JPS63104903A - Herbicide composition - Google Patents

Abstract

PURPOSE:To obtain a herbicide composition showing high selectivity without causing drug damages, by combining S-(4-chlorobenzyl)N,N-diethyl thiocarbamate with a specific chloromethanesulfonic acid-substituted phenyl ester derivative. CONSTITUTION:S-(4-Chlorobenzyl)N,N-diethyl thiocarbamate is blended with a chloromethanesulfonic acid-substituted phenyl ester derivative (e.g. chloromethanesulfonic acid 4-isopropylphenyl ester, etc.) shown by the formula (X is H, alkyl, alkoxy, cylcoalkyl, acylalkyl, CF3, halogen, OH, phenoxy, alkenyl, methylthio, etc.) in a weight ratio of preferably 10:10-0.1 to give a herbicide composition. The composition can be applied from germination period of rice plant 5-6 leaves period and has excellent soil adsorbing properties.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a new herbicidal composition.

The object of the present invention is to provide a herbicide having high selectivity between weeds and crops.

(Prior art) Herbicides utilize selective toxicity among closely related higher plants, and when used under normal usage conditions, they do not cause any phytotoxicity to crops. Paddy rice can often be damaged by special conditions during cultivation, such as soil conditions, weather conditions, physiological conditions of rice, unfavorable conditions for spraying herbicides, and other adverse conditions. . Application of a large amount of immature organic matter that leaves undecomposed organic matter after the paddy field is flooded, poor water permeability and aeration, aging of the paddy field, abnormal temperature rise after the paddy field is flooded, etc., can cause strong reduction of the paddy soil. In such a reduced state, the decomposition ability of the drug in the plant body is weakened, and large amounts or uneven spraying of the herbicide may cause chemical damage to paddy rice.5-(4-chlorobenzyl)N according to the present invention, N-diethylthiocarbamate (hereinafter referred to as bentiocarb) may also cause chemical damage to rice plants under these adverse conditions.

Substances that prevent the harmful effects of bentiocarb on rice have already been provided (Japanese Patent Laid-Open Nos. 58-105904, 58-116403 and 58-1283).
05 Specification).

However, conventional antidotes have a limited range of action due to weather conditions, especially abnormally high temperatures, heavy rain, etc., or the nature of soil conditions, so they have not always been able to produce sufficient effects. . The reason for this is thought to be, for example, due to the physicochemical properties of the antidote.

(Problems to be Solved by the Invention) As a result of intensive research in order to obtain a herbicide that does not cause phytotoxicity even under these adverse conditions, the present inventors found that a specific chloromethanesulfonic acid-substituted phenyl ester derivative was added to bentiocarb. The present invention has been completed based on the discovery that a herbicide with high selectivity between weeds and crops can be obtained without causing phytotoxicity by incorporating the following.

(Means for Solving the Problems) The herbicidal composition of the present invention comprises a bentiocarb and a general formula (wherein, , trifluoromethyl group, halogen atom.

Cyano group, nitro group, thiadiazolyl group, hydroxyl group, alkoxyalkoxy group, phenoxy group, benzyloxy group, alkenyl group, methylthio group.

Group -N (wherein R and R3 represent a methyl group or a phenyl group).

or a methyl group, and R4 represents a hydrogen atom or a chloromethanesulfonyloxy group).

or a group -CH=CH-CR, (wherein Rs represents a phenyl group or a methyl-substituted piperidinyl group).

Moreover, X can also form a 5-membered ring or a 6-membered ring that may contain a sulfur atom or a nitrogen atom around adjacent carbon atoms at the 2nd and 3rd positions or the 3rd and 4th positions on the benzene ring. . n represents an integer of 1 to 5, and a chloromethanesulfonic acid substituted phenyl ester derivative represented by ).

Margin below Next, the compounds of the present invention are illustrated in Table 1.

Compounds represented by the general formula (1) in Table 1 and below are phenols and chloromethanesulfonyl halide represented by the general formula (wherein X and n have the same meanings as above).

