JPS6054954B2 - Diphenyl ether derivatives and herbicides containing diphenyl ether derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention is based on the general formula (wherein, group, N,N-dimethylcarbamoyl group.

), and also provides a herbicide containing this novel diphenyl ether derivative as an active ingredient. Many herbicides containing diphenyl ether derivatives as active ingredients have been proposed for a long time, and many are commercially available, such as NIP (active ingredient: 2'',4-dichloro-4-
nitrodiphenyl ether), CNP (2″, 4″, 6
″-1・richloro-4-nitrodiphenyl ether),
Examples include herbicides such as TOPE (3″-monomethyl-4-nitrodiphenyl ether).

These conventionally known diphenyl ether herbicides have excellent soil treatment ability against annual gramineous weeds that generally occur in rice fields, but they have poor foliage treatment ability against various weeds or herbicidal effects against annual broad-leaved weeds and perennial weeds. They have a common characteristic of being inferior. In addition, as with other organic compounds, these derivatives differ in their chemical structure due to differences in the type, number, or position of substituents, depending on their herbicidal effect, size, slowness, or herbicidal effect on crops. In many cases, the presence or absence of drug-induced harm to other substances differs unexpectedly. The inventors have conducted various studies with the aim of obtaining industrially useful diphenyl ether derivatives that have not been previously described in literature.

As a result, the general formula (wherein X, n and R have the same meanings as above) is obtained.

), and this new diphenyl ether derivative has an excellent herbicidal effect on various weeds, and is free from chemical damage to various crops, human hoarding, and toxicity to fish and shellfish. The present invention was achieved by discovering that the diphenyl ether derivative in this invention has no foreign odor.
It has the ability to spray on the soil and kill weeds before and after they emerge, which is the so-called soil treatment ability and foliage treatment ability.It is effective against a wide range of annual and perennial grass weeds and broad-leaved weeds that occur in rice fields and fields. It is effective against various weeds.

Therefore, the herbicide of the present invention is effective as an early-stage herbicide before and after rice planting in rice fields, or as a mid-stage herbicide 1 to 2 weeks after rice planting targeting perennial weeds and broad-leaved weeds, and is also effective in rice fields. It can be used as a soil treatment herbicide before and after sowing crops, or as a foliar treatment herbicide against various weeds in orchards, tea fields, mulberry fields, and non-agricultural lands. The herbicide of the present invention also has the characteristic of exhibiting extremely high herbicidal activity against weeds of the Caryophyllaceae family, which have not been able to be controlled at all by conventionally known diphenyl ether herbicides. Table 1 lists examples of novel diphenyl ether derivatives in this invention.

In the herbicide of the present invention, salts of these diphenyl ether derivatives are also useful as active ingredients, and representative salts include 7,4'',6''-trichloro-3-
The sodium salt of methoxycarbonylaminosulfonyl-4-nitrodiphenyl ether is listed as compound number 25, and the sodium salt of 7,4'',-dichloro-3-methoxycarbonylaminosulfonyl-4-nitrodiphenyl ether is listed as compound number 36. The diphenyl ether derivative can be synthesized, for example, by the following reaction steps.It has a meaning.Next,
A synthesis example of each step is shown.

Synthesis Example 1 Synthesis example of the first step, 1.41 isopropyl alcohol, 1-nitro 2,
86 g (0.4 mol) of 4-dichlorobenzene and 56 g (0.45 mol) of benzyl mercaptan were dissolved, and while stirring, 30 g of potassium hydroxide, 20 ml of water and 7 ml of ethanol were dissolved.
Gradually drop 0 mt of the mixed solution, and after dropping, place on a water bath for 3 minutes.
Refluxed for an hour.

