KR840000269B1 - Insect compositions - Google Patents

Abstract

A compn. contg. 5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazolin-2-one(A) and pyrazoles(I;X=phenacyl, 4-methylphenacyl) is a synergistic rice paddy herbicide. Thus, a compn. contg. (A) and 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole (0.5+3 g/are) controlled Echinochloacrus-galli, Scirpus juncoides, Sagittaria pygmaea, Cyperus serotinus, and various broad-leaf weeds, whereas sep. application of the components failed to control the weeds. Preparative data is given.

Description

Herbal composition

In the present invention, 5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazolin-2- is represented by (A) and general formula (I). The pyrazole derivatives (b) are formulated in (a) 1 to 10 parts by weight with respect to 1 part by weight of (b) to exhibit a remarkable synergistic effect that cannot be expected for single use alone. It relates to a mixed herbicide composition characterized by being capable of killing problem weeds.

In the above general formula, X represents a penacyl group or 4-methylphenacyl group.

At present, a number of herbicides have been put into practical use as power herbicides and are widely used as a single agent and a mixed agent. However, there are many types of hydrangea and there are many herbicides effective for annual weeds, but few herbicides are effective for perennial weeds. As a result, perennial weeds are increasing and control is urgently desired.

Perennial weeds are generally very active, long-lived, and strong seaweeds. Therefore, as a herbicide, the thing of the property which broadened the herbicide spectle which can kill many kinds of weeds is desired.

In addition, in recent years, the introduction of mechanization and the early stage of transplantation are spreading rapidly, giving a suitable place for the development of weeds more than in the past, and it is a tendency that complete weed control cannot be expected with a single herbicide use. .

For this reason, the same or different herbicides are repeatedly used several times, and the repeated use of such herbicides is not only large and requires much effort, but also poses undesirable problems such as weakness of water and soil residue due to the large amount of application.

The present inventors have continued to search for safe herbicides which completely control all the weeds by one spray and further have a high safety against water and have very low toxic toxicity in order to improve these problems of conventional herbicides. The present invention was completed by knowing that an excellent herbicide having improved these problems can be obtained by blending two active ingredients.

That is, the present invention is a 5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazolin-2-one known as a herbicide for water. And a pyrazole compound (I) of the general formula (I).

When explaining the present invention in more detail, (A), which is one of the components of the herbicidal composition, is highly effective against wild grasses, and is active as an early growth treatment for algae, a perennial weed, which has become a problem recently. As you progress this effect becomes weaker.

On the other hand, pyrazole-based compounds (B) do not cause any detriment to the water supply in the faucet, and the annual fresh grass weeds, the lateral weeds, the beetles, and the peels have effects on the perennial weeds. However, when the weeds are grown to some extent, the effect is lowered, and the effect on the grass in particular is insufficient.

However, the mixed application of both of them examined herbicidal effects, weaknesses, and the like, and as a result, it was surprising that the herbicide width was extended beyond the scope of application as an individual herbicide. It has been found that weeds, tadpoles, beetles, and perennial weeds, such as snares, can extend to the spread of spraying without compromising safety on water.

In addition, this herbicide is sufficiently effective as a mixture of doses much lower than the sweet rice usage, and the herbicidal effect is sufficiently increased as a single treatment agent, and its effect lasts for a long time.

The compound (I) of formula (I), which is an active ingredient of one of the herbicides of the present invention, is, for example, substituted alkylation of compound (1) as a substituted alkylating agent corresponding to the group X, as shown in the following reaction scheme. Therefore, it can manufacture easily.

(Wherein X is the same as the foregoing).

As the substituted alkylating agent corresponding to the group X, for example, halides such as chlorides, sulfides and oxides are particularly suitably used.

