JPS6127962A - N-substituted dicarboximide and herbicide comprising it as active ingredient - Google Patents

Abstract

NEW MATERIAL:An N-substituted dicarboximide shown by the formula I (X is halogen; Y is H, or halogen; Q is heterocyclic ring selected from group shown by the formula II or formula III; A is -O-R<1>, or group shown by the formula IV; R<1> is alkyl, or alkynyl, etc.; R<2> and R<3> are H, alkyl, alkenyl, alkynyl, etc.; or R<2> and R<3> with N atom in the formula form heterocyclic group which may contain O atom). EXAMPLE:N-[4-Chloro-5-( 2-N,N-dimethylcarbamoylvinyl )-2-fluorophenyl]-3,4,5,6- tetrahydrophthalimide. USE:Useful as a herbicide. Having no damage to crops, controlling wild morning glory, bulrush, water nutgrass, etc. which can not be destroyed completely with ease. PREPARATION:For example, an aniline derivative shown by the formula V is reacted with a compound shown by the formula VI at 60-200 deg.C to give a compound shown by the formula I where Q is group shown by the formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to novel N-substituted dicarboximides and herbicides containing the same as an active ingredient.

[Prior art]

Conventionally, N-aryl dicarboximides.

It is known to have excellent herbicidal activity.

For example, in JP-A-J/-J/L Co. No. 1, N-(darkrolow-cofluorophenyl)-3,4t,j,ts-
Although tetrahydrophthalimide is mentioned.

Slight modification of these structures (class a, number of substituents.

In many cases, the presence or absence of herbicidal activity, strength, or selectivity differs significantly depending on the position, etc., and it is difficult to predict the herbicidal activity of a new compound based on mere chemical structural similarity. .

[Problem that the invention seeks to solve]

The present inventors have discovered that herbicidal activity is brown<, and h# has less chemical damage.
As a result of extensive research into herbicides containing N-substituted dicarboximides as active ingredients in order to obtain a fungicide, it was found that the novel N-aryl dicarboximides of the present invention exhibit extremely excellent herbicidal activity.

[Means for solving problems]

The gist of the invention is as follows.

General formula [wherein, X represents a halogen atom, Y#i hydrogen atom or a halogen atom, Q represents a heterocycle selected from
N<8. The group represented by is shown below. Among the above substituents, R1 is
Indicates an alkyl group, an alkenyl group, or an alkynyl group, -R2 and the other are mutually JC (ifJ - or different), a hydrogen atom, an alkyl group, an alkenyl group,
Alkynyl group, aryl group, aralkyl group, cycloalkyl group, alkoxy group.

represents an alkenyloxy group, an alkynyloxy group, a cyanoalkyl group, an alkylsulfonyl group, or R2
and Hs represents a heterocyclic ring which may contain an R atom together with the nitrogen atom in the formula. ] It is expressed as . N-substituted dicarboximides.

and herbicides containing this as an active ingredient.

Next, the present invention will be explained in more detail.

In the present invention, the N-substituted dicarboximides used as herbicides have the above general formula (1)% formula%.In the above general formula (I), Y, Q and Compounds in which A is as follows are preferably used.

That is, X represents a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom or a bromine atom;
i represents a hydrogen atom, -fluorine atom, or chlorine atom, preferably a hydrogen atom or a fluorine atom.

Q is Indicates a heterocycle selected from

Person represents a group represented by 10-R1 or -N<R2. Among the above substituents, R1 is an alkyl group having carbons a/-o,
Alkenyl group having 3 to 4 carbon atoms, or 3 to 4 carbon atoms
represents an alkynyl group, and more preferably represents an alkyl group having 1 to 2 carbon atoms, which may be linear or branched. R
2 and R8 are the same or different from each other, a hydrogen atom,
Number of carbon atoms/alkyl group, number of carbon atoms 3~! alkenyl group.

Number of carbons is 3~! an alkynyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkoxy group having 1 to 2 carbon atoms,
Number of carbons is 3~! a fluorenyloxy group, an alkynyloxy group having 3 to 3 carbon atoms.

It represents a cyanoalkyl group having V/-3 carbon atoms, an alkylsulfonyl group having 7-3 carbon atoms, or.

