JP3134552B2 - Cinnamyl piperazine derivatives, their preparation and agricultural and horticultural fungicides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fungicide for agricultural and horticultural use containing a novel cinnamyl piperazine derivative or an acid addition salt thereof as an active ingredient.

[0002]

2. Description of the Prior Art Cinnamyl piperazine derivatives such as the compounds of the present invention have not been reported at all. Therefore, it is not known that the compound of the present invention has a fungicidal activity for agricultural and horticultural use.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fungicide for agricultural and horticultural use containing a novel cinnamyl piperazine derivative or an acid addition salt thereof as an active ingredient.

[0004]

Means for Solving the Problems The present inventors have conducted studies to solve the above problems, and as a result, have found that a novel cinnamyl piperazine derivative has a remarkable activity as an agricultural and horticultural fungicide. The invention has been completed. That is,
The present invention is as follows. The first invention provides the following formula (I):

[0005]

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Wherein X and Y are a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms,
4 haloalkyl groups, a carbonyl group having an alkoxy group having 1 to 4 carbon atoms, a benzyloxycarbonyl group, a carbonyl group having an alkynyloxy group having 2 to 5 carbon atoms, or 3 to 10 carbon atoms May have a cycloalkylalkyleneoxycarbonyl group having a cycloalkyl and an alkylene having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, 2 to 5 carbon atoms Represents an alkoxycarbonyl group, a benzyloxy group, a hydroxyl group, or an alkylsulfonyloxy group having 1 to 4 carbon atoms; or condensed with X and Y together with a carbon atom to which they are bonded to a benzene ring 5 or 6 containing two oxygen atoms
Form a member ring. Z is an alkyl group having 1 to 10 carbon atoms,
Represents a phenyl group or a halogen atom. R is a phenyl group which may have a substituent, a cycloalkyl group having 3 to 10 carbon atoms, a phenoxy group which may have a substituent, a benzyloxy group, a halogen atom,
It represents 6 alkyl groups, alkenyl groups having 2 to 4 carbon atoms, or phenylthio group. m represents an integer of 1 to 10. n represents 1, 2, or 3. The present invention relates to a cinnamyl piperazine derivative or an acid addition salt thereof.

The compound (I) of the present invention may exist in E-form (trans form) and Z-form (cis form) which are geometric isomers, but the compound (I) of the present invention is a pure isomer and isomer. Contains a mixture of bodies. A second invention provides the following formula (II):

[0008]

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(Wherein X, Y, Z and n are as defined above) and the following formula (III):

[0010]

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Wherein R and m have the same meanings as described above, and W represents a leaving group. The compound represented by the formula (I) The present invention relates to a method for producing a milpiperazine derivative.

The third invention relates to a fungicide for agricultural and horticultural use containing a cinnamyl piperazine derivative or an acid addition salt represented by the above formula (I) as an active ingredient.

Hereinafter, the present invention will be described in detail. X, Y, Z, m, n and W in the novel cinnamyl piperazine derivative (I) as the target compound and the raw materials for the production thereof (II) to (III) are as follows.

X and Y each represent a hydrogen atom; a halogen atom; a linear or branched alkyl group having 1 to 6 carbon atoms; a linear or branched haloalkyl group having 1 to 4 carbon atoms. A carbonyl group having a linear or branched alkoxy group having 1 to 4 carbon atoms, a benzyloxycarbonyl group, a carbonyl group having a linear or branched alkynyloxy group having 2 to 5 carbon atoms Or a straight chain having 1 to 4 carbon atoms which may have a cycloalkylalkyleneoxycarbonyl group having a cycloalkyl having 3 to 10 carbon atoms and an alkylene having 1 to 8 carbon atoms, or A branched alkoxy group; a nitro group; a linear or branched alkoxycarbonyl group having 2 to 5 carbon atoms; a benzyloxy group; a hydroxyl group; a linear or branched chain having 1 to 4 carbon atoms. Such as alkylsulfonyloxy group include the.

