WO1993008167A1 - Novel heterocyclic derivative and agrohorticultural bactericide containing same - Google Patents

Abstract

A compound represented by general formula (I), a salt thereof, a process for the production thereof, and an agrohorticultural bactericide containing same, wherein m represents an integer of 1 to 4; R1 represents hydrogen, lower alkyl, lower alkoxy, etc.; X represents C=Z [wherein Z represents oxygen, CH(OH), Cr1(r2) (wherein r?1 and r2¿ represent each cyano, alkoxycarbonyl, carbamoyl, etc.) or Nr3 (wherein r3 represents lower alkyl, phenyl, lower alkoxy, lower alkylamino, hydroxy, phenylamino, lower alkoxycarbonylamino, etc.)], CH(OH) or CH¿2?; Y represents N or C(R?4¿) (wherein R4 represents hydrogen or lower alkoxycarbonyl); R2 represents hydrogen, S(O)¿nr?5 (wherein r5 represents lower alkyl, and n represents 0, 1 or 2), lower alkoxy, etc.; and R3 represents hydrogen, lower alkoxy, lower alkyl, phenyl, a 5- or 6-membered heterocyclic group containing one or two atoms selected among N, S and O, etc.

Description

 SPECIFICATION New heterocyclic derivatives and fungicides for agricultural and horticultural use

 The present invention relates to a novel heterocyclic derivative and a fungicide for agricultural and horticultural use.

Background technology:

 In the cultivation of agricultural and horticultural crops, a large number of control agents are used for crop diseases.However, their control efficacy is insufficient, and their use is limited due to the emergence of drug-resistant pathogens and pests. In addition, since many plants cause phytotoxicity and contamination, or are highly toxic to livestock and fish, many of them are not always satisfactory control agents. Therefore, there is a strong demand for a drug that can be used safely with few such disadvantages.

 An object of the present invention is to provide a novel compound which can be advantageously synthesized industrially and which can be used as a fungicide for agricultural and horticultural use which is effective and secure and can be used safely.

 The present invention has the general formula (I)

[I]

(In the formula, m is an integer of 1 to 4, R ¹ is the same or different and is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a lower haloalkyl group, a lower alkoxycarbonyl group, a nitro group, a mono- or di-optionally substituted force be Rubamoiru group or a halogen atom lower alkyl, X is C = Z [Z represents an oxygen atom, CH (0H), Cr ' (r 2) 1, r ² is the same or different and represents a cyano group, an alkoxycarbonyl group, or a rubamoyl group which may be mono- or di-substituted by lower alkyl. ), Nr ³ (r ³ is a lower alkyl group, may be substituted A phenyl group, a lower alkoxy group, a lower alkylamino group, a hydroxy group, a phenylamino group and a lower alkoxycarbonylamino group which may be substituted. )], Represents CH (0H), CH ₂ , Y represents N, C (R ⁴ ) (R ⁴ represents a hydrogen atom or a lower alkoxycarbonyl group.), R ² represents a hydrogen atom, S (0) „r ⁵ (r ⁵ is a lower alkyl group which may be substituted, n represents 0, 1 or 2), a lower alkoxy group, a lower alkylsulfonylamino group, or a substituted R ³ represents a hydrogen atom, a phenylsulfonylamino group, a cyano group, a halogen atom, a hydroxy group, a morpholino group, or an amino group optionally substituted with phenylalkyl or lower alkyl which may be substituted; A lower alkoxy group, a lower alkyl group, a cycloalkyl group, an optionally substituted benzoinole group, an optionally substituted phenylcarbonyl group, an optionally substituted pyridylcarbonyl group, a lower alkoxyalkyl group, a lower alkylthio group, Replaced Phenyl group, 5- to 6-membered heterocyclic group containing 1-2 values of N, S, 0 which may be substituted, alkyl group substituted with phenyl which may be substituted, phenyl which may be substituted An alkyl group substituted with an optionally substituted viridyl, or an alkyl group substituted with a 5- to 6-membered heterocyclic ring containing 1 to 2 cyano, nitro, N, S, 0 And an amino group which may be substituted with phenyl, lower alkoxy or lower alkyl which may be substituted.] A fungicide for agricultural and horticultural use containing one or more of the compound represented by the formula: It is.

 "^ The substituent of formula (I) will be further described.

When r ³ represents a phenyl group which may be substituted or a phenylamino group which may be substituted, examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an alkylamino group, an alkylthio group, a cyano group, and a nitro group. Group, an optionally substituted rubamoyl group and the like.

R ⁵ may be substituted, and when it represents a lower alkyl group, examples of the substituent include a halogen atom, an alkoxy group, an alkylthio group, an alkylamino group, a phenyl group, an alkoxycarbonyl group, and a substituent. Power such as canolebamoinole group. When r ⁵ represents a phenylsulfonylamino group which may be substituted, examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an alkylamino group, an alkylthio group, a nitro group, a cyano group, and a substituent. And a carbamoyl group which may be used.

The types of substituents Fuweniruarukiru in if r ⁵ represents an amino group which may be substituted by which may be Fuweniruarukiru substituted, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a nitro group, Shiano group, an alkyl Examples include an amino group, an alkoxycarbonyl group, an optionally substituted cal / moyl group, and the like.

R ³ is a benzoyl group which may be substituted, a phenyl group which may be substituted, a phenyl group which may be substituted, a phenyl group which may be substituted, an alkyl substituted by a phenyl which may be substituted. Group, an alkyl group substituted with an optionally substituted phenyl, an alkyl group substituted with an optionally substituted pyridyl, or an amino group optionally substituted with an optionally substituted phenyl. Examples of the type of the substituent include a halogen atom, an alkyl group, an alkoxy group, an alkylamino group, an alkylthio group, a nitro group, and a substituted rubamoyl group.

5 to 6-membered heterocyclic group containing 1 to 2 N, S, 0, or 5 to 6-membered heterocyclic ring containing 1 to 2 N, S, 0, which R ³ may be substituted When the heterocyclic ring represents an amino group which may be substituted with alkyl substituted with, thiophene, furan, imidazole, thiazol, oxazole, pyrazole, pyridine, pyrimidine, virazine, pyrrolidine, piperidine, piperazine, Examples of the substituent include halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkylamino groups, nitro groups, carbamoyl groups which may be substituted, and the like. The compound of the present invention can be produced by the following method c

 ①

CHaCOONHi / CHsCOOH

 [R-i]

In the formula, ⁵ is a lower alkyl group, a cycloalkyl group, a lower alkoxyalkyl group, an optionally substituted phenyl group, an optionally substituted N, S, or a 5- to 6-membered hetero ring containing 1 or 2 N, S, 0 (But bonded by an atom), an alkyl group substituted with an optionally substituted phenyl, an alkyl group substituted with an optionally substituted phenyl, and an alkyl group substituted with an optionally substituted pyridyl. And R ¹ m has the same meaning as described above.

[—Ι] can be obtained by reacting mn with an ammonium salt such as ammonium diacid in a solvent such as drip acid at a reaction temperature of 10 to 10 ° C.

 [VI]

CH ₃ I CH ₃ I base

式中 R⁶ は低級アルコキシカルボ二ル基を示し、 R¹、 mは前記と同じ意味を 示す。

In the formula, R ⁶ represents a lower alkoxycarbonyl group, and R ¹ and m have the same meaning as described above.

 Compounds of formula [VI] and are known or can be synthesized by conventional methods. (Pharmaceutical Magazine, 104 (2), p. 127 (1984)) [I'12] and [I'13] are reacted at a reaction temperature of 10 to 100 ° C in a solvent in the presence of a base. Is obtained.

