JPH06100560A - Oxazoline derivative, its production and insecticide/ miticide/bactericide therefrom - Google Patents

Abstract

PURPOSE:To provide the subject new compound useful as an insecticide/miticide/ bactericide. CONSTITUTION:The objective compound of formula I [R<1> is 1-20C alkyl, 1-20C alkoxy or halogen; R<2> is 1-5C alkyl, 1-5C alkoxy or halogen; n is 0-2; A is (substituted) heteroatom-contg. five to six-membered heteroaromatic ring], e.g. 2-(3-chloro-2-thienyl)-4-(4-methylphenyl)-2-oxazoline. The compound of the formula I can be obtained by treating an amidoethyl halide derivative of formula II (Y is halogen) with an alkali followed by cyclization.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel oxazoline derivative useful as an insecticidal, acaricidal or fungicide.

[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]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel oxazoline derivative having an excellent controlling effect as an insecticidal, acaricidal or bactericidal agent.

[0004]

[Means for Solving the Problems]
-Heteroaromatic ring group-substituted oxazoline derivative is insecticidal, acaricidal,
They found that they have a remarkable control activity as a bactericide, and completed the present invention.

The first invention is the following formula:

[0006]

[Chemical 3]

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or R ² is an alkyl group having 1 to 5 carbon atoms, 1 to 5 carbon atoms.
Represents an alkoxy group or a halogen atom, n represents an integer of 0, 1 or 2, and A represents a substituted or unsubstituted 5 or 6-membered heteroaromatic ring group having 1 or 2 heteroatoms).
And an oxazoline derivative represented by

The second invention is the following formula (II):

[0009]

[Chemical 4]

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and R ² represents an alkyl group having 1 to 5 carbon atoms, 1 to 5 carbon atoms.
Represents an alkoxy group or a halogen atom, n represents an integer of 0, 1 or 2, A represents a substituted or unsubstituted 5 or 6-membered heteroaromatic ring group having 1 or 2 heteroatoms,
Y represents a halogen atom) is treated with an alkali to cyclize the amidoethyl halide derivative, and to a method for producing the oxazoline derivative represented by the above formula (I).

A third aspect of the present invention relates to an insecticidal, acaricidal and fungicide containing the oxazoline derivative represented by the above formula (I) as an active ingredient.

The present invention will be described in detail below. In the oxazoline derivative of the formula (I), R ¹ has 1 carbon atom.
To 20 straight-chain or branched alkyl groups include, for example, methyl, ethyl, n-propyl, i-propyl, n
-Butyl, sec-butyl, t-butyl, n-pentyl,
n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-
Tridecyl, n-tetradecyl, n-pentadecyl, n
-Hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, etc .; carbon number 1 to
Examples of the alkoxy group of 20 include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy,
sec-butoxy, t-butoxy, n-pentyloxy,
n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-
Undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, n- Eicosyloxy and the like; Examples of the halogen atom include chlorine, iodine, bromine, and fluorine, but a methyl group, an n-pentyloxy group, and an n-decyloxy group are preferable.

Examples of the alkyl group having 1 to 5 carbon atoms for R ² include methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, etc .; Examples of the alkoxy group of to 5 include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t-butoxy, n.
-Pentyloxy and the like; examples of the halogen atom include chlorine, iodine, bromine and fluorine,
A methyl group, a methoxy group, an ethoxy group and a chlorine atom are preferred. n is an integer of 0, 1 or 2, but 0 or 1 is preferable.