The preferred X and Y are as follows. As the halogen atom, a chlorine atom, a bromine atom and a fluorine atom are preferred.

The linear or branched alkyl group having 1 to 6 carbon atoms preferably has 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group,
i-propyl, n-butyl, i-butyl, t-butyl and the like); more preferably methyl, ethyl and i-propyl.

A straight-chain or branched haloalkyl group having 1 to 4 carbon atoms (for example, trifluoromethyl group, difluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2-trialkyl group) Fluoroethyl group, 3,3
As the 3-trifluoropropyl group, a trifluoromethyl group is preferable.

A linear or branched alkoxy group having 1 to 4 carbon atoms (for example, methoxy, ethoxy, n-
Propoxy group, i-propoxy group, n-butoxy group, i
-Butoxy group, t-butoxy group and the like) are preferably methoxy group and ethoxy group. 2-5 carbon atoms
As the linear or branched alkynyloxy group,
Preferably, it has 3 to 4 carbon atoms (for example, 1-propynyloxy group, 2-propynyloxy group, 2-butynyloxy group, etc.); more preferably, 2-propynyloxy group.

The cycloalkyl group having 3 to 10 carbon atoms is preferably a cycloalkyl group having 5 to 8 carbon atoms; more preferably a cyclohexyl group. The alkylene group having 1 to 8 carbon atoms is preferably an alkylene group having 1 to 4 carbon atoms (for example, methylene, ethylene,
Propylene, butylene, etc.); more preferably, an ethylene group.

And a straight-chain or 1 to 4 carbon atom
Carbon with a carbonyl having a branched alkoxy group
A linear or branched alkoxy group having 1 to 4 atoms
-OCH_TwoCOOC_TwoH_FiveIs most preferred; Ben
Having a carbon number of 1 to 4 having a zyloxycarbonyl group;
Examples of the linear or branched alkoxy group include -OCH _Two
COOCH_TwoC₆H_FiveIs most preferred; having 2 to 2 carbon atoms
Has 5 linear or branched alkynyloxy groups
A straight chain having 1 to 4 carbon atoms having a carbonyl group or
As a branched alkoxy group, propargyloxyca
Most preferred is a rubonylmethoxy group;
Zero cycloalkyl and alkylene having 1 to 8 carbon atoms
And cycloalkylalkyleneoxy carbonyl
Linear or branched having 1 to 4 carbon atoms having
As the alkoxy group, -OCH _TwoCOOCH_TwoCH_Two
C₆H₁₁Is most preferred. And these alkoxy
The substitution position of the group is not particularly limited, but is preferably a 2-position
Is good.

The straight-chain or branched alkoxycarbonyl group having 2 to 5 carbon atoms is preferably a straight-chain or branched alkoxy group having 1 to 3 carbon atoms (for example, methoxy group, ethoxy group). Group, n-propoxy group, i-
A carbonyl group having a propoxy group or the like is preferred; an ethoxycarbonyl group is more preferred. And the substitution position of these alkoxy groups is not particularly limited;
Preferably, the 2-position is good.

The straight-chain or branched alkylsulfonyloxy group having 1 to 4 carbon atoms is preferably a straight-chain or branched alkoxy group having 1 to 3 carbon atoms (for example, as described above). And the like; and more preferably a methylsulfonyloxy group. The substitution position of these alkoxy groups is not particularly limited; however, the 2-position is preferable.

The combinations of X and Y are as follows. [When X is a hydrogen atom and n in Y is 1, 2, or 3] As Y, all of those described above as X and Y can be mentioned. [When X is other than a hydrogen atom and n in Y is 1 or 2] Examples of X and Y include all of those described above for X and Y. And, when n is 1, Y is preferably a hydrogen atom, a halogen atom,
An alkoxy group having 1 to 4 carbon atoms (when X is a nitro group), a nitro group (when X is an alkoxy group having 1 to 4 carbon atoms), or an alkyl group having 1 to 4 carbon atoms. Y; when n is 2, Y is preferably a hydrogen atom,
A halogen atom and an alkoxy group having 1 to 4 carbon atoms are preferred.

