JPS5818375A - Thiophenecarbonanilide derivative and fungicide containing the same - Google Patents

Abstract

NEW MATERIAL:The N-methyl-2-thiophenecarbonanilide derivative of formulaI(R1 is lower alkyl; R2 is H, lower alkyl or lower alkoxy). EXAMPLE:N-Methyl-4'-methoxy-2-thiophenecarbonanilide. USE:A fungicide exhibiting remarkably high activity against phytopathogens especially of downey mildew of cucumber, and having low toxicity and high safety. PROCESS:The compound of formulaIcan be prepared either by reactin the compound of formula II (X is halogen) with the compound of formula III preferably in a solvent, in the presence of a base, or by reacting the compound of formula III preferably in a solvent, in the presence of a base, or by reacting the compound of formula IV with the compound of formula V preferably in a solvent, in the presence of an alcoholate or an alkali hydride, or by reacting the compound of formula VI with the compound of formula VII preferably in a solvent, in the presence of a base.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (wherein R5 represents a lower alkyl group, and +R represents a hydrogen atom, a lower alkyl group, or a lower alkoxy group).

) and a fungicide containing the same as an active ingredient.

Protecting crops from diseases helps stabilize yields.

This is extremely important from the standpoint of maintaining crop quality or ensuring increased yield. Conventionally, many chemicals such as organometallic compounds and organic chlorine-based chemicals have been used to control plant diseases. Many of them have drawbacks such as contamination.

In addition, some of these drugs may reduce their control effects due to the drug being applied to the plant body or due to the appearance of resistant bacteria.

Due to this unique situation, it is highly safe.

There is a strong demand for a fungicide that also has a stable pesticidal effect. The inventors synthesized a variety of compounds and examined their control effects against Yuzumo fungi.

The N-methyl-2-thiophanecarphonanilide derivative represented by the general formula (1) exhibits extremely excellent activity against plant diseases yJ fungi that cause great damage to crops. All headings.

This completes the present invention.

The uninvented compound has features that are not found in conventional drugs for treating kidney disease. That is, the uninvented compound has both a preventive effect and a therapeutic effect against cucumber diseases, and also has excellent permeability through the roots, and exhibits a very stable control effect. Historically, it has extremely low toxicity to warm-blooded animals and fish, and has very low residual levels in crops and the environment, making it excellent in terms of safety.

=3- Examples of the uninvented compounds represented by the general formula (1) are shown in Table 1. Compound numbers are referenced in the following description.

R.

The compound of general formula CI) in Table 1 is a new compound that has not been described in any literature, and can be produced by the following synthetic method. R1 and B in the formula,
has the above-mentioned meaning, and X represents a halogen atom.The reaction in the fi+ method is preferably carried out in a solvent in the presence of a base. Examples of bath agents include 9, ketone thread solvents such as acetone and methyl ethyl ketone, halogenated hydrocarbons, and ethers.
Petroleum solvents and aromatic hydrocarbon solvents such as benzene, toluene, xylene, and water are used. Examples of the base include bases commonly used as dehydrohalogenating agents, such as sodium hydrogen carbonate, potassium carbonate, and pyridine.

Triethylamine, dimethylaniline, sodium hydroxide, potassium hydroxide, etc. are used. Free VC can be selected for the reaction within the range of o'o to the boiling point of the solvent, but in general, slight heating is sufficient to quickly complete the reaction.

(The reaction of process 21 is preferably carried out in a solvent 9 such as benzene, toluene, xylene, dimethylformamide, dimethylacetamide, dioxane, etc. in the presence of an alcoholade or an alkali hydride. Alcoholades include 2 such as sodium methylate, Sodium ethylate, potassium butylade, etc. are used as alkali hydrides.

For example, sodium hydride may be used. The reaction temperature 1 may range from 0°C to the boiling point of the solvent, but may range from room temperature to 10°C.
A range of 0°C is preferred.

The reaction in method (3) is also preferably carried out in a solvent in the presence of a base. Examples of solvents include alcohols such as methanol and ethanol, and acetone.

