WO1996017841A1

WO1996017841A1 - Pyridylpyrrole compounds, process for production, and agrohorticultural bactericide

Info

Publication number: WO1996017841A1
Application number: PCT/JP1995/002479
Authority: WO
Inventors: Kenji Hagiwara; Haruo Saso; Kosuke Ichinose; Chinami Yokota; Shinsuke Sano
Original assignee: Nippon Soda Co., Ltd.
Priority date: 1994-12-06
Filing date: 1995-12-05
Publication date: 1996-06-13
Also published as: AU3994795A

Abstract

A pyridylpyrrole compound represented by general formula (I) or a salt thereof wherein R1 represents hydrogen, optionally substituted C¿1?-C10 alkyl, C3-C7 cycloalkyl, hydroxy, aralkyl, carboxy, alkoxycarbonyl, nitro, amino, halogeno, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, thiocyanato or cyano; R?2¿ represents hydrogen, formyl, C¿1?-C6 alkoxymethyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, , C1-C6 alkylsulfonyl, substituted benzoyl, substituted benzenesulfonyl, N-substituted carbamoyl, C1-C6 alkylcarbonyloxymethyl, C1-C6 alkylthiomethyl, C1-C6 alkylsulfonylmethyl or C1-C6 alkylthio; X represents hydrogen, halogeno, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, cyano, nitro, formyl, C1-C6 haloalkoxy, phenoxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkoxycarbonyl, etc.; Y represents hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or halogeno; Z represents hydrogen, halogeno, C1-C6 alkyl, cyano, nitro, carboxy, C1-C6 alkoxycarbonyl or amino; m represents an integer of 0 to 5; and n represents an integer of 0 to 4.

Description

Specification

Pyridylpyrroyl compounds, manufacturing methods and fungicides for agricultural and horticultural use

The present invention relates to a novel pyridylpyrrole compound, a production method, and an agricultural and horticultural fungicide. Conventional technology:

In the cultivation of agricultural and horticultural crops, a large number of control agents are used against crop diseases.However, their control efficacy is insufficient, and their use is limited by the emergence of drug-resistant pathogens. In addition, because they cause phytotoxicity and contamination of plants and are highly toxic to fish and livestock, they are not necessarily satisfactory control agents. Accordingly, there is a strong demand for a drug that can be used safely with few such disadvantages.

As a synthesis example related to the present invention, J. Med. Chem., 36, 36558 (1993) describes the synthesis of the following compound (Α) as a synthesis intermediate. However, its biological activity is not described.

[A]

In Heterocycles 35, 1171 (1993), the following compound (B) has been synthesized, but its biological activity is not described.

[B]

In addition, US Pat. No. 5,169,855 states that the following compounds are useful as insecticides.

Disclosure of the invention:

An object of the present invention is to provide a novel compound that can be synthesized industrially advantageously, is a fungicide for agricultural and horticultural use that is safe and can be used safely.

The present invention is a pyridylpyrrole compound represented by the formula [I] or a salt thereof, a production method, and a fungicide for agriculture and horticulture.

[I]

In the formula, R ¹ is a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, t_butyl, pentyl, hexyl, heptyl, octyl, nonyl, nonyl, decyl, or other straight-chain or branched C, to C, (, Alkyl group (this alkyl group is a halogen atom such as fluorine, chlorine and bromine, methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, pentyloxy, hexyloxy and other C, — _1; which may be substituted by a C, -alkoxycarbonyl group such as an alkoxy group, a methoxycarbonyl, an ethoxyquincarbonyl, a propoxycarbonyl, a t-butoxycarbonyl or a cyano group), a cyclopropyl, C-Cylalkyl groups such as cyclobutyl, cyclopentyl and cyclohexyl, and benzene Aralkyl group, Main Bok alkoxycarbonyl, et butoxycarbonyl, propoxycarbonyl, C, such as t-butoxide aryloxycarbonyl, - ₆ alkoxycarbonyl group, full Tsu-containing, chlorine, C port Gen atom such as bromine, human Dorokishi group, a carboxyl group, two Uguchi group, amino group, cyano group

Alkylthio groups such as thiocyanato group (SCN), methylthio, ethylthio, propylthio and isopropylthio; C alkylsulfinyl groups such as methylsulfinyl, ethylsulfinyl and isopropylsulfinyl; methylsulfonyl, ethylsulfonyl and propyl It represents a C alkylsulfonyl group such as sulfonyl and isopropylsulfonyl.

R ² is a hydrogen atom, a substituent which is easily hydrolyzed as shown below, for example, a holyl group,

Main Tokishimechiru, et Tokishimechiru, Provo carboxymethyl, C, such as Lee Seo propoxymethyl group, - ₆ alkoxymethyl group,

Asechiru, propionyl, C alkyl group such as propyl carbonyl, main Bok alkoxycarbonyl, et butoxycarbonyl, propoxycarbonyl, i Sopu port Po alkoxycarbonyl, blanking butoxycarbonyl, t part Tokishikarubo C such as a secondary le, - _e alkoxy force Rubonyl group,

C alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, t-butylsulfonyl, pentylsulfonyl, and hexylsulfonyl;

(Halogen atom, lower alkyl group, lower alkoxy group, nitro group, cyano group, alkylthio group, alkylsulfonyl group, haloalkyl group, alkylamino group, alkoxycarbonyl group, alkylcarbonyl group) A benzoyl group which may have

(Halogen atom, lower alkyl group, lower alkoxy group, sulfur group, cyano group, alkylthio group, alkylsulfonyl group, haloalkyl group, alkylamino group, alkoxycarbonyl group, alkylcarbonyl group) A benzenesulfonyl group which may have

Methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, isopropylcarbamoyl, butylcarbamoyl, t-butylcarbamoyl, hexylcal N — C, alkyl rubamoyl groups such as bamoyl,

Alkylthiomethyl groups such as methylthiomethyl, ethylthiomethyl, propylthiomethyl, and butylthiomethyl;

D alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, t-butylthio,

(Halogen atom, lower alkyl group, lower alkoxy group, nitro group, cyano group, alkylthio group, alkylsulfonyl group, haloalkyl group, alkylamino group, alkoxycarbonyl group, alkylcarbonyl group) N-phenylcarbamoyl group,

§ Se Tokishime chill, C, such as pro Pioniruokishime chill, - ₆ alkylcarbonyl Okishime butyl group,

Main Chiruchiome Chill, Echiruchiome Chill, C, such as pro Piruchiome chill, - ₆ alkyl Ruchiome butyl group,

Represents a C alkylsulfonylmethyl group such as methylsulfonylmethyl, ethylsulfonylmethyl and propylsulfonylmethyl.