Examples of the solvent include alcohols such as methanol, ethanol and n-butanol, Ethers such as dioxane; aromatic hydrocarbons such as benzene and toluene; pyridine; DMF; Examples of the base include sodium methoxide, potassium metal butoxide and other metal alkoxides, organic bases such as triethylamine, N, N-dimethylaniline, pyridine and DBU, metal hydrides such as sodium hydride, and the like. Inorganic bases such as carbonated lime, sodium hydroxide, and silver carbonate are exemplified.

 ③

CI '5] cr-16] wherein R ⁷ is a lower alkoxy group, a cyano group, a halogen atom, a hydroxy group, a morpholino group, or an amino which may be substituted with a phenylalkyl or a lower alkyl which may be substituted. And R ¹ , m, and n have the same meaning as described above.

 [1′-4] can be obtained by reacting [Γ1] with an oxidizing agent such as metachloroperbenzoic acid and hydrogen peroxide in a solvent such as chloroform and sulfonic acid.

[I'-5] can be obtained by reacting [I'1-1] with a reducing agent such as sodium borohydride in a solvent such as methanol or ethanol. [I'16] can be obtained by reacting [核 4] with a nucleophile in a solvent in the presence of a base.

 ④

[1′-1 9] [1′-1 8] wherein R ⁸ is a hydrogen atom, a lower alkoxy group, a lower alkyl group, a cycloalkyl group, a lower alkoxyalkyl group, a lower alkylthio group, a phenyl group which may be substituted. A 5- or 6-membered heterocyclic group containing 1 or 2 Ν, S, 0 which may be substituted, an alkyl group which may be substituted by phenyl, or a phenyl which may be substituted. A substituted alkyl group, an alkyl group substituted with an optionally substituted pyridyl, or an alkyl substituted with a 5- to 6-membered heterocyclic ring containing 1 to 2 cyano, nitro, Ν, S, 0, R represents an amino group which may be substituted with phenyl, lower alkoxy or lower alkyl which may be substituted, R ^fl represents a lower alkyl group or a phenyl group which may be substituted, and R ¹ and m are as defined above. Indicates the same meaning.

[I ′ — 7] is a reaction of [Π] and [Cor] in a solvent in the presence of a base at a reaction temperature of 10 It is obtained by reacting at 1010 ° C.

 Examples of the solvent include water, alcohols such as methanol, ethanol and n-butanol, ethers such as dioxane, aromatic hydrocarbons such as benzene and toluene, pyridine, DMF, and DMS0. Bases include sodium metal alkoxides such as sodium methoxide and potassium t-butoxide; organic bases such as triethylamine, N, N-dimethylaniline, pyridine and DBU; metal hydrides such as sodium hydride; And inorganic bases such as sodium hydroxide.

 [Γ-8] can be obtained by reacting [Γ-7] with a reducing agent such as sodium borohydride in a solvent such as methanol or ethanol.

[1 'single 9] is [1' -7] and the ^{_{R e S0 2 NH 2, DMF}} , in a solvent such as DMS 0, the reaction using a metal hydride such as hydride Natoriumu as base temperature 10-150 It is obtained by reacting at ° C.

[XI] CI ^A -10] wherein R ¹⁰ represents a lower alkyl group, and R ⁸ has the same meaning as described above. [—10] can be obtained by heating I] and polyphosphoric acid (ΡΡΑ) to 100 ° C for 2 hours at 0 ° C. ⑥

[Γ—11] [—12] In the formula, R ¹¹ represents an optionally substituted phenyl group, an optionally substituted phenyl group or an optionally substituted pyridyl group, and R ¹ , m, and R ^{2 each} represent Has the same meaning as

 [— 12] is [1'-11] (synthesized under the same conditions as when [Γ – 7] is produced using [Ε] as a raw material). Ethers such as dioxane and alcohols such as ethanol. It is obtained by heating to reflux for 1 to 24 hours with selenium dioxide in a solvent of benzene, water and mixtures thereof. Further, it can also be obtained by using an oxidizing agent such as chromic anhydride and manganese dioxide described in ACS Monograph 186 "Oxidations in Organic Chemistry 1990, 103-104."

CXI) [I′—9] In the formula, R ¹ , m and R ⁸ have the same meanings as described above.

The compound of the formula [XII] is known or can be synthesized by a conventional method (for example, Tetrahedron, 42 (12), 3029-96 (1986)). The compound of the formula [1′-1 9] can be obtained by reacting under the same conditions as in the production of the compound of the [1′-1 7]. ⑧

 cr-10]

CHOH

CI′-11] wherein R ¹ , m, R ⁸ and Y have the same meaning as described above.

The compound of [1'-11] is heated in a solvent such as DMF, DMSO, or the like, or without solvent, with the compound of CI'10] and N, N-dimethylformamide dimethyl acetal, and then subjected to silica gel column chromatography. It is obtained by purification.

⑨

 CI'-1 12)

[1′-1 13] In the formula, R ¹ , m, R ⁸ and Y have the same meaning as described above.

The compound of the formula (xm) represents an active methylene compound, and R ¹² and R ¹³ are the same or different and each represents a carbamoyl group which may be mono- or di-substituted by a cyano group, an alkoxycarbonyl group, or a lower alkyl group. . The compound of the formula [1′—13] can be synthesized by a conventional method (Liebigs Ann. Chen 1984, 618-21).

©

CI '1 12] CI'-14] In the formula, R ¹ , m, R ⁸ and Y have the same meaning as described above.

The compound of the formula ααπ represents a primary amine, hydrazine, hydroxyamine or alkoxyamine, and R ¹⁴ is a lower alkyl group, an optionally substituted phenyl group, a lower alkoxy group, a lower alkylamino group, a hydroxy group, A phenylamino group and a lower alkoxycarbonylamino group.

 The compound [114] can be obtained by reacting a solvent in a solvent in the presence of an acid at a reaction temperature of 10 to 150 ° C.

 Examples of the solvent include alcohols such as methanol, ethanol and n-butanol, ethers such as dioxane, aromatic hydrocarbons such as benzene and toluene, halogenated carbons such as dichloromethane, chloroform, and 1,2-dichloroethane. Hydrogens, DMF, DMSO and the like. Examples of the acid include an inorganic acid such as hydrochloric acid and sulfuric acid, an organic acid such as oxalic acid and p-toluenesulfonic acid, and a Lewis acid such as boron trifluoride etherate.

⑪

 C I 'I 12)

CI′—15] c-1 16] wherein R ¹ , m, R ⁸ and Y have the same meaning as described above. The compounds of the formulas [Γ15] and [Γ16] can be obtained by adding sodium hypochlorite in a solvent at 15 to 40 ° C. in the presence of an acid.

 Examples of the solvent include water and halogenated hydrocarbons such as dichloromethane. Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid.

 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 was determined from IR, NMR, MASS and the like. BEST MODE FOR CARRYING OUT THE INVENTION

 Next, the present invention will be described in more detail with reference to Examples and Reference Examples.

