JPH0529352B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (): (However, in the formula, R is an alkyl group substituted with a halogen atom; a cycloalkyl group; a cyanoalkyl group; an alkenyl group; an alkynyl group; a lower alkoxyalkyl group; a lower alkylthioalkyl group;
lower alkylsulfinylalkyl group; lower alkylsulfonylalkyl group; hydroxycarbonylalkyl group; lower alkoxycarbonylalkyl group; benzyl group; benzyl group substituted with a halogen atom or lower alkyl group; phenethyl group, R ¹ represents a haloethyl group, and X represents a halogen atom. ) Δ ² -1,2,4-triazoline-
This invention relates to 5-one derivatives, their production methods, and their uses. The present inventors have discovered that the compound represented by the above general formula () is a compound useful as an agricultural drug, especially a herbicide. Unexamined Japanese Patent Publication 1987
-181069 discloses compounds similar to the compounds of the present invention as herbicides. However, the compound of the present invention has not been disclosed at all and is a new compound that has not been described in any literature. Surprisingly, it was discovered that the compound of the present invention exhibits an excellent herbicidal effect at a lower dose than the compound disclosed in the above-mentioned publication, and is also a compound with less phytotoxicity to crops. It has been completed. The compound represented by the general formula () of the present invention can be produced, for example, by the method shown below. (In the formula, R, R ¹ and X have the same meanings as above,
Z represents a halogen atom. ) That is, the compound represented by the general formula () can be obtained by reacting the compound represented by the general formula () with the compound represented by the general formula () in the presence of an inert solvent. Inert solvents used in the reaction of the present invention include:
Any substance may be used as long as it does not significantly inhibit the progress of this type of reaction, such as aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as n-hexane and cyclohexane, methanol, ethanol, propanol, and glycol. alcohols such as, ketones such as acetone, methyl ethyl ketone, cyclohexanone, lower fatty acid esters such as ethyl acetate, ethers such as tetrahydrofuran, dioxane, lower fatty acid amides such as dimethylformamide, dimethylacetamide, water,
Dimethyl sulfoxide and the like can be mentioned. These solvents are used alone or in mixtures. Bases that can be used in this reaction include:
Inorganic bases such as sodium carbonate, sodium hydride, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide and alcoholates of alkali metals, pyridine, trimethylamine, triethylamine, diethylaniline, 1,8-diazabicyclo −[5,
Organic bases such as 4,0]-7-undecene can be mentioned. The reaction of the present invention can be allowed to proceed at an appropriately determined temperature within the range of, for example, 0°C to 150°C. The reactions of the compounds in each reaction route are equimolar reactions, but it is okay to add one or the other in slightly excess. The reaction time is preferably selected from the range of 0.5 to 48 hours. After the reaction is completed, the target product can be collected by treating the reaction product in a conventional manner. Further, the compound represented by the general formula () can also be produced by the formula shown below. (In the formula, R, R ¹ and X have the same meanings as above,
R ⁴ represents a hydroxyl group or a halogen atom. ) That is, it can also be obtained by reacting a compound represented by general formula (-a) with a corresponding alcohol. In addition, a compound represented by the general formula () in which R represents a lower alkylsulfinyl alkyl group or a lower alkylsulfonylalkyl group is a compound represented by the general formula () in which the corresponding R is a lower alkylthioalkyl group. It can also be obtained by oxidizing with a suitable oxidizing agent. Representative examples of compounds represented by the general formula () are shown in Table 1 as follows. General formula:

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[Table] The compound represented by the general formula () can be synthesized by the following reaction route. (In the formula, R ¹ , Z and X are the same as above, R ² and R ³
represents a lower alkyl group, A represents an oxygen atom or a sulfur atom, and Z ¹ may be the same or different and represent a halogen atom. ) That is, the compound represented by the general formula () is
Compounds represented by general formula () and general formula ()
A compound represented by the formula () is reacted with heating in an inert solvent, and the resulting compound represented by the general formula () is isolated, or without isolation, a ring-closing reaction is performed in the presence of a base to form the compound represented by the general formula ( ), and the compound () has the general formula () or ().
