JPH06100546A - 4-naphthyl-substituted oxazoline derivative, its production and insecticidal miticide - Google Patents

Abstract

PURPOSE:To provide a new compound useful as an insecticidal miticide. CONSTITUTION:The compound of formula I (R<1> and R<2> are halogen), e.g. 2-(2,6- difluorophenyl)-4-(2-naphthyl)-2-oxazoline. The compound of formula I can be produced by cyclizing an amidoethyl halide derivative of formula II (Y is halogen) with an alkali (e.g. NaOH) at 50-80 deg.C in a solvent (e.g. THF) or without using a solvent. The concentration of the compound of formula II is adjusted to 5-80wt.% by selecting the amount of the solvent. The amount of the alkali is 1-10mol based on 1mol of the compound of formula II. The compound is effective for the control of agricultural and horticultural vermin such as planthopper and army worm, spider mite, hygienic vermin such as fly, mosquito and cockroach, grain vermin such as bean weevil, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel 4-naphthyl-substituted oxazoline derivative useful as an insecticidal acaricide.

[0002]

2. Description of the Related Art Conventionally, some oxazoline derivatives as agricultural chemicals have been known. For example, Pesticide Bioche
mistry and Physiology 30, 19197, Tokusho 57-50
A 4-phenyl-substituted oxazoline derivative is reported as an insecticidal acaricide in 1962, JP-A-2-85268, JP-A-2-304069, JP-A-3-232867 and JP-A-4-89484. Has been done.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel 4-naphthyl-substituted oxazoline derivative having an effect superior to that of 4-phenyl-substituted oxazoline derivatives known as insecticides and acaricides.

[0004]

[Means for Solving the Problems]
The present inventors have found that a naphthyl-substituted oxazoline derivative has a remarkable controlling activity as an insecticidal acaricide, and have completed the present invention.

The first invention is the following formula:

[0006]

[Chemical 3]

The present invention relates to a 4-naphthyl-substituted oxazoline derivative represented by the formula (wherein R ¹ and R ² represent a halogen atom).

The second invention is the following formula (II):

[0009]

[Chemical 4]

The amide ethyl halide derivative represented by the formula (wherein each of R ¹ , R ² and Y represents a halogen atom) is treated with an alkali for cyclization and is represented by the above formula (I). It relates to a method for producing a 4-naphthyl-substituted oxazoline derivative.

The third aspect of the present invention is the fourth aspect of the formula (I).
-The present invention relates to an insecticidal and acaricidal agent containing a naphthyl-substituted oxazoline derivative as an active ingredient.

The present invention will be described in detail below. In the novel 4-naphthyl-substituted oxazoline derivative (I), examples of the halogen atom of R ¹ and R ² include chlorine, iodine, bromine and fluorine. R ¹ is preferably fluorine and R ² is Fluorine or chlorine is preferred. The bonding position of the naphthyl group is 1-position or 2-position, but 2-position is preferable.

The compound (I) of the present invention can be synthesized by the following three steps.

[0014]

[Chemical 5]

(In the formula, R ¹ and R ² are as defined above, and X and Y represent a halogen atom)

The intermediate amide ethanol derivative (V) of the present invention can be synthesized by reacting the starting compound (III) with the compound (IV) in a solvent or without solvent. It is preferable to react in the presence of a base to promote the reaction.

The solvent is not particularly limited as long as it does not directly participate in this reaction, and for example, benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform. Chlorinated or unchlorinated aromatics, aliphatic, such as dichloromethane, dichloroethane, trichloroethylene, cyclohexane,
Alicyclic hydrocarbons; ethers such as diethyl ether, tetrahydrofuran, dioxane; ketones such as acetone and methyl ethyl ketone; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; triethylamine, Organic bases such as pyridine and N, N-dimethylaniline; 1,3-dimethyl-2
-Imidazolidinone; dimethylsulfoxide; and mixtures of these solvents can be used. The amount of the solvent used is such that the concentration of the compound (III) is 5 to 80% by weight, preferably 10 to 70% by weight.

The base is not particularly limited, and examples include triethylamine, pyridine, N, N-dimethylaniline,
Organic bases such as DBU; sodium methoxide,
Alkali metal alkoxides such as sodium ethoxide; inorganic bases such as sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate can be used, but triethylamine, pyridine, Organic bases such as N, N-dimethylaniline, DBU are preferred.
The amount of the base used is 0.001 to 5 with respect to the compound (III).
A double mole, preferably 1 to 1.5 times mole can be used.