Reference example 1

 2- [3-oxo-1-3-phenyl-1-methylthiopropylidene] 1-indane-1, 3-dione

12.5 g of 2-bis (methylthio) methylene-indane-1,3-dione 12.5 g, 6.0 g of acetophenone, 6.6 g of well-ground potassium hydroxide and 200 ml of anhydrous DMF were suspended, and the mixture was suspended at room temperature. And stirred overnight. The reaction solution was poured into ice water, and the pH was adjusted to 3 to 4 by adding 1N—HC1. The precipitated crystals were filtered under reduced pressure and dried to obtain 12 g of 2- [3-oxo-13-phenyl-11-methylthiopropylidene] -1-indane-1,3-dione. Example 1

 2-phenyl-2-methylthio-15H-indeno [1,2-b] pyridin-5-one (Compound No.I-13)

 12 g of the compound obtained in Reference Example 1, 28.5 g of ammonium sulfate and 750 ml of acid were stirred at 100 ° C. for 6 hours, and left overnight. The precipitated crystals were filtered and washed with acetone and ether to obtain 4.5 g of the desired product (mp 179-80 ° C). Example 2

 2- (2-Methoxyphenyl) 1-4-methylthio-15H-indeno [1,2-b] pyridin-5-one (Compound No. 1-6)

2—ビス （メチルチオ） メチレン一インダン一 1, 3—ジオン 2.5 g、 2—メ トキシァセトフエノン 1.5 g、 よくすりつぶした水酸化力リウム 6.6 g及び無水 DMF4 Omlを懸濁し、 70でで 3時間、 続いて 1 00 °Cで 1時間攪拌した。 反応液を氷水中に注ぎ 1 N— H C 1を加え p Hを 3〜 4にして析出した結晶を減 圧濾過し、乾燥して 1.4 gの結晶を得た。 得られた結晶 1.4 gと酢酸アンモニゥ ム 3.07 gを酢酸 75mlに懸濁し、 100 °Cで 6時間攪拌した。 反応液を氷水 中に注ぎ、析出した結晶を濾取し乾燥した。 得られた粗生成物をシリカゲルカラ ムクロマトグラフィー （溶出液；クロ口ホルム）精製して、 目的物 0.4 g (mp 200 - 2 °C) を得た。

2.5 g of 2-bis (methylthio) methylene-indane-1,3-dione, 1.5 g of 2-methoxyacetophenone, 6.6 g of well-ground lithium hydroxide and 6.6 ml of anhydrous DMF4 were suspended, and the mixture was suspended at 70 for 3 hours. Subsequently, the mixture was stirred at 100 ° C for 1 hour. The reaction solution was poured into ice water, 1 N—HC1 was added to adjust the pH to 3 to 4, and the precipitated crystals were filtered under reduced pressure and dried to obtain 1.4 g of crystals. 1.4 g of the obtained crystals and 3.07 g of ammonium acetate were suspended in 75 ml of acetic acid and stirred at 100 ° C for 6 hours. The reaction solution was poured into ice water, and the precipitated crystals were collected by filtration and dried. The obtained crude product was purified by silica gel column chromatography (eluent; black form) to obtain 0.4 g (mp 200-2 ° C) of the desired product.

Example 3

 2- (2-Hydroxyphenyl) -14-methylthio-5H-indeno [1,2—b] pyridin-5-one (Compound No. I-10)

0.95 g of 2- (2-methoxyphenyl) -14-methylthio-15H-indeno [1,2-b] pyridin-5-one and 10 g of pyridine hydrochloride were stirred under a nitrogen atmosphere at 150 ° C. for 20 minutes. After allowing to cool, ice-water was added, and the mixture was extracted with chloroform. The extract was washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting! Te product was purified by silica gel column chromatography (eluent, chloroform) to obtain 0.45 g of the desired product (mp 228-30 ° C).

Example 4

2-phenyl-1-4-methylsulfinyl 5-H-indeno [1,2-b] pyri 5-N-one (Compound No. 1-11)

Dissolve 0.64 g of 2-phenyl-14-methylthio-15H-indeno [1,2-b] pyridine-5-one in 50 ml of chloroform, and add 0.41 g of methacrylic acid perbenzoic acid dissolved in 20 ml of chloroform. The mixture was dropped at room temperature and stirred for 3 hours. The reaction solution was washed with a 1N aqueous solution of sodium hydroxide and then with saturated water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained ite product was purified by silica gel gel chromatography (eluate, chloroform) to obtain 0.55 g of the desired product (mp 228-19.C).

Example 5

2-phenyl-2-methylsulfonyl-5H-indeno [1,2-b] pyridin-1-5-ofofanimation compound number 1-12)

Dissolve 0.64 g of 2-phenyl-2-methylthio-15H-indeno [1,2-b] pyridin-5-one in 5 ml of chloroform and 5 ml of chloroform in 1.2 ml of metabenzoic perbenzoic acid. The mixture was added dropwise and refluxed for 1 hour. After allowing to cool, the reaction solution was washed with a 1 N aqueous solution of sodium hydroxide and then with a saturated saline solution, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent, chloroform) to obtain 0.4 g (mp232-13 ° C) of the desired product.

Example 6

 2-phenyl-1-4-methoxy-5 H-indeno [1,2-b] pyridine-15-one (Compound No. I-13)

2—フエニル一 4ーメチルスルホニル一 5 H—インデノ 〔1, 2— b〕 ピリジ ン一 5—オン 0,53 gをメタ.ノール 15mlに懸濁し、 28%ナトリゥムメチラ ートメタノール溶液 0.32 gを滴下し、 20分還流した。 反応液を氷一水中に注 ぎ、析出した結晶を濾取して乾燥した。 得られた胜成物をシリカゲルカラムク 口マトグラフィー （溶出液， クロ口ホルム） 精製して、 目的物 0.25 g (mp 192-5)を得た。

0.53 g of 2-phenyl-1-methylsulfonyl-5H-indeno [1,2-b] pyridin-5-one is suspended in 15 ml of methanol, and 0.32 g of a 28% sodium methanolate methanol solution is added dropwise. Refluxed for 20 minutes. The reaction solution was poured into ice and water, and the precipitated crystals were collected by filtration and dried. The resulting product was purified by silica gel column chromatography (eluate, black form) to obtain 0.25 g of the desired product (mp 192-5).

Example 7

 2-phenyl-2- (dimethylamino) -5H-indeno [1,2-b] pyridin-5-one (Compound No. 1-14)

0.53 g of 2-phenyl-4-methylsulfonyl-5H-indeno [1,2-b] pyridin-15-one was suspended in 10 ml of DMF, and 0.3 g of a 50% aqueous dimethylamine solution was added. After stirring at 100 ° C for 1 hour, the mixture was poured into ice-water, and the precipitated crystals were collected by filtration and dried to obtain 0.38 g of the desired product (mp 112 -4 ° C).

Example 8

2-Phenyl-1-4-H-5-Indeno [1,2-b] Pyridine-15-one (Compound No. I-15)

2-Phenyl-4-methylsulfonyl-5H-indeno [1,2-b] pyridin-5-one 0.53 g and sodium cyanide 0.26 g were suspended in 10 ml of DMSO and stirred at 60 ° C for 10 minutes. . After allowing to cool, the reaction solution was poured into ice-water and the precipitated crystals were collected by filtration, washed sufficiently with water and dried to obtain 0.25 g (mp 245-6 ° C) of the desired product. Example 9

 2-Methoxy 3 -Methoxycarboxy 4-methylthio-1 5H-indeno [1,2-b] pyridin-5-one (Compound No. 1-16)

2,5-Dihydro-3-methoxycarbonyl-2-methylthio-1H-indeno [1,2-b] pyridine 1,2,5-dione 1.5 g is dissolved in anhydrous DMF 15 ml 1 and 60% hydrogenated sodium hydrogen Add 0.2 g of real oil dispersion and stir at room temperature for 15 minutes After stirring, 4 g of methyl iodide was added and the mixture was stirred overnight. The reaction solution was poured into ice water and extracted with benzene, washed with saturated saline and dried over anhydrous magnesium sulfate. The product obtained by distilling off the solvent under reduced pressure was purified by silica gel gel column chromatography (eluent, benzene) to obtain 0.1 g of the desired product (m 145-7 ° C).

 Example 10

 2-Phenyl-5-methylthio-15H-indeno [1,2-b] pyridin-5-ol (Compound No. Π-4)

0.3 g of 2-phenyl-4-methylthio-15H-indeno [1,2-b] pyridin-5-one and 0.25 g of sodium borohydride were suspended in 20 ml of ethanol and stirred at room temperature for 2 hours. The SiS solution was poured into ice-water, 1-HC1 was added to make it slightly acidic, and the precipitated crystals were collected by filtration and dried. The obtained product was purified by silica gel column chromatography (eluent, chromatographic form) to obtain the desired product 0.23 s (mp 200-13 ° C).

