JPS5939880A - Carbamolytriazole derivative, its preparation and herbicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The carbamoyltriazole derivative of formula I (n is 0-2; R1 and R2 are lower alkyl or together form a lower alkylene forming a ring; X is halogen or lower alkyl; when R3 is H, m is 1-3, and when R3 is lower alkyl, m is 0-3). EXAMPLE:1-(Diethylcarbamoyl)-3-(2-chlorobenzylthio)-1,2,4-triazole. USE:Herbicide effective to the gramineous weeds such as barnyard grass, broad- leaved weeds such as false pimpernel, and cypraceous weeds such as slender spikerush, and having no phytotoxicity to rice plant. It is also effective to the gramineous weeds such as oat, broad-leaved weeds such as cockleburm etc. in plowed land. PROCESS:The compound of formula I can be prepared by reacting the triazole derivative of formula II with the carbamoyl halide of formula III (Y is halogen) in a solvent such as benzene in the presence of a base such as sodium hydroxide, preferably at 0-150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein n is θ,/or 2, R1 and R2 are lower alkyl groups, and R1 and R2 form a ring, a lower alkylene group,
X represents a halogen atom or lower atom or 3, and when R3 is a lower alkyl group, 1m represents /1.2 or 3.

] The present invention relates to a carbamoyltriazole nm form shown by (hereinafter referred to as the compound of the present invention), a method for producing the same, and a herbicide containing the same as an active ingredient.

The compound of the present invention has a herbicidal effect on grass weeds such as Japanese millet grass, broad-leaved weeds such as 7 xena, common chickweed, and chickweed, and cyperaceous weeds such as pine cabbage and bulrush in the treatment of soil and foliage in paddy fields, and is also effective against rice. It does not show any drug damage that would cause problems.

However, in the pre-emergence soil mixing treatment of upland fields, grass weeds such as oats, black grass, and grasshopper, broad-leaved grasses such as Japanese fir, and yellow nut sedge (W
It has a herbicidal effect against Cyperaceae weeds such as Cyperus esculentus ).

Certain carbamoyltriazole derivatives, such as i
-(diethylcarbamoyl)-J-benzylsulfonyl-/, :2. ll-triazole (comparative control compound A)
Its usefulness as an active ingredient in herbicides is described in US Pat. No. 1.2g0g3/. However, as shown in Test Examples/2 and 2 below, contrary to the fact that this compound exhibits phytotoxicity to rice, the compound of the present invention does not exhibit phytotoxicity to rice. Formula [wherein, R3, X, m and n have the same meanings as above. ] Triazole derivatives represented by the general formula /~/6.2 equivalents [wherein Y represents a halogen atom, R1 and Rg are iI
! and the carbamoyl halide represented by O] in a solvent, θ, ? ~t
, s"k-Tm can be produced by reacting in the presence of a base. Examples of solvents include hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as chloroform, methylene chloride, and C + lobenzene. ethers such as diethyl ether and tetrahydrofuran, ketones such as 7setone and methyl ethyl ketone, pyridine, triethylamine, N
, N-diethylaniline, etc., acetonitrile, N,N-dimethylformamide P, dimethyl sulfoxide, water, etc. Bases include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, bicarbonate. Examples include inorganic bases such as sodium, organic bases such as pyridine, triethylamine, N,N-diethylaniline, etc.The reaction temperature is from the freezing point to around the boiling point of the solvent.

Preferably, the temperature is from 0°C to 750°C, and the reaction time is about 70 minutes to 100 minutes.After the reaction is completed, the usual treatment is carried out, and if necessary, recrystallization, column chromatography, etc. The triazole visiting conductor represented by the general formula (n) can be produced according to the method described in the above-mentioned US Patent No. 4T2Zg37.
It can also be produced by oxidizing the compound of the present invention represented by the following formulas: /T or -, meaning the same as 0] using an oxidizing agent.

