), etc.

When the compound of the present invention is used as an active ingredient of a plant disease control agent, it may be used as it is without adding any other components, but usually mixed with a solid carrier, a liquid carrier, a surfactant, or other formulation adjuvants. Then, it is used in the form of emulsion, wettable powder, suspension, powder, granule and the like. These preparations contain the compound of the present invention as an active ingredient in a weight ratio of usually 0.1 to 99.9%, preferably 1 to 90%.
Examples of the solid carrier used in the formulation include kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite and other minerals, corn cob flour, and walnut shell flour. Examples include natural organic substances such as urea, synthetic organic substances such as urea, fine powders or particulates such as ammonium sulfate and synthetic silicon hydroxide, and examples of liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, and isopropanol. , Alcohols such as ethylene glycol and cellosolve, ketones such as acetone, cyclohexanone and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, acetonitrile and water.

  Examples of the surfactant include alkyl sulfate ester salts, alkyl aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphate esters, lignin sulfonates, naphthalene sulfonate formaldehyde polycondensates, and the like. Anionic surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl polyoxypropylene block copolymers, and nonionic surfactants such as sorbitan fatty acid esters.

  Examples of other adjuvants for preparation include water-soluble polymers such as polyvinyl alcohol and polyvinyl pyrrolidone, gum arabic, alginic acid and salts thereof, polysaccharides such as CMC (carboxymethylcellulose) and xanthan gum, aluminum magnesium silicate, alumina sol And stabilizers such as inorganic substances such as preservatives, colorants, PAP (isopropyl acid phosphate), and BHT.

The plant disease control agent of the present invention is used to protect the plant from plant diseases, for example, by treating the plant body, and also protects plants growing in the soil from plant diseases by treating the soil. Used for.
When the plant disease control agent of the present invention is used by treating foliage to a plant body or when it is used by treating the soil, the treatment amount is the type of crops, etc., the type of control target disease, control Although it can be changed depending on the degree of occurrence of the target disease, formulation form, treatment time, weather conditions, etc., it is usually 1 to 5000 g, preferably 5 to 1000 g as the compound of the present invention per 10,000 m ² .

  Emulsions, wettable powders, flowables and the like are usually treated by diluting with water and spraying. In this case, the concentration of the compound of the present invention is usually 0.0001 to 3% by weight, preferably 0.0005 to 1% by weight. Powders, granules, etc. are usually processed without dilution.

  Moreover, the plant disease control agent of this invention can also be used by processing methods, such as seed disinfection. As the method, for example, a method of immersing plant seeds in the plant disease control agent of the present invention prepared so that the concentration of the compound of the present invention is 1-1000 ppm, the concentration of the compound of the present invention is 1-1000 ppm in the plant seeds. And the method of spraying or smearing the plant disease control agent of the present invention and the method of dressing the plant disease control agent of the present invention on the seeds of plants.

  In the plant disease control method of the present invention, the effective amount of the plant disease control agent of the present invention is usually treated to the plant where the occurrence of the disease is predicted or the soil where the plant grows, and / or the occurrence of the disease is confirmed. It is carried out by treating the plant or the soil where the plant grows.

The plant disease control agent of the present invention is usually used as an agricultural and horticultural plant disease control agent, that is, a plant disease control agent for controlling plant diseases such as upland, paddy fields, orchards, tea gardens, pastures, and lawns.
The plant disease control agent of the present invention can be used together with other plant disease control agents, insecticides, acaricides, nematicides, herbicides, plant growth regulators and / or fertilizers.

