JPS60218380A - Triazole derivative and preparation and use thereof - Google Patents

Abstract

NEW MATERIAL:A 3-(2-propynyloxy)-1-(2-propynyl)-1H-1,2,4-triazole derivative expressed by formula I (X is H, halogen, lower alkyl, lower alkoxyl, lower haloalkyl, lower haloalkoxyl or lower haloalkyltio; n is an integer 1-3). EXAMPLE:5-Phenyl-3-(2-propynyloxy)-1-(2-propynyl)-1H-1,2,4-triazole. USE:A herbicide, leading injurious weeds to death even in a small amount of chemical in paddy field by pre- and post-emergence treatment without phytotoxicity to rice plants, and exhibiting herbicidal activity against weeds in upland field by the pre- and post-emergence treatment. PREPARATION:A 1,2,4-triazolin-5-one derivative expressed by formula II is reacted with a 2-propynyl halide expressed by formula III (Z is halogen) in an inert solvent in the presence of a base at 0-150 deg.C for several min-6hr to give the aimed compound expressed by formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel compound 11214-)! This article relates to azole conductor, its manufacturing method, and its uses.

The 3-(2-propynyloxy)-1-(2-propynyl)-1H-1,2,4-triazole derivative of the present invention is.

General formula (I): (However, in the formula, X may be the same or different.

It represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, or a lower haloalkylthio group, and n represents an integer of 1 to 3.

In addition to the above-mentioned derivatives, the present invention also includes the following manufacturing method for manufacturing the derivatives. Namely.

General formula (■): (However, in formula 1, X and n are the same as above.) A 1,2,4-) riazolin-5-one derivative and general formula (■): CH3CCH2Z (III) (However, in the formula, 2 represents a halogen atom.) This is a method for producing a derivative represented by the general formula (1), which is characterized by reacting with a 2-propynyl halide represented by 0 representing a halogen atom.

Also, the present invention.

6 represented by general formula (I) (wherein X and n are the same as above)
-(2-''/l ropynyloxy)-i-(2-propynyl)-1H-1,2,4-)lyazole derivative as an active ingredient. 〇The present inventors, in order to create a new exclusion JA,
As a result of extensive research, we found that 3- expressed by the general formula (1)
(2-propynyloxy)-1-(2-propynyl)-
We discovered that 1H-1,2,4-) lyazole derivatives are new compounds that have not been described in literature, and that these compounds have strong herbicidal activity.

This completes the present invention.

The herbicidal effect of the compound of the present invention is characterized by killing harmful weeds at low doses in both pre-emergence and post-emergence treatments in paddy fields, and causing no chemical damage to rice. It also shows herbicidal activity in both pre- and post-emergence treatments.

The method for producing the compound of the present invention is shown schematically as follows, for example.

(1) (Ill) (1) (However, in formula 1, X, z and n are the same as above.) That is, the 1,2,4-) riazolin-5-one derivative represented by general formula (n) and the general formula By reacting 2-propynyl halides represented by (fil) in the presence of a base and an inert solvent, 3-(2-propynyloxy)-1-(2-propynyl) represented by general formula (1) is produced. -IH-1
゜2.4-) Liazole derivatives can be obtained - Inert solvents that can be used in the present invention may be those that do not significantly inhibit this type of reaction, such as benzene,
Aromatic hydrocarbons such as toluene and xylene; methanol and ethanol.

Alcohols such as glopanol and glycol; ethers such as diethyl ether, tetrahydrofuran, and dioxa7; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; lower fatty acid esters such as ethyl acetate; lower aliphatic amides such as dimethylformamide and dimethylacetamide. , water, dimethyl sulfoxide, etc. These solvents can be used alone or as a mixture.

Examples of bases that can be used in the reaction in accordance with the invention include inorganic bases such as sodium carbonate, sodium hydride, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and alcolades of alkali metals; Pyridine, trimethylamine.

Examples include organic bases such as F9"7Syt-/""'9'."°-1diazabicyclo-[5,4,O)-7-undecene.

Phase transfer catalysts such as lJ ethylpendylammonium chloride can also be used.

The reaction temperature in the reaction of the present invention is appropriately selected from the range of 0°C to 150°C, and the reaction time is selected from the range of several minutes to 6 hours.

In the present invention, the general formula (I[
It is sufficient to use 2 moles of the 2-propynyl halide represented by I), but an excess amount may be used.

After completion of the reaction, by processing according to a conventional method, the desired 3-(2-propynyloxy)-1 represented by the general formula (1) is obtained.
-(2-propynyl)-1H-1,2,4-)lyazole derivatives can be obtained.

The compound represented by general formula (Il) used in this production method can be synthesized by a known method.

