JPH05201979A - New pyridylphenyl ether derivative and herbicide with the same as active ingredient - Google Patents

Abstract

PURPOSE:To provide the subject new compound useful as a selective herbicide. CONSTITUTION:The objective compound of formula I [Y is halogen; X is H, halogen, lower alkyl or OR<3>; R<1> to R<3> are each H, (substituted) lower alkyl, etc.], e.g. methyl 4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-2-ethylpropionatoxy-o- methylbenzohydroximate. The compound of the formula I can be obtained by reaction of a 2-chloropyridine derivative of formula II with a phenol derivative of formula III in the presence of a base in an organic solvent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel pyridyl phenyl ether derivative which has not been described in the literature and a herbicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art A number of diphenyl ether compounds having herbicidal activity have been proposed, including 2,4-dichloro-4'-nitrodiphenyl ether (generic name nitrophen). Further, JP-A-63-165359 proposes to use a 2-nitro-5- (substituted phenoxy) benzohydroxymic acid derivative as a herbicide.

[0003]

However, the compounds described in the above-mentioned documents have many points to be improved in terms of herbicidal spectrum, dosage amount, selectivity and the like.

The present inventors have conducted extensive studies to develop a compound having a wide herbicidal spectrum, a high herbicidal effect, and excellent safety against crops. As a result, a benzohydroxymic acid derivative having a pyridyloxy group at the 4-position is novel. It was found that this compound has an excellent herbicidal effect not only on annual but also on perennial weeds, and has high safety against certain kinds of crops, and thus completed the present invention.

That is, the present invention has the general formula

[0006]

[Chemical 3]

(Wherein Y represents a halogen atom, X represents a hydrogen atom, a halogen atom, a lower alkyl group or a group —OR
Indicates ³ . R ¹ , R ² and R ³ are each independently substituted with a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, an aralkyl group, a lower alkyl group substituted with a hydroxycarbonyl group or a lower alkoxycarbonyl group. A lower alkyl group, a lower alkyl group substituted with a lower alkenyloxycarbonyl group, a lower alkyl group substituted with a lower alkynyloxy group or a lower alkylcarbonyl group is shown. The present invention provides a novel pyridyl phenyl ether derivative represented by (4) and a herbicide containing the same as an active ingredient.

[0008]

The compound of the present invention has the following general formula (I):

[0009]

[Chemical 4]

(In the formula, Y represents a halogen atom, X represents a hydrogen atom, a halogen atom, a lower alkyl group or a group —OR.
Indicates ³ . R ¹ , R ² and R ³ are each independently substituted with a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, an aralkyl group, a lower alkyl group substituted with a hydroxycarbonyl group or a lower alkoxycarbonyl group. A lower alkyl group, a lower alkyl group substituted with a lower alkenyloxycarbonyl group, a lower alkyl group substituted with a lower alkynyloxy group or a lower alkylcarbonyl group is shown. ) Is a novel pyridyl phenyl ether derivative.

In the general formula (I), Y, X,
In the definitions of R ¹ , R ² and R ³ , specific examples of each group are shown below.

Halogen atom ; for example, fluorine, chlorine,
Bromine, lower alkyl group ; for example, lower alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl group, lower alkenyl group ; for example, allyl group Carbon number such as 2
~ 5 lower alkenyl group, lower alkynyl group ; for example, lower alkynyl group having 2-5 carbon atoms such as 2-propynyl group, aralkyl group ; for example, lower alkyl group substituted with benzyl group, hydroxycarbonyl group ;
For example, the alkyl moiety such as hydroxycarbonylmethyl and 1-hydroxycarbonyl-ethyl group has 1 carbon atom.
5 lower alkyl group substituted with a hydroxycarbonyl group, a lower alkyl substituted with lower alkoxycarbonyl group
Group ; for example, lower alkyl group and lower alkenyloxycarbonyl group in which an alkyl moiety such as methoxycarbonylmethyl, 1-methoxycarbonyl-ethyl, 1-ethoxycarbonyl-ethyl group is substituted with a lower alkoxycarbonyl group having 1 to 5 carbon atoms Lower-order substituted with
Alkyl group ; for example, allyloxycarbonylmethyl,
A lower alkyl group in which an alkenyl moiety such as a 1-allyloxycarbonyl-ethyl group and an alkyl moiety are substituted with a lower alkenyloxycarbonyl group having 2 to 5 and 1 to 5, respectively, and a lower alkyl group substituted with a lower alkynyloxy group. Group ;
For example, propargyloxycarbonylmethyl, 1-
An alkynyl moiety such as a propargyloxycarbonyl-ethyl group and an alkyl moiety each have 2 to 5 carbon atoms.
And 1-5 lower alkyl group substituted with a lower alkyl group, a lower alkylcarbonyl group; for example, methylcarbonyl, such alkyl portion of the tert-butyl group is a lower alkyl group having 1 to 5 carbon atoms.

