JPH0529224B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention is directed to 1, which is used as a herbicide component.
2,4-triazole-3-carboxylic acid amide,
The present invention relates to a method for producing the same and a herbicide containing the same as an active ingredient. BACKGROUND ART Rice, wheat, corn, etc. are important crops, and the use of herbicides is essential to protect these crops from weed damage and increase yield. However, in recent years, there has been a strong demand for herbicides that have a selective action that kills only weeds without harming the crops even when applied to useful crops and weeds at the same time. Conventionally, 1,5-diphenyl-1H-1,2,4-triazole-3-
Products containing carboxylic acid amide as an active ingredient are known (for example, JP-A-57-193406, JP-A-59
−98004). However, herbicides containing the above-mentioned compounds as active ingredients have still low herbicidal activity and are not satisfactory. Problems to be Solved by the Invention The present inventors have investigated compounds that exhibit excellent herbicidal effects on the above-mentioned crops and do not cause harm to these crops, and have found that the following general formula ()
It was discovered that 1,2,4-triazole-3-carboxylic acid amide represented by the following formula has an excellent selective herbicidal effect, and the present invention was completed. [In the formula, R is (a) a saturated alkyl group or an unsaturated alkyl group having an unsubstituted or fluorine-substituted linear, branched or cyclic structure having 2 to 10 carbon atoms, (b) An aryl group or an aralkyl group represented by the following formula, (In the formula, n represents 0 or 1, m represents an integer of 0 to 5, and R ¹ represents a halogen atom, a lower alkoxy group, a lower alkyl group, or a lower alkyl group substituted with fluorine.) ) Straight-chain or branched saturated alkoxyalkyl group or unsaturated alkoxyalkyl group having 3 to 10 carbon atoms; (d) Phenoxy having a phenyl group that is unsubstituted or substituted with a halogen atom or a lower alkyl group. It is an alkyl group or an aralkoxyalkyl group. ] A preferred embodiment of the compound of the present invention as a herbicide is a general formula () in which R is (a) a C ₂ to C ₁₀ linear chain;
(b) Saturated alkyl group having C ₃ to C ₇ branched or C ₃ to C ₆ cyclic structure (b) C ₂ to _{C 10} linear or C ₃ to C ₆ branched fluorinated alkyl group Saturated alkyl group (c)C ₃ ~
_C5 unsaturated alkyl group (d) Phenyl group substituted or unsubstituted with a halogen atom, lower alkyl group, lower alkoxyl group, or fluorine-containing lower alkyl group (e) Halogen atom, lower alkyl group, or lower alkoxyl group benzyl group substituted or unsubstituted with a group, (f) C ₃ to _{C 10} linear or branched alkoxyalkyl group (g) Benzyl group substituted or unsubstituted with a halogen atom or lower alkyl group on the ring. Examples include compounds that are an enoxyalkyl group or (h) an unsubstituted aralkosialkyl group. The compound represented by the above general formula () has -CH ₂ -O-R(R
represents the same meaning as in the general formula ())
It is different from the above-mentioned known compounds as herbicidal components in that it has this, and the above-mentioned compound is a substance that has not been described in any literature. Incidentally, the above-mentioned JP-A No. 59-98004 exemplifies a compound having a -CH ₂ OCH ₃ group in the phenyl group at the 1-position of the triazole, but the herbicidal activity of the exemplified compound is based on the above general formula () It is far inferior to the compound shown in (see Examples below regarding this point). Therefore, the present invention exhibits excellent herbicidal activity against grasses and broad-leaved plants, especially broad-leaved plants, while exhibiting selective herbicidal activity that does not cause phytotoxicity against crops such as rice, wheat, and corn. It is an object of the present invention to provide a 1,2,4-triazole-3-carboxylic acid amide having the above-mentioned properties, a herbicide containing the compound as an active ingredient, and a method for producing the compound. The present invention will be explained in detail below. Structure of the Invention The present invention is characterized by a 1,2,4-triazole-3-carboxylic acid amide represented by the above general formula (), a herbicide containing this compound as an active ingredient, and a postscript for producing the above compound. It's in the method. Examples of the compounds represented by the general formula () and their physical properties according to the present invention are shown in the table below. Table 2 also shows the elemental analysis results of the compound represented by the general formula ().