On the other hand, X and Y can form a 5- or 6-membered ring containing two oxygen atoms by condensing with X and Y together with the carbon atom to which they are bonded to a benzene ring; Membered ring [for example, 3,4- (OCH
₂ O) etc. are preferred.

The positions of the substituents for X and Y are not particularly limited, but are preferably as follows. In the case of halogen atoms, 2-, 3-, 4-, 5- and / or 6-positions are preferred for chlorine atoms; 2-, 3- and / or 5-positions are preferred for fluorine atoms; The 2-position is preferred.

In the case of a straight-chain or branched alkyl group having 1 to 6 carbon atoms, the 2-, 4- and / or 5-position is preferred;
The-, 4- and / or 5-position is good, and the 2- and / or 4-position is good for the i-propyl group. A straight-chain or branched haloalkyl group having 1 to 4 carbon atoms, a carbonyl having 1 to 4 carbon atom alkoxy group, a benzyloxycarbonyl group, and an alkynyloxy group having 2 to 5 carbon atoms A carbonyl group or an alkoxy group having 1 to 4 carbon atoms which may have a cycloalkylalkyleneoxycarbonyl group having a cycloalkyl having 3 to 10 carbon atoms and an alkylene having 1 to 8 carbon atoms In the case of an alkoxycarbonyl group having 2 to 5 carbon atoms, a benzyloxy group, a hydroxyl group, and an alkylsulfonyloxy group having 1 to 4 carbon atoms, the 2-position is preferable.

In the case of a nitro group, the 5-position is preferred.
When a 5- or 6-membered ring containing two oxygen atoms is formed by condensing X and Y together with the carbon atom to which they are bonded to a benzene ring, the bonding sites of the benzene rings of X and Y are 3- and 4- Position is preferred.

M represents an integer of 1 to 10, preferably 2 to 8, and more preferably 2 to 7.

Z represents an alkyl having 1 to 10 carbon atoms.
Kill group, phenyl group, halogen atom, etc.
Yes; the alkyl group is preferably one having 1 to carbon atoms.
8 linear or branched alkyl groups, more preferably
Is a linear or branched alkyl group having 1 to 7 carbon atoms
(For example, those shown for X and Y, nC₇H _Fifteen
And the like; preferably the halogen atom is bromine
Atom and chlorine atom are good.

R represents a phenyl group which may have a substituent, a cycloalkyl group having 3 to 10 carbon atoms,
Examples thereof include a phenoxy group, a benzyloxy group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, and a phenylthio group which may have a substituent. The preferred R is as follows.

Examples of the phenyl group which may have a substituent include a phenyl group and a phenyl group having a substituent.
The substituent in the phenyl group may be a group having 1 carbon atom.
Up to four linear or branched alkoxy groups (e.g., X
And Y, the methoxy group is preferable. The position of the substituent is not particularly limited, but is preferably in the 3- or 4-position. A phenoxy group (the position of this substituent is not particularly limited, but is preferably the 4-position); a halogen atom (for example, those shown in the case of X and Y, such as a chlorine atom, A fluorine atom is preferred, and
The position of the substituent is not particularly limited, but is preferably a 3- or 4-position for a chlorine atom, and a 2- or 4-position for a fluorine atom.
-, 3- or 4-position is preferred. ); A linear or branched alkyl group having 1 to 4 carbon atoms (for example, those shown in the case of X and Y can be mentioned, but a methyl group and an ethyl group are preferable. The position of the group is not particularly limited, but is preferably 2- or 4-position for a methyl group, and preferably 2-position for an ethyl group.); Linear or branched having 1 to 4 carbon atoms. (E.g., those shown in the case of X and Y can be mentioned, but a trifluoromethyl group is preferred. The position of this substituent is not particularly limited, but preferably the 3-position is Good)).

