JPH02233665A - Novel triazole-based compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R1 and R2 are lower alkyl, cycloalkyl or alkinyl; A is expressed by formula II or formula III, etc. (R3 is H or lower alkoxy; p is 2-5); n is 0-2; with a proviso that compound expressed by formula IV (R is lower alkyl or halogen) is omitted]. EXAMPLE:1-(diethylcarbamoyl)-3-(2,4-6-trimethylphenyl sulfonyl)-1,2-4-triazole. USE:Used as a herbicide. Especially exhibits excellent weeding effect with a small dosage to Echinochloa oryzicola Vasing. of strong weed in paddy field and useful for Cyperaceous weed, or broad-leaf weeds such as Monochoria vaginalis Presl or Lindernia procumbens Philcox, also. PREPARATION:A compound expressed by formula V is reacted with a compound expressed by formula VI (Y is halogen) preferably in the presence of deoxidizer (e.g., NaOH) in a solvent such as benzene at 0-100 deg.C and oxidized, as necessary, to afford the compound expressed by formula I.

Description

Detailed Description of the Invention: X represents a lower alkyl group, a hydroxyl group, a lower alkyl group substituted with a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, a phenoxy group, a benzyl group, α - represents a hydroxybenzyl group, halogen or nitro group, and R3 represents a hydrogen atom or a lower alkoxy group. Cocoon represents the number 1, 2.3 or 4, where n is 0
．． Represents the number 1 or 2, p. q is 2 and 3.4 respectively
Or represents the number 5. However, the following general formula (wherein R represents a lower alkyl group or a halogen atom.
》Excluding compounds represented by 》 It concerns a new triazole compound represented by . (Prior Art) The fact that some triazole compounds have activity as herbicides is known, for example, as described in West German Patent No. 2132.
No. 618 specification, U.S. Patent No. 4,280,831 specification,
JP-A-59-39880 and JP-A-60-
It is described in Publication No. 100561. (Problems to be Solved by the Invention) However, conventional triazole herbicides cause phytotoxicity to crops, and sufficient herbicidal effects cannot be obtained unless used in large quantities. There was a need for the development of triazole compounds. Therefore, the present invention shows almost no chemical damage to crops, and is effective against Japanese millet, which is a highly harmful weed in paddy fields.
It exhibits excellent herbicidal effects at low doses, and is also effective against other herbivores,
The purpose of the present invention is to provide a triazole compound that exhibits a strong herbicidal action against broad-leaved weeds such as azalea, sycamore, and cyperus, and against weeds of the Cyperaceae family, such as firefly and cyperus.

(Means for Solving the Problems) The compound of the present invention is a novel compound represented by the above formula I and having a structure different from that of conventionally known triazole compounds in the part of symbol A. The compound of the present invention can be produced, for example, as follows. One-shell formula r as starting material
I: (wherein A and n represent the above-mentioned meanings. However, the following general formula (wherein, R represents a lower alkyl group or a halogen atom, and n represents the number of 0, 1 or 2) Excluding the compound represented by the following formula III: n (wherein, Y, R, and R2 represent the above-mentioned meanings).
By reacting the compound and oxidizing it with a suitable oxidizing agent if necessary, a compound of the general formula (2) can be obtained.

In the above reaction, the target compound (■) is a sulfinyl compound (n=1) or a sulfonyl compound (n
= 2), a compound of formula (1) in which the S moiety is similarly oxidized may be used as a starting material, or alternatively, a compound of formula I in which S is not oxidized may be prepared first, and if necessary, this may be prepared. may be oxidized. The step of reacting oxidized or unoxidized compound (1) with compound (2) is performed by reacting 1 to 2 equivalents of compound H in an appropriate solvent in the presence of a deoxidizing agent of 1 equivalent or more, preferably 1 to 2 equivalents. , preferably 1 to 1.2 equivalents of compound (2) are reacted. The reaction temperature is 0 to 100°C, preferably 20°C.
~70°C is suitable. Here, deoxidizing agents include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and sodium hydride; organic bases such as triethylamine and pyridine; and solvents include carbonized bases such as benzene, toluene, and xylene. Hydrogen type, halogenated hydrocarbon type such as methylene chloride and chloroform, ether type such as diethyl ether, tetrahydrofuran, dioxane, ketone type such as acetone and methyl ethyl ketone,
Other solvents include acetic acid ethyl ester, acetonitrile, dimethylformamide, pyridine, dimethyl sulfoxide, water, etc., or a suitable mixed solvent thereof. Further, the oxidation step may be performed, for example, in a suitable solvent.
This can be done by oxidizing with an oxidizing agent. Examples of the oxidizing agent used here include inorganic oxidizing agents such as hydrogen peroxide, potassium permanganate, and chromic acid, and organic oxidizing agents such as peracetic acid and chloroperbenzoic acid. Examples of solvents that can be used include methylene chloride, chloroform, acetone, acetic acid, water, etc., and mixed solvents thereof. The appropriate reaction temperature is 0 to 50°C, but depending on the type of solvent or the progress of the reaction, heating or cooling may be used as appropriate. The starting compounds of the formula (■), except those in which A represents an unsubstituted phenyl group, nitrophenyl group and dinitrophenyl group,
As such, it is a new compound and forms part of the present invention.
To produce this compound (1), for example, a compound of the formula: A-Z (wherein A represents the above meaning and Z represents a halogen atom) is added to a compound of the following formula (2). It can be obtained by reacting in an appropriate solvent. Also, compound A-NH
It can also be obtained by dissolving 2 in concentrated hydrochloric acid, adding N a N O 2 to use it as a diazonium salt solution, and adding compound 2 to the solution. 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.

