JPS617278A - Pyridazinotriazine derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is lower alkyl; X is halogen, alkyl or alkoxy; n is 1 or 2). EXAMPLE:5-(2-Chlorobenzoylhydrazino)-4-chloro-2-methyl-3(2H)-pyridazin one. USE:Herbicide exhibiting remarkable selectivity to the crops such as rice, corn, wheat, soybean, etc. Useful for the control of weeds such as cockspur-grass, large crab-grass, umbrella sedge, smooth pigweed, etc. PREPARATION:The objective compound of formula I can be prepared by treating dichloropyridazinone of formula I with hydrazine and then with benzoyl chloride or substituted phenyl ester to obtain the compound of formula III, and heating the compound in the presence of methanol saturated with ammonia to effect the simultaneous cyclization and dehydrogenation reactions.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel pyridazinotriazine derivatives and herbicides containing one or more of the pyridazinotriazine derivatives as an active ingredient.

Conventional 3 Selective herbicides having a (2H)-pyridazinone ring include 5-amino-4-chloro-2-phenylpyridazin-3(2H)-one (-ship name Pyrazone), 4-chloro-5-methylamino -2-(3-trifluoromethylphenyl)pyridazin-3(2H)-one (-ship name: norflurazone) is known. On the other hand, examples of herbicides having an I,2,4-triazine ring include 4-amino-6-tert-butyl-3-methylthio-1.2.
4-1-Ryazin-5(4H)-one (generic name metribuzin) is in practical use. However, 3(2H
)-pyridazinone ring and 1,2,4-triazine ring are condensed, and the pyridazinotriazine derivative represented by the following general formula (1) is a completely new compound, and its herbicidal activity is completely unknown. It's not.

[However, in the formula, R represents a straight-chain or branched lower alkyl group, X represents a halogen atom, an alkyl group, or an alkoxy group, and n does not represent 1 to 2. ] As a result of extensive research into these pyridazinotriazine derivatives, the present inventors have found that these compounds exhibit high herbicidal activity against various weeds when treated with soil and foliage, as shown in the test examples below. The present invention was completed based on the discovery that the present invention exhibits remarkable selectivity for major crops such as grass, rice, corn, wheat, and soybean.

The compound of the present invention can be synthesized by the following method.

(TIT) (IV) (IV) [However, in the formula, R represents a linear and branched lower alkyl group, X represents a halogen atom, an alkyl group, or an alkoxy group, and n represents 1 to 2. ] That is, by treating dichloropyridazinone represented by the formula (old) with hydrazine to obtain a pyridazinone derivative represented by the formula (TII), and treating this with hendiyl chloride or substituted phenyl carbonate ester, the formula ( An intermediate represented by V) is obtained. This intermediate is also a new compound that has not been described in any literature, but it is heated in a sealed tube with methanol saturated with ammonia to simultaneously carry out ring-closing and dehydrogenation reactions. , the desired compound (I) can be obtained in good yield.

The compounds included in the present invention are specifically shown in Table 1 below,
The present invention is not limited to these.

Table 1 Next, a specific synthesis example will be described below.

Point 11 Synthesis of compound Nll 2-chlorohendiylchloride 3 in 20 ml of dioxane
．． A solution of 85 g (2,20x 10-2 mol) of 4-chloro-5-hydrazino-2-methyl-3 (
2H)-pyridazinone 3.49 g (2,00x 1
It was slowly added dropwise at room temperature to a mixed solution of 300 ml of dry pyridine and 300 ml of dry pyridine. After stirring for one day and night, excess pyridine was distilled off under reduced pressure. Water was added to the resulting residue, and insoluble solids were filtered. This was recrystallized from ethanol to obtain the desired 5-(2-chlorobenzoylhydrazino)-4-
Chlor-2-methyl-3(2H)-pyridazinone 2.7
5g was obtained. Melting point 233-235°C, then 50 ml of methanol saturated with ammonia gas at 0°C and 2.75 g of the obtained 5-(2-chlorobenzoylhydrazino)-4-chloro-2-methyl-3(2H)-pyridazinone. was heated in a pressure-tight sealed container in an oil bath at 120°C for 5 hours. After cooling, the container was opened and the contents were dried under reduced pressure. The residue was recrystallized from ethanol to obtain 11 liters of compound N.
．． I got 8g.

