JPH11222483A - 2,4-diphenyl-2-oxa (thia) zoline derivative and herbicide with the same as active ingredient - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a herbicide excellent in such selective herbicidal activity as to be high in herbicidal effect against undesirable weeds and cause no chemical injury to useful crops. SOLUTION: This new compound is shown by formula I(X1 and X2 are each H or the like; Y1 is H or the like; Y2 is a lower alkyl or the like; Z is oxygen or the like), e.g. 2-(5-chloro-2-methylphenyl)-4-(4-fluorophenyl)-2-oxazoline. The compound of formula I is obtained, for example, by reaction of an amino alcohol derivative of formula II [e.g. 2-amino-2-(4-fluorophenyl)ethyl alcohol] with a benzoic acid derivative of formula III (e.g. 5-chloro-2-methylbenzoyl chloride) normally in an inert solvent such as anhydrous tetrahydrofuran in the presence of a base such as triethylaine to form the corresponding amido alcohol which, in turn, is reacted with a sulfonating agent such as methanesulfonyl chloride in the presence of a base followed by cyclization of the reaction product with a base such as potassium hydroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to 2,4-diphenyl-2.
Oxa (thia) azoline derivatives and their use as pesticides, in particular as herbicides.

[0002]

2. Description of the Related Art WO93 / 24470, WO95 / 04
726, JP-A-2-85268, JP-A-3-23
No. 2867 and JP-A-4-89484 disclose that certain 2,4-diphenyl-2-oxa (or thia) azoline derivatives are effective as insecticides, acaricides and the like. . However, these documents do not describe that 2,4-diphenyl-2-oxa (or thia) azoline derivatives have herbicidal activity.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a herbicidal compound having a large herbicidal effect on undesired weeds and having excellent selective herbicidal activity without harm to useful crops.

[0004]

SUMMARY OF THE INVENTION The present inventors have developed a process for the synthesis of certain 2,4-diphenyl-2-oxa (or thia) zoline derivatives for the purpose of developing insecticides and acaricides. It has been discovered that compounds having substituents introduced at the 2- and 5-positions on the 2-position phenyl group of the oxa (or thia) azoline ring exhibit herbicidal activity, and the herbicidal activity thereof is intensively studied. As a result, it has been found that the compound represented by the following general formula (I) exerts excellent herbicidal activity on various paddy field weeds and upland field weeds at a low dose without harming useful crops. completed.

That is, the present invention provides a compound represented by the following general formula (I):

[0006]

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[Wherein X ₁ and X ₂ each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylthio group, a halogen atom or a trifluoromethyl group; Y ₁ represents a hydrogen atom, a lower alkyl group, a lower alkyl group; Represents an alkoxy group, a lower alkylthio group, a halogen atom, a trifluoromethyl group or a nitro group; Y ₂ represents a lower alkyl group, a lower alkoxy group, a lower alkylthio group, a halogen atom, a trifluoromethyl group, a trifluoromethoxy group or a nitro group Z represents an oxygen atom or a sulfur atom], a pesticide characterized by containing this compound as an active ingredient, and in particular, herbicide. The agent is provided.

In the present specification, "lower alkyl group",
Alternatively, the alkyl portion of the “lower alkoxy group” or the “lower alkylthio group” can be linear or branched, and the term “lower” has 1 to 1 carbon atoms in the group to which the term is attached. 5 is within the range.

Thus, as the "lower alkyl group",
For example, methyl group, ethyl group, n-propyl group, iso
-Propyl group, n-butyl group, iso-butyl group, sec.-
Butyl group, tert.-butyl group, n-pentyl group, neopentyl group, tert.-pentyl group and the like. Examples of the “lower alkoxy group” include, for example, methoxy group, ethoxy group, n-propoxy group, iso- Propoxy group, n-
Butoxy group, iso-butoxy group, sec.-butoxy group, ter
t.-butoxy group, n-pentyloxy group and the like, and the “lower alkylthio group” includes, for example, methylthio group, ethylthio group, n-propylthio group, iso-
Propylthio, n-butylthio, iso-butylthio, sec.-butylthio, tert.-butylthio, n-
And a pentylthio group.

