WO2015068773A1 - Nitrogen-containing saturated heterocyclic compound - Google Patents

Abstract

　Provided is an agricultural and horticultural fungicide manifesting a high control effect against a wide range of plant pathogens. The present invention is a compound represented by formula (I) or a salt thereof, an agricultural and horticultural fungicide containing this compound or a salt thereof as an active ingredient, and a method for controlling plant pathogens and a method for controlling plant diseases by applying this compound or salt thereof. [Each symbol is defined in the same way as in the specification.]

Description

Nitrogen-containing saturated heterocyclic compounds

The present invention relates to a novel compound having a nitrogen-containing saturated heterocyclic ring or a salt thereof, an agricultural and horticultural fungicide containing the compound or the salt as an active ingredient, and a method for controlling phytopathogenic fungi, wherein the compound or the salt is applied. The present invention relates to a method for controlling plant diseases.

Aminoquinazoline compounds and aminopyrimidine compounds useful as pharmaceuticals are known. As an aminoquinazoline compound having a nitrogen-containing saturated heterocyclic ring, Patent Document 1 discloses an aminoquinazoline compound having a piperidine ring substituted at the 3-position with an ethenyl group, which is useful as an antibacterial agent.
As aminopyrimidine compounds having a nitrogen-containing saturated heterocyclic ring, Patent Documents 2 and 3 describe aminopyrimidine compounds characterized by substituents on the pyrimidine ring, which are useful as BTK (Bruton's tyrosine kinase) inhibitors.
As an aminothienopyrimidine compound having a nitrogen-containing saturated heterocyclic ring, Patent Document 4 discloses an aminothienopyrimidine compound substituted with an alkenyl group as a drug useful for neuropathic pain.

Moreover, although diflumetrim (generic name) which is an aminopyrimidine compound is used as an agricultural and horticultural fungicide, it does not have a nitrogen-containing saturated heterocyclic ring (nonpatent literature 1).
Thus, a compound represented by the following formula (I) having a nitrogen-containing saturated heterocyclic ring that is useful as an agricultural and horticultural fungicide is not known.

International Publication No. WO00 / 021948 International Publication WO2012 / 170976 International Publication WO2006 / 004658 US Publication No. US2010 / 017389

The Pesticide Manual (16th edition; BRITISH CROP PROTECTION COUNCIL) 358-359

Conventionally, many drugs provided for controlling plant diseases are characterized by their spectrum and plant pathogen control effect. For example, the effect on specific plant diseases is not enough, the therapeutic effect is slightly inferior to the preventive effect, the rain resistance is inferior, the residual effect is relatively short, and depending on the application scene In some cases, it exhibits only a practically insufficient control effect against plant pathogens. Accordingly, there is a demand for the creation of agricultural and horticultural fungicides that exhibit a high control effect against a wide range of plant pathogens regardless of the application situation.

As a result of researches aimed at solving the above-mentioned problems, the present inventors have found that the compound represented by the formula (I) or a salt thereof has useful properties as an agricultural and horticultural fungicide and has various plant diseases. The present invention was completed by obtaining knowledge that an excellent control effect was exhibited.

That is, the present invention applies the compound represented by formula (I) or a salt thereof (hereinafter also referred to as the present compound), an agricultural and horticultural fungicide containing the present compound as an active ingredient, and the present compound. Provided are a method for controlling plant pathogens and a method for controlling plant diseases.

Formula (I):

A is a group represented by the following formula;

(Wherein X ¹ to X ¹⁸ , X ²⁰ , X ²¹ , X ²³ to X ²⁶ , and X ²⁸ to X ³³ are the same or different and each represents hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, Selected from the group consisting of alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio, haloalkylthio, alkylamino and dialkylamino;
X ¹⁹ and X ²⁷ are the same or different and are selected from the group consisting of hydrogen, alkyl, haloalkyl and alkoxycarbonyl;
X ²² is selected from the group consisting of hydrogen, halogen, alkyl, haloalkyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio, haloalkylthio, alkylamino and dialkylamino)
R ¹ is hydrogen, alkyl, cycloalkyl, haloalkyl or alkoxyalkyl;
Za is a bond or alkylene;
The dashed line

Represents;
R ² is hydrogen, alkyl or haloalkyl;
B is pyrrolidine, piperidine or azepan, which may be crosslinked with alkylene;
R ³ is halogen or alkyl;
n is an integer from 0 to 4;
Zb is a bond or a group represented by -Zb ¹ -Zb ^2- ,
Zb ¹ is carbonyl, thiocarbonyl, sulfonyl, sulfinyl, alkylene or haloalkylene, Zb ² is a bond, carbonyl, thiocarbonyl, sulfonyl, sulfinyl, alkylene, haloalkylene or —NR ^a — (R ^a is hydrogen Or Zb ¹ and Zb ² are not the same;
R ⁴ is alkyl which may be substituted by Y ^1, alkenyl which may be substituted with Y ^1, cycloalkyl which may be substituted by Y ^2, hydroxy, alkoxy substituted by Y ^1, by Y ¹ optionally substituted alkenyloxy, Y ² may aryloxy substituted with, Y good heterocyclyloxy be substituted ^with, alkylthio be substituted with Y ^1, amino which may be substituted by Y ^2, aryl which may be substituted by Y ^2, or is substituted with Y ² be heterocyclyl, optionally;
Y ¹ is selected from the group consisting of halogen, cycloalkyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylcarbonyl, alkylthio, haloalkylthio, aryl and heterocyclyl;
Y ² is selected from the group consisting of halogen, alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylcarbonyl, alkylthio, haloalkylthio, aryl and heterocyclyl. ;
However, when X ³ is halogen, X ² is not hydrogen, alkylamino, dialkylamino, alkoxy or haloalkoxy.

The compound of the present invention has a high control effect against a wide range of plant pathogens.

In the present specification, unless otherwise specified, examples of the halogen or the halogen as a substituent include fluorine, chlorine, bromine and iodine. The number of halogens as a substituent may be 1 or 2 or more, and in the case of 2 or more, each halogen may be the same or different. Further, the halogen substitution position may be any position.

In the present specification, unless otherwise specified, the alkyl or alkyl moiety may be linear or branched, and specific examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t- Examples thereof include those of C _1-6 such as butyl, pentyl, isopentyl, neopentyl and hexyl.

In the present specification, unless otherwise specified, the alkenyl or alkenyl moiety may be linear or branched, and specific examples thereof include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl. , 3-butenyl, 1,3-butadienyl, C _2-6 such as 1-hexenyl, and the like.

In this specification, unless otherwise specified, cycloalkyl may be bridged, and specific examples thereof include C _3-10 such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornanyl, adamantyl, and indanyl. Things.

In the present specification, unless otherwise specified, examples of the aryl or aryl moiety include those of C _6-10 such as phenyl, naphthyl, and indenyl.

In the present specification, unless otherwise specified, the heterocyclyl or heterocyclyl moiety is derived from a saturated or unsaturated ring containing 1 to 4 heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom as ring members. Group to be used. The heterocyclyl or heterocyclyl moiety may be monocyclic or polycyclic and may be substituted with an oxo group (═O).
Specific examples thereof include three-membered rings such as oxiranyl; furyl, dihydrofuryl, tetrahydrofuryl, thienyl, dihydrothienyl, tetrahydrothienyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, dioxolanyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, imidazolinyl, 5-membered rings such as imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl; Benzofuranyl, isobenzofuranyl, dihydrobenzofuranyl, dihydroisobenzofura Benzothienyl, isobenzothienyl, dihydrobenzothienyl, dihydroisobenzothienyl, tetrahydrobenzothienyl, indolyl, isoindolyl, benzoxazolyl, benzothiazolyl, indazolyl, benzimidazolyl, benzodioxolanyl, benzodioxanyl, chromenyl, Chromanyl, isochromanyl, chromonyl, chromanonyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, indolizinyl, quinolidinyl, imidazopyridyl, naphthyridinyl, pteridinyl, dihydrobenzoxazinonyl, dihydrobenzoxazolinonyl, dihydrobenzoxazolinonyl 8- to 10-membered condensed rings such as thioxanyl; and those substituted with an oxo group It is.

In the present specification, unless otherwise specified, alkylene may be linear or branched, and specific examples thereof include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, (methyl C _1-6 things like methylene, (ethyl) methylene, (propyl) methylene, (isopropyl) methylene, di (methyl) methylene, (methyl) (ethyl) methylene, 1-methylethylene, 2-methylethylene Is mentioned.

A is a group represented by the following formula.

X ¹ to X ¹⁸ , X ²⁰ , X ²¹ , X ²³ to X ²⁶ , and X ²⁸ to X ³³ may be the same or different and are each hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy Selected from the group consisting of haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio, haloalkylthio, alkylamino and dialkylamino;
X ¹⁹ and X ²⁷ may each be the same or different and are selected from the group consisting of hydrogen, alkyl, haloalkyl and alkoxycarbonyl;
X ²² is selected from the group consisting of hydrogen, halogen, alkyl, haloalkyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio, haloalkylthio, alkylamino and dialkylamino.

X ¹ is preferably selected from the group consisting of hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, alkoxycarbonyl, alkylamino and dialkylamino, more preferably hydrogen, alkyl, Selected from the group consisting of haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro and alkoxycarbonyl, more preferably hydrogen or alkyl.
X ² is preferably selected from the group consisting of halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio, haloalkylthio, alkylamino and dialkylamino, and more Preferably, selected from the group consisting of halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio and haloalkylthio, more preferably halogen, alkyl, haloalkyl, or Alkoxycarbonyl.
X ³ is preferably selected from the group consisting of hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, cyano, alkoxycarbonyl, alkylthio, haloalkylthio, alkylamino and dialkylamino, and more Preferably, selected from the group consisting of hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, cyano, alkoxycarbonyl, alkylthio and haloalkylthio, more preferably hydrogen, halogen, alkoxy, or Alkoxycarbonyl.
Further, it is preferable that both X ² and X ³ are not hydrogen.