Representative examples of the 3-(2-propynyloxy)-1-(2-propynyl)-1H-1,2,4-triazole derivatives represented by the general formula (1) are shown in Table 1, and the present invention is directed to these. It is not limited.

General formula (I): Table 1 The compound represented by general formula (1) of the present invention is a herbicide for paddy fields that has selectivity in pre-emergence and post-emergence treatment and has little toxicity to rice. ◇It is also a useful herbicide for all grass species in the field as a pre-emergence and post-emergence treatment.

When using the compound of the present invention as a herbicide.

Generally, the above compound is formulated into a form convenient for use according to the conventional method for agricultural chemical formulations.In other words, the above compound is mixed with a suitable inert carrier and, if necessary, an auxiliary agent.
Mix in appropriate proportions, dissolve, disperse, suspend, mix, and impregnate.

Adsorption or adhesion may be used to formulate appropriate dosage forms such as suspensions, emulsions, solutions, aqueous preparations, powders, 1 granule, 1 tablet, etc.

The blend of active ingredients can be adjusted as necessary. When used as a powder or granule, the amount is usually 15 to 20 inches (by weight), and when used as an emulsion or aqueous solution.

11 to 50 inches (weight) is suitable.

The herbicide of the present invention kills or suppresses the growth of various weeds, or protects useful plants from weed damage, either as it is or in the form of dilution or suspension as appropriate with water, etc. The amount of the herbicide of the present invention to be used depends on various factors, such as the purpose and the target weed. , weed or crop occurrence/growth conditions, weed outbreak trends, weather, environmental conditions, dosage forms.

It varies depending on the application method, place of application, time of application, etc.

When the herbicide of the present invention is used alone as a selective herbicide, 1
For example, the dosage of the herbicide of the present invention is 10-5 per 10 ares.
It is appropriate to select based on the ratio of 0019 (active ingredient), but when the herbicide of the present invention is used in combination with other herbicides, in many cases it is effective at a lower dose than when used alone. Taking this into consideration, the dosage of the compound of the present invention can be selected from a smaller dosage range.

The herbicide of the present invention is highly valuable as a pre-emergence or early-emergence treatment agent in paddy fields or as an early to mid-stage herbicide in paddy fields. It is also possible to use it in combination with other herbicides to measure the

Synthesis examples, formulation examples, and test examples of representative compounds of the present invention are shown below, but the present invention is not limited thereto. 1 part in the prescription examples indicates parts by weight.

Synthesis Example 1 5-phenyl-3-(2-propionyloxy)-1-
Synthesis of (2-propynyl)-1H-1,2゜4-triazole (compound AI) 3-phenyl-Δ2-1.2.4
-) Riazolin-5-one 0.61 (α0037 mol)
, 1.6 g of anhydrous potassium carbonate and 2-propynyl bromide were heated and reacted in soml of 2dQ acetone. After the reaction was completed, inorganic substances were filtered off, acetone was distilled off, and the residue was separated by silica gel column chromatography to obtain 0.2II of the desired product as crystals.

Melting point 116-119°C Yield 24% Synthesis example 2 5-(m-bromophenyl)-3-(2-propynyloxy)-1-(2-propynyl)-1H-1,2,4-
Synthesis of triazole (compound A6) 3-(m-bromophenyl)-Δ2-1.2.4-triazolin-5-one α! M (0,002 mol).

Potassium hydroxide 0.51 and 2-p-tetrapinyl chloride 2
rnl was heated and reacted in 25 g of ethanol.

After the reaction was completed, inorganic substances were filtered off, ethanol was distilled off, and the residue was separated by silica gel chromatography to obtain the desired product as a viscous oil (L219).

Yield 36 Synthesis Example 3 5-(0-methoxyphenyl)-3-(2-propynyloxy)-1-(2-propynyl)-1H-1,2,4
-) Synthesis of lyazole (compound A11) 3-(0-methoxyphenyl)-Δ”-1,2゜4-triazolin-5-one α3BF (0,002 mol), 2
-Propynyl bromide α5I and 0.6.9 of 18-diazabicyclo-(5,4,0)-7-undecene were subjected to a heating reaction in 50 rnl of acetonitrile. After the reaction was completed, acetonitrile was distilled off, and the residue was separated using a silica gel column chromatogram 2-fee to obtain the desired product as a viscous oil. Yield 38 Synthesis Example 4 5-(m-difluoromethoxyphenyl)-3-(2-
propynyloxy)-1-(2-propynyl)-1H-
Synthesis of 1,2,4-triazole (compound A17) 3-(m-difluoromethoxyphenyl)-Δ”1,2
．． 4-) Riazolin-5-one A heating reaction was carried out in α5I (0,0022 mol), 2 ml of 2-propynyl bromide, and 301 nl of dimethyl sulfoxide containing 0.5 F'i of sodium carbonate. After the reaction is complete.

