JPH02152964A - Ureidocarbamate derivative and herbicide containing the same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A ureidocarbamate 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 1-6C alkylthio or 1-6C alkoxy; A is NR<3>R<4> (R<3> and R<4> are H, alkyl, alkylthio, alkoxy, alkenyl or aryl), formula II (l is 1-10) or formula III (Y<3> is O or S; m and n are 1-10)]. EXAMPLE:3-Aminophenyl N-(6-methoxy-2-pyridyl)-N-ethylthiocarbamate. USE:A herbicide, having high herbicidal activity and safety for crops and especially safely usable for rice plant, wheat, corn, soybean, etc. PREPARATION:For example, a compound expressed by formula IV is reacted with a compound expressed by formula V to afford the compound expressed by formula I.

Description

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

[Prior Art] The herbicidal activity of ureidocarbamate derivatives has been known, for example, Carbutyre-1 is shown in Farm Chemicals Handbook 88, C128.

However, conventional ureidocarbamate derivatives do not necessarily have sufficient herbicidal activity or have insufficient selectivity between crops and weeds, and therefore pose a problem in terms of safety when applied to crops.

[Problems to be Solved by the Invention] An object of the present invention is to provide a new compound that has high herbicidal activity and high safety for crops when used as a car remover, and a new herbicide containing the same as an active ingredient. It is about sharing.

[Means and effects for solving the problem] As a result of intensive research, the present inventors have found that a new ureido carbamate derivative has an extremely excellent ability to remove '+I:? It was discovered that the present invention has +'i property and selectivity, and the present invention has been completed.

In other words, the present invention is based on the general formula [I] (where YY represents an oxygen atom or a sulfur atom,
Y Y2 may be the same or different. R is hydrogen)
t'it T or CI-CB alkyl group, R represents C, -C6 alkylthio group or C, -C6 alkoxy group, A is NR3R' (however, R, R are hydrogen atoms, C1Ce furkyl U, C -C8 alkylthio group, C
1-C[B represents an alkoxy group, a C1-C6 alkenyl group, or an aryl group, R and R may be the same or different, and ■ represents an integer of 1 to 10. ) or (wherein, Y3 represents an oxygen atom or a sulfur atom, and Ill and 11 represent an integer of 1 to 10). ) and a ureido carbamate derivative (hereinafter referred to as the compound of the present invention) which is represented by the above general formula [1] as an active ingredient.

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

In addition, the herbicide of this invention containing the compound of the present invention as an active ingredient can be used in various miscellaneous herbicides, as will be made clear in the Examples described below. It is a highly active exterminator that can accurately exterminate S., and is effective against various crops, especially rice,
It is highly safe and can be used extremely safely for wheat, corn, and dice 9.

Preferred specific examples of the present invention are shown in Tables 1, 2, and 3, but the compounds of the present invention are not limited thereto.

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

[11] [m] General formula [ ] [] [] General formula [■] [VI] [■] - General formula [I] % formula % - General formula [11(4) General formula [tl] in the above reaction formula ] General formula [■] - General formula [IV] General formula [V] General formula [■] General formula [
■], y I in general formula [■] or general formula [IX]
y 2 RI R2 and A are the same as those in the general formula [1], and Xl in the general formula [■], the general formula [■], or the general formula [■] represents a halogen atom. Preferably, the halogen atom is a chlorine atom or a bromine atom r.

The above reaction is carried out in a solvent or without solvent with a base (i(1
0°C or in the absence of a base, preferably from 0°C to 1
．． This can be carried out by reacting at 50°C, more preferably from 20°C to 100°C for several minutes to 48 hours.

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

In addition, triethylamine, as a base used in the reaction,
Pyridine, 1,8-diazabicyclo[5゜4.01-7
-Quaternary amines such as undecene and dimethylaniline; alkali hydroxides such as sodium hydroxide and potassium hydroxide;
Examples include alkaline earth hydroxides such as calcium hydroxide; alkali carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; and metal hydrides such as sodium hydride.

In reaction (1゛), the amount of reagent used in the reaction (!ζ) is usually 1 to 10 equivalents of the compound of general formula [I11] per 1 equivalent of the compound of general formula [11], and 1 equivalent of the base. In reaction (2), usually 1 to 10 equivalents of the compound of general formula [V] and 1 to 10 equivalents of the base are used per 1'5 amounts of the compound of general formula [IV], and 10 equivalents of the base.
L′1 amount, and in reaction (3), the general formula C
Compound 1 of general formula [■] per equivalent of compound VII
The base is 10 equivalents from i j'j H, and in reaction (4), usually 1 equivalent to 10 equivalents of the compound of general formula [IX] is used for 1 equivalent of the compound of general formula [■]. , the base is 1711 to 10 equivalents.

The raw materials for the compounds of the present invention are obtained by -numerical methods.

