JPH05345779A - New triazole derivative - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a herbicide and agricultural chemicals, showing synergistic activity in treatment of upland field. CONSTITUTION:The compound of formula I (R1 and R2 are lower alkyl; X and Y are lower alkoxy, halo-lower alkoxy or lower alkyl; n is 0-2; p and q are 0-4 and p+q=1-4) such as 1-(N,N-diethylcarbamyl)-3-(2-methoxy-3- pyridylthio)-1,2,4-triazole. The compound of formula I is obtained by reacting a triazole-based compound of formula II with a compound of formula III (L is halogen) and optionally oxidizing with an oxidizing agent.

Description

Detailed Description of the Invention

[0001]

The present invention relates to general formula (I) useful as a pesticide.

[Chemical 2]

(In the formula, R ₁ and R ₂ are the same or different and represent a lower alkyl group. X and Y are the same or different and represent a lower alkoxy group, a halo lower alkoxy group or a lower alkyl group, and n is n. An integer of 0 to 2 and p and q are the same or different and represent an integer of 0 to 4, provided that the sum of p and q is in the range of 1 to 4).

[0003]

2. Description of the Related Art Conventionally, it has been known that certain triazole compounds have a herbicidal effect (US Pat. No. 4).
No. 280831, JP-A-59-39880, JP-A-60-100562, and JP-A-61-1.
78980, JP-A-63-14776, JP-A-1-121279, JP-A-2-1481 and JP-A-3-279368).

Further, Japanese Laid-Open Patent Publication No. 1-106883 discloses that
A triazole-based compound in which a 2-pyridyl group is substituted in a sulfonyl group is described.

[0005]

These conventional triazole compounds show a certain effect as paddy field herbicides, but their activity was not sufficient in the case of field soil treatment.

[0006] The present inventors have aimed to develop a herbicide which has a lower dose than these triazole compounds and which has an excellent herbicidal effect particularly in the treatment of upland soil, and which does not show phytotoxicity to crops. As a result of earnest studies, surprisingly, it is represented by the general formula (I) in which a 3-pyridyl group is introduced as a substituent of a sulfonyl group of a series of triazole compounds and the pyridyl group is substituted with a specific group. The present inventors have found that the compound exhibits an effect superior to that of the 2-pyridyl-based compound and other triazole-based compounds described in JP-A-1-106883, and completed the present invention.

[0007]

The compound of the present invention represented by the general formula (I) can be produced, for example, as follows.

That is, the general formula (II)

[Chemical 3]

(Wherein X, Y, n, p and q have the same meanings as described above)
General formula (III)

[Chemical 4]

(Wherein L is a halogen atom, R ₁ and R
₂ has the same meaning as above) and is obtained by reacting with a compound represented by the formula (1) and, if necessary, oxidizing with a suitable oxidizing agent.

In the above reaction, the desired compound represented by the general formula (I) is a sulfinyl compound (n =
In the case of 1) or a sulfonyl compound (n = 2), a compound represented by the general formula (I) in which the S moiety is unoxidized may be prepared as a starting material, and the compound may be oxidized if necessary. The step of reacting the oxidized or unoxidized compound represented by the general formula (II) with the compound represented by the general formula (III) is 1 equivalent or more, preferably 1 equivalent or more relative to the compound represented by the general formula (II). Is 1 to 2 equivalents in a suitable solvent in the presence of a deoxidizing agent.
~ 2 equivalents, preferably 1 to 1.2 equivalents of the general formula (II
The compound represented by I) is reacted. Reaction temperature is 0 to 1
A temperature of 00 ° C, preferably 20 to 70 ° C is suitable.

Examples of the solvent used here include hexane, heptane, ligroin, petroleum ether, and other aliphatic hydrocarbons; benzene, toluene, xylene, and other aromatic hydrocarbons; chloroform, carbon tetrachloride, dichloroethane, Halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and diethylene glycol dimethyl ether; acetone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, nitroethane,
Nitrides such as nitrobenzene; Nitriles such as acetonitrile and isobutyronitrile; Tertiary amines such as pyridine, triethylamine, N, N-diethylaniline, tributylamine, N-methylmorpholine; N, N-
Acid amides such as dimethylformamide; sulfur compounds such as dimethylsulfoxide and sulfolane; and mixtures thereof.

Deoxidizing agents include organic bases such as pyridine, triethylamine and N, N-diethylaniline; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride; sodium methoxide. , Alkali metal alkoxides such as sodium ethoxide, and the like.

