JP3158905B2 - Oxazoline derivatives, their production method and pesticides for agricultural and horticultural use - 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 derivative which is an agricultural and horticultural pesticide useful as an insecticide, acaricide, fungicide and the like.

[0002]

DESCRIPTION OF THE PRIOR ART As oxazoline derivatives similar to the present invention, the following are known. (1) Pesticide Biochemistry and Physiology 30 , 190-
197 contains the following equation:

[0003]

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Wherein R represents a phenyl group, a cyclohexyl group or a benzyl group.
Is limited to this equation only. It is described that the compound represented by) is effective as an insecticide and acaricide. (2) JP-A-57-501962 discloses that

[0005]

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(Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxy group;
Represents an alkoxycarbonyl group. R ² represents an aryl group or the like. Note that R ¹ and R ² defined by this equation are limited to this equation only. Is described as being effective as a pharmaceutical intermediate. (3) JP-A-2-85268 discloses that

[0007]

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[Wherein, X ¹ and X ² represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a trifluoromethyl group, or a trifluoromethoxy group. Y ¹ and Y ² represent a hydrogen atom, an alkyl group, a halogen atom, or the like. n represents 0 or 1. Provided that when n is 0 and X ¹ and X ² are simultaneously hydrogen atoms, or n is 1 and X ¹ and X ² are simultaneously selected from a hydrogen atom or a halogen atom (excluding an iodine atom) When it is an arbitrary combination of groups, Y ¹ and Y ² exclude the case where it is an arbitrary combination of substituents selected from a hydrogen atom or a halogen atom. Note that X ¹ ,
X ² , Y ¹ , Y ² and n are limited to this equation only. ]
It is described that the compound represented by is effective as an insecticide and acaricide. (4) JP-A-2-304609 discloses the following formula:

[0009]

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(In the formula, X represents a lower alkyl group, a lower alkoxy group, a halogen atom or a CF ₃ group. Y represents a halogen atom. M and n each represent an integer of 0 to 2. X, Y, m and n defined in (1) are limited to this formula only.) Is described as being effective as an insecticide and acaricide. (5) JP-A-3-223867 discloses that

[0011]

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[Wherein R ¹ and R ² represent a halogen atom or the like. R ³ represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group. R ⁴ is an alkyl group having 7 or more carbon atoms, an alkoxy group having 7 or more carbon atoms, an alkylthio group, a lower alkoxy-lower alkyl group, a lower alkoxy-lower alkoxy group, an alkenyloxy group having 3 or more carbon atoms, a lower alkynyl An oxy group, a tri (lower alkyl) silyl group, a cycloalkyl group optionally substituted with a lower alkyl group, or

[0013]

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Wherein B represents a direct bond, an oxygen atom, a lower alkylene group, a lower alkyleneoxy group, a lower alkylenedioxy group or a di (lower alkyl) silyl group.
Q represents CH or N. n is an integer of 0 to 5;
Each substituent R ⁵ represents a halogen atom, an alkyl group, an alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, or a tri (lower alkyl) silyl group. A represents a direct bond or an alkylene group. Note that R defined by this equation
^{1 ~R 5, B, Q,} n and A are limited only to this formula. Is described as being effective as an insecticide and acaricide. (6) JP-A-4-89484 discloses the following formula:

[0015]

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(In the formula, X ¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a lower alkyl group or a lower alkoxy group.
X ^{2 to} X ⁴ represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a lower alkyl group or a lower alkoxy group.
X ⁵ represents a hydrogen atom, a fluorine atom, a methyl group or a methoxy group. However, three or more of X ^{1 to} X ⁵ do not simultaneously represent a hydrogen atom. Y ¹ represents a hydrogen atom, a fluorine atom or a chlorine atom. Y ² represents a fluorine atom or a chlorine atom. Note that X ^{1 to} X ⁵ defined by this equation,
Y ¹ and Y ² are limited to this equation only. It is described that the compound represented by) is effective as an insecticide and acaricide. (7) Japanese Patent Application Laid-Open No. 4-217673 discloses that

[0017]

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(Wherein R ¹ represents phenoxymethyl which may be substituted by halogen, alkyl, trifluoromethyl, alkoxy or thioalkoxy, etc.)
R ² represents phenyl which may be substituted with halogen. Note that R ¹ and R ² defined by this equation are limited to this equation only. It is described that the compound represented by) is effective as an insecticide and acaricide. (8) JP-A-5-1060 discloses the following formula (A)

[0019]

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[In the formula (A), X ¹ and X ² represent a hydrogen atom,
Represents an alkyl group, an alkoxy group, a halogen atom, a trifluoromethyl group, a trifluoromethoxy group or a group of the formula (B). Y ¹ and Y ² represent a halogen atom or the like.
Note that X ¹ , X ² , Y ¹ and Y ² defined by this equation are:
Limited to this equation only. Formula (B):

[0021]