After standing overnight, the crystals were collected and then re-crystallized from a mixture of ethanol and a small amount of benzene to obtain 87 g of benzyl-2-nitro-5-chlorophenyl sulfide (melting point: 131-134 °C) in the form of yellow prisms (yield: 70 °C). %)Obtained.
Synthesis Example 2 Synthesis example of second step, dimethylacetamide 30
ml, 16.3 g of 2,4-dichlorophenol (0.
After dissolving 1 mole of potassium hydroxide, 5.6 g of potassium hydroxide (0
．． 1 mol) was added thereto, and the mixture was heated and stirred at 120°C to dissolve potassium hydroxide.

Then, after cooling, 28 g (0.1 mol) of benzyl-2-nitro-5-chlorophenyl sulfide was added, and about 15
After heating and stirring at 5° C. for 6 hours, the mixture was cooled, water was added, and the precipitated oil was extracted with benzene. The extract was then washed with a dilute aqueous sodium hydroxide solution and water, dried over sodium sulfate, and after distilling off the benzene, the residue was recrystallized from ethanol to form yellow powdery crystals of 2'',4''-dichloromethane. 27 g (yield 67%) of 3-benzyl mercapto 4-nitrodiphenyl ether (melting point 104-105°C)
Obtained.

Synthesis Example 3 Synthesis example of 3rd step and 4th step, 2″, 4″
- 33 g (0.008 mol) of dichloro-3-benzylmercapto-4-nitrodiphenyl ether was mixed with 2 ml of glacial acetic acid.
The suspension was suspended in a mixed solution of 00ml and 30mL of water, chlorine gas was blown into the suspension at about 17C under stirring, and the suspension was left overnight at room temperature. Next, the contents were poured into water, the precipitated oil was extracted with benzene, the extract was washed with water, dried over sodium sulfate, the solvent was distilled off, and a dark red oily substance 2", 4"
-Dichloro-3-chlorosulfonyl-4-nitrodiphenyl ether This was then dissolved in ethyl acetate and then added dropwise into saturated ethyl acetate of ammonia. After the addition was completed, the mixture was stirred three times at room temperature, water was added and the reaction solution was washed with water, and then dried over sodium sulfate.
The solvent was distilled off and the residue was recrystallized from ethanol to give pale yellow powder crystals of 2'',4''-dichloro-3-aminosulfonyl-4-nitrodiphenyl ether (Compound No. 8: melting point 95-98°C). 22.7g (yield 78%)
Obtained. Synthesis Example 4 Synthesis example of the 5th step, (1) 2″, 4″-
Synthesis of dichloro-3-ethoxycarbonylaminosulfonyl-4-nitrodiphenyl ether (compound No. 10), 1.25 Wt% sodium hydroxide aqueous solution 4
To 0 mL, 3.6 g (0.01
After dissolving 3.6 g (0.033 mol) of ethyl chloroformate and a 10 wt% aqueous sodium hydroxide solution at about 25°C with stirring, the pH was adjusted to 10-11.
Adjusted to.

After the dropwise addition was completed, the mixture was stirred three times, and then a dilute aqueous hydrochloric acid solution was added dropwise to adjust the LPH to 6.5, and the insoluble matter was removed. Next, the solution was acidified with strong hydrochloric acid, the precipitated crystals were collected, and after drying, they were re-crystallized from benzene to form pale yellow prismatic crystals with 2"
, 4″-dichloro-3-ethoxycarbonylaminosulfonyl-4-nitrodiphenyl ether (melting point 138~
140° C.) was obtained (2.5 g (yield 57%)). (2) 2″
, 4″-dichloro-3-chloroacetylaminosulfonyl-4-nitrodiphenyl ether (compound No. 12) synthesis, 2wt% sodium hydroxide aqueous solution2.
After dissolving 3.6 g (0.01 mol) of 7,4''-dichloro-3-aminosulfonyl-4-nitrodiphenyl ether in 5 ml of water, 4.5 g (0.01 mol) of chloroacetyl chloride was dissolved at about 20° C. under stirring. 04 mol) and 10 wt%
Add sodium hydroxide aqueous solution dropwise alternately to adjust the pH to 10~
Adjusted to 11.

