JPS63165369A - Phenylcyclopropane derivative, production thereof and fungicide containing said derivative as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R<1> and R<2> are H, halogen or 1-4C alkyl; R<3> and R<4> are H or 1-4C alkyl; X is H, halogen, nitro, cyano, 1-4C alkyl, 1-4C halo-substituted alkyl, phenyl or halo-substituted phenyl; A is pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl or salt thereof; n is 1-5). EXAMPLE:1-(4'-Chlorophenyl)-2-(3'-pyridyl)cyclopropane. USE:Useful as a fungicide showing excellent effects especially on late blight of tomato, blast of rice plant, anthracnose of cucumber, etc., having no phytotoxicity to plants. PREPARATION:A pyrazoline derivative shown by formula II is thermally decomposed at 150-250 deg.C, preferably 180-200 deg.C to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new compound, a phenylcyclopropane derivative, an efficient method for producing the same, and a bactericidal agent containing the same with high bactericidal activity.

[Problems to be solved by the prior art and the invention In general, it is essential to use fungicides to protect useful crops from diseases, and various fungicides have been developed in recent years.
It is also used.

There are various commercially available agricultural fungicides, but -C-based ones include 5-butyl-2-dimethylamino-6-methylpyridin-4-ol and zinc ion-coordinated Manganese ethylene. Bisdithiocarbamates and the like are known.

However, the former bactericide has limited uses, and the latter bactericide requires a large amount of fungicide for sufficient prevention, which poses problems in terms of practicality and residual toxicity.

The present inventors have carried out extensive research in order to solve the problems of the above-mentioned conventional fungicides and to develop a new compound that has high fungicidal activity and is easy to manufacture.

[Means for solving problems]

As a result, it was discovered that a specific phenylcyclopropane derivative, which has a completely different formulation from conventional fungicides, can achieve objective 1. The present invention was completed based on this knowledge.

That is, the present invention general formula In formula 0, R1 and R2 are each a hydrogen atom.

Represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R3 and R4 are each a hydrogen atom or a C1-C4 alkyl group.
~4 alkyl group, X represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, a halo-substituted alkyl group having 1 to 4 carbon atoms, a phenyl group, or a halo-substituted phenyl group. A represents a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, or a salt thereof. Moreover, n represents an integer of 1 to 5. Note that when n is plural, each X may be the same or different. In addition to providing a phenylcyclopropane derivative represented by the following, the following three methods for producing this phenylcyclopropane derivative are provided.

That is, the general formula [wherein R', R', X, A and n are the same as above]. ]
A general formula characterized by thermally decomposing a pyrazoline derivative represented by [where R', R', X, A and n are the same as above]. ]
A method for preparing a phenylcyclopropane derivative represented by the general formula (hereinafter referred to as "Method I"), where R', R', X, A and n are the same as above. ]
A general formula characterized by thermally decomposing a pyrazoline derivative represented by [where R', R', X, A and n are the same as above]. ]
A method for producing a phenylcyclopropane derivative represented by (hereinafter referred to as "Method 2") and a general formula [wherein R3, R4, Δ, X and n are the same as above. ]
The styrene derivative represented by the general formula R"R"R'CH [wherein Rlo, R2' and Rs each represent a halogen atom. ] A general formula characterized by reacting trihalomethane represented by [where Rlo R2°+R'+R'+LA+n is the same as above. ] A method for producing a phenylcyclopropane derivative represented by (hereinafter referred to as "Method 3") is provided.

Furthermore, the present invention also provides a disinfectant containing a phenylcyclopropane derivative represented by the above general formula (1,).

The phenylcyclopropane derivative of the present invention is represented by the general formula (I) as described above.

The compound represented by this general formula (1) has R1 to
There are various types depending on the type of R'1XIAIn and the bonding position of X. Here, R1 and R2 are each a hydrogen atom, a halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom) or an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, n -butyl group, isobutyl group, 5ec-butyl group, ter
t-butyl group). R3 and R4 are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl l, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 5ec-butyl group, jert-
butyl group). Moreover, X is a hydrogen atom, a halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom).

