JPH01226884A - Novel triazole derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [A represents formulae II-IV (B represents H, halogen, nitro, methyl or trifluoromethyl; n is 0-2); X represents H or methyl; Y and Z represent lower alkyl or cyclopropyl together with adjacent C atom]. EXAMPLE:1-Dimethylcarbamyl-3-tertiary butyl-5-(2-pyridylthio)-1,2,4-triazole. USE:An agricultural and horticultural insecticide or synthetic intermediate therefor. PREPARATION:A triazole based compound expressed by formula V [example; 3-tert-butyl-5-(2-pyridylthio)-1,2,4-triazole] is reacted with dimethylcarbamyl chloride to afford a compound expressed by formula I. The starting raw material expressed by formula V is novel and produced by reacting a 5- mercaptotriazole compound expressed by formula VI with halogenopyridines, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to the general formula (1), which represents a rogene atom, a nitro group, a methyl group, or a trifluoromethyl group, and n represents an integer of O to 2. X represents a hydrogen atom or a methyl group, and Y and Z each independently represent a lower alkyl group or form a ring together with adjacent carbon atoms to represent a cyclopropyl group. The present invention relates to a triazole urea derivative represented by the following formula, a method for producing the same, an agricultural and horticultural insecticide containing the triazole urea derivative as an active ingredient, and a synthetic intermediate.

[Prior Art] It is known that certain triazole urea derivatives have insecticidal efficacy.

For example, published patent publication No. 52-122624. 1972-
122625 has a substituent A in the above-maximum [1]
Triazole urea derivatives are described in which is an aliphatic (optionally unsaturated) substituent.

Published Patent Publication No. 56-32469 describes a derivative in which A in formula 13 is alkoxyalkyl.

German Patent No. 3,031,191 describes a group of triazole urea derivatives in which A is a substituted benzyl group.

Compounds according to the invention -substituted MA at maximum [1)
It is a novel urea derivative that differs from these known ones by having a pyridine ring which is a heterocyclic compound.

[Problems to be Solved by the Invention] The compound of the present invention represented by general formula (1) is suitable for Hemiptera pests,
For example, they exhibit strong insecticidal activity against aphids, planthoppers, and leafhoppers, and some have stronger insecticidal activity against aphids at lower doses than known compounds. In addition, some compounds exhibit superior properties that are different from known compounds in that they exhibit strong insecticidal power against planthoppers and leafhoppers that are resistant to carbamates and phosphorus agents, which are currently a problem in pest control. It was discovered that.

Furthermore, the compounds of the present invention can control harmful pests without any effect on useful plants, and can be applied directly to pests by contact, or by treating them in the soil.
By osmotically transferring the drug to the leaves and leaves,
It has the characteristic of exhibiting a pest control effect.

As described above, the present invention is a novel compound that has not been described in any prior art literature, and provides an industrially useful drug.

[Means for Solving the Problems] The triazole urea derivative represented by the general formula (1) of the present invention can be produced by the following method.

General formula (II) [In the formula, A, X, Y and Z have the same meanings as above.

] can be produced by reacting the triazole compound represented by dimethylcarbamyl chloride in the presence of an acid binder.

In this reaction, as an acid binder, an organic base such as triethylamine, pyridine, N,N-dimethylaniline,
Inorganic bases include sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium hydride.

This reaction can be carried out in the presence of a solvent or without a solvent, but in order to carry out the reaction more smoothly, a solvent is usually used and the reaction is carried out at a temperature from 0°C to the boiling point of the solvent, preferably in a room a- It is carried out at a temperature of 150°C for usually 1 to 50 hours.

The solvents used here include ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, amides such as dimethylformamide and dimethylacetamide, hydrocarbons such as benzene and toluene, ethyl acetate, dimethyl sulfoxide, and water. or a mixed solvent thereof.

