JPS5984892A - Thionophosphoric acid amide derivative, its preparation and plant blight controlling agent containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R1 is mono- or di-(lower alkoxy)- substituted lower alkyl; R2 is lower alkyl]. EXAMPLE:O-Methyl O-(4,5-methylenedioxy-2-nitrophenyl) N-(1-methoxymethyl- propyl) phosphoroamidothioate. USE:A plant blight controlling agent especially effective to the blight caused by phycomycetes, e.g. downy mildew, blight, etc. It exhibits not only preventive effect but also remedying effect and controlling effect by systemic migration. PROCESS:The thionophosphoric acid amide chloride of formula II [e.g., O- methyl N-(1-methoxymethylpropyl) thionophosphoric acid amide chloride] is condensed with 4,5-methylenedioxy-2-nitrophenol in a solvent such as acetonitrile using an acid acceptor such as potassium carbonate.

Description

[Detailed Description of the Invention] The present invention relates to general Ttrt] In formula 1, the river is! It represents a trino- or di-lower alkoxy-substituted lower alkyl group, and auxiliary represents a lower alkyl group. ] The present invention relates to a thionolinic acid amide derivative represented by (hereinafter referred to as the compound of the present invention), a method for producing the same, and a plant disease control agent containing the same as an active ingredient.

Conventionally, many fungicides have been used to control plant diseases caused by algal fungi such as downy mildew and late blight, but all of them have a preventive effect, and once the pathogen has invaded the plant body, the fungicide is Even when applied, sufficient control could not be expected.

The inventors have learned that the compound of the present invention represented by the above general formula [■] is effective against many plant diseases, but is particularly effective against plant diseases caused by algae and fungi such as downy mildew and late blight. It was discovered that it not only has a preventive effect, but also a curing effect and a systemic and migratory control effect.

Plant diseases related to algae and fungi include cane cabbage and radish root disease (1'eronospora bra*5ioae).
), spinach downy mildew (Peronospora
II pinaciae), tobacco downy mildew (Peron
osparn Labacina), PIIeudoperonospora cuben
sis), Grape field rot (Plasrrtopar)
a viticola), mildew (1'
lasmopara n1vea), apple, strawberry,
Late blight of ginseng (PI + yt opbt amount 10 racactornt), gray late blight of tomato and cucumber (Phytoph + bora caps ici)
), pineapple blight (Pbytopbtho)
ra cinnamomi), potatoes, tomatoes,
Eggplant o> Late blight (yen + ytophthora 1nfes
tans), tobacco, faba beans, and leek blight (1'by
tophtboranicotianae var n
1cotianae), cucumber seedling damping-off (Pythi
um apb, anidermatum), spinach damping-off (Pythi+nn sp, ), wheat brown snow rot (summer'yll+iumsp, ), tobacco 1'
tW I”T, Pythium debarya
num), Dice CI) I'ytl+in+n Ro
t (Pytl+ium aphanidermatu
mP, +leba ryan++m, I'i
rregul a r e, l', myr
io tyl +, +m.

P, u l t imum '1, etc.

The compound of the present invention has the general formula: [In the formula, R1 and R2 have the same meanings as above. ] It can be produced by condensing thionolinic acid amide chloride shown in I] and 4°5-methylenedioxy-2-ditrophenol in a solvent using a deoxidizing agent.

As a solvent, aromatic hydrocarbons such as benzene, toluene, xylene, etc., ketones such as acetone, methyl isobutyl ketone, acetonitrile, dibutylfornoamide, etc. are used as a solvent, and as a deoxidizing agent, potassium carbonate, sodium hydroxide, etc. Examples include inorganic bases and organic bases such as pyridine and triethylamine.

The reaction temperature and reaction time may vary depending on the type of solvent or deoxidizing agent, but are usually from room temperature to about 120°C.
It lasts from one hour to several hours.