Example 11

2-phenyl-2-methylthio-5H-indeno [1,2-d] pyrimidin-5-one (Compound No. 1-5)

2.3 g of 2-bis (methylthio) methylene-indane-1,3-dione, 1.83 g of benzamidine hydrochloride and 1.27 g of carbonic acid rim were suspended in anhydrous DMF and stirred at 50 to 60 ° C for 1 hour. The reaction solution was poured into ice water and extracted with benzene, and the organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was recrystallized from benzene-hexane to obtain 1.0 g (mp 228-9 ° C) of the desired product.

Example 12

2- (6-Methyl-2-pyridyl) -14-methylthio-5H-indeno [1,2-d] pyrimidin-5-ol (Compound No.H-3)

Two

 Two

 N ゝ 3

2- (6-Methyl-1-pyridyl) 1-4-methylthio-5H-indeno [1,2-d] pyrimidin-5-one 0.6 g and sodium borohydride 0.5 g are suspended in 30 ml of ethanol, and the suspension is carried out at room temperature. The mixture was stirred for 2 hours. The reaction solution was poured into ice water and neutralized by adding 1N-HC1, and the precipitated crystals were collected by filtration and dried. The resulting product was purified by silica gel column chromatography (eluate, black form) to obtain 0.51 g of the desired product (mp 204-6 ° C).

5- (N, N-dimethylcarbamoyl) 1-indan-1,3-dione

無水酢酸 (3 L7 g) に、 4— (N, N—ジメチルカルバモイル）無水フタル 酸（13.5 g, 61.6讓 ol) とァセト酔酸 t—ブチル（19.5 g, 123腿 ol) とを加え、 トリェチルァミン （12.5 g, 123腿01) を滴下し、 70〜80°C で 4時間反応させた。 反応後減圧下に過剰の無水酢酸と、 生じた酢酸を留去し、 残渣を水 （200ml) と濃塩酸 (13ml) より調製した塩酸水に注加し、 ク ロロホルム （50m 1 X 5)で抽出した。

To 4- (N, N-dimethylcarbamoyl) phthalic anhydride (13.5 g, 61.6 benzyl) and t-butyl acetohydrate (19.5 g, 123 t ol) were added to acetic anhydride (3 L7 g), and triethylamine was added. (12.5 g, 123 thigh 01), and drop at 70-80 ° C For 4 hours. After the reaction, excess acetic anhydride and generated acetic acid were distilled off under reduced pressure, and the residue was poured into aqueous hydrochloric acid prepared from water (200 ml) and concentrated hydrochloric acid (13 ml), and added with chloroform (50 ml × 5). Extracted.

 The chloroform layer was washed with water (5 Om 1 X 2) and dried over anhydrous magnesium sulfate, and chloroform was distilled off under reduced pressure.

 The residue was crystallized by adding a mixed solvent of black form-ether to give 5.4 g (mp 133-5 ° C) of the title compound.

Reference example 3

 2-bis (methylthio) methylene-1-5- (N, N-dimethylcarbamoyl) -1-indane-1,3-dione

5- (N, N-Dimethylcarbamoyl) -indane-1,3-dione (5 g, 23.26 tmol) was dissolved in DMF (50 ml). To this solution was added a solution of sodium hydroxide (1.86 g, 46.5 t) dissolved in water (5 ml) at room temperature, and then carbon disulfide (2.65 g, 34.9 ol) at room temperature. The mixture was added dropwise and stirred for 2 hours. To this solution, methyl iodide (13.2 g, 93 tmol) was added dropwise over 1 hour under water cooling, followed by stirring overnight. The reaction solution was poured into water (300 ml), and the resulting crystals were collected by filtration, washed with water, dried and recrystallized from ether. Yield 6.0 g, 80% yield, mp 145-7. C

Example 13

2-Methyl-4-methylthio-17- (N, N-dimethylcarbamoyl) -5H-indeno [1,2-d] pyrimidin-5-one and 2-methyl-14-methylthio-8- (N, N- Dimethylcarbamoyl) 1 5 H-indeno [1, 2-d] Pyrimidine-1 5 years old ({Dragon compound number HE-1, E-2)

2-bis (methylthio) methylene-1-5- (N, N-dimethylcarba'moyl) -indane-1,3-dione (1.50 g, 4.67 / 1) was dissolved in DMF (30 ml) and added to this solution. Cetamidine hydrochloride (0.44 g, 4.67 g ol) and anhydrous carbon dioxide (0.64 g, 467 mmol) were added, and the mixture was reacted overnight at 60 to 70 ° C. The SiE solution was poured into water (200 ml), extracted with black-mouthed form (3 Oml x 3), the mouth-shaped form layer was washed with water (5 Oml X2), dried over anhydrous magnesium sulfate, and then left on the mouth under ffi. I left. The residue was purified by column chromatography, and 0.55 g (m 155-6 ° C) of the 7-force rubamoinole form and 0.45 g (mp l 69- °) obtained.

Example 14

2-Methyl-4-methylsulfonylamino-5H-indeno [1,2-d] pyrimidin-5-one (Compound No.E-13)

0.8 g of 60% hydrogenated sodium oil despurgeon was suspended in 5 ml of anhydrous DMF, cooled to 0 ° C, and 0.19 g of methanesulfonamide was added little by little. After stirring for 20 minutes, 0.48 g of 2-methyl-1-methylthio-15H-indeno [1,2-d] pyrimidin-1-one was added, and the mixture was stirred at room temperature overnight. The temperature was further raised gradually, and the mixture was stirred at 120 ° C for 2 hours. After allowing to cool, pour into ice-water, acidify with 1N-hydrochloric acid, dry the precipitated crystals, and purify by silica gel column chromatography (eluent, methanol: chloroform = 1: 1: 9) to obtain 0.15 g of the desired product ( mp 1 85-7 ° C). Reference example 4

 2,4-diphenylpyrimidine 5-ethyl ether

3-Dimethylamino-2-ethyl benzoyl acrylate 2 g, benzamidine hydrochloride 1.25 g, and lium carbonate 1.1 g are suspended in anhydrous DMF and stirred at 70 ° C for 2 hours. did. After allowing to cool, the reaction solution was poured into ice-water and extracted with benzene, washed with saturated solution: ft ^ 7], and dried over anhydrous magnesium sulfate. The product obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography (eluent, ethyl acetate: benzene = 1 r3) to obtain 56 g of the desired product L (mp 50-2 ° C). Obtained.

 -Reference example 5

 2,4-diphenylpyrimidine-1-5-Rubonic acid

1.56 g of 2,4-diphenylpyrimidine-15-potassium ethyl rubonate was dissolved in 16 ml of methanol and heated to 50 ° C. Sodium carbonate dissolved in 7 ml of water was added and refluxed for 5 hours. After cooling, water was added, the mixture was acidified with 1N-hydrochloric acid, extracted with chloroform, washed with saturated water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 1.1 g of the desired product.

