JPH05155866A - N-aminouracil derivative, method for producing the same, and herbicide containing the same as an active ingredient - Google Patents

Abstract

(57) [Summary] [Structure] General formula [Formula 1] [Wherein, R represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy lower alkyl group, a halo lower alkyl group or a halo lower alkenyl group, and X represents
Represents a chlorine atom or a bromine atom, and Y represents a halomethyl group. ] The N-amino uracil derivative shown by these, its manufacturing method, and the herbicide which makes it an active ingredient. [Effect] Since it has excellent herbicidal activity and shows selectivity between crops and weeds, it can be used as an active ingredient of a herbicide.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel N-aminouracil derivative, a method for producing the same, and a herbicide containing the same as an active ingredient.

[0002]

2. Description of the Related Art It has been known that some uracil derivatives have herbicidal activity. For example, bromacil is a commercially available herbicide. In addition, JP-A-48-92533
The publication describes that certain aminouracil derivatives can be used as active ingredients of herbicides.

[0003]

However, these compounds are not necessarily satisfactory because they have insufficient herbicidal efficacy and poor selectivity between crops and weeds.

[0004]

DISCLOSURE OF THE INVENTION As a result of various investigations made by the present inventors in view of such circumstances, the N-aminouracil derivative having a phenyl group having a specific substituent has few drawbacks as described above. It has an excellent herbicidal effect and can
The inventors have found that the compound exhibits selectivity among weeds and completed the present invention.

That is, the present invention has the general formula

[0006]

[Chemical 3]

[Wherein R represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy lower alkyl group, a halo lower alkyl group and a halo lower alkenyl group, X represents a chlorine atom or a bromine atom, and Y represents Represents a halomethyl group. ] The N-amino uracil derivative (it is hereafter described as this invention compound) shown by these, its manufacturing method, and the herbicide which makes it an active ingredient are provided.

The substituent R in the above chemical formula 3 is C _{1 to} C ₆
Alkyl group, C ₃ -C ₆ alkenyl group, C ₃ -C ₆ alkynyl group, C ₁ -C ₄ alkoxy (C ₁ ~C ₃₎ alkyl group, halo (C ₁ ~C ₅₎ alkyl group, halo (C ₃ ~ C
₅ ) Examples include alkenyl groups.

Next, a method for producing the compound of the present invention will be described. The compound of the present invention has the general formula

[0010]

[Chemical 4]

[In the formula, R, X and Y have the same meanings as described above. ] It can manufacture by aminating the uracil derivative shown by these using an aminating agent.

This reaction is usually carried out in a solvent in the presence of a base, the reaction temperature is in the range of 0 to 100 ° C., the reaction time is in the range of 0.5 to 20 hours. The amount is 1 to 5 equivalents of the aminating agent and 1 to 5 equivalents of the base with respect to 1 equivalent of the uracil derivative represented by Chemical formula 4.

Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and dichlorobenzene. Halogenated hydrocarbons, diethyl ether, diisopropyl ether, dioxane,
Tetrahydrofuran, ethers such as diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, ethyl formate, ethyl acetate, butyl acetate, esters such as diethyl carbonate, pyridine, triethylamine, N, N-diethyl Tertiary amines such as aniline, tributylamine and N-methylmorpholine, N, N
Examples thereof include acid amides such as dimethylformamide and N, N-dimethylacetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, liquid ammonia, water and the like, or a mixture thereof.

Examples of the base include organic bases such as pyridine, triethylamine and N, N-diethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride, sodium methoxide and sodium ethoxy. Examples of the aminating agent include alkali metal alkoxides such as amide, and examples of the aminating agent include 2,4-dinitrophenoxyamine, O-mesitylenesulfonylhydroxyamine, hydroxyamine-O-sulfonate, and the like.

After completion of the reaction, the reaction solution is poured into water, and the resulting crystals are subjected to usual post-treatments such as filtration or extraction with an organic solvent and concentration, and if necessary, purification by operations such as chromatography and recrystallization. As a result, the desired compound of the present invention can be obtained.

The compounds of the present invention produced according to the above production method are shown in Tables 1 to 16.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[0021]

[Table 5]

[0022]

[Table 6]

[0023]

[Table 7]

[0024]

[Table 8]

[0025]

[Table 9]

[0026]

[Table 10]

[0027]

[Table 11]

[0028]

[Table 12]

[0029]

[Table 13]

[0030]

[Table 14]

[0031]

[Table 15]

[0032]

[Table 16]

The compounds of the present invention also include optical isomers derived from asymmetric carbon. The uracil derivative represented by Chemical formula 4, which is a starting compound for the compound of the present invention, is disclosed in JP-A-63-41466.
It can be manufactured by the method described in the publication.

