JPH0676406B2 - N- (Benzoxazinyl) tetrahydrophthalimide derivative and herbicide containing it as an active ingredient - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel N- (benzoxazinyl) tetrahydrophthalimide derivative and a herbicide containing the derivative as an active ingredient.

<Prior Art> Japanese Patent Publication No. Sho 48-11940 discloses that an N-phenyltetrahydrophthalimide derivative can be used as an active ingredient of a herbicide.

<Problems to be Solved by the Invention> However, it is hard to say that these compounds are not necessarily satisfactory in herbicidal activity at low doses.

An object of the present invention is to provide a new and superior herbicide.

<Means for Solving the Problem> In view of such circumstances, the present inventors have conducted various studies in order to develop compounds having excellent efficacy against various weeds, and as a result, have found that N- (benz of the present invention The present inventors have found that the oxazinyl) tetrahydrophthalimide derivative shows effective herbicidal activity at a lower dose and does not show a harmful phytotoxicity to crops, and thus reached the present invention.

That is, the present invention has the general formula [In the formula, R represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower alkoxymethyl group,
X represents a hydrogen atom or a fluorine atom. ] The N- (benzoxazinyl) tetrahydrophthalimide derivative shown by these (henceforth compound compound), and the herbicide which makes it an active ingredient are provided.

Next, the manufacturing method will be described in detail. The compound of the present invention has the general formula [In the formula, X represents the same meaning as described above. ] The tetrahydrophthalimide derivative shown by these and general formula RY [III] [In formula, R represents the same meaning as the above, Y is a chlorine atom,
Represents a bromine atom or an iodine atom. ] It can manufacture by making it react with the halide shown by these.

This reaction is usually performed in the presence of a dehydrohalogenating agent in a solvent, the reaction temperature is 0 to 100 ° C., and the reaction time is 1 to 12
The amount of the reagent to be used in the reaction is 1 to 1.5 equivalents of the halide [III] and the dehydrohalogenating agent per 1 equivalent of the tetrahydrophthalimide derivative [II].
It is equivalent.

As the solvent, diisopropyl ether, dioxane,
Tetrahydrofuran, ethers such as ethylene glycol dimethyl ether, acetonitrile, nitriles such as isobutyronitrile, formamide, acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane Etc., or a mixture thereof.

Examples of the dehydrohalogenating agent include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride, and alkali metal alkoxides such as sodium methoxide and sodium ethoxide.

After completion of the reaction, the reaction solution is added with water or poured with ice water, and then subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, purified by operations such as recrystallization and chromatography. The desired compound of the present invention can be obtained.

The tetrahydrophthalimide derivative [II], which is a raw material compound of the compound of the present invention, is produced by the following route.

[In the formula, X represents the same meaning as described above, and Z represents a lower alkyl group. That is, the nitrophenol derivative represented by the general formula (IV) (described in Hodgson et al., J. Chem, Soc., 1928 1880) is represented by the general formula A-CH ₂ COOZ [IX] [wherein A is a halogen. Represents an atom, and Z has the same meaning as described above.] To produce a nitrophenoxyacetic acid compound represented by the general formula [IX].

This reaction is usually carried out in the presence of a base in a solvent at 25 to 100 ° C., and the amount of the reagent to be used in the reaction is such that the amount of the base and α-haloacetic ester [IX] is 1 equivalent of the nitrophenol derivative [IX]. Are 1 to 1.05 equivalents respectively, and examples of the solvent include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone, and sulfur compounds such as dimethylsulfoxide and sulfolane. As, sodium hydride, potassium carbonate,
Examples include potassium hydroxide. After completion of the reaction, the reaction solution is poured into water, subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, purified by chromatography or the like.

Further, nitrophenoxyacetic acid [IX], a nitrobenzene derivative represented by the general formula [V] and a general formula HO—CH ₂ COOZ [X] [wherein, Z represents the same meaning as described above. ] It can manufacture also by making it react with the glycolic acid ester shown by these.

