JPS5817743B2 - Method for producing o-trifluoromethyl-m'-isopropoxybenzoic acid anilide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a fluoromethyl-isopropoxybenzoic acid anilide having the structure =tg): o-)') useful as a rice sheath blight control agent.

The compound produced by the production method of the present invention is a new compound having a melting point of 95 to 97°C, and can be synthesized by the method described below.

It consists of reacting 0-trifluoromethylbenzoic acid chloride and m-impropoxyaniline in the presence of a base.

This reaction route is diagrammatically shown as follows.

Examples of inert solvents used in the production method of the present invention include aromatic hydrocarbons such as benzene, toluene, and xylene; chlorinated alkanes such as dichloromethane, chloroform, and carbon tetrachloride; and ketones such as acetone, methyl ethyl ketone, and cyclohexanone. ethers such as ether, dioxane, and tetrahydrofuran; and lower fatty acids such as acetic acid, among which it is advantageous to use benzene and tetrahydrofuran.

Suitable bases that can be used in the present invention include organic amines such as triethylamine and pyridine, and inorganic bases such as potassium carbonate and sodium carbonate.

The reaction molar ratio is o-)') 1 mole of fluoromethylbenzoyl chloride to 1 m-isopropoxyaniline.
The base can be suitably selected from the range of 1 to 15 moles, but is not limited thereto.

The reaction temperature is appropriately selected from -5°C to the boiling point of the solvent.

Conventionally, organic arsenic agents have been used as agents for controlling rice sheath blight, but for reasons of environmental pollution, residual toxicity, and other reasons, alternatives to these agents are eagerly desired.

Antibiotics such as polyoxin and validamycin have been developed to meet this demand, but they have disadvantages such as being extremely expensive and having insufficient or unstable effects.

The present inventors have been conducting research on a new rice sheath blight agent under these circumstances, and have discovered that the compound produced by the production method of the present invention has a very specific effect on rice sheath blight.

Conventional rice seed blight control agents were effective only in foliage treatment, but the compound produced by the production method of the present invention surprisingly has an excellent control effect in both foliage treatment and water surface treatment.

Furthermore, the compound produced by the production method of the present invention has superior effects when compared with known compounds having a similar structure, and can be said to have an inventive step.

When the compound prepared by the production method of the present invention is used as a rice sheath blight control agent, it is generally diluted with an inert diluent and formulated into an appropriate form using a conventional method for agricultural chemical formulations.

That is, the compound produced by the production method of the present invention is dissolved, dispersed, mixed, impregnated, or adsorbed in a suitable inert carrier, with the addition of auxiliary agents if desired, to form an appropriate dosage form, such as a solution,
It may be formulated into emulsions, aquariums, powders, granules, pastes, etc.

At this time, it is of course possible to add adhesives, wetting agents, pigments, etc. to ensure or increase the effect.

The inert carrier may be either solid or liquid; in the case of the former, soybean flour, wheat flour, tobacco stem powder, walnut shell powder, mineral powder, wood flour, bark powder, bran, cellulose powder, and plant extracts. Plant powders such as residues after extraction; Textile products such as paper, cardboard, and furugiri; Pulverized synthetic resins; Clays (e.g. kaolin, bentonite, acid clay), talcs (e.g. talc, pyrophyllite), silicas ( Inorganic mineral powders such as diatomaceous earth, crushed sand, mica, synthetic silicates, synthetic highly dispersed silicic acid), sulfur powder, activated carbon, pumice, sand, etc. Chemicals such as ammonium sulfate, ammonium phosphorus, ammonium nitrate, urea, ammonium chloride, etc. Examples include fertilizers and other soluble substances such as mirabilite and sugars.

Materials that can serve as liquid carriers are selected from those that themselves have solvent ability, as well as those that have solvent ability but can disperse the active ingredient compound with the aid of an auxiliary agent, such as the following: These may be used alone or in the form of a mixture of two or more.

