JPH066561B2 - N- (3-chloro-4-isopropylphenyl) -2-methyl-2-pentenoic acid amide and selective herbicide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention comprises N- (3-chloro-4-isopropylphenyl) -2-methyl-2-pentenoic acid amide and this compound as an active ingredient. The present invention relates to a selective herbicide characterized in that, particularly, in the cultivation of wheat, which is an important crop of the Gramineae family in the agricultural industry, the selective and effective control of harmful weeds by foliar spraying. is there.

[Prior art]

Conventionally, the most widely used herbicides for wheat are phenoxy herbicides.

Typical examples thereof include 2,4-D, MCPA, MCPB and 2,4-DB. These herbicides are used as foliar treatments only to control broadleaf weeds. However, due to the problem of phytotoxicity to wheat, it cannot be used unless the wheat has grown considerably.

Many urea compounds have also been put to practical use as herbicides for wheat. For example, 3- (3,4-dichlorophenyl) -1
-Methoxy-1-methylurea (linuron; linuro
n), 3- (3-chloro-4-methoxyphenyl) -1,1
-Dimethylurea (metoxuron), 3-
(3-Chloro-4-methylphenyl) -1,1-dimethylurea (chlortoluron), 3- (4-isopropylphenyl) -1,1-dimethylurea (isoproturon), 3- (2 -Benzothiazolyl) -1,3-dimethylurea (metabenzthiazulone; m
ethabenzthiazuron) etc. These urea-based herbicides show herbicidal effects both in soil treatment and foliar treatment, and their herbicidal spectrums also vary widely depending on the compound, but they are relatively broad from broadleaf weeds to grass weeds. However, because of concern over phytotoxicity to wheat, many are used as soil treatment agents. Even with herbicides used as foliar treatment agents, their selectivity greatly differs depending on the variety, cultivation conditions, and the like. The herbicide spectrum does not cover everything, and it is usually used as an admixture.

In addition, 2- (2-chloro-4-ethylamino-S-triazin-6-ylamino) -2-methylpropionitrile (cyanazine), 3,4-dimethyl-2,
6-dinitro-N-1-ethylpropylaniline (pendimethaline) α, α, α-trifluoro-2,6-dinitro-N-2-chloroethyl-N-pyropull-p-toluidine (fluchloralin; fluchloral)
in), 2,4-dichlorophenyl-3-methoxycarbonyl-4-nitrophenyl ether (Biphenox;
Although herbicides such as bifenox) have been put to practical use by trying to apply them to wheat, the mainstream of these is that they are mother agents of admixtures and do not have sufficient herbicidal spectrum alone. In recent years, a completely new highly active herbicide for wheat has attracted attention.
It is 2-chloro-N- (4-methoxy-6-methyl-1,3,5-triazin-2-yl-aminocarbonyl)
Benzenesulfonamide (chlorosufuron; chlorosu
lfuron). The herbicide had a very low dose, excellent soil treatment effect, long residual effect, and was harmless to wheat.However, it was found that despite the low dose, it exerts great phytotoxicity on subsequent crops. , Its use has become extremely limited. Currently, pesticides are required to have not only excellent performance but also safety for human storage and properties that have little effect on the environment.

In addition, as a special agent for wild weed oats, which is a highly damaging weed,
4-chloro-2-butynyl-N- (3-chlorophenyl) carbamate (barban), ethyl N-benzoyl-N- (3,4-dichlorophenyl) -2-aminopropionic acid ester (benzoylpropethyl;
benzoylpropethyl) 1,2-dimethyl-3,5-diphenyl-
1H-pyrazolium methylsulfate (difenzoquat), methyl 2- (4- (2,4-dichlorophenoxy) phenoxypropionate (diclofopmethyl), etc. have been developed. However, its practical effect is not yet sufficient.

As a foliar treatment agent having excellent selectivity for wheat, 3-isopropyl-1H-2,1,3-benzothiadiazin- (4) -3H-one 2,2-dioxide (ventazone; bentazone) However, the target weeds are limited to broad-leaved weeds, and the herbicidal spectrum is not always wide even for broad-leaved weeds.

