JPS6282A - Thiophenesulfonamide compound and herbicide containing same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [one of X and Y is CH2Z (Z is Br, alkoxy, or alkylthio, etc., which maybe substituted with halogen) and the other is group of formula II (R1 and R2 are methyl or methoxy; A is =N- or =CH-)]. EXAMPLE:N-[(4, 6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-(2,2,2-trifluoroetho xymethyl)-2-thiophenesulfonamide. USE:Herbicide effective to control the noxious weeds in paddy field at a low rate of application without causing phytotoxicity to paddy rice plant. PREPARATION:The compound of formula I can be produced by reacting the compound of formula III (one of X1 and Y1 is CH2Z and the other is aminosulfonyl) with the compound of formula IV (R is alkyl, alkenyl or phenyl) in a solvent such as methylene chloride at 0-80 deg.C for 0.5-24hr.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a thio-fensulfonamide compound represented by the following general formula (1) and its salt, and a herbicide containing them as an active ingredient [formula Inside, X and Y are -C
Hz group (wherein 2 is a bromine atom, an alkoxy group optionally substituted with a halogen atom, an alkylthio group optionally substituted with a halogen atom, an alkoxyalkoxy group, a phenoxy group optionally substituted with a trifluoromethyl group, A thiophene sulfonamide compound represented by a cyano group, a thiocyanato group, a nitro group, or a dialkylamino group, and A is mono, N-, or -Ctt-.

(Disclosure of the Invention) The alkyl moiety of the alkoxy group, alkylthio group, alkoxyalkoxy group, dialkylamino group or dialkylphosphono group represented by Z in the general formula CI) may include carbon atoms such as methyl, ethyl, propyl, butyl, etc. Number 1
-6 alkyl groups are mentioned, and examples of the halogen atom which may be substituted with the substituent represented by 2 include a chlorine atom, a bromine atom, a fluorine atom, and the like.

The thiophene sulfonamide compound of the present invention includes alkali metal salts such as sodium and potassium, magnesium,
Alkaline earth metal salts such as calcium or amine salts such as dimethylamine, triethylamine, etc. can also be formed.

The compound of the present invention can be produced, for example, by the following method.

(In the formula, one of xI and Y is a -CHt2 group (2 is as described above) and the other is an aminosulfonyl group,
One of xt and Y8 is a CHt Z group (2 is as described above), the other is an isocyanatosulfonyl group, R is an alkyl group, an alkenyl group, or a phenyl group, and A1RI and R2 are the above-mentioned That's right. ) The above reaction is carried out in the presence of a solvent, if necessary.

As a solvent, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; cyclic or acyclic aliphatic hydrocarbons such as chloroform, carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, hexane, and cyclohexane; Examples include ethers such as dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; nitriles such as acetonitrile, propionitrile, and acrylonitrile; and aprotic polar solvents such as dimethyl sulfoxide and sulfolane.

In the reaction (A), 1,8-diazabicyclo(5,4,0)-7 may be used to accelerate the reaction if necessary.
. good.

The chemical compound represented by (II) in the reaction formula (A) can be produced, for example, by the following method.

(1) When Z is a bromine atom (2) When Z is substituted with an alkoxy group in which some or all of the water atoms are substituted with a halogen atom, an alkylthio group which may be substituted with a halogen atom, or a trifluoromethyl group (3) When z is a phenoxy group, a nitro group, a dialkylamino group, or a dialkylphosphono group (these substituents are represented by
In the above formula, Mal is a halogen atom, and x4 is a hydrogen atom in which some or all of the hydrogen atoms are substituted with a halogen atom. an alcohol, an alkylthiol that may be substituted with a halogen, or a phenol that may be substituted with a trifluoromethyl group;
Or trimethyl phosphite.

The starting compound represented by (IV) in the reaction formula (B) above can be produced, for example, by the following method.

(In the formula, X+1Yt,
ar is an alkyl such as t-butyl. ) Reaction conditions for each reaction in the method for producing raw material compounds, such as reaction temperature, reaction time, solvent used if necessary, alkaline substance, etc., can be appropriately selected from reaction conditions for similar reactions.

