JPH02152965A - Biscarbamate derivative and herbicide containing the same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A biscarbamate derivative expressed by formula I (Y<1> and Y<2> are O or S; R<1> is H or 1-6C alkyl; R<2> is H, 1-6C alkyl or 1-6C alkenyl; R<3> is 1-6C alkoxy or 1-6C alkylthio). EXAMPLE:3-Aminophenyl N-(6-methoxy-2-puridyl)-N-methylthiocarbamate. USE:A herbicide having high herbicidal activity and safety for crops. PREPARATION:For example, a compound expressed by formula II is reacted with a compound expressed by formula III (X<1> is halogen) to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel biscarbamate derivative and a herbicide containing the same as an active ingredient.

[Prior Art] The herbicidal activity of biscarbamate derivatives has been known, for example, fenmedipham is disclosed in Farm Chemicals Handbook 88, C172.

However, conventional biscarbamate derivatives do not necessarily have sufficient herbicidal activity or have insufficient selectivity between crops and miscellaneous crops, and therefore pose a problem in terms of safety for crops.

[Problems to be Solved by the Invention] The purpose of the present invention is to provide a new compound that has high herbicidal activity and is highly safe for crops when used as a herbicide, and a new herbicide containing the same as an active ingredient. That's true.

[Means for Solving the Problems] As a result of intensive research, the present inventors discovered that a novel biscarbamate derivative has extremely excellent herbicidal activity and selectivity, and completed the present invention.

That is, the present invention relates to the general formula [13 (where YY'' represents an oxygen atom or a sulfur atom, YY may be the same or different, and R2
represents a hydrogen atom, a C-C alkyl group, or a C-C alkenyl group, and R3 represents a C-CG alkoxy group or a C-C alkoxy group or
-C6 alkylthio group. ) (hereinafter referred to as the compound of the present invention) is provided.

The present invention also provides a herbicide containing the compound of the present invention represented by the above general formula CI] as an active ingredient.

The present invention provides a novel compound having excellent herbicidal activity and safety as a herbicide.

In addition, the J'3 remover of the present invention containing the compound of the present invention as an active ingredient, as will become clear from the examples described below,
It has a high moth removal activity that can accurately exterminate various types of moths, and is extremely safe to use on various crops, especially rice, wheat, corn, soybeans, etc. .

As mentioned above, the compound of the present invention is represented by the above general formula [L]. General formula [I] Width, Y Y2 represents an oxygen atom or a sulfur atom, and YY may be the same or different. R1 represents a hydrogen atom or a C-C6 alkyl group, R is a hydrogen atom, c, -
represents a c6 alkyl group or a C1-C6 alkenyl group,
R represents a C1-06 alkoxy group or a C-C6 alkylthio group.

■ Among these examples, preferred examples of compounds of general formula [11] include R1 being a methyl group, ethyl group, propyl group, or butyl group, and R2 being a methyl group, ethyl group, propyl group, butyl group, or Examples include compounds in which the allyl group is -9° and R3 is a methoxy group, ethoxy group, propoxy group, butoxy group, thiomethoxy group, or thioethoxy group.

Table 1 shows preferred specific examples of the present invention, but the compounds of the present invention are not limited thereto.

The above-mentioned compound of the present invention can be produced by various methods, and for example, it can be produced based on the following reaction formula.

[VI] [■] General formula CI] Or, [11] CI [[] General formula [I] [■] [IX] Or, [TV] General formula [11 [] - General formula [11(4)] Above In the reaction formula, general formula [■] general formula [III] general formula [I
V] General formula EV] General formula [■] General formula [■]
General formula [■], and general formula [Yl Y2 in IXl
R1R and R3 are the same as the general formula [1],
General formula Cm] General formula [■C] and general formula [■Xl in J represents a halogen atom. Preferably, the halogen atom is a chlorine atom or a bromine atom.

The above reaction is carried out in a solvent or without a solvent, in the presence of a base/1:
or in the absence of a base, preferably from O'C to 15
0'C1, more preferably 20'C to 100'C
This can be carried out by reacting for several minutes to 48 hours.

Solvents used in the reaction include ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as ethyl ether, tetrahydrofuran, and dioxane; chlorobenzene, chloroform, carbon tetrachloride, dichloroethane, and dichloromethane. halogenated hydrocarbons such as; tertiary amines such as triethylamine, pyridine, and dimethylaniline; and polar solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, and hexamethyltriamide phosphate.

In addition, triethylamine,
Pyridine, 1,8-diazabicyclo[5゜4, (l]-
Tertiary amines such as 7-undecene and dimethylaniline;
Alkali hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth hydroxides such as calcium hydroxide; alkali carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; and hydrogen such as sodium hydride. Examples include chemical metals and the like.

