JPH03106865A - 4-substituted-1,2,4-triazolin-5-one derivated and agricultural and horticultural fungicide - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R<1> is H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, acyl, phenylalkyl, aminocarbonyl, etc.; R<2> is H or alkyl; R<3> is halogen, NO2, alkyl, sulfinylalkyl or A-R<4> (A is O or S; R<4> is R, alkyl, cycloalkyl, alkenyl, etc.), etc.; X is halogen, alkyl, alkoxy or NO2]. EXAMPLE:4-(4-Chloro-2-fluoro-5-isopropoxyphenyl)-1,3-dimethyl- <2>-1,2,4-triazolin-5- one. USE:An agricultural and horticultural fungicide. PREPARATION:For example, a semicarbadide shown by formula II is subjected to ring closure reaction in the presence of an inert solvent and a base to give a compound shown by formula I wherein R<1> is H.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (1) (wherein, RIFi hydrogen atom, an alkyl group having 1 to 12 carbon atoms, 1 to 120 carbon atoms/~roalkyl group, 1 cyanoalkyl group, a carbon atom) cycloalkyl group of number 3 to 6,
Lower alkenyl group, lower haloalkenyl group, cycloalkenyl group, lower alkynyl group, lower alkoxyalkyl group, lower alkylthioalkyl group, lower alkylsulfonyl group. One or more substituents selected from a low alkoxyalkoxyalkyl group, a lower acyl group, a lower acylalkyl group, a cycloalkyl group, which may be the same or different, a halogen atom or a lower haloalkylthio group, on the phenyl ring. a 7-enyl alkyl group which may have one or more halogen atoms on the cyclo ring, a cycloalkylalkyl group which may have one or more halogen atoms on the cyclo ring, a lower alkoxyl ponyl alkyl group, an oxirane alkyl which may be substituted with a lower alkyl group. groups, which may be the same or different; aminocarbonyl alkyl groups which may have 14 to 2 substituents selected from lower alkyl groups or phenyl groups;
A lower alkoxyiminoalkyl group or the same or different groups, a lower alkyl group, a phenyl group or <Fi1
R! represents a hydrogen atom or a lower alkyl group, Hg represents a halogen atom, a nitro group, a lower alkyl group, a sulfinyl alkyl group, a sulfonylalkyl group, -A-R' (wherein A represents 101 or -S1) , R4 is a hydrogen atom, the number of carbon atoms is 1
-8 alkyl group, haloalkyl group having 1 to 8 carbon atoms, cycloalkyl group having 3 to 6 carbon atoms, lower cyanoalkyl group, lower alkenyl group, lower haloalkenyl group,
Lower alkynyl group, lower alkoxyalkyl group, cycloalkylalkyl group which may be substituted with a halogen atom, aminoalkyl group which may be the same or different and may be substituted with 1 to 2 lower alkyl groups, the same or A 7-enylsulfonyl group which may be different and which may have one or more lower alkyl groups on the phenyl ring, or one or more substituents which may be the same or different and are selected from a halogen atom or a lower alkoxycarbonyl group. Indicates a phenylalkyl group that may be present on the phenyl ring. )
, -A-(CHR')n-CO-R meeting (where AFi
Same as above <t, . R'' represents a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and R● is a hydroxy group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower halo-1/koxy group, which may be the same or different.
Indicates an amino group or phenyl group that may be substituted with ~2 lower alkyl groups, and represents an integer of nFiO ~2. ), -Co-RS (wherein, R'H -A-R'' (
In the formula, Atl is a hydrogen atom, an alkali metal atom, a lower alkyl group, a 7-enyl group or a phenylalkyl group which may be substituted by one or more hydrogen atoms, which may be the same or different. shows.

) or may be the same or different <, lower alkyl group or <
Fi7 represents an amino group which may have 1 to 2 substituents selected from enyl groups. ), or one NCR')R?
(In the formula, R6 and R'ti may be the same or different, and may be a hydrogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkenyl group, a lower alkylcarbonyl group, a lower haloalkylcarbonyl group, a lower alkylsulfonyl group, or 10 ( Rll ) RlACO-OR' (in the formula, Rll and Rllij may be the same or different and represent a hydrogen atom or a lower alkyl group, and Htx represents a lower alkyl group). Also, Rl and R'Fi X#i may be the same or different and represent a halogen atom, a lower alkyl group, a lower alkoxy group or a nitro group. ) 4-monosubstituted phenyl-1. 2. 4-}
The present invention relates to a lyazolin-5-one derivative, a method for producing the same, and an agricultural and horticultural fungicide characterized by containing the compound as an active ingredient.

As a result of extensive research in order to create a new agricultural and horticultural fungicide, the present inventors found that 4-monosubstituted phenyl-1. 2. 4-}Ryazolin-5-one derivative is a new compound that has not been described in literature, and has excellent control effects against various plant diseases at low doses, especially against rice potato disease The present invention was completed based on the discovery that the present invention has the following properties.

Prior art related to the present invention includes Japanese Patent Publication Nos. 41-16, 52467/1983, 52468/1982, and 56/1982.
-54675, lfiJ57-181069, same 6
No. 1-206264, No. 62-99566, No. 62-
No. 99568 and the like disclose triazoline derivatives. However, the 4-substituted phenyl-1. 2. 4
- }Ryazolin-5-one derivatives are not disclosed at all, and their effects are, for example, anti-inflammatory, tonic, and sedative as medicines in Japanese Patent Publication No. 41-16, and Japanese Patent Publication No. 56-52467. , No. 56-52468, No. 5
No. 7-181049, No. 61-206264, No. 62
No. 99566, No. 62-99568, etc. disclose \2-propenyloxy)phenyltriazoles having a falcon-killing effect, but nothing is described about the bactericidal effect of the present invention.

Although it is disclosed as an agricultural and horticultural fungicide in JP-A-56-54675, the structure of the compound is different from that of the present invention.

4-@conversion 7 engineering 2 Ru 1 represented by the general formula (1) of the present invention
．． 2. Typical methods for producing 4-triazolin-5-one derivatives include, for example, the production methods illustrated below, but the present invention is not limited to these production methods.

(Method A) (In the formula, R3, R3 and 4-monosubstituted phenyl-1.2 represented by general formula (1-2)
-propenyloxy)phenyl}1ruTzolin-5-one derivatives can be prepared.

As the inert solvent that can be used in the present invention, for example, polar solvents such as water are preferably used.

Examples of bases include hydroxides of alkaline earth metals such as sodium, potassium, magnesium or calcium;
Carbonates, etc. can be used. The amount of the base to be used may be selected from the range of equimolar to excess molar relative to the semicarpazide represented by the general formula (F/-1).

The reaction temperature can be selected from room temperature to the boiling point of the inert solvent used. The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but it is sufficient as long as the reaction is completed (for example, it can be selected from a range of several minutes to 48 hours).

After the reaction is completed, the reaction solution containing the target product is neutralized with an appropriate acid, subjected to operations such as solvent extraction, and purified by recrystallization, column chromatography, etc., if necessary. and 4 expressed by the general formula (1-1')
Monosubstituted fer-1,2-propenyloxy)phenyl}riazolin-5-one derivatives can be produced. (Method B) (1-1) (1) (In the formula, Rl, ip%R3 and X are the same as above, R
1-1 is an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, a cyanoalkyl group, a cycloalkyl group having 3 to 6 carbon atoms, a lower alkenyl group, a lower 1-loalkenyl group, a cyclo alkenyl group, lower alkynyl group, lower alkoxyalkyl group, lower alkylthioalkyl group, lower alkylsulfonyl group, lower alkoxyalkoxyalkyl group, lower acyl group, lower acylalkyl group, cycloalkylcarbonyl group, which may be the same or different; - A phenylalkyl group which may have one or more substituents selected from a cyclogen atom or a lower alkoxy group on the phenyl ring, and a phenylalkyl group which may have one or more halogen atoms on the cyclo ring. Aminocarbonyl which may have 1 to 2 substituents selected from a cycloalkylalkyl group, a lower alkoxycarbonylalkyl group, an oxirane alkyl group which may be substituted with a lower alkyl group, a lower alkyl group or a phenyl group Indicates an alkyl group, lower alkoxyiminoalkyl group, R
l-4 represents a phenyl group which may be substituted with one or more halogen atoms which may be the same or different, and 2 represents a halogen atom. ) That is, 4-monosubstituted phenyl-1. represented by the general formula tt.
The 2-propenyloxy)phenyltriazolin-5-one derivative is a 4-monosubstituted 7enyl-1,2-propenyloxy)phenyl}riazolin-5-one derivative represented by the general formula (1-1) and the general formula ( By reacting halides represented by It-1) or incyanates represented by general formula (II-2) in the presence or absence of an inert solvent and in the presence of a base, 0》
A 4-monosubstituted phenyl-1,2-propenyloxy)phenyl}riazolin-5-one derivative represented by the formula can be produced.