Further, the compound of the present invention has the general formula [In] [wherein the auxiliary has the same bitterness as described above]. ]Thionophosphoric acid chloride represented by the general formula [IV]RI NO3[
:IV] [In the formula, 1 has the same meaning as above] Produced by condensing the amine represented by 1 (1 has the same meaning as above) in a solvent using a deoxidizing agent
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Examples of solvents include aromatic hydrocarbons such as benzene, toluene, and carbon, ethers such as diethyl ether and diisopropyl needle, and halogenated hydrocarbons such as dichloromethane and chloroborm.As deoxidizers, , potassium carbonate, inorganic bases such as sulfur hydroxide and sulfur hydroxide, and organic bases such as pyridine, 1-redilium hydroxide, N,N-diethylaniline, etc. can be removed.

The reaction temperature and reaction time vary depending on the solvent and deoxidizing agent, and usually 0 = 50°C.
1:00 + 70 to several hours.

Next, production examples of the compounds of the present invention will be shown.

Production Example 1 [Production of the compound of the present invention (lO)] 4.5
- Noji 1.・Dioxy-2-nitrophenol 1
．． 88 g (0.01 mol) and ()-methyIt/N--(
1-Methoxymethylpropyl)thionolamide chloride 2.821I (0.01 mol) was added to the acetonide of ROme, and then anhydrous potassium carbonate powder 1.49 (0.0
1 mol) was added thereto and stirred at 50 to 70°C for 5 hours.

Inorganic salts were filtered off, and acetonitrile was distilled off.

The residue was dissolved in toluene, washed with a dilute aqueous acid solution, a dilute aqueous alkali solution and water, and then dried over anhydrous magnesium sulfate. After filtering off the desiccant, toluene was distilled off, and the residue was purified by silica gel column chromatography to obtain O-methyl 0-(4.5-methylenedioxy-2-nitrophenyl) N-(1-methoxymethylpropyl). ) Bosphophoramide thioer-1-2.621 was obtained. (Yield 69.8
9i, ■□) 1.5505 1 Production Example 2 [Production of Compound (1) of the Present Invention] -Ethyl 0-(4.5-methylenedioxy-2-nitrophenyl) Thionophosphate ester chloride 8.26·f (0.0 mol) was dissolved in 50-l luene.

0.89 g (0.01 mol) of 1-methoxymethylethylamine was added dropwise to the solution of the starch seeds (while maintaining the temperature at 1° C.). After the dropwise addition, the mixture was stirred at room temperature for 8 hours.

This was washed with a dilute aqueous acid solution and dried with anhydrous magnesium sulfate. After separating the desiccant, distill off the toluene)
-Ethyl 0-(4.5-methylenedioxy-2-nitrophenyl) N-(1-methoxymethylethyl) phosphoroamide thioether-1-8.62M5- was obtained.

27,5 (Yield 9 G. 0 9iF n□, 1.55
90) Compounds of the present invention obtained by similar operations are summarized in Table 1. When the thionolinic acid 5-do-rus conductor represented by the above general formula t+ is used as an active ingredient of a plant disease control agent, It can be used as is without adding any other ingredients, or it can be mixed with solid phase, RF (body phase, surfactant and other formulation auxiliaries) to form powders, granules, and hydrated formulations. It may be used in formulations such as tablets, emulsions, fine granules, flowables, and aerosols.

The business card agent contains a T1 nolinic acid amide derivative represented by the above general formula 1 as a self-effective ingredient in a weight ratio of 0.1 to 99.9.
%, preferably 2.0 to 80.096%.

The 41 solids include vegetable carriers (e.g., tobacco, corn, wheat flour, soybean flour, Kuru F, W& flour, wood flour, cellulose powder), synthetic resins (e.g., vinyl chloride, polystyrene, polyethylene, petroleum). clays such as tapalgas clay, kaolin clay, bentonite, acid clay, sericite, vermiculite, and phyllite, talc, anhydrite, diatom, zeolite, pumice, silica sand, activated carbon, powai (~ carbon, front right), fertilizers (e.g. ammonium sulfate, ammonium phosphorus, ammonium chloride, urea, or these chemical fertilizers), etc.