The halides represented by are reacted to form a compound represented by the general formula (), and the compound ()
By reacting with hydrogen bromide, the general formula ()
A compound represented by can be obtained. Note that when producing the compound represented by the general formula from the compound represented by the general formula (), hydrogen iodide or an alkyl thiolate may be used instead of hydrogen bromide. Examples of the present invention are shown below, but the present invention is not limited thereto. Example 1 1-{2,4-dichloro-5-[1-(3-chloropropoxycarbonyl)ethoxy]phenyl}-4-(1,1,2,2-tetrafluoroethyl)-3-methyl-Δ ² -1,2,4-triazolin-5-one (compound No. 7) 1-(2,4-dichloro-5-hydroxyphenyl)-3-methyl-4-(1,1,2,2-tetrafluoroethyl)-Δ ² -1,2,4-triazolin-5-one 1.8 g (0.0051 mol) was dissolved in 40 ml of anhydrous dimethyl sulfoxide, 0.3 g (0.0053 mol) of powdered potassium hydroxide was added to this solution, and after stirring for 30 minutes, α-chloropropionic acid 3-chloropropyl ester 1.0 g (0.0053 mol) was added thereto, and the reaction was carried out at 80°C for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature, poured into ice water, and the product was extracted with diethyl ether. After washing the extract with water and drying, diethyl ether was distilled off to obtain 2.3 g of the desired product. n ²⁴ _D 1.5139 Yield 89% Example 2 1-{4-chloro-2-fluoro-5-[1-
((3-chloropropyl)carbonyl)ethoxy]phenyl}-4-(1,1,2,2-tetrafluoroethyl-3-methyl-Δ ² -1,2,
4-triazolin-5-one (compound No. 8) 0.52 g (0.0037 mol) of potassium carbonate was suspended in 50 ml of N,N-dimethylformamide, and 1-(4-chloro-2-fluoro-5-hydroxyphenyl)-3-methyl-4- (1, 1,
2,2-tetrafluoroethyl)-Δ ² -1,2,
After adding 1.17 g (0.0034 mol) of 4-triazolin-5-one and stirring at room temperature for 30 minutes, 0.85 g of α-promopropionic acid 3-chloropropyl ester
g (0.0034 mol) was added thereto, and the reaction was carried out at 50°C for 3 hours. After the reaction was completed, the reaction solution was brought to room temperature, poured into ice water, and the product was extracted with diethyl ether. After washing the extract with water and drying, diethyl ether was distilled off to obtain 1.36 g of the desired product. n ²⁴ _D 1.4989 The obtained oil was purified by silica gel column chromatography (ether:n-hexane=1:2) and left at room temperature to obtain the desired product as crystals. mp48.5℃ Yield 82% Example 3 1-{4-chloro-2-fluoro-5-[1-
((2-ethylthio)ethoxycarbonyl)ethoxy]phenyl}-4-(2-chloro-1,1,
2-trifluoroethyl)-3-methyl-Δ ² −
1,2,4-triazolin-5-one 0.15 g (0.0037 mol) of 60% NaH was suspended in 30 ml of tetrahydrofuran, and 1-
(4-chloro-2-fluoro-5-hydroxyphenyl)-3-methyl-4-(2-chloro-1,
1,2-trifluoroethyl)-Δ ² -1,2,4
-triazolin-5-one 1.26 g (0.0034 mol)
After stirring for 30 minutes, add 0.89 g of ethyl ethyl α-promopropionic acid (2-ethylthio).
(0.0037 mol) was added and heated under reflux for 5 hours.
After the reaction was completed, the reaction solution was cooled to room temperature, poured into ice water, and the product was extracted with diethyl ether. After washing the extract with water and drying, diethyl ether was distilled off and the residue was purified by dry column chromatography to obtain 1.33 g of the desired product. Yield 75% Example 4 1-{4-chloro-2-fluoro-5-[1-
(4-chlorobenzyloxycarbonyl)ethoxy]phenyl}-4-(1,1,2,2-tetrafluoroethyl)-3-methyl-Δ ² -1,
2,4-triazolin-5-one (compound no.
