JP2599964B2 - Carbamate derivatives and herbicides containing the same as an active ingredient - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel carbamate derivative, a method for producing the same, and a herbicide containing the same as an active ingredient.

(Prior art and its problems) Wheat, corn, beet, etc. are important crops,
Many herbicides are used to increase the yield of these crops.

The herbicidal activity of carbamates is already known, and the basic structure is (A) N-phenyl carbamate Ar-NHCOO-R, (B) thiol carbamate And a large number of compounds are known.

For example, as the former type of N-phenyl carbamate, JP-A-56-139449 discloses that And U.S. Pat.No. 3,976,470 as the latter type of carbamate, Is disclosed.

However, conventionally known herbicides are not yet sufficient in terms of herbicidal activity and safety to target crops.A safe herbicide that kills harmful weeds in a small amount and does not cause phytotoxicity to target crops is known. What is desired is the current situation.

(Means for Solving the Problems) The present inventors have conducted intensive studies on herbicides that have no phytotoxicity to the target crop and can kill harmful weeds in a small amount.
The present inventors have found that the novel carbamate derivatives described below have selectivity to a target crop and excellent herbicidal activity, and have completed the present invention.

The novel carbamate derivative of the present invention has the general formula [I], In the formula, Ar is the following formula, Or (Wherein R _{1 to} R ₁₄ represent a hydrogen atom, a hydroxyl group, a lower alkyl group or a lower alkoxy group, which may be the same or different), and X is a hydrogen atom or chlorine Represents an atom, and Y represents a lower alkyl group.

This new carbamate derivative has the general formula [II] An aniline derivative represented by the general formula [III] With the chloroformate represented by the general formula [IV] Is obtained by reacting an isocyanate derivative represented by the formula with an alcohol represented by the general formula [V], HO-Y... [V].

In the general formulas [II] to [V], A in the formulas
rX and Y are the same as those of the general formula [I].

According to the present invention, there is provided a herbicide containing the carbamate derivative as an active ingredient.

(Preferred Embodiment of the Invention) Carbamate Derivative The carbamate derivative of the present invention has the following general formula [I], Is represented by

In the above formula, Ar is the following formula Or Represents a group represented by

In these formulas (1a) to (1d), R _{1 to} R ₁₄ represent a hydrogen atom, a hydroxyl group, a lower alkyl group or a lower alkoxy group.

Examples of the lower alkyl group include 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.

Examples of the lower alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a sec-butoxy group.

Of course, these groups R _{1 to} R ₁₄ may be the same or different from each other.

Specific examples of the Ar group in the general formula [I] described above are not limited thereto, but are as follows.

Further, the general formula [I], that is, In the above, the group X represents a hydrogen atom or a chlorine atom;
Represents a lower alkyl group.

Examples of the lower alkyl group of the group Y include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-
Examples thereof include a butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.

As understood from the above description, the carbamate derivative of the present invention can be classified into the following four types according to the type of the group Ar.

Tables 1 to 4 show typical examples of the carbamate derivative of the present invention according to this type.

Production Method (1) The carbamate derivative of the present invention can be obtained by reacting an aniline derivative corresponding to a desired derivative with a chloroformate in the presence of a base.

That is, the aniline derivative used is represented by the general formula [II] In the formula, Ar and X have the same meaning as described above, and the chloroformate is represented by the general formula [II
I], In the formula, Y represents the above-mentioned meaning, and is represented by

As the base used in the reaction, for example, pyridine,
Pyridine bases such as picoline, lutidine and collidine, tertiary amines such as triethylamine, 1,8-diazabicyclo [5,4,0] undecene-7, N, N-dimethylaniline, NaHCO ₃ , KHCO ₃ and Na ₂ Examples thereof include inorganic bases such as CO ₃ , K ₂ CO ₃ , NaOH, and KOH.

The amount of the base to be used is 0.5 to 20, preferably 1 to 10, as a molar ratio to the chloroformate [III].

The reaction solvent may not be used, but a solvent inert to the reaction, for example, benzene, toluene, aromatic hydrocarbons such as xylene, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, Halogenated hydrocarbons such as dichlorobenzene, tetrahydrofuran, ethyl acetate, dimethylformamide and the like may be used alone or in combination.

In the reaction, chloroformate is used usually in an amount of 0.8 to 3 times, preferably 1 to 2 times the mole of the aniline derivative. Stir at -20 to 100 ° C, preferably 0 to 80 ° C, for 0.3 to 30 hours.

After the reaction, the desired product can be obtained by a conventional method as described in Examples below.

Production Method (2) The carbamate derivative of the present invention can also be obtained by reacting an isocyanate derivative corresponding to the desired derivative with an alcohol.