After the dropwise addition was completed, the powder was stirred, and then 200ml of water was added to dissolve the precipitate, and then a dilute hydrochloric acid aqueous solution was added dropwise.
H was adjusted to 4 and insoluble materials were removed. Next, the liquid solution was acidified with strong hydrochloric acid, the precipitated crystals were collected, dried, and re-crystallized from a mixture of benzene and n-hexane to form light brown prismatic crystals of 2'',4-dichloro-3-chloroacetyl. Aminosulfonyl-4-nitrodiphenyl ether (melting point 1
41-143°C) was obtained (3.3 g (yield 75%)). (3
) Synthesis of sodium salt of 2″,4″,6″-trichloro-3-methoxycarbonylaminosulfonyl-4-nitrodiphenyl ether (compound No. 25), 2
．． 2″ to 40ml of 5Wt% sodium hydroxide aqueous solution,
4″,6″-trichloro-3-aminosulfonyl-4-
Nitrodiphenyl ether 7.2g (4). After dissolving 7.5 g of methyl chloroformate (a) at about 20° C. while stirring. 08 mol) and a 10 wt% aqueous sodium hydroxide solution were added dropwise alternately to adjust the pH to 10-11.

After dropping, the powder was stirred for 3 minutes, and the precipitate was collected, washed with water, dehydrated, and dried to form colorless powdery crystals of 2″, 4″,
6.6 g (yield 7
7%) obtained. (4) 2″, 4″, 6″ one trichrome low 3
Synthesis of -N,N-dimethylaminocarbonylaminosulfonyl-4-nitrodiphenyl ether (compound number 26), 2″, 4″, 6″ in 80 ml of acetone
Mono-trichloro-3-aminosulfonyl-4-nitrodiphenyl ether? (stomach). After dissolving 1.1 g (0.008 mol) of potassium carbonate and 0.9 g (0.008 mol) of N,N-dimethylcarbamoyl chloride, the mixture was boiled and refluxed for a period of time.

Next, Ase. After distilling off the residue, the residue was dissolved in a dilute aqueous sodium hydroxide solution, the pH was adjusted to 5.8 with dilute hydrochloric acid, and the insoluble matter was removed. The solution was made acidic with strong hydrochloric acid, the precipitated crystals were collected, and after drying, they were re-crystallized from a mixture of benzene and n-hexane to form 2", 4", 2", 2", and 2" colorless powder crystals.
1 g (yield: 43%) of 6"-trichloro-3-N,N-dimethylaminocarbonylaminosulfonyl-4-nitrodiphenyl ether (melting point 186-1900C) was obtained.]) 2",4"-dibromo-3-methoxycarbonylamino Synthesis of sulfonyl-4-nitrodiphenyl ether (compound No. 33), in 80 mt of acetone,
2'',4''-dibromo 3-aminosulfonyl-4-nitrodiphenyl ether 2.3g (a). 005 mol)
and then 1.1 g (0.007
5 mol) was added, and while stirring, methyl chloroformate 0
．． After 7 g (0.0075 mol) was added dropwise, the mixture was heated under reflux for 3 hours.

After cooling, the precipitated inorganic salt was removed, and the solvent was distilled off from the solution, and the residue was dissolved in a dilute aqueous sodium hydroxide solution. Next, what about insoluble matter? After removing the solution, a dilute aqueous hydrochloric acid solution was added dropwise to adjust the pH to 6, and the precipitated crystals were removed. Make the solution acidic with strong hydrochloric acid and remove the precipitated crystals? After drying, it was re-crystallized from a mixture of benzene and n-hexane to give '2',4''-dibromo-3-methoxycarbonylaminosulfonyl-4-nitrodiphenyl ether (melting point 167-177C) in the form of pale yellow needle-like crystals. 1.1g (yield 44%
)Obtained. 3) Synthesis of 2″,4″-dichloro6″-fluoro3-methoxycarbonylaminosulfonyl-4-nitrodiphenyl ether (compound No. 38), 2″,4″-dichloro6″-fluoro3-aminosulfonyl- 2.0 g of 4-nitrodiphenyl ether (
4). 005 mol) in 80 mt of acetone, 1.2 g (0.008 mol) of potassium carbonate and 0.8 g (0.008 mol) of methyl chloroformate were added, and the mixture was heated under reflux for 6 hours.