Inert solvents that can be used in this reaction include aromatic hydrocarbons such as benzene, toluene, and xylene, methylene chloride, chloroform, Halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene, chain ethers such as methyl cellosolp and diethyl ether, tetrahydrofuran,
Examples include cyclic ethers such as dioxane, esters such as acetic acid ethyl ester, nitriles such as acetonitrile and penzonitrile, aliphatic amides such as dimethylformamide and dimethylacetamide, sulfolane, dimethylsulfone, dimethylsulfoxide, and water. I can do it,
These inert solvents may be used alone or in combination of two or more. For example, a mixture of two or more organic solvents may be used as the solvent, or a mixture of water and an organic solvent may be used. Examples of bases that can be used in this reaction include inorganic bases and organic bases. Examples of inorganic bases include hydroxides and carbonates of alkali metals or alkaline earth metals such as sodium, potassium, magnesium, or calcium. Examples of organic bases include triethylamine, pyridine, 1,8-diazabicyclo(5,4.0)-7-undecene, and N,N-dimethylaniline. Furthermore, when water and a polar organic solvent are used as the inert solvent, it is also possible to use a phase transfer catalyst such as triethylbenzylammonium chloride. Since this reaction is an equimolar reaction, the 4-monosubstituted phenyl group represented by the general formula (1) is 1. 2.4 - Triazoline -
Equimolar moles of the 5-one derivative and the halides represented by the general formula (II-1) or the incyanates represented by the general formula (II-2) may be used; It is also possible to use an excess of the halides represented by the formula (II-2) or the isocyanates represented by the general formula (II-2). In addition, the amount of the base to be used is appropriately selected from the range of equimolar to excess molar relative to the 4-monosubstituted phenyl-1,2-propenyloxy)phenyl lyazolin-5-one derivative represented by the general formula (1). Just do it. The reaction temperature may be selected from the range of 0°C to the boiling point of the inert solvent used.
The temperature may be selected from the range of 0°C to 150°C.

The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but it is sufficient as long as the reaction is completed, and can be selected from a range of, for example, several minutes to 48 hours.

After the reaction is completed, the reaction solution containing the target product is subjected to D, such as solvent extraction, in a conventional manner, and if necessary, purified by recrystallization, column chromatography, etc. to obtain the general formula (1).
) can be produced.

(Method C) (III-1) (1-2) (1-4) (1-4) (In the formula, Rl, Rs and X are the same as above.) That is, represented by the general formula (In-1) The compound is nitrated with a nitrating agent in the presence of an inert solvent to give a 4-monosubstituted phenyl-'+2m'-}' liazolin-5-one derivative represented by the general formula (1-2), and the general A reduction reaction of formula (1-2) with a reducing agent in the presence or absence of an inert solvent is performed to obtain 4-monosubstituted phenyl-1,2 represented by the general formula
, 4-triazolin-5-one derivative, and the general formula (
1-5) is diazotized in the presence or absence of an inert solvent and further thermally decomposed to form a 4-monosubstituted phenyl-'#21'- represented by the general formula (1-4).
}Ryazolin-5-one derivatives can also be produced.

(1) Nitration. Examples of inert solvents that can be used in this reaction include sulfuric acid,
Examples include acetic acid and dichloroethane. The nitrating agent used in this reaction may be any nitrating agent that can generally be used to nitrate the aromatic ring of an aromatic compound (for example, a mixture of nitric acid and sulfuric acid, a mixture of nitric acid and acetic anhydride, Alternatively, a mixture of an alkali metal salt of nitric acid and sulfuric acid can be exemplified.

The amount of the nitrating agent to be used may be appropriately selected from the range of equimolar to twice the molar amount of the compound represented by the general formula (1-1).

The reaction temperature may be selected from the range of -10°C to 50°C.

Although the reaction time is not constant depending on the reaction scale and reaction temperature (L
It may be selected from the range of 5 to 10 hours.

After completion of the reaction, the desired 4-substituted 7-enyl group represented by general formula (1-2) 1.
2-propenyloxy)phenyl(2-chloro-5-one derivatives can also be prepared.

(II) Reduction. Examples of inert solvents that can be used in this reaction include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and dioxane, and water. These inert solvents may be used alone or in combination. can be used. Further, an aqueous solution of an acid used as a reducing agent shown below can also be used as an inert solvent.

Examples of reducing agents used in this reaction include metal monoacids and sodium polysulfide. Examples of metals include iron, tin, and zinc, and examples of acids include hydrochloric acid, sulfuric acid, and acetic acid. Examples include mineral acids and tin chloride.
It is also possible to use these in combination.

The amount of reducing agent used is expressed by the general formula (1-2)4
For monosubstituted phenyl-1,2-propenyloxy)phenyl}riazolin-5-one derivatives, the metal is
0 mol, the acid (LO5 to 10 mol) may be selected as appropriate. The reaction temperature may be selected from the range of 0°C to 150°C. The reaction time is constant depending on the reaction scale and reaction temperature. No, but 0.
You can choose from a range of 5 to 10 hours. Further, the reduction reaction can also be carried out by a catalytic hydrogenation method in the presence of a catalyst, and examples of the catalyst include palladium on carbon.

After the reaction is completed, the desired 4-monosubstituted phenyl-1.
2-propenyloxy)phenyl}riazolin-5-one derivatives can be produced.

(1) Diazotization/decomposition reaction. This reaction can be carried out according to a conventional method, for example, by diazotizing with sodium sulfite in an aqueous sulfuric acid solution and thermally decomposing without isolation.

The reaction amount of this reaction is 4-11 expressed by general formula (1-4)
The amount of sodium nitrite ranges from 1 to 2 times the mole of the 7enyl-1,2-propenyloxy)phenyltriazolin-5-one derivative, and the amount of sulfuric acid ranges from 1.5 to 15 times the mole.
It may be selected appropriately from the molar range. Diazotization reaction,
For example, if the reaction is carried out in an aqueous sulfuric acid solution, water will be added again during the subsequent decomposition reaction, but it is also possible to add water as appropriate in order to obtain a highly pure target product. In the case of diazotization, the reaction temperature of this reaction is preferably carried out at 5°C or less under cooling, and the decomposition reaction can be carried out in the range of room temperature to 150°C, preferably in the range of 60 to 90°C. is good.

Although the reaction time varies depending on the reaction scale, reaction temperature, etc.1
You may select an appropriate time from the range of 6 hours to 6 hours. After the reaction is completed, the reaction solution containing the target product is poured into water, the precipitated crystals are collected by filtration, and if necessary, purified by a recrystallization method etc. to obtain the target general formula (1- 4)
4-monosubstituted phenyl-1 . 2.4-}Ryazolin-5-one derivatives can be produced. (Method D) (1-5) (1-4) (In the formula, R1, R3 and ) 4-monosubstituted phenyl-
1.2-propenyloxy)phenyl}riazoline-5
By reacting the -one derivative with a dealkylating agent in the presence of an inert solvent, the compound 4-
Substituted phenyl-1,2-propenyloxy)phenyl}
Reasorin-5-one derivatives can be produced.

Inert solvents that can be used in this reaction may be those that do not significantly inhibit the progress of this reaction (e.g., acetic acid, N,
Examples include N-dimethylformamide and water, and these inert solvents may be used alone or in combination. As the dealkylating agent used in this reaction, for example, hydrobromic acid (HBr), hydriodic acid (HI), boron trichloride, or alkylthiolate can be used. The amount of the dealkylating agent used in the present invention is determined by the general formula (
The reaction temperature may be selected from the range of equimolar to excess molar relative to the 4-monosubstituted phenyl-1,2-propenyloxy)phenyl lyazolin-5-one derivative represented by 1-5). It may be selected from the range of the boiling point of the active solvent.

The reaction time varies depending on the reaction scale, reaction temperature, etc., but may be selected from the range of 1 to 24 hours.

After the completion of the reaction, the product of the general formula ( 4-monosubstituted phenyl-1,2-propenyloxy)phenyltriazoline represented by 1-4)
5-one derivatives can be produced. (Method E) (11-1) (1-2) 0 x CI-6> (In the formula, R1, ljfi and X are the same as above.) That is,
A compound represented by the general formula (II-1) is reacted with fuming sulfuric acid and then bromine tetrachloride in the presence of an inert solvent, and the compound represented by the general formula (
II-2), and further the compound (I
4-f1-substituted 7-enyl-1.2.4-triazolin-5-one derivative represented by general formula (I-6) by isolating or not isolating fi-2) or performing a reduction reaction. can be manufactured. (1) Chlorosulfonylation.