X represents a hydrogen atom, a halogen atom such as fluorine, chlorine, or bromine; a straight-chain or branched C, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, and hexyl; -(; Alkyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, pentyloxy, hexyloxy and other C> _-ΰalkoxy groups, trifluoromethyl, trifluorethyl, pentafluoroethyl C, haloalkyl, trifluoromethoxy, difluoromethoxy, trichloromethoxy, trifluoroethoxy, difluoroethoxy, penfluorofluoroalkoxy, cyano, etc. , Nitro group, formyl group

An alkylthio group such as a phenyl group which may have a substituent, methylthio, ethylthio, propylthio, isopropylthio, butylthio, t-butylthio, pentylthio, hexylthio, etc., methylsulfinyl, Etilsulfinyl

, Pro Pirusurufu I alkenyl, Lee Sopuro Pirusurufu I alkenyl, Puchirusurufu I cycloalkenyl, t Buchirusurufu I alkenyl, C such Penchirusurufu I alkylsulfonyl, to Kishirusurufu I alkenyl, _ ₆ Arukirusurufu I group, main Chirusuruhoniru, Echirusuruhoniru, propyl Sulfonyl, with isopropyl, butylsulfonyl, t - Buchirusuruhoni Le, C, such pentylsulfonyl to, Kishirusuruhoniru, - ₆ alkylsulfonyl group, main Bok alkoxycarbonyl, et butoxycarbonyl, propoxycarbonyl, i Sopu port Po alkoxycarbonyl C,-such as, butoxycarbonyl, t-butoxycarbonyl, etc.

₆ represents an alkoxycarbonyl group.

Y is a hydrogen atom, methyl, Echiru, propyl, i Sopuro pills, heptyl, t chromatography Bed chill, straight or branched, such as hexyl pentyl, C, - ₆ alkyl group, Application Benefits Furuoromechiru, Application Benefits chloro C, _-G haloalkyl groups such as methyl, trifluoroethyl, pentafluoroethyl,

C, alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, s-butoxy, t-butoxy,

Or represents a halogen atom such as fluorine, chlorine, or bromine.

Z is a halogen atom such as a hydrogen atom, fluorine, chlorine, bromine,

Straight or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, etc.

Represents a C, alkoxycarbonyl group, a nitroxy group, an amino group or a carboxyl group such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl and the like.

m represents an integer of 0 to 5, when 2 or more, X may be different, n represents an integer of 0 to 4, and when 2 or more, Y may be different.

Where 2 — (4 — fluorophenyl) — 3 — (2 — pyridyl) 1 5 — (1-methyltyl)-1 H _ pyrrole, and 2,3-dimethyl-5-phenyl-4-(2-pyridyl). Jill)-1H-excluding pyrrole.

The salt of the compound represented by the formula [I] is not particularly limited as long as it is acceptable in agriculture and horticulture, and examples thereof include salts of mineral acids such as hydrochloric acid and sulfuric acid, and salts such as acetic acid. Salts of mechanical acids, salts of alkali metals such as sodium, potassium and lithium, salts of alkaline earth metals such as calcium and magnesium, and salts of transition metals such as copper, zinc and manganese. Can be mentioned.

(Production of compounds)

-D- The compound of the present invention can be produced by the following method.

Manufacturing method (1)

C I ')

(Wherein R ¹ ′ is a hydrogen atom, (which may be substituted by a halogen atom, an alkoxy group, a d-ii alkoxycarbonyl group, or a cyano group)) C! -I.

, C alkoxycarbonyl group, C ₃ - represents a _cycloalkyl group or Ararukiru group, X, Y, m, n are as defined above. Z 'is a hydrogen atom, main Bok kill carbonyl, et butoxycarbonyl, propoxy force carbonyl, Lee Sopuropokishikaru Boniru, blanking butoxycarbonyl, C have _G alkoxy carbonyl group such as t part butoxycarbonyl, ₆ alkyl group or a carboxyl group Represents

Compound (11), compound (Π1) and compound (IV) in the absence or presence of a suitable organic solvent at 0 ° C to 150 ° C in the presence of a trivalent phosphorus compound and a dehydrating agent React down. The reaction proceeds with evolution of C 0 _2.

Solvents that can be used include hydrocarbons such as benzene and toluene, ethers such as THF, amides such as DMF, esters such as ethyl acetate, DMSO, and acetate. And nitrometan.

Examples of the trivalent phosphine compound include trialkylphosphine such as trimethylphosphine, triethylphosphine, tripropylphosphine, and tributylphosphine. Good triphenyl phosphine, trinotyl phosphite, triethyl phosphite, tripropyl phosphite, triptyl phosphite And trialkyl phosphites such as tributyl, etc., and tributyl phosphine is particularly preferred.

Examples of the dehydrating agent include an acid anhydride and dicyclohexylcarpoimide, and a compound represented by the formula [III] is preferably used.

The amounts used are 1 to 5 equivalents of compound (III), 1 to 3 equivalents of compound (IV), 0.5 to 5 equivalents of trivalent phosphorus compound, and 1 to 5 dehydrating agents for 1 equivalent of compound (II). It is an equivalent, and a combination of compounds having an equivalent amount is particularly preferable. Manufacturing method (2)

II

(V) 0 CIV)

Trivalent phosphorus compound

Dehydrating agent

C I ']

[Wherein, X, R ¹ ′, Y, Ζ ′, m, and n represent the same meaning as described above. ]

The compound [V] and the compound [IV] are reacted in a solvent-free or organic solvent as described above with a trivalent lin compound in the presence of a dehydrating agent at 0 to 150. The reaction proceeds with the evolution of C 02. Manufacturing method (3)

C I ')

[Wherein, X, Y, R ′ ′, Z ′, m, and n represent the same meaning as described above, and V represents a halogen atom. ]

The compound [VI] and the compound [VII] are reacted in a solvent-free or suitable organic solvent at 0 ° C to 200 ° C.

At this time, the reaction yield is improved if an amine or a trivalent phosphorus compound is co-present. Solvents that can be used in the reaction include hydrocarbons such as benzene and toluene, ethers such as THF, amides such as DMF, esters such as ethyl acetate, DMSO, and acetate. Nitriles, nitrometers and the like can be mentioned. Examples of the amines include tertiary amines such as triethylamine and ethyldiisopropylamine. Examples of the trivalent linoleic compound include trialkylphosphine such as trimethylphosphine, triethylphosphine, tripropylphosphine, and tributylphosphine; Trialkyl phosphites such as triphenyl phosphine, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, and triptyl phosphite which may have And the like. Manufacturing method (4)

C I ']

[Wherein, X, Y, R ′ ′, Z ′, V, m, and n represent the same meaning as described above. The compound [II] and the compound [111] and the compound [VII] are mixed with each other in the absence of a solvent or in the above-mentioned organic solvent in the presence of a dehydrating agent and an amine or a trivalent phosphorus compound. React at 200 ° C.