X ⁴ is more preferably hydrogen.
X ⁵ is more preferably hydrogen or halogen (particularly fluorine).
X ⁶ is more preferably hydrogen.
X ⁷ is preferably selected from the group consisting of hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, nitro, cyano, alkoxycarbonyl, alkylthio and haloalkylthio, more preferably hydrogen.
X ⁸ is preferably selected from the group consisting of hydrogen, fluorine, chlorine, iodine, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio and haloalkylthio, and more Preferred is hydrogen or fluorine.
In addition, when X ⁸ is halogen, X ⁵ is preferably halogen.

X ⁹ , X ¹⁰ and X ¹¹ may be the same or different and are preferably hydrogen or alkyl, more preferably hydrogen.

X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ and X ¹⁶ are more preferably hydrogen.

X ¹⁷ and X ¹⁸ may be the same or different, and are preferably hydrogen or alkyl, more preferably hydrogen.
X ¹⁹ is more preferably alkyl.

X ²⁰ and X ²¹ are more preferably hydrogen.
X ²² is preferably hydrogen, alkyl, halogen, or haloalkyl, more preferably hydrogen or halogen.

X ²³ and X ²⁴ are preferably hydrogen or alkyl, and more preferably hydrogen.

X ²⁵ and X ²⁶ may be the same or different and are preferably hydrogen, alkyl, halogen, haloalkyl, or alkoxy, more preferably hydrogen or alkyl.

X ²⁷ is more preferably an alkyl.
X ²⁸ is preferably hydrogen, alkyl, halogen, haloalkyl, or alkoxy, more preferably alkyl.
X ²⁹ is more preferably hydrogen or halogen.

X ³⁰ is more preferably hydrogen.
X ³¹ and X ³² are more preferably hydrogen.
X ³³ is more preferably hydrogen or halogen.

R ¹ is hydrogen, alkyl, cycloalkyl, haloalkyl, or alkoxyalkyl, preferably hydrogen, alkyl, or haloalkyl.

Za is a bond or alkylene, more preferably a bond, methylene, ethylene, (methyl) methylene, or (ethyl) methylene.

The broken line is

Preferably represents

It is. Here, the left side of the wavy line is bonded to the Za group, and the right side is bonded to the B ring. Of the three carbon atoms constituting the cyclopropylene ring, one carbon atom overlapping the wavy line is the B ring. It is also a part of.

R ² is hydrogen, alkyl or haloalkyl, preferably hydrogen or alkyl.

The ring represented by B in formula (I) is pyrrolidine, piperidine, or azepane, and may be bridged with alkylene. The alkylene to be bridged is preferably C _1-3 such as methylene and ethylene, and the crosslinking position is not particularly limited. The ring represented by B in formula (I) is preferably piperidine.

The ring represented by B may be substituted with R ³ , and when n is 2 or more, 2 or more R ³ may be the same or different. Moreover, the substitution position of R ³ may be any position.
R ³ is halogen or alkyl, preferably halogen.

Zb is a bond or a group represented by —Zb ¹ —Zb ² —.
Here, Zb ¹ and Zb ² are not the same, Zb ¹ is carbonyl, thiocarbonyl, sulfonyl, sulfinyl, alkylene or haloalkylene, and Zb ² is a bond, carbonyl, thiocarbonyl, sulfonyl, sulfinyl, alkylene , Haloalkylene or —NR ^a — (R ^a is hydrogen or alkyl).
Zb ¹ is preferably carbonyl, thiocarbonyl, sulfonyl, or alkylene, and Zb ² is preferably a bond, carbonyl, alkylene, haloalkylene, or —NR ^a — (R ^a is as defined above. ).

Specific examples of Zb include a bond, carbonyl, sulfonyl, alkylene, carbonyl-alkylene, carbonyl-haloalkylene, thiocarbonyl-alkylene, alkylene-carbonyl, carbonyl-NR ^a- (R ^a is as defined above), Alternatively, thiocarbonyl-NR ^a — (R ^a is as defined above) can be mentioned.

R ⁴ is alkyl which may be substituted by Y ^1, alkenyl which may be substituted with Y ^1, cycloalkyl which may be substituted by Y ^2, hydroxy, alkoxy substituted by Y ^1, by Y ¹ optionally substituted alkenyloxy, Y ² may aryloxy substituted with, Y good heterocyclyloxy be substituted ^with, alkylthio be substituted with Y ^1, amino which may be substituted by Y ^2, aryl which may be substituted by Y ^2, or heterocyclyl, optionally substituted by Y ^2. Preferably, the alkyl may be substituted by Y ^1, Y ² which may be substituted with a cycloalkyl, Y ¹ in an optionally substituted alkoxy, which may be aryloxy optionally substituted with Y ^2, is substituted with Y ² which may be heterocyclyloxy, aryl which may be substituted by Y ^2, or heterocyclyl, optionally substituted by Y ^2.
The number of substitutions for Y ¹ and Y ² may be 1 or 2 or more, and in the case of 2 or more, these substituents may be the same or different. Further, the substitution position of Y ¹ and Y ² may be any positions.

Specific examples of Y ¹ include halogen, aryl and the like, and specific examples of Y ₂ include halogen, alkyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyl and the like.

Examples of the salt of the compound of the present invention include any salt that is acceptable in the technical field, for example, salts with inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid; tartaric acid, Salts with organic carboxylic acids such as formic acid, acetic acid, citric acid, fumaric acid, maleic acid, trichloroacetic acid and trifluoroacetic acid; methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, mesitylenesulfonic acid and naphthalenesulfonic acid, etc. And salts thereof with sulfonic acid.

The compound of the present invention may have isomers such as geometric isomers, tautomers and optical isomers, and the present invention includes both isomers and isomer mixtures.
In this specification, isomers are described as a mixture unless otherwise specified.
The present invention also includes various isomers other than those described above within the scope of technical common sense in the technical field.

Depending on the type of isomer, the chemical structure may differ from the described structural formula, but those skilled in the art can fully recognize that these are related to the isomer, and therefore are within the scope of the present invention. Obviously.

Preferred embodiments of the compound of the present invention include the following compounds, but the compound of the present invention is not limited to these.

(1) A compound represented by the formula (I) or a salt thereof.
(2) Formula (Ia):

[Each symbol is as defined above] or a salt thereof.

(3) Formula (Ia-1):

[Each symbol is as defined above] or a salt thereof.

(4) A is the following formula:

The compound or salt thereof according to any one of (1) to (3) above, wherein each symbol is as defined above.
(5) A is the following formula:

The compound or salt thereof according to any one of (1) to (3) above, wherein each symbol is as defined above.

(6) X ¹ is selected from the group consisting of hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, alkoxycarbonyl, alkylamino and dialkylamino. Compound or salt thereof.
(7) X ² is selected from the group consisting of halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio, haloalkylthio, alkylamino and dialkylamino. The compound or its salt as described in said (4).
(8) X ³ is selected from the group consisting of hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, cyano, alkoxycarbonyl, alkylthio, haloalkylthio, alkylamino and dialkylamino; The compound or its salt as described in said (4).

(9) The compound according to (5) above, wherein X ⁷ is selected from the group consisting of hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, nitro, cyano, alkoxycarbonyl, alkylthio and haloalkylthio Its salt.
(10) X ⁸ is selected from the group consisting of hydrogen, fluorine, chlorine, iodine, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio and haloalkylthio. The compound or a salt thereof according to (5) above.

(1 ′) A is a group represented by the following formula; the other symbols are as defined above; provided that when X ³ is halogen, X ² is not hydrogen, and the formula (I) Or a salt thereof.

X ¹ to X ⁸ are the same or different and are selected from the group consisting of hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio and haloalkylthio. The
(2 ′) Formula (Ia):

The compound or a salt thereof according to (1 ') above, wherein each symbol is as defined in (1') above.

(3 ') Formula (Ia-1):

The compound or a salt thereof according to (1 ') above, wherein each symbol is as defined in (1') above.

(4 ') A is represented by the following formula:

The compound or a salt thereof according to any one of (1 ′) to (3 ′) above, wherein each symbol is a group represented by the same meaning as (1 ′) above.
(5 ′) A is the following formula:

The compound or a salt thereof according to any one of (1 ') to (3') above, wherein each symbol is a group represented by the same meaning as (1 ') above.

(6 ′) The compound or salt thereof according to (4 ′) above, wherein X ¹ is selected from the group consisting of hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro and alkoxycarbonyl. .
(7 ′) Said (4 ′) wherein X ² is selected from the group consisting of halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio and haloalkylthio Or a salt thereof.
(8 ′) Said (4 ′), wherein X ³ is selected from the group consisting of hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, cyano, alkoxycarbonyl, alkylthio and haloalkylthio Or a salt thereof.

(9 ′) X ⁷ is selected from the group consisting of hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, nitro, cyano, alkoxycarbonyl, alkylthio, and haloalkylthio, according to (5 ′) above. Compound or salt thereof.
(10 ′) X ⁸ is selected from the group consisting of hydrogen, fluorine, chlorine, iodine, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio and haloalkylthio. The compound or a salt thereof according to (5 ′) above.

The compound of the present invention can be produced according to the following production method and ordinary salt production method, but is not limited to these methods.

The compound of the present invention can be produced by any of the following production methods [1] to [6].
As the compounds of formula (II) to formula (XI) used in the production methods [1] to [6], commercially available compounds may be used, or those prepared from commercially available compounds by known methods may be used. it can.