The compounds of the present invention represented by the general formula (I) are shown in Table 1.

[0014]

[Table 1]

[0015]

[Table 2]

The compound of the present invention represented by the above general formula (I) can be produced, for example, by the following reaction formula.

Reaction formula A

[0018]

[Chemical 5]

In the formula, Y, X, R ¹ and R ² are the same as defined above. As shown in Reaction Formula A, the compound of the present invention can be produced by reacting a 2-chloropyridine derivative and a phenol derivative (II) in the presence of a base in an organic solvent. Reaction is 2 with respect to compound (II)
1 to 1.5 molar equivalents of the chloropyridine derivative are carried out at temperatures from room temperature to about 110 ° C. for 1 to 8 hours. Examples of preferable bases used in the reaction include potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride and the like. Examples of preferred solvents used in the reaction include tetrahydrofuran, N, N-
Examples thereof include dimethylformamide, dimethyl sulfoxide, methanol and the like. After completion of the reaction, the compound of interest of the present invention can be isolated by pouring the reaction mixture into water and treating with an organic solvent according to a conventional method such as extraction, recrystallization, column chromatography and the like.

Reaction formula B

[0021]

[Chemical 6]

In the formula, Y, R ¹ , R ² and R ³ are the same as defined above, and A is chlorine, bromine, iodine, methanesulfonyloxy group and p-toluenesulfonyloxy group. As shown in the above reaction formula B, the phenol derivative (III) and the halogen or sulfonate derivative (I
The compound of the present invention can be produced by reacting V) in the presence of a base in the same manner as in reaction formula A in an organic solvent. In the reaction, (IV) is converted to 1 against compound (III)
It is carried out for 1 to 8 hours at a temperature of room temperature to about 110 ° C. using about 1.5 molar equivalents.

Reaction formula C-1

[0024]

[Chemical 7]

Reaction formula C-2

[0026]

[Chemical 8]

In the formula, Y, X and R ¹ are the same as defined above. As shown in the above reaction formulas C-1 and C-2, the acid chloride derivative (VI) and the hydroxylamine derivative (VII) are reacted in an organic solvent in the presence of a base to give a hydroxymic acid derivative (VIII). Obtained, and (V
III) can be reacted with diazomethane in an organic solvent such as diethyl ether or tetrahydrofuran to produce the hydroxamic acid derivative (IX). Reaction formula C-
The reaction (1) is carried out at 0 ° C. to room temperature for 0.5 to 8 hours using 1 to 1.5 molar equivalents of (VII) to (VI). The reaction of reaction formula C-2 is carried out at 0 ° C. to room temperature for 0.5 to 2 hours using 1 to 1.5 molar equivalents of diazomethane to (VIII). Examples of preferred bases used in Reaction Formula C-1 include triethylamine, pyridine, potassium carbonate, sodium hydroxide and the like. Tetrahydrofuran, diethyl ether, pyridine, toluene, etc. are mentioned as an example of a preferable organic solvent used for Reaction formula C-1. Reaction formula C-
After completion of the reaction at 1, (VIII) is obtained by pouring the reaction mixture in water and treating with an organic solvent according to a conventional method such as extraction, recrystallization, column chromatography and the like. Reaction formula C
After the reaction at −2, the excess diazomethane is treated with acetic acid, concentrated, and then treated by a conventional method such as recrystallization or column chromatography to isolate the compound of interest of the present invention. ..

Next, the synthesis examples of the compound (I) of the present invention will be specifically described with reference to Examples.