This reaction is usually carried out in the presence of potassium fluoride in a solvent at 50
The amount of the reagent used for the reaction is 1 to 2 equivalents of the glycolic acid ester [X] and 1 to 2 equivalents of potassium fluoride, relative to 1 equivalent of the nitrobenzene derivative [V]. Examples of the solvent include 1,4-dioxane, 1,2-dimethoxyethane, N, N-dimethylformamide, N, N-dimethylacetamide and the like.

After completion of the reaction, the reaction solution is poured into water, subjected to usual post-treatments such as extraction with an organic solvent and concentration, and purified by chromatography if necessary.

Then, the obtained nitrophenoxyacetic acid [VI] is reacted with nitric acid in the presence of sulfuric acid to give a compound of the general formula [VI]
The dinitrophenoxyacetate represented by I] can be produced.

This reaction is usually carried out at 0 to 40 ° C., and the amount of reagents to be used in the reaction is 1 to 1.5 equivalents of nitric acid and 1 to large excess amount of sulfuric acid with respect to 1 equivalent of nitrophenoxyacetic acid [VI]. Is.

The reaction solution after completion of the reaction is poured into ice water and the resulting crystals are filtered off or extracted with chloroform, methylene chloride or the like, and then subjected to usual post-treatments such as washing with water and concentration, recrystallization, if necessary,
Purify by chromatography or the like.

Furthermore, the obtained dinitrophenoxyacetate [VI
The aminobenzoxazinone derivative represented by the general formula [VIII] can be produced by subjecting I] and iron powder to ring closure by reduction in the presence of an acid.

This reaction is usually carried out at 70 to 90 ° C., and the amount of the reagent used for the reaction is 5 to 10 equivalents of iron powder and 3 to large excess amount of acid with respect to 1 equivalent of dinitrophenoxyacetate [VII]. Is. Examples of the acid include organic acids such as acetic acid and propionic acid.

The reaction solution after completion of the reaction is subjected to usual post-treatments such as extraction with an organic solvent and concentration, and is purified by chromatography or the like, if necessary.

Finally, the obtained aminobenzoxazinone derivative [VI
By reacting II] with 3,4,5,6-tetrahydrophthalic anhydride, a tetrahydrophthalimide derivative represented by the general formula [II] can be produced.

This reaction is usually carried out in a solvent at 70 to 85 ° C. for 30 minutes to 3 hours, and the amount of the reagent to be used in the reaction is 3,4, or 3 with respect to 1 equivalent of the aminobenzoxazinone derivative [VIII]. 5,6-Tetrahydrophthalic anhydride is 1 to 1.1 equivalents. Examples of the solvent include water, acetic acid, propionic acid and the like.

After completion of the reaction, the reaction solution is poured into water, subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, purified by recrystallization, chromatography and the like.

The aminobenzoxazine derivative [VIII] is not usually isolated and is used for the next reaction with 3,4,5,6-tetrahydrophthalic anhydride as it is in the reaction solution after the reduction ring closure reaction.

When the compound of the present invention is used as an active ingredient of a herbicide,
Usually, it is mixed with a solid carrier, a liquid carrier, a surfactant and other auxiliaries for formulation to prepare an emulsion, a wettable powder, a granule and the like.

These formulations contain the compound of the present invention as an active ingredient in an amount of 0.05 to 90% by weight, preferably 0.1 to 80%.

Examples of the solid carrier include kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, fine powder or particles of synthetic hydrous silicon oxide, and the like. As the liquid carrier, xylene, aromatic hydrocarbons such as methylnaphthalene, isopropanol, ethylene glycol, alcohols such as cellosolve, acetone, cyclohexanone, ketones such as isophorone, soybean oil, vegetable oil such as cotton oil, dimethyl sulfoxide, N, N
-Dimethylformamide, acetonitrile, water and the like.

Surfactants used for emulsification, dispersion, moistening, etc. include anionic surface active agents such as alkyl sulfate ester salts, alkyl aryl sulfonates, dialkyl sulfosuccinates, and polyoxyethylene alkyl aryl ether phosphate ester salts. Agent, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether,
Examples thereof include nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Examples of the auxiliaries for formulation include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate) and the like.