Rt and R8 represent a heterocycle which may contain an oxygen atom together with the nitrogen atom in the formula. Preferably, a hydrogen atom, a linear or branched alkyl group having 7 to 2 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, and @3 to 4 carbon atoms.
Alkynyl group of t, aralkyl group of 7 to 9 carbon atoms, cycloalkyl group of longitudinal cord 151j to 2, alkoxy group of 7 to - carbon atoms, which may be straight chain or branched, alkoxy group of 7 to 9 carbon atoms, 3 carbon atoms
~4t alkenyloxy group, a cyanoalkyl group having -2 to 3 carbon atoms, an alkylsulfonyl group having 11 [/~3 carbon atoms, or R2 and RA contain an oxygen atom together with the nitrogen atom in the formula. represents a saturated heterocycle forming a 3- to 2-membered ring, which may be

The compound of the present invention represented by formula (1) can be produced using various raw materials, for example, according to the following reaction formula.

(I) (In the above reaction formula,
In aromatic hydrocarbons such as benzene and toluene, alcohols such as methanol and ethanol, and solvents such as water, 40
Performed at ~200°C.

Similarly, the aniline derivative represented by the general formula (1), which is a raw material for the above reaction, can be obtained by oxidizing a toluene derivative to a benzaldehyde derivative, and then nitrating the resulting compound, with malonic acid, according to the reaction formula below. This is used as a teiichic acid derivative, which is then used as an alcohol.

Alternatively, it can be obtained by condensing with amines and then reducing the nitro group.

(In the above reaction formula, X, Y and A have the same meaning as above.) Y (III) (PI) (In the above reaction formula, X, Y and A have the same meaning as above,
]! i represents a hydrogen atom, a cation such as a sodium ion or a potassium ion, or a lower alkyl group such as a methyl group or an ethyl group; Aromatic hydrocarbons such as chlorobenzene, acetate esters such as ethyl acetate and inbutyl acetate, diethyl ether, diisopropyl ether, and tetrahydrofuran.

Ethers such as dioxane, aprotic polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N-methylbidaylidone, ketos such as acetone, ethyl methyl ketone, methanol, ethanol, ingropanol, butanol, etc. An intermediate represented by general formula (IV) is obtained by reacting in a solvent such as an alcohol, water, or a mixed solvent thereof at a temperature range of -jO to ioo°C.

This can be heated and dissolved in alcohols such as methanol and ethanol, and diethyl ether.

In solvents such as ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene and toluene, aprotic polar solvents such as NJ-dimethylformamide and dimethyl sulfoxide, ketones such as acetone and ethyl methyl ketone, and water, or in a mixed solvent thereof.

Mineral acids such as hydrochloric acid and sulfuric acid, organic fatty acids such as formic acid and acetic acid,
Methanesulfone #, p-) Sulfonic acids such as luenesulfonic acid, alkali metal hydroxides such as sodium (potassium) hydroxide.

Cyclization in the presence or absence of alkali metal alkoxides such as sodium methoxide and potassium butoxide, alkali metal carbonates such as sodium (potassium) carbonate, etc. at a temperature range of 11θ to /♂O℃. It is done well.

It is also possible to isolate and use intermediate (IV).

The isocyanate derivative (II
I) can be synthesized from the above-mentioned aniline derivative (It) according to the following reaction formula.

(It) (I[) (In the above reaction formula, X, Y, Q and A have the same meanings as above.) The above reaction may be carried out without solvent or with benzene.

Aromatic hydrocarbons such as toluene, 710-glycanized hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, ethers such as tetrahydronsine, dioxane, ether, and diisopropyl ether, ketones such as acetone and ethyl methyl ketone, In solvents such as nitriles such as acetonitrile, organic amines such as pyridine, aprotic polar solvents such as N,N-dimethylformamide, N-methyl-copyrrolidone, and sulfolane, mineral acids such as hydrochloric acid and sulfuric acid,
Methanesulfonic acid, 1)-) In the presence of organic sulfonic acids such as luenesulfonic acid, or thionyl chloride, phosphorus oxychloride, methyl chlorocarbonate.

Sodium bicarbonate in the presence of a condensing reagent such as N,N/-dicyclohexylcarbodiimide.

Sodium carbonate, sodium hydroxide, pyridine, 4t-
Dimethylaminopyridine, triethylamine, N, N
- lower right in the presence or absence of a base such as diethylaniline,
The amount of each alcohol or amine to the compound represented by the general formula (V) is 120~/! This is done by operating in a temperature range of θ°C.

In this combination reaction, the carboxylic acids represented by the general formula (V), which are the starting materials, form various intermediates such as sulfate chloride, acid anhydride, mixed acid anhydride, etc. In some cases, it is also possible to isolate and use the intermediate.