The reaction represented by the above formula is suitably carried out in the presence of a solvent, and the solvent is not particularly limited as long as it is not involved in the reaction. For example, diethyl ether, tetrahydrofuran, dioxane and the like Aromatic hydrocarbons such as ethers, benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and trichloroethane, ketones such as acetone and isobutyl methyl ketone, ethyl acetate, amyl acetate and the like Esters, acetonitrile and the like, and mixed solvents thereof, but aromatic hydrocarbons and ethers are suitably used.

When using a halide as a substituted alkylating agent, it is preferable to use a deoxidizer, and as such a deoxidizer, inorganic bases, such as sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, N, N-diethyl aniline, for example Organic bases, such as these, are mentioned.

The reaction temperature is not particularly limited and is performed as a reflux temperature of the room temperature to the solvent. The reaction time depends on the reactant and the reaction temperature and is usually 30 minutes to 24 hours.

After the completion of the reaction, the target product is isolated according to a conventional method, and purified by column chromatography, recrystallization or the like as necessary.

The manufacturing method of the compound of Formula [I] which is an active ingredient of this invention is demonstrated according to the following preparation examples.

[Production Example 1]

A mixture of 1.425 g of 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-hydroxypyrazole, 15 ml of benzene, 0.505 g of triethylamine and 0.995 g of phenacylbromide was heated to reflux for 1 hour with stirring. do. After cooling, water was added to separate the salts, washed with 5% aqueous sodium bicarbonate solution, followed by water, dried over anhydrous sodium sulfate, and the solvent was distilled off to give 1.75 g of an oily substance. This was separated by column chromatography (silica gel: benzene: eluted as ethyl acetate = 6: 1), and 1.2 g (yield: 59.6%) of 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-phena Siloxypyrazole (Na-1) is obtained. Melting point 109.5-110.5 ° C. (recrystallized from n-hexane).

[Production Example 2]

To 10 g of 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-hydroxypyrazole, 70 ml of acetonitrile and 4.85 g of potassium carbonate (anhydrous) were added, stirred at room temperature for 2 hours, and phenacyl bromide 7.7 The solution which melt | dissolved g in 10 ml of acetonitriles was added, it stirred, and it refluxed for 1 hour. The salts are filtered off and the filtrate is concentrated to add benzene, followed by washing with a dilute aqueous sodium bicarbonate solution followed by water. It was dried over anhydrous sodium sulfate, crystallized by adding 3-hexane to the residue obtained by distilling off the solvent, and the resultant was filtered. 12.88 g (yield: 91.2%) of 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5- Phenaciloxypyrazole (Na-1) is obtained. Melting point 109.5-110.5 ° C. (recrystallized from n-hexane).

According to the method of Preparation Examples 1 to 2, the following compounds were prepared.

5-benzyloxy-4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazole

4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5- (2-oxopropyloxy) pyrazole

νC = 0; 1740 cm ^-1 , 1640 cm ^-1

4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5- (4-chlorobenzyloxy) pyrazole

Melting Point 138 ~ 139 ℃

4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5- (4-nicobenzyloxy) pyrazole

Melting Point 146 ~ 147 ℃

4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-ethoxycarbonylmethoxypyrazole

C = O: 1760 cm ^-1 , 1650 cm ^-1

4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5- (4-methylphenacyloxy) pyrazole

(나-1)

(B-1)

The mixing agent shown in this invention is a novel combination of undocumented documents, and of course, there is no document mentioning the specific potentiation effect.

The synergism concerning this invention is recognized as a mixing ratio of a wide range, A compound herbicide represented by General formula (I) with respect to 1 weight part of compound (A) can be mixed as a ratio of 1-10 weight part, and a useful herbicide can be made. The herbicide of the present invention thus completed has an effect even when treated with weeds before germination and after germination, and high effects are obtained even in soil treatment and transverse spraying treatment. It is useful not only for water, but also for various grains, legumes, cotton, vegetables, orchards, grass, grasslands, tea gardens, fields, woodlands, and non-crop lands.

