JP2007161621A - Nitrogen-containing heterocyclic compound and agricultural/horticultural fungicide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new nitrogen-containing heterocyclic compound and salts of the same, synthesized with industrial advantage and able to be an agricultural/horticultural fungicide having certain effects and safely used, and provide an agricultural/horticultural fungicide containing the same as an effective ingredient. <P>SOLUTION: The nitrogen-containing heterocyclic compound expressed by formula (1) [wherein R<SP>1</SP>expresses a 1-6C alkoxy or the like; R<SP>2</SP>expresses a halogen atom or the like; m expresses 0-4 integer; R<SP>3</SP>to R<SP>6</SP>express each H or the like; A expresses either one of (A1) to (A3) (wherein R<SP>a</SP>to R<SP>g</SP>express each H or the like): Q expresses a heterocyclic group which may have substituents] or salts of the same and the agricultural/horticultural fungicide containing at least one species of the same as an effective component are provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel nitrogen-containing heterocyclic compound or a salt thereof, and an agricultural and horticultural fungicide containing one or more of these compounds as active ingredients.

In the cultivation of agricultural and horticultural crops, many control agents are used against crop diseases, but their control efficacy is insufficient, their use is restricted by the emergence of drug-resistant pathogens, and From the viewpoints of causing phytotoxicity and pollution to plants, or toxicity to human and livestock fish and impact on the environment, there are many things that are not necessarily satisfactory control agents.
Accordingly, there is a strong demand for the emergence of such a drug that can be safely used with few defects.

  In relation to the present invention, Patent Document 1 discloses that a phenoxyphenylhydrazine derivative, which is a compound similar to the compound of the present invention, has bactericidal and insecticidal activities.

International Publication No. 05/005376 Pamphlet

  The present invention provides a novel nitrogen-containing heterocyclic compound or a salt thereof that can be synthesized industrially advantageously, can be used safely and safely, and can be used safely, and one or more of these compounds. It is an object to provide an agricultural and horticultural fungicide contained as an active ingredient.

As a result of intensive studies to solve the above problems, the inventors of the present invention can synthesize a nitrogen-containing heterocyclic compound represented by the following formula (1) or a salt thereof industrially advantageously, and can be used safely and reliably. The inventors have found that it can be an active ingredient of agricultural and horticultural fungicides, and have completed the present invention.
Thus, according to the first of the present invention, the formula (1)

{In the formula, R ¹ represents a C _1-6 alkyl group or a C _1-6 alkoxy group, R ² represents a halogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, and m represents 0 to Represents an integer of 4. When m is 2 or more, R ² may be the same or different.
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a C _1-6 alkyl group. ^{Further, -C (R 3) (R} 4) -, or ^{-C (R 5) (R 6} ) - is, -C (= O) - and may form.
A represents any group represented by the following (A1) to (A3).

(In the formula, R ^a , R ^b , R ^c , R ^d , R ^e , R ^f and R ^g each independently represent a hydrogen atom or a C _1-6 alkyl group.)
Q represents a heterocyclic group which may have a substituent when A is (A1), or any group represented by the following (Q1) and (Q2), and A represents (A2) or ( In the case of A3), it represents a heterocyclic group which may have a substituent.

[In the formula, R ^h represents a hydrogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, or a group represented by the formula: Si (R ^j ) (R ^k ) (R ^l )] R ^j , R ^k , and R ^l each independently represent a C _1-6 alkyl group or a phenyl group that may have a substituent.
R ⁱ may be substituted with a hydrogen atom, a C _1-6 alkyl group, a C _3-8 cycloalkyl group, a C _3-8 cycloalkyl C _1-6 alkyl group, a C _1-6 haloalkyl group, or G 1. Represents a good phenyl group. G1 represents a halogen atom, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _1-6 haloalkyl group, a C _1-6 haloalkoxy group, or a hydroxyl group. G1 may be the same or different and may be substituted by a plurality, or a plurality of G1 may be bonded to form a ring.

D represents a hydrogen atom, a C _1-12 alkyl group, a C _3-8 cycloalkyl group, a C _3-8 cycloalkyl C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-10 alkynyl group, optionally substituted by G2 (C _7-20 aralkyl group, pyridyl C _1-6 alkyl group, piperidyl C _1-6 alkyl group, tetrahydropyranyl C _1-6 alkyl group, tetrahydrofuryl C _1-6 alkyl group, benzoyl group, C _7-20 aralkylcarbonyl group), C _1-6 alkylcarbonyl group, C _3-8 cycloalkylcarbonyl group, or C _3-8 cycloalkylcarbonyl C _1-6 alkyl group Represents. G2 represents a halogen atom, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _1-6 haloalkyl group, a C _1-6 haloalkoxy group, or a hydroxyl group. A plurality of G2 may be the same or different and may be substituted, or a plurality of G2 may be bonded to form a ring. ]}
The nitrogen-containing heterocyclic compound shown by these, or its salt is provided.

  In the nitrogen-containing heterocyclic compound or a salt thereof of the present invention, in the formula (1), Q contains at least one heteroatom selected from an oxygen atom, a nitrogen atom and a sulfur atom. , Preferably a heterocyclic group which may have a substituent, and in the formula (1), Q is (Q3)

[Wherein, R ^m represents a hydrogen atom, a C _1-6 alkyl group, or an optionally substituted G3 (phenyl group or C _7-20 aralkyl group), G 3 represents a halogen atom, C _{1- A 6} alkyl group, a C _1-6 alkoxy group, or a C _1-6 haloalkyl group; G3 may be the same or different and a plurality of G3 may be substituted, or a plurality of G3 may be bonded to form a ring. R ⁿ represents a hydrogen atom or a C _1-6 alkyl group. It is more preferable that it is a group represented by

  Secondly, the present invention provides an agricultural and horticultural fungicide containing one or more of the nitrogen-containing heterocyclic compound represented by the formula (1) or a salt thereof as an active ingredient.

The nitrogen-containing heterocyclic compound and its salt of the present invention are novel compounds, have excellent bactericidal activity, and are useful as active ingredients of agricultural and horticultural fungicides.
The agricultural and horticultural fungicide of the present invention is an agent that has an excellent control effect, does not cause phytotoxicity or contamination on the plant body, and has little toxicity to human fish and environmental impact.

Hereinafter, the present invention will be described in detail.
1) Nitrogen-containing heterocyclic compound (1) Nitrogen-containing heterocyclic compound The nitrogen-containing heterocyclic compound of the present invention is a compound represented by the formula (1).
In the formula (1), R ¹ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n- _{C 1-6} alkyl groups such as hexyl group; a; or a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, sec- butoxy group, isobutoxy group, _{C 1-6} alkoxy group such as t- butoxy To express.
R ² represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; or a C _1-6 alkyl group or a C _1-6 alkoxy group similar to those exemplified for R ¹ above.
m represents an integer of 0 to 4. When m is 2 or more, R ² may be the same or different.

R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a C _1-6 alkyl group similar to those exemplified for R ¹ . R ³ and R ⁴ , or R ⁵ and R ⁶ are combined to form —C (R ³ ) (R ⁴ ) —, or —C (R ⁵ ) (R ⁶ ) —, which is —C (= O)-may be formed.