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[In the formula (B), M ¹ and M ² represent a hydrogen atom,
Represents an alkyl group, an alkoxy group, a halogen atom, a trifluoromethyl group or a trifluoromethoxy group. A represents CH ₂ or a nitrogen atom. n represents 0 or 1.
Note that M ¹ , M ² , A and n defined in this equation are limited to this equation only. Is described as being effective as an insecticide and acaricide. (9) JP-A-5-271206 discloses the following formula (C)

[0023]

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[In the formula (C), R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 16 carbon atoms, and 2 to 16 carbon atoms.
Alkoxyalkyl groups, alkoxy groups having 1 to 16 carbon atoms, cycloalkyl groups having 3 to 16 carbon atoms, alkylcycloalkyl groups having 4 to 16 carbon atoms, 5-1 carbon atoms
It represents 6 cycloalkoxy groups, an alkoxycycloalkoxy group having 5 to 16 carbon atoms, a group of the formula (D) and the like. R
² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or an alkylthio group having 1 to 3 carbon atoms; p represents an integer of 1 to 4;
R ³ represents a hydrogen atom or the like. R ⁴ represents a group of the formula (E). Note that R ^{1 to} R ⁴ and p defined by this equation are limited to this equation only. Formula (D)

[0025]

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[In the formula (D), R ⁵ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, Represents an alkylthio group having 1 to 8 carbon atoms. X represents a single bond, an oxygen atom, a sulfur atom, a methylene group or a methyleneoxy group (—CH ₂ O—, —OCH ₂ —). q represents an integer of 1 to 5. Y represents a methine group (-CH =) or a nitrogen atom (-N =). Note that R ⁵ , X, Y and q defined by this equation are limited to this equation only. Formula (E)

[0027]

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[In the formula (E), R⁶And R⁷Is a hydrogen atom,
Halogen atom, alkyl group having 1 to 3 carbon atoms or carbon number
Represents 1 to 3 alkoxy groups. Note that this expression defines
R ⁶And R⁷Is limited to this equation only. ]
Compounds are effective as insecticides and acaricides
Has been described. (10) JP-A-6-48907 discloses the following formula (F)

[0029]

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[In the formula (F), R¹And R^TwoIs a halogen field
Represents a child, etc. R^ThreeAnd R^FourIs a hydrogen atom, a halogen atom
Trifluoromethyl group, trifluoromethoxy group,
An alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms
Lucoxy group, alkylthio group having 1 to 20 carbon atoms, lower
Alkoxy-lower alkyl group, lower alkoxy-lower alkyl
Alkoxy group, alkenyloxy group having 3 or more carbon atoms, low
Lower alkynyloxy group, tri (lower alkyl) silyl
Represents a group, a cycloalkyl group or a group of the formula (G). A is straight
It represents a tangent bond or a lower alkylene group. Note that in this equation
R defined¹~ R ^FourAnd A are limited to this formula only
You. Formula (G):

[0031]

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[In the formula (G), B represents a direct bond, an oxygen atom,
Represents a lower alkylene group, a lower alkyleneoxy group, a lower alkylenedioxy group or a di (lower alkyl) silyl group; Q represents CH or a nitrogen atom. n represents the integer of 0-5. R ⁵ represents a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group or a tri (lower alkyl) silyl group. Note that B, Q, R ⁵ and n defined in this equation are limited to this equation only. Is described as being effective as a tick control agent.

However, there is no disclosure of an oxazoline derivative in which the 4-position of the oxazoline ring is substituted with a phenoxyalkyl group having an alkylene chain of ethylene or more as in the present invention. Therefore, since the oxazoline derivative of the present invention is a novel compound, it can be used as an insecticide, acaricide,
It is not known that it has a pest control activity for agricultural and horticultural use useful as a fungicide and the like.

[0034]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel oxazoline derivative, a process for producing the same, and a pesticidal composition for agricultural and horticultural use which is useful as an insecticide, acaricide, fungicide and the like. To provide.

[0035]

Means for Solving the Problems The present inventors have studied to solve the above-mentioned problems, and as a result, it has been found that a novel oxazoline derivative is useful as a pesticide, acaricide, fungicide and the like for agricultural and horticultural use. The present inventors have found that they have a remarkable controlling activity as a biological control agent, and have completed the present invention. That is, the present invention is as follows. According to a first aspect, the following formula (1):

[0036]