The 5- or 6-membered heteroaromatic ring group having 1 or 2 heteroatoms of A includes N, S and / or O such as thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, aazolyl and oxazolyl. A 5-membered heteroaromatic ring group having 1 or 2 heteroatoms; a 6-membered heteroaromatic ring group such as pyridyl can be mentioned, but a thienyl group, a furyl group, a pyrrolyl group, a pyrazolyl group and a pyridyl group are preferable. Examples of the substituent of these heteroaromatic ring groups include halogen atoms such as chlorine, bromine and fluorine; lower alkyl groups such as methyl and ethyl; and alkylene groups such as trimethylene. As the substituent A, for example, 2-
Thienyl, 3-chloro-2-thienyl, 3-bromo-2
-Thienyl, 3-fluoro-2-thienyl, 3-methyl-2-thienyl, 3-chloro-5-methyl-2-thienyl, 2-furyl, 3-chloro-2-furyl, 3-bromo-2-furyl , 3-chloro-1-methyl-2-pyrrolyl, 3-bromo-1-methyl-2-pyrrolyl, 4-chloro-1-methyl-5-pyrazolyl, 4-bromo-1-methyl-5-pyrazolyl, 4 -Chloro-1,3-dimethyl-5-pyrazosyl, 4-bromo-1,3-dimethyl-5
-Pyrazolyl, 1,3,4-trimethyl-5-pyrazolyl, 4-chloro-3-ethyl-1-methyl-5-pyrazolyl, 4-bromo-3-ethyl-1-methyl-5-pyrazolyl, 3-ethyl -1,4-Dimethyl-5-pyrazolyl, 1-methyl-3,4-trimethylene-5-pyrazolyl, 1-methyl-3,4- (2-methyl-trimethylene) -5-pyrazolyl, 5-chloro-1 , 3-dimethyl-4-pyrazolyl, 1-methyl-5-pyrazolyl, 3-
Pyridyl, 2-pyridyl, 4-pyridyl, 2-chloro-
3-pyridyl, 2-chloro-3-thienyl, 1-methyl-2-imidazolyl, 4-chloro-1-methyl-5-imidazolyl, 5-chloro-4-thiazolyl, 4-chloro-5-thiazolyl, 5- Mention may be made of methyl-4-oxazolyl. Specific examples of the oxazoline derivative of the formula (I) are shown in Tables 1 to 3.

[0015]

[Table 1]

[0016]

[Table 2]

[0017]

[Table 3]

The compound (I) of the present invention can be synthesized by the following 3 steps.

[0019]

[Chemical 5]

(In the formula, R ¹ , R ² , A and n have the same meanings as described 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 includes, for example, 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 and DBU are preferable because they can serve as a solvent. The amount of the base used is 0.001 to 5 times mol, preferably 1 to 5 times, of the compound (III).
1.5 times the molar amount 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 used or less, and 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 phenylglycines (VI) according to the method described in t, 1977, 3527 and the like.

[0026]

[Chemical 6]

(Wherein R ¹ , R ² and n are as defined above) The compound (IV) is, for example, J. Am. Chem. Soc., 42, 599.
According to the method described in (1920) and the like, it can be easily produced using the corresponding carboxylic acid (VII) and oxalyl halide (VIII).

[0028]

[Chemical 7]

(In the formula, A has the same meaning as 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 prepared by reacting the compound (V) with a thionyl halide (SOY ₂ ) in a solvent or without a 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 it 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 pest, for example, Hemiptera (planthoppers, leafhoppers, aphids, whiteflies, etc.), Lepidoptera (Beetle beetles, diamondback moths, leaf beetles, leaf moths, symphysis). , 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 (Rhododendron japonicum, weevil, etc.), and plant diseases such as wheat red rust, barley powdery mildew, cucumber downy mildew, rice blast, and tomato epidemic. Compound (I) is nontoxic to humans 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 surfactants that can be used to improve the performance of this agent such as adhesion to animals and plants, 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 according to the purpose.

[0039]

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- (3-chloro-2-thienyl) -4- (4-methylphenyl) -2-oxazoline (Compound No. 1) 2-amino-2- (4-methyl) in 15 ml of tetrahydrofuran. Phenyl) ethanol (1.20 g) and triethylamine (0.74 g) were dissolved in tetrahydrofuran (10 ml).
1.00 g of 3-chloro-2-thiophenecarboxylic acid chloride dissolved in ml was added dropwise over 20 minutes while stirring with ice cooling. After the 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 15 ml of chloroform, 3.2 g of thionyl chloride was added, and the mixture was heated under reflux with stirring for 2 hours.
After cooling, excess thionyl chloride and the solvent were distilled off under reduced pressure. This concentrate was dissolved in 15 ml of methanol, 7 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 ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The oily substance obtained was subjected to column chromatography (Wako-Gel C).
-200, eluted with toluene: ethyl acetate = 9: 1) to obtain 1.48 g of the desired product as a colorless oil. n _D ^19.0 1.6211 ¹ H-NMR (CDCl ₃ ), δ ppm: 2.34 (3H, S), 4.25 (1H, t, J
= 8Hz), 4.77 (1H, dd, J = 10 and 8Hz), 5.38 (1H, dd, J = 1
0 and 8Hz), 7.02 (1H, d, J = 5Hz), 7.18 (4H, s), 7.41 (1
(H, d, J = 5Hz)