Liquid J [1 substance includes aliphatic and alicyclic hydrocarbons (such as kerosene, machine oil, mioral oil, etc.)
11 naphtha), aromatic δ hydrocarbons (for example: ■Si 1/
Alcohols (methyl alcohol, blue alcohol, polyethylene glycol, polypropylene glycol), ethers (such as dioxane and cellosolve), alcohols (for example, dioxane, cellosolve), For example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone),
halogenated hydrocarbons (e.g. dichloroethane, trichloroethane, carbon tetrachloride), esters, nitriles, amides and other solvents (e.g. dioctyl phthalate, tricresyl phosphate, lower setonitrile, dimethylpolamide, dimethyl sulfoxide, nonylphenol,
These include fats and oils (M) and water.

Formulation auxiliaries, such as surfactants, wetting agents, fixing agents,
Dispersants, thickeners, and stabilizers include alkyl sulfonates,
Sulfuric ester salts such as sulfosuccinates, alkylaryl sulfodates, ester H salts, alkyl sulfates, ether sulfates, alkylaryl ether sulfates, phosphoric ester salts such as alkylaryl needle phosphates, formalin condensation Anionic surfactants such as sulfonates and other carboxylates, ethers such as alkyl and alkylaryl polyoxyethylene ethers and block polymers based on polyoxypropylene, polyoxyethylene ethers of sorbitan esters,
Nonionic surfactants such as polyolefin diethylene phenylphenol polymers, ether esters such as esters of sorbitol polyoxyethylene ether, polyoxyethyl l/one fatty acid esters, esters such as glycerin esters, sorbitan esters, and sicosugar esters, casein , gelatin, starch, CMC (carboxydimethylcellulose), PVA (polyvinyl alcohol), gum arabic, alginic acid, molasses, agar, and other water-soluble polymers, calcium geninsulfonate, sulfonate ligninsulfonate, lithium, stearic acid, Various fatty acids such as leic acid, palmitic acid, pine oil, 1-l oil, pine oil, soybean oil or their nistyl derivatives, liquid paraffin, epoxy Yuyu, 'I''CP (tricresyl phosphate), PA, P (
(isopropyl acid phosphate), bentonite These preparations can be applied as is, diluted with water, mixed with soil conditioners, etc., or applied simultaneously without mixing.

Examples of formulations are shown below. In addition, the compound number is indicated by the compound number in the WS1 table.

Formulation Example 1 Powder 2 parts by weight of Compound (1B), kaolin clay 88TIt Kakibe, and 10 parts by weight of talc are thoroughly ground and mixed to obtain a 2% powder.

Formulation Example 2 Hydrating agent compound (1) 8 parts (1 mm part, 45 parts by weight of diatoms, 20 parts by weight of poite carbon, 8 parts by weight of wetting agent (sodium lauryl sulfate) and 2 parts of dispersing agent (calcium sulfonate) By thoroughly grinding and mixing the heavy parts, a wettable powder of 8096 is obtained.

Formulation Example 3 Hydrating agent compound (r+) fs 0 parts by weight, 45 parts by weight on diatoms,
Moisturizing agent (calcium albenzene sulfonate lh)
2. 5 parts [11 parts and 2.5 parts of dispersant (calcium lignin sulfonate)] If Ichikawabe is thoroughly ground and mixed, it will be 50 parts.
9B hydrating agent is obtained.

Formulation Example 4 Emulsion A 20% emulsion is obtained by mixing 20 parts by weight of compound (17), 60 parts by weight of xylene, and 2011 tm parts of an emulsifier (polyoxyethylene phenylphenol polymer).

The application rate of the agent for controlling plant diseases caused by algae and fungi of the present invention is usually 1 to 200 f per 10 are, and the application concentration is a wettable powder, emulsion, etc. When applied diluted with water, 0.001~0, 2! It is X. In the case of powders, granules, etc., they are usually applied as is without any dilution. These application amounts and concentrations vary depending on the type of formulation, and also vary depending on the time of application, location of application, method of application, type of disease, severity of disease, and other conditions, and also vary depending on the type of crop. Furthermore, it may be increased or decreased [7] without being limited to the above range.