On the other hand, many studies have been conducted on N-phenylcarboxylic acid amide derivatives, and excellent herbicides have been developed. A typical example thereof is N- (3,4-dichlorophenyl) propionamide (propanil). This herbicide is one of the most widely used herbicides as a foliar treatment agent for rice. British patent 869,169, West German patent 1,166,547,
Japanese published patent 59-193806, Japanese published patent 41
No. 14240, U.S. Pat. No. 3,816,092 and the like disclose N-arylalkaneamide derivatives, but there is no disclosure about selectivity for wheat, or there is no selectivity, or even if there is selectivity for wheat. The effect is unstable.

British Patent 885,043 discloses compounds represented by the following general formula as herbicides.

However, in this prior art, X is limited to chlorine atoms and methyl groups, and there is no disclosure or suggestion of selectivity for wheat.

West German Patent 2,249,547 discloses compounds represented by the following general formula.

(R is an alkyl group of C ₂ -C _6, R ¹ is an alkyl group, a cycloalkyl group of C ₃ -C alkenyl or C ₃ -C _{8 6} of C ₂ -C _8, X is a halogen Is an atom).

There are very few exemplified compounds of this prior art, and when R is an isopropyl group, only examples in which R ¹ is an ethyl group are disclosed, and the herbicidal activity is not yet sufficient.

[Problems to be Solved by the Invention]

INDUSTRIAL APPLICABILITY In the cultivation of wheat, which is an important crop of the family Gramineae, the present invention has herbicides which are not affected by physical factors such as soil conditions or phytotoxicity, and in particular, have an essential selectivity for wheat in foliar treatment. An object of the present invention is to provide a herbicide, that is, a foliar treatment type highly selective herbicide that is effective at a lower dose and is simple and has a reliable effect on important gramineous crops, particularly wheat.

[Means and Actions for Solving the Problems]

The present inventors have studied a number of compounds with the goal of developing highly selective herbicides in important crops of grass, especially wheat, and as a result, N- (3-chloro-4-isopropylphenyl) -2- Methyl-2-pentenoic acid amide
When foliar treatment was carried out using this, while having an extremely wide range of herbicidal spectra, important grass crops, especially wheat, did not cause any phytotoxicity even at extremely high concentration spraying, and had excellent selective herbicidal activity. The present invention has been completed by finding out that it has an action and has a characteristic to solve the above problems.

In general, it is considered that compounds of the same family and compounds close to the structure have similar properties, but at present, their action characteristics cannot be easily inferred, and the alkyl chain of only one substituent is used. However, the herbicidal activity against weeds and the phytotoxicity against crops are significantly changed even if the amount is increased.

The N- (3-chloro-4-isopropylphenyl) -2-methyl-2-pentenoic acid amide according to the present invention is a novel compound.

The herbicide containing N- (3-chloro-4-isopropiniphenyl) -2-methyl-2-pentenoic acid amide according to the present invention as an active ingredient has almost the same action characteristics when treated with foliage. Harmful weeds in the field, such as
Wild grass oats, Oozuumenotepon, Western Suzumenotepon, Suzumenoteppo, Suzumenocatabira, novier, grassgrass weeds such as burlapea, Echinocloga, and velvetgrass, Periwinkle, Onami, Yaemgra, Shiloza, Hakobe, Musabinagaagao Very effectively control highly damaging weeds such as Gumbai azuna, mustard, communis, corn sorghum, Scutellaria baicalensis, Scutellaria baicalensis, Scutellaria baicalensis, Nobogaku, chamomile, thorns and nettle. On the other hand, no phytotoxicity was observed on important gramineous crops, especially wheat.

Thus, the N- (3-chloro-4-isopropylphenyl) -2-methyl-2-pentenoic acid amide according to the present invention is an important crop of Gramineae, especially in the cultivation of wheat,
It has an essential foliar treatment selectivity and can be used extremely safely. At present, various herbicides used in wheat cultivation are soil treating agents, and the drawbacks of these herbicides, namely, effects due to physical factors such as soil conditions and fluctuations in phytotoxicity are related to the killing of the present invention. Nothing is observed with herbicides. In addition, there is no problem with the effect on subsequent crops.