Nitro group, cyano group, alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group 5
n-butyl group, isobutyl 7f5. -butyl group, tert-butyl group), halo-substituted alkyl group having 1 to 4 carbon atoms (trifluoromethyl group, tetrafluoroethyl group, monofluoromethyl group, difluoromethyl group,
Heptafluoropropyl group.

pentafluoroethyl group, difluoroethyl group, etc.),
Indicates a phenyl group or a halo-substituted phenyl group (chlorophenyl &, -7'romophenyl group, fluorophenyl group, etc.). Furthermore, A is a pyridyl group (2-pyridyl group,
3-pyridyl group, 4-pyridyl group), pyrimidyl group (2
-pyrimidyl group.

4-pyrimidyl group, 5-pyrimidyl group), pyridazinyl group (3-pyridazinyl group, 4-pyridazinyl group), pyrazinyl group or their inorganic acid salts (hydrochloride, hydrobromide, hydroiodide, phosphorus) salts) and organic acid salts (acetate, citrate, maleate, malate, succinate, tartrate).

cinnamate, benzoate, etc.). Note that the pyridyl group is preferably a 3-pyridyl group, and the pyrimidyl group is preferably a 5-pyrimidyl group. Further, n represents an integer of 1 to 5, and 1 or 2 is particularly preferable. Note that when n is a plurality of numbers, that is, an integer from 2 to 5, the number of X's that exist may be the same or different.

This general formula [■] (This is general formula (1-A).

Specific examples of phenylcyclopropane derivatives represented by (including (1-B) and [1-C]) include 1-phenyl-2-(5'-pyridyl)cyclopropane 1f-(
2'-chlorophenyl)-2-(3'-pyridyl)cyclopropane, l-(3'-chlorophenyl)-2-
(3'-pyridyl)cyclopropane;1-(4'-10
lophenyl)-2-(3'-pyridyl)cyclopropane;1-(3',4'-dichlorophenyl)-2-(3
'-pyridyl)cyclopropane;1-(2'+4'+5
'-Trichlorophenyl)-2-(3'-pyridyl)cyclopropane;1-(4'-)lyl)-2-(3'-pyridyl)cyclopropane;1-(4''5'-dimethylphenyl)-2-(3'-pyridyl)cyclopropane; 1
-mesityl-2-(5'-pyridyl)cyclopropane;
1-pentafluorophenyl-2-(5'-pyridyl)
Cyclopropane; 1-(4'-fluorophenyl)-2
-(3'-pyridyl)cyclopropane;1-(3'-nitrophenyl)-2-(3'-pyridyl)cyclopropane1t-(3'-cyanophenyl)-2-(3'-pyridyl)cycloPropane;1-(3'-1-lifluoromethylphenyl)-2-(3'-pyridyl)cyclopropane;1-(4'-phenylphenyl)-2-(3'-pyridyl)cyclopropane i 1- (4”-(4-chlorophenyl)phenyl) -2-(3'-pyridyl)cyclopropane;l-phenyl-2-(5'-pyridazinyl)cyclopropane;1-phenyl-2-(2'-pyrazinyl) Cyclopropane: 1-phenyl-2-(2'-
pyrazinyl) cyclopropane.