When R ¹ ′ is a haloalkyl group such as CF ₃ or C ₂ F 5, it is preferable to use the production method (3) or (4) to synthesize a pyrrole ring in the presence of amines. . Manufacturing method (5)

ί 1 "] [In the formula, X, Y, R ¹ ′, m and n have the same meanings as described above, and represents a C! —S alkyl group. ]

Compound [VIII] and compound [IX] in the presence of a metal such as zinc or tin in an equivalent amount of 0 to 200, using a carboxylic acid such as acetic acid as a solvent. React with C. Manufacturing method (6)

When Z is a nitrogen group, an amino group or a halogen atom, it can also be produced by the following method.

That is, a compound in which Z is a nitrogen group or a halogen compound can be produced by di- or halogenating a compound in which Z is a hydrogen atom by an ordinary synthetic chemistry technique. Further, a compound in which Z is a nitrogen group can be reduced to a compound in which Z is an amino group by reducing the compound by a general synthetic chemistry technique.

Manufacturing method (Ί)

S0 ₂ R ' The compound in which R ¹ is CF ₃ is hydrolyzed and decarboxylated to produce a compound in which R ¹ and Z are both hydrogen atoms, and this is further halogenated, thiosylated or nitrated. In this way, it is possible to produce a compound in which R ¹ is halogen, thiocyanato or nitro.

Further, the compound in which R ′ is a two-mouth can be further reduced to produce a compound in which R ^{1 is} amino. Compound of R ¹ is Chioshina one I wherein R ¹ is SR ⁴ in a conventional manner (R ⁴ is C, -. Representing the _B group) and a Ki out to induce the compounds, R ¹ by further oxidation Wherein S is SOR ₄ or S 0 ₂ R ⁴ .

-—

Two

Manufacturing method (8)

A compound in which R ¹ is a cyano group can be produced by reacting a compound in which R] is CF ₃ with aqueous ammonia in an autoclave.

aq. NH ₃

Manufacturing method (9)

In the case of an alkylthio, alkoxycarbonyl or formyl group, it can also be produced by the method shown below.

Manufacturing method (10)

A compound in which R ¹ 'is a hydroxyl group can be produced by the following method.

[Wherein, X, Y, m, and n represent the same meaning as described above, and represent an alkyl group of R ⁸ it C]. Production method (1 1)

When R ² is other than a hydrogen atom and R ² is a substituent that easily becomes a hydrogen atom by hydrolysis, those compounds can be produced by a general synthetic chemistry method as described below.

0

(Expressed in the formula, XY, RZ, the V mn as defined above, R ² 'ho le mils, C alkoxy methylation, C alkylcarbonyl, C, - (; an alkoxy carbonyl, C, - _s alkyl Represents a sulfonyl, an optionally substituted benzoyl, an optionally substituted benzenesulfonyl, or an Ν, Ν-dialkyl-substituted rubamoyl group, and R ⁹ represents a C, -K alkyl or an optionally substituted phenyl group. )

The structure of the compound of the present invention was determined by two-dimensional NMR, IR, MS and the like in addition to ordinary NMR. BEST MODE FOR CARRYING OUT THE INVENTION

Examples Next, the compounds of the present invention will be described in more detail.

Example 1 Synthesis of 2- (3,5-dichlorofurnyl) -1-5-methyl-3- (2-pyridyl) pyrrol

C1

2479

3,5-dichlorophenylglycine 12.76 g (58 mimol), acetic anhydride 11.83 g (116 mimol), and 2-ethynylviridine 5.97 g (58 mmol) was added to 60 ml of toluene, and 1.72 g (58 mmol) of triptylphosphine i was added dropwise at room temperature with stirring. The reaction was heated to reflux for 2 hours. The reaction mixture was concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 5.58 g of the desired product. Yield 3 1%, mp.177-179 ° C Example 2

2-(3, 5 — dimethyl phenyl) 1 3 — (2 — pyridyl) — 5 — Synthesis of trifluoromethylpyrrol

4 — (3, 5 — dimethyl phenyl) 1 2 — trifluoromethyl-2, 5 — dihydroxazole 1 5-one 1.70 g (6.61 mmol) and 2 — (1 Dissolve 0.92 g (6.69 mm 01) of polyvinylidene) in 10 ml of acetone tri-oil, and stir with stirring, 0.85 g of diisopropylpyrethylamine. (6.59 mm 01) was added dropwise. After the mixture was heated under reflux for 2 hours, the reaction mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 0.994 g of the desired product. Yield 49 ° '. mp. 1 7 1-1 7 3 ° C Example 3

Synthesis of 2- (3-chlorophenyl) -1-3- (2-pyridyl) pyrroyl-5-carboxylic acid and its ethyl ester

C0 ₂ Et

2-(3-Chlorofanil) 1 3-(2-Pyridyl) 1 5-Trifluoromethyl rubilol 2. Dissolve 25 g (6.98 mmol) of ethanol in 35 ml of ethanol and add water to this. A solution prepared by dissolving 1.12 g (27.9 mmol) of sodium oxide in 35 ml of water was added dropwise. Further, 55 ml of THF was added, and the mixture was heated and refluxed for 2 hours as a homogeneous solution. The reaction solution was concentrated under reduced pressure, and 30 ml of water and ethyl acetate were added thereto, respectively, to carry out liquid separation. The ethyl acetate layer was separated, dehydrated and concentrated, and purified by silica gel column chromatography to obtain 0.19 g of ethyl ester. Yield 8.4% m p. 15 4-15 7 ° C

The aqueous layer was neutralized with dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was dehydrated and concentrated to obtain 1. Og of carboxylic acid. Yield: 48% mp. 225-227 ° C In the above reaction, only the carboxylic acid can be selectively obtained by changing the reaction solvent from ethanol to acetonitrile. Example 4

Synthesis of 2- (3-chlorophenyl) -3- (2-pyridyl) pyrrole

2— (3—Cross phenyl) -1- 3— (2—Pyridyl) pyrroyl-5—Hydronic acid 0.90 g (3.02 nimol) in diethyl glycol 45 And heated under reflux for 2 hours. The solvent was concentrated under reduced pressure, and water and ethyl acetate were added to carry out liquid separation. The ethyl acetate layer was washed with water, dehydrated and concentrated, and the residue was purified by silica gel column chromatography to obtain 0.55 g of the desired product. Yield 71% mp. 157-159. C Example 5

5 — Black mouth 2 — (3 — Black mouth phenyl) (2 — Pyridyl) Synthesis of pyrrole

Dissolve 0.54 g (2.12 mmol) of pyrrole in 2 — (3 — phenyl) 1- 3 — (2 — pyridyl) in DM F O ml and stir at 0 ° C. Then, a solution of 0.28 g (2.12 mm 01) of N-chlorosuccinimide in 5 ml of DMF was added dropwise. After stirring at room temperature overnight, the reaction mixture was poured into water, and the precipitated crystals were purified by silica gel column chromatography to obtain 0.444 g of the desired product. Yield 7 2% mp. 15 5-15 7 ° C Example 6

2 — (3 — cyanophenyl) 1 5 — methyl 1 3 — (2 — pyridyl) pyrrole

2—Hydroxyimino 2— (3—Cyanophenyl) 1-1— (2—Pyridyl) ethanone 7.50 g (31.3 mmol), methyl acetate acetate 6.3 8.19 g (125 mmo 1) of zinc powder was carefully added to a mixture of 2 g (5.50 mm 01) and 4.5 ml of acetic acid. The mixture that generated heat to 60 ° C. was further heated and refluxed for 3 hours. After unreacted zinc was filtered through celite, the filtrate was concentrated, and the residue was poured into water and extracted with ethyl acetate. The organic layer was washed successively with an aqueous solution of sodium hydrogen carbonate and saturated saline, dried over anhydrous magnesium sulfate, concentrated, and the residue was purified by silica gel column chromatography (5% ethanol / monochrome). 2-(3-cyanophenyl)-1-5-methyl-3-(2-pyridyl)-1-pyrroyl-4-methyl rubonic acid methyl ester 3.22 g (yield 32 4%).

