JPH07149756A - Azoxycyanobenzodioxane derivative - Google Patents

Abstract

PURPOSE: To obtain the subject compound represented by a specific formula which exhibits good antibacterial activity against a certain kind of phytopathogenic fungus, e.g. of tomato late blight or the like.

CONSTITUTION: There is provided a compound of formula I [wherein (n) is 0, 1 or 2; R is a halogen, a (substituted) alkyl or an alkoxy; R¹ is H or a haloalkyl; and R² and R³ are each H or a (halo)alkyl], e.g. 6-azoxycyano-1,3- benzodioxane or the like. This compound is preferably obtained by treating a compound of formula II with a mixture containing hydrogen peroxide and methanoic acid and/or with peroxymethanoic acid, or by reacting a compound of formula III with cyanamide or a metal salt thereof and an oxidizing agent.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

The present invention relates to certain azoxycyanobenzodioxane derivatives, a process for their preparation, compositions comprising such compounds and their use as fungicides.

[0002]

EP 0371560 A1 discloses a method for controlling fungi and / or bacteria, and / or yeast and / or nematodes in fixed places. Is the general formula (A)

[0003]

[Chemical 4]

Wherein R ² and R ³ together or R ³ and R ⁴ together represent an optionally substituted hydrocarbyloxy chain; the ring of which is the remaining moiety, R ⁵ , R ⁶ and either R ² or R ⁴ , or each optionally substituted; n is
Represents 0 or 1, and X represents a cyano group, -COO
Treating the site with a compound, which represents the H group or salts, ester or amide derivatives thereof. The term "hydrocarbyloxy chain" is used to mean a chain of carbon atoms interrupted by one or more (but preferably only one) oxygen atom. In each of the examples, the hydrocarbyloxy chain contains only one oxygen atom, which is located at one end of the chain.

European Patent Application Publication No. 0518436 has the general formula (B)

[0006]

[Chemical 5]

Wherein m is 0 or 1; each of R ¹ and R ² , and R ³ and R ⁴ , if present, is independently a hydrogen or halogen atom, or optionally X represents a substituted alkyl, cycloalkyl or aryl group, or R ¹ and R ² together, or R ³ and R ⁴ together represent an optionally substituted alkylene chain; Is a cyano group, -C
Represents an OOH group or a salt, ester or amide derivative thereof, Y represents an alkyl group or a halogen atom; and n represents 0, 1, 2, or 3.
Of the compounds and their use as fungicides.

[0008]

SUMMARY OF THE INVENTION It has now been discovered for the first time that certain azoxycyano-1,3-benzodioxane derivatives exhibit good antibacterial activity against certain phytopathogenic fungi. Therefore, according to the invention, the general formula (I)

[0009]

[Chemical 6]

Wherein n is 0, 1 or 2; each R, if present, is independently a halogen atom,
Or an optionally substituted alkyl or alkoxy group; R ¹ represents a hydrogen atom or a haloalkyl group; and R ² and R ³ independently represent a hydrogen atom or an alkyl or haloalkyl group. Provided.

If the compound of the invention contains an alkyl group, this may be straight-chain or branched.
It may contain up to 2, preferably up to 6, especially up to 4 carbon atoms.

When any of the above substituents are shown to be optionally substituted, the optional substituents are used to determine the development of the insecticidal compound and / or their structure / activity. It can be any one or more commonly used in the modification of compounds to affect their persistence, permeability or other properties. Specific examples of such a substituent include, for example, a halogen atom, nitro, cyano, hydroxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, amino, alkylamino, dialkylamino, formyl, alkoxycarbonyl, carboxyl, alkanoyl, alkylthio, alkyl. Includes sulfinyl, alkylsulfonyl, carbamoyl and alkylamido groups. If any of the aforementioned substituents represent or contain an alkyl substituent, this may be straight-chain or branched, up to 12, preferably up to 6, especially May contain up to 4 carbon atoms. Typically, 0-3 substituents may be present, most usually 0 or 1.

Preferably, each R, if present, is independently a halogen atom, or each group is one or more substituents selected from halogen atoms, nitro, cyano, hydroxyl and amino groups. Represents a C _1-6 alkyl or C _1-6 alkoxy group optionally substituted by. Further, it is preferable that n is 0 or 1.
When n is 1, R is preferably located at the 8 position on the 1,3-benzodioxane ring.

More preferably, R is a halogen (particularly chlorine or bromine) atom, or C _1-4 in which each group is optionally substituted with one or more substituents selected from a halogen atom and a hydroxyl group. Represents an alkyl (especially methyl) or C _1-4 alkoxy (especially methoxy) group.

R ¹ preferably represents a hydrogen atom or a C _1-6 haloalkyl group.

More preferably, R ¹ represents a hydrogen atom or a C _1-4 haloalkyl group in which each halogen atom in the haloalkyl group is preferably a fluorine or chlorine atom.