That is, the isocyanate derivative used has the general formula [IV], In the formula, Ar and X represent the groups described above, and are represented by the following formula. Alcohols are represented by the general formula [V], HO-Y... [V] In the formula, Y represents the groups described above.

For the reaction of both, a catalyst is not particularly necessary,
In order to allow the reaction to proceed efficiently, Lewis acids such as aluminum chloride and boron trifluoride ether complexes, mineral acids such as hydrochloric acid, pyridine bases and tertiary amines used in the production method (1), etc. Is preferably used as a catalyst.

These catalysts are usually used in an amount of 0.01 to 1, especially 0.05 to 0.5, in a molar ratio to the alcohol of the general formula [V].

If necessary, the same solvent as used in the production method (1) can be used.

In the reaction, the alcohol is usually used in an amount of 0.8 to 5 times, preferably 1 to 2 times the mole of the isocyanate ester derivative, and both and, if necessary, the catalyst are mixed without a solvent or in the above solvent. Stir at 20-100 ° C, preferably 0-50 ° C, for 0.5-30 hours.

After the reaction, the desired product can be obtained by a conventional method as described in Examples below.

Herbicide The herbicide of the present invention contains the compound of the present invention as an active ingredient.As the use form, the compound of the present invention can be used alone. For example, a diluent, a solvent, a surfactant and the like can be blended and used in the form of an emulsion, a wettable powder, a powder, a granule, or the like.

Examples of the diluent include clay, talc, bentonite, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, and the like.

Solvents include alcohol, dioxane, acetone,
Examples include cyclohexanone and dimethylformamide.

Surfactants include alkyl benzene sulfate, alkyl benzene sulfonate, polyoxyethylene glycol ether, polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan monoalkylate, sodium alkyl sulfate, sodium alkyl naphthalene sulfonate, lignin sulfonic acid Sodium can be exemplified.

These additives can be blended in an appropriate ratio.

The herbicide of the present invention is applied as it is or in a form appropriately diluted or suspended with water or the like, in an amount effective for controlling the weeds. When the compound of the present invention is used as a herbicide, it is effective to apply it in an amount of 50 g to 8 kg per hectare, although it varies depending on the form of preparation, applied crops, applied weeds, weather conditions and the like. The herbicide of the present invention can be mixed with other pesticides or fertilizers if desired. Among them, the following can be mentioned as herbicides that can be mixed. For example, 2,4-dichlorophenoxyacetic acid:
2-methyl-4-chlorophenoxyacetic acid; phenoxy herbicides such as 2,4-dichlorophenoxybutyric acid, 2- (2-methyl-4-chlorophenoxy) butyric acid (including respective esters and salts), 2,4 -Dichlorophenyl-4'-nitrophenyl ether; 2,4,6-trichlorophenyl-
4'-nitrophenyl ether; 2,4-dichlorophenyl-4'-nitro-3'-methoxyphenyl ether; 2,4
-Dichlorophenyl-3'-methoxycarbonyl-4 '
Diphenyl ether herbicides such as -nitrophenyl ether; 2-chloro-4,6-bisethylamino-1,3,5-triazine; 2-chloro-4-ethylamino-6-isopropylamino-1,3,5 -Triazine; 2-methylthio-4,6-
Triazine herbicides such as bisethylamino-1,3,5-triazine; 2-methylthio-4,6-bisisopropylamino-1,3,5-triazine; 4-amino-6-tert-butyl-3- Triazine herbicides such as methylthio-1,2,4-triazin-5 (4H) one; 3- (3,4-dichlorophenyl) -1,1-dimethylurea; 3- (3,4-dichlorophenyl) -1 -Methylurea; 3- (3-chloro-4-difluorochloromethylthiophenyl) -1,1-dimethylurea; 3- [4 (4-chlorophenoxy) phenyl] -1,1
-Dimethylurea; 3- (α, α, α-trifluoro-m
Urea herbicides such as -tolyl) -1,1-dimethylurea;
Isopropyl-N- (3-chlorophenyl) carbamate; methyl-N- (3,4-chlorophenyl) carbamate; 4-chloro-2-butynyl-m-chlorocarbanilate, 33- (methoxycarbonylamino) -phenyl-N
Carbamate herbicides such as-(3-methylphenyl) carbamate; 8- (4-chlorobenzyl) -N, N-diethylthiolcarbamate: 8-ethyl-N, N-hexamethylenethiolcarbamate; 8-ethyldipropyl Thiol carbamate herbicides such as thiol carbamate,
3,4-dichloropropionanilide; N-methoxymethyl-2 ', 6'-diethyl-2-chloroacetanilide; 2-
Acid anilide-based herbicides such as chloro-2 ', 6'-diethyl-N-butoxymethylacetanilide; 5-bromo-3-
uracil herbicides such as sec-butyl-6-methyluracil; 3-cyclohexyl-5,6-trimethyleneuracil;
Pyridinium salt herbicides such as 1,1'-dimethyl-4,4'-bispyridinium chloride; N-phosphonomethylglycine; o-ethyl-o- (2-nitro-5-methylphenyl) -N-sec -Butyl phosphoramidothioate; o-
Methyl-o- (2-nitro-4-methylphenyl-N-
Phosphorus-based herbicides such as isopropylphosphoramidothioate, α, α, α-trifluoro-2,6-dinitro-N, N-
Dipropyl-p-toluidine, N- (cyclopropylmethyl) -α, α, α-trifluoro-2,6-dinitro-
Toluidine herbicides such as N-propyl-p-toluidine, 2-ethoxy-2,3-dihydro-3,3-dimethyl-5
Methyl benzofuranylsulfonate, N-sec-butyl-4-tert-butyl-2,6-dinitroaniline; 3,5-dinitro-N, N-dipropylsulfanylamide; 5-ter
t-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxyazolin-2-one; 3-isopropyl-1H-2,1,3-benzothiadiazine (4 ) -3
H-one-2,2-dioxide (including salts); α- (β-
Naphthoxy) propionanilide; 2- (α-naphthoxy) -N, N-diethylpropionamide; 3,3-amino-
2,5-dichlorobenzoic acid; 2-sec-butyl-4,6-dinitrophenol; N-1 naphthylphthalamic acid; 2- [1-
(N-allyloxyamino) -butylidene] -5,5-dimethyl-4-methoxycarbonyl-cyclohexane-1,
3-dione (including salts), 2- (N-ethoxybutylidyl) -5- (2-ethylpropyl) -3-hydroxy-2-cyclohexen-1-one, and the like,
Of course, it is not limited to this.