Example 15

 2-Phenyl-1-H-indeno [1,2-d] pyrimidin-5-one (Compound 1-1)

2， 4-ジフエニルピリミジン一 5—力ルボン酸 0.4 gとポリリン酸 6.1 gを 窒素雰囲気下、 170°Cで一夜攪拌した。 放冷後水を加えてクロ口ホルム抽出し、 飽和食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した。 溶媒を減圧留去して得 られた粗生成物をシリ力ゲル力ラムクロマトグラフィー （溶出液， メタノール： クロ口ホルム = 1 ： 9)精製して目的物 0.2 g (mp 171— 3°C) を得た。 実施例 16

0.4 g of 2,4-diphenylpyrimidine-1-5-carboxylic acid and 6.1 g of polyphosphoric acid were stirred overnight at 170 ° C. under a nitrogen atmosphere. After cooling, water was added, and the mixture was extracted with chloroform. The extract was washed with saturated saline and dried over anhydrous magnesium sulfate. The crude product obtained by evaporating the solvent under reduced pressure was purified by silica gel gel chromatography (eluent, methanol: chloroform = 1: 9) and the desired product was purified to 0.2 g (mp 171-3 ° C). I got Example 16

 2-Benzyl-1-methylthio-5H-indeno [1,2-d] pyrimidin-5-one (Compound No.!-26)

1.3 g of 2-benzyl-4-methylthio-5H-indeno [1,2-d] pyrimidin-5-one was suspended in 13 ml of dioxane and 0.6 ml of water, and 1.4 g of selenium dioxide was added thereto and refluxed for 2 hours. The reaction solution was filtered through celite, and water and ethyl acetate were added to the filtrate to separate the filtrate. The organic layer was washed with a saturated saline solution and dried over anhydrous magnesium sulfate. The product obtained by distilling off the solvent under reduced pressure is purified by silica gel column chromatography (eluent; chromate form: hexane 1: 1), and the desired product is 0.14 g (mp 21 1-4 ° C) I got Example 6

 2-[3-oxo-3- (4-pyridyl) -1-methylthiopropylidene] one indane one 1,3-dione \

8.0 g of 60% sodium hydride oil despargeon was suspended in 300 ml of anhydrous DMF, and 4-acetylviridine was added dropwise. The mixture was stirred at room temperature for 20 minutes, 25 g of 2-bis (methylthio) methylene-indan-11,3-dione was added, and the mixture was stirred at room temperature for 1 minute. The SiSS solution was poured into ice water, 1 N hydrochloric acid was added to adjust the pH to 7, and the precipitated crystals were collected by filtration and dried. The obtained ffi product was purified by silica gel column chromatography (eluate, liquid form) to obtain 18.6 g of the desired product.

Morpholine mono 1-carboxyamidine acid salt

Recitation ₃

NH

0 NC image ₃

Hz 4.35 g of morpholine and 2.0 1 g of 3,5-dimethylpyrazole-1-carboxamidine nitrate were refluxed under a nitrogen atmosphere for 3 hours. Excess morpholine was distilled off under reduced pressure, and ethyl acetate was added to the obtained crude product, followed by extraction with water. The aqueous layer was distilled off under reduced pressure to obtain 2.5 g of the target substance.

Example 17

 2- (4-pyridyl) -1-methylthio-5H-indeno [1,2-d] pyrimidin-5-one (Compound No. 1-8)

16.32 g of 2-bis (methylthio) methylene-indane-1,3-dione, 10.22 g of 4-pyridinecarboxyamidine hydrochloride and 9.01 g of carbonic acid rim are suspended in anhydrous DMF and stirred at 70-80 ° C for 1 hour. did. The reaction solution was poured into water and ice, and the precipitated crystals were collected by filtration. The extract was washed with water and hexane and dried to obtain 16.19 g of the desired product (mp 267-9 ° C).

Example 18

2-morpholino 4-methylthio-5H-indeno [1,2-d] pyrimidin-5-one (Compound No. Π—41)

Suspension of 2-bis (methylthio) methylene-indane-1 I, 3-dione 3 * 13 g, morpholine-111-carboxyamidine nitrate 2.4 g and carbonic acid lime 1.73 g in anhydrous DMF, 70-80 ° C Stir for 4 hours. The reaction solution was poured into ice and water, and the precipitated crystals were collected by filtration and dried. The obtained 3te product was recrystallized from phenol-form-hexane to obtain 1.25 g of the desired product (mp 237 -8 ° C).

Example 19

 2-phenyl-2-methylthio-5H-indeno [1, 2-d] birimidine (Compound No. It— 6)

2 -ビス （メチルチオ） メチレンィンダノン 2.36 g、 ベンズァミジン塩酸塩 1.57 g及び炭酸カリウム 1.38 gを無水 DMFに懸濁し、 70〜80°Cで 2時 間攪拌した。 反応液を氷一水中に注ぎ、 ベンゼン抽出し、 飽和食塩水で洗浄した 後、 無水硫酸マグネシウムで乾燥した。 溶媒を減圧留去して、 得られた粗生成物 をシリカゲルカラムクロマトグラフィー （溶出液、 ベンゼン）精製して、 目的物 0.87 g (mp 137 - 9 °C) を得た。

2.36 g of 2-bis (methylthio) methylene indanone, 1.57 g of benzamidine hydrochloride and 1.38 g of potassium carbonate were suspended in anhydrous DMF and stirred at 70 to 80 ° C. for 2 hours. The reaction solution was poured into ice-water, extracted with benzene, washed with saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent, benzene) to obtain 0.87 g of the desired product (mp 137-9 ° C).

Example 20

 2-phenyl-2-methylthio-5-hydroxymethylidene-5H-indeno [1,2-d] pyrimidin-5-one (compound number m-8)

0.29 g of 2-methyl-4-methylthio-5H-indeno [1,2-d] pyrimidine was dissolved in 0.6 g of N, N-dimethylformamide dimethyl acetal and refluxed for 1 hour. After the reaction, excess acetal was distilled off under reduced pressure, and the obtained dimethylaminomethylene was hydrolyzed by subjecting it to silica gel column chromatography (eluent, benzene) to give 0.12 g of the desired product (mp 24 1- 3 ° C dec). Example 21

2-Fueneru 4-Benzylthio-5-H-indeno [1,2-b] pyridin-5-one (Compound No. 1-19)

60% hydrogenated sodium oil dispersion 0.0 & g was suspended in 15 ml of anhydrous DMF, and 0.2 g of benzyl mercaptan dissolved in 5 ml of anhydrous DMF was added dropwise. After stirring at room temperature for 5 minutes, 0.53 g of 2-phenyl-4-methylsulfonyl-15H-indeno [1,2-b] pyridin-5-one was added, and the mixture was stirred at 100 for 1 hour. After cooling, the mixture was poured into ice water and extracted with black hole form, washed with saturated saline and dried over anhydrous magnesium sulfate. The resulting product obtained by evaporating the solvent was purified by silica gel column chromatography (eluent, chloroform) to obtain 0.35 g of the desired product (mp I 56-8 ° C).

Example 22

 [2-C4- (1-Methynole) pyridinium] 1-4-methylthio-15H-indeno [1,2-d] pyrimidin-5-one] iodide

2- (4-Pyridyl) -14-methylthio-15H-indeno [1,2-d] pyrimidin-5-one 0.23 "and methyl iodide 0.35 g were added to dioxane 10m1. The mixture was refluxed for 5 hours. After cooling, the precipitated crystals were collected by filtration to obtain 0.23 g (mp: 270 ° C or more) of the target product.

 NMR (DMSO): 62.8 ppm (s, 3H), 4.5 (s, 3H), 7.8 (m,

 3H), 8.0 (d, 1H), 9.0 (d, 2H), 9.2 (d, 2H)

Example 23

 2- (4-Pyridyl) -14-methylthio-5-ethoxycarbonylhydrazono-5H-indeno [1,2-d] pyrimidin-5-one (Compound No. 11-5)

2- (4-pyridyl) 1-4-methylthio-5H-indeno [1,2-d] pyrimidin-5-one 0.53 g, ethylcarbazate 0.20 g and paratoluenesulfonate monohydrate 0.1 g in DMSO 10m 1 And toluene (10 ml), and the mixture was refluxed for 2 hours while distilling off water using Gene Stark. After allowing to cool, the precipitated crystals were collected by filtration and washed with ether to give 0.43 g of the desired product (mp 246-8 ° C).