[0010] The "halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The 2,4-formula represented by the general formula (I) of the present invention
Among the diphenyl-2-oxa (or thia) zoline derivatives, preferred are those represented by the following general formula (I-1)

[0012]

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Wherein X represents a hydrogen atom, a methylthio group or a fluorine atom; Y ₁₁ represents a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom; and Y ₁₂ represents a methyl group, a fluorine atom or a chlorine atom. Z represents an oxygen atom or a sulfur atom].

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

[0015]

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In the formula, X ₁ , X ₂ , Y ₁ , and Y ₂ represent the above-mentioned general formula
Q represents the same meaning as in (I); Q represents a chlorine atom, a methanesulfonyloxy group, a toluenesulfonyloxy group, or the like.

First, the amino alcohol derivative (II)
And benzoic acid derivative (III) in the presence of a base
The amide alcohol (IV) is obtained. This amide alcohol
(IV) with a sulfonating agent in the presence of a base
Or by reacting with a halogenating agent
(V) is obtained. Next, the obtained compound (V) is closed with a base.
The above general formula wherein Z represents an oxygen atom
Compound of (I), ie, oxazoline derivative (Ia)
Is obtained. On the other hand, the above amide alcohol (IV)
In an inert solvent with a sulfurizing agent such as phosphorus pentasulfide
By flowing, the above general formula wherein Z represents a sulfur atom
The compound of (I), that is, the thiazoline derivative (Ib)
can get. Hereinafter, the reaction conditions of each step are further specifically described.
Will be explained. Step of obtaining amide alcohol (IV): As a base
Are tertiary amines such as triethylamine and pyridine.
Mines; use of inorganic bases such as potassium carbonate
Can be. The reaction can be carried out without a solvent.
Usually, it is desirable to carry out in a solvent inert to the reaction,
As the solvent, for example, carbon tetrachloride, chloroform, salt
Halogenated hydrocarbons such as methylene halide; benzene,
Aromatic hydrocarbons such as ruene and xylene; diethyl ether
Ter, tetrahydrofuran, dimethoxyethane, etc.
Ethers; keto such as acetone and methyl ethyl ketone
Acetonitrile, N, N-dimethylformamide, di
Use aprotic polar solvents such as methyl sulfoxide
Can be. The reaction is usually carried out at 0 ° C to 80 ° C.
The reaction can be performed at a temperature for 30 minutes to 24 hours. this
The compound (IV) obtained in the step is usually particularly purified
It can be used in the next step without using.

Step of obtaining compound (V): The compound (IV) obtained above is reacted with a sulfonating agent to give a compound in the case where Q is a sulfonate group such as a methanesulfonyloxy group and a toluenesulfonyloxy group. Compound (V) is obtained. At this time, as the sulfonating agent, for example, methanesulfonyl chloride, benzenesulfonyl chloride, toluenesulfonyl chloride and the like can be used. As the base, for example,
Tertiary amines such as triethylamine and pyridine; inorganic bases such as potassium carbonate and the like can be used. The reaction can be carried out without a solvent, but it is usually desirable to carry out the reaction in a solvent inert to the reaction. Examples of the solvent include carbon tetrachloride, chloroform, halogenated hydrocarbons such as methylene chloride, and the like. Aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, tetrahydrofuran and dimethoxyethane; ketones such as acetone and methyl ethyl ketone can be used. The reaction is usually performed at 0 ° C. to 80 ° C.
At a temperature of 30 minutes to 24 hours. The compound (V) obtained in this step can be usually used in the next step without particular purification.

