JPH0559009A - Isoquinolinecarbonitrile derivative and agricultural and horticultural fungicide - Google Patents

Abstract

(57) [Summary] [Object] An object of the present invention is to provide an isoquinolinecarbonitrile derivative having excellent bactericidal activity. [Structure] The isoquinolinecarbonitrile derivative of the present invention is represented by the general formula (1). General formula (1) (In the formula, X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group,
A phenoxy group which may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group, and n represents 1 or 2)

Description

Detailed Description of the Invention

[0001]

[Object of the Invention]

FIELD OF THE INVENTION The present invention relates to a novel isoquinolinecarbonitrile derivative. More specifically, it relates to a 1,2-dihydro-2-phenyl-4-isoquinolinecarbonitrile derivative represented by the following general formula (1) and an agricultural and horticultural fungicide containing the derivative as an active ingredient. Therefore, the present invention is useful in the chemical industry and the agricultural and horticultural fields, particularly in the agrochemical manufacturing field.

[0002]

2. Description of the Related Art Up to now, several compounds which are similar in chemical structure to the compound of the present invention are known. For example, for isoquinoline carbonitrile derivatives, Chemical and Pharmaceutical Bulletin (Chemical
& Pharmaceutical Bulletin) Volume 21, Page 1914-
P. 1926 (1973), 1,2-dihydro-4
- isoquinoline carbonitrile is described that obtained by NaBH ₄ reduction of the 4-isoquinoline carbonitrile.

However, the following general formula (1) of the present invention is given.
The 1,2-dihydro-2-phenyl-4-isoquinolinecarbonitrile derivative represented by is not known.

[0004]

The known 1,2-dihydro-4-isoquinolinecarbonitrile does not show any bactericidal activity for agricultural and horticultural use at all, as shown in the test examples below. On the other hand, various drugs have been used for downy mildew, plague, powdery mildew, rust, etc., which are important diseases of fruit trees, vegetables, and cereals, but they are not used because of drug resistance. It can no longer be used or its use is restricted. Therefore,
In these fields, the emergence of new fungicides having a skeleton different from that of conventional drugs is desired. It is an object of the present invention to provide a germicide that meets these needs.

[0005]

[Constitution of the invention]

[Means for Solving the Problems] The inventors of the present invention synthesized many compounds in order to achieve the above-mentioned object, and diligently studied their usefulness. As a result, we succeeded in synthesizing the isoquinolinecarbonitrile derivative represented by the following general formula (1), and these derivatives are novel compounds which have not been described in the literature, and have high activity and safety as agricultural and horticultural fungicides. Have been found.

Therefore, the gist of the first aspect of the present invention lies in the following general formula (1):

[Chemical 3] (In the formula, X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group,
A phenoxy group which may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 1 or 2
In the isoquinoline carbonitrile derivative.

The lower alkyl group as used herein may be linear or branched. The term "lower" as used herein means one having 1 to 6 carbon atoms.

The gist of the second aspect of the present invention is an agricultural and horticultural fungicide containing the isoquinolinecarbonitrile derivative of the general formula (1) as an active ingredient.

Specific examples of the compound of the present invention represented by the general formula (1) are shown in Table 1.

Compound No. Is also referred to in the following examples and test examples.

[0011]

[Table 1]

[0012]

The compound of the general formula (1) of the present invention is a novel compound. Then, the compound of the general formula (1) acts as an active ingredient of the agricultural and horticultural fungicide.

[0013]

EXAMPLES (Method for producing the compound of the present invention) The general formula (1) according to the present invention
The compound can be produced by the method described below. That is, it can be produced by a method of reacting α- (2-bromomethylphenyl) -β-methoxyacrylonitrile represented by the formula (2) with the aniline derivative represented by the general formula (3).

[0014]

[Chemical 4] (In the formula, X and n are the same as above).

This condensation reaction is usually carried out in an organic solvent. As the solvent that can be used, hydrocarbons such as toluene and hexane, halogenated hydrocarbons such as chloroform and chlorobenzene, ethers such as ethyl ether, dioxane, and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, acetone, Examples thereof include ketones such as methyl isobutyl ketone, alcohols such as methanol and ethanol, amides such as dimethylformamide and dimethylacetamide, and dimethyl sulfoxide.

