JPH0751565B2 - Aralkylamine derivative, its manufacturing method and bactericide - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aralkylamine derivative, a method for producing the same, and a fungicide containing the same as an active ingredient.

(Prior Art and Problems to be Solved by the Invention) Many aralkylamine derivatives have been conventionally known. For example, Journal of American Chemicals
The Society (JACS) 80, 2189 (1958 ), 4- benzylamino-6-chloropyrimidine is is disclosed as a diuretic intermediates, these compounds were not observed bactericidal activity.

Further, JP-A-59-36666, JP-A-59-36667,
Various aminopyrimidine derivatives are disclosed in JP-A-59-42387, JP-A-61-286373, JP-A-62-67 and JP-A-63-225364. These compounds all have insecticidal, acaricidal and bactericidal activity, for example, diamondback moth, aphids, citrus spider mite, pests such as spider mites, mites and rice blast, tomato blight, tomato downy mildew, cucumber. It is known to be effective against various agricultural and horticultural diseases such as powdery mildew.

However, although these compounds have strong efficacy as insecticides and acaricides, they are not sufficiently effective as fungicides.

(Means for Solving the Problems) The inventors of the present invention have made extensive studies in order to obtain a compound having more excellent bactericidal activity than the above-mentioned known compounds. As a result, the compound represented by the following general formula is significantly improved. The present invention was completed by discovering that it has bactericidal activity.

The present invention has the general formula: (In the formula, R ¹ is a hydrogen atom, a halogen atom, a halo lower alkyl group, an alkanoyl group, a nitro group, a cyano group or 1,3-
Represents a dioxolan-2-yl group, R ² and R ³ each represent a halogen atom or a lower alkyl group, or R ² and R ³
Represents an unsaturated 5- or 6-membered ring which may be condensed with a carbon atom to which they are attached to a pyrimidine ring and may have one sulfur atom constituting the ring, R ⁴ is a hydrogen atom, a halogen atom, A lower alkyl group, a cycloalkyl group, a lower alkoxy group or an amino group which may be substituted by lower alkyl, R ⁵ represents a hydrogen atom, a lower alkyl group or a cycloalkyl group, and Z represents a carbon atom or a nitrogen atom. Represent, Z
When R is a nitrogen atom, R ¹ is unsubstituted) or an acid addition salt thereof, a process for producing the same, and a fungicide containing the compound as an active ingredient.

In the above formula (I), examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the alkanoyl group include formyl, acetyl, propionyl, butyryl, isobutyryl and valeryl.

Examples of the halo lower alkyl group include trifluoromethyl, difluoromethyl, 2-fluoromethyl, 2,2,2-trifluoroethyl and the like.

As the lower alkyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, for example, methyl, ethyl, propyl,
Isopropyl, butyl, isobutyl, sec-butyl, t
-Butyl, pentyl, isopentyl and neopentyl.

Examples of the cycloalkyl group include cycloalkyl groups having 3 to 6 carbon atoms, such as cyclopropyl, cyclopentyl and cyclohexyl.

Examples of the lower alkoxy group include alkoxy groups having 1 to 5 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy and pentyloxy.

As the amino group which may be substituted by lower alkyl,
An unsubstituted amino group or an amino group having 1 or 2 alkyl having 1 to 5 carbon atoms, such as amino, monomethylamino, dimethylamino, monoethylamino, diethylamino, monopropylamino, dipropylamino, monobutylamino, Examples thereof include dibutylamino, monopentylamino and dipentylamino.

= The CH-R ⁵ _{group, -CH 2 -, - CH (} CH 3) -, - CH
_{(C 2 H 5) -,} - CH (n-C 3 H 7) -, - CH (i-C 3 H 7)
-, _{-CH (t-C 4 H 9} ) - and _{-CH (n-C 5 H 11} ) - and the like.

In the formula (I), preferable groups are as follows.

As the pyrimidinyl group substituted by R ² , R ³ and R ₄ , the following groups are preferable.