Inert solvents that can be used in this reaction may be those that significantly inhibit the progress of this reaction, such as halogenated hydrocarbons such as methylene chloride, dichloromethane, chloroform, and carbon tetrachloride, and aliphatic solvents such as acetonitrile. Examples include chain ethers such as nitriles and methyl cellosolve, cyclic ethers such as dioxane and tetrahydrofuran, and mineral acids such as concentrated sulfuric acid. Chlorosulfonylated hachlorosulfonic acid, etc. may be used; sulfonation is performed with fuming sulfuric acid, the resulting sulfonic acid is converted into an alkali metal salt, and the alkali metal salt is chlorinated with phosphorus pentoxide to obtain the desired chlorosulfone. It can be produced using a method of producing a chlorosulfonate, a method of reacting fuming sulfuric acid, and then reacting with carbon tetrachloride to produce the desired chlorosulfonate.

The amount of chlorosulfonic acid to be used may be appropriately selected from the range of equimolar to excess molar, preferably excess molar. The amount of fuming sulfuric acid to be used may be selected from the range of equimolar to excess molar, preferably equal molar.

The amount of carbon tetrachloride used can be selected from the equimolar to supermolar range. The reaction temperature may be selected from the range of 0°C to 180°C, and preferably within the range of 10°C to 100°C.

The reaction time varies depending on the reaction scale, reaction temperature, etc., but may be selected from a range of several minutes to 48 hours.

After the reaction is completed, the reaction solution containing the target product is poured into water, isolated by solvent extraction method, etc., and purified by recrystallization method, column chromatography method, etc. as necessary, to obtain the general formula (1-2).
The compound represented by can be produced. Moreover, after the completion of the reaction, the compound represented by general formula (II-2) can be subjected to the next reaction without being isolated.

(1) Thiolation. This reaction may be carried out in the presence of an inert solvent such as glacial acetic acid. Examples of reducing agents that can be used in this reaction include zinc, tin, and tin chloride.

The reducing agent may be used in an amount equal to or in excess of the compound represented by the general formula (Ill-2), preferably 5 times or more in mole or more.

The reaction time varies depending on the reaction scale, reaction humidity, etc., but may be selected from a range of several minutes to 48 hours. After the reaction is complete, the reaction solution containing the target product is poured into water, isolated by a solvent extraction method, etc., and purified by a recrystallization method, a column chromatography method, etc. if necessary, to obtain a compound of the general formula (1-6).
A 4-monosubstituted phenyl-1,2-propenyloxy)phenyltriazolin-5-one derivative represented by the formula can be produced.

(F method) (1-7) (1-8) (
In the formula, R1, R3, A%X and 2 are the same as above, and R
←3 is an alkyl group having 1 to 8 carbon atoms, 1 to 8 carbon atoms
8 haloalkyl group, cycloalkyl group having 3 to 6 carbon atoms, lower cyanoalkyl group, lower alkenyl group, lower haloalkenyl group, lower alkynyl group, lower alkoxyalkyl group, cycloalkylalkyl optionally substituted with a halogen atom groups, which may be the same or different, 1
An aminoalkyl group optionally substituted by ~2 lower alkyl groups, which may be the same or different; one or more lower alkyl groups replaced by a phenylsulfonyl group, which may be the same or different; A phenylalkyl group s-Ic1l(CHR')n-CO-Rt' which may have one or more substituents selected from a halogen atom or a lower alkoxycarbonyl group on the phenyl ring, which may be different
(In the formula, A is the same as above, R● is the same as above (L,
Rt: i Hydroxy group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, amino group or phenyl group which may be substituted with 1 to 2 lower alkyl groups which may be the same or different , and n is an integer from 0 to 2. ) That is, 4-monosubstituted phenyl- represented by general formula (1-7)
1.2-propenyloxy)phenyl}riazoline-5
-one derivative with the general formula (
4-monosubstituted phenyl expressed by general formula (1-8) by reacting with halides expressed by n-3) 1.2
-propenyloxy)phenyl}riazolin-5-one derivatives can be produced.

By carrying out this reaction in the same manner as (Method B), it is possible to produce a 4-monosubstituted phenyl-1,2-propenyloxy)phenyl}riazolin-5-one derivative represented by the general formula (1-8). .

(Method G) (1-9) (I-4) (1-10) (In the formula, Ra is the same as above, and H tos is a lower alkoxy group, a lower alkoxy group, a tllil- or different represents an amino group which may be substituted with 1 to 2 lower alkyl groups, and n represents an integer of 0 to 2.) That is, 4-monosubstituted phenyl 1,2-propenyloxy)phenyl(2-chloro-5
-one is subjected to /Sa genation in the presence of an inert solvent to form tR/%rides represented by the general formula (II-4), and the acid-ones are isolated or unisolated without isolation. Producing 4-monosubstituted phenyl-1,2-propenyloxy)phenyltriazolin-5-one represented by m general formula (l-10) by reacting with alcohols or amines in the presence of an active solvent and a base. can do. 1. Examples of inert solvents that can be used in the halogenation reaction include halogenated hydrocarbons such as methylene chloride, dichloromethane, quaa form, and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene, and xylene, and methyl cellosolve, diechi rho
Examples include chain ethers such as polyester and diisopro[9]4 ether, and cyclic ethers such as dioxane and tetrahydrofuran.

Examples of the halogenating agent include thionyl chloride, phosphorus pentachloride, and phosphorus trichloride.

The amount of halogenating agent used is expressed by general formula (1-9) 4
The monosubstituted phenyl-1,2-propenyloxy)phenyltriazolin-5-one may be used in an amount ranging from an equimolar amount to an excess molar amount, and it is preferable to use an excess molar amount.

For the purpose of promoting this reaction, it is also possible to use a catalytic amount or equimolar to excess molar amount of triethylamine, pyridine, dimethylformamide, etc. The reaction temperature may be selected from the range of room temperature to the boiling point of the inert solvent used.

The reaction time varies depending on the reaction scale, reaction time, etc., but may be selected from a range of several minutes to 48 hours.

After the reaction is completed, excess halogenating agent and inert solvent are distilled off from the reaction solution containing the target product, and the target product is formed into a single layer. If necessary, purification methods such as recrystallization or distillation are used to It can be purified and isolated. Alternatively, the product may be subjected to the next reaction without purification.

L As the inert solvent that can be used in the esterification or acid amidation reaction, for example, the solvent used in the above halogenation reaction can be used.
In addition, in the case of esterification, it is also possible to use an excess amount of an alcohol corresponding to the ester and use it as an inert solvent and a reactant. The amount of alcohols or amines used is according to the general formula (Kawa-4)
It may be used in an equimolar to excess molar amount relative to the acid halide represented by. As the base that can be used in this reaction, an inorganic base or an organic base can be used. Examples of the inorganic base include hydroxides and carbonates of alkali metal atoms such as sodium and potassium, or alkaline earth metal atoms such as calcium. Examples of organic bases include tertiary amines such as triethylamine, organic bases such as 4-dimethylaminopyridine, and 1,8-diazabicyclo(5,4,0)-17-undecene. I can give an example. The reaction temperature may be selected from the range of 0°C to the boiling point of the inert solvent used, preferably 0°C to 150°C.
It is best to select from the range of . The reaction time may be selected from a range of several minutes to 48 hours, which varies depending on the reaction scale, reaction time, etc. After completion of the reaction, perform operations such as solvent extraction using conventional methods from the reaction solution containing the target product, and if necessary, purify by ## production method such as recrystallization method or color chromatography method. A 4-monosubstituted phenyl-1-2t4-triazolin-5-one represented by the general formula (1-1o) can be produced.

(Method H) (1-3) (1-1 1) ■Rt2 (1-12) (In the formula, Rl1R, X and 2 are the same as above, and R@
``''''l and R←3 may be the same or different. Rll)
-CO-ORI" (In the formula, RAI and Hu are the same as above.) That is, 4-monosubstituted 7enyl'*2e'-}9azoline- represented by the general formula (1-3) A 5-one derivative is reacted with a halide represented by the general formula (II-5) in the presence of an inert solvent and a base to form a 4-monosubstituted phenyl group represented by the general formula (1-1 1 ). -propenyloxy)phenyltriazolin-5-one derivative, and the 4-monosubstituted phenyl-1,2-propenyloxy)phenyltriazolin-5-one derivative represented by the general formula (.I-1 1 ) The 4-monosubstituted phenyl group represented by the general formula (1-12) may be reacted with the halide represented by the general formula (It-4) with or without isolation. ' - }Ryazolin-5-one derivatives can be produced.This reaction is carried out in the same manner as (Method B) to produce general formula (1-11) or (1-12
) 4-substituted phenyl'#21' −
}Ryazoline-5-one derivatives can be produced. In addition, when R-1 and R●-2 are the same, the halide is converted into a 4-monosubstituted phenylene-1,2-propenyloxy compound represented by the general formula (1-12) in the first reaction step. ) phenyl}lyazolin-5-one derivatives can also be used.