The reaction temperature is not particularly limited, but is within a temperature range from the ice-cooling temperature to the boiling point of the solvent to be used, 0 ° C.
-10 degreeC is preferable. The reaction time varies depending on the above-mentioned concentration and reaction temperature, but can usually be 0.3 to 3 hours. The amount of the raw material compound used is 0.5 to 2 times, preferably 1 to 1 times, the compound (IV) with respect to the compound (III).
It is 5 times the molar amount.

The compound (III) is, for example, Tetrahedron Let
It can be easily produced by reducing naphthylglycine (VI) according to the method described in t, 1977, 3527 and the like.

[0021]

[Chemical 6]

The compound (IV) is, for example, J. Am. Chem. So.
According to the method described in c., 42, 599 (1920), etc., it can be easily produced using benzoic acid (VII) and oxalyl halide (VIII).

[0023]

[Chemical 7]

(In the formula, R ¹ and R ² have the same meanings as described above, and X represents a halogen atom.) The intermediate compound (V) produced as described above is
After completion of the reaction, usual post-treatments such as filtration and concentration can be carried out for use in the next reaction.

The intermediate amide ethyl halide derivative (II) of the present invention is synthesized by reacting compound (V) with thionyl halide (SOY ₂ ) in a solvent or without solvent as shown below. However, it is preferable to carry out the reaction under heating to accelerate the reaction. The solvent is not particularly limited as long as it does not directly participate in this reaction, and the above-mentioned chlorinated or non-chlorinated aromatic, aliphatic, alicyclic hydrocarbons, ethers and mixtures of these solvents. Can be used. The amount of the solvent used can be such that the concentration of the compound (V) is 5 to 80% by weight, preferably 10 to 70% by weight.

The reaction temperature is not particularly limited, but it is within the temperature range from the ice cooling temperature to the boiling point of the solvent to be used, 50
C. to 80.degree. C. is preferable. The reaction time varies depending on the above-mentioned concentration and reaction temperature, but can usually be 0.3 to 2 hours. The amount of thionyl halide used is 1 to 5 times mol, preferably 1.1 to 2 times mol, of the compound (V). Compound (II) produced as described above
Can be subjected to usual post-treatments such as concentration and used in the next reaction.

The compound (I) of the present invention can be prepared by treating the intermediate compound (II) with a solvent or without a solvent and cyclizing the compound as shown below. In order to accelerate the reaction, it is preferable to react under heating. The solvent is not particularly limited as long as it does not directly participate in this reaction, and the above-mentioned chlorinated or non-chlorinated aromatic, aliphatic or alicyclic hydrocarbons; ethers; methanol, ethanol, Alcohols such as propanol, butanol; and mixtures of these solvents can be used, but tetrahydrofuran, dioxane, methanol and ethanol are preferred. The amount of the solvent used can be such that the concentration of the compound (II) is 5 to 80% by weight, preferably 10 to 70% by weight.

The reaction temperature is not particularly limited, but it is within the temperature range from the ice cooling temperature to the boiling point of the solvent to be used, 50
C. to 80.degree. C. is preferable. The reaction time varies depending on the above-mentioned concentration and reaction temperature, but can usually be 0.3 to 2 hours. The amount of alkali used is 1 to 10 times mol, preferably 2 to 5 times mol, of the compound (II).
The alkali is not particularly limited, and for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate can be used, but sodium hydroxide and potassium hydroxide are preferable.

The compound (I) of the present invention produced as described above is subjected to usual post-treatments such as extraction, filtration and concentration, and if necessary, known means such as recrystallization and various chromatographies. It can be appropriately purified.

The compound (I) of the present invention is an agricultural and horticultural insect pest, for example, Hemiptera (planthoppers, leafhoppers, aphids, whiteflies, etc.), Lepidoptera (Beetle beetles, diamondback moths, leaf beetles, leaf moths, scuttleflies). , Pseudomonas aeruginosa), Coleoptera (Galloridae, Weevil, Chrysomelidae, Scarabaeidae, etc.), Acarina (Citrus spider mites of the family Acaridae, citrus red mite, etc.), sanitary pests (fly, mosquito, cockroach) , Etc.), and stored grain pests (Euphoria japonicum, bean weevils, etc.), and Compound (I) is nontoxic to livestock and fishery products.