R ¹ is preferably a hydrogen atom, a fluorine atom, a difluoromethyl group, a trifluoromethyl group or a formyl group.

R ⁵ is preferably a methyl group, an ethyl group, an isopropyl group or a cyclopropyl group.

Z is preferably a carbon atom.

Basis: The substitution position of is preferably the 3-position or 4-position with respect to> CH—R ⁵ .

As can be understood from the above formula (I), the compound of the present invention has an amino group and easily forms an acid addition salt, and such a salt is also included in the present invention.

Examples of the acid forming an acid addition salt include inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid and phosphoric acid; formic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid and aconitic acid. Such carboxylic acids; methanesulfonic acid, benzenesulfonic acid, organic sulfonic acids such as p-toluenesulfonic acid, and saccharin.

In the above formula (I), when the carbon atom marked with * is an asymmetric carbon atom, any of the individual optical isomers and racemates or mixtures thereof are included in the present invention.

Table 1 exemplifies the compounds of the present invention, but the present invention is not limited thereto.

The compound (I) of the present invention can be easily produced, for example, by a method known per se shown below.

Manufacturing method A (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and Z have the same meanings as described above, and X represents a leaving group.) This reaction is known per se. There is no limitation, for example, a halogen atom such as chlorine, bromine or iodine; an alkylthio group such as methylthio, ethylthio, propylthio, butylthio; a halogen atom such as methanesulfonyloxy, ethanesulfonyloxy, trifluoromethanesulfonyloxy. Alkanesulfonyloxy group which may be present; arylsulfonyloxy groups such as benzenesulfonyloxy and p-toluenesulfonyloxy, and hydroxyl groups.

As is clear from the above reaction formula, in this reaction, the compound H-
Since X is released, it is preferable to react in the presence of a base in order to capture it and to make it react smoothly. The reaction is usually performed in the presence of a solvent, but without the solvent, the compound of formula (II)
Alternatively, the compound of formula (III) can be heated and melted to react.

The solvent is not particularly limited as long as it does not participate in this reaction, for example, benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane,
Chlorinated or unchlorinated aromatic, aliphatic or alicyclic hydrocarbons such as chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloroethane, trichloroethylene, cyclohexane; diethyl ether, dimethyl ether, tetrahydrofuran, Ethers such as dioxane; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, and ethylene glycol, or hydrates thereof; N, N-dimethylformamide (DMF), N, N-dimethylacetamide Amides such as; pyridine, organic bases such as N, N-diethylaniline; 1,3-dimethyl-2-imidazolidinone (DMI); dimethyl sulfoxide (DMS
O) and mixtures of the above solvents.

Examples of the base include triethylamine, pyridine, organic bases such as N, N-diethylaniline, sodium methoxide,
Examples thereof include alkali metal alkoxides such as sodium ethoxide, inorganic bases such as sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.

Further, it is preferable to add 4- (N, N-dimethylamino) pyridine as a catalyst in order to increase the reaction rate.

The reaction temperature is not particularly limited, but is usually room temperature or higher and not higher than the boiling point of the solvent used, and it is preferable to heat the reaction to shorten the reaction time.

Manufacturing method B (Where Y is And R ¹ , R ² , R ³ , R ⁴ , R ⁵ , Z and X have the same meanings as described above.) This method is a method of synthesizing an intermediate (V) and then reacting it with a compound (VI). Is. The solvent, base, etc. used in this method are
What was described in the said manufacturing method A can be used suitably.

In the production methods A and B, the formula (I
The compounds of II) and (IV) can also be produced, for example, by a method known per se shown below.

(In the formula, R ⁵ has the same meaning as described above; Y ′ has the same meaning as Y described above or represents a hydrogen atom.) The compound of the formula (I) obtained by each of the above methods can be used for recrystallization, various chromatography, etc. It can be appropriately purified by a known means.

The acid addition salt can be easily obtained, for example, by introducing an acid into the reaction liquid after the reaction and then removing the solvent.