Incidentally, it is a raw material for the above reaction. The compound represented by the general formula (V) is, for example, as shown in the reaction formula below, the compound represented by the above (1)
Alternatively, the compound of the present invention represented by the general formula (VI) obtained by the method (2) (corresponding to A=-OR+ in the general formula (1)) is synthesized by hydrolysis. (In the above reaction formula, X, Y, Q and R1 have the same meanings as above.) The compound of the present invention obtained in this way can be used as a herbicide as it is, but it is usually used in an inert liquid carrier or solid. Mix with carrier, add appropriate surfactant, etc.
Emulsion, powder, 1 tablet.

It is used in the form of tablets, irrigators, etc.

Liquid carriers include toluene, xylene, methylnaphthalene, cyclohexane, butanol.

Glycol, dimethyl sulfoxide, dimethyl formamide, acetone, methyl imbutyl ketone, animal and vegetable oils, fatty acids, fatty acid esters.

Solid carriers include clay, kaolin clay, talc, bentonite, and diatomaceous earth.

Examples include silica, calcium carbonate, and vegetable powders such as soybean flour and wheat flour.6 If necessary, other active ingredients such as agricultural fungicides, insecticides, nematicides or other herbicides, It can also be used in combination with plant growth regulators, soil conditioners, fertilizers, etc. In addition, in order to obtain a reliable herbicidal effect, auxiliary agents such as spreading agents, emulsifiers, wetting agents, and stimulants may be appropriately mixed.

The application amount of the herbicide of the present invention varies depending on the type of compound used, the target weed, the treatment time, the treatment method, the nature of the soil, etc., but it is usually used as an active ingredient.
0.0/~gog2m.

Preferably 0. A range of / to co-θ gram is appropriate.

[For production]

Regarding the compound of the present invention, the present inventors have discovered that it exhibits high herbicidal activity in upland fields and paddy fields, while having almost no effect on crops. That is, in farmland, for example.

Shiroza, pigweed, Japanese knotweed, hartade, dogweed, sedgeweed, leaf lily, silverwort, silverwort, hackberry, sparrow gnome, cyperus, and in rice fields, for example, azalea.

Kikashigusa, Abs.
Weeds such as thornweed, cypress, and weed can be controlled by both pre-emergence treatment and growing season treatment. And one compound of the present invention is, for example, rice, soybean, sunflower.

It can be used as a selective herbicide in the cultivation of crops such as cotton, potatoes, wheat, sugarcane, and corn.

As described above, the compounds of the present invention have the excellent property of being able to control many weeds while causing almost no harm to crops.

Furthermore, the compound of the present invention can be used to control weeds that have been difficult to control with existing herbicides, such as wild morning glory, Japanese yam, Japanese morning glory, wild mustard, Japanese grass, Johnson grass, etc. in rice fields. For example, firefly, cypress, and urikawa.

It was also found that it has high herbicidal activity against grasshoppers such as lilycystis. As described above, the compound of the present invention has a very wide herbicidal spectrum and is highly safe for one crop.

The scope of application of the compounds of the present invention is not limited to one or more types of plants, but can also be used for other plants by the same application method.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.
The invention does not go beyond its gist.

The present invention is not limited to the following examples.

Example 7 N-[mod-chloro-j-(,2-N,N-
Production of dimethylcarbamoylvinyl)-1-fluorophenyl)-3,a,j,t-tetrahydrophthalimide M-(J--(,2-carboxyvinyl)-guchloro-2-fluorophenyl)-3,'I, j, 5-tetrahydrophthalimide λ, λF, thiodichloride k j f
A mixture of O and benzene 201d was heated under reflux for 2 hours while stirring. Thereafter, the solvent and excess thionyl chloride were distilled off under reduced pressure. The residue was again dissolved in 20 yd of benzene, and while stirring at room temperature, 0.0 g of dimethylamine and 0.0 g of triethylamine were added. A mixture of j9 and benzene/θ- was added dropwise. Mu! After stirring for an hour, ethyl acetate and O- were added to the reaction mixture.

The body was washed successively with water and saturated saline, and dried with Glauber's salt. The solvent was distilled off under reduced pressure, and the residue was applied to a silica gel column using ethyl acetate:n-βxane-2:/ as a developing solvent to obtain the compound (A/) 8 listed in Table 1 ! I got f.

Actual M Example 2 N-("g-chloro-fluoro-j-
(2-methoxycarbonylvinyl)phenyl) -3,
Production of 4t, t, t-tetrahydrontalimide A mixture of talic anhydride/jg and acetic acid/θ- was heated under reflux for 3 hours with stirring.

Thereafter, acetic acid was distilled off under reduced pressure to leave a residue fio.