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[Table] Since each of these compounds has the above-mentioned selective herbicidal activity, they can be widely used as herbicides in rice fields, upland fields, etc. Means for Solving the Problems The compound according to the present invention represented by the above general formula () can also be produced by any of the methods (A) to (B) shown below. Synthesis method of (A): Formula () A compound represented by the formula and an alcohol derivative represented by the general formula R-OH (in which R represents the same meaning as above) are combined with an inorganic or organic base such as sodium metal, sodium hydride, caustic soda, caustic potash, potassium carbonate. , triethylamine, etc. to obtain the target compound. The reaction can be carried out using the alcohol derivative itself as a solvent, but a solvent such as hexamethylphosphoric triamide, dimethylformamide, dimethyl sulfoxide, acetonitrile, etc. may also be used. The reaction temperature is 30° C. or lower, which is higher than the melting point of the solvent. The raw material compound () can be synthesized using 3-aminobenzyl alcohol () as a starting material according to the reaction sequence shown below. 3-Aminobenzyl alcohol () is reacted with sodium nitrite in the presence of hydrochloric acid, sulfuric acid or hydroborofluoric acid at 15°C or below to convert it into a diazonium salt. The diazonium salt thus obtained was mixed with 2-phenyl-2-oxazolin-5-one () at 60°C.
4-[3-hydroxymethyl)phenylhydrazono]-2-phenyl-
2-oxazolin-5-one () is obtained. When compound () is reacted with an equivalent amount or more of sodium hydroxide in an aprotic organic solvent, benzamide derivative () is produced. Without isolating it, add hydrochloric acid to make it acidic and then heat it to 100℃.
When heated below, 1-[3-(hydroxymethyl)
Phenyl]-5-phenyl-1H-1,2,4-triazole-3-carboxylic acid () is obtained. When compound () and thionyl chloride are reacted at a temperature of 60 to 100°C, 1-[3-(chloromethyl)phenyl]-5-phenyl-1H-1,2,4-triazole-3-carboxylic acid chloride () is produced. is obtained, and the ammonia is heated to -20℃ without isolating it.
When reacted at ~room temperature, 1-[3-(chloromethyl)phenyl]-5-phenyl-1H-1,2,
4-triazole-3-carboxylic acid amide ()
is obtained. Synthesis method of (B): General formula () The target compound can be obtained by reacting 1H-1,2,4-triazole-3-carboxylic acid chloride represented by the formula (wherein R represents the same meaning as above) with ammonia. Raw material mixture (general formula) used in this method
can be synthesized by the reaction shown below. 1-[3-(chloromethyl)phenyl]-5-phenyl-1H-1,2,4 obtained by synthesis method (A)
-triazole-3-carboxylic acid chloride ()
an equivalent or more alkoxide; R-OM (in the formula, R
has the same meaning as above. M represents a sodium ion or a potassium ion) at 0 to 100°C, the compound of general formula () can be derived. When this is hydrolyzed, a carboxylic acid of general formula (XI) is obtained. By heating the carboxylic acid of general formula (XI) with thionyl chloride to 60-100℃, the general formula ()
acid chloride can be obtained. In order to utilize the 1,2,4-triazole-3-carboxylic acid amide obtained by each of the above methods as a herbicide, a wide variety of carriers (diluents) and carriers used in the preparation of agricultural chemicals can be used. It is used in the form of wettable powders, emulsions, granules, powders, etc. by applying auxiliary agents. EXAMPLES AND EFFECTS The method for producing the compound according to the present invention, the preparation of a herbicide containing the compound as an active ingredient, and the herbicidal effect thereof will be specifically explained with reference to Examples below. Example 1 1-[3-[(3-methylbutoxy)methyl]phenyl]-5-phenyl-1H-1,2,4-triazole-3-carboxylic acid amide (compound No. 8 in Table 1) Synthesis 1-[3-(hydroxymethyl)phenyl]-5
-Phenyl-1H-1,2,4-triazole-
A mixture of 1.48 g (5 mM) of 3-carboxylic acid (compound) added to 5 ml of thionyl chloride and 5 ml of benzene was refluxed for 1.5 hours. The resulting reaction mixture was diluted with benzene after distilling off benzene and excess thionyl chloride under reduced pressure, and diluted with isoamyl alcohol.