For example, 3-aminophenyl represented by the general formula [■]
The carbamate derivative can be obtained by reacting a 3-nitrophenyl lyloloformate derivative with an aminopyridine derivative in the presence of a base, and further reducing the reaction mixture.

Further, the 3-isocyanatophenyl carbamate derivative represented by the general formula [IV] can be obtained by reacting the 3-aminophenyl carbamate derivative represented by the general formula [11] with phosgene or the like.

The moth remover of the present invention containing the compound of the present invention as a U-active ingredient,
It has a herbicidal activity against various weeds, but it has particularly excellent herbicidal activity against broad-leaved weeds in upland areas. Examples of such miscellaneous species include Aobiyu, Purslane, Onamomi,
Sendangusa, pigweed, red gourd, koakaza, whiteweed, Japanese knotweed, Japanese knotweed, chickweed, shepherd's purse, Japanese knotweed, white-breasted morning glory, American hornwort, Ebisugusa, Malva morning glory, Japanese dogweed,
Examples of the examples include walnuts, hotokenoza, plantain, ichibia, American cypress, oxalis, japonica, buckwheat, dog's lily, chinensis, wormwood, serpentine, and chinensis.

In addition, the herbicide of the present invention can be used to attack various weeds that are problematic in rice fields, such as Japanese millet, azalea, commonweed, chickweed, Japanese cypress, Japanese cypress, scallop, and other broad-leaved weeds. It has a moth removal 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 generally prepared by adding an appropriate amount of one or more compounds of the present invention represented by the above general formula [I] to a Q drug formulation using a pesticide adjuvant commonly used in this field. It is used in the form of formulations, such as emulsions, wettable powders, oils, granules, and powders, prepared by the methods currently in use. 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, ethers, alcohol ethers, ketones, esters, amides, sulfoxides, kerosene, mineral oil, and the like.

In addition, fillers and solid carriers include inorganic powders such as quicklime, magnesium lime, gypsum, calcium carbonate, finishing, perlite, pumice, diatom, °7' lumina, zeolite, clay minerals (talc, vermiculite, kaolinite). , plant powder (for example, starch, grain, glucose), synthetic resin powder (for example, phenol resin, carbon resin, vinyl chloride resin), and the like.

Furthermore, as surfactants, anionic surfactants (e.g. alkyl sulfates, arylsulfonic acids,
succinates, polyethylene glycol alkylaryl ether sulfates), cationic surfactants (e.g. alkylamines, polyoxyethylene alkyl amines), nonionic surfactants (e.g. polyoxyethylene glycol ethers, polyoxyethylene glycol esters) esters, polyhydric alcohol esters), amphoteric surfactants, and the like.

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 of paddy rice. It can be used for soil treatment. In addition, the herbicide of the present invention can be used to treat soil or foliage before the germination of upland weeds or during the 'JlJJ' stage.

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 the occurrence of grasshoppers, but it is usually 10g to 1% of the active ingredient per hectare.
0 kg, preferably 50 g to 5 kg.

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-chlorophenoxybutyric acid; 2-methyl-4-chlorophenoxyacetic acid (including esters and salts); 4-') Chlorphenyl-4'-nitrophenyl ether, 2,4.6-) Lichlorphenyl = 4°-nitrophenyl ether; 2-
Chlor-4-trifluoromethylphenyl-3'-ethoxy-4°-nitrophenyl ether; 2,4-dichlorophenyl-4'-ditro-3'-methoxyphenyl 7-yl; Diphenyl ether herbicides such as chlorphenyl-3゜-methoxycarbonyl-4'-nitrophenyl ether, 2-chloro-4,6-
Pisethylamino-1,3.5-triazine; 2-methylthio-4,6-pisisobrobylamino-1.3.5
- Triazine herbicides such as triazine, 3- (3,4
-dichlorophenyl)-1,1-dimethylurea; 3-
(3,4-dichlorophenyl)-methoxy-1-methylurea; 1-(2,2-dimethylbenzyl)-3-l
)-Urea herbicides such as tolylurea, isopropyl-N
-(3-chlorophenyl)carbamate; methyl-N-
Carbamate herbicides such as (3,4-dichlorophenyl)carbamate, 5-(4-chlorobenzyl)-N,N
-diethylthiol carbamate; S-ethyl-N,N
- Thiolcarbame-1-based moth removal agents such as hexamethylenethiol carbamate, 3,4-dichloropropionanilide; N-methoxymethyl-2,6-ethyl-α-
Chloracetanilide; 2-chloro-2°6-diethyl-N-(butoxymethyl)-acetanilide; 2
-Chlor-2'6'-diethyl-N(1-propoxyethyl)-acetanilide; acid anilide-based removal agent such as N-chloroacetyl-N-(2,6-ethylphenyl)-glycine ethyl ester, 5 -Brom-3-
Secondary-butyl-6-methyluracil; uracil-based herbicides such as 3-cyclohexyl-5,6-trimethyleneuracil, pyridinium chlorine-based herbicides such as 1,1゛-dimethyl-4,4゛-bispyridinium chloride agent, N
, N-bis(phosphonomethyl)-glycine, 〇-ethyl〇-(2-nitro-5-methylphenyl)-N-secondary-butylphosphoroamide thionyi 1., 5-(2
-Methyl-1-piperidylcarbonylmethyl) 0.0
Phosphorus herbicides such as -di-n-butyldithiophosphate-1-;5-(2-methyl-1-piperidylcarbonylmethyl)0.0-diphenyldithiophosphate, α, α.