  Examples of such bactericides include chlorothalonil, fluazinam, diclofluranide, fosetyl-Al, cyclic imide derivatives (captan, captahol, phorpet, etc.), dithiocarbamate derivatives (manneb, mancozeb, thyram, diram, dineb, propineb Etc.), inorganic or organic copper derivatives (basic copper sulfate, basic copper chloride, copper hydroxide, oxine copper, etc.), acylalanine derivatives (metalaxyl, furaxyl, off-race, cyprofuran, benalaxyl, oxadixyl, etc.), strobilurin series Compounds (cresoxime methyl, azoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, dimoxystrobin, etc.), anilinopyrimidine derivatives (cyprodinil, pyrimethanil, mepanipyrim, etc.), fe Lupyrrole derivatives (phenpiclonyl, fludioxonil, etc.), imide derivatives (procymidone, iprodione, vinclozoline, etc.), benzimidazole derivatives (carbendazim, benomyl, thiabendazole, thiophanatemethyl, etc.), amine derivatives (fenpropimorph, tridemorph, fenpropidin, spiroxamine, etc.) ), Azole derivatives (propiconazole, triadimenol, prochloraz, penconazole, tebuconazole, flusilazole, diniconazole, bromoconazole, epoxyconazole, difenoconazole, cyproconazole, metconazole, triflumizole, tetraconazole, microbutanyl , Fenbuconazole, Hexaconazole, Fluquinconazole, Triticonazole, Viterta , Imazalyl, flutriahol, etc.), simoxanyl, dimethomorph, famoxadone, fenamidone, iprovalicarb, benchavaricarb, cyazofamide, zoxamide, ethaboxam, boscalid, fenhexamide, quinoxyphene, dietofencarb and acibenzoral S methyl Is mentioned.

  Hereinafter, although this invention is demonstrated in more detail by a manufacture example, a formulation example, a test example, etc., this invention is not limited only to these examples.

First, the manufacture example of this invention compound is shown.
For measurement of ¹ H-NMR in the physical property data, tetramethylsilane (TMS) was used as an internal standard (= 0 [ppm]) unless otherwise specified.
(Production Example 1)
To a mixture of 0.50 g of 4-hydroxy-2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline, 0.21 g of triethylamine, 0.08 g of 4-dimethylaminopyridine and 10 ml of tetrahydrofuran, the solution was cooled under ice-cooling. 4-Ethoxybenzoyl 0.38g was added and it stirred at room temperature for 3 hours. The reaction mixture was poured into 30 ml of ice water and extracted twice with 60 ml of ethyl acetate. The organic layers were combined, washed successively with 1% hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography, and 4- (4-ethoxybenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 1). .) 0.55 g was obtained.
Compound 1 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.42 (3H, t), 3.96 (2H, q), 4.10 (2H, q), 6.92 (2H, d), 7 .38 (1H, t), 8.00 (2H, d), 8.22 (1H, d), 8.75 (1H, s), 9.12 (1H, s)

The following compounds were produced in the same manner as in (Production Example 1) above.
4- (4-methoxybenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 2)
Compound 2 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.87 (3H, s), 3.98 (2H, q), 6.92 (2H, d), 7.38 (1H, t), 8 0.00 (2H, d), 8.22 (1H, d), 8.74 (1H, s), 9.11 (1H, s)

4- (4-Isopropoxybenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 3)
Compound 3 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.35 (6H, d), 3.98 (2H, q), 4.65 (1H, m), 6.90 (2H, d), 7 .39 (1H, t), 7.98 (2H, d), 8.21 (1H, d), 8.74 (1H, s), 9.10 (1H, s)

4- (4-tert-butoxybenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 4)
Compound 4 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.43 (9H, s), 3.98 (2H, q), 7.00 (2H, d), 7.38 (1H, t), 7 .96 (2H, d), 8.22 (1H, d), 8.75 (1H, s), 9.11 (1H, s)

4- (4-trifluoromethoxybenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 5)
Compound 5 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.99 (2H, s), 7.30 (2H, d), 7.40 (1H, t), 8.08 (2H, d), 8 .22 (1H, d), 8.78 (1H, s), 9.12 (1H, s)

4- (4-Methylbenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 6)
Compound 6 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 2.42 (3H, s), 3.97 (2H, s), 7.26 (2H, d), 7.38 (1H, t), 7 .94 (2H, d), 8.20 (1H, d), 8.75 (1H, d), 9.10 (1H, s)

4- (4-Ethylbenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 7)
Compound 7 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.25 (3H, t), 2.70 (2H, q), 3.81 (2H, s), 7.25 (2H, d), 7 .38 (1H, t), 7.93 (2H, d), 8.22 (1H, d), 8.75 (1H, d), 9.11 (1H, s)