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(Wherein R ¹ is a halogen atom, a hydrogen atom,
C1-C10 alkyl group, C1-C8 alkoxy group, C1-C4 haloalkyl group, C1-C1
A halogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a phenyl group having a haloalkoxy group having 1 to 4 carbon atoms, a halogen atom as an unsubstituted or substituted group; Atom, carbon number 1
A phenoxy group having 4 haloalkyl groups or a haloalkoxy group having 1 to 4 carbon atoms, a benzyl group having a halogen atom as an unsubstituted or substituted group, a benzyloxy group having a halogen atom as an unsubstituted or substituted group, A pyridyloxy group having a haloalkyl group having 1 to 4 carbon atoms or a halogen atom as a substituent or a substituent,
A pyridylmethyloxy group having a halogen atom as an unsubstituted or substituted group, an alkyl group having 1 to 4 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyanomethyloxy group, It represents four haloalkylsulfonyloxy groups, an alkylsulfonyloxy group having 1 to 4 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms. R ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or Represents a haloalkoxy group having 1 to 4 carbon atoms. R ¹ and R ² may form a saturated 6-membered ring or an unsaturated 6-membered ring together with an oxygen atom which may be substituted by one or two methyl groups. R ³ represents a hydrogen atom, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. R ⁵ is a hydrogen atom,
Represents a halogen atom or an alkyl group having 1 to 6 carbon atoms. X ¹ is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or 1
Represents up to 4 alkoxy groups. X ² is a halogen atom,
Represents a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms. X ³ represents a hydrogen atom or a halogen atom. n
Represents an integer of 2 to 5. )). The second invention provides the following formula (2):

[0038]

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Wherein R ¹ -R ⁴ , X ¹ -X ³ and n
Has the same meaning as in claim 1. Y represents a halogen atom. )). The third invention relates to a method for producing an oxazoline derivative represented by the above formula (1), wherein the amide ethyl halide derivative represented by the above formula (2) is treated with an alkali to cyclize the derivative. is there. The fourth invention relates to a pesticide for agricultural and horticultural use containing the oxazoline derivative represented by the above formula (1) as an active ingredient.

Hereinafter, the present invention will be described in detail. For the target compound and the starting compound, R ^{1 to} R ⁵ represented by the oxazoline derivative [compound (1)] represented by the above formula (1), the starting compound (2), etc.
X ^{1 to} X ³ , n and Y are as follows.

[R ¹ ] R ¹ represents a halogen atom, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
Alkoxy groups, haloalkyl groups having 1 to 4 carbon atoms,
A haloalkoxy group having 1 to 4 carbon atoms, a phenyl group, a phenoxy group, a benzyl group, a benzyloxy group, a pyridyloxy group, a pyridylmethyloxy group, an alkyl group substituted with an alkoxy group, a nitro group, a cyanomethyloxy group,
Haloalkylsulfonyloxy group having 1 to 4 carbon atoms, alkylsulfonyloxy group having 1 to 4 carbon atoms, 1 carbon atom
And up to 4 alkylthio groups.

Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom. Examples of the alkyl group include linear or branched ones; preferably those having 1 to 8 carbon atoms; and more preferably those having 1 to 6 carbon atoms.

The alkoxy group may be a straight-chain or branched one; preferably, it has 1 carbon atom.
~ 6; more preferably 4 ~ 6 carbon atoms
Individual. Examples of the haloalkyl group include linear or branched ones; preferably those having 1 to 4 carbon atoms and a halogen atom having a fluorine atom; more preferably a trifluoromethyl group. is there.

The haloalkoxy group has 1 to 1 carbon atoms.
There can be mentioned four straight or branched ones; preferably trifluoromethoxy, bromodifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, 2-chloro-1,1 , 2-trifluoroethoxy group and 1,1,2,3,3,3-hexafluoropropoxy group.

Examples of the phenyl group include an unsubstituted one and a phenyl group having a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkoxy group having 1 to 4 carbon atoms. The halogen atom for the substituent is preferably a chlorine atom; the haloalkyl group is preferably a trifluoromethyl group; and the haloalkoxy group is preferably a trifluoromethoxy group, a difluoromethoxy group, a 2-chloro- 1,1,
2-trifluoroethoxy group. And the position of these substituents is not particularly limited; in the case of a haloalkyl group and a haloalkoxy group, it is preferably the 4-position.

Examples of the phenoxy group include an unsubstituted group and a group having a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkoxy group having 1 to 4 carbon atoms. The halogen atom for the substituent is preferably a chlorine atom or a fluorine atom;
A haloalkyl group is preferably a trifluoromethyl group; a haloalkoxy group is preferably a trifluoromethoxy group. The position of these substituents is not particularly limited; however, in the case of a haloalkyl group and a haloalkoxy group, the position is preferably the 4-position.

Examples of the benzyl group include an unsubstituted group and a benzyl group having a halogen atom as a substituent. The halogen atom for the substituent is preferably a chlorine atom. The position of the substituent is not particularly limited, but is preferably the 4-position. Examples of the benzyloxy group include an unsubstituted group and a benzyloxy group having a halogen atom as a substituent. The halogen atom for the substituent is preferably a chlorine atom. The position of the substituent is not particularly limited, but is preferably the 4-position.

