JPS5919085B2 - Satsuzouzai - Google Patents

Description

[Detailed description of the invention] The present invention is based on the general formula x)m “゜゜ｑ２；0.0′”.

(In the formula, X is a chlorine atom, a fluorine atom, or a methyl group,
m represents an integer of 0 to 2, Y represents a hydrogen atom, a chlorine atom, or a CH3S(O)n group, and n represents an integer of 0 to 2.

This invention relates to a herbicide characterized by containing at least one type of diphenyl ether compound represented by the following as an active ingredient. It is a well-known fact that certain types of diphenyl ether compounds have excellent herbicidal properties, such as 2,4-dichlorophenyl-4-nitrophenyl ether (hereinafter referred to as NIP).
It is abbreviated as.

) and 2,4,6-trichlorophenyl-4-nitrophenyl ether (hereinafter abbreviated as CNP) are widely used as herbicides for initial use in paddy fields, and many other diphenyl ether compounds are also effective as herbicides. The practicality of these compounds as herbicidal agents is being studied, but slight differences in their chemical structure, such as the type, number, or position of substituents, may affect the presence or absence, degree, and manner of expression of herbicidal activity. In many cases, the herbicidal activity of these compounds is extremely difficult to predict based on the similarity of their chemical structures, as they often differ markedly in their properties, selectivity, and persistence of efficacy. The inventors
As a result of synthesizing various new diphenyl ether compounds and examining their herbicidal activity, we discovered that the compound represented by the general formula [I] has extremely superior herbicidal properties compared to NIP and CNP. Based on this, the present invention was completed.

That is, the general formula [1] which is the active ingredient of the herbicide of the present invention
Compared to NIP or CNP, this compound exhibits superior herbicidal activity against many weeds as well as beetles, and its herbicidal activity does not decrease due to concentration dilution, and the chemical damage to paddy rice and other useful crops is extremely small. It has various excellent herbicidal properties. Next, a typical synthesis example of the compound represented by the general formula [1] will be described.

Synthesis Example 1 Synthesis of 2,4-dichlorophenyl-3-(2,2,2-tolylfluoroethoxy)-4-nitrophenyl ether (compound 1) 2,4-dichlorophenyl dissolved in 50 ml of dioxane
Bis(2,4-dichlorophenoxy)nitrobenzene 8
．． Add 2t (0.03 mol) of 86% potassium hydroxide to a solution of 97 (0.02 mol), and add 30 to 3 mol while stirring.
2,2,2-trifluoroethanol 4r (0.
04 mol) was added dropwise, stirred at the same temperature for 2 hours, and then
00ml of cold water.

The resulting yellow-brown oil was extracted and separated by shaking using 50 ml of benzene, and the resulting benzene layer was thoroughly washed with water and then dehydrated with anhydrous sodium sulfate. Benzene was distilled off under reduced pressure to obtain a crystalline yellow-brown substance as a crude product of Compound 1. This was recrystallized from ethanol with a melting point of 76-7.
4.8 y of purified product of No. 7 was obtained. (Yield 63.1%) Elemental analysis value (%) Cl4H8Cl2F3NO4. Synthesis example 22-chloro-4-methylthiophenyl-31 (2
・Synthesis of 2,2-trifluoroethoxy)-4-nitrophenyl ether (compound 2) 2,4-bis(2-chloro-4-methylthiophenoxy)nitrobenzene 10
．． 2y (0.02 mol) was dissolved in dioxane 507TL1, and 86% potassium hydroxide 2f (0.02 mol) was dissolved in dioxane 507TL1.
03 mol) and heated at 30 to 35°C while stirring.
2,2-trifluoroethanol 4V (0.04 mol)
was added dropwise.

