JPS5899467A - 1-acylpyrazole derivative, its preparation and herbicide - Google Patents

Abstract

NEW MATERIAL:The 1-acryl-3-t-butyl-5-acylaminopyrazole derivative of formula I[R is H, lower alkyl, lower haloalkyl or lower alkenyl; R' is lower alkyl, lower haloalkyl, lower alkenyl or (substituted) phenyl]. USE:Herbicide exhibiting especially high herbicidal activity by foliar treatment. PROCESS:The compound of formulaIcan be prepared by reacting the compound of formula II with the compound of formula (R'CO)2O or R'COX (X is Cl or Br) in a solvent such as benzene or in the absence of solvent at 0-120 deg.C. The reaction may be carried out in the presence of a base such as pyridine, sodium carbonate, etc.

Description

Detailed Description of the Invention The present invention is based on the general formula (1) (wherein R is a hydrogen atom, a lower alkyl group, a lower haloalkyl group, or a lower □alkenyl group; R/ is a lower alkyl group, a lower haloalkyl group, or a lower alkenyl group) , 1-acyl-3-tert-butyl-5-acylaminopyrazole derivative, which is a new compound represented by a phenyl group or an alkyl group, and which has not been described in literature, etc., and its production method, and the compound as an active ingredient. Contains herbicides.

The compound of the present invention is characterized by having a tert-butyl group at the 3-position of the pyrazole ring, which has a very significant herbicidal activity. Furthermore, by introducing an acyl group into the 1-position, the herbicidal activity especially in foliage treatment is increased compared to the case without substitution.

The compound of general formula I exhibits strong herbicidal activity against a wide range of weeds, and when 90.5 to 10 kg of this active ingredient is applied per hectare just before the weeds germinate or at the early stage of their growth, approximately 2. Within 3 weeks, a wide range of weeds as described below can be killed.

In addition, by limiting the amount of this compound applied or by applying an appropriate application method, it is possible to cultivate specific crops such as corn, potatoes, sugarcane, peanuts, soybeans, sunflowers, barley, wheat, turgsum, cotton, and fruit trees. Weeds can be selectively controlled in the field.

Typical examples of the compounds of the present invention include those shown in Table 1.

The compounds in the table are numbered, and the following description will be indicated by the compound number.

The melting point values in the table are uncorrected, and the NMR values are 60
Measured at megahertz using tetramethylsilane in deuterated chloroform as a reference material, symbols s, d% t, q
, m indicate a peak pattern of 1.2.3.4, multiplet, ar indicates a peak due to aromaticity (7)H, and br indicates a wide peak pattern, and J indicates a spin coupling constant. .

The compound of the present invention can be produced, for example, according to the following reaction formula. (In the formula, R and R' are as described above.)
.

This reaction is usually carried out in an organic solvent such as benzene, toluene, xylene, carbon tetrachloride, chloroform, methylene chloride, dioxane or acetonitrile acetone, or optionally in the absence of a solvent at a temperature of about 0 to 120°C. A base such as pyridine, triethylamine, sodium carbonate, potassium carbonate, etc. may be present in some cases. Also, if R and R' are the same,
It can also be produced directly from the raw material amine according to the following reaction formula.

H or (RCO)20 The reaction conditions in this case are the same as above.

Compounds produced by the above reaction (1) are generally poorly soluble in water, but alcohols, acetone, benzene, toluene, carbon tetrachloride, chloroform, etc. are well soluble in most organic solvents, and carbonized hexane, etc. It is also soluble in hydrogen solvents.

Next, synthesis examples will be shown for reference, and the method for producing the active compound of the present invention will be specifically described.

Example 1 100.9 of 3-tert-butyl-5-propionylaminopyrazole was suspended in 300 of dioxane,
After adding 6 g of propionyl chloride, heat under reflux for 4 hours. After the reaction, the solvent is distilled off, and hexane and bicarbonate are added.) IJ
After adding and stirring an aqueous solution of aluminum, insoluble matter was filtered out, the hexane layer was washed with water, concentrated, and crystallized, resulting in 98 g of 3-
Tert-butyl-1-propionyl-5-propionylaminopyrazole (Compound 7) was obtained.