The triazole compound represented by the general formula (II) used as an intermediate in the production of triazole urea is a new compound that has not been described in any literature, and this also constitutes the object of the present invention. . The compound of formula (n) is
General formula (III) which is a known compound [wherein X, Y and Z represent the same meanings as above]. It can be produced by reacting the 5-mercaptotriazole compound represented by the following with a halogenopyridine or a pyridine diazonium salt.

This reaction can be carried out in the presence of a solvent or without a solvent, but in order to carry out the reaction more smoothly, a solvent is usually used at a temperature of 20°C to 200°C, preferably 20°C to 150°C. It is usually carried out at a temperature of 1 to 50 hours.

The solvent used here is not particularly limited as long as it is inert to the reaction, but preferably ketone-based solvents such as acetone and methyl ethyl ketone, ether-based solvents such as tetrahydrofuran and dioxane, and amide-based solvents such as dimethylformamide and dimethylacetamide are used. , benzene, toluene, etc., acetic acid ethyl ester, dimethyl sulfoxide, water, etc., or a mixed solvent thereof.

Hereinafter, the production of the compounds of the present invention will be explained in more detail with reference to Examples.

Example 1゜1-dimethylcarbamyl-3-tert-butyl-5-(2
-pyridylthio)-1,2,4-triazole production 3-Tertiary butyl-5-(2-pyridylthio)-1,2
To a suspension of 1.0 g of ,4-triazole and 1.0 g of potassium carbonate in 20 ml of dry acetone was added 0.48 ml of dimethylcarbamyl chloride, and the mixture was heated under reflux with vigorous stirring for 10 hours. Insoluble matter was filtered off and the solvent was removed under reduced pressure. The oily residue was chromatographed on silica gel (solvent =
The solid substance obtained was recrystallized from ethyl acetate and n-hexane to obtain crystals with a melting point of 69.9°C.

Elemental analysis value: HN as C14H, N50S (molecular weight 305.412) Calculated value (%) 55.06 6.27 22.9
3 Analysis value (%) 54.95 6.19 22.85 Example 2゜1-dimethylcarbamyl-3-tert-butyl-5-(4
-pyridylthio) -1,2,4-) riazole 3-tert-butyl-5-(4-pyridylthio) -1
,2,4-triazole1. Otr and potassium carbonate 1.
0.46 ml of dimethylcarbamyl chloride was added to a suspension of 0 g in 20 ml of dry acetone, and the mixture was heated under vigorous reflux for 5 hours. Insoluble matter was filtered off and the solvent was removed under reduced pressure.

The remaining oily substance was purified by silica gel chromatography (solvent: 2% methanol-chloroform) to obtain an oily substance. This oil crystallized on standing. The melting point was 88.7°C.

Elemental analysis value: HN calculated value (%) as C14H19N50S (molecular weight 305.412) 55.06 B, 27 22.
93 Analysis value (%) 55.00 B, 21 2
2.73 Example 3゜1-dimethylcarbamyl-3-tert-butyl-5-(5
-Preparation of 3-tert-butyl-5-(5-chloro-2-pyridylthio)-1,2,4-triazole 1.35 g and potassium carbonate 1 g Dimethylcarbamyl chloride o, ag was added to a 1% suspension of dried acetone in 20ml, and the mixture was heated under reflux for 6 hours. After filtering off potassium carbonate and salts, the solvent was removed under reduced pressure. The residue was subjected to silica gel column chromatography (solvent: chloroform), and the obtained solid was recrystallized from ethyl acetate and n-hexane to obtain crystals with a melting point of 103.3°C.

Elemental analysis value: C14H18CfIN50S (molecular weight 33
9.881) as CHN Calculated value (%) 49.48 5.34 20.6
1 analysis value (%) 49.47 5.39 2 (1
, 4B Example 4゜3-tertiary butyl-5-(5-)lifluoromethyl-2
-pyridylthio) -Production of 1,2,4-triazole 3.9 g (0,025 mol) of 3-tert-butyl-1,2,4-triazoline-5-thione was dissolved in 20 ml of N,N-dimethylformamide. Then, 1 g of 60% sodium hydride was added thereto. When no new hydrogen generation is observed, a catalytic amount of sodium iodide and 4.5 sr of 2-chloro-5-trifluoromethylruviridine (0
,025 mol) was added thereto, and the reaction was carried out at 100°C for 35 hours. After cooling to room temperature, ethyl acetate was added to the reaction solution, water,
It was sequentially washed with brine and dried over anhydrous magnesium sulfate.

