JP3253727B2 - New triazole derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound of the general formula (I) useful as a pesticide:

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Wherein 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 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).

[0003]

2. Description of the Related Art It has been known that certain triazole compounds have a herbicidal effect (see US Pat.
280831, JP-A-59-39880, JP-A-60-100561, JP-A-61-1
78980, JP-A-63-14776, JP-A-1-121279, JP-A-2-1481, and JP-A-3-279368.

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

[0005]

These conventional triazole compounds have a certain effect as a paddy field herbicide, but have insufficient activity in field soil treatment.

The inventors of the present invention have developed a herbicide having a lower dose than these triazole compounds, exhibiting an excellent herbicidal effect especially in field soil treatment, and showing no phytotoxicity to crops. As a result of extensive studies, surprisingly, a series of triazole compounds is represented by the general formula (I) in which a 3-pyridyl group is introduced as a substituent of a sulfonyl group and the pyridyl group is substituted with a specific group. The present inventors have found that the compound exhibits an effect superior to the 2-pyridyl-based compound and other triazole-based compounds described in JP-A-1-106883, and have reached 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)

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

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Wherein L is a halogen atom, R ₁ and R
₂ has the same meaning as described above), and is optionally oxidized with an appropriate oxidizing agent.

In the above reaction, the desired compound represented by the general formula (I) is converted to 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 not oxidized may be produced as a starting material, and this may be oxidized as 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 preferably at least 1 equivalent to the compound represented by the general formula (II), and more preferably Is 1 in an appropriate solvent in the presence of 1-2 equivalents of a deoxidizing agent.
To 2 equivalents, preferably 1 to 1.2 equivalents, of the formula (II)
The compound represented by I) is reacted. Reaction temperature is 0-1
00 ° C, preferably 20-70 ° C, is suitable.

The solvents used herein include, for example, hexane, heptane, ligroin, petroleum ether and the like; aliphatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; chloroform, carbon tetrachloride, dichloroethane, and the like. 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,
Nitrates 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.

Examples of the deoxidizing agent 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 And alkali metal alkoxides such as sodium ethoxide.

The oxidation step can be performed, for example, by oxidizing with an oxidizing agent in a suitable solvent. Examples of the oxidizing agent used herein include inorganic oxidizing agents such as hydrogen peroxide, potassium permanganate, and chromic acid; and organic oxidizing agents such as peracetic acid and m-chloroperbenzoic acid. Examples of the solvent to be used include methylene chloride, chloroform, acetone, acetic acid, water and the like, or a mixed solvent thereof. The reaction temperature is suitably from 0 to 50 ° C., but 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 equation (IV)

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The compound represented by the general formula (V)

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Wherein Z is a halogen atom, X, Y, p
And q have the same meanings as described above)) in a suitable solvent.

In addition, the general formula (VI)

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(Wherein X, Y, p and q have the same meanings as described above) are dissolved in concentrated hydrochloric acid,
It can also be obtained by adding NO ₂ and using it as a diazonium salt solution, into which a compound represented by the formula (IV) is added.

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

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

When the compound of the present invention is used as an active ingredient of a herbicide, it is mixed with commonly used carriers and other pharmaceutical auxiliaries to prepare emulsions, wettable powders, oils, powders, flowables and granules. And the like.

The carriers which can be usually used herein include, for example, talc, clay, bentonite, kaolin, diatomaceous earth, calcium carbonate, charcoal, starch, acacia, water, alcohol, kerosene, naphtha, xylene,
Cyclohexane, methylnaphthalene, benzene, acetone, dimethylformamide, glycol ether, N-
Methylpyrrolidone and the like.

Examples of the auxiliary include polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan monooleate, ethylene oxide propylene oxide copolymer, lignin sulfonate, sorbitan ester, soaps, sulfated oils, alkyl sulfate esters Salts, petroleum sulfonates, dioctyl sulfosuccinate salts, alkyl benzene sulfonic acids, aliphatic amine salts, quaternary ammonium salts, alkyl pyridinium salts, alkyl dimethyl betaine, alkyl amino ethyl glycine, polyglycol sulfate, alkyl amine sulfonic acid, Examples include isopropyl phosphate, carboxymethyl cellulose, polyvinyl alcohol, hydroxypropyl cellulose, ethylene glycol, xanthan gum and the like.