60) 1-(4-chloro-2-fluoro-5-hydroxyphenyl)-3-methyl-4-(1,1,2,
2-tetrafluoroethyl)-Δ ² -1,2,4-
1.75 g (0.0051 mol) of triazolin-5-one,
1.5 g of potassium carbonate and 1.27 g (5.6 mmol) of α-bromopropionic acid 4-chlorobenzyl ester were added to 50 ml of methyl ethyl ketone, and the mixture was heated under reflux for 5 hours. After the reaction was completed, the reaction solution was cooled to room temperature, insoluble matter was separated, the solution was concentrated, and the residue was purified by dry cam chromatography to obtain 1.87 g of the desired product. n ¹⁸ _D 1.5329 Yield 68% Example 5 1-{2,4-dichloro-5-[1-(2-methylsulfinyl)ethoxycarbonyl]-ethoxyphenyl}-3-ethyl-4-(1 ,1,
2,2-tetrafluoroethyl)-Δ ² -1,
2,4-triazolin-5-one (compound no.
47) 5.05 g (0.01 mol) of 1-{2,4-dichloro-5-[1-(2-methylthio)-ethoxycarbonyl]-ethoxyphenyl}-3-methyl-4-
(1,1,2,2-tetrafluoroethyl)-Δ ²
100ml of -1,2,4-triazolin-5-one
was dissolved in methylene chloride, and 20 g (0.0106 mol) of m-chloroperbenzoic acid was added thereto and reacted at room temperature for 5 hours. The reaction product was poured into ice water and the methylene chloride layer was treated in a conventional manner to obtain 48 g of the desired product. get. n ²⁵ _D 1.5195 Yield 92.1% Δ ² −1, represented by the general formula () of the present invention,
The 2,4-triazolin-5-one derivative is, for example, a grasshopper (common name for Japanese grasshopper), an annual grass of the Poaceae family.
Typical harmful grass of paddy fields)
Annual grass. A harmful grass of paddy fields), Cyperus japonica (an annual grass of the Cyperaceae family, a harmful grass of rice fields), Matsubai (a perennial grass of the Cyperaceae family, which occurs in wetlands, waterways, and rice fields. A typical perennial harmful grass of rice fields), Urikawa (family Cyperaceae). (perennial harmful grasses that occur in rice fields, wetlands, and ditches),
Annual and perennial weeds in rice fields such as firefly (a perennial grass in the Cyperaceae family. Occurs in rice paddies, wetlands, and ditches), oat (an annual grass in the Poaceae family. Occurs in plains, wastelands, and fields), mugwort (a perennial grass in the Asteraceae family. Occurs in fields, mountains, and fields), (occurs in fields and roadsides), snail grass (an annual grass of the Poaceae family, which is a typical harmful grass in fields and orchards), Gishigishi (a perennial grass of the Polygonaceae family, which occurs in fields and roadsides), and cyperus (an annual grass of the Cyperaceae family, which occurs in fields and roadsides) ),
It has the effect of controlling annual and perennial weeds that occur in fields and orchards, such as Aobiyu (an annual grass of the family Asteraceae, which occurs in vacant lots, roadsides, and fields) and Japanese staghorn (an annual grass of the Asteraceae family, which is a strong pest of soybeans). have Triazoline represented by the above general formula ()
Since 5-one derivatives exhibit excellent herbicidal activity against weeds before emergence and during the growing season, they can be used, for example, in soil treatment before sowing (planting) and after sowing (planting) of upland crops such as soybeans, cotton, and corn. The compound of the present invention is useful as a herbicide for soil treatment during the crop growing season, foliage treatment before sowing (planting) of crops, and foliage treatment during the crop growing season.The compound of the present invention is also useful as an herbicide for early and mid-season herbicides in paddy fields, and for weeding general weeds. It is useful as an agent for exterminating general weeds such as mowing remains, fallow fields, ridges, farm roads, waterways, pasture