Examples of the pyridyloxy group include an unsubstituted group and a group having a haloalkyl group having 1 to 4 carbon atoms or a halogen atom as a substituent. The haloalkyl group for the substituent is preferably a trifluoromethyl group; the halogen atom is a chlorine atom. The position of the substituent is not particularly limited, but in the case of a pyrid-2-yloxy group, preferably the 5-position in the case of a haloalkyl group; and the 3-position in the case of a halogen atom. Examples of the pyridylmethyloxy group include an unsubstituted group and a group having a halogen atom as a substituent. The halogen atom is a chlorine atom. The position of this substituent is not particularly limited, but in the case of a pyrid-3-ylmethyloxy group, it is preferably at the 6-position.

Examples of the alkyl group substituted with an alkoxy group include a linear or branched alkyl group substituted with a linear or branched alkoxy group. Examples of the alkoxy group for the substituent include those having 1 to 4 carbon atoms, preferably those having 1 to 2 carbon atoms, and more preferably an ethoxy group; And an alkyl group having 1 to 4 carbon atoms, preferably an ethyl group. The most preferred alkyl group substituted with an alkoxy group includes a 2-ethoxyethyl group. The haloalkylsulfonyloxy group may be straight-chain or branched; preferably, it is trifluoromethylsulfonyloxy. Examples of the alkylthio group include a linear or branched one; preferably, a methylthio group and an n-propylthio group.

[R ² ] R ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, Examples thereof include 1 to 4 alkylthio groups and haloalkoxy groups having 1 to 4 carbon atoms. Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom;
It is a fluorine atom. Alkyl groups can include straight or branched ones; preferably a methyl group. Haloalkyl groups can include straight or branched ones; preferably trifluoromethyl groups. Alkoxy groups can be straight or branched; preferably methoxy groups. Alkylthio groups include linear or branched ones; preferably a propylthio group. Haloalkoxy groups can include straight or branched ones; preferably a trifluoromethoxy group.

[R¹& R^Two] R¹And R^TwoAnd, for example,
-OC (CH_Three)_TwoCH_TwoCH_Two-, -CH_TwoCH _TwoC
(CH_Three)_TwoO-, -CH = CH-CH = CH-, etc.
A saturated or unsaturated 6-membered ring which may have an oxygen atom
And may have 1 or
It may have two methyl groups. [R^Three] R^ThreeInclude hydrogen atom, halogen atom, carbon
Examples thereof include an alkoxy group having 1 to 4 atoms.
Halogen atoms include chlorine, iodine and bromine atoms.
And fluorine atom, etc .;
Is a chlorine atom or a fluorine atom. As an alkoxy group
Can be straight-chain or branched;
Preferably it is a methoxy group.

[R ⁴ ] Examples of R ⁴ include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom. Alkyl groups can include straight or branched ones; preferably a methyl group. Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; preferably a chlorine atom and a fluorine atom.

[R ⁵ ] Examples of R ⁵ include a hydrogen atom, a halogen atom, and an alkyl group having 1 to 6 carbon atoms. Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; preferably a chlorine atom and a fluorine atom. Examples of the alkyl group include linear or branched alkyl groups; preferably those having 1 to 4 carbon atoms; and more preferably methyl groups and t-butyl groups.

[X ¹ ] X ¹ includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. . Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; preferably a chlorine atom, a fluorine atom and a bromine atom. Alkyl groups can include straight or branched ones; preferably a methyl group. Haloalkyl groups can include straight or branched ones; preferably trifluoromethyl groups. Alkoxy groups can be straight or branched; preferably methoxy groups.

[X ² ] X ² includes a halogen atom, a hydrogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; preferably a chlorine atom and a fluorine atom. Alkoxy groups can be straight or branched; preferably methoxy groups.

[X ³ ] Examples of X ³ include a hydrogen atom and a halogen atom. Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; preferably a chlorine atom and a fluorine atom. The position of these substituents is not particularly limited; however, it is preferably the 4-position. [N] n can be an integer of 2 to 5; preferably 2 or 3. [Y] Examples of Y include a halogen atom.

As the compound (1), compounds obtained by combining the above-mentioned various substituents can be mentioned, and preferable compounds from the viewpoint of drug efficacy are as follows. (1) R ¹ , X ¹ and X ² are halogen atoms, and R ² to
A compound wherein R ⁵ and X ³ are a hydrogen atom and n is 2. (2) R ^{1 to} R ⁵ and X ³ are hydrogen atoms, and X ¹ and X
^A compound wherein ² is a halogen atom and n is 2. (3) R ^{1 to} R ⁵ and X ³ are hydrogen atoms, and X ¹ and X
^A compound in which ² is a halogen atom and n is 3. (4) R ¹ , R ³ , X ¹ and X ² are halogen atoms,
A compound wherein R ² , R ⁴ , R ⁵ and X ³ are a hydrogen atom and n is 2. (5) R ¹ is 1 to 10 alkyl group carbon atoms, R ²
To R ⁵ and X ³ are hydrogen atoms, X ¹ and X ² is a halogen atom, compounds wherein n is 2. (6) R ¹ is 1-8 alkoxy group having a carbon number, R ²
To R ⁵ and X ³ are hydrogen atoms, X ¹ and X ² is a halogen atom, compounds wherein n is 2. (7) R ¹ , R ² , X ¹ and X ² are halogen atoms,
A compound wherein R ^{3 to} R ⁵ and X ³ are a hydrogen atom and n is 2.