Specific examples of the formulation of the herbicide of the present invention are shown below. still,
% In each formulation example is based on weight.

Formulation Example 1 (Wettable powder) 10% of the compound of the present invention, 3% of sodium salt of higher alcohol sulfate and 78% of kaolin are uniformly mixed and pulverized to obtain a wettable powder.

Formulation Example 2 (Emulsion) 25% of the compound of the present invention, 10% of polyoxyethylene alkylaryl ether, 30% of cyclohexanone and 40% of dimethylformamide are uniformly dissolved to form an emulsion.

Formulation Example 3 (granules) Compound 5% of the present invention, bentonite 40%, clay 50%
And 5% sodium ligninsulfonate are uniformly mixed and pulverized, kneaded by adding water, and then granulated and dried to obtain granules.

Formulation Example 4 (Dust) 3% of the compound of the present invention and 97% of clay are uniformly mixed and pulverized to give a dust.

(Effect of the Invention) The herbicide of the present invention includes various weeds, particularly various weeds that are problematic in upland fields, such as, for example, scallop, crabgrass, locust beetle, onamimomi, kosendangsa,
Including important weeds such as strawberry, Asteraceae, Rubiaceae, Scrophulariaceae, Solanaceae, Apiaceae, Violets, Oxaceae,
It shows a high herbicidal effect on weeds of Euphorbiaceae, Brassicaceae, Papilionidae, Amaranthaceae, Acalyptaceae and Polygonaceae by foliage treatment, and is safe against important crops such as wheat, maize, and Azabia bead. And can kill a wide range of weeds at low doses.

Furthermore, the herbicide of the present invention can also be used as a herbicide for turf, orchards, pastures and non-agricultural lands.

(Examples) The following Examples 1 to 3 are synthesis examples of the novel carbamate derivative of the present invention. The compound number in each example is
This corresponds to the compound number of the compounds listed in Tables 1 to 4.

Example 1 N- [4- (3-methyl-2,3-dihydro-6-benzofuranyloxy) phenyl] methyl carbamate (Compound No. 1); 4- (3-methyl-2,3-dihydro-6 -Benzofuranyloxy) aniline 0.5g pyridine 0.2g, toluene 6.
After dissolving in 0 ml, 0.23 g of methyl chloroformate and 4.
0 ml of the solution was added dropwise at room temperature and stirred for another 5 hours. Water was added to the reaction mixture, and extracted with ethyl acetate. The extract was washed with saturated saline and dried over anhydrous magnesium sulfate. The crystals obtained by distilling off methyl acetate under reduced pressure were washed with n-hexane to obtain 0.58 g of the desired product as white crystals (96% yield).

The melting point, mass spectrum, IR spectrum and NMR spectrum of this substance were as follows.

