JP3239508B2 - Oxazoline compounds, intermediates thereof and insecticides and acaricides containing the same as an active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel oxazoline compound, an intermediate thereof, and an insecticide and acaricide containing the compound as an active ingredient.

[0002]

2. Description of the Related Art It has been reported that certain oxazoline derivatives have insecticidal and acaricidal effects, for example, as disclosed in
-85268 and JP-A-3-232867.

[0003]

However, these compounds are not always sufficient as active ingredients for insecticides and acaricides.

[0004]

Means for Solving the Problems In view of the above situation, the present inventors have made intensive studies to find a compound having an excellent insecticidal and acaricidal effect, and as a result, the following general formula:
An oxazoline compound represented by Chemical formula 6 is an excellent insecticide,
The present inventors have found that they have acaricidal activity and completed the present invention.
That is, the present invention provides a compound represented by the general formula:

Embedded image [Wherein, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₁₆ alkyl group which may be substituted with a halogen atom, C ₂ -C
₁₆ alkoxyalkyl groups, C ₁ -C ₁₆ alkoxy groups optionally substituted with halogen atoms, C ₁ -C ₁₆ alkylthio groups optionally substituted with halogen atoms, C ₃ optionally substituted with halogen atoms -C ₁₆ cycloalkyl group,
A C ₄ -C ₁₆ alkylcycloalkyl group, a C ₅ -C ₁₆ cycloalkoxy group which may be substituted with a halogen atom,
A C ₅ -C ₁₆ alkylcycloalkoxy group or formula 7

Embedded image Wherein R ⁵ is the same or different and is a hydrogen atom, a halogen atom, a C ₁ -C ₈ alkyl group which may be substituted by a halogen atom, a C ₂ -C ₈ alkoxyalkyl group, a halogen atom in an optionally substituted alkoxy group C ₁ -C _8, which may be substituted by a halogen atom C ₁ -
An alkylthio group of C _8, X is a single bond, an oxygen atom,
Sulfur atom, methylene group or methyleneoxy group (-CH
_{2 O -, - OCH 2 -} ) represents, q represents an integer of 1 to 5, Y is methine group (-CH =) or nitrogen atom (-N
= ² ) wherein R ² is a hydrogen atom, a halogen atom, C ₁ -C
₃ alkyl groups, C ₁ -C ₃ alkoxy groups or C ₁
—C ₃ represents an alkylthio group, p represents an integer of 1 to 4, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents

Embedded image Wherein R ⁶ and R ⁷ are the same or different and each is a hydrogen atom, a halogen atom, a C ₁ -C ₃ alkyl group which may be substituted with a halogen atom or a C ₁ -C ₃ alkyl group which may be substituted with a halogen atom. an alkoxy group having ₁ -C _3. (Hereinafter referred to as the compound of the present invention), an intermediate thereof, and an insecticide and acaricide containing the same as an active ingredient.

In the compound of the present invention, a "halogen atom"
Is a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or a chlorine atom. In the compound of the present invention, a C ₁ -C ₁₆ alkyl group optionally substituted by a halogen atom represented by R ¹ , a C ₁ -C ₁₆ alkoxy group optionally substituted by a halogen atom and a halogen atom Examples of the alkyl moiety constituting the C ₁ -C ₁₆ alkylthio group include, for example, methyl, ethyl, propyl, 1-methylethyl, butyl,
-Methylpropyl, 1-methylpropyl, 1,1-dimethylethyl, pentyl, 3-methylbutyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, hexyl, peptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, etc. Can be given. Among the above alkyl moieties, particularly preferred alkyl moieties substituted with halogen atoms include, for example, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-
Trifluoroethyl, 2,2-dichloro-1,1-difluoroethyl, 1,1,2,2,2-pentafluoroethyl, 2-bromo-1,1,2,2-tetrafluoroethyl, 2-chloro −
1,1,2,2-tetrafluoroethyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 1,1,2, 3,3,3-hexafluoropropyl, 10-
Examples include fluorodecyl, 10-bromodecyl, 13-fluorotridecyl, 13-bromotridecyl, 16-fluorohexadecyl, 16-bromohexadecyl and the like. Examples of the C ₂ -C ₁₆ alkoxyalkyl group represented by R ¹ of the compound of the present invention include a 2-methoxyethyl group and a 2-methoxyethyl group.
Ethoxyethyl group, 2-propyloxyethyl group, 2-
Butyloxyethyl group, 2-pentyloxyethyl group,
2- (1-methylethoxy) ethyl group, 2-hexyloxyethyl group, 2-decyloxyethyl group, 2-tetradecylethyl group, 4-ethyloxybutyl group, 4-butyloxybutyl group, 4-decyloxy Examples thereof include a butyl group and a 4-dodecyloxybutyl group. Examples of the C ₃ -C ₁₆ cycloalkyl group which may be substituted with the halogen atom represented by R ¹ of the compound of the present invention include, for example,
Cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, 2-chlorocyclohexyl group, 3-fluorocyclopentyl group, 3
-Chlorocyclopentyl, 3-bromocyclopentyl, 4-chlorocycloheptyl and the like. The alkylcycloalkyl group C ₄ -C ₁₆ represented by R ¹ of the compound of the present invention, for example, 1-methylcyclopropyl group, 4-methylcyclohexyl group, 4-
(1,1-dimethylethyl) cyclohexyl group, 4- [1
-(1,1-dimethyl) butyl] cyclohexyl group, 4-
[1- (3,7-dimethyl) octyl] cyclohexyl group and the like. Examples of the C ₅ -C ₁₆ cycloalkoxy group which may be substituted by the halogen atom represented by R ¹ in the compound of the present invention include, for example, cyclopentyloxy group, cyclohexyloxy group, 2-chlorocyclohexyloxy group, cycloheptyloxy group Group, cyclodecyloxy group,
Examples thereof include a 3-fluoropentyloxy group, a 3-chloropentyloxy group, a 3-bromopentyloxy group, and a 4-chlorocycloheptyloxy group. Among them, C ₃ -C ₁₀ is preferred. R ^{1 of the} compound of the present invention
In the alkyl cycloalkoxy group C ₅ -C ₁₆ represented, for example, 4-methylcyclohexyl group, 4- (1,1 - dimethylethyl) cyclohexyl group, 4- [1- (1,1 Dimethyl) butyl] cyclohexyloxy group, 4- [1- (3,7-dimethyl) octyl]
And a cyclohexyloxy group. C _{1 of the} compound of the present invention which may be substituted by a halogen atom represented by R ⁵
Alkyl group -C _8, C ₁ constituting the alkylthio group optionally C ₁ -C ₈ optionally substituted with an alkoxy group and a halogen atom good C ₁ -C ₈ optionally substituted by a halogen atom
The alkyl moiety of the -C _8, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl, 1-methylbutyl, 1,1-dimethylethyl, pentyl, 3-methylbutyl, 1-methylbutyl,
1,1-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl and the like can be mentioned.
Among the above-mentioned alkyl moieties, particularly preferred C ₁ -C ₈ alkyl moieties substituted with halogen atoms include, for example, difluoromethyl, trifluoromethyl, 1,
1,2,2-tetrafluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-1,1,2-trifluoroethyl, 2
-Bromo-1,1,2-trifluoroethyl, 1,1,2,2,2-
Pentafluoroethyl, 1,1,2,3,3,3-hexafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,
2,2,3,3,3-heptapropyl, 6-fluorohexyl group, 8-fluorooctyl group and the like. Examples of the alkoxyalkyl group C ₂ -C ₈ represented by R ⁵ of the compound of the present invention, for example, methoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-propyloxyethyl group, 2-butyl Oxyethyl group, 2-pentyloxyethyl group, 2- (1-methylethoxy) ethyl group, 2-hexyloxyethyl group and the like can be mentioned. C constituting the C ₁ -C ₃ alkyl group, alkoxy group and alkylthio group represented by R ² of the compound of the present invention.
Alkyl moiety of ₁ -C _3, namely, methyl, ethyl, propyl, 1-methylethyl. Examples of the C ₁ -C ₃ alkyl group which may be substituted with a halogen atom represented by R ⁶ and R ⁷ of the compound of the present invention include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group,
Examples thereof include a difluoromethyl group, a trifluoromethyl group, and a 3-chloropropyl group. Of the compound of the present invention
Examples of the C ₁ -C ₃ alkoxy group which may be substituted with a halogen atom represented by R ⁶ and R ⁷ include a methoxy group, an ethoxy group, a propoxy group, a 1-methylethoxy group, a difluoromethoxy group, Fluoromethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2,2-pentafluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, 2-chloro-1,1 , 2-trifluoroethoxy group, 2,2,3,3,3-pentafluoropropyl group, 3-bromopropyl group and the like.

The above R 'is represented by the following formula:

Embedded image [Wherein, R ⁵ are the same or different and are each substituted with a hydrogen atom, a halogen atom, a C ₁ -C ₈ alkyl group, a C ₂ -C ₈ alkoxyalkyl group, or a halogen atom which may be substituted with a halogen atom. Represents a C ₁ -C ₈ alkoxy group or a C ₁ -C ₈ alkylthio group which may be substituted with a halogen atom, and X represents a single bond, an oxygen atom, a sulfur atom,
Methylene group or a methyleneoxy group (-CH ₂ O -, -
OCH ₂ -) represents, Y represents a methine group (-CH =) or nitrogen atom (-N =), R ² represents a hydrogen atom, a halogen atom, an alkyl group of _{C 1 -C 3, C 1 -C} 3 Represents an alkoxy group or a C ₁ -C ₃ alkylthio group, and q represents 1
Which represents an integer from 4 to 4]
0

Embedded image [Wherein, R ⁵ is the same or different and the p-position of the benzene ring with respect to the substituent X is a hydrogen atom, a halogen atom, a C ₁ -C ₈ alkyl group or a halogen atom which may be substituted with a halogen atom. Represents an optionally substituted C ₁ -C ₈ alkoxy group, X represents a single bond or an oxygen atom, Y represents a methine group (—CH ＝), and q represents 1.]. . R ³ is preferably a hydrogen atom. R ⁴ is the one in which the 6-position of the benzene ring is substituted with R ⁷ , that is, the 2-position of the benzene ring is substituted with R ⁶ ,
It is preferable that the substituent is substituted by R ⁷ ,
⁶ and R ⁷ are the same or different and are preferably a hydrogen atom or a halogen atom, more preferably a halogen atom, and most preferably a fluorine atom.

In the compounds of the present invention, R ¹ has the general formula
1

Embedded image Represents a group represented in, R ⁵ may be the same or different, a hydrogen atom, a halogen atom, an alkyl group optionally C ₁ -C ₈ optionally substituted by a halogen atom, a C ₁ -C be substituted with a halogen atom represents an ₈ alkoxy or alkylthio group of C ₁ -C ₈ of, X represents a single bond, an oxygen atom or a methylene group, Y represents a methine group (-CH =) or nitrogen atom (-N =), q Represents 1 or 2, R ² represents a hydrogen atom, a halogen atom, a C ₁ -C ₃ alkyl group or C 2
Represents ₁ -C ₃ alkoxy group, p represents an integer from 1 3, R ³ represents a hydrogen atom, R ⁴ is formula of 12

Embedded image Wherein R ⁶ and R ⁷ are the same or different and represent a halogen atom. ] Are preferred. Among the compounds of the present invention,

Embedded imageRepresents a group represented by^FiveAre the same or different and are replaced
With respect to the group X, the para position of the benzene ring is a hydrogen atom or a halogen.
Atom optionally substituted by a halogen atom₁-C ₈No
Alkyl group, C which may be substituted with a halogen atom₁-C₈
X represents a single bond, an oxygen atom or a
Represents a tylene group, q represents 1, and Y represents a methine group (-CH
=), R^TwoIs a hydrogen atom, a halogen atom, C₁-C
_ThreeAlkyl group or C₁-C_ThreeThe alkoxy group of
And p represents an integer of 1 to 3, and R^ThreeRepresents a hydrogen atom
Then R^FourIs the formula 14

Embedded image Wherein R ⁷ is substituted at the 6-position of the benzene ring, R ⁶ and R ⁷ are the same or different and represent a halogen atom, especially a fluorine atom. ] Are more preferable.