A represents any group represented by the above (A1) to (A3).
In the (A1) to (A3), R ^{a to} R ^g each independently represent a hydrogen atom or a C _1-6 alkyl group similar to those exemplified for the R ¹ .

  Q represents a heterocyclic group which may have a substituent when A is (A1), or any group represented by the above (Q1) or (Q2), and A represents (A2) or ( In the case of A3), it represents a heterocyclic group which may have a substituent.

  Examples of the heterocyclic group that may have a substituent of Q include a 3- to 8-membered saturated or unsaturated heterocyclic group, and include an oxygen atom, a nitrogen atom, and a sulfur atom. A 5-membered or 6-membered heterocyclic group containing at least one heteroatom selected from is preferable.

  Specific examples of the 5-membered or 6-membered heterocyclic group containing at least one heteroatom selected from an oxygen atom, a nitrogen atom and a sulfur atom include 5-membered saturated heterocyclic rings such as tetrahydrofuran-2-yl group Group: 6-membered saturated heterocyclic group such as morpholin-2-yl group; 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, pyrazol-3-yl group, pyrazole-4- Yl group, imidazol-2-yl group, imidazol-4-yl group, oxazol-2-yl group, oxazol-4-yl group, oxazol-5-yl group, isoxazol-3-yl group, isoxazol-4 -Yl group, isoxazol-5-yl group, thiazol-2-yl group, thiazol-4-yl group, thiazol-5-yl group, isothiazol-3-yl group, isothiazol 4-yl group, isothiazol-5-yl group, 1,2,4-oxadiazol-3-yl group, 1,2,4-oxadiazol-5-yl group, 1,2,5-oxa Diazol-3-yl group, 1,3,4-oxadiazol-2-yl group, 1,2,4-thiadiazol-3-yl group, 1,2,4-thiadiazol-5-yl group, 1 , 2,5-thiadiazol-3-yl group, 1,3,4-thiadiazol-2-yl group and the like 5-membered unsaturated heterocyclic group; 2-pyridyl group, 3-pyridyl group, 4-pyridyl group , 5-pyridyl group, pyrimidin-2-yl group, pyrimidin-4-yl group, pyrazin-2-yl group, pyran-2-yl group and the like 6-membered unsaturated heterocyclic group; and the like.

The substituent of the heterocyclic group of Q is not particularly limited. For example, halogen atoms such as fluorine atom, chlorine atom and bromine atom; C ₁ such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group and t-butyl group _-6 alkyl group; C _1-6 alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butbutoxy group, isobutoxy group, t-butoxy group; chloromethoxy group, trifluoromethoxy group C _1-6 haloalkoxy group such as cyano; a cyano C _1-6 alkoxy group such as cyanomethoxy group, 2-cyanoethoxy group; methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutyl thio, sec- butylthio group, _{C 1-6} alkylthio group such as t- butylthio group; Mechirusuruhoni Group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl C _1-6 alkylsulfonyl group such as a group; chloromethyl group, fluoromethyl group, C _1-6 haloalkyl group such as trifluoromethyl group; a methoxycarbonyl group, ethoxycarbonyl C _1-6 alkoxycarbonyloxy groups such as carbonyloxy group, propoxycarbonyloxy group, isopropoxycarbonyloxy group, butoxycarbonyloxy group, t-butoxycarbonyloxy group; acetoxy group, propionyloxy group, propylcarbonyloxy group, butyl C _1-6 alkylcarbonyloxy group such as a carbonyl group; methylsulfonyloxy group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl C _1-6 alkylsulfonyl such group Alkoxy group; a methoxycarbonyl methoxy group, an ethoxy carbonyl methoxy group, propoxycarbonyl methoxy, isopropoxycarbonyl methoxy group, butoxycarbonyl methoxy group, C _1-6 alkoxycarbonyl C _1-6 alkoxy group such as t- butoxycarbonyl methoxy group; Carbamoyloxy group; mono-C _1-6 alkylcarbamoyloxy group such as N-methylcarbamoyloxy group; di-C _1-6 alkylcarbamoyloxy group such as N, N-dimethylcarbamoyloxy group; amino group; monomethylamino group, etc. Mono-C _1-6 alkylamino group; di-C _1-6 alkylamino group such as dimethylamino group; cyano group; nitro group; and optionally substituted (phenyl group, phenoxy group, aralkyloxy group, Heteroyloxy group, aryl Carbonyloxy group) and the like.

Examples of the aralkyloxy group of the aralkyloxy group which may have a substituent include benzyloxy group, 1-phenylethoxy group, 2-phenylethoxy group, 1-phenyl-1-methylethoxy group, and 1-phenylpropoxy group. Group, 2-phenylpropoxy group, 3-phenylpropoxy group and the like.
Examples of the heteroyloxy group of the heteroyloxy group that may have a substituent include a 2-pyridyloxy group, a 3-pyridyloxy group, a 4-pyridyloxy group, and a 5-pyridyloxy group.
Examples of the arylcarbonyloxy group of the arylcarbonyloxy group which may have a substituent include a benzoyloxy group, a 1-naphthylcarbonyloxy group, and a 2-naphtholcarbonyloxy group.

  In addition, examples of the substituent such as the above-described substituent (phenyl group, phenoxy group, aralkyloxy group, heteroyloxy group, arylcarbonyloxy group) include alkyl groups such as methyl group and ethyl group; A halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; A plurality of substituents may be the same or different and may be substituted with a phenyl group or the like, or a plurality of substituents may be combined to form a ring.

In the (Q1), R ^h is a hydrogen atom; the same C _1-6 alkyl group as exemplified for the R ¹ ; a vinyl group, a 1-propenyl group, a 2-propenyl group, a butenyl group, a pentenyl group, etc. C _2-6 alkenyl group; a group represented by the formula: Si (R ^j ) (R ^k ) (R ^l ), such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, triphenylsilyl group (in the formula, , R ^j , R ^k and R ^l each independently represents a C _1-6 alkyl group or a phenyl group which may have a substituent.

In (Q2), R ⁱ represents a hydrogen atom; a C _1-6 alkyl group similar to that exemplified for R ¹ ; a C _3-8 cycloalkyl group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group; C _3-8 cycloalkyl C _1-6 alkyl group such as propylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group; chloromethyl group, fluoromethyl group, bromomethyl group, dichloromethyl group, difluoromethyl group, dibromomethyl group, trichloro A C _1-6 haloalkyl group such as a methyl group, a trifluoromethyl group, a tribromomethyl group, a trichloroethyl group, a trifluoroethyl group, a pentafluoroethyl group; or a phenyl group optionally substituted by G1.

G1 is a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom; similar to that exemplified in the R 1, C 1-6 alkyl or C 1-6 alkoxy groups; exemplified by the R i A C 1-6 haloalkyl group as defined above; C 1-6 haloalkoxy groups such as chloromethoxy group, dichloromethoxy group, trichloromethoxy group, trifluoromethoxy group, 1-fluoroethoxy group, 1,1-difluoroethoxy group Represents a hydroxyl group.
A plurality of G1 may be the same or different and may be substituted with a phenyl group, or a plurality of G1 may be bonded to form, for example, a condensed ring such as a coumaran ring or a chroman ring as a whole.

