JP2017001954A - Nitrogen-containing saturated heterocyclic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bactericidal agent for agriculture exhibiting high controlling effect on wide range of plant pathogens.SOLUTION: There are provided a compound represented by the formula (I), where each symbol has the same meaning in the specification, or a salt thereof, a bactericidal agent for agriculture containing the compound as an active ingredient and a method for controlling plant pathogens and a method for controlling plant diseases with using the compound.SELECTED DRAWING: None

Description

  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 an aminopyrimidine compound having a nitrogen-containing saturated heterocyclic ring, Patent Document 2 discloses an aminopyrimidine compound characterized by a substituent on a pyrimidine ring useful as a BTK (Bruton's tyrosine kinase) inhibitor.

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, an aminoquinazoline compound or aminopyrimidine compound 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

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

  Conventionally, many drugs provided for controlling plant diseases are each characterized in their spectrum and plant pathogen control effect. For example, the effect on specific plant diseases is not sufficient, the treatment effect is slightly inferior to the preventive effect, or the rain resistance is inferior or the residual effect is relatively short, depending on the application scene, It may show only practically insufficient control effects 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 studies to solve 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 is useful for various plant diseases. On the other hand, the present invention was completed by obtaining knowledge that an excellent control effect was exhibited.

  That is, the present invention relates to the formula (I):

Formula (I):

[Where:
A is the formula:

(In the formula, X ^{1 to} X ⁸ are the same or different and each consists of hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio and haloalkylthio. Selected from the group);
R ¹ is hydrogen, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, or alkoxycarbonyl;
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, optionally substituted alkoxy with Y ^1, with Y ² optionally substituted aryloxy, Y ² which may be substituted with heterocyclyloxy, Y alkylthio be substituted by ^1, Y ² amino which may be substituted with, which may be aryl substituted with Y ^2, or Heterocyclyl optionally substituted with Y ² ;
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]
Or a salt thereof (hereinafter also referred to as the compound of the present invention), an agricultural and horticultural fungicide containing the compound of the present invention as an active ingredient, and a method for controlling phytopathogenic fungi and plant diseases, which apply the compound of the present invention Provide a control method.

  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 include C _1-6 such as butyl, pentyl, isopentyl, neopentyl, hexyl, and the like.

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

In the present specification, unless otherwise specified, cycloalkyl may be bridged, and specific examples thereof include those of C _3-10 such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornanyl, adamantyl and the like. Is mentioned.

In the present specification, unless otherwise specified, examples of the aryl or aryl moiety include 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 constituent atoms. Group. 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, pyrrolyl, pyrrolinyl, pyrrolidinyl, dioxolanyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl, pyrazolinyl, 5-membered rings such as pyrazolidinyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl; 6-membered rings such as pyranyl, pyridyl, piperidinyl, dioxanyl, oxazinyl, morpholinyl, thiazinyl, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl, triazinyl; benzofuranyl, isobenzofuranyl , Dihydrobenzofuranyl, dihydroisobenzofuranyl, 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, dihydrobenzoxazinyl, dihydrobenzoxazolinonyl, dihydrobenzoxazinonyl, benzothioxanyl Membered condensed rings; and those substituted with an oxo group.

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 such as)) methylene, (ethyl) methylene, (propyl) methylene, (isopropyl) methylene, di (methyl) methylene, (methyl) (ethyl) methylene, 1-methylethylene, 2-methylethylene Is mentioned.

  A is the formula:

(In the formula, X ^{1 to} X ⁸ are the same or different and each consists of hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio and haloalkylthio. Selected from the group, and when X ³ is halogen, X ² is not hydrogen.

X ¹ is preferably selected from the group consisting of hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro and alkoxycarbonyl, more preferably hydrogen, alkyl.
X ² is 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, alkoxycarbonyl.
X ³ is 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 and alkoxycarbonyl.
Moreover, those both X ² and X ³ is not hydrogen are preferred.

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 Of these, hydrogen and fluorine are preferred.
In addition, when X ⁸ is halogen, X ⁵ is preferably halogen.

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

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

The dashed line

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 shows that it is a part.

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 cross-linked is preferably C _1-3 such as methylene or ethylene, and the cross-linking 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), 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, optionally substituted alkoxy with Y ^1, with Y ² optionally substituted aryloxy, Y ² which may be substituted with heterocyclyloxy, Y alkylthio be substituted by ^1, Y ² amino which may be substituted with, which may be aryl substituted with Y ^2, or substituted by Y ² is also heterocyclyl, preferably substituted, alkyl which may be substituted with Y ^1, Y ² cycloalkyl which may be substituted with, which may be an alkoxy-substituted with Y ^1, with Y ² which may aryloxy, Y may heterocyclyloxy be substituted by ^2, Y aryl which may be substituted with ² or Y ² may be substituted with Heteroshikuri It is.
The number of substitution of 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 and aryl, and specific examples of Y ₂ include halogen, alkyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, and alkylcarbonyl.