Melting point 104.5-105.5 ° C Mass spectrum m / z 299 IR spectrum (KBr disk; cm ^-1 ) 3270,1705,1677,15
92,1238,1209,1069,978 ¹ H-NMR spectrum (CDCl ₃ solution: ppm) (A) 2.31 (3H, d, J = 7.2 Hz) (b) 3.48 (1 H, m) (c) 3.77 (3H, s) (d) 4.08 (1H, dd, J = 8.1, 9.0 Hz) (e) ) 4.70 (1H, t, J = 9.0 Hz) (f) 6.71 (1H, brs) (g) 6.30-7.44 (7H, m) Example 2 N- [4- (2,2-dimethyl-2,3) -Dihydro-7-benzopyranyloxy) phenyl] methyl carbamate (Compound No. 21) Pyridine was added to a solution of 0.2 g of methanol and 3 ml of toluene.
After dropwise addition, 4- (2,2-dimethyl-2,3-dihydro-6
-Benzopyranyloxy) phenyl isocyanate 0.5g
And a solution of toluene (3 ml) were added dropwise at 0 ° C., and the mixture was stirred at room temperature for 2 hours. Toluene was distilled off under reduced pressure, and the precipitated crystals were washed with n-hexane to give 0.53 of the desired product as white crystals.
g was obtained (96% yield).

 The melting point and the like of this substance were as follows.

Melting point 89-90 ° C Mass spectrum m / z 327 IR spectrum (KBr disk; cm ^-1 ) 3290,1702,1603,12
25,1070 ¹ H-NMR spectrum (CDCl ₃ solution; ppm) (A) 1.32 (6H, s) (b) 1.78 (2H, t, J = 7.2Hz) (c) 2.73 (2H, t, J = 7.2Hz) (d) 3.77 (3H, s) (e) 6.39 −7.17 (8H, m) Example 3 In accordance with the manufacturing method shown in Example 1 or Example 2,
The remaining compounds shown in Tables 1 to 4 were synthesized.

Table 5 shows the melting points and spectrum data of the obtained compounds.

The NMR spectrum was measured in CDCl ₃ , and the IR spectrum was measured on a KBr disk for a solid compound and as it was for a liquid compound.

Example 4 Next, with respect to the herbicide of the present invention, a herbicidal test was performed by foliage treatment in a field, and the effect was confirmed.

The sieved field soil was filled in a porcelain pot having an inner diameter of 12 cm, and seedlings of corn fir, kosendangsa, ichibi, shiroza, datura asiatica, porpoise, wheat, corn, and beads were sowed and covered with 1 cm of soil. After the corn is grown at room temperature until the second true leaf develops, the compound produced in the above Example according to Formulation Example 1 is used as a wettable powder, and a predetermined amount thereof is 15 liters of water per 1 are. (Neonesterin containing 500ppm) was dispersed in the foliage from above the plant with a small sprayer. After the chemical treatment, the plants were grown for another 20 days in a greenhouse, and the herbicidal effect and the phytotoxicity of each plant were examined in accordance with the criteria in Table 6. Table 7 shows the results.

For comparison, as well as The same test was carried out for, and the results were also shown in Table 7.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Isao Hashimoto 6-1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd.

Claims (4)

(57) [Claims] 1. A compound of the general formula [I], In the formula, Ar is the following formula, Or (Wherein R _{1 to} R ₁₄ represent a hydrogen atom, a hydroxyl group, a lower alkyl group or a lower alkoxy group, which may be the same or different), and X is a hydrogen atom or chlorine A carbamate derivative represented by the formula: wherein Y represents an lower alkyl group; 2. The compound of the general formula [II], In the formula, Ar is the following formula, Or (Wherein R _{1 to} R ₁₄ represent a hydrogen atom, a hydroxyl group, a lower alkyl group or a lower alkoxy group, which may be the same or different), and X is a hydrogen atom or chlorine An aniline derivative represented by the following general formula [III]: In the formula, Y represents a lower alkyl group, and is reacted with a chloroformate represented by the following formula in the presence of a base: General formula [I], In the formula, Ar, X and Y represent the groups described above, and a method for producing a carbamate derivative represented by the following formula: 3. The compound of the general formula [IV], In the formula, Ar is the following formula, Or (Wherein R _{1 to} R ₁₄ represent a hydrogen atom, a hydroxyl group, a lower alkyl group or a lower alkoxy group, which may be the same or different), and X is a hydrogen atom or chlorine Reacting an isocyanate derivative represented by the following formula with an alcohol represented by the general formula [V], HO-Y ... [V] wherein Y represents a lower alkyl group. The general formula [I], In the formula, Ar, X and Y represent the groups described above, and a method for producing a carbamate derivative represented by the following formula: 4. A compound of the general formula [I], In the formula, Ar is the following formula, Or (Wherein R _{1 to} R ₁₄ represent a hydrogen atom, a hydroxyl group, a lower alkyl group or a lower alkoxy group, which may be the same or different), and X is a hydrogen atom or chlorine A herbicide containing, as an active ingredient, a carbamate derivative represented by the formula: wherein Y represents an atom; and Y represents a lower alkyl group.