D is a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-hexyl group, n-heptyl group, etc. A C _1-12 alkyl group; a C _3-8 cycloalkyl group or a C _3-8 cycloalkyl C _1-6 alkyl group similar to that exemplified for R ⁱ ; a C similar to that exemplified for R ^h above; _2-6 alkenyl group; 1-chlorovinyl group, 2-fluorovinyl group, 1-bromovinyl group, 1,2-dichlorovinyl group, 1,2-difluorovinyl group, 2,2-dibromovinyl group, perchlorovinyl group, perfluorovinyl group, perbromooctyl vinyl group, _{perchloro-1-C 2-6} haloalkenyl group such as a propenyl group; ethynyl, 2-propynyl group, 2-butynyl group, 4-pentynyl Pyridyl _{C 1-6} alkyl group such as 2-pyridylmethyl group;; _{C 7-20} aralkyl group such as optionally substituted with G2 (benzyl; _{C 2-10} alkynyl group such 2-piperidyl methyl group 2-tetrahydrofuryl tetrahydrofuryl C _1-6 alkyl group such as a methyl group; a benzoyl group; benzylcarbonyl 2-tetrahydropyranyl tetrahydropyranyl C _1-6 alkyl group such as a methyl group, piperidyl C _1-6 alkyl group C _7-20 aralkylcarbonyl group such as a group; C _1-6 alkylcarbonyl group such as acetyl group, propionyl group, butyryl group, isobutyryl group; C _3-8 cycloalkylcarbonyl group such as cyclohexylcarbonyl group; 1 -(Cyclohexylcarbonyl) ethyl group, 2- (cyclohexylcarbonyl) ethyl group, etc. It represents a; _3-8 cycloalkylcarbonyl _{C 1-6} alkyl group.

G2 represents a halogen atom, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _1-6 haloalkyl group, a C _1-6 haloalkoxy group, or a hydroxyl group, similar to G1. A plurality of G2 may be the same or different and may be substituted with a phenyl group or the like, and a plurality of G2 may be bonded to form, for example, a condensed ring such as a coumaran ring or a chroman ring as a whole. .

  Among these, Q is a 5- or 6-membered heterocyclic group optionally having a substituent containing at least one heteroatom selected from an oxygen atom, a nitrogen atom and a sulfur atom. It is more preferably a 5-membered or 6-membered unsaturated heterocyclic group which may have a substituent, and a group represented by the following (Q3) is particularly preferable.

In formula (Q3), R ^m represents a hydrogen atom; a C _1-6 alkyl group similar to that exemplified for R ¹ above; a phenyl optionally substituted with G3 such as a phenyl group or a 4-fluorophenyl group; A C _7-20 aralkyl group _optionally substituted with G3, such as a benzyl group, a 2-fluorobenzyl group, a 2-chloro-6-fluorobenzyl group;

G3 represents the same halogen atom, C _1-6 alkyl group, C _1-6 alkoxy group, or C _1-6 haloalkyl group as exemplified in G1. G3 may be the same or different and may be substituted by a plurality, or a plurality of G3 may be bonded to form a ring.
R ⁿ represents a hydrogen atom; a C _1-6 alkyl group similar to that exemplified for R ¹ above.

(2) Method for producing nitrogen-containing heterocyclic compound The nitrogen-containing heterocyclic compound represented by the formula (1) of the present invention (hereinafter sometimes referred to as “the present compound”) is produced, for example, by the following method. can do. However, the manufacturing method of this invention compound is not limited to the method shown below.

(Manufacturing method 1)
Among the compounds of the present invention, a compound represented by the following formula (1-1) can be produced according to the following reaction formula.

(In the formula, R ^{1 to} R ⁶ , R ^m , R ⁿ , A and m represent the same meaning as described above. L represents a leaving group such as a halogen atom.)
That is, a compound represented by the formula (I) (hereinafter referred to as “compound (I)”) and a compound represented by the formula (II) (hereinafter referred to as “compound (II)”) are optionally mixed with a base. By reacting in the presence, the compound represented by the formula (1-1) can be produced.

  The usage-amount of compound (II) is 0.5-5 times mole normally with respect to compound (I), Preferably it is 0.7-2 times mole.

  Examples of the base used include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; pyridine, triethylamine, N, N-dimethylaniline, 4-dimethylaminopyridine, N -Organic bases such as methylpyrrolidine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU);

  When using a base, the usage-amount of a base is 1-10 times mole normally with respect to compound (I), Preferably it is 1-3 times mole.

This reaction can be performed in the presence or absence of a solvent.
The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene, xylene; dichloromethane, 1,2-dichloroethane, chloroform, tetrachloride Halogen solvents such as carbon; alcohols such as methanol and ethanol; nitrile solvents such as acetonitrile and propionitrile; ether solvents such as diethyl ether, dioxane and tetrahydrofuran (THF); N, N-dimethylformamide (DMF) Amide solvents such as N, N-dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; water; and mixed solvents in which two or more of these solvents are mixed;

  The reaction temperature is usually in the temperature range of −78 ° C. to + 200 ° C., preferably −20 ° C. to + 100 ° C. The reaction time varies depending on conditions such as the amount of reaction reagent, temperature, etc., but is in the range of 30 minutes to 100 hours.

(Production of Compound (I))
Compound (I), which is a raw material for producing compound (1-1), can be produced according to the following reaction formula.

^{(Wherein, .R 9 R 1 ~R 6,} A and m represent the same meaning as above, represents a _{C 1-6} alkyl group such as a methyl group, an ethyl group.)
That is, a compound represented by formula (III) (hereinafter referred to as “compound (III)”) and hydrogen sulfide or a thioalkylamide represented by formula (IV) (hereinafter referred to as “compound (IV)”), If desired, compound (I) can be produced by reacting in the presence of a base or acid.

When hydrogen sulfide is used, the amount of hydrogen sulfide used is usually 1 to 100 times mol, preferably 10 to 20 times mol, of compound (III).
When using compound (IV), the usage-amount of compound (IV) is 1-5 times mole normally with respect to compound (III), Preferably it is 1-3 times mole.

Examples of the base used include organic bases such as triethylamine, pyridine, N, N-dimethylaniline, 4-dimethylaminopyridine, N-methylpyrrolidine, N-methylmorpholine and DBU.
When using a base, the usage-amount of a base is 1-100 times mole normally with respect to compound (III), Preferably it is 1-20 times mole.

Examples of the acid used include organic acids such as formic acid and acetic acid; inorganic acids such as hydrochloric acid (hydrogen chloride) and hydrobromic acid; and the like.
When using an acid, the usage-amount of an acid is 1-100 times mole normally with respect to compound (III), Preferably it is 1-10 times mole.

This reaction can be performed in the presence or absence of a solvent.
The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene, xylene; dichloromethane, 1,2-dichloroethane, chloroform, tetrachloride Halogen solvents such as carbon; ether solvents such as diethyl ether, dioxane and THF; amide solvents such as DMF and N, N-dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; water; and these solvents A mixed solvent composed of two or more of the following.