4- (4-tert-butylbenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 8)
Compound 8 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.32 (9H, s), 3.97 (2H, s), 7.36 (1H, t), 7.50 (2H, d), 8 0.00 (2H, d), 8.20 (1H, d), 8.75 (1H, d), 9.10 (1H, s)

4- (4-Chlorobenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 9)
Compound 9 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.97 (2H, s), 7.38 (1H, m), 7.44 (2H, d), 7.96 (2H, d), 8 .20 (1H, d), 8.75 (1H, d), 9.10 (1H, s)

4- (4-trifluoromethylbenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 10)
Compound 10 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 4.00 (2H, s), 7.38 (1H, m), 7.74 (2H, d), 8.20 (2H, d), 8 .22 (1H, d), 8.77 (1H, d), 9.11 (1H, s)

4- (4-Cyanobenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 11)
Compound 11 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.99 (2H, s), 7.38 (1H, t), 7.76 (2H, d), 8.13 (2H, d), 8 .22 (1H, d), 8.76 (1H, s), 9.11 (1H, s)

4- (4-methoxycarbonylbenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 12)
Compound 12 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.95 (3H, s), 4.00 (2H, s), 7.40 (1H, t), 8.14 (4H, s), 8 .22 (1H, d), 8.77 (1H, s), 9.11 (1H, s)

4- (4-phenoxybenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 13)
Compound 13 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.98 (2H, q), 7.00 (2H, d), 7.08 (2H, d), 7.22 (1H, t), 7 .38 (3H, m), 8.00 (2H, d), 8.22 (1H, d), 8.75 (1H, s), 9.11 (1H, s)

4- (3-methoxybenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 14)
Compound 14 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.83 (3H, s), 3.97 (2H, s), 7.16 (1H, d), 7.36 (2H, m), 7 .54 (1H, s),
7.66 (1H, d), 8.22 (1H, d), 8.75 (1H, d), 9.10 (1H, s)

4- (2-methylbenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 15)
Compound 15 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 2.59 (3H, s), 3.98 (2H, q), 7.27 (2H, m), 7.42 (2H, m), 8 0.00 (1H, d), 8.22 (1H, d), 8.75 (1H, s), 9.11 (1H, s)

4- (3-methylbenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 16)
Compound 16 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 2.40 (3H, s), 4.00 (2H, s), 7.38 (3H, m), 7.84 (2H, s), 8 .20 (1H, d), 8.75 (1H, d), 9.10 (1H, s)

4- (2-chlorobenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 17)
Compound 17 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 4.00 (2H, q), 7.38 (2H, m), 7.47 (2H, m), 8.00 (1H, d), 8 .22 (1H, d), 8.75 (1H, s), 9.11 (1H, s)

4- (3-Chlorobenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 18)
Compound 18 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.98 (2H, s), 7.40 (2H, m), 7.58 (1H, d), 7.93 (1H, d), 8 0.00 (1H, s), 8.22 (1H, d), 8.77 (1H, d), 9.11 (1H, s)

4- (4-propoxybenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 19)
Compound 19 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.02 (3H, t), 1.83 (2H, m), 3.98 (4H, m), 6.90 (2H, d), 7 .38 (1H, t), 7.98 (2H, d), 8.22 (1H, d), 8.74 (1H, s), 9.11 (1H, s)

4- (4-Butoxybenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 20)
Compound 20 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.00 (3H, t), 1.50 (2H, m), 1.80 (2H, m), 4.00 (4H, m), 6 .92 (2H, d), 7.38 (1H, t), 8.00 (2H, d), 8.22 (1H, d), 8.74 (1H, s), 9.11 (1H, s)

4- (4-methoxymethylbenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 21)
Compound 21 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.38 (3H, s), 3.98 (2H, s), 4.52 (2H, s), 7.38 (1H, m), 7 .40 (2H, d), 8.02 (2H, d), 8.22 (1H, d), 8.74 (1H, d), 9.10 (1H, s)

4- (4-allyloxybenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 22)
Compound 22 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.96 (2H, q), 4.60 (2H, d), 5.38 (2H, dd), 6.04 (1H, m), 6 .95 (2H, d), 7.38 (1H, t), 7.99 (2H, d), 8.21 (1H, d), 8.74 (1H, s), 9.11 (1H, s)