It is also preferred that R ² and R ³ independently represent a hydrogen atom or a C _1-6 alkyl or C _1-6 haloalkyl group.

[0018] More preferably, R ² and R ³ are independently hydrogen atom, each a halogen atom in the C _1-4 alkyl or haloalkyl group, C _1-4 haloalkyl group is preferably a fluorine or chlorine atom Represents

Preferably, an azoxycyano group

[0020]

[Chemical 7]

Is a 5- or 1,3-benzodioxane ring
It is located at the 6- or 7-position, with the 6-position being particularly preferred.

Particularly preferred subgroups of compounds of formula I are those in which n is 0 or 1; R represents a chlorine or bromine atom, or a hydroxymethyl or methoxy group; each of R ¹ and R ² Each independently represents a hydrogen atom or a trichloromethyl group; and R ³ represents a hydrogen atom.

The compounds of general formula I also have the following isoelectronic forms:

[0024]

[Chemical 8]

In the formula, Ar is

[0026]

[Chemical 9]

It is also to be noted that the scope of the invention covers all such forms. Moreover, it should be appreciated that compounds of formula I have chiral centers and therefore may exist as different optical isomers. The invention thus includes both the individual isomers and mixtures of such isomers.

The present invention also relates to the general formula (II)

[0029]

[Chemical 10]

Wherein n, R, R ¹ , R ² and R ³ are as defined above, using a mixture of hydrogen peroxide and methanoic acid and / or peroxymethanoic acid. There is provided a process for the preparation of a compound of formula I above, which comprises treating

If a mixture of hydrogen peroxide and methanoic acid is used, the concentration of hydrogen peroxide is less than about 75% by weight,
Preferably, about 50% by weight or less, and more preferably 40% by weight or less are suitable. In a preferred embodiment, the hydrogen peroxide concentration is about 30% by weight.

The process is preferably carried out at or above ambient temperature, more preferably above ambient temperature. The method can be carried out at a temperature in the range of 25 ° C to 75 ° C, preferably in the range of 30 ° C to 50 ° C.

Preferably, the compound of general formula II is mixed with methanoic acid and hydrogen peroxide at ambient temperature. The mixture is then preferably heated, but at about 60 ° C. for several hours is suitable. Then the mixture is
For example, it is cooled in an ice bath. Then the desired product is
It can be isolated by standard techniques.

A general method for preparing compounds of formula II is described in "R.
JW LeFevre and H. Vine, J. Chem. Soc., (1938), 4
Offered by 31 ”.

Further, the present invention provides the compound of the general formula (III)

[0036]

[Chemical 11]

Wherein n, R, R ¹ , R ² and R ³ are as defined above, wherein the compound of formula I above is reacted with cyanamide or a metal salt thereof and an oxidizing agent. Another method for producing the compound of

The oxidizer may be any compound which, together with cyanamide or its metal salt, produces cyanonitrene. Suitable examples include iodobenzene diacetate, dibromoisocyanuric acid and cyclic or chain N-halogens or pseudohalogenamides or imides, especially N-bromosuccinimide.

If a cyanamide metal salt is used in the process of the present invention, the metal salt is preferably an alkali metal salt or an alkaline earth metal salt. Alternatively, such metal salts can be formed in situ by reacting cyanamide with an alkali metal hydroxide or alkaline earth metal hydroxide. The use of monosodium cyanamide is particularly preferred. Alternatively, it can be replaced by a concentrated aqueous solution of cyanamide with sodium hydroxide, which efficiently produces monosodium cyanamide in situ. The reaction is suitably carried out in the presence of an organic solvent, preferably dimethylformamide or a halogenated hydrocarbon such as dichloromethane. Preferably, the reaction is carried out at a temperature in the range of -20 ° C to 50 ° C.

The compound of formula III may be prepared as follows:

[0041]

[Chemical 12]

In this case, Ar is as defined above.

Reaction A comprises, for example, a nitro compound and hydrazine hydrate in the presence of a hydrogen transfer catalyst such as rhodium-carbon, suitably in the presence of an inert polar organic solvent such as tetrahydrofuran, preferably with cooling. Or with water, stannous chloride as a reducing agent, an inert polar organic solvent such as tetrahydrofuran, in the presence of sodium acetate, under an atmosphere of an inert gas such as nitrogen gas. And preferably at ambient temperature.

Reaction B is an oxidant such as a Fe ³⁺ compound,
It is preferably carried out by treatment of the hydroxylamine derivative with ferric chloride. The reaction is mixed water /
It can be carried out in a polar organic solvent, preferably with cooling.

Reaction C is preferably an inert organic solvent,
For example by irradiation with a nitro compound dissolved in benzene. The irradiation is performed using a medium pressure mercury lamp.

