JPH0480030B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention relates to 4,5-dihydro-1H-1,2,4-triazole-3-carboxylic acid amide derivatives used as active ingredients in herbicides, and herbicides containing the derivatives as active ingredients. Regarding. 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. Conventionally, 4,5-dihydro-1H-1,2,4-
There are few reports on triazole-3-carboxylic acid derivatives, and JP-A-61-171475 and JP-A-61-
General formula (′) for 210075: (In the formula, X represents H, 3-CH ₃ or 4-Cl)
Only the compounds represented by are described. JP-A-61-210075 states that the compound represented by the above general formula (') has herbicidal activity, but the herbicidal effect of this compound is not sufficient;
In addition, it cannot be said that it has excellent selectivity; it shows excellent herbicidal activity and has excellent herbicidal activity that kills only weeds without harming useful crops such as rice, wheat, and corn. There is a strong demand for the development of such compounds. Problems to be Solved by the Invention As a result of research to provide a compound that exhibits excellent herbicidal effects and does not harm useful crops such as rice, wheat, and corn, the present inventors have found the following general formula (): (In the formula, R is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or an alkyl group having an alicyclic structure. , alkenyl group having 3 to 8 carbon atoms, alkynyl group having 3 to 8 carbon atoms, 3 carbon atoms
to 8 alkoxyalkyl groups, phenyl groups,
4,5-dihydro-1H-1,2,4-triazole-3 represented by an aralkyl group, a halogen-substituted phenyl group, or a fluorine-substituted alkyl group having 2 to 8 carbon atoms It was discovered that -carboxylic acid amide derivatives have an excellent selective herbicidal effect, and based on this finding, the present invention was accomplished. The compound represented by the above general formula () is 4,5
-CH ₂ OR (R is the general formula ()
It differs from the compound represented by the general formula (') described in JP-A-61-171475 and JP-A-61-210075 in that it has the same meaning as in
Moreover, it is a compound that has not been described in any literature. That is, the present invention exhibits excellent herbicidal activity against grass weeds and broad-leaved plants, especially broad-leaved plants,
On the other hand, 4, which has selective herbicidal activity that does not cause phytotoxicity on crops such as rice, wheat, and corn,
The object of the present invention is to provide a 5-dihydro-1H-1,2,4-triazole-3-carboxylic acid amide derivative and a herbicide containing the compound as an active ingredient. Structure of the Invention The present invention is based on the general formula (): 4,5-dihydro-1H-1,2,4 represented by
The present invention relates to a triazole-3-carboxylic acid amide derivative and a herbicide containing the compound as an active ingredient. In the above general formula (), R is a linear alkyl group having 1 to 8 carbon atoms, preferably 3 to 6 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms, Cyclic alkyl group having 3 to 8 carbon atoms, preferably 4 to 7 carbon atoms, 4 to 8 carbon atoms
an alkyl group having preferably 4 to 7 alicyclic structures, 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms
number of carbon atoms substituted with an alkenyl group, an alkynyl group having 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms, an alkoxyalkyl group having 3 to 8 carbon atoms, preferably an alkoxy group having 1 to 4 carbon atoms 2 to 4 alkyl group, phenyl group, carbon number 7 to 9
aralkyl group, a phenyl group substituted with halogen, preferably 1 to 3 halogens, or a phenyl group having 2 to 8 carbon atoms substituted with fluorine atoms, preferably 1 to 15 fluorine atoms, preferably Represents 2 to 7 alkyl groups. Table 1 shows examples of the compounds represented by the general formula () and their physical and chemical properties according to the present invention. Further, Table 2 shows the results of elemental analysis 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 paddy fields, field crops, etc. The compound according to the present invention represented by the above general formula () can be synthesized very easily by the reaction shown in Reaction Formula 1. Reaction formula 1 (in the formula, R has the same meaning as above) That is, an oxamide derivative represented by the general formula () and benzaldehyde () are combined with, for example, acetic acid,