As the acid binder, an inorganic base such as sodium hydride, sodium amide, sodium hydroxide or potassium carbonate, or an organic base such as triethylamine or pyridine can be used.

The reaction proceeds even at room temperature, but the reaction time can be shortened by heating within the range up to the boiling point of the solvent. After the completion of the reaction, if salts of acid binders and the like are present, these can be filtered off and the solvent can be distilled off to obtain the desired product. The compound of the present invention can also be obtained by adding water and an organic solvent such as benzene, toluene, tetrahydrofuran, or chloroform to fractionate the desired product and distill off the solvent.

Examples of production of the compound of the present invention by this method are shown in Examples 1 and 2.

The starting compounds (2) and (3) are known compounds.

Example 1 1,2-Dihydro-2- (3'-trifluoromethylphenyl) -4-isoquinolinecarbonitrile (Compound N
Preparation of o.11) α- (2-bromomethylphenyl) -β-methoxyacrylonitrile 25.2 in a 500 ml four-necked flask.
g, 3-trifluoromethylaniline 16.1 g, anhydrous potassium carbonate 13.8 g and acetonitrile 200 ml
Was charged and refluxed for 10 hours. After cooling, the inorganic salt is filtered off,
The solvent was distilled off under reduced pressure to obtain 29.2 g of the title compound as brown crystals. Recrystallization from a mixed solvent of diisopropyl ether-acetone gave colorless crystals (yield 20.7).
g) and a melting point of 160-162 ° C.

Example 2 1,2-Dihydro-2- (3 ', 5'-dichlorophenyl) -4-isoquinolinecarbonitrile (Compound No.
20) Production of α- (2-bromomethylphenyl) -β-methoxyacrylonitrile 25.2 in a 500 m1 four-necked flask.
g, 3,5-dichloroaniline (16.2 g), anhydrous potassium carbonate (13.8 g) and dimethylformamide (200 ml) were added and the mixture was refluxed for 5 hours. After cooling, the reaction solution was poured into water and extracted with ethyl acetate, the organic layer was washed with water and dried over anhydrous sodium sulfate. After that, when the solvent is distilled off under reduced pressure,
27.0 g of the title compound was obtained as a brown oil. Purification by silica gel column chromatography using a hexane-ethyl acetate mixed solvent gave colorless crystals (yield 19.8 g), mp 183-185 ° C.

[0022]

【Example】

(Method for formulating agricultural / horticultural fungicide) Further, the agricultural / horticultural fungicide of the second aspect of the present invention can be used by formulating the compound of the general formula (1) by a conventional formulation. That is, the compound of the general formula (1) and a suitable carrier and auxiliary agent,
For example, by blending a surfactant, a binder, a stabilizer, etc., a wettable powder, an emulsion, a liquid agent, a sol agent (flowable agent), an oil agent, a powder agent, a DL (driftless type) powder agent, a fine particle agent, a coarse powder agent, etc. It may be formulated as. The content of the compound of the present invention in these preparations is in the range of 1 to 90% (% by weight: the same applies hereinafter) in the case of wettable powder, emulsion, sol and oil, powder, D
In the case of L powder, fine powder, and coarse powder, it can be contained in the range of 0.5 to 5%, and in the case of granules, it can be contained in the range of 1 to 10%.

The method of using the agricultural and horticultural germicide of the present invention is generally as follows. That is, in the case of a wettable powder, a liquid preparation, an emulsion, a sol preparation (flowable preparation) and an oil preparation, the active ingredient is generally diluted to 1 to 500 times with water.
The solution is adjusted to a concentration of 10,000 ppm. Then, this diluted solution is sprayed onto the foliage at the disease occurrence site of the plant in an amount of 50 to 300 liters, usually 100 to 200 liters, per 10 ares.

Further, liquid solutions, emulsions, and sol agents (flowable agents) are not diluted with water and remain as a concentrated solution or with water.
Dilute to within 0 times and mainly use a small amount of spraying agent for air spraying (LV
As a spraying agent, ULV spraying agent) 50 per 10 are
A volume of 3000 ml is sprayed using a helicopter.