1 H-NMR (CDC 1 _{; f} , δ ppm) 2.39 (s, 3H), 3.60 (s, 3H), 7.1-7.4 (m, 6H), 7 7 2 (dt, 1 H; J = 3 Hz, 6.3 Hz), 8.58 (d, 1 H; J = 6.3 Hz)

A mixture of 0.40 g (1.3 mmol) of the obtained methyl methyl pyrocarboxylate derivative and 0.90 g (6.7 mm 01) of lithium iodide in 10 ml of DMF was mixed with 1 Heat to reflux for 5 hours, pour the reaction mixture into water, extract with ethyl acetate, organic layer Is washed with water, dried over anhydrous sodium sulfate, concentrated, and the residue is purified by silica gel column chromatography to obtain the desired 2 — (3 — cyanophenyl) 15 — methyl One 3— (2-pyridyl) pyrrole was obtained in an amount of 0.12 g (yield 36%). mp. 1 5 2-15 3 ° C Reference example

(A)

As shown in the formula, 2—hydroxyminoketone (A) has the following formula: 2—Pyridine carboxy cyanoaldehyde, et al., J. Chem. Soc., Chem. Commun. With reference to 73, 55 and Synthesis 1975, 391, 2 — (3 — cyanophenyl) 1 1 induced by reaction with 3 — cyanobenzyl bromide — (2_pyridyl) ethanonone is reacted with nitrite in the presence of a base (sodium ethoxide) to give 2 — hydroxymino 2 — (3 — Cyanophenyl) 1 1- (2-pyridyl) ethanone was synthesized.

Ή-NMR (DMSO, δ ppm) 7.5-8.0 (m, 7H), 8.68 (dt, 1H) Example 7

Synthesis of 5-Methyl-2— (3-methylthiophenyl) -1-3— (2-pyridyl) pyrrol

2-(3-bromophenyl)-5-methyl-3-(2-pyridyl) pyrrole 0.7-1 g (2 3.5 ml (5.0 mmo 1) of a 1.6 N n-butyllithium hexane solution was added dropwise to 10 ml of a THF solution of 0.3 mm 01). After stirring at 170 ° C for 30 minutes, 0.32 g (3.4 mmol) of dimethyl disulfide was added dropwise.After the addition was completed, the dry ice bath was removed, and the temperature was raised to room temperature and stirring was continued. Continued. An aqueous solution of ammonium chloride was added to the reaction mixture, extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate and concentrated to obtain a crude product. After washing with ether-hexane, 0.63 g of pure 2- (3-methylthiophenenyl) -1-methyl-3- (2-pyridyl) pyrrole was obtained as white crystals.

(Yield 98%) mp.145-146 ° C Example 8

5-(3_Cro- mouth phenyl) 1-41 (2-Pyridyl) 2-Trifluoromethyl rubilol-3-Synthesis of ethyl ethyl rubonate

To 3.69 g (20 mm 01) of 3-cyclohexyl glycine, 8.40 g (40 mm 01) of trifluoroacetic anhydride was added dropwise at room temperature. After reacting at 70-80 ° C for 2 hours, the mixture was concentrated and azeotroped with toluene (twice) to obtain a crude oxazolone product. To this toluene solution (20 ml) was added 3.50 g (20 mm 01) of ethyl 3- (2-pyridyl) propiolate, and then 4.0 g of tributylphosphine. (20 mm o 1) was added dropwise. After heating the mixture under reflux for 1 hour, the reaction mixture was concentrated and purified by silica gel gel chromatography to obtain 2.43 g of the desired product (yield 31%). (White crystals)

.. 'H - NM R ( . CDC 1 3 δ ppm): 1 1 1 (t, 3 H), 4 1 5 (q, 2 H), 6. 9 - 7. 3 (m, 6 H), 7.63 (m, 1H), 8.64 (dd, 1H), 9.46 (brs, 1H)

Ethyl 3- (2-pyridyl) propiolate is obtained by reacting 2-ethynylviridine with nBuLi in THF at —Ί8 ° C and then condensing it with ethyl chloroformate. Obtained by

(Yield 37%, b p. 13 2-13 4 ° C / 2 mm H g)

Example 9

Synthesis of 2- (3,5—dimethyltyl) (2—pyridyl) -1-5-thiocyanatopyrrole

H

2-(3,5-dimethylphenyl) 1-3-(2-pyridyl) pyrrole 1.30 g (5.2 mm 0 1) dissolved in 20 ml of dimethicethane? Then, 1.76 g of dried ammonium thiosuccinate was added, and the mixture was stirred at room temperature for 30 minutes. Then, 1.89 g of copper sulfate was added, and the mixture was stirred in a dark room at room temperature for 24 hours. Then, celite was added to the reaction mixture, followed by filtration. The filtrate was concentrated, and the obtained residue was subjected to silica gel column chromatography. Graph

— 1 — Then, 0.71 g of the desired product was obtained. Yield 4 mp. 17 0-17 1 ° C Example 10

2-(3, 5 dimethyl phenyl) — 3 — (2 — pyridyl)-1 5 — Synthesis of methylthiopyrrole

H ₃

2 — (3, 5 — dimethylphenyl) 1-3 — (2 — pyridyl) _ 5 — thiocyanatovirol 0.36 g (l.Ommol) was dissolved in 20 ml of methanol, and 0.08 g of ground calcium hydroxide was added, and the mixture was stirred at room temperature for 3 hours. The residue obtained by distilling off the solvent under reduced pressure was dissolved in ethyl acetate and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 0.22 g of the desired product. Yield 63% mp.175-176 ° C Example 11

2-(3,5-dimethyl phenyl) 1-3-(2-pyridyl) 5-methylsulfinylpyrroyl and 2-(3,5-dimethyl phenyl) 3-(2-pyridyl)- 5 — Synthesis of methylsulfonyl bilol