The cycloalkyl group having 3 to 10 carbon atoms is preferably a cycloalkyl group having 3 to 8 carbon atoms, more preferably 4 to 7 carbon atoms (more preferably cyclopentane and cyclohexane. .) Is good.

Examples of the phenoxy group which may have a substituent include a phenoxy group and a phenoxy group having a substituent. As the substituent in the phenoxy group, a halogen atom (for example, those shown in the case of X and Y can be mentioned, but a chlorine atom and a fluorine atom are preferable.
The position of the substituent is not particularly limited, but is preferably 2-, 3- or 4-position for chlorine atom, and 4-position for fluorine atom. ); A linear or branched alkyl group having 1 to 6 carbon atoms (e.g., those shown in the case of X and Y, but having 1 to 4 carbon atoms
Are preferred. The position of the substituent is not particularly limited, but is preferably in the 2- or 4-position. ); A straight-chain or branched alkylcarbonyl group having 2 to 4 carbon atoms (for example, those shown in the case of X and Y can be mentioned, and a methoxycarbonyl group is preferable. Is not particularly limited, but preferably 4-position.); A linear or branched alkylthio group having 1 to 4 carbon atoms (for example, methylthio group, ethylthio group, n-propylthio group, i -Propylthio group, n-butylthio group, i-butylthio group, t
-Butylthio group, etc., and a methylthio group is preferable. The position of the substituent is not particularly limited, but is preferably 4-position. A nitro group (the position of this substituent is not limited, but is preferably 4-
Good place. A formyl group (the position of this substituent is not limited, but preferably the 2-position is preferred);
Up to 4 alkylamino groups (preferably having 1 to
Four dialkylamino groups are preferred, and a diethylamino group is more preferred. The position of the substituent is not limited, but is preferably in the 3-position. ).

As the halogen atom, those described for X and Y can be mentioned, and a chlorine atom is preferable. Examples of the alkyl group having 1 to 6 carbon atoms include those described in the case of X and Y, and preferably a linear or branched one having 1 to 4 carbon atoms, More preferred are a methyl group and an i-propyl group.

The alkenyl group having 2 to 4 carbon atoms is preferably a vinyl group. W is a leaving group,
For example, a halogen atom, p-toluenesulfonyloxy and the like can be mentioned. Compound (I) is N, N '
-It has a di-substituted piperazine skeleton, so that an acid addition salt can be easily formed.

Examples of the acid forming an acid addition salt include, for example,
Inorganic acids (hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, etc.), organic carboxylic acids (formic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid, aconitic acid, etc.), organic sulfonic acids (methane, etc.) Sulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), and saccharin.

The synthesis of the compound (I) of the present invention can be usually carried out by reacting the starting compounds (II) and (III) in a solvent or without solvent.
In order to accelerate the reaction, the reaction is preferably performed in the presence of a base.

The solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, and the like. Chlorinated or unchlorinated aromatics, aliphatics, such as chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane,
Alicyclic hydrocarbons; ethers such as diethyl ether, tetrahydrofuran, dioxane; ketones such as acetone, methyl ethyl ketone; N, N
Amides such as -dimethylformamide, N, N-dimethylacetamide; organic bases such as triethylamine, pyridine, N, N-dimethylaniline;
1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; and a mixture of the above solvents.

The amount of the solvent used depends on the amount of the compound (I
The compound (I) can be used in a concentration range of 5 to 80% by weight, but it is preferable to use the compound (II) in a concentration of 10 to 70% by weight.