The compound of the present invention is usually formulated and subjected to soil treatment, foliage treatment or flooding treatment before or after emergence of weeds. The soil treatment includes a soil surface treatment, a soil admixture treatment, and the like, and the foliage treatment includes a treatment from above the plant body and a local treatment for treating only the weeds so as not to adhere to the crop.

When the compound of the present invention is used as an active ingredient of a herbicide, its treatment amount is different depending on weather conditions, formulation form, treatment time, method, place, target weed, target crop, etc., but usually 1
It is 0.02 to 100 g, preferably 0.05 to 50 g per are, and emulsions, wettable powders, suspensions and the like usually have a predetermined amount of 1 to 10 liters per are (if necessary, a spreading agent, etc.). It is diluted with water (to which an auxiliary agent is added) and treated, and granules and the like are usually treated as they are without any dilution.

As the spreading agent, in addition to the above-mentioned surfactant, polyoxyethylene resin acid (ester), lignin sulfonate,
Examples thereof include abietic acid salt, dinaphthyltylmethane disulfonic acid salt, and paraffin.

<Examples> Hereinafter, the present invention will be described in more detail with reference to production examples, formulation examples, and test examples, but the present invention is not limited to these examples.

First, production examples of the compound of the present invention will be shown.

Production Example 2- (5-Fluoro-2H-1,4-benzoxazine-4H
-3-on-2-yl) -4,5,6,7-tetrahydro-2H
-Isoindole-1,3-dione 0.7 g was added to a mixed solution of sodium hydride 0.11 g and N, N-dimethylformamide 10 ml at 0 ° C.
Added below. Propargyl bromide after generation of hydrogen
0.4 g was added and reacted at 20 to 30 ° C. for 6 hours. The reaction solution was poured into ice water and extracted with diethyl ether. The extract was washed with water, dried and concentrated to give 2- (5-fluoro-4-propargyl-2H-1,4-benzoxazin-3-on-6-yl) -4,5,6-7-tetrahydro-2H. 0.55 g of isoindole-1,3-dione was obtained.

mp 207.8 ° C Table 1 shows some of the compounds of the present invention which can be produced by such a production method.

Next, production examples of raw material compounds will be shown as reference examples.

Reference Example 1 22 g of 3-fluoro-2-nitrofer was dissolved in 50 ml of dimethylformamide, and 6.7 g of sodium hydride and N, N-
A slurry of 100 ml of dimethylformamide was added dropwise at -5 to 0 ° C. After dropping, the mixture was stirred at the same temperature for 30 minutes, 25 g of α-prom ethyl acetate was added, and the mixture was reacted at 20 to 30 ° C for 2 hours and further at 40 to 50 ° C for 1 hour. After allowing to cool, the reaction mixture was poured into ice water and extracted with ether. The extract was washed with water, dried and concentrated to obtain 38 g of oily ethyl 3-fluoro-2-nitrophenoxyacetate.

Reference Example 2 3.7 g of ethyl glycolate was added to a mixed solution of 5.3 g of 2,4,6-trifluoronitrobenzene, 2.1 g of potassium fluoride and 50 ml of 1,4-dioxane, and the mixture was refluxed for 4 hours under a nitrogen stream. After allowing to cool, the reaction solution was poured into water and extracted with ether. The extract was dried and concentrated, and the residue was purified using a silica gel column to obtain ethyl 3,5-difluoro-2-nitrophenoxyacetate (1.6 g). mp 39.3 ° C Reference Example 3 2.4 g of ethyl 3-fluoro-2-nitrophenoxyacetate,
1 g of nitric acid (d = 1.5) was added dropwise to a mixed solution of 10 ml of concentrated sulfuric acid at 10 to 20 ° C. After dropping, the mixture was stirred at 10 to 20 ° C for 30 minutes, poured into ice water and extracted with ether. The ether layer was washed with water, dried and concentrated. The residue was crystallized to obtain 1.7 g of ethyl 2,4-dinitro-3-fluorophenoxyacetate. mp68 ° C Similarly, methyl 2,4-dinitro-3,5-difluorophenoxyacetate was obtained from methyl 3,5-difluoro-2-nitrophenoxyacetate. mp 68.3 ° C. Reference Example 4 2,4-Dinitro-3-fluorophenoxyethyl acetate 1.7
g in 20 ml of acetic acid and 20 ml of ethyl acetate
The mixture was added dropwise to a mixed solution of 5.6 g and 5 ml of 5% acetic acid water at 75 to 80 ° C. After dropping, the mixture was stirred for 1 hour, 0.93 g of 3,4,5,6-tetrahydrophthalic anhydride was added, and the mixture was stirred at 74-80 ° C for 2 hours. After cooling, iron was filtered off and the filtrate was extracted with ethyl acetate. After washing with water, it was dried and concentrated. The residue was crystallized from hexane to give 2- (5
-Fluoro-2H-1,4-benzoxazin-3-one-
1 g of 6-yl) -4,5,6,7-tetrahydro-2H-isoindole-1,3-dione was obtained.

