JPH0345075B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () (In the formula, X represents a chlorine atom or a bromine atom, Y represents an oxygen atom or a sulfur atom, and R represents a lower alkyl group having 1 to 3 carbon atoms.) ) Triazolo[1,2a][1.2]-diazepine derivative (hereinafter referred to as the compound of the present invention), a method for producing the same, and a herbicide containing the same as an active ingredient. The present inventors have continued their research with the aim of developing highly selective and highly active herbicides to protect important crops such as soybean, cotton, wheat, corn, and rice from weed damage and maintain high yields. As a result, we have discovered that the compound of the present invention represented by the general formula () has excellent herbicidal efficacy and is hardly harmful to important crops such as dice and cotton. completed. It is shown in JP-A-50-160429 that certain 2-phenyl-(1,2,4)triazolo[1,2a][1,2]diazepine derivatives have herbicidal activity. However, compared to the similar compounds described in the publication, the compound of the present invention has a much superior herbicidal effect, as is clear from the examples below, and has a significantly superior herbicidal effect on annual and perennial weeds in fields and paddy fields. Alternatively, in post-emergence treatment, extremely high herbicidal effects can be shown at low doses. Next, a method for synthesizing the compound of the present invention will be described. For the synthesis method of 1,2,4-triazole derivatives, please refer to Heterocyclic Compound
It is described in detail in vol37 (Jiyeon Willy and Son). The compound of the present invention can be synthesized according to the following formula. (In the formula, It is obtained by treating with phosphorus at a temperature such as reflux for 5 to 10 hours. The urazole derivative of the general formula () is produced by alkali metallizing the urazole derivative of the general formula () with a metalizing agent such as sodium methoxide, sodium hydride, butyl lithium, etc., and then combining it with dihalopentane such as 1,5-dibromopentane and dimethyl It is synthesized in the presence of a polar aprotic solvent such as formamide or dimethyl sulfoxide, with heating if necessary. The urazole derivative () is synthesized from phenyl isocyanate () by the method described in Organic Synthesis 51 121 (1971). This isocyanate () is manufactured by the Journal of the American Chemical Society (J.
Am.Chem.Soc.) 81 94 (1959) 2-
It can be obtained by alkyl etherifying chloro-4-fluorophenol or 2-bromo-4-fluorophenol, nitrating it with nitric acid-sulfuric acid, and reducing the resulting aniline with phosgene. Alternatively, it can be obtained by converting phenol into a carbonate ester, followed by nitration, hydrolysis of the carbonate ester, etherification, and reduction, and then reacting the resulting aniline with phosgene. Next, examples will be shown to explain the compounds of the present invention in more detail. Example 1 (1) (Production of Compound No. 1) Dissolve 0.46 g of metallic sodium in 20 ml of methanol, and add 4-(4-chloro-2-fluoro-5
2.6 g of (methoxyphenyl)-urazole was dissolved, and methanol was concentrated under reduced pressure. The residue was dissolved in 20 ml of dimethylformamide, 2.3 g of 1,5-dibromopentane was added, and the mixture was stirred at 110-120°C for 4 hours. After cooling, water was added and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography and then recrystallized from methanol to obtain 0.42 g of colorless crystals.
mp 121.5-123℃ IR νmax cm-1 1750, 1680 Example 2 (Production of compound number (5)) 2-(4-bromo-5-ethoxy-2-fluorophenyl)-1H,5H-(1, 2,4) Triazolo[1,2a][1,2]-diazepine-1,3
(2H) - Dissolve 0.63g of dione in 10ml of xylene,
0.46 g of phosphorus pentasulfide was added and the mixture was refluxed for 8 hours. The lower solution was separated and xylene was distilled off under reduced pressure. The residue was crystallized and washed with methanol to obtain 0.65 g of colorless crystals. mp 173.5-174.5℃ IR νmax cm-1 1290 Compounds (1), (2), and (3) in Table 1 were prepared according to Example 1, and compounds (4) and (4) in Table 1 were prepared according to Example 2. Compound (5) was synthesized.

[Table] The spectral data of the compounds in Table-1 are shown in Table-2. The compound numbers are the same as those listed in Table-1.