Next, synthesis examples related to the compounds of the present invention will be described. .

Synthesis example 1. N-((4,6-cymethoxypyrimidin-2-yl)aminocarbonyl]-3-(2,2,2
, -trifluoroethoxymethyl)-2-thiophenesulfonamide [1] 14m j! After dropping -4
Stir for 1.5 hours at 0°C or below, gradually lower to -10°C, and -
The mixture was further stirred at 10°C for 1 hour.

This solution was poured into water little by little and extracted with methylene chloride. The extracted layer was washed with water, dried over anhydrous sodium sulfate, filtered, and 20.5 mj of tertiary butylamine was added to the filtrate.
was added and reacted at reflux temperature for 17.5 hours.

After the reaction, the cooled reaction product was filtered, the obtained solid was washed with ethyl acetate, the washing liquid and the filtrate were combined, washed with dilute hydrochloric acid, dried over anhydrous sodium sulfate, and the solvent was removed. Distilled under reduced pressure and purified by silica gel column chromatography (developing solvent: toluene:methylene chloride-1:l) to obtain N-tert-butyl-3-methyl-2-thiophenesulfonamide having a melting point of 122-125°C4. 5
4g was obtained.

[2] Sulfonamide 4.5 obtained in the above step [1]
4 g of carbon tetrachloride, 50 ml of carbon tetrachloride, and 3.82 g of N-bromosuccidiimide were mixed and heated at reflux temperature under light irradiation for 15 minutes.
．． The reaction was allowed to proceed for 5 hours.

After the reaction was completed, the cooled reaction product was filtered, the resulting solid was washed with carbon tetrachloride, the entire filtrate was evaporated under reduced pressure, and subjected to silica gel/ram chromatography (
Developing solvent; toluene:methylene chloride-1; purified with 1) to yield 3-bromomethyl-N-tert-butyl-2-thiophenesulfonamide with a melting point of 88-94°C5.
2g was obtained.

(3)2.2.2-)Refluoroethanol 15Ili
0.42 g of sodium was added to the solution, and the mixture was stirred at room temperature until the sodium was completely consumed. To this, the above step [
2] 2.8 g of the sulfonamide obtained in step 2] was mixed with 10 m of dry methylene chloride. Add the solution dissolved in
The reaction was allowed to proceed for 5 hours.

After the reaction was completed, water was added to the cooled reaction mixture, diluted hydrochloric acid was added to adjust the pH to 3 or less, and the mixture was extracted with methylene chloride. After drying the extract layer over anhydrous sodium sulfate, the solvent was distilled off and purified by column chromatography (developing solvent: methylene chloride: n-hexane-8:1) to obtain an oily N-tertiary-butyl-3°- 2.45 g of (2,2,2-trifluoroethoxymethyl)-2-thiophenesulfonamide was obtained.

[4] Sulbonamide obtained in the previous step [3] 2.
45 g and 12 ml of trifluoroacetic acid were mixed and reacted at room temperature for 16 hours with stirring.

After the reaction was completed, the reaction product was poured into water, an aqueous sodium sulfite solution was added, and the mixture was extracted with ethyl acetate. After washing the extracted layer with water and drying with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure.
Purified by silica gel column chromatography (developing solvent: methylene salt), 3-(
1.47 g of 2,2,2-trifluoroethoxymethyl)-2-thiophenesulfonamide was obtained.

[5] Sulfonamide obtained in the above step [4] 0.2
1 g and 0.21 g of phenyl N-(4,6-cymethoxypyrimidin-2-yl)carbamate in 5 mj of acetonitrile! Add 0.12 g of 1,8-diazabicyclo(5,4゜0)-7-undecene to the dissolved Yugon,
The reaction was allowed to proceed at room temperature for 17 hours with stirring.

After the reaction is complete, water is added to the reaction mixture and acidified with dilute hydrochloric acid.
The precipitated crystals are filtered and dried to a melting point of 129-131°C.
0.22 g of the desired product was obtained.

