JPH0673030A - 2-@(3754/24)2,6-dihalophenyl)-4-@(3754/24)2-alkoxy-4-alkyl, halo or trifluoromethylphenyl)-2-oxazolines and agricultural and horticultural insecticide comprising the same active ingredient - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as an agricultural and horticultural insecticide effectively controlling especially hemipterous insect pests with a small amount. CONSTITUTION:A compound of formula I (R is methyl, Cl, Br, F or trifluoromethyl; R' is methyl, ethyl, n-propyl or isopropyl; X is F or Cl) such as 2-(2,6-difluorophenyl)-4-(4-chloro-2-n-propoxyphenyl)-2-oxazoline. The compound of formula I is obtained by reacting a 2-phenylglucinol of formula II with fluorophenylbenzoyl chloride in the presence of a base (e.g. triethylamine) in a solvent such as THF and subjecting to ring closure. The compound of formula II is obtained by subjecting ethyloxalyl chloride and anhydrous aluminum chloride to Friedel Crafts reaction to give a keto-ester derivative, converting the keto-ester derivative to an oxime derivative and reducing.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to 2- (2,6-dihalophenyl) -4- (2-alkoxy-4-alkyl, halo or trifluoromethylphenyl) -2-oxazolines, and their active ingredients. The present invention relates to an agricultural and horticultural insecticide.

[0002]

2. Description of the Related Art There have been some reports on 2,4-diphenyl-2-oxazolines. For example, Tetrahedron Letters (Vol. 22, No. 45, 4471)
~ 4474, 1981), Chemical Abstracts (Vol.98, No.19, 160087k, 1983), Journal of Organic Chemistry (Vol.522523-).
2530, 1987), there is a description of its production method.

Further, in Japanese Patent Publication No. 57-501962, there is a description of 2-oxazolines in the disclosure regarding the method for producing a Δ ² -N-heterocyclic compound. The disclosed compounds have been described as intermediates for the manufacture of active ingredients of pharmaceuticals and as such have been shown to be useful, for example as antidiabetic agents. However, the above cited document is not known for use in the field of agriculture and horticulture.

On the other hand, the present inventors have previously found that 2,4-diphenyl-2-oxazolines have an acaricidal effect on plant parasitic mites (Japanese Patent Laid-Open No. 2-8).
No. 5268, No. 3-23287, and No. 3-89484.
Issue).

[0005]

The compound of the present invention is a compound included in the general formula of the claims of JP-A-2-85268, but among the compounds not described in the specification, 2- 2- (2,6-dihalophenyl) -having a substituent on the benzene ring substituted at the 4-position of the oxazoline ring, having an alkoxy group at the 2-position and a halogen atom, a trifluoromethyl group or an alkyl group at the 4-position 4-
As a result of repeated studies on (2-alkoxy-4-alkyl, halo or trifluoromethylphenyl) -2-oxazolines, the compound showed extremely strong insecticidal activity as compared with the compounds described in JP-A-2-85268, and The present invention has been completed by finding out that it is a practical insecticide with very little chemical damage to useful plants.

That is, the present invention provides the following formula (I):

[Chemical 2] (In the formula, R represents a methyl group, a chlorine atom, a bromine atom, a fluorine atom or a trifluoromethyl group, R ′ represents a methyl group, an ethyl group, a normal propyl group or an isopropyl group, and X represents a fluorine atom or a chlorine atom. 2- (2,6-dihalophenyl) -4- (2-
Alkoxy-4-alkyl, halo or trifluorophenyl) -2-oxazolines, and agricultural and horticultural insecticides containing the same.

Next, a method for producing the compound of the present invention will be described. 2- (2,6) represented by the above formula (I) according to the present invention
-Dihalophenyl) -4- (2-alkoxy-4-alkyl, halo or trifluoromethylphenyl) -2-oxazolines can be prepared according to the following reaction schemes I, II and III. 2-phenylglycinols, which are intermediates in the synthesis of the compound of the present invention, are 2-
Although it can be produced by reducing phenylglycines, 2-phenylglycinol derivatives having a substituent on the benzene ring (compounds 7 and 7 ') are generally substituted benzenes (compound 11). Can be synthesized from.