The reaction temperature is 20 to 20 when using compounds A-Z.
0°C, preferably 50-150°C, and the compound A-N
When using H2, the temperature is 0 to 100°C, preferably 0 to 100°C.
The temperature is 70℃. The present invention will be explained in more detail with reference to Examples below. The following Example 1 is an example of a method for producing the starting compound of the present invention represented by formula (1).

3.89 Kasuichi chloraniline with concentrated hydrochloric acid from 5 companies and 5g
Dissolve the solution in crushed ice, and while cooling to 0°C, gradually add a solution of 2.2 g of sodium nitrite in 5 ml' of water at a rate not exceeding 4°C. This solution was mixed with 4.5 g of 3-mercap}-1.
2. Add the potassium salt of 4-triazole in 30 ml of water at 40-50°C and stir for an additional 30 minutes at the same temperature. After cooling, the product is extracted with chloroform, washed with water, and dried over magnesium sulfate. The solvent was distilled off, and the remaining oil was purified by silica gel chromatography (elution solvent: chloroform) to obtain 4.3 g of an oil. Yield: 68
%. ' H N M R (C D C fa)
δ: 7.2 to 7.6 (4H, m), 8.8 (IH, s)
．． 12.0 (1M, br.s) Elemental analysis value (%): CIHICIF3N3S (Mill 211.6F4)
As C HN Calculated value 45.39 2.86 19.85 Analytical value 45.43 2.72 19.73 Examples 2 to 4 below are examples regarding the method for producing the final compound of the present invention. 3-(2,4,64-limethylphenylthio)-1.2.
4-}! Dissolve 2.29 g of J7sol in 50 ml, and add 1.2 g of jetyl rubamoyl chloride to this solution.
Drop 5g. After stirring at room temperature for 1 hour and at 70'C for 2 hours, pyridine was distilled off. The residue was extracted with chloroporum and dried over magnesium sulfate to give 1-(diethylrubamoyl)-3-(2,4.6-trimethylphenylthio)-1. 2. 4-} Obtain a crude product of lyazole. Cool this to O'C, add 4 g of --chloroperbenzoic acid, and stir at room temperature for 4 hours. The product was then diluted with 10
% potassium carbonate aqueous solution, drying over magnesium sulfate, distilling off the solvent, and recrystallizing from n-hexane-ethyl acetate.