1-phenyl-2-(4'-pyridazinyl)cyclopropane;l-phenyl-2-(5'-pyridazinyl)cyclopropane;1-phenyl-2-(3'-pyrimidinyl)cyclopropane;1-(2' -chlorophenyl) -
2-(3'-pyridazinyl)cyclopropane; 1-
(3',4'-dichlorophenyl)-2-(2'-pyrazinyl)cyclopropane;1-(4'-tolyl)-2
-(3'-pyridazinyl)cyclopropane;1-(3'
-cyanophenyl”) -2-(5゛-pyrimidinyl)
Cyclopropane; l-methyl-2-phenyl-5-(3
'-pyridyl)cyclopropane;1-(3'-chlorophenyl)-2-propyl-5-(3'-pyridyl)cyclopropane;1-methyl-2-phenyl-1-(5'-
pyridyl) cyclopropane; l-°methyl-1-(5'
-pyridyl)-2-(2-tolyl)cyclopropane; l
-ethyl-2-phenyl-1-(5''-pyridyl)cyclopropane;1-methyl-1-phenyl-2-(5'-
pyridyl)cyclopropane;1,2-dimethyl-1-phenyl-5-(3'-pyridyl)cyclopropane; 1-
(2',4'-dimethylphenyl)-2-methyl-5-
(2'-pyrazinyl)cyclopropane;2-(4'-fluorophenyl)-1-methyl-1-(5'-pyridazinyl)cyclopropane;1-(3''-pyridazinyl)-
3,3-dichloro-2-(5-trifluoromethylphenyl)cyclopropane;1,2-dimethyl-3,3-dichloro-1-phenyl-2-(2'-pyrazinyl)cyclopropane; 1,2- Dimethyl-3-chloro-1-phenyl-2-(2'-pyrazinyl)cyclopropane; 1,
2-dimethyl-3-chloro-1-(4-chlorophenyl)-2-(2'-pyrazinyl)cyclopropane; 1,2
-dimethyl-3,3-dichloro-1-phenyl-2-(
2'-pyrimidyl)cyclopropane;1,2-dimethyl-3-chloro-1-phenyl-2-(2'-pyrimidyl)cyclopropane: l,2-dimethyl-3-chloro-1
-(4-chlorophenyl)-2-(2'-pyrimidyl)
Cyclopropane 1L2-dimethyl-3,3-';chloro1-phenyl-2-(2'-pyridazinyl)cyclopropane;1°2-dimethyl-3-chloro-1-phenyl-2-(2'-pyridazinyl)cycloPropane; 1,2
-dimethyl-3-chloro-1-(4-chlorophenyl)
Examples include -2-(2''-pyridazinyl)cyclopropane.

The phenylcyclopropane derivative represented by the above general formula (1) can be produced by various methods, but
Among these, the most efficient manufacturing methods are methods 1 to 1 above.
3 can be given.

According to method 1, by thermally decomposing a pyrazoline derivative represented by general formula (II), a desired phenylcyclopropane derivative represented by general formula (1-A) (which in general formula (1), A compound in which both R2 and R3 are hydrogen atoms is obtained. In thermally decomposing the pyrazoline derivative represented by the general formula (n),
Although it is possible to carry out the reaction without a solvent, it is usually carried out using a suitable solvent, such as a high-boiling alcohol such as ethylene glycol, diethylene glycol or decyl alcohol, an ether such as diethylene glycol dimethyl ether or diethylene glycol diethyl ether, an aromatic hydrocarbon such as cymene, or Preferably, the reaction is carried out in a high boiling inert solvent such as a hydrocarbon such as n-dodecane, decane or decalin.

In addition, the thermal decomposition temperature varies depending on the type of pyrazoline derivative of general formula (II) that is the raw material, but is usually 150 to 2
The temperature is 50°C, preferably in the range of 180 to 200°C. If the temperature is less than 150°C, decomposition will not proceed or the decomposition will proceed slowly, and if it exceeds 250°C, a large amount of by-products such as char or excessive decomposition products will be produced, which is not preferable.

Note that the above thermal decomposition reaction proceeds under various conditions, but
The reaction proceeds more smoothly when carried out in the presence of a base or in the presence of a base and platinum. Examples of the base used here include organic bases such as dimethylaniline and quinoline, and inorganic bases such as sodium hydroxide, potassium hydroxide, and barium hydroxide. Further, as platinum, platinum asbestos and platinum black, which have a large specific surface area, are preferable, and platinum asbestos is particularly preferable.

The pyrazoline derivative represented by the general formula (II) used as a raw material compound in the above method 1 is: -R', R', X, A
There are various types depending on the type of and n, but specifically, R
2, R3 is a hydrogen atom).

Further, the pyrazoline derivative of the general formula C11) can be produced by various methods, but usually, the pyrazoline derivative of the general formula C11) is produced by the general formula [wherein R', R', X, A and n are the same as above. ]
It is obtained by reacting an α,β-unsaturated ketone represented by with hydrazine hydrate. This reaction is carried out in the presence of a base such as an alkali metal (Na, etc.) hydroxide or an alkaline earth metal (Ca, Ba, etc.) hydroxide in an appropriate solvent such as methanol, ethanol, isopropanol, etc. alcohols such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, di-n-butyl ether, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, nitriles such as acetonitrile, dimethylformamide (DMF) or dimethyl sulfoxide. (DMSO
It is preferable to proceed in an inert solvent such as ).