Water, alcohols (e.g. evaporative methyl alcohol, ethyl alcohol, ethylene glycol), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. ethyl ether, dioxane, tetrahydrofuran,
cellosolve), aliphatic hydrocarbons (e.g. gasoline, kerosene), aromatic hydrocarbons (e.g. echandzene, toluene, xylene, solvent naphtha, methylnaphthalene)
, halogenated hydrocarbons (e.g. dichloroethane, chlorinated benzene, carbon tetrachloride), acid amides (e.g. dimethylformamide, dimethylacetamide), esters (e.g. ethyl acetate), nitriles (e.g. acetonitrile), dimethyl Sulfoxide etc.

Examples of surfactants include, but are not limited to, the following:

These may be used alone or in a mixture of two or more: polyoxyethylene alkylaryl ether,
Polyoxyethylene zorbitan monolaure-1-,
Alkyl aryl sorbitan monolaurate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, lignin sulfonate, higher alcohol sulfate ester salt.

Further, examples of adhesives and dispersants include, but are not limited to, the following.

Casein, gelatin, starch, alginic acid, CMC, gum arabic, agar, polyvinyl alcohol, pine oil, sugar oil, bentonite, lignin, sulfite waste liquid.

The blending ratio of the active ingredient can be adjusted as required.When preparing powder or granules, it is usually 0.5 to 20% (parts by weight);
When used as an emulsion or an aqueous phase agent, the appropriate amount is 10 to 50% (parts by weight).

The composition containing the compound produced by the production method of the present invention as an active ingredient can be used as it is or in the form of diluting or suspending it with water etc. to prevent or treat rice sheath blight. Apply an effective amount to the crop or the environment containing it.

That is, it includes an embodiment in which the complement to be protected is applied prophylactically or therapeutically directly to the above-ground part of the complement, or via paddy water or soil.

The amount of the composition containing the compound produced by the production method of the present invention as an active ingredient varies depending on various factors, such as the degree of damage caused by the target disease, tendency of occurrence, weather, environmental conditions, dosage form, etc.

For example, when ultimately used in a liquid form such as an emulsion or a wettable powder, the final concentration of the active ingredient is generally 100 ppm.
(weight) or more.

In powders and granules, the active ingredient is 6 per 10 ares.
It is practical to use it at a ratio of 0 to 600 g, but the ratio is not limited to this.

In addition, the composition containing the compound produced by the production method of the present invention as an active ingredient may be used in a mixed composition or in combination with one of other similarly used pesticides, fertilizers, plant nutrients, etc. in the scene where it is applied. You can also do it.

For example, when controlling rice sheath blight with a composition containing the compound produced by the production method of the present invention as an active ingredient, a pesticide (or fungicide in some cases) for a rice pest that occurs at the same time as the disease outbreak is mixed. It can also be used as a pest control agent for various purposes.

Typical pesticides used for this purpose include:

For example, bactericidal agents include antibiotics such as plasticidin S and kasugamycin, 0,0-diisopropyl S-benzylthiophosphate, 0-ethyl 5-8-diphenyl dithiophosphate, and 4,5,6,7-titrachlorphthalide. , diisopropyl 1,3-dithiolane-
2-Synthetic fungicides such as indene malonate.

Insecticides include organophosphorus insecticides such as fenitrothion, EPN, diazinon, marathon, and dipterex, and carbamate insecticides such as ■-naphthyl N-methyl carbamate, m-tolyl N-methyl carbamate, and 2-see 7-butylphenyl N-methyl carbamate. Insecticides, formamidine insecticides such as chlorzenamidine, and others such as cartap.

Next, examples of the present invention will be shown.

In addition, parts indicate parts by weight.

Example 1 Synthesis of o-trifluoromethyl-isopropoxybenzoic acid anilide m-isopropoxyanilide 71.5P (0.01 mol)
, into a solution of 1.21 (0,011 mol) of triethylamine in tetrahydrofuran under cooling in ice water, o -)
2.31 (0,011 moles) of refluorobenzoic acid chloride are slowly added.

After stirring at room temperature for 2 hours, triethylamine hydrochloride was removed and the solvent was distilled off under reduced pressure.