In the formulation, the mixing ratio can be freely selected generally from 0.05 to 95% by weight of the compound of the present invention.
70%, the carrier is 5-99%, preferably 70-99%
Formulations containing 90%, adjuvants 0-20%, preferably 1-7% are preferred. In addition, a wider range of effects can be expected by mixing and using other fungicides, herbicides, plant growth regulators, pesticides, pesticides such as acaricides, fertilizers, and the like.

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

[0027]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

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

1) A solution containing 3.2 g of concentrated amino acid (3.2 g, 0.026 M) of 3-amino-2-methoxypyridine 5
A 0 ml aqueous solution is diazotized at −5 ° C. with an aqueous solution of 1.8 g of NaNO ₂ . 5 containing 3 g of 3-mercapto-1,2,4-triazole (0.05 M) and 6.6 g of potassium hydroxide
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 kept at 5 ° C. or lower, and the reaction is further carried out 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 oil is extracted with ethyl acetate. The ethyl acetate layer was washed once with water, dried over sodium sulfate, and then 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 were 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 acetone 1
0 ml, and dissolved in diethylcarbamic acid chloride.
5 ml and 2 g of potassium carbonate are added, and the mixture is reacted at room temperature for 1 hour and further at 40 ° C. for 3 hours. The potassium carbonate was removed by filtration, and the acetone was distilled off to obtain a brown oily substance. Purification by silica gel flash chromatography (eluent: ethyl acetate: n-hexane = 1: 1) yielded oily 1- (N, N-diethylcarbamyl) -3- (2-methoxy-3-pyridylthio) -1. 3.1 g of 2,, 4-triazole were 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-methoxy
(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. 2. m-chloroperbenzoic acid at room temperature
Oxidize with 8 g. After reacting at room temperature for 2 hours, the reaction solution is washed with a saturated sodium hydrogen carbonate solution and dried over sodium sulfate. After the chloroform was distilled off, a solid residue remained. Purification by flash chromatography on silica gel (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 were obtained.

Melting point: 120-121 ° C.

[0036]Example 3 1- (N, N-diethylcarbamyl) -3- [2-
(2,2,2-trifluoroethoxy) -3-pyridyl
Thio] -1,2,4-triazole (Compound No. 3)
Manufacture

1) 3.8 g of 2- (2,2,2-trifluoroethoxy) -3-aminopyridine, 200 ml of water,
4 ml of concentrated hydrochloric acid was placed in a four-necked flask, and a solution of 1.4 g of sodium nitrite in 10 ml of water was added at 0 ° C. under stirring at a speed such that the internal temperature did not exceed 5 ° C. to synthesize a corresponding diazonium salt.

2) 3 g of 3-mercapto-1,2,4-triazole, 100 ml of water,
2.2 g of potassium hydroxide is added, and the diazonium salt obtained in 1) is added while maintaining the internal temperature at 5 ° C. or lower while stirring. The mixture was stirred until the internal temperature reached room temperature, neutralized with concentrated hydrochloric acid, and the resulting oil 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) gave 3- [2- (2,2,2-trifluoroethoxy) -3-pyridylthio] -1,2,2 with a melting point of 86-87 ° C.
3.8 g of 4-triazole were obtained.

3) 3- [2- obtained by the method of the above 2)
(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 heated at 70 ° C. Stirred for hours. Thereafter, pyridine was distilled off, and water and chloroform (100 ml each) were added to the residue, followed by liquid separation. 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- The 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)

[0041]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-
A 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 three times with 100 ml of 30% aqueous sodium bicarbonate, 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 1,2,4-triazole crystals were obtained. Recrystallization from ethyl acetate gave the desired product having a melting point of 85-86 ° C.