4- (4-propargyloxybenzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 23)
Compound 23 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 2.55 (1H, s), 3.98 (2H, q), 4.78 (2H, s), 7.02 (2H, d), 7 .38 (1H, t), 8.02 (2H, d), 8.21 (1H, d), 8.75 (1H, s), 9.11 (1H, s)

4- (Benzoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 24)
Compound 24 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.98 (2H, s), 7.38 (1H, m), 7.45 (2H, m), 7.62 (1H, t), 8 .05 (2H, d), 8.22 (1H, d), 8.75 (1H, d), 9.11 (1H, s)

4- (2-Furoyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 25)
Compound 25 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.97 (2H, s), 6.54 (1H, d), 7.29 (1H, d), 7.38 (1H, m), 7 .65 (1H, s), 8.21 (1H, m), 8.75 (1H, d), 9.09 (1H, s)

4- (2-thiophenecarbonyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 26)
Compound 26 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.98 (2H, s), 7.12 (1H, m), 7.38 (1H, m), 7.62 (1H, d), 7 .86 (1H, d), 8.22 (1H, m), 8.75 (1H, d), 9.10 (1H, s)

4- (3-thiophenecarbonyloxy) -2- (3-pyridyl) -4-trifluoromethyl-2-thiazoline (hereinafter referred to as the present compound 27)
Compound 27 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.98 (2H, s), 7.35 (1H, m), 7.39 (1H, m), 7.53 (1H, d), 8 .22 (2H, m), 8.75 (1H, d), 9.10 (1H, s)

式中のＡを（表１）に表す。なお、表中のＰｈはフェニル基を表し、“４−ＯＣＨ₂ＣＨ₃”等における“４−”とは、フェニル基に結合する当該置換基のベンゼン環上の炭素原子の位置、具体的には下記式（IV）

の式中の数字の位置を表す。
Each compound produced by the above production example is shown below together with the compound number of the present invention.
A compound represented by the following formula (I);

A in the formula is represented in (Table 1). In the table, Ph represents a phenyl group, and “4-” in “4-OCH ₂ CH ₃ ” or the like means the position of the carbon atom on the benzene ring of the substituent bonded to the phenyl group, specifically Is the following formula (IV)

Represents the position of the number in the formula.

(Formulation example)
Next, formulation examples are shown. In addition, a part represents a weight part and this invention compound is shown by the compound number as described in (Table 1).

Formulation Example 1
A wettable powder is obtained by thoroughly pulverizing and mixing 50 parts of each of the compounds 1 to 27 of the present invention, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic silicon hydroxide.

Formulation Example 2
25 parts of each of the compounds 1 to 27 of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water were mixed and suspended by wet grinding until the active ingredient particle size was 5 microns or less. Get a suspending agent.

Formulation Example 3
A powder is obtained by thoroughly pulverizing and mixing 2 parts of each of the present compounds 1 to 27, 88 parts of kaolin clay and 10 parts of talc.

Formulation Example 4
An emulsion is obtained by thoroughly mixing 20 parts of each of the compounds 1 to 27 of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 60 parts of xylene.

Formulation Example 5
2 parts of each of the compounds 1 to 27 of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are added to each other and mixed well. Granules are obtained by drying the granules.

Formulation Example 6
20 parts of each of the compounds 1 to 27 of the present invention and 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol and pulverized with a sand grinder (particle size 3 μm). Thereafter, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate is added thereto, and further 10 parts of propylene glycol is added thereto, followed by stirring and mixing. Get a suspending agent.

Formulation Example 7
10 parts of each of the compounds 1 to 27 of the present invention, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt and 55 parts of water are mixed and finely pulverized by a wet pulverization method to obtain each preparation. .

