JPH02233602A - Herbicide - Google Patents

Abstract

PURPOSE:To obtain a herbicide containing a 5,6-dihydro-1,4,2-dioxazine derivative as an active ingredient, having excellent herbicidal activity as for paddy field and upland and high safety to useful crops and men and beasts. CONSTITUTION:A compound, e.g. 3-(4-fluorophenyl)-5,6-dihydro-1,4,2-dioxazine, expressed by formula I (R is H, alkyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkylthioalkyl, aryl, arylalkyl, aryloxyalkyl or arylthioalkyl, etc.) is contained as an active ingredient. Furthermore, the compound expressed by formula I is obtained by reacting an acylhydroxylamine derivative expressed by formula II with a 1,2-dihaloethane expressed by formula III (X and Y are halogen).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a herbicide containing a 5,6-dihydro-1,4,2-dioxazine derivative represented by the general formula (I) below as an active ingredient. Therefore, the present invention is useful in the chemical industry and agriculture, particularly in the field of agrochemical manufacturing. Until now, compounds with a 5,6-dihydro-1,4,2-dioxazine structure that are known to have physiological activity as agricultural chemicals have carboxylic acid derivatives as substituents. Limited to those with a special structure that is a modification of known agricultural chemicals (Japanese Patent Application Laid-Open No. 57-154161, German Patent No. 3)
220525). However, the herbicidal activity of the compound represented by general formula (I) described later in the present invention is not known. 5,6-dihydro-1.4.2-dioxazine derivatives, which are known to have herbicidal activity, have herbicidal activity against some grass species, as shown in the test examples below, but they do not cause phytotoxicity to crops. Therefore, it is difficult to use. Therefore, the present invention provides a herbicide that has superior herbicidal activity and is highly safe for useful crops, humans and livestock, and can be used as a herbicide for paddy rice and field herbicide in place of similar compounds known to have herbicidal activity. The aim is to provide drugs for In order to achieve the above object, the present inventors synthesized a number of dioxazine derivatives and conducted extensive studies on their usefulness. As a result, it was found that the 5,6-dihydro-1,4,2-dioxazine derivative represented by p in the general formula (1) below has high herbicidal activity and safety.
Therefore, the gist of the first invention is the following general formula (I) (wherein R is a hydrogen atom, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkoxylalkyl group, an alkylthioalkyl group, Aryl group, arylalkyl group, aryloxyalkyl group, arylthioalkyl group, arylalkyloxyalkyl group, arylalkylthioalkyl (however, alkyl may be saturated or unsaturated, and aryl may be a benzene nucleus,
It means a pyridine nucleus, a thiophene nucleus or a furan nucleus, and these nuclei can contain up to two identical or different halogen atoms, a lower alkyl group, a lower haloalkyl group,
Hydroxy group, lower alkylcarbonyloxy group, lower alkoxycarbonyloxy group, lower alkylsulfonyloxy group, lower kylaminocarbonyloxy group, lower dialkylaminocarbonyloxy group, lower alkoxy group, lower alkylthio group, cyano group, nitro group, A herbicide characterized by containing as an active ingredient a 5,6-dihydro-1,4,2-dioxazine derivative represented by the following formula (which may be substituted with a phenoxy group or a phenylthio group). Next, Table 1 shows typical examples of the compounds of general formula (I) used in the herbicide of the present invention. In addition, compound decomposition. is also referred to in the following examples and test examples. Table 1 The compound of general formula (!), which is the active ingredient of the herbicide of the present invention, is produced by the method described below. In other words, the general formula 《! ] can be produced by a method consisting of reacting an acylhydroxylamine visiting conductor of the following general formula (II) with 1,2-dihaloethane of the following general formula (m). U (n) (m)
(I) (wherein R has the same meaning as above,
X and Y represent halogen atoms which may be the same or different. This reaction involves mixing the compound of formula (II) and the compound of formula (m) in the presence of an acid binder, usually in a solvent. This can be accomplished by Examples of solvents include hydrocarbons such as benzene, toluene, and xylene, ethers such as tetrahydrofuran and dioxane, nitriles such as acetonitrile and probionitrile, alcohols such as ethanol and ethylene glycol, and amides such as dimethylformamide and dimethylacetamide. and dimethyl sulfoxide can be used. As the binder, inorganic bases such as sodium hydroxide, sodium hydride, and potassium carbonate, and organic bases such as sodium methoxide, sodium ethoxide, triethylamine, and pyridine can be used. Although the reaction proceeds at room temperature, the reaction time can be shortened by heating it up to the boiling point of the solvent. After the reaction is complete, the target compound can be obtained by filtering off salts of the acid binder, if present, and distilling off the solvent. The target compound can also be obtained by adding water and an organic solvent such as benzene, toluene, tetrahydrofuran, or chloroform, extracting the target compound, and distilling off the solvent. Production examples of compounds of formula <<I>> are shown in Production Examples 1 to 6. The compound of formula (II) used as a raw material is a known compound or can be easily prepared by a known similar method, for example, the reaction of the corresponding ester with hydroxylamine, or the reaction of the corresponding acid halide with hydroxylamine. can be obtained. Moreover, all the compounds of formula (m) are known compounds. 4-fluoropenzhydroxamic acid 15.5g
A mixture of 18.8 g of ,1,2-dibromoethane, 30.4 g of anhydrous potassium carbonate, and 200 mJl of acetonitrile was refluxed for 2 hours with stirring. After cooling, the salts were filtered off and the filtrate was concentrated. The residue was dried with coum. When the solvent was distilled off under reduced pressure, the title compound was obtained as a pale brown oil.