4.4g (50mM) and 1.6g (40mM) of 60% NaH were reacted in 50ml of benzene, and the mixture was added to an alkoxide solution obtained, and the mixture was stirred for 30 minutes at room temperature and 30 minutes under heating under reflux for hydrolysis. Water (50 ml) was added to the obtained product and the product was stirred for 30 minutes at room temperature for hydrolysis, and then separated into an aqueous layer and an organic layer, and then the aqueous layer was separated. The organic layer was further extracted with water, combined with the alkaline aqueous layer, and made acidic with dilute hydrochloric acid. The obtained oil was extracted with benzene, the organic layer was dehydrated, and the benzene was distilled off.
Thioninyl chloride (5 ml) and benzene (5 ml) were added to the residue and refluxed for 1.5 hours, and excess thionyl chloride was distilled off. The obtained oily acid chloride was mixed with dioxane (3
ml) and added dropwise to ice-cooled concentrated ammonia (20 ml). After vigorously stirring this for 30 minutes, it was neutralized with dilute hydrochloric acid and extracted with benzene. The obtained organic layer was washed with water, then with saturated saline, dried over Glauber's salt, and then benzene was distilled off. The crude product thus obtained was purified by silica gel chromatography (eluted with ethyl acetate-hexane = 2:1),
Recrystallized from ethyl acetate-hexane to give white crystals 1.15%
g (63.3% yield) of the title compound was obtained. The absorption characteristics of this compound in the infrared spectrum are as follows. IR (KBr, cm ^-1 ): ν _NH 3470, 3230 ν _CO 1710, 1680 Example 2 1-[3-[(2,2,3,3,4,4,4-heptafluorobutoxy)methyl]phenyl ]−
5-phenyl-1H-1,2,4-triazole-3-carboxylic acid amide (No. 6 in Table 1)
Synthesis of compound) 1-[3-(chloromethyl)phenyl]-5-phenyl-1H-1,2,4-triazole-3-
313mg (1mM) of Carboxylic Acid Amide (Compound)
, 1.4 g (7 mM) of 2,2,3,3,4,4,4-heptafluorobutanol and 0.1 g of 60% NaH.
(2.5mM) was added to the alkoxide in hexamethylphosphoric triamide (20ml) and stirred overnight. The resulting reaction mixture was made acidic with dilute hydrochloric acid and extracted with benzene. The obtained benzene layer was washed with water, then with saturated saline, dried with Glauber's salt, and treated in the same manner as described in Example 1 to obtain 312 mg of white crystals.
(65.4%) of the title compound was obtained. The properties of this compound on the infrared absorption spectrum are as follows. IR (KBr, cm ^-1 ): ν _NH 3430, 3350, 3240, ν _CO 1660, Example 3 1-[3-(toxymethyl)phenyl]-5-phenyl-1H-1,2,4-triazole-3
-Synthesis of carboxylic acid amide (compound No. 1 in Table 1) 1-[3-(chloromethyl)phenyl]-5-phenyl-1H-1,2,4-triazole-3-
Carboxylic acid amide [Compound () 313mg (1mM)
was added to 10 ml of ethanol containing 2.5 mM sodium ethoxide and stirred overnight. The resulting reaction mixture was made acidic with dilute hydrochloric acid, ethanol was distilled off, water was poured, and the mixture was extracted with benzene. The resulting benzene layer was treated as described in Example 1 to yield 205 mg (63.6%) of the title compound as white crystals. IR (KBr, cm ^-1 ): ν _NH 3400, ν _CO 1700, Example 4 1-[3-(heptyloxymethyl)phenyl]
-5-phenyl-1H-1,2,4-triazole-3-carboxylic acid amide (No. in Table 1)
Synthesis of compound 10) 1-[3-(hydroxymethyl)phenyl]-5
-Phenyl-1H-1,2,4-triazole-
A mixture of 1.48 g (5 mM) of 3-carboxylic acid (compound) added to 5 ml of thionyl chloride and 5 ml of benzene was refluxed for 1.5 hours. After distilling off benzene and excess thionyl chloride, the resulting reaction mixture was diluted with benzene and diluted with sodium heptyl oxide.
