JPH0822803B2 - Agro-horticultural fungicide containing a copper chelate compound of 8-oxyquinoline and anthranilic acid or substituted anthranilic acid - Google Patents

Description

The present invention relates to a compound of the general formula (I) (In the formula, R represents a halogen atom or a lower alkyl group,
and n represents 0 or 2) as an active ingredient.

Conventional technology Formula (III) The 8-hydroxyquinoline copper chelate compound represented by the formula (1) is widely used not only for agriculture, but also for industry and medicine, because of its strong bactericidal activity and a wide range of bactericidal activity against various kinds of pathogenic fungi. It is a useful compound. However, since this compound has a unique color tone (dark yellow-green color), when it is used as an agricultural and horticultural fungicide, the contamination of agricultural crops is conspicuous and the market value thereof is significantly impaired. Further, since the copper chelate compound of 8-oxyquinoline represented by the formula (III) is expensive, it is difficult to use a bactericide containing this as an active ingredient, which makes it extremely difficult to use. At present, it is extremely limited. Therefore, it has a bactericidal activity equivalent to or higher than that of the copper chelate compound of 8-oxyquinoline represented by the formula (III), has less contamination to the treated material, and is relatively inexpensive in terms of cost. The appearance was strongly desired.

Problems to be Solved by the Invention It is an object of the present invention to establish a novel compound that has a fungicidal activity equal to or higher than that of a copper chelate compound of 8-oxyquinoline, is inexpensive, and has little pollution to crops, and a method for producing the same. Is.

Means for Solving the Problems As a result of various studies, the present inventors have shown the following general compounds as a novel compound which does not impair the bactericidal activity of a copper chelate compound of 8-oxyquinoline, has little pollution on crops, and is inexpensive. Formula (I) (In the formula, R represents a halogen atom or a lower alkyl group,
n is 0 to 2) (hereinafter referred to as the present compound).

The present inventors also reacted 8-oxyquinoline, a substituted anthranilic acid, and inorganic copper salts in an aqueous solution under alkaline conditions in the absence of ethanol to give a highly pure compound of the present invention at a high yield. Moreover, they have found that they can be manufactured at low cost.

Furthermore, the present inventors have found by actual application tests that this compound is a very useful fungicide which shows a fungicidal effect equivalent to or higher than that of a copper chelate compound of 8-oxyquinoline and does not pollute crops at all. The invention was completed.

The 8-oxyquinoline copper represented by the above formula (III) contains a large amount of two molecules of expensive 8-oxyquinoline as shown by its chemical structural formula. Since the compound of the present invention is composed of one molecule of 8-oxyquinoline and inexpensive anthranilic acid or a substituted compound thereof, it is a great advantage that it can be produced at extremely low cost.

The physical properties of main compounds of the present invention obtained by the method of the present invention are shown in Table 1.

In the actual use of these present compounds, the present compound is mixed with one or more conventional pesticide additives or adjuvants in accordance with the usual method of pesticide formulation, and a wettable powder, granules, powder, liquid formulation It can be used as an arbitrary dosage form such as an agent or a paste. For example, these present compounds are clay,
Solid carriers such as talc, white carbon, diatomaceous earth, bentonite, etc. and ionic or nonionic emulsifiers or dispersants such as higher alkoxy sulfonates, polyoxyethylene sorbitan, alkylphenoxypolyethoxyethanols, lignin sulfonates, and if necessary wetting. It can be mixed and pulverized with an agent, a protective colloid agent and the like.

It has been found that the compound has a very wide range of applicability in its bactericidal effect. For example, apple spot leaf spot, scab, pear spot, scab, persimmon anthracnose, powdery mildew, leaf spot, grape brown spot, downy mildew, gray mold,
Leaf rot of peach, scab of citrus, black spot, ulcer, soft rot of Chinese cabbage, black rot of cabbage, cucumber, chlorotic spot of melon, downy mildew, anthracnose, plague, spot of lettuce It has an excellent bactericidal effect against bacterial diseases, soft rot, snow rot of lawn and wheat, plague of bell pepper, plague of onion, wilting bacterium of carnation and the like. Moreover, the fresh green color is not impaired in crops to which this compound is applied,
No contamination is seen as occurs when applying the copper chelate of 8-oxyquinoline. Therefore, a fungicide containing the present compound cucumber, eggplant, watermelon, as a fungicide for spraying fruits and vegetables such as pumpkin, or as a fungicide for spraying leaf vegetables such as cabbage, cabbage, lettuce, spinach, or apples. , Pears, butterflies, peaches,
It can be safely applied as a fungicide for spraying fruit trees such as citrus fruits and persimmons, or as a fungicide for spraying foliage of ornamental plants such as turf, which requires aesthetics, without worrying about contamination of crops.