(8) R ¹ is a haloalkyl group having 1 to 4 carbon atoms, R ^{2 to} R ⁵ and X ³ are hydrogen atoms, and X ¹
And compounds wherein X ² is a halogen atom and n is 2. (9) R ¹ is a haloalkoxy group having 1 to 4 carbon atoms,
A compound wherein R ^{2 to} R ⁵ and X ³ are a hydrogen atom, X ¹ and X ² are a halogen atom, and n is 2. (10) R ¹ is a phenyl group, R ^{2 to} R ⁵ and X ³ are hydrogen atoms, X ¹ and X ² are halogen atoms, n
Is 2. (11) R ¹ is a phenoxy group, R ^{2 to} R ⁵ and X ³ are hydrogen atoms, X ¹ and X ² are halogen atoms,
A compound wherein n is 2. (12) R ¹ is a phenoxy group, R ² , R ⁵ and X ³ are hydrogen atoms, R ³ , X ¹ and X ² are halogen atoms, and R ⁴ is alkyl having 1 to 8 carbon atoms. A compound wherein n is 2. (13) R ¹ is a benzyl group, R ^{2 to} R ⁵ and X ³ are hydrogen atoms, X ¹ and X ² are halogen atoms, n
Is 2. (14) R ¹ is an alkyl group having 1 to 4 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, and R ^{2 to} R ⁵ and X
^A compound in which ³ is a hydrogen atom, X ¹ and X ² are halogen atoms, and n is 2.

[0059] (15) R ¹ is a pyridyloxy group, R ²
To R ⁵ and X ³ are hydrogen atoms, X ¹ and X ² is a halogen atom, compounds wherein n is 2. (16) R ¹ is a pyridyloxy group, R ² , R ⁵ , X ¹
And X ² is a halogen atom, R ³ , R ⁴ and X ³ are hydrogen atoms and n is 2. (17) R ¹ is a pyridyloxy group, and R ² , X ¹ and X
^A compound wherein ² is a halogen atom, R ^{3 to} R ⁵ and X ³ are hydrogen atoms, and n is 2. (18) R ¹ is a haloalkoxy group having 1 to 4 carbon atoms,
Compounds wherein R ^{2 to} R ⁴ and X ³ are hydrogen atoms, R ⁵ , X ¹ and X ² are halogen atoms, and n is 2. (19) R ¹ is a haloalkoxy group having 1 to 4 carbon atoms,
A compound in which R ^{3 to} R ⁵ and X ³ are a hydrogen atom, R ² , X ¹ and X ² are a halogen atom, and n is 2. (20) R ¹ is a haloalkoxy group having 1 to 4 carbon atoms,
R ³ , R ⁴ and X ³ are hydrogen atoms, and R ² , R ⁵ , X
^A compound wherein ¹ and X ² are a halogen atom and n is 2. (21) R ¹ , R ³ , X ¹ and X ² are a halogen atom,
A compound wherein R ² , R ⁴ , R ⁵ and X ³ are a hydrogen atom and n is 2.

(22) R ¹ is a haloalkyl group having 1 to 4 carbon atoms, R ² , R ⁴ , R ⁵ and X ³ are hydrogen atoms, and R ³ , X ¹ and X ² are halogen atoms. Yes, n is 2
A compound that is (23) R ¹ is a haloalkoxy group having 1 to 4 carbon atoms,
R ² , R ⁴ , R ⁵ and X ³ are hydrogen atoms, and R ³ , X
^A compound wherein ¹ and X ² are a halogen atom and n is 2. (24) The compound wherein R ¹ is a phenoxy group, R ² , R ⁴ , R ⁵ and X ³ are hydrogen atoms, R ³ , X ¹ and X ² are halogen atoms and n is 2. (25) R ¹ is an alkyl group having 1 to 10 carbon atoms,
R ² , R ⁴ , R ⁵ and X ³ are hydrogen atoms, and R ³ , X
^A compound wherein ¹ and X ² are a halogen atom and n is 2. (26) R ¹ is a haloalkyl group having 1 to 4 carbon atoms,
^A compound in which ^{2 to} R ⁵ and X ³ are hydrogen atoms, X ¹ and X ² are halogen atoms, and n is 3. (27) R ¹ is a haloalkyl group having 1 to 4 carbon atoms;
^A compound in which ^{2 to} R ⁵ and X ³ are hydrogen atoms, X ¹ and X ² are halogen atoms, and n is 5. (28) R ¹ is a phenyl group, R ² is an alkyl group having 1 to 4 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms, and R ³ , R ⁴ and X ³ are A compound in which X ¹ and X ² are a hydrogen atom, and n is 2.