On the other hand, compound (IV) obtained in the above step
Is reacted with a halogenating agent to obtain a compound (V) in which Q is a halogen atom. In this case, as the halogenating agent, for example, thionyl chloride, phosphorus pentachloride and the like can be used. The reaction can be carried out without a solvent, but it is usually desirable to carry out the reaction in a solvent inert to the reaction. Examples of the solvent include halogenated hydrocarbons such as carbon tetrachloride, chloroform and methylene chloride; Aromatic hydrocarbons such as benzene, toluene, and xylene can be used. The reaction can be carried out usually at a temperature between 0 ° C. and the boiling point of the solvent for 30 minutes to 24 hours. The compound (V) obtained in this step can be usually used in the next step without particular purification.

Process for obtaining oxazoline (Ia) (ring closure)
Step: As the base, for example, inorganic bases such as sodium hydroxide, potassium hydroxide and potassium carbonate; alkali alkoxides such as sodium methoxide and potassium tert.-butoxide can be used. The reaction is
Usually, it is desirable to carry out in a solvent inert to the reaction,
Examples of the solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and dioxane; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, and dimethylsulfoxide. The reaction can be usually performed at room temperature to the reflux temperature of the solvent for 20 minutes to 10 hours. The resulting oxazoline (Ia) can be separated and purified from the reaction mixture by a method known per se, for example, extraction, recrystallization, chromatography and the like.

Step for obtaining thiazoline (Ib) (ring closure):
As the sulfurizing agent, for example, diphosphorus pentasulfide, Lawson's reagent and the like can be used. Usually, the reaction is desirably carried out in a solvent inert to the reaction. Examples of usable solvents include aromatic hydrocarbons such as toluene and xylene. The reaction can be performed at the reflux temperature of the solvent for 3 to 24 hours. Separation and purification of the resulting thiazoline (Ib) from the reaction mixture can be performed by a method known per se, for example, extraction, recrystallization, chromatography and the like.

Specific examples of the compound of the general formula (I) of the present invention obtained as described above are shown in Table 1 below.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

[Table 4]

[0027]

[Table 5]

[0028]

EXAMPLES The production of the compound of the present invention will be described more specifically with reference to synthetic examples.

Synthesis Example 1 2- (5-chloro-2-methylphenyl) -4- (4-fluorophenyl) -2-oxazoline (Compound No. 39) 2-amino-2- (4-fluorophenyl) ethyl alcohol 1
g and 0.72 g of triethylamine were dissolved in anhydrous tetrahydrofuran, cooled with ice water, and stirred.
A solution of 1.22 g of chloro-2-methylbenzoyl chloride in anhydrous tetrahydrofuran was added dropwise. After stirring at room temperature for 3 hours, the reaction solution was filtered, and the filtrate was concentrated. This concentrate and 0.72 g of triethylamine were dissolved in anhydrous tetrahydrofuran, cooled with ice water, and a solution of 0.81 g of methanesulfonyl chloride in anhydrous tetrahydrofuran was added dropwise with stirring. After stirring at room temperature for 3 hours, the reaction solution was filtered, and the filtrate was concentrated. Dissolve the concentrated residue in methanol,
0.85 g of potassium hydroxide was added and reacted at 50 ° C. for 30 minutes. The reaction solution was poured into water and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, concentrated, and subjected to silica gel column chromatography (hexane: ethyl acetate =
4: 1) to give 1.10 g of a colorless solid (yield 58.9%). mp 55-58 ° C; ¹ H-NMR (δ
ppm): 2.58 (3Hs) 4.12 (1H t) 4.69 (1H dd) 5.38 (1H dd)
6.83-7.53 (6H) 7.87 (1H d).