Example 2 Synthesis of 2- (3-chloro-2-thienyl) -4- (4-n-pentyloxyphenyl) -2-oxazoline (Compound No. 2) 2-amino-2- (in 10 ml of tetrahydrofuran. 4-Pentyloxyphenyl) ethanol (0.89 g) and triethylamine (0.44 g) were dissolved, and 3-chloro-2-thiophenecarboxylic acid chloride (0.72 g) dissolved in tetrahydrofuran (5 ml) was stirred for 20 minutes under ice-cooling. Dropped. After the dropwise addition, 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. Dissolve this concentrate in 10 ml of chloroform,
2.4 g of thionyl chloride was added, and the mixture was heated under reflux with stirring for 2 hours. Then, in the same manner as in Example 1, 0.84 g of the desired product which is a colorless oily substance was obtained. n _D ^23.2 1.5824 ¹ H-NMR (CDCl ₃ ), δ ppm: 0.93 (3H, t, J = 6Hz), 1.20〜
1.88 (6H, m), 3.95 (3H, t, J = 6Hz), 4.25 (1H, t, J = 8H
z), 4.76 (1H, dd, J = 10 and 8Hz), 5.35 (1H, dd, J = 10
and 8Hz), 6.87 (2H, d, J = 8Hz), 7.03 (1H, d, J = 5Hz),
7.21 (2H, d, J = 8Hz), 7.42 (1H, d, J = 5Hz)

Example 3 2- (4-chloro-1-methyl-5-pyrazolyl) -4
Synthesis of-(4-n-pentyloxyphenyl) -2-oxazoline (Compound No. 7) Instead of 3-chloro-2-thiophenecarboxylic acid chloride in Example 2, 4-chloro-1-methyl-5-pyrazolecarboxylic acid was used. 0.82 g of the desired product as a colorless oily substance was obtained in the same manner except that 0.72 g of acid chloride was used. n _D ^23.5 1.5597 ¹ H-NMR (CDCl ₃ ), δ ppm: 0.92 (3H, t, J = 6Hz), 1.16 ~
1.92 (6H, m), 3.96 (2H, t, J = 6Hz), 4.18 (3H, s), 4.24
(1H, t, J = 8Hz), 4.76 (1H, dd, J = 9 and 8Hz), 5.37 (1H,
dd, J = 9 and 8Hz), 6.90 (2H, d, J = 8Hz), 7.21 (2H, d,
J = 8Hz), 7.49 (1H, s)

Example 4 Synthesis of 2- (3-chloro-2-thienyl) -4- (4-n-decyloxyphenyl) -2-oxazoline (Compound No. 12) 2-Amino-2- (in 20 ml of tetrahydrofuran. 4-n
1.47 g of decyloxyphenyl) ethanol and 0.55 g of triethylamine were dissolved, and 0.90 g of 3-chloro-2-thiophenecarboxylic acid chloride dissolved in 10 ml of tetrahydrofuran was added dropwise over 20 minutes while stirring with ice cooling. did. After dropping, after stirring for 3 hours at room temperature,
The precipitated triethylamine hydrochloride was filtered off, and the filtrate was concentrated under reduced pressure. Dissolve this concentrate in 20 ml of toluene,
2.4 g of thionyl chloride was added, and the mixture was heated under reflux with stirring for 2 hours. Thereafter, in the same manner as in Example 1, 1.26 g of the desired product, which was a pale yellow crystal, was obtained. mp 32-33 ° C ¹ H-NMR (CDCl ₃ ), δ ppm: 0.88 (3H, t, J = 6Hz), 1.02-
1.87 (16H, m), 3.93 (2H, t, J = 6Hz), 4.23 (1H, t, J = 8H
z), 4.75 (1H, dd, J = 9 and 8Hz), 5.36 (1H, dd, J = 9 an
d 8Hz), 6.88 (2H, d, J = 8Hz), 7.01 (1H, d, J = 5Hz), 7.
21 (2H, d, J = 8Hz), 7.41 (1H, d, J = 5Hz)