Water was added to the reaction mixture, extracted with ethyl acetate, and purified by column chromatography to obtain the desired product (0.319) as a viscous oil.

Yield: 45% Prescription Example 1 Compound A1 of the present invention: 50 parts Clay/white carbon mixture: 45 parts (1 Polyoxyethylene nonyl phenyl ether sulfate ammonium salt: 5 parts or more) Prescription example for a wettable powder obtained by uniformly mixing and pulverizing 5 parts or more of polyoxyethylene nonyl phenyl ether sulfate ammonium salt 2 Compound A5 of the present invention 5 parts Bentonite clay mixture 90 parts Calcium ligninsulfonate 5 parts or more are uniformly mixed and ground, and an appropriate amount of water is added and kneaded well.
Prescription example 3 of granulated granules Compound of the present invention 415 50 parts Konagi.

A predetermined amount of a drug containing the compound of the present invention as an active ingredient was applied with a pipette to O which had been adjusted to a pre-emergence stage. After 21 days of O treatment, the samples were compared with those without treatment. The herbicidal effects of each were investigated and judged based on the primary criteria.

5: 100% weed killing 4: 90 inches or more, less than 100 inches Weed killing 3: 80% or more, 510% 1 2 Near 01% or more 80 inches 1 Near 0 inches Weed killing results are shown in Table 20 Table 2 Test Example 2 Effect on paddy field weeds after emergence Soil was packed in a 1/10,000-are pot, the condition was set as a paddy field, and the following weeds were grown.Furthermore, 25 leaves were treated with the chemical containing the compound of the present invention as an active ingredient on the day before treatment. Seasonal paddy rice seedlings (variety: Nipponbare)
was transplanted and treated with 1 leaf agent.

21 days after the treatment, the herbicidal effect and the degree of phytotoxicity on paddy rice were investigated in comparison with the untreated condition.

・Test weed species and their cuttings Novie 1 leaf stage Konagi 2-3 leaf stage Tamagayatsuri 1-21 Firefly 2~3r Urikawa 3-leaf stage Judgment criteria for O drug damage H2 large (including withering) N: 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.

Test Example 3 Effect on field weeds before emergence 10 [X 2
Fill a polyethylene vat with 0cIIL x 5cIIL depth with soil to remove oat, which is a field weed.

We sowed and covered the soil with wild grass, black-and-white grass, blueberry, mugwort, staghorn, and cypress. These were treated with a spray solution containing an uninvented compound as an active ingredient at a predetermined concentration, and 21 days after the treatment, the herbicidal effects of each were investigated in comparison with no treatment.

The herbicidal effect was determined in accordance with Test Example 1.

The results are shown in Table 4.

Table 4 Test Example 4 Effect on field weeds after germination 10 [X20
[Noxious weeds and dice seeds shown below were sown in a polyethylene bat having a depth of 5 degrees and covered with soil, allowed to grow until the following cuttings were reached, and treated with a drug containing the compound of the present invention as an active ingredient at a predetermined concentration.

21 days after the treatment, the herbicidal effect and the degree of phytotoxicity on dice were investigated in comparison with the untreated condition.

Test weed species and their cuttings and soybean cutting oat 2
Leaf stage P. elegans 2I Aobiyu 1g Mugwort 1N Kishigishi 2I Kogomegayarri 1 leaf stage Dice The criteria for the herbicidal activity in the first compound leaf stage are in accordance with Test Example 1.

The results are shown in Table 5.

Table 5

Claims (3)

[Claims] (1) General formula (I): (However, in formula 1, X may be the same or different, and is a hydrogen atom. A halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, or a lower haloalkylthio 3-(2
-propynyloxy)-1-(2-propynyl)-1
H-1,2,4-) lyazole derivative. (2) General formula (■): (However, in formula 6. represents a haloalkylthio group; n represents an integer from 1 to 3; ) represented by 1, 2.
4-) Reacting a riazolin-5-one derivative with a 2-globinylno-1lide represented by the general formula (■): CH3CCHzZ (Ill) (where 2 in formula 1 is) and O representing a rogen atom. General formula (1) characterized by: 6-(2-propynyloxy) represented by (wherein X and n in formula 1 are the same as above)
- A method for producing a 1-(2-propynyl)-1H-1,2,4-triazole derivative. (3) General formula (I): (However, in formula 1. X may be the same or different, and is a hydrogen atom. A halogen atom, a lower alkyl group, a lower alkoxy x,
Lower haloalkyl & represents a lower haloalxy group or a lower haloalkylthio group. n represents an integer from 1 to 3. ) represented by 3-(2
-propynyloxy)-1-(2-propynyl)-1H
-1,2,4-) Herbicide containing a lyazole derivative as an active ingredient ◇