Or chloromethanesulfonic anhydride and a dehydrohalogenating agent, such as an alkali hydroxide such as caustic soda or caustic potash, alkali carbonate such as sodium pentacarbonate, potassium carbonate, or sodium bicarbonate, or a tertiary alkali carbonate such as triethylamine, dimethylaniline, or pyridine. Bottom right in the presence or absence of organic or inorganic bases such as amines, acetone, methyl ethyl ketone, dimethyl formamide, dimethyl sulfoxide.

Tetrahydrofuran, benzene, toluene, xylene.

-20°C in the presence or absence of a reaction solvent such as chlorobenzene, dichlorobenzene, chloroform, carbon dioxide tetrachloride, etc.
A good yield can be obtained by carrying out the reaction at a reaction temperature of ~150°C for 1 to 20 hours. Also.

(2) Using a dehydrohalogenating agent, chloromethanesulfonyloxyphenol represented by the general formula and a halide represented by the general formula (wherein, R represents an alkyl group or an aralkyl group, and Y represents a halogen atom) , for example, in the presence or absence of an organic or inorganic base such as an alkali hydroxide such as caustic soda or caustic potash, an alkali carbonate such as sodium carbonate, potassium carbonate, or sodium bicarbonate, or a tertiary amine such as triethylamine, dimethylaniline, or pyridine. Bottom right, acetone, methyl ethyl ketone, dimethyl formamide, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, xylene, chlorobenzene, dichloromethane, chloroform.

If the reaction is carried out in the presence of a reaction solvent such as carbon tetrachloride at a reaction temperature of -20°C to 150°C for 1 to 20 hours, a chloromethane sulfone represented by (wherein R represents an alkyl group or an aralkyl group) can be obtained. Acid phenyl ester derivatives can be obtained.

Next, a specific manufacturing method will be described with reference to Examples.

Example 1 Production of 4-isopropylphenyl chloromethanesulfonic acid (compound 10) 6.8 g (0.05 mol) of 4-isopropylphenol
was dissolved in 80 ml of toluene, 10 g (0.1 mol) of triethylamine was added thereto, cooled to around 0°C, and while stirring, 8.9 g (0.0 mol) of chloromethanesulfonyl chloride was dissolved.
6 mol) was gradually added dropwise. 711 and stirred at room temperature for 1 hour. The reaction solution was washed with saturated brine, further washed with 10% aqueous sodium hydroxide solution, washed with water, dried over anhydrous sodium sulfate, filtered, and concentrated the filtrate to obtain a residue. was distilled under reduced pressure.

4-isoprophenyl chloromethanesulfonic acid with a boiling point of 126-128°C10. 9.3 g (yield: 75%) was obtained as a pale yellow liquid in a fraction of O8 mmHg.

Example 2 Production of 2.4-dimethylphenyl chloromethanesulfonic acid (compound 26) 2.4-dimethylphenol log (0, os mol) and 10.1 g (0,1 mol) of triethylamine were added to 100 m 11 of methylene chloride. While stirring at room temperature, 12.4 g (0.08 mol) of chloromethanesulfonyl chloride was gradually added dropwise. After the addition, stirring was continued for an additional 30 minutes, and the reaction solution was washed with 10% hydrochloric acid and 10% caustic soda aqueous solution. and further washed with water. After drying the organic layer with anhydrous sodium sulfate.

Filter and concentrate the filtrate. The obtained residue was purified by column chromatography using a solvent of hexane-ethyl acetate (2:1) to obtain 2,4-dimethylphenyl chloromethanesulfonate as a pale yellow transparent liquid. s g (yield 97%)
(Refractive index n”p 1.5250) Example 3 Production of 4-(1-ethoxycarbonyl)inbutylphenyl chloromethanesulfonic acid (Compound 3
9) 10 g (0,045 mol) of 4-(1-ethoxycarbonyl)isobutylphenol and 7.1 g of triethylamine
(0°07 mol) was dissolved in 200 ml of ethyl acetate and stirred at room temperature to dissolve 7.8 ml of chloromethanesulfonyl chloride.
g (0,052 mol) was gradually added dropwise. The reaction solution was washed with water, dried over anhydrous sodium sulfate, and then filtered. The filtrate was concentrated, and the resulting residue was distilled under reduced pressure.
13.7 g (yield 91%) of (1-ethoxycarbonyl)isobutylphenyl was obtained as a pale yellow transparent liquid in a fraction with a boiling point of 156 to 159'C10, O3 mmHg.