Manufacturing method [1]

In the production process [1], L ¹ is halogen (chlorine, bromine, iodine, etc.), and other symbols are as defined above.

In the production method [1], the compound of formula (I) can be produced by reacting the compound of formula (II) with the compound of formula (III). The compound of formula (II) may use an acid addition salt thereof (for example, hydrochloride, hydrobromide, methanesulfonate, trifluoroacetate, etc.).

The compound of the formula (III) can be used in a ratio of 1 to 50 equivalents, desirably 1 to 5 equivalents, relative to 1 equivalent of the compound of the formula (II).

This reaction can usually be performed in the presence of a base. The base is not particularly limited as long as the reaction proceeds. For example, alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; calcium carbonate And alkaline earth metal carbonates; organic amines such as triethylamine, diisopropylethylamine, pyridine, 4- (N, N-dimethylamino) pyridine; and the like.
The base can be used in a proportion of 1 to 20 equivalents, preferably 1 to 5 equivalents, relative to 1 equivalent of the compound of formula (II).

This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as the reaction proceeds. For example, alcohols such as methanol, ethanol, propanol and butanol; aromatic hydrocarbons such as benzene, toluene and xylene; diethyl ether, diisopropyl ether, dioxane Ethers such as butyl ether, tetrahydrofuran, dioxane and ethylene glycol dimethyl ether; nitriles such as acetonitrile and propionitrile; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride and 1,2-dichloroethane; N, Acid amides such as N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; hexamethylphosphor Phosphoric acid amides such as de; and although one or more kinds from and mixtures of these solvents are appropriately selected, among them acid amides are preferred.

The reaction temperature is usually 0 to 200 ° C, preferably 70 to 120 ° C. The reaction time is usually 1 to 48 hours.

Manufacturing method [2]

In the production method [2], L ² is halogen (chlorine, bromine, iodine, etc.) or hydroxy, Zb ′ is a bond or carbonyl, and other symbols are as defined above.

In the production method [2], a compound of formula (I ′) can be obtained by reacting a compound of formula (IV) with a compound of formula (V). The compound of formula (IV) may use an acid addition salt thereof (for example, hydrochloride, hydrobromide, methanesulfonate, trifluoroacetate, etc.).

The compound of the formula (V) is used in a ratio of 1 to 50 equivalents, preferably 2 to 10 equivalents with respect to 1 equivalent of the compound of the formula (IV).

When using a compound of formula (V) where L ² is halogen, the reaction can usually be carried out in the presence of a base. The base is not particularly limited as long as the reaction proceeds. For example, alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; calcium carbonate And alkaline earth metal carbonates; organic amines such as triethylamine, diisopropylethylamine, pyridine, 4- (N, N-dimethylamino) pyridine; and the like.
The base is used in a proportion of 1 to 20 equivalents, desirably 1 to 5 equivalents, relative to 1 equivalent of the compound of formula (IV). When the compound of formula (IV) is an acid adduct, the base is preferably used in a ratio of 2 to 6 equivalents per 1 equivalent of the acid addition salt.

This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as the reaction proceeds. For example, aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether. Nitriles such as acetonitrile and propionitrile; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride and 1,2-dichloroethane; N, N-dimethylformamide, N, N-dimethylacetamide, N- Acid amides such as methyl pyrrolidinone; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Phosphoric amides such as hexamethylphosphoramide; and a mixed solvent thereof. It is appropriately selected but, among them acid amides are preferred.

The reaction temperature is usually 0 to 200 ° C, preferably 70 to 120 ° C. The reaction time is usually 1 to 48 hours.

When using the compound of the formula (V) in which L ² is hydroxy, this reaction can be usually carried out in the presence of a condensing agent and optionally in the presence of a base. The condensing agent is not particularly limited as long as the reaction proceeds. For example, carbodiimides such as N, N′-dicyclohexylcarbodiimide; benzotriazol-1-yloxy-trisdimethylaminophosphonium salt, O- (benzotriazole-1 -Yl) -N, N, N ′, N′-tetramethyluronium BOP reagents such as tetrafluoroborate;
The condensing agent is used in a proportion of 1 to 20 equivalents, desirably 1 to 5 equivalents, relative to 1 equivalent of the compound of formula (IV).
The base is not particularly limited as long as the reaction proceeds. For example, alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; alkalis such as calcium carbonate And earth metal carbonates; organic amines such as triethylamine, diisopropylethylamine, pyridine, 4- (N, N-dimethylamino) pyridine; and the like.
The base is used in a proportion of 1 to 20 equivalents, preferably 2 to 5 equivalents, relative to 1 equivalent of the compound of formula (IV).

This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as the reaction proceeds. For example, aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether. Nitriles such as acetonitrile and propionitrile; acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidinone; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; 1 type or 2 types or more are appropriately selected from the following: phosphoric acid amides such as hexamethylphosphoramide; and mixed solvents thereof, among which ethers and acid amides are preferable.

The reaction temperature is usually 0 to 200 ° C, preferably 70 to 120 ° C. The reaction time is usually 1 to 48 hours.

Manufacturing method [3]

In the production method [3], L ³ is isocyanato or isothiocyanate, Zb ″ is — (C═O) —NH— or — (C═S) —NH—, and other symbols are as defined above. .

In the production method [3], a compound of formula (I ″) can be produced by reacting a compound of formula (IV) with a compound of formula (VI). The compound of formula (IV) may use an acid addition salt thereof (for example, hydrochloride, hydrobromide, methanesulfonate, trifluoroacetate, etc.).

The compound of formula (VI) is used in a ratio of 1 to 50 equivalents, preferably 1 to 10 equivalents, relative to 1 equivalent of the compound of formula (IV).

When using an acid addition salt of the formula (IV), this reaction can usually be carried out in the presence of a base. The base is not particularly limited as long as the reaction proceeds. For example, alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; alkalis such as calcium carbonate And earth metal carbonates; organic amines such as triethylamine, diisopropylethylamine, pyridine, 4- (N, N-dimethylamino) pyridine; and the like.
The base is used in a ratio of 1 to 20 equivalents, preferably 2 to 5 equivalents, relative to 1 equivalent of the acid addition salt of formula (IV).

This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as the reaction proceeds. For example, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene, toluene and xylene; Ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether; nitriles such as acetonitrile and propionitrile; halogens such as chloroform, dichloromethane, carbon tetrachloride and 1,2-dichloroethane Hydrocarbons; acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidinone; sulfoxides such as dimethyl sulfoxide; Sulfones such as; phosphate acid amides such as hexamethylphosphoramide; but and one or more kinds from and mixtures of these solvents are appropriately selected, among others ketones is preferable.

The reaction temperature is usually 0 to 200 ° C, preferably 70 to 120 ° C. The reaction time is usually 1 to 48 hours.

Manufacturing method [4]

In the production process [4], R ^1a is alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, or alkoxycarbonyl, and other symbols are as defined above.

In the production method [4], the compound of the formula (I ″ ″) can be produced by reacting the compound of the formula (I ′ ″) with the compound of the formula (VII).
The compound of the formula (I ′ ″) can be produced by any of the above production methods [1] to [3].

The compound of the formula (VII) is used in a ratio of 1 to 50 equivalents, preferably 1 to 5 equivalents, relative to 1 equivalent of the compound of the formula (I ′ ″).

This reaction can usually be performed in the presence of a base. The base is not particularly limited as long as the reaction proceeds. For example, alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; alkalis such as calcium carbonate And earth metal carbonates; organic amines such as triethylamine, diisopropylethylamine, pyridine, 4- (N, N-dimethylamino) pyridine; and the like.
The base is used in a proportion of 1 to 20 equivalents, preferably 1 to 5 equivalents, relative to 1 equivalent of the compound of (VII).

This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as the reaction proceeds. For example, alcohols such as methanol, ethanol, propanol and butanol; aromatic hydrocarbons such as benzene, toluene and xylene; diethyl ether, diisopropyl ether and dibutyl ether , Ethers such as tetrahydrofuran, dioxane and ethylene glycol dimethyl ether; nitriles such as acetonitrile and propionitrile; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride and 1,2-dichloroethane; N, N -Acid amides such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; hexamethylphosphor Phosphoric acid amides such as de; and although one or more kinds from and mixtures of these solvents are appropriately selected, among them acid amides are preferred.

The reaction temperature is usually 0 to 200 ° C, preferably 70 to 120 ° C. The reaction time is usually 1 to 48 hours.

Manufacturing method [5]

In the production process [5], L ⁴ is a leaving group (chlorine, bromine, iodine, trifluoromethanesulfonyloxy, etc.), R ^A is alkyl, and other symbols are as defined above.

The production method [5] can be carried out by reacting the compound of formula (VIII), carbon monoxide and the compound of formula (IX) in the presence of a base and a transition metal catalyst.

Carbon monoxide is usually used in an amount of 1 to 10 equivalents, preferably 1 to 4 equivalents, relative to 1 equivalent of the compound of formula (VIII). The pressure is usually 0.1 to 10 MPa, preferably 0.5 to 5 MPa. However, depending on the reaction conditions, amounts and pressures outside these ranges can be used.

The compound of the formula (IX) can be used in an amount of 1 equivalent or more with respect to 1 equivalent of the compound of the formula (VIII), preferably 3 equivalents or more. An excess amount of the compound of formula (IX) can also be used as a solvent. Usually, 1000 equivalent or less is preferable.

Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkali metals such as sodium carbonate and potassium carbonate. Carbonates; alkaline earth metal hydrogen carbonates such as calcium hydrogen carbonate and magnesium hydrogen carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkali metal carboxylates such as sodium acetate and potassium acetate Carboxylic acid alkaline earth metal salts such as calcium acetate and magnesium acetate; trimethylamine, triethylamine, diisopropylamine, triisopropylamine, diisopropylethylamine, pyridine, 4- (N, N-dimethylamino) pyridine, 2,6-dimethylpyri Gin, 4-pyrrolidinopyridine, N-methylmorpholine, N, N-dimethylaniline, N, N-diethylaniline, N-ethyl-N-methylaniline, 1,8-diazabicyclo [5.4.0] -7 -Undecene, organic amines such as 1,4-diazabicyclo [2.2.2] octane; and one or more of these bases are appropriately selected, among which alkali metal carbonates, alkali metal carbonates Hydrogen salts, alkali metal carboxylates or organic amines are desirable.

The base can be generally used in an amount of 1 to 10 equivalents, preferably 1 to 3 equivalents, relative to 1 equivalent of the compound of the formula (VIII). However, depending on the reaction conditions, an amount outside this range can be used.

Examples of transition metal catalysts include catalysts containing transition metals such as palladium, rhodium, ruthenium, nickel, cobalt, and molybdenum. As the transition metal catalyst, those having various known structures used for the carbonylation reaction of organic halides can be used, and a transition metal catalyst containing palladium is particularly useful for this reaction. For example, palladium-carbon, palladium chloride, palladium acetate, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium, bis (dibenzylideneacetone) palladium, bis (acetylacetonato) palladium, dichlorobis (triphenylphosphine) palladium, dichlorobis (Triisopropylphosphine) palladium, tetrakis (triphenylphosphine) palladium, dichloro (1,4-bis (diphenylphosphino) butane) palladium, dichlorobis (triphenylphosphite) palladium and the like. Moreover, a tertiary phosphine and a tertiary phosphite can be used as a ligand as needed. Tertiary phosphines and tertiary phosphites include triphenylphosphine, phenyldimethylphosphine, tri-o-tolylphosphine, tri-p-tolylphosphine, 1,2-bis (diphenylphosphino) ethane, 1, Examples include 3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1′-bis (diphenylphosphino) ferrocene, and triphenylphosphite.

The transition metal catalyst is usually used in an amount of 0.001 to 0.5 equivalent, preferably 0.001 to 0.1 equivalent, relative to 1 equivalent of the compound of the formula (VIII). The ligand can be used usually in an amount of 1 to 50 equivalents, preferably 1 to 10 equivalents, relative to 1 equivalent of the transition metal catalyst. However, depending on the reaction conditions, an amount outside this range can be used.

This reaction can be performed in the presence of a solvent, if necessary.
The solvent is not particularly limited as long as the reaction proceeds. For example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons such as chlorobenzene, dichloromethane and dichloroethane; ethers such as diethyl ether, butyl ethyl ether, methyl tert-butyl ether, dimethoxyethane, tetrahydrofuran and dioxane; nitriles such as acetonitrile and propionitrile; N , N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acid amides such as 1,3-dimethyl-2-imidazolidinone; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane Esters such as methyl acetate, ethyl acetate, propyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; heterocyclic compounds such as pyridine, thiophene; water; and one of these mixed solvents Alternatively, two or more are appropriately selected. When the compound of the formula (IX) does not serve as a solvent, aromatic hydrocarbons, ethers and the like are desirable.

Manufacturing method [6]

In the production method [6], Za ′ is alkylene, Za ″ is alkylene having 1 fewer carbon atoms than Za ′, and each symbol is as defined above.

The production method [6] can be carried out by reacting the compound of formula (X) with formula (XI) in the presence of a reducing agent.

The reducing agent is usually used in an amount of 1 to 10 equivalents, preferably 1 to 4 equivalents, relative to 1 equivalent of the compound of the formula (X). However, depending on the reaction conditions, amounts outside these ranges can also be used.

The compound of the formula (XI) can be used usually in an amount of 1 to 10 equivalents, desirably 1 to 4 equivalents with respect to 1 equivalent of the compound of the formula (X).

Examples of the reducing agent include sodium cyanoborohydride, sodium triacetoxyborohydride, sodium borohydride and the like, and sodium triacetoxyborohydride is preferable.

This reaction can be performed in the presence of a solvent, if necessary.
The solvent is not particularly limited as long as the reaction proceeds. For example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons such as chlorobenzene, dichloromethane, dichloroethane; ethers such as diethyl ether, butyl ethyl ether, methyl tert-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane; N, N-dimethylformamide, N, N-dimethyl Acid amides such as acetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone; Halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane; formic acid, acetic acid Carboxylic acids such as : Water; and one or more of these mixed solvents are appropriately selected. Among them, halogenated hydrocarbons are preferable.

The compounds of the present invention include, for example, Mastigomycotina, Ascomycotina, Basidiomycotina, Deuteromycotina, Zygomycotina, etc. Can control plant pathogens belonging to.

More specific examples of the plant pathogen include the following.

As the flagellum subfamily, potato or tomato plague (Phytophthora infestans), tomato gray plague (Phytophthora capsici) genus Phytophthora genus; Pseudoperonospora cubensis Pseudoperonos Pseudoperonospora genus; Plasmopara genus such as Plasmoparaolaviticola; Pythium 、 graminicola, Pythium genus such as wheat brown snow rot fungus (Pythium iwayamai) And so on.

As the Aspergillus subtilis, Erysiphe genus such as wheat powdery mildew (Erysiphe graminis); Sphaerotheca genus Sphaerotheca humuli, genus Sphaerotheca humuli Genus Uncinula such as Uncinula necator; Podosphaera genus such as Podosphaera leucotricha; Mycosphaerella pinodes, Mycosphaerellanode ), Banana black sigatoka (Mycosphaerella musicola), oyster circle deciduous fungus (Mycosphaerella nawae), Mycosphaerella fragariae genus Mycosphaerella (Mycosphaerella) genus; Venturia genus such as Venturia nashicola); Pyrenophora teres, Pyrenophora graminea, such as Pyrenophora ；; Sclerotiniainsclerotiorum, Sclerotinia 属; rice sesame leaf blight (Cochliobolus miyabeanus) genus Cochliobolus; Cucumber vine wilt (Didymella ybryoniae) genus Didymela genus; Gibberella zeae (Gibberella ブ ド ウ zeae) genus Gibberella genus; grape Elsinoe ampelina, Elsinoe genus such as citrus scab (Elsinoe fawcettii); Diaporthe citri, Diaporthe sp. Genus Diaporthe sp. Genus Monilinia, such as Monilinia mali, Monilinia fructicola; A genus Glomerella such as Glomerella cingulata; a genus Magnaporthe such as Magnaporthe grisea; and the like.

As a basidiomycete subfamily, Rhizoctonia genus such as rice rot fungus (Rhizoctonia solani); Ustilago genus such as wheat naked smut fungus (Ustilago nuda); Oat crown rust fungus (Puccinia coronata), Puccinia recondita, Puccinia striiformis genus Puccinia, and the like.

As an imperfect fungal subfamily, Septoria nodorum, Septoria tritici genus Septoria tritici; Botrytis cinerea genus Botrytis ；; Cercospora genus such as sugar beet brown fungus (Cercospora beticola), oyster horn spot fungus (Cercospora kakivola); Colletotrichum genus such as Colletotrichum orbiculare; apple pathotype), pear black spot fungus (Alternaria alternata Japanese pear pathotype), potato summer or tomato ring mold fungus (Alternaria solani), cabbage black spot fungus (Alternaria brassicae), Alternaria spp. Pseudocercosporella (Pseudocercosporella herpotrichoides) Genus; genus Pseudocercospora such as Pseudocercospora vitis; genus Rhynchosporium such as Rhynchosporium secalis; genus Rhynchosporium; Cladosporium carpophilum Cladosporium genus; Phomopsis genus such as Pomoopsis sp .; Gloeosporium genus such as Gloeosporium kaki; Tomato leaf mold (Fulvia fulva) such as (Fulvia fulva); Corynespora 属 genus such as cucumber brown spot fungus (Corynespora cassiicola);

Examples of zygomycetes include the genus Rhizopus イ チ ゴ stronifer and the genus Rhizopus such as Rhizopus nigricans.

The compound of the present invention is useful as an active ingredient of agricultural and horticultural fungicides, such as rice blast, sesame leaf blight, coat blight; wheat powdery mildew, red mold, rust, snow rot , Bare black spot disease, eye spot disease, leaf blight disease, blight disease; citrus black spot disease, common scab; apple monilia disease, powdery mildew, spotted leaf disease, black star disease, anthracnose disease, brown spot disease, Ring rot, soot spot, soot spot, sunspot disease; pear scab, black spot, powdery mildew, plague; pear ring rot, powdery mildew; Homopsis rot; grape black rot, late rot, powdery mildew, downy mildew, gray mold, brown spot, branch rot; oyster anthracnose, defoliation, powdery mildew, soot spot; Anthracnose of cucumber, powdery mildew, vine blight, downy mildew, plague, brown spot; tomato ring-rot, leaf mold, plague, gray mold, powdery mildew; Brassicaceae Vegetable downy mildew, black spot disease; Potato summer plague, plague; Strawberry powdery mildew, gray mold, anthracnose; various crops downy mildew, plague, gray mold, mycorrhizal disease, udon Although it is effective for controlling plant diseases such as mildew, it exhibits an excellent control effect especially for the epidemics of fruit trees and vegetables, downy mildew, and blight of wheat. It is also effective in controlling soil diseases caused by phytopathogenic fungi such as Fusarium, Psium, Rhizoctonia, Verticillium, and Plasmodiohora.