Details of the above method can be found in the applicant's co-pending European patent application No. 92120580.3 and TS8009EPC. Other suitable methods for making compounds of Formula I, and further description of the methods described herein, can be found in The Journal of Antibiotics, Jan. 1975, p. 87-90.
And June 1986, p.864-868; Eur. J. Med. Chem.-Ch.
im.Ther., 1982, 17 , No. 5, p.482-484, and 1980,
15 , No.5, p.475-478, and 1977, 12 , No.1, p.59-6
2; J. Chem. Soc., Chem. Commun., 1984, p.323-324;
Chem.Ind. (Milan), 1977, 59 (5), p. 385; Gazetta C
himica Italiana, 106 , 1976, p.1107-1110; Tetrahedr
on Letters, No. 38, 1974, p. 3431-3432; and U.S. Pat. Nos. 4,558,040 and 4,550,121.

The compounds of general formula I have been found to have fungicidal activity. Accordingly, the invention further provides a fungicide composition comprising a carrier and, as active ingredient, a compound of formula I as defined above.
Also provided is a process for the preparation of such a composition comprising combining a compound of formula I as defined above with at least one carrier. Such compositions may contain a single compound of the invention or a mixture of several compounds. It is also contemplated that different isomers or mixtures of isomers may have different activity levels or spectra so that the composition may contain individual isomers or mixtures of isomers. .

The compositions according to the invention preferably contain 0.5 to 95% by weight of active ingredient.

The carrier of the composition according to the invention is such that the active ingredient facilitates its application to the locus such as plants, seeds or soil to be treated, or facilitates storage, transport or handling. Can be any material used to be formulated. The carrier may be a solid or liquid, usually gaseous, but may include materials formed into a liquid under pressure, and may be any carrier commonly used to formulate fungicidal compositions. Can be done.

Suitable solid carriers are natural and synthetic clays and silicates, natural silicas such as diatomaceous earth; magnesium silicates such as talc; magnesium aluminum silicates such as attapulgite and vermiculite; aluminum silicates such as kaori. Night, montmorillonite and mica; calcium carbonate; calcium sulfate; ammonium sulfate; synthetic hydrated silicon oxide and synthetic calcium or aluminum silicate; elements such as carbon and sulfur; natural and synthetic resins such as coumarone resin, polyvinyl chloride and styrene polymers and Copolymers; solid polychlorophenols; bitumens; waxes such as beeswax, paraffin waxes, and chlorinated inorganic waxes; and solid fertilizers such as superphosphorus Including the salt.

Suitable liquid carriers are water; alcohols such as isopropanol and glycols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic or araliphati.
c) Hydrocarbons such as benzene, toluene and xylene; petroleum fractions such as kerosene and light mineral oils; chlorinated hydrocarbons such as carbon tetrachloride, perchlorethylene and trichloroethane. Mixtures of different liquids are often also suitable.

The fungicide composition is often formulated and shipped in concentrated form, which is subsequently diluted by the user prior to application. The presence of a small amount of carrier, which is a surfactant, facilitates this process of dilution. Thus, preferably at least one carrier in the composition according to the invention is a surfactant. For example,
The composition may contain at least two carriers, at least one of which is a surfactant.

The surfactant may be an emulsifying agent, a dispersing agent or a wetting agent; it may be nonionic or ionic. Examples of suitable surfactants are sodium or calcium salts of polyacrylic acid and lignin sulfonic acid; condensation of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and / or propylene oxide. Products; fatty acid esters of glycerol, sorbitol, sucrose or pentaerythritol; their condensation products with ethylene oxide and / or propylene oxide; of fatty alcohols or alkylphenols, for example of p -octylphenol or p- octylcresol, Condensation products with ethylene oxide and / or propylene oxide; sulfates or sulfonates of these condensation products; at least 10 carbon atoms in the molecule
Alkali or alkaline earth metal salts of sulfuric acid or sulfonates, including sodium salts,
Includes, for example, sodium lauryl sulphate, secondary sodium alkyl sulphates, sodium salts of sulphonated castor oil, and sodium alkylaryl sulphonates such as dodecylbenzene sulphonic acid; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