【table】

[Table] When actually using the compound of the present invention, emulsions, wettable powders, suspensions,
It is generally formulated into easy-to-use forms such as granules and powders. In this case, the content of the compound of the present invention in each preparation is 0.1 to 90%, preferably 1 to 80%. Examples of solid carriers used in preparing these pharmaceutical products include kaolin, bentonite, talc, diatomaceous earth, ziecrite, and synthetic hydrous silicon oxide. Liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, cyclohexanone,
Examples include ketones such as inholone, chlorobenzene, dimethylformamide, cellosolve, ethylene glycol, and water. emulsification, dispersion,
Examples of surfactants used for purposes such as expansion include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene stylaryl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and Examples include nonionic surfactants such as ethylene oxypropylene polymer and anionic surfactants such as alkyl sulfate ester salts, alkyl sulfonates, dialkyl sulfosuccinates, and alkylaryl sulfonates, and these may be used alone or in combination. Just use it. Furthermore, if necessary, a lignin sulfonate, polyvinyl alcohol, or a cellulose derivative such as methyl cellulose can be used as an adjuvant. Of course, the carriers, surfactants, etc. that can be used are not limited to those shown here. Next, a detailed explanation will be given by giving a formulation example, but it goes without saying that the formulation ratio and carrier can be changed. Note that parts in each example indicate parts by weight. Formulation Example 1 80 parts of compound (1), 5 parts of polyoxyethylene alkylaryl ether, and 15 parts of synthetic hydrated silicon oxide are thoroughly ground and mixed to obtain a wettable powder. Formulation Example 2 10 parts of compound (2), 7 parts of polyoxyethylene alkylaryl ether, 3 parts of alkylaryl sulfonate and 80 parts of cyclohexanone are thoroughly mixed to obtain an emulsion. Formulation Example 3 1 part of compound (5), 1 part of synthetic hydrated silicon oxide, 5 parts of lignin sulfonate and 93 parts of clay are thoroughly ground and mixed, water is added, the mixture is thoroughly kneaded, and then granulated and dried to obtain granules. . Formulation Example 4 3 parts of compound (1), 0.5 parts of isopropyl phosphate, 66.5 parts of clay and 30 parts of talc are thoroughly ground and mixed to obtain a powder. Formulation Example 5 20 parts of compound (5) was mixed with 60 parts of an aqueous solution containing 3% by weight of polyoxyethylene sorbitan monooleate, wet-pulverized until the particle size of the active ingredient was 3μ or less, and alginic acid was added as a dispersion stabilizer. A suspension formulation is obtained by mixing 20 parts of a large solution containing 3% by weight of sodium. When the compounds of the invention are used either pre- or post-emergence, the application rate can vary over a fairly wide range, but is usually 0.1-50 g per are, preferably 0.2-30 g. Furthermore, the compound of the present invention can be used in combination with other herbicides to improve its effectiveness as a herbicide, and in some cases, a synergistic effect can be expected. Examples of this include 2,4-dichlorophenoxyacetic acid (2,4-D); 2-methyl-4-chlorophenoxyacetic acid (MCPA); 2-methyl-4-
Chlorphenoxybutyric acid (MCPB); 2,4-dichlorophenoxybutyric acid (2,4-DB); 2-(2
