JPH04124107A - Control agent of phycomycete plant disease, containing 2-chloronicotinic acid amide derivative as active ingredient - Google Patents

Abstract

PURPOSE:To provide a treating agent of plant diseases, containing one of partially novel 2-chloroisonicotinic acid amide derivatives as an active ingredient and exhibiting excellent preventing and treating effects on plant diseases such as downy mildews and epidemics caused by phycomycetes. CONSTITUTION:An agent for controlling plant diseases caused by phycomycetes contains one of compounds of the formula [R is lower alkyl or allyl capable of having a halogen substituent, 3-5C alkinyl, CH2S(O)nR' (R' is lower alkyl; (n) is 0, 1, 2), CH2Z (Z is SCN, azolyl, triazolyl, morpholino, 2, 6- dimethylmorpholino, pyridyl, 2-chloroisonicotinyl amino), etc.; but when R is alkyl excluding propargyl, CH2SOR', CH2Z (Z is morpholino, 2- chloroisonicotinylamino), the compounds are new)] as an active ingredient, has the above-mentioned effects and can further be expected to have sufficient control effects even when the control effects are reduced due to the occurrence of agent-resistant microbials.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides an agent for controlling plant diseases caused by algae and fungi, which is characterized by containing as an active ingredient a 2-chloroisonicotinic acid amide derivative containing a partially novel compound. It is related to.

[Conventional technology]

Currently, cabtane, captafol, dithiocarbamate fungicides, chlorothalonil, and the like are widely used to treat plant diseases caused by algal fungi.

However, these drugs mainly have a preventive effect and have almost no therapeutic effect, so they have the disadvantage that they cannot be used for control by chemical treatment after the onset of the disease is recognized.

On the other hand, whether the asolalanine-based 12 fungal agents that have been developed since then, such as metallaquinol, also have therapeutic effects?
Due to the emergence of drug-resistant bacteria, the control effect has already been reduced and is becoming a problem.

Regarding 2-chloroisonicotinic acid amide derivatives, the present applicant has disclosed in Japanese Patent Application No. 1-48609,
Although it has been disclosed that it has a high control effect on rice blast and single-leaf defoliation of rice, there has been no report on its control effect on plant diseases caused by algal fungi such as downy mildew and late blight.

[Problem to be solved by the invention]

An object of the present invention is to provide a fungicide that has a new action and exhibits preventive and therapeutic effects against plant diseases caused by algal fungi.

Means for Solving Problem C1] In order to solve the above problem, as a result of intensive research on isonicotinamide derivatives, a group of compounds with the general formula shown below, including some new compounds, have been found to be effective against mildew, late blight, etc. The present inventors have discovered that the present invention exhibits excellent preventive and therapeutic effects against plant diseases caused by algae and fungi, leading to the completion of the present invention.

That is, the present invention is based on the general formula % [wherein R is a lower alkyl group optionally substituted with a halogen atom, an allyl group optionally substituted with a halogen atom, a C1-C, alkynyl group, a group - c) 1.5 (0)
,,R' thionanatomethyl group, azolylmethyl group, triazolylmethyl group, morpholinomethyl group, 2,6
-dimethylmorpholinomethyl group, 2,3-evoquinpropyl group, pyridylmethyl group, 2-chloroisonicotinylaminomethyl group, or a Hensyl group optionally substituted with a halogen atom, where R' is a lower It represents an alkyl group, and n represents 0 or an integer of 1-2. The present invention relates to an agent for controlling plant diseases caused by algal fungi, which is characterized by containing a 2-chloroisonicotinic acid amide derivative represented by the following as an active ingredient.

In the general formula El), a compound in which R is an alkynyl group of the propargyl group, a lower alkylsulfinylmethyl group, a morpholinomethyl group,
Compounds that are 2-chloroisonicotinylaminomethyl groups are new compounds.

The compound of general formula CI) of the present invention can be produced by the following method.

2-chloroisonicotinic acid chloride represented by I,
- % formula %[ [wherein R'' is a lower alkyl group which may be substituted with a halogen atom, an allyl group which may be substituted with a halogen atom, a C2-C, alkynyl group, a pyridylmethyl group,
It can be obtained by reacting with an amine derivative represented by ], which represents a hensenol group optionally substituted with a halogen atom, in an inert solvent, optionally in the presence of a base.

The bases mentioned here include tertiary amines such as triethylamine, tributylamine, N,N-dimethylaniline, N-methylmorpholine, pyridine, and 4-dimethylaminopyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, and carbonic acid. Examples include inorganic bases such as potassium, sodium hydrogen carbonate, and sodium hydride. Examples of inert solvents include water or organic solvents such as aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as henzene and toluene, halogenated hydrocarbons such as nochloromethane and chloroform, diethyl ether, tetrahydrofuran, etc. ethers such as acetone, ketones such as methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, aprotic polar solvents such as ethyl acetate, propionate esters, dimethylformamide, dimethyl sulfokide, and pyridine. The above base and solvent can be used together. Moreover, the above-mentioned solvents can also be used in combination. The reaction temperature and reaction time are -10°C to 100°C, preferably O'C to
50'C range, about 30 minutes to 24 hours, preferably 1
It is carried out for a period of ~8 hours.