6.5g was obtained. It crystallized shortly at room temperature, and when recrystallized from a mixed solvent of hexane and ethyl acetate, it became white crystals with a melting point of 56-58°C. fLLaλ)3-(%+lifluoromethylphenylated compound - 13.9 g was obtained as pale yellow crystals. Recrystallization from cyclohexane resulted in white crystals, melting point 62-63.
It showed ℃. 4-Tri-7-methylbenzhydroxam haze 20.5
g,t-bromo-2-chloroethane 14.4 g. A mixture of 30.4 g of 1M potassium hydrocarbonate and 200 m of methanol was refluxed for 5 hours with stirring. After cooling, treatment was carried out in the same manner as in Preparation Example 1 to obtain 20.61 g of the title compound as a pale brown oil. Recrystallization from a hexane-acetone mixed solvent gave white crystals with a melting point of 76-78°C. 3-pyridylcarponylhydroxyamine 13.8
g. 1.2-diiodoethane 28.2g. A mixture of 11.5 g of potassium hydroxide and 200 ml of ethanol was stirred and reacted at 50° C. for 2 hours. After cooling, the product is treated in the same manner as in Production Example 1. 20.2 g of 2-chlorophenoxyacetohydroxamic acid and 18.8 g of 1,2-dibromoethane are used, and the reaction is carried out in the same manner as in Production Example 1. 20.7 g of the compound was obtained as a light brown oil. This product crystallized shortly at room temperature, and when recrystallized from a mixed solvent of cyclohexane and ethyl acetate, it became white crystals with a melting point of 51-53°C. Using 18.1 g of penzyloxyacetohydroxamic acid and 14.4 g of l-bromo2chloroethane, the reaction was carried out in the same manner as in Production Example 2 to obtain 19.3 g of the title compound as a pale yellow oil. Purification by silica gel column chromatography using a mixed solvent of toluene and acetone yields a colorless oil. no3=1.44
It showed 63. 4-Phenoxyphenoxyacetohydroxamic acid 25.
9 and 1,2-diiodoethane28. It was. This product crystallized shortly at room temperature, and recrystallized from cyclohexane to give white crystals with a melting point of 38-40°C. In addition, the herbicide of the present invention can be prepared by adding the compound of general formula (I) to emulsions, permanent agents, liquids, flowable (sol) agents, powders, driftless (DL) powders, It can be prepared as appropriate forms such as granules, microgranules, and tablets. The carrier used here can be either solid or liquid, as long as it is commonly used for agricultural and horticultural chemicals, and is not limited to any particular carrier. For example, solid carriers include mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite, white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc.), and plants. powder (soybean flour, wheat flour, wood flour, tobacco flour, starch, crystalline cellulose, etc.), polymer compounds (petroleum resin, polyvinyl chloride, ketone resin, dammargum, etc.), alumina, silicate, sugar polymer, polymer Examples include dispersible silicic acid and waxes.
Examples of liquid carriers include water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, butanol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (toluene, benzene, xylene, ylbenzene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, dichloromethane, chloroethylene, monochlorobenzene, trichlorofluoromethane, dichlorodifluoromethane, etc.), ethers (ethyl ether, ethylene oxide, etc.) , dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone,
isophorone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc.)
, acid amides (dimethylformamide, dimethylacetamide), etc. (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.)