Synthesis Example 2 2- (2,5-dichlorophenyl) -4- (4-fluorophenyl) -2-
Oxazoline (Compound No. 31) 2-Amino-2- (4-fluorophenyl) ethyl alcohol 1
g and 0.72 g of triethylamine were dissolved in anhydrous tetrahydrofuran, cooled with ice water, and stirred,
A solution of 1.35 g of 5-dichlorobenzoyl chloride in anhydrous tetrahydrofuran was added dropwise. After stirring at room temperature for 3 hours, the reaction solution was filtered, and the filtrate was concentrated. This concentrate and 0.72 g of triethylamine were dissolved in anhydrous tetrahydrofuran, cooled with ice water, and a solution of 0.81 g of methanesulfonyl chloride in anhydrous tetrahydrofuran was added dropwise with stirring. After stirring at room temperature for 3 hours, the reaction solution was filtered, and the filtrate was concentrated. The concentrated residue was dissolved in methanol, 0.85 g of potassium hydroxide was added, and the mixture was reacted at 50 ° C. for 30 minutes. The reaction solution was poured into water and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, concentrated, and subjected to silica gel column chromatography (hexane: ethyl acetate = 4:
Purification in 1) gives 1.25 g of a colorless solid (yield 6).
2.5%). mp 48-49.5 ° C; ¹ H-NMR (δpp
m): 4.17 (1Ht) 4.73 (1Hdd) 5.37 (1Hdd) 6.79-7.47 (6
H) 7.75 (1H dd).

Synthesis Example 3 2- (5-fluoro-2-methylphenyl) -4- (4-fluorophenyl) -2-oxazoline (Compound No. 37) 2-amino-2- (4-fluorophenyl) ethyl alcohol 1
g and 0.72 g of triethylamine were dissolved in anhydrous tetrahydrofuran, cooled with ice water, and stirred.
1.11 g of fluoro-2-methylbenzoyl chloride
Of anhydrous tetrahydrofuran was added dropwise. After stirring at room temperature for 3 hours, the reaction solution was filtered, and the filtrate was concentrated. This concentrate and 0.72 g of triethylamine were dissolved in anhydrous tetrahydrofuran, cooled with ice water, and a solution of 0.81 g of methanesulfonyl chloride in anhydrous tetrahydrofuran was added dropwise with stirring. After stirring at room temperature for 3 hours, the reaction solution was filtered, and the filtrate was concentrated. Dissolve the concentrated residue in methanol,
0.85 g of potassium hydroxide was added and reacted at 50 ° C. for 30 minutes. The reaction solution was poured into water and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, concentrated, and subjected to silica gel column chromatography (hexane: ethyl acetate =
4: 1) to give a colorless oil (1.05 g).
(59.6% yield). _{^{N D 26 ℃ 1.5629; 1 H}} -NM
R (δppm); 2.57 (3Hs) 4.08 (1Ht) 4.65 (1Hdd) 5.34
(1H dd) 6.75-7.37 (6H) 7.50 (1 H dd).

Synthesis Example 4 2- (2,5-dichlorophenyl) -4- (4-methylthiophenyl)-
2-thiazoline (Compound No. 101) N- [2-hydroxy-1- (4-methylthiophenyl) ethyl] -2,
1.5 g of 5-dichlorobenzamide and 0.1 g of diphosphorus pentasulfide.
94 g was suspended in toluene and heated under reflux for 8 hours. The reaction solution is returned to room temperature, and a 20% sodium hydroxide solution 10 ml
Was added and heated under reflux for 1 hour. The reaction solution was poured into water, saturated saline was added, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, concentrated, and purified by silica gel column chromatography (hexane: ethyl acetate = 5: 1) to obtain 1.10 g of a colorless oil (yield: 77.2).
%). _{^{N D 26 ℃ 1.6598; 1 H}} -NMR (δppm): 2.4
5 (3H s) 3.31 (1H dd) 3.82 (1H dd) 5.63 (1H t) 7.07-7.
73 (7H).

The compound of the formula (I) of the present invention has an excellent herbicidal effect as shown in the test examples described later, and is useful as a herbicide. When the compound of the present invention is used as a herbicide, it can be used as it is, but it is generally used in a usual formulation. As the formulation form,
Examples thereof include powders, granules, wettable powders, liquid preparations, emulsions, flowable preparations, and jumbo preparations. These preparations can be produced by mixing the compound of the present invention with carriers or diluents, additives, auxiliaries and the like by a method known per se.

