JPS58167588A - Pyrazole derivative, its preparation and herbicide containing the same - Google Patents

Abstract

NEW MATERIAL:A compound of formulaI(X is H, halogen, lower alkyl). EXAMPLE:4-( 2,4-Dichlorobenzoyl )-1-methyl-5-( 5-chlorothiazol-2-yl )-methoxypyrazole. USE:A herbicide: it shows high herbicidal effect against MIZUGAYATSURI (Cyperus serotinus Rottb.) and HOTARUI (Bulrush, Scirpus juncoides Rxob), tough weeds in rice paddies. It is in no need of combination or mixing with another herbicide unlike the other compounds. PREPARATION:In accordance with reaction equations, a compound of formula III is obtained from an ethoxymethylenemalonic ester and methylhydrazine and subjected to dehydrohalogenation with sodium hydroxide or potassium hydroxide to give a compound of formula II. The resultant intermediate undergoes the condensation reaction with a thiazole derivative to give the compound of formulaI. The condensation reaction is effected in a solvent such as acetone in the presence of a dehydrohalogenating agent such as sodium carbonate.

Description

Detailed Description of the Invention The present invention provides a thiazole ring-containing molecule F'3 represented by the general formula (1) (wherein, X represents a hydrogen atom, a halogen atom, or a lower alkyl group). A new pyrazole derivative.

This relates to its manufacturability and the herbicide contained as an active ingredient in #Conductor 1*.

The pyrazole # conductor (hereinafter referred to as the compound of the present invention) represented by the above general formula (1) is useful as an active herbicide compound, and has the characteristic of causing weeds to whiten and die. It also has strong herbicidal power against weeds controlled by S in the fourth stage, even when applied in a small amount.

Conventionally, many compounds have been known as pyrazole # conductors, and one example is
No. 54-41872 and 脣@lTiB57-1197
Publication No. 9 describes that benzoyl-substituted pyrazole # conductors are useful as herbicides.

However, among the benzoyl-substituted pyrazole # conductors, the compound that has been put to practical use and is commercially available is one of the compounds having the following structural formula (hereinafter referred to as compound A).
There are only points.

Compound A: Compound A has excellent herbicidal activity as a herbicide for paddy fields, but it is one of the weeds that can be controlled in water, such as Cyperus spp.
The activity of Ha and So against firefly etc. has the disadvantage that the herbicidal efficacy decreases rapidly as the dosage is applied, but this herbicide has a strong herbicidal power against weed control. The emergence of drugs was highly anticipated.

The compound of the present invention is an excellent defoxant compound that completely satisfies the above *iit. In other words, the herbicidal activity of the compound 1 is extremely high against paddy field weeds that are conventionally difficult to control, such as cypress and bulrush.
[I-・It is. This has extremely important practical meaning. In other words, to maintain and strengthen its effectiveness against snails and fireflies.

It was necessary to apply a dedicated herbicide against these weeds in combination with or in combination with the commercially available compound AK, but in the case of the compound of the present invention, there is no need to use such a dedicated herbicide, and the present invention This compound alone has the great advantage of being able to sufficiently kill annual weeds such as Japanese oak, and perennial axes such as cypress and firefly.

Next, one of the compounds of the present invention is prepared by the following formula (g) (wherein,
R represents a thiazole term residue. ), and I! on this chemical structure. #The mold point is 5 on the pyrazole ring
position is a hydrogen atom, and R is a specific heterocyclic residue.

The pyrazole # conductor described in JP-A-54-41872 Publication No. 11 marked # is such that the 3rd position of the compound represented by the above formula α) is only a CH group or a CF group, All R's are non-complex Eno* rings.

Furthermore, in the pyrazole spinner described in the above-mentioned Japanese Patent Publication No. 5<-56648-'ij, the 5-position of the compound represented by the above formula (5) is almost a lower alkyl group, and the substituent at the 5-position is is oH, sH, its salts or esters with certain organic acids.

However, when the 5-position is a hydrogen atom, the following formula (V)
As shown in , only one example is specifically described as an example.