In reaction (1), the reagent melon used in the reaction (1) is usually one equivalent of the compound of the general formula [I] per equivalent of the compound of the general formula [n].
The amount of the compound I[] is 1 to 10 equivalents, and the base is 1 to 10 equivalents, and in reaction (2), the compound of general formula [V] is usually used for 1 equivalent of the compound of general formula [IV]. 1 equivalent to 10 equivalents, the base is 1 equivalent to 10 equivalents, and in reaction (3), usually 1 equivalent of the compound of the general formula [■] to 1 equivalent of the compound of the general formula [VI], 1 equivalent of the melon to 10 equivalents, The base is 1 to 10 equivalents, and in reaction (4), the compound of general formula [IX] is usually 1 to 10 equivalents per 1 equivalent of the compound of general formula [■], and the base is 1 to 10 equivalents. It is.

The raw material for the compound of the present invention can be obtained by a known method.

For example, the 3-aminophenyl carbamate derivative represented by the general formula [11] can be obtained by reacting the 3-nitrophenyl lyroformate derivative with the aminopyridine derivative 9 under the base layer and further reducing the 3-nitrophenyl carbamate derivative. 11
I can do that.

The compound of the present invention containing the compound of the present invention as an active acid component: f
, the agent has herbicidal activity against various miscellaneous f.
It has excellent herbicidal activity, especially against broad-leaved weeds in upland areas. Such miscellaneous plants include, for example, bluetail, purslane, Japanese thornweed, sentangusa, pigweed, gourd, koakaza, whiteweed, Japanese knotweed, giant knotweed, chickweed,
Examples include shepherd's shepherd, Japanese occidentalis, white-bellied morning glory, American occidentalis, Ebisu-sugusa, Maruva morning glory, Japanese algae, Japanese algae, Hotokenoza, plantain, Japanese sardine, American golden deer, Oxalis, Japanese occidentalis, buckwheat snail, Japanese puffer, Greater aceratops, Japanese mugwort, Japanese serpentine, Japanese cypress, etc. be able to. In addition, the pest control agent of the present invention has excellent control over various weeds that are problematic in rice fields, such as weeds such as Japanese millet, Japanese azalea, Japanese chickweed, Japanese chickweed, Japanese cypress, Japanese cypress, bulrush, and other broad-leaved weeds. It has a powerful effect. Furthermore, the herbicide of the present invention is highly safe, causing almost no phytotoxicity to crops such as corn, wheat, soybeans, and rice.

The herbicide of the present invention is prepared by adding an appropriate amount of one or more compounds of the present invention represented by the general formula [1F] to a pesticide formulation, using a commonly used pesticide adjuvant. It is used in the form of formulations, such as emulsions, wettable powders, oils, granules, and powders, which are prepared by the method described above. When these various preparations are actually used,
It can be used as is or diluted with water to a predetermined concentration.

Examples of pesticide adjuvants include diluents, surfactants, stabilizers, solidifying agents, aerosol sprays, synergists, bulking agents, solid carriers, potency extenders, dispersion stabilizers, etc. . Examples of diluents include water, hydrocarbons, alcohols,
Examples include ethers, alcohol ethers, ketones, esters, amides, sulfoxides, kerosene, mineral oil, and the like.

In addition, as fillers and solid 11λ substances, inorganic powders such as quicklime, magnesium lime, gypsum, calcium carbonate,
Finish, perlite, pumice, diatom, alumina, zeolite, clay minerals (talc, vermiculite, kaolinite), synthetic resin powder (e.g. phenolic resin, carbon resin,
(vinyl chloride resin), etc. Examples of surfactants include anionic surfactants (e.g. alkyl sulfates, aryl sulfonic acids, succinates, polyethylene glycol alkyl aryl ether sulfates), cationic surfactants (e.g. alkyl amines,
Examples include polyoxyethylene alkyl amines), nonionic surfactants (for example, polyoxyethylene glycol ethers, polyoxyethylene glycol esters, polyhydric alcohol esters), and amphoteric surfactants.

The herbicide of the present invention can be used in the same manner as ordinary herbicides. For example, for paddy field weeds, the herbicide of the present invention may be used before or immediately after the weeds emerge after transplanting active pipes of paddy rice. It can be used for soil treatment. Also,
The herbicide of the present invention can be used to treat soil or foliage before the germination of upland weeds or at the early stage of well-planting.

The amount of the herbicide of the present invention to be applied can be appropriately selected depending on the method of application, purpose, timing of application, and weed growth situation, but it is usually 10 g to 1 g of active ingredient per hectare.
0 kg, preferably 50 g to 51 c g.