12ml of heptyl alcohol containing 40mM and benzene
Add to 20 ml of the mixture, stir at room temperature for 30 minutes, then heat under reflux for 30 minutes, add water (50 ml) and stir at room temperature for 30 minutes for hydrolysis, then add dilute hydrochloric acid to acidify, dilute with hexane, and then The aqueous layer was separated. After separating the aqueous layer, the organic layer was washed with water, then with saturated saline, dried over Glauber's salt, and the solvent was distilled off.
Furthermore, excess heptyl alcohol was distilled off using a vacuum pump. After adding 5 ml of thionyl chloride and 5 ml of benzene to the obtained residue and refluxing for 1.5 hours, excess thionyl chloride was distilled off. The obtained oily acid chloride was mixed with dioxane (3
ml) and ice-cold concentrated ammonia water (20 ml).
ml), stirred vigorously for 30 minutes, neutralized with dilute hydrochloric acid, and extracted with benzene. The obtained benzene layer was washed with water, washed with saturated brine, dried over Glauber's salt, and then benzene was distilled off. The obtained crude product was purified by silica gel chromatography (eluting with ethyl acetate-hexane=2:1) to obtain 1.27 g (64.9%) of the title compound as a pale yellow oil. IR (liquid film, cm ^-1 ): ν _NH 3470, 3230, 3170, ν _CO 1690 Example 5 1-[3-{(2,2,2-trifluoroethoxy)methyl}phenyl]-5-phenyl- 1H−
Synthesis of 1,2,4-triazole-3-carboxylic acid amide (compound No. 2 in Table 1) 0.3 g of 2,2,2-trifluoroethanol and
0.1g (2.5mM) of 60% NaOH was reacted in hexamethylphosphoric triamide and converted into alkoxide. To this, 313 mg of 1-[3-(chloromethyl)phenyl]-5-phenyl-1H-1,2,4-triazole-3-carboxylic acid amide (compound)
(1mM) and stirred overnight. The resulting reaction mixture was made acidic with dilute hydrochloric acid and extracted with benzene. The benzene layer was sequentially washed with dilute hydrochloric acid, water, and saturated brine, dried over Glauber's salt, and then purified in the same manner as described in Example 1 to obtain 210 mg (55.8%) of the title compound as white crystals. IR (KBr, cm ^-1 ): ν _NH 3480, 3350 ν _CO 1680 Example 6 1-[3-(Butoxymethyl)phenyl]-5-
Phenyl-1H-1,2,4-triazole-
Synthesis of 3-carboxylic acid amide (compound No. 5 in Table 1) 1-[3-(hydroxymethyl)phenyl]-5
-Phenyl-1H-1,2,4-triazolecarboxylic acid (compound) 1.18g (4mM) was added to 5ml of thionyl chloride and benzene 5ml to make 1.5ml of a mixture.
Refluxed for an hour. After that, benzene and excess thionyl chloride were distilled off under reduced pressure, diluted with benzene, and this was mixed with 5.9 g (80 mM) of butanol and 1.6 g of 60% NaH.
(40mM) was added to the alkoxide solution obtained by reacting in 50ml of benzene, and the mixture was heated at room temperature for 30 minutes and stirred under reflux for 30 minutes. Add water (50 ml) to the obtained product and mix at room temperature.