The reaction temperature is usually in the temperature range of 0 ° C to 200 ° C, preferably 0 ° C to 100 ° C.
The reaction time varies depending on conditions such as the amount of reaction reagent, temperature, etc., but is in the range of 30 minutes to 100 hours.

(Production of Compound (III))
Compound (III), which is a raw material for producing compound (I), can be produced according to the following reaction formula.

(In the formula, R ^{1 to} R ⁶ , A and m represent the same meaning as described above. L ′ represents a leaving group such as a halogen atom.)
That is, a compound represented by the formula (V) (hereinafter referred to as “compound (V)”) and a compound represented by the formula (VI) (hereinafter referred to as “compound (VI)”) are optionally added in the presence of a base. Compound (III) can be produced by reacting with.

  The usage-amount of compound (VI) is 1-5 times mole normally with respect to compound (V), Preferably it is 1-2 times mole.

Examples of the base used include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride; triethylamine, pyridine, N, N-dimethylaniline, 4- And organic bases such as dimethylaminopyridine, N-methylpyrrolidine, N-methylmorpholine, DBU, and the like.
When using a base, the usage-amount of a base is 1-10 times mole normally with respect to compound (V), Preferably it is 1-5 times mole.

This reaction can be performed in the presence or absence of a solvent.
The solvent to be used is not particularly limited as long as it is an inert solvent for the reaction, and specific examples thereof include the same solvents as listed in the method for producing compound (I).

The reaction temperature is usually in the temperature range of −78 ° C. to + 200 ° C., preferably −20 ° C. to + 100 ° C.
The reaction time is usually 30 minutes to 100 hours, although it varies depending on conditions such as the amount of reaction reagent and temperature.

(Manufacturing method 2)
Among the compounds of the present invention, the compound represented by the formula (1-2) can be produced according to the following reaction formula.

^(Wherein, R 1 ^{to R} 6, A and m are .R ^o represent the same meaning as above, the same meanings as defined above ^{R m.)}
A compound represented by the formula (1-2) can be produced by ring-closing a compound represented by the formula (VII) (hereinafter referred to as “compound (VII)”) in the presence of a base or an acid, if desired. it can.

Examples of the base used include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; triethylamine, pyridine, N, N-dimethylaniline, 4-dimethylaminopyridine, N -Organic bases such as methylpyrrolidine, N-methylmorpholine, DBU;
When a base is used, the amount of the base to be used is generally 0.01 to 10-fold mol, preferably 0.1 to 3-fold mol based on compound (VII).

Examples of the acid used include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as trifluoroacetic acid and p-toluenesulfonic acid; and the like.
When using an acid, the usage-amount of an acid is 0.01-10 times mole normally with respect to compound (VII), Preferably it is 0.1-3 times mole.

This reaction can be performed in the presence or absence of a solvent.
The solvent to be used is not particularly limited as long as it is an inert solvent for the reaction, and examples thereof include those listed as the solvents used in Production Method 1.

  The reaction temperature is −78 ° C. to + 200 ° C., preferably −20 ° C. to + 100 ° C. The reaction time varies depending on conditions such as the amount of reaction reagent and temperature, but is usually in the range of 30 minutes to 100 hours.

(Production of Compound (VII))
Compound (VII), which is a raw material for producing compound (1-2), can be produced according to the following reaction formula.

(In the formula, R ^{1 to} R ⁶ , R ^o , A and m represent the same meaning as described above. X represents a leaving group such as a hydroxyl group or a halogen atom.)
A compound represented by formula (VIII) (hereinafter referred to as “compound (VIII)”) and a compound represented by formula (IX) (hereinafter referred to as “compound (IX)”) are optionally present in the presence of a base or a dehydrating agent. Compound (VII) can be manufactured by making it react below.

  The amount of compound (IX) to be used is generally 1 to 5 mol, preferably 1 to 2 mol per mol of compound (VIII).

Examples of the base used include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; triethylamine, pyridine, N, N-dimethylaniline, 4-dimethylaminopyridine, N -Organic bases such as methylpyrrolidine, N-methylmorpholine, DBU;
When a base is used, the amount of the base to be used is generally 1 to 10 times mol, preferably 1 to 3 times mol, of compound (VIII).

  Examples of the dehydrating agent to be used include carbodiimides such as N, N-dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride. As a reaction method using a dehydrating agent, the Mitsunobu reaction method (see, for example, J. Chem. Soc., Perkin Trans I., 1708 (1976)) can also be employed.

This reaction can be performed in the presence or absence of a solvent.
Solvents that can be used are not particularly limited as long as they are inert to the reaction. For example, hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene, xylene; dichloromethane, chloroform, carbon tetrachloride, 1, 2 -Halogen solvents such as dichloroethane; nitrile solvents such as acetonitrile and propionitrile; ether solvents such as diethyl ether, dioxane and THF; amide solvents such as DMF and N, N-dimethylacetamide; dimethyl sulfoxide and the like And a mixed solvent composed of two or more of these solvents.

  The reaction temperature is usually in the temperature range of −78 ° C. to + 200 ° C., preferably −20 ° C. to + 100 ° C. The reaction time is usually 30 minutes to 100 hours, although it varies depending on conditions such as the amount of reaction reagent and temperature.

(Production of Compound (VIII))
Compound (VIII), which is a raw material for producing compound (VII), can be produced according to the following reaction formula.

(Wherein R ^{1 to} R ⁶ , A and m have the same meaning as described above).
That is, compound (VIII) can be produced by reacting compound (III) with hydroxylamine, if desired, in the presence of a base.

In this reaction, hydroxylamine can be used in the form of a hydroxylamine salt or an aqueous hydroxylamine solution.
The amount of the hydroxylamine salt or hydroxylamine aqueous solution used is usually 1 to 10 times mol, preferably 1 to 3 times mol, in terms of pure component (hydroxylamine), relative to compound (III).

Examples of the base used include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; triethylamine, pyridine, N, N-dimethylaniline, 4-dimethylaminopyridine, N -Organic bases such as methylpyrrolidine, N-methylmorpholine, DBU;
The amount of the base to be used is generally 1 to 10 times mol, preferably 1 to 3 times mol, of compound (III).

  This reaction can be performed in the presence or absence of a solvent. Solvents that can be used are not particularly limited as long as they are inert to the reaction. For example, hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene, xylene; dichloromethane, 1,2-dichloroethane, chloroform, four And halogen solvents such as carbon chloride; ether solvents such as diethyl ether, dioxane and THF; alcohol solvents such as methanol and ethanol; water; and a mixed solvent composed of two or more of these solvents;

The reaction temperature is usually in the temperature range of −78 ° C. to + 200 ° C., preferably −20 ° C. to + 100 ° C.
The reaction time is usually 30 minutes to 100 hours, although it varies depending on conditions such as the amount of reaction reagent and temperature.

(Manufacturing method 3)
Among the compounds of the present invention, a compound represented by the following formula (1-3) can be produced according to the following reaction formula.