The compositions of the present invention may be formulated, for example, as wettable powders, dusts, granules, aqueous solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders usually contain 25, 50 or 75% by weight of the active ingredient, usually 3-10% by weight of dispersant in addition to a solid inert carrier and, if necessary, stabilizer (s) 0-10. % By weight and / or other additives such as penetrants or adhesives. Dusts are usually formulated as a powder concentrate, which is a composition similar to that of wettable powders, but without dispersants, and further diluted in the farm with a solid carrier, usually 0.5-
The composition comprises 10% by weight. Granules are usually 10-100 BS mesh (1.676-0.15
2 mm) and can also be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 0.5-75% by weight of active ingredient and 0-10% by weight of additives such as stabilizers, surfactants, sustained release modifiers and binders. So-called "dry flowable powder"
ders) "consists of relatively small granules having a relatively high concentration of active ingredient. Emulsifiable concentrates usually contain the active ingredient 1 in addition to the solvent and, if necessary, a co-solvent. -50 w / v%, emulsifier 2-20 w /
v% and other additives 0-20 w / v% such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are usually formulated for the purpose of obtaining a stable, non-settling fluid, usually 10-75% by weight active ingredient, 0.5 dispersant.
-15% by weight, protective colloids and suspending agents such as thixotropic agents 0.1-10% by weight, antifoams, corrosion inhibitors, stabilizers, penetrants and other additives such as adhesives 0-10 %, And water or organic liquids in which the active ingredient is essentially insoluble; certain organic or inorganic salts are dissolved in the formulation in order to prevent sedimentation or to act as a cryoprotectant against water May exist.

Aqueous dispersions and emulsions, for example compositions obtained by diluting the wettable powders or concentrates according to the invention with water, are also within the scope of the invention. The emulsions can be of the water-in-oil or oil-in-water type and have a strong'mayonnaise'-like consistency. The composition of the present invention also comprises
It may also contain other ingredients, for example other compounds having herbicidal, insecticidal or fungicidal properties.

To enhance the duration of the prophylactic activity of the compounds according to the invention, of particular interest is the use of carriers which provide a slow release of the fungicidal compound in the environment of the plant to be prevented. Such sustained release formulations include, for example:
Could be inserted into the soil close to the roots of the vines,
Alternatively, an adhesive component can be included so that it is applied directly to the vine trunk.

Furthermore, the present invention relates to the use of a compound of general formula I as defined above or a composition as defined above as a fungicide and, for example, plants susceptible to or actually attacked by fungi, Controlling the fungus in a certain place, including treating the seeds of such plants, or the places where such plants grow or will grow, with such compounds or compositions. Provide a way to. The above location is 0.05-4kg / h
Suitably it will be treated with Compound I at an application rate in the range of a, preferably 0.1-1 kg / ha.

The present invention has broad applicability in the protection of crop plants against fungal attack. Typical crops that can be prevented include cereal crops such as grapes, wheat and barley, apples and tomatoes.
The duration of prophylaxis usually depends on the particular compound selected, and also usually on various external factors whose impact is mitigated by the use of suitable dosage forms, such as climate.

The invention is further illustrated by the following examples.

[0060]

【Example】

(Example 1A) 6- Azokishishiano-1,3 preparation of benzodioxane ^{(n = 0; R 1 =} R 2 = R 3 = H) (a) 6- Azoshiano-1,3-benzodioxane tone
Ltd. 6-amino-1,3-benzodioxane (4g, 26.
5 mmol), water (6.5 ml) and hydrochloric acid (7.5
ml, 35% w / w). Crushed ice (30
After the addition of g), the solution is treated with sodium nitrate (1.87).
g, 27 mmol) to diazotize. The cooled solution is then treated with sodium hydroxide (10% w /
neutralized with w). Trichloromethane (50 ml) was added and the reaction mixture was cooled to about 0 ° C. Water (14
ml) dissolved in potassium cyanide (1.84 g, 2
8.3 mmol), the organic layer is separated off, dried over sodium sulphate, evaporated to dryness and the orange crystals obtained are filtered off to give 2.52 g of crude 6-azocyano-1,3-benzodioxane. Obtained.

(B) 6-azoxycyano-1.3-ben
Preparation of Zodioxane The crude 6-azocyano-1,3 benzodioxane (1.5 g, 7.9 mmol) obtained in the above (a) was converted into methane acid (3
0 ml) and hydrogen peroxide (10 ml, 30% / w) were suspended. The mixture was heated to 60 ° C. for 24 hours then cooled in an ice bath. The crystals obtained are then collected and washed with water to give 6-azoxycyano-1.3.
-0.62 g (38% yield) of benzodioxane was obtained as orange crystals.

M. pt: 157 ° C., m / e (M ⁺ ): 205 ¹ H-NMR (CDCl ₃ ): δ (ppm) = 4.92
(S; ArCH ₂ O); 5.35 (s; OCH ₂ O);
6.88,7.95,8.08 (m; Ar-H) ( Example 1B) 6- Azokishishiano-1,3 preparation of benzodioxane ^{(n = 0; R 1 =} R 2 = R 3 = H ) 6-nitroso-1,3-benzodioxane (2.5 g,
15.0 mmol) and cyanamide (0.94 g, 2
1.7 mmol) was dissolved in dichloromethane (190 ml). Dichloromethane (19
Iodobenzene diacetate (5.34 g, 1
6.6 mmol) solution was added dropwise at 0 ° C.
The mixture was stirred overnight at ambient temperature, filtered and evaporated to dryness. By column chromatography on silica using 1: 1 petroleum ether: ethyl acetate as eluent,
6-azoxycyano-1.3-benzodioxane 2.3
g (yield 75%) was obtained as a yellow powder.