The α,β-unsaturated ketone represented by the above general formula (III) can be obtained by several methods, but is usually obtained from the general formula [where R′, X, and n are the same as above]. ] and the general formula A-C-R'
......(V) [In the formula, R' and A are the same as above. ] It is obtained by reacting a nitrogen-containing heterocyclic compound represented by the following in the presence of a base such as sodium hydroxide.

Next, according to method 2, by thermally decomposing the pyrazoline derivative represented by the general formula [■'], the desired phenylcyclopropane derivative represented by the general formula (1-B) (this In -IYa formula (1), R", R'
are both hydrogen atoms) is obtained. The conditions for this thermal decomposition are the presence or absence of a solvent.

The type of solvent, temperature, use of base and platinum, etc. are the same as in method 1 above.

The pyrazoline derivative represented by the general formula [■'] used as a raw material compound in the above method 2 has various types depending on the types of R1゜R3, ) Phenylcyclopropane AM "Specific compounds of the L form (provided that Rl and R3 in -C formula CI) correspond to hydrogen atoms).

The pyrazoline derivative of the general formula [■゛] can be obtained by various methods, but is usually obtained from the general formula [where R', R3, X, A and n are as defined above].

The α,β-unsaturated ketone represented by can be obtained by several methods, but is usually obtained by the general formula [wherein R', X and n are the same as above]. ] and the general formula A-C-CH2R'...[■][
In the formula, R1 and A are the same as above. ] can be obtained by reacting a nitrogen-containing heterocyclic compound represented by the following in the presence of a base such as sodium hydroxide.

Subsequently, according to method 3, 8 styrene vM bodies represented by the general formula [■] are converted to the general formula RloR''R'CH [wherein R1'' RZo and R5 are the same as above. ] By reacting with trihalomethane represented by the following, the desired phenylcyclopropane derivative represented by the general formula rI-c] is obtained.

Although it is possible to react the styrene derivative represented by the general formula [■] with trihalomethane without a solvent, a suitable solvent may be used.

For example, it can be carried out in an inert solvent such as alcohol such as tert-butyl alcohol and tert-amyl alcohol.

Further, the reaction temperature varies depending on the type of the styrene derivative of the general formula [■] which is a raw material, but is usually in the range of 10 to 100°C, preferably 20 to 50°C.

The trihalomethane used in the above reaction is
Trifluoromethane, trichloromethane.

Examples include tribromomethane, triiodomethane, dichlorofluoromethane, chlorodifluoromethane, and chlorodibromomethane.

Further, the above reaction proceeds smoothly in the presence of a base or in the presence of a base and an alkylammonium compound. Examples of the base used here include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as tert-butquin sodium, terL-butoxypotassium, tert-amyloxy sodium, and tart-amyloxypotassium. .

In addition, as alkylammonium compounds, hensyltriethylammonium bromide, benzyltriethylammonium chloride, benzyltrimethylammonium bromide, hensyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium hydroxide, cetyltriethylammonium Bromide, cetyltriethylammonium chloride, octyltriethylammonium bromide,
Octyltriethylammonium chloride and trioctylmethylammonium chloride are preferred.

Further, when an inorganic base is used, the inorganic base is usually used as an aqueous solution. In that case, the concentration of the inorganic base is usually 20 to 70 wt%, preferably 40 to 60 wt%.

As mentioned above, according to method 3 of the present invention, the general formula (1-C
) can be produced, but by further heating in the presence of diethyl phosphite or triethylamine, RI (RI'
) or R” (R”) is a hydrogen atom, the general formula [■
, ] can also be used as a phenylcyclopropane derivative.

General formula [I] produced by methods 1 to 3 as described above
A phenylcyclopropane derivative represented by the general formula (
'IA), (1-B) and [1-C). ] is a new compound and exhibits excellent bactericidal activity.

The disinfectant of the present invention contains the phenylcyclopropane derivative of the above-mentioned general formula [1], particularly as an active ingredient, and the derivative may be used as it is, but usually, Dilute with liquid such as water or organic solvent, solid powder, or other suitable medium, and add auxiliary agents such as wetting agents, emulsifiers, fixing agents, etc. as necessary to form wettable powders, solutions, and emulsions. , sol, powder (D
(including L-type powder), fine particles, etc.