The oxidation step can be carried out, for example, by oxidizing with an oxidizing agent in a suitable solvent. Examples of the oxidizing agent used here include inorganic oxidizing agents such as hydrogen peroxide, potassium permanganate, and chromic acid; organic oxidizing agents such as peracetic acid and m-chloroperbenzoic acid. Examples of the solvent used include methylene chloride, chloroform, acetone, acetic acid, water and the like, or a mixed solvent thereof. The reaction temperature is suitably 0 to 50 ° C., but it may be appropriately heated or cooled depending on the type of solvent or the progress of the reaction.

The starting material represented by the general formula (II) can be produced, for example, as follows. That is, the following formula (IV)

[Chemical 5]

The compound represented by the general formula (V)

[Chemical 6]

(Wherein Z is a halogen atom, X, Y, p
And q have the same meanings as described above) and can be obtained by reacting in a suitable solvent.

Further, the general formula (VI)

[Chemical 7]

The compound represented by the formula (wherein X, Y, p and q have the same meanings as described above) is dissolved in concentrated hydrochloric acid to give Na.
It can also be obtained by adding NO ₂ and using it as a diazonium salt solution, and adding the compound represented by the formula (IV) therein.

The solvent used here may be any solvent so long as it is an inert solvent for the reaction components, and for example, those described above such as dimethylformamide can be used. The reaction temperature is 20 to 200 ° C., preferably 50 to 150 ° C. when using the compound represented by the general formula (V), and when using the compound represented by the general formula (VI),
It is 0 to 100 ° C, preferably 0 to 70 ° C.

The compound of the present invention shows excellent herbicidal effect in paddy field and upland treatment without showing phytotoxicity to crops,
In particular, it shows an excellent herbicidal effect against various weeds which are problematic in soil treatment of upland fields.

When the compound of the present invention is used as an active ingredient of a herbicide, it is mixed with a carrier which can be usually used, other auxiliaries for formulation and the like to prepare an emulsion, a wettable powder, an oil, a powder, a flowable agent and a granule. And the like.

Examples of the carriers that can be usually used here include talc, clay, bentonite, kaolin, diatomaceous earth, calcium carbonate, charcoal, starch, gum arabic, water, alcohol, kerosene, naphtha, xylene, and the like.
Cyclohexane, methylnaphthalene, benzene, acetone, dimethylformamide, glycol ether, N-
Methylpyrrolidone and the like can be mentioned.

Examples of the auxiliary agent include polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan monooleate, ethylene oxide propylene oxide copolymer, lignin sulfonate, sorbitan ester, soaps, sulfated oils, alkyl sulfate ester. Salts, petroleum sulfonates, dioctyl sulfosuccinate salts, alkylbenzene sulfonic acids, aliphatic amine salts, quaternary ammonium salts, alkylpyridinium salts, alkyldimethylbetaines, alkylaminoethylglycines, polyglycol sulfates, alkylamine sulfonic acids, Examples thereof include isopropyl phosphate, carboxymethyl cellulose, polyvinyl alcohol, hydroxypropyl cellulose, ethylene glycol, xanthan gum and the like.

In the formulation, the mixing ratio can generally be freely selected as the ratio of the compound of the present invention in the range of 0.05 to 95% by weight, preferably 1 to
70%, the carrier is 5 to 99%, preferably 70 to
A formulation containing 90% and an auxiliary agent of 0 to 20%, preferably 1 to 7% is preferable. In addition, a wider range of effects can be expected by mixing with other pesticides such as fungicides, herbicides, plant growth regulators, insecticides, acaricides and fertilizers.

When the compound of the present invention is actually used, the amount to be used can be appropriately selected depending on the time of use, method, dosage form, location, weather conditions, target weeds, crops, etc. The compound of the present invention is generally 10
5 to 500g, preferably 10 to 200g per are
Is.

[0027]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 1- (N, N-diethylcarbamyl) -3- (2-meth)
Xy-3-pyridylthio) -1,2,4-triazole
Production of (Compound No. 1)

1) 5-amino-3-methoxypyridine containing 3.2 g (0.026M) of concentrated hydrochloric acid (5.2 ml) 5
A 0 ml aqueous solution is diazotized at −5 ° C. with an aqueous solution of 1.8 g NaNO ₂ . 5 g (0.05 M) of 3-mercapto-1,2,4-triazole and 6.6 g of caustic potash
The 0 ml aqueous solution is cooled to 0 ° C., and the above diazo solution is gradually added with stirring. During this period, the reaction temperature is maintained at 5 ° C. or lower, and the reaction is further continued for 1 hour under cooling and then at room temperature overnight. The reaction solution is neutralized to pH 7 with acetic acid, and the precipitated oily substance is extracted with ethyl acetate. The ethyl acetate layer was washed once with water, dried over sodium sulfate, and then the ethyl acetate was distilled off to obtain a brown oily substance. Purification by silica gel flash chromatography (eluent ethyl acetate: n-hexane = 1: 1) gave oily 3- (2-methoxy-3-pyridylthio)-.
2.6 g of 1,2,4-triazole was obtained.