Next, the control effect on plant diseases caused by algae and fungi will be shown using test examples.Among the test compounds, the thionolamide rust conductor represented by the general formula 1゛■] was used as a comparative control with the compound number in Table 1. The compounds used in the preparation are shown in Table 2.

Table 2 I (Test Example 1 Cucumber and disease control (preventive effect) test Plastic bowls) Fill with sandy loam soil and sow cucumbers (quality, semi-white). Plant this in a greenhouse for 140 minutes. A water diluted solution of the test compound prepared as an emulsion or a wettable powder according to the above formulation example was applied to young cucumbers (1°a), which had been intercultivated and developed cotyledons, until the drug Yf (J: sea urchin) adhered sufficiently to the leaf surface. Sprayed on foliage.

Seedlings grown in a greenhouse for 5 days after leaf spraying were infected with cumacribe and disease fA (Pseudoperoru+5pora c
ubensis') was inoculated by spraying with a conidial suspension.

This was placed in a humid condition F at 20°C for 8 days, and then at 20°C.
After cultivation under fluorescent lighting for 8 days to induce disease, the disease state was observed.

'yPr disease severity was calculated by the method described in F17.

1-that is, 0.0.5 depending on the degree of appearance of lesions on the leaves
．． It was classified into indexes of 1.2.4 and the degree of onset was calculated using the following formula d, 1.

(Incidence index) (Infection state) θ　　　No bacterial flora or lesions are observed on the leaf surface.

0.5 Bacterial flora on less than 5% of the leaf area on the surface or 1? i spots are observed.

1 7) Bacterial flora or lesions are observed on less than 2096 of the leaf area on the V side.

2. Bacterial flora or lesions are observed on the leaf surface in less than 5,096 leaf areas.

4. Bacterial flora or lesions are observed on 5096 or more leaf areas.

-1, and the control value was calculated from the following formula.

The results are shown in Table 8.

Table 8 Test Example 2 Cucumber and disease control (therapeutic effect) test Plastic pots were filled with sandy loam and cucumbers (variety: Yome Hanshiro) were sown.

This was cultivated in a greenhouse for 14 days to obtain 1°/r young cucumber with expanded cotyledons. This young cucumber seedling has a downy mildew fungus (1'
5eudnperonospora cubensis
) was spray-inoculated with conidial suspension 11'f, and the temperature was 20°C.
1[1@ was there under humid conditions. Thereafter, a water diluted solution of the test compound prepared in an emulsion or a wettable powder according to the above-mentioned formulation example was sprayed on the leaves so that the drug solution was sufficiently attached to the leaf surface. The plants were cultivated under fluorescent lighting at 20° C. for 5 days to develop the disease, and then the disease state was observed. The disease severity and control value were determined in the same manner as in Test Example 1. The results are shown in Table 4.

Table 4 Test Example S: Cucumber and disease control (systemic transfer effect) test A plastic pot was filled with sandy loam, and cucumbers (variety: Sumo Half-day) were sown and cultivated in a greenhouse for 14 days, and cotyledons developed. I got a young Gyūri. In this video, according to the formulation example above, an emulsion was prepared by diluting the test compound (Y1) in water into a hydrating powder, and pouring it into a pot, and after 6 days, it was mixed with nicurribe and diseased bacteria (I'5 eudoperonospo).
A suspension of 51 live spores of S. racubensis was inoculated by spraying, and the apparatus was kept at 20°C under humid conditions. After that, the plants were cultivated for 5 days at 20° C. under firefly (firefly) Y lamp lighting to avoid the onset of disease, and then the disease state was observed.

The disease severity and control value were determined in the same manner as in Test Example 1.

The results are shown in Table 5.

Table 5 Test Example 4 Test for disease control (therapeutic effect) on grapevines A plastic container was filled with sandy loam, and grapes (
Variety: Delaware) was sown.