(In the formula, R ^{1 to} R ⁶ , R ^h , A and m represent the same meaning as described above. L ″ represents a bromine atom or an iodine atom.)
A compound represented by formula (IX) (hereinafter referred to as “compound (IX)”) and a compound represented by formula (X) (hereinafter referred to as “compound (X)”) in the presence of a Pd complex and a base. The compound shown by Formula (1-3) can be manufactured by making it react.

  The amount of compound (X) to be used is generally 1 to 10 times mol, preferably 1 to 3 times mol, of compound (IX).

Examples of the Pd complex used include tetrakistriphenylphosphine palladium and dichlorobis (triphenylphosphine) palladium. A combination of palladium acetate and triphenylphosphine can also be used as the Pd complex.
The usage-amount of Pd complex is 0.001-1 times mole normally with respect to compound (IX).

Examples of the base to be used include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; organic bases such as propylamine, diethylamine, triethylamine, pyrrolidine and piperidine; It is done.
The amount of the base to be used is generally 1 to 20-fold mol, preferably 1 to 3-fold mol based on compound (IX).

This reaction can be performed in the presence or absence of a solvent.
Solvents that can be used are not particularly limited as long as they are inert to the reaction. For example, hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene, xylene; dichloromethane, 1,2-dichloroethane, chloroform, four Halogen solvents such as carbon chloride; nitrile solvents such as acetonitrile and propionitrile; ether solvents such as diethyl ether, dioxane and THF; amide solvents such as DMF and N, N-dimethylacetamide; dimethyl sulfoxide and the like And a mixed solvent composed of two or more of these solvents.

In this reaction, in addition to the Pd catalyst, another catalyst may be used in combination. Other catalysts include copper halides such as copper (I) iodide, ammonium salts such as tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, and the like.
The usage-amount of another catalyst is 0.001-1 times mole normally with respect to compound (IX).

The reaction temperature is usually in the temperature range of −78 ° C. to + 200 ° C., preferably −20 ° C. to + 100 ° C.
The reaction time is usually 30 minutes to 24 hours, although it varies depending on conditions such as the amount of reaction reagent and temperature.

(Manufacturing method 4)
Among the compounds of the present invention, a compound represented by the following formula (1-4) can be produced according to the following reaction formula.

(In the formula, R ^{1 to} R ⁶ , R ⁱ , A, D and m have the same meaning as described above.)
That is, a compound represented by the formula (XI) (hereinafter referred to as “compound (XI)”) and a compound represented by the formula (XII) (hereinafter referred to as “compound (XII)”) are optionally converted to an acid. By reacting in the presence, the compound represented by the formula (1-4) can be produced.

  The amount of compound (XII) to be used is generally 1 to 5 mol, preferably 1 to 2 mol per mol of compound (XI).

Examples of the acid used include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; organic acids such as formic acid, acetic acid, methanesulfonic acid, and p-toluenesulfonic acid; and the like.
When using an acid, the usage-amount of an acid is 0.01-100 times mole normally with respect to compound (XI), Preferably it is 1-3 times mole.

This reaction can be performed in the presence or absence of a solvent.
Solvents that can be used are not particularly limited as long as they are inert to the reaction. For example, hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene, xylene; dichloromethane, 1,2-dichloroethane, chloroform, four Halogen solvents such as carbon chloride; nitrile solvents such as acetonitrile and propionitrile; ether solvents such as diethyl ether, dioxane and THF; amide solvents such as DMF and N, N-dimethylacetamide; dimethyl sulfoxide and the like And a mixed solvent composed of two or more of these solvents.

The reaction temperature is usually in the temperature range of −78 ° C. to + 200 ° C., preferably −20 ° C. to + 100 ° C.
The reaction time is usually 30 minutes to 24 hours, although it varies depending on conditions such as the amount of reaction reagent and temperature.

In any reaction, after completion of the reaction, the desired product can be isolated by purifying by a conventional post-treatment operation and, if desired, known and conventional purification means such as distillation, recrystallization and column chromatography.
The structure of the target product can be identified and confirmed by known analytical means such as IR spectrum, NMR spectrum, mass spectrum, and elemental analysis.

The salt of the compound of the present invention is not particularly limited as long as it is an agricultural and horticulturally acceptable salt. For example, salts of inorganic acids such as hydrochloric acid and sulfuric acid; salts of organic acids such as acetic acid and lactic acid;
These salts can be produced by a conventionally known method using an acid corresponding to the nitrogen-containing heterocyclic compound represented by the formula (1).

2) Agricultural and horticultural fungicides The agricultural and horticultural fungicides of the present invention are characterized by containing one or more of the compounds of the present invention or salts thereof as active ingredients.

  The compounds of the present invention and salts thereof (hereinafter sometimes referred to as “the compounds of the present invention”) are a wide variety of filamentous fungi, such as algae (Oomycetes), Ascomycetes, It has excellent bactericidal power against bacteria belonging to complete fungi (Deuteromycetes) and basidiomycetes (Basidiomycetes).

  Therefore, the agricultural and horticultural fungicide according to the present invention containing the compound of the present invention as an active ingredient is used for seed treatment, foliage spray, It can be used by soil application or water surface application.

The agricultural and horticultural fungicide of the present invention is, for example,
Sugar beet brown spot (Cercospora beticola)
Peanut brown spot (Mycosphaerella arachidis)
Black astringent disease (Mycosphaerella berkeleyi)
Cucumber powdery mildew (Sphaerotheca furiginea)
Vine Blight (Mycosphaella melonis)
Sclerotinia sclerotiorum
Gray mold disease (Botrytis cinerea)
Black star disease (Cladosporium cucumerinum)
Tomato gray mold (Botrytis cinerea)
Leaf mold (Cladosporium fulvum)
Eggplant gray mold (Botrytis cinerea)
Black blight (Corynespora melogenae)
Powdery mildew (Erysiphe cichoracerarum)
Strawberry Gray mold disease (Botrytis cinerea)
Powdery mildew (Sohaerotheca humuli)
Onion gray rot (Botrytis allii)
Gray mold disease (Botrytis cinerea)
Kidney bean sclerotia (Sclerotinia sclerotiorum)
Gray mold disease (Botrytis cinerea)
Apple powdery mildew (Podosphaera leukotrica)
Venturia inaequalis
Moniria disease
Oyster powdery mildew (Phyllactinia kakicola)
Anthracnose (Gloeosporium kaki)
Spotted leaf disease (Cercospora kaki)
Peach out ash scab (Monilinia fracticola)
Grapes Gray mold (Botrytis cinerea)
Powdery mildew (Uncinula necator)
Late rot (Glomerella cingulata)
Pear black scab (Venturia nashicola)
Red Star Disease (Gymnosporium asiaticum)
Black spot disease (Alternaria kikuchiana)
Cha ring spot disease (Pestaloti theae)
Anthracnose (Colletotrichum theae-sinensis)
Citrus common scab (Elsinoe fawceti)
Blue mold disease (Penicillium italicum)
Green mold (Penicillium digitatum)
Gray mold disease (Botrytis cinerea)

Barley powdery mildew (Erysiphe graminis f.sp.hordei)
Nasty Black Blight (Ustilago nuda)
Wheat Red mold disease (Gibberella zeae)
Red rust (Puccinia recondita)
Spot disease (Cochliobolus sativus)
Eye disease (Pseudocercosporella herpotriochoides)
Blight disease (Leptosphaeria nodorum)
Powdery mildew (Erysiphe graminis f. Sp. Tritici)
Scarlet Snow Rot (Microlectriella nivalis)
Rice blast disease (Pyricularia oryzae)
Rhizoctonia solani
Idiot Seedling (Gibberella fujikuroi)
Sesame leaf blight (Cochliobolus niyabeanus)
Tobacco sclerotia (Sclerotinia sclerotiorum)
Powdery mildew (Erysiphe cichoracerarum)
Tulip Gray mold disease (Botrytis cinerea)
Bentgrass (Sclerotinia borealis)
Orchardgrass powdery mildew (Erysiphe graminis)
Soybean Purpura (Cercospora kikuchii)
Potato tomato plague (Phytophthora infestans)
Cucumber downy mildew (Pseudoperonospora cubensis)
Grape downy mildew (Plasmopara viticola)
It can be used for the control of etc.