-Methyl-4-chlorophenoxy)propionic acid (mecoprop); Methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propionate (dichlorohopmethyl); Butyl-2-[4-(5)
-trifluoromethyl-2-pyridyloxy)phenoxy]propionate (fluazihopbutyl); 2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionic acid (including), 2, 4-
Dichlorophenyl-4'-nitrophenyl ether (nitrophene); 2,4,6-trichlorophenyl-4'-nitrophenyl ether (chlornitrophen); 2-chloro-4-trifluoromethylphenyl-3'-Ethoxy-4'-nitrophenyl ether (oxyfluorophene); 2,4-dichlorophenyl-4'-nitro-3'-methoxyphenyl ether (chloromethoxynyl); 2,4-dichlorophenyl-3'-methoxy Carbonyl-4′-
Nitrophenyl ether (bifuenox); 5
-[2-chloro-4-(trifluoromethyl)phenoxy]-diphenyl ethers such as 2-nitrobenzoic acid (acifluorofene), 2-chloro-4,6-bisethylamino-
1,3,5-triazine (simazine); 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (atrazine); 2-
Methylthio-4,6-bisethylamino-1,
3,5-triazine (simetrine); 2-methylthio-4,6-bisisopropylamino-1,
3,5-triazine (promethrin); 2-chloro-4,6-bisisopropylamino-1,3,
5-triazine (propazine); 2-(2-chloro-4-ethylamino-S-triazin-6-ylamino) 2-methylpropionitrile (cyanazine); 4-amino-6-tert-butyl-
3-methylthio-1,2,4-triazine-5
(4H)-one (metribuzin); 3-cyclohexyl-6-dimethylamino-1-methyl-S-triazine-2,4-dione (hexazinone); 2
-Methylthio-4-ethylamino-6-isopropylamino-1,3,5-triazine (amethrine); 2-methylthio-4-(1,2-dimethylpropylamino)-6-ethylamino-1,3,
5-triazine (dimetamethrin); triazine series such as 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (metamitron), 3-(3,4-dichlorophenyl) -1,1-dimethylurea (diuron); 3
-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (linyuron); 1-(2,
2-dimethylbenzyl)-3-p-tolylurea (Daimron); 1,1-dimethyl-3-(3-trifluoromethylphenyl)urea (fluoromethyuron); 3-(4-bromo-3-chlorophenyl)-1 -Methoxy-1-methylurea (chlorobromulon); 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea (chloroxuron); 3-(4-isopropylphenyl)
-1,1-dimethylurea (isoprotyuron); 3-(2-benzothiazolyl) -1,3-
Dimethylurea (metabenzthiazuron); 3-
(5-tert-butyl-3,4-thiadiazol-2-yl)-4-hydroxy-1-methyl-
2-imidazolidone (butidazole); 3-(3
-Chloro-4-methoxypheenyl)-1,1-
Urea-based drugs such as dimethylurea (methoxuron),
Isopropyl-N-(3-chlorophenyl)carbamate (chloroprofum); Methyl-N-
(3,4-dichlorophenyl)carbamate (swep); 4-chloro-2-butynyl-N-
(3-chlorophenyl) carbamate (barban); 3-(methoxycarbonylamino)-phenyl-N-(3-methylphenyl) carbamate (fuemmediphum); methyl-N-(4-aminobenzenesulfonyl) carbamate (asylum) ; Carbamate series such as 3-isopropoxycarbonyl-aminophenyl-N-ethyl carbanilate (Fenisofam), S-(4-chlorobenzyl)-N,N-diethylthiol carbamate (benthocab); S-ethyl-N,N -Hexamethylenethiol carbamate (molinate); S-ethyl-N,N-di-n-propylthiol carbamate (EPTC); S-ethyl-N,
N-diisobutylthiol carbamate (butyrate); S-n-propyl-N,N-di-n-propylthiol carbamate (burnerate);
S-2,3,3-trichloroallyl-N,N-diisopropylthiol carbamate (trialate); S-ethyl-N-ethyl-N-cyclohexylthiol carbamate (cycloate);
- Thiol carbamate series such as (3-chlorobenzyl)-N,N-dise-butylthiol carbamate (thiocarbasil), 3,4-dichloropropionanilide (propanyl); N-
Methoxymethyl-2,6-diethyl-α-chloroacetanilide (alachlor); 2-chloro-
2',6'-diethyl-N-(butoxymethyl)-acetanilide (butachlor); 2-chloro-N
-(2-ethyl-6-methyl-phenyl)-N-
(2-methoxy-1-methylethyl)acetamide (metolachlor); N-chloroacetyl-N
-(2,6-diethylphenyl)-glycine ethyl ester (diethyl); 2-chloro-N-isopropylacetanilide (propachlor);