- in ethyl acetate, washed successively with water and saturated brine, and dried over Glauber's salt. The solvent was distilled off under reduced pressure, and the residue was applied to a silica gel column using ethyl acetate:n-hexane=/:4t as a developing solvent to obtain the compound (A/)//9 listed in Table 1. Obtained.

Example 3 J-[a-ri four-fluoro-fluoro-z-(J
-methoxycarbonylvinyl)phenyl) -t, r-
Production of tetramethylenehydantoin Pipecolic acid da, Otsu Jf, sodium hydroxide y4tt
and water λOgd with stirring.

Chloro-@2 dissolved in Chloro-p benzene Od
- Fluoro! -methoxycarbonylvinylphenyl incyane)? , 4tf was added.

After stirring at room temperature for 3 hours,! The mixture was extracted once with ether and concentrated hydrochloric acid was added to the aqueous layer to make it acidic, and an oily substance was precipitated. This was extracted with ethyl acetate, washed with water, dried, and then the solvent was distilled off under reduced pressure. Dioxane 10- and 2N hydrochloric acid roWd were added to the residue at 10°C/! Stirring was performed for hours. After extracting the reaction mixture with ethyl acetate, the mixture was washed sequentially with water, saturated sodium bicarbonate, water, and saturated brine.
Dried with Glauber's salt. After distilling off the solvent, the residue was applied to a silica gel column using ethyl acetate:n-hexane/2/w as a developing solvent, and the compound listed in Table 1 (A2B) was obtained.
! , 7f was obtained.

Similarly, the compounds listed in Table 1-1 were produced according to the method of Example Todoroki listed in the table.

The structures of all the compounds listed in Table 7 were confirmed by the EMR spectrum and/or the IH-NMR spectrum.

Next, examples of formulations of the compounds of the present invention will be shown. In addition, hereafter, K "Department J
, r%, and J refer to "heavy lid part" and "weight%," respectively.
” means.

Formulation example/: Irrigation table/Compound of the present invention &! , 4tO part, Carplex #
? θ (Shionogi & Co., trade name) 2 parts.

3 parts of N,N kaolin clay (Ueya Kaolin Co., Ltd., trade name) and 5 parts of a higher alcohol sulfate ester surfactant Tsurupol R070 (Toho Chemical Co., Ltd., trade name) are mixed and pulverized uniformly to make an effective Inventive hardware store of ingredient list/,!
3 parts of clay (manufactured by Nippon Talc Co., Ltd.), 3 parts of bentonite (manufactured by IL Junyoko Co., Ltd.), and 2 parts of the succinate surfactant Eyarol O'r-/ (trade name, Toho Kagaku Co., Ltd.), After mixing and pulverizing, 70 parts of water was added and stirred.Furthermore, this was kneaded and granulated using a granulator to give a diameter of 0.411 mm.
After extruding through the hole and drying at to℃ for 2 hours,
Cut to length and use the active ingredients! Formulation Example 3: Emulsion 23.3 parts of the compound A of the present invention shown in Table 7 was dissolved in a mixed solvent consisting of 30 parts of xylene and 1 part of dimethylformamide, and a polyoxyethylene-based granule was obtained. Surfactant Tsurupol 300j'K (Toho Chemical Co., Ltd., trade name)/! An emulsion containing 30 parts of the active ingredient was obtained.

Preparation Example 47.30 parts of the compound of the present invention in mite floorable agent Table 1 was mixed in ethylene glycol/IB.

Tsurupol A03032 (Toho Chemical Co., Ltd., trade name)! part, xanthan gum 0. / part and well mixed and dispersed in 6.9 parts of water. Next, this slurry-like mixture was wet-ground using a sand grinder (Igarashi Kikai Co., Ltd.) to obtain 30% of the active ingredient.
A stable flowable agent containing %.

〔Effect of the invention〕

Test Example/Flooded Soil Treatment Test Paddy alluvial clay loam was filled into a resin vat of λ, jOo/R, and after fertilization, an appropriate amount of water was added and plowing was performed. Seeds of Japanese millet, Kikashigusa, and Firefly are mixed into the θ and ja layers from the soil surface, and the tubers of Urikawa and Mizugayatsu are added to the vat! An individual was transplanted.

On the other hand, paddy rice seedlings at the λ/leaf stage (variety: Akinishiki).