The N- (3-chloro-4-isopropylphenyl) -2-methyl-2-pentenoic acid amide according to the present invention is a novel compound and is produced by the following method.

That is, to 3-chloro-4-isopropylaniline,
By reacting the carboxylic acid anhydride represented by the formula (II) or the carboxylic acid halide represented by the formula (III), the compound can be easily synthesized according to the following formula.

The reaction is carried out without solvent or in an inert solvent. Examples of the inert solvent include aromatics such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene,
Acetone, ketones such as methyl ethyl ketone, acetonitrile, nitriles such as propionitrile, ethers such as ethyl ether, tetrahydrofuran, dioxane, aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, hexamethylphosphoric acid amide, etc. To be When using an acid halide or an acid anhydride, triethylamine, pyridine, dimethylaniline, 1,8-diazabicyclo (5,4,0) may be used as necessary.
An organic base such as -7-undecene or an inorganic base such as potassium carbonate, sodium carbonate, caustic soda, caustic potash and sodium hydrogen carbonate may be used as the deoxidizing agent.
The reaction temperature is -10 ° C to 150 ° C, preferably 5 ° C to 90 ° C.
C., more preferably 15 to 70.degree. The reaction may be carried out at the reflux temperature of the solvent used. Although the reaction time varies depending on the reaction temperature or the solvent used,
Seconds to 10 hours, preferably 1 minute to 5 hours, more preferably 20 minutes to 3 hours.

The application amount of N- (3-chloro-4-isopropylphenyl) -2-methyl-2-pentenoic acid amide of the present invention is
It can be used in any amount depending on the necessity of suppressing the growth of weeds, and in general, the amount of the active ingredient is in the range of 0.1 to 10 kg per hectanol, preferably in the range of 0.2 to 3 kg per hectare. Is.

The herbicide according to the present invention contains N- (3-chloro-4-isopropylphenyl) -2-methyl-2-pentenoic acid amide according to the present invention as a main component. The N- (3-chloro-4-isopropylphenyl) -2-methyl-2-pentenoic acid amide according to the present invention may be used as it is in its original form for the plants to be treated. However, in general, the compound of the present invention is mixed with a carrier and, if necessary, other auxiliary agents to prepare a commonly used preparation form, for example, powder, granules, wettable powder, emulsion, flowable preparation, etc. Used as a herbicide.

As the carrier, inorganic substances such as clays, talc, bentonite, calcium carbonate, diatomaceous earth, zeolite and silicic acid anhydride; plant organic substances such as wheat flour, soybean flour, starch, crystalline cellulose; petroleum resin, polyvinyl chloride , High molecular compounds such as polyalkylene glycols;
Urea; waxes and the like. Further, liquid carriers such as various oils, organic solvents and water can also be used.

As the auxiliary agent, for example, a wetting agent, a dispersant, a fixing agent, a spreading agent, etc. can be appropriately used alone or in combination as necessary.

As an auxiliary agent used for the purpose of wetting, dispersing, spreading, stabilizing components, stabilizing physical properties, various surfactants, or
Examples thereof include polymer compounds such as gelatin, albumin, sodium alginate, methyl cellulose, polyvinyl alcohol, xanthan gum, and other auxiliary agents. Further, in the case of a flowable agent, an antibacterial agent for industrial use and an antibacterial / antifungal agent for industrial use are added depending on the case for antibacterial / antifungal.

As the surfactant, nonionic, anionic, cationic and amphoteric surfactants can be appropriately used.
Preferred examples include those obtained by polymerizing ethylene oxide such as alkylphenol, higher alcohol, alkylnaphthol, higher fatty acid, fatty acid ester and dialkylphosphate amine, those obtained by polymerizing ethylene oxide and propion oxide, and alkyl sulfate ester salts (sodium lauryl sulfate). Etc.), alkyl sulfonates (sodium 2-ethylhexene sulfonate, etc.), and aryl sulfonates (sodium lignin sulfonate, sodium dodecylbenzene sulfonate, etc.).

