JPH04124178A - Heterocyclic compound and herbicide containing the same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (X1 is of formula II, III or O; R1 is lower alkyl, phenyl, etc.; Y1 is lower alkyl, lower alkenyl, etc.) or formula IV. USE:A herbicide. PREPARATION:In accordance of the reaction formulas, a compound of formula V is reduced with hydrogen in methanol in the presence of Pd-carbon catalyst, or reduced, in the presence of both the hydrochloric acid and iron in a mixed solvent of THF and water, into a compound of formula VI, which is then reacted with a compound of formula VII, thus obtaining the objective compound of the formula I. This reaction is carried out in the presence of 0.5-50 (pref. 1-5) mol per mol of the compound of the formula VII of a base such as pyridine, picoline or lutidine.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a novel heterocyclic compound and a herbicide containing the two compounds, and more specifically, to a novel heterocyclic compound and a herbicide containing the two compounds, and more specifically to a novel heterocyclic compound that has excellent herbicidal activity and has less phytotoxicity to crops. This invention relates to cyclic compounds and herbicides containing these compounds.

Technical Background of the Invention Wheat, corn, beets, rice, etc. are important crops, and many herbicides are used to control weeds that occur in their cultivation fields and to increase yields. Examples of photosynthesis-inhibiting herbicides that play an important role among herbicides include MC, which has a phenylcarbamate structure.
C, IPC, DCMU having a phenyl urea structure, linuron, propanyl having an anilide structure, etc. are known. To date, many studies have been conducted on phenyl substitution in these photosynthesis-inhibiting compounds, and no compound substituted with a heterocyclic group is known to exhibit herbicidal activity.

Such herbicides are required to have the following properties.

(1) Do not cause chemical damage to crops.

(u) It should have excellent herbicidal activity against weeds such as Japanese grasshopper, Japanese grasshopper, Japanese thornweed, Ichihito, Aobiyu, Pigweed, and Hymemitsohaki.

(ii) It has herbicidal activity against the above-mentioned weeds in foliar spraying after crop germination.

The present inventors conducted intensive studies to develop a herbicide having the above-mentioned properties, and discovered that a novel heterocyclic compound has the above-mentioned properties, leading to the completion of the present invention. Ta.

Purpose of the Invention The present invention was completed in view of the prior art as described above, and provides a novel compound that has excellent herbicidal activity and less phytotoxicity to crops, and also provides a herbicide containing this compound. is intended to provide.

Summary of the Invention The novel heterocyclic compound according to the present invention is characterized by being represented by the following formula [I] or []I].

R3 is a lower alkyl group, phenyl group or substituted phenyl group, Yl is a lower alkyl group, lower alkenyl group, lower alkoxy group, lower alkenyloxy group, N,
It is an N-disubstituted lower alkylamino group or an N-lower alkyl-N-lower alkokynamino group. ] Furthermore, the herbicide according to the present invention is characterized in that it contains the above-mentioned heterocyclic compound as an active ingredient.

The above-mentioned novel heterocyclic compounds have excellent herbicidal activity against weeds and have little phytotoxicity to crops.

DETAILED DESCRIPTION OF THE INVENTION The novel heterocyclic compound and herbicide containing the compound according to the present invention will be specifically explained below.

The novel heterocyclic compound according to the present invention has the following formula [I]
Or [II].

[In the formula, XI is -N--N- or -〇-theaIHMe, R1 is a lower alkyl group, phenyl group or substituted phenyl group, and Y is a lower alkyl group, a lower alkenyl group, a lower alkoxy group, lower alkenyloxy group, N,
N-disubstituted lower alkylamino group or N-lower alkyl-N-lower alkoxyamino group. ] Examples of the lower alkyl group include a methyl group, an ethyl group, a low-propyl group, an i-propyl group, an n-butyl group, a l-butyl group, a 5eC-butyl group, and a t-butyl group.

Further, the substituted phenyl group is represented by formula [II[] or formula [IV
].

[Wherein, X2 is the same or different lower alkyl group as described above, a lower alkoxy group as described below, a lower alkylamino group, or a halogen; be. This will be shown.

Examples of lower alkoxy groups include methoxy group, nidoxy group,
Examples include n-propoxy group, 1-propoxy group, n-butoxy group, i-butoxy group, 5ec-butoxy group, and t-butoxy group.

N, N-) substituted lower alkylamino group includes N, N
-dimethylamino group, N, N-noethylamino group, N-
Examples include methyl-N-n-butyl group.

Examples of the N-lower alkyl-N-lower alkoxyamino group include N-methyl-N-methoxy group.

Examples of lower alkenyl groups include allyl group and 1-pentenyl group.