The following procedure was carried out in the same manner as in Synthesis Example 1 to obtain 7.47 g of a yellowish brown oil as a crude compound of Compound 2. This was purified using column chromatography (carrier: silica gel, solvent: benzene/n-hesaquin = 2/1), and purified product 5.
I got 67. (Yield 71.8%) Elemental analysis value (%) C
Synthesis example as l5HllClF3NO4S Synthesis of 32-chloro-4-methylsulfinyl-31 (2,2,2-trifluoroethoxy)-4nitrophenyl ether (compound 3) Compound obtained by the method of Synthesis example 2 23.9f
(0.01 mol) was added to 50W11 of glacial acetic acid, and 1.2y of 35% hydrogen peroxide solution was added dropwise at below 10°C, and
The temperature was raised to 0°C and stirred for 2 hours.

The reaction solution was left standing for a day and night, and then discharged into 200 ml of water. The resulting yellow-brown oil was extracted using 50 ml of benzene, and the resulting benzene layer was thoroughly washed with water and then dehydrated with anhydrous sodium sulfate. Benzene was distilled off under reduced pressure.
3.5y of a crystalline pale yellow substance was obtained as a crude product of Compound 3. This was recrystallized from ethanol, with a melting point of 153~
A purified product of 2.9V at 154°C was obtained. (yield 70.7%)
Elemental analysis value (%) Synthesis example 4 as C,5HllClF3NO5S 2-chloro-4-methylsulfonylphenyl 3-(2.
Synthesis of 2,2-trifluoroethoxy)4-nitrophenyl ether (compound 4) Compound 23.97 (0.01 mol) obtained by the method of Synthesis Example 2 was added to 50 ml of glacial acetic acid;
(After adding 2.57 g of 35% hydrogen peroxide solution at below 10℃,
The temperature was raised to 90°C and stirred at the same temperature for 2 hours.

The reaction product was cooled and discharged into 200 ml of water. The resulting yellow-brown oil was extracted using 50 ml of benzene, and the resulting benzene layer was washed with water and then dehydrated with anhydrous sodium sulfate. Benzene was distilled off under reduced pressure to obtain compound 4.
3.87% of a crystalline pale yellow substance was obtained as a crude product. This was recrystallized from ethanol with a melting point of 139-140°C.
A purified product of 3.37% was obtained. (Yield 76.7%) Elemental analysis value (%) Cl5HllClF3NO6S Active ingredient compounds other than those mentioned above related to the present invention can also be synthesized according to the method of the above synthesis example.

Table 1 shows representative examples of those compounds. In the herbicide of the present invention, the active ingredient compound represented by the general formula [1] may be used as it is, but generally, depending on the purpose of use, it may be dissolved or Dispersed, mixed or adsorbed onto a suitable solid carrier (eg diluent, filler).

At that time, by adding various auxiliary agents (e.g. emulsifiers, stabilizers, dispersants, suspending agents, spreading agents, warming agents, penetrating agents) as necessary, emulsions, hydrating agents, granules, etc. It can be used in various dosage forms such as powders and powders. The herbicide of the present invention can be used in combination with one or more other herbicides, pesticides such as insecticides, fungicides, plant growth regulators, soil conditioners, or fertilizing substances. , and mixed preparations with these are also possible.

For example, herbicides used in combination with the herbicide of the present invention include:
These include urea-based herbicides, thiol carbamate-based herbicides, organophosphorus-based herbicides, acid amide-based herbicides, triazine-based herbicides, and allyloxy fatty acid-based herbicides. The content of the active ingredient of the herbicide of the present invention is 1 to 10% in granules and 40% in wettable powders.
-80%, and 10-50% for emulsions (all percentages are by weight).

) is desirable. Next, Examples of the herbicide of the present invention will be shown.

"Parts" in the examples represent "parts by weight." In addition, the active ingredient compounds are shown in Table 1 and by the compound number of the synthesis example. Example 1 14 parts of a granule compound, 73 parts of bentonite, 20 parts of talc, 2 parts of Tuda dodecylbenzenesulfonate, and 1 part of sodium ligninsulfonate were mixed, and an appropriate amount of water was added and kneaded, followed by an extrusion granulator. The mixture is granulated using a conventional method to obtain 100 parts of granules.

Example 2 After mixing 21 parts of a granule compound, 80 parts of bentonite, 17 parts of talc, 1 part of polyoxyethylene glycol monolaurylate, and 1 part of sodium naphthalene sulfonate, an appropriate amount of water was added and kneaded, followed by extrusion manufacturing. The mixture is granulated in a conventional manner using a granulator to obtain 100 parts of granules.