land, cemeteries, parks, roads, playgrounds, open spaces around buildings, cleared land, railroad tracks, forests, etc. It can also be used for. In this case, it is economically most effective to treat weeds before they begin to emerge, but this is not necessarily the case. By the way, when the compound of the present invention is used as a herbicide, it is generally formulated into a convenient form for use according to conventional methods for agricultural chemical formulations. That is, the above-mentioned compound is dissolved, separated, suspended, mixed, impregnated, adsorbed or attached to an appropriate inert carrier, together with an auxiliary agent if necessary, in an appropriate proportion, and then prepared into an appropriate dosage form. For example, it may be formulated into suspensions, emulsions, solutions, tablets, powders, granules, tablets, etc. The inert carrier that can be used in the present invention may be either solid or liquid, and examples of materials that can be solid carriers include soybean flour,
Vegetable powders such as grain flour, water powder, bark powder, saw flour, tobacco stem powder, walnut shell powder, bran, cellulose powder, residue after extracting plant extracts; textile products such as paper, cardboard, and shrugi; pulverization Synthetic polymers such as synthetic resins; clays (e.g. kaolin, bentonite, acid clay), talcs (e.g. talc, pyrophyllite), silicas (e.g. diatomaceous earth, silica sand, mica,
White carbon (synthetic highly dispersed silicic acid, also known as hydrated fine powder silicon or hydrated silicic acid; some products contain calcium silicate as the main component), activated carbon,
Sulfur powder, pumice, calcined diatomaceous earth, crushed bricks,
Inorganic mineral powders such as fly ash, sand, calcium carbonate, calcium phosphate; ammonium sulfate, phosphorus solution, glass solution,
Examples include chemical fertilizers such as urea and ammonium chloride, and fertilizers. These may be used alone or in the form of a mixture of two or more. Materials that can serve as liquid carriers are selected from those that themselves have solvent ability, as well as those that do not have solvent ability but can disperse the active ingredient compound with the help of an adjuvant, such as the following: , these may be used alone or in the form of a mixture of two or more; water, alcohols (e.g. methanol, ethanol, isopropanol, butanol, ethylene glycol),
Ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone), ethers (e.g. methyl ether, dioxane, cellosolve, dipropyl ether, tetrahydrofuran), aliphatic hydrocarbons (e.g. gasoline, mineral oil), aromatics Hydrocarbons (e.g. benzene, toluene, xylene,
Solvent naphtha, alkylnaphthalene), halogenated hydrocarbons (e.g. dichloroethane, chlorinated benzene, chloroform, carbon tetrachloride), esters (e.g. ethyl acetate, diptylphthalate, diisopropylphthalate, dioctyl phthalate), acid amides (e.g. dimethylformamide, diethylformamide, dimethylacetamide), nitriles (e.g. acetonitrile), dimethylsulfoxide, etc. The following may be mentioned as adjuvants. These adjuvants are used depending on the purpose.
In some cases, two or more adjuvants are used together. In other cases, no adjuvant may be used at all. Surfactants are used for the purpose of emulsifying, dispersing, solubilizing or wetting the active ingredient compounds. Examples include: polyoxyethylene, alkylaryl ether, polyoxyethylene, alkyl ether, polyoxyethylene, higher fatty acid ester, polyoxyethylene,
Resin acid ester, polyoxyethylene, sorbitan monolaurate, polyoxyethylene, sorbitan monooleate, alkylaryl, sulfonate, naphthalene sulfonic acid condensate, lignin sulfonate, higher alcohol sulfate, etc.
