JP3086893B2 - Carbamate amide derivative and herbicide containing the same as active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel carbamate amide derivative and a herbicide containing the same as an active ingredient.

[0002]

BACKGROUND OF THE INVENTION Carbetamide (Farm Chemicals Handbook '90, C58) is known as a herbicide having a carbamate and amide skeleton.
French Patent Nos. 1,249,434 and 1,274,421 disclose carbamate amide derivatives, and also disclose that these carbamate amide derivatives have herbicidal activity.

[0003] However, all known carbamate amide derivatives are N-alkyl-2-phenylcarbamoyloxyacetamide derivatives, and the N-aryl-2-phenylcarbamoyloxyacetamide derivatives of the present invention are not known. No known herbicidal activity is known.

[0004]

The conventional carbamate amide derivatives do not always have sufficient herbicidal activity or have insufficient selectivity between crops and weeds.
There is a problem with crop safety.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a novel carbamate amide derivative has extremely excellent herbicidal activity and selectivity, and completed the present invention.

That is, the present invention provides a carbamate amide derivative represented by the general formula (I):

[0007]

Embedded image

(Wherein X and Z may be the same or different and each represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and Y represents a sulfur atom or an oxygen atom. , R represents a hydrogen atom or a lower alkyl group, A represents a CH or a nitrogen atom, and n represents 1 or 2.) and the general formula (I)
The present invention provides a herbicide containing a carbamate amide derivative represented by the following formula as an active ingredient:

[0009]

The present invention will be described below in detail.

As examples of the compound of the present invention represented by the general formula (I), X and Z may be the same or different and include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group. , N-butyl group, isobutyl group, s
C ₁ -C ₆ lower alkyl groups such as ec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, hexyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy Group, n-butoxy group, isobutoxy group, sec-butoxy group, ter
a C ₁ -C ₆ lower alkoxy group such as a t-butoxy group, an n-pentoxy group, an isopentoxy group, and a hexoxy group;
Examples thereof include halogen atoms such as fluorine, chlorine, bromine, and iodine. Y can be a sulfur atom or an oxygen atom. R represents a C ₁ -C ₆ lower alkyl group such as a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Can be mentioned. A can be a CH or a nitrogen atom.

Specific examples of the carbamate amide derivative represented by the general formula (I) according to the present invention are shown in Tables 1 to 3, but the compounds of the present invention are not limited thereto.

[0012]

[Table 1]

[0013]

[Table 2]

[0014]

[Table 3]

The compound of the general formula (I) can be synthesized, for example, according to the following reaction formula.

[0016]

Embedded image

A compound represented by the general formula (II) (where X, Y and n are the same as described above) and a compound represented by the general formula (III)
(However, Z, R and A are the same as described above.) The compound represented by the above formula is preferably used in a solvent or in the absence of a solvent, in the presence or absence of a base, preferably from 0 ° C to 150 ° C, more preferably from 0 ° C to 150 ° C. The compound of the present invention can be produced by reacting at 20 ° C. to 100 ° C. for several minutes to 48 hours.

Examples of the solvent used in the reaction include aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, diethyl ether, diisopropyl ether, and the like.
Dioxane, tetrahydrofuran, diethylene glyco-
Ethers such as dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and dichlorobenzene, acetonitrile and isobutyro Examples thereof include nitriles such as nitriles and polar solvents such as dimethylformamide and dimethylsulfoxide.

The base used in the reaction includes triethylamine, pyridine, 1,8-diazabicyclo [5,4,
0] -7-undecene, organic bases such as N, N-dimethylaniline, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, carbonates of alkali metals such as sodium carbonate and potassium carbonate, and sodium hydride And the like.

The amount of the reagent used in the reaction is usually 1 to 10 equivalents of the compound of the formula (III) and 1 to 10 equivalents of the base, relative to 1 equivalent of the compound of the formula (II).
It is 0 equivalent.

The herbicide of the present invention containing the compound of the present invention as an active ingredient has herbicidal activity against various weeds.
In particular, it has excellent herbicidal activity against paddy weeds. Such weeds include, for example, annual weeds and perennial weeds, such as red snapper, azalea, kikasigusa, mizohakobe, tamayatsuri, pine bye, firefly, and serrata. Further, the herbicide of the present invention hardly causes harm to crops such as rice and is highly safe.

The herbicide of the present invention is prepared by adding one or two or more of the compounds of the present invention represented by the above general formula (I) to a pesticide formulation using a pesticide adjuvant usually used in this field. It is used in the form of, for example, emulsions, wettable powders, oils, granules, powders, etc., formulated by the above generally used methods. These various preparations can be used as they are in actual use, or can be used after being diluted to a predetermined concentration with water.