, minutes (baraffins, kerosene, diesel oil, etc.). In addition, various surfactants or emulsifiers are used for the purposes of emulsification, dispersion, solubilization, wetting, foaming, lubrication, and spreading when preparing formulations such as emulsions, wettable powders, and flowables. Such surfactants include nonionic W (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc.). j*Ionic type《Alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfonate, etc.》
, cationic type (alkylamines (laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, etc.), polyoxyethylene alkylamines), amphoteric type (carboxylic acid (betaine type), sulfuric acid ester salts, etc.) However, it is of course not limited to these examples.In addition to these, polyvinyl alcohol, carboxymethyl cellulose, gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate,
Various adjuvants such as gum tragacanth can be used. In the present invention, when producing the various preparations described above, the compound of formula (I) is contained in the range of 0.0015% to 95% (weight %; the same applies hereinafter), preferably 0.01% to 90%. It can be formulated into a formulation. For example, in the case of powders, DL powders, and fine powders (F), 0.
0.01% to 5% in the case of granules, 1% to 75% in the case of wettable powders, emulsions, and solutions. For example, in the case of a granule, the preparation thus prepared may be directly sprayed onto the soil surface, into the soil, or into water in an effective amount of about 0.3 g to 300 g.
In the case of wettable powders, emulsions, and sol preparations, they may be diluted with water or a suitable solvent and sprayed in an effective amount of about 0.3 to 300 g. In addition, when using the compound of formula (1) as a herbicide,
It can be used in combination with known herbicides, insecticides, or plant regulators to expand its applicability, and in some cases, a synergistic effect can be expected. A method for formulating the compound of formula (I) as a herbicide will be explained using Examples 1-12. However, the present invention is not limited to these examples, and can be mixed with various other additives in any proportion, and may also be mixed with other herbicides such as herbicides in any proportion to form a formulation. You can also. In addition, all parts in the examples indicate parts by weight.衷JIL 工IJ1- Compound decomposition. 2 parts of compound No. 56. PAP (physical property improver)
1m and 97 parts of clay are uniformly mixed and ground to obtain a powder containing 2% of the active ingredient.衷 [υIL Compound animal. Compound 211 of No. 93 was prepared in the same manner as in Example 1 to obtain a powder containing 2% of the active ingredient. 3《Hydrating agent》 Compound agent. 30 parts of compound No. 30, 3 tlA. of calcium alkylbenzenesulfonate. Polyoxyethylene nonyl phenyl ether sag and 62 parts of clay are mixed uniformly and ground to obtain a wettable powder containing 30% of the active ingredient. Compound animals. A wettable powder containing 30% of the active ingredient is obtained by preparing in the same manner as in Example 3 using 30 parts of the compound No. 82. Compound 1' (L Kogo Ju Compound Animal. 68 compound 30 parts, methyl ethyl ketone 4
By mixing and dissolving 0 parts of polyoxyethylene nonylphenyl ether and 30 parts of polyoxyethylene nonylphenyl ether, an emulsion containing 30% of the active ingredient is obtained.衷JLfL! L Engineering 5] 1 Compound flb. Example 5 using 30 parts of compound No. 112
Prepare in the same manner as above to obtain an emulsion containing 30% of the active ingredient. Ura IJLL Engineering 1j1- Compound Animal. 5 parts of compound No. 23, 1 part of lauryl sulfate
．． 5 parts of calcium ligninsulfonate, 1.5 parts of bentonite, and 671J of white carbon were uniformly mixed together, 15 parts of water was added thereto, and the mixture was kneaded and granulated using a mixer, and then dried using a fluidized fluid dryer. Granules containing 5% of the active ingredient are obtained. Back 1'' ULL 1st edition top compound animal. A granule containing 5% of the active ingredient is obtained by preparing in the same manner as in Example 7 using 5 parts of the compound No. 85. Ura m01 晟上 compound animal. 10 parts of the compound No. 49 and 90 parts of ethyl cellosolve are mixed and dissolved to obtain an oil solution containing 10% of the active ingredient. l O Compound Nb. Example 9 using compound 101s of 123
An oil solution containing lθ% of the active ingredient is obtained by preparing in the same manner as above. l1 Sol 10J&compound powder crushed to below. 40 parts of compound No. 30, 2 parts of lauryl sulfate, 2 parts of sodium alkylnaphthalene sulfonate, human xyprobyl cellulose lt
s and water SSS are uniformly mixed to obtain a sol containing 40% of the active ingredient. l2 Sol Compound Animal. A sol containing 40% of the active ingredient is obtained by preparing in the same manner as in Example 1l using 40 parts of the compound No. 73. The herbicide of the present invention, which has a class M and M class, has superior herbicidal activity and safety compared to known similar herbicides. Namely, barnyard grass, firefly,
It has a wide range of effects on paddy field weeds such as Prunus japonicus, Prunus elegans, Azena, and Kikashigusa, and is effective against these weeds.