2-Phenylglycinols have a form in which two carbon atoms are added to a substituted benzene which is a starting material. Therefore, as a general production method, a Friedel-Crafts reaction is used to produce ethyloxalyl chloride. And a method of synthesizing a ketoester derivative (Compound 12) with anhydrous aluminum chloride (Production Process Diagram II; Reference: J. Med. Ch.
em. 15, 1029 (1972)) or substituted benzene is brominated with bromine gas or the like, and then the Grignard reagent is induced, and this is reacted with diethyl oxalic acid to synthesize a ketoester derivative (Compound 12) (process diagram) II
I; References: J. Org. Chem. 52.5026
(1987)). The ketoester derivative (compound 12) is converted to an oxime derivative (compound 13; reference: Ber.40.1676 (1907)) and then reduced (reference: Org. Syn. 65,173).
(1977)) to give 2-phenylglycinols (compound 7 ').

By the way, when benzenes having different substituents at the 2,4 position are used as a starting material, two types of isomers having different substitution positions are usually produced in the Friedel-Crafts reaction or the bromination reaction. Isomers of ketoester derivatives (Compound 12) and isomers of brominated derivatives (Compound 14)
Is often difficult to separate by distillation, crystal precipitation or column chromatography. We started from an acetyl derivative of phenol having a substituent at the meta position (Compound 1) as a starting material, and did not contain isomers of 2- (2-alkoxy-4-alkyl, halo or trifluoromethylphenyl) glycinols (Compound The manufacturing method of 7) was examined and the manufacturing process shown below was found.

The feature of this step is that the isomer-free 2-
The reaction of A was used in the production of (2-alkoxy-4-alkyl, halo or trifluoromethylphenyl) glycinols (Compound 7). Compound 2
In synthesizing, the Friedel-Crafts reaction of m-substituted phenols with acetyl chloride and anhydrous aluminum chloride produces two isomers and a considerable proportion of unnecessary 4-hydroxyacetophenones. . The reaction of A is generally called Fries rearrangement, but 4-hydroxyacetophenones are
Rarely generated (Reference: Chem. Rev. 7
0,295 (1970); Org. Rea. 1,342
(1942); Tetrahedron, 26, 100.
1 (1970)).

This reaction can usually be carried out without a solvent, and the temperature is in the range of 60 to 150 ° C. It is said that the higher the temperature, the higher the production rate of the desired 2-hydroxyacetophenones. A short reaction time of about 15 to 30 minutes is sufficient. As a reaction agent, usually 1.2 to
Although 1.3 equivalents of anhydrous aluminum chloride is used, Lewis acids such as titanium tetrachloride, ferric chloride and tin chloride can also be used.

Step B is an etherification reaction of phenol and can be usually carried out by various methods. When the reaction is carried out at room temperature with an alkyl halide in the presence of an alkali such as sodium hydroxide or potassium hydroxide in a basic polar solvent such as dimethylformamide or dimethylsulfoxide,
The target product (Compound 3) can be obtained in a short time and in high yield.

Step C is also a commonly known method. Since acetophenones are highly reactive, they are generally diluted with acetic acid or the like and then brominated with bromine gas or the like.

The step D seems to be useless at first glance,
Since phenacyl bromides (compound 4) are highly reactive, they cannot undergo oximation (step E) or reduction (step F). By reacting an acetate salt such as potassium acetate in an inert polar solvent such as acetonitrile in the presence of a catalyst such as crown ether such as 18-crown-6, a target product (compound 5) is produced in high yield. can do. The temperature is in the range of room temperature to 60 ° C., and the reaction is completed in about 1 to 3 hours.

The oxime formation in the step E can be carried out by a usual method. When hydroxylamine hydrochloride is used as a nitrogen source, the abnormal reaction is suppressed by carrying out the reaction in the presence of a weak base such as pyridine, and the target product (Compound 6) is produced in a relatively short time and with high yield. can do.

The reduction of the oxime in the step F is a general catalytic reduction method (reference: J. Am. Che.
m. Soc. 60, 1951 (1938); Z. Phy
siol. Chem. 148, 294 (1925)) and a reduction method using a metal hydride complex salt compound such as lithium aluminum hydride (reference: Org. Syn. 65,
173 (1977)).