After stirring vigorously for a period of time for hydrolysis, the mixture was divided into an aqueous layer and an organic layer, and then the aqueous layer was separated. The organic layer was further extracted with water, combined with the alkaline aqueous layer, and acidified with dilute hydrochloric acid. The obtained oily carboxylic acid was extracted with benzene, the organic layer was dehydrated, and the benzene was distilled off. Add 5 ml of thionyl chloride and 5 ml of benzene to the residue.
was added and refluxed for 1.5 hours to distill off excess thionyl chloride. The obtained oily acid chloride was dissolved in 3 ml of dioxane and added dropwise to 20 ml of ice-cooled concentrated ammonia water. After stirring vigorously for 30 minutes, the mixture was neutralized with dilute hydrochloric acid and extracted with benzene. The obtained organic layer was mixed with water,
After washing with saturated brine and drying with sodium sulfate, benzene was distilled off. The crude product thus obtained was purified in the same manner as described in Example 1, yielding 460 mg of white crystals.
(33.0% yield) was obtained. IR (KBr, cm ^-1 ): ν _NH 3470, 3000, 3250 ν _CO 1720, 1670 Reference example 1 Raw material compound: 4-[3-(hydroxymethyl)phenylhydrazono]-2-phenyl-2-oxazoline- Synthesis of 5-one (compound) Add 89.5 g (0.5 M) of hippuric acid to 270 ml of acetic anhydride.
Stirring was carried out at 60°C for 1.5 hours to obtain a homogeneous solution of 2-phenyl-2-oxazolin-5-one (compound), which was cooled to -20°C. 3-aminobenzyl alcohol (compound)
49.2g (0.4M) was dissolved in 210ml of acetic acid and 69ml of concentrated hydrochloric acid, and a solution of 27.6g (0.4M) of sodium nitrite dissolved in 55ml of water was added dropwise at 0 to 5°C to obtain a solution of diazonium salt. Anhydrous sodium acetate to the cooled solution of the compound 63.1
g (0.77M), the previously obtained solution of diazonium salt was added all at once while stirring, and the mixture was stirred at -20°C to -15°C for 4 hours, and then at room temperature for 1 hour. 600 ml of water was added, and the precipitate was collected by filtration, washed with water, and dried. 87.9g (74.5%) of orange-yellow crystals were obtained. Recrystallized from methyl ethyl ketone mp172~4
It turned into orange-yellow crystals at ℃. The properties of the infrared spectrum (IR) and nuclear magnetic resonance absorption spectrum (NMR) of the compound are as follows. IR (KBr, cm ^-1 ): ν _NH , ν _OH 3500-3200 ν _CO 1790 NMR (d ₆ -DMSO, δ, ppm): 4.51 (2H, d, J=6Hz: CH ₂ ), 5.20 (1H, t, J = 6Hz; OH), 6.9-8.2 (9H, m; ArH), 12.80 (1H, s;
NH) Elemental analysis value: Calculated value as C ₁₆ H ₁₃ N ₃ O ₃ (%) C: 65.08, H: 4.44, N: 14.23 Actual value C: 64.97, H: 4.39, N: 14.20 Reference example 2 Raw material compound : Synthesis of 1-[3-(hydroxymethyl)phenyl]-5-phenyl-1H-1,2,4-triazole-3-carboxylic acid (compound) 4-[3 obtained by the method described in Reference Example 1 -(Hydroxymethyl)phenylhydrazono]-2-phenyl-2-oxazolin-5-one (compound) 85.6
g (0.29M) was dispersed in acetone 2, a solution of 30g (0.75M) of caustic soda dissolved in 200ml of water was poured into the solution, and the mixture was stirred at room temperature for 1 hour to obtain a solution of the benzamide derivative (compound). After carefully pouring 108 ml (1.3 M) of concentrated hydrochloric acid into the mixture, it was boiled for 30 minutes. After distilling off the acetone, the crystals were collected by filtration, thoroughly washed with water, and dried. 72.7g (84.9%
White crystals were obtained with a yield of 192°C (decomposition) and a mp of 192°C (decomposition). The properties of the infrared absorption spectrum (IR) and nuclear magnetic resonance spectrum (NMR) of this compound are as follows. IR (KBr, cm ^-1 ): ν _NH,COOH 3350 3000-2200, 1730 NMR (d ₆ -DMSO, δ, ppm): 4.50 (2H, s; CH ₂ ), ca6.0 (2H, bs, COOH+OH ), 7.0 to 7.6 (9H, m; ArH), Elemental analysis value: Calculated value as C ₁₆ H ₁₃ N ₃ O ₃ (%) C: 65.08, H: 4.44, N: 14.23 Actual value C: 65.14, H :4.52, N:14.10 Reference example 3 Starting compound: Synthesis of 1-[3-(chloromethyl)phenyl]-5-phenyl-1H-1,2,4-triazole-3-carboxylic acid amide (compound) Reference example 1-[3-(hydroxymethyl)phenyl]-5-phenyl-1H-1,2, obtained by method 2.