The compound of the present invention has the general formula

Embedded image [In the formula, R ¹ , R ² , R ³ and p represent the same meaning as described above. And a general formula R ⁴ —C (O) —L ¹ wherein R ⁴ has the same meaning as described above, and L ¹ represents a hydroxyl group or a halogen atom. And a carboxylic acid derivative represented by the following formula:

(I) In the above production method, the compound represented by the general formula R ⁴
If -C (O) L ¹ of the carboxylic acid derivative represented by -L ¹ represents a hydroxyl group, the reaction is carried out in the presence of a dehydrating agent. Examples of the dehydrating agent to be used include sulfuric acid, phosphorus pentoxide, polyphosphoric acid and the like. The reaction is generally performed in an inert organic solvent, and examples of such an inert solvent include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and nitrobenzene. The reaction temperature is preferably about 60 ° C. to near the boiling point of the solvent, and the reaction time is usually about 1 to about 50 hours. Although the molar ratio of the raw materials can be arbitrarily set, usually, 1 mole of the amino alcohol derivative represented by the general formula (1) is added to the general formula R ^2-
Carboxylic acid derivatives represented by C (O) -L ¹ 0.5-2
Mole ratio, and the dehydrating agent is a ratio of 1 to 100 mole. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound.
If necessary, it can be further purified by a usual operation such as chromatography, distillation, recrystallization and the like.

[0010] (ii), in the above production method, if L ¹ of the carboxylic acid derivative represented by the general formula R ⁴ -C (O) -L ¹ represents a halogen atom, step (a) the general formula of 15 Is reacted with the carboxylic acid derivative in the presence of a base.

Embedded image Wherein R ¹ , R ² , R ³ , R ⁴ and p have the same meaning as described above. And then subjecting the amide derivative to a ring closing reaction by reacting the amide derivative with a dehydrating agent to produce the compound of the present invention. In the step (a), the base used includes:
For example, sodium hydroxide, potassium hydroxide, inorganic bases such as sodium carbonate, triethylamine, pyridine,
Organic bases such as N, N-dimethylaniline and the like can be mentioned. The reaction is generally performed in an inert organic solvent,
Examples of such an inert solvent include alcohols such as methanol, ethanol, isopropyl alcohol, and n-butanol; ethers such as diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol dimethyl ether; benzene, toluene, xylene, chlorobenzene, and dichlorobenzene. Such as aromatic hydrocarbons, dichloromethane, chloroform, carbon tetrachloride,
Examples thereof include chlorinated hydrocarbons such as 1,2-dichloroethane, aliphatic hydrocarbons such as n-hexane, n-pentane, n-heptane, petroleum ether, water and the like, and mixtures thereof. The reaction temperature is preferably from about -10C to about 50C, and the reaction time is usually from about 1 hour to about 30 hours. Although the molar ratio of the reagents can be set arbitrarily, the carboxylic acid derivative represented by the general formula R ⁴ —C (O) -L ¹ is usually 0.5 to 1 mol per 1 mol of the amino alcohol derivative represented by the general formula 15 2.0 moles, base 1 to
5 mole ratio. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, chromatography,
Further purification can be performed by ordinary operations such as distillation and recrystallization. In the step (b), examples of the dehydrating agent used include sulfuric acid, phosphorus pentoxide, polyphosphoric acid and the like. The reaction is generally performed in an inert organic solvent, such as, for example,
Examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene, and the like, and mixtures thereof. The reaction temperature is preferably about 60 ° C. to near the boiling point of the solvent, and the reaction time is usually about 1
Hours to about 50 hours. Although the molar ratio of the reagent can be set arbitrarily, the dehydrating agent is usually in a ratio of 1 to 100 mol per 1 mol of the amide derivative represented by the general formula (16). After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound.
If necessary, it can be further purified by a usual operation such as chromatography, distillation, recrystallization and the like.

Further, in the step (c), the amide derivative represented by the general formula
Formula 17

Embedded image [In the formula, R ¹ , R ² , R ³ , R ⁴ and p have the same meaning as described above, and Q represents a halogen atom. The compound of the present invention can also be produced by obtaining a haloamide derivative represented by the following formula, and then subjecting the haloamide derivative to a base and subjecting it to a ring closure reaction in step (d). In the step (c), examples of the halogenating agent to be used include thionyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus tribromide and the like. The reaction is generally performed in an inert organic solvent, such as benzene, toluene, xylene, chlorobenzene,
Aromatic hydrocarbons such as dichlorobenzene, chlorinated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and 1,2-dichloroethane, n-hexane, n-pentane,
Examples thereof include aliphatic hydrocarbons such as n-heptane and petroleum ether, and the like, and mixtures thereof. The reaction temperature is preferably about −10 ° C. to near the boiling point of the solvent, and the reaction time is usually about 1 hour to about 10 hours. Although the molar ratio of the reagents can be set arbitrarily, the halogenating agent is usually 1 to 1 mol of the amide derivative represented by the general formula
10 moles. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, chromatography,
Further purification can be performed by ordinary operations such as distillation and recrystallization. In the step (d), the base used includes, for example, sodium hydroxide, potassium hydroxide,
Inorganic bases such as sodium carbonate and calcium hydroxide, triethylamine, pyridine, N, N-dimethylaniline,
Organic bases such as 4-N, N-dimethylaminopyridine and the like can be mentioned. The reaction is generally performed in an inert organic solvent, such as, for example,
Methanol, ethanol, isopropyl alcohol, n
Alcohols such as butanol, ethers such as diethyl ether, tetrahydrofuran, dioxane, and dielene glycol dimethyl ether, benzene, toluene,
Aromatic hydrocarbons such as xylene, chlorobenzene and dichlorobenzene, chlorinated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and 1,2-dichloroethane, n
-Hexane, n-pentane, n-heptane, aliphatic hydrocarbons such as petroleum ether, water and the like, and mixtures thereof. Reaction temperature is about 0 ° C to about 110 ° C
Is preferred, and the reaction time is usually about 0.5 hour to about 5 hours. Although the molar ratio of the reagents can be set arbitrarily, the base is usually in a ratio of 1 to 10 mol per 1 mol of the haloamide derivative represented by the general formula (17). After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as organic solvent extraction and concentration,
The desired compound can be obtained. If necessary, it can be further purified by a usual operation such as chromatography, distillation, recrystallization and the like.

Among the starting compounds in the above-mentioned production, the amino alcohol derivative represented by the general formula (I) can be appropriately prepared by a conventional method as shown in the following chemical formulas (I) and (II). It can be obtained from commercially available compounds.

Embedded image

Embedded image [Wherein R ¹ , R ² , R ³ and p
Represents the same meaning as described above, R ⁸ represents a lower alkyl group, M represents a hydrogen atom, a sodium atom or a potassium atom, and L ² represents a halogen atom. ]

Step 1 [Phenol compound (I)
Is usually carried out in an inert solvent in the presence of a base in a temperature range of about 0 ° C. to about 150 ° C. for about 0.5 to 50 hours. The molar ratio of the phenol compound (I) to the ether compound (III) is not particularly limited, but is preferably from 1: 1 to 1: 3.
Although the amount of the base used is not particularly limited, it is preferably 1 to 5 mol per 1 mol of the phenol compound (I). Examples of usable reaction solvents include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene; aliphatic hydrocarbons such as hexane, heptane, and petroleum ether; dichloromethane, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as
Ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile; nitro compounds such as nitrobenzene; N, N-dimethylformamide; N, N-dimethyl Examples include polar solvents such as acetamide, dimethyl sulfoxide, and sulfolane, water, and mixtures thereof. Examples of the base that can be used include alkali metals such as sodium and potassium, sodium hydride, hydrides of alkali metals such as potassium hydride, sodium hydroxide, hydroxides of alkali metals such as potassium hydroxide, sodium carbonate, and the like. Examples include alkali metal carbonates such as potassium carbonate, and alkali metal alkoxides such as sodium ethylate and sodium methylate. If necessary, an ammonium salt such as triethylbenzylammonium chloride or tetrabutylammonium bromide may be added to the reaction system as a catalyst. Further, an alkali metal salt of the phenol compound (I) may be used instead of the phenol compound (I). After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, it can be further purified by a usual operation such as chromatography, distillation, recrystallization and the like.

The step 2 (reaction for obtaining the aldehyde compound (IV) from the ether compound (III)) is usually carried out in an inert solvent in the presence of an acid in a temperature range of about -10 ° C to about 50 ° C for 0.5 This takes place over 10 hours. The amount of the acid used is not particularly limited, but is preferably 1 to 50 mol per 1 mol of the ether compound (III). Examples of the inert solvent used include carboxylic acids such as acetic acid and trifluoroacetic acid, alcohols such as methanol and ethanol, water, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to isolate the aldehyde compound (IV). However, since the aldehyde is relatively unstable, the next reaction step is immediately performed. Is preferably used.

Step 3 [Aldehyde compound (IV)
Is usually carried out in an inert solvent in the presence of ammonia in a temperature range of about -20 ° C to 50 ° C for about 0.5 to about 50 hours. The molar ratio of the aldehyde compound (IV) to the cyano compound (V) is not particularly limited, but is preferably 1: 1 to 1:10. Although the amount of ammonia used is not particularly limited, it is preferably 1 mol or more per 1 mol of the aldehyde compound (IV). Examples of the inert solvent used include alcohols such as methanol and ethanol, water, and mixtures thereof. When a cyano compound (V) in which M is a sodium or potassium atom is used for the reaction, the cyano compound (V) 1
It is preferred to carry out the reaction in the presence of an ammonium salt of a strong acid (e.g. ammonium chloride) in a proportion of 1 mol or more per mol. After completion of the reaction, a usual post-treatment such as extraction with an organic solvent and concentration is performed to obtain a target product. If necessary, it can be further purified by chromatography, distillation, recrystallization and the like.

Step 4 (the reaction for obtaining the amino acid compound (VII) from the amine compound (VI)) is usually carried out in an inert solvent such as water in the presence of an acid (a mineral acid such as hydrochloric acid or sulfuric acid). It is performed at a temperature range of 30 ° C. to 50 ° C. for about 1 to about 50 hours. The molar ratio of the acid is not particularly limited, but is preferably 1 mole of the amine compound (VI).
The ratio is from 0.01 to 100 mol. After the completion of the reaction, the target substance can be obtained by a method such as cooling and collecting the precipitated solid by filtration.

The above step 5 (reaction for obtaining amino alcohol derivative 15 from amino acid compound (VII)) is usually carried out in an inert solvent in the presence of a reducing agent (such as diisobutyl aluminum hydride, aluminum hydride or lithium aluminum hydride). The reaction is performed at a temperature of 0 ° C. to 150 ° C. for about 0.5 to about 30 hours. The use molar ratio of the reducing agent is not particularly limited,
The ratio is preferably 1 to 10 mol per 1 mol of the amino acid compound (VII). Examples of the inert solvent include ethers such as diethyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene; and mixtures thereof. Further, Step 5 can also be performed by reducing with hydrogen gas in the presence of a catalyst such as ruthenium oxide, rhenium oxide, copper chromite, and the like.

Further, the oxazoline derivative 6 has the general formula 20

Embedded image [Wherein, R ³ and R ⁴ represent the same meaning as described above, and W represents a hydroxyl group, a halogen atom, a tosyloxy group, or a methyloxy group. And the phenol compound (I). (i) Oxazoline compound In the formula (20), when W is a hydroxyl group, the reaction is usually carried out in an inert solvent in the presence of a dehydrating agent at a temperature in the range of -50 ° C to 110 ° C for about 0.5 hr.
From about 100 hours. The molar ratio of the oxazoline compound (20) to the phenol compound (I) is not particularly limited, but is preferably 2: 1 to 1:10. Although the molar ratio of the dehydrating agent is not particularly limited, it is preferably based on 191 mol of the oxazoline compound.
0.001 to 100 moles. Examples of the inert solvent include ethers such as diethyl ether, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, Examples thereof include halogenated hydrocarbons such as 2-dichloroethane, aliphatic hydrocarbons such as hexane, pentane, heptane and petroleum ether, water, and mixtures thereof. Examples of the dehydrating agent include dicyclohexylcarbodiimide, diethylazodicarboxylate, diisopropylazodicarboxylate, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, sulfuric acid, phosphorus pentoxide, and polyphosphoric acid. Can be After completion of the reaction, a usual post-treatment such as extraction with an organic solvent and concentration is performed to obtain a target product.
If necessary, it can be further purified by chromatography, distillation, recrystallization and the like. (ii) In the oxazoline compound In the case where W is a halogen atom, a tosyloxy group or a mesyloxy group in the chemical formula 20, the reaction is usually carried out in the presence of a base at a temperature in the range of about 0 ° C. to about 110 ° C. for about 0.5 to about 500 hours. Done.
Oxazoline compound and phenol compound (I)
The molar ratio to be used is not particularly limited, but is preferably 2:
1 to 1:10. The molar ratio of the base used is not particularly limited, but is preferably 0.5 to 100 mol per 201 mol of the oxazoline compound. Examples of the inert solvent include alcohols such as methanol, ethanol, isopropyl alcohol, and butanol; ethers such as diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol dimethyl ether; and aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene. Hydrogens, dichloromethane, chloroform, carbon tetrachloride, halogenated hydrocarbons such as 1,2-dichloroethane, hexane, pentane, heptane,
Examples thereof include aliphatic hydrocarbons such as petroleum ether, water, and mixtures thereof. Examples of the base used include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and calcium hydroxide;
Organic bases such as triethylamine, pyridine, N, N-dimethylaniline, 4-N, N-dimethylaminopyridine and the like can be mentioned. After the reaction, extraction with organic solvent,
An ordinary post-treatment such as concentration is performed to obtain the desired product. If necessary, it can be further purified by chromatography, distillation, recrystallization and the like.