Melting point: 233-235°C The intermediate obtained here is also a new compound and can be synthesized according to the above example, and specific data thereof are shown in Table 2 below. Here, the compound shade corresponds to the compound shade in Table 1 above.

Table 2 When applying the compounds of the invention as herbicides, suitable carriers are generally used, such as clay, talc, bentonite,
Solid carriers such as diatomaceous earth, water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons! ! Can be applied in combination with liquid carriers such as (benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), acid amides (dimethylformamide, etc.). , an emulsifier, a dispersant, if desired,
By adding suspending agents, penetrating agents, spreading agents, stabilizers, etc., liquid formulations,
It can be put to practical use in any form such as emulsions, wettable powders, powders, and granules.

Next, examples of formulations of herbicides containing the compound of the present invention as an active ingredient will be shown, but the invention is not limited thereto.

In addition, in the following formulation examples, "1 part" means part by weight.

Inflammation Hydrating agent Compound of the present invention] ----------50
Part Sieglite A ----------------
−−−−−−−16 parts (Kaolin clay: Sieglite Kogyo ■Product name) Tsurupol 5039 −−−−−−−
−−−−−−−−−− 2 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■trade name) Carplex (anticaking agent) −−−−2 parts ( White carbon (Shionogi & Co., Ltd. G1 trade name) is mixed and pulverized uniformly to make a wettable powder. When using, add 50% of the above hydrating agent.
It is diluted ~5,000 times and sprayed so that the amount of active ingredient is 0.05 kg to 10 kg per hectare.

Sake Kaikan Flame Wettable Dispersible Compound of the Invention It, 4 -------------
---75 parts Sieglite A ---------
----------] 99 parts kaolin clay: Zikrite Kogyo 01 trade name) Tsurupol 5039 -------
--------- 2 parts (mixture of nonionic surfactant and anionic surfactant: Toho Kagaku ill brand name) Carplex (anti-caking agent) ------
At least 4 parts (white carbon: Shionogi & Co., Ltd. commercial name) are mixed and pulverized uniformly to make a wettable powder.

Hydration Hydration Compound of the present invention Floor 7 ----------------
50 parts Sieglite A
−−−−−−−−46 parts (Kaolin clay: Sieglite Kogyo ■Product name) Tsurupol 5039 −−−−−−
−−−−−−−−−− 2 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical's trade name) Carplex (anticaking agent) −−−−−2 parts (White Carbon: Shionogi & Co., Ltd. trade name) The above is mixed and pulverized uniformly to make a wettable powder.

Formulation Example 4 Emulsion Compound of the Invention Floor 8
−20 copies −−−−−−−−
−−−−−−−−−−−−75 parts Tsurupol 2680
----1111---5 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■ trade name) The above is mixed uniformly to form an emulsion. When used, the above emulsion is diluted 10 to 5,000 times and sprayed at an amount of active ingredient of 0.05 kg to 10 kg per hectare.

Formulation example 5 Flowable compound of the present invention
25 parts Ageli Seal S-710---10 parts (
Non-ionic surfactant: Kao Atlas product name) Lunosoxl OOOC---------------------0, 5
(Anionic surfactant: Toho Chemical brand name) 1% Rhodobol water ---------------20
Part (thickener: Lone Boulin product name) water
−−−−−−−−−−−−−−−−−−−−−−−−−
------- 44. 5 parts or more are mixed uniformly to form a flowable agent.

Compound J Granules Compound of the Invention 2 −−−−−−−−−−−−−−
− 5 parts bentonite −−−−−−−−−−
------50 parts talc ---------
−−−−−−−−After uniformly mixing and pulverizing 45 parts or more,
Add a small amount of water, mix and knead with stirring, increase the granules using an extrusion type granulator, and dry to form granules.

Formulation Example 7 Granules Compound of the Invention 1h7 -------------
−−− 8 parts bentonite −−−−−−−−−
-----------55 parts talc --------
−−−−−−−−−−−− After uniformly mixing and pulverizing 37 parts or more, adding a small amount of water, stirring and kneading, increasing the granules with an extrusion type granulator, and drying them into granules. Make it into a drug.