The melting point after hexane recrystallization was 68-69°C. Compound identification was performed by infrared and NMR. Moreover, the position of the propionyl group substituted for the nitrogen atom of the pyrazole nucleus was determined by C-C-13N and X-ray analysis.

Example 2 Dissolve 14 g of 5-amino-3-tert-butylpyrazole in 100 d of benzene, add 21 g of acetic anhydride, and heat under reflux for 5 hours. After reaction, wash with aqueous sodium carbonate solution and water, concentrate and crystallize. By filtering and washing with a small amount of hexane, 18 g of doacetyl-5-acetylamino-3,-tert-butylpyrazole (1) was obtained.

Example 3. 2 g of 3-tert-butyl-5-propionylaminopyrazole and 30 m of methylene chloride! 1.2 g of monochloroacetyl chloride is added. After reacting at room temperature for 1 hour, the reaction mixture was washed with an aqueous sodium chloride solution and water, concentrated and crystallized to obtain 2.11 3-tert-butyl-1-chloroacetyl-5-propionylaminopyrazole Ql.

Example 4 Compound 10 can be obtained by reacting in the same manner as in Example 3, using monochloroacetic anhydride instead of monochloroacetyl chloride and using benzene as the solvent.

Example 5 4.59 of 3-tert-butyl-5-pivaloylaminopyrazole was suspended in 50 carbon tetrachloride, 3.2 g of dichloroacetyl chloride was added, and the reaction was carried out at room temperature for 1 hour, followed by carbonation.
3.8 g of 3-tert-butyl-
1-Dichloroacetyl-5-pivaloylaminopyrazole 4 was obtained.

Example 6 2.29 ゜''3-tert-butyl-5-bivaloylaminopyrazolyl is suspended in toluene, 1 g of pyridine and 1.4 g of benzoyl chloride are added, and the mixture is heated under reflux for 5 hours.Aqueous sodium carbonate solution and water After washing with
After adding hexane and filtering out the insoluble matter, it was concentrated and crystallized.1.
89 1-pensoyl-3-tertiaryifthyl-5-pivaloylamide, nopyrazole (24) was obtained.

Example 7. 2 g of 3-tert-butyl-5-methacryloylaminopyrazole is suspended in 30-dioxane, 1.6 g of p-methylbenzoyl chloride is added, and the mixture is heated under reflux for 2 hours.

After the reaction, the solvent is distilled off, hexane and water are added, and insoluble matter is filtered off. After washing the hexane layer with water and water, it was concentrated and crystallized to obtain 1.69 3-tert-butyl-5-methacryloylamino-1-(p-methylbenzoyl)pyrazole. .

Example 8 3-tert-butyl-5-crotonoyl 1:□ 4 g of minopyrazole was added to 30% of acetic anhydride and heated under reflux for 2 hours. Unreacted acetic anhydride was removed, hexane was added, and the mixture was washed with sodium carbonate water and water, concentrated and crystallized.
．． 89 of 1-acetyl-3-tert-butyl-5-crotonoylaminopyrazole was obtained.

Although some production examples have been shown above, other compounds can also be synthesized by similar methods.

The active compounds according to the invention can be formulated into dosage forms such as emulsions, wettable powders, pastes, flowable powders, granules, etc. by applying conventional formulation methods.

Furthermore, the compounds of the present invention can be mixed with other herbicides. Furthermore, in order to expand the range of action, it can be used in combination with agricultural chemicals other than herbicides, such as insecticides, nematicides, and fungicides.

Next, examples of typical dosage forms will be given. "Department" in the description
indicates parts by weight.

Example 1. Effective by mixing and pulverizing 50 parts of the compounds listed in Table 1, 10 parts of quince, 35 parts of clay, 3 parts of sodium polyoxyethylene alkyl acrylic ether sulfonate, and 2 parts of sodium alkylnaphthalene sulfonate as an active ingredient of an irrigation agent. A wettable powder containing 50 components is obtained.