Step G. H. 2- (2-alkoxy-4-alkyl, halogen or trifluoromethylphenyl) glycinols (compound 7) in I to 2-
(2,6-dihalophenyl) -4- (2-alkoxy-
4-alkyl, halo or trifluoromethylphenyl)
The 2-oxazolines (compound 10) can be produced according to the method disclosed in JP-A-2-85268.

Manufacturing process I

[Chemical 3] (Wherein R, R ′ and X have the same meanings as described above, and W
Represents a halogen atom or an alkanesulfonyloxy group. )

Manufacturing process II

[Chemical 4] (In the formula, R and R ′ have the same meanings as described above.) The same as the manufacturing step I below.

Manufacturing process III

[Chemical 5] (In the formula, R and R ′ have the same meanings as described above.) The same as the manufacturing step II below.

[0021]

EXAMPLES Next, the synthesis of the compounds of the present invention will be described in more detail, but the invention is not limited to the following examples. Synthesis Example 1 Synthesis of 2- (2,6-difluorophenyl) -4- (4-chloro-2-normalpropoxyphenyl) -2-oxazoline (Compound No. 16) Step A: m-Chlorophenylacetate 116.6 g
(0.684 mol), anhydrous aluminum chloride 109.6
A mixture of g (0.821 mol) was heated on an oil bath with stirring. The reaction started when the oil bath temperature exceeded 80 ° C., and the reaction products became individual within minutes. Dilute hydrochloric acid was added to dissolve the solid, and the mixture was extracted with ethyl acetate. After drying and concentration, silica gel column chromatography (hexane:
Purification with ethyl acetate = 9: 1) yielded 99.0 g of colorless oil of 4-chloro-2-hydroxyacetophenone (yield 8
4.9%).

Step B: A mixture of 99.0 g (0.581 mol) of 4-chloro-2-hydroxyacetophenone, 39.0 g (0.696 mol) of potassium hydroxide and 200 ml of dimethyl sulfoxide was stirred with stirring at room temperature. -
85.6 g (0.696 mol) of normal propyl was added dropwise. After stirring overnight at room temperature, water was added and the mixture was extracted with ethyl acetate. After drying and concentration, hexane was added, and the precipitated crystals were collected by filtration to obtain 80.2 g (yield 65.0%) of colorless crystals of 4-chloro-2-n-propoxyacetophenone.

Step C: Bromine 6 was added to a mixture of 80.2 g (0.377 mol) of 4-chloro-2-normal propoxyacetophenone and 200 ml of acetic acid with stirring at room temperature.
6.4 g (0.415 mol) was added dropwise over 1 hour.
After further stirring at room temperature for 2 hours, the reaction product was poured into ice water and extracted with ethyl acetate, and the organic layer was washed with an aqueous sodium thiosulfate solution. After drying and concentrating, hexane was added, and the precipitated crystals were collected by filtration and 105.0 g of 4-chloro-2-normal propoxyphenacyl bromide colorless crystals (yield 95.5).
%) Was obtained.

Step D: 4-chloro-2-normal propoxyphenacyl bromide 105.0 g (0.360 mol), potassium acetate 53.0 g (0.541 mol), 1
1.9 g of 8-crown-6, 500 m of acetonitrile
The mixture of 1 was stirred at room temperature for 3 hours. After heating under reflux on an oil bath for 1 hour, water was added and the mixture was extracted with ethyl acetate. After drying and concentration, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 8: 2) to obtain a colorless oil of α-acetyloxy-4-chloro-2-normalpropoxyacetophenone 93.2 g (yield 95.7%). Got

Step E: 93.2 g of α-acetyloxy-4-chloro-2-normal propoxyacetophenone
(0.345 mol), hydroxylamine hydrochloride 35.
While stirring at room temperature in a mixture of 9 g (0.517 mol) and 600 ml of ethanol, 41.0 g (0.5
19 mol) was added slowly. After heating under reflux on an oil bath for 2 hours, water was added and the mixture was extracted with ethyl acetate. It was dried, concentrated and used as is in the next step.