INDUSTRIAL APPLICABILITY The compound of the present invention is extremely effective against barley powdery mildew and wheat leaf rust, and is also useful as a fungicide for agricultural and horticultural diseases such as rice blast, cucumber bean disease, and tomato late blight.

Further, the compound of the present invention is effective against agricultural and horticultural pests, and shows activity against citrus mites and spider mites as well as planthoppers, leafhoppers, aphids, weevil, diamondback moth and the like.

As described above, the compound of the present invention has an extremely wide range of uses and application situations, is highly effective, and can be put to practical use in various dosage forms.

The fungicide of the present invention contains one or more compounds of the formula (I) as an active ingredient.

The compound of the formula (I) may be used as it is, but it is usually mixed with a carrier, a surfactant, a dispersant or an auxiliary agent and the like, and then, for example, powders, emulsions, fine granules, granules, water, etc. It is used after being prepared into a composition such as a solvate or an oily suspension, an aerosol.

Suitable carriers are, for example, talc, bentonite, clay,
Solid carriers such as kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea;
Kerosene, hydrocarbons such as mineral oil, benzene, toluene, aromatic hydrocarbons such as xylene, chloroform, chlorinated hydrocarbons such as carbon tetrachloride, ethers such as dioxane and tetrahydrofuran, ketones such as acetone, cyclohexanone and isophorone, Examples thereof include esters such as ethyl acetate, ethylene glycol acetate and dibutyl maleate, alcohols such as methanol, n-hexanol and ethylene glycol, polar solvents such as dimethylformamide and dimethyl sulfoxide, and liquid carriers such as water. Further, air, nitrogen, carbon dioxide gas, Freon or the like may be used as the gas carrier, and mixed injection may be performed.

In addition, examples of surfactants and dispersants for improving the performance of the agent, such as adhesion to animals and plants, absorption, dispersion of agents, emulsification, spreading, and the like, include alcohol sulfates and alkyl sulfonates. , Lignin sulfonate, polyoxyethylene glycol ether and the like are used.

Further, in order to improve the properties of the preparation, for example, carboxymethyl cellulose, polyethylene glycol, gum arabic, etc. are used as an auxiliary agent.

The above-mentioned carrier, surfactant, dispersant and auxiliary agent are used alone or in combination according to the purpose.

When the compound of the present invention is formulated, the concentration of the active ingredient is usually 1 to 50% by weight for emulsions and 0.3 to 25 for powders.
% By weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, usually 0.5 to 5% by weight for oil solutions, and usually 0.1 to 5% by weight for aerosols.

These preparations may be diluted to an appropriate concentration and sprayed on the plant foliage, soil, water surface of paddy fields, or applied directly to them for various purposes according to their respective purposes.

(Examples of the Invention) Hereinafter, the present invention will be described in more detail with reference to Examples, but these Examples do not limit the scope of the present invention.

Example 1 dl-5-chloro-6-ethyl-4- (α-ethyl-4-
Synthesis of pentafluorophenoxybenzylamino) pyrimidine A mixture of 0.3 g of potassium hydroxide and 30 ml of dimethyl sulfoxide was heated and stirred at 100 ° C for 30 minutes, then cooled to 50 ° C, and d
l-5-chloro-6-ethyl-4- (α-ethyl-4-
1 g of (hydroxybenzylamino) pyrimidine was added, and the mixture was stirred for 30 minutes. Hexafluorobenzene (1 g) was added to this solution, and the mixture was reacted at 70 ° C. for 8 hours. After completion of the reaction, the reaction solution was poured into water and extracted with toluene. Wash the extract with water,
After drying over anhydrous sodium sulfate, toluene was distilled off under reduced pressure. The obtained oily substance was isolated by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 10: 1) to obtain 1 g of the desired product as colorless crystals.