Below, 4-monosubstituted 7-enyl-1.
Typical compounds of 2-propenyloxy)phenyl}riazolin-5-one derivatives are illustrated in Table 1, but the present invention is not limited to these compounds. ♂( (Futo・zu?1xy-}ノSO-U->7I〆P, 4-monosubstituted phenyl-1 represented by the general formula +11 of the present invention
．． 2-propenyloxy)phenyl}riazoline-5-
Semicarpazides represented by the general formula (■-t), which are the basic compounds of on derivatives, can be produced, for example, by the method illustrated below.

(In the formula, RI.Rs and /-2
), and by reacting the incyanates with a compound represented by 2), a compound represented by the general formula (F/- 1) can be produced. can.

In addition, the compound represented by the general formula (1-1) is a compound represented by the general formula (
A compound represented by IV-5) in which 81 is a hydrogen atom can be produced by the above method, method A, and method B.

Below, 4-fit substituted phenyl-1 represented by general formula 111 of the present invention. 2. 4-} IJ Asorin-5-
Although representative examples of ON derivatives are shown, the present invention is not limited to these examples.

[Example 1] Synthesis of 4-chloroa-2-fluoro-5-isobu-a-poxyphenyl isocyanate. -25 units of -5-improboxyaniline were added dropwise at room temperature. After the addition, the solution was refluxed for 3 hours. After distilling off the toluene under reduced pressure, hexane was added to the residue, and the resulting precipitate was filtered out. Concentration yielded 272 of the target product a (yield 9
614) NMR (δppm. CDC#..'rM8
) t35 (d, 6H) 438 (hgpt, IH) Mr. 50 (d. IH) 7,1o (a. IH) 1-2 1-acetyl-4-(4-chloro-2-fluoro-5-
Synthesis of isopropoxyphenylnosemicarbazide or tetrahydrofuran 150- to acetohydrazide 9.0-
9 and triethylamine (L12) were added.

A solution of 28 g of 4-chloro-2-fluoro-5-4-soproboxyphenyl isocyanate dissolved in 25-f-trahydrofuran was added dropwise thereto at room temperature. After the addition was completed, the mixture was stirred for 6 hours, and the resulting crystals were collected in an oven. Ff[ was concentrated and crystals were obtained from it. Combined with the previous crystal, 2279 of the target product was obtained. (Yield 624) NMR (δppm. DMSO-d@, TM8)1.
35(d6H) 1,1o (s 3H) tas (hept 1H) y. as (d 1H ) &3-methyl-Δ2 (d 1}1 )l14
5 (brs 2H) 9.55 (brs IH) 1-3 4-(4-chloro-2-fluoro-5-improboxyphenyl)-3-methyl-j''-L2-propenyloxy)phenyltriazoline- Combination of 5-ono (compound 1-7 cetyl-4-(4-chloro-2-fluoro-5-
Improboxyphenyl) Semicarbazide 17-49
The mixture was added to 300% of a 2% potassium hydroxide aqueous solution and refluxed for 5 hours. After the reaction was completed, the reaction solution was allowed to cool and then neutralized with 2N hydrochloric acid while cooling with water. The resulting precipitate was extracted with ethyl acetate,
After washing with water and drying, the solvent gold was distilled off under reduced pressure to obtain 11.5 g of the desired product. Physical properties 151.3°C Yield 71 yen Example 2 4-(4-chloro-2-fluoro-5-imbroboxy-3-methyl-Δ2-3-methyl-1pro[9]4-Jt
-1, Otsu 4-triazolin-5-one combination (compound &
S1) (2-Chloro-4-methyl-/-1.2-propenyloxy)phenyltriazolin-5-one (167: 2.09% proqiodide and 2.09% potassium carbonate)
was added to 200 mg of A7-ton and refluxed for 4 hours. After cooling, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water and dried.

The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain the desired product Il629.
(Yield 95%) n1) t5322 (23°C) Example 3 4-(2,4.5-trichloro3-methyl-Δ2-1-ethylaminocarbonyl-3-methyl-mo2.4-triazoline-5 Synthesis of -one (compound Todoroki 330) 4-(4-chloroo-2-fluoro-5-isozumi 559 4-(trichloro3-methyl-Δ2-5-methyl-1"
-1.2-propenyloxy)phenyltriazoline-
5-one was dissolved in 20-tetrahydrofuran. CL169 ethyl isocyanate and several drops of triethylamine were added thereto, and the mixture was refluxed for 1 hour. After completion of the reaction, tetrahydrofuran was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain the desired product (L53 9. m.p. 177.3°C, yield 76, Example 4 4-(2 -chloro-4-methyl-5-nitro3-methyl-Δ2-(4-chloro-2-fluoro-3-methyl-,
1t-1,2-propenyloxy)phenyltriazolin-5-one (compound &557) 4-triazoline-4-methyl3-methyl-Δ2-(4-chloro-2-
Fluoro-3-methyl-l-2.4-triazoline-5-one (259 g) was dissolved in concentrated sulfur @100, and a mixed acid consisting of concentrated nitric acid &9- and concentrated sulfuric acid 15- was added until the reaction solution temperature was 5.
It was added dropwise while cooling so as not to exceed ℃. After the dropwise addition was completed, the mixture was further stirred at a temperature below 5°C. After the reaction was completed, the reaction solution was poured into 500 dIC of ice water, extracted 5 times with 200 ml of ethyl acetate, washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 2 and 3 crystals of the desired product. (Yield 94 excellent) NMR (δppm, CDCA3) t41
(d, 6H) 108 (S, 5H) 267 (s, 3H) 48 (m, IH) 7.56 (s, IH) [02 (s. IH) Example 5 4-(5-amino-2- Chloro-4-methyl3-methyl-Δ2-1-4-triazoline-3-methyl-At-1
．． 2-propenyloxy)phenyltriazoline-5-
(Compound 4338) 4-triazoline-4-
Methyl-5-nitrophenyl)-1-isop a[9]4
-3-Methyl-, p-%2-propenyloxy)phenyl}riazolyy-s-, tyzaog (Il09 mol)
was dissolved in 200 dK of acetic acid, and using 10 g of palladium on carbon as a catalyst, hydrogen gas was passed under a pressure of 5 noodles/1 until no hydrogen gas was consumed. After the reaction was completed, the catalyst was removed from the furnace, the solution was concentrated, and the residue was recrystallized from ethyl acetate to obtain 210 g of the desired product. (Yield 85 excellent) NMR (δpp
m, CD (, #3) 1.38 (d, 6H) 2-00 (S, AH) 2.07 (a, SH) 591 (s, 2H) br 4.4+6 (r. IH) Melon 54 (s, IH) 7.10 (s. IH) Example 6 4-triazoline-5-hydroxy-4-methyl3-methyl-Δ2-1-inpro[9]4-3-methyl-,p
Synthesis of -1.2-propenyloxy)phenyl}riazolin-5-one (compound 164 8 )i 4(5-amino-2-chloro-4-methylphenyl)-
1-isobro[9]4-3-methylno2-L2. A-
tIJ7zo13 7-5-t72cL09 (107
13 moles) 1&:s o * (v/v) sulfuric acid 150
- dissolved in. Sodium nitrite & 929k water 5
A diazonium salt was prepared by adding a solution of I dissolved in the same solution dropwise at 5° C. or below and reacting with stirring for 30 minutes. Next, this diazonium salt solution was added dropwise into 30 mm sulfur fR150 heated to 110°C, and a reaction was carried out for 20 minutes. After the reaction was completed, 100 g of ice was added and cooled, and the precipitated crystals 'kF
I took it. After washing with water and drying, 5 g of the target product 1a was obtained. m. 9. 1846°C (Yield: 92 pieces) Example 7 4-(4-chloro-2-fluoro-5-hydroxyphenyl)-3-methyl-1-pro[9]44! -1.2-
Synthesis of propenyloxy)phenyl}riazolin-5-one (compound A559) was added, and the mixture was extracted with ethyl acetate.
After washing with water and drying, ethyl acetate was distilled off under reduced pressure to obtain the desired product t-2.
I got 669. Physical properties m. p. 19α5℃ (Yield, $8
5%) Example 8 8-1 4-(2-/Rolo-5-chlorosulfonyl-4-methylphenyl)-1-i7F*Hil-s-methyl is-mo2-
The combination of 4-(4-chloro-2-fluoro-5-yn(2-chloro-4-methyl-5-methyl-1-pro[9]4) of propenyloxy)phenyltriazolin-5-one is -1
．． 2-propenyloxy)phenyl}riazoline-5-
7g of Ongo was dissolved in 1122mK of vinegar. 45 Hydrogen polybromide@&7- was added thereto, and the mixture was refluxed for 3 hours. After the reaction is complete,
The reaction solution was concentrated under reduced pressure, and ice water was added to the residue to give 4-triazoline-4-methyl3-methyl-Δ2-1-ingro[9]4
-3-Methyl Snow-'L 2. 4-Triazolin-5-one 5Qg of melon was dissolved in 15-15% of concentrated sulfuric acid, and -5
It was cooled to ℃. Add 22sj of fuming sulfuric acid to SoC at a reaction temperature of 0.
The mixture was added dropwise so as not to exceed 0°C, and then the reaction was continued for 1 hour below 0°C. The reaction solution was returned to room temperature, 37 Wlt of carbon tetrachloride was added dropwise thereto, and the reaction was carried out at 5°C for 2 hours.
It happened.