[0029]

Examples Example; 4- (3-chloro-5-trifluoromethyl-
2-Pyridyloxy) -2-ethylpropionate oki
Methyl cy-O-methylbenzohydroxymate (Compound No.
No. 6) synthesis

[0030]

[Chemical 9]

4- (3-chloro-5-trifluoromethyl-2-pyrimidyloxy) -2-ethylpropionateoxybenzoic acid (4.0 g, 8.37 mmol) was dissolved in 5 ml of thionyl chloride and heated under reflux for 3 hours. To do. The excess thionyl chloride is distilled off to obtain the acid chloride. Dissolve 5 g (0.125 mol) of sodium hydroxide in 30 ml of water,
30 ml of diethyl ether was added, and 2.1 g (0.025mo) of O-methylhydroxylamine hydrochloride under ice cooling.
l) was added and the mixture was stirred for 30 minutes, and then separated to obtain an ether layer, which was dried over anhydrous sodium sulfate to obtain an ether solution of O-methylhydroxylamine. To this, 1.16 ml (8.37 mmol) of triethylamine was added, the tetrahydrofuran solution of the acid chloride obtained above was added dropwise under ice cooling, and the mixture was stirred for 2 hours. Water was added to the reaction solution, extraction was performed with ether, and the ether layer was washed successively with diluted hydrochloric acid and saturated brine. The ether layer is dried over anhydrous sodium sulfate, the solvent is distilled off, and the crude product is purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 4/1) to give 4- (3-chloro-5). -Trifluoromethyl-
2.8 g of methyl 2-pyridyloxy) -2-ethylpropionateoxybenzohydroxamic acid (yield 66%)
Got

The hydroxamic acid obtained above was dissolved in 20 ml of diethyl ether, and 20 ml of an ether solution of diazomethane prepared from 1.75 g (0.017 mol) of N-nitrosomethylurea was added dropwise under stirring with ice cooling, and the mixture was stirred for 1 hour. Stir. The crude product obtained by decomposing excess diazomethane with acetic acid and distilling off the solvent is subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate 10 /
1. Purify in step 1 to give the desired methyl 4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) -2-ethylpropionateoxy-O-methylbenzohydroxymate (Compound No. 6) 2. 6 g (yield 92%) was obtained.

The compounds shown in Table 1 above were synthesized by the same method. Table 2 shows the NMR data of these compounds.

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

[0037]

[Table 6]

[0038]

[Table 7]

The compound (I) of the present invention has herbicidal activity. In that case, a carrier or diluent,
Used by mixing with additives and adjuvants by a method known per se, and prepared into a formulation form usually used as an agricultural chemical, for example, powder, granule, wettable powder, emulsion, water solvent, flowable agent, etc. .. Other pesticides such as fungicides, insecticides, acaricides, other herbicides, plant growth regulators, fertilizers,
Alternatively, they can be used as a mixture or in combination with a soil conditioner or the like. Especially when mixed with other herbicides,
Not only can the amount of drug used be reduced and labor saving can be achieved, but a broader herbicidal spectrum due to the synergistic action of both drugs and a higher effect due to a synergistic action can be expected.

As the carrier or diluent used in the preparation, solid or liquid carriers generally used in agriculture are used. Examples of solid carriers include clays and talc represented by kaolinite group, montmorillonite group, illite group or apatargite group; diatomaceous earth, magnesium lime, apatite, zeolite, silicic acid anhydride, synthetic calcium silicate, etc. Other inorganic substances; soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch, ether alcohols such as diethylene glycol butyl ether such as crystalline cellulose; polar solvents such as dimethylformamide and dimethylsulfoxide; and water.

In addition, emulsification, dispersion of the compound of the present invention,
Surfactants and other auxiliary agents may be used for the purposes of wetting, spreading, binding, controlling disintegration, stabilizing active ingredients, improving fluidity, and preventing rust. Examples of surfactants used may be nonionic, anionic, cationic and zwitterionic, but are usually nonionic and / or anionic. A compound is used.

Suitable nonionic surfactants include, for example, lauryl alcohol, stearyl alcohol,
Compounds obtained by polymerizing addition of ethylene oxide to higher alcohols such as oleyl alcohol; Compounds obtained by polymerizing addition of ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol; Compounds obtained by polymerizing addition of ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; Palmitin acid,
Compounds obtained by polymerizing addition of ethylene oxide to higher fatty acids such as stearic acid and oleic acid; higher fatty acid esters of polyhydric alcohols such as sorbitan and those obtained by polymerizing addition of ethylene oxide; compounds obtained by polymerizing addition of ethylene oxide and propylene oxide, etc. Can be mentioned.