Next, the production method of the compound of the present invention will be described in more detail with reference to synthetic examples of the present compound.

Synthesis Example 1 Copper chelate compound of 8-oxyquinoline and anthranilic acid (Compound No. 1) 1.45 g of 8-oxyquinoline (0.01 g) in 30 ml of sodium hydroxide aqueous solution containing 0.8 g (0.02 mol) of sodium hydroxide.
Mol) and 1.37 g (0.01 mol) of anthranilic acid,
It was heated to 0 ° C. and stirred to dissolve it. Copper sulfate 5 in this solution
A solution of 2.5 g (0.01 mol) of water salt dissolved in 20 ml of warm water was added little by little. Then, heating and stirring were continued at 80 ° C. for 1 hour.
This was allowed to cool, and the precipitated crystals were collected by filtration. The crystals were washed twice with water, thoroughly dehydrated, and then dried in a dryer at 70 ° C. for 5 hours to obtain 3.33 g of yellow-green crystals. Yield 96.8% Synthesis example 2 Copper chelate compound of 8-oxyquinoline and 5-methylanthranilic acid (Compound No. 2) 30 ml of an aqueous solution of sodium hydroxide containing 0.8 g (0.02 mol) of sodium hydroxide was added to 8-oxy Quinoline 1.45 g (0.01
Mol) and 5-methylanthranilic acid 1.51 g (0.01 mol)
Was added, and the mixture was heated to about 50 ° C. and stirred to dissolve it. To this solution, a solution prepared by dissolving 2.5 g (0.01 mol) of copper sulfate pentahydrate in 20 ml of warm water was added little by little. Then, heating and stirring were continued at 80 ° C. for 1 hour. This was allowed to cool, and the precipitated crystals were collected by filtration. The crystals were washed twice with water and thoroughly dehydrated,
By drying in a dryer at 70 ° C. for 5 hours, 3.50 g of yellow-green crystals was obtained. Yield 97.3% Synthetic Example 3 Copper chelate compound of 8-oxyquinoline and 4-chloroanthranilic acid (Compound No. 3) 8-Oxyoxy was added to 30 ml of sodium hydroxide aqueous solution containing 0.8 g (0.02 mol) of sodium hydroxide. Quinoline 1.45 g (0.01
Mol) and 4-chloroanthranilic acid 1.72 g (0.01 mol)
Was added, and the mixture was heated to about 50 ° C. and stirred to dissolve it. To this solution, a solution prepared by dissolving 2.5 g (0.01 mol) of copper sulfate pentahydrate in 20 ml of warm water was added little by little. Then, heating and stirring were continued at 80 ° C. for 1 hour. This was allowed to cool, and the precipitated crystals were collected by filtration. The crystals were washed twice with water and thoroughly dehydrated,
By drying in a dryer at 70 ° C. for 5 hours, 3.75 g of yellowish green crystals were obtained. Yield 98.6% Synthesis Example 4 Copper chelate compound of 8-oxyquinoline and 5-chloroanthranilic acid (Compound No. 4) 30 ml of an aqueous solution of sodium hydroxide containing 0.8 g (0.02 mol) of sodium hydroxide was added to 8-oxy Quinoline 1.45 g (0.01
Mol) and 1.72 g (0.01 mol) of 5-chloroanthranilic acid
Was added, and the mixture was heated to about 50 ° C. and stirred to dissolve it. To this solution, a solution prepared by dissolving 2.5 g (0.01 mol) of copper sulfate pentahydrate in 20 ml of warm water was added little by little. Then, heating and stirring were continued at 80 ° C. for 1 hour. This was allowed to cool, and the precipitated crystals were collected by filtration. The crystals were washed twice with water and thoroughly dehydrated,
By drying in a dryer at 70 ° C. for 5 hours, 3.70 g of yellow-green crystals was obtained. Yield 97.3% Synthesis Example 5 Copper chelate compound of 8-oxyquinoline and 3,5-dichloroanthranilic acid (Compound No. 5) 30 ml of an aqueous sodium hydroxide solution containing 0.8 g (0.02 mol) of sodium hydroxide, 8-oxyquinoline 1.45 g (0.01
Mol) and 2.05 g (0.01 mol) of 3,5-dichloroanthranilic acid were added, and the mixture was heated to about 50 ° C. and stirred to dissolve. To this solution, a solution prepared by dissolving 2.5 g (0.01 mol) of copper sulfate pentahydrate in 20 ml of warm water was added little by little. Then heat at 80 ℃ for 1 hour,
Stirring was continued. This was allowed to cool, and the precipitated crystals were collected by filtration. The crystals were washed twice with water, thoroughly dehydrated, and then dried in a dryer at 70 ° C. for 5 hours to obtain 4.05 g of green crystals. Yield 97.7% Next, formulation examples of agricultural and horticultural fungicides containing this compound as an active ingredient are given.