The reaction solution was poured into water, extracted with dichloromethane, washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 57 g of the desired product as an oily substance.

Physical Properties Oil Yield 45 kn 8-2 4-(2-chloro-5-mercapto-4-methylphenyl)-1-477'rohil-3-71 fruJ!
1.2-propenyloxy)phenyltriazoline-5
Synthesis of -(2-chloro-5-1-rosulfonyl-4-methylphenyl)-(4-chloro-2-fluoro-5-methyl-1,2-propenyloxy)phenyl}riazolin-5-one 7 g of acetic acid was dissolved in 50 Frt of acetic acid, 8 g of zinc powder was added thereto, and the mixture was refluxed for 2 hours. After the reaction solution was allowed to cool to room temperature, insoluble materials were removed and the P solution was concentrated under reduced pressure. The residue was dissolved in ethyl acetate, washed with water, dried over magnesium sulfate, and the solvent was removed under reduced pressure to give the desired product as crystals (L67
I got 9.

Yield 304I NMR (δppm, TMS) 1.48 (d
6H) zOB(ts 3H) 'L57(S 5}{) 550(S tH) a. sz (h IH) 7.29 (S IH) 7. s8(-s 1H) 8-3 4-triazoline-5-isopropylthio 4-methulfenyl)-1-{sobro[9]4-3-methyl-,
Synthesis of p-1.2-propenyloxy)phenyltriazolin-5-one. (Compound 4160) 4-triazoline-5-mercabuto-4-methylphenyl)-1-inguro[9]4-s-mer,1m-1,2-propenyloxy)phenyltriazolin-5-one ( L67g
is dissolved in benzene 20- and iodide isopro[9]4(
L811, tetrabutylammonium bromide (L42g>
and potassium hydroxide (by adding 2L aqueous solution of L21,
Refluxed for 30 minutes. The reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, and dried over magnesium chloride. After removing the solvent, the residue was purified by gold silica gel column chromatography to obtain the desired product L569.

Yield: 95 m. p・94・7℃Example 9 4=(2-propenyloxy)phenyldimethyl-5-
N-methyl-N-n-butylaminophenyl)-1-inguro[9]4-5-methyl-43-L2.4-triazoline (4-(5-7mino-2-propenyloxy)phenyldimethyl 3-Methyl-Δ2-1-isoproα[9]4-3-methyl-is-Z4-1 riazolin-5-one% L279-n-butyl iodide and c
A solution of L449 sodium bicarbonate in sulfolane 201 was stirred at 145-150°C for 1 hour. After cooling to room temperature, 50 g of methyl iodide and 139 g of sodium bicarbonate were added thereto, heated to 150° C. over 1 hour, and then stirred at this temperature for 1 hour.

After cooling to room temperature 1, water was extracted with ethyl acetate. Washing with water 2> Then drying with magnesium sulfate. After ethyl acetate was distilled off, the residue was purified by silica gel column chromatography to obtain 42 g of the desired product as an oil. nD- L5176 (20°C) Yield 32 scratches Example 10 2-chloro-4-fluoro-5-(3-methyl-1-pro[9]4-propenyloxy)phenyltriazoline-5 -on-4-yl) phenoxyacetic acid ethyl ester (Compound Todoroki 36) Example 11 2-chloroo-4-fluoro-5-(3-methyl-1-pro[9]4- is -1. Synthesis of 2-propenyloxy)phenyltriazolin-5-one-4-yl)phe/xyacetic acid ethyl ester (Compound Shop 36) 4-(4-kαrho-2-fluoro-5-hydroxyphenyl)- 1 g of 3-methyl-1-gulo[9]4-1-1.2-propenyloxy)phenyl 1-riazoli/-5-one and bromoacetic acid ethyl ester (L711 dissolved in 201 acetone).
-f: 1 g of potassium carbonate was added to this, and the mixture was refluxed for 2 hours.
After the reaction was completed, the reaction solution was poured into ice water and extracted with ethyl acetate. After washing with water and drying, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography;
I got 89. rr1. p. 117.5℃ Astringency 43% 2-chloro-4-fluoro-5-(3-methyl-1-pro[9]4
1.059 of -1L2-propenyloxy)phenyl}lyazolin-5on-4-yl)phenoxyacetic acid was dissolved in 20 cc of thionyl chloride. After refluxing for t-3 hours, thionyl chloride was removed under reduced pressure to quantitatively obtain acid chloride. This acid chloride 089 and ethanol A21 were dissolved in tetrahydrofuran. There, triethylamine (
A solution of LAg in 5 volumes of tetrahydrofuran was added dropwise at room temperature. After the dropwise addition was completed, the reaction was allowed to proceed at room temperature for 4 hours. The reaction solution was poured into ice water and extracted with ethyl acetate. After washing with water and drying, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 9 g of the desired product.

m. p. 117.5°C Yield 80% Example 12 4-(4-chloro-2-methyl-5-methoxy3-methyl-Δ2-1-4-triazoline-3-methyl, 1t-
1,2-propenyloxy)phenyltriazoline-5
-one synthesis was added to 20 ml of acetone and refluxed for 5 FI#. The reaction mixture was poured into ice water and extracted with ethyl acetate.
After washing with water and drying over sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 11L69g of the desired product. m. p. 154-159
Yield 'P3% Example 151-(1-ethylpro[
9] 4) Synthesis of -4-(2-QQ-4-fif-5-proboxy3-methyl-Δ2-3-methylJR-1.2-propenyloxy)phenyltriazolin-5-one 4-( 4-chloro-3-methyl-Δ2-lj”-1,2-propenyloxy)phenyl}methyl iodidez0 Rho-2-methyl-5- (4-chloro-2-fluoro-3 liazoline-5-oncyl and potassium carbonate Hydromethy(170g, 12.0g 4-triazoline-4-methyl-5-propoxy3-methyl-Δ2-3-methyl-j”-1.2-propenyloxy)phenyltriazoli/-5one tag, 3- Pua a
Mopentane 23g, tetra-n-butylammonium bromide▲
t2g and potassium hydroxide rL629 were added to a mixed solvent of water and benzene 15, and refluxed for 6 hours. After the reaction was completed, it was extracted with benzene, washed with water, and dried with magnesium sulfate. Benzene was removed under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 1.89% of the desired product. m. p. 115 4°C Yield 6B% 4-monosubstituted phenyl L represented by the general formula (1) of the present invention 2,
4-triazolin-5-one derivatives are useful as agricultural and horticultural fungicides, for example, for rice blast disease (Piricu).
laria oryzae), powdery mildew (Erysiphe graminis) on barley and wheat, and powdery mildew (Sphaerotheca) on K.
fulginea), apple powdery mildew (Po
dosphaera leucotricha) and powdery mildew of grapes (Uncinula necato
Powdery mildew, wheat rust ( Pucciniavecondita
), oat crown disease (Puccjnia coron)
ate) and other host plant rusts, tomato gray late blight (Phytophthora capsici), and other host plant blights, etc. shows a high control effect on leaf blast and Japanese root blast when applied on the water surface or by spraying. 4-substituted phenylene L represented by the general formula 11) of the present invention
When the 2-propenyloxy)phenyltriazolin-5-one derivative is used as a fungicide for agriculture and horticulture, it may be prepared into a dosage form convenient for use as in the conventional method for pesticide formulations. It is prepared by mixing with dosage forms such as powders, granules, fine granules, wettable powders, emulsions, oils, aerosols, flow dusts, smoke agents, transpiration agents, tablets, and auxiliaries, and is used for rice,
It can be applied to the stems and leaves of wheat, vegetables, flowers, special crops, fruit trees, trees, etc. by diluting it with water, etc.
Furthermore, 4-11-substituted phenyl L represented by the general formula II) of the present invention 2. Agricultural and horticultural pesticides containing a 4-to-1 asorin-5-one derivative as an effective component can be used preventively before the outbreak of a disease or for treatment after the outbreak of a disease. The application amount of the agricultural and horticultural disinfectant★1 of the present invention is not necessarily constant depending on the species of the compound, the target crop, the target disease, the method of use, etc., but the effective amount is in the range of b1 to 500 k per 10 are. You can select and apply it as appropriate. The agricultural and horticultural fungicide of the present invention can be mixed with or used in combination with other agricultural chemicals, fertilizers, plant nutrients, etc. that can be applied at the same time as the fungicide.

