JPS6178788A - Tetrahydrotriazolopyridazine derivative, its preparation, and herbicide comprising same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R<1> is H, or methyl; R<2> is lower alkyl, lower alkenyl, lower alkynyl, or lower alkoxymethyl; X is H, or F). EXAMPLE: 2-(4-Allyl-7-fluoro-2H-benzoxazin-3(4H)-on-6-yl)hexahy-dr-o-3-thioxo-1 H-[1,2,4]triazole[1,2-a]pyridazin-1-one. USE:A herbicide. PREPARATION:A tetrahydropyridazine derivative [e.g., 1-(4-allyl-7-fluoro-2H-benzoxazin-3(4H)-on-6-ylaminothiocar-bonyl)-2-e thoxycarbonylhexahydropyridazine, etc.] shown by the formula II (R<3> is lower alkyl) is heated in the presence of preferably 0.01-1 equivalent base (e.g., sodium methoxide, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein R1 represents a hydrogen atom or a methyl group;
2 represents a lower alkyl group, lower alkenyl group, lower alkynyl group or lower alkoxymethyl group, and X represents a hydrogen atom or a fluorine atom. ] and is a tetrahydrotriazolopyridazine derivative (
Hereinafter, it will be referred to as the compound of the present invention. ), its production method, and herbicides containing it as an active ingredient.

The compounds of the present invention can be used to treat various weeds that are problematic in the treatment of foliage and soil in upland areas, such as freckle weeds, Japanese knotweed, purslane, chickweed, whiteweed, Japanese radish, Japanese radish, Japanese hornwort, Ebisu grass, Japanese radish, and other problematic weeds. , broad-leaved weeds such as golden deer, field pansies, Japanese violets, morning glories, commonweeds, hotokenosa, Japanese morning glories, Japanese snails, Japanese staghorns, Japanese firs, sunflowers, dog mottles, corn marigolds, barnyard grass, golden millet, foxtail grass, black grass, The compound of the present invention has a herbicidal effect on weeds of the Poaceae family, such as Prunus cerevisiae, Prunus japonicum, Oats, Oats, and Seiban sorghum, Weeds of the Araceae family, such as Asiatic dayflower, and Cyperaceae, such as Cyperaceae, and moreover, the compound of the present invention , does not cause any harmful effects on major crops such as rice, soybeans, and cotton.

In addition, the compound of the present invention can be used to eliminate various weeds that are problematic in the treatment of 7-crystalline water in paddy fields, such as grass weeds such as Japanese millet,
It has a herbicidal effect on broad-leaved weeds such as azalea, japonica, and common chickweed, on cyperaceous weeds such as bulrushes and cyperus, and on cyperus, and on rice, and does not cause any problem with rice.

The compound of the present invention has the general formula: [wherein R1, R2 and X have the same meanings as above, and R3 represents a lower alkyl group. ] It can be manufactured by reacting the tetrahydropyrigine derivative shown in the following in the presence of a base at 40°C to 100°C for 0.5 to 24 hours.

In this ;), the use of a base F'1) is a tetrahydropyridazine derivative 7! R body [mouth] o, oi ~ l for 1 allowance
It's an elbow.

7.7 As a solvent, alcohols such as methanol, ethanol, i/propertool, [-butanol, octatool, cyclohexanol, and methyl cellosolve;
Formamide, N, N-dimethylacetamide, N
.

Examples include acid amides such as N-dimethylacetamide Qf, sulfur compounds such as dimethylsulfoxide, and mixtures thereof.

Examples of the salt-8 include alkali gold monoalkoxides such as sodium methoxide and sodium ethoxide, and fluorides such as sodium fluoride and potassium fluoride.

After the reaction is completed, the reaction solution is subjected to normal post-treatments such as organic solvent extraction and concentration after adding water, and if necessary, purified by chromatography, recrystallization, etc. compound can be obtained.

Next, Table 1 shows the compounds of the present invention produced by this production method.

Table 1 \、 \、 Next, production examples of the compounds of the present invention will be shown.

Production Example 1 ■-(4-allyl-7-fluoro-2H-benzoxazin-3(4)f)-one-6-ylaminothiocarbonyl)-2-ethoxysulfonylhexahydropyridazine (0.71) was dissolved in methanol. In addition to 148 ml, a catalytic amount of sodium methoxide was added, and the mixture was heated under reflux for 1.5 hours. After the reaction mixture was cooled, water was added and extracted with ethyl acetate. The extract was washed with water, dried, and concentrated, and the residue was purified by silica gel thin layer chromatography (developing solvent: ethyl acetate:hexane = 2:3) to obtain 2-(4-allyl-
7-fluoro-2H-benzoxazine-8(4H)-
on-6-yl)hexahydro-3-thioxo-IH-
(1,2,4)TriazoC1(1)2-a)Pyridazin-1-one0. l5? I got it.

m, p, 218-219°C Some of the compounds of the present invention that can be produced by such a production method are shown in Table 2.