It can be synthesized by conducting a dehydration reaction preferably at -10 to 150°C for 0.1 to 40 hours in the presence of an acid catalyst such as p-toluenesulfonic acid. At this time, the yield is generally improved if the reaction is carried out in an inert gas atmosphere. The oxamide derivative (), which is a raw material compound for the compound of the present invention, can be synthesized by the reaction shown in Reaction Formula 2. First, 3-nitrobenzyl chloride () and a compound represented by the general formula () are reacted, for example, in the presence of a hydrogen chloride scavenger such as KOH or NaH, preferably at -10 to 150°C for 0.1 to 100 hours,
A nitrobenzene derivative represented by the general formula () is obtained. This nitrobenzene derivative is then reduced according to a conventional method to give an aniline derivative ( ). Reaction formula 2 (R in the formula has the same meaning as above) Next, the aniline derivative is converted into a diazonium salt ( ) using sodium nitrite in hydrochloric acid, and then the 2-chloroacetoacetic ester ( ) is preferably converted to -10 When reacted at ~50℃, chloro(arylhydrazono) easily represented by the general formula ()
Acetate ester is obtained. Finally, the general formula ()
When the compound is reacted with ammonia preferably at -10 to 50°C, more preferably at 0 to 30°C, the oxamide derivative () which is the raw material compound of the compound of the present invention is produced.
can be synthesized. 4,5-dihydro-1H-1,2,4 of the present invention
-Triazole-3-carboxylic acid amide derivatives can be used alone or in combination with a wide variety of carriers (diluents) and/or auxiliary agents conventionally used in the preparation of agricultural chemicals to form wettable powders, emulsions, etc. It can also be used as a composition such as granules or powders. 4,5-dihydro-1H- of the present invention in the composition
The weight ratio of the 1,2,4-triazole-3-carboxylic acid amide derivative is preferably 0.1 to 50%. 4,5-dihydro-1H-1,2,4 of the present invention
- Triazole-3-carboxylic acid amide derivatives and herbicides containing these compounds as active ingredients can be applied to the soil and/or fields of paddy fields and fields by conventionally known spraying methods.
Alternatively, the compound is sprayed onto the foliage of the plant in an amount of preferably 0.1 to 500 g per 10 acres. Effects of the Invention The 4,5-dihydro-1H-1,2,4-triazole-3-carboxylic acid amide derivative of the present invention shown by the general formula () exhibits excellent herbicidal activity and It is a highly selective compound that kills only weeds without harming crops. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the Examples. Synthesis Example 1 Synthesis of 1-[(3-methylbutoxy)methyl]-3-nitrobenzene (a compound in which R represents a 3-methylbutyl group in the general formula ()) 158.1 g (0.92 mol) of 3-nitrobenzyl chloride was mixed with 500 ml (4.59 mol) of 3-methyl-1-butanol.
mol, 5 equivalents) and 140 ml of dimethylformamide. While cooling in a water bath and stirring vigorously, add 78 g of KOH pellets (1.39 mol, 1.5
equivalent amount) was added. The reaction temperature rose to 43°C and then gradually returned to room temperature. The reaction was completed by stirring at room temperature for 7 hours. The solid in the reaction mixture was filtered off, and the filtrate was PHed with hydrochloric acid.
2, excess alcohol and dimethylformamide were distilled off. The residue was diluted with n-hexane 450
ml-dissolved in a mixed solvent of 50 ml of ethyl acetate and diluted with 1N-
It was washed successively with HCl and saturated saline, and dried over magnesium sulfate. After distilling off the solvent, perform fractional distillation.