  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, formic acid , Salts with organic carboxylic acids such as acetic acid, citric acid, fumaric acid, maleic acid, trichloroacetic acid and trifluoroacetic acid; such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, mesitylenesulfonic acid and naphthalenesulfonic acid And salts 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 the present specification, unless otherwise specified, isomers are described as a mixture. 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.

  Desirable embodiments of the compound of the present invention include the following compounds, but the compound of the present invention is not limited thereto.

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

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

(3) Formula (Ia-1):

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

(4) A is the formula:

(Wherein each symbol has the same meaning as above), the compound of (1) to (3) or a salt thereof.
(5) A is the formula:

(Wherein each symbol has the same meaning as above), the compound of (1) to (3) or a salt thereof.

(6) The compound of (4) or a salt thereof, wherein X ¹ is selected from the group consisting of hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro and alkoxycarbonyl.
(7) The compound of (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) The compound of (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) The compound of (5) or a salt thereof, wherein X ⁷ is selected from the group consisting of hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, nitro, cyano, alkoxycarbonyl, alkylthio and haloalkylthio .
(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 of the above (5) or a salt thereof.

  Although this invention compound can be manufactured in accordance with the following manufacturing methods and the manufacturing method of a normal salt, it is not limited to these methods.

The compound of the present invention can be produced by the following production methods [1] to [4].
As the compounds of formula (II) to formula (VII) used in the following production methods [1] to [4], commercially available compounds are used, or those prepared from commercially available compounds by known methods are used. be able to.

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 its acid addition salt (for example, hydrochloride, hydrobromide, methanesulfonate, trifluoroacetate, etc.) 1-.

  The compound of Formula (III) can be used in the ratio of 1-50 equivalent with respect to 1 equivalent of compounds of Formula (II), desirably 1-5 equivalent.

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.
A base can be used in the ratio of 1-20 equivalent with respect to 1 equivalent of compounds of Formula (II), desirably 1-5 equivalent.

  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 , Tetrahydrofuran, dioxane, ethers such as 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; hexamethylphosphoramide Phosphoric acid amides such as; 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 ° C to 200 ° C, desirably 70 ° C 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], the compound of the formula (I ′) can be obtained by reacting the compound of the formula (IV) with the compound of the 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 proportion of 1 to 50 equivalents, preferably 2 to 10 equivalents, relative to 1 equivalent of the compound of the formula (IV).

When a compound of the formula (V) in which L ² is halogen is used, 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 formula (IV). When the compound of formula (IV) is an acid adduct, the base is 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 ° C to 200 ° C, desirably 70 ° C 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) -Il) -N, N, N ′, N′-tetramethyluronium BOP reagents such as tetrafluoroborate;
The condensing agent is used in a proportion of 1 to 20 equivalents, preferably 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 ° C to 200 ° C, desirably 70 ° C 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], the compound of the formula (I ″) can be produced by reacting the compound of the formula (IV) with the compound of the 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 proportion of 1 to 50 equivalents, desirably 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, per 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 ° C to 200 ° C, desirably 70 ° C 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 the production methods [1] to [3].

  The compound of the formula (VII) can be used at a ratio of 1 to 50 equivalents, desirably 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 ratio 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 , Tetrahydrofuran, dioxane, ethers such as 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 ° C to 200 ° C, desirably 70 ° C to 120 ° C. The reaction time is usually 1 to 48 hours.

  The compound of the present invention can be applied to, for example, Mastigomycotina, Ascomycotina, Basidiomycotina, Deuteromycotina, Zygomycotina, etc. Can control plant pathogens to which it belongs.

  More specific examples of the plant pathogenic bacteria 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 like Plasmopara viticola; Pythium graminicola, Pythium genus like wheat brown snow rot fungus (Pythium iwayamai) And so on.