Example 5 1- (N, N-diethylcarbamyl) -3- [4-methyl
Ru-2- (2,2,2-trifluoroethoxy) -3-
Pyridylthio] -1,2,4-triazole (compound number
No. 5) Manufacturing

3- [4-methyl-2- (2,2,2-) obtained in the same manner as 1) of Example 1 or 2) of Example 3
Trifluoroethoxy) -3-pyridylthio] -1,
A catalytic amount of N, N-dimethylaminopyridine was added to a solution of 0.3 g of 2,4-triazole in 5 ml of anhydrous pyridine. 0.25 ml of diethylcarbamic acid chloride was added to this solution at room temperature, stirred overnight at room temperature, poured into water, extracted with ether, washed with water, and dried over anhydrous sodium sulfate. After the desiccant is filtered off, the solvent is distilled off under reduced pressure.
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-methyl
Ru-2- (2,2,2-trifluoroethoxy) -3-
Pyridylsulfonyl] -1,2,4-triazole
Production of compound No. 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 0.4 ml of m-chloroperbenzoic acid at room temperature.
3 g were added. The solution was refluxed for one and a half hours and then left in a refrigerator overnight. Add to the aqueous sodium bisulfite solution and add
After stirring for 0 minutes, the mixture was extracted with ether. The extract was washed with sodium bicarbonate-water and water in that order, and dried over anhydrous sodium sulfate. After the desiccant was removed by filtration, 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 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 below in Table 1.

[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 paddy field soil was filled in a 1/5000 arel Wagner pot, water was added for padding, and seeds of red snapper, oak, broadleaf weeds (Azena, Kikasigusa) and firefly were sown, and then the second leaf stage Was transplanted with one strain (three strains). For the treatment of the drug, a predetermined amount of the granules obtained according to Preparation Example 1 described later was hand-sprayed on the water surface three days after seeding of the weeds and transplantation of the rice. Management and rearing were performed in a greenhouse, and after 4 weeks of chemical treatment, the herbicidal effect and the phytotoxicity of rice were investigated. Table 2 shows the results.

The numerical values in the table show the herbicidal effect and the phytotoxicity of the rice test crops, and are as follows.

Numerical value Herbicidal effect Crop harm 5 100% control (weed amount 0%) Withering 4 80% control (weed amount 20%) Serious harm 360% control (weed amount 40%) Medium damage 2 40% control (weed amount) 60%) Minor harm 1 20% control (weed amount 80%) Minor harm 0 0% control (weed amount 100%) Harmless

[0054]

[Table 2]

Test Example 2 Field soil was filled in a 1/5000 arel Wagner pot, soybean and cotton seeds were sown, and covered with field soil containing weed seeds. For the treatment of the chemical, after covering the soil, a predetermined amount of the wettable powder obtained according to Formulation Example 2 described below was diluted with 5 ml of water per pot and sprayed on the soil surface. Management and rearing were performed in a greenhouse, and after 4 weeks of chemical treatment, the herbicidal effect and the phytotoxicity of soybean cotton were investigated. Table 3 shows the results.

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

[0057]

[Table 3]

Test Example 3 Field soil was filled in a 1/5000 are Wagner pot, soybean and cotton seeds were sown, and covered with field soil containing weed seeds. After covering the soil, a predetermined amount of the emulsion obtained in accordance with Formulation Example 3 described below was added to the medicine in an amount of 5 per pot.
It was diluted in ml of water and sprayed on the soil surface. Management and rearing were performed in a greenhouse, and after 4 weeks of chemical treatment, the herbicidal effect and the phytotoxicity of soybean cotton were investigated. The following 2-pyridyl-based compounds (Comparative Compound 1 and Comparative Compound 2) described in JP-A-1-106883 were used as comparative compounds. Table 4 shows the results.

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

[0061]

[Table 4]

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

Formulation Example 1 Compound No. 2 0.5 parts by weight Sodium ligninsulfonate 2 parts by weight Bentonite 30 parts by weight Talc 67.5 parts by weight These components are thoroughly mixed until uniform, granulated, and granulated. obtain.

Formulation Example 2 Compound No. 3 50 parts by weight Sodium alkyl sulfate 2.5 parts by weight Polyoxyethylene alkyl 2.5 parts by weight Phenyl ether clay 45 parts by weight These components are thoroughly mixed until uniform, and finely pulverized. To obtain a wettable powder.

Formulation Example 3 Compound No. 4 20 parts by weight Alkyl benzene sulfonate 3 parts by weight Polyoxyethylene alkyl 10 parts by weight Phenyl ether xylol 67 parts by weight These components are thoroughly mixed until uniform, 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 that the herbicidal effect is superior to the compound of the formula (1), and exhibits excellent herbicidal activity especially in field treatment. It is also a useful herbicide with very little phytotoxicity to crops.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) C07D 401/12 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula (I) (Wherein, 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 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.)