Table 2 General formula: 1<= [In the formula, R1, R2, and X represent laziness, which is the same as deletion. ] Intiocyanate shown as 1.0
-1.1 equivalent m, general formula [wherein R3 does not contain any lower alkyl group]. ] in a solvent with l-alkoxycarbonyltetrahydropyridazine in the presence of a base of catalyst ￥I() at 10°C to 100°C.
, can be produced by reacting for 1 hour to 48 hours.

Examples of solvents used in this reaction include aromatic hydrocarbons such as toluene and benzene, halogenated hydrocarbons such as chloroform, and ethers such as dioxane and dimethoxyethane. Examples of bases include triethylamine and diethylaniline. Examples include organic bases.

After the reaction is completed, water is added, followed by conventional post-treatments such as organic solvent extraction and ml concentration, and if necessary, chromatography and distillation can be carried out.

When using the compound of the present invention as an active ingredient of a herbicide,
It is usually mixed with solid carriers, adult carriers, surfactants and other formulation auxiliaries to formulate emulsions, wettable powders, ill preparations, granules and the like.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.03 to 90%, preferably 0.05 to 80%.

As solid carriers, fine powders or granules of kaolin clay, attapulgite clay, ben I night, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut, urea, ammonium sulfate, synthetic hydrous silicon oxide) are used. Examples of primary carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, isopropanol,
Alcohols such as ethylene glycol and cellosolve; ketones such as acetone, cyclohexanone and isophorone;
Vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, N
, N-dimethylformamide, acetonyl-IJ, water and the like.

Surfactants used for emulsification, dispersion, humidity, etc. include anionic surfactants such as alkyl sulfate salts, alkylaryl sulfonate salts, dialkyl sulfosuccinate salts, and polyoxyethylene alkylaryl ether phosphate salts. , polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether,
Examples include nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Adjuvants for formulation include lignin sulfonate, alginate, polyvinyl alcohol, arabic gum, CMC (carboxymethyl cellulose), PA
Examples include P (isopropyl acid phosphate).

Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 2. Parts indicate parts by weight.

Formulation Example 1 9.50 parts of the compound of the present invention, 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 2 4.5 parts of the compound of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 30 parts of xylene, and 45 parts of N,N-dimethylformamide were combined to form an emulsion. obtain.

Formulation Example 3 2.2 parts of the compound of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignosulfonate, 30 parts of bentonite, and 65 parts of kaolin clay were thoroughly ground and mixed, water was added, and the mixture was thoroughly kneaded. The granules are dried to obtain granules.

Formulation Example 4 6.25 parts of the compound of the present invention, 31 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC, and 69 parts of water were mixed and wet-pulverized until the particle size became 5 microns or less! 71
．． Get an adjuvant.

The compound of the present invention thus formulated is treated with soil, foliage, or flooding before or after the emergence of weeds. Soil treatment includes soil surface treatment, soil mixing treatment, etc., and foliage treatment includes treatment from above the plant body, as well as local treatment that treats only weeds so that they do not attach to crops.

Furthermore, by mixing it with other herbicides, it can be expected to increase the herbicidal efficacy. Furthermore, it can be used in combination with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners, and the like.

The compound of the present invention can be used in rice fields, fields, orchards, pastures,
It can be used as an active ingredient in herbicides for lawns, forests, non-agricultural lands, etc.

When the compound of the present invention is used as an active ingredient of a herbicide, the treatment rate will vary depending on weather conditions, dosage form, dosage period, method, location, target weeds, target crops, etc., but is usually 0 per are. .014~1o
or, preferably O,0a5P~501, and emulsions, wetting agents, suspending agents, etc. usually have a prescribed fik of 1 liter to 1 J liter per are (if necessary,
Granules and the like are usually treated as they are without any dilution.

In addition to the surfactants mentioned above, the spreading agents include polyoxyethylene resin acid (ester), lignin sulfonate,
Abietate, dinaphthylmethane disulfonate, paraffin, etc. can be extracted.

Next, test examples demonstrate that the compounds of the present invention are useful as active ingredients of herbicides. The compounds of the present invention are indicated by the compound numbers in Table 2, and the compounds used for comparison are indicated by the compound numbers in Table 2.
Indicated by compound symbol in the table.

Table 3 In addition, the herbicidal efficacy was determined by visually observing the degree of budding and growth inhibition of the test plants during the survey, and ``0'' indicates that there was no or almost no difference from the case where the compound was not tested. If the plant is withered or its growth is completely inhibited, it is evaluated as ``5'', and evaluated on a scale of θ to 5, 0, 1, 2.
3.4.5.

Test Example 1 Upland Soil Treatment Test A cylindrical plastic pot with a diameter of 10 LM and a depth of 1 OCrn was filled with upland soil, sown with Japanese barnyard grass, Japanese morning glory, and Japanese crocodile, and covered with soil.

The test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water equivalent to 10 liters per are, and the emulsion was applied to the soil surface using a small sprayer. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 4.

Table 4 Test Example 2 Upland Stem and Leaves Treatment Test A cylindrical plastic pot with a diameter of 10 cnt and a depth of 1 OCrn was filled with upland soil, and Japanese barnyard grass, Japanese radish, and Japanese radish were sown and grown for 10 days in a greenhouse. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water containing a spreading agent equivalent to 10 liters per are, and the foliage was treated from above the plant using a small sprayer. 20 days after treatment
The plants were grown in a greenhouse for one day and their herbicidal efficacy was investigated. The results are shown in Table 5.