The oxazoline compound 20 can be obtained from an appropriate commercially available compound according to the following scheme 21.

Embedded image [Wherein, R ⁹ represents a hydroxyl group or —OC (O) R ⁴ ,
R ³ , R ⁴ , L ¹ , L ² and W represent the same meaning as described above. ]

Step 11 [Carboxylic acid derivative R ⁴
Reaction for obtaining amide compound (XII) from —C (O) —L ¹ ]
Is usually carried out in an inert solvent in the presence of a base at a temperature of about -10 ° C to about 50 ° C for about 1 to about 30 hours. The molar ratio of 2-amino-1,3-propanediol to the carboxylic acid derivative R ⁴ —C (O) —L ¹ is not particularly limited, but is preferably 2: 1 to 1: 4. Although the molar ratio of the base used is not particularly limited, 2-amino-
Preferably, based on 1 mol of 1,3-propanediol,
0.5 to 5 moles. Examples of the inert solvent include methanol, ethanol, isopropyl alcohol, alcohols such as butanol, diethyl ether,
Ethers such as tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, benzene, toluene, xylene, chlorobenzene, aromatic hydrocarbons such as dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, halogenated hydrocarbons such as 1,2-dichloroethane, Examples include aliphatic hydrocarbons such as hexane, pentane, heptane and petroleum ether, water, and mixtures thereof. Examples of the base used include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, potassium hydride, etc., triethylamine, pyridine, N, N-dimethylaniline, 4-N, Organic bases such as N-dimethylaminopyridine and the like can be mentioned. After completion of the reaction, a usual post-treatment such as extraction with an organic solvent and concentration is performed to obtain a target product. If necessary, it can be further purified by chromatography, distillation, recrystallization and the like.

Step 12 [from the amide compound (XII) wherein R ⁹ is a hydroxyl group to the oxazoline compound 20 (X
= Hydroxyl group) is usually carried out in an inert solvent in the presence of a dehydrating agent at a temperature ranging from about 60 ° C. to the boiling point of the solvent for about 1 to about 50 hours. The molar ratio of the dehydrating agent is not particularly limited, but is preferably from 1 to 10 based on 1 mol of the amide compound (XII) wherein R ⁹ is a hydroxyl group.
0 mole ratio. Examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene, and mixtures thereof. Examples of the dehydrating agent include sulfuric acid, phosphorus pentoxide, and polyphosphoric acid. After the reaction, extraction with organic solvent,
An ordinary post-treatment such as concentration is performed to obtain the desired product. If necessary, it can be further purified by chromatography, distillation, recrystallization and the like.

Step 13 [R ⁹ is —OC (O) R
⁴ to the haloamide compound (VI
II) is usually carried out in an inert solvent or in the absence of a solvent, in the presence or absence of a halogenating agent, at about −10 ° C.
From about 1 to about 10 hours in the temperature range from to the boiling point of the solvent. Although the molar ratio of the halogenating agent is not particularly limited, it is preferably 1 to 100 mol with respect to 1 mol of the amide compound (XII) wherein R ⁹ is —OC (O) R ⁴ . Examples of the inert solvent include benzene, toluene, xylene, chlorobenzene, aromatic hydrocarbons such as dichlorobenzene, dichloromethane, chloroform,
Examples include halogenated hydrocarbons such as carbon tetrachloride and 1,2-dichloroethane, aliphatic hydrocarbons such as hexane, pentane, heptane, petroleum ether, and mixtures thereof. Examples of the halogenating agent include thionyl chloride, phosphorus oxychloride, phosphorus trichloride, and phosphorus bromide.
After completion of the reaction, a usual post-treatment such as extraction with an organic solvent and concentration is performed to obtain a target product. If necessary, it can be further purified by chromatography, distillation, recrystallization and the like.

Step 14 [R ⁹ is —OC (O) R
^The reaction for obtaining the oxazoline compound 19 (X = hydroxyl group) from the haloamide compound (VIII) which is ⁴ ) is usually carried out in an inert solvent in the presence of a base in a temperature range of about 0 ° C. to about 110 ° C. and a temperature of about 0.5 to about 110 ° C. It takes about 5 hours. The molar ratio of the base used is not particularly limited, but R ⁹ is —OC (O) R
⁴ is a haloamides compound (VIII) per 1 mol of preferably 1 to 100 mol. Examples of the inert solvent include methanol, ethanol, isopropyl alcohol, alcohols such as butanol, diethyl ether, tetrahydrofuran, dioxane, ethers such as diethylene glycol dimethyl ether, benzene,
Aromatic hydrocarbons such as toluene, xylene, chlorobenzene, and dichlorobenzene; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; and aliphatic hydrocarbons such as hexane, pentane, heptane, and petroleum ether Examples include hydrogens, water, and mixtures thereof. Examples of the base used include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium chloride, sodium carbonate, potassium carbonate, sodium hydride and the like. After completion of the reaction, a usual post-treatment such as extraction with an organic solvent and concentration is performed to obtain a target product. If necessary, it can be further purified by chromatography, distillation, recrystallization and the like.

Step 21 [Carboxylic acid derivative R ⁴
-C (O) L ¹ to obtain an amide ester compound (IX)] is usually carried out in an inert solvent in the presence of a base at about -10
The reaction is performed at a temperature in the range of about 50 ° C. to about 50 ° C. for about 1 to about 30 hours. The molar ratio of serine methyl ester to the carboxylic acid derivative R ⁴ —C (O) L ¹ is not particularly limited, but is preferably 2: 1 to 1: 4. The molar ratio of the base used is not particularly limited, but the carboxylic acid derivative R ⁴ -C
The ratio is preferably 0.5 to 5 mol ^per 1 mol of (O) -L ¹ . Examples of the inert solvent include alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ethers such as diethyl ether, tetrahydrofuran, dioxane and diethylene glycol dimethyl ether, benzene, toluene, xylene,
Aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2
-Halogenated hydrocarbons such as dichloroethane, aliphatic hydrocarbons such as hexane, pentane, heptane, petroleum ether, pyridine, water, and mixtures thereof. As the base used, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, potassium hydride, triethylamine, pyridine, N,
Organic bases such as N-dimethylaniline and 4-N, N-dimethylaminopyridine can be exemplified. After completion of the reaction, a usual post-treatment such as extraction with an organic solvent and concentration is performed to obtain a target product. If necessary, it can be further purified by chromatography, distillation, recrystallization and the like.

The step 22 [reaction for obtaining the oxazoline ester compound (XI) from the amide ester compound (IX)] is usually carried out in an inert solvent in the presence of a dehydrating agent at about -5.
The reaction is performed at a temperature ranging from 0 ° C. to 110 ° C. for about 1 to about 50 hours. The molar ratio of the dehydrating agent to be used is not particularly limited, but is based on 1 mol of the amide ester compound (IX).
Preferably, the ratio is 1 to 100 mol. Examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene, and mixtures thereof. Examples of dehydrating agents include:
Sulfuric acid, phosphorus pentoxide, polyphosphoric acid, diethyl azodicarboxylate, dicyclohexylcarbodiimide, diisopropyl azodicarboxylate, 1-ethyl-3-
(3-dimethylaminopropyl) -carbodiimide hydrochloride and the like. After completion of the reaction, a usual post-treatment such as extraction with an organic solvent and concentration is performed to obtain a target product. If necessary, it can be further purified by chromatography, distillation, recrystallization and the like.

The step 23 [reaction for obtaining the oxazoline compound 20 (X = hydroxyl group) from the oxazoline ester compound (XI)] is usually carried out in an inert solvent in the presence of a reducing agent at about -10 ° C to about 100 ° C. In the temperature range up to
It takes about 0.5 to about 30 hours. Although the molar ratio of the reducing agent is not particularly limited, it is preferably 1 to 100 mol per 1 mol of the oxazoline ester compound (XI). Examples of the inert solvent include ethers such as diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol dimethyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene; and mixtures thereof. Examples of reducing agents include diisobutylaluminum,
Aluminum hydride, lithium aluminum hydride and the like can be given. After the reaction, extraction with organic solvent,
An ordinary post-treatment such as concentration is performed to obtain the desired product. If necessary, it can be further purified by chromatography, distillation, recrystallization and the like.

The step 24 (reaction for obtaining the chloroamide ester compound (XI) from the amide ester compound (X)) is usually carried out in an inert solvent or in the absence of a solvent at about −10 ° C. in the presence of a chlorinating agent. The reaction is performed in a temperature range up to the boiling point of the solvent for about 1 to about 10 hours. The molar ratio of the chlorinating agent is not particularly limited, but is preferably 1 to 100 mol per 1 mol of the amide ester compound (X). Examples of the inert solvent include benzene, toluene, xylene, chlorobenzene, aromatic hydrocarbons such as dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, halogenated hydrocarbons such as 1,2-dichloroethane,
Examples include aliphatic hydrocarbons such as hexane, pentane, heptane, petroleum ether, and mixtures thereof. Examples of chlorinating agents include thionyl chloride, phosphorus oxychloride,
And phosphorus trichloride. After completion of the reaction, a usual post-treatment such as extraction with an organic solvent and concentration is performed to obtain a target product. If necessary, it can be further purified by chromatography, distillation, recrystallization and the like.

Step 25 (the reaction for obtaining the oxazoline ester compound (XI) from the chloroamide ester compound (X)) is usually carried out in an inert solvent in the presence of a silver salt in the presence of a silver salt.
From about 0.5 to about 100 in the temperature range from ℃ to the boiling point of the solvent.
It takes place over time. The molar ratio of the silver salt is not particularly limited, but is preferably 1 to 100 mol per 1 mol of the chloroamide ester compound (X). Examples of the inert solvent include benzene, toluene, xylene, chlorobenzene, aromatic hydrocarbons such as dichlorobenzene, hexane, pentane, heptane, aliphatic hydrocarbons such as petroleum ether, diethyl ether, tetrahydrofuran,
Ethers such as dioxane and diethylene glycol dimethyl ether; Examples of silver salts include silver trifluoromethanesulfonate, silver acetate, silver carbonate and the like. After completion of the reaction, a usual post-treatment such as extraction with an organic solvent and concentration is performed to obtain a target product. If necessary, by chromatography, distillation, recrystallization, etc.
It can be further purified.

Step 31 or Step 32 [from oxazoline compound 19 (X = hydroxyl) to oxazoline compound 19 (X = halogen) or oxazoline compound 19 (X = tosyloxy, mesyloxy)
Can be easily carried out according to well-known methods such as halogenation and sulfonation. After completion of the reaction, a usual post-treatment such as extraction with an organic solvent and concentration is performed to obtain a target product. If necessary, it can be further purified by chromatography, distillation, recrystallization and the like.

In the above-mentioned various reactions, the presence of a phase transfer catalyst, if necessary, allows the reactions to proceed smoothly. Examples of usable phase transfer catalysts include, for example, quaternary ammonium salts such as benzyltriethylammonium chloride and tetra-n-butylammonium bromide.

Next, the compounds of the present invention (compounds represented by general formula 6) are shown in Tables 1 to 18. However, these compounds are for illustration only, and the present invention is not limited to these. Among the compounds of the present invention, in the case of a compound having an asymmetric carbon atom, the compound of the present invention is an optically active isomer having biological activity ((+)-isomer,
(-)-Isomer) and mixtures thereof in all proportions.