When using, dilute with water to the specified concentration and spray.

Example 23 Granules: Mix 5 parts of the compound shown in Table 1, 20 parts of bentonite, 73 parts of clay, and 2 parts of sodium dodecylbenzenesulfonate, add about 20 parts of water, mix and knead in a 9-machine, and then use a granulator. The granules are granulated through a filter, and then dried and sized to obtain granules containing 5 parts of the active ingredient.

Example 3. Emulsion 50 parts of the compounds shown in Table 1 as active ingredients, 45 parts of xylene and 5 parts of polyoxytylene alkyl allyl ether are mixed to form a homogeneous solution to obtain an emulsion containing 50 parts of the active ingredient. When using, dilute with water to the specified concentration and spray.

The novel pyrazole derivatives of General 2 have excellent herbicidal activity and are therefore suitable for controlling weeds growing in fields, orchards, non-agricultural lands, etc. When this active compound is applied to the soil surface or mixed into the soil, it can significantly inhibit the growth of weeds and cause them to die. Weeds can also be controlled by spraying the main agent on the stems and leaves of growing weeds.

The dosage of this compound is regulated and the application amount per hectare (#)
When the amount is selected to be 0.5 to 5 kg, it can be used as a selective herbicide in fields where corn, wheat, barley, sugar cane, soybean, peanuts, sunflowers, potatoes, cotton, or fruit trees are cultivated. Moreover, when the application rate is increased, it can be applied as a non-selective herbicide.

The compounds of the present invention can be used, for example, to control the following weeds: i.e. dicots, e.g.
% Kohe (8tellaria media), Shiroza (Chenopodium album), Sagima japo-nica, Chonopodium f 1cifolium
), Polygonum nodos
um), Portulaca oler
acea), shepherd’s purse (Capsella bursa-
pastoris), Lepidi
um virgini-cum), dogfish (Po
rippa 1ndica), Tanetsukebana (C
ardamine Hexuosa), Ichibi (Ab
utilonav 1cennae), American Golden Deer (5ida 5pino-sa), Ipomoea purpurea (Ipomoea purpurea), Enecio vulgaris (8enecio vulgaris), Japanese poppy (8o-r+t, hus asper), American Helium (B idensfrondosa), pigweed (Ambrosia artemisiaefo)
lia) Aster 5ubulatus
), Hotokenoza (Lamium an plexic
avle), Oxalis (Qxaliscornico)
late), Amaranthus re
troful-xus), Crow Tree Pea (Vic
ia 5ativa), Yaemugura (Galium)
spurium), Inuhouzu-'P (8o1-
anum nigrum), Datura (D.
Atura st-ramonium), Poaceae plants, such as Poa annua
, Alopecu-1us aeq
ulis), crabgrass (Digitalia ads
endens), Eleusine 1n
dica), wild foxtail (8e-taria vi)
ridis), Echinochloa x (Echinochloa
crus-gal-1i), Agro
pyron tsukushiensis ), honmugi (Lolium perenne), dogwheat (
Bromuscatharticos), oat (Avena tatua),
pogon Higegaweri), Panicum dichotomiflorom
), Cyperaceae weeds, such as Cyperus
perus m1croiria), Cyperus 1ria, Care
xrugata) etc.

The compounds of the present invention have excellent herbicidal efficacy against a wide range of weeds as described above, and are particularly effective when applied to the surface of fields or the foliage of plants just before or after weeds germinate. High pest control effect can be obtained.

Also, when the compound of the present invention is mixed into soil, an extremely excellent weed control effect can be obtained.

In order to show the herbicidal effect of the herbicide according to the present invention, some representative test examples will be given and explained in more detail.

