JPH03145480A - Carbamate derivative and herbicide containing the derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [X is 0 or S; R<1> and R<2> are lower alkyl, cycloalkyl or lower alkoxyalkyl; R<1> and R<2> may together form a group of formula II (E is CH2, N or O; m, n, o and p are 0-2; R<3> to R<6> are H or lower alkyl)]. EXAMPLE:S-3-1,2,5-thiadiazolylmethyl N,N-diethylthiol carbamate. USE:A herbicide. PREPARATION:The objective compound can be produced by reacting a corresponding amine with a carbonyl sulfide and 3-chloromethyl-1,2,5-thiadiazole in a solvent (preferably water, ethanol, toluene or pyridine) at 0-100 deg.C for 1-24hrs optionally in the presence of a base (preferably sodium hydroxide).

Description

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

[Prior Art] Conventionally, 2.1.3-benzothiadiazole derivatives,
The herbicidal activity of 1.2.4- or 1.3.4-thiadiazole derivatives is known. However, it is not known that 1,2,5-thiadiazole derivatives such as those represented by general formula [1] have herbicidal activity.

[Problems to be solved by the invention] Conventionally, triarylate, bentiocarb, molinate, etc. (Farm Chemical Handbook 1989) have been used as carbamate herbicides, but these do not have sufficient herbicidal activity, have a narrow herbicidal spectrum, It had problems such as causing chemical damage to crops.

[Means for Solving the Problems] As a result of extensive research, the present inventors have discovered that a novel carbamate derivative having a thiadiazole skeleton has extremely excellent herbicidal activity and selectivity, and has developed the present invention. completed.

That is, the present invention is based on the general formula [I] [X represents O or S, RR2 is each independently a straight or branched lower alkyl group, cycloalkyl group, lower alkoxyalkyl group, or RI and o+p is selected from O to 2 positive numbers. RR4R5
R6 each independently represents a hydrogen atom or a lower alkyl group. ) is shown. The present invention provides a carbamate derivative represented by

The present invention also provides a herbicide containing the compound of the present invention represented by the above general formula [1] as an active ingredient.

[Effects of the Invention] The present invention provides a novel compound having excellent herbicidal activity and a wide herbicidal spectrum as a herbicide. In addition, herbicides containing the compound of the present invention as an active ingredient include:
It can control various weeds from pre-emergence to growth stage, is highly safe for crops, and can be effectively used for weed control in paddy fields, various grain fields, various vegetable fields, fruit trees, mulberry fields, and non-agricultural land.

It is particularly effective in controlling weeds in rice fields.

[Detailed Description of the Invention] The present invention is based on the general formula [I] 2 [X represents O or S, and RR each independently represents a straight or branched lower alkyl group, a cycloalkyl group, a lower alkoxyalkyl group, or , R1R2 are connected to each other, and n, o, and p are selected from positive numbers from 0 to 2. R3R4R
5R6 each independently represents a hydrogen atom or a lower alkyl group. ) is shown. ] is provided.

The present invention also provides a herbicide containing the compound of the present invention represented by the above general formula [1] as an active ingredient.

Preferred examples of RR2 in formula C2F include C1 to methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.
C6 linear and branched lower alkyl groups, C1 to C7 cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl;
Examples include alkoxyalkyl groups substituted with 1 to C6 linear or branched lower alkoxy groups.

Preferred examples of the cyclic amine formed by linking R1 and R2 to each other include virodidine, piperidine, hexamethyleneamine, and morpholine, which may be unsubstituted or optionally substituted with C1 to C4 linear or branched lower alkyl U. , piperazine and the like.

Particularly preferred are lower alkyl groups, cycloalkyl groups and alkylene amines.

The thiol carbamates of the compounds of the present invention can be prepared by combining the corresponding amine, carbonyl sulfide and 3-chloromethyl-1,2,5-
It can be easily produced by reacting thiadiazole (hereinafter abbreviated as halogenide) in a solvent in the presence or absence of a base.

Dithiol carbamates can be produced in the same manner by reacting an amine with carbon disulfide and a chloride in a solvent in the presence or absence of a base.

These reactions are usually carried out in a solvent at 0 to 100°C and 1 to 2
The compound of the present invention can be obtained by reacting for 4 hours.

Preferred examples of the solvent used in the reaction include water, alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, and pyridine. More preferred are water, ethanol, toluene, and pyridine.

As a base, pyridine, triethylamine, N, N-
Organic bases such as dimethylaniline, sodium hydroxide,
Examples include inorganic bases such as potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride. More preferred is sodium hydroxide.

The amount of amine used may be at least 2 equivalents per equivalent of the halide in the absence of the amine, and at least 1 equivalent per equivalent of the halide in the presence of a base.