Examples of pesticidal auxiliaries include diluents, surfactants, stabilizers, fixing agents, sprays for aerosols, synergists,
Examples include bulking agents, solid carriers, potency extenders, dispersion stabilizers and the like. Examples of the diluent include water, hydrocarbons, alcohols, ethers, alcohol ethers, ketones, esters, amides, sulfoxides, kerosene, mineral oil and the like.

As the extender and the solid carrier, inorganic powders such as quicklime, magnesium lime, gypsum, calcium carbonate, silica, pearlite, pumice, diatomaceous earth, alumina,
Examples include zeolite, clay minerals (talc, vermiculite, kaolinite), and synthetic resin powders (eg, phenolic resin, vinyl chloride resin). Examples of the surfactant include anionic surfactants (eg, alkyl sulfates, aryl sulfonic acids, succinates, polyethylene glycol alkylaryl ether sulfates), and cationic surfactants (eg, alkylamines,
Polyoxyethylene alkylamines), nonionic surfactants (eg, polyoxyethylene glycol ethers, polyoxyethylene glycol esters, polyhydric alcohol esters), amphoteric surfactants, and the like.

The herbicide of the present invention can be used in the same manner as a normal herbicide. For example, for a paddy weed, the herbicide of the present invention can be used after transplantation of rice and before or immediately after the emergence of the weed. Can be used for soil treatment. Also,
Soil treatment or foliage treatment using the herbicide of the present invention can also be performed before or early in germination of the field weed.

The application rate of the herbicide of the present invention can be appropriately selected depending on the method of application, the purpose, the time of application, and the occurrence of weeds. Usually, the amount of the active ingredient per hectare is 10 g to 10 kg, preferably 10 g to 10 kg. 50 g to 5 kg.

The compound of the present invention can be used in combination with other herbicides for the purpose of improving the efficacy as a herbicide, and in some cases, a synergistic effect can be expected. Examples of this include, for example, 2,4-dichlorophenoxyacetic acid;
-Methyl-4-chlorophenoxybutyric acid; 2-methyl-4
Phenoxy herbicides such as chlorphenoxyacetic acid (including esters and salts), 2,4-dichlorophenyl-4 ′
-Nitrophenyl ether; 2,4,6-trichlorophenyl-4'-nitrophenyl ether; 2-chloro-
4-trifluoromethylphenyl-3'-ethoxy-
Diphenyl ethers such as 4'-nitrophenyl ether; 2,4-dichlorophenyl-4'-nitro-3'-methoxyphenyl ether; 2,4-dichlorophenyl-3'-methoxycarbonyl-4'-nitrophenyl ether Herbicide, 2-chloro-4,6-bisethylamino-1,3,5-triazine; 2-methylthio-4,6
Triazine herbicides such as -bisisopropylamino-1,3,5-triazine; 3- (3,4-dichlorophenyl) -1,1-dimethylurea; 3- (3,4-dichlorophenyl)- Methoxy-1-methylurea; 1-
Urea herbicides such as (2,2-dimethylbenzyl) -3-p-tolylurea, 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-
Anilide-based herbicides such as (2,6-diethylphenyl) -glycine ethyl ester, 5-bromo-3-sec-butyl-6-methyluracil; 3-cyclohexyl-5
Uracil herbicides such as 6-trimethyleneuracil;
toluidine herbicides such as α, α-trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine;
-Tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazirin-2-one; 3-isopropyl-1H-2,1,3-
Benzothiadiazine- (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.

[0028]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 Synthesis of N-methyl-2- (phenylthiocarbamoyloxy) acetanilide (Compound No. 1) Under a nitrogen atmosphere, 0.24 g of sodium hydride was suspended in 15 ml of dry dimethylformamide. After adding 0.83 g of methyl glycolanilide, the mixture was stirred at room temperature for several minutes. Next, 1.0 g of phenylisothiocyanate dissolved in 5 ml of dry dimethylformamide was added dropwise,
Stirred at room temperature for 2 hours. After completion of the reaction, water was added and the mixture was extracted with chloroform. The chloroform layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was mixed with ethyl acetate and hexane. Further recrystallization gave 1.1 g of N-methyl-2- (phenylthiocarbamoyloxy) acetanilide.

