JPS60193971A - Iodopropargyloxypyrimidine derivative, its preparation and fungicide for agricultural and horticultural purposes - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [R is 1-4C alkyl, allyl, propargyl, benzyl, cyano, SR<2> (R<2> is 1-3C alkyl); R<1> is 1-3C alkyl]. EXAMPLE:2,4-Dimethoxy-6-iodopropargyloxy-5-methylthiopyrimidine. USE:A fungicide for agricultural and horticultural purposes: it shows excellent effect against potato's late blight, cucumber's gray mold, cucumber's downy mildew and rice blast with no chemical injury to crops and no toxicity to animals. PREPARATION:Iodation of a propargyloxypyrimidine derivative of formula II is conducted using elementary iodine in a solvent such as alcohol in the presence of a base such as sodium hydroxide at 20-40 deg.C for 1-2hr to give the compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the general formula (1) [wherein R is an alkyl group having 1 to 4 carbon atoms, an allyl group, a propargyl group, a benzyl group, a cyan group, or SR2, (
In the formula, R2 represents an alkyl group having 1 to 3 carbon atoms. ), and R1 represents an alkyl group having 1 to 3 carbon atoms. ] Iodopropargyloxypyrimidine derivatives represented by
The present invention relates to a method for producing the same and an agricultural and horticultural fungicide containing the same as an active ingredient.

The present inventors have been conducting intensive studies with the main purpose of finding useful fungicides for agriculture and horticulture, especially developing agents that are effective against late blight and downy mildew, which are economically devastating. In particular, since the pyrimidine nucleus is thought to play a special role in interactions with living organisms, we focused on pyrimidine derivatives and conducted various studies.

A great deal of research has been carried out on pyrimidine derivatives, a huge number of compounds have been synthesized, and many compounds with characteristic physiological activities have been discovered in the field of agricultural medicine. However, there are still many unexplored fields regarding pyrimidine derivatives.

The present inventors have already discovered that many pyrimidine derivatives are useful as agricultural and horticultural fungicides and have filed applications (Japanese Patent Laid-Open Nos. 58-124773 and 58-198472).
issue). As a result of various studies to further improve the effect, it was found that the effect was dramatically improved by substituting the terminal of the propargyloxypyrimidine derivative, which is a compound included in the invention described in JP-A-58-124776, with iodine. They discovered this and completed the present invention.

Propargyloxypyrimidine derivatives are used as spraying agents and soil treatment agents to treat plant diseases caused by so-called oomycetes, such as potato late blight, tomato late blight, tobacco late blight, green pepper late blight, and Kieribe mildew, as well as apple leaf spot and gray mold. However, the iodopropargyloxypyrimidine derivative, which is a compound of the present invention, is also effective against the above-mentioned diseases, as well as powdery mildew and rice blast, and the range of diseases to which it can be applied has been greatly expanded. In addition, it is highly effective and is effective against many diseases at one-half the dosage of the propargyloxypyrimidine derivative of the previous invention.

Furthermore, there are no problems with regard to chemical damage to crops and toxicity to animals, as with the compounds of the previous invention.

Next, a method for producing the compound of the present invention will be explained.

Compounds of the invention can be prepared according to the following formula.

That is, general formula (■) [wherein R represents an alkyl group having 1 to 4 carbon atoms, an allyl group, a propargyl group, a benzyl group, a cyan group, or sR7 (in the formula, R2 represents an alkyl group having 1 to 6 carbon atoms] ), and R1 represents an alkyl group having 1 to 6 carbon atoms. ] is achieved by iodizing the propargyloxypyrimidine derivative represented by iodine with iodine in the presence of a base.

In addition, the propargyloxypyrimidine derivative represented by the general formula (II), which is a starting material, is disclosed in JP-A-58-1247.
It can be easily produced by the method disclosed in Japanese Patent No. 73.

This reaction will be explained in more detail below.

Alcohols such as methanol, ethanol, propatool, and impropatool are suitable as reaction solvents.
It is also possible to mix and use other solvents based on these. Examples of other solvents include water, pyridine, quinoline, picoline, tetrahydrofuran, and dioxane. As bases it is possible to use hydroxides or carbonates of alkali metals or alkaline earth metals. Organic bases can also be used. These bases can be used in solid form, but those that dissolve in a solvent are preferably used as a solution or added as an aqueous solution.

The reaction temperature can range from 0°C to the boiling point of the solvent, but is preferably 20-40°C.

Propargyloxypyrimidine derivatives, bases and derivatives,
Although any combination of charging orders is possible, usually the base is charged and dissolved or suspended in the solvent, and then the propargyloxypyrimidine derivative is added. Furthermore, if T2 is added little by little in solid form while stirring at a predetermined temperature, the reaction proceeds smoothly. The reaction time is in the range of 0.5 to 5 hours, but it is usually completed in 1 to 2 hours.