Synthesis example 2. N-((Synthesis of 4,6,-dimethoxypyrimidinemethoxymethyl-2-thiophenesulfonamide [1] 3-methylthiophene 8g5N-promosuccinimide 16.0. and carbon tetrachloride Loom j! were mixed and irradiated with light. The mixture was reacted at reflux temperature for 4.5 hours.

After the reaction is complete, the cooled reaction product is filtered, the resulting solid is washed with carbon tetrachloride, and the entire filtrate is
The solvent was evaporated under reduced pressure at 0'C to give a brown oil.

On the other hand, a solution was prepared by dissolving 4.85 g of sodium methylate in 100 m It of methanol, and the above-mentioned oil was added to this solution, followed by reaction at reflux temperature for 1 hour.

After the reaction was completed, the cooled reaction product was filtered, the filtrate was distilled off at 30°C, and purified by silica gel column chromatography (developing solvent: methylene chloride: n-hexane-1:1) to give a yellow oil. 5.91 g of 3-methoxymethylthiophene was obtained.

[2] Under a nitrogen atmosphere, 5.91 g of thiophene obtained in the above step [1] was dissolved in 100 ml of dry ether, and 32.7 mjl of n-butyllithium was dissolved at -70 to -60 ml of dry ether.
The mixture was added at -70°C for 1.5 hours and then at room temperature for 1 hour with stirring. It was again cooled to -70°C and sulfur dioxide gas was blown in at a temperature below -40°C. After the heat generation subsided, the temperature was raised to room temperature and the solvent was distilled off under reduced pressure. After drying the obtained white solid at 50°C for 3 hours, it was suspended in about 10°C ml of dry isopropanol, cooled to 0 to -5°C, and 6.80 g of N-chlorosuccinimide was added. In addition,
Water was added to the reactant reacted at 0°C for 6 hours, extracted with methylene chloride, cooled to 0°C, and ammonia gas was added to 0°C.
Bubble at ˜10° C. and allow reaction under stirring at room temperature overnight.

After the reaction was completed, water was added to the reaction mixture, and the mixture was extracted again with methylene chloride. The extracted layer was washed with brine, dried over anhydrous sodium sulfate, the solvent was distilled off, and purified by silica gel column chromatography (developing solvent: methylene chloride: ethyl acetate - 8:2) to give a solution with a melting point of 61- 3-Methoxymethyl-2-thiophenesulfonamide 3.25 at 64°C
I got g.

3] Sulfonamide 190 obtained in the above step [2]
mg, phenyl N-(4,6-cymethoxypyrimidin-2-yl)carbamate 252 mg and 1,8-diazabicyclo(5,4,0)-7-undecene 140n+g
Dry acetonyl 10@j! and reacted overnight at room temperature.

After the reaction is complete, the reaction product is poured into ice water, and the pH is adjusted to 5~5 with dilute hydrochloric acid.
6, and the obtained white crystals were filtered, washed with water and toluene, and dried to obtain 225 g of the desired product having a melting point of 152-154.5°C.

Synthesis Example 3 Synthesis of N-(4,6-cymethoxypyrimidin-2-yl)aminocarbonyl-3-cyanomethyl-2-thiophenesulfonamide [1] Obtained by the same method as step (2) of Synthesis Example 1 above. 3-Bromomethyl-N-tertiary chain J-ray 2
- 2.0 g of thiophene sulfonamide was dissolved in IQIIIt trifluoroacetic acid and reacted overnight at room temperature.

After completion of the reaction, water was added to the reaction product and filtered, and the obtained white crystals were washed with water and toluene and dried under reduced pressure at 60°C to obtain 3-bromomethyl-2-thiophene=3-bromomethyl-2-thiophene having a melting point of 159-160°C. =F; #1.8 g of sulfonamide was obtained.

[2] Sulfonamide 1.8 obtained in the above step [1]
g, 60mj of ethanol! , 60 ml of water and 528 mg of potassium cyanide were mixed and allowed to react overnight at room temperature.

After the reaction was completed, ethanol was distilled off from the reaction product under reduced pressure, the pH was adjusted to 2 with diluted hydrochloric acid, and the mixture was extracted with ethyl acetate. After washing the extracted layer with brine and drying with anhydrous sodium sulfate,
The solvent was distilled off and subjected to silica gel column chromatography (
Purified with methylene chloride:ethyl acetate (8:2) to obtain 3-cyanomethyl-2- with a melting point of 131-135°C.
Thiophene sulfonamide 621B was obtained.