Table 1 Compounds represented by the general formula:

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[Table 13]

[Table 14]

[Table 15]

[Table 16]

[Table 17]

[Table 18]

Pests and harmful effects of the compounds of the present invention
Examples of mites include the following. Hemiptera pestLaodelphax striatellus), Toby
Roanka (Nilaparvata lugens),So
gatella furcifera) Such as grasshoppers
by(Nephotettix cincticeps), Thai bluefin tuna
Leafhopper (Nephotettix virescens) And leafhopper
, Aphids, stink bugs, whiteflies, and mosquitoes
Lepidoptera, pests, lice, etc.Chilo suppressalis), Kobunomeiga
(Cnaphalocrocis medinalis), European Co
Bomber (Ostrinia nubilalis), Shibattoga (Pa
rapediasia teterrella), Watanomeiga (Notarcha 
derogata),Plodia interpunct
ella), Such as the potato beetle,Spodoptera 
litura), Armyworm (Pseudaletia separata), Yo
Touga (Mamestra brassicae), Tamanayaga (Agroti
s ipsilon), Turkish Prussia, Heliotis,
Noctuids such as Helicoverpa,Pieris
 rapae crucivora), White butterflies, adoxo
Fies spp.Grapholita molesta
), Codling moss (Cydia pomonella)
Oysters, peach sinkiga (Carposina niponensis)
Singing moths, such as Rio netia
Doga, such as genus Limantria and Euproctis
Kinaga, Conaga (Plutella xylostella)
Red beetle (Pectinophora gossypiella)
Bugs, american white hitori (Hyphantria cunea) Such
Hydriga, iga (Tinea translucens), Koiga
(Tineola bisselliellaDiptera pestsCulex pipiens pallens), Kogataa
Cayeca (Culex tritaeniorhynchus) Etc.
Kind,Aedes aegypti,Aedes albopictusA
Death genus,Anopheles sinensisAnopheles, such as
Chironomid, housefly (Musca domestica), Oy
Fly (Muscina stabulans) And house flies
Flies, flies, flies, and flies (De
lia platura), Onion fly (Delia antigua)
Such as flies, fruit flies, Drosophila,
Drosophilids, blackflies, tabbys, flies, and leafhoppers
Coleoptera, pests, etc. Western corn rootworm (Diabrotica virgifer
a), Southern Corn Root Worm (Diabrotica undeci
mpunctataCorn worms, etc., Douganeb
Eve (Anomala cuprea), Himekogane (Anomala 
rufocuprea) And Maize Weeville
(Sitophilus zeamais), Rice water weevil (Lissor
hoptrus oryzophilus), Alfalfa takozoum
Shi (Hypera pastica), Adzuki beetle (Calosobruchy
s chinensisWeevils such as
Mimi beetle (Tenebrio molitor), Kokunustomod
Ki (Tribolium castaneum)
Kind, beetles (Aulacophora femoralis), Kisuji
Flea beetle (Phyllotreta striolata), Colorado
Insect(Leptinotarsa decemlineata) And other beetles,
Siban beetlesEpilachna 
vigintioctopunctataEpilacunas such as
Bark beetles, Nagasin beetles, longhorn beetles,
Obaarigatahanekushi (Paederus fuscipesOrthoptera pteridophyta German cockroaches (Blattella germanica), Black logo
Cockroach (Periplaneta fuliginosa), American cockroach (P
eriplaneta americana),Perip
laneta brunnea), Tokyo cockroach (Blatta ori
entalisThrips pests Thrips palmiformis (Thrips palmi), Negiaza
Miuma (Thrips tabaci), Thrips (Thrips 
hawaiiensisHymenoptera pests Ants, honeybees, stag bees, Japanese kabura
Mallet(Athalia rosae ruficornis)
Orthoptera pests Laceae, grasshoppers, etc.Purex irritansLice pestsPediculus humanus capitis, Psyllium (Phthirus
 pubis) Etc. Termite pest Yamato termite (Reticulitermes speratus), Yesi
Roari (Coptotermes formosanus) And other mitesTetranychus uriticae), Nisenamihada
D (Tetranychus cinnabarinus), Kanzawa spider mite
(Tetranychus kanzawai), Citrus red mite (Panonych
us citri), Apple spider mite (Panonychus ulmi), Oh
Spider mites such as Rignonica spp.Aculop
s pelekassi),Calacarus cari
natus) And other ticks,Polyph
aqotarsonemus latus) Such as dust mites, Himeha
Mites, red spider mites,Boophilus microplusSuch
Ticks, acarids, Pyroglyphidae, ticks
The compounds of the present invention include mites, especially fruit trees, and so on.
It has an excellent effect on spider mites that damage greens and tea.

By the addition of other insecticides and / or miticides, the pest control of the compounds according to the invention enables a practical application to a greater variety of insect pests and more diverse use situations. Suitable additives include, for example, fenitrothion [O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphorothioate], fenthion [O, O-dimethyl O- (3-methyl-4- (methylthio) phenyl) Phosphorothioate], diazinon [O, O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate], chlorpyrifos [O, O-diethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate] ], Acephate [O, S-dimethylacetylphosphoramidothioate], methidathione [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazole-3-]
Ylmethyl O, O-dimethyl phosphorodithioate], disulfoton [O, O-diethyl S-2-ethylthioethyl phosphorothioate], DDVP [2,2
-Dichlorovinyl dimethyl phosphate], sulphophos [O-ethyl O-4- (methylthio) phenyl S
-Propyl phosphorodithioate], cyanophos [O-
4-cyanophenyl O, O-dimethyl phosphorothioate], dioxabenzophos [2-methoxy-4H-
1,3,2-benzodioxaphosphinin-2-sulfide], dimethoate [O, O-dimethyl-S- (N-
Methylcarbamoylmethyl) dithiophosphate], fentoate [ethyl 2-dimethoxyphosphinothioylthio (phenyl) acetate], malathion [diethyl (dimethoxyphosphinothioylthio) succinate], trichlorfon [dimethyl 2,2,2-trichloro- 1-hydroxyethylphosphonate], azinphosmethyl [S-3,4-dihydro-4-oxo-1,
2,3-benzotriazin-3-ylmethyl O, O-
Dimethyl phosphorodithioate], monocrotophos [dimethyl (E) -1-methyl-2- (methylcarbamoyl) vinyl phosphate], ethion [0,0,0 ′,
Organic phosphorus compounds such as 0'-tetraethyl S, S'-methylenebis (phosphorodithioate)], BPMC
(2-sec-butylphenylmethylcarbamate), benfracarb [ethyl N- [2,3-dihydro-2,
2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N-isopropyl-β-alaninate], propoxur [2-isopropoxyphenyl N-methylcarbamate], carbosulfan [2,3-dihydro-2, 2-dimethyl-7-benzo [b] furanyl N-dibutylaminothio-N-methylcarbamate], carbaryl [1-naphthyl-N-methylcarbamate], mesomil [S-methyl-N-[(methylcarbamoyl) oxy] Thioacetimidate),
Ethiophenecarb [2- (ethylthiomethyl) phenylmethylcarbamate], aldicarb [2-methyl-
2- (methylthio) propionaldehyde O-methylcarbamoyloxy], oxamyl [N, N-dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide], phenothiocarb [S-4-phenoxybutyl) -N, N Carbamate compounds such as dimethylthiocarbamate, etofenprox [2-
(4-ethoxyphenyl) -2-methylpropyl-3-
Phenoxybenzyl ether], fenvalerate [(RS) -α-cyano-3-phenoxybenzyl (R
S) -2- (4-chlorophenyl) -3-methylbutyrate], esfenvalerate [(S) -α-cyano-
3-phenoxybenzyl (S) -2- (4-chlorophenyl) -3-methylbutyrate], fenpropatrin [(RS) -α-cyano-3-phenoxybenzyl 2,
2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin [(RS) -α-cyano-3-
Phenoxybenzyl (1RS, 3RS)-(1RS, 3
RS) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl (1RS, 3RS)-(1
RS, 3RS) -3- (2,2-dichlorovinyl)-
2,2-methylcyclopropanecarboxylate], cyhalothrin [(RS) -α-cyano-3-phenoxybenzyl (Z)-(1RS, 3RS) -3- (2-chloro-3,3,3-trifluoro Olopropenyl) -2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S) -α-cyano-m-phenoxybenzyl (1R, 3R) -3 (2,2-dibromovinyl) -2,
2-dimethylcyclopropanecarboxylate], cycloprothrine [(RS) -α-cyano-3-phenoxybenzyl (RS) -2,2-dichloro-1- (4-ethoxyphenyl) cyclopropanecarboxylate], fluvari Nate (α-cyano-3-phenoxybenzyl N
-(2-chloro-α, α, α-trifluoro-p-tolyl) -D-valinate), bifensulin (2-methylbiphenyl-3-ylmethyl) (Z)-(1RS) -ci
s-3- (2-Chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate, acrinasulin ([1R- {1α (S
^* ), 3α (Z)｝]-2,2-dimethyl-3- [3-
Oxo-3- (2,2,2-trifluoro-1- (trifluoromethyl) ethoxy-1-propenyl] cyclopropanecarboxylic acid cyano (3-phenoxyphenyl)
Methyl ester, 2-methyl-2- (4-bromodifluoromethoxyphenyl) propyl (3-phenoxybenzyl) ether, tralomethrin [(1R, 3S) 3
[(1′RS) (1 ′, 2 ′, 2 ′, 2′-tetrabromoethyl)]-2,2-dimethylcyclopropanecarboxylic acid
(S) -α-cyano-3-phenoxybenzyl ester, silafluofen [4-ethoxyphenyl [3-
(4-fluoro-3-phenoxyphenyl) propyl]
Pyrethroid compounds such as dimethylsilane, buprofezin (2-tert-butylimino-3-isopropyl-5-
Phenyl-1,3,5-triasiadinan-4-one)
Thiadiazine derivatives such as imidacloprid [1- (6
-Chloro-3-pyridylmethyl) -N-nitroimidazolidin-2-indeneamine], cartap (S, S '-(2-dimethylaminotrimethylene) bis (thiocarbamate)], thiocyclam [N, N -Dimethyl-1,2,3-trithiane-
Nereistoxin derivatives such as 5-ylamine], bensultap [S, S'-2-dimethylaminotrimethylene di (benzenethiosulfonate)], N-cyano-
N-cyanoamidine derivatives such as N'-methyl-N '-(6-chloro-3-pyridylmethyl) acetamidine; endosulfan [6,7,8,9,10,10-hexachloro-1,5,5a, 6,9,9a-hexahydro-
6,9-methano-2,4,3-benzodioxathiepine oxide], γ-BHC (1,2,3,4,5,6-
Hexachlorocyclohexane], chlorinated hydrocarbon compounds such as 1,1-bis (chlorophenyl) -2,2,2-trichloroethanol, chlorofluazurone [1- (3,
5-dichloro-4- (3-chloro-5-trifluoromethylpyridin-2-yloxy) phenyl) -3-
(2,6-difluorobenzoyl) urea], teflubenzuron [1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl)
Urea], flufenoxuron [1- (4- (2-chloro-4-trifluoromethylphenoxy) -2-fluorophenyl] -3- (2,6-difluorobenzoyl)
Urea] and other benzoylphenylurea-based compounds, amitraz [N, N '[(methylimino) dimethylidin] di-2,4-xylysine], chlordimeform [N'-
Formamidine derivatives such as (4-chloro-2-methylphenyl) -N, N-dimethylmethinimidamide, diafenthiuron [N- (2,6-diisopropyl-4-phenoxyphenyl) -N′-tert Thiourea derivatives such as -butylcarbodiimide], bromopropylate [isopropyl 4,4'-dibromobenzylate], tetradiphone [4-chlorophenyl 2,4,5-trichlorophenylsulfone], quinomethionate [S, S-6-methyl] Quinoxaline-2,3-diyldithiocarbonate], propargate [2- (4-tert-butylphenoxy) cyclohexylprop-2-yl sulfite], fenbutatin oxide [bis [tris (2
-Methyl-2-phenylpropyl) tin] oxide], hexthiazox [(4RS, 5RS) -5-
(4-chlorophenyl) -N-chlorohexyl-4-methyl-2-oxo-1,3-thiazolidine-3-carboxamide], clofentezine [3,6-bis (2-chlorophenyl) -1,2,4 , 5-tetrazine, pyridathioben [2-tert-butyl-5- (4-tert-butylbenzylthio) -4-chloropyridazine-3 (2H)-
On], fenpyroximate [tert-butyl (E)-
4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl) methyleneaminooxymethyl] benzoate], tebufenpyrad [N-4-tert-butylbenzyl) -4-chloro-3-ethyl-1-methyl -5-pyrazolecarboxamide], polynactin complex [tetranactin, dinactin, trinactin], milbemectin, avermectin, ivermectin, azadirachtin [AZAD], pyrimidifen [5-chloro-
N- [2- {4- (2-ethoxyethyl) -2,3-dimethylphenoxy} ethyl] -6-ethylpyrimidine-
4-amine and the like.