¹ H-NMR (CDCl ₃ ) δ: 4.0 (3H, s), 6.8-8.1 (3H,
m), 8.2 (1H, S)

2) 2.5 g of 3- (2-methoxy-3-pyridylthio) -1,2,4-triazole was added to 1 part of acetone.
Dissolve in 0 ml, diethylcarbamic acid chloride 1.
5 ml and 2 g of potassium carbonate are added, and the mixture is reacted at room temperature for 1 hour and at 40 ° C. for 3 hours. Potassium carbonate was filtered off and acetone was distilled off to obtain a brown oily substance. Purification by silica gel flash chromatography (eluent ethyl acetate: n-hexane = 1: 1) gave oily 1- (N, N-diethylcarbamyl) -3- (2-methoxy-3-pyridylthio) -1. 3.1 g of 2,2,4-triazole was obtained.

¹ H-NMR (CDCl ₃ ) δ: 1.2 (6H, t), 3.5 (4H, q), 4.0
(3H, s), 6.9 (1H, m), 7.8-8.2
(2H, m), 8.8 (1H, s)

Example 2 1- (N, N-diethylcarbamyl) -3- (2-meth)
Xy-3-pyridylsulfonyl) -1,2,4-tria
Production of sol (Compound No. 2)

2.0 g of 1- (N, N-diethylcarbamyl) -3- (2-methoxy-3-pyridylthio) -1,2,4-triazole obtained in Example 1 was dissolved in 50 ml of chloroform, M-chloroperbenzoic acid at room temperature 3.
Oxidize at 8 g. After reacting for 2 hours at room temperature, the reaction solution is washed with saturated sodium hydrogen carbonate solution and dried over sodium sulfate. When the chloroform was distilled off, a solid residue remained ,. Purification by silica gel flash chromatography (eluent ethyl acetate: n-hexane = 1: 1) gave crystalline 1- (N, N-diethylcarbamyl) -3.
-(2-Methoxy-3-pyridylsulfonyl) -1,
2.2 g of 2,4-triazole was obtained.

Melting point: 120 to 121 ° C.

Example 3 1- (N, N-diethylcarbamyl) -3- [2-
(2,2,2-trifluoroethoxy) -3-pyridyl
Of thio] -1,2,4-triazole (Compound No. 3)
Manufacturing

1) 2- (2,2,2-trifluoroethoxy) -3-aminopyridine 3.8 g, water 200 ml,
4 ml of concentrated hydrochloric acid was placed in a four-diameter flask, and a solution of 1.4 g of sodium nitrite in 10 ml of water was added with stirring at 0 ° C. at an internal temperature not exceeding 5 ° C. to synthesize a corresponding diazonium salt.

2) 3 g of 3-mercapto-1,2,4-triazole, 100 ml of water in a 500 ml four-diameter flask,
Add 2.2 g of caustic potash, keep the internal temperature at 5 ° C or lower with stirring, and add the diazonium salt obtained in 1) above. After stirring until the internal temperature reached room temperature, the mixture was neutralized with concentrated hydrochloric acid, and the resulting oily matter was extracted with ethyl acetate, dried and concentrated to give 3-
A crude product of [2- (2,2,2-trifluoroethoxy) -3-pyridylthio] -1,2,4-triazole was obtained. Recrystallization from n-hexane-ethyl acetate (1: 1) yielded 3- [2- (2,2,2-trifluoroethoxy) -3-pyridylthio] -1,2, melting point 86-87 ° C.
3.8 g of 4-triazole was obtained.

3) 3- [2-obtained by the method of 2) above
(2,2,2-trifluoroethoxy) -3-pyridylthio] -1,2,4-triazole (5.5 g), diethylcarbamic acid chloride (2.7 g) and pyridine (50 ml) were placed in a 200 ml four-necked flask and the temperature was adjusted to 2 at 70 ° C. Stir for hours. After that, pyridine was distilled off, and 100 ml each of water and chloroform was added to the residue to separate the layers. The chloroform layer was dried over anhydrous sodium sulfate, and 1- (N, N-diethylcarbamyl) -3- [2- (2,2,2-trifluoroethoxy) -3-pyridylthio] -1,2,4- Triazole was obtained.