For the purpose of dispersion stabilization, adhesion or binding of the active ingredient compounds, the following may be used, for example: casein, gelatin, starch, alginic acid, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, pine oil, Bran oil, bentonite, lignin sulfonate, etc. For the purpose of improving the flowability of solid products, the following may also be used: waxes, etc., stearates, phosphoric acid alkyl esters, etc. The following may also be used as peptizers for suspendable products: naphthalene sulfonic acid condensates, condensed phosphates, etc. It is also possible to add antifoaming agents such as silicone oil. The combination of active ingredients can be adjusted as necessary. Usually 0.5 to 20% (by weight) when used as a powder or granule, and 0.1 to 20% (by weight) when used as an emulsion or wettable powder.
50% (by weight) is appropriate. The herbicide of the present invention kills or suppresses the growth of various weeds or protects useful plants from weed damage, either as is or in the form of dilution or suspension as appropriate with water, etc. An effective amount is applied to the weeds or to the foliage or soil in cases where the emergence or growth of the weeds is undesirable. The amount of the herbicide of the present invention to be used depends on various factors, such as the purpose, target weeds, weed or crop emergence/growth conditions, weed emergence trends, weather, environmental conditions, dosage form, application method, application location, and application time. It changes over time. When the herbicide of the present invention is used alone as a selective herbicide, it is appropriate to select the dosage of the compound of the present invention from 0.1 to 500 g per 10 ares. Considering that when mixed with a drug, the compound of the present invention is often effective at a lower dosage than when used alone, the dosage of the compound of the present invention can be selected from an even smaller dosage range. . The herbicide of the present invention is particularly valuable as a treatment agent for weeds in field crops during their pre-emergence and growth stages, or as an early to mid-stage herbicide in paddy fields. It is also possible to use it in combination with other herbicides in order to reduce the amount of herbicides, and this falls within the scope of the present invention. For example, phenoxy fatty acid herbicides such as 2,4-PA (e.g. 2,4
-ethyl dichlorophenoxyacetate), MCP (e.g. ethyl 2-methyl-4-chlorophenoxyacetate, sodium 2-methyl-4-chlorophenoxyacetate, allyl 2-methyl-4-chlorophenoxyacetate), MCPB (ethyl 2-methyl-4-chlorophenoxyacetate), Diphenyl ether herbicides such as NIP (2,4-dichlorophenyl-4'-nitrochlorophenol); phenyl ether), CNP (2,4,
6-trichlorophenyl-4'-nitrophenyl ether), chromethoxynil (2,4-dichlorophenyl-3'-methoxy-4'-nitrophenyl ether), acifluorfen (5-(2-chloro-α) , α, α-trifluoro-p-tolyloxy)-2-nitrobenzoic acid and its salts), fluadihop-butyl ((±)-2[4-
[[5-(trifluoromethyl)-2-pyridyl]oxy]phenoxy]propionic acid butyl ester); triazine herbicides such as CAT [2-chloro-4,6-bis(ethylamino)-s-triazine], Promethrin [2-methylthio-4,6
-bis(isopropylamino)-s-triazine], simetrine [2-methylthio-4,6-bis(ethylamino)-s-triazine], metribuzine (4-amino-6-t-butyl-3-methylthio-1 , 2,4-triazin-5(4H)-one); carbamate herbicides such as molinate (s-ethylhexahydro-1H-azepine-1-
carbothioate), MCC [methyl N-(3,4-
dichlorophenyl)-carbamate], IPC [isopropyl N-(3-chlorophenyl)carbamate], benthicaope (s-(4-chlorobenzyl)dimethylthiocarbamate); toluidine herbicides such as trifluralin (α,α,α-trifluoro- 2,6-dinitro-N,N-dipropyl-p-toluidine), benzimesalin (N-
(1-ethylpropyl)-2,6-dinitro-3,
4-xylidine); acid amide herbicides, e.g.
DCPA (3,4-dichloropropionanilide), butachlor [2-chloro-2',6'-diethyl-N
-(butoxymethyl)-acetanilide], alachlor [2-chloro-2',6'-diethyl-N-
(methoxyethyl)acetanilide], metolachlor (2-chloro-N(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide), pretilachlor (2-chloro-2',6 '-Diethyl-N-(2-propoxyethyl)acetanilide; other herbicides e.g.