The base is not particularly limited.
Organic bases such as triethylamine, pyridine, N, N-dimethylaniline, DBU, etc .; alkali metal alkoxides such as sodium methoxide, sodium ethoxide; sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate And inorganic bases such as sodium hydrogencarbonate and potassium carbonate, and inorganic bases such as potassium carbonate and sodium carbonate are preferred.

The compound can be used in an amount of 0.001 to 5 moles per mole of the compound (II).
Preferably it is 0.8 to 1.5 times mol. Although the reaction temperature is not particularly limited, it is in the temperature range from room temperature to the boiling point of the solvent used or lower, and preferably from 20C to 60C. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be carried out for 0.3 to 8 hours.

The amount of the starting compound to be used is 0.5 to 2 times, preferably 0.8 to 1.5 times, the molar amount of the compound (III) with respect to the compound (II).

After completion of the reaction, the target compound (I) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, filtration and the like, and if necessary, recrystallization, various kinds of chromatography and the like. Can be appropriately purified by the above-mentioned means.

As the compound (I), for example, Tables 1 to 1
Compound (I) [Compounds 1 to 120] ].

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

[Table 5]

[0050]

[Table 6]

[0051]

[Table 7]

[0052]

[Table 8]

[0053]

[Table 9]

[0054]

[Table 10]

[0055]

[Table 11]

[0056]

[Table 12]

[0057]

[Table 13]

[0058]

[Table 14]

[0059]

[Table 15]

The compound (II) used in the present invention is a compound represented by the general formula
It can be easily produced by a method for producing a secondary amine (see, for example, EP-A-266,549). Compound (II) may also have geometric isomers. Embodiments 3 and 4 show typical examples. Table 16 shows compound (II) synthesized by the same method.

[Table 16] As the compound (II), for example, each compound having each substituent corresponding to the compounds 1 to 120 shown in Tables 1 to 15 (I
I) [Compound (II) ₁ to (II) ₁₂₀ . ].

The compound (III) used in the present invention can be easily produced by usual production methods such as haloalkylation and tosylation. As the compound (III), for example,
Each compound (III) having a substituent corresponding to Compounds 1 to 120 shown in Tables 1 to 15 and having Br as a leaving group W [Compound (III) ₁ to (III) ₁₂₀ Called. ].

Examples of the pathogenic fungi for agricultural and horticultural use in which the compound (I) of the present invention has a fungicidal effect for agricultural and horticultural use include, for example, wheat rust, barley powdery mildew, cucumber downy mildew, rice blast fungus, tomato late blight and the like. Can be mentioned.

The agricultural and horticultural fungicide of the present invention has a remarkable agricultural and horticultural fungicidal effect and contains at least one compound (I) which is a novel cinnamyl piperazine derivative as an active ingredient. is there. The compound (I) can be used alone, but it is usually compounded with a carrier, a surfactant, a dispersant, an auxiliary agent and the like (for example, powder, emulsion,
(Prepared as a composition such as fine granules, granules, wettable powders, oily suspensions, and aerosols).

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), water, etc .; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection) out and the like.

Examples of surfactants and dispersants which can be used to improve the performance of the agent, such as adhesion to animals and plants, improvement in absorption, and dispersion, emulsification, spreading of drugs, include alcohol sulfates and alkyls. Sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like can be mentioned. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as an auxiliary agent.

In the preparation of the present preparation, the above-mentioned carrier, surfactant, dispersant and auxiliary can be used alone or in appropriate combination according to the respective purposes.
When the compound (I) of the present invention is formulated, the concentration of the active ingredient is usually from 1 to 50% by weight in the emulsion, and usually from 0.3 to 0.3 in the powder.
25 to 25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils and 0.1 to 5% by weight for aerosols. is there.

These preparations can be diluted to an appropriate concentration and sprayed on the foliage of plants, soil, or the surface of paddy fields, or applied directly to various applications depending on the purpose.