¹ H = NMR (CDCl ₃ ) δ: 1.2 (6H, t), 3.5 (4H, q), 4.8
(2H, q), 6.9-7.1 (1H, m), 7.8-
8.2 (2H, m), 8.7 (1H, s)

Example 4 1- (N, N-diethylcarbamyl) -3- [2-
(2,2,2-trifluoroethoxy) -3-pyridyl
Sulfonyl] -1,2,4-triazole (compound number
4) Manufacturing

1- (N, N-) obtained in 3) of Example 3
Diethylcarbamyl) -3- [2- (2,2,2-trifluoroethoxy-3-pyridylthio] -1,2,4-
The chloroform solution of triazole is cooled to 0 ° C., and 6.8 g of m-chloroperbenzoic acid is added with stirring. 3 at room temperature
After stirring for an hour, the mixture was washed 3 times with 100 ml of 30% aqueous sodium hydrogen carbonate, and the chloroform layer was dried and concentrated to give 1- (N,
N-diethylcarbamyl) -3- [2- (2,2,2-
Trifluoroethoxy) -3-pyridylsulfonyl]-
6.4 g of crude crystals of 1,2,4-triazole were obtained. Recrystallization from ethyl acetate gave the desired product having a melting point of 85 to 86 ° C.

Example 5 1- (N, N-diethylcarbamyl) -3- [4-methyi]
Ru-2- (2,2,2-trifluoroethoxy) -3-
Pyridylthio] -1,2,4-triazole (Compound No.
Production of No. 5)

3- [4-methyl-2- (2,2,2-) obtained in the same manner as in Example 1 1) or Example 3 2)
Trifluoroethoxy) -3-pyridylthio] -1,
A catalytic amount of N, N-dimethylaminopyridine was added to a solution of 0.3 g of 2,4-triazole dissolved in 5 ml of anhydrous pyridine. To this solution was added 0.25 ml of diethylcarbamic acid chloride at room temperature, the mixture was stirred overnight at room temperature, poured into water, extracted with ether, washed with water, and dried over anhydrous sodium sulfate. After the desiccant was filtered off, the solvent was distilled off under reduced pressure,
Oily 1- (N, N-diethylcarbamyl) -3- [4
-Methyl-2- (2,2,2-trifluoroethoxy-
3-Pyridylthio] -1,2,4-triazole 0.3
g was obtained.

¹ H-NMR (CDCl ₃ ) δ: 1.1 (6H, t), 2.5 (3H, s), 3.5
(4H, q), 4.7 (2H, q), 7.0 (1H,
d), 8.0 (1H, d), 8.7 (1H, s)

Example 6 1- (N, N-diethylcarbamyl) -3- [4-methy !
Ru-2- (2,2,2-trifluoroethoxy) -3-
Pyridylsulfonyl] -1,2,4-triazole
Production of compound number 6)

1- (N, N-diethylcarbamyl) -3- [4-methyl-2- (2,2,2) obtained in Example 5
-Trifluoroethoxy) -3-pyridylthio] -1,
To a solution of 0.3 g of 2,4-triazole in 5 ml of chloroform was added m-chloroperbenzoic acid 0.4 at room temperature.
3 g was added. The solution was refluxed for one and a half hours and then left in the refrigerator overnight. Add to sodium bisulfite aqueous solution and add 3
After stirring for 0 minutes, the mixture was extracted with ether. It was washed with sodium bicarbonate-water and water in this order and dried over anhydrous sodium sulfate. After the desiccant was filtered off, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel flash chromatography (eluent: ethyl acetate: n-hexane = 1: 1) to give an oily 1-
(N, N-diethylcarbamyl) -3- [4-methyl-
2- (2,2,2-trifluoroethoxy) -3-pyridylsulfonyl] -1,2,4-triazole 0.16
g was obtained.

¹ H-NMR (CDCl ₃ ) δ: 1.3 (6H, t), 2.9 (3H, s), 3.6
(4H, q), 4.7 (2H, q), 6.9 (1H,
d), 8.1 (1H, d), 8.8 (1H, s)

The compounds of the present invention synthesized in the same manner are shown in Table 1 below.

[Table 1]

Next, the herbicidal effect of the compound of the present invention will be described with reference to test examples.