4-triazole-3-carboxylic acid (compound)
20.65g (0.07M) of thionyl chloride 80ml (1.1M)
and 80 ml of benzene and boiled for 2 hours. The oil obtained by distilling off excess thionyl chloride and benzene was dissolved in 30 ml of dioxane, and this was added dropwise to 300 ml of ice-cooled concentrated ammonia water while stirring vigorously. The mixture was stirred for 30 minutes, and the precipitate deposited was collected by filtration, washed with water, and dried. 20.2 g (92.3% yield) of almost white solid was obtained. Recrystallization from a mixture of ethyl acetate and hexane gave white crystals with a mp of 158-160°C. The properties of the infrared absorption spectrum (IR) and nuclear magnetic resonance spectrum (NMR) of this compound are as follows. IR (KBr, cm ^-1 ): ν _NH , 3350-3150, ν _CO 1690, 1660 NMR (CDCl ₃ , δ, ppm): 4.56 (2H, s; CH ₂ ), 6.8-7.7 (11H, m; ArH+NH ₂ ), Elemental analysis value: Calculated value as C ₁₆ H ₁₃ N ₄ O (%) C: 61.44, H: 4.19, N: 17.92 Actual value C: 61.51, H: 4.21, N: 17.83 Comparative example 1 JP-A In Example 2, the compound of formula XII disclosed in No. 59-98004 was used in place of the compound of formula used as the starting material, and the reaction was carried out under exactly the same reaction conditions as in Example 2, but the compound of formula XII was The compound did not react. The following Examples 7 to 9 show the preparation of the herbicide according to the present invention, and Example 10 and Example 11 show the herbicidal activity thereof. "Parts" in each example represent weight unless otherwise specified. In addition, those shown as comparative examples in these Examples contain as an active ingredient a compound having the following formula disclosed in JP-A No. 59-98004. Example 7 Herbicide in the form of a wettable powder: Compound No. 7 (see Table 1) 50 parts lignin sulfonate 5 parts alkyl sulfonate 3 parts diatomaceous earth 42 parts The mixture of the above formulation was ground, and a wettable powder was prepared. Use it by diluting it with water. Example 8 Herbicide in emulsion form: Compound No. 8 (see Table 1) 25 parts xylene 65 parts polyoxyethylene alkyl allyl ether 10 parts The above formulation is uniformly mixed to form an emulsion, and the emulsion is diluted with water before use. Example 9 Herbicide in granule form: Compound No. 2 8 parts bentonite 40 parts clay 45 parts ligninsulfonic acid 7 parts Water was added to the above mixture, kneaded, and granulated using an extrusion granulator. It is then dried and used as granules. Example 10 Application test for soil before plant germination: A fixed amount of seeds of various test plants were sown in a planter (650 x 210 x 220 cm) filled with soil and made into a field, and after covering with soil, the Example The hydrating agent prepared according to 10 was added to the compound containing 1 as an active ingredient.
A diluted solution adjusted to an amount equivalent to 20 g per area was uniformly spread over the soil surface, and the plants were grown in a greenhouse. 25 days after the above treatment, the effects on each plant were evaluated according to the following criteria. Evaluation criteria 0... No herbicidal effect 1... Less than 30% herbicidal effect 2... 31-50% herbicidal effect 3... 51-70% herbicidal effect 4... 71-90 % herbicidal effect 5...91-100% herbicidal effect The results of the above test are shown in Table 3.