The compound of the present invention is used for various weeds which are problematic in the treatment of foliage and soil in the field, for example, buckwheat vine, sanaetade, purslane, chickweed, white azalea, aogateto, Japanese radish, velvetleaf, nazuna, hornwort, Ebisugusa, Abutilon, American Stag Deer, Field Pansy, Yaemgra, American Morning Glory, Malaga Morning Glory, Convolvulus vulgaris, Anemone duckweed, Physcomitrella patens, White-billed Morning Glory, Puercus persica, Stellaria japonica, Onami, Sunflower,
Dog chamomile, corn marigold, Euphorbiaceae,
Broad-leaved weeds such as St. John's wort, barnyard grass, dog millet, green foxtail, crabgrass, bluegrass, thornybug, oat, oats, oat, corn, etc. It has a herbicidal effect on Cyperaceae weeds and the like, and the compound of the present invention does not show a harmful effect on major crops such as corn, wheat, rice, soybean and cotton.

Further, the compound of the present invention can be used for various kinds of weeds that are problematic in the flooding treatment of paddy fields, for example, weeds such as rice grass, broad-leaved weeds such as Azena, Kishigusa, Mizohakobe, Tamagaya, Firefly, Matsubayai and the like. It has a herbicidal effect on Cyperaceae weeds, eels, sea urchins, and the like, and does not show any harmful phytotoxicity to rice.

When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant or other auxiliaries for formulation to prepare emulsions, wettable powders, suspensions, granules. It is formulated into a drug, a wettable granule, etc. In these formulations, the compound of the present invention is contained as an active ingredient in a weight ratio of 0.02 to 80.
%, Preferably 0.05 to 70%.

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

Surfactants used for emulsification, dispersion, wet extension, etc. include alkyl sulfate ester salts, alkyl sulfonates, alkyl aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates. Anionic surfactants such as ester salts, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. Can be given. Other formulation adjuvants include lignin sulfonate,
Alginate, polyvinyl alcohol, gum arabic,
Examples include CMC (carboxymethyl cellulose), PAP (acidic isopropyl 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. Soil treatment includes soil surface treatment and soil admixture treatment, and foliage treatment includes treatment from above the plant,
There are local treatments that treat only weeds so that they do not adhere to crops.

Further, it is expected to enhance the herbicidal effect by using it in combination with other herbicides. Furthermore, it can be used by mixing with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners and the like.

The compound of the present invention can be used as an active ingredient of a herbicide for paddy fields, fields, orchards, meadows, lawns, forests or non-agricultural lands. When the compound of the present invention is used as an active ingredient of a herbicide, the treatment amount thereof varies depending on weather conditions, formulation form, treatment time, method, place, target crop, target weed, etc.
The amount is 05 g to 80 g, preferably 0.01 g to 40 g, and emulsions, wettable powders, suspensions, granule wettable powders and the like are usually used in a predetermined amount of 1 liter to 10 liters per 1 are (if necessary, It is diluted with water (to which an auxiliary agent such as a spreading agent is added) and treated, and granules and the like are generally treated without being diluted.

Examples of the spreading agent include polyoxyethylene resin acid (ester), ligninsulfonic acid salt, abietic acid salt, dinaphthylmethanedisulfonic acid salt, and paraffin in addition to the above-mentioned surfactant.

The compound of the present invention can also be used as an active ingredient of a harvesting aid such as cotton defoliant, desiccant and potato desiccant.

[0044]

EFFECTS OF THE INVENTION The compound of the present invention has an excellent herbicidal effect against various weeds which are problematic in the soil treatment and foliage treatment of upland fields, and the flooding treatment of paddy fields, and the selectivity between major crops and weeds. Therefore, it can be used for various purposes as an active ingredient of a herbicide.