The compound of the present invention can be used in combination with other herbicides in order to improve its effectiveness as a herbicide, and in some cases,
A synergistic effect can also be expected.

Examples include phenoxy herbicides such as 2,4-dichlorophenoxyacetic acid: 2-methyl-4-chlorophenoxyacetic acid; 2-methyl-4-chlorophenoxyacetic acid (including esters and salts); -dichlorophenyl-4'-nitrophenyl ether, 2,4.6-dolychlorophenyl-4'-nitrophenyl ether; 2-chloro-4-trifluoromethylphenyl-3'-ethoxy-4'-di Diphenyl ether-based herbicides such as trophenyl ether; 2,4-dichlorophenyl-4′-nitro-3°-methoxyphenyl ether; 2,4-dichlorophenyl-3′-methoxycarbonyl-4′-nitrophenyl ether triazine herbicides such as 2-chloro-4,6-pisethylamino-1,3.5-triazine; 2-methylthio-4,6-pisisobrobylamino-1,3.5-triazine; 3 - (3,4-dichlorophenyl)-1,,1-dimethylurea; 3- (
3,4-dichlorophenyl)-methoxy-1-methylurea, 1-(2,2-dimethylbenzyl)-3-ph
Urea-based herbicides such as dilurea, isopropyl-N-(3
-chlorophenyl)carbamate; methyl-N-(3,
Carbamate herbicides such as 4-dichlorophenyl) carbamate; thiol carbamate herbicides such as 5-(4-chlorobenzyl)-N,N-diethylthiol carbamate; S-ethyl-N,N-hexamethylenethiol carbamate; , 3,4-dichloropropionanilide;
N-methoxymethyl-2,6-diethyl-α-chloroacetanilide; 2-chloro-2° 6°-diethyl-
N-(butoxymethyl)-acetanilide; 2-chloro-2',6'-diethyl-N(n-propoxyethyl)-acetanilide; N-chloroacetyl-N-(2
, 6-ethylphenyl)-glycine ethyl ester, etc., 5-bromo-3-secondary-
Butyl-6-methyluracil; 3-cyclohexyl-5
゜Uracil herbicides such as 6-trimethylene uracil, 1
, pyridinium chlorine herbicides such as 1°-dimethyl-4,4°-bispyridinium chloride, N,N-bis(
phosphonomethyl)-glycine, 0-ethyl-o-(2-
Nitro-5-methylphenyl)-N-secondary-butylphosphoroamidothioate, 5-(2-methyl-1-
5-(2-methyl-1-piperidylcarbonylmethyl)0.0-diphenyldithiophosphate, α, α.

Toluidine-based debt release agents such as α-trifluoro-2,6-sinitro N, N-dipropyl-p-toluidine, 5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1゜3.4-Oxadiazilin-2-one; 3-isopropyl-IH-2,1,3-benzothiadiazin-(4)-3H-one-2,2-dioxide, α-(β-naphthoxy)- Propionanilide, 4-(2,4-dichlorobenzoyl)-1,3-
Examples include, but are not limited to, dimethylpyrazol-5-yl p-toluenesulfonate.

[Examples] The present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Production of 3-methoxycarbamoylphenyl N-(6-medoxy 2-pyridyl)-N-methylthiocarbamate (Compound No. 1) 15 g of m-nitrophenylchlorothioformate was dissolved in 100 ml of acetonitrile and 2-methylamino- 6
- 10 g of medoxyviridine and 11.3 g of potassium carbonate were added and reacted at room temperature for 3 hours, followed by refluxing for 1 hour. After cooling, insoluble matter was filtered, the solvent of the filtrate was distilled off, diluted hydrochloric acid was added, and the mixture was extracted with dichloromethane. The solvent was distilled off to obtain 3-nitrophenyl N-(6-medoxy-2-pyridyl)-N-methylthiocarbamate.

After adding 3.12 g of 3-nitrophenyl N-(6-medoxy-2-pyridyl)-N-methylthiocarbamate to a mixed solution of 15 ml of concentrated hydrochloric acid and 10 ml of ethanol, 7.0 g of tin dichloride dihydrate was added to 10 ml of ethanol. A solution dissolved in was added dropwise at room temperature, and then reacted at 40° C. for 3 hours. After the reaction was completed, an aqueous sodium hydroxide solution was added and the mixture was extracted with chloroform. 1F separated by column chromatography 1.9 g of 3-aminophenyl N-(6-medoxy-2-pyridyl)-N-methylthiocarbamate
I got it.