Example 5 2- (4-chloro-1-methyl-5-pyrazolyl) -4
Synthesis of-(4-n-decyloxyphenyl) -2-oxazoline (Compound No. 15) In place of 3-chloro-2-thiophenecarboxylic acid chloride in Example 4, 4-chloro-1-methyl-5-pyrazolecarboxylic acid was used. 1.18 g of the desired product as pale yellow crystals was obtained in the same manner except that 0.90 g of acid chloride was used. mp 47-49 ° C ¹ H-NMR (CDCl ₃ ), δ ppm: 0.88 (3H, t, J = 6Hz), 1.09-
1.89 (16H, m), 3.95 (2H, t, J = 6Hz), 4.18 (3H, s), 4.2
2 (1H, t, J = 8Hz), 4.77 (1H, t, J = 9Hz), 5.37 (1H, t, J
= 9Hz), 6.89 (2H, d, J = 8Hz), 7.20 (2H, d, J = 8Hz), 7.4
8 (1H, s)

Example 6 Synthesis of 2- (4-chloro-1,3-dimethyl-5-pyrazolyl) -4- (4-n-decyloxyphenyl) -2-oxazoline (Compound No. 16) In Example 4 4-chloro-1,3-dimethyl-instead of 3-chloro-2-thiophenecarboxylic acid claloid
1.24 g of the desired product as white crystals was obtained in the same manner except that 0.97 g of 5-pyrazolecarboxylic acid chloride was used. mp 55-57 ° C ¹ H-NMR (CDCl ₃ ), δ ppm: 0.89 (3H, t, J = 6Hz), 1.02-
1.85 (16H, m), 2.27 (3H, s), 3.95 (2H, t, J = 6Hz), 4.1
2 (3H, s), 4.23 (1H, t, J = 8Hz), 4.75 (1H, dd, J = 10 and
8Hz), 5.36 (1H, dd, J = 10 and 8Hz), 6.90 (2H, d, J = 8
Hz), 7.21 (2H, d, J = 8Hz)

Example 7 Synthesis of 2- (5-chloro-1,3-dimethyl-4-pyrazolyl) -4- (4-n-decyloxyphenyl) -2-oxazoline (Compound No. 19) In Example 4 5-chloro-1,3-dimethyl-instead of 3-chloro-2-thiophenecarboxylic acid chloride
The reaction was carried out using 0.92 g of 4-pyrazolecarboxylic acid chloride, the resulting 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. Certain object 0.8
8 g was obtained. mp 51-53 ° C ¹ H-NMR (CDCl ₃ ), δ ppm: 0.88 (3H, t, J = 6Hz), 1.10〜
1.86 (16H, m), 2.45 (3H, m
s), 3.82 (3H, s), 3.94 (2H,
t, J = 6 Hz), 4.12 (1H, t, J
= 8 Hz), 4.66 (1H, dd, J = 9 an
d 8 Hz), 5.30 (1H, dd, J = 9)
and 8 Hz), 6.87 (2H, d, J = 8)
Hz), 7.21 (2H, d, J = 8Hz)

Example 8 2- (1-Methyl-5-pyrazolyl) -4- (4-n-)
Synthesis of decyloxyphenyl) -2-oxazoline (Compound No. 20), except that 0.69 g of 1-methyl-5-pyrazolecarboxylic acid chloride was used in place of 3-chloro-2-thiophenecarboxylic acid chloride in Example 4. In the same manner, 1.08 g of the desired product which was a pale yellow oily substance was obtained. n _D ^22.5 1.5324 ¹ H-NMR (CDCl ₃ ), δ ppm: 0.89 (3H, t, J = 6Hz), 1.09〜
1.89 (16H, m), 3.95 (3H, t, J = 6Hz), 4.17 (1H, t, J = 8H
z), 4.24 (3H, s), 4.70 (1H, dd, J = 9 and 8Hz), 5.37 (1
H, dd, J = 9 and 8Hz), 6.76 (1H, d, J = 3Hz), 6.89 (2H,
d, J = 8Hz), 7.20 (2H, d, J = 8Hz), 7.51 (1H, d, J = 3Hz)