(29) R ¹ is a benzyloxy group and R ²
To R ⁵ and X ³ are hydrogen atoms, X ¹ and X ² is a halogen atom, compounds wherein n is 2. (30) R ¹ is a pyridylmethyloxy group, and R ^{2 to} R ⁵
And X ³ is a hydrogen atom, X ¹ and X ² are halogen atoms, and n is 2. (31) The compound wherein R ¹ is a nitro group, R ^{2 to} R ⁵ and X ³ are hydrogen atoms, X ¹ and X ² are halogen atoms, and n is 2. (32) R ¹ is a haloalkylsulfonyloxy group having 1 to 4 carbon atoms, R ^{2 to} R ⁵ and X ³ are hydrogen atoms,
A compound wherein X ¹ and X ² are a halogen atom and n is 2. (33) R ¹ , X ¹ and X ² are halogen atoms, R ² is a haloalkyl group having 1 to 4 carbon atoms, R ^{3 to} R ⁵ and X ³ are hydrogen atoms, and n is 2 Certain compounds. (34) R ¹ , X ¹ and X ² are halogen atoms, and R ² ,
R ⁴ , R ⁵ and X ³ are hydrogen atoms, and R ³ has 1 carbon atom
A compound having 4 to 4 alkoxy groups, wherein n is 2. (35) R ¹ is an alkylthio group having 1 to 4 carbon atoms;
¹ and X ² are halogen atoms, and R ^{2 to} R ⁵ and X ³
Is a hydrogen atom and n is 2.

(36) R ¹ , R ^{3 to} R ⁵ and X ³ are hydrogen atoms, R ² is an alkylthio group having 1 to 4 carbon atoms, X ¹ and X ² are halogen atoms, n Is 2. (37) R ¹ and R ² may form a saturated or unsaturated 6-membered ring which may have an oxygen atom, and may have 1 or 2 methyl groups as a substituent of the ring. well, R ³ ~R ⁵
And X ³ is a hydrogen atom, X ¹ and X ² are halogen atoms, and n is 2. (38) R ^{1 to} R ³ , R ⁵ , X ¹ and X ² are halogen atoms, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms, and X ³
Is a hydrogen atom and n is 2. (39) R ¹ is a haloalkoxy group having 1 to 4 carbon atoms,
A compound in which R ² , R ³ , R ⁵ , X ¹ and X ² are a halogen atom, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms, X ³ is a hydrogen atom, and n is 2. (40) R ¹ is a haloalkoxy group having 1 to 4 carbon atoms,
R ^{2 to} R ⁵ and X ³ are hydrogen atoms, and X ¹ has ¹ carbon atom.
A compound having 4 to 4 haloalkyl groups, wherein X ² is a halogen atom and n is 2. (41) R ¹ is a haloalkoxy group having 1 to 4 carbon atoms,
R ^{2 to} R ⁵ and X ² are hydrogen atoms, and X ¹ has 1 to ¹ carbon atoms.
4 alkyl groups, X ³ is a halogen atom,
A compound wherein n is 2. (42) R ¹ is a haloalkoxy group having 1 to 4 carbon atoms,
A compound wherein R ^{2 to} R ⁵ are hydrogen atoms, X ^{1 to} X ³ are halogen atoms, and n is 2. (43) R ¹ is a haloalkoxy group having 1 to 4 carbon atoms,
A compound in which R ^{2 to} R ⁵ and X ³ are a hydrogen atom, X ¹ and X ² are an alkoxy group having 1 to 4 carbon atoms, and n is 2. (44) R ¹ is a haloalkoxy group having 1 to 4 carbon atoms,
A compound wherein R ^{2 to} R ⁵ and X ^{1 to} X ³ are hydrogen atoms, X ¹ is an alkyl group having 1 to 4 carbon atoms, and n is 2. (45) R ¹ , R ^{3 to} R ⁵ and X ³ are hydrogen atoms, and R ²
Is a haloalkoxy group having 1 to 4 carbon atoms, X ¹ and X ² are halogen atoms, and n is 2.

The preferred combination (1)
R ^{1 to} R ⁵ , X ^{1 to} X ^{3 of} the compound (1) represented by (45)
And n are the above-mentioned preferable ones and further preferable ones. Specific examples of these compounds (1) include compounds 1 to 15, 17 to 19, 21 to 27, 31 to 35, and 37 described in Tables 1 to 14 described below.
~ 40,42 ~ 44,49 ~ 61,63 ~ 65,68 ~
73, 75, 77, 79, 82 to 104, 106.

Compound (1) can be synthesized by the following method. Synthesis of Compound (2) Compound (2) was synthesized as shown below.
And thionyl halide (SOY ₂ ) in a solvent or in the absence of a solvent;
In order to accelerate the reaction, the reaction is preferably performed under heating.