The compound of the present invention is usually prepared by mixing the compound with various agricultural adjuvants, powders, granules, granule wettable powders, wettable powders, aqueous suspensions, oily suspensions, aqueous solvents, emulsions, It can be used in various forms such as liquids, pastes, aerosols, microdispersions, etc., but it can be made into any conventional form used in the art as long as it meets the purpose of the present invention. it can.
Adjuvants used in the formulation include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, starch; water, Solvents such as toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, alcohol Fatty acid salts, benzoates, alkyl sulfosuccinates, dialkyl sulfosuccinates, polycarboxylates, alkyl sulfate esters, alkyl sulfates, alkylaryl sulfates, alkyl diglycol ether sulfates, Cole sulfate ester salt, alkyl sulfonate salt, alkyl aryl sulfonate salt, aryl sulfonate salt, lignin sulfonate salt, alkyl diphenyl ether disulfonate salt, polystyrene sulfonate salt, alkyl phosphate ester salt, alkyl aryl phosphate salt, styryl Aryl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate Anionic surfactants such as salts, salt of naphthalene sulfonic acid formalin condensate; sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid polyglyceride Fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyoxyethylene fatty acid ester, Nonionic surfactants such as polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxypropylene fatty acid ester; olive oil, kapok oil, castor oil, palm oil, palm oil, palm Oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, persimmon oil, liquid paraffin And vegetable oils and mineral oils.

Each component of these adjuvants can be used by appropriately selecting one or two or more types without departing from the object of the present invention. Further, in addition to the above-mentioned adjuvants, it can also be used by appropriately selecting from those known in the art, a bulking agent, a thickener, an anti-settling agent, an antifreezing agent, a dispersion stabilizer, a safener, Various commonly used adjuvants such as antifungal agents can also be used.

The compounding ratio of the compound of the present invention and various adjuvants is generally 0.005: 99.995 to 95: 5, preferably 0.2: 99.8 to 90:10. Therefore, the content of the compound of the present invention in the agricultural and horticultural fungicide is 0.005 to 95% by weight, preferably 0.2 to 90% by weight. In actual use of these preparations, use them as they are or dilute them to a predetermined concentration with a diluent such as water, and add various spreading agents (surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.

The concentration of the compound of the present invention varies depending on the target crop, method of use, formulation, application rate, etc., and cannot be defined unconditionally, but in the case of foliage treatment, it is usually 0.1 to 10,000 ppm per active ingredient, Desirably, it is 1 to 2,000 ppm. In the case of soil treatment, it is usually 10 to 100,000 g / ha, preferably 200 to 20,000 g / ha. In the case of seed treatment, it is usually 0.01 to 100 g / Kg seed, preferably 0.02 to 20 g / Kg seed.

The compound of the present invention is generally applied for application of its various preparations or dilutions thereof, that is, spraying (spraying, spraying, misting, atomizing, dusting, water surface application, etc.), soil application (Mixing, irrigation, etc.), surface application (application, powder coating, coating, etc.) can be used. It can also be applied by the so-called ultra-low concentration volume application method. In this method, it is possible to contain 100% of the active ingredient.

The compound of the present invention may contain other agricultural chemicals such as bactericides, insecticides, acaricides, nematicides, soil insecticides, antiviral agents, attractants, herbicides, plant growth preparations as necessary. It can be mixed and used together.

In the above-mentioned other agricultural chemicals, as an active ingredient compound of a bactericide (generic name; including some pending applications or Japan Plant Protection Association test code), for example,
Anilinopyrimidine compounds such as mepanipyrim, pyrimethanil, cyprodinil;
Tria like 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) [1,2,4] triazolo [1,5-a] pyrimidine Zolopyrimidine compounds;
Pyridinamine compounds such as fluazinam;
Triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, microbutanil, cyproconazole cyproconazole, tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole, tetraconazole, o Oxpoconazole fumarate, prothioconazole, triadimenol, flutriafol, difenoconazole, fluquinconazole azole), fenbuconazole, bromuconazole, diniconazole, tricyclazole, probenazole, simeconazole, pefazoate, ipconazole, imibenconazole Azole compounds such as (imibenconazole), azaconazole, triticonazole, imazalil;
Quinoxaline compounds such as quinomethionate;
Dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb, thiram;
Organochlorine compounds such as fthalide, chlorothalonil, quintozene;
Imidazole compounds such as benomyl, thiophanate-methyl, carbendazim, thiabendazole, fuberiazole, cyazofamid;
Cyanoacetamide compounds such as cymoxanil;
Metalaxyl, metalaxyl-M (also known as mefenoxam), oxadixyl, offurace, benalaxyl, benalaxyl-M, also known as kiralaxyl, ralaxyl )), Flaxaxyl, cyprofuram, carboxin, oxycarboxin, thifluzamide, boscalid, bixafen, isothianil, tiadinil Anilide compounds such as sedaxane;
Sulfamide-type compounds such as dichlofluanid;
Copper-based compounds such as cupric hydroxide and oxine copper;
Isoxazole compounds such as hymexazol;
Organophosphorus compounds such as fosetyl-Al, tolclofos-Methyl, edifenphos, iprobenfos;
Phthalimide compounds such as captan, captafol, folpet;
Dicarboximide compounds such as procymidone, iprodione, vinclozolin;
Benzanilide compounds such as flutolanil, mepronil, benodanil;
Penthiopyrad, penflufen, furametpyr, isopyrazam, silthiopham, fenoxanil, fenfuram, flufurapiroxad, benzovindiflupyr Amide compounds such as
Benzamide compounds such as fluopyram and zoxamide;
Piperazine compounds such as triforine;
Pyridine compounds such as pyrifenox and pyrisoxazole;
Carbinol compounds such as fenarimol and nuarimol;
Piperidine compounds such as fenpropidin;
Morpholine compounds such as fenpropimorph and tridemorph;
Organotin compounds such as fentin hydroxide and fentin acetate;
Urea-based compounds such as pencycuron;
Synamic acid compounds such as dimethomorph, flumorph;
Phenyl carbamate compounds such as dietofencarb;
Cyanopyrrole compounds such as fludioxonil and fenpiclonil;
Azoxystrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin ( dimoxystrobin), pyraclostrobin, fluoxastrobin, enestroburin, pyroxystrobin, pyrametostrobin, coumoxystrobin, enoxast Strobilurin-based compounds such as enoxastrobin, fenaminstrobin, flufenoxystrobin, triclopyricarb;
Oxazolidinone compounds such as famoxadone;
Thiazole carboxamide compounds such as ethaboxam;
Valinamide compounds such as iprovalicarb, benchthiavalicarb-isopropyl;
Acylamino acid compounds such as valifenalate;
Imidazolinone compounds such as fenamidone;
Hydroxyanilide compounds such as fenhexamid;
Benzenesulfonamide compounds such as flusulfamide;
Oxime ether compounds such as cyflufenamid;
Anthraquinone compounds;
Crotonic acid compounds;
Antibiotics such as validamycin, kasugamycin, polyoxins;
Guanidine compounds such as iminoctadine and dodine;
Quinoline compounds such as tebufloquin;
Thiazolidine compounds such as flutianil;
Sulfur-based compounds such as sulfur;
Other compounds include pyribencarb, isoprothiolane, pyroquilon, diclomezine, quinoxyfen, propamocarb hydrochloride, chloropicrin, dazomet, metam Sodium salt (metam-sodium), metrafenone, nicobifen, UBF-307, diclocymet, proquinazid, amisulbrom (aka amibromdole), mandipropamid, fluopide fluopicolide, carpropamid, meptyldinocap, isofetamid, pyriofenone, ferimzone, spiroxamine (spiro) xamine), fenpyrazamine, ametoctradin, oxathiapiprolin, tolprocarb, picarbutrazox, NK-1001, SB-4303, MIF-1001, MIF-1002, BAF-1107, SYJ-247, NNF-0721, etc. are mentioned.