This was cultivated in a greenhouse for about a month, and the young grape seedlings, which had developed 2 to 8 leaves, were infected with grape beetles and disease bacteria (Plasmopara.
viticola) (7) A conidial suspension was spray-inoculated and kept under humid conditions at 28°C for one day. After that, in this video, a water-diluted solution of the test compound prepared as an emulsion or a wettable powder according to the formulation example above was sprayed onto the grass so that the chemical solution was sufficiently attached to the leaf surface [Step 7]. Thereafter, the plants were cultivated for 14 days at 28° C. under fluorescent lamp illumination to induce disease, and then the disease state was observed. The disease severity and control value were calculated in the same manner as in Test Example 1. The results are shown in Table 6.

Table 6 Test Example 5 Potato late blight control (therapeutic effect) test A Wagner pot was filled with sand JjlLt and potato tubers (
Variety, Baron) was sown. 4. This was kept in a greenhouse for two months. u
, lir. This seedling is infected with Potato Phytophthora blight (Pbyt).
After inoculating by spraying a zoospore suspension of opbtl+ora 1nfestans) and keeping it humid at 20°C for 20 hours, it was inoculated into an emulsion or wettable powder according to the above-mentioned Example 11.
Made 1. Apply a water diluted solution of the test compound to the leaves. lf, in 1 minute (d3′i), then 2
The plants were cultivated in a greenhouse at 0°C for 6 days, and the diseased state of I-Yamara was observed. The severity of the disease is 1″, 1lIli (
9. The extraction was carried out in the same manner as in Test Example 1. result! c f(S
It is shown in Table 7.

Table 7 Procedural Amendment l) (Voluntary) February 3, 1980 Mr. Kazuo Wakasugi, Commissioner of the Patent Office■, Indication of the Case 1982 Patent Application No. 195035 2, Name of Invention f'r Thionolinamide Derivative , its manufacturing method and its r
Relationship between Plant Disease Control Agent 8 Containing T-Effective Acid and Amendment A Case Patent Applicant Address 5-15 Kitahama, Higashi-ku, Osaka Name (
209) Sumitomo Chemical Co., Ltd. Representative Desk Upper
Take 4, Agent Address: 5-5 Kitahama, Higashi-ku, Osaka City, 5-5, Yamagami-san, Detailed Explanation of the Invention in the Specification (1-6, Contents of Amendment (1) From page 9 of the specification, on line 9 of the paper, 1 phosphoho 11 amino acids 1 .

(2) 1”0.89 f/ (0
,01 mole) is 1 and J) is rO,89f (0,01
mol) and triethylamine 1.01g (0.01 mol)
``to'' and revised iE '1''ro.

(3) In the R+ column of compound layers (6) and (18) in Table 1 on page 11, [-C2050C! [14J
[CgO+, 0(C1i2)2-
, I (4) On page 18, line 11, [
- Correct the phrase ``for example'' to ``for example''.

1 so, 2 1027-1

Claims (4)

[Claims] (1) General formula 17 In the formula, R1 represents a mono- or di-lower alkoxy-substituted lower alkyl group, and auxiliary represents a lower alkyl group. ] A thionolinamide derivative represented by (2) Thionolinic acid amide chloride represented by the general formula [wherein R1 represents a mono- or di-lower alkoxy-substituted lower alkyl group], and R2 represents a lower alkyl group] and 4゜5- Methylenedioxy-2-2-di-l is condensed with lophenol.
In the general formula 1'', R1 and 1t2 have the same meanings as above.] An I!Ji production method of the thionolinamide conductor represented by the following. (3) Thionophosphoric acid chloride represented by the general formula [wherein k2 represents a lower alkyl group and 1'4t] and the general formula R+N112 [wherein R1 represents a mono- or di-lower alkoxy-substituted lower alkyl group]. [In the formula, R1 and R2 have the same meanings as above.] ] A method for producing a thianophosphoric acid amide 4-conductor. (4) General Formula [In the formula, RI represents a mono- or di-lower alkoxy-substituted lower alkyl group, and R2 represents a lower alkyl group. ] A plant disease control agent characterized by containing a thionolinic acid amide derivative represented by the following as an active ingredient.