[0045]

EXAMPLES 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 1 3- (4-chloro-2-fluoro-5-propargyloxyphenyl) -6-trifluoromethyl-1,2,
3,4-tetrahydropyrimidine-2,4-dione (2
g) was added to a solution of 60% sodium hydride (0.22 g) suspended in N, N-dimethylformamide (10 g) under ice cooling, and then 2,4-dinitrophenoxyamine (1.1
g) is slowly added at 5 to 20 ° C and the mixture is allowed to stand at room temperature for 3
Stir for hours. After the reaction was completed, the reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent; hexane-ethyl acetate mixed solvent) to give the compound (5) of the present invention.
0.9 g was obtained. ¹ H-NMR [60 MHz (CDCl ₃ ); δ (pp
m)] 2.54 (1H, t, J = 3Hz), 4.59 (2H, bs), 4,70 (2H, d, J = 3Hz)
, 6.23 (1H, s), 7.05 (1H, d, J = 6Hz), 7.16 (1H, d, J = 9Hz)

Production Example 2 3- [4-Bromo-2-fluoro-5- (2-fluoroethoxy) phenyl] -6-trifluoromethyl-1,
A solution of 2,3,4-tetrahydropyrimidine-2,4-dione (0.4 g) in dimethylformamide (10 ml) was added to 60%.
After adding dropwise to a dimethylformamide (10 ml) solution in which sodium hydride (0.05 g) was suspended at 5 to 10 ° C, at 10 to 20 ° C
Stir for 30 minutes. 2,4-Dinitrophenoxyamine (0.22 g) was slowly added thereto at 10 to 20 ° C., and the mixture was stirred at room temperature for 1 hr. After completion of the reaction, the reaction solution is poured into ice water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, purified by silica gel column chromatography, and 1-amino-3-.
[4-Bromo-2-fluoro-5- (2-fluoroethoxy) phenyl] -6-trifluoromethyl-1,2,
3,4-Tetrahydropyrimidine-2,4-dione is obtained.

Production Example 3 3- (4-Bromo-2-fluoro-5-methoxymethoxyphenyl) -6-trifluoromethyl-1,2,3,3
4-tetrahydropyrimidine-2,4-dione (0.4
The dimethylformamide (10 ml) solution of g) was added dropwise to a dimethylformamide (10 ml) solution in which 60% sodium hydride (0.05 g) was suspended at 5 to 10 ° C, and then the mixture was stirred at 10 to 20 ° C for 30 minutes. 2,4-Dinitrophenoxyamine (0.22 g) was slowly added thereto at 10 to 20 ° C., and the mixture was stirred at room temperature for 1 hr. After completion of the reaction, the reaction solution is poured into ice water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to give 1-amino-3- (4-bromo-2-fluoro-5-methoxymethoxyphenyl).
-6-Trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione is obtained.

Next, Table 17 shows some of the compounds of the present invention produced according to the above Production Examples.

[0050]

[Table 17]

Formulation examples are shown below. The compounds of the present invention are shown by the compound numbers in Table 17. Parts are parts by weight.

Formulation Example 1 Compounds of the present invention (1) to (4), (6), (7), 5 each
0 part, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain wettable powders. Formulation Example 2 5 parts each of the compounds (1) to (7) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 25 parts of xylene and 50 parts of cyclohexanone are mixed well to form an emulsion. obtain.

Formulation Example 3 Compounds (1) to (7) of the present invention, 2 parts each, 1 part synthetic silicon oxide hydroxide, 2 parts calcium lignin sulfonate, 30 parts bentonite and 65 parts kaolin clay were thoroughly pulverized and mixed, and water was added. After adding and kneading well, it is granulated and dried to obtain granules. Formulation Example 4 Compounds of the present invention (1) to (4), (6), (7), 2 each
5 parts, polyoxyethylene sorbitan monooleate 3
Parts, 3 parts of CMC, and 69 parts of water are mixed, and wet pulverized until the particle size becomes 5 microns or less to obtain suspension agents. Formulation Example 5 The compounds (1) to (7) of the present invention, 0.05 part each, 1 part synthetic silicon oxide hydroxide, 2 parts calcium lignin sulfonate, 30 parts bentonite and 66.95 parts kaolin clay are thoroughly pulverized and mixed, and water is added. After kneading well, granulation and drying are performed to obtain granules.

Next, it is shown in Test Examples 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 17, and the compounds used for comparison and control are shown by the compound symbols in Table 18.

[0055]

[Table 18]

In the evaluation of herbicidal efficacy and phytotoxicity, "0" was given to the plants (weeds and crops) at the time of the survey, which had no or almost no difference in their emergence and growth conditions as compared with those of untreated plants. , "5" means that the test plant is completely killed or the emergence or growth of the plant is completely suppressed, and is divided into 6 stages of 0 to 5, and is shown as 0, 1, 2, 3, 4, 5.