  As a subfamily of Aspergillus oryzae, the genus Erysiphe such as wheat powdery mildew (Erysiphe graminis); the genus Sphaerotheca such as Sphaerotheca fuliginea and Sphaerotheca humuli ; Uncinula genus such as Uncinula necator; Podosphaera genus such as Podosphaera leucotricha; Mycosphaerella pinodes, Mycosphaerella pomi ), Banana black sigatoka fungus (Mycosphaerella musicola), oyster lobster fungus (Mycosphaerella nawae), Mycosphaerella fragariae, Mycosphaerella genus; Venturia genus such as Venturia nashicola); Pyrenophora teres, Pyrenophora graminea, Pyrenophora genus; Sclerotinia sclerotiorum, Sclerotinia genus; Rice sesame leaf blight (Cochliobolus miya Cochliobolus genus such as); Didymella genus such as Didymella bryoniae; Gibberella genus such as Gibberella zeae; Grape rot fungus (Elsinoe ampelina), the genus Elsinoe like Elsinoe fawcettii; the genus Diaporthe like Diaporthe citri, Diaporthe sp .; Apple Moniria Monilinia mali, Monilinia genus like Monilinia fructicola; grape late rot fungus ( Glomerella cingulata), and the like.

  As a basidiomycete subfamily, Rhizoctonia genus such as rice rot (Rhizoctonia solani); Ustilago genus (Ustilago nuda); Puccinia coronata; Puccinia recondita, Puccinia genus such as wheat yellow rust fungus (Puccinia striiformis);

  As an imperfect subgenus, the genus Septoria such as Septoria nodorum, Septoria tritici; the genus Botrytis such as Botrytis cinerea; Pyricularia genus such as rice blast fungus (Pyricularia oryzae); Cercospora genus such as Cercospora beticola, Cercospora kakivola; Colletotrichum orbiculare Colletotrichum genus such as; Alternaria alternata apple pathotype, Alternaria alternata Japanese pear pathotype, potato summer or Alternaria solani, cabbage black spot fungus ( Alternaria genus such as Alternaria brassicae; Pseudocercosporella herp genus Pseudocercosporella such as otrichoides; genus Pseudocercospora such as Pseudocercospora vitis; Rhynchosporium such as Rhynchosporium secalis Genus; genus Cladosporium such as Cladosporium carpophilum; genus Phomopsis such as Phomopsis sp .; grouse such as Gloeosporium kaki Examples include the genus Gloeosporium; the genus Fulvia such as tomato leaf mold fungus (Fulvia fulva); and the genus Corynespora such as Corynespora cassiicola.

  Examples of the zygomycota include genus Rhizopus such as strawberry soft rot fungus (Rhizopus stronifer) and peach black mold fungus (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; ring tomato, leaf mold, plague, gray mold, powdery mildew; Brassicaceae Downy mildew, black spot disease; potato summer plague, plague; strawberry powdery mildew, gray mold, anthracnose; various crops downy mildew, plague, gray mold, mycorrhizal disease, powdery mildew Although it is effective in controlling plant diseases such as diseases, it exhibits excellent control effects especially on the plague 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 , 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, etc. Solvent; fatty acid salt, benzoate, alkylsulfosuccinate, dialkylsulfosuccinate, polycarboxylate, alkylsulfate, alkylsulfate, alkylarylsulfate, alkyldiglycolethersulfate, a 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 form, application rate, etc., and cannot be defined unconditionally, but in the case of foliage treatment, 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 (for example, spraying, spraying, misting, atomizing, dusting, water surface application, etc.), soil It can be performed by application (mixing, irrigation, etc.), surface application (application, powder coating, coating, etc.) and the like. It can also be applied by the so-called ultra low 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 as necessary, such as fungicides, insecticides, acaricides, nematicides, soil insecticides, antiviral agents, attractants, herbicides, plant growth preparations, etc. Can be used together or in combination.

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 kiralaylyl )), 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;
Fosetyl aluminum (fosetyl-Al), tolclofos-Methyl, S-benzyl O, O-diisopropyl phosphorothioate, O-ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogen phosphonate, edifenphos, iprobenphos Organophosphorus compounds such as (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 methyl N- (isopropoxycarbonyl) -L-valyl- (3RS) -3- (4-chlorophenyl) -β-valaniphenate;
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, valifenalate, oxathiapiprolin, tolprocarb, picarbutrazox, NK-1001, SB-4303, MIF -1001, MIF-1002, BAF-1107, SYJ-247, NNF-0721 and the like.

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. First, the synthesis example of this invention compound is described.

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) 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. After the solution was concentrated, the residue was dissolved in ethanol (25 ml), 35% 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)

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, 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. Further, in Tables 1 to 3, “*” indicates binding at the portion.

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)
Cultivate wheat (variety: Norin 61) in a plastic pot with a diameter of 6.0 cm. When reaching the leaf stage from 1.5 to 2.5, use a spray gun to mix the chemicals to which each test compound is adjusted to the prescribed concentration. 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, 1-144, 1-151, 1-152, 2-3, 2-7, 3-3, 3-7 were tested, and the effect of control index 4 or higher at 400 ppm showed that.