N,N-dimethyl-2,2-diphenylacetamide (diphenamide); N-naphthylphthalamic acid (naptalam); N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamide (pronamide) ; Ethyl-N-benzoyl-
N-(3,4-dichlorophenyl)-2-aminopropionate (benzoyl propionate); Methyl-N-benzoyl-N-(3-chloro-4-fluorophenyl)-2-aminopropionate Amides such as 5'-(trifluoromethanesulfonamide) aceto-2',4'-xylidide (mefluidide), 5-bromo-3
-Secondary-butyl-6-methyluracil (Bromacyl); 3-cyclohexyl-5,6-trimethyleneuracil (Renacil); 3-tertiary-butyl-5-chloro-6-methyluracil (Turbasil) and other uracil-based, 2,5-dichloro-3-aminobenzoic acid (chloramben); 3,6
-Dichloro-2-methoxybenzoic acid (Dicamba); Benzoic acids such as dimethyltetrachloroterephthalate (DCPA), N,N-bis(phosphonomethyl)glycine (glyfuosate); O
-Ethyl-O-(2-nitro-5-methylphenyl)-N-secondary butylphosphoroamidothioate (butamiphos); S-(2-methyl-1
-piperidylcarbonylmethyl)O,O-di-n
-Propyldithiophosphate (piperophos);
O,O-diisopropyl-S-(2-benzene-
sulfonylaminoethyl) phosphorus dithioate (Benslide), α,
α,α-trifluoro-2,6-dinitro-N,
N-dipropyl-p-toluidine (trifluralin); 3,4-dimethyl-2,6-dinitro-N
-1-ethylpropylanilide (pendimethalin); α,α,α-trifluoro-2,6-dinitro-N-propyl-N-cyclopropyl-p-
Toluidine (profluralin); Toluidine series such as 4-(methylsulfonyl)-2,6-dinitro-N,N-dipropylaniline (nitraline), disodium methane arsonate (DSMA);
Arsenic-based materials such as monosodium methane arsonate (MSMA), malate hydrazide (MH); 3
-(2,4-dichloro-5-isopropoxyphenyl)-5-tert-butyl-3,4-oxadiazol-2(3H)-one (oxadiazone); 2-(3,4-dichlorophenyl) )-4-
Methyltetrahydro-1,2,4-oxadiazole-3,5-dione (methazole); 3-isopropyl-1H-2,1,3-benzothiadiazine-(4)-3H-one-2,2 -Dioxide (bentazone); 4-(2,4-dichlorobenzoyl)
-1,3-dimethylpyrazol-5-yl-p-
Diazines such as toluene-sulfonate (pyrazolate), 4-amino-3,5,6-trichloro-picolinic acid (picloram);
Pyridine series such as 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-pyridin-4(1H)-one (fluridone), 2,6-dichlorobenzonitrile (diclobenyl); 3,5
-Diiodo-4-hydroxybenzonitrile (Ioxynil); Nitriles such as 3,5-dibromo-4-hydroxybenzonitrile (Bromoxynil), 2,2-dichloropropionic acid (Darapon); 2,2,3,3- Fatty acids (including salts) such as tetrafluoropropionic acid (tetrapion), α-(β-naphthoxy)propionanilide (naproanilide); 1,2-dimethyl-3,
5-Diphenyl-1H-pyrazolium methyl sulfate (diphenzoquat); 2-methyl-
4-Phenylsulfonyltrifluoromethyl-
Sulfoanilide (perfluidone); 3-amino-1,2,4-triazole (amitrole); 4-chloro-5-methylamino-2-(3
-trifluoromethylphenyl)pyridazine-3
(2H)-one (norflurazone); 2-secondary-butyl-4,6-dinitrophenol (dinoseb); 2-ethoxy-2,3-disidro-3,
3-dimethyl-5-benzofuranyl methanesulfonate (ethofumesate); 5-amino-4-
Chloro-2-phenyl-pyridazine-3(2H)-
On (pyrazone); 1,1'-dimethyl-4,4'-
Bipyridylium dichloride (balaquat); 1,
1′-ethylene-2,2′-bipyridylium dipromide (Diecoat); 2[1-(N-allyloxyamino)-butylidene]-5,5-dimethyl-4
-Methoxy-carbonyl-cyclohexane-1,
3-Dione Na salt (aloxydim-sodium); 2
-(N-ethoxybutyridyl)-5-(2-ethylpropyl)-3-hydroxy-2-cyclohexen-1-one:2-chloro-N[(4-methoxy-6-methyl-1,3,5 Examples include, but are not limited to, -triazin-2-yl)aminocarbonyl]benzenesulfonamide (chlorosulfuron). Furthermore, the compound of the present invention can be used in combination with insecticides, nematicides, fungicides, plant growth regulators, fertilizers, etc., if necessary. Next, the compounds of the present invention will be explained in more detail by giving examples related to herbicidal efficacy. The control compounds in the examples are listed in Table 3.