The mixture of the present invention may be sprayed as it is, but is usually used as a herbicide by mixing with a carrier and other auxiliary agents, if necessary, for example, powders, powders, granules, granules, hydrates, emulsions, and aqueous solutions. It is prepared by using as a water-soluble, suspending agent and the like.

Suitable solid carriers used to prepare the herbicides of the present invention include clays, talc, mica, flanks, pumice, burr mukilite, gypsum, calcium carbonate, and the like represented by kaolinite group, montmorillonite group or attabarzite group. Inorganic substances such as dromite, diatomaceous earth, magnesium lime, apatite, zeolite, silicic anhydride, synthetic calcium silicate, soybean flour, edible powder, hoe powder, wheat flour, wood powder, starch, vegetable organic materials such as crystalline cellulose, Kumar Synthetic or natural polymer compounds such as ron resins, petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums, cobar gums, damar gums, waxes such as carnabarab, beeswax or Urine and the like.

Suitable liquid carriers include paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil and white oil, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalin, carbon tetrachloride, chloroform, Chlorinated hydrocarbons such as trichloroethylene, monochlorbenzene, and 0-chlortoluene, ethers such as dioxane and tetrahydrofuran, acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetphenone, and isophorone Ketones, ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, esters such as diethyl succinate, methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol, etc. Alcohols, ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether And polar solvents such as teral alcohols, dimethylformamide and dimethyl sulfoxide, and water.

Surfactants used for the purpose of emulsification, dispersion, wetting, expansion, binding, disintegration control, effective component stabilization, fluidity improvement, rust prevention, etc. can be used for any of nonionic, cationic and zwitterionic, Usually nonionic and / or anionic ones are used.

As a suitable nonionic surfactant, ethylene oxide is added to alkylphenols, such as those in which ethylene oxide is polymerized by higher alcohols such as lauryl alcohol, stearyl alcohol, oleyl alcohol, and isooctyl phenol and nonyl phenol. Polymerization addition of ethylene oxide to alkylnaphthol such as butylnaphthol and octylnaphthol, polymerization addition of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid and oleic acid, stearic acid, dilauryl phosphate, and the like. Polymerization of ethylene oxide to mono or dialkyl phosphoric acid; Polymerization of ethylene oxide to amines such as dodecylamine and stearic acid amide; Higher fatty acid esters of polyhydric alcohols such as sorbitan and ethylene oxide The thing which superposition | polymerization addition, the thing which superposed | polymerized addition of ethylene oxide, and propylene oxide is mentioned.

Suitable anionic surfactants include, for example, alkyl sulphate ester salts such as sodium lauryl sulphate and oleyl alcohol sulphate ester amine salts, sodium sulphate dioctyl ester, sodium 2-ethylhexanesulfonate, sodium methylenebisnaphthalenesulfonate, Aryl sulfonates, such as aryl sulfonate, such as sodium lignin sulfonate and sodium dodecylbenzene sulfonate, etc. are mentioned.

In addition, the herbicide of the present invention includes a polymer such as casein, gelatin, glue, sodium arginate, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, etc. for the purpose of improving the properties of the formulation and enhancing the biological effect. Compounds or other auxiliaries may also be used in combination.

The above carriers and various auxiliaries are suitably used alone or in combination according to the purpose in consideration of the formulation of the preparation, the application scene, and the like.

The powder is, for example, usually contains 1 to 25 parts by weight of the active ingredient compound, and the balance is a solid carrier.

The hydrating agent usually contains, for example, 25 to 90 parts by weight of the active ingredient compound, and the balance is added to the protective colloid agent, thixotropy agent, antifoaming agent and the like as a solid carrier and a dispersion wetting agent.

The granules usually contain, for example, 1 to 35 parts by weight of the active ingredient compound, and the balance is mostly a solid carrier.

The active ingredient compound is uniformly mixed with the solid carrier or is uniformly fixed or adsorbed on the surface of the solid carrier, and the grain diameter is about 0.2 to 1.5 mm.