When used in the form of a wettable powder, diatomaceous earth, white carbon, etc. are added to the above active ingredients, and further a wetting agent such as an alkylbenzene sulfonate, an alkyl sulfate, or a polyethylene glycol ether is added, and the mixture is stirred. Is it okay to use water when using? Just dilute it to the agricultural level. In addition, in order to form an emulsion, a hydrocarbon such as xylene, benzene, toluene, etc. is added to the above active ingredients, and polyoxyethylene-alkylaryl ether such as polyoxyethylene nonylphenyl ether or polyoxyethylene-aliphatic alcohol is added. Add an emulsifier such as ether and mix. (When using this, just dilute it with water to a predetermined 4 degrees.

To form a powder, add clay to the above-mentioned active ingredients.

Add clay minerals such as talc and kaolin, mix and crush,
It is sufficient to set the particle size to a predetermined value and use it by scattering it as it is.

To form a granule, add diatoms to the above-mentioned active ingredients.

Add calcium carbonate, bentonite, clay, etc., then add lignin sulfonate, polyvinyl alcohol, a caking aid such as starch, and in some cases, add a surfactant to improve dispersibility, and granulate it. . When using it, just spray it as it is.

The fungicide of the present invention has the general formula [!] as described above. The phenylcyclopropane derivative represented by ] is used as an active ingredient, but it is also effective to use other active ingredients in combination.

In addition, among the compounds represented by the general formula in this specification, only one type of stereoisomers such as cis form and trans form is shown for convenience, but this does not mean that other stereoisomers are also included. shall be indicated.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Production Example 1 3.52 g of l-(4'-chlorophenyl)-3-(3'-pyridyl)-2-propen-1-one.

A solution of 2.51 g of potassium hydroxide and 1.79 g of 85% Eiwa hydrazine (N Hz NH2.H2O) dissolved in 14 ml of diethylene glycol was heated at 110°C.
．． Stirred for 5 hours.

Next, a distillation tube was attached to the upper part of the reaction flask, and the temperature was gradually raised and maintained in the range of 180 to 190°C for 4 hours.

After cooling, add water and extract the organic matter with ethyl acetate.
After normal treatment, 1-(4'-chlorophenyl)
-2-(3'-pyridyl) cis of cyclopropane,
3.2 g of a mixture of trans isomers (yield 96.2%)
) was obtained. By gas chromatography (GC) and gas chromatography mass spectrometry (GCMS), the isomer ratio of this is cis : trans
It was found that = 32.1: 67.9.

cis of the cyclopropane derivative obtained by the above operation,
Using 0.4 g of a mixture of trans isomers, a reversed-phase Roper column (Roper column, RP-18°310
Fractionation was performed using cis.X25φ).

1 g and 0.22 g of the trans isomer were obtained, respectively.

Obtaining letter 1-(4',-10lophenyl)-2-(3
'-pyridyl) cyclopropane cis, trans
The spectral data and physical property data of the isomer are shown below.

Structural formula refractive index 1.57 or more (70”C) Proton NMR (270MH2, /!j11 constant solvent CC
1a) Ha (1,33ppm, IH,m)
.

Hb (1,48 ppm, 1) (, m).

Hc Hc-(2,43ρρm, 2H,m)
Jc-c・18. 3Hz.

Ha (6,92ppm, 6H,m).

Ha (8,23ppm, 2jl, m)tr
ans form (compound 2) Structural formula % Formula % (70) Proton NMR (270 MHz, measurement solvent CCj24
)Ha (1,41ppm, 2H,m)
.

Hb Hb・(2,09ppm, 2H,m) Jb
-ts 14.811z.

Hc (7.25ppm, 6H,m).

Ha (8,35 ppm, 2 H, m) Production Example 2 ■-Phenyl-5-(3'-pyridyl)-2-propen-1-one 3.0 g and 85% hydrated hydrazine 6 m
A solution of A dissolved in 30 mρ of diethylene glycol was added to 1
Stirred at 10''C for 1.5 hours.