M. pt: 156-158 ° C, m / e (M
⁺ ): 205 ¹ H-NMR (CDCl ₃ ): δ (ppm) = 4.92
(S; ArCH ₂ O); 5.35 (s; OCH ₂ O);
6.88,7.95,8.08 (m; Ar-H) ( Example 1C) 6- Azokishishiano-1,3 preparation of benzodioxane ^{(n = 0; R 1 =} R 2 = R 3 = H ) 6-nitroso-1,3-benzodioxane (1.0 g,
6.1 mmol) and N-bromosuccinimide (1.1 g, 6.2 mmol) were dissolved in dimethylformamide (20 ml). Monosodium cyanamide (0.61 g, 9.5 mmol) was added. The mixture was stirred for 1 hour at ambient temperature, poured onto ice water (80 ml), filtered, washed with water, dried and 0.9 g of 6-azoxycyano-1,3-benzodioxane (yield 7
1.9%) as a yellow powder.

M. pt: 156-158 ° C.

Example 2 6-azoxycyano-8-chloro-1,3-benzodio
Hexane for preparing ^{(n = 1; R 1 =} R 2 = R 3 = H; R = 8-Cl) 6- nitroso-8-chloro-1,3-benzodioxane (3.4g, 17.0mmol), It was dissolved in dichloromethane (75 ml). Then, cyanamide (0.6
7 g, 16.0 mmol) and iodobenzene diacetate (6.2 g, 19.5 mmol) were added. The mixture was stirred for 1 hour at 0 ° C. and 1 hour at ambient temperature,
The resulting yellow suspension was then filtered and evaporated to dryness. By column chromatography on silica using toluene as the eluent, 6-azoxycyano-8-chloro-
2.7 g (66% yield) of 1,3-benzodioxane was obtained as a yellow solid.

M. pt: 158-160 ° C, m / e (M
⁺ ): 239/2411 ¹ H-NMR (CDCl ₃ ): δ (ppm) = 4.91
(S; ArCH ₂ O); 5.40 (s; OCH ₂ O);
7.85, 8.20 (m; Ar-H) (Example 3) 6-azoxycyano-8-methoxy-1,3-benzodi
Preparation of dioxane the ^{(n = 1; R 1 =} R 2 = R 3 = H; R = 8-OCH 3) 6- nitroso-8-methoxy-1,3-benzodioxane (2.3 g, 11.8 mmol) , Dissolved in dichloromethane (70 ml). Then, cyanamide (0.5
g, 11.9 mmol) and dibromoisocyanuric acid (1,3-dibromo-1.3.5-triazine-2,
4,6 (1H, 3H, 5H) -trione; 3.4 g, 1
1.8 mmol) was added at 0 ° C. under a nitrogen gas atmosphere. The mixture is stirred for 2 hours at ambient temperature, then
The resulting suspension was filtered and evaporated to dryness. 6-azoxycyano-8 by column chromatography on silica using 2: 1 petroleum ether: ethyl acetate as eluent.
0.8 g (29% yield) of -methoxy-1,3-benzodioxane was obtained as a yellow solid.

M. pt: 188-190 ° C, m / e (M ⁺ ): 235 ¹ H-NMR (CDCl ₃ ): δ (ppm) = 3.95
_{(S; OCH 3); 4.93} (s; Ar-CH 2 O);
_{5.25 (s; OCH 2 O)} ; 7.62 (m; Ar-
H) Examples 4-9 Other compounds in accordance with the invention were prepared as described in Table I below by methods similar to those described in Examples 1-3 above. In this table,
The compounds are identified according to formula I. Examples 4-9
Melting point, mass spectrometric and ¹ H-NMR data for the compounds in Table ¹ are shown in Table IA.

[0068]

[Table 1]

[0069]

[Table 2]

Example 10 The fungicidal activity of the compounds of the invention was investigated by the following test method.

(A) Tomato late wilt disease (phytophthora
Infestation (Phytophthora inf)
The direct preventive activity test against estans); PIP) is a direct preventive test using foliar application. The upper surface of the leaves of a tomato plant having two spread leaves (First in cv. Field) showed 0.04% "TWEE".
It is sprayed with a solution of the active substance in 1: 1 water / acetone containing N20 "(trademark; polyoxyethylene sorbitan ester surfactant). The plants are treated using an automatic spray system with spray nozzles. The concentration of the compound is 1000 ppm, and its application rate is 7
It is 00 l / ha. After 24 hours under normal glass house conditions, the upper surface of the leaves is 2 × 10 ⁵ zoospores / ml.
The plant is inoculated by spraying an aqueous suspension containing. The inoculated plants are kept in a high humidity cabinet for 24 hours and under growth room conditions for 5 days. The rating is based on the percentage of diseased leaf area compared to the control leaf area.