For example, when controlling diseases with an agricultural and horticultural fungicide containing the 4-monosubstituted phenyl-1, Otsu 4-triazolin-5-one derivative represented by the general formula +1) of the present invention as an active ingredient, the target disease It is also possible to create a multi-purpose pest control agent by mixing it with a control agent for other pests that occur at the same time as the outbreak.

Typical test examples and formulation examples of the present invention are illustrated below, but the present invention is not limited thereto. Test example 1. Rice blast disease control test by spraying diameter 9/I
7c rice planted in II clay pot (variety: Nipponbare, 5 leaf stage, 1
A chemical solution containing a drug containing the compound of the present invention as an active ingredient at a predetermined concentration was sufficiently sprayed with a spray gun, and one day after the spraying, rice blast fungi (Pyricular
Ia oryzae) was inoculated by spraying with a spore suspension.
After inoculation, the leaves were placed in a damp room for 20 hours, then transferred to a greenhouse, and 6 days after inoculation, the number of lesions was investigated, and the control value was calculated by comparing with the untreated area, and the effectiveness was judged using the following criteria. Ta. (3 series per ward) 4... Control value 100-95 3... Control value 94-80% 2... Control value 79-604 1... ... Control value: 59 to 0 Excellent results are shown in Table 2.

Table 2 Test Example 2 Rice blast disease control test by water surface application Paddy rice grown in 1/10,000 are porcelain pots (variety Nipponbare,
4:l [6 plants planted in the season] K Apply a prescribed amount of the chemical to the water surface, leave it at room temperature for one week, and then
A spore suspension of lalia oryzae) was inoculated by spraying. Greenhouse [After being left for 20 hours, it was transferred to a greenhouse, and 6 days after inoculation, the number of lesions on each VC leaf was investigated, the control value was calculated, and the evaluation was made using the same criteria as Test Example 1. (1 ward 5 consecutive games) The results are shown in Table 3. Table 3 Prescription example 1. Compound Todoroki 1 50 parts Polyoxyethylene nonylphenyl ether 5
Mix and grind evenly more than 100% to make an irrigation agent. Formulation example 2 Compound A64 5 parts clay●
Bentonite mixture 90 parts Calcium ligninsulfonate 5 parts or more are mixed and ground uniformly, mixed with an appropriate amount of water, and granulated to form granules. Prescription Example 5 Compounds 247 50 parts xylene 40 parts Applicant Nippon Nohyaku Co., Ltd.