Example 9 Synthesis of 2- (2-furyl) -4- (4-n-decyloxyphenyl) -2-oxazoline (Compound No. 21) of 3-chloro-2-thiophenecarboxylic acid in Example 4 Instead, 0.67 g of 2-furancarboxylic acid chloride
In the same manner as in Example 1, except that the target compound 1.
35 g are obtained. mp 63-65 ° C ¹ H-NMR (CDCl ₃ ), δ ppm: 0.90 (3H, t, J = 6Hz), 1.03-
1.87 (16H, m), 3.95 (2H, t, J = 6Hz), 4.24 (1H, t, J = 8H
z), 4.75 (1H, dd, J = 9 and 8Hz), 5.34 (1H, dd, J = 9 an
d 8Hz), 6.47 ~ 6.57 (1H, m), 6.88 (2H, d, J = 8Hz), 7.0
1 ~ 7.10 (1H, m), 7.22 (2H, d, J = 8Hz), 7.57 (1H, s)

Example 10 Synthesis of 2- (3-pyridyl) -4- (4-n-decyloxyphenyl) -2-oxazoline (Compound No. 22) 2-amino-2- (4-n in 10 ml of tetrahydrofuran.
(Decyloxyphenyl) ethanol (1.00 g) and triethylamine (0.38 g) were dissolved, and 3-pyridinecarboxylic acid chloride (0.61 g) dissolved in tetrahydrofuran (5 ml) was added dropwise thereto over 20 minutes while stirring with ice cooling. After the dropwise addition, 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 10 ml of toluene, 1.6 g of thionyl chloride was added, and the mixture was heated under reflux for 2 hours with stirring. Thereafter, in the same manner as in Example 1, 0.63 g of the desired product as white crystals was obtained. mp 60-61 ° C ¹ H-NMR (CDCl ₃ ), δ ppm: 0.88 (3H, t, J = 6Hz), 1.08-
1.88 (16H, m), 3.93 (2H, t, J = 7Hz), 4.29 (1H, t, J = 9H
z), 4.80 (1H, dd, J = 10 and 9Hz), 5.35 (1H, dd, J = 10
and 9Hz), 6.88 (2H, d, J = 8Hz), 7.20 (2H, d, J = 8Hz),
7.31 ~ 7.43 (1H, m), 8.26 ~ 8.35 (1H, m), 8.67 ~ 8.79
(1H, m), 9.23 (1H, s)

Example 11 Synthesis of 2- (4-chloro-1,3-dimethyl-5-pyrazolyl) -4- (4-methylphenyl) -2-oxazoline (Compound No. 31) 2-amino-in 20 ml of tetrahydrofuran 2- (4-Methylphenyl) ethanol (1.51 g) and triethylamine (1.11 g) were dissolved in tetrahydrofuran (10).
1.93 g of 4-chloro-1,3-dimethyl-5-pyrazolecarboxylic acid chloride dissolved in ml was added dropwise over 20 minutes while stirring with ice cooling. After the dropwise addition, 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 added with chloroform 20
Dissolve it in ml, add 4.8 g of thionyl chloride, and add 2 with stirring.
Heated to reflux for hours. Thereafter, in the same manner as in Example 1, 2.18 g of the desired product which was a colorless oily substance was obtained. n _D ^20.1 1.5780 ¹ H-NMR (CDCl ₃ ), δ ppm: 2.26 (3H, s), 2.34 (3H, s),
4.12 (3H, S), 4.23 (1H, t, J = 8Hz), 4.77 (1H, dd, J = 10
and 8Hz), 5.48 (1H, dd, J = 10 and 8Hz), 7.18 (4H,
s)

Example 12 (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 13 (Mite Ovulation Test) (1) Efficacy Test Against Egg Mite Eggs Five adult female adult mites were parasitized on kidney leaf pieces (diameter 20 mm) and allowed to lay eggs for 24 hours, and then female adults were removed.
On the other hand, the compound shown in Table 4 was used as a wettable powder according to Example 12, and was diluted with water containing a surfactant (0.01%) to a chemical solution having an active ingredient concentration of 300 ppm. Soaked for 2 seconds. Table 4 shows the results of examining the number of hatched larvae after 7 days of standing in a constant temperature room at 25 ° C and determining the ovicidal rate.