However, this compound onds, mentioned above
As is clear from the description of the biological test data in Publication No. 48, the herbicidal activity is inferior to that of the commercially available compound AK. This fact has also been confirmed by tests conducted by the present inventors.

In addition, %KOKAI Publication No. 57-11979 describes a pinzole derivative described by a general formula with a broad concept that also includes one compound of the present invention. In the exemplified compounds and the compounds described in the examples, all the 3-positions of the compounds represented by the formula y) are lower alkyl groups, and the compounds described in the examples have Rfi
The compound of the present invention 9 has only an imide group, and the A-form is not disclosed at all. The present inventors had been intensively conducting tests and studies on uninvented compounds in which the 3-position of the pyrazole ring is a hydrogen atom even before the publication of the above-mentioned publication, and as mentioned above, the present invention was not disclosed in the publication.

It is not specifically stated at all.

In addition, 1 unexploded MA Nagisa et al. attempted #single activity test tl- for the compound described as an example in 9% of the compounds specifically disclosed above, but the commercially available compound AK
In comparison, it was confirmed that the herbicidal activity was weak. In other words, it was reported that the herbicidal activity was very inferior to that of the compound of the present invention.

Conventionally, a large number of pyrazole conductors have been synthesized and herbicidal activity tests have been conducted, but the compound in which the 6-position of the pyrazole ring is a hydrogen atom is the compound represented by the above formula (V). 1? It was only ll. The reason for this is that compounds having 11 substituents such as alkyl at the 5-position are relatively easy to synthesize, but in the case of unsubstituted hydrogen atoms, the synthesis is extremely difficult. It is thought that the results were not satisfactory in terms of debasement activity as mentioned above.

The present inventors investigated two types of compounds in which the 5-position of the pyrazole ring is a hydrogen atom, and found an easy synthesis method. As a result of conducting experiments on rings, we found that 1% constant heterocycles, specifically a-rings selected from thiazole rings, have particularly strong killing power as shown in #. .

Next, 9 examples of each compound of the present invention are shown in Table 1.

However, the compounds of the present invention are not limited to these.

In addition, compound numbers are referred to in the following description.

The compounds of the present invention represented by Table 1 and 9 can be easily synthesized according to the following reaction formula.

(Ino
(
(In the formula, ) (at represents a halogen atom, and X represents the same meaning as above.) Reaction formula (1) is 4-carboethoxy-5- as ethoxymethylene malonic acid ester and methylhydrazine tm material.
This figure shows a reaction in which hydroxy-1-methylpyrazole is synthesized and then hydrolyzed and decarboxylated to obtain 5-hydroxy-1-methylpyrazole. Intermediates of the compounds of the present invention ← The compound (a) can be synthesized according to the reaction formula (2) as a starting material.
J t-de-rogenated water-wood agent (preferably sodium hydroxide, potassium hydroxide, sodium carbonate, triethylamine) #! which is inactive in one reaction. 2.4 in medium
- React with dichlorobenzoic acid...ride to form an ester, and rearrange the ester to obtain (b)t-. For example, acetonitrile, benzene,
Not only can a single solvent such as toluene or chloroform be used, but also a two-phase system such as water-toluene or water-chloroform can be used in combination with an appropriate phase threshold transfer probe.

The reaction formula (3) shows the reaction to obtain the compound (1) of the present invention, which is a thiazole compound having an intermediate (loff) and romether group. This reaction is anti-shiro to a small viscous bath rope (for example, to A?
acetonitrile, benzene, toluene.

Dehydrohalogenation in chloroform)
Preferably, the reaction is carried out in the presence of sodium, potassium carbonate, triethylamine).

It is also advantageous to set the reaction reassembly at the boiling point of the bath used or at the top of the operation. Under appropriate conditions taking into account the above conditions, Takenae reacted with the reaction shown by reaction formula (3)K.
1) can be obtained in a good yield.

Next, a synthesis example of the compound of the present invention will be specifically described as an example. However, it is not limited to this only.