In recent years, resistance to benzimidazole fungicides, dicarboximide fungicides, and the like has developed in various pathogenic bacteria, resulting in insufficient efficacy of these drugs, and drugs effective against resistant bacteria are desired.
The compound of the present invention has an excellent bactericidal effect not only on pathogenic bacteria sensitive to these drugs but also on resistant bacteria.

For example, gray mold fungus (Botrytis cinerea), sugar beet brown fungus (Cercospora beticola), Venturia inaequalis, Venturia ina ol (Venturia inaequilis), Venturia in ol The compounds of the present invention are also effective against).
Furthermore, the compounds of the present invention and the like are also effective against gray mold fungi (Botrytis cinerea) that are resistant to dicarboximide fungicides (for example, vinclozoline, procymidone, iprodione).
More preferable diseases to be applied include apple black spot, wheat powdery mildew, tomato plague, wheat red rust, and the like.

  The agricultural and horticultural fungicide of the present invention is a highly safe drug with little phytotoxicity, low toxicity to fish and warm-blooded animals.

  When actually applying the agricultural and horticultural fungicide of the present invention, the compound of the present invention can be used in a pure form without adding other components, and a form that can be used by general pesticides for the purpose of use as a pesticide. That is, it can also be used in the form of an agrochemical formulation such as a wettable powder, granule, powder, emulsion, aqueous solvent, suspension, or granular wettable powder.

  Additives and carriers that can be added to the agrochemical formulation include plant powders such as soybean flour and wheat flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, Mineral fine powders such as clay, organic and inorganic compounds such as sodium benzoate, urea, and mirabilite are used.

  For liquid dosage forms, kerosene, xylene, petroleum aromatic hydrocarbons, cyclohexane, cyclohexanone, DMF, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, Water or the like can be used as a solvent.

  Furthermore, in order to take a uniform and stable form in these preparations, a surfactant may be added as necessary. The surfactant that can be added is not particularly limited. For example, alkyl phenyl ether added with polyoxyethylene, alkyl ether added with polyoxyethylene, higher fatty acid ester added with polyoxyethylene, sorbitan higher fatty acid ester added with polyoxyethylene, tristyryl added with polyoxyethylene Nonionic surfactants such as phenyl ether, sulfates of alkylphenyl ethers added with polyoxyethylene, alkylbenzene sulfonates, sulfates of higher alcohols, alkylnaphthalene sulfonates, polycarboxylates, lignin sulfones Acid salt, formaldehyde condensate of alkyl naphthalene sulfonate, isobutylene-maleic anhydride copolymer, and the like.

  The wettable powder, emulsion, flowable powder, aqueous solvent, and granular wettable powder thus obtained are diluted with water to a predetermined concentration to obtain a powder, granule as a solution, suspension or emulsion. Is used as it is by spraying on plants.

  The amount of the active ingredient is usually preferably 0.01 to 90% by weight and more preferably 0.05 to 85% by weight with respect to the entire composition (formulation).

  The formulated agricultural and horticultural fungicide composition of the present invention is applied to a plant body, seeds, water surface or soil as it is or diluted with water or the like. The application amount varies depending on weather conditions, formulation form, application time, application method, application place, disease to be controlled, target crop, etc., but usually 1 to 1,000 g, preferably 10 in terms of the amount of active ingredient compound per hectare. ~ 100 g.

  When a wettable powder, emulsion, suspension, aqueous solvent, granular wettable powder and the like are diluted with water and applied, the applied concentration is 1-1000 ppm, preferably 10-250 ppm. If so, apply as is without dilution.

  In addition, it cannot be overemphasized that this invention compound etc. are enough and effective, but it can also be used, mixing with 1 type, or 2 or more types of various bactericides, insecticides, acaricides, or synergists. it can. These agents can be preliminarily contained in the agricultural and horticultural fungicide of the present invention, or can be mixed when the agricultural and horticultural fungicide of the present invention is actually applied (so-called tank mix).

  Representative examples of fungicides, insecticides, acaricides, and plant growth regulators that can be used in combination with the compounds of the present invention are shown below.

Fungicide:
Captan, folpette, thiuram, ziram, dineb, manneb, mancozeb, propineb, polycarbamate, chlorothalonil, quintosen, captaphor, iprodione, prosaimidon, fluoroimide, mepronil, flutolanil, pencyclon, oxycarboxyl, fosetyl aluminum, propamocurve, triazimephone, Triadimenol, propiconazole, diclobutrazole, viteltanol, hexaconazole, microbutanyl, flusilazole, metconazole, etaconazole, flutrimazole, cyproconazole, epoxiconazole, flutriaphene, beconazole, diniconazole, cyside Proconazose, phenalimol, triflumizole, prochloraz, imazalil, pefazoate Tridemorph, Fenpropimorph, Trifolin, Butiobate, Pyriphenox, Anilazine, Polyoxin, Metalaxyl, Oxazixyl, Furaraxil, Isoprothiolane, Probenazole, Pyrrnitrin, Blasticidin S, Kasugamycin, Validamycin, Dihydrostreptomycin Sulfate, Benomyl, Carbendazim Thiophanate methyl, hymexazole, basic copper chloride, basic copper sulfate, phentin acetate, triphenyltin hydroxide, dietophanecarb, quinomethionate, binapacryl, lecithin, baking soda, dithianon, dinocup, phenaminosulfur, dichromedin, guazatine, dodine, IBP, edifene Phos, mepanipyrim, fermzone, trichlamide, metasulfocarb, fluazinam, Toquinolac, dimethomorph, pyroxylone, teclophthalam, fusalide, phenazine oxide, thiabendazole, tricyclazole, vinclozolin, simoxanyl, cyclobutanyl, guazatine, propamocarb hydrochloride, oxolinic acid, hydroxyisoxazole, iminoctazine acetate, cyflufenamide, trisoxenhexamide , Ciazofamide, Cyprodinil, Prothioconazole, Fenbuconazole, Trifloxystrobin, Azoxystrobin, Imibenconazole, Tebuconazole, Difenoconazole, Quinomethionate, Carpropamide, Acibenzoral Smethyl, Ambam, Ipconazole, Iminotazine Albesylate, Pyra Crostrobin, chloronebu, dichroic Tsu DOO, diflumetorim, Tazometto, thiadiazine, tiadinil, thifluzamide, triclofos methyl, nonylphenol sulfonate, pyrimethanil, famoxadone, furametpyr, fludioxonil, flusulfamide, boscalid, myclobutanil, mildiomycin, metominostrobin like.