Next, after cooling, the precipitated inorganic salt was removed and the solvent was distilled off from the resin solution, and the residue was dissolved in a dilute aqueous sodium hydroxide solution. Next, what about insoluble matter? After removing the solution, a dilute aqueous hydrochloric acid solution was added dropwise to adjust the pH to 6, and the precipitated crystals were removed.

The liquid was made acidic with strong hydrochloric acid, the precipitated crystals were collected, dried, and re-crystallized from benzene to form pale yellow prismatic crystals of 2",
1.3 g (yield 57%) of 4''-dichloro6'-fluoro3-methoxycarbonylaminosulfonyl-4-nitrodiphenyl ether (melting point 152-156°C) was obtained.Diphenyl ether derivative in this invention,
When used as a herbicide, be sure to use pesticide formulations! According to 1.1, it can be used in any dosage form such as granules, powders, emulsions, wettable powders, tablets, oils, aerosols, smokes, etc. using inert solid carriers, liquid carriers, emulsifying dispersants, etc. I can do it. Examples of these inert carriers include talc,
Clay, kaolin, diatomaceous earth, calcium carbonate, potassium chlorate, saltpeter, wood flour, nitrocellulose, starch, benzene, xylene, n-hexane, gum arabic,
Examples include vinyl chloride, carbon dioxide, freon, butane, and butane. Further, auxiliary agents for formulation, such as spreading agents, diluents, surfactants, solvents, etc., may be appropriately added. Furthermore, it can be used by appropriately mixing with fungicides, insecticides, other agricultural chemicals, urea, ammonium sulfate, ammonium phosphorous, potassium salts and other fertilizer substances, soil conditioners, and the like. Next, examples of the herbicide according to the present invention will be given.

In addition, parts in each example mean parts by weight. Example 12
8 parts of ″,3″-dichloro-3-aminosulfonyl-4-nitrodiphenyl ether (compound No. 5),
After uniformly mixing 9 parts of bentonite, 5 parts of talc, 1 part of Neoperex powder [trade name: manufactured by Kao Atlas Co., Ltd.] and 2 parts of sodium lignin sulfonate, then adding a small amount of water and kneading. , granulation, and drying to obtain granules.

Example 2 2″,4″-dichloro-3-methoxycarbonylaminosulfonyl-4-nitrodiphenyl ether (compound No. 9) 505, 48 parts of kaolin, and 2 parts of Neopelex powder were uniformly mixed and then ground. A hydrating agent was obtained.

Example 3 2″,4″-dichloro-3-ethoxycarbonylaminosulfonyl-4-nitrodiphenyl ether (compound No. 10) 5 parts, xylene 4 parts, dimethylformamide 5 parts, and toxanone [Product name: Sanyo Chemical Industries (
Co., Ltd.] were uniformly mixed and dissolved to obtain an emulsion.

Example 4 2″,4″,6″-trichloro-3-methoxycarbonylaminosulfonyl-4-nitrodiphenyl ether (
5 parts of Compound No. 23), 50 parts of talc, and 45 parts of kaolin were uniformly mixed to obtain a powder.

Next, the effects of the herbicide in this invention will be specifically explained using experimental examples.