As the lower alkenyloxy group, allyloxy group, 1
-pentenyloxy group and the like.

Examples of the halogen include chlorine, bromine, and fluorine.

Specific examples (1) to (24) of such heterocyclic compounds are shown below. Incidentally, the following explanation will be given using compound No.

N-~ He-he N-N H Next, regarding such compounds, α resistance, NMRl Table of physical properties of IP show.

Table (Continued) Table (Continued) In addition, in the compound represented by the above formula [IF and CIr1, when Xl or -NH-, the compound represented by the above formula [I] and the above formula [II] The compounds that are used are tautomers.

Such a heterocyclic compound can be produced, for example, as follows. In the following explanation,
The method for manufacturing the compound represented by formula [I] will be described, or the compound represented by formula [II] can be manufactured in the same manner.

First, a compound represented by formula [A] is reduced with hydrogen in methanol in the presence of a palladium-carbon catalyst, or in the presence of hydrochloric acid and iron in a mixed solvent of tetrahydrofuran and water, Aniline derivative [B] is produced.

[A] [B] Then, the obtained aniline derivative [B] and the formula [] React the compound shown in

Note that in formula [C], Yl is the same as Yl in formula [I3].

In the above reaction, a base is used, specifically, pyridine such as pyridine, picoline, lutidine, collidine, triethylamine, 1,8-diazabicyclo(5,4,
Amines such as 0 undecene-7, N, N-dimethylaniline, Na, HCO2, K HCO,, Na 2 COz,
Inorganic bases such as K2CO3, NaOH, and the like are used.

Such a base is desirably used in an amount of 0.5 to 50 mol, preferably 1 to 5 mol, per 1 mol of the compound represented by formula [C].

The aniline derivative is used in an amount of 1 to 5 mol, preferably 1 to 3 mol, per 1 mol of the compound represented by formula [C]. The reaction is carried out between -20 and 100'C, preferably between 0 and 8
At a temperature of 0°C, for 0.1 to 30 hours, preferably 0.5 to 30 hours.
It is carried out for 10 hours.

The above reaction may be carried out in the presence of a solvent or in the absence of a solvent. As a solvent, an inert solvent is used for the reaction, and specifically, aromatic hydrocarbons such as benzene, toluene, and xylene, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, Halokene hydrocarbons such as dichlorobenzene, tetrahydrofuran, ethyl acetate, trimethylformamide, etc. are used alone or in combination.

The heterocyclic compound which is the reaction product can be purified according to conventional methods.

The compound represented by formula [A] can be produced by a known production method.

That is, the compound represented by the formula [A, ] is, for example, published in the Journal of the American Chemical Society
(J, Am, Chem, 5oc) 65.1585
8 (1943).

The heterocyclic compound represented by formula [I] or [II] according to the present invention exhibits strong herbicidal activity against a wide range of weeds. 0.1 per hectare as a component
-], Okg can be applied to control a wide range of weeds as described below. In addition, by limiting the applied amount of the heterocyclic compound according to the present invention or by applying an appropriate application method, it is possible to apply it to corn, barley, wheat, corn, sugar cane, peanut, soybean, sunflower, cotton, etc. It is possible to selectively control weeds in fields where specific crops such as paddy rice are grown. In particular, in fields where major crops such as maize and wheat are cultivated, strong weeds such as field weeds, grasshopper, Japanese grasshopper, and grasshopper can cause phytotoxic damage to crops even when foliar spraying is applied in the early to mid-stages after crop germination. It is possible to control , bluetail, swineweed, and yellowtail.

Weeds that can be controlled by the heterocyclic compound according to the present invention include, more specifically, broad-leaved weeds, such as Stellaria media, Chenopodium album, Sagina japonica, and Koakasa (Chenopodium album).
Chenopodium ficifolium), Polygonum nodosum
, Portulaca oleracea
), shepherd’s purse (Ca, psellabursapasto
ris), Lepidium vi
rginicum), Rorippa
1nndica), Tanetsukebana (Cardamine)
flexuosa), Ichibi (Abutilon t)
heopharasji), American Kinkono Power (S
ida 5pinosa), Marunoku morning glory (l p
omoeapurp+1rea)
necio vulgaris), Oninokeshi (Son
chus asper), American Kinkono Power (Bi
ndens frondosa), pigweed (Arnb
rosia artemisiaefolia), Astersubula, ntus, Lamium amplexicaule, Oxalis corniculata, Amaranthus retroflexu s
), Vicia 5ativa,
Galium asparine, Solanum nigrum, Datura stramoni
um) and weeds of the grass family, such as Sparrow grass (
Alopecurus aequalis), Sparrow fern (Alopecurus aequalis)
),Mehishino<(Digitaliaadscend
ens), Eleusine 1ndica
), Setaria viridis
) Golden millet (Echinochloa crus-
galli), Agnropyron K.
amoji), Hosomugi (Loliumperenne)
), dog wheat (Bromus unioloides)
, oat (Avcnafatua), Japanese oat (Avcnafatua),
P o r y p O[? On Higegawer
i), Panicum dichotom
ifloru+t+), Cyperaceae weeds, such as Cyperus m1croiri
a) Cyperus lria
And so on.