The content of the compound of the present invention in the herbicide according to the present invention varies depending on the formulation form, but usually 1 to 2 in the case of powder.
0% by weight, 20-90% by weight for wettable powder, 1-for granules
30% by weight, 1 to 50% by weight for emulsion, 10 to 90% by weight for flowable formulation, 20 for dry flowable formulation
Is about 70% by weight. Auxiliary agent content 0-80% by weight
The content of the carrier is 100% by weight minus the contents of the active ingredient compound and the auxiliary agent.

The herbicide of the present invention is one or more kinds of other herbicides,
Not only can it be used as a mixture with pesticides such as insecticides and plant growth regulators, soil conditioners or fertilizers, but it is also possible to make a mixed preparation with these, and in some cases a synergistic effect. Can be expected.

〔Example〕

A synthesis example of N- (3-chloro-4-isopropylphenyl) -2-methyl-2-pentenoic acid amide according to the present invention is shown below.

Synthesis Example 30 g of benzene, 1.0 g of 3-chloro-4-isopropylaniline (6.4 × 10 ⁻³ mol) and triethylamine
0.6 g was added, further 0.9 g (6.8 × 10 ⁻³ mol) of 2-methyl-2-pentenoic acid chloride was added, and the mixture was stirred at room temperature for 30 minutes. After separating the precipitated crystals, 100 ml of benzene was added to the liquid, washed with a saturated aqueous solution of sodium hydrogencarbonate, dried over anhydrous sodium sulfate, and concentrated by an evaporator to obtain crude crystals. Hexane: benzene 2: 1
The crystals were recrystallized from a mixed solvent of (v / v) to obtain 1.46 g of N- (3-chloro-4-isopropylphenyl) -2-methyl-2-pentenoic acid amide crystals. m.p71.0-73.0
° C, ▲ IR ^cm-1 _max ▼ 3320,1665, yield: 3-chloro-4
-85.0% relative to isopropylaniline.

Next, formulation examples and herbicidal activity test examples of the herbicide according to the present invention are shown.

Formulation example 1 (wettable powder) Compound of the present invention: 20 parts by weight, sodium alkylbenzenesulfonate: 2 parts by weight, polyoxyethylene alkylphenyl ether: 2 parts by weight and di-crite: 76
A wettable powder was obtained by thoroughly pulverizing and mixing parts by weight.

Formulation Example 2 (wettable powder) Compound of the present invention: 30 parts by weight, polyoxyethylene alkylphenyl ether ammonium sulfate salt: 6 parts by weight, sodium naphthalenesulfonate formalin condensate: 2 parts by weight, sodium alkylbenzenesulfonate: 1 part by weight, 2 parts by weight of polyvinyl alcohol and 59 parts by weight of diatomaceous earth were well pulverized and mixed to obtain a wettable powder.

Formulation example 3 (wettable powder) Compound of the present invention: 50 parts by weight, white carbon: 3 parts by weight, polyoxyethylene alkylphenyl ether sulfate ammonium salt: 4 parts by weight, sodium alkylbenzene sulfonate: 2 parts by weight and diatomaceous earth: 41 parts by weight The parts were well pulverized and mixed to obtain a wettable powder.

Formulation Example 4 (wettable powder) Compound of the present invention: 50 parts by weight, white carbon: 5 parts by weight, polyoxyethylene alkylphenyl ether sulfate ammonium salt: 4 parts by weight, sodium lignin sulfonate: 2 parts by weight and diatomaceous earth: 34 parts by weight The parts were well pulverized and mixed to obtain a wettable powder.

Formulation Example 5 (wettable powder) Compound of the present invention: 80 parts by weight, white carbon: 5 parts by weight, ammonium polyoxyethylene alkylphenyl ether sulfate salt: 7 parts by weight, sodium naphthalene sulfonate formalin condensate: 2 parts by weight, alkylbenzene sulfone Sodium acid (2 parts by weight) and diatomaceous earth (4 parts by weight) were well pulverized and mixed to obtain a wettable powder.