Yield 2.69 (yield 75%) Melting point 113-4°C Elemental analysis value (%) C,,H. ．． N.O. S(MJ.:35
C IN calculated value as 0.44) 54.84 6.33. 15.99 Analysis value 54.60 6.42 16.02 As a starting compound, 3-(5,6.7.8-tetrahydride-1-
The desired product was obtained in the same manner as above, except that 2.3 g of naphthylthio)-1.2.4-}lyazole was used. Yield 2.6g (Yield 73z》Oil 'H-NMR (CDCI,): 1.11 (all,
t), 1.52-1.75 (4H, scales), 2.65-3
．． 05 (411, plow), 3.42 (4Lq). 7.15
~7.34 (2H, plow), 7.85~8.01 (ill
, theory), 8.71 (IH, s). Elemental analysis value ($) C. , H22N. 03S (MJ.:
3B2.45) To L Te C ON Calculated value 56.33 6.12 27.44 Analysis value 55,12 6.23 27.37 No. (3
0)) Production of 3-(2.4.5-}limethyl-6-methoxyphenylthio)-1.2.4-}riazole 2.5 g to 601 liters
Dissolve it in pyridine and use it! Add 1.49 g of lebamoyl chloride dropwise. 1 hour at room temperature
After stirring at 70° C. for 2 hours, pyridine is distilled off. The residue was extracted with chloroform, dried over magnesium sulfate, and
-(diethyl rubbermoyl)-3-(2,4.5
- }Limethyl-6-methoxyphenylthio》-1.
2. A crude product of 4-triazole is obtained. This is 0℃
Cool to room temperature, add 4g of chloroperbenzoic acid, and cool at room temperature for 2 hours.
The mixture was further stirred at 60° C. for 2 hours. The product is then washed with a 10% aqueous potassium carbonate solution, dried over magnesium sulfate, the solvent is distilled off, and then recrystallized from n-hexane-ethyl acetate. Yield: 2.6g (yield: 74%) Melting point:
138-9℃. Elemental analysis value (%): CI? H24N. Synthesized from the starting material corresponding to C I1N calculated value 5° 8.60 6.94 16.08 as 02S (8lll348.471). The compound of the present invention can be used as a herbicide for weeding rice fields, fields, orchards, and non-agricultural land. The timing of its use can be selected as appropriate, such as before sowing, at the time of sowing, at the time of transplanting, seedling stage, and growing season, and the method of use can be appropriately selected from among water surface treatment, soil treatment, soil mixing treatment, foliage treatment, etc. Can be done. When actually using the compound of the present invention,
To make it more convenient to use, it can be mixed with various solid and liquid carriers used in the preparation of general agricultural chemicals to produce wettable powders, emulsions, oils, powders, granules, flowables, etc. Furthermore, auxiliary agents such as dispersants, diluents, emulsifiers, spreading agents, wetting agents, adsorbents, thickeners, antifoaming agents, and antifreeze agents may be added to the drug. The carrier referred to herein may be either solid or liquid, or a combination thereof. Examples include talc, clay, bentonite, kaolin, diatomaceous earth, calcium carbonate, charcoal, starch, gum arabic, water, alcohol, kerosene, naphtha, xylene, cyclohexane,
Examples include methylnaphthalene, benzene, acetone, dimethylformamide, glycol ether, and N-methylpyrrolidone. Examples of the adjuvant include polyoxyethylene alkyl phenyl 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, alkyl dimethyl betaine, alkylaminoethyl glycine,
Examples include polyglycol sulfate, alkylamine sulfonic acid, isoprobyl phosphate, carboxymethyl cellulose, polyvinyl alcohol, hydroxypropyl cellulose, ethylene glycol, and xanthan gum. In formulating the formulation, the mixing ratio of the monster of the present invention can be freely selected within the range of 0.05 to 951% by weight, but preferably 1 to 951% by weight.
70% and carrier from 1 to 99%, preferably from 40 to 99%.
Preference is given to formulations containing 90% and 0 to 20%, preferably 1 to 7% of adjuvants. Furthermore, by mixing it with other fungicides, herbicides, plant growth regulators, insecticides, acaricides, and other agricultural chemicals and fertilizers, a wider range of effects can be expected. When actually using the compound of the present invention, it is up to those skilled in the art to appropriately select the amount to be used depending on the time of use, weather conditions, method of use, dosage form, place of use, target weeds, target crops, etc. Obviously, the dosage used is generally 5 to 500 g per 10 ares of the compound of the present invention;
Preferably it is 10 to 200 g per 10 are. Next, the usefulness of the compounds of the present invention as herbicides will be explained using test examples. Test Example 1 A 1/5,000 are Wagner pot was filled with paddy soil (planting soil), water was added, and the rice was plowed.
After sowing seeds of Aspergillus japonica, broad-leaved weeds (Azaena, Abundum, Kikashigusa, and Chickweed) and Firefly, and placing tubers of Cyperus japonica on the surface, 3 rice plants at the 2-leaf stage were planted at a depth of 2 c rings.