Furthermore, the compound of the present invention may be applied in combination with other herbicides, various insecticides, fungicides, synergists, etc. when preparing or spraying, if necessary.

Other types of herbicides mentioned above include, for example, Farm Chemicals Handbook.
Handbook) 70th edition (1984).

In addition, the compound of the present invention can be used to control various weeds in agricultural and horticultural areas such as fields, paddy fields, orchards, and in non-agricultural areas such as sports fields, vacant lots, and railway edges, and the amount of application depends on the application situation. There are differences depending on the application time, application method, target grass species, cultivated crops, etc., but in general, the appropriate amount of active ingredient is about 0.05 to 10 kg per hectare.

Next, the usefulness of the compounds of the present invention as herbicides will be specifically explained in the following test examples.

Test Example-1 Weeding effect test by soil treatment Sterilized diluvial soil was placed in a plastic box measuring 15 cm in length, 22 cm in width, and 5 cm in depth, and rice, wild grass, crabgrass, cyperus, and
Mixed seeding of Koakaza, Portulaca, Trifolium elegans, and Doggrass, about 1. After covering the soil to a depth of 5 cm, the soil surface was uniformly dispersed so that the amount of active ingredient was at a predetermined ratio.

The chemical solution used for spraying was the wettable powder of the formulation example described above diluted with water and sprayed over the entire surface with a small sprayer. Four weeks after spraying the chemical solution, the herbicidal effect on rice and various weeds was investigated according to the following criteria.

The results are shown in Table 3.

Some of the compounds of the invention have selectivity for certain crop species.

Judgment Criteria 5- Weed killing rate 90% or more (almost complete death) 4-
Weed killing rate 70-90% 3- Weed killing rate 40-70% 2- Weed killing rate 20-40% 1- Weed killing rate 5-20% 0- Weed killing rate 5% or less (mostly ineffective) However,
The above-mentioned weed killing rate was determined by the following formula by measuring the weight of grass in the ground-F part of the chemical-treated area and the weight of above-ground grass in the untreated area.

Table 3. Weeding effect test using stem and foliage treatment Sterilized diluvial soil was placed in a plastic box measuring 15 cm long, 22 cm wide, and 5 cm deep.
Seeds of Koakaza, Portulaca trifoliata, C. japonica, and C. elegans were sown in spots and covered with soil to a depth of about 1.5 cm. When each plant reached the 2-3 leaf stage, the active ingredient was uniformly sprayed onto the stems and leaves so that the amount of the active ingredient was at a predetermined ratio.

The chemical solution used for spraying was the hydrating agent of the formulation example described above diluted with water and sprayed over the entire surface of the stems and leaves of various weeds using a small sprayer. Four weeks after spraying the chemical solution, the herbicidal effect on rice and various weeds was examined 8 times according to the criteria of Test Example-1.

The results are shown in Table 4.

Table 4 Test Example-3 Selectivity test for crops Place sterilized diluvial soil in a plastic box measuring 15 cm long, 22 cm + n wide, and 6 cm + n deep, and sow seeds of corn, wheat, barley, turgid, and soybean in spots. The soil was covered with approximately 1.5c+n of soil.

When the various plants reached the 2-3 leaf stage, the active ingredients were uniformly sprayed onto the grass blades at a predetermined ratio.

The chemical solution used for spraying was the hydrating agent of the formulation example described above diluted with water and sprayed over the entire surface of the stems and leaves of various weeds using a small sprayer. Four weeks after spraying the chemical solution, the herbicidal effect on rice and various weeds was investigated according to the criteria of Test Example-1.

The results are shown in Table 5.

Margin below t1 Table 5

Claims (2)

[Claims] (1) Formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [However, in the formula, R represents a straight chain or branched lower alkyl group, and X represents a halogen atom, an alkyl group, or an alkoxy group. represents a group, and n represents 1 to 2. ] A pyridazinotriazine derivative represented by. (2) Formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [However, in the formula, R represents a straight chain or branched lower alkyl group, and X represents a halogen atom, an alkyl group, or an alkoxy group. represents a group, and n represents 1 to 2. ] One or two pyridazinotriazine derivatives represented by
A herbicide whose active ingredients are seeds or more.