Insecticides, acaricides, nematicides or soil pesticides in the above-mentioned other pesticides, that is, active ingredient compounds of pesticides (generic name; including some pending applications or Japan Plant Protection Association test code) ), For example,
Profenofos, dichlorvos, fenamiphos, fenitrothion, EPN, diazinon, chlorpyrifos, chlorpyrifos-methyl, acephate, prothiophos, prothiophos Fosthiazate, cadusafos, disulfoton, isoxathion, isofenphos, ethion, etrimfos, quinalphos, dimethylvinphos, dimethoate ), Sulprofos, thiometon, bamidothion, pyraclofos, pyridaphenthion, pirimiphos-methyl, pirimiphos-methyl Propaphos, phosalone, formothion, malathion, tetrachlorvinphos, chlorfenvinphos, cyanophos, trichlorfon, methidathion , Phenthoate, ESP, azinphos-methyl, fenthion, heptenophos, methoxychlor, parathion, phosphocarb, demeton-S-S- such as methyl, monocrotophos, methamidophos, imicyafos, parathion-methyl, terbufos, phosphamidon, phosmet, phorate Machine phosphoric ester compound;
Carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, fenobucarb, fenobucarb Carbamates such as carbosulfan, benfuracarb, bendiocarb, furathiocarb, isoprocarb, metolcarb, xylylcarb, XMC, fenothiocarb Compound;
Nereistoxin derivatives such as cartap, thiocyclam, bensultap, sodium thiosultap-sodium;
Organochlorine compounds such as dicophor, tetradifon, endosulfan, dienochlor, dieldrin;
Organometallic compounds such as fenbutatin oxide and cyhexatin;
Fenvalerate, permethrin, cypermethrin, deltamethrin, cyhalothrin, tefluthrin, etofenprox, flufenprox, cyfluthrin , Fenpropathrin, flucythrinate, fluvalinate, cycloprothrin, lambda-cyhalothrin, pyrethrin, esfenvalerate, tetramethrin (Tetramethrin), resmethrin, protrifenbute, bifenthrin, zeta-cypermethrin, acrinathrin, alpha-cypermethrin alpha-cypermethrin, allethrin, gamma-cyhalothrin, theta-cypermethrin, tau-fluvalinate, tralomethrin, profluthrin, beta -Pyrethroid compounds such as cypermethrin, beta-cyfluthrin, methfluthrin, phenothrin, flumethrin;
Diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, lufenuron, novaluron, triflumuron, hexaflumuron, hexaflumuron Benzoylurea compounds such as (bistrifluron), nobifluuron, fluazuron;
Juvenile hormone-like compounds such as metoprene, pyriproxyfen, fenoxycarb, diofenolan;
Pyridazinone compounds such as pyridaben;
Pyrazole compounds such as fenpyroximate, fipronil, tebufenpyrad, ethiprole, tolfenpyrad, acetoprole, pyrafluprole, pyriprole;
Imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, nidinotefuran, dinotefuranit, dinotefuranit A noid compound;
Hydrazine compounds such as tebufenozide, methoxyfenozide, chromafenozide, halofenozide;
Pyridine compounds such as pyridalyl and flonicamid;
Cyclic ketoenol compounds such as spirodiclofen, spiromesifen, spirotetramat;
Strobilurin-based compounds such as fluacrypyrim;
Pyrimidinamine compounds such as flufenerim;
Dinitro compounds;
Organic sulfur compounds;
Urea compounds;
Triazine compounds;
Hydrazone compounds;
Other compounds include buprofezin, hexythiazox, amitraz, chlordimeform, silafluofen, triazamate, pymetrozine, pyrimidifen, chloridmefen ), Indoxacarb, acequinocyl, etoxazole, cyromazine, 1,3-dichloropropene, diafenthiuron, benclothiaz , Bifenazate, propargite, clofentezine, metaflumizone, flubendiamide, cyflumetofen, chlorantani Chlorantraniliprole, cyantraniliprole, cyenopyrafen, pyrifluquinazone, phenazaquin, amiazaflumet, sulfluramid, hydramethylnon, aldehyde , Compounds such as sulfoxaflor, cypropene, fluensulfone, ryanodine, verbutin; and the like. Furthermore, Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis israelensis, Bacillus thuringiensis japonensis, Bacillus thuringiensis tenebrionis or crystalline protein toxins produced by Bacillus thuringiensis, entomopathogenic fungi, nematode pathogenic fungi, etc. Microbial pesticides such as: avermectin, emamectin benzoate, milbemectin, milbemycin, spinosad, ivermectin, lepimectin, DE-175, abamectin ), Antibiotics such as emamectin, spinetoram and semi-synthetic antibiotics; natural products such as azadirachtin and rotenone; repellents such as deet; Mixed with , Can be used together.

Next, examples of the present invention will be described, but the present invention is not limited thereto.

Synthesis example 1
Synthesis of t-butyl 4- (2-((5-chloro-6-ethylpyrimidin-4-yl) amino) ethylpiperidine-1-carboxylate (Compound No. 1-96)

A mixed solution of 4,5-dichloro-6-ethylpyrimidine (0.3 g), t-butyl 4- (2-aminoethyl) piperidine-1-carboxylate (0.46 g), and N, N-dimethylformamide (5 mL) Triethylamine (0.34 g) was added thereto and stirred at 80 ° C. for 13 hours. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: ethyl acetate / heptane = 50/50 (volume ratio, the same shall apply hereinafter)) to give t-butyl 4- (2-((5-chloro -6-Ethylpyrimidin-4-yl) amino) ethyl) piperidine-1-carboxylate (0.52 g) was obtained.
_{^{1 H NMR (Solvent: CDCl 3}} /300MHz):δ(ppm)=8.41(1H,d),5.33(1H,br),4.15(2H,br),3.57(2H,q),2.79(4H,m ), 1.74 (2H, d), 1.62 (12H, m), 1.28 (6H, m)

Synthesis example 2
Synthesis process 1 of 2-phenyl-1- (4- (2- (quinazolin-4-ylamino) ethyl) piperidin-1-yl) ethanone (Compound No. 1-28)
Synthesis of t-butyl 4- (2- (quinazolin-4-ylamino) ethyl) piperidine-1-carboxylate (Compound No. 1-18)

To a mixed solution of 4-chloroquinazoline (1.6 g), t-butyl-4- (2-aminoethyl) piperidine-1-carboxylate (2.22 g), and N, N-dimethylformamide (50 mL), triethylamine (1.98 g) was added and stirred at 70 ° C. for 12 hours. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by amino silica gel column chromatography (eluent: ethyl acetate / heptane = 40/60) to give t-butyl 4- (2- (quinazolin-4-ylamino) ethyl) piperidine-1-carboxyl. The rate (2.83g) was obtained.
_{^{1 H NMR (Solvent: CDCl 3}} /300MHz):δ(ppm)=8.65(1H,s),7.86(3H,m),7.49(1H,t),5.82(1H,br),4.15(2H,t ), 3.75 (2H, q), 2.72 (2H, t), 1.87 (5H, m), 1.46 (9H, s), 1.32 (2H, m)

Process 2
Synthesis of N- (2- (piperidin-4-yl) ethyl) quinazolin-4-amine hydrochloride

t-Butyl 4- (2- (quinazolin-4-ylamino) ethyl) piperidine-1-carboxylate (2.83 g) was dissolved in chloroform (30 ml), trifluoroacetic acid (5 ml) was added, and the mixture was stirred at room temperature for 3 hours. did. After concentrating the solution, the residue was dissolved in ethanol (25 ml), 35% by weight hydrochloric acid (5 ml) was added, and the mixture was stirred at room temperature for 1 hour. The solution was concentrated and the residue was azeotropically dehydrated with ethanol to give N- (2- (piperidin-4-yl) ethyl) quinazolin-4-amine hydrochloride (2.06 g).
¹ H NMR (Solvent: DMSO-d6 / 300 MHz): δ (ppm) = 10.08 (1H, m), 9.02 (1H, br), 8.89 (2H, m), 8.06 (1H, m), 7.92 (1H, m), 7.89 (1H, m), 7.82 (1H, m), 7.65 (1H, m), 3.76 (2H, s), 3.23 (2H, d), 2.85 (2H, q), 1.92 (2H, d ), 1.65 (3H, m), 1.32 (2H, m)

Process 3
Synthesis of 2-phenyl-1- (4- (2- (quinazolin-4-ylamino) ethyl) piperidin-1-yl) ethanone (Compound No. 1-28)

To a suspension of N- (2- (piperidin-4-yl) ethyl) quinazolin-4-amine hydrochloride (0.1 g), triethylamine (0.1 g) and tetrahydrofuran (5 mL) at 0 ° C. under 2-phenylacetyl Chloride (0.08 g) was added and stirred at the same temperature for 1 hour. Then, it heated up to room temperature and stirred for 15 hours. Water was added to stop the reaction, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The resulting residue was purified by amino silica gel column chromatography (eluent: ethyl acetate) to give 2-phenyl-1- (4- (2- (quinazolin-4-ylamino) ethyl) piperidin-1-yl) ethanone (0.03 g) was obtained.
¹ H NMR (Solvent: CD ₃ OD / 300 MHz): δ (ppm) = 8.41 (1H, s), 8.09 (1H, d), 7.77 (2H, m), 7.51 (1H, m), 7.49 (5H, m), 4.56 (1H, m), 3.96 (1H, m), 3.66 (2H, s), 3.62 (2H, m), 2.91 (1H, t), 2.54 (1H, t), 1.60 (5H, m) ), 1.11 (2H, m)

Synthesis example 3
Synthesis of 2- (2-chlorophenyl) -1- (4- (2- (quinazolin-4-ylamino) ethyl) piperidin-1-yl) ethanone (Compound No. 1-35)

N- (2- (piperidin-4-yl) ethyl) quinazolin-4-amine hydrochloride (0.1 g), 2-chlorophenylacetic acid (0.06 g), diisopropylethylamine (0.13 g) and N, N-dimethylformamide (5 mL ) At 0 ° C., O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate (TBTU) (0.16 g) was added at the same temperature. The mixture was stirred for 1 hour. Then, it heated up to room temperature and stirred for 17 hours. Water was added to stop the reaction, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were washed with saturated brine and saturated aqueous sodium hydrogen carbonate, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The resulting residue was purified by amino silica gel column chromatography (eluent: ethyl acetate) to give 2-phenyl-1- (4- (2- (quinazolin-4-ylamino) ethyl) piperidin-1-yl) ethanone (0.03 g) was obtained.
¹ H NMR (Solvent: CD ₃ OD / 300 MHz): δ (ppm) = 8.42 (1H, s), 8.08 (1H, d), 7.73 (2H, m), 7.50 (1H, t), 7.36 (1H, d), 7.22 (3H, m), 4.53 (1H, d), 3.95 (3H, m), 3.60 (2H, t), 3.05 (1H, t), 3.63 (1H, t), 1.82 (2H, d ), 1.62 (3H, m), 1.21 (2H, m)

Synthesis example 4
Synthesis of methyl 5-methoxy-6-((2- (1- (2-phenylacetyl) piperidin-4-yl) ethyl) amino) pyrimidine-4-carboxylate