Real Jm? lll 4-(2,4-dicC1ruhenzoyl)-1-mete-5-(5-chlorothiazole-2
-yl)-methoxypyrazole (compound 1 bud 92) 4-(2,4-dichlorobenzoyl)-1-methyl-5
-Hydroxypizol 1.36F (α005 mol),
1.07 f (L005 mol) of 2-bromomethyl-5-chlornaazole was added to a mixture of triethylamine (151f (L005 mol)) and benzene 50 - 2-bromomethyl-5-chlornaazole under stirring at room temperature.
5 mol) was added thereto, and then heated under reflux for 2 hours. After the completion of the reaction, the reaction mixture was cooled, 20 mm of water was added, and after stirring briefly, the benzene layer was separated, washed with water and an aqueous solution of sodium bicarbonate, and after drying, the solvent was removed under reduced pressure. The title compound 1.85F was obtained.

Yield 91s0 Melting point: 97.0-91110°C NMR (δ, ppm, eDO4): i66
(3rd, s).

5.75(2)], s).

7.28 to 7.58 (5H) Next, the compounds shown in Table 2 were synthesized by the same synthesis method as in Example h1. The compounds obtained in Example 1 are also included in Table 2.

When applying the compound of the present invention as a herbicide, it is generally carried out using a suitable carrier, such as an integral carrier such as clay, talc, bentonite, diatomaceous earth, or water, alcohol (
It can be applied in combination with a liquid carrier such as methanol, ethanol, etc.), aromatic hydrocarbons, ethers, chloroforms, esters (ethyl acetate, acid amide a (dimethylformamide, etc.), etc.), and can be applied as desired. emulsifier 1 dispersant,
Suspending agent, 1! By adding penetrating agents, spreading agents, stabilizers, etc., it can be put to practical use in any form such as emulsions, wettable powders, 8-drugs, 8-drugs, etc.

Depending on demand, other types of herbicides, woodcutter insecticides, pesticides, synergists, etc. may be mixed and applied at the time of spraying.

Next, formulation examples of formulations in which the compounds of the present invention are specifically used are shown.

However, 1 part indicates a part by weight.

After uniformly mixing and pulverizing the above ingredients, a small amount of water is added, the mixture is stirred and kneaded, and the mixture is granulated using an extrusion granulator.

Dry to make 1li11 grains.

Formulation example 2 Hydrating agent The above is homogenized and pulverized to form a wettable powder.

To use, dilute the above irrigation agent with water 50 to 1000 times and the amount of active ingredient is less than 1 hectare (Asahi).
Spray at a rate of ~1 okf.

In addition, the compound of the present invention can be used not only in fields such as fields, wetlands, and orchards, but also in non-agricultural ponds such as grass, vacant lots, and roadsides. It can also be applied to control falcons, and the amount of application depends on the situation and timing of application.

Although there are differences depending on the application method, target woodcutter, and cultivated crops,
Generally, a ratio of about 5 to 10 LD per hectare (h&) is appropriate.

Next, the usefulness of the compound of the present invention as a herbicide will be specifically explained in the following test examples.

Test town 1 Single effect rice test under hot water conditions 1/10,0
After placing the alluvial soil in a 00 are soybacquel pot, water was added to warm the pot and the water was flooded to a depth of 2 m. Rice plants of stage 2 to sII (
Nipponbare) was transplanted to 2 locations, 2 plants per pot.

In the above pots, each type of dianthus (Japanese grasshopper, Japanese oak, Japanese azalea, Kikashigusa, and Firefly) were mixed and seeded, and further, tubers of Japanese cucumber and tubers of ξ.

The next day, a diluted solution of the * agent was applied to the water surface under the shaft using a graduated pipette so that a predetermined amount of the drug was obtained.

Five weeks after dropping the chemical solution, the herbicidal effect on each ridge j# was investigated according to the following criteria.