mp 226.8 ° C. Similarly, from methyl 2,4-dinitro-3,5-difluorophenoxyacetate, 2- (5,7-difluoro-2H-1,4-benzoxazin-3-one-6-yl) -4, 5,6,7-Tetrahydro-2H-isoindole-1,3-dione was obtained. mp252 ° C (decomposition) Next, formulation examples are shown. The compounds of the present invention are shown by the compound numbers in Table 1. Parts indicate parts by weight.

Formulation Example 1 50 parts of the present compound 1, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain a wettable powder.

Formulation Example 2 An emulsion is obtained by thoroughly mixing 3 parts by weight of the compound of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzene sulfonate, 30 parts of xylene and 45 parts of cyclohexanone.

Formulation Example 3 1 part of the present compound 6, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 66 parts of kaolin clay are well pulverized and mixed, and water is added and kneaded well, and then granulated. Dry to obtain granules.

Formulation Example 4 The compound of the present invention (9, 25 parts), polyoxyethylene sorbitan monooleate (3 parts), CMC (3 parts) and water (69 parts) are mixed and wet-ground until the particle size becomes 5 μm or less to obtain a suspension agent.

Next, Test Examples will show that the compound of the present invention is useful as an active ingredient of a herbicide. The compounds of the present invention are shown by the compound numbers in Table 1, and the compounds used for comparison and control are shown by the compound symbols in Table 2.

Regarding the herbicidal efficacy, the degree of budding and growth inhibition of the test plant at the time of the survey was visually observed, and when there was no or almost no difference from when the compound was not tested, the test plant died. Or, the one whose growth is completely inhibited is defined as "5" and evaluated in 6 levels of 0 to 5, 0, 1, 2,
Shown as 3, 4, and 5.

Test Example 1 Upland soil treatment test Field soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and seeds of green flesh, Malaga morning glory and velvetleaf were sown.
Covered with soil. The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with water equivalent to 10 liters per are, and the soil surface was treated with a small sprayer. After the treatment, the plants were grown in a greenhouse for 20 days and the herbicidal efficacy was investigated. The results are shown in Table 3.

Test Example 2 Field foliage treatment test Field soil was filled in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and seeds of millet, Japanese radish and velvetleaf were sown and grown in a greenhouse for 10 days. Then, the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the compound was diluted with water containing 10 liters of spreading agent per are, and the leaves were treated from above the plant with a small sprayer. Grow in the greenhouse for 20 days after treatment,
The herbicidal efficacy was investigated. The results are shown in Table 4.

Test Example 3 Paddy field flood treatment test Paddy field soil was packed in a cylindrical plastic pot having a diameter of 8 cm and a depth of 12 cm, and seeds of the rice ball millet and broad-leaved weeds (Azena, Kishigusa, Mizochabe) were mixed at a depth of 1 to 2 cm. After inundation and making it into a paddy field, 1 to 1 tuber of Urikawa
It was embedded at a depth of 2 cm, and rice at the two-leaf stage was further transplanted and grown in a greenhouse. Six days later (the initial stage of the development of each weed), the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with 5 ml of water and treated on the water surface. After the treatment, the plants were grown in a greenhouse for 20 days and the herbicidal efficacy was investigated. The result is the fifth
Shown in the table.