The chemical treatment was carried out by manually scattering a predetermined amount of granules obtained in accordance with Preparation Example 1 below on the water surface at the time of germination of wild plants. The plants were managed and grown in a greenhouse, and four weeks after the chemical treatment, the herbicidal effect and chemical damage to rice were investigated. The results are shown in Table 2. The numerical values in the table indicate the herbicidal effect and the chemical damage to the test crops, and are specifically as follows. Numerical value Herbicidal effect Crop damage 5 10
0% control (weed amount 0%) Death 4 80% control《
Weed amount 20%》 Severe damage 3 60% control (weed amount 4
0%) Chusho 2 40% control (weed amount 60%) Slight damage 1 20% control <m weed amount 80%> Slight damage 0.
0°% control (100% weed amount) Harmless In addition, the following compounds in Table 2 were used as control compounds for comparison: Comparison I (see U.S. Pat. No. 4,280,831) Comparison ■ (see U.S. Pat. No. 4,280,831) Comparison■ (Refer to JP-A-59-39880) Comparison-■ (Refer to JP-A-59-39880) Comparison V (Refer to JP-A-48-77030) Test Example 2 Paddy field in 1/5,000 are Wagner pot Fill with soil (planting soil), add water, and plow through the rice.
Seeds of Aspera sativa and broad-leaved weeds (Azaena, Apnome, Lamina, and Lythrum) were sown, and 3 rice plants at the 2-leaf stage were planted at a depth of 2 cm. The water depth was set to 3c. The drug treatment was carried out at the 2nd leaf stage to the 2.5th leaf stage of the wild grass using the formulation PA described below.
A predetermined amount of the permanent agent obtained according to 2 was weighed, diluted with 5 parts of water per pot, and sprayed on the water surface. Management and cultivation are carried out in a greenhouse, and 1g of pharmaceuticals! After 4 weeks, the herbicidal effect and the damage to rice were investigated. The results are shown in Table 3. The meanings of the numerical values in the table and the comparative compounds are as follows: Test Example 1
This is the same as shown in . Table 3 Table 4 Test Example 3 Fill a 1/5,000 are Wagner pot with field soil (planting soil) and sow wheat and soybean seeds to a depth of 2 cm with field soil containing weed seeds. It was covered with soil. Immediately thereafter, a predetermined amount of the emulsion obtained according to Formulation Example 3 below was weighed, diluted with 5 liters of water per pot, and sprayed on the soil surface. The plants were managed and grown in a greenhouse, and the herbicidal effects and chemical damage to wheat and soybean were investigated 4 weeks after the chemical treatment. The results are shown in Table 4. The numerical values in the table are the same as those shown in Test Example 1.

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

Formulation Example 1 1 Compound No. 1 1.5 parts by weight Sodium lignin sulfonate 2 parts by weight Bentonyl 30 parts by weight Talc 66.5 parts by weight These ingredients are mixed well until homogeneous and granulated to make granules. obtain. Formulation Example 2 Kokoro Compound No. 2 50 parts by weight Sodium alkyl sulfate 2.5 parts by weight Clay
45 parts by weight These ingredients are thoroughly mixed until homogeneous and pulverized to obtain a wettable powder. Formulation Example 3u Compound No. 10 20 parts by weight Alkylbenzenesulfonate 3 parts by weight Xylene 67 parts by weight These components are thoroughly mixed until uniform and dissolved to obtain an emulsion.

Claims (1)

[Claims] 1. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, (In the formula, R_1 and R_2 are the same or different,
Represents a lower alkyl group, cycloalkyl group, or alkynyl group, and A is the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Represents the group ▼ where X is a lower alkyl group, a lower alkyl group substituted with a hydroxyl group, a cycloalkyl group, an alkoxy group, or an alkoxy group. It represents a carbonyl group, an alkylcarbonyl group, a phenoxy group, a benzyl group, an α-hydroxybenzyl group, a halogen or a nitro group, and R_3 represents a hydrogen atom or a lower alkoxy group. m represents the number 1, 2, 3 or 4, and n is 0, 1
or represents the number 2, and p and q represent the number 2, 3, 4, or 5, respectively. However, compounds represented by the following general formula ▲Mathematical formula, chemical formula, table, etc.▼ (wherein R represents a lower alkyl group or a halogen atom) are excluded. ) A triazole compound represented by 2. General formulas: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A is the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ represents the group where X is a lower alkyl group, a hydroxyl group, Represents a lower alkyl group substituted with a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, a phenoxy group, a benzyl group, an α-hydroxybenzyl group, or a halogen, and R_3 represents a hydrogen atom or a lower alkoxy group. And m represents the number 1, 2, 3 or 4, n is 0,
It represents the number 1 or 2, and p and q represent the number 2, 3, 4 or 5, respectively. However, a compound represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (wherein R represents a lower alkyl group or a halogen atom, and n represents a number of 0, 1 or 2) except. ) A triazole compound represented by 3. General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A and n represent the meanings given in claim 1.) The compound represented by the following formula: ▲ Mathematical formula , chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 represent the meanings given in claim 1, and Y represents a halogen.) The compounds shown in the formula are reacted, and if necessary, the product is General formulas characterized by oxidizing: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (wherein A, R_1, R_2 and n represent the meanings given in claim 1). ) A method for producing a triazole compound represented by 4. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A, n, R_1 and R_2 represent the meaning given in claim 1.) Triazole compound represented by A herbicide composition containing as an active ingredient.