Melting point: 136 ° -137 ° C. IR (KBr, cm ^-1 ): 3250 1655 1540 1160 ¹ H-NMR (CDCl ₃ , δ ppm): 3.30 (S, 3H) 4.9
0 (S, 2H) 7.10-7.60 (m, 10H) 9.00 (b, 1H)

Example 2 Synthesis of N-methyl-2-phenylcarbamoyloxyacetanilide (Compound No. 47) 1.0 g of N-methylglycolanilide was added to benzene 30
Then, the mixture was dissolved in ml, and 0.72 g of phenyl isocyanate was added. After completion of the reaction, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/2).
0.80 g of methyl-2-phenylcarbamoyloxyacetanilide was obtained.

Physical properties: OIL IR (neat, cm ^-1 ): 3300 1730 1670 1500
1220 ¹ H-NMR (CDCl ₃ , δ ppm): 3.30 (S, 3H) 4.
40 (S, 2H) 6.90-7.50 (m, 10H) Tables 4 to 9 show typical examples of the compounds of the present invention obtained by the same method and physical properties thereof.

[0033]

[Table 4]

[0034]

[Table 5]

[0035]

[Table 6]

[0036]

[Table 7]

[0037]

[Table 8]

[0038]

[Table 9]

Example 3 (Emulsion) 5 parts by weight of Compound No. 1 of the present invention, 75 parts by weight of xylene, and Solpol 2806B (trade name: manufactured by Toho Chemical Industry Co., Ltd.) 2
0 parts by weight were uniformly stirred and mixed to obtain an emulsion. Example 4 (Wettable powder) 10 parts by weight of Compound No. 1 of the present invention, 86.5 parts by weight of Siglite (trade name: manufactured by Siglite Chemical Mining), Newcalgen NV-406 (trade name: manufactured by Takemoto Yushi) 2 Parts by weight and Disczol WA (trade name: manufactured by Daiichi Kogyo Seiyaku)
1.5 parts by weight were mixed and pulverized to obtain a wettable powder.

Example 5 (Granules) 10 parts by weight of Compound No. 1 of the present invention, 50 parts by weight of bentonite, 35 parts by weight of Kunilite (trade name: Kokumine Kogyo) and Solpol 800A as a surfactant (trade name: Toho Chemical Co., Ltd.) After mixing and pulverizing 5 parts by weight (manufactured by Kogyo Co., Ltd.), water was added and the mixture was uniformly stirred, extruded through a sieve hole having a diameter of 0.7 mm, dried, and then cut into a length of 1 to 2 mm to obtain 10% granules. Example 6 (Dust) 2% by weight of Compound No. 1 of the present invention was uniformly mixed and pulverized with 5 parts by weight of diatomaceous earth and 93 parts by weight of clay to obtain a 2% dust.

Example 7 Soil treatment test on transplanted paddy rice A 100 cm ² plastic pot was filled with paddy soil in a scraped state, and weed seeds shown in Table 10 were sown.
Two leaf rice (variety: Yamahoushi) per pot 2
The strain was transplanted and maintained in a flooded state of about 2 cm. In the early stage of the emergence of the weeds shown in Table 10, a predetermined amount of the 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 on the water surface. Then, it was left still in a greenhouse and sprinkled as needed. Twenty days after the chemical treatment, the herbicidal effect and the phytotoxicity were investigated, and the results shown in Tables 10 to 12 were obtained.

The evaluation of the herbicidal effect was represented by a number from 0 to 5 as follows. In addition, phytotoxicity to crops was shown on the same basis as the herbicidal effect. 0 ... weed rate 0-9% 1 ... weed rate 10-29% 2 ... weed rate 30-49% 3 ... weed rate 50-69% 4 ... weed rate 70-89% 5 ... weed rate 90-100%

[0043]

[Table 10]

[0044]

[Table 11]

[0045]

[Table 12]

[0046]

As described above, the present invention provides a carbamate amide derivative which is a novel compound, and a herbicide containing the carbamate amide derivative as an active ingredient can be used for various annual weeds and perennial weeds. It has high herbicidal activity, and particularly has excellent herbicidal activity against paddy weeds, and has little safety to crops such as rice.

────────────────────────────────────────────────── (5) References US Pat. No. 3,089,887 (US, A) US Pat. No. 3,177,061 (US, A) US Pat. No. 3,859,332 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C07C 271/28 C07C 333/08 C07D 213/75 A01N 47/20 CAPLUS (STN) CAOLD (STN) REGISTRY (STN) MARPAT (STN)

Claims (2)

(57) [Claims] 1. A carbamate amide derivative represented by the general formula (I). Embedded image (Wherein X and Z may be the same or different and each represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, Y represents a sulfur atom or an oxygen atom, and R represents , A hydrogen atom or a lower alkyl group, A represents a CH or a nitrogen atom, and n represents 1 or 2.) 2. A herbicide comprising the carbamate amide derivative according to claim 1 as an active ingredient.