Judgment Criterion 5: Weed killing 490% or more (almost complete death) 4.
... 170 -S-90% 3... 1 40 to 70 inches 2... 120 to 40 inches 1-1 5 to 2.0% 0... l 5 inches or more F" (mostly effective (None) However, the above herbicidal rate was determined by the following formula by adjusting the above-ground fresh grass weight in the chemical-treated area and the above-ground live plant weight 1 in the non-treated area.

The control drug in Table 3 is a commercially available herbicide in the form of granules containing a compound represented by the following structural formula as an active ingredient.

As is clear from Table 3, the compound of the present invention has strong grazing power against weeds and perennial weeds throughout the year, but with the control agent, the drug dose decreases, resulting in rapid grazing activity against perennial weeds. Potency is decreasing.

Test Example 2 Weeding effect test under flooded conditions (2) 1/\
After placing the alluvial soil in a Hugner pot of 000 are, water was added and mixed to obtain a full water condition of R21.

Kl in the soil of a Wagner pot under the above-mentioned full-water conditions was determined by using tubers of Cyperus japonica collected from a flood of perennial weeds in the previous year.
I found one and scattered firefly seeds in the area. Immediately after the weeds germinated, a diluted drug solution was applied to the water surface using a graduated pipette to treat Class F at a predetermined dose.

Five weeks after dropping the chemical solution, the fresh weight of each weed was measured, and the weed killing rate (-) was calculated. However, the whitened part of the weed was counted as the dead part.

The results are shown in the 4th machine.

#! 4 Table 1. Is the control drug a test? It is the same as 111.

As is clear from Table 4, the two compounds of the present invention have low drug efficacy against water cypress and firefly, two weeds to be controlled in water.
Although Ik also shows strong herbicidal activity, the herbicidal activity of the control drug rapidly decreases as the dose is lowered.

Test 3 Rice damage test under flooded conditions 1/10. The alluvial soil was packed in a Rolo 0 Earl Neubawael pot, water was added and mixed to create a full water condition of water depth 23.

After dropping a prescribed amount of diluted drug into Mizuide.

The two surface layers of soil damage were mixed and stirred again. Two days later, the 2nd and 5th leaf stages of yuzu (variety: Japan l1), which had been grown in the nursery medium
1) were transferred to the above-mentioned Neubaquer pots at 5 locations, and the growth status of the yuzu was examined one month later.

The processing amount of the compound-A2 of the present invention increased to 1 hectare 4, 2
The test was carried out in each of the test plots at ke and 1 o'clock.

The results of these test plots are compared with the untreated plot.

The growth conditions were almost the same in terms of plant height and number of violets, and no chlorosis (whitening) was observed, confirming that there was no phytotoxicity.

Patent applicant: Nissan Chemical Industries, Ltd. Continuation of page 1 0 shots light blue electric light Oaza Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Prefecture 1470 Nissan Chemical Industries, Ltd. Biology Inside the chemical research institute 0 shots by Tsutomu Nawamaki Oaza Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Prefecture 1470 B San Kagaku Kogyo Co., Ltd. Biology Inside the chemical research institute

Claims (1)

[Scope of Claims] A pyrazole derivative represented by (in the formula, or a hydrogen atom, a halogen atom, or a lower alkyl group). %iI, which is an s4 body represented by ! Pyrazole # conductor according to item 1 of the FM requirement. (3) The pyrazole derivative according to claim 2, which is a compound represented by the following formula (1): A compound represented by wrinkles. The reaction with a compound represented by the following formula (■): (wherein, Hat represents a halogen atom, and X represents a hydrogen atom, a halogen atom, or a lower alkyl atom) is considered to be mildew. Yuzoho of a pyrazole derivative represented by the general formula (I): (wherein, X has the same meaning as above). (5) General formula (1): (In the formula, X is a hydrogen atom,) represents a rogen atom or a lower alkyl group. A herbicide containing a pyrazole derivative represented by ) as an active ingredient, priced at $4.11. Claim 5 containing 1114 bodies represented by
Herbicides listed in the ring. Claim 6JJ containing the compound represented by
The herbicide described in j.