Suitable anionic surfactants are, for example, alkyl sulphate salts such as sodium lauryl sulphate, oleyl alcohol sulphate amine salts; alkyl sulphonic acids such as sodium sulfosuccinate dioctyl ester and sodium 2-ethylhexene sulphonate. Salts: aryl sulfonates such as sodium isopropyl naphthalene sulfonate, sodium methylenebisnaphthalene sulfonate, sodium lignin sulfonate, sodium dodecylbenzene sulfonate, and the like.

Further, the herbicide of the present invention is a polymer such as casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, etc. for the purpose of improving the properties of the preparation and enhancing the herbicidal effect. Compounds and other auxiliary agents can also be used in combination.

The above-mentioned carrier and various auxiliary agents are appropriately used alone or in combination depending on the purpose, taking into consideration the dosage form of the preparation, the application scene and the like.

The content of the compound (active ingredient) of the present invention in the various dosage forms thus obtained varies depending on the dosage form, but is usually 0.1 to 99% by weight, and particularly preferably 0.1 to 99% by weight. Most preferred is 1-80% by weight.

In the case of powders, for example, the active ingredient compound is usually contained in an amount of 1 to 25% by weight, and the balance is a solid carrier.

In the case of a wettable powder, for example, the active ingredient compound is usually contained in an amount of 25 to 90% by weight, and the balance is a solid carrier and a dispersion wetting agent, and if necessary, a protective colloid agent, a defoaming agent and the like are added. Be done.

In the case of granules, for example, the active ingredient compound is usually contained in an amount of 1 to 35% by weight, and the balance mainly comprises a solid carrier and a surfactant. The active ingredient compound is uniformly mixed with the solid carrier, or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.2 to 1.5 mm.

In the case of an emulsion, for example, the active ingredient compound is usually contained in an amount of 5 to 60% by weight, and it contains about 5 to 2%.
It contains 0% by weight of an emulsifier, the rest is a liquid carrier, and a rust inhibitor is added if necessary.

In the case of a flowable agent, for example, the active ingredient compound is usually contained in an amount of 5 to 50% by weight, which contains a dispersion wetting agent in an amount of 3 to 10% by weight, and the balance is water. A protective colloid agent, an antiseptic agent, an antifoaming agent and the like are added.

The pyridyl phenyl ether derivative of the present invention can be applied as it is to the compound of the general formula (I) or in any of the above-mentioned preparation forms.

The herbicide of the present invention can be applied to the control or control of various weeds growing in paddy fields and upland fields from the pre-emergence stage to the growing season. The application amount is 0.001 to 5 k per ha as the amount of the compound represented by the general formula (I) (the amount of the active ingredient).
It is about g, preferably about 0.01 to 1 kg, and can be appropriately selected and changed depending on the kind of the target weed, the growth stage, the application place, the application time, the weather and the like.

Next, several embodiments of formulation examples using the compound of the present invention will be shown. "Parts" in the following formulation examples are based on weight.

Formulation Example 1 (Granule) Compound No. 1 5 parts Bentonite 40 parts Talc 52 parts Sodium lignin sulfonate 2 parts Polyoxyethylene alkylaryl ether 1 part After thoroughly mixing, an appropriate amount of water is added and kneaded. Then, 100 parts of granules were obtained by granulating using a granulator.

Formulation Example 2 (wettable powder) Compound No. 1 20 parts Diatomaceous earth 60 parts White carbon 15 parts Sodium lignin sulfonate 3 parts Sodium dialkylnaphthalene sulfonate 2 parts are mixed and uniformly mixed and pulverized with a jet mill. Wettable powder 1
I got 00 parts.

Formulation Example 3 (Emulsion) Compound No. 1 30 parts Xylene 55 parts Cyclohexanone 10 parts Calcium dodecylbenzene sulfonate 3 parts Polyoxyethylene alkylaryl ether 2 parts were uniformly mixed and dissolved to obtain 100 parts of an emulsion.

Drugs using the compound of the present invention were each prepared according to the above-mentioned preparation examples.

[0059]

The effect of the present invention is represented by the above general formula (I),
The pyrimidylphenyl derivative is a novel compound described in the end of the literature.