Example 4 Production of 4-fluorophenyl chloromethanesulfonic acid (compound part 52) 10 g (0.09 mol) of 4-fluorophenol and 14 g (0.14 mol) of triethylamine were added to 1 mol of toluene.
The mixture was dissolved in 0.00 m2, cooled to around 0.degree. C., and 14 g (0.094 mol) of chloromethanesulfonyl chloride was gradually added dropwise while stirring.

After the dropwise addition, stirring was continued for 1 hour at room temperature. 1. The reaction solution was washed with 10% aqueous sodium hydroxide solution, further washed with water, and dried over anhydrous sodium sulfate. 1. Next, the filtrate was concentrated, and the resulting residue was distilled under reduced pressure and diluted with chloromethane. 14.5 g (yield 73%) of sulfone @ 4-fluorophenyl was obtained as a colorless liquid in a fraction with a boiling point of 98 to 101 °C and 10.09 mmHg. Example 5 4-Impropoxyphenyl chloromethane sulfonate (compound Production of 73) 4-chloromethanesulfonyloxyphenol 3.3g
(0,015 mol) in acetonitrile 50 m 11
&'-Add 2.8 g (0.02 mol) of dissolved potassium carbonate and stir at room temperature.

3-4 g (0.02 mol) of isopropyl iodide was gradually added dropwise. After the addition, stirring was carried out for 5 hours at a bath temperature of around 90° C. After cooling, the reaction solution was filtered and the filtrate was concentrated. The obtained residue was dissolved in 50 mQ of benzene and washed with a 10% aqueous solution of caustic soda.

After further washing with water, it was dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated, and the resulting residue was distilled under reduced pressure to dissolve 4-isopropoxyphenyl chloromethanesulfonate into a fraction with a boiling point of 143-145°C, 10.19 mmHg. 2.0 g (yield 50%) was obtained as a yellow liquid.

Example 6 Chloromethanesulfone ill 3,4-
Production of methylenedioxyphenyl (compound, 83) 3.
5.5 g (0.04 mol) of 4-methylenedioxyphenol was dissolved in 60 mA of toluene, 8.1 g (0.08 mol) of triethylamine was added thereto, cooled to around 0°C, and 8-9 g of chloromethanesulfonyl chloride was dissolved with stirring. (0
, 06 mol) was gradually added dropwise. After the addition, the reaction solution was stirred at room temperature for 2 hours. The reaction solution was washed with water and dried over anhydrous sodium sulfate.

Then, the filtrate was filtered, and the resulting residue was distilled under reduced pressure.

Chloromethanesulfonic acid 3,4-methylenedioxyphenyl with a boiling point of 144-146°C10. 4.8 (yield 48%) was obtained as a yellowish liquid in the lmmHg fraction.

Next, the herbicide composition of the present invention contains benchocarb and one of the compounds represented by the above general formula (Natsu), and is usually prepared by adding a carrier, a surfactant, a dispersant, or an auxiliary agent, etc., using a conventional method. For example, it is formulated into a single granule, a wettable powder, an emulsion, a fine granule, or a powder. Suitable carriers include, for example, talc.

Examples include solid carriers such as bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, monomer, and liquid carriers such as isopropyl alcohol, xylene, and cyclohexanone.

Examples of surfactants and dispersants include alcohol sulfate salts, alkyl sulfonate salts, lignin sulfone ugly salts, polyoxyethylene alkylaryl ethers, and polyoxyethylene sorbitan monoalkylates.

These preparations can be diluted to an appropriate concentration and sprayed, or applied directly.