When the compound of the present invention is used as an active ingredient of an insecticide or acaricide, it may be used as it is without adding any other components. However, usually, a solid carrier, a liquid carrier, a gaseous carrier, Mix with feed, etc., and add surfactants and other auxiliaries for formulation as required, and flowables such as oils, emulsions, wettable powders, suspensions in water and emulsions in water, granules, powders ,
Aerosol, self-burning type smoke agent, chemical reaction type smoke agent, heating smoke agent such as perforated ceramic plate smoke agent, ULV agent, poison bait and the like are used. These preparations usually contain the compound of the present invention as an active ingredient in an amount of 0.1% to 95% by weight. Examples of solid carriers used in the formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.),
Fine powder or granules such as talc, ceramics, other inorganic minerals (sericite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), and chemical fertilizers (ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea, salt ammonium, etc.) Liquid carriers include, for example, water, alcohols (eg, methanol, ethanol), ketones (eg, acetone, methyl ethyl ketone), and aromatic hydrocarbons (eg, benzene, toluene, xylene, ethylbenzene, methylnaphthalene). , Aliphatic hydrocarbons (hexane, cyclohexane, kerosene, gas oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.),
Acid amides (N, N-dimethylformamide, N, N-
Dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethylsulfoxide, vegetable oils such as soybean oil, cottonseed oil and the like. , LPG (liquefied petroleum gas),
Examples include dimethyl ether and carbon dioxide. Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. can give.
Examples of pharmaceutical auxiliaries such as fixatives and dispersants include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl alcohol) , Polyvinylpyrrolidone, polyacrylic acids, etc.), and as a stabilizer, for example, PAP
(Acidic isopropyl phosphate), BHT (2,6-di-te
rt-butyl-4-methylphenol), BHA (2-te
a mixture of rt-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof, and the like. Examples of the base material of the self-combustion type smoke agent include combustion exothermic agents such as nitrates, nitrites, guanidine salts, potassium chlorate, nitrocellulose, ethylcellulose, and wood flour; alkali metal salts; alkaline earth metal salts; Stimulants such as acid salts and chromates, oxygen supply agents such as potassium nitrate, flame retardants such as melamine and wheat starch,
Examples include fillers such as diatomaceous earth and binders such as synthetic paste. Examples of the base material of the chemical reaction type smoke agent include exothermic agents such as sulfides, polysulfides, hydrosulfides, hydrated salts and calcium oxide of alkali metals, and catalyst agents such as carbonaceous materials, iron carbide and activated clay. Organic foaming agents such as azodicarbonamide, benzenesulfonylhydrazine, dinitrosopentamethylenetetramine, polystyrene and polyurethane; and fillers such as natural fiber fragments and synthetic fiber fragments. Examples of the bait bait include bait components such as cereal flour, vegetable essential oil, sugar, and crystalline cellulose; antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid; preservatives such as dehydroacetic acid; and pepper powder. Examples include inadvertent flavors such as a mistaken eating preventive, a cheese flavor, and an onion flavor. Formulation of flowables (water suspension or emulsion)
Generally, 1 to 75% of the compound of the present invention is used in an amount of 0.5 to 15% of a dispersant, 0.1 to 10% of a suspending aid (for example, a compound for imparting protective colloid or thixotropy), and 0 to 10% of a suitable auxiliary. (For example, defoamers, rust inhibitors, stabilizers,
It can be obtained by finely dispersing in water containing a spreading agent, a penetration aid, an antifreezing agent, an antibacterial agent, and an antismoking agent. It is also possible to use an oil in which the compound hardly dissolves in place of water and use it as a suspension in oil. As the protective colloid, for example, gelatin, casein, gums, cellulose ether, polyvinyl alcohol and the like are used. Examples of the compound imparting thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, polyacryl and the like. The preparation thus obtained is used as it is or diluted with water or the like. Also, with or without mixing with other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners, animal feed, etc. Can be used simultaneously.

When the compound of the present invention is used as an agricultural insecticide or acaricide, the application rate is usually 1 g to 500 g, preferably 10 g to 1 g per 10 ares.
00 g. When the emulsion, wettable powder, flowable and the like are diluted with water and used, the application concentration is usually 0.1 ppm to 10 ppm.
It is 00 ppm, and granules, powders, etc. are applied as they are without dilution. In addition, when used as an insecticide for insect control and acaricide, emulsions, wettable powders, flowables, etc.
Usually diluted with water to 0.01ppm to 10,000ppm and applied, oils,
Aerosols, smokers, ULVs, poison baits and the like are applied as they are. These application rates and application concentrations differ depending on the type of preparation, application time, application place, application method, type of pest, degree of damage, etc. can do.