Toluidine-based moth removal agents such as a-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-toluenesulfone-1.

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

Example 1 3-(N'N'-dimethylureido)phenyl
Preparation of N-(6-medoxy-2-pyridyl)-N-ethylthiocarbamate (Compound No. 1) 15 g of m-nitrophenylchlorothioformate was dissolved in 100 g of acetonitrile.
After adding 10 g of 2-ethylamino-6-medoxyviridine and 11.3 g of potassium carbonate to the solution and reacting at room temperature for 3 hours, the mixture was refluxed for 1 hour. After cooling, insoluble matter was filtered, the solvent of the filtrate was washed away, diluted hydrochloric acid was added, and the mixture was extracted with dichloromethane. The solvent was distilled off and 3-nitrophenyl N-(6-
Medoxy 2-pyridyl)-N-ethylthiocarbamate was obtained. This 3-nitrophenyl N-(6-medoxy-2-pyridyl)N-ethylthiocarbamate 2.4
g to a mixed solution of 15 ml of concentrated hydrochloric acid and 15 ml of ethanol, and then 7.5 g of tin chloride dihydrate was added to 15 ml of ethanol.
The solution dissolved in m1 was soaked at room temperature, and then reacted at 40°C for 3 hours. After the reaction was completed, the solvent was distilled off, the residue was made alkaline with sodium hydroxide, and then extracted with chloroform. Isolated by column chromatography, 3-aminophenyl N-(6-medoxy-2-pyridyl)-N
-2.0 g of ethyl thiocarbamate was obtained.

'H-NMR (solvent: CDCI unit: δppn
+) 1.30 (L, 311.J=711z), 3. [
15 (s, 211), 3.85 (s, 311) 4.30
(Q, 211.J=711z), 6.30-7.37(
1.20 g of 3-aminophenyl N-(6-medoxy-2-pyridyl)-N-ethylthiocarbamate thus obtained and 0 g of N,N-dimethylcarbamyl chloride.
．． After adding 62 g to 10 parts of acetonitrile and further adding 0.80 g of potassium carbonate, the mixture was heated under reflux for 16 hours with stirring.

After cooling the reaction mixture, insoluble materials were filtered, and the filtrate was removed under reduced pressure. The residue was purified by column chromatography to obtain 0.54 g of [i].

Melting point: 132-134°C 'H-NMR (mW; CDCI j11th position: δ
ppm) 1.25 (L, 311.J-711z), 2
．． 95 (s, Qll), 3.92 (s, 311) 4.1
2 (q, 211.J-711z), (i, 50-7.8
0(+n, 711) elemental bone t'i("0) ' C1
Calculated value as 8H22N40a S: C; 57.73.
II:5.92. N; 14.9G actual 71PI value C; 5
7.50. Il; 5.88. N;15.32 Example 2 U-(N'-methoxyN°-methylureido)phenyl Preparation of N-(6-medoxy2-pyridyl)-N-ethylthiocarbamate (Compound No. 2)'U-aminophenyl N-(6-medoxy-2-pyridyl)-N-ethylthiocarbamate 0°8'B was dissolved in 10 ml of toluene, 0.35 g of phosgene was added at room temperature, and the mixture was refluxed for 3 hours.

After cooling the JIL, the solvent was distilled off, and 0.5 g of 3-isocyanatophenyl N-(6-medoxy 2-pyridyl)-N-ethylthiocarbamate was removed. It's lI. This product is
This was confirmed by determining the Δ value of the infrared absorption spectrum.

3-isocyanatophenyl N- thus obtained
Add 0.85 g of (6-medoxy-2-pyridyl)-N-ethylcarbame-1 to 1[]...l of acetonitrile, 1.59 g of N-methyl N-methoxyamine hydrochloride, and 0.83 g of potassium carbonate. The reaction mixture was heated under reflux for an hour. After cooling the reaction mixture, insoluble materials were filtered, the filtrate was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 0.50 g of the desired product.

Melting point: 102-105°C 'H-NMR (Solvent: CDCl Unit: δppm
) 1.30 (L, 31. J=711z),
3.05 (s, 311), 3. (io(s, 311
).