The mixing ratio of Benthiocarb and the chloromethanesulfonic acid-substituted phenyl ester derivative represented by the general formula (1) is preferably in the range of 10 to 0.1 by weight for the former and 10 to 0.1 for the latter, respectively.

The herbicide composition of the present invention has 10
Apply 50g to 1000g per area.

Next, examples will be given to specifically explain the invention. In the examples below, % means weight percentage.

Example 8 (Granules) 40% bentonite, 56.5% clay, 3% sodium alkylbenzenesulfonate, and 0.5% polyvinyl alcohol were kneaded with an appropriate amount of water, granulated using an extrusion granulator, and then dried. After sizing to 14 to 32 meshes, 89.9% of the resulting granules were mixed with Benthiocarb 1.
0% and compound (s) o, i% are adsorbed with stirring to form granules.

Example 9 (Granules) A herbicide composition having a target blending ratio by setting 89.9% of the granules in the composition of Example 8 to 89% and setting 0.1% of compound (6) to 1%. can be manufactured.

Example 10 (Granules) Example 8 A herbicide composition having a desired blending ratio by setting 89.9% of the granules in the composition to 80% and 0.1% of compound (6) to 10%. can be manufactured.

Example 11 (Granules) Benthiocarb 10%, compound (1O) 0.1%, sodium ligninsulfonate 2%, white carbon 5%
.

57.9% bentonite and 25% talc are uniformly ground and mixed, mixed with an appropriate amount of water, granulated using an extrusion granulator, dried, and sized to 14 to 32 meshes to form granules. did.

Example 12 (Grain) A herbicide composition having the desired blending ratio was prepared by changing 0.1% of compound (10) in the composition of Example 11 to 1% and changing 57.9% of bentonite to 57%. It can be manufactured.

Example 13 (Wettable powder) 10% Benthiocarb, 0.1% Compound (34), 2% sodium dinaphthyl methanesulfonate, 1% polyoxyethylene furkylphenyl ether and diatom ±86°9% were mixed, Grind it uniformly and use it as a wettable powder.

Example 14 (Wettable powder) A herbicide having the desired blending ratio by setting 0.1% of the compound moiety (34) in the composition of Example 13 to 1% and setting diatom ±86.9% to 86%. A composition can be manufactured.

Example 15 (hydrating agent) 0.1% of the compound moiety (34) in the composition of Example 13 was added to 10%
By setting the diatom ±86.9% to 77%, a herbicide composition having the desired blending ratio can be produced.

Example 16 (Emulsion) An emulsion was prepared by uniformly dissolving 30% of bentiocarb, 3% of compound moiety (67), 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate, and 32% of methylnaphthalene. And so.

Example 17 (Powder) Benthiocarb 3%, Compound (72) 0.3%, Diatom ±
5% and 91.7% of clay were uniformly mixed and pulverized to form a powder.

The herbicide composition of the present invention can be applied to the 5th to 6th leaf stage of rice after germination, and can be used for direct sowing cultivation, seedling transplant cultivation, adult seedling transplant cultivation, etc.

Margins below (Effects of the Invention) The compound represented by the general formula (1) of the present invention can be used in special rice fields where rice fields are in a state of strong luck due to the application of large amounts of immature organic matter or other normal environmental factors. It is possible to prevent the harmful effects that Benthiocarb may have on rice plants.

Substances that prevent this harmful effect have already been proposed (Japanese Unexamined Patent Publication Nos. 58-105904 and 58-116403).
Furthermore, the compounds of the present invention can prevent adverse effects at extremely low doses. This is also useful in the sense that the impact on the environment is further reduced. In addition, the compounds of the present invention have improved soil adsorption properties, and are therefore effective in preventing the harmful effects of benchocarb even when field water is runoff due to rainfall, etc. after treatment. It has the advantage of being stable. Furthermore, the compound of the present invention is rapidly decomposed in the soil and has very little effect on soil microorganisms, so it is a safe substance with no effect on the soil microorganism environment.

Next, the effects of the herbicide composition of the present invention will be explained with reference to test examples.