- Tsuzuriyo CI), the compound in which R is a 2,3-epoquinprobyl group is prepared by adding the compound in which R1 is an allyl group obtained by the above method to an organic compound such as m-chloroperbenzoic acid in a halogenated hydrocarbon such as chloroform. Obtained by reaction with peracid at room temperature to 100"C.

Compounds in which R in the general formula [I] is a group other than R1 or a 2,3-epoxyprobyl group can be produced by the following routes.

I I (IV) [V j SOCI□ C In the formula, M represents a monovalent cation such as potassium, sodium, ammonium, etc., R' represents a lower alkyl group,
n' is an integer of 1 to 2, and Z represents an azolyl group, a triazolyl group, a morpholino group, a 2,6-dimethylmorpholino group, or a 2-chloroisonicotinylamine group. ] As shown in the above reaction formula, the compound of formula (V) is obtained by heating the amide represented by formula CIV) with formalin in the presence of an alkali metal bicarbonate, and this is reacted with toluene etc. Compound 2 (■) can be obtained by heating and reacting with thionyl chloride using aromatic hydrocarbons or halogenated hydrocarbons such as chloroform as a solvent.

A compound of formula CVl) is mixed with a nitrile such as a7tonitrile, a halogenated hydrocarbon such as chloroform, or an aromatic hydrocarbon such as toluene as a solvent (M has the same meaning as above). A compound of the formula [■] is obtained by a heating reaction with a thiocyanate represented by the formula [■].

The compound of formula (Vl) is a nitrile such as a7tonitrile,
Formula Z1 ([Z has the same meaning as above.] A compound of the general formula (IXI) can be obtained.

Further, the compound 2 [Vl] is mixed with a lower alkylthiol in an alcohol such as methanol, or a nitrile such as acenitrile, in the presence of a base such as an alkali metal alcoholade, an alkali metal hydride, or an alkali metal carbonate. By reacting with, a compound of -Tsuzuriyo [■] is obtained, and by oxidizing this compound with an organic peracid such as m-chloroperbenzoic acid in a halogenated hydrocarbon solvent such as chloroform, -i formula (Compound Xl is obtained.

To isolate the target product from the reaction compound, after washing with water, usual post-treatments such as concentration of the organic layer under reduced pressure are performed, and if necessary, further purification is performed by recrystallization, column chromatography, etc.

Plant diseases caused by algae and fungi for which the control agent of the present invention exhibits an excellent control effect include downy mildew of grapes (Plasmopar
e viLicota), downy mildew of cucurbits (P5
eudoperonospora cubensis)
, downy mildew of cruciferous vegetables (Peronosp, :+
ra brassicae) 2. Downy mildew (Per.
onospora destructor), downy mildew of spinach (Peronospora 5pinac)
iae) downy mildew of soybean (Peronospora
manshuirca), broad bean downy mildew (Per
onospora viciae), hop downy mildew (
P5eudopernospora husuli)
Gray late blight of tomatoes and cucumbers (P1iytophth)
ora (apsjci), potato, phytophthora, phytophthora, 1nfes
tans), pineapple blight (P hytopht)
hora cinnasoni), tobacco blight (P
hytophthora n1cotiana var
, n1cotiana), damping-off of various crops caused by bacteria of the genus Bysum, etc.

When the compound of the present invention is used as an active ingredient of an agent for controlling plant diseases caused by algae and fungi, one or more compounds of the present invention may be used.

When the compound of the present invention is used as a control agent for plant diseases caused by algae and fungi, depending on the purpose of use, it may be used as is, or it may be mixed with an agrochemical adjuvant to enhance or stabilize the effect.
By the method commonly used in the agricultural chemical manufacturing field,
iii) It can be used in the form of manufacturing forms such as mulberry, fine granules, granules, wettable powders, flowable tablets, and emulsions.

In actual use, these various formulations can be used directly or diluted with water to a desired concentration.

Examples of the agrochemical auxiliary agent herein include carriers (diluents) and other auxiliary agents such as spreading agents, emulsifiers, wetting agents, dispersants, fixing agents, and disintegrants.

Liquid carriers include aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methylnaphthalene, nclohexane, animals and plants. Examples include oil, fatty acids, fatty acid esters, etc.

Solid carriers include clay, kaolin, talc, diatomaceous earth,
Examples include calcium carbonate, montmorillonite, hentonite, feldspar, quartz, alumina, and sawdust.

In addition, surfactants are usually used as emulsifiers or dispersants, such as anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine, and cationic surfactants. , nonionic surfactants, and amphoteric surfactants.

Spreading agents include polyoxyethylene nonylphenyl ether, polyoxene ethylene lauryl ether, etc. Wetting agents include polyoxyethylene nonylphenyl ether, dialkyl sulfosuccinate, etc., and fixing agents include carboxymethyl cellulose, polyvinyl alcohol, etc. However, examples of disintegrants include sodium pyrogenin sulfonate and sodium lauryl sulfate.

Not only can each formulation be used alone, but
It can also be used in combination with other agricultural and horticultural fungicides, insecticides, plant growth regulators, and acaricides.

The active ingredient compound content in the M disease control agent caused by algae type 2 of the present invention varies depending on the formulation form, application method, and other conditions. In some cases, only the active ingredient compound may be used, but it is usually 0.5 to 95%. (Weight preferably 2~
It is in the range of 70% (by weight).

In the present invention, the disinfectant preferably has an active ingredient concentration of 10 to 4.
000ppm can be sprayed on the foliage of plants, and when spraying on soil, the dispersion amount is 0.02~10k
g/l Oa Strong.

〔Effect of the invention〕

The plant disease control agent using algae and fungi according to the present invention has excellent preventive and therapeutic effects against downy mildew and late blight, and is also sufficient even in situations where the control effect is reduced due to the appearance of drug-resistant bacteria. A great pest control effect can be expected.

In this way, plant disease control 11 caused by algae and fungi according to the present invention
f'l ; It has one excellent characteristic and is useful.

〔Example〕

A reference synthesis example of a 2-chloroisonicotinic acid amide derivative will be specifically described below.

Reference Synthesis Example I Synthesis of N-(1,1-dimethyl-2-propynyl)2-chloroisonicotinic acid amide (No. 7): 1.39 g (16
, 7 mmol), triethylamine 1,67 g (16,
5 mmol), 2.64 g of 2-chloroisonicotinic acid chloride in a solution of 30 ml of ether kept at 0°C.
(15 mmol) was added dropwise, and the mixture was further stirred at room temperature for 5 hours. After the reaction was completed, it was poured into water and extracted with ethyl acetate.

After washing the organic layer with saturated brine and drying over anhydrous sodium sulfate, the solvent was distilled off, and the resulting crude product was purified by phosphoric gel chromatography to obtain N-(L, 1-
dimethyl-2-propynyl) 2-chloroisonicotinic acid amide 2, 71. g (yield 81.2%) was obtained.

m, p, 98-99°C Reference synthesis example 2゜N-(222-)lifluoroethyl) Synthesis of 2-chloroisonicotinic acid amide (No. 8): 222-i Lifluoroethylamine 1.78 g (17,
97 mmol), triethylamine 1.67 g (16,
2.6 mmol) of 2-chloroisonicotinic acid chloride in a solution of 30 i.
4 g (15 mmol) was added dropwise, and the mixture was further stirred at room temperature for 6 hours.

The reaction solution was poured into water and extracted with ethyl acetate, and the organic layer was washed with saturated brine and dried over sodium sulfate. After distilling off the solvent, the resulting residue was purified by Nori gel chromatography to obtain N-(2,2,2-trifluoroethyl)-2-chloroinnicotinamide 3.03ε (yield 84 .7%).

m, p, 85.5 - 86.5 °C Reference synthesis example 3 ° Synthesis of N-(2,6-dimethylmorpholinomethyl)2-chloroisonicotinic acid amyl' (Nct15) N-(hydroxymethyl) -1.8 g (9.65 mmol) of 2-chloroisonicotinic acid amide in chloroform (
30d) Add 0.9 d (1
2.5 mmol) was added dropwise thereto, followed by heating under reflux for 2.5 hours. After cooling, the solvent and excess thionyl chloride were distilled off under reduced pressure to obtain N-(chloromethyl)-2-chloroisonicotinic acid amide.

Subsequently, 3.5 g of 2,6 dimethylmorpholine (30,4
Into a solution of tetrahydrofuran (60IIf) of
-2-chloroisonicotinic acid amide was added, and the mixture was further stirred at room temperature for 2 hours.

The reaction solution was poured into water and extracted with ethyl acetate, and the organic layer was washed with saturated brine and dried over sodium sulfate. After distilling off the solvent, the resulting residue was purified by licage gel chromatography to obtain 9 g (yield: 69.4%) of N(2, rho-dimethylmorpholinomethyl)-2-chloroisonicotinic acid amide. I got it.

n'8 1. , 5405 Reference Synthesis Example 4 Synthesis of N-(2,3-epoxypropyl)-2-chloroisonicotinic acid amide F' (Nα16) N-allyl-2-
To a solution of 2.8 g (14.2 mmol) of amyl chlorisonicotinic acid F in chloroform (30d) was added 3° Ig (14.4 mmol) of folic acid at room temperature by 80%, and the mixture was further heated at room temperature for 1 hour. Stirred at 50-60°C for 3 hours. After cooling, it was poured into water and extracted with ethyl acetate, and the organic layer was washed with an aqueous sodium bicarbonate solution and dried over anhydrous sodium chloride. After evaporating the solvent, the resulting residue was purified by silica gel chromatography to obtain N-(2,3-epoxypropyl)2-chloroisonicotinic acid amide 1. O
g (yield 33.0%) was obtained.

m, p, 89-9doC Representative examples of the 2-chloroisonicotinic acid amide derivative represented by the general formula (1) are shown in Table 1 along with their physical properties.

Table 1 I Examples of formulations are shown below, but the types and mixing ratios of agricultural chemical adjuvants are not limited to these, and can be used in a wide range. Note that "parts" means parts by weight.

Formulation example 1. Powder 8.2 parts of the compound and 98 parts of clay are mixed and ground to form a powder.

Formulation example 2. A wettable powder is prepared by mixing and pulverizing 16.20 parts of a wettable powder compound, 75 parts of kaolin, 3 parts of higher alcohol sodium sulfate, and 2 parts of sodium ligninsulfonate.

Formulation example 3. After mixing 7.8 parts of the finely ground compound NQ, 24 parts of diatom ±36 parts of hentonaim, 30 parts of talc and 2 parts of disintegrant, 18 parts of water was added, the mixture was evenly moistened, and then extruded through an injection molding machine. After granulating and sizing using a granulator, the mixture is dried to form granules with a powder diameter of 0.6 to IIIm.

Formulation example 4. Dissolve 1 & 21.5 parts of the fine granule compound in 5 parts of methanol and
The mixture was mixed and dropped into 95 parts of granular clay of 250 ml and dried to form fine granules.

Formulation example 5. 5.30 parts of the emulsion compound Na I was dissolved in 52 parts of Kirsin, and a mixture of an alkylphenol ethylene oxide condensate and a carunium alkylhenzenesulfonate (8:
2) Mix and dissolve 18 parts to make an emulsion.

The powder is diluted with water and used as an emulsion.

Next, test examples regarding the effects of the present invention will be shown.

Test example 1. Grape Vine Disease Control Test (Preventive Effect) A hydrating powder and an emulsion of the present invention prepared in the same manner as in Formulation Example 2.5 were diluted to a predetermined concentration and sprayed onto the leaves of potted grapes (diameter: 10 cm). Mildew (Plasmopave) after air drying
Viticola) was inoculated with an aqueous spore suspension and incubated at 20°C.
The seeds were left in an inoculation box at ~22'C and 100% humidity for 2 days, and then placed in a greenhouse (20~30'C) for 7 days, and then the degree of disease onset was investigated.

The results are shown in Table 2.

Table 2 Note) *Incidence level 0: No lesions 1: Lesion area 5% or less 2: 5-20% 3: 20-50% 4: 50% or more **: Control drug TPN 75% permanent agent (Tetra Chlorisophthalonitrile) Product No.: Daconyl Permanent Agent Test Example 2 Grapevine disease control test (therapeutic effect) Potted plants (
Downy mildew (P lasmop) on grape leaves with a diameter of 10 cm
are inoculated with a 7' suspension of aqueous spores of A. viLicola) and placed in an inoculation box at 20°C to 22°C and 100% humidity.
After standing for a day, the wettable powder and emulsion of the present invention prepared in the same manner as Formulation Example 2.5 were diluted to a predetermined concentration and sprayed. Furthermore, after being left in a greenhouse (20'C to 30'C) for 7 days, the degree of disease onset was investigated.

The results are shown in Table 3.

Table 3 note) Degree of onset No disease onset Lesion area 5% or less Lesion area: 5-20% 20-50% 50% or more control drug Metalaxyl 10-man section mixing rule (Product name Ridomil MZ permanent agent) (10%+55%)

Claims (1)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [I] [In the formula, R is a lower alkyl group that may be substituted with a halogen atom, an allyl group that may be substituted with a halogen atom, C_3 ~C_5 alkynyl group, group -CH_2S(
O)_nR', thiocyanatomethyl group, azolylmethyl group, triazolylmethyl group, morpholinomethyl group, 2,
6-dimethylmorpholinomethyl group, 2,3-epoxypropyl group, pyridylmethyl group, 2-chloroisonicotinylaminomethyl group, or a benzyl group optionally substituted with a halogen atom, where R' is a lower It represents an alkyl group, and n represents 0 or an integer of 1-2. An agent for controlling plant diseases caused by algae and fungi, characterized by containing a 2-chloroisonicotinic acid amide derivative represented by the following as an active ingredient.