Test Example 1 Pre-emergence soil treatment (pre-emergence 5oi
Weeding effect on plants when using volcanic ash soil (Digitaria sanguinaria) in a pot with an area of 100 cm + 4
, Echinochloa crus-ga
Po-1ygonum), Po-1ygonum
nodosum), Amaranthus
re-troflexus), corn (7
Jeamays), wheat (Triticum aes)
tivum), Yaenari (Phaseo-1 us r
adiatus) seeds and cover with soil to a depth of about 5 m+. Immediately after that, the compounds listed in Table 1 were prepared into an irrigation agent according to Example 1, and this was diluted with water to extract the active ingredients. A dose equivalent to 10 Kf per hectare was administered to the soil surface of each pot. The herbicidal effect on the plants was investigated for two weeks after treatment. The herbicidal effect was observed with the naked eye. 0: no effect to 5: complete death. It is shown in Table 2 using a 6-level index.

Test Example 2 Foliar 5play treat
Herbicidal effect on plants when using volcanic ash soil in pots with a surface area of 100 d, Digitaria sanguinalis,
Golden millet (FSchinochloa crus-ga)
Polygonum n.
odosum), Arnaranth
-us retroflexus), Zea mays, wheat (Triticum)
aestivum), Pha-5e
olus radiatus), sow the seeds to a height of about 1 m.
When the weeds have 1 to 2 leaves, apply an irrigation agent containing the compound of the present invention to 9 in 10 days per hectare.
The amount of the drug was diluted with water equivalent to 100OA'/ha and sprayed using a sprayer. Ten days after the chemical spraying, the test was conducted using the same criteria as in Test Example 1, and the results were expressed using a 6-level index. The test results are as shown in Table 3.

Test Example 3 Herbicidal effect on paddy field weeds and phytotoxicity test on paddy rice A pot with a surface area of 120 cIII was filled with paddy soil,
(Echinochioa crus-gaili)
), Monochoria, vaginali
Seeds of Pinus spp.
Eleocharis acicu-1aris) and paddy rice fungi at the two-leaf stage were each transplanted to two locations, and the water depth was maintained at approximately 3 m.゛After 3 days, an irrigation agent prepared according to Example 1 containing the compound of the present invention was applied at a rate of 10K per hectare.
The drug was administered in water in a dose corresponding to 100 g. Three weeks after chemical treatment, the herbicidal effect and chemical damage to paddy rice were investigated. The herbicidal effect and the chemical damage to crops were investigated using the same criteria as in Test Example 1, and expressed using a 6-level index. The test results are shown in Table 4.

From Table 4, it can be seen that the compounds of the present invention are effective in killing weeds, which are important weeds in paddy fields, such as grasshoppers, Japanese grasshoppers, and Japanese grasshoppers. However, this group of compounds also affects paddy rice.

From the above results, it is clear that the compounds of the present invention exhibit strong herbicidal activity against a wide range of weeds, and can be applied as herbicides for various crops.゛Patent applicant Showa Denko K.K. Continued from page 1 0 Inventor Tetsuo Tsuruya Inside the Biochemistry Laboratory of Showa Denko K.K., 2-24-25 Tamagawa, Ota-ku, Tokyo

Claims (1)

[Claims] l) General formula (wherein R represents a hydrogen atom, a lower alkyl group, a lower haloalkyl group, or a lower alkenyl group, and represents a tunyl group polysubstituted with R, Kinoya, Geshima, etc.) ) is expressed as
1-acyl-3-tert-butyl-5-acylaminopyrazole derivative. 2) A compound represented by the general formula (wherein R represents a hydrogen atom, a lower alkyl group, a lower haloalkyl group, or a lower alkenyl group) and the general formula (R'CO). 0 or R'COX (wherein R' is a lower alkyl group or a lower polysubstituted phenyl group, and X is a chlorine atom or a bromine atom). It is represented by the general formula (wherein R and R' are as defined above). 1-
A method for producing an acyl-3-tert-butyl-5-acylaminopyrazole derivative. 3) Represented by the general formula COR' (wherein R represents a hydrogen atom, a lower alkyl group, a lower haloalkyl group, or a lower alkenyl group, and R' represents a lower alkyl group, a lower haloalkyl group, or a lower R group). A herbicide containing l-acyl-3-tert-butyl-5-acylaminopyrazole as an active ingredient.