Grass height two? , J'3. Seedling quality: good) was placed in a bat with 3 plants/2 plants, and deep insertion/plying was done. After that, about 3.
Granules containing 4/2-2 of the compound of the present invention obtained according to Formulation Example λ as an active ingredient were obtained in the same manner as Formulation Example λ, while maintaining the water depth of 1 mouth. N-(4t-chloro-λ-fluorophenyl) -3,a,r,t-tetrahydrontalimide (hereinafter abbreviated as 6) and 5-(4t-tritetrabenzyl) -N,N- Granules containing diethyl-thiol carbamate (hereinafter abbreviated as Comparative Agent B) as an active ingredient were prepared as follows:
6,2. A predetermined amount of the sample was dropped onto the flooded surface so as to give J-, j, and 10 g/a each. After treatment, the plants were given a water reduction method for 7 days (jcm), and then cultivated in a greenhouse, and the herbicidal effect and herbicidal damage were investigated on day 0 after the chemical treatment.

The results are shown in Table λ. Furthermore, the evaluation of the herbicidal effect is was calculated and expressed as a herbicidal effectiveness coefficient based on the following standard.

In addition, the evaluation of drug damage is j was calculated and expressed as a chemical toxicity coefficient based on the following criteria.

Table - Test example K Upland soil treatment test λ, 600 min/R resin vat was filled with upland Kuroboku soil, and after fertilization, each seed of wheat, corn, and cotton was sown to cover 2 to 3 cm of Enoki soil. went.

After sowing and mixing seeds of crabgrass, Japanese knotweed, Japanese radish, and mustard seeds in this soil layer, 4/, 2°J', 2/, and 71B of the compound of the present invention obtained according to Formulation Example 1 were added. Comparative agents obtained in the same manner as Irrigation and formulation examples/3-(3,a-dichlorophenyl)-/ as active ingredients
,/-dimethylurea (hereinafter abbreviated as comparative agent C)
Wettable powders containing as an active ingredient were diluted with water and uniformly sprayed onto the soil surface using a small power pressurized sprayer so that the active ingredient amount was 1, 10, and 20 g/a.

14 meals with weeding effect were given on day 20 after spraying the chemical.

At the same time, we also investigated chemical damage to each crop.

The results are shown in Table 3. Evaluation of herbicidal effect and phytotoxicity was carried out in the same manner as in Test Example/.

Table 3 Test Example 3 Stem and leaf treatment test? ,/! A θ minute/R/J% type polyethylene pot is filled with upland blackberry soil, and after fertilization, seeds of edible whiteberry, blueberry, blackberry, and Japanese fir are sown in each pot separately.

Cultivation management was continued in the greenhouse, and when the growth level of the test plants reached the single-leaf stage for edible Aphrodisa, and the first or second true-leaf stage for A. spp.

Formulation of the compound of the present invention obtained according to Formulation Example 3, 6-
Emulsion containing /j, /♂~2/,, 23.26 as an active ingredient and j, 4t-dichloropropionic acid anilide (hereinafter abbreviated as comparative agent 6) obtained in the same manner as in Formulation Example 3. An emulsion with an active ingredient concentration of 60,100. ．． 1
The mixture was diluted with water to a concentration of 100 pp, and 7 ar of the spray liquid t/θ was sprayed using a small power pressurized sprayer. Continuing to observe inside the mud room, the agent was sprayed with CI! We conducted a survey on the effects of sunflower.

The results are shown in Table 3. In addition, the monovalent herbicidal effect was determined in the same manner as in Test Example/.

table da

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is a halogen atom, Y is a hydrogen atom or a halogen atom, Q is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Numerical formula, Chemical formulas, tables, etc. are available ▼ indicates a heterocyclic ring selected from -O-R^1 or ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ indicates a group. Among the above substituents, R^1 represents an alkyl group, an alkenyl group, or an alkynyl group, and R^2 and R^3 are the same or different from each other, and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, aralkyl group,
represents a cycloalkyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a cyanoalkyl group, an alkylsulfonyl group, or R^2 and R^3 are
Indicates a heterocyclic group which may contain an oxygen atom together with the nitrogen atom in the formula. ] N-substituted dicarboximides represented by these. (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is a halogen atom, Y is a hydrogen atom or a halogen atom, and Q is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formula , chemical formula, table, etc. ▼ indicates a heterocyclic ring selected from -O-R^1 or ▲ Numerical formula, chemical formula, table, etc. ▼ indicates a group. In the above substituents, R^1 represents an alkyl group, an alkenyl group, or an alkynyl group, and R^2 and R^3 are the same or different from each other, and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group. , a cycloalkyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a cyanoalkyl group, an alkylsulfonyl group, or even if R^2 and R^3 contain an oxygen atom together with the nitrogen atom in the formula. Shows a good heterocycle. ] A herbicide containing an N-substituted dicarboximide represented by the following as an active ingredient.