The compound and the herbicide of the present invention can control weeds that grow on agricultural land from the pre-emergence stage to the growing season. For example, paddy weeds such as Nobie, Firefly, Mizuhigai, Konagi, Azaena, Mizohabe, Kishigusa, Matsubayai, Urikawa, etc., and Crabgrass, Enocorogusa, Ohishiba, Suzunohie, Suzunotsutsupou, Azaleas japonicus, Acacia serrata, Acacia serrata, Acacia serrata, Acacia, It is possible to control weeds such as morning glory, morning glory, ragweed, ragweed, herb, rapeweed, sengangusa, yaemgra and buckwheat vine. In addition to paddy fields and fields, orchards, mulberry fields,
It can also be used on lawns and non-cultivated lands.

Moreover, the compounds of the present invention have selectivity for certain cultivated crops, and particularly excellent selectivity for crops such as rice, cotton, soybean and corn.

Next, the herbicidal effect will be described with reference to test examples.

Test Example 1 (Treatment of Paddy Leaves) A square pot (16 × 20 × 12 cm) was filled with paddy soil, and after weeding, various weed seeds shown in Table 3 were sown in fixed amounts, and then 2.5. Leaf stage rice was transplanted. 1.5 for each weed
~ Growing in the greenhouse until the 2 leaf stage, the compound of the present invention shown in Table 1 is prepared into a wettable powder according to Formulation Example 2, and the water dilution thereof becomes the amount of active ingredient shown in Table 2. So that it was sprayed. Twenty-one days after spraying the chemicals, the herbicidal effect on various weeds and the degree of phytotoxicity of rice were determined according to the following criteria. The results are shown in Table 3.

[0064]

[Table 8]

[0065]

[Table 9]

[0066]

[Table 10]

Test Example 2 (Soil Treatment Before Germination of Paddy Field) A square pot (16 × 20 × 12 cm) was filled with paddy soil, and after weeding, various weed seeds shown in Table 4 were sown in fixed amounts, and then 2 Rice was transplanted at the 5th leaf stage. The next day, the compounds of the present invention shown in Table 4 were prepared into wettable powders according to Preparation Example 2,
The diluted solution was sprayed dropwise so that the amount of active ingredient shown in Table 4 was obtained. Twenty-one days after the chemical spraying, the herbicidal effect on various weeds and the degree of phytotoxicity of rice were determined according to the criteria of Test Example 1. The results are shown in Table 4.

[0068]

[Table 11]

[0069]

[Table 12]

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[Procedure amendment]

[Submission date] December 5, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0066

[Correction method] Change

[Correction content]

[0066]

[Table 10]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsuru Hikido 8-3-1 Chuo, Ami-machi, Inashiki-gun, Ibaraki Sanryo Petrochemical Co., Ltd. Tsukuba Research Laboratory (72) Inventor Takashi Kaji Ami-cho, Inashiki-gun, Ibaraki Chuo 8-3-1 Sanritsu Yuka Co., Ltd. Tsukuba Research Institute

Claims (2)

[Claims] 1. A general formula: (In the formula, Y represents a halogen atom, and X represents a hydrogen atom, a halogen atom, a lower alkyl group or a group —OR ³ .
R ¹ , R ² and R ³ are each independently substituted with a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, an aralkyl group, a lower alkyl group substituted with a hydroxycarbonyl group or a lower alkoxycarbonyl group. A lower alkyl group, a lower alkyl group substituted with a lower alkenyloxycarbonyl group, a lower alkyl group substituted with a lower alkynyloxy group or a lower alkylcarbonyl group is shown. ) Is a novel pyridyl phenyl ether derivative. 2. A general formula: (In the formula, Y represents a halogen atom, and X represents a hydrogen atom, a halogen atom, a lower alkyl group or a group —OR ³ .
R ¹ , R ² and R ³ are each independently substituted with a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, an aralkyl group, a lower alkyl group substituted with a hydroxycarbonyl group or a lower alkoxycarbonyl group. A lower alkyl group, a lower alkyl group substituted with a lower alkenyloxycarbonyl group, a lower alkyl group substituted with a lower alkynyloxy group or a lower alkylcarbonyl group is shown. ) A herbicide containing a novel pyridyl phenyl ether derivative represented by (4) as an active ingredient.