[0036]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Formulation Examples and Test Examples, but the present invention is not limited to these Examples. First, Production Examples of the compound of the present invention will be shown. Production Example 1 (Method for producing compound (1)) 1.46 g (6.54 mmol) of 2-amino-3- [4- (1,1-dimethylethyl) phenoxy] propanol, 0.86 g (8.50 mmol) of triethylamine and 20 ml of anhydrous tetrahydrofuran To this mixture was added dropwise a solution of 1.15 g (6.54 mmol) of 2,6-difluorobenzoyl chloride in 10 ml of anhydrous tetrahydrofuran at 5 to 10 ° C. over 5 minutes. After the addition, the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the mixture was concentrated under reduced pressure. 20 ml of benzene and 10 ml of thionyl chloride were added to the obtained residue, and the mixture was heated under reflux for 3 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure, and 20 ml of ethanol was added to the obtained residue.
ml was added dropwise at 60 ° C. for 5 minutes with stirring. After dropping,
Stirred at 60 ° C. for 3 hours. After completion of the reaction, the mixture was cooled to room temperature and concentrated under reduced pressure. Ethyl acetate 10 was added to the obtained residue.
After adding 0 ml, the mixture was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography to obtain the desired 2- (2,2)
6-difluorophenyl) -4- [4- (1,1-dimethylethyl) phenoxymethyl] -2-oxazoline 1.
72 g were obtained as a colorless oil (n _D ^19.1 1.5391). Production Example 2 (Production method of compounds (2), (49), (50) and (51)) 2-amino-3- [4- (1,1-dimethylethyl) phenoxy] propanol is replaced by 2-amino -3-
Using [2,3-dimethyl-4- (2-ethoxyethyl) phenoxy] propanol, 2- (2,6-difluorophenyl) -4- [ 2,3-dimethyl-4- (2-
(Ethoxyethyl) phenoxymethyl] -2-oxazoline (compound (2)) was obtained, and 2-amino-3- (4
-Benzyl-2,3-dimethylphenoxy) propanol to give 2- (2,6-difluorophenyl) -4-
[4-benzyl-2,3-dimethylphenoxymethyl]
2-oxazoline (compound (49)) was obtained, and 2- (2,6-difluorophenyl) -4 was obtained using 2-amino-3- [4- (2-ethoxyethyl) -2-methylphenoxy] propanol. -[4- (2-ethoxyethyl) -2
-Methylphenoxymethyl] -2-oxazoline (compound (50)) to give 2-amino-3- (4-benzyl-2).
-Methylphenoxy) propanol to give 2- (2,2
6-difluorophenyl) -4-{(4-benzyl-2
(Methylphenoxy) methyl} -2-oxazoline (compound (51)) is obtained. Production Example 3 (Production Method of Compounds (52) and (53)) Instead of 2,6-difluorobenzoyl chloride, 2-
Using chloro-6-fluorobenzoyl chloride, 2- (2
-Chloro-6-fluorophenyl) -4-{[4-
(1,1-dimethylethyl) phenoxy] methyl} -2
-Oxazoline (compound (52)) was obtained, and 2- (2-chlorophenyl) -4-{[4- (1,1-dimethylethyl) phenoxy] methyl} -2- was similarly obtained using 2-chlorobenzoyl chloride. Oxazoline (compound (53)) is obtained. Production Example 4 (Production method of compound (36)) 1.14 g (4.40 mmol) of 2-amino-3- (4-phenoxyphenoxy) propanol, 0.58 g of triethylamine
(5.72 mmol) and 20 ml of anhydrous tetrahydrofuran, a solution of 0.78 g (4.40 mmol) of 2,6-difluorobenzoyl chloride in 10 ml of anhydrous tetrahydrofuran was added dropwise at 5 to 10 ° C. with stirring over 5 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. The formed precipitate was removed using a glass filter, and the filtrate was concentrated under reduced pressure. 20 ml of toluene and 10 ml of thionyl chloride were added to the obtained residue,
The mixture was refluxed for 5 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure, and methanol (20 ml) was added to the obtained residue.
1 ml of an aqueous N sodium hydroxide solution was added dropwise at 60 ° C. for 5 minutes with stirring. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 5 hours.
After completion of the reaction, the mixture was cooled to room temperature and concentrated under reduced pressure. After 100 ml of ethyl acetate was added to the obtained residue, the mixture was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting oil was subjected to silica gel column chromatography to obtain the desired 2- (2,6-difluorophenyl)-
1.28 g of 4-[(4-phenoxyphenoxy) methyl] -2-oxazoline were obtained as a colorless oil (n _D ^19.1 1.5814). Production Example 5 (Production method of compound (13)) 2- (2,6-difluorophenyl) -4-hydroxymethyl-2-oxazoline 200 mg (0.938 mol), 468 μl (1.87 mmol) of tri-n-butylphosphine and To a mixture of 2 ml of anhydrous tetrahydrofuran, 296 µl of diethyl azodicarboxylate (1.
(88 mmol) was added dropwise over 5 minutes. Thereafter, the reaction mixture was returned to room temperature over 6 hours and further stirred at room temperature. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain 2- (2,6
-Difluorophenyl) -4-{[2,6-dimethyl-
4- (4-chlorophenyl) phenoxy] methyl} -2
-Oxazoline was obtained as a colorless oil (n _D ^23.5 1.5552). Production Example 6 (Production method of compound (17)) 2- (2,6-difluorophenyl) -4-methanesulfonyloxymethyl-2-oxazoline 200 mg (0.68
7 mmol), 4- (4-chlorophenyl) phenol 232
A mixture of mg (1.00 mmol), 24 mg (1.0 mmol) of sodium hydroxide and 3 ml of N, N-dimethylformamide was stirred at room temperature for 24 hours. After completion of the reaction, the reaction solution was poured into 50 ml of a 10% aqueous ammonium chloride solution and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue obtained was subjected to silica gel column chromatography to give 2- (2,6-difluorophenyl) -4-
{[4- (4-chlorophenyl) phenoxy] methyl}
50 mg of -2-oxazoline as a white solid (mp 99.5 ° C)
As obtained. Production Example 7 (Compounds (54), (55), (56), (57) and (58)
Production method of 4- (4-Chloro-2,6-dimethylphenyl) phenol and 4- (4-methoxyphenoxy) phenol in place of 4- (4-chloro-2,6-dimethylphenyl) phenol, using the same method and the same molar ratio as in Production Example 5, (2,6-difluorophenyl) -4-
{[4- (4-Methoxyphenoxy) phenoxy] methyl} -2-oxazoline (compound (54)) was obtained. Similarly, 4- (4-ethylphenoxy) phenol, 4
Using-(4-methoxyphenyl) phenol, 4-benzylphenol or 2-methoxy-4- (4-chlorophenyl) phenol, 2- (2,6-difluorophenyl) -4-{[4- (4 -Ethylphenoxy) phenoxy] methyl} -2-oxazoline (compound (55)), 2- (2,6-difluorophenyl) -4-
{[4- (4-methoxyphenyl) phenoxy] methyl} -2-oxazoline (compound (56)), 2- (2
6-difluorophenyl) -4-[(4-benzylphenoxy) methyl] -2-oxazoline (compound (57))
Or 2- (2,6-difluorophenyl) -4-
{[2-Methoxy-4- (4-chlorophenyl) phenoxy] methyl} -2-oxazoline (compound (58)) is obtained. Similarly, the following compound is obtained. (1) 2- (2,6-difluorophenyl) -4-
{[4- (1,1-dimethylethyl) phenoxy] methyl} -2-oxazoline n _D ^19.1 1.5391 (2) 2- (2,6-difluorophenyl) -4-
{[2,3-dimethyl-4- (2-ethoxyethyl) phenoxy] methyl} -2-oxazoline n _D ^20.9 1.5200 (3) 2- (2,6-difluorophenyl) -4-
{[2,6-dimethyl-4- (2-ethoxyethyl) phenoxy] methyl} -2-oxazoline n _D ^24.6 1.4804 (4) 2- (2,6-difluorophenyl) -4-
[(4-cyclohexylphenoxy) methyl] -2-oxazoline n _D ^24.0 1.5373 (5) 2- (2,6-difluorophenyl) -4-
[(4-cyclopentylphenoxy) methyl] -2-oxazoline n _D ^24.0 1.5399 (6) 2- (2,6-difluorophenyl) -4-
[(4-n-heptylphenoxy) methyl] -2-oxazoline n _D ^24.0 1.5215 (7) 2- (2,6-difluorophenyl) -4-
{[4- (1,1,2,2-tetrafluoroethylthio) phenoxy] methyl} -2-oxazoline n _D ^23.1 1.5310 (8) 2- (2,6-difluorophenyl) -4-
{[3,5-dimethyl-4-[(4-ethylphenoxy] methyl] phenoxy] methyl} -2-oxazoline (9) 2- (2,6-difluorophenyl) -4-
{[4-[(4-Trifluoromethoxyphenoxy] methyl] phenoxy] methyl} -2-oxazoline (10) 2- (2,6-difluorophenyl) -4-
{[4- (4-bromophenyl) phenoxy] methyl}
-2-oxazoline mp 121.7 ° C (11) 2- (2,6-difluorophenyl) -4-
{[2-Chloro-4- (4-chlorophenyl) phenoxy] methyl} -2-oxazoline n _D ^23.4 1.5780 (12) 2- (2,6-difluorophenyl) -4-
{[4- (3-chlorophenyl) phenoxy] methyl}
-2-oxazoline resinous (13) 2- (2,6-difluorophenyl) -4-
{[3,5-dimethyl-4- (4-chlorophenyl) phenoxy] methyl} -2-oxazoline n _D ^23.5 1.5552 (14) 2- (2,6-difluorophenyl) -4-
{[4- (4-ethylphenyl) phenoxy] methyl}
-2-oxazoline mp 92.0 ° C (15) 2- (2,6-difluorophenyl) -4-
{[3,5-dimethyl-4- (4-ethylphenyl) phenoxy] methyl} -2-oxazoline n _D ^23.6 1.5525 (16) 2- (2,6-difluorophenyl) -4-
{[4- (3-methylphenyl) phenoxy] methyl}
-2-oxazoline n _D ^23.6 1.5717 (17) 2- (2,6-difluorophenyl) -4-
{[4- (4-chlorophenyl) phenoxy] methyl}
-2-oxazoline mp 99.5 ° C (18) 2- (2,6-difluorophenyl) -4-
{[2-chloro-4- (4-methylphenyl) phenoxy] methyl} -2-oxazoline n _D ^23.6 1.5726 (19) 2- (2,6-difluorophenyl) -4-
{[4- (4-methylphenyl) phenoxy] methyl}
-2-oxazoline mp 88.1 ° C (20) 2- (2,6-difluorophenyl) -4-
{[4- (3,4-dichlorophenyl) phenoxy] methyl} -2-oxazoline resinous (21) 2- (2,6-difluorophenyl) -4-
[(4-phenylphenoxy) methyl] -2-oxazoline n _D ^21.4 1.5389 (22) 2- (2,6-difluorophenyl) -4-
[(2-Chloro-4-phenylphenoxy) methyl]-
2-oxazoline resinous (23) 2- (2,6-difluorophenyl) -4-
{[2-Chloro-4- (3,4-dichlorophenyl) phenoxy] methyl} -2-oxazoline mp 120.7 ° C (24) 2- (2,6-difluorophenyl) -4-
{[2-Chloro-3,5-dimethyl-4- (4-chlorophenyl) phenoxy] methyl} -2-oxazoline n _D ^22.4 1.5748 (25) 2- (2,6-difluorophenyl) -4-
{[4- (4-Chloro-2-methylphenyl) phenoxy] methyl} -2-oxazoline n _D ^23.1 1.5765 (26) 2- (2,6-difluorophenyl) -4-
{[4- (3,5-dichlorophenyl) phenoxy] methyl} -2-oxazoline n _D ^23.0 1.5965 (27) 2- (2,6-difluorophenyl) -4-
{[4- (4-trifluoromethylphenyl) phenoxy] methyl} -2-oxazoline mp 137.0 ° C (28) 2- (2,6-difluorophenyl) -4-
{[4- (4-trifluoromethoxyphenyl) phenoxy] methyl} -2-oxazoline mp 115.0 ° C (29) 2- (2,6-difluorophenyl) -4-
{[2-Chloro-4- (4-trifluoromethylphenyl) phenoxy] methyl} -2-oxazoline mp 114.7 ° C (30) 2- (2,6-difluorophenyl) -4-
{[2-Chloro-4- (4-trifluoromethoxyphenyl) phenoxy] methyl} -2-oxazoline mp 90.5 ° C (31) 2- (2,6-difluorophenyl) -4-
[(4-benzyloxyphenoxy) methyl] -2-oxazoline resinous (32) 2- (2,6-difluorophenyl) -4-
{[4- (4-methylbenzyloxy) phenoxy] methyl} -2-oxazoline mp 102.4 ° C (33) 2- (2,6-difluorophenyl) -4-
{[4- (4-Chlorobenzyloxy) phenoxy] methyl} -2-oxazoline mp 114.8 ° C (34) 2- (2,6-difluorophenyl) -4-
{[4- (2,4-Dichlorobenzyloxy) phenoxy] methyl} -2-oxazoline mp 118.8 ° C (35) 2- (2,6-difluorophenyl) -4-
｛[4- (4-methoxybenzyloxy) phenoxy]
Methyl} -2-oxazoline mp 99.5 ° C (36) 2- (2,6-difluorophenyl) -4-
[(4-phenoxyphenoxy) methyl] -2-oxazoline n _D ^19.1 1.5814 (37) 2- (2,6-difluorophenyl) -4-
{[4- (4-methylthiophenoxy) phenoxy] methyl} -2-oxazoline n _D ^26.6 1.5959 (38) 2- (2,6-difluorophenyl) -4-
{[4- (2-Chloro-4-trifluoromethylphenoxy) phenoxy] methyl} -2-oxazoline n _D ^22.8 1.5409 (39) 2- (2,6-difluorophenyl) -4-
{[2-Chloro-4- (2-chloro-4-trifluoromethylphenoxy) phenoxy] methyl} -2-oxazoline
Resin-like (40) 2- (2,6-difluorophenyl) -4-
{[4- (4-Chlorophenoxy) phenoxy] methyl} -2-oxazoline n _D ^23.1 1.5849 (41) 2- (2,6-difluorophenyl) -4-
{[4- (2-Chloro-4-methoxycarbonylphenoxy) phenoxy] methyl} -2-oxazoline mp 103.1 ° C (42) 2- (2,6-difluorophenyl) -4-
{[4- (3-Chloro-5-trifluoromethylpyrid-2-yloxy) phenoxy] methyl} -2-oxazoline
n _D ^23.7 1.5298 (43) 2- (2,6-difluorophenyl) -4-
{[4- (5-Trifluoromethylpyrid-2-yloxy) phenoxy] methyl} -2-oxazoline n _D ^23.6 1.5221 (44) 2- (2,6-difluorophenyl) -4-
{[3-chloro-4- (3-chloro-5-trifluoromethylpyrid-2-yloxy) phenoxy] methyl}
-2-oxazoline n _D ^24.6 1.5337 (45) 2- (2,6-difluorophenyl) -4-
{[3,5-dichloro-4- (3-chloro-5-trifluoromethylpyrid-2-yloxy) phenoxy] methyl} -2-oxazoline resinous (46) 2- (2,6-difluorophenyl) -4-phenoxymethyl-2-oxazoline
n _D ^22.4 1.5473 (47) 2- (2,6-difluorophenyl) -4-
[(4-methoxyphenoxy) methyl] -2-oxazoline n _D ^24.0 1.5399 (48) 2- (2,6-difluorophenyl) -4-
{[4- [4-Chloro-2-methylphenoxy) methyl] phenoxy] methyl} -2-oxazoline n _D ^24.0 1.5215 (49) 2- (2,6-difluorophenyl) -4-
[(4-benzyl-2,3-dimethylphenoxy) methyl] -2-oxazoline (50) 2- (2,6-difluorophenyl) -4-
{[4- (2-ethoxyethyl) -2-methylphenoxy] methyl} -2-oxazoline (51) 2- (2,6-difluorophenyl) -4-
[(4-benzyl-2-methyl-phenoxy) methyl]
-2-oxazoline (52) 2- (2-chloro-6-fluorophenyl) -4
-{[4- (1,1-dimethylethyl) phenoxy] methyl} -2-oxazoline (53) 2- (2-chlorophenyl) -4-{[4-
(1,1-dimethylethyl) phenoxy] methyl} -2
-Oxazoline (54) 2- (2,6-difluorophenyl) -4-
{[4- (4-methoxyphenoxy) phenoxy] methyl} -2-oxazoline (55) 2- (2,6-difluorophenyl) -4-
{[4- (4-Ethylphenoxy) phenoxy] methyl} -2-oxazoline (56) 2- (2,6-difluorophenyl) -4-
{[4- (4-methoxyphenyl) phenoxy] methyl} -2-oxazoline (57) 2- (2,6-difluorophenyl) -4-
[(4-benzylphenoxy) methyl] -2-oxazoline (58) 2- (2,6-difluorophenyl) -4-
{[2-methoxy-4- (4-chlorophenyl) phenoxy] methyl} -2-oxazoline