After the desiccant was filtered off, the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (solvent: chloroform), and the resulting solid was recrystallized from ethyl acetate and n-hexane to obtain crystals with a melting point of 2034°C.

Elemental analysis value: Cl2H13F3N4S (molecular weight 302J23), HN calculated value (%') 47.8 & 4.33 18
．． 53 analysis value (%) 47.81 4.38 1
8.49 Example 5゜3-tert-butyl-5-(3-pyridylthio) river, 2.
Preparation of 4-triazole 1.9 g (0.02 mol) of 3-aminopyridine was added to 5 g of water and 13 ml of concentrated hydrochloric acid. To this solution, while cooling with ice-methanol, an aqueous solution prepared by dissolving 1.5 g of sodium nitrite in 3 ml of water was added dropwise at 0° C. or lower. After stirring for 15 minutes, the diazonium salt solution was mixed with 3-tert-butyl-1,2,4-) at room temperature.
Riazoline-5-1000 ions 3. It was added dropwise to a suspension of br (0.02 mol) in 10 ml of water. After dropping, add 0.2g of cuprous chloride and 0.1g of cupric chloride dihydrate to 6N hydrochloric acid.
ml solution was added. After the reaction was completed, the reaction solution was made weakly basic with a dilute aqueous sodium hydroxide solution and extracted with chloroform. After drying the solvent with anhydrous magnesium sulfate,
It was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (solvent: chloroform), and the obtained solid was recrystallized from ethyl acetate and n-hexane, with a melting point of 131.
．． Crystals at 1°C were obtained.

Elemental analysis value 2C1□H14N4S (molecule ffi 234J25), HN Calculated value (%) 5848 6.02 23.91
Analysis value (%) 5BJ5 5.99 24.01
It can be produced in the same manner [Representative examples of compounds of formula 81 are shown in
Representative examples of compounds of formula (1) are shown in Table 2.

Table 1 Table 1 (continued) Table 1 (continued) (Note) Nα13 is the compound of Example 4, and Nα15 is the compound of Example 5.

Note that the above compound numbers also apply to the following examples and formulation examples. Since the compound of the present invention thus obtained has systemic transferability to plants, it can be used in conventional application methods such as above-ground foliage treatment, water surface treatment, soil treatment, etc.

Furthermore, the compounds of the present invention do not have any adverse effects on useful plants, so they can be used at any stage of useful plants, including before sowing, during the seedling stage, during the growing stage, and during the fruiting stage.

When actually using the compound of the present invention, it is possible to use it as it is without adding other ingredients, but for more convenient use, it may be mixed with various solid and liquid carriers used in general agricultural chemical formulations. In addition, auxiliary agents such as wetting agents, diluents, emulsifiers, spreading agents, wetting agents, youth absorbing agents, thickeners, antifoaming agents, and antifreezing agents may be added.

The carrier referred to herein may be either solid or liquid, or a combination thereof. These examples include talc, clay, bentonite, kaolin, diatomaceous earth, calcium carbonate, wood flour, starch, gum arabic, water,
Examples include alcohol, kerosene, naphtha, xylene, cyclohexanone, methylnaphthalene, benzene, acetone, dimethylformamide, glycol ether, and N-methylpyrrolidone.

Examples of adjuvants include polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan monooleate, ethylene oxide propylene oxide copolymer, lignin sulfonate, sorbitan ester, soaps, sulfated oils, alkyl sulfate esters, petroleum Sulfonates, dioctyl sulfosuccinate salts, alkylbenzene sulfonic acids, aliphatic amine salts, quaternary
Ammonium salts, alkylpyridinium salts, alkylaminoethylglydine, alkyldimethylbetaine, polyglycol sulfate, alkylamine sulfonic acid, isopropyl phosphate, carboxymethylcellulose, polyvinyl alcohol, hydroxypropylcellulose, ethylene glycol, xanthan gum, etc. It will be done.