The compound (I) may be used alone, but may be mixed with a carrier, a surfactant, a dispersant, an auxiliary agent and the like by a conventional method, for example, powders, emulsions, fine granules, granules, It is preferably prepared and used in a composition such as a wettable powder, an oily suspension and an aerosol. As the carrier, for example, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime,
Solid carriers such as silica sand, ammonium sulfate, urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform,
Carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n) -Hexanol,
Liquid carriers such as ethylene glycol), polar solvents (dimethylformamide, dimethylsulfoxide, etc.), water; gas carriers such as air, nitrogen, carbon dioxide, and freon (in this case, mixed injection can be performed). be able to.

Examples of the surfactant that can be used to improve the performance of the present agent such as adhesion to animals and plants, improvement of absorption, dispersion of drug, emulsification, spreading and the like include alcohol sulfates, alkyl sulfonates, Examples thereof include lignin sulfonate and polyoxyethylene glycol ether. In order to improve the properties of the preparation, for example, carboxymethyl cellulose, polyethylene glycol, gum arabic or the like can be used as an auxiliary agent.

In the preparation of the present agent, the above-mentioned carrier, surfactant and auxiliary agent can be used alone or in suitable combination according to the purpose. When the compound (I) of the present invention is formulated, the content of the active ingredient in the emulsion is 1 to 50% by weight, the powder is 0.3 to 25% by weight, the wettable powder is 1 to 90% by weight, and the granules are 0% by weight. 0.5 to 5% by weight, the oil agent is 0.5 to 5% by weight, and the aerosol is 0.1 to 5% by weight. These formulations can be diluted to an appropriate concentration and sprayed on plant foliage, soil, water surface of paddy fields or the like, or can be directly applied to pests for various purposes depending on the purpose.

[0034]

EXAMPLES The present invention will be specifically described below with reference to examples. It should be noted that these examples do not limit the scope of the present invention.

Example 1 Synthesis of 2- (2,6-difluorophenyl) -4- (2-naphthyl) -2-oxazoline (Compound 1) 2-amino-2- (2-naphthyl) ethanol 1 in 20 ml of tetrahydrofuran 0.87 g and triethylamine 1.
11 g of 2,6-difluorobenzoyl chloride 1.77 dissolved in 10 ml of tetrahydrofuran were dissolved.
g was added dropwise over 20 minutes while stirring with ice cooling. After dropping, the mixture was stirred at room temperature for 3 hours, the precipitated triethylamine hydrochloride was filtered off, and the filtrate was concentrated under reduced pressure. This concentrate was dissolved in 20 ml of toluene, 4.8 g of thionyl chloride was added, and the mixture was heated under reflux for 2 hours with stirring. After cooling, excess thionyl chloride and the solvent were distilled off under reduced pressure. This concentrate was added to methanol 2
It was dissolved in 0 ml, 10 ml of 15% aqueous sodium hydroxide solution was added, and the mixture was stirred at 70 ° C. for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the mixture was extracted with toluene. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained oily substance was isolated by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 4: 1) to obtain 1.74 g of the desired product as white crystals. ¹ H-NMR δ (ppm): 4.38 (1H, t), 4.79 (1H, dd), 5.65 (1
H, dd), 6.96 ~ 7.95 (10H, m) mp 53 ~ 56 ℃

Example 2 2- (2-chloro-6-fluorophenyl) -4- (2
Synthesis of -naphthyl) -2-oxazoline (Compound 2) Example except that 1.77 g of 2,6-difluorobenzoyl chloride in Example 1 was replaced by 1.93 g of 2-chloro-6-fluorobenzoyl chloride. The same procedure as in 1 was carried out to obtain 1.55 g of the desired product as a pale yellow oily substance. ¹ H-NMR δ (ppm): 4.40 (1H, t), 4.91 (1H, dd), 5.67 (1
H, dd), 7.03 ~ 7.97 (10H, m) n _D ^24.0 1.6210