Next, to explain the herbicide according to the present invention, the herbicide according to the present invention contains a heterocyclic compound represented by the above formula [I] or [II] as an active ingredient, and its use In terms of the form, the above-mentioned heterocyclic compound can be used alone, or it can be mixed with various auxiliary agents such as diluents, solvents, surfactants, etc. to form emulsions, aqueous agents, and granules. It can also be used in a flowable form. Furthermore, in order to expand the range of action of this compound or this herbicide, other herbicides or agricultural chemicals other than herbicides, such as insecticides, fungicides, nematicides, plant growth regulators, fertilizers, etc., may be mixed. You can also do that.

The herbicide according to the present invention is applied as it is, or in the form of an appropriate dilution or suspension with water or the like, in an amount suitable for controlling the weeds described in Section 2. When using the compound according to the present invention as a herbicide, it may be particularly effective depending on the formulation form, the crops to which it is applied, the weeds to which it is applied, weather conditions, etc., or whether it is applied at a dose of 0.1 to 5 kg per hectare. .

Effects of the Invention The novel heterocyclic compound represented by formula [I] or [I] according to the present invention has excellent herbicidal activity against weeds and causes less phytotoxicity to crops.

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example I (Preparation of the compound) 2.7 g of 3-phenyl-5-(3-dito-lophenyl)isoxazole are autoclaved using 100 μg of palladium/carbon in a solvent of ethanol at a hydrogen partial pressure of 2 atm. I returned it for 2 hours.

After filtering palladium/carbon from the resulting reaction mixture and distilling it off under reduced pressure, 3-phenyl 5-(3°-
(aminophenyl) isoxazole was abandoned.

Obtained 3-phenyl-5-(3°-aminophenyl)
The isoxasol solution was dissolved in 100 g of dichloroethane, and after adding 2 ml of pyridine to this solution, 1.5 g of methyl chloroformate was added dropwise at room temperature, and the mixture was further stirred for 5 hours.

Dilute hydrochloric acid was added to the reaction mixture thus obtained, followed by extraction with ethyl acetate. The extract was washed with saturated sodium bicarbonate and then dried over anhydrous sodium sulfate. When the crystals obtained by distilling off ethyl acetate under reduced pressure were washed with a mixed solvent of chloroform-hexane, 2.4 g of the target compound (compound No. 22) as white crystals was obtained (yield: 85%).

Example 2 (Production of Compound) 2.8 g of 5-phenyl-3-(3°-nitrophenyl)-1-methylpyrazole was heated at 300 J! of methanol and 10 ml of water, and 5 d of concentrated hydrochloric acid was added dropwise to the resulting solution and stirred. Add 2 iron powder to this solution.
．． Add 5 g gradually and stir under reflux for 12 hours.

The resulting reaction mixture was made alkaline by adding an aqueous potassium hydroxide solution, filtered under suction while still warm, and the solvent was concentrated under reduced pressure. This was extracted with chloroform, the extract was dried over anhydrous sodium sulfate, and then evaporated under reduced pressure.
5-phenyl-3-(3-aminophenyl)-1-methyl-pyrazole was obtained.

After recrystallizing the reaction product thus obtained with ethanol, 100 mN of toluene and 3 mN of triethylamine were added.
The mixture was dissolved in a mixed solvent of 1.5 g of methyl chloroformate under water cooling, and further stirred at room temperature for 5 hours.

Dilute hydrochloric acid was added to the reaction mixture thus obtained, and the mixture was extracted with ethyl acetate. This extract was washed with saturated sodium bicarbonate and then dried over anhydrous sodium sulfate.

The powder obtained by distilling off ethyl acetate under reduced pressure is
When washed with a mixed solvent of hexane, the desired product (compound No.) was found as a white powder.

5 g of 2N was obtained (yield 50%).

Example 3 (Production of compound) 3-t-Butyl-5-(3"-aminophenyl) obtained by reducing 3-t-butyl-5-(3°-nitrophenyl)-pyrazole by a conventional method - After 2.2 g of pyrazole was dissolved in 3 ml of pyridine, 1.5 g of methyl chloroformate was added to this solution under water cooling, and the mixture was further stirred at room temperature for 5 hours.