Table 5 Test Example 3 Paddy field flooding treatment test A cylindrical plastic pot with a diameter of 8α and a depth of 12 cm was filled with paddy soil, and 1 to 2 cm of seeds of Japanese millet, broad-leaved weeds (Azaena, Kikashigusa, Chickweed), and firefly were added to the pot.
It was mixed to a depth of . After flooding the rice field to form a paddy field, tubers of Urikawa were buried at a depth of 1 to 2 crn and grown in a greenhouse. After 6 days (at the beginning of each weed's emergence), the test compound was prepared into an emulsion using Formulation Example 2, and a predetermined amount of the emulsion was diluted with 5 milliliters of water and applied to the water surface. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated.

The results are shown in Table 6.

Table 6 Test・1. Row 4 Upland soil treatment test/painted surface E 33 x 23 cd, depth lIL: Fill Jn vats with field ground 1, soybeans, corn, Japanese fir, Japanese mulberry, Japanese crocodile, blueberry, Japanese staghorn,
The plants were planted with cuttings of American hornwort, foxtail grass, and silver grass, and covered with soil to a thickness of 1 to 2 cm. The test compound is made into an emulsion according to Special Provisions Example 2, and the prescribed amount is 1 per are.
It was diluted with 0 liter of water and applied to the surface of the soil using a small sprayer.

After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated.

The results are shown in Table 7.

Test Example 5 Upland soil treatment test Area: 33 x 2: 3 d 1 depth: 1 lcr It filled with up field soil, and wheat, Japanese violet, Japanese violet,
Chickweed, whiteweed, Japanese knotweed, buckwheat, and sycamore were sown, and the soil was covered with soil to a thickness of 1 to 2 CIn. Make the test compound into an emulsion according to Formulation Example 2, dilute the specified amount of 5k with water equivalent to 101 J tutle per are,
The soil surface was treated with a small sprayer. After treatment, the plants were grown in a greenhouse for 27 days and their herbicidal efficacy was investigated. The results are shown in Table 8.

\, Test Example 6 Field stem 1 treatment test rotation 83X23c1). Fill a vat with a depth of 1lCrn with the field ground, and harvest corn, wheat, sugar beet, Japanese fir tree, Japanese radish, Japanese Physalis, Maruba morning glory, Shiroza,
Green foxtail was sown and grown for 18 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of it was
The mixture was diluted with 5 liters of water per area containing a spreading agent, and applied evenly over the entire stem and leaves from the top of the plant using a small sprayer. At this time, the growth conditions of weeds and crops vary depending on the grass species, but the 1-4 leaf stage and the plant height are 2-12L:r.
It was. The herbicidal efficacy was investigated 20 days after the treatment. The results are shown in Table 9. Note that this test was conducted in a greenhouse throughout the entire period.

Test Example 7 Paddy field flooding treatment test 1 / 5000a A Wagner pot was filled with paddy soil, and seeds of Japanese millet, broad-leaved weeds (Azeena, Azalea, Chickweed) 5, and overwintering buds of Pinus cabbage were mixed in at a depth of 1 to 2 liters. . After flooding the fields to create a paddy field, tubers of Urikawa were buried at a depth of 1 to 2 leaps, and then rice at the 3-leaf stage was transplanted and grown in a greenhouse. After 6 days (the beginning of germination of Japanese millet), the test compound was made into an emulsion according to Formulation Example 2.
A predetermined amount of the diluted solution was diluted with 10 milliliters of water and applied to the water surface to a depth of 4 CrIt.

After treatment, the plants were grown in a greenhouse for 20 days, and the herbicidal efficacy was evaluated as A-fI. The results are shown in Table 10.

3 days per day for 2 days after treatment.
Water leaked in an amount equivalent to - water depth;

No.1 θ Table

Claims (1)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1 represents a hydrogen atom or a methyl group,
^2 represents a lower alkyl group, lower alkenyl group, lower alkynyl group or lower alkoxymethyl group, and X represents a hydrogen atom or a fluorine atom. ] A tetrahydrotriazolopyridazine derivative represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 represents a hydrogen atom or a methyl group, and R
^2 represents a lower alkyl group, lower alkenyl group, lower alkynyl group or lower alkoxymethyl group, X represents a hydrogen atom or a fluorine atom, and R^3 represents a lower alkyl group. ] A general formula characterized by heating the tetrahydropyridazine derivative shown in the presence of a base ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1, R^2 and X have the same meanings as above. represents. ] A method for producing a tetrahydrotriazolopyridazine derivative. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents a hydrogen atom or a methyl group, and R
^2 represents a lower alkyl group, lower alkenyl group, lower alkynyl group or lower alkoxymethyl group, and X represents a hydrogen atom or a fluorine atom. ] A herbicide characterized by containing a tetrahydrotriazolopyridazine derivative represented by the following as an active ingredient.