2-(3, 5-dimethyl phenyl) 13-(2-pyridyl) 15-methylthiopyrrole 1.0 g (3.4 mmol) of methanol and 40 ml of water 0 ml was added, and 1.7 g of oxone was added little by little under stirring. After stirring at room temperature overnight, 300 ml of water was added to the concentrated solution under reduced pressure, and neutralized by adding sodium bicarbonate powder. The residue obtained by extraction with ethyl acetate, dehydration, and concentration under reduced pressure was purified by silica gel column chromatography, and 2-(3, 5-dimethylphenyl)-3-(2- 0.75 g (yield 71% mp. 77-80.C) and 2-(3,5-dimethyl phenyl) 1 3- (2-pyridyl) -5-methylsulfonyl bilol 0.26 g was obtained. Yield 23% mp. 70-73 ° C Example 1 2

4 Synthesis of 1-bromo-2- (3,5-dichlorophenyl) methyl 3- (2-pyridyl) pyrrole

1

2 — (3, 5 — diphenyl phenyl) 1 5 — methyl 1 3 — (2 — pyridyl) pyrrole 0.7 g (2.3 mmol) And 0.37 g (2.31 mmo 1) of bromine was added dropwise with stirring at room temperature. After stirring at room temperature for 1 hour, the reaction solution was washed with an aqueous sodium sulfite solution, dehydrated with anhydrous magnesium sulfate, and concentrated to obtain 0.85 g of the desired product. Yield 96% mp. 2 13-2 16 ° C Example 13

2 — (3, 5 — dimethyl phenyl) 1 1 — methoxymethyl (2 — pyridyl) 1 5 — synthesis of trifluorometyl pyrrole

H

2 — (3, 5 — dimethyl phenyl) 1 3 — (2 — pyridyl) 1 5 — trifluor rometyl pyrrole 0.95 g (3.0 mm 0 1) and anhydrous carbon dioxide 0. 5.4 g (3.4 mm 01) was added to 35 m 1 of acetonitrile, and 0.31 g (3.9 mm 01) of chloromethyl methyl ether was added dropwise with stirring. After further stirring at room temperature for 1 hour, the reaction solution was poured into ice water and eluted with ethyl acetate. The ethyl acetate layer was dehydrated with anhydrous magnesium sulfate, and the residue obtained by concentration was purified by silica gel column chromatography to obtain 1.0 g of the desired product.

20.

Yield 9 2% n 1.5543

Example 14

2-(3-C □□ 5-Methyl phenyl) 1 5-Cyano 1 3-(2-Pyridyl) Synthesis of pyrrole

2-(3-black mouth-5-methylphenyl) 1 3-(2-pyridyl) 1 5-trifluoromethylpyrrole 0.43 g (l. 2 8 1111110 1), 25% 1.88 ml of aqueous ammonia and 3.6 ml of dioxane were added, and the mixture was heated at 180 ° C. for 24 hours in an autoclave. After cooling, water and ethyl acetate were added to the reaction solution, and the mixture was separated. The ethyl acetate layer was washed with water, dehydrated with anhydrous magnesium sulfate and concentrated, and the obtained residue was purified by silica gel column chromatography to obtain 0.2 lg of a desired product. Yield 60% mp .208-210 ° C

Table 1 shows typical examples of the compounds of the present invention synthesized in the same manner.

Compound No. X, Y, z R Physical constant (° C)

1 3-C1 HH CH ₃ H [142-143]

2 3-C1 HH PhCH ₂ H [164-169]

5 4- CI HH CH ₃ H [201-203] 6 3-C1 HH C2H5 H [125-127] 7 3-CH ₃ HH CH ₃ H [160-162] 82-CI HH CH ₃ H

9 2,4-Cl: HH CH ₃ H [172-176]

10 3-C1 5-C1 H CH ₃ H [145-147] 11 3,4-CHH CH, H [173-175 Table 1 (continued)

Compound Να Χ „Υ„ ζ R Physical constant (° C)

12 3,4- Cl ₂ CH ₃ CH ₂ 0Et n _D 1.6154

13 3, 5-Cl ₂ CH ₃ H [177-179]

14 3- CI H [157-159]

15 3, 5-Cl ₂ -4-0CH ₃ CH ₃ H [173-174]

16 3, 5-Cl ₂ Br CHa H [213-216] 17 3-CFa CF ₃ [159-160] 18 3-CI C0 _z Et CHa

19 3-C1 C0 ₂ H CH ₃

20 3- CI CH ₃ CH ₃

21 3, 5-Cl ₂ 6-CH ₃ CH ₃ [193-195] 22 3, 5-CI: N0 ₂ CH ₃ H

23 3, 5- (0CH ₃ ) _; CF ₃ H [165-167] 24 2,5-Cl: CH ₃ H [215-216] '25 2,3-C CH ₃ H

26 3-CF _s CHa H [146-147] ' Table 1 (continued)

Compound No. Y „Z Ri Physical constant (° C)

27 3-CI H N0 ₂ CF ₃ [200-203] 28 3,5-Cl ₂ HH CH ₃ S0 ₂ CH ₃ 29 3,5-Cl 2 HH CH ₃ C0 ₂ C ₂ H ₅ [94-95] 30 3, 5-Cl ₂ CH ₃ COCHa 31 3, 5-C "CH ₃ CONHCHa 32 3, 5-CI ₂ CH ₃ CHO

0

II

33 3, 5-Cl ₂ CH ₃ c-

\ H

35 3, 5-Ch H CH ₃ Lee NCO-36 3,5-Cl ₂ H CH ₃ H HCl salt [230] '37 2, 3, 5-Cl H CH ₃ [213-215] 38 3-Br H CH ₃ [136-137] 39 3-OCH3 H CH ₃ [154-155] 40 3,5- (CH ₃ ); H CH ₃ [167-173] 1 (continued)

Compound No. Xr Z R 'R Physical constant rc)

41 HH CH ₃ H [184-186] 42 3-OPh H CH ₃ H [128-129] 43 3-0C ₂ H ₅ H CH ₃ H [145-146] 44 3, 5-Cl ₂ 4-CFs CH ₃ H [181-182]

45 3,5- (0CH ₃ ): CHa H [159-160]

46 3-CN CH ₃ H [152-153]

47 3-C2H5 CH ₃ H [159-160]

48 3-SCHa CH ₃ H [145-146]

49 3, 5- (0C ₂ H ₅ ) _; CH ₃ H [182-183]

50 3, 5- (0CH ₃ ) ₂ -4-CH ₃ H CH ₃ H [70-75]

51 3-CHO CH ₃ H [61-64] 52 3-C0 ₂ C ₂ H ₅ CH ₃ H [143-145] 53 3-CI OH H [200-202] 54 3, 5- (CH ₃ ) 2 HH [171-173] 55 3, 5-Cl ₂ CF ₃ H [180-184] 1 (continued) Compound No. Xr Yn z R Physical constant (° C)