Dilute hydrochloric acid was added to the reaction mixture thus obtained, and the mixture was extracted with ethyl acetate. This extract was washed with saturated sodium bicarbonate and then dried over anhydrous sodium sulfate.

The powder obtained by distilling off ethyl acetate under reduced pressure is
When washed with a mixed solvent of hexane, the desired product (compound N) was found as a white powder.

17) 2.5 g was obtained (yield 90%).

Example 4 (Production of compound) 3-(3-chloro-phenyl) obtained by reducing 3-(3-chloro-phenyl)-5-(3''-nitrophenyl)-pyrazole by a conventional method After dissolving 2.7 g of -5-(3-aminophenyl)pyrazole in 3 ml of pyridine, 0 g of N,N-dimethylcarbamic acid chloride l' 2 was added to the solution under water cooling, and the mixture was further heated at room temperature. Stirred for 5 hours.

Dilute hydrochloric acid was added to the reaction mixture thus obtained, and the mixture was extracted with ethyl acetate. This extract was washed with saturated sodium bicarbonate and then dried over anhydrous sodium sulfate.

The reaction mixture obtained by distilling off ethyl acetate under reduced pressure was recrystallized with chloroporm to obtain 2.9 g of the desired product (compound No. 19) as a white powder.

Example 5 (Production of wettable powder) 50 parts of the compound of the present invention as an active ingredient, 35 parts of talc,
A wettable powder containing 50% of the active ingredient compound was obtained by mixing and pulverizing 5 parts of diatomaceous earth, 5 parts of white carbon, and 5 parts of polyoxyethylene alkyl allyl ether.

Example 6 (Preparation of emulsion) 15 parts of the compound of the present invention as an active ingredient, 80 parts of xylene and 5 parts of polyoxyethylene alkyl allyl ether are mixed to form a homogeneous solution to obtain an emulsion containing 15% of the active ingredient. When using, dilute with water to the specified concentration and spray.

Next, representative test examples will be given to demonstrate the herbicidal activity of the heterocyclic compound according to the present invention.

In addition, in the test examples, the herbicidal effect and chemical damage were observed with the naked eye, and 0
: Displayed on an 11-level index from no effect or phytotoxicity to IO complete blight.

Test Example 1 (Stem and leaf contact treatment) Surface area 150an! Fill a pot with field soil, sow seeds of corn, goldenrod, Japanese knotweed, Japanese fir, pigweed, and rapeseed, cover with about 1 cm of soil, place in a greenhouse, and when the weeds reach the 1-2 leaf stage. Using a hydrating powder prepared according to Example 5 for the compound of the present invention, doses corresponding to 4 kg, 2 kg, and I kg per hectare were applied to the leaves using a sprayer, respectively. After processing 2
On day 0, the herbicidal effect on weeds and the chemical damage to corn were visually observed, and the results are shown in Table 2.

Test Example 2 Flooded soil treatment (after weed emergence) Area 80cm2
Fill a pot with paddy soil, sow weed seeds of Japanese commonweed, bulrush, Japanese cypress, and Japanese grasshopper, transplant rice at the two-leaf stage, and grow in a greenhouse for 10 days. A suspension prepared using a wettable powder of the invention compound was dropped into rice field water to a predetermined dose. Three weeks after chemical treatment, the herbicidal effect and chemical damage to paddy rice were investigated.

The results are shown in Table 3.

/ /

Claims (2)

[Claims] (1) A novel heterocyclic compound characterized by being represented by the following formula [I] or [II]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] ▲Mathematical formulas, chemical formulas, tables, etc. There is▼... [II] [In the formula, X_1 is ▲a mathematical formula, chemical formula, table, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ or -O-, where R_1 is a lower alkyl group, phenyl group, or substituted phenyl group, and Y_1 is a lower alkyl group, lower alkenyl group, lower alkoxy group, or lower alkenyloxy group. , N
, N-disubstituted lower alkylamino group, or N-lower alkyl-N-lower alkoxyamino group. ] (2) Herbicides characterized by containing a heterocyclic compound represented by the following formula [I] or [II] as an active ingredient: ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] ▲ There are mathematical formulas, chemical formulas, tables, etc.▼... [II] [In the formula, X_1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ or -O-, where R_1 is a lower alkyl group, phenyl group, or substituted phenyl group, and Y_1 is a lower alkyl group, lower alkenyl group, lower alkoxy group, or lower alkenyloxy group. , N
, N-disubstituted lower alkylamino group, or N-lower alkyl-N-lower alkoxyamino group. ]