[0068]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below.
Note that these examples do not limit the scope of the present invention. Example 1 [Synthesis Example of Compound (I)] N- (β-methyl-2-chlorocinnamyl) -N′-
Synthesis of (3-phenylpropyl) piperazine (Compound 7) N- (β-methyl-2-chlorocinnamyl) piperazine (2.5 g, 10 mmol), 1-bromo-3-phenylpropane (2.0 g, 10 g) Mmol) and potassium carbonate (1.5 g, 11 mmol) were dissolved in N, N-dimethylformamide (30 ml), and the mixture was heated with stirring at 40 ° C. for 2 hours. After the completion of the reaction, water was added, and then diethyl ether was added for extraction.
An aqueous solution of N hydrochloric acid was added, and the precipitated salt was collected by filtration. This salt was dissolved in a 1N aqueous sodium hydroxide solution, and extracted with dichloromethane. After the dichloromethane layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was isolated by silica gel column chromatography (Wako gel C-200, elution with hexane: ethyl acetate = 4: 1) to obtain 3.0 g of a target product of a mixture of E / Z isomers as a yellow oil.

[0069]

[Table 17]

Example 2 [Synthesis Example of Compound (I)] N- (β-methyl-2-chlorocinnamyl) -N′-
Synthesis of (5-hexenyl) piperazine (Compound 101) N- (β-methyl-2-chlorocinnamyl) piperazine (2.5 g, 10 mmol), 6-bromo-1-hexene (1.6 g, 10 mmol) And potassium carbonate (1.
(5 g, 11 mmol) was dissolved in N, N-dimethylformamide (30 ml), and the mixture was heated and stirred at 40 ° C. for 2 hours. After completion of the reaction, water was added, and then diethyl ether was added for extraction, and the diethyl ether layer was acid-extracted with a 1N aqueous hydrochloric acid solution. The acid extract was made alkaline with a 1N aqueous sodium hydroxide solution, and extracted with dichloromethane. After the dichloromethane layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained residue is subjected to silica gel column chromatography (Wakogel C-20).
0, hexane: ethyl acetate = 4: 1 elution) to obtain 3.2 g of the target compound as a colorless oily E / Z isomer mixture.
g was obtained.

[0071]

[Table 18]

Example 3 Synthesis Example of Compound (II) Synthesis of N- (β-methyl-2-chlorocinnamyl) piperazine 2-chlorobenzaldehyde (28.1 g, 0.2 mol), propionaldehyde (11 (0.6 g, 0.2 mol) and potassium hydroxide (1.0 g) were added to the solvent, ethyl alcohol, and the mixture was heated and stirred at 50 ° C. for 2 hours.
After completion of the reaction, the reaction solution was ice-cooled, sodium borohydride (2.1 g, 0.055 mol) was added thereto, and the mixture was returned to room temperature and stirred. After completion of the reaction, an aqueous 1N-HCl solution was added to treat excess sodium borohydride, and the solvent was distilled off to obtain 32.9 g of a residue. This residue was dissolved in ethyl ether, and then phosphorus tribromide (1
(7.9 g, 0.066 mol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the mixture was treated with a saturated aqueous solution of sodium hydrogen carbonate, and the ether layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 44.2 g of a residue. This residue was added dropwise to a solution of piperazine (69.7 g, 0.81 mol) in ethyl alcohol at room temperature together with ethyl alcohol. After stirring for 2 hours, the solvent was distilled off,
An aqueous solution of NaOH was added and this was extracted with methylene chloride. The methylene chloride layer is dried over anhydrous sodium sulfate,
The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to give a pale yellow oil, E
29.2 g of the target compound as a / Z isomer mixture was obtained.