Propargyloxypyrimidine derivatives, bases and ■2
Although various combinations of molar ratios are possible, it is preferable to use stoichiometric ratios.

When the product is poured into a large amount of water after the reaction is completed, the product precipitates or separates in the form of a solid or oil. ! It is removed by filtration or extraction and purified according to conventional methods.

The method for producing the compound of the present invention will be specifically explained below by giving synthesis examples.

Synthesis Example 1 Synthesis of 2,4-dimethoxy-6-iodopropargyloxy-5-methylthiopyrimidine (1.5 t of methanol was charged into a compound four-volume flask, and 37.Of (0,925 mol) of granular sodium hydroxide was added. Then, 2,4-dimethoxy-6-glopargyloxy-5-methylthiopyrimidine 7185.O
f (0,771 mol) was charged.

Part of the solution remained undissolved and became suspended. Next, while stirring at 20°C, I,19/)r (0,771 mol) was added little by little in a crystalline state over 30 minutes. The reaction solution slowly generated heat and reached 29°C. Thereafter, stirring was continued for 2 hours at 20°C. The color of the reaction solution was a deep iodine color that gradually faded to yellow. After the reaction was completed, it was poured into a large amount of water. The precipitated solid was collected, dried, and then recrystallized from a small amount of benzene to obtain a purified product of 259.7 f (yield: 85 Ω%). m, p, 106-8℃ elemental analysis value (C1oH, □
As IN2O35) C! H Engineering NS Word tN: f Direct (%) 32.80 3:03 54.6
6 7.65 8.76 Actual value C%) 32.542.
8734.227.2L8.65 Compounds synthesized in a similar manner are summarized in Table 1.

Although the compound of the present invention can be used as it is as an agricultural and horticultural fungicide, it is actually mixed with a carrier and other adjuvants as necessary to form a formulation commonly used as an agricultural and horticultural fungicide, such as a powder (active ingredient concentration, 1 to 1 [1%], fine granules (active ingredient concentration, 1 to 25%), granules (active ingredient concentration,
2-30%), irrigation agent (active ingredient concentration, 20-q
oi), emulsion (active ingredient concentration, 10-4O*), oil suspension (active ingredient concentration 10-yo%), oil agent (active ingredient concentration 10-50%), smoke agent (active ingredient concentration 2-70%) Section)
etc. are prepared and used.

The term "carrier" here refers to a synthetic or natural carrier that is incorporated into agricultural and horticultural fungicides to help the active ingredient reach the area to be treated and to facilitate the storage, transportation, and handling of the active ingredient compound. means any inorganic or organic substance.

Suitable solid carriers include clays such as montmorillonite and kaolinite, inorganic substances such as diatomite, clay, cruzi, vermiculite, gypsum, calcium carbonate, silica gel, and ammonium sulfate, vegetable organic substances such as soybean flour, sawdust, and wheat flour; Examples include urea.

Suitable liquid carriers include aromatic hydrocarbons such as benzene, toluene, xylene and cumene, paraffinic hydrocarbons such as kerosene and mineral oil, halogenated hydrocarbons such as carbon tetrachloride, chloroform and dichloroethane, acetone and methyl ethyl ketone. Examples include ketones, ethers such as dioxane and tetrahydrofuran, alcohols such as methanol, propatool, and ethylene glycol, dimethylformamide, and dimethyl sulfoxide.

Furthermore, in order to enhance the efficacy of the compound of the present invention, the following adjuvants may be used alone or in combination depending on the purpose, taking into account the dosage form of the preparation, the application situation, etc.

For the purpose of emulsification, dispersion, spreading, wetting, binding, stabilization, etc., water-soluble bases such as pyrogenin sulfonate, anionic surfactants such as alkylbenzene sulfonate, alkyl sulfate, polyoxyethylene allyl ether, etc. Examples include nonionic surfactants, calcium stearate, lubricants such as wax, stabilizers such as inglobilhydrodiene phosphate, and others such as methylcellulose, carboxymethylcellulose, casein, and gum arabic.

However, these components are not limited to the above.

Furthermore, when the compound of the present invention is used as a fungicide,
It can also be used in combination with other agricultural chemicals, such as insecticides, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers, etc., or as a mixture.

The various preparations or spray preparations containing the compounds of the present invention can be applied by conventional application methods, such as spraying, dusting, dusting, surface application, fumigation, dipping, and dusting.

Next, the content of the present invention will be specifically explained with reference to Examples.
However, the present invention is not limited thereto.

The active ingredient compounds are indicated by compound numbers in Table 1 above. "1 part" means "part by weight".

Formulation Example 1 Wettable powder compound (1): 300 parts, diatomaceous earth: 440 parts,
White clay: 200 parts, sodium ligninsulfonate: 25
parts, sodium alkylbenzenesulfonate: 15 parts,
and polyoxyethylene nonylphenyl ether = 2
0 parts were uniformly ground and mixed to obtain the compound (
An irrigation agent containing 60 units of 1) was obtained.

Formulation Example 2 Emulsion Compound (3): 300 parts, Cyclohexanone: 10
0 parts of xylene, 500 parts of xylene, and 100 parts of Nlupol (a surfactant manufactured by Toho Chemical Co., Ltd.) were uniformly dissolved and mixed to obtain an emulsion containing 30% of compound (3) as an active ingredient.

Formulation Example 6 Granules Compound (2): 1 part, bentonite = 62 parts, talc: 20 parts, sodium dodecylbenzenesulfonate:
After mixing 2 parts and 1 part of sodium ligninsulfonate, adding an appropriate amount of water and kneading, the mixture is granulated in a conventional manner using an extrusion granulator, and compound (2) is added as an active ingredient. Granules containing 10 pieces were obtained.

Formulation Example 4 Powder Compound (11): 20 parts, calcium stearate: 5 parts, powdered silica gel = 5 parts, diatomaceous earth = 200 parts, white clay: 300 parts, and LLU: 4ro parts were uniformly added. The mixture was ground and mixed to obtain a powder containing 2 parts of the compound (1 part) as an active ingredient.

Formulation Example 5 Oil Compound (2): 1 part, and ethyl cellosolve: 9 parts
Mix and dissolve 0 parts to prepare 10 parts of compound (2) as an active ingredient.
An oil solution containing % was obtained.

Next, the effect of the compound of the present invention as a fungicide will be explained using test examples. The test compounds are indicated by the compound numbers mentioned above.

Test Example 1 Potato Phytophthora control test (preventive effect) Potatoes grown in pots in a greenhouse (variety: 1, diluted with water to a predetermined concentration) were sprayed with a spray gun (1,0 k = y
ctd) at a dose of 50 mg per 6 pots and air-dried. A suspension of zoospores of Potato Phytophthora blight was previously cultured on potato sections for 7 days. This suspension was spray inoculated onto the potato plants sprayed with the drug, and the test plants were kept at 17-19° C. and humidity of 95° C. or more for 6 days, and then the degree of lesion formation was investigated.

The evaluation criteria are as follows.

Morbidity 0: Percentage of lesion area The value was calculated and used as the disease severity of the treated area.

The results are shown in Table 2.

Table 2 Control compound A: 2,4-dimethoxy-5-methylthio-6-propargyloxypyrimidine (invention compound described in JP-A-58-124775) Control compound B: Zinc ethylene bis(dithiocarbamate) Control compound C : Tetrachloroinophthalonitrile Comparative compound B10 is a commercially available agent for controlling potato late blight or Kieribe.

As shown in Table 2, the compounds of the present invention have an excellent control effect on potato late blight.

The compound 2,4-dimethoxy-5-methylthio-6-propargyloxypyrimidine contained in the previous invention (Patent Publication No. 58-124773) has an active ingredient concentration of 500 pp+
At 250 ppm, there is almost no effect. On the other hand, compounds 1 to 4 of the present invention have 250 +
) It can be seen that it also shows an excellent control effect on PM. Moreover, Compound 5 shows the same effect as the above-mentioned compound of the previous invention. Compounds 6 to 11 showed excellent effects at 500 ppm, but were slightly inferior to the compounds of the previous invention.

However, these compounds have cucumber powdery mildew control effects that were not observed in the compounds of the previous invention. (See Test Example 5) From the above results, 2, 4-
It is said that the compound in which the terminal of the glopargyl group of diftquine-5-methylthio-6-bropargyloxypyrimidine is substituted with iodine and its analogs included in the present invention have enhanced the effects of the previous invention or have significantly expanded the types of diseases to which they can be applied. be able to.

Test Example 2 Cucumber and disease control test (preventive effect) Cucumbers grown in pots in a greenhouse (variety: Sokore diluted with water to a specified degree) were sprayed with a spray gun (1 OK9 /
arI) was applied at 50 ral per funnel and air-dried. Downy mildew fungi were collected from lesions on cucumber leaves infected with downy mildew, a spore suspension was prepared with demineralized water, and the suspension was spray-inoculated from the underside of the leaves.

Immediately keep the inoculated pots at 18-20°C and humidity of 95°C or higher for 24 hours, then place them in a greenhouse (room temperature: 18°C-27°C).
), and 7 days later, the degree of lesion formation was examined.