The carriers or diluents used in the preparation include, for example, the following: Solid carriers include, for example, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, gypsum, carbonate Examples of the liquid carrier include water, alcohols (methanol, n-hexanol, ethylene glycol, and the like), ketones (acetone, cyclohexanone, and the like).
Isophorone), ethers (dioxane, tetrahydrofuran, etc.), aliphatic and aromatic hydrocarbons (kerosene, mineral oil, xylene, cumene, methylnaphthalene, etc.), halogenated hydrocarbons (trichloroethylene, monochlorobenzene, etc.), esters (E.g., ethyl acetate, ethylene glycol acetate, dibutyl maleate) and polar solvents (e.g., dimethylformamide, dimethyl sulfoxide).

In addition, emulsification and dispersion of the compound of the present invention,
Surfactants and other additives can also be used for purposes such as spreading, disintegration control, and stabilizing the active ingredient.

Examples of the surfactant which can be used at that time include polyoxyethylene glycol ether, alkyl sulfate, alkyl sulfate, aryl sulfate and the like. Further, in order to improve the shape of the preparation and enhance the effect, an auxiliary agent such as carboxymethylcellulose, polyvinyl alcohol, or polyethylene glycol can be used in combination.

In preparing the above-mentioned preparations, the above-mentioned carriers and various additives and auxiliaries can be used alone or in combination according to the respective purposes. The active ingredient content of the compound of the present invention in various formulations,
For example, the appropriate amount is usually 1 to 50% by weight for emulsions, 1 to 90% by weight for wettable powders, 1 to 30% by weight for granules, and 1 to 50% by weight for flowables.

The herbicide containing the compound of the present invention can be applied to a variety of weeds growing before and after growing on agricultural lands such as paddy fields and fields and non-agricultural lands. Examples of the method of use include soil treatment, water surface treatment, foliage treatment, and the like. Further, the herbicide of the present invention, other active ingredients that do not inhibit the herbicidal activity of the active ingredient, for example, other herbicides, insecticides, fungicides, plant growth regulators, fertilizers, soil improvers and the like It is also possible to mix or use together. In particular, by mixing and using other herbicides, it is possible to reduce the amount of the drug used, to broaden the herbicidal spectrum by synergistic action of both drugs, and to increase the effect by synergistic action.

Next, preparation examples will be shown. "Parts" in the following preparations represent parts by weight.

Formulation Example 1 (Emulsion) <Compound No. 39> 20 parts, xylene 70 parts, calcium dodecylbenzenesulfonate 5 parts and polyoxyethylenestyrylphenyl ether 5 parts were uniformly mixed and stirred to obtain an emulsion.

Formulation Example 2 (Wettable powder) <Compound No. 39> 15 parts, polyoxyethylene styrylphenyl ether ammonium salt 3 parts, white carbon 5 parts, clay 75 parts and ligninsulfonic acid sodium salt 2 parts were uniformly mixed and ground to obtain a wettable powder.

Formulation Example 3 (Granules) After uniformly mixing 40 parts of bentonite, 2 parts of calcium ligninsulfonate and 53 parts of talc, water was added and kneaded, and base granules were prepared by an extrusion granulator. <Compound N
o. 39> 5 parts were uniformly impregnated in the base particles to obtain granules.

Formulation Example 4 (Flowable) <Compound No. 39> 20 parts, polyoxyethylene styryl phenyl ether phosphate 5 parts, propylene glycol 5 parts, defoamer 0.5 part, xanthan gum 0.2
Parts and 69.3 parts of water were mixed and pulverized using a wet pulverizer,
A flowable was prepared.

Next, the herbicidal activity of the compound of the present invention will be described with reference to test examples.