[0073]

[Table 19]

Example 4 Synthesis Example of Compound (II) Synthesis of N- (β-methyl-2-methylcinnamyl) piperazine 2-Methylbenzaldehyde (24.0 g, 0.2 mol), propionaldehyde (11 (0.6 g, 0.2 mol) and potassium hydroxide (1.0 g) were added to the solvent, ethyl alcohol, and the mixture was heated and stirred at 50 ° C. for 2 hours.
After completion of the reaction, the reaction solution was ice-cooled, sodium borohydride (2.1 g, 0.055 mol) was added thereto, and the mixture was returned to room temperature and stirred. After completion of the reaction, an aqueous 1N-HCl solution was added to treat excess sodium borohydride, and the solvent was distilled off, followed by extraction with ethyl acetate / water. After the ethyl acetate layer was dried over anhydrous sodium sulfate, the ethyl acetate was distilled off under reduced pressure to obtain 27.5 g of a residue. This residue was dissolved in ethyl ether, and then phosphorus tribromide (1
(7.9 g, 0.066 mol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the mixture was treated with a saturated aqueous solution of sodium hydrogen carbonate, and the ether layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 34.3 g of a residue. This residue was added dropwise to a solution of piperazine (69.7 g, 0.81 mol) in ethyl alcohol at room temperature together with ethyl alcohol. After stirring for 2 hours, the solvent was distilled off,
An aqueous solution of NaOH was added and this was extracted with methylene chloride. The methylene chloride layer is dried over anhydrous sodium sulfate,
The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to give a pale yellow oil, E
31.7 g of the target compound as a / Z isomer mixture was obtained.

[0075]

[Table 20]

Example 5 [Preparation of preparation] (1) Preparation of granule 5 parts by weight of compound 7, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of Neoperex powder (trade name; manufactured by Kao Corporation) And 2 parts by weight of sodium ligninsulfonate were uniformly mixed, then kneaded by adding a small amount of water, and then granulated and dried to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound 7, 67.5 parts by weight of kaolin, 20 parts by weight of white carbon, 2 parts by weight of Neoperex powder (trade name, manufactured by Kao Corporation) and Demol (trade name) Name; manufactured by Kao Corporation)
Then, it was ground to obtain a wettable powder.

(3) Preparation of Emulsion To 20 parts by weight of compound 7 and 70 parts by weight of xylene, 10 parts by weight of toxanone (trade name; manufactured by Sanyo Chemical Industries) was added, mixed uniformly, and dissolved to obtain an emulsion. .

(4) Preparation of powder 5 parts by weight of compound 7, 50 parts by weight of talc and kaolin 4
5 parts by weight were uniformly mixed to obtain a powder.

Example 6 [Efficacy test] (1) Control effect test against barley powdery mildew (preventive effect) 10 barleys (variety; black wheat) were grown per pot in a plastic flowerpot having a diameter of 6 cm. To each of the five-leaf seedlings, each wettable powder of compound (I) shown in Tables 1 to 15 prepared according to Example 2 was used as a surfactant (0.05%).
Was diluted to 200 or 40 ppm, respectively, and 20 ml of each of these chemicals was sprayed per pot. These were cultivated in a glass greenhouse for 2 days, and then barley powdery mildew spores were collected from the diseased leaves and sprinkled evenly over each plant for inoculation. Next, these were grown in a glass greenhouse for one week, and the degree of barley powdery mildew spots that appeared on each first leaf was investigated. The evaluation of the bactericidal effect was performed in 6 stages (0: the area of the lesion was 81 to 100%, 1: the area of the lesion was 51 to 80%) in comparison with the degree of the lesion in the non-treated section.
Degree 2: Lesion area is about 31 to 50% 3: Lesion area is about 11 to 30% 4: Lesion area is 1 to 10%, 5:
(Lesion area is 0%). In addition, as a comparative drug,
Trifolin as shown below was used in place of compound (I).

[0081]

Embedded image

Table 21 shows the results.