If the remaining residue is recrystallized from 0-hexane, the melting point is 95-97.
The target product 2.1' (yield 91%) is obtained at .

Example 2 o-)') Synthesis of fluoromethyl-goyne propoxybenzoic acid anilide m--Impropoxyaniline 1°El' (0,01 mol) Hiricine 0.9P (0,011 mol) was dissolved in benzene, While cooling in ice water, fluorobenzoic acid chloride 2.3P (0,011 mol) is slowly added dropwise.

After stirring at room temperature for 2 hours, pyridine hydrochloride was removed and Example 1
If you do the same operation as above, you will get 28.82 objects.

Melting point: 95-97°C Yield: 90% Next, the usefulness of the compound produced by the production method of the present invention will be demonstrated through test examples.

Test Example 1 Control effect test on rice sheath blight (pot test) A prescribed concentration of chemicals was applied to paddy rice grown in a greenhouse (variety Nijukoku, plant height 20 CrrL) using a spray gun (1,51 y/cr; t). Spray on the turntable at a rate of 10m1/pot,
One day and five days later, the rice sheath blight fungus cultured in rice straw is inoculated onto the plant base.

The length of the developed lesions was measured 5 and 10 days after inoculation, and the control value per stem was calculated.

The results are shown in Table 1 below.

Test Example 2 Control effect on rice sheath blight by water surface application Plant height approximately 20C
A predetermined amount of 50 ml of the diluted drug solution is applied to the water surface of an 8.5 cm pot containing rice grown in rn.

After 5 days in the greenhouse, 6-7
The rice sheath blight fungus cultured for one day is inoculated at the base of rice plants.

The lesion length of sheath blight that developed 5 days after inoculation was investigated, and the control value was calculated using the calculation method of Example 1.

The results are shown in Table 2 below.

Test Example 3 Effect test for preventing invasion of rice sheath blight bacteria (preventive effect) A 1% hydrating powder containing the compound of the present invention as an active ingredient was sprayed at a predetermined concentration on rice (variety: Nipponbare) at the 5th to 6th leaf stage. Spread.

After 11 days, artificial rainfall of 10 mm and 17 minutes was applied, and after further discharge in the greenhouse for 1 day, the plant was inoculated with rice sheath blight fungus cultured in a rice husk/bran medium and stored in an inoculation box at 30°C for 1 day.

Afterwards, the disease was allowed to develop in a plastic case kept at high temperature (28℃) and high humidity (humidity 90% or more). Seven days after inoculation, the lesion length of rice sheath blight was investigated, and control was achieved using the calculation method in Test Example 1. The value was calculated.

The results are shown in Table 3.

Test example 4 Rice sheath blight progression prevention effect test (therapeutic effect test)
Rice sheath blight bacteria cultured in wheat bran medium was inoculated into rice plants (quality: Nipponbare) at the 5th to 6th leaf stage, stored in an inoculation box at 30°C for 1 day, and then placed in a high temperature and humid environment as in Test Example 3. They were placed in a plastic case and allowed to form lesions.

A 1% hydrating powder containing the compound according to the present invention as an active ingredient was sprayed onto this as a spray solution at a predetermined temperature.

After that, the disease was stored in the above-mentioned plastic cage to promote the onset of the disease, and the newly developed lesion length was investigated 6 days after treatment. Test Example 1
The control value was calculated in the same manner as above.

In addition, in order to examine rain resistance, artificial rain was applied according to Test Example 3 one day after the treatment.

The results are shown in Table 4.

Test Example 5 Preventive effect (residual effect) test on rice sheath blight A test was conducted according to Test Example 1, and the length of the lesion developed 18 days after inoculation was measured, and the control value was calculated in the same manner as Test Example 1. .

Claims (1)

[Claims] 1. It is characterized by reacting o-fluoromethylbenzoic acid chloride represented by the structural formula (II'): with m-isopropoxyaniline represented by the structural formula: Structure (1): A method for producing 0-)lifluoromethyl-isopropoxybenzoic acid anilide.