The evaluation criteria and disease severity display method were as described in Test Example 1 above.

The results are shown in Table 3.

As shown in Table 6 and Table 3, the compound of the present invention is a compound of Zinc Ethylene Bis (commercially available as a disease control agent).
dithiocarbamate) and tetrachloroisophthalonitrile, it is clear that it has a much better effect at an active ingredient concentration of 500 pI)m.

Test Example 6 Potato late blight control test (therapeutic effect) A suspension of potato Phytophthora zoospores was prepared on the same potato as used in Test Example 1, and used as an irrigation agent using the method of spray inoculation Example 1. A spray gun (1,01 (y/...y)) was used to spray 50 liters per 6 pots.
After maintaining the temperature at 5 cm or more for 5 days, the degree of lesion formation was examined.

The evaluation criteria and disease severity display method were as described in Test Example 1 above.

The results are shown in Table 4.

Table 4 Test Example 4 Cucumber and disease control test (therapeutic effect) A suspension of cucumber and disease fungus spores was prepared on cucumbers similar to those used in Test Example 2 and inoculated by spraying.

The solution was prepared as an irrigation agent by diluting it with water to a predetermined concentration) and was sprayed at 30 m/per bowl using a spray gun (1,00/c4). Greenhouse (temperature 18-27℃)
After 6 days, the degree of lesion formation was examined.

The evaluation criteria were as described above (Test Example 1).

The results are shown in Table 5.

Table 5

As shown in Tables 4 and 5, it can be seen that the I-L compound of the present invention has a very excellent therapeutic effect on late blight of potato and mildew of potato at an active ingredient concentration of 500 ppm. This is due to zinc ethylene bis(dithiocarbamate), which is commercially available for controlling both of the above diseases.
In comparison with the fact that tetrachloroisophthalonitrile has no effect at all, this property can be said to be extremely excellent.

Test Example 5 Cucumber udon disease control test 4 cucumbers grown in 12 cWt clay pots (not used as an irrigation agent)
dilute this with water to a specified concentration) with a spray gun (
1.0Kg/cal) was used to spray 30 times per filter bowl. Air-dried layer, inoculated with cucumber powdery mildew spores,
After being kept in a greenhouse (17°C to 26°C) for 8 days, the degree of lesion formation on the leaves was investigated.

The evaluation criteria are as follows.

Diseased dust 0: Percentage of lesion area 0chi 1: 1-5% 2: 6-25chi 3: 26-50% 4: Investigate diseased dust on each leaf of 51cm or more, and calculate the average value for the entire collection of each area. Therefore, the diseased dust of each ward was used.

The results are shown in Table 6.

Comparative compound C in Table 6 is a commercially available agent for controlling powdery mildew of cucumber.

As shown in Table 6, the compound of the present invention has an active ingredient concentration of 500% compared to 4゜4'-0-phenylenebis(3-thioallophanate) dimethyl, which is commercially available as a cucumber powdery mildew control agent. It is clear that it has an extremely excellent pesticidal effect at pPm.

patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (3)

[Claims] (1) General formula (1) [wherein R is an alkyl group having 1 to 4 carbon atoms, an allyl group, a glopargyl group, a benzyl group, a cyan group, or 5R2 (in the formula, R2 is an alkyl group having 1 to 6 carbon atoms) ), and R1 represents an alkyl group having 1 to 6 carbon atoms. ] An iodopropargyloxypyrimidine derivative represented by (2) General formula (II) [wherein R is an alkyl group having 1 to 4 carbon atoms, an allyl group, a globargyl group, a benzyl group, a cyano group, or SR'' (
In the formula, R2 represents an alkyl group having 1 to 3 carbon atoms. ), and R1 represents an alkyl group having 1 to 6 carbon atoms. General formula (1) characterized by reacting iodine with the propargyloxypyrimidine derivative represented by ] in the presence of a base. In formula C, R is an alkyl group having 1 to 4 carbon atoms, an allyl group, a glopargyl group, or a benzyl group. group, cyan group or SR” (
In the formula, R2 represents an alkyl group having 1 to 2 carbon atoms. ), and R1 represents an alkyl group having 1 to 3 carbon atoms. ] A method for producing an iodopropargyloxypyrimidine derivative. (3) General formula (1) [In the formula, ■ is an alkyl group having 1 to 4 carbon atoms, an allyl group, a propargyl group, a benzyl group, a cyan group, or 5R2 (in the formula, R2 is an alkyl group having 1 to 4 carbon atoms) ), and R1 represents an alkyl group having 1 to 2 carbon atoms. ] An agricultural and horticultural fungicide characterized by containing an iodopropargyloxypyrimidine derivative represented by the following as an active ingredient.