It can also be used as an aerosol agent by mixing with a propellant such as fluorotrichloromethane or dichlorodifluoromethane, or as a fumigant or smoke agent by mixing with an appropriate blowing agent or combustion agent. .

In formulation, the mixing ratio is generally 0.05 to 95%, preferably 1 to 70% by weight of the compound of the present invention.
Contains 70-99% as a carrier and 0-99% as an adjuvant.
20% is optimal. In addition, a wider range of effects can be expected by mixing with pesticides and fertilizers such as pond insecticides, acaricides, herbicides, plant growth regulators, and fungicides.

When actually using the compound of the present invention, the timing of use,
Weather conditions, method of use, dosage form, location of use, target pests,
It goes without saying that it is selected appropriately depending on the target crop, etc., but the concentration used is generally 0.5 to 11,000 ppm, preferably 3 to 500 ppm, and the amount of the drug used (as the compound of the present invention) is - is 0.5 to 5 per lO are
00sr - preferably from 1 to 250 g per IO are.

Next, the usefulness of the compounds of the present invention as agricultural and horticultural insecticides will be explained using test examples.

The insecticidal activity of the compounds of the present invention was evaluated against the following pests.

In order to evaluate the insecticidal activity of the compounds of the present invention, tests were conducted according to the following procedure.

To make test solutions of 200 ppm or 500 ppm, test compounds were dissolved in the solvent N,N-dimethylformamide (within 0.5% of the test solution) and emulsifier (
820g of 221 Calgen M was dissolved in a 1:1 mixture of Kijirol and cyclohexane to make loOml) 5m
l and a spreading agent (sodium polynaphthyl methanesulfonate 5%, polyoxyethylene nonylphenyl ether 15
%, polyoxyethylene butyl ether lO%, water 70
%) was diluted with a solution prepared by adding 2 ml to 10 liters of water and used for an initial evaluation test.

In an initial evaluation test for insecticidal activity using a topical application method, the test compound was diluted by adding 1 ml of acetone per 1 mg of the test compound.

In both cases, in low-dose tests conducted to determine the strength of activity, compound solutions were prepared by serially diluting them with water or acetone to which the above-mentioned emulsifier and spreading agent were added, depending on the activity. .

Test example 1゜Evaluation method for insecticidal activity against peach aphid and cotton aphid A damp filter paper was placed at the bottom of a glass petri dish with a diameter of 3c11, and a cabbage leaf piece or a cucumber leaf piece cut out to a diameter of 3 cm with cork polar was placed on top of it. .

Using a small brush, 20 oil-free viviparous female adult green peach aphids were inoculated onto the cabbage leaf pieces, and 20 oil-free viviparous female adult cotton aphids were inoculated onto the cucumber leaf pieces. The petri dish inoculated with aphids was placed in a specimen storage box on a rotating chemical dispersion base, and a 200pp solution of the compound was applied in an initial evaluation test.
For low dose tests, 280 mm1 of the appropriate serially diluted solution
4m1 with a wind pressure of 1g (the amount of chemical solution deposited at this time is 21g/c)
j) After spraying, the plants were taken out, covered, and placed in a constant temperature room at 25±2°C, and 24 hours later, whether they were alive or dead was determined.

Insecticidal activity was evaluated in the initial evaluation test according to the evaluation criteria in Table 3, and in the low dose evaluation test, the half lethal concentration - LC50 value (ppm) was calculated from the obtained concentration-mortality rate curve using the probit calculation method. I went looking for it. The respective test results are shown in Tables 4 and 5.