The emulsion contains, for example, 5 to 30 parts by weight of an active ingredient compound, which contains 5 to 20 parts by weight of an emulsifier, the remainder being a liquid carrier, and a rust inhibitor is added as necessary.

The formulation example of this herbicide is shown below.

Formulation Example 1

20 parts by weight of compound (B-1) 20 parts by weight of compound (A), 2.5 parts by weight of dodecylbenzenesulfonate, 2.5 parts by weight of lignin sulfonate and 55 parts by weight of diatomaceous earth are well ground and mixed to obtain a hydrating agent.

Formulation Example 2

15 parts by weight of compound (B-2), 5 parts by weight of compound (A), 15 parts by weight of emulsifier sorbol SM100 (Tohoka Kagaku®) and 65 parts by weight of xylene are mixed well to obtain an emulsion.

Formulation Example 3

5 parts by weight of compound (B-2), 3 parts by weight of compound (a), 3 parts by weight of white carbon, 5 parts by weight of lignin sulfonate and 84 parts by weight of clay are mixed and mixed well. Get granules

Formulation Example 4

40 parts by weight of bentonite, 5 parts by weight of lignin sulfonate and 55 parts by weight of clay are pulverized and mixed, granulated and dried after watering and training to obtain granules containing no active ingredient. 91.5 parts of this granular material is impregnated with 7 parts by weight of compound (B-1) and 1.5 parts by weight of compound (A) to obtain granules.

Next, test examples will be described in order to show the usefulness of the present invention in more detail.

[Test Example 1]

A faucet soil was filled in a polyethylene pot having an inner diameter of 8 cm, and the dog skin was grown in the faucet state, and a predetermined amount of each drug prepared with a hydrous agent was treated with fresh water soil. The pots were kept in a greenhouse at 25 to 30 ° C, nurtured, and after 30 days of treatment, the ground by-product weights of the remaining skin peels were measured, and the preparedness of the treatment was calculated.

The results are shown in the first table.

[Table 1]

The numbers in Table (1) above are the estimates of the formulation, and (a) the a / 2g ⁺ (b) b / 2g estimates (a) ag and (b) bg, respectively. Is calculated as 1/2.

As a result, the actual measured value of the formulation is significantly smaller than expected, which proves a synergistic effect.

[Test Example 2]

Water is put into a 1 / 5000a wagnell pot filled with 3 kg of faucet soil and placed in a faucet state, and sowing seeds of lateral weeds, such as dog skin, tadpoles, field grass, and flower buds, You planted the tubers of the garden. After transplanting 2.5 seedling rice seedlings, plants are grown in a greenhouse at 20-25 ° C, and on the 7th day after sowing, a certain amount of medicine is formulated with a hydrating agent and diluted in water at the time of the first seedling stage. 10 μs per next port. It was then grown in a greenhouse, and herbicidal effects were examined 25 days after drug treatment. The herbicidal effect was expressed as numbers of 0 to 10 as described below according to observations of absorptivity, degree of whitening, and the like.

The results are shown in Table 2.

Retardation rate

[Table 2]

The number in Table (2) above is the estimated value (PE) of weed control value of the compounding formula calculated by the following formula of general Colby as a synergy test method.

PE = Pa + Pb (10-Pa) / 10 (inhibited value in Pa = herbicide ag)

(Inhibition value in Pb = herbicide my bg)

As a result, the measured value (PC) of the inhibitory value of a compounding agent is larger than the expected value (PE), and it demonstrates that the synergistic effect is remarkable.

Claims (1)

5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazolin-2- is pyrazole represented by (A) and general formula (I) A composition for acquiring, characterized in that the derivative (b) is mixed with (a) 1 to 10 parts by weight of (a) in an amount of 1 to 10 parts by weight.

In the above general formula, X represents a penacyl group or 4-methylphenacyl group.