DCMU(3-(3,4-dichlorophenyl)-1,
1-dimethylurea), pentazone (3-isopropyl-(1H)-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide, pyrazolate (4-(2,4-dichloro benzoyl)−
1,3-dimethylpyrazol-5-yl-p-toluninsulfonate, pyrazoxyfen (1,3
-dimethyl-4(2,4-dichlorobenzoyl)-
5-phenacyloxypyrazole, MY-71 (4
-(2,4-dichloro-3-methylbenzoyl)-
An embodiment may be mentioned in which the herbicide is used in combination with one or more herbicides such as 1,3-dimethylpyrazol-5-yl-p-toluenesulfonate. Some test examples and prescription examples are shown below, but the present invention is not limited thereto. Test example 1 Effect on paddy field weeds before budding Soil was packed in a 1/10,000-area pot, set to paddy field condition, and paddy field weeds such as field weeds, Japanese grasshopper, Japanese cypress, firefly seeds, and tubers of Paddy field weeds were adjusted so that they were in a state before budding. did. This was treated with active ingredients (compounds listed in Table 1) as a spray solution at a predetermined concentration. After 21 days of treatment, the herbicidal effects of each treatment were compared with those without treatment, and judgments were made based on the following criteria. Judgment criteria for herbicidal activity 5... 100% weed killing 4... 90% or more but less than 100% weeding 3... 80% or more but less than 90% weeding 2... 70% or more and less than 80% weeding 1... less than 70% weeding Results Shown in Table 2.

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[Table] As the control compound A, compound 7 (1-(2,4-dichloro-5-((1-ethoxycarbonyl)ethoxy)) disclosed in JP-A-57-181069 was used.
phenyl)-4-difluoromethyl-3-methyl-Δ ² -1,2,4-triazolin-5-one)
and compound 14 (1-(2-chloro-
4-fluoro)phenyl-4-(1,1,2,2
-tetrafluoroethyl)-3-methyl-Δ ² -
1,2,4-triazolin-5-one) was tested. Test Example 2 Effect on paddy field weeds after germination Soil was put into a 1/10,000-are pot, and the noxious weeds in the following leaf stages were grown in a paddy field condition. Furthermore, the day before the chemical treatment, paddy rice seedlings (variety: Nipponbare) at the 2.5 leaf stage were transplanted and treated with the chemical. 21 days after the treatment, the herbicidal effect and the degree of chemical damage to paddy rice were investigated in comparison with no treatment. Tested weed species and their leaf stages: Nobie, 1-leaf stage Konagi, 2-3 leaf stage Japanese cypress, 1-2 leaf stage Hotaru, 2-3 leaf stage Urikawa, 3-leaf stage Mizugaya cypress Judgment criteria for chemical damage in 1-2 leaf stage H...Large (death) ) M...Medium L...Small N...None The criteria for determining herbicidal activity are in accordance with Test Example 1. The results are shown in Table 3.

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[Table] Test Example 3 Effect on upland weeds before emergence Fill a polyethylene bucket measuring 10 cm x 20 cm x 5 cm deep with soil, and sow upland weeds such as oat, wild grass, blackberry, blueberry, mugwort, staghorn grass, staghorn snail, and staghorn fir. Covered with soil. This was treated with the active ingredient after being sprayed at a predetermined concentration, and 21 days after the treatment, the herbicidal effects of each were investigated in comparison with the untreated condition. The criteria for determining herbicidal activity were in accordance with Test Example 1. The results are shown in Table 4.