Example 3 350 parts of hydrating compound, 40 parts of talc, 7 parts of sodium lauryl sulfate
1 part and 3 parts of sodium alkylnaphthalene sulfonate are mixed and ground to obtain 100 parts of a wettable powder.

Example 4 550 parts of a hydrating agent compound, 40 parts of diatomaceous earth, and 10 parts of sodium dodecylbenzenesulfonate were mixed and ground to form a hydrating agent 1.
Get 00 copies.

Example 5 710 parts of emulsion compound, Solpol 800A (Toho Chemical Co., Ltd.)
10 parts of emulsifier) and 80 parts of solvent naphtha were mixed to obtain 100 parts of an emulsion.

Next, the effects of the herbicide of the present invention will be specifically explained using test examples.

Test 1 Test Example 1 Field Cultivation Grass Killing Test by Pre-Emergence Soil Treatment Field air-dried fine soil (passed through 14 meshes of blue) 3.
Put 5k9 into a/5000 Wagner pot and add N to it.
．． Apply 1r each of P2O5 and K2O to the entire layer with chemical fertilizers,
After adjusting the soil moisture to 60% of the maximum water capacity, a certain amount of seeds of the test plants are sown and the soil is covered.

The test compound was prepared into an emulsion according to the method of Example 5, a predetermined amount of the emulsion was diluted in water equivalent to 101 parts per a, and the soil in the pot was uniformly treated with a pipette, and then the emulsion was placed in a greenhouse. They were left behind to grow crops. One month after the treatment, germination and growth conditions of crops and weeds were observed and investigated.

The results are shown in Table 2. In this table, "0" indicates that there is no or almost no difference in the germination, growth, or emergence of crops or weeds compared to those in the untreated area.
'', those whose growth was completely suppressed were given a ``5'', and those in between were classified into 6 levels and displayed. Test Example 2 Paddy field initial weed killing test Paddy field soil (14
(through mesh blue) 3.3kg a/50
00 into a Wagner pot, and add NlP2O5 and K2 to it.
After fertilizing the entire layer with 0.8 y of O each of chemical fertilizers, add an appropriate amount of water and stir to create a hydrated state.

In addition, two paddy rice seedlings (seedlings, leaf age 3 and 0) that had been previously grown in a greenhouse were used as one plant, and the two plants were transplanted and grown in the greenhouse. Those who applied the prescribed amount of the test compound at the beginning of weed emergence 5 days after rice transplantation as described in Examples 1 to 3 above*
*Processed under stagnant water using granules prepared in accordance with the law.

One month after the treatment, the appearance of weeds and the degree of chemical damage to paddy rice were investigated by observation, and the results shown in Table 3 were obtained.

In this table, the display classification of the weed outbreak status is in 6 levels as in Test Example 1, and the display classification of the degree of chemical damage to paddy rice is "severe damage", "major damage", "moderate damage", "slight damage", and " Minor Harm” and [
The rating was set at 6 levels: ``Harmless.'' Please note that during the exam period, 1 per day
CTn's water leakage treatment has reduced the depth of stagnant water in the pot to 30f1.
I kept it at L.

Test Example 3 Paddy Field Initial Grass Killing Field Test A paddy field 5 days after rice planting was divided into 1 section of 10Tr1, and a predetermined amount of the test compound was added using granules prepared according to the method described in Examples 1 to 3 above. Te-tan was sprayed under water.

] (One month after spraying, the amount of weeds per plant in the test plot and the chemical damage to paddy rice were observed and investigated, and the results shown in Table 4 were obtained. In this table, the degree of chemical damage to paddy rice is indicated for test agent 2 and It's the same.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X is a chlorine atom, a fluorine atom or a methyl group,
m is an integer from 0 to 2, Y is a hydrogen atom, a chlorine atom, or a C
In the F_3S(O)n group, n represents an integer of 0 to 2. ) A herbicide characterized by containing at least one type of diphenyl ether compound represented by the following as an active ingredient.