bp.116-117℃ (0.08mmHg) fraction 185.2g
(90.1% yield) was obtained. Synthesis Example 2 Synthesis of 3-[(3-methylbutoxy)methyl]aniline (compound in which R represents a 3-methylbutyl group in general formula ()) 130g of nitrobenzene derivative obtained in Synthesis Example 1
(0.58 mol) was dissolved in 150 ml of ethanol, and 0.6 g of 10% palladium on carbon was added. While stirring, 89 ml (1.84 mol) of hydrazine hydrate was added dropwise at a rate that did not cause excessive foaming. After the dropwise addition was completed, the mixture was refluxed on a hot water bath for 3 hours to complete the reaction. After the reaction mixture was allowed to cool, the catalyst was filtered off and washed with ethanol. The filtrate was concentrated, then dissolved in 300 ml of dichloromethane, washed successively with a 10% aqueous sodium carbonate solution and saturated brine, and dried over anhydrous potassium carbonate. The solvent was distilled off and the residue was fractionated to bp.105-106℃ (0.19
mmHg) fraction (109.2 g (97.1% yield)) was obtained. Synthesis Example 3 Chloro[3-[(3-methylbutoxy)methyl]
Synthesis of phenylhydrazono]acetic acid methyl ester (compound in which R represents a 3-methylbutoxy group in the general formula ()) 19.3 g (0.1 mol) of 3-[(3-methylbutoxy)methyl]aniline obtained in Synthesis Example 2 was dissolved in 30 ml of acetic acid, 26 ml of concentrated hydrochloric acid was added, and the mixture was cooled to 0°C. A solution of 6.9 g (0.1 mol) of sodium nitrite dissolved in 12 ml of water was added dropwise to this solution while keeping the reaction temperature below 5° C. to prepare a diazonium salt solution. 2-
15.1 g (0.1 mol) of methyl chloroacetoacetate was added to a mixture of 70 ml of methanol, 50 ml of water, and 40.8 g (0.3 mol) of sodium acetate trihydrate, and the mixture was cooled to 0°C. The diazonium salt solution prepared above was added to this over 15 minutes, and the mixture was stirred at 0°C for 1 hour and at room temperature for 3 hours. Add 100ml of water and add benzene.
Extraction was carried out twice with 150 ml, and the organic layer was washed with water-saturated sodium bicarbonate solution and saturated brine, and dried over anhydrous sodium sulfate. The melt obtained by distilling off the solvent was purified by silica gel chromatography (developing solution: dichloromethane) to obtain 29.3 g (93.8% yield) of a pale yellow oil. Synthesis Example 4 Synthesis of oxamide 3-[(3-methylbutoxy)methyl]phenylhydrazone] (compound in which R represents a 3-methylbutyl group in general formula ()) 15.9 g of chloroacetate derivative obtained in Synthesis Example 3
(0.05 mol) in 20 ml of dichloromethane was added to an ice-cooled ammonia methanol solution (ammonium 20 ml).
% content) was carefully poured into 100ml, stirred for 30 minutes, sealed and left overnight. The residue obtained by distilling off the solvent was extracted with ethyl acetate/water, and the organic layer was separated.
The mixture was washed with water and then with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained brown oil was subjected to silica gel chromatography [Developing solution: dichloromethane/ethyl acetate = 4/1 (v/
v)] to give 11.4 g (80.6% yield) of a pale yellow oil. Example 1 4,5-dihydro-1-[3-[(3-methylbutoxy)methyl]phenyl]-5-phenyl-
Synthesis of 1H-1,2,4-triazole-3-carboxylic acid amide (compound No. 4) 2.78 g (0.01 g) of the oxamide derivative obtained in Synthesis Example 4
mol) was dissolved in 12 ml of acetic acid saturated with nitrogen, 1.17 g (0.011 mol) of benzaldehyde was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 16 hours. Water saturated with nitrogen was added, and the precipitated crystals were collected by filtration and dried in vacuo. Nitrogen saturated ethyl acetate/n-
Recrystallization from hexane yielded 3.11 g (84.4% yield) of 4,5-dihydro-1-[3-[(3-methylbutoxy)methyl]phenyl]-5-phenyl-1H-
1,2,4-triazole-3-carboxylic acid amide was obtained (yellow needles, mp. 144-146°C). Example 2 4,5-dihydro-1-[3-(phenoxymethyl)phenyl]-5-phenyl-1H-1,2,
Synthesis of 4-triazole-3-carboxylic acid amide (compound No. 10) 2.84 g (0.01 mol) of oxamide 3-(phenoxymethyl)phenylhydrazone obtained in the same manner as described in Synthesis Examples 1 to 4 was added to nitrogen Dissolve in 15 ml of saturated acetic acid and add 1.17 g of benzaldehyde.