Next, a distillation tube was attached to the top of the reaction flask, and the temperature was 120.
Water and excess hydrated hydrazine were distilled off at °C.

After cooling, 1.22 g of potassium hydroxide was added, and the temperature was gradually raised and maintained in the range of 180 to 190°C for 4 hours.

Thereafter, the reaction product obtained by cooling, adding water, extracting organic matter with ethyl acetate, and distilling off the ethyl acetate was purified by silica gel chromatography, and 1-phenyl-2-(5'-pyridyl)cyclo 0.91 g of mixture of cis and trans isomers of propane (compound 3)
(yield 32.2%). By GC and GCMS, the isomer ratio of this is cis : trans
= 43.2: 56.8. The measurement results of this product are shown in Table 1.

Production Examples 3 to 6 In Production Example 2, instead of 1-phenyl-5-(3'-pyridyl)-2-propen-1-one: 1-(2'-
chlorophenyl)-3-(3'-pyridyl)-2-propen-1-one (Production Example 3).

1-(4'-chlorophenyl)-3-(3'-pyridyl)-2-propen-1-one (Production Example 4).

1-(4'-methylphenyl)-3-(3'-pyridyl)-2-propen-1-one (Production Example 5) or 1
-(3',4'-dichlorophenyl)-3-(3'-pyridyl)-2-propen-1-one (Production Example 6) phenylcyclopropane derivatives were produced. Results first
Shown in the table.

Production Example 7 l-(4'-chlorophenyl)-3-(3'-pyridyl)-1-propen-3-one 2 g, potassium hydroxide 1
．． 5g and 85% Eiwa Hydrazine 2II+1 in diethylene glycol lomff? The dissolved solution was heated to 110
Stirred at ℃ for 1.5 hours.

Next, a distillation tube was attached to the upper part of the reaction flask, and the temperature was gradually raised and maintained in the range of 180 to 190°C for 4 hours.

After cooling, water was added and organic matter was extracted with ethyl acetate, followed by normal treatment to obtain 1-(4'-chlorophenyl).
-2-(3'-pyridyl)cyclopropane (i3.
A mixture of trans isomers was prepared at 150+w(H (yield 8.
0%) was obtained. By gas chromatography (GC) and gas chromatography mass spectrometry (GCMS), the isomer ratio of this is cis : tran
It was found that s = 40.9:59.1.

The infrared absorption spectrum of this product was the same as that of Compound 5 obtained in Production Example 4.

Example 1 (11 Biological Test (Stem and Leaf Treatment) Barley planted in a plastic pot with a diameter of 7 cm (
When the first leaf of cultivar: Kashima) develops, a predetermined concentration of the test compound (Compounds 1 to 7 obtained in Production Examples 1 to 6) 5 nu
was scattered.

The barley thus treated was sprinkled with spores of barley powdery mildew (Erysiphe graminis) one day later. After cultivating at 18°C for 7 days, the disease state was observed. The results are shown in Table 2.

(2) Biological test (soil treatment) Barley seeds were sown in a 1/2000 are Wagner pot filled with upland soil, and after covering with soil, the test compound was irrigated at a concentration of 100 to 200 g/10 are. .

When the first leaf of barley treated in this way develops,
Sprinkle with barley powdery mildew spores.

After cultivating at 18°C for 7 days, the disease state was observed. The results are shown in Table 2.

(Severity of disease) The disease index was evaluated in six stages from 0 to 5 according to the lesion area of the investigated leaves, and the disease severity was calculated using the following formula.

Incidence index Disease state 0 Lesions observed 1 Lesion area less than 2% 2 Lesions area less than 5% 3 Lesions area less than 10% 4 Lesions area less than 25% 5 Lesions area 50% The comparative compound in Table 2 above is 5-butyl-2-dimethylamino-6-methylpyridin-5-ol (commercially available fungicide nidimethylimole) Example 2 Biological test (foliage treatment) Planted in a plastic bot with a diameter of 7 cm Oat (
When the first leaf of the cultivar Haruaoba) develops, 5 ml of the test compound at the predetermined concentration is added to tt3! I clothed it.