_{_{56 3,5- (CH 3) 2 3-}} CI CH 3 H 57 3, 5- (CH 3): CI H [180-182] 58 3, 5- (CH 3): Br H [185-189] 59 3-C1 CF ₃ H [144-149]

F

60 3-C1 HH C0 ₂ Et H [154-157] 61 3- CI HH C0 ₂ HH [225-227] 62 3-CI HH CI H [155-157] 63 3-C1 HH NO 2 H [250- 251] 64 3-C1 NH ₂ H 65 3- CI CI CF ₃ H 66 3- CI NH ₂ CF ₃ H [130-135 67 3, 5- (CH ₃ ) _; C ₂ F ₅ H 68 3-C1 3 -CH ₃ CF ₃ H 69 3-C1 3-C1 H Table 1 (continued)

Compound No. Y _n ζ RR ^; Physical constant (T)

70 3-C1 C0 ₂ C ₃ H ₇ H [153-154]

71 3, 5-F ₂ CF ₅ H [182-185]

72 3,4- (CH ₃ ) _; CF _S H [176-179]

73 3,5- (CH ₃ ) ₂ [165-167]

74 3.5- (CH ₃ ) ₂ [184-187]

75 3-C1-5-CH3 CF ₃ [175-178]

76 3, 5- (CH ₃ ) _2-4 -FH CF ₃ [184-185]

_{_{78 3,5- (CH 3) 2 -}} 4- CI HH CF 3 [191-192]

79 3-CI H CH ₂ C0 ₂ CH ₃ H

80 3, 5- (CH ₃ ): H NH,

81 3,5- (CH ₃ ) _; SCH _S [175-176]

82 3, 5- (CH ₃ ): SCN [170-191]

83 3, 5- (CH ₃ ): SO2CH3 [70- 73] 1 (continued) Compound No. Ynz R Physical constant (° C)

_{_{84 3,5- (CH 3) 2 CF}} 3 CHO 85 3, 5- (CH 3) 2 CF 3 C0CH 3

HHHHHHHHHHHHHH H

86 3, 5- (CH ₃ ) ₂ CF ₃ CH ₂ 0C0CH ₃ [103-105] 87 3,5- (CH ₃ ) ₂ HH cc H CF _S S0 ₂ CH ₃ 88 3,5- (CH ₃ ) ₂ CF _a CH2SCH3 89 3, 5- (CH ₃ ) ₂ CI CF ₃ -co- 90 3, 5- (CH ₃ ) ₂ N0 ₂ 91 3.5- (CH ₃ ) ₂ CF ₃ SCH ₃ 92 3, 5- (CH ₃ ) ₂ CF ₃ H, cupric chloride [15-153] 93 3.5- (CH ₃ ) ₂ CF ₃ CII ₂ S0 ₂ CH ₃ 94 2,3- (CH ₃ ) ₂ CF _a [138-141] _{95 3, 5- (CH 3)} 2 CI [193-195] 96 3.5- (CH 3). CF 3 CH 2 0CII 3 n D 1.5543 97 3,5- (CH,) 2 CF 3 98 3-C1 H CH ₂ CN

1 (continued) Compound No. X, Υπ ζ Physical constant (T)

114 3-Cl-5-CH ₃ CN [208-210] 115 3.5- (CH ₃ ) ₂ H CFa CH ₂ 0CH ₃

116 3,5- (CH ₃ ) ₂ H CF3 CH2OCH2CH3 117 3, 5-(CH ₃ ): CF3 CH ₂ 0C ₃ H ₇ ^:

118 3.5- (CH ₃ ): CF ₃ CH2SC3H7 '

119 3,5- (CH ₃ ) ₂ H CF ₃ CH2OC4H9

120 3,5- (CH ₃ ) ₂ H CF ₃ CH2OC4 H9

121 3, 5- (CH ₃ ): CF _S CH ₂ 0C0C ₂ H ₅

122 3,5- (CH ₃ ): CF ₃ CH, S0, C ₂ H _s

123 2.3,5- (Cl); N0 ₂

124 2, 3, 5- (CH ₃ ) ₃ H CH ₂ 0CH ₃

125 2, 3, 5-(CI): CF _S

126 2-C1-3, 5- (CH ₃ ): CF _S

127 4-Br- 3,5- (CH ₃ ) ₂ H CF _a

128 3-CH3-5-OCH3 HH CH 3 H Note) X _m, the phrase H during column Y ", refers to the case of all hydrogen atoms. If a substituent is shown with substitution positions, other The substituent at the position is a hydrogen atom. Since the compound of the present invention has excellent bactericidal activity against a wide variety of fungi, it can be used for controlling various diseases that occur when cultivating agricultural and horticultural crops including flowers, turf, and pasture. . For example,

Rice yellow dwarf (Phytophthora macrospora)

Rye bark brown rot (Pythium spp.)

Wheat brown snow rot (Pythium spp.)

Potato plague (Phytophthora infestans)

Soybean Tomb Plague (Phytophthora raegasperma)

Azuki (Phytophthora vignae)

Phytophthora parasitica

Sugar beet seedling blight (Pythium spp.)

Cube bee disease (Pseudopcronospora cubens i s

Phytophthora infestans

Noksaibe disease (Pernospora brass ikae)

Cabbage downy mildew (Pernospora brass i cae)

Evening onion white blight (Phytophthora porr i)

Lacciata White Blight (Phytophthora porri)

Spinach and downy mildew (Pernospora s inac i ae)

Phytophthora caps i c i

Strawberry plague (Phytophthora nicot ianae)

Budobe disease (Plasmopara viticola)

Western Shiba Red blight (Pythium aphanidermatum)

It can be used for pest control.

In recent years, various pathogens have developed resistance to the acylylalanine drugs, resulting in a lack of efficacy of the drugs. Therefore, drugs that are effective against pathogenic bacteria of resistant strains are desired. The compound of the present invention is an agent having an excellent bactericidal effect not only on sensitive strains but also on pathogenic bacteria of the asialalanin resistant strain.

Diseases that are more preferable to apply include downy mildew of cucumber, downy mildew of bud, potato blight, and the like. The compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to aquatic organisms such as ship bottoms and fish nets.

The compound of the present invention can be used as a fungicidal or fungicidal agent for walls and bathtubs, or shoes and clothes by mixing it with paints and fibers.

〔Fungicide〕

When the thus-obtained compound of the present invention is actually applied, it can be used in a pure form without adding other components, and can be in a form that a general pesticide can take for the purpose of being used as a pesticide, that is, It can also be used in the form of wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, flowables and the like. When solid additives are used as additives and carriers, soybean grains, vegetable powders such as flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay, etc. Organic and inorganic compounds such as mineral fine powder, sodium benzoate, urea, and sodium sulfate are used. For liquid dosage forms, petroleum fractions such as kerosene, xylene and sorbent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, aceton, Use chloroethylene, methylisobutyl ketone, mineral oil, vegetable oil, water, etc. as solvents. Surfactants can be added, if necessary, to obtain a uniform and stable form in these preparations.