[0083]

[Table 21]

(2) Test for Control Effect of Wheat Leaf Rust (Preventive Effect) Wheat (cultivar: Kobushi wheat) was grown 10 per pot in a plastic flower pot having a diameter of 6 cm. A wettable powder of compound (I) shown in Tables 1 to 15 prepared according to Example 2 was added to a surfactant (0.05
%) To 200 or 40 ppm, and sprayed at 20 ml per pot. After spraying, cultivation is performed in a glass greenhouse for 2 days, and then a spore suspension of wheat leaf rust (2
-3 × 10 ⁵ / ml) was spray-inoculated uniformly on the plant.
After inoculation, the plants were grown for one week in a glass greenhouse, and the degree of wheat leaf rust spots on the first leaves was examined. The results are shown in Table 22 using the comparative drug similar to the above (1) and the evaluation method of the six steps described in the above (1).

[0085]

[Table 22]

(3) Test for controlling efficacy against cucumber downy mildew One cucumber (cultivar: Sagami Hanshiro) is grown per pot in a plastic flower pot having a diameter of 6 cm, and the seedlings are grown on a 1.5-leaf seedling. A wettable powder prepared according to Example 2 from the target compound (I) shown in Nos. 1 to 15 was added to a surfactant (0.05
%) To 500 ppm with water containing
Sprayed at 0 ml. After spraying, cultivate in a glass greenhouse for 2 days, and then cucumber downy mildew (Pseudoperonospora cu
zoospores were prepared from diseased leaves and sprayed evenly on the underside of plant leaves. 2 days after inoculation for 2 days
After being kept in the dark at 0 ° C., they were grown in a glass greenhouse for 5 days, and the degree of cucumber downy spots appearing on the first leaves was examined. The results are shown in Table 23 using the comparative drug similar to the above (1) and the evaluation method of the six steps described in the above (1).

[0087]

[Table 23]

[0088]

Industrial Applicability The novel cinnamyl piperazine derivative of the present invention has an excellent agricultural and horticultural bactericidal effect.

Continuation of the front page (51) Int.Cl. ⁷ identification symbol FI C07D 319/18 C07D 319/18 (56) References JP-A-49-92082 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 295/00-295/32 A01N 43/60 C07D 317/00-317/72 C07D 319/00-319/24 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] (1) The following formula: (Wherein X and Y are a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a carbonyl group having an alkoxy group having 1 to 4 carbon atoms) , A benzyloxycarbonyl group, a carbonyl group having an alkynyloxy group having 2 to 5 carbon atoms, or a cycloalkylalkyleneoxy having a cycloalkyl having 3 to 10 carbon atoms and an alkylene having 1 to 8 carbon atoms An alkoxy group having 1 to 4 carbon atoms which may have a carbonyl group, a nitro group, an alkoxycarbonyl group having 2 to 5 carbon atoms, a benzyloxy group, a hydroxyl group, or a group having 1 to 4 carbon atoms Represents an alkylsulfonyloxy group; or X and Y, together with the carbon atom to which they are attached, are fused to a benzene ring to form an oxygen atom 5, or 6 membered ring formation contain a number.
Z is an alkyl group having 1 to 10 carbon atoms, a phenyl group,
Or a halogen atom. R is a phenyl group which may have a substituent, a cycloalkyl group having 3 to 10 carbon atoms, a phenoxy group which may have a substituent, a benzyloxy group, a halogen atom, It represents 6 alkyl groups, alkenyl groups having 2 to 4 carbon atoms, or phenylthio group. m represents an integer of 1 to 10. n is 1,
Represents 2 or 3. A) a cinnamyl piperazine derivative or an acid addition salt thereof. 2. The following formula: (Wherein X, Y, Z and n are as defined in claim 1) and a compound represented by the following formula: (Wherein R and m have the same meanings as in claim 1 and W represents a leaving group). The compound represented by the formula (I) according to claim 1, wherein A method for producing the cinnamyl piperazine derivative shown. 3. A fungicide for agricultural and horticultural use comprising a cinnamyl piperazine derivative represented by the formula (I) according to claim 1 or an acid addition salt thereof as an active ingredient.