1- (4- (2-((6-Chloro-5-methoxypyrimidin-4-yl) amino) ethyl) piperidin-1-yl) -2-phenylethane-1-one (0.20 g), triethylamine (0.10 g), dichlorobis (acetonitrile) palladium (II) (0.03 g) and 1,1′-bis (diphenylphosphino) ferrocene (0.09 g) were dissolved in methanol (10 ml) and charged into an autoclave. After sealing the container, a pressure of 1 MPa was applied with carbon monoxide, the temperature in the container was set to 120 ° C., and the mixture was stirred for 17 hours. After cooling to room temperature, the reaction mixture was filtered using Celite to remove insoluble matters, and then the solvent was distilled off under reduced pressure. The resulting residue was purified by amino silica gel column chromatography (eluent: ethyl acetate) to give methyl 5-methoxy-6-((2- (1- (2-phenylacetyl) piperidin-4-yl) ethyl) Amino) pyrimidine-4-carboxylate (0.06 g) was obtained.
1H NMR (Solvent: CD ₃ OD / 300MHz): δ (ppm) = 8.16 (1H, s), 7.33 (5H, m), 4.54 (1H, d), 3.98 (4H, m), 3.80 (3H, s ), 3.75 (2H, s), 3.50 (2H, t), 3.02 (1H, tt), 2.64 (1H, tt), 1.76 (5H, m), 1.22 (1H, m), 0.87 (1H, m)

Synthesis example 5
Synthesis of t-butyl 4- (2-((4-chloro-1,3-dimethyl-1H-pyrazol-5-yl) amino) ethyl) piperidine-1-carboxylate

4-chloro-1,3-dimethyl-1H-pyrazol-5-amine (0.20 g), t-butyl 4- (2-oxoethyl) piperidine-1-carboxylate (0.62 g), acetic acid (0.2 mL) and chloroform To a solution of (5 mL) was added sodium triacetoxyborohydride (0.58 g) at 0 ° C., and the mixture was stirred at room temperature for 17 hours. Saturated aqueous sodium bicarbonate was added to stop the reaction, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by amino silica gel column chromatography (eluent: ethyl acetate / heptane = 40/60) to obtain t-butyl 4- (2-((4-chloro-1,3-dimethyl-1H- Pyrazol-5-yl) amino) ethyl) piperidine-1-carboxylate (0.32 g) was obtained.
_{^{1 H NMR (Solvent: CDCl 3}} /300MHz):δ(ppm)=4.09(3H,m),3.64(3H,s),3.12(2H,q),2.68(2H,t),2.16(3H,s ), 1.58 (5H, m), 1.45 (9H, s), 1.14 (2H, m)

In Tables 1 to 3, the numerical values shown as physical properties are melting points (° C.). These compounds can be synthesized based on the above synthesis examples or the above-described production method of the compound of the present invention.
In Tables 1 to 3, Me represents methyl, Et represents ethyl, Pr represents propyl, iPr represents isopropyl, nBu represents butyl, iBu represents isobutyl, and tBu represents t-butyl.
In Tables 1 to 3, “−” in the Za column and the Zb column indicates a bond, and when the (R ³ ) n column is blank, n indicates 0. In Tables 1 to 3, “*” indicates binding at the relevant part.

Table 4 shows ¹ H-NMR data [measured by ¹ H-nuclear magnetic resonance spectroscopy (Varian NMR-300 MHz); δ is a chemical shift value (ppm)] of some of the compounds of the present invention. .

Below, the test example of this invention composition is described. In each test, the control index followed the following criteria.
[Control index of various preventive effect tests] [Disease level: Visual observation]
5: No lesion or sporulation is observed.
4: The lesion area, the number of lesions, or the spore formation area is less than 10% of the untreated area.
3: The lesion area, the number of lesions, or the sporulation area is less than 40% of the untreated area.
2: The lesion area, the number of lesions, or the sporulation area is less than 70% of the untreated area.
1: The lesion area, the number of lesions, or the spore formation area is 70% or more of the untreated area.

Test example 1 (wheat powdery mildew prevention effect test)
Growing wheat (variety: Norin 61) in a plastic pot with a diameter of 6.0 cm, and when reaching the leaf stage from 1.5 to 2.5, a mixed drug solution with each test compound adjusted to a predetermined concentration is applied to the spray gun. 10 ml per seedling was sprayed. After the drug solution was dried, it was inoculated with conidia spores of wheat powdery mildew (Erysiphe graminis) and kept in a constant temperature room at 20 ° C. The number of lesions was investigated 7 or 8 days after the inoculation, and the control index was determined according to the evaluation criteria.
Compound No. 1-2, 1-3, 1-11, 1-18, 1-20, 1-21, 1-28, 1-30, 1-40, 1-46, 1-47, 1-89, 1- 95, 1-97, 1-104, 1-131, 1-134, 1-144, 1-151, 1-152, 1-212, 1-240, 1-270, 2-3, 2-7, When 3-3 and 3-7 were tested, an effect of controlling index 4 or more was shown at 400 ppm or 200 ppm.

Test example 2 (wheat blight prevention effect test)
Wheat (variety: Norin 61) is cultivated in a plastic pot with a diameter of 6.0 cm, and when the 1.5 to 2.5 leaf stage is reached, the chemical solution in which the compound of the present invention is adjusted to a predetermined concentration is spray gun. A sufficient amount was sprayed. After the drug solution was dried, a conidial spore suspension of wheat wilt (Septoria nodorum) was spray-inoculated and kept in an inoculation box at 20 ° C. for about 1 day, and then kept in a constant temperature room at 20 ° C. The number of lesions was investigated 10 days or 11 days after the inoculation, and the control index was determined according to the above evaluation criteria.
Compound No. When 1-1, 1-128, 1-133, 1-151, 1-205, 1-246, 2-8, and 3-7 were tested, the control index was 4 or more at 400 ppm.

Test example 3 (wheat red rust prevention effect test)
Growing wheat (variety: Norin 61) in a plastic pot with a diameter of 6.0 cm, and when reaching the leaf stage from 1.5 to 2.5, a mixed drug solution with each test compound adjusted to a predetermined concentration is spray gun 10 ml per seedling was sprayed. After the drug solution was dried, the conidia of Puccinia recondita were sprinkled and inoculated, kept in an inoculation box at 20 ° C. for about 1 day, and then kept in a constant temperature room at 20 ° C. The number of lesions was investigated 7 to 9 days after the inoculation, and the control index was determined according to the above evaluation criteria.
Compound No. 1-2, 1-11, 1-96, 1-97, 1-98, 1-99, 1-100, 1-101, 1-102, 1-103, 1-104, 1-144, 1- 145, 1-146, 1-204, 1-212, 1-213, 1-220, 1-223, 1-258, 1-259, 1-260, 1-266, 1-267, 1-279, When 2-3, 3-3, 3-4, and 3-7 were tested, an effect of a control index of 4 or more was shown at 400 ppm.

Test Example 4 (Tomato plague prevention effect test)
Cultivate tomato (variety: yellow pair, the world's best) in a 7.5cm diameter plastic pot, and when the 3 to 6 leaf stage is reached, use a spray gun to squeeze a sufficient amount of the drug solution adjusted to the prescribed concentration Scattered. After the chemical solution was dried, a zoosporangium suspension of Phytophthora infestans was spray-inoculated and kept in a constant temperature room at 20 ° C. The lesion area was investigated 3 or 4 days after the inoculation, and the control index was determined according to the above evaluation criteria.
Compound No. 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-9, 1-10, 1-11, 1-12, 1-13, 1-17, 1- 18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1-28, 1-29, 1-30, 1-31, 1-32, 1-33, 1-34, 1-35, 1-36, 1-37, 1-38, 1-39, 1-40, 1-41, 1-42, 1-43, 1-44, 1-45, 1- 47, 1-48, 1-49, 1-50, 1-51, 1-53, 1-54, 1-55, 1-56, 1-65, 1-66, 1-67, 1-91, 1-93, 1-94, 1-95, 1-96, 1-97, 1-98, 1-99, 1-100, 1-101, 1-102, 1-103, 1-104, 1- 130, 1-131, 1-133, 1-134, 1-136, 1-137, 1-139, 1-140, 1-142, 1-143, 1-144, 1-145, 1-146, 1-147, 1-149, 1-150, 1-151, 1-152, 1-154, 1-155, 1-157, 1-158, 1-163, 1-164, 1-169, 1- 170, 1-176, 1-186, 1-187, 1-188, 1-190, 1-191, 1-192, 1-193, 1-194, 1-196, 1-197, 1-198, 1-199,1-200,1-201,1-202,1-204,1-205,1-206,1-207,1-208,1-209,1-210,1-211,1- 212, 1-213, 1-214, 1-215, 1-216, 1-217, 1-218, 1-219, 1-220, 1-221, 1-222, 1-223, 1-224, 1-225, 1-226, 1-227, 1-228, 1-229, 1-231, 1-232, 1-234, 1-326,1-240,1-241,1-242,1-243,1-244,1-245,1-246,1-247,1-248,1-249,1-250,1- 251, 1-252, 1-253, 1-254, 1-255, 1-256, 1-257, 1-258, 1-259, 1-260, 1-261, 1-262, 1-263, 1-264, 1-265, 1-266, 1-267, 1-268, 1-269, 1-271, 1-272, 1-273, 1-274, 1-275, 1-276, 1- 277, 1-278, 1-279, 1-280, 1-281, 1-282, 1-283, 1-284, 1-285, 1-286, 1-287, 1-288, 1-289, 1-290, 1-291, 1-292, 1-293, 1-294, 1-295, 1-296, 1-297, 1-298, 1-299, 1-300, 1-301, 1- 302, 1-303, 1-304, 1-305, 1-306, 1-315, 1-317, 1-318, 1-319, 1-325, 1-326, 2-1, 2-2, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 3-1, 3-2, 3-3, 3-4, 3-5, 3- When tested for 8, 3-9, and 3-10, 400 ppm or 200 ppm showed an effect of controlling index 4 or more.