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[Table] As control C (control compound C), JP-A-58-
Compound No. 17 listed in Table 1 of Publication No. 225070
(1-[2,4-dichloro-5-(methoxycarbonyl)phenyl]-3-methyl-4-difluoromethyl-Δ ² -1,2,4-triazoline-5-
on) compound was used. Test Example 4 Effect on field weeds after germination In a polyethylene vat measuring 10 cm x 20 cm x 5 cm deep, the noxious weeds and soybean seeds shown below were sown and covered with soil, and each was allowed to grow until the leaf stage shown below. The drugs were processed to achieve the desired dosage. 21 days after the treatment, the herbicidal effect and the degree of phytotoxicity on soybean were investigated in comparison with the untreated condition. Test weed species and their leaf stages, soybean oat, two-leaf grass, two-leaf blueberry, one-leaf mugwort, one-leaf Japanese grass, two-leaf cypress, one-leaf Japanese fir tree, one-leaf soybean, first compound-leaf stage Criteria for herbicidal activity and the criteria for determining drug damage were in accordance with Test Examples 1 and 2, respectively. The results are shown in Table 5.

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[Table] Formulation example 1 Compound No. 8 50 parts Clay/white carbon, a clay-based mixture 45 parts Polyoxyethylene nonyl phenyl ether 5 parts A wettable powder made by uniformly mixing and pulverizing 5 parts of polyoxyethylene nonyl phenyl ether. Formulation Example 2 Compound No. 30 5 parts Bentonite clay mixture 90 parts Calcium ligninsulfonate 5 parts are uniformly mixed and pulverized, and an appropriate amount of water is added and thoroughly kneaded to make granules. Formulation example 3 Compound No. 45 50 parts xylene 40 parts Mixture of polyoxyethylene nonyl phenyl ether and calcium alkylbenzenesulfonate
An emulsion made by uniformly mixing 10 parts.

[Claims]

1 containing hydrogen fluoride or trifluoropropionyl fluoride or mixtures thereof2,
2, characterized in that 2,3,3-tetrafluorooxetane is made into a gas and brought into contact with silica gel or alumina particles or a mixture thereof to adsorb and remove hydrogen fluoride or trifluoropropionyl fluoride or a mixture thereof. , 2,3,3-tetrafluorooxetane purification method. 2 The concentration of hydrogen fluoride and trifluoropropionyl fluoride in untreated 2,2,3,3-tetrafluorooxetane is 500 to 500, respectively.
The purification method according to claim 1, wherein the concentration is 1000 ppm. 3. The purification method according to claim 1 or 2, wherein the 2,2,3,3-tetrafluorooxetane mixture is treated in a gaseous state at 30 to 70°C. 4. The purification method according to any one of claims 1 to 3, wherein the silica gel or alumina particles have an average particle size of 4 to 8 mm and a filling void ratio of 50 to 60%.

Claims (1)

2 General formula (): (In the formula, R ¹ represents a haloethyl group, and X represents a halogen atom.) and the general formula (): (However, in the formula, R is an alkyl group substituted with a halogen atom; a cycloalkyl group; a cyanoalkyl group; an alkenyl group; an alkynyl group; a lower alkoxyalkyl group; a lower alkylthioalkyl group;
lower alkylsulfinylalkyl group; lower alkylsulfonylalkyl group; hydroxycarbonylalkyl group; lower alkoxycarbonylalkyl group; benzyl group; benzyl group substituted with a halogen atom or lower alkyl group; Indicates a halogen atom. ) General formula () characterized by reacting with a compound represented by: A method for producing a Δ ² -1,2,4-triazolin-5-one derivative represented by the formula (wherein R, R ¹ and X are the same as above). 3 General formula (): (However, in the formula, R is an alkyl group substituted with a halogen atom; a cycloalkyl group; a cyanoalkyl group; an alkenyl group; an alkynyl group; a lower alkoxyalkyl group; a lower alkylthioalkyl group;
lower alkylsulfinylalkyl group; lower alkylsulfonylalkyl group; hydroxycarbonylalkyl group; lower alkoxycarbonylalkyl group; benzyl group; benzyl group substituted with a halogen atom or lower alkyl group; phenethyl group, R ¹ represents a haloethyl group, and X represents a halogen atom. ) Δ ² -1,2,4-triazoline-
A herbicide characterized by containing a 5-one derivative as an active ingredient.