Step F: Lithium aluminum hydride 2
6.2 g (0.689 mol), tetrahydrofuran 50
A solution of α-acetyloxy-4-chloro-2-normal-2-propoxyacetophenone oxime (concentrate of step E) in 500 ml of tetrahydrofuran was slowly added dropwise to 0 ml of the mixture while stirring at room temperature. After the dropping was completed, the mixture was heated and refluxed for 30 minutes. After returning to room temperature, a solution prepared by dissolving 3.9 g of sodium hydroxide in 127 ml of water was added dropwise. After completion of the dropwise addition, the mixture was heated under reflux for 30 minutes, the precipitated solid was filtered, concentrated, and purified by silica gel column chromatography (running with chloroform, then chloroform: methanol = 9: 1) to give 2-amino-2-. (4-chloro-2-normal propoxyphenyl) ethanol 5
8.3 g (73.7% yield in steps E and F) of a pale yellow oil was obtained.

Steps G, H, I: 2-amino-2- (4-
Chlor-2-normal propoxyphenyl) ethanol 58.3 g (0.254 mol), triethylamine 2
8.2 g (0.279 mol), tetrahydrofuran 40
Cool 0 ml of the mixture with ice-water and stir 2,6.
-Difluorophenylbenzoyl chloride 44.8 g
100 ml of tetrahydrofuran (0.254 mol)
The solution dissolved in was slowly added dropwise. After returning to room temperature and stirring overnight, the reaction mixture was filtered and the filtrate was concentrated. A mixture of this concentrate, 28.2 g (0.279 mol) of triethylamine and 400 ml of tetrahydrofuran was chilled with ice-water, and stirred while stirring 32.0 g of methanesulfonyl chloride.
A solution of (0.279 mol) in 100 ml of tetrahydrofuran was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, the reaction mixture was filtered, and the filtrate was concentrated. This concentrate is dissolved in 400 ml of methanol, 33.5 g (0.508 mol) of potassium hydroxide is added, and the temperature is 60 ° C.
It was stirred for 1 hour. Water was added to the reaction product and the mixture was extracted with ethyl acetate. After drying and concentration, the product was purified by silica gel column chromatography (hexane: ethyl acetate = 8: 2) to give 2-
(2,6-Difluorophenyl) -4- (4-chloro-)
57.5 g of 2-normal propoxyphenyl) -2-oxazoline (colorless crystals, melting point 87-88 ° C, yield 64.
4%).

Nuclear magnetic resonance spectrum (solvent CDC1 ₃ ) δTMSppm 1.00 (3H, t, J = 7 Hz), 1.46-2.1
6 (2H, m), 3.73-4.23 (3H, m),
4.80 (1H, dd, J = 9Hz, 8Hz), 5.5
6 (1H, dd, J = 9Hz, 8Hz), 5.73-
7.46 (6H, m). Infrared absorption spectrum (KBr plate): νmaxCm ^-1 1680 (C = N)

Synthesis Example 2 Synthesis of 2- (2,6-difluorophenyl) -4- (2-isopropoxy-4-methylphenyl) -2-oxazoline (Compound No. 5) Step A: 73 g of m-methylphenylacetate (0.4
86 mol), 71.4 g (0.5
34 mol) was heated on an oil bath with stirring.
The reaction started when the oil bath temperature exceeded 60 ° C., hydrogen chloride gas was vigorously ejected, and the contents became individual within a few minutes, and the reaction was completed. Dilute hydrochloric acid was added to dissolve the solid, and the mixture was extracted with ethyl acetate. The organic layer was dried, ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1) to give 2-hydroxy-4-methylacetophenone colorless oil (60.9 g). Yield 83.5%) was obtained.

Step B: 32-hydroxy-4-methylacetophenone 32 g (0.213 mol), potassium hydroxide 9.4 g (0.256 mol), dimethyl sulfoxide 1
32.4 g (0.263 mol) of isopropyl bromide was added dropwise to 00 ml of the mixture with stirring at room temperature. After stirring at room temperature for 1 hour, the mixture was stirred at 40 to 50 ° C. for 3 hours. The reaction solution was poured into water and ethyl acetate was added for extraction. The organic layer was dried, ethyl acetate was distilled off under reduced pressure, and 36.5 g of 2-isopropoxy-4-methylacetophenone colorless crystals were obtained.
(Yield 89.2%) was obtained.

Step C: 2-isopropoxy-4-methylacetophenone 36 g (0.187 mol), acetic acid 100
37g of bromine (0.
205 mol) was slowly added dropwise. After stirring at room temperature for 2 hours, the reaction product was poured into ice-water and extracted with ethyl acetate, and the organic layer was washed with an aqueous sodium thiosulfate solution. The organic layer was dried and ethyl acetate was distilled off under reduced pressure, followed by silica gel column chromatography (hexane: ethyl acetate = 1).
It was purified by 0: 1) to obtain 44 g of 2-isopropoxy-4-methylphenacyl bromide (yield 86.8%).

Step D: A mixture of 40 g (0.147 mol) of 2-isopropoxy-4-methylphenacyl bromide, 14.5 g (0.177 mol) of potassium acetate, about 1 g of 18-crown-6 and 200 ml of acetonitrile was added. The mixture was heated at room temperature for 1 hour and heated under reflux for 3 hours. The reaction solution was poured into water and ethyl acetate was added for extraction. Dry the organic layer,
After distilling off ethyl acetate under reduced pressure, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1) and pale yellow α-acetyloxy-2-isopropoxy-4-methylacetophenone 27.4 g ( Yield 7
4.2%) was obtained.

Step E: 27 g (0.10) of α-acetyloxy-2-isopropoxy-4-methylacetophenone
8 mol), 15 g of hydroxylamine hydrochloride (0.21
25.2 g (0.32 mol) of pyridine was slowly added to the mixture of 5 mol) and 150 ml of ethanol with stirring at room temperature. After heating under reflux for 2 hours on an oil bath, the reaction solution was poured into water and ethyl acetate was added for extraction. The organic layer was dried, ethyl acetate was distilled off under reduced pressure, and it was directly used in the next step.

Step F: Lithium aluminum hydride 8.
2 g (0.216 mol), tetrahydrofuran 300 m
1-acetyloxy-2-isopropoxy-4-methylacetophenone oxime (concentrate of step E) in 100 m of tetrahydrofuran while stirring in a mixture of 1 at room temperature.
The solution dissolved in 1 was slowly added dropwise. After the dropping was completed, the mixture was heated and refluxed for 30 minutes. After returning to room temperature, 41 ml of water was added dropwise. After completion of the dropwise addition, the mixture was heated under reflux for an additional 1 hour, the precipitated solid was filtered off, concentrated and purified by silica gel column chromatography (running with chloroform, then chloroform: methanol = 9: 1) to give a pale yellow 2- Amino-2-
14 g of (2-isopropoxy-4-methylphenyl) ethanol (62.2% yield in steps E and F) were obtained.

Steps G, H, I: 2-amino-2- (2-
Isopropoxy-4-methylphenyl) ethanol 3.
5 g (0.016 mol), triethylamine 1.9 g
While stirring a mixture of (0.019 mol) and 100 ml of tetrahydrofuran with ice-water under cooling and stirring, 2.95 g (0.01-mol) of 2.6-difluorophenylbenzoyl chloride was obtained.
A solution of 6 mol) in 20 ml of tetrahydrofuran was slowly added dropwise. Stir overnight at room temperature. The reaction solution was filtered and the filtrate was concentrated. To this concentrate, 1.9 g (0.019 mol) of triethylamine and tetrahydrofuran 1
The mixture (00 ml) was cooled with ice-water, and a solution of 2.17 g (0.019 mol) of methanesulfonyl chloride in 10 ml of tetrahydrofuran was slowly added dropwise while stirring. After completion of dropping, the mixture was stirred at room temperature for 3 hours, the reaction solution was filtered, and the filtrate was concentrated. This concentrate is added to methanol 80
2.3 g (0.057 mol) of water-solubilized potassium was added and the mixture was stirred at 60 ° C. for 30 minutes. The reaction product was poured into water and ethyl acetate was added for extraction. The organic layer was dried, ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1) to give 2- (2,6-difluorophenyl) -4- (2.
-2.4 g (isopropoxy-4-methylphenyl) -2-oxazoline (colorless crystals, melting point 98-100 ° C, yield 47.0%) were obtained.

Nuclear magnetic resonance spectrum (solvent CDC1 ₃ ) δTMSppm 1.36 (6H, d, J = 6Hz), 2.33 (3H,
S), 4.03 (1H, dd, J = 8Hz, 9Hz),
4.26-5.00 (2H, m), 5.54 (1H, d
d, J = 8 Hz, 9 Hz), 6.63-7.58 (6
H, m). Infrared absorption spectrum (KBr plate): νmaxCm ^-1 1680 (C = N)

Synthesis Example 3 2- (2-chloro-6-fluorophenyl) -4- (2
-Ethoxy-4-trifluoromethylphenyl) -2-
Synthesis of oxazoline (Compound No. 25) Step III: 25 g of m-trifluoromethylphenol
(0.154 mol) and 8 ml of bromine were slowly added dropwise while stirring a solution of 50 ml of acetic acid. After stirring at room temperature for 2 hours, the reaction solution was poured into ice-water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated. This concentrate was dissolved in 50 ml of dimethylsulfoxide, and a solution prepared by dissolving 11.2 g (0.170 mol) of 85% potassium hydroxide in 10 ml of water was added. After stirring at room temperature for 30 minutes, 26.5 g (0.170 mol) of ethyl iodide was added dropwise. After stirring overnight at room temperature, water was added and the mixture was extracted with ethyl acetate. After drying over anhydrous sodium sulfate and concentration, 34.8 g (yield 8
(3.6%) of 4-bromo-3-ethoxybenzotrifluoride and 2-bromo-5-ethoxybenzotrifluoride were obtained.

Diethyl oxalate 20.8 g (0.142
Mol) and tetrahydrofuran 50 ml solution was cooled to −60 ° C. in a dry ice-acetone bath, and 34.8 g (0.129 mol) of the mixture obtained in the above reaction while stirring.
Then, a Grignard reagent prepared from 3.1 g (0.128 mol) of magnesium and 70 ml of tetrahydrofuran was slowly added dropwise. After removing the dry ice-acetone bath and stirring at room temperature for 3 hours, a saturated ammonium chloride aqueous solution was added, water was further added, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, concentrated, and purified by distillation under reduced pressure to obtain 8.7 g (yield 23.2%) of a keto ester mixture.

8.7 g of this ketoester mixture (0.0
30 mol), 2.3 g of hydroxyamine hydrochloride (0.0
33 mol) and 50 ml of ethanol were stirred and heated under reflux for 3 hours. Add water and extract with ethyl acetate,
The extract was dried over anhydrous sodium sulfate and then concentrated to obtain 9.1 g of an oxime ester mixture. Lithium aluminum hydride 2.3 g (0.061 mol), tetrahydrofuran 50
A solution of 9.1 g (0.030 mol) of the oxime ester mixture and 30 ml of tetrahydrofuran was slowly added dropwise to the ml suspension while stirring at room temperature. After heating under reflux for another 30 minutes, return to room temperature and 0.3 g of sodium hydroxide.
(0.075 mol), a solution of 11 ml of water was added dropwise at such a rate that a gentle reflux continued. After heating and refluxing for another hour, the precipitated solid was filtered through a glass filter with Celite, and the filtrate was concentrated and purified by silica gel column chromatography (running with chloroform and then chloroform: methanol = 9: 1) to give an amino acid. 4.3 g (yield 57.3%) of an alcohol mixture was obtained.

2-amino-2- (2-ethoxy-4-trifluoromethylphenyl) ethanol and 2-amino-
4.3 g (0.017 mol) of a mixture of 2- (4-ethoxy-2-trifluoromethylphenyl) ethanol,
While stirring a mixed solution of 1.9 g (0.019 mol) of triethylamine and 30 ml of tetrahydrofuran with ice-water and stirring, 3.3 g (0.017 mol) of 2-chloro-6-fluorophenylbenzoyl chloride was dissolved in 30 ml of tetrahydrofuran. The solution was slowly added dropwise.
After returning to room temperature and stirring overnight, the reaction mixture was filtered and the filtrate was concentrated. 1.9 g of this concentrate and triethylamine
(0.019 mol) and tetrahydrofuran (30 ml) were cooled with ice-water and stirred while stirring 2.2 g (0.019 mol) of methanesulfonyl chloride in tetrahydrofuran (1).
The solution dissolved in 0 ml was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, the reaction mixture was filtered, and the filtrate was concentrated. This concentrate was dissolved in 50 ml of methanol, and 2.3 g (0.035 mol) of 85% potassium hydroxide was added.
Was added and the mixture was stirred at 60 ° C. for 1 hour. Water was added to the reaction product and the mixture was extracted with ethyl acetate. After drying over anhydrous sodium sulfate and concentration, silica gel column chromatography (hexane:
Purified with ethyl acetate = 8: 2). Hexane was added to the obtained oily mixture to precipitate crystals, and 2- (2-chloro-6-fluorophenyl) -4- (2-ethoxy-4-) was obtained.
Trifluoromethylphenyl) -2-oxazoline 2.
2 g (colorless crystal, melting point 72 to 73 ° C., yield 32.9%)
Got

Nuclear magnetic resonance spectrum (solvent CDC1 ₃ ) δTMSppm 1.46 (3H, t, J = 7 Hz), 3.95-4.2
8 (3H, m), 4.85 (1H, dd, J = 9Hz,
10Hz), 5.76 (1H, dd, J = 9Hz, 10
Hz), 6.83-7.70 (6H, m). Infrared absorption spectrum (KBr plate): νmaxCm ^-1 1680 (C = N)

Examples of compounds included in the present invention are shown in Tables 1 and 2 including the compounds synthesized in the above Examples. However, the compound of the present invention is not limited to these. The abbreviations in the table have the following meanings. Me = methyl group,
Et = ethyl group, n-Pr = normal propyl group, i-
Pr = isopropyl group

[0043]

[Table 1]

[0044]

[Table 2]

When the compound of the present invention thus obtained is used as an insecticide, it may be used alone, but usually an auxiliary agent is used in the same manner as general pesticides to prepare powders, wettable powders,
It is produced in the form of emulsion, flowable agent, etc. and used as it is or diluted with water.

As the auxiliaries, those usually used in the preparation of general agricultural chemicals are used. For example, solid carriers such as diatomaceous earth, talc, clay, alumina, kaolin, montmorillonite, silicic acid, white carbon, starch, soybean flour, wheat flour, fish meal; water, methanol, xylene, hexane,
Liquid carriers such as kerosene, dioxane, tetrahydrofuran, dichloromethane, trichloroethane, dimethylformamide, acetic acid ethyl ester, acetonitrile, dimethylsulfoxide, soybean oil, olive oil; polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether, polyoxyalkylene fatty acid ester, Surfactants such as polyoxyalkylene sorbitan fatty acid ester, alkyl allyl sulfate ester salt, polyoxyalkylene alkyl allyl sulfate ester salt, etc .; or lignin sulfonate, naphthalene sulfonate formalin condensate, alginate, starch, cellulose derivative, montmorillonite , Synthetic water-soluble polymers, synthetic resins, phosphates, glycols, nonionic surfactants, aromatic diamines , Vegetable oils, dispersing agents such as epoxidized oils, sticking agents, stabilizing agents and the like.

The content of the compound of the present invention in the preparation is 0.01 to 95.0% by weight, preferably 0.1 to 90.
0% is included, and the application amount is usually 1 to 1000 g, preferably 5 to 500 g in terms of the amount of active ingredient per 10 are.

If desired, the compounds of the present invention can be used in admixture or in combination with other insecticides, acaricides, fungicides or plant growth regulators.

The compound of formula (I) provided by the present invention has an extremely excellent insecticidal activity as shown in the test examples described below. For example, the leafhopper leafhopper (Nephotet).
sixcincticeps), brown planter (Ni
laparvata lugens), Pondweed planthopper (Laodelphax striatellus),
White-tailed planthopper (Sogatella furcifer)
It exerts an excellent control effect against hemiptera pests such as a).