Next, a production example of a production intermediate will be described. Production Example 8 (Step 1) 5.33 g (0.133 mol) of sodium hydride (60%) and
A mixture of 200 ml of anhydrous N, N-dimethylformamide
To 4- (1,1-dimethylethyl) at 5 ° C to 10 ° C.
2) g (0.133 mol) of phenol in anhydrous N, N-di
A 50 ml solution of methylformamide is stirred for 10 minutes.
It was dropped. Thereafter, the reaction mixture is heated at 5 ° C to 10 ° C for 30 minutes.
Stirred for minutes. At the same temperature, add bromoacetoate to the mixture.
24.75 g (0.146 mol) of aldehyde dimethyl acetal
The water N, N-dimethylformamide solution was stirred for 30 minutes.
And dropped. The reaction mixture was stirred at room temperature for 20 hours
Was. After the completion of the reaction, the reaction mixture was poured into water, and ethyl acetate was added.
Extract and wash the organic layer 3 times with a saturated aqueous solution of ammonium chloride
The extract was washed, dried over magnesium sulfate, and concentrated under reduced pressure.
The residue was subjected to silica gel chromatography to give 2- [4
-(1,1-dimethylethyl) phenoxy] -1,1-
3methoxy g of dimethoxyethane was added to a pale yellow oily substance (n _D ^22.6
 1.4911). Production Example 9 (Step 1) Instead of 4- (1,1-dimethylethyl) phenol
Using 4-phenoxyphenol and the same method as in Production Example 8
Depending on the method and the molar ratio of similar raw materials,
Nonoxyphenoxy) -1,1-dimethoxyethane in pale yellow
Colored oil (n _D ^22.8 1.5488). Production Example 10 (Step 2) 2- [4- (1,1-dimethylethyl) phenoxy]-
5.00 g (0.021 mol) of 1,1-dimethoxyethane and vinegar
6 ml of concentrated hydrochloric acid (36N) was added to a mixture of 60 ml of the acid, and
Stirred at room temperature for 1 hour. Thereafter, the reaction mixture was cooled with cold water 300
The mixture was poured into the precipitate, and filtered quickly to collect a white precipitate. The sink
The residue was not dried too much, and the 2- [4- (1,1-di
Methylethyl) phenoxy] acetaldehyde
The resulting product was immediately used in the next reaction. Production Example 11 (Step 3) 2.92 g (54.6 mmol) of ammonium chloride, sodium cyanide
2.47g (50.4mmol) and 28% ammonia aqueous solution
18 ml (296 mmol) of the mixture at 10 ° C.
The obtained 2- [4- (1,1-dimethylethyl) phenoki
A) Methanol 8 in wet cake of acetaldehyde
The solution was added dropwise over 30 minutes with stirring, and at the same temperature for 3 more minutes.
Stirred for 0 minutes. Thereafter, the reaction mixture is treated with ammonia gas.
The mixture was stirred at room temperature for 2 days under a nitrogen atmosphere. After the reaction,
Pour the mixture into cold water, extract with ethyl acetate, and wash the organic layer with water.
Washed and concentrated under reduced pressure. The residue is purified by silica gel chromatography.
To the 2-amino-3- [4- (1,1-dimension)
3.89 g of propylethyl) phenoxy] propionitrile
Yellow resinous substance (60 MHz¹H-NMR (CDCl_Three, TMS) δ (ppm)
1.26 (9H, s), 4.05 (2H, d, J = 5Hz), 4.63 (1H, t, J = 5Hz),
6.72 (2H, d, J = 10Hz), 7.21 (2H, d, J = 10Hz)]
Was. Production Example 12 (Steps 2 and 3) 2- [4- (1,1-dimethylethyl) -1,1-dimethyl
2- [4- (1,1-dimethyl) obtained from toxicethane]
Instead of tylethyl) phenoxy] acetaldehyde
2- (4-phenoxyphenoxy) -1,1-dimethyl
2- (4-phenoxypheno obtained from toxicethane
Production Examples 10 and 11 using xylene) acetaldehyde
According to the same method and the molar ratio of the same raw materials, 2-
Amino-3- (4-phenoxyphenoxy) propioni
The tolyl was obtained as a pale yellow solid (mp 76.7 ° C). Production Example 13 (Step 4) The 2-amino-3- [4- (1,1) obtained in Production Example 11
-Dimethylethyl) phenoxy] propionitrile 3.89
g (17.8 mmol), 100 ml of 5N hydrochloric acid aqueous solution was added, and the mixture was stirred.
The mixture was heated under reflux with stirring for 10 hours. Cool the reaction to 0 ° C.
Filtration gave pale yellow crystals. After drying, 2-amino-3-
[4- (1,1-dimethylethyl) phenoxy] propyl
2.50 g of ononic acid were obtained. Production Example 14 (Step 5) 4.00 g (105 mmol) of lithium aluminum hydride
Preparation example in a mixture of 50 ml of anhydrous tetrahydrofuran
2-amino-3- [4- (1,1-dimethyl) obtained in Step 13.
Ethyl) phenoxy] propionic acid 2.50 g (10.5 mmol)
50 ml of anhydrous tetrahydrofuran solution is stirred and heated to reflux
The mixture was added dropwise over 30 minutes, and the mixture was further heated under reflux for 2 hours.
After completion of the reaction, the reaction solution was cooled from 5 ° C. to 10 ° C.
100 ml of water, 10 ml of water and 5N
An aqueous sodium solution was slowly added. Organic layer of sulfuric acid mug
Dried with cesium, filtered through celite, concentrated under reduced pressure,
2-amino-3- [4- (1,1-dimethylethyl) phenyl
Enoxy] 2.10 g of propanol was added to a pale yellow solid (mp 10
1.7 ° C). Production Example 15 (Steps 4 and 5) 2-amino-3- [4- (1,1-dimethylethyl) phenyl
Enoxy] 2-amino- obtained from propionitrile
3- [4- (1,1-dimethylethyl) phenoxy] p
Instead of ropionic acid, 2-amino-3- (4-pheno
2-A) obtained from (xyphenoxy) propionitrile
Mino-3- (4-phenoxyphenoxy) propionic acid
Using the same method as in Production Examples 13 and 14, and
Depending on the molar ratio of 2-amino-3- (4-phenoxy
Phenoxy) propanol in pale yellow solid (mp 61.9 ° C)
As obtained. Production Example 16 (Step 11) 2-amino-1,3-propanediol 29.11 g (320 mm
ol) and 22 ml of pyridine in dichloromethane.
1.3 l were added with stirring at room temperature. This is 2,6-difluo
Stir 56.2 g (350 mmol) of lobenzoyl chloride at the same temperature
The solution was added dropwise over 30 minutes and stirred at the same temperature for another hour.
Was. The reaction solution was filtered through a glass filter, and the precipitate was removed by filtration.
The filtrate was concentrated under reduced pressure. Silica gel chromatography of the residue
And subjected to N, O-di- (2,6-difluoro
Benzoyl) -2-amino-1,3-propanediol
 7.2 g of a colorless oil (n_D ^24.0 1.5314)
N, O, O'-tri (2,6-difluorobenzoy
1) 2-amino-1,3-propanediol 17.3 g
Colorless oil (n_D ^24.2 1.5169). Production Example 17 (Step 13) The N, O-di- (2,6-difluorobenzene) obtained in Production Example 16
(Nzoyl) -2-amino-1,3-propanediol 5.
A mixture of 00 g (17.1 mol) and 15 ml of thionyl chloride
Was heated at 80 ° C. with stirring for 1 hour. Cool reaction to room temperature
And concentrated under reduced pressure to give crude 2- [N- (2,6-difur
Orobenzoyl) amino] -3- (2,6-difluoro
5.52 g of benzoyloxy) -1-chloropropane
Was. Production Example 18 (Step 14) 2- [N- (2,6-difluorobenzene) obtained in Production Example 17
Zoyl) amino] -3- (2,6-difluorobenzoi
Loxy) -1-chloropropane 5.0 g (13.7 mmol) of 4
5% hydroxyl solution in 5 ml ethanol solution at 70 ° C. with stirring
Slowly add 20 ml of an aqueous sodium solution over 5 minutes.
Stirred at temperature for another 30 minutes. After the reaction is completed,
After cooling to room temperature, ethanol was distilled off under reduced pressure. Vinegar residue
Extract with ethyl acid, wash twice with water, dry magnesium sulfate
And dried under reduced pressure. Silica gel chromatography of the residue
Subjected to 2- (2,6-difluorophenyl)
L) -4-Hydroxymethyl-2-oxazoline 2.49 g
Was obtained as a white solid (mp 90.4 ° C.). Production Example 19 (Step 21) 39.0 g (251 mmol) of DL-serine methyl ester hydrochloride
And pyridine in a mixture of 800 ml under stirring at room temperature.
-37 ml (324 mol) of difluorobenzoyl chloride in 5 parts
The mixture was added dropwise over time, and the mixture was further stirred at room temperature for 2 hours. reaction
After completion, the reaction solution was concentrated under reduced pressure, and chloroform 5
00 ml was added. After washing with water, extract with chloroform
The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure.
The residue was subjected to silica gel chromatography to give N-
(2,6-difluorobenzoyl) serine methyl ester
25.88 g of a colorless oily substance (n_D ^22.9 1.5038)
Was. Production Example 20 (Step 24) N- (2,6-difluorobenzoy) obtained in Production Example 19
2) To 25.4 g (98.1 mmol) of serine methyl ester,
20 ml (274 mmol) of luchloride are added at room temperature, and
Raise the temperature to 80 ° C over time and stir at 80 ° C for an additional hour.
Stirred. After completion of the reaction, the reaction solution is cooled to room temperature, and
Concentrated. 500 ml of acetic ester was added to the residue,
Wash twice with an aqueous solution of sodium hydrogen oxy
Dry over sodium and concentrate under reduced pressure to give N- (2,6-di
Fluorobenzoyl) -2-amino-3-chloropropyl
Onic acid methyl ester as white crystals (mp 93.5 ℃)
Obtained. Production Example 21 (Step 25) N- (2,6-difluorobenzoy) obtained in Production Example 20
M) -2-amino-3-chloropropionic acid methyl ester
5.91 g (21.3 mmol) of ter, silver trifluoromethanes
14.2 g (55.3 mol) of rufonate and anhydrous tetrahydrofur
The mixture of 120 ml of the run was stirred at room temperature. Reaction solution is colorless
After heating to reflux, heat the reaction mixture for 1 hour while stirring.
did. After the completion of the reaction, the reaction solution was washed with saturated aqueous sodium hydrogen carbonate
300 ml of the solution were poured at room temperature. Filter through Celite,
The precipitate was removed and extracted twice with ethyl acetate.
Dried over cesium and concentrated under reduced pressure. Silica gel residue
To 2- (2,6-difluoro)
Rophenyl) -4-methoxycarbonyl-2-oxazo
4.54 g of phosphorous was added to a colorless oil_D ^23.2 1.5170)
Was. Production Example 22 (Step 23) 0.58 g (15.3 mmol) of lithium aluminum hydride and
While stirring a mixture of 50 ml of anhydrous tetrahydrofuran,
Heated to reflux for minutes. Thereafter, the mixture was cooled to 0 ° C.
Then, the 2- (2,6-difluorophene) obtained in Production Example 21 was prepared.
Nyl) -4-methoxycarbonyl-2-oxazoline 4.
54 g (18.8 mmol) of 13 ml of anhydrous tetrahydrofuran
Under stirring, the mixture was added dropwise at 0 ° C over 20 minutes. At the same temperature
After reacting for 10 minutes, add 0.58 ml of water at the same temperature for 5 minutes
And the mixture was further stirred at the same temperature for 5 minutes. Under stirring,
0.58 ml of 30% aqueous solution of potassium hydroxide at the same temperature
1.74 ml was added and stirred vigorously at room temperature overnight. Moisten the precipitate
After removal with a lath filter, the mixture was concentrated under reduced pressure. Residue
Was subjected to silica gel chromatography to give 2- (2,6
-Difluorophenyl) -4-hydroxymethyl-2-
Obtaining 3.0 g of oxazoline as white crystals (mp 90.4 ° C)
Was. Production Example 23 Instead of D, L-serine methyl ester hydrochloride, D-
From Production Example 19 using serine methyl ester hydrochloride
In the same manner as in Example 22, optically active 2- (2,6-diph
Fluorophenyl) -4-hydroxymethyl-2-oxa
Get zoline. Similarly, the following compound is obtained. (101) 2- (2,6-difluorophenyl) -4-hydr
Roxymethyl-2-oxazoline
 mp 90.4 ° C (102) 2- (2,6-difluorophenyl) -4-chloro
Romethyl-2-oxazoline
 n_D ^22.6 1.5280 (103) 2- (2,6-difluorophenyl) -4-toshi
Roxymethyl-2-oxazoline (104) 2- (2,6-difluorophenyl) -4-mesi
Roxymethyl-2-oxazoline (105) 2- (2-chloro-6-fluorophenyl) -4
-Hydroxymethyl-2-oxazoline (106) 2- (2-chlorophenyl) -4-chloromethyl
-2-oxazoline (107) 2- (2,6-dichlorophenyl) -4-chloro
Methyl-2-oxazoline (108) 2- (2-fluorophenyl) -4-hydroxy
Methyl-2-oxazoline