Test Example 1 A 1/5000 ares Wagner pot was filled with paddy soil, water was added to perform scavenging, and seeds of rice, millet, broad-leaved weeds (Azena, Kishigusa) and firefly were sowed, and then the two-leaf stage 1 rice plant (3 strains 1 strain) was transplanted. As for the treatment of the drug, 3 days after sowing of the weeds and transplantation of rice, a predetermined amount of the granule obtained according to Formulation Example 1 below was hand-sprinkled on the water surface. Management and growth were performed in a greenhouse, and 4 weeks after the chemical treatment, the herbicidal effect and the phytotoxicity of rice were investigated. The results are shown in Table 2.

The numerical values in the table show the herbicidal effect and the phytotoxicity of the rice trial product, and are specifically as follows.

Numerical value Herbicidal effect Crop phytotoxicity 5 100% control (weed amount 0%) Death 4 80% control (weed amount 20%) Harmful damage 3 60% control (weed amount 40%) Poisoning 2 40% control (weed amount) 60%) Small harm 1 20% control (weed amount 80%) Minor harm 0 0% control (weed amount 100%) Harmless

[0054]

[Table 2]

Test Example 2 A 1/5000 arena Wagner pot was filled with field soil, soybean and cotton seeds were sown, and the soil was covered with field soil containing weed seeds. After the soil was covered with the chemicals, a predetermined amount of the wettable powder obtained according to Formulation Example 2 below was diluted with 5 ml of water per pot and sprayed onto the soil surface. The management and growth were performed in a greenhouse, and the herbicidal effect and the phytotoxicity of soybean and cotton were investigated 4 weeks after the chemical treatment. The results are shown in Table 3.

The numerical values in the table are the same as those shown in Test Example 1.

[0057]

[Table 3]

Test Example 3 A 1/5000 arena Wagner pot was filled with field soil, soybean and cotton seeds were sown, and soil was covered with field soil containing weed seeds. After the soil was covered with the chemicals, the prescribed amount of the emulsion obtained in accordance with Formulation Example 3 described below was applied at a rate of 5 per 1 pot.
It was diluted with ml of water and sprayed on the soil surface. The management and growth were performed in a greenhouse, and the herbicidal effect and the phytotoxicity of soybean and cotton were investigated 4 weeks after the chemical treatment. As the comparative compound, the following 2-pyridyl compounds (Comparative Compound 1 and Comparative Compound 2) described in JP-A-1-106883 were used. The results are shown in Table 4.

Comparative Compound 1: 1- (N, N-diethylcarbamyl)-
3- (3-chloro-5-trifluoromethyl-2-pyridylthio) -1,2,4-triazole Comparative compound 2: 1- (N, N-diethylcarbamyl)-
3- (5-chloro-2-pyridylsulfonyl) -1,
2,4-triazole

The numerical values in the table are the same as those shown in Test Example 1.

[0061]

[Table 4]

Next, formulation examples of the compound of the present invention will be shown.

Formulation Example 1 Compound No. 2 0.5 parts by weight Sodium lignin sulfonate 2 parts by weight Bentonite 30 parts by weight Talc 67.5 parts by weight These ingredients were mixed well until uniform and granulated to give granules. obtain.

Formulation Example 2 Compound No. 3 50 parts by weight Sodium alkyl sulphate 2.5 parts by weight Polyoxyethylene alkyl 2.5 parts by weight Phenyl ether clay 45 parts by weight These components were mixed well until uniform and pulverized. To obtain a wettable powder.

Formulation Example 3 Compound No. 4 20 parts by weight Alkylbenzene sulfonate 3 parts by weight Polyoxyethylene alkyl 10 parts by weight Phenyl ether xylol 67 parts by weight These components are well mixed and dissolved to obtain an emulsion. ..

[0066]

The compound of the present invention can be prepared by introducing a 3-pyridylsulfonyl (sulfinyl or thio) group into a conventional triazole compound and by introducing a specific substituent into the 3-pyridyl group. It can be expected to have a higher herbicidal effect than that of the above compound, and particularly exhibits excellent herbicidal activity in field treatment. In addition, it is a useful herbicide with very little chemical damage to crops.

Claims (1)

[Claims] 1. A compound represented by the general formula (I): (In the formula, R ₁ and R ₂ are the same or different and represent a lower alkyl group. X and Y are the same or different and represent a lower alkoxy group, a halo lower alkoxy group or a lower alkyl group, and n is 0 to 2 , And p and q are the same or different and each represents an integer of 0 to 4, provided that the sum of p and q is in the range of 1 to 4).