The amount of base should be at least 1 equivalent per 1 equivalent of halide.

While the compounds of the present invention exhibit excellent herbicidal efficacy, they have almost no effect on crops. That is, the compound of the present invention can be used to kill various weeds that are problematic in fields, such as
Bluetail, Purslane, Japanese fir, Japanese knotweed, pigweed, Japanese knotweed, Japanese knotweed, chickweed, shepherd's purse, watermelon, white-spotted morning glory, American hornwort, common morning glory, dogweed, hotokenoza, plantain, Japanese croaker, oxalis, Japanese occidentalis, buckwheat,
Great aperture, Japanese mugwort, Japanese violet, Japanese goldenrod, foxtail grass, black-tailed grass, sycamore,
In addition, in paddy fields, various weeds that are problematic, such as Japanese millet, Japanese azalea, Japanese weed, Japanese cypress, scallop, Japanese oat, Japanese sorghum, etc.
It has a herbicidal effect on pre-emergence and growing-season treatments for weeds such as Prunus elegans and Urinaria, and has a herbicidal effect on major crops such as corn, wheat, rice, rhubarb, cotton, and sugar beet. does not indicate.

As described above, the compound of the present invention has excellent herbicidal efficacy and a wide herbicidal spectrum, and can control various weeds from the pre-emergence stage to the growing stage. Furthermore, since it is highly safe for crops, it can be effectively used for weed control in paddy fields, various grain fields, various vegetable fields, fruit trees, mulberry orchards, and non-agricultural land. In particular, it can be effectively used to control weeds in rice fields.

Furthermore, the herbicide of the present invention can be mixed with or used in combination with other agricultural chemicals such as fungicides, insecticides, herbicides, plant growth regulators, fertilizers, soil conditioners, and the like. In particular, by using it in combination with other herbicides, it can be expected not only to save labor, but also to expand the herbicidal spectrum and to have even higher effects.

Other herbicides include, for example, 2,4-bis(ethylamino)-6-ethylthio-1,3,5-1 riazine [generic name: simetrine], 2,4-bis(isopropylamino)-6-methylthio -1゜3.5-) riazine [generic name; promethrin] 2- (1,2-dimethylpropylamino)-4-ethylamino-6-methylthio-1,
Triazine herbicides such as 3,5-triazine [generic name: dimethamethrine], 2.4-D, MCPB, 2-(2
-Naphthyloxy)propionanilide [generic name: nabroanilide] Phenoxy herbicides such as 2-(2,4-dichloro-3-methylphenoxy)propionanilide [generic name: clomeprop]; 2.4.6-)-dichlorophenyl -4-nitrophenyl ether (common name:
Chlornitrophen] 2,4-dichlorophenyl 3-
Methoxy-4-nitrophenyl ether [generic name: chlormethoxynil], 2,4-dichlorophenyl-1I3-
Methoxycarbonyl-4-nitrophenyl ether [-
Generic name: Bifenox], diphenyl ether herbicides such as 2-chloro-4-trifluoromethylphenyl-4-nitro-3-(tetrahydropyran-3-yloxy)phenyl ether; N-butoxymethyl-2-chloro-2 °, 6° -Diethyl acetanilide (common name: butachlor) N-propoxyethyl-2-chloro-
2', 6° -') ethyl acetanilide [generic name: pretilachlor], N-methyl-2-(2-benzothiazolyloxy)acetanilide [generic name: mefenacet] 2", 3° -dichloro-4-ethoxy Methoxybenzanilide, N-(α,α-dimethylbenzyl)-2
- Amide herbicides such as bromo-3,3-dimethylbutyramide [generic name: bromobutide] 3°, 4° -dichloropropionanilide [generic name: pronoknil];
1-(α,α-dimethylbenzyl)-3-(4-methylphenyl)urea [generic name: Daimeron] 1-(
Urea herbicides such as 2-chlorobenzyl)-3-(α,α-dimethylbenzyl)urea; quinone herbicides such as 2-amino-3-chloro-1°4-naphthoquinone [generic name: ACN]; 4-(2,4-dichlorobenzoyl)-
1,3-dimethyl-5-pyrazolyl-p-toluenesulfonate [generic name: pyrazolate] 4(2,4-dichlorobenzoyl)-1,3-dimethyl-5-phenacyloxypyrazole [-ship name: virazoxifene] 4 −
(2,4-dichloro-3-methylbenzoyl)-1,3
-dimethyl-5-(4-methylphenacyloxy)pyrazole [generic name: benzofenatub], 5-benzyloxy-4-(2,4-dichlorobenzoyl)1-methylpyrazole, 5-tert-butyl-3-( 2,4-
dichloro-5-isopropoxyphenyl)-1,3,4
-Oxadiazol-2-(3H)-one [generic name: oxacyacin] 3,7-dichloro-8-quinolinecarboxylic acid [generic name: quinchlorac] 3-chloro-2-
(,2-Fluoro-4-chloro-5-(1-propynyloxy)phenyl)-4,5,6,7-tetra/Xhydro2H-indazole, 3-isopropyl-2,1°3-benzothiadiazole Zinone-4)-2,2-dioxide [generic name: pentacine], 1-(3-methylphenyl)
-5-phenyl-IH-1,2,4-triazole-3
-Heterocyclic herbicides such as carboxamide, organophosphorus herbicides such as 0.0-diisopropyl-2-(benzenesulfonamide) ethylenedithiophosphate [common name: 5AP]; Methyl 2-[[[[(4 ,6-cymethoxypyrimidin-2-yl)aminococarbonyl]amino]
sulfonyl]methyl]benzoate [common name: Rondax], ethyl 5-[3-(4,6-cymethoxypyrimidin-2-yl)ureidosulfonylgo 1-methylpyrazole-4-carboxylate [common name: pyra Examples include, but are not limited to, sulfonylurea herbicides such as zosulfuron-ethyl].