(B) Broad bean gray mold (Botrytis
Cinerea (Botrytis cinerea); BC
The direct preventive activity test against B) is a direct preventive test using foliar application. The upper surface of the leaves of broad bean plants (cv The Shutton) are sprayed with the test compound at a dose of 1000 ppm using an automated spray system as described in (a). 24 hours after spraying, the leaves had 10 ⁵ spores / m 2.
Inoculate with an aqueous suspension containing 1 For 4 days after inoculation, the plants are kept moist in a 21 ° C humidified cabinet. On day 4 of inoculation, disease is assessed based on the percentage of diseased leaf area.

(C) Wheat leaf spot (leptosperia
Nodrum (Leptosphaeria nodoru)
m); LN. ) Activity The test for is a direct therapeutic trials one using a foliar spray. The leaves of single leaf stage wheat plants (cv Norman) are inoculated by spraying an aqueous suspension containing 1 × 10 ⁶ spores / ml. The inoculated plants are kept in a humid room for 24 hours before treatment. 4 days after inoculation, the plant
Humidity is maintained in a 21 ° C humidification cabinet. The plants are sprayed with a solution of the test compound at a dose of 1000 ppm using an automatic spray system as described in (a). After drying, the plants are kept at 22 ° C. in moderate humidity for 6-8 days and then evaluated. The rating is based on the disease density per leaf compared to the leaves of control plants.

(D) Barley powdery mildew (Ericife
Graminis Parasitic Holdy (Erysiphe gr
aminis f. sp. to hordei); EG)
Activity Against The test is a direct therapeutic test using foliar spray. Leaves of barley seedlings (cvGolden Promise) are inoculated by spraying powdery mildew spores one day before treatment with the test compound. The inoculated plants are kept overnight in a humid glass house at ambient temperature before treatment. The plants are sprayed with the test compound at a dose of 1000 ppm using an automatic spray system as described in (a). After drying, the plants are returned to a room of moderate humidity at 20-25 ° C for 7 days and then evaluated.
The evaluation is based on the percentage of leaf area covered by sporulation compared to the leaves of control plants.

(E) Tomato early wilt disease (alternaria )
・ Solani (Alternaria solani); A
Activity against S) This test measures the contact-preventing activity of test compounds applied as foliar application. Tomato seedlings (cv Outd)
oor Girl) is grown to the stage where the second true leaf spreads. The plants are treated using an automatic spray system as described in (a). The test compound is 0.0
It is applied by solution or suspension of a mixture of acetone / water (50:50 v / v) containing 4% surfactant (“TWEEN20” -Trademark). After treatment 1 day, the seedlings, including 10 ⁴ spores / ml A. It is inoculated by spraying a suspension of Solani spores on top of the leaves. After inoculation 4
Humidity is maintained in a humidified room at 21 ° C for a day. The pathology is evaluated 4 days after inoculation based on the surface area percentage of diseased leaves.

(F) In vitro wheat eye spot disease (pseudo)
Serco Sporella Herpotrichoides (Pseudoc
ercosporella herpotrichoi
des); activity against PHI) This test measures the in vitro activity of the compounds against fungi that cause wheat eye spot disease. The test compound is
Dissolved or suspended in acetone and distributed in 25-section Petri dishes with a half-concentration of potato dextrose.
Broth was added to each 4 ml to give a final concentration of compound 50
ppm, 2.5% acetone. Each section is described in P. F
Inoculated with an agar / mycelium in-line 6 mm plug obtained from a 14 day culture of Rupotrichoides The plates are incubated at 20 ° C for 12 days until evaluation of mycelial growth.

(G) Fusarium bacterium (Fusariu ) in a test tube
Fusarium culmoru
m); activity against FSI) This test measures the in vitro activity of the compounds against one of Fusarium causing stem and root rot. Test compounds are dissolved or suspended in acetone and added to melted half-concentrated potato dextrose agar to a final concentration of 50 ppm compound, 3.5% acetone. After the agar has been fixed, the plates are inoculated with a 6 mm plug of agar / mycelium line obtained from a 7-day culture of Fusarium spp. The plates were incubated for 5 days at 20 ° C,
Radial growth from the plug is measured.

The degree of disease control in all the above tests was expressed as an assessment compared to either untreated control or diluent-spray-control, according to the following criteria: 0 = 50% disease control or less 1 = disease Control about 50-80% 2 = Disease control over 80%.

The results of these tests are displayed in Table II below.

[0080]

[Table 3]

Example 11 The fungicidal activity of the compounds of the invention was further investigated by the following test method.