Test Example 4 Upland soil treatment test Field up soil was packed in a vat with an area of 33 × 23 cm ² and a depth of 11 cm,
Soybean, corn, cotton, malaga morning glory, velvetleaf, red-necked stalk, physalis chinensis, barnyard grass, and green foxtail were sown and covered with a soil having a thickness of 1 to 2 cm. The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with water equivalent to 10 liters per are, and the soil surface was treated with a small sprayer. After the treatment, the plants were grown in a greenhouse for 20 days and the herbicidal efficacy was investigated. The results are shown in Table 6.

Test Example 5 Upland soil treatment test Field up soil was packed in a vat with an area of 33 × 23 cm ² and a depth of 11 cm,
Wheat, Scutellaria baicalensis, Chickweed, Shiroza, field pansy, and buckwheat vine were sown and covered with a soil having a thickness of 1 to 2 cm. The test compound was made into an emulsion according to Formulation Example 2, and the predetermined amount thereof was diluted with 10 liters of water per are.
The soil surface was treated with a small sprayer. After the treatment, the plants were grown in a greenhouse for 20 days and the herbicidal efficacy was investigated. The results are shown in Table 7.

Test Example 6 Field foliage treatment test A bat having an area of 33 × 23 cm ² and a depth of 11 cm was filled with field soil,
Maize, velvetleaf, malaga morning glory, dog physalis, and blue-toothed plant were sown and grown for 18 days. afterwards,
The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with 5 liters of water per 1 are containing a spreading agent, and uniformly treated on the entire foliage from above the plant with a small sprayer. . At this time, the growth conditions of weeds and crops differed depending on the grass species, but at the 1 to 4 leaf stage, the plant height was 2 to 12 cm. The herbicidal efficacy was investigated 20 days after the treatment. The result is No. 8
Shown in the table. This test was conducted in a greenhouse throughout the entire period.

<Effects of the Invention> As described above, the compound of the present invention is a variety of weeds that are problematic in the foliar treatment and soil treatment of upland fields, for example, buckwheat vine, sana edode, purslane, chickweed, white rosa, pearl millet, Japanese radish, radish, White-faced Pepper, American hemlock, Nebula serrata, Echinacea, Golden stag, Field pansy, Yaemgra,
Broad-leaved weeds such as American morning glory, Malva morning glory, Hirugosa bindweed, Datura serrata, Prunus densiflora, Scutellaria baicalensis, Salad, sunflower, dog chamomile, corn marigold, etc. ,
It has herbicidal activity against gramineous weeds such as horsetail and communis weeds such as Commelina communis, Cyperaceae weeds such as Coccinella communis, and weeds, and the compound of the present invention is a major crop such as corn, wheat, rice, soybean, and cotton. Does not show any phytotoxicity.

In addition, the compound of the present invention is a variety of weeds that are problematic in the flooding treatment of paddy fields, for example, grass weeds such as Taenia japonicus, aena, broadleaf weeds such as Aedes aegypti, P. persicae, firefly, cyperaceae such as matsubai, eel, weeds, urchins. It has a herbicidal effect on rice, etc., and does not show any problematic leaf damage to rice.

Furthermore, the compound of the present invention can be used as an active ingredient of a herbicide for paddy fields, upland fields, orchards, meadows, lawns, forests or non-agricultural fields, and can be mixed with other herbicides. By using it, the herbicidal effect can be expected to be enhanced.
Furthermore, it can be used by mixing with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners and the like.

Claims (2)

[Claims] 1. A general formula [In the formula, R represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower alkoxymethyl group,
X represents a hydrogen atom or a fluorine atom. ] N- (benzoxazinyl) tetrahydrophthalimide derivative shown by these. 2. General formula [In the formula, R represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower alkoxymethyl group,
X represents a hydrogen atom or a fluorine atom. ] The herbicide characterized by using N- (benzoxazinyl) tetrahydrophthalimide derivative shown by these as an active ingredient.