Insecticides and acaricides:
Organophosphorus and carbamate insecticides:
Fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, bamidthione, phentoate, dimethoate, formothione, marathon, trichlorfone, thiometone, phosmet, dichlorvos, acephate, EPBP, methyl parathion, oxydimethone methyl, ethion, salicione, cyanophos, isoxathione, cyanophos, isoxathione Methidathione, Sulprophos, Chlorfenvinphos, Tetrachlorvinphos, Dimethylvinphos, Propafos, Isophenphos, Ethylthiomethone, Profenofos, Piracrofos, Monocrotophos, Adinfosmethyl, Aldicarb, Mesomil, Thiodicarb, Carbofuran, Carbosulfan, Benhracarb, Furatiocarb Propoxur, BPMC, M MC, MIPC, carbaryl, pirimicarb, ethiofencarb, fenoxycarb, EDDP, and the like.

Pyrethroid insecticides:
Permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatoline, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propraslin, phenothrin, protorin, fulvalinate, cyfluthrin, cyhalothrin, flucitrinate, etofenprox, cycloprotorin, thoramethrin , Silafluophene, brofenprox, aclinasrin, etc.

Benzoylurea and other insecticides:
Diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, benzoepin, diafenthiuron, acetamiprid, imidacloprid, nitenpyram, fipronil, cartap , Thiocyclam, bensultap, chlorfenapyr, nitenpyram, thiacloprid, clothianidin, thiamethoxam, dinotefuran, indoxacarb, pymetrozine, spinosad, emamectin, pyridalyl, tebufenozide, chromafenozide, methoxyphenozide, tolfenpyrad, nicotine T Microbial pesticides such as insect pathogenic viruses.

Nematicides:
Fenamifos, Phostiazate, Kazusafos etc.
Acaricide:
Chlorbenzilate, phenisobromolate, dicofol, amitraz, BPPS, benzomate, hexithiazox, fenbutazin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentedin, cihexatin, pyridaben, fenpyroximate, tebufenpyrad, thiomidibene Dienochlor, fluacrylpyrim, acequinosyl, bifenazate, etoxazole, spirodiclofen, phenazaquin and the like.
Plant growth regulator:
Gibberellins (eg, gibberellin A3, gibberellin A4, gibberellin A7) IAA, NAA and the like.

  EXAMPLES Next, although an Example is given and this invention is demonstrated still in detail, this invention is not limited to a following example at all.

Example 1 Preparation of methyl 2- {2-chloro-5- [4- (4-fluorophenyl) thiazol-2-yl] phenyl} pyrazolidine-1-carboxylate (1) Methyl 2- (2-chloro Preparation of -5-cyanophenyl) pyrazolidine-1-carboxylate

  Methyl N ′-(2-chloro-5-cyanophenyl) hydrazinecarboxylate (5.0 g, 32.9 mmol) was dissolved in 40 ml of N, N-dimethylformamide (DMF). To this solution, 1.13 g (28.0 mmol) of 60% oily sodium hydride was added at 0 ° C., followed by 8.4 g (28.0 mmol) of 1,3-diiodopropane, and the same temperature was maintained for 1 hour. After stirring, the mixture was warmed to room temperature and stirred overnight. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (solvent: n-hexane-ethyl acetate = 6: 1-3: 1 (volume ratio)) to obtain the desired methyl 2- (2-chloro-5-cyanophenyl). ) 1.5 g of pyrazolidine-1-carboxylate was obtained as yellow crystals. Yield 25%

(2) Production of methyl 2- (2-chloro-5-thiocarbamoylphenyl) pyrazolidine-1-carboxylate

  To 10 ml of N, N-dimethylformamide saturated with hydrogen chloride, 0.47 g (1.77 mmol) of methyl 2- (2-chloro-5-cyanophenyl) pyrazolidine-1-carboxylate obtained in (1) above was added. In addition, 0.27 g (3.59 mmol) of thioacetamide was further added at 40 ° C., and the mixture was stirred at the same temperature for 6 hours. The reaction mixture is allowed to cool to room temperature and then poured into ice water. The precipitated crystals are collected by filtration and washed with water followed by n-hexane to give methyl 2- (2-chloro-5-thiocarbamoylphenyl) pyrazolidine. As a result, 0.39 g of -1-carboxylate was obtained. Yield 74%

(3) Production of methyl 2- {2-chloro-5- [4- (4-fluorophenyl) thiazol-2-yl] phenyl} pyrazolidine-1-carboxylate

A solution of 0.38 g (2.4 mmol) of bromine in benzene (3 ml) was added to a solution of 0.30 g (2.1 mmol) of 1- (4-fluorophenyl) ethanone in 5 ml of benzene, and the mixture was added at 40 ° C. for 2 hours. Stir. By concentrating the reaction solution, a crude product of 2-bromo-1- (4-fluorophenyl) ethanone was obtained.
The obtained crude product was dissolved in 10 ml of methanol, and 0.19 g (0.63 mmol) of methyl 2- (2-chloro-5-thiocarbamoylphenyl) pyrazolidine-1-carboxylate obtained in (2) above. Was added and stirred for 1 hour. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue is purified by silica gel column chromatography (solvent: benzene-ethyl acetate = 19: 1 (volume ratio)) to give the desired methyl 2- {2-chloro-5- [4- (4-fluoro). 0.14 g of (phenyl) thiazol-2-yl] phenyl} pyrazolidine-1-carboxylate was obtained. Yield 54%

Specific examples of the compound of the present invention including the above examples are shown in the following Tables 1 to 3, but the compound of the present invention is not limited to these compounds.
In addition, the numerical value described in the physical property value column is the melting point of the compound. The ¹ H-NMR data is shown in Table 4.

Next, some examples of the agricultural and horticultural fungicide composition of the present invention are shown. Additives and addition ratios should not be limited to these examples, but can be varied over a wide range.
In addition, the part in a formulation example shows a weight part.

Formulation Example 1 wettable powder Compound of the present invention 40 parts Clay 48 parts Dioctylsulfosuccinate sodium salt 4 parts Sodium lignin sulfonate 8 parts The above ingredients are uniformly mixed and finely pulverized to obtain a wettable powder of 40% active ingredient. Got.

Formulation Example 2 Emulsion Compound of the present invention 10 parts Solvesso 200 53 parts Cyclohexanone 26 parts Calcium dodecylbenzenesulfonate 1 part Polyoxyethylene alkylallyl ether 10 parts The above components were mixed and dissolved to obtain an emulsion containing 10% active ingredient.

Formulation Example 3 Powder Compound of the present invention 10 parts Clay 90 parts The above was mixed uniformly and finely pulverized to obtain a powder of 10% active ingredient.

Formulation Example 4 Granules Compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctylsulfosuccinate sodium salt 1 part Potassium phosphate 1 part After pulverizing and mixing well, adding water and kneading well, granulation drying As a result, granules having an active ingredient content of 5% were obtained.