Ketone I' such as methyl ethyl ketone is mixed with solvents, halokenated hydrocarbons, ethers 9 petroleum solvents, amide thread solvents such as dimethylformamide and dimethylacetamide, dimethyl sulfoxide and aromatic hydrocarbon solvents such as benzene, toluene and xylene, and water. used. As the base (in addition to the same ones as in method 1+, sodium methylate, sodium ethylate, potassium butylade, hydrogen ib sodium, etc. can also be used). The reaction temperature can be freely selected within the range of 0°C to the boiling point of the solvent, but in general, a temperature range of room temperature to 100°C is preferred in order to quickly complete the reaction.

Next, a detailed explanation will be given by giving a synthesis example.

Synthesis example 1. Synthesis of N-methyl 41-methoxy-2-thiophenecarbonanilide (compound 1) 13.7F (0.1 mol) of 4-methoxyN-methylaniline and 8.4r (0.1 mol) of sodium bicarbonate were dissolved in 150 ml of acetone. 13.1 f (0.1 mol) of 2-child offenecarboxylic acid chloride was added dropwise to the solution while stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours to carry out the reaction δ.

The reaction mixture is then poured into water and crystals precipitate out. After removing P and drying, re-crystallization with a benzene-hexane mixed solvent yields N-methyl 4'-methoxy-2-naophenecarbonani') to 2 as colorless needle crystals with a melting point of 101-102°C t o t is obtained. The Ill rate is 908chi.

Synthesis Example 2 Synthesis of N-methyl 4'-methquin-2'-methyl-2-thio7ene carbonanilide (compound 4) 4-methoxy-2I-methyl-2-thio7ene carbonanilide conductor 12.4 t (0.05 mol) was dissolved in 100 az of dimethylacetamide, added with 1,2 F sodium hydroxide (0.05 mol), and stirred at room temperature for 60 minutes. Methyl iodide 7,8F (0,055 mol) was added to this and the mixture was stirred at room temperature for 2 hours to complete the reaction. When the reaction mixture is poured into cold water, crystals precipitate out. If this is dried several times and then recrystallized with a benzene-hexane mixed solvent, N-methyl 4〆-methoxy 2'-methyl-2-offene carbonani 'J)'' 12. o y is obtained.

Combined G Example 5. Synthesis of N-methyl 41-ethoxy-2-thio7enecarbonanilide (Compound 2) 117 t (0.05 mol) of N-methyl 4'-hydroxy-2-thousophenecarbonanilide, 7 potassium carbonate
, 6 t (0,055 mol) and ethyl iodide 8.6
t (0,055 mol) was reacted in 100μ of ethanol under heating and reflux [stirring for 5 hours]. When the reaction mixture is allowed to cool and then poured into cold water, crystals are precipitated. If this is dried several times and then recrystallized with a benzene-hexane mixed solvent, N-methyl 4'-ethky8=cy-2-thiophenecarbonanilide 12.2F is obtained as colorless frism-like crystals with a melting point of 108 to 109 υ. can get. The yield is 961.

Other compounds can also be synthesized in the same manner as in Synthesis Examples 1 to 3.

The fungicide of the present invention may use one or more of the compounds of the present invention represented by the general formula (υ) as is, but usually,
When formulating agrochemicals, commonly used diluents, surfactants, dispersants, adjuvants, etc. are blended into formulations, such as powders, wettable powders, and emulsions, by conventional methods.

It is used after being formulated into fine granules or granules. Suitable diluents include, for example, talc and bentonite.

Clay, kaolin, diatomaceous earth, white carbon.

Examples include solid diluents such as vermikeyite, slaked lime, silica sand, ammonium sulfate, and urea, and liquid diluents such as inpropyl alcohol, xylene, and cyclohexanone etherselunlube. Examples of surfactants and dispersants include alcohol sulfate esters, alkylaryl sulfonates, lignin sulfonates, phoroxyethylene glycol ethers, polyoxyethylene alkyl ethers, polyoxyethylene turbitan monoalkylates, etc. can be mentioned. Examples of adjuvants include carboxydimethylcellulose, polyethylene glycol, gum arabic, etc. The preparations described above may be diluted with an appropriate concentration of 8 or 8 times or applied in an hourly manner.

The uninvented fungicide can be used in combination with other fungicides, plant growth control 11rl fertilizer, etc., or in combination.

The use of the fungicide of the present invention is 100 to 5 per 10 are.
It is 00t. For liquid preparations, the concentration of the active ingredient should be reduced by 1
It is preferable to use it after diluting it to 00 to 100 Q ppm.