[0053]

[Table 4]

(2) Efficacy test against citrus red mite eggs 10 female adults of citrus red mite were parasitized on mulberry leaf pieces (diameter 20 mm), and the ovicidal rate was determined in the same manner as in the above-mentioned test for citrus red mite eggs. In Table 4, the ovicidal rate of 100% is A, 99-80% is B, 7
9 to 60% is shown as C, and 59% or less is shown as D. In addition, 2,4-diphenyloxazolidine described in JP-A-57-501962 is similarly prepared,
It was similarly tested as a comparative compound.

[0055]

[Table 5]

Example 14 (Bactericidal test) (1) Control efficacy test against rice blast (preventive effect) Ten rice (cultivar: Nihonbare) was grown in a plastic flower pot with a diameter of 6 cm to grow 1.5 leaves. The wettable powder prepared according to Example 12 was diluted to 500 ppm of the active ingredient concentration with water containing a surfactant (0.01%), and 20 ml per pot was sprayed on the seedlings in the early stage. After spraying, it was cultivated in a glass greenhouse for 2 days, and then the rice blast fungal conidia suspension was uniformly spray-inoculated on rice leaves. 5 days after inoculation 2
After growing in a humid chamber at 8 ° C, the degree of rice blast lesions appearing on the leaves was investigated. The results are shown in Table 6.

[0057]

[Table 6]

(2) Control efficacy test against wheat leaf rust (preventive effect) Ten wheat (cultivar: Kobushi wheat) per pot was grown in a plastic flower pot with a diameter of 6 cm, and seedlings of 1.5 leaf stage were grown. A wettable powder prepared according to Example 12 was treated with water containing a surfactant (0.01%) to give an active ingredient concentration of 500.
Diluted to ppm and sprayed 20 ml per pot. After spraying 2
The plants were cultivated in a glass greenhouse for one day, and then the leaves were spray-inoculated uniformly with wheat rust spore suspension (7 × 10 ⁴ spores / ml). After inoculation, the seedlings were grown in a glass greenhouse for 1 week, and the degree of wheat leaf rust lesions appearing on the first leaf was investigated. The results are shown in Table 7. In addition, the sterilization evaluation is shown in 6 stages of 5 to 0 in comparison with the degree of lesions in the untreated section, and those without lesions are 5,
The lesion area is 10% or less, 4, 20% is 3, 40% is 2, 60% is 1, and the diseased area is 0.

[0059]

[Table 7]

[0060]

The novel oxazoline derivative of the present invention is
Has excellent insecticidal, acaricidal and bactericidal effects

Front page continuation (72) Inventor Satoshi Fujii 5 1978, Ube City, Ube City, Yamaguchi Prefecture 5 1978, Ube Research Co., Ltd. In the laboratory (72) Inventor Shoji Shikida 5 1978, Kozugushi, Ube, Ube City, Yamaguchi Prefecture Ube Research Co., Ltd. Ube Laboratory

Claims (3)

[Claims] 1. The following formula (I): (In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms and 1 carbon atom.
To 20 alkoxy group or halogen atom, R ² represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom, n represents an integer of 0, 1 or 2, and A Represents a substituted or unsubstituted 5- or 6-membered heteroaromatic ring group having 1 or 2 heteroatoms). 2. The following formula (II): (In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms and 1 carbon atom.
To 20 alkoxy group or halogen atom, R ² represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom, n represents an integer of 0, 1 or 2, and A Represents a substituted or unsubstituted 5- or 6-membered heteroaromatic ring group having 1 or 2 heteroatoms, and Y represents a halogen atom), and treated with an alkali to cyclize the amidoethyl halide derivative. The method for producing an oxazoline derivative represented by the formula (I) according to claim 1, wherein 3. An insecticidal, acaricidal and fungicide containing the oxazoline derivative represented by the formula (I) according to claim 1 as an active ingredient.