Test Example 1 (Soil Treatment in Paddy Field) A pot of 1 / 10,000 R was filled with paddy soil, and an appropriate amount of water and a chemical fertilizer were added and kneaded to form a paddy field. Various seedlings of nobie, firefly, conger, and broadleaf were sown on this, and 2.0-leaf rice (cultivar: Koshihikari) was transplanted and kept in a flooded state. The next day, a wettable powder was prepared according to Formulation Example 2, diluted with an appropriate amount of water, and dropped with a pipette so as to have a predetermined dose per are. The herbicidal activity on the test weeds and the phytotoxicity on the rice plant 20 days after the chemical treatment were determined according to the criteria shown in Table 2, and the results are shown in Table 3.

Test Example 2 (Field Soil Treatment) A 1 / 6,000 are pot was filled with field soil, and an appropriate amount of chemical fertilizer was added. To this, seeds of Mehishiba, Shiroza, Aobuyu and Purslane are sowed, and 0.5 c
m of soil. The next day, a wettable powder was prepared according to Formulation Example 2 and diluted to a predetermined dose, and 15
Spraying was carried out with a liter of spray water. The herbicidal activity on the test weeds 20 days after the treatment was determined according to the criteria shown in Table 2, and the results are shown in Table 4.

Test Example 3 (Field foliage treatment) A 1 / 6,000 are pot was filled with field soil, and an appropriate amount of chemical fertilizer was added. To this, seeds of Mehishiba, Shiroza, Aobuyu and Purslane are sowed, and 0.5 c
m of soil. After growing the green crabgrass in the greenhouse until the 2.0 leaf stage, a wettable powder was prepared according to Formulation Example 2,
The mixture was diluted to a predetermined dose and sprayed with a spraying water amount of 15 liters per are. The herbicidal activity on the test weeds 20 days after the treatment was determined according to the criteria shown in Table 2, and the results are shown in Table 5.

[0048]

[Table 6]

[0049]

[Table 7]

[0050]

[Table 8]

[0051]

[Table 9]

[0052]

As is clear from the results of the above test examples,
The 2,4-diphenyl-2-oxa (or thia) azoline derivative represented by the general formula (I) of the present invention can be used for various weeds that are problematic in soil treatment and foliage treatment in upland fields, for example, Shiroza, It has excellent herbicidal activity even at low doses against broadleaf weeds such as Aoubi, Ichibai, Yaegura, and grasses such as Nobie and Meishibashi, and it is also used in major crops such as corn, wheat, soybean, cotton It does not cause harmful chemical damage.

Further, the compound of the present invention is useful for various weeds which are problematic in paddy fields, for example, annual weeds such as barnyardgrass, snapper, oak, kikasigusa and azalea, and perennial weeds such as fireflies, pine trees, swelling moss, etc. Has excellent herbicidal activity even at low doses,
Moreover, it shows little phytotoxicity to transplanted rice.

Further, the compound of the present invention can be advantageously used as an active ingredient of a herbicide exhibiting an excellent herbicidal effect not only in paddy fields and fields, but also in orchards, lawns and non-agricultural lands. As described above, according to the present invention, an agriculturally useful herbicide can be provided.

Claims (2)

[Claims] 1. A compound of the general formula (I) Wherein X ₁ and X ₂ each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylthio group, a halogen atom or a trifluoromethyl group; Y ₁ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, Y ₂ represents a lower alkylthio group, a halogen atom, a trifluoromethyl group or a nitro group; Y ₂ represents a lower alkyl group, a lower alkoxy group, a lower alkylthio group, a halogen atom, a trifluoromethyl group, a trifluoromethoxy group or a nitro group; Z represents an oxygen atom or a sulfur atom.], A 2,4-diphenyl-2-oxa (or thia) azoline derivative represented by the formula: 2. An agricultural chemical comprising the 2,4-diphenyl-2-oxa (or thia) azoline derivative represented by the general formula (I) according to claim 1 as an active ingredient.