As the oxidizing agent, peroxide water ice, m-chloroperbenzoic acid,
# aromatic peracids, peracetic acid, aliphatic peracids such as perfluoroacetic acid, and the like. A solvent does not necessarily need to be used, but if it is used, it depends on the type of oxidizing agent.1 For example, water, glacial acetic acid, acetone, etc. are used for peroxide water ice, and halogenated oxidizers such as chloroform, methylene chloride, etc. are used for aromatic peracids. 1 gM of hydrocarbon water, ethers such as diethyl ether and dioxane are preferred, and the reaction temperature ranges from θ°G to 706°C, and the reaction time ranges from 70 minutes to 2
It takes about 1 hour. To complete the reaction, a conventional edge treatment is performed, and if necessary, the compound is purified by recrystallization, column chromatography, etc. The compounds of the present invention include the following.

Next, a formulation example of the compound of the present invention is shown.Production Example 7 Production of compound (1) of the present invention Melt it,
After adding diethylcarbamoyl chloride/36y and leaving it at room temperature for 7 hours, add water Jθml and mix with chloroform/3;0 ml! Extracted twice. Chloroform layer / normal hydrochloric acid / jθrint! [Rinse and add water θθml
After washing seven times with , it was dried over magnesium sulfate, and the solvent was distilled off to give /-(diethylcarbamoyl)-3-(,2-chlorobenzylthio)-/, 2. '+-) Riazorko, 3
Obtained θ. IHy rate 77% Melting point 79~0°C Production example - Production of the compound of the present invention (//)/-(diethylcarbamoyl)-3-(,2-methylbenzylthio)-/, 2. '%-1-rifsol3.
θGuar was boiled in a chloroform/θθIK bath, metachloroperbenzoic acid (70%) Nige 7Y was added over 5 minutes at 5 to 70°C, and the mixture was further stirred at 5 to 70°C for 1 hour. After that, it was washed once with an aqueous potassium carbonate solution, dried over magnesium sulfate, and the solvent was distilled off to give /-(diethylcarbamoyl)-3-(,2-methylbenzylsulfinyl)-/
, , 2.4t-) lyazole 3. θθノ was obtained. Yield: 2j Melt: 7j - 76°C Production Example 3 Compound of the present invention (
/4t) production/-(diethylcarbamoyl)-J-(
2゜j-dimethylbenzylthio)-/, 2.41-triazolej-J was bathed in chloroform/()θ layer 1, and metachloroperbenzoic acid (content 7θ) g was added to 5 to 2θ
The mixture was added at 70°C for 70 minutes and then left at room temperature for 70 hours. Washed three times with an aqueous potassium carbonate solution, dried over magnesium sulfate, and distilled off the solvent to give /-(diethylcarbamoyl)-3-2. J-dimethylbenzylsulfonyl)
-/,,2. Dartrifsol j4.2θ1 was obtained.

Yield 2/chi Melting point/~g2°C Example 3-(2,A
-dichlorobenzylthio)-/, 2. Production of gut triazole 3-mercapto-/, co, dart triazole, θSy
was dissolved in methanol 23; at, and a solution of hydroxide, 2sy, dissolved in 26 ml of water was added, and β,
1 was added and stirred at room temperature for 3 hours. The reaction solution was poured into water and extracted with chloroform. After drying the chloroform layer over magnesium sulfate, the solvent was distilled off to give 3-(2,A-dichlorobenzylthio)-/, 2.9-triazole/θ. /3
I got y. Yield 27% Melting point //, 5-,! ;〜／／Otsu0
．． Table 7 shows some of the compounds of the invention that can be prepared by methods such as 5°.

When using the compound of the present invention with the general formula in Table 1 as an active ingredient of a herbicide,
It is usually mixed with a solid phase, a liquid carrier, a surfactant, and other formulation auxiliaries to formulate emulsions, wettable powders, suspensions, granules, etc.

These preparations contain the compound of the present invention as an active ingredient in an amount of 1 to 90% by weight, preferably -0.

Solid extrusions include fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide, and liquid carriers. Examples include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, and acetonitrile. , water, etc. 6 (Surfactants used for emulsification, dispersion, wet spreading, etc.) Ionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether [non-block copolymer, SOJ Levitan Illi 1
There are nonionic surfactants such as 17j acid ester and polyoxysorbitan 11 acid ester. Seisai 1j
Examples of the auxiliary agents include lignin sulfonate, alginate, polyvinyl alcohol, arapiano gum, CMC (carboxymethyl cellulose), and pAp (M isopropyl phosphate).

Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 1. The part indicates the multiphase sound 1i'r-.

Formulation example/Compound of the present invention (1) s 0 parts, lignin sulphate II; l
3 parts of calcium tonate, λ part of sodium lauryl sulfate, and synthetic hydrated silicon oxide lIs sound [1 Thoroughly grind and mix to form a hydrating powder. r - get.

Formulation example: Compound of the present invention (,?),? 79 parts of polyoxyethylene styryl phenyl ether, 2 parts of calcium dodecylbenzenesulfonate, 30 parts of xylene and 29 parts of isophoro were thoroughly mixed to obtain an emulsion gold.

Formulation Example 3 Compound of the present invention (Isu.2@I, synthetic hydrated silicon oxide/
1 part, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 4j parts of kaolin clay were thoroughly ground and mixed, water was added and the mixture was thoroughly kneaded, followed by granulation and drying to obtain granules.

Formulation Example: 2.5 parts of the compound of the present invention (1?), 3 parts of polyoxyethylene sorbitan mono-1-noate, 3 parts of CMC,
2. Mix 27 parts of water and wet-mill the self-effective ingredient BL (with a degree of less than Sμ) to obtain a suspension (a). It is used to control weeds by diluting it with a water sea lion, mixing it with the soil surface and applying it to the foliage.It can also be mixed with other herbicides. By using it, it is expected that the control effect will be enhanced.Furthermore, it can be used in combination with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners, etc.

The compound of the present invention can be used as an active ingredient of a herbicide for paddy fields, fields, orchards, lawns, pastures, forests, or non-agricultural lands, and the fields where it is applied.

Although it varies depending on the type of preparation, the crops to which it is applied, the weeds to which it is applied, and the weather conditions, it usually contains 0.0% as an active ingredient per area. ,! ; g −,200g, preferably J
g to 100 g. In particular, the compound of the present invention is applied to emulsions, wettable powders, suspensions, etc. by diluting it with water of /I to /Q per /A, and applying it as it is without diluting it to granules etc. Test examples show that the compound is useful as an active ingredient in herbicides. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are the following -92.
The herbicidal efficacy of the weeds and crops shown in the table was determined by visually observing the degree of germination and growth inhibition of the test plants during the field test, and by testing the compound '!r-(Jt). If there is no difference or not at all (5, there is almost no difference), mark it as "(ノ)", and if the test plant dies or its sprouting is inhibited by light and sound, mark it as "S", from 0 to S. Rated on a 6-point scale: 0, /, J, ,
7, II, and j.

Test example / Paddy field soil treatment test A circular plastic pot with a diameter of CTn and a depth of 2 crh was filled with rice paddy soil, and rice grass, broad-leaved weeds (Azeena, Azalea, Chickweed), firefly, yuzu tongue, etc.
I mixed it into the floor of ~,2e,,,. After flooding the rice field and making it into a paddy field, rice plants at the two-leaf stage were transplanted and grown in a greenhouse.
One day later (in the early stages of the growth of the famous weed), the prescribed amount of the test compound prepared as a water lubrication according to Formulation Example νC was diluted with S milliliter of water per pot and dropped onto the water surface. , were grown in a greenhouse for 20 days, and their herbicidal efficacy was investigated.The results are shown in Table 3.O Table 3: Gune Test Example: Paddy field foliage treatment test//5oooaWagner pot with paddy soil-+ Stuffed Japanese millet, broad-leaved weeds (Azeena, Kikashigusa, Chickweed), Japanese name of firefly, L- and °npai overwintering buds/
It was mixed to a depth of ~, 2-. After flooding the paddy fields, tubers of Urikawa were buried in the VC to a depth of ~2 cln, and the rice was completely transferred to ML at the J stage. In the greenhouse (
7,77 days later (Chinoi Nubie, 2nd period, -fne 3~t
Leaf I7. lI) DC? ! i;・l j9'i/
A test compound made into an aquarium according to the method was diluted with 10 milliliters of water per predetermined amount of water per bot, and the solution was dropped onto the water surface.