Example 24

2-phenyl 4-methylthio-5-bis (ethoxycarbonyl) methylidene — 5 H—indeno [1, 2—d] pyrimidine-1-5-one (Compound No. IE—10)

窒素雰西気下で、 2—フエニル一 4—メチルチオ一 5 H—インデノ 〔1 , 2— d〕 ピリミジン一 5—オン 0. 7 2 gとマロン酸ジェチル 0. 5 7 gをジクロロメ タン 2 Omlに溶解し、 0 °Cに冷却して四塩化チタン 1. 5 m 1を滴下した。 0でで 2 0分攒 ^、無水ピリジンを 2 2 m 1滴下した。 0でで 2時間、室温で 2時間 反応させ、氷一水中に注ぎ、 クロ口ホルム抽出した。 1 N—塩酸、 1 N—水酸ィ匕 ナトリウム水溶液、次いで飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し た。溶媒を 留去して得られた & ^物をシリカゲルカラムクロマトグラフィ- (溶出液、 グロ口ホルム）で精製して目的物 0. & 6 g (mp 1 5 3— 6 °C) を得 た。

Under a nitrogen atmosphere, 2-phenyl-14-methylthio-15H-indeno [1,2-d] pyrimidin-5-one 0.72 g and getyl malonate 0.57 g in dichloromethane 2 Oml And cooled to 0 ° C., and 1.5 ml of titanium tetrachloride was added dropwise. At 0 ° for 20 minutes, 22 ml of anhydrous pyridine was added dropwise. The reaction was carried out at 0 for 2 hours and at room temperature for 2 hours, poured into ice-water and extracted with black-mouthed form. The mixture was washed with a 1 N hydrochloric acid, a 1 N aqueous sodium hydroxide solution and then with a saturated saline solution, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting & ^ product was purified by silica gel column chromatography (eluent, glo-mouth form) to obtain the desired product (0.5 & 6 g, mp 15 3-6 ° C).

Example 2 5

 2-Phenyl-1-methylthio-5-ethoxymino 5 H-indeno [1,2-d] pyrimidin-5-one (Compound No. M-9)

2—フヱニルー 4ーメチルチオ一 5 H—インデノ 〔1， 2— d〕 ピリ ミジン一 5—オン 1.01 g及びエトキシアミン 0.43 gを 1, 2—ジクロロェタン 10ml に懸濁し、三フッ化ホウ素エーテラ一トを 0.3ml加え 4時間還流した。 放冷後 溶媒を減圧留去し、得られた粗生成物をシリ力ゲル力ラムクロマトグラフィー (溶出液、 クロ口ホルム：へキサン = 1 ： 1) で精製し、 目的物 1.1 g (mp 160— 2 °C) を得た。

1.01 g of 2-phenyl-4-methylthio-5H-indeno [1,2-d] pyrimidin-5-one and 0.43 g of ethoxyamine are suspended in 10 ml of 1,2-dichloroethane, and boron trifluoride etherate is suspended in 0.3 ml. After adding ml, the mixture was refluxed for 4 hours. After cooling, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel chromatography (eluent, chloroform: hexane = 1: 1) to obtain 1.1 g of the desired product (mp 160 — 2 ° C).

Example 26

 2-phenyl-2-methylsulfonyl-5H-indeno [1,2-d] pyrimidin-5-one and 2-phenyl-2-chloro-5H-indeno [1,2-d] pyrimidin-5-one (Compound number)!-54, 1- 55)

1.52 g of 2-phenyl-2-methylthio-5-indeno [1,2-d] pyrimidin-5-one, 2.5 ml of concentrated hydrochloric acid and 37.5 ml of water were dissolved in 12.5 ml of dichloromethane and cooled to 0 ° C. 18.8 g of a 5% aqueous solution of sodium hypochlorite was added dropwise, and the mixture was stirred at 0 ° C for 5 hours. After separating the organic layer and washing with saturated saline, anhydrous magnesium sulfate Dried with Nesium. The solvent was distilled off under reduced pressure, and the resulting ffi ^ product was purified by column chromatography (eluent, chromatographic form), and 0.38 g of the chloro form of the title compound (mp 1 8 4-7 ° C ) And 0.30 g of a sulfonyl compound (mp 230-3 ° C) were obtained. Representative examples of the compounds of the present invention, including the above Examples, are shown in Tables 1, 2 and 3.

First

Structural formula

Physical constant compound [] mp number CO

R ^! R ⁴

I-I 1 SCH ₃ H [218-20]

I-1 2 -0CH ₃ (172-5)

1 -3 C179-80)

1 -4 CI [239-41]

1 -5 [253-5]

I-1 6 (200-2)

1 -7 H ₃ (190-3)

I-1 8 CH ₃ (180-2) (Continued)

(つづき）

(Continued)

搆

Iron

 Physical constant compound [] mp number (.C)

R ²

I-I 1 SCH ₃ -CHs [213-4]

IE-2 [138-40]

E-3 then C151-2]

 CHs

 1-4 -C-CH3 (127-8)

-8 〔267-9〕 (つづき） CHs -5 (228-9) -6 (220-2) -7 (237-8)

-8 〔267-9〕 (Continued)

CH ₃

1-9 SCH ₃ [236-7]

I -10 -0CH ₃ (215-6)

E-11 〃 -SCH ₃ [234-6] NO CH3

 1-12 (244-5)

CH ₃

1-13 -NHSO2CH3 -CH ₃ (185-7)

1-14 H [171-3]

CH ₃

-15 〃 -6 [158-9] -16 〃 [198-200] -17 〃 [239-41] -18 SCH ₃ -HCH3 [248-250] -19 〃 -NH2 [270 or more] (Continued)

(つづき）

(Continued)

(つづき）

(Continued)

(つづき） ]

(Continued)

第 2 表 (つづき）

Table 2 (continued)

-匿 (DMSO- d_e-CDCl₃), δ： ppm I-59 -SCH ₃ (218-21)

- Anonymous _{(DMSO- d e -CDCl 3),} δ: ppm

 U 2.5 (s, 3H), 7.3 (s, broad 2H), 7.6 (m, 4H)

 * 5 2.6 (s, 3H), 7.7 Cm, 4H)

(IR (KBr): 1 _co 1700 cm-1 ¹ _CN 2200 cm— ¹ )

δ： ppm

δ: ppm

 D 6 2.8 (s, H), 4.5 (s, 3H), 7.8 (m, 3H), 8.0 (d, IH), 9.0 (d, 2H),

 9.2 (d, 2H)

 Π L6 (t, 3H), 2.8 (s, 3H), 4.8 (q, 2H), 7.8 (m, 3H), 8.0 (d, IH), 9.0 (d, 2H), 9.3 (d, 2H)

 * 8 1.7 (d, 6H), 2.8 (s, 3H), 5.2 (m, lH), 7.8 (m.3H), 8.l (d, IH), 9.0 (d, 2H), 9.4 (d, 2H)

 * 9 2.8 (s, 3H), 4.0 (m, 2H), 4.8 (m, 2H), 7.8. (M, 3H), 8.0 (d, IH), 9.0 (d, 2H), 9.2 (d, 2H) )

 ^-MRCCDCls), δ: ppm

o 2.3 (s, 3H), 2.4Cs, 3H), 2.5 (s, 3H), 2.60n, 2H), 3.4 (d, 3H), 3.9 Cm, 2H), L6 (m, 4H)

Physical constant Compound number Formula [] mp

 CO

n-1 (155-6)

Four

 7

Π-2 [169-70]

m-3 〔204-6〕

m—4 [200-3] (Continued)

M-5 [246-8]

Π-6 [137-9]

Π-7 [253-4]

CHOH

SCHs

m-8 (241-3) dec

 N

N (Continued)

N0C ₂ H

m-9 (160-2)