[0065]

Embedded image

(Wherein R ^{1 to} R ⁵ , X ^{1 to} X ³ , n and Y have the same meanings as described above). The solvent is not particularly limited as long as it does not directly participate in the reaction. For example, chlorinated or unaromatic aromatic, aliphatic and alicyclic hydrocarbons (benzene, toluene, xylene, methyl naphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride , Chloroform, dichloroethane, trichloroethylene, cyclohexane, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), and mixtures of the above solvents.

The amount of the solvent used can be such that the concentration of compound (3) is in the range of 5 to 80% by weight; preferably, compound (3) is used.
Is preferably used in such a manner that the concentration thereof becomes 10 to 70% by weight. As the thionyl halide, a commercially available product can be used. The amount of the thionyl halide to be used is 1 to 5 moles relative to compound (3); preferably, it is 1.1 to 2 moles.

The reaction temperature is not particularly limited, but is in the range of from the ice cooling temperature to the boiling point of the solvent to be used or lower; preferably 50 to 80 ° C. The reaction time varies depending on the above-mentioned concentration and temperature; it can be usually carried out for 0.3 to 2 hours. After completion of the reaction, the compound (2) produced as described above is subjected to ordinary post-treatments such as extraction, concentration and filtration, and if necessary, appropriately purified by known means such as recrystallization and various types of chromatography. can do.
When the compound (2) is used as a raw material for synthesizing the compound (1), the compound (2) can be used as it is without post-treatment after completion of the synthesis reaction.

As the compound (2), the following Tables 1 to 14
Compounds having each substituent corresponding to each compound shown therein can be mentioned [compound (2) having each substituent corresponding to compounds ₁ to _{106 is} replaced with compound (2) ₁ to compound (2) ₁₀₆ Called. For example, in the compound (2) ₁ having each substituent corresponding to the compound ₁ , R ¹ is a chlorine atom, R ^{2 to} R ⁵ and X ³ are hydrogen atoms, X ¹ and X
² is a fluorine atom, n is 2, and Y is a halogen atom. ].

Method for synthesizing compound (1) Compound (1) can be usually produced by subjecting compound (2) as a raw material to alkali treatment with or without a solvent to effect cyclization. In order to promote the reaction, the reaction is preferably performed under heating. The solvent is not particularly limited as long as it does not directly participate in the reaction. For example, chlorinated or non-chlorinated aromatic, aliphatic and alicyclic hydrocarbons (benzene, toluene, xylene, methyl Naphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloroethane, trichloroethylene, cyclohexane, etc., ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), alcohols (methanol, ethanol, propanol) , Butanol, etc.), and mixtures of the above-mentioned solvents. Preferred are ethers and alcohols.

The amount of the solvent used may be such that the concentration of compound (2) is in the range of 5 to 80% by weight; preferably, compound (2) is used.
Is preferably used in such a manner that the concentration thereof becomes 10 to 70% by weight. The type of alkali is not particularly limited, for example,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic bases such as potassium carbonate, sodium bicarbonate and the like can be used;
Potassium hydroxide is preferred. The amount of the alkali to be used is 1 to 10 moles relative to compound (2); preferably 2 to 5 moles.

The reaction temperature is not particularly limited, but is in the range from the ice-cooling temperature to the boiling point of the solvent used or lower; preferably 50 to 80 ° C. The reaction time varies depending on the above-mentioned concentration and temperature; it can be usually carried out for 0.3 to 2 hours. After completion of the reaction, the compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and if necessary, appropriately purified by known means such as recrystallization and various types of chromatography. can do.
Examples of the compound (1) include the compounds 1 to 106 shown in Tables 1 to 14 below. [The compound 1 is a compound represented by the formula (1) in which R ¹ is a chlorine atom and R ² To R ⁵ and X ³ are hydrogen atoms, X ¹ and X
² is a fluorine atom and n is 2. ].

Pest control agent for agricultural and horticultural use [Control effect] The pests in agricultural and horticultural activities which are controlled by the compound (1) of the present invention include agricultural and horticultural insect pests, for example, Hemiptera (Coleoptera, leafhopper). , Aphids,
Whiteflies, etc.), lepidoptera (armyworms, moths,
Coleoptera, Pests, Pests, and White butterfly, Coleoptera (Tenebrionidae, Weevils,
Chrysomelidae, Scarabaeids, etc.), Acarina (Rutaceae, Citrus spider mite, Tetranychidae, etc.), Sanitary pests (for example, flies, mosquitoes, cockroaches, etc.), and grain storage pests (Merberidae, Bean weevil) Etc.), root-knot nematodes, pine wood nematodes, mite, etc. in the soil, and agricultural and horticultural pathogens (eg, wheat leaf rust, barley powdery mildew, cucumber downy mildew, rice blast, tomato late blight). Can be mentioned.