It was grown in a greenhouse, and 20 days after the drop, its herbicidal efficacy was investigated. The results are shown in Table 9.

1.15 Test Example 3 Upland Soil Treatment Test Area J J
Sow seeds such as sugar beet, cotton, soybean, Japanese radish, and strawberry.
Tubers of S. s) were sprinkled with Yuyu and raised in a turret. After this, the test compound made into a hydrating agent according to Hayabusa's formulation example / per full /
It was diluted with θ liters of water and sprayed on the soil surface using a small proboscising device to mix the surface layer of the soil to a depth of nrr'. Thereafter, they were grown in a greenhouse for -0 days and their herbicidal efficacy was investigated. The results are shown in Table 5.

・Procedure Masasuke Sode (addressed to himself) Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case 1937 Patent 1 No. 1486062, Name of the invention Carbamoyl triazole conductor, its manufacturing method, and its active ingredient Herbicide 3: Relationship with the person making the amendment Patent applicant address 5-15 Kitahama, Higashi-ku, Osaka Name (
209) Sumitomo Chemical Co., Ltd. Representative Hijikata
Take 4, agent address 6, 154 Kitahama 5-chome, Tsuka-ku, Osaka n Contents of amendment (1) In the specification, page 5, lines 6 to 7, it says ``m represents 8.-1'' Correct it to [m represents 0, l, 2, or 8.].

(2) On page 6, line 9 of the same page, ``Replace 1 below with ``Postscript-''.
Correct it to 1.

(3) Page 6, line 1, 1-No chemical damage to rice is shown. 7 for 1 rice does not show any harmful chemical damage. Correct it as j.

(4) In the last line of page 11, replace [-Formulation example] with “
"Manufacturing example" is corrected.

(5) On page 12, line '1 from the bottom, the phrase [-Production of uninvented compound (1)] is corrected to read, "Production 1 of the compound of the present invention (8)."

(6) On page 13, line 6 of the same page, 1.Production of the present invention compound (14)-1 is corrected to ``Production of the present invention compound (11).'' 1 or more

Claims (1)

[Claims] A class alkyl group or l (a lower alkylene group in which 1 and R2 form a ring, X is a halogen atom or a lower alkyl group, R
3 represents a hydrogen atom or a lower alkyl group. However, when ridge 3 is a hydrogen atom, m represents /1.2 or 3, and when horse is a lower alkyl group, m represents θ, /, 2 or 3. ] A carbamoyltriazole derivative represented by (2) In General Formula 1, n represents θ and/or 3, X represents a halogen atom or a lower alkyl group, and R3 represents a hydrogen atom or a lower alkyl group. However, when R3 is a hydrogen atom, 1m represents 1.2 or 3, and when R3 is a lower alkyl group, 1m is θ,
/1,. Represents 2 or 3. ] 4 triazole rlr represented by the general formula [In the formula, R 1 (2 is a lower alkyl group or a lower alkylene group formed by R1 and R2 to form a ring, and Y represents a halogen atom)] A carbamoyltriazole complex represented by the general formula [wherein R1, R2, R31,'<, n and m have the same meanings as above]. (3) General formula [wherein R1 and B2 are lower alkyl groups or R1 and R2
and a lower alkylene group forming a ring, X represents a halogen atom or a lower alkyl group, and R3 represents a hydrogen atom or a lower alkyl group. However, when R3 is a hydrogen atom, m represents /1.2 or 3, and when R3 is a lower alkyl group, m represents θ, /, 2 or 3. ] Represents a general formula meaning characterized by oxidizing a carbamoyltriazole derivative represented by the following, where n is/or co. ] A method for producing a carbamoyltriazole derivative.・、. , -ri: [wherein n is θ,/or), R1 and R2 are a lower fulkyl group or an alkylene group formed by R□ and R2 to form a ring, X is a halogen atom or a lower fulkyl group, m is θ, / 1.2
or 3, R3, and when B3 is a lower furkyl group, 1m represents θ, /, co, or 3; ] A herbicide characterized by containing a carbamoyltriazole derivative represented by the following as an active ingredient.