[Table] All evaluations of chemical damage to crops and efficacy against weeds in the following Examples were expressed as evaluation values using integers from 0 to 5 in accordance with the criteria described below. The fresh weight of the above-ground parts of the plants that remained withered at the time of the survey was measured, and the ratio (%) compared to the untreated area.
Calculate. Plant damage and herbicidal efficacy for crops and weeds were evaluated using numbers from 0 to 5 based on the criteria shown in the table below.

[Table] Example 3 Pre-emergence Soil Treatment Efficacy Comparison Test for Upland Field Field soil was packed into a cylindrical plastic beaker with a diameter of 10 cm and a height of 10 cm, and weed seeds of millet, oat, mulva morning glory, and Japanese yam, and crop seeds of soybean and cotton were sown. did. After covering with soil, a predetermined amount of the raw material was made into an emulsion, diluted with water, and the soil was treated with a hand sprayer. After that, it is grown in a greenhouse and after treatment.
The herbicidal efficacy was observed on the 20th day, and the results are shown in Table 4.

[Table] Example 4 Post-emergence treatment test Tubers of lily pads were planted in plastic pots with an inner diameter of 10 cm and a height of 10 cm and grown in a greenhouse for 4 weeks. Seeds of barnyard grass, oat, wild mustard, and Japanese crocodile were sown in separate pots of the same type and grown in a greenhouse for two weeks. The treatment agent was formulated into an emulsion, dispersed in a predetermined amount in water (including a spreading agent), and applied to the leaves and foliage of the above two types of pots using a hand sprayer at a rate of 5 liters per area. After being grown in a greenhouse for 3 weeks after the chemical treatment, each plant was examined for herbicidal efficacy. For the Japanese perilla, we left them in the greenhouse for another two weeks and checked the number of new shoots that had regenerated.
Comparison was made with the untreated area. A is one that has no regeneration at all.
B, 11- where the regeneration is 1-10% of the untreated area.
Efficacy was evaluated with 50% as C and 51% or higher as D. These results are shown in Table-5.

[Table] Example 5 Pre-germination test A plastic tray with a height of 35 cm, a width of 25 cm, and a height of 15 cm was filled with field soil, and a field soil was used to inject field soil into a plastic tray. Weeds and soybeans were sown. A predetermined amount of the hydrating agent was dispersed in water and sprayed over the entire surface of the soil using a small sprayer from above the tray at a rate of 5 liters per are. After treatment,
The plants were kept in a greenhouse for 20 years and their phytotoxicity and herbicidal efficacy were investigated. The results are shown in Table-6.

【table】

[Table] Example 6 Paddy-like soil treatment test A 1/5000a Wagner pot was filled with Takarazuka paddy soil, seeds of annual weeds were mixed in at a depth of 2 to 3 cm from the soil surface layer, and the pot was flooded with water. After flooding, tubers and overwintering buds of perennial weeds were planted. Five days later, when each weed started to germinate, a predetermined amount of the chemical was dropped onto the water surface using an emulsion. The herbicidal efficacy was investigated 4 weeks after treatment, and the results are shown in Table 7.

【table】

【table】

Claims (1)

[Claims] 1. General formula (In the formula, X represents a chlorine atom or a bromine atom, R represents a lower alkyl group having 1 to 3 carbon atoms, and Y represents an oxygen atom or a sulfur atom.) ) Triazolo[1,2a][1,2]-diazepine derivatives. 2 General formula (In the formula, X represents a chlorine atom or a bromine atom, Y represents an oxygen atom or a sulfur atom, and R represents a lower alkyl group having 1 to 3 carbon atoms.) ) A herbicide characterized by containing a triazolo[1,2a](1,2]-diazepine derivative as an active ingredient.