3.85 (s, 311), 4-, 25 (q,
211. J-711z), 0.50-7.80
(s, 711z) Elemental analysis (%): Cl8H22
Calculated value as N404S C; 55.37. lI;5.
07. N; 14.34 actual Δ-1 value C, 55, 73, 1
+, 5. Q4. N: 14.1 (111th, Representative examples of the compounds of the present invention obtained by the Q method and their physical properties are shown in Tables 4 and 5.
and shown in Table 6.

Example 3 (Emulsion) 5 parts 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 Kagaku Nigyo) were uniformly stirred and mixed to prepare an emulsion.

Example 1% I4 (aqueous phase agent) 10 parts by weight of Compound No. 1 of the present invention, Zikrite (trade name: Nidikrite Kagaku Mining Co., Ltd.) 86.5%! fi amount part, 221 Calgen NV-406 (product name = 11 Honura Resin) 2
Parts of ifi and 1.5 parts by weight of Discsol WA (trade name: manufactured by Dai-Kogyo Seiyaku Co., Ltd.) were mixed and ground to obtain an aqueous phase agent.

Example 5 (granules) 10 parts by weight of compound number 1 of the present invention, bentonite 5 (l
fflfi L part, Kunilite (product name: Kunimine Kogyo) 3
5 parts by weight and Tsurupol 8 (10A) as a surfactant.
(Product name: Toho Chemical Industry Co., Ltd.) Mix 5 fff parts &amp;
After pulverizing, add water and stir evenly to make a powder with a diameter of 0゜7r.
After extrusion through n rn sieve holes and drying, the mixture was cut into lengths of 1 to 2 mm to obtain 10% granules.

Example 6 Stalk Treatment Test A 20 cm x 20 cm resinous pot was filled with field soil, and seeds of crops such as wheat, corn, and soybean, as well as seeds of the miscellaneous positions shown in Table 3, were sown, and the pots were covered with soil to the extent that they were no longer visible. When the number of wild animals reached 1.5 to 2.0, a predetermined amount of the aqueous phase agent of the compound of the present invention prepared according to Example 4 was diluted with 20 ml of water per bot and uniformly sprayed. . Thereafter, the plants were left in a greenhouse, and the stems and leaves were not watered for 3 days after the chemical treatment, and then watered at appropriate times. The growth conditions of weeds and crops were observed at 11 days after the chemical spraying, and the results shown in Table 7 were 7++.

The evaluation of the removal effect was expressed as a number from 0 to 5 as shown below. In addition, chemical damage to crops was also shown on the same basis as the extermination effect.

0- ・Suppression rate 0~9% 1 ・Suppression rate 10~29% 2. ・Suppression rate 30~49% ゛3. ・Suppression rate 50~69% 4# ・Suppression rate 70~ 89% 5. - Ramie suppression rate 90-100% Example 7 Soil treatment test on transplanted paddy rice 100 cm
Fill the plastic pots No. 2 with 111 water and soil in a puddling state, sow the seeds of the weeds shown in Table 4, and transplant two paddy rice plants (variety Nyamahoushi) into each pot to a depth of about 2 cm. I felt emotional in a water state. At the early stage of the development of miscellaneous dirt shown in Table 8, a prescribed amount of the hydrating agent (Jltj ILL) of the compound of the present invention prepared according to Example 4 was added per pot.
It was diluted with 0ml of water and applied dropwise to the water surface. The plants were then placed in a greenhouse and watered at appropriate times. The violet removal effect and drug damage were investigated on day 20 after the chemical treatment, and the results shown in Table 8 were obtained.

Exclusion f:+: Evaluation of efficacy and evaluation of drug damage were performed in the same manner as in Example 6.

Claims (2)

[Claims] (1) General formula [I] ▲There are 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. May be different. R^1 represents a hydrogen atom or a C_1-C_6 alkyl group, and R^2 represents a C_1-C_6 alkylthio group or C_
1-C_6 alkoxy group, A is NR^3R^4(
However, R^3 and R^4 are hydrogen atoms, C_1-C_6 alkyl group, C_1-C_6 alkylthio group, C_1-C
It represents a _6 alkoxy group, a C_1-C_6 alkenyl group, or an aryl group, and R^3 and R^4 may be the same or different. ), ▲Mathematical formulas, chemical formulas, tables, etc.▼(
However, l represents an integer from 1 to 10. ) or ▲Mathematical formulas, chemical formulas, tables, etc.▼ (However, Y^3 represents an oxygen atom or a sulfur atom, and m
, n represents an integer of 1 to 10. ) is shown. } A ureido carbamate derivative represented by. (2) A herbicide containing a ureidocarbamate derivative represented by the general formula [I] as set forth in claim 1 as an active ingredient.