[3] Sulfonamide 202 obtained in the above step [2]
mg, phenyl N-(4,6-simethoxymethylpyrimidin-2-yl)carbamate 275+sg and 1.mg.
8-Diazabicyclo[5°4.0)-7-undecene 1
52a+g was dissolved in dry acetonitrile 10a+It and reacted for 2.5 hours at room temperature.

After the reaction, the reaction product was put into ice water and made weakly acidic with dilute hydrochloric acid, and the obtained white crystals were washed with water and toluene and
It was dried under reduced pressure at ℃ to obtain N-((4
, 6-cymethoxypyrimidin-2-yl)aminocarbonyl-3-cyanomethyl-2-thiophenesulfo, one of X and Y is -CI! Z group, and the other is Table 1 (Continued from Table 1) (Continued from Table 1) (Note) Compound NO, 31 has -CH at the 2-position of the thiophene nucleus, and -CH , Z group is the one to which is bonded.

As shown in the test examples described later, the thiophene sulfonamide compound of the present invention exhibits excellent herbicidal effects when used as an active ingredient of a herbicide. In particular, harmful weeds that grow in paddy fields can be controlled selectively and at low doses without causing chemical damage to paddy rice. In addition, it is suitable as a herbicide for paddy fields because it can control even those harmful weeds that have relatively advanced growth. Furthermore, it is preferable because it can also control harmful weeds in fields.

In addition to the above-mentioned agricultural land, the herbicide of the present invention is applicable to
It can be applied to a wide variety of areas, including orchards, mulberry orchards, mountain forests, farm roads, grounds, and factory sites, and the application method can be selected as appropriate, including soil treatment and foliage treatment.

When the herbicide of the present invention is applied, it is usually applied in the form of air, mixed with various adjuvants such as diluents, solvents, emulsifiers, spreading agents, and surfactants as necessary, to form granules, wettable powders, emulsions, etc. It is used in liquid form, etc. The appropriate blending weight ratio of the active ingredient compound and agricultural chemical adjuvant is generally 0.05:99.95.
~90:10, preferably 0.1:99.9~60
: 40. The appropriate amount of the active ingredient compound to be used cannot be determined unconditionally due to differences in weather conditions, soil conditions, drug formulation, type of target weed, application period, etc.; .1 to 10
0g.

The amount is preferably 0.1 to 50 g.

The herbicide of the present invention can be mixed or used in combination with other agricultural chemicals, fertilizers, soil, phytotoxicity reducers, etc., and in this case may exhibit even better effects and action. When mixed or used in combination with other herbicides, examples of the active ingredients of the herbicides to be mixed include the following.

2.4-dichlorophenyl-31-methoxy-41-nitrophenyl ether, 2=4-dichlorophenyl-3
1-Methoxycarbonyl-4'-nitrophenyl ether, 2-chloro-2'.

6'-diethyl-N-(butoxymethyl)acetanilide, 2-chloro-2',6'-diethyl-N-(propoxyethyl)acetanilide, S-(2-methyl-1-
piperidyl-carbonylmethyl)-0,0-di-n-propyldithiophosphate, 5-(4-chlorobenzyl)N,N-diethylthiol carbamate, S-benzyl-N-(1,2-dimethylsoyal) Thiol carbamate, s-ethyl-hexahydro-IH-azepine-1
-carbothioate, S-(1-methyl-1-buenethyl)piperidine-1-carbothioate, 5-te
rt-Butyl-3-(2,4-dichloro-5-
isopropoxyphenyl) 1,3,4-oxadi7zolin-2-one, benzthiazol-2-yloxy-
Acetic acid N-methylanilide, 4-(2,4-dichlorobenzoyl)-1゜3-dimethyl-5-phenacyloxypyrazole, 4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazole-5- yl-p-toluenesulfonate, 4-(2.,4-dichloro-3-methylbenzoyl)-1,3-dimethyl-5-phenacyloxypyrazole Next, test examples of the herbicide of the present invention will be described.