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[Table] As shown in Table 3, Compounds No. 1 to 63 of the present invention exhibited almost 100% herbicidal effects against a wide range of weeds, and on the other hand, against wheat and corn. It can be seen that there is no drug damage. On the other hand, in the comparative example, almost no herbicidal effect was observed against weeds. Example 11 Application test at early stage of plant growth: Following the same procedure as described in Example 10,
Seeds of various plants are sown, and when each plant reaches the 1-2 leaf stage, an aqueous suspension containing the compound as an active ingredient in an amount equivalent to 20g per are is applied to the foliage and soil surface of each plant. It was evenly distributed and grown in a greenhouse. After 25 days from the above treatment, evaluation was made using the same evaluation criteria as shown in Example 10. The results of the above test are shown in Table 4.

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[Table] As shown in Table 4, even after plant growth, the compound according to the present invention is effective against weeds at
It exhibits 100% herbicidal effect, while showing almost no phytotoxicity to useful crops. On the other hand, it can be seen that the compounds of Comparative Examples had inferior herbicidal effects and lacked practicality.

[Claims]

1 General formula (): (However, in the formula, R represents a hydrogen atom; an alkali metal atom; an ammonium salt; an alkyl group having 1 to 6 carbon atoms; a lower alkoxyalkoxyalkyl group; R ¹ represents a haloethyl group; and X represents a halogen atom. ) Δ ² -1,2,4-triazoline-
5-one derivative. 2 General formula ():

Claims (1)

(c) A straight-chain or branched saturated alkoxyalkyl group or unsaturated alkoxyalkyl group having 3 to 10 carbon atoms; (d) A phenyl group that is unsubstituted or substituted with a halogen atom or a lower alkyl group; It is an enoxyalkyl group or an aralkoxyalkyl group. ] 1,2,4-triazole-3-carboxylic acid amide shown by these. 2 General formula () A herbicide containing 1,2,4-triazole-3-carboxylic acid amide represented by the formula (wherein R represents the same meaning as above) as an active ingredient. 3 formula () A general formula () characterized by reacting a chloromethyl derivative represented by the following with an alcohol derivative represented by the general formula R-OH (R represents the same meaning as above) in the presence of an inorganic or organic base. A method for producing a compound represented by the formula (wherein R represents the same meaning as above). 4 General formula () (In the formula, R represents the same meaning as above.) 1,2,4-triazole-3-carboxylic acid chloride represented by the general formula (() A method for producing a compound represented by the formula (wherein R represents the same meaning as above). 5 (i) Formula () 3-Aminobenzyl alcohol represented by the formula and sodium nitrite are reacted at 15°C or lower in the presence of hydrochloric acid, sulfuric acid or hydroborofluoric acid, and (ii) the obtained formula is [In the formula, X represents Cl, 1/2(SO ₄ ) or BF ₄ ]. The diazonium salt and the formula shown by () 2-phenyl-2-oxazoline-
5-one is reacted at a temperature below 60°C, (iii) the obtained formula (): After reacting 4-[(3-hydroxymethyl)phenylhydrazone]-2-phenyl-2-oxazolin-5-one shown by adding more than an equivalent amount of sodium hydroxide in an aprotic organic solvent, Add hydrochloric acid to make it acidic and then heat it to below 100°C. (iv) The obtained formula (): 60 1-[3-(hydroxymethyl)phenyl]-5-phenyl-1H-1,2,4-triazole-3-carboxylic acid and thionyl chloride
Reacted at a temperature of ~100°C, (v) obtained formula (): 1-[3-(chloromethyl)phenyl]-5-phenyl-1H-1,2,4-triazole-3-carboxylic acid chloride and ammonia are reacted in the range of -20°C to room temperature (vi) The resulting formula (): A compound represented by the above formula and a compound represented by the general formula R-OH (in which R has the same meaning as above) were heated at -20°C to 50°C in the presence of an inorganic or organic base.
General formula () consisting of reacting in the range of °C: (In the formula, R represents the same meaning as described above.) A method for producing a 1,2,4-triazole-3-carboxylic acid amide compound represented by the following.