mp 57-59 ° C Example 2 dl-5-chloro-6-ethyl-4- {α-ethyl-4-
(4-cyano-2,3,5,6-tetrafluorophenoxy)
Synthesis of benzylamino} pyrimidine dl-5-chloro-6-ethyl-4- (α-ethyl-4-
A mixture of 0.76 g of hydroxybenzylamino) pyrimidine, 0.5 g of pentafluorobenzonitrile, 0.4 g of anhydrous potassium carbonate and 20 ml of 1,3-dimethyl-2-imidazolidinone (DMI) was heated with stirring at 70 ° C. for 8 hours. After completion of the reaction, the reaction solution was poured into water and extracted with toluene. The extract was washed with water, dried over anhydrous sodium sulfate, and toluene was distilled off under reduced pressure. The obtained oily substance was subjected to column chromatography (Wako Gel C-200, toluene: ethyl acetate = 10: 1).
The product was isolated by elution) to obtain 0.8 g of the desired product as a colorless oily substance.

▲ n ^24.4 _D ▼ 1.5677 Example 3 dl-5-chloro-6-ethyl-4- {α-ethyl-4-
Synthesis of (4-trifluoromethyl-2,3,5,6-tetrafluorophenoxy) benzylamino} pyrimidine dl-5-chloro-6-ethyl-4- (α-ethyl-4-
A mixture of 1 g of hydroxybenzylamino) pyrimidine, 1 g of perfluorotoluene, 0.24 g of powdered potassium hydroxide and 20 ml of 1,3-dimethyl-2-imidazolidinone (DMI) was heated and stirred at 70 ° C. for 8 hours. After completion of the reaction, the reaction solution was poured into water and extracted with toluene. The extract was washed with water, dried over anhydrous sodium sulfate, and toluene was distilled off under reduced pressure. The obtained oily substance was isolated by column chromatography (Wakogel C-200, toluene: ethyl acetate = 30: 1 elution) to obtain 1.5 g of the desired product as colorless crystals.

mp 58-61 ° C. Example 4 Synthesis of dl-4- (α-ethyl-4-pentafluorophenoxybenzylamino) quinazoline 4-chloroquinazoline 0.52 g, dl-α-ethyl-4-pentafluorophenoxybenzylamine 1.0 g And 1 ml of triethylamine were dissolved in 20 ml of toluene, and a catalytic amount of 4-
(N, N-Dimethylamino) pyridine was added, and the mixture was heated under reflux for 8 hours. After completion of the reaction, the reaction solution was washed with water, dried over anhydrous sodium sulfate, and toluene was distilled off under reduced pressure. The obtained oily substance was subjected to column chromatography (Wako Gel C-
200, toluene: ethyl acetate = 3: 1 elution),
As a result, 0.5 g of the desired product which is a colorless crystal was obtained.

mp 172-176 ° C. Example 5 Synthesis of dl-4- (α-methyl-4-pentafluorophenoxybenzylamino) thieno [2,3-d] pyrimidine 0.4 g of 4-chlorothieno [2,3-d] pyrimidine, dl−α
0.7 g of -methyl-4-pentafluorophenoxybenzylamine and 1 ml of triethylamine were dissolved in 20 ml of toluene, a catalytic amount of 4- (N, N-dimethylamino) pyridine was added, and the mixture was heated under reflux for 8 hours. After completion of the reaction, the reaction solution was washed with water, dried over anhydrous sodium sulfate, and toluene was distilled off under reduced pressure. The obtained oily substance was isolated by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 3: 1) to obtain 0.4 g of the desired product as colorless crystals.

mp 158-161 ° C. Example 6 With 5 parts by weight of the compound of Compound No. 1, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of Neoperex powder (trade name; manufactured by Kao Atlas) and 2 parts by weight of sodium ligninsulfonate. Was uniformly mixed, a small amount of water was added, and the mixture was kneaded, then granulated and dried to obtain granules.

Example 7 50 parts by weight of the compound of Compound No. 1, 48 parts by weight of kaolin and Neoperex powder (trade name; manufactured by Kao Atlas) 2
1 part by weight was uniformly mixed and then pulverized to obtain a wettable powder.