Example 3 Synthesis of 2- (2,6-difluorophenyl) -4- (1-naphthyl) -2-oxazoline (Compound 3) 2-amino-2- (2-naphthyl) ethanol in Example 1 The same procedure as in Example 1 was repeated except that 1.87 g of 2-amino-2- (1-naphthyl) ethanol was used in place of the above compound to obtain 1.98 g of the desired product as a pale yellow oily substance. ¹ H-NMR δ (ppm): 4.24 (1H, t), 5.10 (1H, dd), 6.20 (1
H, dd), 6.96 ~ 8.00 (10H, m) n _D ^23.0 1.6170

Example 4 2- (2-chloro-6-fluorophenyl) -4- (1
Synthesis of -naphthyl) -2-oxazoline (Compound 4) In place of 2-amino-2- (2-naphthyl) ethanol in Example 2, 1.87 g of 2-amino-2- (1-naphthyl) ethanol was used. Except for the above, the same procedure as in Example 2 was carried out to obtain 1.76 g of the desired product as white crystals. ¹ H-NMR δ (ppm): 4.26 (1H, t), 5.12 (1H, dd), 6.23 (1
H, dd), 7.04 ~ 8.03 (10H, m) mp 95 ~ 97 ℃

Example 5 (1) Preparation of granules 5 parts by weight of compound 1, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of neoperex powder (trade name; manufactured by Kao Corporation) and sodium ligninsulfonate. 2 parts by weight were uniformly mixed, a small amount of water was added, and the mixture was kneaded, then granulated and dried to obtain granules. (2) Preparation of wettable powder 10 parts by weight of compound 1, 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of neoperex powder (trade name; manufactured by Kao Corporation) and demol (trade name; Kao Corporation) 0.5 part by weight was uniformly mixed and then pulverized to obtain a wettable powder. (3) Preparation of Emulsion 20 parts by weight of Compound 1 and 70 parts by weight of xylene were added with 10 parts by weight of toxanone (trade name; manufactured by Sanyo Kasei Co., Ltd.), uniformly mixed and dissolved to obtain an emulsion. (4) Preparation of powder 5 parts by weight of compound 1, 50 parts by weight of talc and kaolin 4
A powder was obtained by uniformly mixing 5 parts by weight.

Example 6 (Efficacy test) (1) Efficacy test against Nymphalid mite eggs Five adult females of Nymphalid mite were parasitized on kidney leaf pieces (20 mm in diameter) to lay eggs for 24 hours, and then the female adults were removed.
On the other hand, the leaves shown in Table 1 were used as wettable powders according to Example 5 and diluted with water containing a surfactant (0.01%) to an active ingredient concentration of 300 ppm to prepare 15 ppm leaf pieces. Soaked for 2 seconds. The number of hatched larvae was examined after 7 days in a constant temperature room at 25 ° C., and the ovicidal rate was determined. The results are shown in Table 1.

(2) Efficacy test against citrus red mite eggs Ten adult female citrus mites are parasitized on mulberry leaf pieces (diameter 20 mm), and the ovicidal rate was determined in the same manner as in the above-described test for citrus red mite eggs. In Tables 1 and 2, those with an ovicidal rate of 100% are A, those with 99-80% are B, those with 79-60% are C, and those with 59% or less are D.
Displayed as. In addition, 2,4-diphenyloxazolidine described in JP-A-57-501962 was similarly prepared, and the same test was conducted as a comparative example.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

INDUSTRIAL APPLICABILITY The novel 4-naphthyl-substituted oxazoline derivative of the present invention is a useful pesticide having a better insecticidal and acaricidal effect than known 4-phenyl-substituted oxazoline derivatives.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Fujii 5 1978, Oji City, Ube, Yamaguchi Prefecture 5 1978, Ube Institute of Industrial Research, Ltd. Ube Institute Co., Ltd. (72) Inventor Shoji Shikida 1-12-32 Nishihonmachi, Ube City, Yamaguchi Prefecture Ube Institute Co., Ltd.

Claims (3)

[Claims] 1. The following formula (I): A 4-naphthyl-substituted oxazoline derivative represented by the formula: wherein R ¹ and R ² represent a halogen atom. 2. The following formula (II): The formula (I) according to claim 1, wherein the amidoethyl halide derivative represented by the formula (wherein R ¹ , R ² and Y each represent a halogen atom) is treated with an alkali for cyclization. And a method for producing a 4-naphthyl-substituted oxazoline derivative. 3. A compound represented by formula (I) according to claim 1
An insecticide and acaricide containing a naphthyl-substituted oxazoline derivative as an active ingredient.