Further, the powder, DL powder, fine powder and coarse powder are 2 to 5 kg per 10 ares (50 to 50 as the active ingredient amount).
(About 500 g) is applied to the foliage at the disease occurrence site of the plant, the soil surface, the soil or the water surface.

The method of formulating the compound of the present invention represented by the general formula (1) as an agricultural and horticultural fungicide is described in Example 3 below.
~ 6.

Example 3 (Dust) 2 parts of the compound of Compound No. 11, 1 part of PAP (physical property improver) and 97 parts of clay are uniformly mixed and ground to obtain a powder containing 2% of the active ingredient. To get

Example 4 (Wettable powder) 20 parts of the compound of compound No. 20, 3 parts of potassium alkylbenzene sulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 72 parts of clay were uniformly mixed and pulverized. A wettable powder containing 20% of active ingredient is obtained.

Example 5 (Emulsion) 30 parts of compound No. 2 compound, methyl ethyl ketone
40 parts and 30 parts of polyoxyethylene nonyl phenyl ether are mixed and dissolved to obtain an emulsion containing 30% of active ingredient.

Example 6 (Sol agent) Compound No. 16 compound 40 parts, lauryl sulfate 2 parts, sodium alkylnaphthalene sulfonate 2 parts,
1 part of acetoxypropylcellulose and 55 parts of water are uniformly mixed to obtain a sol preparation containing 40% of the active ingredient.

[0031]

INDUSTRIAL APPLICABILITY The compound of the present invention exhibits a high control effect against downy mildew, epidemic disease, powdery mildew, rust, etc., which are important diseases of fruit trees, vegetables and cereals, and therefore, as a fungicide for agricultural and horticultural use. It is useful.

Specific examples of the usefulness of the compound of the present invention represented by the general formula (1) are shown in Test Examples 1 to 4.

[Test Example 1] Cucumber downy mildew control effect test Second test in which soil was cultivated in a greenhouse in a clay pot with a diameter of 9 cm
20 ml of a dilute solution of the wettable powder having a predetermined concentration prepared according to Example 4 was sprayed on the leaf stage cucumber seedlings (cultivar: Sagamihanjiro).
Then, spores of cucumber downy mildew ( Pseudoperonospora cubensis ) were scraped off with a moistened brush from leaves affected by cucumber downy mildew, and 50 ppm of a spreading agent (polyoxyethylene alkyl ether) was scraped off.
Suspended in aqueous solution. Then, the spore concentration was adjusted to 5 × 10 ⁶ spores (pieces) / ml, and one day after spraying the drug, a spore suspension of cucumber downy mildew was spray-inoculated. Then, it was allowed to stand in a greenhouse at 20 ° C. and a humidity of 100% for 2 days to cause cucumber downy mildew. Six days after the inoculation, the lesion area ratio (%) per leaf was investigated, and the control value (%) was calculated by the following formula.

This test was carried out in duplicate for each chemical concentration group, the average control value (%) was determined, and the evaluation value was determined according to the following criteria. In addition, phytotoxicity to cucumber was investigated according to the following criteria. The results are shown in Table 2.

The evaluation value of the control effect and the investigation index of the chemical damage were similarly used in the following Test Examples 2 to 4.

[0036]

[Equation 1]

Evaluation value of control effect Control value 5 100% 4 80 to less than 100% 3 60 to less than 80% 2 40 to less than 60% 1 20 to less than 40% 0 less than 20%

Investigation index of phytotoxicity 5: severe 4: severe 3: high 2: slight 1: slight 0: none

[0039]

[Table 2] Note 1) The figures in parentheses for non-scatter plots indicate the average diseased area rate per leaf. Note 2) Comparative drug A used the following.