Test Example 1 A cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm was filled with upland soil, and seeds of millet, Malaga morning glory and velvetleaf were sown to cover the soil. The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the compound was diluted with water equivalent to 10 liters per are, and the soil surface was treated with a small sprayer. After processing 1
It was grown in a greenhouse for 9 days, and the herbicidal effect was investigated. The results are shown in Table 19.

[0058]

[Table 19]

TEST EXAMPLE 2 A cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm was filled with upland soil, sowed with Malaga morning glory and velvetleaf and cultivated in a greenhouse for 10 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2 and the predetermined amount thereof was changed to 10 per 1 are.
It was diluted with water containing a spreading agent equivalent to 1 liter, and foliage was treated from above the plant with a small sprayer. After the treatment, the plants were grown in a greenhouse for 19 days, and the herbicidal efficacy was investigated. The results are shown in Table 20.

[0060]

[Table 20]

Test Example 3 A paddy soil was filled 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, Scutellariae, Mizochabe) were mixed to a depth of 1 to 2 cm. After flooding to make paddy fields, rice at the second leaf stage was further transplanted and grown in a greenhouse. 6 days later (early generation of each weed)
The test compound was made into an emulsion in accordance with Preparation 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 herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 21.

[0062]

[Table 21]

Test Example 4 A vat having an area of 33 × 23 cm ² and a depth of 11 cm was filled with upland soil, and corn, Malva morning glory, Salad fir, velvetleaf, Ebisugusha, physalis physalis and barnyard grass were sown and grown in a greenhouse for 16 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2 and the predetermined amount thereof was changed to 10 per 1 are.
It was diluted with water equivalent to 1 liter, and the whole foliage was uniformly treated 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 5 to 30 cm. After the treatment, the plants were grown in a greenhouse for 18 days, and herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 22.

[0064]

[Table 22]

Test Example 5 A vat having an area of 33 × 23 cm ² and a depth of 11 cm was filled with field soil, and wheat, sanaetade, yaemgra, chickweed, red-spotted gall, field pansy and oats were sown and grown in a greenhouse for 31 days. Then, the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount thereof was diluted with 10 liters of water per are, and the whole foliage was treated uniformly from above the plant with a small sprayer. At this time, the growth conditions of weeds and crops differ depending on the grass species, but 1 to 4
At the leaf stage, the plant height was 3 to 25 cm. After the treatment, the plants were grown in a greenhouse for 25 days, and herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 23.

[0066]

[Table 23]

Test Example 6 A vat having an area of 33 × 23 cm ² and a depth of 11 cm was filled with upland soil, and corn, velvetleaf, physalis sycamore, syringa sorghum, and Anoenochogokosa were sown to cover the soil with a thickness of 1 to 2 cm. The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the compound was diluted with 10 liters of water equivalent to 1 are, and the soil surface was uniformly treated with a small sprayer. After the treatment, the plants were grown in a greenhouse for 18 days, and herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 24.

[0068]

[Table 24]

Test Example 7 A vat having an area of 33 × 23 cm ² and a depth of 11 cm was filled with upland soil, and wheat, barley, sunflower, field staghorn and field pansy were sown and covered with a thickness of 1 to 2 cm. The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the compound was diluted with 10 liters of water equivalent to 1 are, and the soil surface was uniformly treated with a small sprayer. After treatment,
It was grown in a greenhouse for 25 days, and herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 25.

[0070]

[Table 25]

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Shinsuke Ikushima 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Eiki Nagano 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd.

Claims (3)

[Claims] 1. A general formula: [Wherein, R represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy lower alkyl group, a halo lower alkyl group or a halo lower alkenyl group, and X represents
Represents a chlorine atom or a bromine atom, and Y represents a halomethyl group. ] N-amino uracil derivative shown by these. 2. A general formula: ## STR2 ## [Wherein, R represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy lower alkyl group, a halo lower alkyl group or a halo lower alkenyl group, and X represents
Represents a chlorine atom or a bromine atom, and Y represents a halomethyl group. ] The uracil derivative shown by these is aminated, The manufacturing method of the N-amino uracil derivative of Claim 1 characterized by the above-mentioned. 3. A herbicide containing the N-aminouracil derivative according to claim 1 as an active ingredient.