Example 8 Toxanone (trade name; manufactured by Sanyo Kasei Co., Ltd.) (10 parts by weight) was added to 20 parts by weight of the compound of Compound No. 1 and 70 parts by weight of xylene, and the mixture was uniformly mixed and dissolved to obtain an emulsion.

Example 9 5 parts by weight of the compound of Compound No. 1, 50 parts by weight of talc and 45 parts by weight of kaolin were uniformly mixed to obtain a powder.

Example 10 Control efficacy test against wheat leaf rust (prophylactic efficacy) Ten wheats (cultivar: Kobushi-komugi) were cultivated in a plastic flower pot having a diameter of 6 cm, and 10 seeds were cultivated at 1.5 leaf stage, according to Example 7. The prepared wettable powder was diluted to 100 ppm with water containing a surfactant (0.01%) and
20 ml was sprinkled. Cultivated in a glass greenhouse for 2 days after spraying, then spore suspension of wheat leaf rust fungus (7 × 10 ⁴ spores / ml)
Was spray-inoculated uniformly.

After inoculation, the seedlings were grown in a glass greenhouse for 1 week, and the degree of wheat leaf rust lesions appearing on the first leaf was investigated. The drug effect was judged by comparing with the degree of lesions in the untreated section. The results are shown in Table 2.

The evaluation is shown in 6 levels from 5 to 0, 5 without lesions, 4 with lesion area 10% or less, 3 with 20%, 40% with 40% compared to the untreated section. Is shown as 1, and 0 is shown if the whole is affected.

The following compounds described in JP-A-63-225364 were used as controls.

Example 11 Control efficacy test against barley powdery mildew (preventive efficacy) Ten barleys (cultivar: black wheat) were cultivated in a plastic flower pot with a diameter of 6 cm, and 10 plants were cultivated at 1.5 leaf stage, and Example 7 was used. Prepare a wettable powder prepared according to the procedure 1) to 100ppm with water containing a surfactant (0.01%) and add 20
ml was sprinkled. Cultivate in a glass greenhouse for 2 days after spraying, then collect barley powdery mildew conidia from diseased leaves,
This was sprinkled evenly over the plant and inoculated.

After inoculation, the plants were grown in a glass greenhouse for 1 week, and the degree of barley powdery mildew lesions appearing on the first leaf was investigated. The drug effect was judged by comparing with the degree of lesions in the untreated section. The result is the third
Shown in the table.

The evaluation is shown in 6 grades of 5 to 0, and those without lesions are 5,
Compared with the untreated plot, the lesion area was 10% or less, 4 was about 20%, 4 was about 40%, 2 was about 60%, and 1 was totally infected.

The same compound as in Example 10 was used as the control compound.

Example 13 Control efficacy test against cucumber downy mildew (preventive efficacy) One cucumber (cultivar; Sagamihanjiro) was grown in a plastic flower pot with a diameter of 6 cm, and seedlings were planted at 1.5 leaf stage. The wettable powder prepared according to 7 is diluted to 500 ppm with water containing a surfactant (0.01%), and 20
ml was sprinkled. After spraying, the plants were cultivated in a glass greenhouse for 2 days, and then cucumber downy mildew zoospores were prepared from diseased leaves, which were evenly spray-inoculated from above the plants.

After inoculation, it was kept in the dark at 20 ° C. for 2 days and then grown in a glass greenhouse for 5 days to examine the degree of cucumber downy mildew lesions appearing on the first leaf. The drug effect was judged by comparing with the degree of lesions in the untreated section. The results are shown in Table 4.

The evaluation is shown in 6 grades of 5 to 0, and those without lesions are 5,
The lesion area is 10% or less, 4 is about 20%, 3 is about 40%, 2 is about 60%, and 1 is about 60%, and 0 is the diseased area.

The same compound as in Example 10 was used as the control compound.