Table 3 Insecticidal activity evaluation criteria Table 4 Insecticidal activity of test compounds against various insects Table 5 Insecticidal activity intensity against green peach aphid and cotton aphid Activity value according to this local application method (Note) Target drug MEP Fenitrothion test example 2゜Method for evaluating insecticidal activity against brown planthoppers: Acetone in which a compound has been dissolved in advance (1 ml of acetone per 1 g of compound III) is applied to the abdominal surface of a female adult brown planthopper that has been lightly anesthetized with carbon dioxide using a microdose treatment device.
Q (the amount of compound at this time is OJttg/head) was added dropwise. After the treatment, the brown planthoppers were placed in a 30 ml glass test tube, fed with rice seedlings, and placed in a thermostatic chamber at 25±2°C.

24 hours after treatment, survival was determined, and initial evaluation of insecticidal activity was performed based on the mortality rate obtained according to the evaluation criteria in Table 6. The test results are shown in Table 7.

Table 6 Insecticidal Activity Evaluation Criteria Table 7 Test Examples of Insecticidal Activity of Test Compounds Against Various Insects 3゜Evaluation Method for Insecticidal Activity against Adzuki Bean Weevils 20 female adult adzuki bean weevils were placed in an acrylic cylinder with a diameter of 4 ctns and a height of 1 c+n with wire mesh on both sides. Insert the head, 500 ml of test compound
The entire cylinder was immersed in the ppm solution for 10 seconds. After air-drying, it was placed in a constant temperature room at 25±2°C, and 24 hours later, it was determined whether it was alive or dead.

Initial evaluation of insecticidal activity was performed based on the mortality rate obtained according to the evaluation criteria shown in Table 8. The test results are shown in Table 9.

Table 8 Insecticidal activity evaluation criteria No. 9 Table 9 Examples of testing the insecticidal activity of test compounds against various insects A 200 ppm solution of the test compound was sprayed on cucumber seedlings using a chromatographic glass spray to an extent that the entire plant was sufficiently wet, and the seedlings were placed in a glass greenhouse.

A corrected density index was calculated from the number of southern thrips parasitized by the following formula before and 2 days after spraying, and initial evaluation of insecticidal activity was performed according to the evaluation criteria shown in Table 1O. The test results are shown in Table 11.

Corrected density index - A/axb/BX100A: Number of parasites before spraying in untreated plot B: Number of parasites before spraying in plot sprayed with test compound a: Number of parasites in untreated plot 2 days after spraying B: 2 days after spraying in plot sprayed with test compound Number of parasitism 2) Evaluation method of soil treatment effect on southern yellow thrips Immediately before transplanting eggplant seedlings grown separately in a small pot into a Wagner pot of 1/10,000 are filled with soil, 50 mg, 25 mg, and 12.5 mg of the test compound were added. A solution of loOml containing -g was irrigated into the planting hole and topsoil.

Eggplant young W were infested with large numbers of adult southern thrips larvae in advance, and placed in a greenhouse to examine the change in the number of parasites to obtain the above-mentioned corrected density index. The absorption and transfer properties of the compound were evaluated. The test results are shown in Table 12.

Table 10 Insecticidal Activity Evaluation Criteria Table 11 Test Example of Insecticidal Activity of Test Compounds Against Various Insects 5゜Evaluation Method for Insecticidal Activity against Green Leafhopper The black leafhopper tested was the drug-susceptible (S) strain of Ageo, and organic phosphorus/carbamate agents. The middle line of the combined resistance (R) line, the weight per adult female at the time of testing was approximately 4 m for both lines.
It was g.

■) Insecticidal activity intensity evaluation method using local application method First, a chemical solution is prepared by dissolving test compound 1a+g in 1 ml of acetone, and then stepwise dilutions are prepared according to the activity. 0.4μ on the ventral surface of anesthetized adult female leafhoppers of each strain.
Dropped Q.

At this time, the amount of test compound treated per leafhopper was the highest (initially, 1 ml of acetone was mixed with test compound l a
+g dissolved) is 0.4mg, which is converted to 100μ per Ig of test insect (4mg/♀)
g.