When using the compound of the present invention as an active ingredient of a herbicide,
It is usually mixed with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries to formulate emulsions, wettable powders, flowables, granules, powders, and the like.

Examples of solid carriers include kaolin, clay, bentonite, diatomaceous earth, acid clay, white carbon, pumice powder, etc., and examples of liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, isopropanol, Examples include alcohols such as ethylene glycol and cellosolve, ketones such as acetone and cyclohexanone, mineral oil, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, and water.

Examples of surfactants include anionic surfactants such as alkyl sulfate salts, alkyl sulfonate salts, and aryl sulfonate salts, polyoxyethylene glycol ethers,
Examples include nonionic surfactants such as polyoxyethylene glycol esters and polyhydric alcohol esters.

Other formulation aids include polyvinyl alcohol, lignin sulfonate, gum arabic, and the like.

The preparation thus obtained contains 0.1 to 90 LIlfQ%, preferably 1 to 90 LIlfQ% of the compound of the present invention as an active ingredient.
Contains 80% by weight.

When the compound of the present invention is applied as a herbicide, the amount applied varies depending on weather conditions, formulation form, treatment time, application method, application location, target weeds, target crops, etc.; at 1~1000 g/10 a,
Preferably, a range of 2 to 500 g/10a is appropriate.

[Examples] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 1.08g of diethylamine in a 50ml eggplant flask,
1.08 g of water was added, and while stirring, 0.89 g of carbonyl sulfide was blown in at 15 to 20° C. under water cooling. Thereafter, 1 g of 3-chloromethyl-1,2,5-thiadiazole was added at room temperature.
was dripped. After completion of the dropwise addition, heating and stirring were performed at 50° C. for 3 hours. After cooling, extraction was performed with ether. The organic layer was washed with IN hydrochloric acid and water, and then dried over anhydrous magnesium sulfate.

After distilling off the solvent under reduced pressure, the residue was distilled to obtain 1.05 g of S-3-1,2°5-thiadiazolylmethyl-N,N-diethylthiol carbamate (Compound No. 1).

Boiling point 106℃10.5mmHg'H-NMR (solvent: CDC1, unit: δppm)1
．． 0 (611, t, d=7Hz), 3.28 (41!
, q, J-7Hz) 4.30 (2+1.S), 8.5 (
Ill, 5) IR (NaCI) 1[i50cm-
'Elemental analysis (%〉2CHN O82 as 8 13
8 Calculated value: C, 41, 5311, 5, 8 [i N; 1
11.10 Actual value: C, 41,101; 5.48
N: 17.99 Example 2 After blowing carbonyl sulfide into a solution of 1.34 g of dimethylamine and 1.34 g of water under water cooling until saturation, 3-
1 g of chloromethyl-1,2,5-thiadiazole was added dropwise. Hereinafter, by the same operation as in Example 1, S-3-1, 2
, 0.73 g of 5-thiadiazolylmethyl-N,N-dimethylthiol carbamate (Compound No. 2) was obtained.