Et0 ₂ C C0 ₂ Et

 \ /

Π- 10 C153-6)

m— 1 1 [263-4 3

The compound of the present invention has excellent bactericidal activity against a wide variety of fungi, various kinds of diseases that occur when agricultural and horticultural crops including flowers, grasses, grasses, and pastures are separated, especially powdery mildew Can be used to control downy mildew. For example, powdery mildew of cucumber (Spha er 0 the c_a fu 1 iginea), powdery mildew of tomato (E rysipecico racea rum.), Powdery mildew of strawberry (Sphae ro the ca humu 1i), and tobacco Powdery mildew (E rysipheci cho racear um), Rinko's picky's disease CP odosphaera I euco tri cha), Oyster's powdery mildew (P hy 1 1 actinia kaki co la), Budow's picky vine (Uncinu) 1 an eca to r), downy mildew (P 1 as mo para viti co la), powdery mildew of pear CPhyl l ac t in iapyr)), powdery mildew of barley CErys iphe grami nisf. S p. Ho rde i), wheat powdery mildew (E rysiphegr am inisf .sp. tritici), ochidodograsu powdery mildew CE rysi phe gr am inis), Himaury powdery mildew Spiiae ro the ca fuligi nea) I Bella powdery mildew (S ae ro the ca fuli ginea) (S p h a e r o t h e c a p anno s a) can be used in disease control, such as.

 In addition, fungicides such as Sphae ro th eca iu ligi nea, which are resistant to benzimidazole fungicides (eg, thiophanate mel, benomyl, carbendazim), and ergosterol biosynthesis inhibiting fungicides (eg, For example, the compounds of the present invention can be used against the fungus powdery mildew (Sha er 0t_t_he c_a fu 1 igi n_e a), which has reduced susceptibility to triadimefon and triflumizol, as well as the susceptible bacteria of these bacteria. It is valid.

 The compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater objects such as ship bottoms and fishing nets.

When the thus-obtained compound of the present invention is actually applied, no other component is added. It can be used in pure form or in the form of general pesticides for pesticide use, i.e., in the form of wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, etc. it can. When a solid agent is used as an additive or carrier, it is possible to use soy flour, wheat flour and other vegetable powders, diatomaceous earth, limestone, gypsum, talc, pyrophyllite, clay, mineral oil, vegetable oil, etc. Mineral fine powder is used. For liquid dosage forms, use kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, mineral oil, vegetable oil, τΚ, etc. Used as a solvent. Surfactants can be added, if necessary, to obtain a uniform and stable form in these preparations. The wettable powders, emulsions and suspensions thus obtained are diluted with water to a predetermined concentration and used as suspensions or emulsions. .

 Next, some examples of the composition of the present invention will be described. However, the additives and the addition ratio should not be limited to these examples, but can be varied over a wide range. Parts in Formulation Examples are parts by weight.

Example 2 7 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. Example 28 Emulsion

 Compound of the present invention (3 parts)

 Xylene 4 5 parts

 Dimethylformamide 4 5 parts

 Polyoxyethylene alkylaryl ether 7 parts

By mixing and dissolving the above, an emulsion containing 3% of the active ingredient is obtained. Example 2 9 Dust

 Compound of the present invention 10 parts

 Talc 8 9 parts

 1 part of polyoxyethylene alkylaryl ether

 If the above are uniformly mixed and finely pulverized, a powder containing 10% of the active ingredient is obtained. Example 30 Granules

 5 parts of the compound of the present invention

 Clay 7 3 parts

 Bentonite 20 parts

 Dioctyl sulfosuccinate sodium salt 1 part

 1 part sodium phosphate

 The above is well ground and mixed, water is added and the mixture is kneaded well.

 Example 3 1 Suspension

 Compound of the present invention 10 parts

 Sodium Ridanine Sulfonate 4 parts

 Sodium dodecylbenzenesulfonate 1 part

 Xanthan gum 0.2 parts

 Water 84.8 parts

 The above mixture is mixed and wet-milled until the knee is less than 1 micron to obtain a 10% active ingredient suspension.

 It goes without saying that the compound of the present invention is sufficiently effective alone, but it is one or two of various fungicides and insecticides and acaricides against inadequate or weak diseases or harmful insects and mites. It can be used in combination with the above.

 Representative examples of fungicides, insecticides, acaricides, and plant growth regulators that can be used by mixing with the compound of the present invention are shown below.

〔Fungicide〕 Kyabtan, Format, Thiuram, Zineb, Maneb, Mancozeb, Provineb, Polycarbamate, Chlorothalonil, Kind Isen, Captahor, Hyperprodion, Procymidone, Vinclozolin, Fluoromid, Thymoxanil, Mepronil, Flutronyl, Flutranil Oxycarboxine, fosetyl aluminum, propamocarb, triadimefon, triadimenol, propiconazole, diclobutrazole, bitertanol, hexaconazole, microbutanyl, flusilazol, etaconazole, fluotrimazole, flutrifen, penconazole, diniconazo , Cyproconazole, fenarimol, triflumizole, prochloraz, imazalil, perfrazoe , Tridemolf, phenpropimorph, trifolin, pyrifenox, anilazine, polyoxin, metalaxyl, oxadixyl, furalaxyl, isoprothiolane, probenazole, pyrrolnitrin, blasticidin S, kasugamycin, validamycin, and dihydromycin dihydrostomycin sulfate Benomyl, carbendazim, thiophanate methyl, himexazole, basic copper chloride; basic copper sulfate, fentin acetate, triphenyltin hydroxide, dietofencarp, metasulfocarb, quinomethionate, pinapacryl, lecithin, baking soda, dithianon, Zinocap, phenaminosulf, diclomedine, guazatine, dozine, IBP, edifenfoss, mepanipyrim, furimzone, triclami , Metasulfocarp ', Fluazinam, Etoquinolac, Dimethomorph, Pyroquilon, Tekuguchi Phtharam, Fusalide.

 (Insecticides and acaricides)

Chlorbenzylate, chlorpropylate, proclonol, phenylisobromolate, dichophor, dinobutone, chlorphenamide, amitraz, BPPS, PPPS, benzomate, hexthiazox, fenbutatin oxide, polynacin, thioquinox, CPCBS, tetraxion, tetraxion Avermectin, lime polysulfide, cloventine, fluvensmin, flufenoxuron, BCPE, sihexatin, pyridaben, fenpyroximate, pentione, Phuenitrothion, Diazinon, Chlorpyrifos, ESP, Bamidothion, Fenthet, Dimethate, Formothion, Malathion, Dipterex, Thiometon, Hosmet, Menazon, Dichlorvos, Acephate, EPBP, Giarihoresole, Lathion, Oxidime Tonmetinore, Etion, Pyraclofos', Monocrotophos, Mezomil Monocrotophos, Aldicarb, Proboxir, B PMC, MTMC, Nack, Cartap, Carbosulfan, Benfracalp, Pirimicarb, Etioffenkarp, Phenoxycarp, permethrin, cypermethrin, decamethrin, fenvalerate, fenpropasulin, pyrethrin, allesulin, tetramethrin, resmethrin, dimethrin, propasulin, bifenthrin, prothrin, funolev'linate, cyfluthrin, cyhalosulin, fluprolinate, cycloproxine, etoprofen Trin, Tiger Mouth Lin, Silaneophan, Difluvenzuron, Chlorfluazin, Triflumuron, Teff Rubenslon, Buprofezin, Machine oil.

 (Plant growth regulator)

Gibberellins (eg Gibberellin A ₃ , Gibberellin A ₄ , Gibberellin A ₇ ) I AA, NAA.

Availability of industrial companies:

 Next, Test Examples show that the compound of the present invention is useful as a crane component of various plant disease controlling agents. The control effect was evaluated by visually observing the diseased state of the test plant at the time of the survey, i.e., the appearance of the lesions on the leaves, stems, etc. Compared to untreated plots, 4% if recognized about 10%, 25%; 3J if recognized; 2% if about 50% recognized; 1J if 75% recognized, If there is no difference from the state, it is set to “0” and the efficiency is evaluated in six stages from 0 to 5, and is indicated by 0, 1, 2, 3, 4, and 5.