'H-NMR (solvent 2 CDC1 unit=δppm)3.
70 (s, 311), 3.90 (s, 311), 3.9
0-4.40 (m, 2!l) 0.40-7.50 (m,
711) IR1710cm-1 After adding 0.82 g of 3-aminophenyl N-(6-medoxy-2-pyridyl)-N-methylthiocarbamate and 0.33 g of methyl chlorocarbonate to 2 omt of acetonitrile, and further adding 0.49 g of potassium carbonate. The mixture was heated to reflux for 2 hours while stirring. After cooling the reaction mixture, insoluble matter was filtered, and the filtrate was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 0.50 g of the target product.

Melting point 107-108°C 'H-NMR (solvent: CDC1 unit = δppm) 3
, [15 (S, 811), 3.95 (S, 311) 8.
40-7.00 (m, 7H) Elemental analysis (%): Calculated value as C16H1□N304S C: 55.32. I14.93. N;12. Q9 actual value C; 55.12. It; 4.93. N; 12.4
3 Representative examples of the compounds of the present invention obtained by the same method and their physical properties are shown in Table 2.

Example 2 (Emulsion) 5 parts by weight of Compound No. 1 of the present invention, 75 parts by weight of xylene, and 20 parts by weight of Tsurupol 2806B (trade name: manufactured by Toho Chemical Industry Co., Ltd.) were uniformly stirred and mixed to obtain an emulsion.

Example 3 (hydrating agent) 10 parts by weight of the compound No. 1 of the present invention, 86.5 parts by weight of Zikrite (trade name: Nijikrite Kagaku Mining Co., Ltd.), 221 Calgen NV-406 (trade name: Takemoto Yushi) 2 parts by weight of Discsol WA (trade name: 2nd-2 [manufactured by Gyoyakuhin Co., Ltd.])
1.5! A wettable powder is prepared by mixing and pulverizing parts of II.

Example 4 (granules) 10 parts by weight of compound number 1 of the present invention, 5Of bentonite
After mixing and pulverizing 35 parts by weight of Kunilite (trade name; manufactured by Kunimine Industries) and Sfff parts of Tsurupol 800A (trade name: manufactured by Toho Chemical Industry Co., Ltd.) as a surfactant, water was added and the mixture was stirred uniformly to form a powder with a diameter of 0. After extrusion through a .7 mm hole and drying, the mixture was cut into lengths of 1 to 2 nl m to obtain 10% granules.

Example 5 (Stem and Leaf Treatment Test) A 20 cm x 20 cm resinous pot was filled with field soil, seeds of crops such as wheat, corn, and soybean, and seeds of weeds shown in Table 3 were sown, and the pots were covered with soil to the extent that they were no longer visible. When the wildflowers reached the 1.5-2.0 leaf stage, the prescribed dosage of the wettable powder of the compound of the present invention prepared according to Example 4 was diluted with 20 ml of water per pot to make it uniform. Spread. At 14 rl II after the chemical spraying, the misinformation and growth condition of the crops were observed, and the results shown in Table 3 were obtained.

The removal effect was evaluated using a number from 0 to 5 as shown below. In addition, chemical damage to crops was also shown on the same basis as the herbicidal effect.

O... Suppression rate 0-9% 1... Weed suppression rate 10-29% 2...° Weed suppression rate 30-49% 3. Weed suppression rate 50-69% 4. G suppression rate 70-89 % 5...Weed suppression rate 90-100% Example 6 (soil treatment test on transplanted paddy rice) 10100
Fill the plastic pot of e with 111 soil of water in a plowed state, sow the seeds of the weeds shown in Table 4, and transplant 2 plants of 2-leaf rice (product 8 = Yamahoshi) per pot, about 20 Ill. It was managed in a submerged state. At the early stage of the emergence of the weeds shown in Table 4, a predetermined dose of a wettable powder of the compound of the present invention prepared according to Example 4 was diluted with 10 ml of water per pot and dropped onto the water surface. Then leave it in the greenhouse 12
, watering was done in a timely manner. On the 20th day after the chemical treatment, the removal effect and drug damage were investigated, and the results shown in Table 4 were obtained.

Evaluation of moth removal effect and evaluation of chemical damage were performed in the same manner as in Example 5.

Claims (2)

[Claims] (1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (However, Y^1 and Y^2 represent oxygen atoms or sulfur atoms, and Y^1 and Y^2 may be the same. They may be different. R^1 represents a hydrogen atom or C_1-C_6 alkyl, R^2 represents a hydrogen atom or a C_1-C_6 alkyl group or a C_1-C_6 alkenyl group, and R^3 represents C_
Indicates a 1-C_6 alkoxy group or a C_1-C_6 alkylthio group. ) Biscarbamate derivatives shown in (2) A herbicide containing a biscarbamate derivative represented by the general formula [I] according to claim 1 as an active ingredient.