(0.011 mol) was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 16 hours. Nitrogen-saturated water was added, and the precipitated crystals were collected by filtration and dried in vacuo. Recrystallization from nitrogen-saturated ethyl acetate/n-hexane yielded 3.18 g (85.5% yield) of 4,5-dihydro-1-[3-(phenoxymethyl)phenyl]-5.
-Phenyl-1H-1,2,4-triazole-
3-carboxylic acid amide was obtained (mp. 177-178°C). Example 3 1-[3(2,2,3,3,3-pentafluoropropoxy)methyl]phenyl]-4,5-dihydro-5-phenyl-1H-1,2,4-triazole-3-carvone Acid amide (compound no.
Synthesis of 15) Oxamide 3-[(2,2,3,3,3-pentafluoropropoxy)methyl]phenylhydrazone obtained in the same manner as described in Synthesis Examples 1 to 4.
1.02 g (3.0 mmol) was dissolved in 6 ml of acetic acid saturated with nitrogen, and 0.35 g (3.3 mmol) of benzaldehyde was added under a nitrogen atmosphere.
I stirred the time. Water saturated with nitrogen was poured into the mixture, and the precipitated crystals were collected by filtration and dried in vacuo. Recrystallize from nitrogen-saturated ethyl acetate/n-hexane,
1.19 g (92.7% yield) of 1-[3-[(2,2,3,
3,3-pentafluoropropoxy)methyl]phenyl]-4,5-dihydro-5-phenyl-1H
-1,2,4-triazole-3-carboxylic acid amide was obtained (mp. 146-148°C). Example 4 1-[3-(cyclohexylmethoxymethyl)phenyl]-4,5-dihydro-5-phenyl-
Synthesis of 1H-1,2,4-triazole-3-carboxylic acid amide (Compound No. 7) Oxamide 3-(cyclohexylmethoxymethyl) obtained in the same manner as in Synthesis Examples 1 to 4.
502 mg (1.65 mmol) of phenylhydrazone was dissolved in 3.3 ml of acetic acid, the mixture was thoroughly purged with nitrogen, and 193 mg (1.81 mmol) of benzaldehyde was added.
The mixture was stirred at room temperature for 20 hours. Water saturated with nitrogen was added, and the precipitated crystals were collected by filtration and dried in vacuo. After drying, dissolve in nitrogen-saturated dichloromethane (40-50 ml) and add about 40 ml of hexane little by little to precipitate crystals, 616.3 mg (95.2% yield).