Formulation Example 6 (flowable agent) Compound of the present invention: 20 parts by weight, sodium lignin sulfonate: 2 parts by weight, xanthan gum: 0.3 part by weight and polyoxyethylene alkylaryl ether: 1 part by weight, and water: 76.7 parts by weight are added. After mixing, the mixture was finely pulverized using a sand grinder to obtain a flowable agent.

Formulation Example 7 (flowable agent) Compound of the present invention: 40 parts by weight, naphthalene sulfonate
Thorium formalin condensate: 3 parts by weight, lignin sulf
Sodium sulfonate: 2 parts by weight, xanthan gum: 0.1 part
Quantity Department, Dell Top (Industrial fungicide manufactured by Takeda Pharmaceutical Co., Ltd.):
0.1 parts by weight and polyoxyethylene alkylaryl
Ether: 2 parts by weight, and 52.8 parts by weight of water were added and mixed.
After that, use a sand grinder to pulverize and floorable
I got an agent.

Formulation Example 8 (powder) The compound of the present invention: 3 parts by weight, sodium lignin sulfonate: 3 parts by weight, polyoxyethylene alkylaryl ether: 2 parts by weight and clay: 92 parts by weight were mixed and pulverized to obtain a powder.

Formulation Example 9 (powder) The compound of the present invention: 20 parts by weight, sodium lignin sulfonate: 5 parts by weight, polyoxyethylene alkylaryl ether: 4 parts by weight and clay: 71 parts by weight were mixed and ground to obtain a powder.

Formulation Example 10 (Dry flowable agent) Compound of the present invention: 60 parts by weight, sodium alkylbenzene sulfonate: 5 parts by weight and polypropylene glycol polyethylene glycol ether: 35 parts by weight are mixed and finely pulverized using Jet-O-mizer. A dry flowable agent was obtained.

Formulation Example 11 (dry flowable agent) Compound of the present invention: 70 parts by weight, sodium alkylbenzene sulfonate: 2 parts by weight, polypropylene glycol polyethylene glycol ether: 18 parts by weight and white carbon: 10 parts by weight are mixed, and Jet-O-mizer is mixed. Was finely pulverized to obtain a dry flowable agent.

Formulation Example 12 (granules) Finely ground compound of the present invention: 20.5 parts by weight, Gohsenol GL-05
After thoroughly mixing 2.0 parts by weight of S (PVA manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 2.0 parts by weight of Sun Extract P-252 (sodium lignin sulfonate by Sanyo Kokusaku Pulp Co., Ltd.) and 75.5 parts by weight of clay, 75.5 parts by weight, An appropriate amount of water was added to wet it, and then extrusion granulation was performed using an injection molding machine. This was air-dried at 60 to 90 ° C., crushed, and then sized to 0.3 to 1 mm with a sizing machine to obtain a granule.

Formulation Example 13 (granules) Finely ground compound of the present invention: 5 parts by weight, bentonite: 7
2 parts by weight, talc: 20 parts by weight, calcium dodecylbenzene sulfonate: 2 parts by weight and calcium lignin sulfonate: 1 part by weight are mixed well, then an appropriate amount of water is added to wet the mixture, and then an injection molding machine. It was extruded and granulated. This was air-dried at 60 to 90 ° C., crushed, and then sized to 0.5 to 1.2 mm with a sizing machine to obtain a granule.

Formulation Example 14 (granules) Finely ground compound of the present invention: 12 parts by weight, bentonite:
After thoroughly mixing 60 parts by weight, talc: 25 parts by weight, sodium naphthalene sulphonate formalin condensate: 2 parts by weight and dioctyl sulfosuccinate: 1 part by weight, an appropriate amount of water is added to wet the mixture, and then, It was extruded and granulated by an injection molding machine. This was air-dried at 60 to 90 ° C., crushed, and then sized to 0.3 to 1 mm with a sizing machine to obtain a granule.

Formulation Example 15 (emulsion) Compound of the present invention: 10 parts by weight, Solpol 800A (trade name of Toho Chemical Co., Ltd .: mixture of nonionic surfactant and anionic surfactant): 10 parts by weight and benzene:
Emulsion was obtained by mixing and dissolving 80 parts by weight.