Test Example 5 (Cucumber downy mildew prevention effect test)
A cucumber (variety: Sagamihanjiro) is cultivated in a 7.5 cm diameter plastic pot, and when the 1.5 to 2.5 leaf stage is reached, a chemical solution in which the compound of the present invention is adjusted to a predetermined concentration is spray gun. A sufficient amount was sprayed. After the drug solution was dried, a zoosporangium suspension of cucumber downy mildew (Pseudoperonospora cubensis) was spray-inoculated, kept in an inoculation box at 20 ° C. for about 1 day, and kept in a constant temperature room at 20 ° C. The lesion area was examined 7 or 8 days after the inoculation, and the control index was determined according to the above evaluation criteria.
Compound No. 1-1, 1-2, 1-3, 1-6, 1-11, 1-13, 1-16, 1-18, 1-19, 1-20, 1-21, 1-22, 1- 23, 1-24, 1-25, 1-28, 1-30, 1-31, 1-32, 1-33, 1-34, 1-35, 1-37, 1-38, 1-39, 1-40, 1-41, 1-42, 1-44, 1-45, 1-47, 1-49, 1-51, 1-53, 1-54, 1-55, 1-56, 1- 67, 1-94, 1-95, 1-96, 1-97, 1-98, 1-99, 1-100, 1-102, 1-103, 1-104, 1-131, 1-133, 1-136, 1-137, 1-140, 1-142, 1-143, 1-144, 1-145, 1-146, 1-147, 1-148, 1-149, 1-150, 1- 151, 1-152, 1-154, 1-155, 1-186, 1-188, 1-190, 1-191, 1-192, 1-193, 1-194, 1-196, 1-198, 1-199, 1-204, 1-206, 1-207, 1-208, 1-209, 1-210, 1-211, 1-212, 1-213, 1-214, 1-216, 1- 217, 1-218, 1-220, 1-221, 1-222, 1-223, 1-224, 1-225, 1-226, 1-227, 1-228, 1-231, 1-22, 1-339,1-240,1-241,1-242,1-243,1-244,1-246,1-247,1-248,1-249,1-254,1-255,1- 256, 1-257, 1-258, 1-259, 1-260, 1-263, 1-264, 1-265, 1-266, 1-267, 1-268, 1-269, 1-272, 1-273, 1-274, 1-275, 1-276, 1-277, 1-278, 1-279, 1-281, 1-282, 1-283, 1-284, 1-285, 1-286, 1-287, 1-288, 1-289, 1-290, 1-291, 1- 292, 1-293, 1-295, 1-296, 1-299, 1-300, 1-301, 1-306, 1-315, 1-317, 1-318, 1-319, 1-325, 1-326, 2-1, 2-2, 2-3, 2-4, 2-6, 2-7, 2-8, 3-1, 3-2, 3-3, 3-4, 3- When tested for 5, 3-6, 3-8, and 3-9, an effect of controlling index 4 or more was shown at 400 ppm or 200 ppm.

Test Example 6 (Cucumber powdery mildew prevention effect test)
A cucumber (variety: Sagamihanjiro) is cultivated in a 7.5 cm diameter plastic pot, and when the 1.5 to 2.5 leaf stage is reached, a chemical solution in which the compound of the present invention is adjusted to a predetermined concentration is spray gun. A sufficient amount was sprayed. After the chemical solution was dried, a spore suspension of Sphaerotheca fuliginea was spray-inoculated and kept in a constant temperature room at 20 ° C. Seven days after the inoculation, the lesion area was examined, and the control index was determined according to the evaluation criteria.
Compound No. 1-1, 1-2, 1-3, 1-9, 1-11, 1-18, 1-30, 1-37, 1-97, 1-100, 1-102, 1-103, 1- 104, 1-144, 1-146, 1-151, 1-155, 1-204, 1-207, 1-209, 1-212, 1-214, 1-215, 1-216, 1-218, 1-220, 1-266, 1-299, 1-300, 1-301, 2-6, 3-1, 3-3, 3-4, and 3-7 were tested, and the control index was 4 at 400 ppm. The above effects were shown.

Formulation Example 1
(1) Compound of the present invention 20 parts by weight (2) 72 parts by weight of clay (3) Sodium lignin sulfonate 8 parts by weight The above is uniformly mixed to obtain a wettable powder.

Formulation Example 2
(1) Compound of the present invention 5 parts by weight (2) 95 parts by weight of talc The above components are uniformly mixed to form a powder.

Formulation Example 3
(1) 20 parts by weight of the compound of the present invention (2) 20 parts by weight of N, N-dimethylacetamide (3) 10 parts by weight of polyoxyethylene alkylphenyl ether (4) 50 parts by weight of xylene To make an emulsion.

Formulation Example 4
(1) Clay 68 parts by weight (2) Lignin sulfonic acid soda 2 parts by weight (3) Polyoxyethylene alkylaryl ether sulfate 5 parts by weight (4) Fine silica 25 parts by weight Are mixed at a weight ratio of 4: 1 to obtain a wettable powder.

Formulation Example 5
(1) Compound of the present invention 50 parts by weight (2) Oxidated polyalkylphenyl phosphate triethanolamine 2 parts by weight (3) Silicone 0.2 parts by weight (4) Water 47.8 parts by weight (5) 5 parts by weight of sodium polycarboxylate (6) 42.8 parts by weight of anhydrous sodium sulfate are added to the mixed and crushed stock solution, and the mixture is uniformly mixed, granulated, and dried to obtain a granular wettable powder. .

Formulation Example 6
(1) Compound of the present invention 5 parts by weight (2) Polyoxyethylene octylphenyl ether 1 part by weight (3) Polyoxyethylene phosphate ester 0.1 part by weight (4) Granular calcium carbonate 93.9 parts by weight (1) to (3) is uniformly mixed in advance and diluted with an appropriate amount of acetone, and then sprayed onto (4) to remove the acetone and form granules.

Formulation Example 7
(1) Compound of the present invention 2.5 parts by weight (2) N-methyl-2-pyrrolidone 2.5 parts by weight (3) Soybean oil 95.0 parts by weight The above is uniformly mixed, dissolved and sprayed in a trace amount This is an ultra low volume formulation.

Formulation Example 8
(1) Compound of the present invention 20 parts by weight (2) Oxidated polyalkylphenyl phosphate triethanolamine 2 parts by weight (3) Silicone 0.2 parts by weight (4) Xanthan gum 0.1 part by weight (5) Ethylene glycol 5 Part by weight (6) Water 72.7 parts by weight The above is uniformly mixed and pulverized to obtain an aqueous suspension.

Since the compound of the present invention has a high control effect against a wide range of plant pathogenic bacteria and also has high safety, it is useful as an agricultural and horticultural fungicide.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2013-232450 filed on November 8, 2013 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (8)

A compound represented by formula (I) or a salt thereof.

[Wherein, A is a group represented by the following formula;

(In the formula, X ¹ to X ¹⁸ , X ²⁰ , X ²¹ , X ²³ to X ²⁶ , and X ²⁸ to X ³³ may be the same or different and are each hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl. Selected from the group consisting of: hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio, haloalkylthio, alkylamino and dialkylamino;
X ¹⁹ and X ²⁷ may each be the same or different and are selected from the group consisting of hydrogen, alkyl, haloalkyl and alkoxycarbonyl;
X ²² is selected from the group consisting of hydrogen, halogen, alkyl, haloalkyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio, haloalkylthio, alkylamino and dialkylamino)
R ¹ is hydrogen, alkyl, cycloalkyl, haloalkyl or alkoxyalkyl;
Za is a bond or alkylene;
The dashed line

Represents;
R ² is hydrogen, alkyl or haloalkyl;
B is pyrrolidine, piperidine or azepan, which may be crosslinked with alkylene;
R ³ is halogen or alkyl;
n is an integer from 0 to 4;
Zb is a bond or a group represented by -Zb ¹ -Zb ^2- ,
Zb ¹ is carbonyl, thiocarbonyl, sulfonyl, sulfinyl, alkylene or haloalkylene, Zb ² is a bond, carbonyl, thiocarbonyl, sulfonyl, sulfinyl, alkylene, haloalkylene or —NR ^a — (R ^a is hydrogen Or Zb ¹ and Zb ² are not the same;
R ⁴ is alkyl which may be substituted by Y ^1, alkenyl which may be substituted with Y ^1, cycloalkyl which may be substituted by Y ^2, hydroxy, alkoxy substituted by Y ^1, by Y ¹ optionally substituted alkenyloxy, Y ² may aryloxy substituted with, Y good heterocyclyloxy be substituted ^with, alkylthio be substituted with Y ^1, amino which may be substituted by Y ^2, aryl which may be substituted by Y ^2, or is substituted with Y ² be heterocyclyl, optionally;
Y ¹ is selected from the group consisting of halogen, cycloalkyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio, haloalkylthio, aryl and heterocyclyl;
Y ² is selected from the group consisting of halogen, alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylcarbonyl, alkylthio, haloalkylthio, aryl and heterocyclyl. ;
Provided that when X ³ is halogen, X ² is not hydrogen, alkylamino, dialkylamino, alkoxy or haloalkoxy] The compound or its salt of Claim 1 represented by a formula (Ia).

[Each symbol has the same meaning as defined in claim 1] The compound or a salt thereof according to claim 1, which is represented by the formula (Ia-1).

[Each symbol has the same meaning as defined in claim 1] The compound or a salt thereof according to any one of claims 1 to 3, wherein A is a group represented by the following formula.

(Each symbol is synonymous with the definition of Claim 1) The compound or a salt thereof according to any one of claims 1 to 3, wherein A is a group represented by the following formula.

(Each symbol is synonymous with the definition of Claim 1) An agricultural and horticultural fungicide containing the compound according to claim 1 or a salt thereof as an active ingredient. A method for controlling phytopathogenic fungi by applying an effective amount of the compound according to claim 1 or a salt thereof. A method for controlling plant diseases by applying an effective amount of the compound according to claim 1 or a salt thereof.