The wettable powder, emulsion and flowable thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion, and the powder and granules are used as they are by spraying them on plants. You.

The compound of the present invention exerts a sufficient effect even when used alone, but can also be used as a mixture with one or more of various fungicides, insecticides, acaricides, or synergists. Fungicides, insecticides, acaricides, nematicides, and plant growth regulators that can be used by mixing with the compound of the present invention include the following. Fungicide :

Copper agent:

Basic copper chloride, basic copper sulfate, etc. Sulfur agent:

Thiuram, manneb, mancozeb, polycarbamate, provineb, ziram, zineb etc.

Polyhaloalkylthio agent:

Captan, chlorofulanid, foam, etc.

Organic chlorine agent:

Organic phosphorus agents such as chlorothalonil and fusaride:

IBP, EDDPP, Torque mouth phosmethyl, pyrazophos, josetyl, etc.

Benzimidazole:

Thiophanate methyl, benomyl, carbendazim, thiabendazole, etc. Dicarboxymides:

Iprodione, vinculozolin, procymidone, fluorimide, etc.

Power boxing agent:

Oxycarboxin, mepronil, furtranil, techopenphthalam, tricyclamide, pencyclone, etc.

Anlualanine agent:

Metalaxyl, oxadixyl, furaxyl, etc.

SBI agent:

Triazimefone, triazimenol, vitelenol, microbutanil, hexaconazole, propiconazole, trifmizole, prochloraz, perfrazolone, fenarimol , Pyrifenox, trifluorin, flusilazole, etaconazole, dichlorbutrazole, fluotrimazole, flutriafene, penconazole, giniconazole, Cyproconazole, imazalil, tridemorph, fenpropimorph, pthiobate, etc. Antibiotics: Polyoxin, blasticidin S, kasugamycin, noridamicin, dihydrosulfate streptomycin sulfate, etc.

Others:

Propamocalp hydrochloride, quintozene, hydroxyiisoxazole, methasulfocarb, anilazine, isoprothiolane, probenazole, quinomeionate, dithianon, zinocab, diclomedine, mepanipyrim, ferimizone , Fluazinam, pyrokirone, tricyclazole, oxolinic acid, dithianon, iminooctadine acetate, simoxanil, pyrroletriline, methasulfocarp, jetfencapul, pinapacryl , Lecithin, baking soda, phenamino sulphate, dozine, dimethyl morph, phenazine oxide, etc. Insecticides and miticides:

Organophosphorus and carbamate insecticides:

Phenthion, phenythrothione, diazinon, chlorpyrifos, ESP, nomidithion, phentoate, dimethoate, formotion, malathone, trichlorfon, thiomethone, phosmet , Dichlorvos, acephate, EPBP, methyl parathion, oxydimethonmethyl, ethion, salicion, cyano hos, isoxathion, pyridafantione, hosalon, methidathion, sulprophos, chlorf Envinphos, tetrachlorvinphos, dimethylphobinphos, propaphos, isofenphos, ethylthiomethone, profenophos, pyraclophos, monochlorophos, azinphosmethyl, aldicarb, mesomil, Thiojikarpu, Carbofuran, Carbo Ruff § down, benfuracarb, Furachiokarupu, Provo sake, B P M C, M T M C, M I P C, force Rubari Le, pyrimidone curve, Echiofu E Nkarupu, full et Bruno Kishikarupu like. Pyrethroid insecticides:

Permethrin, Cypermethrin, Deltamethrin, Fembrelate, Phenoproprin, Pyretrin, Aresulin, Tetramethrin, Resmethrin Lin, Jimeslin, Propaslin, Phenotrin, Protoline, Full Varinate, Sifult Lin, Shinoguchi Trin, Funorecitrinate, Ethofenprox, Cycloprotrin, Tolometrine, Silafluorfen, Profenprox, Acrynasuri, etc. Benzoyl Rare Other Insecticides:

Difluvenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetravenzuron, flufenoxuron, flucycloxuron, puprofezin, pyriproxyphen, methoprene, benzoprepine , Difenthiuron, acetamipsodo, imidacloprid, nitrene bilam, fipronil, dicotin sulfate, rotenone, cartap, thiocyclam, bensultap, metaaldehyde, machine oil, Microbial pesticides such as BT and insect pathogenic virus. Nematicide:

Fenamiphos, phosthiazetate, etc.

Acaricide:

Chlorbenzilate, phenisobromolate, dichophor, amitraz, BPPS, benzomate, hexithiaox, fenbutatin oxide, polynactin, quinomethionate, CPCBS, tetrazihon, avermetecti , Milbemectin, clofentegine, sihexatin, pyrigben, phenpyroximate, tebufenvirad, pyrimidifene, phenothiocalp, dienochlor and the like.

Plant growth regulator:

Jibere Li emissions (such Jibere Li down A _3, Jibere Li down A _4, Jibere Li down A ₇₎ IAA, NAA.

〔Example〕

(Fungicide)

Next, some examples of the composition 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 Formulation Examples are parts by weight.

Example 15 5 wettable powder Compound of the present invention 40 parts

Diatomaceous earth 5 3 parts

Higher alcohol sulfate 4 parts

Alkyl naphthalene sulfonate 3 parts

If the above are uniformly mixed and finely pulverized, a wettable powder with an active ingredient of 40% is obtained.

[0 0 6

Example 16 Emulsion

Compound of the present invention 30 parts

Xylene 3 3 parts

Dim Chilholm Amid 30

Polyoxyethylene alkyl ether 7 parts

By mixing and dissolving the above, an emulsion containing 30% of the active ingredient is obtained. Example 17 Suspension

Compound of the present invention 10 parts

Sodium ligninsulfonate 4 parts

Sodium dodecylbenzenesulfonate 1 copy

Kisanta Ngam 0.2 parts

Water 84.8 parts

The above ingredients are mixed and wet-pulverized to a particle size of 1 micron or less to obtain a 10% active ingredient suspending agent. Next, Test Examples show that the compounds of the present invention are useful as effective components of various plant disease controlling agents. The control effect was determined by visually observing the growth degree of the diseased flora that appeared on the leaves and stems at the time of the survey.

Test Example 1 Cucumber and disease control test

An emulsion of the compound of the present invention was sprayed at a concentration of 200 ppm on the young seedlings of cucumber (cultivar “Sagami Hanshiro”) cultivated in unglazed pots. After spraying, air-dry at room temperature, cucumber and disease (Pseudoperonosporacuben sis) The spore suspension was spray-inoculated, and kept in a constant temperature room (25 te) where light, darkness and dryness were repeated every 12 hours for 4 days. The following compound showed an excellent control effect of 80% or more.