Claims (8)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a haloalkyl group having 1 to 12 carbon atoms. group, cyanoalkyl group, cycloalkyl group having 3 to 6 carbon atoms, lower alkenyl group, lower haloalkenyl group, cycloalkenyl group, lower alkynyl group, lower alkoxyalkyl group, lower alkylthioalkyl group, lower alkylsulfonyl group, lower alkoxyalkoxy An alkyl group, a lower acyl group, a lower acylalkyl group, a cycloalkylcarbonyl group, which may be the same or different, and may have one or more substituents selected from a halogen atom or a lower haloalkylthio group on the phenyl ring. A phenylalkyl group, a cycloalkylalkyl group that may have one or more halogen atoms on the cyclo ring, a lower alkoxycarbonyl alkyl group, an oxirane alkyl group that may be substituted with a lower alkyl group, even if they are the same or different. an aminocarbonyl alkyl group, a lower alkoxyimino alkyl group, which may have one or two substituents selected from a lower alkyl group or a phenyl group, or a lower alkyl group, a phenyl group, which may be the same or different; Represents an aminocarbonyl group which may have 1 to 2 substituents selected from phenyl groups substituted with one or more halogen atoms which may be the same or different, and R^2 is a hydrogen atom or a lower represents an alkyl group, R^3 is a halogen atom, a nitro group, a lower alkyl group, a sulfinyl alkyl group, a sulfonylalkyl group, -A-R^4 (wherein A represents -O- or -S-, R ^4 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a lower cyanoalkyl group, a lower alkenyl group, a lower haloalkenyl group , a lower alkynyl group, a lower alkoxyalkyl group, a cycloalkylalkyl group optionally substituted with a halogen atom,
An aminoalkyl group that may be the same or different and may be substituted with 1 to 2 lower alkyl groups; an aminoalkyl group that may be the same or different and may have one or more lower alkyl groups on the phenyl ring; It represents a phenylsulfonyl group or a phenylalkyl group which may be the same or different and which may have one or more substituents selected from a halogen atom or a lower alkoxycarbonyl group on the phenyl ring. ), -A- (CHR^8)n-CO-R^9 (wherein A is the same as above, R^8 represents a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and R^9 is hydroxy n represents an integer from 0 to 2), -CO-R^5 (in the formula, R^5 is -A-R^1^0 (in the formula, A is the same as above, and R^1^0 is hydrogen atom, alkali metal atom, lower alkyl group, phenyl group or phenylalkyl group which may be substituted with one or more halogen atoms which may be the same or different) or lower alkyl group which may be the same or different ), or -N(R^6)R^7 (in the formula, R^6
and R^7 may be the same or different, and include a hydrogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkenyl group,
Lower alkylcarbonyl group, lower haloalkylcarbonyl group, lower alkylsulfonyl group or -C(R^1^1
)R^1^2-CO-OR^1^3 (in the formula, R^1^1
and R^1^2 may be the same or different and represent a hydrogen atom or a lower alkyl group, and R^1^3 represents a lower alkyl group. ) is shown. Moreover, R^6 and R^7 can also represent an alkylene group together. ), X may be the same or different, a halogen atom, a lower alkyl group,
Indicates a lower alkoxy group or a nitro group. ) A 4-substituted phenyl-1,2,4-triazolin-5-one derivative represented by: (2) R^1 is an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, a lower alkenyl group,
It represents a lower haloalkenyl group, a lower alkoxyalkyl group, or a cycloalkylalkyl group which may have one or more halogen atoms on the cyclo ring, R^2 represents a hydrogen atom or a lower alkyl group, and R^3 represents - A-R^4 (in the formula, A
represents -O- or -S-, R^4 has 1 to 8 carbon atoms
represents an alkyl group, lower alkenyl group or lower haloalkenyl group. ) or -N(R^6)R^7 (in the formula R^6
and R^7 may be the same or different and represent a hydrogen atom, a lower alkyl group, or a lower alkenyl group. Moreover, R^6 and R^7 can also represent an alkylene group together. ), and X may be the same or different and represents a halogen atom or a lower alkyl group. (3) R^1 represents an alkyl group, lower alkenyl group, lower alkoxyalkyl group, or cycloalkylalkyl group having 1 to 5 carbon atoms, R^2 represents a hydrogen atom or a lower alkyl group, and R^3 represents -A-R^4 (wherein, A is -O
-, and R^4 represents an alkyl group or lower alkenyl group having 1 to 8 carbon atoms. ) or -N(R^6)R^7
(In the formula, R^6 and R^7 may be the same or different,
4-substituted phenyl-1,2,4-triazoline-5 according to claim 2, which represents a hydrogen atom or a lower alkyl group), X may be the same or different, and represents a halogen atom or a lower alkyl group -one derivative. (4) The 4-substituted phenyl-1,2,4-triazolin-5-one derivative according to claim 3, which is selected from the following compounds. [1] 4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-1,3-dimethyl-Δ^2-1,2
,4-triazolin-5-one[2]4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-1-ethyl-Δ^2-1,2,4-
Triazolin-5-one[3]4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-1-ethyl-3-methyl-Δ^2-
1,2,4-triazolin-5-one [4]4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-1-propyl-Δ^2-1,2,4
-triazolin-5-one[5]4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-3-methyl-1-propyl-Δ^2
-1,2,4-triazolin-5-one[6]4-{4-chloro-2-fluoro-5-(2-propenyloxy)phenyl}-3-methyl-1-propyl-Δ^2-1 ,2,4-triazolin-5-one[7]4-(4-chloro-2-fluoro-5-methoxyphenyl)-1-isopropyl-3-methyl-Δ^2-
1,2,4-triazolin-5-one[8]4-(2-chloro-5-ethoxy-4-methylphenyl)-1-isopropyl-3-methyl-Δ^2-1
,2,4-triazolin-5-one[9]4-(2-bromo-5-ethoxy-4-methylphenyl)-1-isopropyl-3-methyl-Δ^2-1
,2,4-triazolin-5-one[10]4-(2-bromo-4-methyl-5-propoxyphenyl)-1-isopropyl-3-methyl-Δ^2
-1,2,4-triazolin-5-one[11]4-(2-chloro-4-methyl-5-propoxyphenyl)-1-isopropyl-3-methyl-Δ^2
-1,2,4-triazolin-5-one[12]4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-1-isopropyl-3-methyl-
Δ^2-1,2,4-triazolin-5-one[13]4-(2-chloro-5-isopropoxy-4-
methylphenyl)-1-isopropyl-3-methyl-Δ
^2-1,2,4-triazolin-5-one[14]4-(2-bromo-5-isopropoxy-4-
methylphenyl)-1-isopropyl-3-methyl-Δ
^2-1,2,4-triazolin-5-one[15]4-(2-fluoro-5-isopropoxy-4
-methylphenyl)-1-isopropyl-3-methyl-
Δ^2-1,2,4-triazolin-5-one[16]4-(5-butoxy-2-chloro-4-methylphenyl)-1-isopropyl-3-methyl-Δ^2-
1,2,4-triazolin-3-one[17]4-(5-s-butoxy-2-chloro-4-methylphenyl)-1-isopropyl-3-methyl-Δ^
2-1,2,4-triazolin-5-one[18]4-(2-chloro-5-ethoxy-4-methylphenyl)-1-s-butyl-3-methyl-Δ^2-1
,2,4-triazolin-5-one[19]4-(2-chloro-4-methyl-5-propoxyphenyl)-1-s-butyl-3-methyl-Δ^2-
1,2,4-triazolin-5-one[20]4-(2-chloro-4-methyl-5-isopropoxyphenyl)-1-s-butyl-3-methyl-Δ^
2-1,2,4-triazolin-5-one[21]4-(5-s-butoxy-2-chloro-4-methylphenyl)-1-s-butyl-3-methyl-Δ^2
-1,2,4-triazolin-5-one[22]4-{2-chloro-4-methyl-5-(2-propenyloxy)phenyl}-1-s-methyl-3-methyl-Δ^2 -1,2,4-triazolin-5-one[23]1-s-amyl-4-(2-chloro-4-methyl-5-methoxyphenyl)-3-methyl-Δ^2-1
,2,4-triazolin-5-one[24]1-s-amyl-4-(2-chloro-5-ethoxy-4-methylphenyl)-3-methyl-Δ^2-1
,2,4-triazolin-5-one[25]4-(2-chloro-4-methyl-5-isopropoxyphenyl)-3-methyl-1-(2-propenyl)-Δ^2-1,2 ,4-triazolin-5-one[26]4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-1-methoxymethyl-3-methyl-Δ^2-1,2,4-triazoline- 5-one[27]1-cyclopropylmethyl-4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-3-
Methyl-Δ^2-1,2,4-triazolin-5-one[28]4-(2-chloro-5-isobutoxy-4-methylphenyl)-1-isopropyl-3-methyl-Δ^
2-1,2,4-triazolin-5-one[29]4-(2-chloro-5-N-ethylamino-4
-methylphenyl)-1-isopropyl-3-methyl-
Δ^2-1,2,4-triazolin-5-one[30]4-(2-chloro-4-methyl-5-N-propylaminophenyl)-1-isopropyl-3-methyl-Δ^2- 1,2,4-triazolin-5-one[31]4-(2-chloro-5-N-methyl-N-propylamino-4-methylphenyl)-1-isopropyl-3-methyl-Δ^2- 1,2,4-triazoline-5
-one[32]4-(2-chloro-4-methyl-5-N,N-
dipropylaminophenyl)-1-isopropyl-5-
Methyl-Δ^2-1,2,4-triazolin-5-one[33]4-(2-chloro-5-N-ethyl-N-methylamino-4-methylphenyl)-1-isopropyl-
5-Methyl-Δ^2-1,2,4-triazoline-5-
one[34]4-(2-chloro-5-ethoxy-4-methylphenyl)-1-(1-ethylpropyl)-3-methyl-Δ^2-1,2,4-triazolin-5-one[ 35] 1-s-methyl-4-(2-chloro-5-N,
N-diethylamino-4-methylphenyl)-3-methyl-Δ^2-1,2,4-triazolin-5-one [36]4-(2,4-dimethyl-5-propoxyphenyl)-1-isopropyl -3-methyl-Δ^2-1,
2,4-triazolin-5-one [37]1-s-methyl-4-(5-ethoxy-2,4
-dimethylphenyl)-3-methyl-Δ^2-1,2,
4-triazolin-5-one[38]1-s-methyl-4-(2,4-dimethyl-5
-propoxyphenyl)-3-methyl-Δ^2-1,2
,4-triazolin-5-one[39]1-s-butyl-4-(5-s-butoxy-2
,4-dimethylphenyl)-3-methyl-Δ^2-1,
2,4-triazolin-5-one[40]-(5-ethoxy-2,4-dimethylphenyl)-1-(1-methylbutyl)-3-methyl-Δ^2-
1,2,4-triazolin-5-one[41]4-(2,4-dimethyl-5-propoxyphenyl)-1-(1-methylbutyl)-3-methyl-Δ^
2-1,2,4-triazolin-5-one [42]4-(5-isopropoxy-2,4-dimethylphenyl)-1-(1-methylbutyl)-3-methyl-
Δ^2-1,2,4-triazolin-5-one[43]1-(1-ethylpropyl)-4-(5-ethoxy-2,4-dimethylphenyl)-3-methyl-Δ^
2-1,2,4-triazolin-5-one [44]1-(1-ethylpropyl)-4-(2,4-
dichloro-5-ethoxyphenyl)-3-methyl-Δ^2-1,2,4-triazoline-5-