Example 14 Control efficacy test against rice blast (preventive efficacy) Ten rice plants (cultivar; Nihonbare) were cultivated in a plastic flower pot with a diameter of 6 cm, and seedlings at 1.5 leaf stage were prepared according to Example 7. The wettable powder prepared by
%) And diluted to 500 ppm, and sprayed with 20 ml per pot. After spraying, it was cultivated in a glass greenhouse for 2 days, and then conidiospores of rice blast fungus were prepared from diseased leaves, which were uniformly spray-inoculated onto plant leaves.

After inoculation, it was grown in a humid chamber at 28 ° C for 5 days, and the degree of rice blast lesions appearing on the leaves was investigated. The drug effect was judged by comparing with the degree of lesions in the untreated section. The results are shown in Table 5.

The evaluation is shown in 6 grades of 5 to 0, and those without lesions are 5,
The lesion area is 10% or less, 4 is about 20%, 3 is about 40%, 2 is about 60%, and 1 is about 60%, and 0 is the diseased area.

The same compound as in Example 10 was used as the control compound.

Example 15 Efficacy test against diamondback moth The compounds shown in Table 1 were prepared according to Example 7, and added to a drug solution adjusted to 1000 ppm with water containing a surfactant (0.01%).
Cabbage leaf pieces (5 cm x 5 cm) were dipped for 30 seconds and placed in a plastic cup. After air-drying, 10 3 larvae of Plutella xylostella were released, covered, and allowed to stand in a constant temperature room at 25 ° C. The number of live and dead insects was counted after 2 days and the mortality rate was calculated. The results are shown in Table 6.

In Table 6, the mortality of 100% is shown as A, 99-80% as B, 79-60% as C, and 59% or less as D.

Example 16 Efficacy test against green leafhopper The compounds shown in Table 1 were prepared according to Example 7, and added to a drug solution containing 1000 ppm of water containing a surfactant (0.01%).
The rice seedlings were soaked for 30 seconds, air-dried, and then placed in a glass cylinder. Four 10-year-old leafhopper leaf larvae were released, capped with a porous plug, and left in a constant temperature room at 25 ° C. After 4 days, the number of live and dead insects was counted and the mortality rate was calculated.

In Table 7, the mortality of 100% is shown as A, 99-80% as B, 79-60% as C, and 59% or less as D.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C07D 401/12 239 405/12 239 495/04 105 105 Z

Claims (4)

[Claims] 1. A general formula: (In the formula, R ¹ is a hydrogen atom, a halogen atom, a halo lower alkyl group, an alkanoyl group, a nitro group, a cyano group or 1,3-
Represents a dioxolan-2-yl group, R ² and R ³ each represent a halogen atom or a lower alkyl group, or R ² and R ³
Represents an unsaturated 5- or 6-membered ring which may be condensed with a carbon atom to which they are attached to a pyrimidine ring and may have one sulfur atom constituting the ring, R ⁴ is a hydrogen atom, a halogen atom, A lower alkyl group, a cycloalkyl group, a lower alkoxy group or an amino group which may be substituted by lower alkyl, R ⁵ represents a hydrogen atom, a lower alkyl group or a cycloalkyl group, and Z represents a carbon atom or a nitrogen atom. Represent, Z
Is a nitrogen atom, R ¹ is unsubstituted) or an acid addition salt thereof. 2. A general formula: (Wherein R ² , R ³ and R ⁴ have the same meanings as defined in claim 1, and X represents a leaving group), and a compound of the general formula: (Wherein Z, R ¹ and R ⁵ have the same meanings as defined in claim 1) and a compound of formula (I) according to claim 1 or a compound thereof. Method for producing acid addition salt. 3. A general formula: (Wherein R ² , R ³ , R ⁴ and R ⁵ have the same meanings as defined in claim 1) and a general formula: (Wherein R ¹ and Z have the same meanings as those described in claim ¹ and X represents a leaving group), and the compound represented by the formula (I ) Or a method for producing an acid addition salt thereof. 4. A fungicide containing the compound of formula (I) or its acid addition salt according to claim 1 as an active ingredient.