Oat crown rust (Pucci) treated in this way
Sprinkle with summer spores of I.ia coronata). 23
After being kept in a greenhouse with a humidity of 95% or more at ℃ for 20 hours, 20~
The disease developed after being placed in a greenhouse at 23°C for one week. The disease severity was calculated in the same manner as in Example 1.

The results are shown in Table 3.

Comparative compound N12 in Table 3 is zinc ion-coordinated Manganese ethylene bisdithiocarhame-1- (commercially available fungicide; mancozeb) [Effects of the invention] The phenylcyclopropane derivative of the present invention is a new compound and is used as an agricultural fungicide. It is also expected to be used as a medicine, as it is effective against bacteria such as Shirofu bacteria and Canbuta.

Further, according to method L2.3 of the present invention, the above phenylcyclopropane derivative can be produced in a simple process and in high yield.

Furthermore, the disinfectant of the present invention exhibits strong antibacterial activity.

It is particularly effective against tomato late blight, rice blast disease, cucumber arachnid blight, etc., and is also effective against plant pathogenic algal fungi and ascomycetes1.
It also shows strong antibacterial activity against Basidiomycetes, Deuteromycetes, and bacteria.

Furthermore, the fungicide of the present invention has the advantage that it causes less phytotoxicity to plants.

Furthermore, among the phenylcyclopropane derivatives represented by the general formula (1), those having a halogen atom as a substituent have high bactericidal activity, and those in which the phenyl group and A have a cis relationship have particularly high bactericidal activity. be.

Claims (7)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R^1 and R^2 each represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and R
^3 and R^4 are each hydrogen atom or carbon number 1
~4 alkyl group, X represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, a halo-substituted alkyl group having 1 to 4 carbon atoms, a phenyl group, or a halo-substituted phenyl group. A represents a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, or a salt thereof. Moreover, n represents an integer of 1 to 5. Note that when n is plural, each X may be the same or different. ] A phenylcyclopropane derivative represented by (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1 and R^4 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a hydrogen atom, a halogen atom, It represents a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, a halo-substituted alkyl group having 1 to 4 carbon atoms, a phenyl group, or a halo-substituted phenyl group, and A is a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, or These salts are shown below. Moreover, n represents an integer of 1 to 5. Note that when n is plural, each X may be the same or different. There are general formulas, mathematical formulas, chemical formulas, tables, etc., which are characterized by the thermal decomposition of pyrazoline derivatives represented by [In the formula, R^1, R^4, X, A and n are the same as above. ] A method for producing a phenylcyclopropane derivative represented by (3) The manufacturing method according to claim 2, wherein the thermal decomposition is carried out in the presence of a base. (4) The manufacturing method according to claim 2, wherein the thermal decomposition is carried out in the presence of a base and platinum. (5) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R^1 and R^3 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a hydrogen atom, a halogen atom, It represents a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, a halo-substituted alkyl group having 1 to 4 carbon atoms, a phenyl group, or a halo-substituted phenyl group, and A is a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, or These salts are shown below. Moreover, n represents an integer of 1 to 5. Note that when n is plural, each X may be the same or different. ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [wherein R^1, R^3, Z, A and n are the same as above. ] A method for producing a phenylcyclopropane derivative represented by (6) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R^3 and R^4 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a hydrogen atom, a halogen atom, It represents a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, a halo-substituted alkyl group having 1 to 4 carbon atoms, a phenyl group, or a halo-substituted phenyl group, and A is a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, or These salts are shown below. Moreover, n represents an integer of 1 to 5. Note that when n is plural, each X may be the same or different. ] The styrene derivative represented by the general formula R^1'R^2'R^5CH [wherein R^1', R^2' and R^5 each represent a halogen atom. ] General formula characterized by reacting trihalomethane represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1', R^2', R^3, R^4, X, A
, n are the same as above. ] A method for producing a phenylcyclopropane derivative represented by: (7) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R^1 and R^2 each represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and R
^3 and R^4 are each hydrogen atom or carbon number 1
~4 alkyl group, X represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, a halo-substituted alkyl group having 1 to 4 carbon atoms, a phenyl group, or a halo-substituted phenyl group. A represents a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, or a salt thereof. Moreover, n represents an integer of 1 to 5. Note that when n is plural, each X may be the same or different. ] A disinfectant containing a phenylcyclopropane derivative represented by