on (5) - General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. Haloalkyl group, cyanoalkyl group, cycloalkyl group having 3 to 6 carbon atoms, lower alkenyl group, lower haloalkenyl group, cycloalkenyl group, lower alkynyl group, lower alkoxyalkyl group, lower alkylthioalkyl group, lower alkylsulfonyl group, having one or more substituents on the phenyl ring selected from a lower alkoxyalkoxyalkyl group, a lower acyl group, a lower acylalkyl group, a cycloalkylcarbonyl group, a halogen atom or a lower haloalkylthio group, which may be the same or different; a phenylalkyl group which may have one or more halogen atoms on the cyclo ring, a lower alkoxycarbonyl alkyl group, an oxirane alkyl group which may be substituted by a lower alkyl group, which may be the same or different; an aminocarbonyl alkyl group, a lower alkoxyimino alkyl group, which may have one or two substituents selected from a lower alkyl group or a phenyl group, or a lower alkyl group, a phenyl group, which may be the same or different; Alternatively, it represents an aminocarbonyl group which may have one or two substituents selected from the phenyl groups substituted with the above halogen atoms which may be the same or different, and R^2 is a hydrogen atom or a lower represents an alkyl group, R^3 is a halogen atom, a nitro group, a lower alkyl group, a sulfinyl alkyl group, a sulfonylalkyl group, -A-R^4 (wherein A is -O-
or -S-, R^4 is a hydrogen atom, carbon number is 1-
8 alkyl group, a haloalkyl group having 1 to 8 carbon atoms,
A cycloalkyl group having 3 to 6 carbon atoms, a lower cyanoalkyl group, a lower alkenyl group, a lower haloalkenyl group, a lower alkynyl group, a lower alkoxyalkyl group, a cycloalkylalkyl group optionally substituted with a halogen atom, the same or different an aminoalkyl group which may be substituted with one or two lower alkyl groups; a phenylsulfonyl group which may be the same or different and which may have one or more lower alkyl groups on the phenyl ring; Alternatively, it represents a phenylalkyl group which may be the same or different and may have one or more substituents selected from a halogen atom or a lower alkoxycarbonyl group on the phenyl ring. ), −
A-(CHR^8)n-CO-R^9 (wherein A is the same as above, R^8 represents a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and R^9 represents a hydroxy group, a lower It represents an alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, an amino group or a phenyl group which may be substituted with 1 to 2 lower alkyl groups which may be the same or different, and n is 0 to 2. Indicates an integer), -
CO-R^5 (in the formula, R^5 is -A-R^1^0 (in the formula, A is the same as above, R^1^0 is a hydrogen atom, an alkali metal atom, a lower alkyl group, the same or a phenyl group or phenylalkyl group which may be substituted with one or more halogen atoms which may be different) or 1 to 2 groups which may be the same or different and are selected from lower alkyl groups or phenyl groups. ), or -N(R^6)R^7 (wherein R^6 and R^7 may be the same or different, hydrogen atom, lower Alkyl group, lower haloalkyl group, lower alkenyl group, lower alkylcarbonyl group, lower haloalkylcarbonyl group, lower alkylsulfonyl group or -C(R^1^1)
R^1^2-CO-OR^1^3 (wherein, R^1^1 and R^1^2 may be the same or different and represent a hydrogen atom or a lower alkyl group, R^1^3 represents a lower alkyl group). Moreover, R^6 and R^7 can also represent an alkylene group together. ), and X may be the same or different and represents a halogen atom, a lower alkyl group, a lower alkoxy group, or a nitro group. ) represented by 4-
An agricultural and horticultural fungicide characterized by containing a substituted phenyl-1,2,4-triazolin-5-one derivative as an active ingredient. (6) R^1 is an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, a lower alkenyl group,
It represents a lower haloalkenyl group, a lower alkoxyalkyl group, or a cycloalkylalkyl group which may have one or more halogen atoms on the cyclo ring, R^2 represents a hydrogen atom or a lower alkyl group, and R^3 represents - A-R^4 (in the formula, A
represents -O- or -S-, R^4 has 1 to 8 carbon atoms
represents an alkyl group, lower alkenyl group or lower haloalkenyl group. ) or -N(R^6)R^7 (in the formula, R^
6 and R^7 may be the same or different and represent a hydrogen atom, a lower alkyl group or a lower alkenyl group. Moreover, R^6 and R^7 can also represent an alkylene group together. ), and X may be the same or different and represents a halogen atom or a lower alkyl group. (7) R^1 represents an alkyl group, lower alkenyl group, lower alkoxyalkyl group, or cycloalkyl group having 1 to 5 carbon atoms, R^2 represents a hydrogen atom or a lower alkyl group, and R^3 represents - A-R^4 (in the formula, A represents -O-, and R^4 represents an alkyl group or lower alkenyl group having 1 to 8 carbon atoms) or -N(R^6)R^7( During the ceremony,
R^6 and R^7 may be the same or different and represent a hydrogen atom or a lower alkyl group), and X may be the same or different and represent a halogen atom or a lower alkyl group. Fungicide for agriculture and horticulture. (8) The agricultural and horticultural fungicide according to claim 7, which contains the following compound as an active ingredient. [1] 4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-1,3-dimethyl-Δ^2-1,2
,4-triazolin-5-one[2]4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-1-ethyl-Δ^2-1,2,4-
Triazolin-5-one[3]4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-1-ethyl-3-methyl-Δ^2-
1,2,4-triazolin-5-one [4]4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-1-propyl-Δ^2-1,2,4
-triazolin-5-one[5]4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-3-methyl-4-propyl-Δ^2
-1,2,4-triazolin-5-one[6]4-{4-chloro-2-fluoro-5-(2-propenyloxy)phenyl}-3-methyl-1-propyl-Δ^2-1 ,2,4-triazolin-5-one[7]4-(4-chloro-2-fluoro-5-methoxyphenyl)-1-isopropyl-3-methyl-Δ^2-
1,2,4-triazolin-5-one[8]4-(2-chloro-5-ethoxy-4-methylphenyl)-1-isopropyl-3-methyl-Δ^2-1
,2,4-triazolin-5-one[9]4-(2-bromo-5-ethoxy-4-methylphenyl)-1-isopropyl-3-methyl-Δ^2-1
,2,4-triazolin-5-one[10]4-(2-bromo-4-methyl-5-propoxyphenyl)-1-isopropyl-3-methyl-Δ^2
-1,2,4-triazolin-5-one[11]4-(2-chloro-4-methyl-5-propoxyphenyl)-1-isopropyl-3-methyl-Δ^2
-1,2,4-triazolin-5-one[12]4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-1-isopropyl-3-methyl-
Δ^2-1,2,4-triazolin-5-one[13]4-(2-chloro-5-isopropoxy-4-
methylphenyl)-1-isopropyl-3-methyl-Δ
^2-1,2,4-triazolin-5-one[14]4-(2-bromo-5-isopropoxy-4-
methylphenyl)-1-isopropyl-3-methyl-Δ
^2-1,2,4-triazolin-5-one[15]4-(2-fluoro-5-isopropoxy-4
-methylphenyl)-1-isopropyl-3-methyl-
Δ^2-1,2,4-triazolin-5-one[16]4-(5-butoxy-2-chloro-4-methylphenyl)-1-isopropyl-3-methyl-Δ^2-
1,2,4-triazolin-5-one[17]4-(5-s-butoxy-2-chloro-4-methylphenyl)-1-isopropyl-3-methyl-Δ^
2-1,2,4-triazolin-5-one[18]4-(2-chloro-5-ethoxy-4-methylphenyl)-1-s-butyl-3-methyl-Δ^2-1
,2,4-triazolin-5-one[19]4-(2-chloro-4-methyl-5-propoxyphenyl)-1-s-butyl-3-methyl-Δ^2-
1,2,4-triazolin-5-one[20]4-(2-chloro-4-methyl-5-isopropoxyphenyl-1-s-butyl-3-methyl-Δ^2
-1,2,4-triazolin-5-one[21]4-(5-s-butoxy-2-chloro-4-methylphenyl)-1-s-butyl-3-methyl-Δ^2
-1,2,4-triazolin-5-one[22]4-(2-chloro-4-methyl-5-(2-propenyloxy)phenyl}-1-s-butyl-3-methylΔ^2- 1,2,4-triazolin-5-one[23]1-s-amyl-4-(2-chloro-4-methyl-5-methoxyphenyl)-3-methyl-Δ^2-1
,2,4-triazolin-5-one[24]1-s-amyl-4-(2-chloro-5-ethoxy-4-methylphenyl)-3-methyl-Δ^2-1
,2,4-triazolin-5-one[25]4-(2-chloro-4-methyl-5-isopropoxyphenyl)-3-methyl-1-(2-propenyl)-Δ^2-1,2 ,4-triazolin-5-one[26]4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-1-methoxymethyl-3-methyl-Δ^2-1,2,4-triazoline- 5-one[27]1-cyclopropylmethyl-4-(4-chloro-2-fluoro-5-isopropoxyphenyl)-3-
Methyl-Δ^2-1,2,4-triazolin-5-one[28]4-(2-chloro-5-isobutoxy-4-methylphenyl)-1-isopropyl-3-methyl-Δ^
2-1,2,4-triazolin-5-one[29]4-(2-chloro-5-N-ethylamino-4
-methylphenyl)-1-isopropyl-3-methyl-
Δ^2-1,2,4-triazolin-5-one[30]4-(2-chloro-4-methyl-5-N-propylaminophenyl)-1-isopropyl-3-methyl-Δ^2- 1,2,4-triazolin-5-one[31]4-(2-chloro-5-N-methyl-N-propylamino-4-methylphenyl)-1-isopropyl-3-methyl-△^2- 1,2,4-triazoline-5
-one[32]4-(2-chloro-methyl-5-N,N-dipropylaminophenyl)-1-isopropyl-3-methyl-△^2-1,2,4-triazolin-5-one[ 33]4-(2-chloro-5-N-ethyl-N-methylamino-4-methylphenyl)-1-isopropyl-
3-Methyl-△^2-1,2,4-triazoline-5-
one[34]4-(2-chloro-5-ethoxy-4-methylphenyl)-1-(1-ethylpropyl)-3-methyl-△^2-1,2,4-triazolin-5-one[ 35]1-s-butyl-4-(2-chloro-5-N,
N-diethylamino-4-methylphenyl)-3-methyl-△^2-1,2,4-triazolin-5-one[36]4-(2,4-dimethyl-5-propoxyphenyl)-1-isopropyl -3-methyl-△^2-1,
2,4-triazolin-5-one [37]1-s-butyl-4-(5-ethoxy-2,4
-dimethylphenyl)-3-methyl-△^2-1,2,
4-triazolin-5-one [38]1-s-butyl-4-(2,4-dimethyl-5
-propoxyphenyl)-3-methyl-△^2-1,2
,4-triazolin-5-one[39]1-s-butyl-4-(5-s-butoxy-2
,4-dimethylphenyl)-3-methyl-△^2-1,
2,4-triazolin-5-one [40]4-(5-ethoxy-2,4-dimethylphenyl)-1-(1-methylbuty)-3-methyl-△^2-
1,2,4-triazolin-5-one [41]4-(2,4-dimethyl-5-propoxyphenyl)-1-(1-methylbutyl)-3-methyl-△^
2-1,2,4-triazolin-5-one [42]4-(5-isopropoxy-2,4-dimethylphenyl)-1-(1-methylbutyl)-3-methyl-
△＾2-1,2,4-triazolin-5-one[43]1-(1-ethylpropyl)-4-(5-ethoxy-2,4-dimethylphenyl)-3-methyl-△＾
2-1,2,4-triazolin-5-one [44]1-(1-ethylpropyl)-4-(2,4-
dichloro-5-ethoxyphenyl)-3-methyl-△^
2-1,2,4-triazolin-5-one