In addition, the test compound number in each experimental example is the same as the compound number mentioned above. In addition, each drug applied in each experimental example was a wettable powder prepared according to Example 2 and diluted with water so that the concentration of the active ingredient was 1000 ppm. Experimental Example 1 Paddy soil treatment experiment - Earl's Wagner pot was filled with Ube soil (alluvial loam), planted with seeds of Japanese cabbage, tubers of Japanese cypress, tubers of Japanese cypress, and stocks of Japanese pine tree. Seeds were sown, and paddy rice seedlings (variety: Nipponbare) at the two-leaf stage were transplanted, and water was added to create a flooded state at a depth of 3 cm.

Then, when the weeds germinated, a predetermined amount of each drug was uniformly dropped using a pipette, and the weeds were kept in a glass room at an average temperature of 25°C. Three weeks after the chemical treatment, the herbicidal effects of each test compound were investigated. The results are shown in Table 2). The herbicidal effects in Table 2 were based on the following criteria.

5: Complete withering 4: Major damage 3: Medium damage 2: Slight damage 1: Slight damage 0: No harm (normal growth) Example 2 Perennial weed growth period treatment experiment ± Earl's Wagner pot was filled with Ube soil 5000-
Fill it up, plant tubers of Mizugaya vine and Urikawa, and add water to a water depth of 3C7! It was assumed to be in a flooded state.

Plant height of 5C71 before germination and 5C71, 10c
When the plant reaches a height of m, and before the germination of urikawa, and
When the leaves reached the leaf stage and the four-leaf stage, a predetermined amount of each drug was uniformly dropped using a pipette, and the plants were kept in a glass room with an average temperature of 25°C. Two weeks after the chemical treatment, the herbicidal effects of each test compound were investigated. The results are shown in Table 3. Note that the criteria for the herbicidal effect in Table 3 are the same as in Experimental Example 1. Experimental example 3
Upland soil treatment experiment - Earl's Wagner pot was filled with Ube soil and wheat (
Seeds of soybean (variety: Kobushi wheat), soybean (variety: Summer soybean No. 1), blackberry grass, goldenrod, purslane, Japanese clover, and ash seedlings were sown, and after covering the soil, a predetermined amount of each chemical was sprayed uniformly under pressure on the soil surface, and the average It was maintained in a glass room at a temperature of 25°C.

Two weeks after the chemical treatment, the herbicidal effects of each test compound were investigated. The results are shown in Table 4. Note that the criteria for the herbicidal effect in Table 4 are the same as in Experimental Example 1.

Experimental Example 4 Field Stem and Leaves Treatment Experiment A Wagner pot in Yaar was filled with Ube soil, and three-leafed crabgrass, two-leafed Japanese fir, two-leafed white locust, and three-leafed Japanese commonweed were grown.

Next, a drug (active ingredient concentration 1000 ppm) prepared by diluting the hydrating agent of each test compound with water containing 100 ppm of the spreading agent Neoesterin [trade name: manufactured by Toa Nohyaku Co., Ltd.] was added to
The leaves and stems were uniformly pressure sprayed at a rate of 5 mt per pot, and maintained in a glass room with an average temperature of 25°C. Two weeks after the chemical treatment, the herbicidal effects of each test compound were investigated. The results are shown in Table 5. In addition, the criteria for herbicidal effectiveness in Table 5 are as follows:
Same as Experimental Example 1.

From the above experimental results, it was found that the herbicide of this invention can effectively control a wide range of weeds without causing any chemical damage to crops by applying soil treatment or foliage treatment. is recognized as an extremely effective herbicide.

Claims (1)

[Claims] 1. General formula▲ Numerical formula, chemical formula, table, etc.▼ (However, in the formula, , acetyl group, chloroacetyl group, N,N-dimethylcarbamoyl group). 2 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, X represents a halogen atom, n represents an integer from 1 to 3, and R represents a hydrogen atom, lower alkoxycarbonyl group, acetyl group, chloroacetyl A herbicide characterized by containing a diphenyl ether derivative represented by (N,N-dimethylcarbamoyl group) as an active ingredient.