Test Example 1 Wheat powdery mildew control test (prevention test)

After spraying a predetermined concentration of a wettable powder of the compound of the present invention on wheat seedlings (cultivar “Norin 61 J 1.0-L. 2 leaf stage”) grown in unglazed pots and air-drying the leaves , Wheat The conidiospores of the powdery mildew fungus (Erysiphegraminisf.sp.tritici) were shaken off and inoculated, grown for 7 days in a greenhouse at 2225 ° C, and the control effect was investigated. Table 4 shows the results.

 Four

* 1: sulfur, sulfur hydrate 5% wettable powder Test Example 2 Test for Control of Powdery Mildew

 After spraying a sufficient amount of a solution of the compound of the present invention with a predetermined concentration of a wettable powder of a compound of the present invention on a cucumber seedling (variety “Sagamihanjiro”) cultivated in a greenhouse for about 3 weeks and air-drying, Sphae ro the _5_ fu 1 igi ne a, a conidia of a drug-sensitive bacterium, a T¾M-sensitive bacterium and a bacterium with reduced susceptibility to a bactericide that inhibits ergostate biosynthesis; The suspension was spray-inoculated, placed in a constant temperature room at 23 to 25, and examined for disease status 10 days after the inoculation of the bacteria, and the results are shown in Table 5.

 Table 5 Concentration of active ingredient control effect

 Compound Number-Takaguchi

 (p pm) Drug-sensitive bacteria Sensitivity-reducing bacteria

1-1 200 4 4 None

 -2 〃 5 5

 -3 5 5 〃

 -4 5-5

 One 8 5 5

 -20 5 5

 -22 〃 5 5

 -25 4 4

 One 26 〃 5 5

 1-5 5 5

 One 6 ff 4 4

 -8 〃 5 5 〃

 -22 4 4

-24 〃 4 4 (Continued)

 * 1: sulfur, 75% wettable powder

 * 2: Triadimefon 25% wettable powder Test example 3 Grape downy mildew control test

Leaves of open-grown grapes (variety "Kaiji", 3rd grade) cut out and punched into a 3 Omm-diameter disc are exposed to a chemical solution of a predetermined concentration of a wettable powder of the compound of the present invention. A suspension of zoospores of (P la sipop araviticola) was sprayed and inoculated, kept in a humidified room at 20 ° C under illumination, and the disease status was examined 10 days after the inoculation. Table 6 shows the results. Table 6

 * 3 Manzeb 75% wettable powder Test example 4 Apple scab control test (prevention test)

After spraying a predetermined concentration of a wettable powder of the compound of the present invention and air-drying it onto apple seedlings (variety “Kunimitsu”, 3-4 leaf stage) cultivated in unglazed pots, apple scab (Ve_nt_u riai) nae qua 1 is) and inoculated in a room at 20 ° C under high light for 2 weeks under light (bright and dark), and the control effect was investigated. Table ⁷ shows the results.

 Table 7

 * 4 Kyabtan 80% 7jc

Claims

1. General formula [I] [I]  Contract

 of (In the formula, m is an integer of 1 to 4, R ¹ is the same or different and is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a lower A haloalkyl group, a lower alkoxycarbonyl group, a nitro group, a rubamoyl group which may be mono- or di-substituted with a lower alkyl or a halogen atom, X is C = Z (Z is an oxygen atom, CH (0H), Cr r ^{2 1} ) and r ² are the same or different and each represents a cyano group, an alkoxycarbonyl group, or a carbamoyl group which may be mono- or di-substituted by lower alkyl. ), Nr ³ (r ³ represents a lower alkyl group, a substituted or unsubstituted phenyl group, a lower alkoxy group, a lower alkylamino group, a hydroxy group, a substituted or unsubstituted phenylamino group or a lower alkoxycarbonylamino group. )] CH (0H), represents CH _2, Y is ^{N, C (R 4) (} R, represents represents.) a hydrogen atom, a lower Arukokishikaru Boniru group, R ² represents a hydrogen atom, S (0 ) »R ⁵ (r ⁵ is a lower alkyl group which may be substituted, n represents 0, 1 or 2), a lower alkoxy group, a lower alkylsulfonylamino group, a phenylsulfonyl which may be substituted R ³ represents a hydrogen atom, a lower alkoxy group, an amino group, a cyano group, a halogen atom, a hydroxy group, a morpholino group, or an amino group optionally substituted with a phenylalkyl or a lower alkyl which may be substituted; , Low al A cycloalkyl group, a benzoyl group which may be substituted, a phenyl group which may be substituted, a pyridylcarbonyl group which may be substituted, a lower alkoxyalkyl group, a lower alkylthio group which may be substituted. 5 to 6 containing 1 to 2 phenyl groups, optionally substituted N, S, 0 Membered heterocyclic group, an alkyl group substituted with an optionally substituted phenyl, an alkyl group substituted with an optionally substituted phenyl, an alkyl group substituted with an optionally substituted pyridyl, or cyano, An alkyl group substituted with a 5- to 5-membered hetero ring containing 1 to 2 nitro, N, S, 0, an optionally substituted phenyl, an amino group optionally substituted with a lower alkoxy or a lower alkyl. Represent. ] The compound represented by these, and its salt.  2. Formula [IV] ]

Wherein R ¹ and Hi represent the same meaning as described above, and R ⁵ represents a lower alkyl group, a cycloalkyl group, a lower alkoxyalkyl group, an optionally substituted phenyl group, an optionally substituted N, S, 0 5- or 6-membered heterocyclic group containing 1 or 2 (but bonded by carbon atom), substituted or unsubstituted phenyl-substituted alkyl group, substituted with phenyl which may be substituted Represents an alkyl group or an alkyl group substituted with an optionally substituted pyridyl. Wherein the compound represented by the formula (1) is characterized in that the compound is ring-closed in the presence of an ammonium salt.

[Wherein R ¹ , m and R ⁵ represent the same meaning as described above. ] The manufacturing method of the compound represented by these. 3. Formula [H] [H]

[Wherein, R ¹ , m, and R have the same meanings as described above. And a compound represented by the formula [Cor]  6  NH R ⁸ — Master C NH ₂ Wherein R ⁸ is a hydrogen atom, a lower alkoxy group, a lower alkyl group, a cycloalkyl group, a lower alkoxyalkyl group, a lower alkylthio group, an optionally substituted phenyl group, an optionally substituted N, S, A 5- or 6-membered heterocyclic group containing 1 or 2 0, an optionally substituted phenyl-substituted alkyl group, an optionally substituted phenyl-substituted alkyl group, an optionally substituted An alkyl group substituted with a good pyridyl, or an alkyl substituted with a 5- to 6-membered heterocyclic ring containing 1 to 2 cyano, nitro, N, S, 0, optionally substituted phenyl, lower alkoxy or Represents an amino group which may be substituted by lower alkyl. Formula Π '— 7] characterized by reacting a compound represented by the formula CI '-1 7)

[Wherein, R ¹ , m and R ⁸ represent the same meaning as described above. ] The manufacturing method of the compound represented by these. 67  62 4. Formula [XI]

[Wherein, R ¹ , m and R ⁸ represent the same meaning as described above. Formula [脱水 -10], which is obtained by dehydrating and condensing a compound represented by the formula (1'-1 10)

[Wherein, R ¹ , m and R ⁸ represent the same meaning as described above. ] The manufacturing method of the compound represented by these. Five. ,  Two (R ¹ ) m '(I  γ  Ί (Wherein, X, Y, R ¹ , R ² , R ³ , and m have the same meanings as described above) and one or more of the salts thereof. Agricultural and horticultural fungicides.