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 chemical solution is dried (on the day of treatment), spray inoculate with a conidial spore suspension of Septoria nodorum, keep it in an inoculation box at 20 ° C for about 1 day, and then keep it in a constant temperature room at 20 ° C. It was. 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, 1-151, 2-8, and 3-7 were tested, an effect of a control index of 4 or more was shown at 400 ppm.

Test example 3 (wheat red rust prevention effect test)
Cultivate wheat (variety: Norin 61) in a plastic pot with a diameter of 6.0 cm. When reaching the leaf stage from 1.5 to 2.5, use a mixed drug solution with each test compound adjusted to a prescribed concentration in a 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 or 8 days after the inoculation, and a 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- When 145, 1-146, 2-3, 3-3, 3-4, and 3-7 were tested, an effect of a control index of 4 or more was exhibited at 400 ppm.

Test Example 4 (Tomato plague prevention effect test)
Tomato (variety: yellow pair) was cultivated in a plastic pot having a diameter of 7.5 cm, and when the 3 to 6 leaf stage was reached, a sufficient amount of a chemical solution adjusted to a predetermined concentration of the compound of the present invention was sprayed with a spray gun. After the chemical solution was dried (on the day of treatment or the next day), 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, 1-65, 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, 1-143, 1-144, 1-145, 1-146, 1-147, 1- 149, 1-150, 1-151, 1-152, 1-154, 1-155, 1-157, 1-163, 2-1, 2-2, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 3-1, 3-2, 3-3, 3-4, 3-5, 3-8, 3-9 tested at 400 ppm or 200 ppm The effect of 4 or more was shown.

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 (on the day of treatment), a zoosporangium suspension of Pseudoperonospora cubensis was spray-inoculated and kept in a 20 ° C. inoculation box 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, 1-67, 1-94, 1-95, 1-96, 1-97, 1- 98, 1-99, 1-100, 1-102, 1-103, 1-104, 1-143, 1-144, 1-145, 1-146, 1-147, 1-148, 1-149, 1-150, 1-151, 1-152, 1-154, 1-155, 2-1, 2-2, 2-3, 2-4, 2-6, 2-7, 2-8, 3- When tested for 1, 3-2, 3-3, 3-4, 3-5, 3-6, 3-8, 3-9, it showed an effect with a control index of 4 or more 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 (on the day of treatment), 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- When tested on 104, 1-144, 1-146, 1-151, 1-155, 2-6, 3-1, 3-3, 3-4, 3-7, the effect of control index 4 or higher at 400 ppm showed that.

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 present compound (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) 0.2 parts by weight of silicone (4) 47.8 parts by weight of water Further mixed into the stock solution obtained by uniformly mixing and grinding the above (5) 5 parts by weight of sodium polycarboxylate (6) anhydrous sodium sulfate Add 42.8 parts by weight, mix uniformly, granulate, and dry to make granule 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 (Ultra low volume formulation).

Formulation Example 8
(1) 20 parts by weight of the present compound (2) Oxidated polyalkylphenyl phosphate triethanolamine
2 parts by weight (3) 0.2 parts by weight of silicone (4) 0.1 parts by weight of xanthan gum (5) 5 parts by weight of ethylene glycol (6) 72.7 parts by weight of water Use a 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.

Claims (8)

Formula (I):

[Where:
A is the formula:

(In the formula, X ^{1 to} X ⁸ are the same or different and each consists of hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, hydroxy, alkoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylthio and haloalkylthio. Selected from the group);
R ¹ is hydrogen, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, or alkoxycarbonyl;
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, optionally substituted alkoxy with Y ^1, with Y ² optionally substituted aryloxy, Y ² which may be substituted with heterocyclyloxy, Y alkylthio be substituted by ^1, Y ² amino which may be substituted with, which may be aryl substituted with Y ^2, or Heterocyclyl optionally substituted with Y ² ;
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. ;
However, when X ³ is halogen, X ² is not hydrogen]
Or a salt thereof. Formula (Ia):

[Wherein each symbol has the same meaning as in claim 1], or a salt thereof. Formula (Ia-1):

[Wherein each symbol has the same meaning as in claim 1], or a salt thereof. A is the formula:

The compound or its salt as described in any one of Claims 1-3 which is group represented by (In formula, each symbol is synonymous with Claim 1.). A is the formula:

The compound or its salt as described in any one of Claims 1-3 which is group represented by (In 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.