Test Example 1 A paddy soil of 115,000 are was filled with paddy soil, seeds of Hotaruikai Sanchu 4≠ and tubers of Urikawa were sown, and the soil was kept moist. Approximately 5 a.m. after the firefly grows to the one-leaf stage
A wettable powder of the compound of the present invention was diluted with water, and the solution was added dropwise with a deep pipette so that the amount of active ingredient was 2.5 g/a. The growth state was visually observed 20 days after the chemical treatment, and the degree of growth inhibition was evaluated based on the following criteria (5-point scale from 1 to 5), and the results shown in Table 2 were obtained.

-Growth inhibition degree 5: Complete withering state 1: Growth similar to untreated plot Table 2 (Note) Compound inhibition 1 to 3 are the observation results 14 days after the chemical treatment.

Test Example 2゜115, OOO Earl pots were filled with paddy soil, watered and raked for 4 generations, and the next day two 2.5-leaf stage Mizusai (variety: Nipponbare) plants were transplanted per pot. On the third day after transplantation, the hydrating powder of the compound of the present invention Hidden 1 was diluted with water, and the amount of active ingredient was 1.
It was dripped with a pipette so that the amount was 25 g/a. Eight days after the drug treatment, the growth condition was visually observed and evaluated based on the criteria of Test Example 1, and the result was 2.

Test Example 3 A test was conducted in the same manner as in Test Example 1, except that wild field seeds were sown and the chemicals shown in Table 3 were applied during the germination period, and the results shown in Table 3 were obtained.

Table 3 (Continuation of Table 3) Next, formulation examples of the herbicide of the present invention will be described.

Formulation example (1) Zikrite 78 parts by weight (2) Labelin S (product name: manufactured by Dai-Kogyo Seiyaku) 2 parts by weight (3) Tsurupol 5039 (product name: manufactured by Toho Chemical Industries) 5 parts by weight (4) Car Plex (Product name: Shionogi & Co., Ltd.)
A wettable powder was obtained by mixing 15 parts by weight or more of the mixture of components (1) to (4) and the compound of the present invention in a weight ratio of 9:1.

Claims (1)

[Claims] 1. General formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, one of X and Y is a -CH_2Z group (in the formula, Z
is a bromine atom, an alkoxy group, an alkylthio group optionally substituted with a halogen atom, an alkoxyalkoxy group, a phenoxy group optionally substituted with a trifluoromethyl group, a cyano group, a thiocyanato group, a nitro group, a dialkylamino group, or a dialkylphosphor group. ) and the other is ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R_
1 and R_2 are methyl or methoxy groups, A is =N
- or =CH-] and salts thereof. 2. General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, one of X and Y is a -CH_2Z group (in the formula, Z
is a bromine atom, an alkoxy group, an alkylthio group optionally substituted with a halogen atom, an alkoxyalkoxy group, a phenoxy group optionally substituted with a trifluoromethyl group, a cyano group, a thiocyanato group, a nitro group, a dialkylamino group, or a dialkylphosphor group. ), and the other is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R
_1 and R_2 are methyl group or methoxy group, A is =N
- or =CH-)] and a salt thereof, as an active ingredient. 3. General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X_1 and Y_1 are one of -CH_2Z group (
In the formula, Z is a bromine atom, an alkoxy group, an alkylthio group optionally substituted with a halogen atom, an alkoxyalkoxy group, a phenoxy group optionally substituted with a trifluoromethyl group, a cyano group, a thiocyanato group, a nitro group, or a dialkylamino group. or dialkylphosphono group) and the other is an aminosulfonyl group], and the general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is an alkyl group, an alkenyl group) or a phenyl group, R_1 and R_2 are a methyl group or a methoxy group, and A is =N- or =CH-), the general formula: ▲Math. , chemical formulas, tables, etc.▼ [In the formula, one of X and Y is a -CH_2Z group (in the formula, Z
is as described above), and the other is ▲mathematical formula, chemical formula,
A method for producing a thiophene sulfonamide compound represented by ▼ (wherein R_1, R_2 and A are as described above).