Next, specific examples of VC will be explained using formulation examples. The numbers in the formulation examples indicate weight.

Formulation Example 1 (Powder) Compound (2) 2, diatomaceous earth 5, and clay 964 are uniformly mixed and ground to obtain a powder.

Formulation Example 2 (Wettable powder) A compound (It 5 Ds, 45 parts of diatomaceous earth, 2% of sodium dinaphthylmethane disulfonate, and 3 parts of sodium lignin sulfonate is uniformly mixed and pulverized to prepare a wettable powder.

Formulation Example 3 (Emulsion) Compound f4 130%, cyclohexane 20%, polyoxyethylene alkyl allyl ether 11.

4% calcium alkylbenzene sulfonate and 35 parts of hythylcellosolve are uniformly mixed (commonly understood as an emulsion).

Formulation Example 4 (Granules) Compound (315'l, sodium salt of lauryl alcohol sulfate 2nd part, sodium lignin sulfonate 5%, carboxymethyl cellulose 2nd part (J, 1st part)
Mix and pulverize Le-86To uniformly. Add 2 ounces of water to this mixture
The mixture is kneaded and processed into granules of 14 to 32 mm using an extrusion type granulator, and then dried to form granules.

Next, the effects of the compounds of the present invention on cucumber root disease will be explained using test examples.

Test Example 1 (Preventive effect against cucumbers and diseases) - A square pot with 9 sides [15 cucumber plants per pot]
A wettable powder prepared according to Formulation Example 2 was diluted with water to a predetermined concentration when Sagami Half Day) was in the Futaba stage.

Using a spray gun, 3 Q me was sprayed per 2 pots.

After the spray solution has air-dried, a conidial suspension of Kuribe and the disease fungus (spore count I
11tI! Jt fog access building was built. After keeping in a trench room at 21° C. for 24 hours, they were transferred to a greenhouse, and 8 days after planting, they were investigated based on the following criteria.

Investigation standard disease index 0...No lesions 1...Infected area is less than μ of leaf area2...No/u% or more but less than 3...
〃 ゑTable 2 Note) Control drug: Daconil (tetrachloroisophthalonitrile) Test Example 2 (Curetic effect on cucumber and disease) - 15 uncultivated cucumbers per pot in a square pot with side 91 (quantity: Sagami) half a day), but at the bifoliate stage, a conidial suspension of cucumber and the disease fungus (spore count I x 10'/-
j) was inoculated by spraying at 2 me per pot and kept in a groove chamber of 21"0 for 24 hours. Thereafter, a wettable powder prepared according to VC Formulation Example 2 was diluted with water to a predetermined concentration, and sprayed using spray gun 1. Sprayed 30M per 2 pots.After spraying, place in the greenhouse.
Eight days after the electrode contact, the same investigation as in Test Example 1 was conducted. The results are shown in Table 6, and the control drug was the same as Test Example 1vc.

Table 3 Test Example 3 (Cucumber and disease control effect due to osmotic transfer from roots) Fill a square pot with 91 cm on each side with river sand, add 10 cucumber seeds (variety: Sagami Gyushiro) per pot, When the concentration is reached, the wettable powder prepared according to Formulation Example 2 is diluted with water to a predetermined concentration [8
He poured out 24 cups of sake per bowl. After that, it was placed in a greenhouse for 3 days, and the cucumber and conidia suspension (spore number i x
02 in which 2ν of i o”ke/mg) was sprayed per pot.
After being kept in a greenhouse at 1℃ for 24 hours? After 8 days of inoculation, the cells were transferred to a filtrate and investigated in the same manner as in Test Example 1. The results are shown in Table 4.

The control mulberry agent was based on Test Example 1.

Table 4 Patented gentleman Kumiai Chemical Industry Co., Ltd. Director and President Tsuki Nozobe 11ter 687-

Claims (1)

[Scope of Claims] fi+ N-methyl-2-thiophenecarbonanilide represented by the general formula (wherein R represents a lower alkyl group, and R1 represents a hydrogen atom, a lower alkyl group, or a lower alkoxy group) derivative. (2) An N-methyl-2-thiophenecarbonanilide derivative represented by the general formula (wherein R1 represents a lower alkyl group, and R1 represents a hydrogen atom, a lower alkyl group, or a lower alkoxy group) as an active ingredient. A disinfectant characterized by containing.