Formulation Example 5 Suspension Compound of the present invention 10 parts Polyoxyethylene alkyl allyl ether 4 parts Polycarboxylic acid sodium salt 2 parts Glycerin 10 parts Xanthan gum 0.2 parts Water 73.8 parts The above is mixed and the particle size is 3 microns or less The suspension was wet pulverized until the suspension became 10% active ingredient.

Formulation Example 6 Granule wettable powder Compound of the present invention 40 parts Clay 36 parts Potassium chloride 10 parts Sodium alkylbenzenesulfonate 1 part Sodium ligninsulfonate 8 parts Formaldehyde condensate of sodium alkylbenzenesulfonate
After mixing 5 parts or more uniformly and finely pulverizing, an appropriate amount of water was added and then kneaded to form a clay. The obtained clay-like product was granulated and then dried to obtain a granulated wettable powder containing 40% of the active ingredient.

  Next, test examples show that the compounds of the present invention are useful as active ingredients of various plant disease control agents.

Test Example 1 Apple Black Spot Control Test An emulsion of the compound of the present invention was sprayed at a concentration of 100 ppm of the active ingredient on apple seedlings (variety “Kokumitsu”, 3-4 leaf stage) cultivated in an unglazed pot. After naturally drying at room temperature, conidia spores of Venturia inaequalis were inoculated and kept for 2 weeks in a room of 20 ° C. and high humidity where brightness and darkness were repeated every 12 hours. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
As a result, the compound Nos. 1-1, 1-3, 1-7, 1-8, 1-50, 1-52, 1-66, 2-1, 2-2 were excellent in 75% or more. The control value was shown.

Test Example 2 Wheat Powdery Mildew Control Test Wheat seedlings grown in an unglazed pot (variety “Chihoku”, 1.0-1.2 leaf stage) were sprayed with a wettable powder of the compound of the present invention at a concentration of 100 ppm active ingredient. . After air-drying the leaves, conidia of wheat powdery mildew (Erysiphe graminis f. Sp. Tritici) were sprinkled off and inoculated in a 22-25 ° C. greenhouse for 7 days. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
As a result, the compound Nos. 1-1, 1-3, 1-7, 1-8, 1-50, 1-52, 1-66, 2-1, 2-2 were excellent in 75% or more. The control value was shown.

Test Example 3 Tomato Blight Control Test Tomato seedlings (variety “Regina”, 4-5 leaf stage) cultivated in an unglazed pot were sprayed with an emulsion of the compound of the present invention at a concentration of 100 ppm active ingredient. After spraying, it was naturally dried at room temperature, sprayed and inoculated with a zoospore sac suspension of Phytophthora infestans, and kept for 4 days in a high-humidity constant temperature room (20 ° C.) repeating light and dark every 12 hours. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
As a result, the compound Nos. 1-1, 1-3, 1-12, 1-50 and 1-52 showed an excellent control value of 75% or more.

Test Example 4 Wheat Red Rust Control Test The wettable powder of the compound of the present invention was sprayed at a concentration of 100 ppm of the active ingredient on wheat seedlings (variety “Noribayashi 61”, 1.0-1.2 leaf stage) cultivated in an unglazed pot. did. After air-drying the leaves, summer spores of wheat red rust fungus (Puccinia recondita) were shaken off and inoculated in a greenhouse at 22-25 ° C. for 10 days. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
As a result, the compound Nos. 1-1, 1-3, 1-7, 1-8, 1-11, 1-12, 1-50, 1-52, and 2-1 were excellent in 75% or more. The control value was shown.

Claims (4)

Formula (1)

{In the formula, R ¹ represents a C _1-6 alkyl group or a C _1-6 alkoxy group, R ² represents a halogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, and m represents 0 to Represents an integer of 4. When m is 2 or more, R ² may be the same or different.
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a C _1-6 alkyl group. ^{Further, -C (R 3) (R} 4) -, or ^{-C (R 5) (R 6} ) - is, -C (= O) - and may form.
A represents any group represented by the following (A1) to (A3).

(In the formula, R ^a , R ^b , R ^c , R ^d , R ^e , R ^f and R ^g each independently represent a hydrogen atom or a C _1-6 alkyl group.)
Q represents a heterocyclic group which may have a substituent when A is (A1), or any group represented by the following (Q1) and (Q2), and A represents (A2) or ( In the case of A3), it represents a heterocyclic group which may have a substituent.

[In the formula, R ^h represents a hydrogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, or a group represented by the formula: Si (R ^j ) (R ^k ) (R ^l )] R ^j , R ^k and R ¹ each independently represents a C _1-6 alkyl group or a phenyl group which may have a substituent.
R ⁱ may be substituted with a hydrogen atom, a C _1-6 alkyl group, a C _3-8 cycloalkyl group, a C _3-8 cycloalkyl C _1-6 alkyl group, a C _1-6 haloalkyl group, or G 1. Represents a good phenyl group. G1 represents a halogen atom, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _1-6 haloalkyl group, a C _1-6 haloalkoxy group, or a hydroxyl group. G1 may be the same or different and a plurality of G1 may be substituted, or a plurality of G1 may be bonded to form a ring.
D represents a hydrogen atom, a C _1-12 alkyl group, a C _3-8 cycloalkyl group, a C _3-8 cycloalkyl C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-10 alkynyl group, optionally substituted with G2 (C _7-20 aralkyl group, pyridyl C _1-6 alkyl group, piperidyl C _1-6 alkyl group, tetrahydropyranyl C _1-6 alkyl group, tetrahydrofuryl C _1-6 alkyl group, benzoyl group, C _7-20 aralkylcarbonyl group), C _1-6 alkylcarbonyl group, C _3-8 cycloalkylcarbonyl group, or C _3-8 cycloalkylcarbonyl C _1-6 alkyl group Represents. G2 represents a halogen atom, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _1-6 haloalkyl group, a C _1-6 haloalkoxy group, or a hydroxyl group. G2 may be the same or different and a plurality of G2 may be substituted, or a plurality of G2 may be bonded to form a ring. ]}
Or a salt thereof.   In the formula (1), Q is a 5- or 6-membered heterocyclic group which may have a substituent, containing at least one heteroatom selected from an oxygen atom, a nitrogen atom and a sulfur atom. The nitrogen-containing heterocyclic compound or a salt thereof according to claim 1. In the formula (1), Q is (Q3).

[Wherein, R ^m represents a hydrogen atom, a C _1-6 alkyl group, or an optionally substituted G3 (phenyl group or C _7-20 aralkyl group), and G 3 represents a halogen atom, C _1- Represents a ₆ alkyl group, a C _1-6 alkoxy group, or a C _1-6 haloalkyl group. G3 may be the same or different and a plurality of G3 may be substituted, and a plurality of G3 may be bonded to form a ring. R ⁿ represents a hydrogen atom or a C _1-6 alkyl group. The nitrogen-containing heterocyclic compound or a salt thereof according to claim 1, which is a group represented by the formula:   An agricultural and horticultural fungicide containing one or more of the nitrogen-containing heterocyclic compounds or salts thereof according to any one of claims 1 to 3 as an active ingredient.