Weeds can be completely killed by treating 50 g of the compound of formula (I) as an active ingredient per 0 are. Also, crabgrass,
Various upland weeds such as foxtail grass, whiteweed, Japanese knotweed, and Japanese knotweed can be completely eradicated by application at an application rate of 100g per 10are. Furthermore, it does not cause any chemical damage to useful crops such as paddy rice, soybeans, corn, beets, rapeseed, and wheat. In addition, human-animal toxicity,
It is safe to use as it is not toxic to fish. Test Examples 1 and 2 are shown to illustrate the herbicidal activity of the herbicide of the present invention. A Wagner pot with a size of 1/5000 are is filled with paddy soil (alluvial loam), and the surface layer is filled with barnyard grass, firefly,
Fifty seeds each of Helaomodaca, Konagi, Azena, and Kikashigusa were uniformly sown. Flooded after sowing,
The water depth was kept at 2 cm. Three days after sowing, two seedlings of 2.5-leaf stage paddy rice were planted, and three plants were transplanted per pot. One day after transplanting the paddy rice, the emulsion prepared according to Example 5 was diluted with water and treated by dropping 10 mjl of the treatment chemical solution per pot (equivalent to 50 g per IO are in terms of the amount of active ingredient used). This test was conducted in duplicate per 1 drug solution concentration section, and
After a few days, the herbicidal effect and the degree of chemical damage to paddy rice were investigated based on the evaluation indicators shown below. The results are shown in Table 2. Table 2 ulL Cap top L O O% 80-less than 100% 6 0-80 〃 40-60II 20-40n Grave it withered at the foot Severe chemical damage Medium II Small II Slight II None (described in German Patent No. 3220525) compound)
"Iris" Ryokan L's
and l) Herbicidal effect test on weeds Field soil (
Alluvial loam) was packed, and 50 seeds each of various weeds such as crabgrass, foxtail grass, whiteweed, Japanese knotweed, and Japanese knotweed were evenly mixed with the soil in the surface layer of 1 cm, and the surface layer was lightly pressed.
Two days after seeding, an emulsion prepared according to Example 5 was diluted with water. The treatment was carried out by spraying a treatment chemical solution of 100 yen per 10 ares (equivalent to toog per 10 ares in terms of the application amount of active ingredient) on the soil surface. This test was conducted in two consecutive sprays per section, and the herbicidal effect was evaluated 30 days after the chemical treatment. was investigated based on the same evaluation index as in Test Example 1. 2) Test for chemical damage to crops Field soil (alluvial loam) was filled in clay pots with a size of 1/10,000 are, and seeds of each crop ( 5 soybean grains, 5 corn grains, 10 beet grains, 10 rapeseed grains, and 10 wheat grains) were sown in separate pots, and the surface layer was lightly pressed. One day after sowing, the emulsion prepared according to Example 5 was diluted with water and treated with 100 J1 treatment agent per 10 are.
The liquid (active ingredient amount equivalent to 100 g per 10 ares) was sprayed onto the soil surface. This test was conducted in two consecutive plots, and 30 days after the chemical treatment, the chemical damage to each crop was investigated based on the same evaluation index as in Test Example 1. The results are shown in Table 3.

Claims (1)

[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R is a hydrogen atom, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkoxylalkyl group, an alkylthioalkyl group, an aryl group, Arylalkyl group, aryloxyalkyl group, arylthioalkyl group, arylalkyloxyalkyl group, arylalkylthioalkyl group (however, alkyl may be saturated or unsaturated, and aryl may be a benzene nucleus,
It means a pyridine nucleus, a thiophene nucleus or a furan nucleus, and these nuclei can contain up to two identical or different halogen atoms, a lower alkyl group, a lower haloalkyl group,
Hydroxy group, lower alkylcarbonyloxy group, lower alkoxycarbonyloxy group, lower alkylsulfonyloxy group, lower alkylaminocarbonyloxy group,
(may be substituted with lower dialkylaminocarbonyloxy group, lower alkoxy group, lower alkylthio group, cyano group, nitro group, phenoxy group or phenylthio group)
A herbicide characterized by containing a 5,6-dihydro-1,4,2-dioxazine derivative represented by the following as an active ingredient.