Formulation example Ingredients% by weight Compound No. 1 50 Sodium lignin sulfonate 5 Polyoxyethylene alkylphenol ether 1 Clay 44 100 The above components are mixed and ground in the above weight ratio to prepare a wettable powder. For spraying, this wettable powder is mixed and diluted with a certain amount of water and sprayed on the entire crop in a sufficient amount.

Next, as a result of comparison of the present compound as an agricultural and horticultural fungicide with the anhydrous copper chelate compound of 8-oxyquinoline represented by the above formula (III), the compound shows a titer equal to or higher than the fungicidal activity, and is contaminated. It will be explained by a test example that there was no such phenomenon.

Test Example 1 Apple Spot Litter Disease Control Test Apple shoot shoots watered in an Erlenmeyer flask were sprayed with a sufficient amount of a prescribed concentration of a wettable powder prepared as described in the formulation example, and air dried 1 After a day, a spore suspension of Alternaria mali was spray-inoculated. This was left in a moist chamber at a temperature of 26 to 28 ° C. for 24 hours and then transferred into a greenhouse. Three days after the inoculation, the number of diseased leaves was investigated according to the degree of disease shown below for the five leaves developed on the top of 3 shoots in 1 ward, and the control value was calculated by the following formula.

Degree of illness Area of lesion area 5 50 to 100% 4 25 to 50% 3 10 to 25% 25 to 10% 11 to 5% 0 0 The pollution degree was evaluated according to the following criteria.

− No pollution (no macroscopic drug adhesion) + Little pollution (visually drug adhesion) ++ Large pollution (visually marked drug adhesion) Test Example 2 Citrus black spot disease control test A sufficient amount of the prescribed concentration of the wettable powder prepared as described in the formulation example was sprayed onto the fresh leaves of potted summer citrus seedlings, and air-dried for 1 day. Later citrus black spot fungus (Diaporthe
citri) spore suspension was spray inoculated. This is the temperature 24-2
After leaving it in a humid chamber at 6 ° C for 24 hours, it was transferred in a greenhouse. Twenty days after the inoculation, the number of diseased leaves was investigated according to the degree of disease shown below for all the new leaves in 4 pots in 1 ward, and the control value was calculated by the following formula.

Degree of onset State of onset 3 Onset of severe 2 Onset of moderate 1 Onset of low 0 No occurrence The standard of the degree of contamination is the same as that shown in Test Example 1.

Test Example 3 Citrus ulcer disease control test A sufficient amount of a prescribed concentration of a wettable powder prepared as described in the formulation example was sprayed on fresh leaves of potted summer citrus seedlings, and air-dried for 1 day. Later citrus ulcer (Xanthomona
s citri) was spray inoculated. 24-26 ℃
After leaving it in the wet room for 24 hours, it was transferred to the greenhouse. 30 days after the inoculation, the number of lesions was investigated on all the new leaves in 4 pots in 1 ward, and the control value was calculated by the following formula.

The standard of the degree of contamination is the same as that shown in Test Example 1.

EFFECTS OF THE INVENTION By using the present compound, which can be provided at an extremely low cost in production, excellent sterilization superior to the copper chelate compound of 8-oxyquinoline without causing contamination of crops, which is caused by the copper chelate compound of 8-oxyquinoline. You can expect an effect.

Claims (1)

[Claims] 1. General formula (I): Containing a copper chelate compound of 8-oxyquinoline and anthranilic acid or a substituted anthranilic acid represented by the formula (wherein R represents a halogen atom or a lower alkyl group and n represents 0 to 2) as an active ingredient. A fungicide for agricultural and horticultural use.