1-[3-(cyclohexylmethoxymethyl)phenyl]-4,5-dihydro-5-phenyl-1H
-1,2,4-triazole-3-carboxylic acid amide was obtained (mp. 165-167°C). Example 5 Preparation of Wettable Dispersible Compound No. 4 50 parts Lignosulfonate 5 parts Alkyl sulfonate 3 parts Diatomiza 42 parts are mixed and ground to form a wettable powder and used by diluting with water. Example 6 Preparation of emulsion Compound No. 4 25 parts Xylene 65 parts Polyoxyethylene alkyl allyl ether
Mix 10 parts uniformly to make an emulsion, dilute with water, and use. Example 7 Preparation of granules 8 parts of compound No. 17, 40 parts of bentonite, 45 parts of clay, and 7 parts of lignin sulfonate were mixed uniformly, water was added, the mixture was kneaded, processed into granules using an extrusion granulator, and dried to form granules. shall be. Next, the 4,5-dihydro-1H-1,2,
A test example is shown to demonstrate the selective herbicidal activity of the 4-triazole-3-carboxylic acid amide derivative. Test example 1 Effect on field weeds (pre-emergence soil treatment) A planter (650 x 210 x 220 mm) was filled with sandy loam soil to form a field, and this was filled with green leaf beetles, kosendan, wild mustard, chickweed, dogweed, Japanese grasshopper, edible millet, crabgrass, After sowing a certain amount of wheat or corn seeds and covering with soil, dilute the wettable powder prepared in the same manner as in Example 5 with water to a predetermined concentration, and use a spray gun to spray the amount of the active ingredient in an amount of 200g/10a. It was spread evenly on the soil surface and then grown and managed in a glass greenhouse. On the 21st day after the above treatment, the herbicidal effect on each weed and the chemical damage to the crops were observed and evaluated based on the following criteria, and the results shown in Table 3 were obtained. Evaluation criteria: 0... No effect 1... Less than 30% herbicidal effect 2... 31-50% herbicidal effect 3... 51-70% herbicidal effect 4... 71-90% herbicidal effect 5... 91-91% herbicidal effect 100% herbicidal effect; chemical damage level; -...Harmless ±...Minor harm +...Moderate harm +++...Severe damage +++...Severe damage

[Table] Test Example 2 Effect on field weeds (post-germination soil treatment) Following the same procedure as described in Test Example 1,
Seeds of various plants are sown, and when each plant reaches the 1-2 leaf stage, spray a hydrating powder diluted with water in the same manner as in Test Example 1 in an amount that makes the amount of active ingredient applied 200g/10a. After uniformly spraying the foliage and soil surface of each plant with a gun, they were grown again in a glass greenhouse, and 21 days after treatment, the results were evaluated using the same criteria as shown in Test Example 1, and the results shown in Table 4 were obtained. .

[Table] Test Example 3 Effect on paddy field weeds and chemical damage A 1/2000 are Wagner pot filled with paddy soil was filled with water and flooded with water, and seeds of Japanese millet, bulrush, Helaomodaka, Konagi, and Cyperus japonica were sown, and tubers of Cyperus spp. was planted. Furthermore, after transplanting two paddy rice seedlings (cultivar Sasanishiki) at the two-leaf stage, the pots were grown in a greenhouse for 3 days, and an emulsion prepared in the same manner as in Example 6 was diluted with water to a predetermined concentration so that the amount of the active ingredient to be sprayed was 200 g/ An amount of 10a was uniformly dropped onto the water surface. 21 days after the chemical solution treatment, the herbicidal effect and the degree of chemical damage to paddy rice were investigated using the same criteria as Test Example 1, and the results shown in Table 5 were obtained.

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Claims (1)

[Claims] 1 General formula () (In the formula, R is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or an alkyl group having an alicyclic structure. , alkenyl group having 3 to 8 carbon atoms, alkynyl group having 3 to 8 carbon atoms, 3 carbon atoms
to 8 alkoxyalkyl groups, phenyl groups,
4,5-dihydro-1H-1,2,4-triazole-3 represented by an aralkyl group, a halogen-substituted phenyl group, or a fluorine-substituted alkyl group having 2 to 8 carbon atoms -Carboxylic acid amide derivatives. 2 General formula () (In the formula, R is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or an alkyl group having an alicyclic structure. , alkenyl group having 3 to 8 carbon atoms, alkynyl group having 3 to 8 carbon atoms, 3 carbon atoms
to 8 alkoxyalkyl groups, phenyl groups,
4,5-dihydro-1H-1,2,4-triazole-3 represented by an aralkyl group, a halogen-substituted phenyl group, or a fluorine-substituted alkyl group having 2 to 8 carbon atoms - A herbicide containing a carboxylic acid amide derivative as an active ingredient.