Test Example 1 (Paddy Rice Plant Harm Reduction Test) Soil collected from a sandy loam paddy field was filled into a Wagner pot equivalent to 115,000 are, mixed with 24 g of shredded rice straw per pot, and subjected to one-generation plowing.

On the day after the plowing, a predetermined amount of the wettable powder prepared according to Examples 13 to 15 was diluted with water and sprayed while still submerged in water.

Immediately after that, the soil from the surface layer up to 30% was mixed with an electric mixer, and on the 5th day after treatment, 1 paddy rice seedling (variety Nikinanpu) was added.
One plant was used, and two plants were transplanted per pot. The pot is
Each treatment was repeated twice, and after the treatment, the temperature was maintained in a glass greenhouse at 20 to 22℃ at night and 29 to 31℃ during the day.A 0gl survey was conducted on the plant height and phytotoxicity index per plant 400 days after transplanting, and the average of the four tested plants was The value was shown.

The following compounds described in JP-A-58-105904 were used as comparative drugs.

The results are shown in Table 2.

Table 2: Plant damage index 0: Normal (same as untreated area) 1: Degree of growth inhibition 10-20% 2: N 21-40% 3: #
41-60% 4: #61
-80% 5: II 81-100% Similarly to compounds 1-7, no inhibition of paddy rice growth was observed in compounds 8-87 in the car plot (0.8-80 g/are).

Below is a margin test example 2 (1) Grass effect test) Using the same method and scale as in test example 1, soil was placed in a Wagner pot and 1 generation plowing was carried out, and the next day after 0 generation plowing, the surface layer water was discarded and removed to expose the soil surface. Approximately 20 seeds of scallops, bulrushes, and bulrushes were sown per pot. These seeds were collected in autumn and stored in a refrigerator under humid, low temperature conditions to break dormancy. The pot was left in the greenhouse for 5 days, and when the weed seeds germinated, it was re-filled with water to a depth of 31°C.The pot was left in the greenhouse for another 5 days, and when the weeds had reached the 1-2 leaf stage. , Examples 13-15
A predetermined amount of a hydrating agent prepared according to the method was diluted with water and sprayed while still in water.

Thirty days after the chemical treatment, the degree of weed growth inhibition per pot was investigated according to the following criteria, and the results are shown in Table 3 as an index.

Weeding effect index 0: Growth suppression degree 0% (same as untreated area) 0
．． 5: 1-10% 1:
11-20% 1.5:
21~30%2: 31~
40%2.5: 41-50%3
: 51-60% 3.5:
61-70%4:
71-80% 4.5: 81-9
0%5: 91st to 100%th
Table 3 As is clear from Table 3, the compound of the present invention had no effect on the herbicidal effect of bentiocarb. In addition,
Regarding Compounds 8 to 87, the results were similar to those shown for Compounds 1 to 7 both in the single use plot and in the penthiocarb mixed plot.

Claims (1)

[Claims] S-(4-chlorobenzyl)N,N-diethylthiocarbamate and general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, X is a hydrogen atom, an alkyl group, Alkoxy group, cycloalkyl group, alkoxycarbonylalkyl group, acylalkyl group, trifluoromethyl group, halogen atom, cyano group, nitro group, thiadiazolyl group, hydroxyl group, alkoxyalkoxy group, phenoxy group, benzyloxy group, alkenyl group, methylthio Groups, groups ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R and R_
1 represents a methyl group or a phenyl group. ), Group ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_2 and R_3 represent a hydrogen atom or a methyl group, and R_4 represents a hydrogen atom or a chloromethanesulfonyloxy group.)
, or a group ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (in the formula, R_5 represents a phenyl group or a methyl-substituted piperidinyl group). Moreover, X can also form a 5-membered ring or a 6-membered ring that may contain a sulfur atom or a nitrogen atom around adjacent carbon atoms at the 2nd and 3rd positions or the 3rd and 4th positions on the benzene ring. . n represents an integer of 1 to 5. ) A herbicidal composition characterized by containing a chloromethanesulfonic acid substituted phenyl ester derivative represented by: