JPH0762006B2 - 2-Substituted phenyl-2-oxa- or thiazoline derivatives, process for their production and insecticides and acaricides containing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel 2-substituted phenyl-2-oxa- or thiazoline derivative, a method for producing the same, and an insecticidal and acaricidal agent containing the derivative as an active ingredient. .

(Prior Art) There have been some reports on 2,4-diphenyl-2-oxa- or thiazoline. For example, TETRAHEDRON
LETTERS (Tetrahedron Letters) Vol. 22 No. 45 4471-4
474, 1981; CHEMICAL ABSTRACTS Vol. 98 No. 19 160087k, 1983; JOURNAL OF ORGAN
IC CHEMISTRY 52: 2523-2530, in 1987, some kind of 2,
It is described with respect to a process for preparing 4-diphenyl-2-oxa- or thiazoline compounds.

In addition, published patent publication Sho 57-501962 or PCT: WO82 /
No. 02046 discloses a method for producing Δ ² -N-heterocyclic compounds. The same publication describes that this compound is useful as an intermediate for the production of an active ingredient of a pharmaceutical product, or as such, as a compound having a biological action as a diabetes drug, No mention is made of the effect of controlling pests that harm agricultural and horticultural crops.

PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY, Vol. 30, pages 190-197, in 1988, some kind of 2-amino-
It is described that the 2-oxazoline derivative is active against mites and aphids.

Furthermore, the present inventors have previously found and proposed a novel 2,4-di-substituted 2-oxa or thiazoline derivative having insecticidal and acaricidal activity (see Japanese Patent Application No. 63-140547).

(Problems to be Solved by the Invention) In developing novel insecticidal and acaricidal agents, the present inventors show a wide range of effects against pests that are not found in conventional techniques and have low toxicity. Research was conducted with the aim of creating compounds.

Plant parasitic pests and mites include cereals such as rice and wheat;
Beans such as soybean and azuki bean; Various fruit trees such as apple, mandarin orange, and pear; Vegetables such as eggplant, cucumber and strawberry; Flowers such as roses and carnations, and special crops such as tea It is well known that it causes various damages, and many insecticides and acaricides are already in practical use.

However, the problem of resistance (resistance) to plant parasitic pests, existing insecticides of mites, and acaricides has become more and more serious in recent years, and it is inevitable that continuous control of the same drug will reduce the control effect. Has become. In order to deal with this problem of drug resistance expression, practically avoid the continuous use of the same drug, and use new types of insecticides and acaricides one after another, or mix and use drugs with different mechanisms of action. Has been proposed.

A derivative of 2-oxazoline, which shows insecticidal and acaricidal activity, PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY
(Pestayside Biochemistry and Physiology) Volume 30, pages 190-197, the 2-amino-2-oxazoline derivative described in 1988 is characterized by having an amino group at the 2-position of the oxazoline ring, Activity in ticks and aphids is shown.

Further, in the Japanese Patent Application No. 63-140547, the 2-oxazoline derivative in which the 2,4-position is di-substituted is described for spider mite ovicidal activity and aphid, leafhopper leafhopper, and brown planthopper insecticidal activity.

As a result of intensive studies in view of the above facts, the present inventors have created a novel 2-substituted phenyl-2-oxa- or thiazoline derivative that is effective against a wide range of pests and mites and has low toxicity. Then, the present invention has been completed.

(Structure of the Invention) Thus, the present invention has the general formula In the formula, R ₁ and R ₂ are the same or different and each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a lower haloalkyl group or a lower haloalkoxy group, provided that R ₁ and R ₂ Does not represent a hydrogen atom at the same time; R ₃ represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group; R ₄ represents an alkyl group having 7 or more carbon atoms, an alkoxy group having 7 or more carbon atoms, an alkylthio group , Lower alkoxy-lower alkyl group, lower alkoxy-lower alkoxy group, alkenyloxy group having 3 or more carbon atoms, lower alkynyloxy group, tri (lower alkyl) silyl group, cycloalkyl optionally substituted with lower alkyl group Group or formula Wherein B represents a direct bond, an oxygen atom, a lower alkylene group, a lower alkyleneoxy group, a lower alkylenedioxy group or a di (lower alkyl) silyl group,
Q represents CH or N, n is an integer of 0 to 5, n substituents R ₅ are the same or different and each is a halogen atom, an alkyl group, an alkoxy group, a lower haloalkyl group,
A 2-substituted phenyl-2-oxa or thiazoline derivative represented by: A represents a lower haloalkoxy group or a tri (lower alkyl) silyl group; A represents a direct bond or a lower alkylene group; and Z represents an oxygen atom or a sulfur atom. Is provided.

In the present specification, the term “lower” means that the group or compound to which this term is attached has 6 or less carbon atoms.

“Halogen atom” includes fluorine, chlorine, bromine and iodine atoms.

The “alkyl group” may be linear or branched, and is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isoamyl. , Neopentyl, n-hexyl, n-heptyl, 1,1-dimethylpentyl, n-octyl,
1-methylheptyl, 1,1-dimethylheptyl, 1,1-dimethyl-4-methylpentyl, n-nonyl, n-decyl, 4,8-dimethylnonyl, n-undecyl, 1-pentylhexyl, n-dodecyl , N-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl,
Examples thereof include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, such as an n-eicosyl group. The "alkoxy group" and "alkylthio group" are a (alkyl) -O- group and a (alkyl) -S- group, respectively, in which the alkyl portion has the above meaning.

The "haloalkyl group" is an alkyl group in which at least one hydrogen atom bonded to a carbon atom of the alkyl group is substituted with a halogen atom, and specifically, chloromethyl, trifluoromethyl, fluoroethyl, trifluoroethyl, perfluoro. An ethyl group and the like are included, and a "haloalkoxy group" is a (haloalkyl) -O- group in which a haloalkyl moiety has the above meaning, for example, a trifluoromethoxy group.

The "lower alkoxy-lower alkyl group" is a (lower alkyl) -O- (lower alkyl) group whose alkyl moiety has the above meaning, and includes, for example, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl. , Isobutoxymethyl, 2-methoxyethyl, 2-ethoxyethyl groups and the like. The "lower alkoxy-lower alkoxy group" is a (lower alkyl) -O- (lower alkyl) -O- group in which the alkyl moiety has the above-mentioned meaning, and examples thereof include 2-methoxy-ethoxy, 2-ethoxyethoxy, 2-n-
Propoxyethoxy, 4-isopropoxybutoxy group and the like are included.

An "alkenyloxy group" is a (alkenyl) -O- group in which the alkenyl moiety is a linear or branched alkenyl group, and includes, for example, allyloxy, butenyloxy, 3-methyl-2-butenyloxy, geranyloxy, farne. Examples thereof include alkenyloxy groups having 3 to 15 carbon atoms such as siloxy and citronellyloxy groups.

Examples of the "lower alkynyloxy group" include a propargyloxy group. Examples of the “tri (lower alkyl) silyl group” include trimethylsilyl, ethyldimethylsilyl, n-propyldimethylsilyl, t-butyldimethylsilyl, triethylsilyl, methyldiethylsilyl groups and the like.

The "cycloalkyl group" includes a cycloalkyl group having 3 to 8 carbon atoms, for example, a cyclohexyl group, and the cycloalkyl group may be optionally substituted with a lower alkyl group. Examples of such substituted cycloalkyl groups include methylcyclohexyl, ethylcyclohexyl, t-butylcyclohexyl groups and the like.

The “lower alkylene group” may be linear or branched, and is, for example, —CH ₂ —, —CH ₂ CH ₂ —, ‐CH ₂ CH ₂ CH ₂ ‐, ‐CH ₂ CH ₂ CH ₂ CH ₂ ‐, Etc. Further, the “lower alkyleneoxy group” and the “lower alkylenedioxy group” are respectively —O lower alkylene whose lower alkylene part has the above meaning)
-Group and -O lower alkylene O- group.

Examples of “di (lower alkyl) silyl group” include Etc.

In the general formula (I), preferable compounds include In the formula, R ₁₁ and R ₂₁ are the same or different and each represents a halogen atom; R ₃ , R ₄ and Z have the above-mentioned meanings, and a 2-substituted phenyl-2-oxa or thiazoline derivative represented by To be

Among the compounds of the above formula (Ia), a more preferable compound group includes a 2-substituted phenyl-2-oxazoline derivative represented by the following formula.

In the above formulas, the n substituents R ₅₁ are the same or different and each represents a halogen atom, an alkyl group, an alkoxy group, a haloalkyl group or a haloalkoxy group; R ₁₁ , R ₂₁ , R ₃ , Q and n are It has the above meaning.

The compounds of the present invention include, for example, (a) general formula In the formula, R ₁ and R ₂ have the above-mentioned meanings and a substituted benzoic acid represented by the general formula Or In the formula, R ₃ , R ₄ and A have the above-mentioned meanings, or are reacted with an aminoalcohol derivative represented by: in the presence of a dehydrating agent, or (b) the general formula Or In the formula, R ₁ , R ₂ , R ₃ , R ₄ and A have the above-mentioned meanings, or the amide alcohol derivative represented by: is treated with a dehydrating agent, or (c) the general formula In the formula, R ₁ , R ₂ , R ₃ , R ₄ and A have the above-mentioned meanings, W is a halogen atom, an alkylsulfonyloxy group (for example, methanesulfonyloxy group) or an arylsulfonyloxy group (for example, p-toluene). It can be produced by treating a compound represented by: which represents a sulfonyloxy group) with a base.

The benzoic acid compound of formula (II) and the formula (II
The reaction of I) or (IV) with the amino alcohol derivative is
Usually, it can be carried out in a suitable solvent, for example, an aromatic hydrocarbon solvent such as benzene, toluene, xylene, nitrobenzene, chlorobenzene and dichlorobenzene, at a temperature between about 70 ° C. and the boiling point of the solvent.

Examples of the dehydrating agent used in the above reaction include sulfuric acid,
Polyphosphoric acid, phosphorus pentoxide, dicyclohexylcarbodiimide (DCC), phosphorus pentasulfide and the like can be mentioned. When a dehydrating agent such as sulfuric acid, polyphosphoric acid, phosphorus pentoxide and DCC is used,
A compound of formula (I) is obtained, wherein Z is an oxygen atom, and
When a dehydrating agent such as phosphorus pentasulfide is used, a compound of formula (I) in which Z is a sulfur atom is obtained.

The reaction molar ratio of the compound of the formula (II) and the aminoalcohol derivative of the formula (III) or (IV) is not strictly limited, but in general, the formula (II The amino alcohol derivative of III) or (IV) is 0.8-1.
It is convenient to use within a range of 2 moles. The amount of the dehydrating agent used is not critically limited, but it is usually suitable to use it in the range of 2 to 8 mol per 1 mol of the compound of the formula (II).

The treatment of the amide alcohol derivative of formula (V) or (VI) with a dehydrating agent in method (b) can be carried out under the same conditions as described above for method (a).

The amide alcohol derivative of the formula (V) or (VI) used as a starting material in the method (b) is a reactive derivative of the substituted benzoic acid of the formula (II), for example, a halide such as chloride or bromide. III) or (IV)
It can be produced by reacting the aminoalcohol derivative of 1) in the presence of a base.

This reaction is usually performed in a solvent. Examples of the solvent that can be used include water, alcohols (eg methanol, ethanol), ethers (eg diethyl ether, tetrahydrofuran, dioxane, diglyme etc.), aromatic hydrocarbons (eg benzene, toluene, xylene etc.), halogen Hydrocarbons (eg dichloromethane,
Chloroform, carbon tetrachloride, dichloroethane, etc.) are used. In addition, the reaction temperature is generally preferably in the range of about 0 ° C to about 50 ° C.

On the other hand, as the base, for example, inorganic bases such as sodium hydroxide, potassium hydroxide and potassium carbonate; tertiary organic bases such as triethylamine, N, N-dimethylaniline, pyridine and 4-N, N-dimethylaminopyridine are used. To be

In the above reaction, the reaction molar ratio between the reactive derivative of the compound of formula (II) and the amino alcohol derivative of formula (III) or (IV) is not particularly limited, but 1 mol of the reactive derivative of the compound of formula (II) On the other hand, the amino alcohol derivative of the formula (III) or (IV) is preferably used within a range of 0.8 to 1.2 mol, and the base is 0.8 to 1.2 mol per 1 mol of the reactive derivative of the compound of the formula (II). It is convenient to use 1.2 equivalent ratios.

In the reaction (c), the compound of the formula (VII) is obtained by reacting the compound of the formula (V) used as a starting material in the reaction (b) with a halogenating agent or a sulfonating agent.

This halogenation or sulfonation reaction can usually be carried out in a solvent. Examples of the solvent include aromatic hydrocarbons (eg, benzene, toluene, xylene etc.), halogenated hydrocarbons (eg dichloromethane, chloroform, carbon tetrachloride, cycloloethane etc.), ethers (eg diethyl ether, tetrahydrofuran, etc.). Dioxane, diglyme and the like). Further, as the halogenating agent, for example, thionyl chloride, thionyl bromide, phosphorus oxychloride, phosphorus trichloride, phosphorus tribromide and the like can be used, and as the sulfonating agent, for example, methanesulfonyl chloride, p-toluene. Sulfonyl chloride or the like can be used.

The reaction temperature is generally about 0 ° C. to the boiling point of the solvent.

The proportion of halogenating agent or sulfonating agent used relative to the compound of formula (V) is also not strictly limited,
Generally, it is appropriate to use the halogenating agent or sulfonating agent in the range of 1 to 6 mol per 1 mol of the compound of the formula (V).

The ring closure reaction of the resulting compound of formula (VII) with a base is
Usually, it can be advantageously carried out in a solvent such as water or alcohols (for example, methanol, ethanol, etc.) at a temperature within the range of about 40 ° C to about 100 ° C. As a base,
The above-mentioned inorganic base can be preferably used in the reaction (b), and its amount used is appropriately within the range of 1 to 6 equivalents relative to 1 mol of the compound of the formula (VII).

The compound of formula (I) of the present invention obtained by the above-mentioned reaction (a), (b) or (c) is isolated by a method known per se, for example, column chromatography, recrystallization and the like, It can be purified. Examples of the solvent for column chromatography and recrystallization include benzene,
Methyl alcohol, ethyl alcohol, chloroform,
n-Hexane, ethyl acetate, etc., or a mixture thereof is used.

The production of the compound of the present invention will be described more specifically by the following synthetic examples.

Synthesis Example 1 Synthesis of 2- (2,6-difluorophenyl) -4- (4-n-decyloxyphenyl) -2-oxazoline: 2-amino-2- (4-n-decyloxyphenyl) -Dissolved in 15 ml of tetrahydrofuran in a 100 ml eggplant-shaped flask containing 2.93 g (10 mmol) of ethanol, 1.01 g (10 mmol) of triethylamine and 30 ml of tetrahydrofuran 2,
1.77 g (10 mmol) of 6-difluorobenzoyl chloride was added over 30 minutes with stirring under ice cooling. After further stirring at room temperature for 3 hours, the produced triethylamine hydrochloride was removed with a glass filter, and the filtrate was concentrated under reduced pressure. To this concentrate, 50 ml of toluene and (2.84 g (20 mmol) of phosphorus pentoxide were added, and the mixture was refluxed for 3 hours on an oil bath. After cooling the reaction solution to room temperature, 50 ml of 10% aqueous sodium hydroxide solution, followed by saturated chlorination. The extract was washed with an aqueous solution of sodium, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure.The concentrate was purified by silica gel column chromatography (mobile phase: n-hexane: ethyl acetate = 8: 2) to give 2- ( 2.6-Difluorophenyl) -4- (4-n-decyloxyphenyl) -2-oxazoline (Compound No. 94) was obtained (pale yellow liquid, ▲ n ²⁵ _D ▼).
1.5236, total yield 2.15g, total yield 51.8%) Synthesis Example 2 Synthesis of 2- (2-chloro-6-fluorophenyl) -4- (3-phenyl-4-methoxyphenyl) -2-oxazoline 2-amino-2- (3-phenyl-4-methoxy) (Phenyl) -ethanol 2.43 g (10 mmol), triethylamine 1.01 g
(10 mmol), 100 m containing 30 ml of tetrahydrofuran
In a l-shaped eggplant-shaped flask, 1.93 g of 2-chloro-6-fluorobenzoyl chloride dissolved in 15 ml of tetrahydrofuran
(10 mmol) was added over 30 minutes while stirring with ice cooling. After further stirring at room temperature for 3 hours, the produced triethylamine hydrochloride was removed with a glass filter, and the filtrate was concentrated under reduced pressure.
To a 100 ml eggplant-shaped flask containing this concentrate and 30 ml of benzene, 4.76 g (40 mmol) of thionyl chloride was added at once, and the mixture was refluxed for 3 hours on a water bath with stirring. The reaction solution was returned to room temperature and then concentrated under reduced pressure. 30 ml of methanol in this concentrate
And 5 ml of 30% aqueous sodium hydroxide solution are added, and the temperature in the hot water bath is 70 ° C.
After stirring for 20 minutes at room temperature, concentrate under reduced pressure and concentrate with benzene.
100 ml was added, washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.

The concentrate was purified by silica gel column chromatography (mobile phase: n-hexane: ethyl acetate = 8: 2) and purified with 2- (2
-Chloro-6-fluorophenyl) -4- (3-phenyl-4-
Methoxyphenyl) -2-oxazoline (Compound No. 14
7) got.

(Pale yellow solid, melting point 80.5-82.0 ° C, total yield 1.8 g, total yield
47.4%) Synthesis Example 3 Synthesis of 2- (2,6-difluorophenyl) -4- (4-n-decylphenyl) -2-oxazoline: 2-amino-2- (4-n-decylphenyl) -ethanol 2.77
In a 100 ml eggplant-shaped flask containing g (10 mmol), triethylamine 1.01 g (10 mmol) and tetrahydrofuran 30 ml, 2,6-difluorobenzoyl chloride 1.77 g (10 mmol) dissolved in tetrahydrofuran 15 ml.
Was added over 30 minutes with stirring under ice cooling. After further stirring at room temperature for 3 hours, the produced triethylamine hydrochloride was removed with a glass filter, and the filtrate was concentrated under reduced pressure. To this concentrate, 50 ml of benzene and 3.57 g (30 mmol) of thionyl chloride were added, and the mixture was refluxed for 3 hours on an oil bath. The reaction mixture was concentrated under reduced pressure, 50 ml of methanol was added, and 2 ml of 50% aqueous sodium hydroxide solution was added dropwise with stirring at 60 ° C. After stirring for another 30 minutes, the mixture was poured into water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.

This concentrate was purified by silica gel column chromatography (mobile phase: n-hexane: ethyl acetate = 8: 2),
(2,6-Difluorophenyl) -4- (4-n-decylphenyl) -2-oxazoline (Compound No. 20) was obtained. (Pale yellow liquid, ▲ n ²⁵ _D ▼ 1.5421, total yield 3.4g, total yield 85.2
%) Synthesis Example 4 Synthesis of 2- (2-chloro-6-fluorophenyl) -5- (4-n-octyloxyphenyl) -2-thiazoline: 2-amino-1- (4-n-octyloxyphenyl) (Enyl) -ethanol 2.65 g (10 mmol), triethylamine 1.01 g (10
Mmol) and 30 ml of tetrahydrofuran were placed in a 100 ml eggplant-shaped flask and dissolved in 10 ml of tetrahydrofuran.
2-chloro-6-fluorobenzoyl chloride 1.93 g (10
(Mmol) was added over 30 minutes while stirring with ice cooling. After further stirring at room temperature for 3 hours, the produced triethylamine hydrochloride was removed with a glass filter, and the filtrate was concentrated under reduced pressure. This concentrate and 30 ml of toluene were placed in a 100 ml eggplant-shaped flask, 4.44 g (20 mmol) of phosphorus pentasulfide was added at once, and the mixture was refluxed for 4 hours on an oil bath with stirring.

After returning the reaction solution to room temperature, 30% aqueous sodium hydroxide solution
40 ml was added, and the mixture was stirred at room temperature for 1 hour. Benzene in the reaction solution
100 ml was added, washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (mobile phase: n-hexane: ethyl acetate = 8: 2), and then 2- (2chloro-6-fluorophenyl) -5- (4-n-octyloxy). Phenyl) -2-thiazoline (Compound No. 91) was obtained (pale yellow solid, melting point 41.0-41.5 ° C., total yield 3.20 g, total yield 76.
2%).

Synthesis Example 5 Synthesis of 2- (2,6-difluorophenyl) -4- (4-n-octylphenyl) -2-oxazoline: 2-amino-2- (4-n-octylphenyl) -ethanol 2.
To a mixture of 49 g (10 mmol), 1.01 g (10 mmol) of triethylamine and 30 ml of tetrahydrofuran was added 1.77 g (10 mmol) of 2,6-difluorobenzoyl chloride dissolved in 15 ml of tetrahydrofuran over 30 minutes while stirring with ice cooling. After further stirring at room temperature for 3 hours, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. 30 ml of this concentrate and benzene,
A mixture of 3.57 g (30 mmol) of thionyl chloride was heated to reflux on an oil bath for 3 hours.

After the reaction solution was returned to room temperature, it was concentrated under reduced pressure, 30 ml of methanol was added to the concentrate, and 4 ml of 30% sodium hydroxide aqueous solution was added for 10 minutes while heating and stirring at 70 ° C.

Further, the mixture was stirred at 70 ° C. for 20 minutes, returned to room temperature, extracted with ethyl acetate, washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (mobile phase: n-hexane: ethyl acetate = 8: 2), and 2- (2,6-difluorophenyl) -4- (4-n-octylphenyl) ) -2-Oxazoline (Compound No. 6) was obtained. (Colorless oil, ▲ n ²⁵ _D ▼ 1.5
226, total yield 3.1g, total yield 83.6%) Synthesis Example 6 Synthesis of 2- (2,6-difluorophenyl) -4- {4- (2,4-dichlorobenzyloxy) phenyl} -2-oxazoline: 2-amino-2- {4- (2, 4-Zinchlorobenzyloxy) phenyl} -ethanol 3.12 g (10 mmol), triethylamine 1.01 g (10 mmol) and tetrahydrofuran 3
To 0 ml of the mixture, under ice-cooling with stirring, 15 ml of tetrahydrofuran
1.67 g of 2,6-difluorobenzoyl chloride dissolved in
(10 mmol) was added over 30 minutes. After further stirring at room temperature for 3 hours, the reaction solution was filtered and the filtrate was concentrated under reduced pressure. To this concentrate, 30 ml of tetrahydrofuran, 1.
01 g (10 mmol) was added, and methanesulfonyl chloride 1.15 dissolved in 15 ml of tetrahydrofuran was stirred under ice cooling.
g (10 mmol) was added over 30 minutes.

After further stirring at room temperature for 3 hours, the reaction solution was filtered and the filtrate was concentrated under reduced pressure.

Methanol 50ml, 85% potassium hydroxide 1.00
g (15 mmol) was added, and the mixture was stirred at 70 ° C. for 2 hours. The mixture was returned to room temperature, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. This concentrate was purified by silica gel column chromatography (mobile phase: n-hexane: ethyl acetate = 8: 2) and purified with 2- (2,6-
Difluorophenyl) -4- {4- (2,4-dichlorobenzyloxy) phenyl} -2-oxazoline (Compound No. 35
9) got. (Colorless crystals, melting point 104.0-104.5 ° C, total yield
3.5g, total yield 80.6%) Synthesis Example 7 2- (2,6-difluorophenyl) -4- (2-fluoro-4-n-
Synthesis of nonylphenyl) -2-oxazoline: 2-amino-2- (2-fluoro-4-n-nonylphenyl) -ethanol 2.81 g (10 mmol), 2,6-difluorobenzoic acid 1.77 g (10 mmol) and toluene 3 g (30 mmol) of concentrated sulfuric acid was added to 20 ml of the mixture, and the mixture was stirred under reflux for 7 hours.
After returning the reaction solution to room temperature, 10% aqueous sodium hydroxide solution
The extract was washed with 30 ml and then with 30 ml of saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. This concentrate was subjected to silica gel column chromatography (mobile phase was n-hexane:
Purification with ethyl acetate = 8: 2) gave 2- (2,6-difluorophenyl) -4- (2-fluoro-4-n-nonylphenyl) -2-oxazoline (Compound No. 42). (Pale brown oil,
▲ n ²⁵ _D ▼ 1.5184, total yield 2.27g, total yield 66.2%) The compounds shown in Table 1 below were synthesized in the same manner as in Synthesis Examples 1 to 7. In addition, Table 1 also describes the compounds obtained in Synthesis Examples 1 to 7.

However, in the table, the physical property values marked with * indicate melting points (° C), and the other values indicate refractive index (▲ n ²⁵ _D ▼).

The compound of general formula (I) provided by the present invention is
As is clear from the test examples described below, it exhibits strong ovicidal, insecticidal, and acaricidal activity against insects and / or mites harmful to agricultural and horticultural and / or epidemic prevention, and has little chemical damage to useful crops, and is used for agricultural and horticultural applications. It is also useful as an active ingredient of an insecticidal and / or acaricidal agent for epidemics.

Thus, the compound of formula (I) of the present invention is useful for insects and mites which are harmful to useful crops and / or epidemics, for example, green peach aphid ( Myzus persicae ), cotton aphid ( Aphis gossypii ), rainbow aphid (aphid) Li
paphiserysimiae ), Amanita aphid ( Aphis c)
itricola ), P. aphis ( Nippolachnus)
aphids such as piri ); Green leafhopper ( Nephote)
ttix cincticeps ), Greater Planthopper ( Laodelphax stri )
Atellus), Sejirounka (Sogatella furcifera), brown planthopper (Nilaparvata lugens), such as planthoppers, leafhoppers, order Hemiptera (Nezara antennata), bombardier Hari bug (Cletus punctiger), stink bugs such as bombardier helicopter bug (Piezodorus clavatus); Chiya Thrips palmi ( Scirtothrips dorsalis ), Thrips palmi ( Thrips palmi ), Thrips palmi ( Po
Thrips such as nticulothrips diospyrosi ); Oxya yezoensis , Locusta
migratoria) Orthoptera pests such as, Anomala cuprea (Anom
ala cuprea ), rice leaf beetle ( Oulema oryza)
e ), Red-spotted ladybird ( Epilachna viginti)
octomaculata ) and other Coleoptera insect pests; housefly ( Musca do)
Diptera such as mestica ), Culex pipiens and Culex pipiens ; Plutella xylostella , Plutella xylostella , Spodoptera litura , Chilo suppr
Lepidopteran pests such as essalis ) and spider mites ( Tetranuchus)
urticae ), spider mites ( Tetranychus cinnabarin)
us), kanzawai (Tetranychus kanzawai), Ringohadani (Panonychus ulmi), citrus red mite (Panonyc
Hus citri ) and other spider mites exhibit an excellent control effect.

Therefore, the active compound of the formula (I) according to the present invention is useful as an active ingredient of agricultural and horticultural and / or epidemic prevention insecticides and acaricides.

When the compound of the present invention is actually used as an active ingredient of insecticides and acaricides, one or two compounds of the formula (I) are used.
Although one or more species may be used as they are, they can usually be formulated into various forms together with an agriculturally and horticulturally acceptable auxiliary agent.

Examples of the auxiliaries that can be used for formulation include carriers or diluents, surfactants, dispersants, fixing agents, stabilizers, and the like, which can be appropriately selected and added depending on the dosage form and the like.

The carrier or diluent includes solid and liquid carriers or diluents, and examples of the solid carrier or diluent include diatomaceous earth, talc, clay, alumina, kaolin, montmorillonite, silicic acid, and mineral powder such as white carbon. Alternatively, granules, animal and vegetable powders such as starch, soybean flour, wheat flour, fish meal and the like can be mentioned, and as a liquid carrier or diluent, water, alcohols (for example, methanol, ethylene glycol,
(Phenoxyethanol etc.), ketones (eg acetone, methyl ethyl ketone etc.), aromatic hydrocarbons (eg xylene, trimethylbenzene, methylnaphthalene, etc.)
Solvent naphtha etc.), aliphatic hydrocarbons (eg hexane, cyclohexane, kerosene, kerosene etc.), ethers (eg dioxane, diisopropyl ether, tetrahydrofuran etc.), halogenated hydrocarbons (eg dichloromethane, trichloroethane etc.), dimethylformamide etc. Acid amides, esters such as ethyl acetate, nitriles such as acetonitrile, sulfur-containing compounds such as dimethylsulfoxide, vegetable oils such as soybean oil and olive oil.

Examples of the surfactant include nonionic polyoxyalkylene alkyl ether, polyoxyalkylene allyl ether, polyoxyalkylene aliphatic ester, polyoxyalkylene sorbitan fatty acid ester, anionic alkyl allyl sulfate ester salt, and polyoxyalkylene. Examples include alkyl allyl sulfate ester salts, or a mixture thereof.

Examples of the dispersant and the fixing agent include lignin sulfonate, naphthalene sulfonate formalin condensate, alginate, starch, cellulose derivative, montmorillonite, synthetic water-soluble polymer, synthetic resin and the like.

Stabilizers include phosphates, glycols, nonionic surfactants, aromatic diamines, vegetable oils, epoxidized oils and the like.

Furthermore, a formulation containing a compound of formula (I) of the present invention may optionally contain other pesticides such as insecticides, acaricides, fungicides,
It may be mixed or used in combination with an attractant and the like, whereby it may exhibit a further excellent effect.

Such insecticides or acaricides include, for example, Fenitr
othion (O, O-dimethyl O-4-nitro-m-tolyl phosphorothioate), Diazinon (O, O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate),
Chlorpyrifos-methyl (O, O-dimethyl O- (3,5,6-trichloro-2-pyridyl) phosphorothioate), Acephate
(O, S-dimethylacetylphosphoramidothioate) and other organic phosphate compounds; Carbaryl (1-naphthylmethylcarbamate), Carbofuran (2,3-dihydro-2,
Carbamate compounds such as 2-dimethylbenzofuran-7-ylmethylcarbamate) and methomyl (S-methylN- (methylcarbamoyloxy) thioacetimidate); Dicofol (2,2,2-trichloro-1,1-bis) (4-Chlorophenyl) ethanol) and other organochlorine compounds; Fenbutati
n oxide (hexakis (β, β-dimethylphenethyl))
Organometallic compounds such as distannoxane; Fenvale
rate ((RS) -α-cyano-3-phenoxybenzyl (R
S) -2- (4-Chlorophenyl) -3-methylbutyrate), Permethrin (3-phenoxybenzyl 1RS) -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclo Pyrethroid compounds such as propanecarboxylate; Diflubenzuron (1- (4-chlorophenyl) -3-
(2,6-difluorobenzoyl) urea), Chlorfluazur
benzoylurea compounds such as on (1- (3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenenyl) -3- (2,6-difluorobenzoyl) urea) Buprofezin (2-t-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazin-4-one), Hexythiazox (trans-5- (4
-Chlorophenyl) -N-cyclohexyl-4-methyl-2-
And compounds such as oxothiazolidinone-3-carboxamide). Examples of fungicides include Iprobenfos (S-
Benzyl O, O-diisopropyl phosphorothioate, Edif
Organic phosphorus compounds such as enphos (O-ethyl S, S-diphenyl phosphorodithioate); Organic chlorine compounds such as Phthalide (4,5,6,7-tetrachlorophthalide); Zinb (zinc ethylene bis ( Polymerization of dithiocarbamate)), Po
dithiocarbamate compounds such as lycarbamate (dizinc bis (dimethyldithiocarbamate)); Captan (3a,
4,7,7a-Tetrahydro-N- (trichloromethanesulfonphenyl) phthalimide, Captafol (3a, 4,7,7a-Tetrahydro-N- (1,1,2,2-tetrachloroethanesulphenyl) phthalimide) N-halogenothioalkyl compounds such as Glycophene (3,5-dichlorophenyl) -N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide), Vinclozplin ((RS) -3- (3, 5-dichlorophenyl) -5-methyl-5-vinyl-1,3-oxazolidine-2,4-
Dione), Procymidone (N- (3,5-dichlorophenyl))
Dicarboxymide compounds such as -1,2-dimethylcyclopropane-1,2-dicarboximide); Benomyl (methyl 1-
Benzimidazole compounds such as (butylcarbamoyl) benzimidazole-2-yl carbamate); Biter
tanol (1- (biphenyl-4-yloxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) butan-2-
All), Triflumizole (1- (N- (4-chloro-2-trifluoromethylphenyl) -2-propoxyacetimidoyl) imidazole) and other azole compounds; Mepronil (3
-Isopropoxy-O-toluanilide), Flutolanil
Examples thereof include benzanilide compounds such as (α, α, α-trifluoro-3-isopropoxy-O-trianilide). As the attractant, for example, benzoic acid, 4-allyl-2-
Methoxyphenol, 4- (p-acetoxyphenyl) -2-
Examples include compounds such as butanone.

The compound of the formula (I) of the present invention is formulated into a wettable powder, granules, powders, emulsions, flowables, microcapsules, etc. according to a method of formulating pesticides known per se using the above-mentioned ingredients. Can be formulated into The compounding ratio of the active compound of the formula (I) in these preparations can be varied over a wide range depending on the kind of the compound, the dosage form, etc., but generally the compound is in the range of 0.01 to 80% by weight. More preferably, depending on the particular dosage form, for example in the case of emulsions, wettable powders and flowables, the compound of formula (I) is 0.01 to 50% by weight, more preferably 0.1 to 20% by weight. The compound of formula (I) may be contained at a concentration of 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, in the case of powders and granules. it can.

The preparation containing the compound of the formula (I) according to the present invention is directly applied to an adult, larva or egg of an insect or a mite harmful to agricultural and horticultural crops and / or epidemics, or a place where the adult, larva or egg inhabits. Can be used to control harmful insects and / or mites. The application amount of the compound of formula (I) in this case depends on the kind of active compound, dosage form,
Although it can be appropriately changed depending on the occurrence of pests, it is generally 1 to 10,000 g, preferably 10 to 1,000 g per hectare.
It can be in the range of g, more specifically, for example, in the case of the above-mentioned emulsion, wettable powder and flowable agent,
Usually, they can be diluted 1,000 to 10,000 times and sprayed at a rate of 1,000 to 10,000 liters per hectare. In the case of powders and granules, they are usually added at a rate of 10 to 100 kg per hectare. It is suitable to spray.

The following are formulation examples of the compound of formula (I) of the present invention, but the present invention is not limited thereto.

In addition, all "parts" in the following examples are parts by weight.

Formulation Example 1 (Emulsion) To 10 parts of the compound of the present invention (Compound No. 6), 5 parts of alkylallyl sulfonate and 5 parts of polyoxyalkylene alkylaryl ether, 80 parts of xylene is added and uniformly dissolved to obtain an emulsion.

Formulation Example 2 (Wettable powder) 10 parts of the compound of the present invention (Compound No. 145), 5 parts of polyoxyalkylene alkylallyl sulfate ester salt, 5 parts of lignin sulfonate salt, 10 parts of white carbon and 70 parts of diatomaceous earth are mixed and ground, and water is added. Use as a Japanese medicine.

Formulation Example 3 (Dust) 1 part of the compound of the present invention (Compound No. 315), 1 part of white carbon and 98 parts of finely divided clay are mixed and ground to give a powder.

Formulation Example 4 (Granule) After uniformly mixing 5 parts of the compound of the present invention (Compound No. 382), 0.5 part of dodecylbenzene sulfonate, 3.5 parts of lignin sulfonate, 30 parts of bentonite and 61 parts of talc,
An appropriate amount of water is added, and the mixture is kneaded, granulated using a granulator, and air-dried in a fluidized dryer to obtain granules.

Formulation Example 5 (flowable) 10 parts of the compound of the present invention (Compound No. 352), 5 parts of polyoxyalkylene alkylaryl ether, 5 parts of ethylene glycol and 79.6 parts of water are uniformly stirred and dispersed, and then 0.4 part of xanthan gum is added as a filler. Mix to make flowable.

Next, test examples are given to demonstrate the excellent insecticidal and acaricidal activity of the compound of the formula (I) of the present invention.

Test Example 1 (Egg-killing test of Nami-dani mite) Water was put into an ice cream container (diameter: 9 cm), a hole was made in a part of the lid, and the entire filter paper was made to absorb water to make it wet, and a kidney bean leaf was placed on it. . The leaves were inoculated with 10 female adult worms, each of which was laid for 24 hours, and then the female adults were removed. A drug having a predetermined concentration (the emulsion of Formulation Example 1 was diluted with water) was sprayed and allowed to stand in a constant temperature room (25 ° C.), and after 7 days, the number of hatched larvae was examined under a microscope to determine the egg-killing rate. The test was carried out in three wards in one ward. The results are shown in Table 2 below.

Test Example 2 (Kanzawa Mite Ovulation Test) Water was put in an ice cream container (9 cm in diameter), a hole was made in a part of the lid, and the entire filter paper was made to absorb water to make it wet, and a kidney bean leaf was placed on it. . Kanzawa no Mite female adults 10 on leaves
Each head was inoculated and allowed to lay eggs for 24 hours, and then female adults were removed. A drug having a predetermined concentration (the emulsion of Formulation Example 1 was diluted with water) was sprayed and allowed to stand in a constant temperature room (25 ° C.), and after 7 days, the number of hatched larvae was examined under a microscope to determine the egg-killing rate. The test was carried out in three wards in one ward. The results are shown in Table 2 below.

** Control A = PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY,
30,190-197 (1988) Compound No.AC-5 *** Control B = PCT: No82 / 02046 Test Example 3 (Insecticidal test against hatching larvae of Nami-dani mite) Water was put in an ice cream container (9 cm in diameter), a hole was made in a part of the lid, and the entire filter paper was made to absorb water to make it moist, and a kidney bean leaf was placed on it. I put it on. The leaves were inoculated with 10 female adult mites, respectively, and laid for 24 hours. After that, the adult female was removed, and it was allowed to stand in a constant temperature room (25 ° C). After 7 days, the number of hatched larvae was counted, and a drug having a predetermined concentration (the emulsion of Formulation Example 1 was diluted with water) was sprayed and allowed to stand in a temperature-controlled room (25 ° C). After 7 days, the number of adults was examined under a microscope. And the insecticidal rate against hatched larvae was determined. The test was carried out in three wards in one ward.

The results are shown in Table 3 below.

** Control A = PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY,
30,190-197 (1988) Compound No.AC-5 *** Control B = PCT: No82 / 02046 Test Example 4 (Insecticidal test against juvenile peach aphid) Five wingless female worms per seedling were infested with radish seedlings at the two-leaf stage of the true leaf, which were prepared for the cut, and the larvae were bred for 3 days. Was removed, and a drug having a predetermined concentration (the emulsion of Formulation Example 1 was diluted with water) was sprayed. The treated seedlings were placed in a greenhouse, and after 96 hours, the number of dead insects was examined to determine the insecticidal rate. The test was carried out in three wards in one ward. The results are shown in Table 4 below.

Test Example 5 (Insecticidal test against juveniles of cotton aphid) Five wingless fetus female adults were infested with 5 cucumber seedlings of one leaf of the true leaf prepared in a cup, and the adult insects were removed after 3 days of offspring. Then, a predetermined concentration of the drug (the emulsion of Formulation Example 1 was diluted with water) was sprayed. The treated seedlings were placed in a greenhouse, and after 96 hours, the number of dead insects was examined to determine the insecticidal rate. The test was carried out in three wards in one ward. The results are shown in Table 4 below.

** Control A = PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY,
30 , 190-197 (1988) Compound No.AC-5 *** Control B = PCT: WO82 / 02046 *** Control C = Pirimicarb Test Example 6 (Insecticidal test against larvae of leafhoppers on green leafhoppers) A rice seedling provided in a cup was sprayed with a drug having a predetermined concentration (the emulsion of Formulation Example 1 was diluted with water), and after air-drying, covered with an acrylic cylinder to give larvae of leafhoppers on leafhoppers. 10 seeds are released per seedling,
I covered it with gauze. The treated seedlings were placed in a greenhouse, and after 7 days, the number of dead insects was examined to determine the insecticidal rate. The test was carried out in three wards in one ward. The results are shown in Table 5 below.

** Control B = PCT: WO82 / 02046 Test Example 7 (insecticidal test against larvae of diamondback moth) Cabbage leaf pieces (2 cm square) were treated with a chemical solution of a predetermined concentration (Formulation Example 1)
(Diluted with water) and air-dried, then put it in an ice cream cup with a diameter of 9 cm together with 15 larvae of the diamondback moth.
It was placed in a constant temperature room at 0 ° C and the insecticidal rate was investigated 3 days later. The test was conducted in two wards in one ward. The results are shown in Table 6 below.

*** Control B = PCT: WO82 / 02046 Test Example 8 (Insecticidal test against larvae of Culex pipiens) Agent adjusted to a predetermined concentration (the emulsion of Formulation Example 1 was diluted with water)
50 ml was put in a 120 ml ice cream cup, a very small amount of dry yeast powder was added as a feed, and about 15 second-instar larvae of Culex pipiens were released there. Five days after releasing, the number of larvae that became 3rd instar was counted to determine the insecticidal rate. The test was carried out in three wards in one ward. The results are shown in Table 7 below.

** Control B = PCT: WO82 / 02046

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C07D 277/10 413/10 213 413/12 213 417/10 213 417/12 213 C07F 7/10 A (72) Inventor, Kazuya Toda, Nagano City, Nagano Prefecture, Oita, Tomitake, Hiroshi 173--2, Yasu Chemical Industry Co., Ltd. (72) Inventor, Miaki, Nagano City, Nagano Prefecture, Otomitake, Hiroshi, 173-2 Yasu Chemical Co., Ltd. Inside the company research institute (72) Inventor Yasuaki Hariya 173-2 Hirotomi Taketomi, Nagano City, Nagano Prefecture Yasu Chemical Industry Co., Ltd. (72) Inventor Tatsuya Ishida Otomi Taketomi Nagano City, Nagano Prefecture 173-2 Yasushi Chemical Co., Ltd. Industrial Co., Ltd. Research Institute (72) Inventor Tatsufumi Ikeda Nagano City, Nagano Oita Tomitake, Hiroshi 173-28 Yasushi Chemical Co., Ltd. Research Institute (72) Inventor Tsukikan Yoshinomiya Nagano-shi, Oita, Tomitake, Hiroshi 173--2 Yasushi Chemical Industry Co., Ltd. (72) Inventor Chiharu Morikawa Nagano-city, Nagano-shi, Tomitake, Hiroshi 173-1 Yasu Chemical Industry Co., Ltd. (56) Reference Reference Japanese Patent Laid-Open No. 2-304069 (JP, A) Japanese Patent Publication No. 4-17952 (JP, B2)

Claims (5)

[Claims] 1. A general formula In the formula, R ₁ and R ₂ are the same or different and each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a lower haloalkyl group or a lower haloalkoxy group, provided that R ₁ and R ₂ Does not represent a hydrogen atom at the same time; R ₃ represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group; R ₄ represents an alkyl group having 7 or more carbon atoms, an alkoxy group having 7 or more carbon atoms, an alkylthio group , Lower alkoxy-lower alkyl group, lower alkoxy-lower alkoxy group, alkenyloxy group having 3 or more carbon atoms, lower alkynyloxy group, tri (lower alkyl) silyl group, cycloalkyl optionally substituted with lower alkyl group Group or formula Wherein B represents a direct bond, an oxygen atom, a lower alkylene group, a lower alkyleneoxy group, a lower alkylenedioxy group or a di (lower alkyl) silyl group,
Q represents CH or N, n is an integer of 0 to 5, n substituents R ₅ are the same or different and each is a halogen atom, an alkyl group, an alkoxy group, a lower haloalkyl group,
A 2-substituted phenyl-2-oxa or thiazoline derivative represented by: A represents a lower haloalkoxy group or a tri (lower alkyl) silyl group; A represents a direct bond or a lower alkylene group; and Z represents an oxygen atom or a sulfur atom. . 2. General formula In the formula, R ₁ and R ₂ have the meanings defined in claim 1, and the substituted benzoic acid represented by Or In the formula, R ₃ , R ₄ and A have the meanings defined in claim 1, and the reaction is carried out in the presence of a dehydrating agent with an aminoalcohol derivative represented by the formula (I). A method for producing a 2-substituted phenyl-2-oxa or thiazoline derivative represented by: 3. General formula Or In the formula, R ₁ , R ₂ , R ₃ , R ₄ and A have the meanings defined in claim 1, wherein the amide alcohol derivative represented by: is treated with a dehydrating agent. A process for producing a 2-substituted phenyl-2-oxa or thiazoline derivative represented by (I). 4. A general formula In the formula, R ₁ , R ₂ , R ₃ , R ₄ and A have the meanings defined in claim 1, W represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group, and the compound represented by A 2-substituted phenyl group represented by the general formula (I) according to claim 1, characterized in that it is treated with
A method for producing a 2-oxa or thiazoline derivative. 5. An insecticide or acaricide containing the 2-substituted phenyl-2-oxa or thiazoline derivative according to claim 1 as an active ingredient.