Formulation Example 16 (emulsion) Compound of the present invention: 50 parts by weight, Gaffac RS-610 (General
Aniline & Film Corporation trade name: polyoxyethylene phosphate): 15 parts by weight and o-xylene: 35 parts by weight were mixed and dissolved to obtain an emulsion.

Formulation Example 17 (emulsion) Compound of the present invention: 25 parts by weight, Prysurf A-210G
(Daiichi Kogyo Seiyaku Co., Ltd. product name: polyoxyethylene phosphate): 15 parts by weight and o-xylene: 60
An emulsion was obtained by mixing and dissolving parts by weight.

Test Example 1 1/10000 ares resin pots are filled with upland soil, and test plants are sown one by one and grown in a greenhouse.
When each plant had 2-3 leaves, each compound was made into a solution with acetone containing polyoxyethylene sorbitan monooleate and sorbitan monolaurate, and a predetermined amount was sprayed with a pressurized micro-sprayer. The amount of spray was 2 kl per hectare. The effects on crops and weeds were observed 21 days after the drug was sprayed. The results are shown in Table 1. The degree of damage to the test plant is shown as follows, where 5 is complete death and 0 is no effect.

Label Damage level (%) Damage status 5 100 Death (complete control in the case of weeds) 4 80 Damage (80% control) 3 60 Moderate (60% control) 2 40 Small (40% control) 1 20 Minor Harm (20% control) 0 0 No harm (complete no control) Test Example 2 1/1000 Earl resin planter is filled with field soil, and wild oats, Astragalus chinensis, Astragalus chinensis,
Weed seeds of chickweed, chylosa and wild mustard. At the same time, seeds of wheat (variety: Norin 61) and barley (variety: Tochigi Sekitori 1) were sown as crops and cultivated in Phytotron (12 to 18 ° C.). When wheat reached a few leaves, a predetermined amount of the test compound prepared according to Formulation Example 15 was diluted with 500 equivalents of water per hectare and treated with a micro pressure sprayer. The effects on weeds and crops were observed and evaluated 3 weeks after the chemical treatment. Table 2 shows the test results. The degree of damage to the test plant was displayed as in Test Example 1.

Test Example 3 Wheat crop field test In October 1984, a wheat crop field test was conducted in Chigasaki City, Kanagawa Prefecture. Seeds of wheat (variety: Norin 61) and barley (variety: Tochigi Sekitori 1) were sown on October 19th. All weeds are naturally occurring. The drug was sprayed on November 13. At this time, the leaf age of wheat was 3 leaves and barley was 2.5 leaves. The size of the test area was 5 m ² for each area, and the test was conducted in two consecutive systems. The amount of spray was 500 equivalents per hectare, and the chemical treatment was performed with a battery-type sprayer. Evaluation is 4 after drug spraying
I went on December 4th. The degree of damage to the test plant is "10" for complete death and "0" for no effect at all 1
The evaluation was made in one stage. The results are shown in Table 3, but the number is 2
The average value of the run is shown.

The compounds of the present invention were emulsions prepared according to the method of Preparation Example 17, and the control compounds propanil, metabenzthiazulone, and bentazone were the commercially available stam emulsion, tribnil wettable powder, and basagran solution, respectively.

[Effect of the Invention] As is clear from the test results, the herbicide containing the compound of the present invention is a foliar treatment that is not affected by soil,
It showed a remarkable herbicidal effect on all the weeds tested even at low doses, while it showed excellent phytotoxicity against useful crops of grasses, especially wheat, even at extremely high doses. It shows selectivity and has a performance superior to that of comparative drugs (metabenzthiazulone, bentazone, propanil, carcil, etc.) or other known compounds.

Claims (2)

[Claims] 1. N- (3-chloro-4-isopropylphenyl) -2-methyl-2-pentenoic acid amide. 2. A selective herbicide containing N- (3-chloro-4-isopropylphenyl) -2-methyl-2-pentenoic acid amide as an active ingredient.