The treated leafhoppers were placed in a 30 ml glass test tube, fed with rice seedlings, and placed in a thermostatic chamber at 25±2°C.

24 hours after treatment, determine whether the animal is alive or dead, and use the probit calculation method to calculate the half-lethal dose - LD5 from the obtained drug dose-mortality rate curve.
The activity strength was evaluated by determining the 0 value (■/1 g of test insect).

The test results are shown in Table 13.

2) Insecticidal activity intensity evaluation method using rice leaf sheath dipping method The test rice used was a seedling of the Nipponbare variety at the 3-leaf stage.

Rice leaf sheaths whose roots had been excised were immersed for 60 seconds in a 500 pp solution of the test compound, which was diluted in stages according to activity. After air-drying, the tubes were transferred to a 30 ml glass test tube, inoculated with 10 female adult leafhoppers of each strain, sealed, and placed in a thermostatic chamber at 25±2°C.

24 hours after treatment, determine whether the animal is alive or dead, and calculate the half-lethal concentration - LC5 using the probit calculation method from the obtained concentration-mortality rate curve.
The 0 value (ppm) was determined, and the difference in activity between the two strains was expressed as an R/S ratio to evaluate the variation in sensitivity to the resistant strain. The test results are shown in Table 14.

Table 13 Intensity of insecticidal activity against leafhopper Activity value according to this topical application method (Note) Target drug MEP Fenitrothion NAC Carbaryl Table 14 Changes in susceptibility to leafhopper of the superior system (S) and intermediate system (R) *Rice leaf sheath Activity value determined by dipping method (Note) Target drug CB) Next, formulation examples will be given and explained.
The adjuvant and the proportion used are not limited to those in this example.

The constituent ratios of the components in this example indicate parts by weight.

Formulation example 1. Powder compound number 2 2 parts -
At least 98 parts are mixed and pulverized to obtain a powder.

Formulation example 2. Emulsion Compound No. 12 parts Calcium alkylbenzenesulfonate 3 parts Polyoxyethylenalkylaryl ether 10 parts Quizylol
85 parts These ingredients are mixed until homogeneous to obtain an emulsion.

Formulation example 3. Wettable powder compound number 6 20 parts Sodium lignin sulfonate 1 part Polyoxyethylenenalkylaryl ether 4 parts -
75 parts Mix each of these ingredients until homogeneous,
It is crushed and used as a hydrating agent.

Formulation example 4. Granule Compound No. 1 3 parts Bentonite 30 parts Sodium alkyl sulfate 2 parts -
65 parts These ingredients are mixed until uniform, kneaded, and granulated by a conventional granulation method to be used as a granule.

Claims (3)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas, chemical formulas, tables, etc. ▼, B represents a hydrogen atom, a halogen atom, a nitro group, a methyl group, or a trifluoromethyl group, and n represents an integer from 0 to 2. X represents a hydrogen atom or a methyl group, and Y and Z each independently represent a lower alkyl group or form a ring together with adjacent carbon atoms to represent a cyclopropyl group. ] A triazole urea derivative represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas, chemical formulas, tables, etc. ▼, B represents a hydrogen atom, a halogen atom, a nitro group, a methyl group, or a trifluoromethyl group, and n represents an integer from 0 to 2. X represents a hydrogen atom or a methyl group, and Y and Z each independently represent a lower alkyl group or form a ring together with adjacent carbon atoms to represent a cyclopropyl group. ] A general formula characterized by reacting a triazole compound represented by dimethylcarbamyl chloride ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A, X, Y and Z represent the same meanings as above. . ] A method for producing a triazole urea derivative. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas, chemical formulas, tables, etc. ▼, B represents a hydrogen atom, a halogen atom, a nitro group, a methyl group, or a trifluorothyl group, and n represents an integer from 0 to 2. X represents a hydrogen atom or a methyl group, and Y and Z each independently represent a lower alkyl group or form a ring together with adjacent carbon atoms to represent a cyclopropyl group. ] A triazole derivative represented by