Next, formulation examples are shown. Parts represent parts by weight, and the compound of the present invention is represented by the above compound number. Formulation Example 1 Emulsion 10 parts of each of the present compounds (1) to (58) are dissolved in 35 parts of xylene and 35 parts of dimethylformamide, and 14 parts of polyoxyethylenestyrylphenyl ether and 6 parts of calcium dodecylbenzenesulfonate are added thereto. In addition, mix well with stirring to obtain each 10% emulsion. Formulation Example 2 Emulsion 5 parts of each of the compounds (1) to (58) of the present invention and 5 parts of fenpropatrin were combined with 35 parts of xylene and dimethylformamide 3
In 5 parts, 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate are added and mixed well with stirring to obtain each emulsion. Formulation Example 3 Emulsion 5 parts of each of the present compounds (1) to (58) and fluvalinate 5
Were dissolved in 35 parts of xylene and 35 parts of dimethylformamide, and 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate were added thereto and mixed well with stirring to obtain each emulsion. Formulation Example 4 Emulsion 5 parts of each of the compounds of the present invention (1) to (58) and 5 parts of esfenvalerate were dissolved in 35 parts of xylene and 35 parts of dimethylformamide, and 14 parts of polyoxyethylenestyrylphenyl ether and 14 parts of dodecylbenzene were added thereto. 6 parts of calcium sulfonate are added and mixed well with stirring to obtain each emulsion. Formulation Example 5 wettable powder 20 parts of each of the compounds of the present invention (1) to (58) are mixed with 4 parts of sodium lauryl sulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrous silicon oxide fine powder and 54 parts of diatomaceous earth. The mixture is stirred and mixed with a juice mixer to obtain each 20% wettable powder. Formulation Example 6 Water dispersant 10 parts of each of the compounds of the present invention (1) to (58) is added to 10 parts of bifenthrin, and 4 parts of sodium lauryl sulfate, 2 parts of calcium ligninsulfonate, and 20 parts of synthetic hydrous silicon oxide fine powder And 54 parts of diatomaceous earth were added to the mixture, followed by stirring and mixing with a juice mixer to obtain each 20% wettable powder. Formulation Example 7 Wettable powder 10 parts of each of the compounds of the present invention (1) to (58) was added to 10 parts of acrinasulin, which were added to 4 parts of sodium lauryl sulfate, 2 parts of calcium ligninsulfonate, and 20 parts of synthetic hydrous silicon oxide fine powder. And 54 parts of diatomaceous earth were added to the mixture, followed by stirring and mixing with a juice mixer to obtain each 20% wettable powder. Formulation Example 8 Granules Compounds of the Present Invention (1) to (7), (11), (13), (15), (16), (18), (2
1), (24) to (26), (36) to (38), (40), (42) to (44), and (46) in 5 parts each of sodium dodecylbenzenesulfonate
Parts, 30 parts of bentonite and 60 parts of clay are added and sufficiently mixed with stirring. Next, an appropriate amount of water is added to the mixture, and the mixture is further stirred, granulated by a granulator, and air-dried to obtain 5% granules of each. Formulation Example 9 Granules Compound of the present invention (10), (14), (17), (19), (23), (27) to (30),
To 5 parts of each of (32) to (35) and (41), 5 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay are added, and they are sufficiently stirred and mixed. Then, add an appropriate amount of water to these mixtures,
The mixture is further stirred, granulated by a granulator, and air-dried.
% Granules are obtained. Formulation Example 10 Dust One part of each of the compounds of the present invention (1) to (58) is dissolved in an appropriate amount of acetone, and 5 parts of synthetic hydrous silicon oxide fine powder, PAP
0.3 parts and 93.7 parts of clay are added, and the mixture is stirred and mixed with a juice mixer, and the acetone is removed by evaporation to obtain 1% powder of each. Formulation Example 11 Flowable agent Compound of the present invention (1) to (7), (11), (13), (15), (16), (18), (2
1), (24) to (26), (36) to (38), (40), (42) to (44), and 10 parts of each of (46) in 40 parts of an aqueous solution containing 2 parts of polyvinyl alcohol. , And stirred with a mixer to obtain a dispersant. To this, added 40 parts of an aqueous solution containing 0.05 parts of xanthan gum and 0.1 parts of aluminum magnesium silicate,
Further, 10 parts of propylene glycol is added and gently stirred and mixed to obtain each 10% flowable agent. Formulation Example 12 Flowable agent Compound of the present invention (1) to (7), (11), (13), (15), (16), (18), (2
1), (24) to (26), (36) to (38), (40), (42) to (44) and (46) were each replaced with 5 parts of polyvinyl alcohol and 2 parts of 2-methyl-2. It is added to 40 parts of an aqueous solution containing-(4-bromodifluoromethoxyphenyl) propyl (3-phenoxybenzyl) ether, and stirred with a mixer to obtain a dispersant.
To this, 40 parts of an aqueous solution containing 0.05 parts of xanthan gum and 0.1 parts of aluminum magnesium silicate are added, and 10 parts of propylene glycol are further added, followed by gentle stirring and mixing to obtain each 10% flowable agent. Formulation Example 13 Oil agent 0.1 part of each of the compounds of the present invention (1) to (58) is dissolved in 5 parts of xylene and 5 parts of trichloroethane, and this is dissolved in deodorized kerosene 8
Mix into 9.9 parts to obtain 0.1% oil for each. Formulation Example 14 Oily aerosol 0.1 part of each of the compounds of the present invention (1) to (58), tetramethrin
0.2 parts, d-phenothrin 0.1 parts, trichloroethane 1
After mixing and dissolving 0 parts and 59.6 parts of deodorized kerosene, filling in an aerosol container, attaching a valve part, and then pressurizing and filling 30 parts of propellant (liquefied petroleum gas) through the valve part to obtain each oily aerosol. . Formulation Example 15 aqueous aerosol 0.2 parts of each of the compounds of the present invention (1) to (58), d-allethrin
An aerosol container is charged with a mixture of 0.2 parts, 0.2 parts of d-phenothrin, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of an emulsifier {Atmos 300 (registered trademark of Atlas Chemical Co.)} and 50 parts of pure water. And attach the valve part, and through this valve part the propellant (liquefied petroleum gas)
40 parts are filled under pressure to obtain each aqueous aerosol. Formulation Example 16 Heat-smoking agent 100 mg of each of the compounds (1) to (58) of the present invention was dissolved in an appropriate amount of acetone, and impregnated on a porous ceramic plate having a size of 4.0 cm × 4.0 cm and a thickness of 1.2 cm. Obtain a smoke agent.

Next, Test Examples show that the compound of the present invention is useful as an active ingredient of insecticides and acaricides and is stable against sunlight. The compounds of the present invention are shown by the compound numbers described in Production Examples, and the compounds used as comparative controls are as shown in Table 19.

[Table 19] Test Example 1 (Insecticidal test against Culex pipiens) The test compound was made into an emulsion according to Formulation Example 1, diluted with water, and 0.7 ml of the solution was added to 100 ml of ion-exchanged water (active ingredient concentration: 3.5 ppm). Twenty last larvae of Culex pipiens were released therein, fed and fed for about 8 days until all untreated plots emerged, and the eclosion inhibition rate was examined. The effect criterion was (eclosion inhibition rate) a: 90% or more b: 80% or more and less than 90% c: less than 80%. As a result, compounds (1), (4), (5), (6), (7), (10),
(11), (12), (13), (14), (15), (16), (17), (18), (19), (20),
(22), (24), (25), (26), (27), (28), (29), (30), (36), (37),
(38), (40), (41), (42), (43) and (44) showed "a" at a concentration of 3.5 ppm. On the other hand, the compounds (A) and (B) showed "b" at the same concentration, and the untreated group showed "c". Test Example 2 (Insecticidal test on Hawthorn armyworm) A test compound was emulsified in accordance with Formulation Example 1, and 2 ml of a diluted solution (500 ppm) of water was prepared in a polyethylene cup having a diameter of 11 cm. 13 g of the feed was impregnated. Ten larvae of the fourth instar larvae of the armyworm were released into the larvae, and after 6 days, their mortality was investigated to determine the mortality. As a result, compounds (11), (13), (1
5), (24), (25), (26), (28), (29), (30), (38), (39), (43) and (44) are 100 ppm at a concentration of 500 ppm. Although the mortality was shown, the compounds (A) and (B) were 0% each at the same concentration,
The mortality was 20%, and the untreated plot showed 0% mortality. Test Example 3 (Egg killing test against Japanese moth) According to Formulation Example 1, the test compound was emulsified, and 100 to 150 Japanese moth eggs were laid in a diluted solution (50 ppm) with water. A total of four radish buds of two days and two laying radishes of unspawned eggs were immersed for 30 seconds, air-dried for one hour, placed in a 5.5 cm diameter polyethylene cup, and examined for hatching after 5 days. And the hatchability were determined. The criteria are as follows. a: hatching rate of 100% b: hatching rate of 90% or more and less than 99% c: hatching rate of less than 90% As a result, compounds (10), (11), (12), (13), (14), (17), (2
5), (26), (27), (28), (30), (42) and (44) show "a", and compounds (A), (B) and the untreated group show "c". Indicated. Test Example 4 (Test on Dermatophagoids spider mite) Seven female seeds of Dermatophagoides farinae were infested with 10 female spider mites per leaf on the potted beetle 7 days after sowing (primary leaf stage).
It was placed in a thermostat at 5 ° C. Six days later, the test compound was made into an emulsion in accordance with Formulation Example 1, and a drug solution diluted to 500 ppm of the active ingredient with water was sprayed on a turntable at a rate of 15 ml per pot, and 2 ml of the same solution was simultaneously irrigated with soil. Eight days later, the degree of spider mite damage to each plant was examined. The criteria for judging the effect were-: Little damage was observed. +: Some damage is observed. ++: Damage similar to the untreated area is observed. And As a result, compounds (1), (2), (4), (5), (6), (11),
(12), (13), (14), (15), (16), (17), (18), (19), (20), (22),
(23), (24), (25), (26), (27), (28), (29), (30), (31), (32),
(33), (34), (35), (36), (37), (38), (39), (40), (41), (42),
(43), (44), (45), (46) and (47) showed "-", and the compound (A) and the untreated group showed "++". Test Example 5 (Stability test against sunlight irradiation) A solution of 10 mg of a test compound dissolved in 3 ml of methylene chloride was spread on a glass petri dish having a diameter of 8 cm, air-dried, and then exposed to sunlight on a sunny day. After a total of 37 hours of sunlight irradiation, the test compound was collected with 5 ml of methylene chloride and HP
The residual ratio was determined by LC. The HPLC conditions are as follows. Carrier: mixed solvent of acetonitrile and water (7: 3 or 8: 2) Column: ODS Flow rate: 1.0 ml / min Detector: UV (254 nm) As a result, compounds (1), (13) and (36) 94.9 each
%, 95.3% and 87.9%, and the compound (A) was 14.6%
showed that.

[0040]

The compounds of the present invention exhibit excellent insecticidal and acaricidal activity.

────────────────────────────────────────────────── ─── Continued from the front page (72) Inventor Hiroaki Fujimoto 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Chemical Industries, Ltd. (56) References US Patent 4702864 (US, A) ATMANI, A. , Et al. , 'FROM OXAZOLINES TO PRECURSORS OF AM INOACIDS', SYNTH. CO MMUN. , 21 (22), pp. 2383-2390 (1991) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 263/00-263/50 A01N 43/00-43/92 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound represented by the general formula: [Wherein, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₁₆ alkyl group which may be substituted with a halogen atom, C ₂ -C
₁₆ alkoxyalkyl groups, C ₁ -C ₁₆ alkoxy groups optionally substituted with halogen atoms, C ₁ -C ₁₆ alkylthio groups optionally substituted with halogen atoms, C ₃ optionally substituted with halogen atoms -C ₁₆ cycloalkyl group,
A C ₄ -C ₁₆ alkylcycloalkyl group, a C ₅ -C ₁₆ cycloalkoxy group which may be substituted with a halogen atom,
C ₅ -C ₁₆ alkylcycloalkoxy group or formula 2 Wherein R ⁵ is the same or different and is a hydrogen atom, a halogen atom, a C ₁ -C ₈ alkyl group which may be substituted by a halogen atom, a C ₂ -C ₈ alkoxyalkyl group, a halogen atom in an optionally substituted alkoxy group C ₁ -C _8, which may be substituted by a halogen atom C ₁ -
An alkylthio group of C _8, X is a single bond, an oxygen atom,
Sulfur atom, methylene group or methyleneoxy group (-CH
_{2 O -, - OCH 2 -} ) represents, q represents an integer of 1 to 5, Y is methine group (-CH =) or nitrogen atom (-N
= ² ) wherein R ² is a hydrogen atom, a halogen atom, C ₁ -C
₃ alkyl groups, C ₁ -C ₃ alkoxy groups or C ₁
Represents an alkylthio group of —C ₃ , p represents an integer of 1 to 4, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents Formula 3. Wherein R ⁶ and R ⁷ are the same or different and each is a hydrogen atom, a halogen atom, a C ₁ -C ₃ alkyl group which may be substituted with a halogen atom or a C ₁ -C ₃ alkyl group which may be substituted with a halogen atom. an alkoxy group having ₁ -C _3. An oxazoline compound represented by the formula: 2. A compound represented by the general formula: [Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ is a compound represented by the formula: Represents a group represented in, R ⁶ is water atom, a halogen atom, an alkyl group or may be substituted with a halogen atom C ₁ -C ₃ good C ₁ -C ₃ optionally substituted by a halogen atom
It represents the alkoxy group, R ⁷ is a halogen atom, halogenoalkyl
A C ₁ -C ₃ alkyl group which may be substituted
Is a C ₁ -C ₃ alcohol which may be substituted with a halogen atom
Represents a xy group. W represents a hydroxyl group, a halogen atom, a tosyloxy group or a mesyloxy group. ] The oxazoline derivative represented by these. 3. An insecticidal or acaricide comprising the oxazoline compound according to claim 1 as an active ingredient.