Boiling point 99℃10.4mmHg 'II-NMR (solvent: CC!, unit: δppm
) 2.95 (811, s), 4.32 (21!, s)
, 8.5(III,5)IR(NaCl) lB
50c+n-' Elemental analysis (%): 693 calculated value as CHN O32: C, 35, 45H; 4.46 N, 20.
78 actual value: C, 35, 78 If; 4.47 N,
20.78 Example 3 Carbonyl sulfide was blown into a solution of 1.50 g of diisoproamine and 165 g of water until it became saturated, and then 1 g of 3-chloromethyl-1,2,5-thiadiazole was added dropwise. The mixture was heated and stirred at 50°C for 3 hours in the same manner as in Example 1, extracted, washed, and dried. The solvent was distilled off under reduced pressure, and the residue was purified using silica column chromatography (developing solvent: benzene/ethyl acetate-10).
/1) to obtain 1.09 g of the target product S-3-4,2,5-thiadiazolylmethyl-N,N-diisopropylthiol carbamate (compound number 3).

Refractive index: -1,5470'H-NMR (solvent: CCl4.Unit: δppm)1
．． 32 (6h, d, J=711z), 3.4-4.
2 (2H, m) 4.38 (211, s) , 8.50 (
111,5) IR (NaCl) 1635ca+-
'Elemental analysis (%): Calculated value as C1oH1□N30S2: C, 46, 30H, 6,80N, 16.19 Actual value: C; 4G, 40 116.89 N; 1B,
29 Example 4 0.67 g of dimethylamine 1. 0.57 g of carbon disulfide was added dropwise to the 1 m aqueous solution under water cooling. After stirring for 30 minutes under water cooling, 1 g of 3-chloromethyl-1°2.5-thiadiazole was added thereto. Hereinafter, by the same operation as in Example 3, the target product S-3-1,2゜5-thiadiazolyl-N,
N-dimethyldithiocarbameth (compound number 6) 1.2
8g was obtained.

Refractive index Cap-1,8508 1H-NMR (Solvent: CCl4. Unit: δpp11) 3
．． 40 (BIl,s), 4.75 (21Ls), 8
．． 52 (111, s) Elemental analysis (X): CHN OS
6 9 3 Calculated value as 2: C; 32.85 H; 4°13 N; 1
9. L5 actual value: C: 32.48 1.4.04
N: 19.03 or less Representative examples obtained in the same manner and their physical property values are shown in Table 1.

Example 8 (Wettable powder) 10 parts by weight of the compound of the present invention, 86.5 parts by weight of Zeekrite (trade name, Zeekrite Chemical Mining Type), 221 Calgen NV-406 (trade name, manufactured by Amagi Yushi Co., Ltd.) 2 parts by weight and Discsol WA (trade name, manufactured by Dai-Kogyo Seiyaku) 1.5
fff amount was mixed and ground to obtain a wettable powder.

Example 9 (Emulsion) 5 parts by weight of the compound of the present invention, 75 parts by weight of xylene, and 20 parts by weight of Tsurpol 2806B (trade name, Toho Chemical Industries type) were uniformly stirred and mixed to obtain an emulsion.

Example 10 (Granules) 10 parts by weight of the compound of the present invention, 50 parts by weight of bentonite,
After mixing and pulverizing 35 parts by weight of Kunilite (trade name, manufactured by Seikako Kogyo Co., Ltd.) and 5 parts by weight of Tsurupol 800A (trade name, Toho Chemical Industries type), water was added and the mixture was stirred uniformly, and granulated and dried to form granules. Obtained.

Example 11 Paddy field flooding treatment test A 100 cm2 plastic pot was filled with paddy soil in a paddy state, seeds of the weeds shown in Table 2 were sown, and
2 paddy rice plants (variety: Yamahoshi) in the leaf stage per pot
The plants were transplanted and maintained under flooding conditions of approximately 2C11. At the early stage of the emergence of the weeds shown in Table 2, a predetermined amount of a wettable powder of the compound of the present invention prepared according to Example 5 was dropped onto the water surface. The plants were then placed in a greenhouse and watered at appropriate times. The herbicidal effect and chemical damage were investigated on the 20th day after the chemical treatment, and the results shown in Table 2 were obtained.

Evaluation of herbicidal effect was expressed as a number from 0 to 5 as shown below.

In addition, chemical damage to crops was shown using the same criteria as herbicidal effects.

Weeding effect Weed suppression rate O0~9% 1 10-29% 2 30-49% 3 50-69% 4 70-89% 5 90-100%

Claims (2)

[Claims] (1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] [X represents O or S, and R^1 and R^2 each independently represent a linear or branched lower alkyl group. , cycloalkyl group, lower alkoxyalkyl group or R^1, R^
2 are connected to each other ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Groups (in the formula, E represents CH_2, N or O, m, n,
o and p are selected from positive numbers from 0 to 2. R^3, R^4
, R^5 and R^6 each independently represent a hydrogen atom or a lower alkyl group. ) is shown. ] A carbamate derivative represented by. (2) A herbicide containing the carbamate derivative according to claim 1 as an active ingredient.