(A) Downy mildew of grapes (Plasmopara bi
Ticora (Plasmoparaviticola);
Antisporulation activity against PVA) This test is a direct antisporulation test using foliar spray. Grape plant (cv. Cabernet Sauv
ignon), height about 8 cm, lower surface of leaf is 5x10
Inoculated with an aqueous suspension containing ⁴ zoosporangium / ml. The inoculated plants are placed in a high humidity cabinet for 21
It is kept at 0 ° C. for 24 hours, followed by 24 hours at 20 ° C. and 40% relative humidity in a glass house. Infected leaves are sprayed on their underside with a solution of the test compound in 1: 1 water / acetone containing 0.04% "TWEEN 20"(trademark; polyoxyethylene sorbitan ester surfactant). The plants are sprayed using a track sprayer with two spray nozzles. The concentration of the compound is 600 ppm and the application rate is 750 1 / ha. After drying, the plants are returned to the glasshouse in a cabinet at 20 ° C. and 40% relative humidity for 24 hours to cause sporulation. The rating is based on the percentage of leaf area covered by sporulation compared to that of control leaves.

(B) Tomato late wilt (phytophthora
Infestation (Phytophthora inf)
estans); PIP) Direct Preventive Activity This test is a direct preventive test using foliar application. Two
Tomato plant with a number of spread leaves (cv.Field
First) is sprayed with the test compound at a dose of 600 ppm as described in (a). After drying, the plants were kept in a glass house for 24 hours at 20 ° C. and 40% relative humidity, followed by inoculation of the upper surface of the leaves with an aqueous suspension containing 2 × 10 ⁵ zoosporangia / ml. It The inoculated plants were placed in a high humidity cabinet at 18 ° C for 24 hours, followed by 5 days, 15 hours light / day, 15 hours.
It is kept in a growth room at ℃ and 80% relative humidity. The rating is based on the area percentage of diseased leaves compared to control leaves.

(C) Tomato early wilt disease (alternaria )
・ Solani (Alternaria solani); A
Activity against S) This test is a direct prophylaxis test using foliar application. Tomato seedlings (cv Outdoor Girl) are sprayed with the test compound at a dose of 600 ppm as described in (a), during the second true leaf spreading stage. After drying, the plants were kept in a glass house for 24 hours at 20 ° C. and 40% relative humidity, followed by 1 × 10 ⁴ spores / m 2.
A containing l . It is inoculated by spraying an aqueous suspension of Solani spores on top of the leaves. After being kept in a high humidity cabinet at 21 ° C for 4 days, the pathology is evaluated based on the surface area percentage of diseased leaves when compared to control plants.

(D) Broad bean gray mold (Botrytis
Cinerea (Botrytis cinerea); BC
The direct preventive activity test against B) is a direct preventive test using foliar application. Broad bean plant with two leaf pairs (cv The Shutto
n) is 600 ppm as described in (a)
Then, the test compound is sprayed. After drying, the glass house is kept for 24 hours at 20 ° C. and a relative humidity of 40%.
The upper surface of the leaf is subsequently inoculated with an aqueous suspension containing 1 × 10 ⁶ spores / ml. The plants are kept at 22 ° C. for 4 days in a high humidity cabinet. The rating is based on the area percentage of diseased leaves compared to control leaves.

(E) Wheat spot disease (leptosperia
Nodrum (Leptosphaeria nodoru)
m); LN. ) Activity The test for is a direct therapeutic trials one using a foliar spray. The leaves of single leaf stage wheat seedlings (cv Norman) are inoculated by spraying an aqueous suspension containing 1.5 × 10 ⁶ spores / ml. The inoculated plants are kept in a high humidity cabinet for 24 hours at 20 ° C. and then sprayed with the test compound at a dose of 600 ppm as described under (a). After drying, the plants are at 22 ° C and 70% relative humidity.
And kept in a glass house for 6-8 days. The rating is based on the disease density per leaf compared to the leaves of control plants.

(F) In vitro wheat eye spot disease (pseudo)
Serco Sporella Herpotrichoides (Pseudoc
ercosporella herpotrichoi
des); activity against PHI) This test measures the in vitro activity of the compounds against fungi which cause wheat eye spot disease. The test compound was dissolved or suspended in acetone and added to 4 ml each of the half-concentrated potato dextrose broth distributed in a 25-section Petri dish to give a final concentration of compound 30p.
pm, 0.825% acetone. The fungal inoculum was P. cerevisiae grown on a half concentration of potato dextrose broth in shake flasks . It consists of mycelium of Herpotricoides , which is added to the broth to give 5 × 10 ⁴ mycelium / ml of broth. Petri dishes are incubated at 20 ° C for 10 days until evaluation of mycelial growth.