（以下、比較化合物（A）と表す。）を同様に供試した。 (Test example)
Next, test examples show that the compounds of the present invention are useful as active ingredients of plant disease control agents.
The control effect of the compound of the present invention is evaluated by visually observing the area of the lesion on the test plant at the time of the investigation, and comparing the area of the lesion in the untreated group with the area of the lesion in the compound-treated group. did.
In order to show the effect of the present invention more clearly, 4-hydroxy-2- (3-pyridyl) -4-trifluoro which is a compound described in J. Heterocyclic Chem., 28, p.907, (1991). Methyl-2-thiazoline

(Hereinafter, referred to as comparative compound (A)) was tested in the same manner.

Test example 1
A plastic pot was filled with sandy loam, sowed with wheat (Shirogane wheat), and grown in a greenhouse for 8 days. Each of the compounds 1 to 26 and 27 of the present invention was formulated according to Formulation Example 7, and then diluted with water to a predetermined concentration (500 ppm) to obtain a spray solution. The spray solution was sprayed on the foliage so that the second leaf was sufficiently attached to the leaf surface of the wheat. After spraying, the spray solution on the leaf surface of the plant was air-dried to the extent that it was dry, and then spores of wheat powdery mildew were inoculated on the leaf surface. After inoculation, they were placed under illumination at 23 ° C. for 7 days, and then the control effect was investigated.
As a result, the lesion area on the plant of each of the treatment groups of the present compounds 1-26 and 27 was 10% or less of the lesion area of the untreated group, whereas the treatment area of the comparative compound (A) The lesion area on the plant was 75% or more of the lesion area in the untreated area.

Test example 2
A plastic pot was filled with sandy loam, sowed with wheat (Shirogane wheat), and grown in a greenhouse for 8 days. Each of the compounds 1, 3-5, 11, 13, 19-23, 25, 26 and 27 of the present invention was formulated according to Formulation Example 7, and then diluted with water to a predetermined concentration (500 ppm) to give a spray solution. Prepared. The spray solution was sprayed on the foliage so that the second leaf was sufficiently attached to the leaf surface of the wheat. After spraying, the spray solution on the leaf surface was air-dried to the extent that it was dry, and then a spore suspension of wheat mold was spray-inoculated on the leaf surface. After the inoculation, it was placed at 23 ° C. under dark and humid conditions for 4 days and further under illumination for 3 days, and then the control effect was investigated. As a result, the lesion area on the plant of each treatment group of the present compounds 1, 3-5, 11, 13, 19-23, 25, 26 and 27 is 10% or less of the lesion area of the untreated group. On the other hand, the lesion area on the plant in the treated group of the comparative compound (A) was 75% or more of the lesion area in the untreated group.

Test example 3
A plastic pot was filled with sand loam, sown with cucumber (Sagamihanjiro), and grown in a greenhouse for 12 days. Each of the compounds 1, 2, 16, 21-24, 26 and 27 of the present invention was formulated according to Formulation Example 7, and then diluted with water to a predetermined concentration (500 ppm) to prepare a spray solution. The spray solution was sprayed on the stems and leaves so that the spray solution was sufficiently attached to the cucumber leaves. After spraying, the spray solution on the leaf surface was air-dried to the extent that it was dry, and then the hyphae-containing PDA medium of cucumber gray mold was placed on the cucumber leaf surface. After the inoculation, the control effect was investigated after being placed at 10 ° C. under high humidity for 4 days. As a result, the lesion area on the plant in each treatment group of the present compounds 1, 2, 16, 21-24, 26 and 27 was 10% or less of the lesion area in the untreated group. The lesion area on the plant in the treated area of the comparative compound (A) was 75% or more of the lesion area in the untreated area.

Claims (3)

Formula (I)

[Where,
A is a furyl group, thienyl group, or C1-C5 alkyl group, C1-C5 haloalkyl group, C1-C5 alkoxy group, C1-C5 haloalkoxy group, C2-C5 alkoxyalkyl group, C2-C5 alkoxycarbonyl group, C3- A C5 alkenyloxy group, a C3-C5 alkynyloxy group, a phenoxy group or a phenyl group which may be substituted with a halogen atom. ] The thiazoline compound shown by this.   A plant disease control agent comprising the thiazoline compound according to claim 1 as an active ingredient. A method for controlling plant diseases, which comprises applying an effective amount of the thiazoline compound according to claim 1 to plants or soil.