Next, formulation examples of the compound of the present invention will be shown. However, it is not limited to these. See also
Indicates parts by weight. Formulation Example 1 Dust: 2 parts of the compound of the present invention (Compound No. 22), 48 parts of talc and 50 parts of clay are uniformly mixed and pulverized to obtain a powder.

Formulation Example 2 Wettable powder 10 parts of the compound of the present invention (Compound No. 5), 3 parts of sodium dodecylbenzenesulfonate, 2 parts of polyoxyethylene nonylphenyl ether, 30 parts of clay and 55 diatomaceous earths.
The parts are uniformly mixed and ground to obtain a wettable powder.

Formulation Example 3 Emulsion Emulsion is obtained by uniformly dissolving 10 parts of the compound of the present invention (Compound No. 16), 8 parts of polyoxyethylene nonylphenyl ether, 2 parts of alkylallyl sulfonate and 80 parts of xylol.

Formulation Example 4 Flowable Agent 10 parts of the compound of the present invention (Compound No. 25), 5 parts of polyoxyethylene styryl phenyl ether sulfate salt,
A flowable agent is obtained by uniformly dissolving 10 parts of a 1% xanthan gum aqueous solution, 3 parts of a smectite-based mineral substance and 72 parts of water, and wet pulverizing with a sand mill.

Next, a test example of the present invention will be shown. Test Example 1: Insecticidal test against juveniles of brown planthoppers A rice plant seedling having a plant height of about 10 cm is sprayed with a drug having a predetermined concentration (the emulsion of Formulation Example 3 is diluted with water), air-dried and covered with an acrylic cylinder. Ten larvae were released per seedling and covered with gauze. The treated seedlings were placed in a temperature-controlled room, and the number of dead insects was examined after 7 days, and the insecticidal rate [(%) = {(number of parasites before spraying-number of parasites at the time of survey) / number of parasites before spraying] × 1
00] was calculated. The test was carried out in three wards in one ward. The results are shown in Tables 3 and 4. In addition, A in the column of compound in Table 4
To F are reference compounds for comparison (Japanese Patent Application Laid-Open No. 2-8526).
No. 8 publication), and the compound is described later.

Test Example 2: Insecticidal test against juvenile larvae of Spodoptera litura Planta rice seedlings planted in a cup and having a plant height of about 10 cm were sprayed with a drug having a predetermined concentration (the emulsion of Formulation Example 3 was diluted with water), air-dried and then an acrylic cylinder Capsule larvae were covered with 10 larvae of each plant and capped with gauze. The treated seedlings were placed in a temperature-controlled room, and the number of dead insects was examined after 7 days, and the insecticidal rate [(%) = {(number of parasites before spraying-number of parasites at the time of survey) / number of parasites before spraying] × 1
00] was calculated. The test was carried out in three wards in one ward. The results are shown in Tables 3 and 4. In addition, A to F in Table 4 are the same as in Test Example 1.

[0056]

[Table 3]

[0057]

[Table 4]

Control compounds (A to F): Formula (II)

[Chemical 6]

[0059]

[Table 5]

As shown by the results of the above-mentioned test examples, the compound of the present invention can be effectively controlled especially against hemiptera pests at a low dose, and is extremely promising as an agricultural and horticultural insecticide.

Claims (2)

[Claims] 1. Formula (I): (In the formula, R represents a methyl group, a chlorine atom, a bromine atom, a fluorine atom or a trifluoromethyl group, R ′ represents a methyl group, an ethyl group, a normal propyl group or an isopropyl group, and X represents a fluorine atom or chlorine. 2- (2,6-dihalophenyl) -4- (2-
Alkoxy-4-alkyl, halo or trifluoromethylphenyl) -2-oxazolines. 2. Containing 2- (2,6-dihalophenyl) -4- (2-alkoxy-4-alkyl, halo or trifluoromethylphenyl) -2-oxazoline according to claim 1 as an active ingredient. An agricultural and horticultural insecticide characterized by.