(H) In- vitro apple scab (Benturi)
A. Inquiry (Venturia inaequa
lis); VII) activity This test shows that Venturia erythema causes apple scab
The in vitro activity of the compound against Nexuris is determined. The test compound is dissolved or suspended in acetone,
Add to each of 4 ml of half-concentrated potato dextrose broth distributed in 25-section Petri dishes,
The final concentration compound is 30 ppm, 0.825% acetone. The fungal inoculum is V. cerevisiae grown on malt agar. Rice kurie
It consists scan hyphal debris and spores, which are added to the broth to be 5x10 ⁴ proliferation body / broth ml.
Petri dishes are incubated at 20 ° C for 10 days until evaluation of mycelial growth. The degree of disease control in all the above tests was
Expressed as an assessment relative to either untreated controls or diluent-spray-controls, according to the following criteria: 0 = less than 50% disease control 1 = about 50-80% disease control 2 = more than 80% disease control.

The results of these tests are displayed in Table III below.

[0090]

[Table 4]

The features and main aspects of the present invention are as follows.

1. General formula (I)

[0093]

[Chemical 13]

Wherein n is 0, 1 or 2; each R, if present, is independently a halogen atom,
Or a compound in which R ¹ represents a hydrogen atom or a haloalkyl group; and R ² and R ³ independently represent a hydrogen atom or an alkyl or haloalkyl group.

2. A compound according to paragraph 1, wherein each R, if present, is independently a halogen atom, or each group is selected from a halogen atom, nitro, cyano, hydroxyl and amino groups. Represents a C _1-6 alkyl or C _1-6 alkoxy group optionally substituted with one or more substituents.

3. The compound according to item 1 or 2, wherein R ¹ represents a hydrogen atom or a C _1-6 haloalkyl group.

4. The compound according to any one of the preceding paragraphs, wherein R ² and R ³ independently represent a hydrogen atom or a C _1-6 alkyl or C _1-6 haloalkyl group. 5. The compound according to any one of the preceding paragraphs, wherein n is 0 or 1; R represents a chlorine or bromine atom, or a hydroxymethyl or methoxy group; each R ¹ and R ² is independently And represents a hydrogen atom or a trichloromethyl group; and R ³ represents a hydrogen atom.

6. The compound according to item 1, which is listed in any one of Examples 1 to 9.

7. General formula (II)

[0100]

[Chemical 14]

Wherein n, R, R ¹ , R ² and R ³ are as defined in any one of the preceding clauses, a compound of hydrogen peroxide and methanic acid Use of and / or treatment with peroxymethanoic acid for the preparation of a compound of general formula I according to any one of the preceding clauses.

8. General formula (III)

[0103]

[Chemical 15]

In the formula, n, R, R ¹ , R ² and R ³ are as defined in any one of the items 1 to 6, and the compound is a cyanamide or a metal salt thereof and an oxidizing agent. A process for the preparation of a compound of general formula I according to any one of claims 1 to 6, which comprises reacting with

9. A method as set forth in paragraph 7 or paragraph 8 which is essentially as described above and for any one of Examples 1-3.

10. A compound of formula I when prepared by the method of any one of paragraphs 7-9.

11. A fungicide composition comprising a carrier and, as active ingredient, a compound of general formula I as defined in any one of paragraphs 1 to 6 and 10.

12. First containing at least two carriers, at least one of which is a surfactant
The composition according to item 1.

13. In place, with a compound of general formula I as defined in any one of paragraphs 1 to 6 and 10, or with a composition as defined in paragraph 11 or 12 , A method of controlling fungi including treating the locus.

14. 14. The locus according to claim 13 including plants susceptible to or actually subject to fungal attack, seeds of such plants, or media in which the plant is or will be growing. Method.

15. A compound of general formula I as defined in any one of clauses 1 to 6 and 10, or
Use as a fungicide of a composition as defined in paragraph 12 or 12.

Claims (5)

[Claims] 1. A compound represented by the general formula (I): Wherein n is 0, 1 or 2; each R, if present, independently represents a halogen atom, or an optionally substituted alkyl or alkoxy group; R ¹
Represents a hydrogen atom or a haloalkyl group; and R
^A compound wherein ² and R ³ independently represent a hydrogen atom or an alkyl or haloalkyl group. 2. A compound represented by the general formula (II): Wherein n, R, R ¹ , R ² and R ³ are as defined in claim 1, using a mixture of hydrogen peroxide and methanoic acid and / or peroxymethanoic acid Claim 1 comprising the following processing:
Process for the preparation of the compounds of general formula I as described. 3. A compound represented by the general formula (III): Wherein n, R, R ¹ , R ² and R ³ are as defined in claim 1, comprising reacting a compound of cyanamide or a metal salt thereof and an oxidizing agent. A process for producing a compound of general formula I as described in 1. 4. A fungicidal composition comprising a carrier and, as active ingredient, a compound of general formula I as defined in claim 1. 5. Treating the locus at a given location with a compound of general formula I as defined in claim 1 or with a composition as defined in claim 4. A method for controlling fungi comprising.