Comparative drug A:

[Chemical 5] [Chemical & Pharmaceutical Bulletin Vol. 21 Vol. 1
Compounds described on pages 914 to 1926 (1973)]

[Test Example 2] Tomato epidemic control effect test Prepared according to Example 4 on the 5th leaf stage seedlings of tomatoes (cultivar: Toko K) cultivated by soil cultivation in a vinyl pot having a diameter of 9 cm in a greenhouse. 30 ml per 3 pots was sprayed with the diluted solution of the wettable powder having a predetermined concentration, using an automatic spraying device. 20 ° C on potato slices pre-sliced the day after drug treatment,
Phytophthora infestan cultivated for 3 days
s : Phytophthora infestans) zoospores of zoospores were roughed (adjusted so that the concentration of zoospores was 10 ⁵ cells / ml) and spray-inoculated on tomatoes using a spray gun. Then, after storing in a humid chamber at 20 ° C and 100% humidity for 5 days,
About the 1st to 4th true leaves Area of disease spread of tomato disease (%)
Was investigated, the average disease area ratio was calculated, and the control value (%) was calculated by the following formula.

This test is carried out in a double system for each concentration of the chemical solution.
The average control value (%) was calculated and converted into an evaluation value. Further, the phytotoxicity to tomato was investigated according to the same criteria as in Test Example 1. The results are shown in Table 3.

[0043]

[Equation 2]

[0044]

[Table 3] Note 1) Comparative drug A is the same as the compound shown in Table 2. Note 2) The figures in parentheses for non-scattering plots indicate the disease area ratio (%) per leaf.

Test Example 3 Barley Powdery Mildew Control Effect Test Same as Example 4 for barley (variety: Azuma Golden) first leaf stage seedlings cultivated in a greenhouse in a clay pot with a diameter of 9 cm. After spraying 10 ml of the prescribed concentration of the wettable powder prepared above, the mixture was allowed to stand overnight, and then barley powdery mildew ( Erysiphe
graminis : Erysiphe graminis ) was spray inoculated with a spore suspension. Seven days after the inoculation, the number of barley powdery mildew lesions was investigated, and the control value (%) was calculated by the following formula, and converted into an evaluation value. The degree of phytotoxicity to barley was investigated and displayed according to the same criteria as in Test Example 1. The results are shown in Table 4.

[0046]

[Equation 3]

[0047]

[Table 4] Note 1) Comparative drug A is the same as the compound shown in Table 2. Note 2) The value in parentheses in the non-scattering plot indicates the number of lesions per leaf.

[Test Example 4] Wheat red rust control effect test [0048] The first of which was cultivated in a greenhouse in a clay pot with a diameter of 9 cm.
Example 4 was applied to wheat seedlings (variety: Norin 61) at the true leaf stage.
A diluted solution of a prescribed concentration of a wettable powder prepared according to the above procedure was sprayed in an amount of 20 ml per 3 pots. After one day, pre-wheat leaf on the wheat leaf rust fungus, which was formed in: so that the concentration of spores per field of view in the summer spores 150 times the microscope (Puccinia recondita Pukushinia recondita) is about 50 or Tween 20 [Kao (Ltd. (Trade name of polyoxyethylene sorbitan monolaurate manufactured by KK) was suspended in sterilized water to which 50 ppm was added, and the spore suspension was spray-inoculated onto wheat leaves.
After keeping it at room temperature of 20 ℃ and humidity of 100% overnight,
The disease was moved to the greenhouse to promote the disease. It was taken out 10 days after the inoculation, and the number of infected summer spore stacks per leaf was examined, and the control value (%) was calculated by the following formula.

This test was carried out in a system of three pots per concentration of one chemical solution, and the average control value was calculated and converted into an evaluation value. In addition, the degree of chemical damage to wheat was investigated using the same criteria as in Test Example 1,
displayed. The results are shown in Table 5.

[0050]

[Equation 4]

[0051]

[Table 5] Note 1) Comparative drug A is the same as the compound shown in Table 2. Note 2) The value in parentheses in the non-scattering plot indicates the number of lesions per leaf.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Kazuo Kajikawa 2385 Toda, Atsugi City, Kanagawa Prefecture

Claims (2)

[Claims] 1. A general formula: (In the formula, X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group,
A phenoxy group which may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 1 or 2
Is shown). 2. A general formula: (In the formula, X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group,
A phenoxy group which may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 1 or 2
And an isoquinolinecarbonitrile derivative represented by the formula (1) as an active ingredient.