Compound No. 1, 6, 7, 13, 3, 23, 36, 38, 39, 40, 43, 45, 54, 55, 57, 58, 59, 6 2, 71, 73, 74, 75, 76, 78, 81, 82, 86, 94, 95, 96 Test Example 2 Budwheat control test

Leaves of field-grown vines (variety “Kaiji”, 3rd grade) were punched into a disk having a diameter of 3 O mm, and immersed in an emulsion of the compound of the present invention and a chemical solution having a concentration of 200 ppm of the active ingredient. After immersion, air-dry at room temperature, inoculate with a zoospore suspension of P. asparagus downy mildew (P1 asm 0 paraviticola), and keep in a constant temperature room (20 ° C) under lighting for 10 days did. As a result of comparing and investigating the appearance of lesions on the leaves with no treatment, the following compounds showed an excellent control effect of 80% or more.

Compound No. 1, 1 3, 36, 40, 42, 50, 52, 54, 55, 57, 58, 59, 71, 74, 94 Availability:

As described above, the compound of the present invention has an excellent control effect on plant diseases, and a drug containing the compound of the present invention is useful as a fungicide for agricultural and horticultural use.

Claims

The scope of the claims

1. A pyridylpyrrole compound represented by the formula [I] or a salt thereof.

[Wherein, R ′ represents a hydrogen atom, (a halogen atom, a C, -alkoxy group, a C, — (; may be substituted with an alkoxycarbonyl group or a cyano group)], a, ₀ alkyl group, C ₃ - ₇ cycloalkyl group, arsenate Dorokishi group, Ararukiru group, carboxyl groups, C alkoxycarbonyl group, nitro group, A Mi amino group, Shiano group, - ₆ alkyl thio group, Chioshiane preparative group, an alkyl sulfide alkylsulfonyl group , Ji, - represents a ₆ alkyl sulfonyl group, or a c port Gen atoms.

R ² is a hydrogen atom, formyl groups, C, - ₆ alkoxymethyl group, ₆ alkylcarbonyl groups, C i alkoxycarbonyl groups, C alkylsulfonyl group which may have a substituent Benzoiru group, a substituent have they may be benzenesulfonic Ruhoniru group, N- ₆ alkyl force Rubamoiru group, an alkylcarbonyl O Kishimechiru group, C, - _beta alkylthiomethyl group, C i alkylsulfonyl methylation group, a C ie alkylthio group or N- substituent Represents a phenylcarbamoyl group which may be possessed.

X represents a hydrogen atom, a halogen atom, a C, _i- alkyl group, an alkoxy group, a C-nitroalkyl group, a cyano group, a nitro group, a formyl group, a C, _-G haloalkoxy group, or a substituent. A phenyl group, a C alkylthio group, a C alkyl sulfinyl group, a C i -alkyl sulfonyl group or a C, -alkoxyl alkoxyl group which may be substituted.

Υ represents a hydrogen atom, a C 1, _-c alkyl group, a _ΰhaloalkyl group, a C, _-alkoxy group or a halogen atom.

Ζ is a hydrogen atom, a halogen atom, C _e alkyl group, two collected by filtration group, carboxyl Represents an amino group, an amino group or a C j alkoxycarbonyl group.

m represents an integer of 0 to 5, and when 2 or more, Xs may be different.

n represents an integer of 0 to 4, and when 2 or more, Y may be different. However, 2- (4-fluorophenyl) -1-3- (2-pyridyl) -1-5- (1-methylethyl) _1H-pyrrole and 2,3-dimethyl-5-phenyl-4 (2-pyridyl) 1H-Excluding pyrrol.

2. Formula [II] [II]

[Wherein, X and m represent the same meaning as described above. ]

A phenylglycine represented by the formula:

(R ¹ 'CO) 0 [III]

Wherein, R '' is a hydrogen atom, (halogen atom, d alkoxy group, 〇 ₆ alkoxides aryloxycarbonyl group also rather may be substituted with Shiano group) C, - ₁₀ alkyl group, C ₃ - ₇ represents a cycloalkyl group or an aralkyl group. ]

An acid anhydride represented by the formula (IV)

(IV)

C≡ C-I Z '

[Wherein, Υ and η represent the same meaning as described above. Z 'represents a hydrogen atom, a C,-"alkyl group, a C,-,; an alkoxycarbonyl or a carboxyl group.] With the presence of a trivalent phosphorus compound and a dehydrating agent Formula [I '] characterized by reacting

A method for producing a pyridylpyrrole compound represented by the formula:

3. Equation [V]

[V]

[Wherein, X, R ¹ ′ and m represent the same meaning as described above. N-acylglycines represented by the formula [IV]

(IV)

[Wherein, Υ, Ζ ′, and η represent the same meaning as described above. [I ′] is reacted with an ethynylviridine represented by the formula (I ′) in the presence of a trivalent phosphorus compound and a dehydrating agent.

[Wherein, X, Y, Z ′, R ¹ ′, m and n represent the same meaning as described above. ]

A method for producing a pyridylpyrrole compound represented by the formula:

4. Formula [VI]

[VI]

[Wherein, X, R ′ ′ and m represent the same meaning as described above. ]

An oxazolone represented by the formula (VII):

CVII]

[Wherein, Υ, n, Z ′ represent the same meaning as described above, and V represents a halogen atom. The formula [I '] is characterized in that it reacts with a vinyl pyridine compound represented by the formula

[Wherein, X, Y, R ¹ ′, Z ′, m and n represent the same meaning as described above. ] The process for producing a pyridylpyrrolyl compound represented by the formula:

5. Formula [II]

NH ₂

[Wherein, X and m represent the same meaning as described above. ]

And the formula [111]

(R ¹ 'CO) 2 0 U

[Wherein, R ¹ ′ represents the same meaning as described above. ]

One four one An acid anhydride represented by the formula (VII):

(VII)

[Wherein, Y, V, Ζ ′, and η represent the same meaning as described above. ]

Reacting a halovinylpyridine and a dehydrating agent represented by the formula (I ′) in the presence of an amine or a trivalent phosphorus compound.

[Wherein, X, Y, R ¹ ′, m, n and Z ′ represent the same meaning as described above. ]

A method for producing a pyridylpyrrole compound represented by the formula:

6. Formula [VIII]

[Wherein, X, Y, m, and n represent the same meaning as described above. A hydroxyminoketone represented by the formula [IX]

R "C0CH ₂ C0 ₂ R ³ [IX]

[Wherein, R ′ ′ represents the same meaning as described above, and R ³ represents an alkyl group of “.”]. The S-ketoesters represented by the formula are reacted in the presence of a metal in acetic acid. Formula [I "]

[Wherein, X, Y, R ′ ′, R ³ , m and n represent the same meaning as described above. ]

A method for producing a pyridylpyrrole compound represented by the formula:

7. Formula [I]

[Wherein, R ¹ , R ² , X, Y, Z, m and n represent the same meaning as described above. ] A fungicide for agricultural and horticultural use, characterized in that the fungicide comprises one or more of a pyridylpyrrole compound represented by the formula (1) or a salt thereof as an active ingredient.