[Pest control agent] The pest control agent for agricultural and horticultural use of the present invention has a remarkable insecticidal, acaricidal and bactericidal effect, and contains at least one compound (1) as an active ingredient. Things. Compound (1) can be used alone, but usually, a carrier, a surfactant,
It is preferable to use a dispersant, an auxiliary agent and the like compounded (for example, prepared as a composition such as powder, emulsion, fine granule, granule, wettable powder, oily suspension and aerosol).

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene, etc.) Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), water, etc .; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection), and the like.

Surfactants and dispersants which can be used to improve the performance of the agent, such as adhesion to animals and plants, absorption, and dispersion, emulsification, and spreading of drugs include alcohol sulfates and alkyls. Sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like can be mentioned. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as an auxiliary agent.

In the preparation of the present agent, the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in an appropriate combination depending on the respective purposes.
When the compound (1) of the present invention is formulated, the concentration of the active ingredient is usually from 1 to 50% by weight in an emulsion, and usually 0.3% in a powder.
25 to 25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils and 0.1 to 5% by weight for aerosols. is there. These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on plant foliage, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0078]

The present invention will be specifically described below with reference to examples. Note that these examples do not limit the scope of the present invention. Example 1 Synthesis of Compound (2) (1) Synthesis of N- [3- (4-bromophenoxy) -1-chloromethylpropyl] -2,6-difluorobenzamide N- [3- (4-bromo [Phenoxy) -1-hydroxymethylpropyl] -2,6-difluorobenzamide (4.80 g) was dissolved in toluene (20 ml), thionyl chloride (2.9 g) was added, and the mixture was stirred at 70 to 80 ° C. for 1 hour. After cooling, the excess thionyl chloride and the solvent were distilled off under reduced pressure, and the resulting oil was purified on a silica gel column (Wakogel C-200, toluene: ethyl acetate = 9: 1 elution).
As a result, 4.55 g of the target compound as white crystals was obtained. m. p. 116-119 ° C

(2) N- [3- (4-methylphenoxy)
Synthesis of -1-chloromethylpropyl] -2,6-difluorobenzamide N- [3- (4-methylphenoxy) -1-hydroxymethylpropyl] -2,6-difluorobenzamide (4.02 g) was dissolved in toluene (20 ml). ), Thionyl chloride (2.9 g) was added, and the mixture was stirred at 70 to 80 ° C for 1 hour. After cooling, the excess thionyl chloride and the solvent were distilled off under reduced pressure, and the resulting oil was purified on a silica gel column (Wakogel C-200, toluene: ethyl acetate = 9: 1 elution).
As a result, 3.91 g of the target compound as white crystals was obtained. m. p. 97-99 ° C (3) Synthesis of other compound (2) having a substituent described in Tables 14 to 14 Other compounds in Tables 14 to 14 according to the method described in the above (1) or (2) (2) was synthesized.

Example 2 [Synthesis of Compound (1)] (1) 2- (2,6-difluorophenyl) -4- [2-
Synthesis of (4-chlorophenoxy) ethyl] -2-oxazoline (Compound 1) N- [3- (4-Chlorophenoxy) -1-chloromethylpropyl] -2,6-difluorobenzamide (3.
74 g) was dissolved in methanol (20 ml), a 15% aqueous sodium hydroxide solution (5 ml) was added, and the mixture was heated under reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate.
After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained oil was isolated by a silica gel column (Wakogel C-200, toluene: ethyl acetate = 9: 1 elution) to obtain 2.42 g of the target compound as a colorless oil.

¹ H-NMR (CDCl ₃ , δ ppm) 2.04 to 2.30 (2H, m), 4.16 (2H,
t, J = 6 Hz), 4.19 to 4.33 (1H, m),
4.37-4.69 (2H, m), 6.79-7.46
(7H, m)

(2) 2- (2,6-difluorophenyl)
-4- [2- (4-bromophenoxy) ethyl] -2-
Synthesis of oxazoline (compound 2) N- [3- (4-bromophenoxy) -1-chloromethylpropyl] -2,6-difluorobenzamide (4.
19 g) was dissolved in methanol (20 ml), a 15% aqueous sodium hydroxide solution (5 ml) was added, and the mixture was heated under reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate.
After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained oil was isolated on a silica gel column (Wakogel C-200, eluted with toluene: ethyl acetate = 9: 1) to give 3.06 g of the target compound as a colorless oil.

¹ H-NMR (CDCl ₃ , δ ppm) 2.02 to 2.29 (2H, m), 4.16 (2H,
t, J = 6 Hz), 4.19 to 4.30 (1H, m),
4.38 to 4.68 (2H, m), 6.73 to 7.46
(7H, m)

(3) 2- (2,6-difluorophenyl)
Synthesis of -4- (3-phenoxypropyl-2-oxazoline (compound 4) N- (1-chloromethyl-4-phenoxybutyl)-
2,6-Difluorobenzamide (3.54 g) was dissolved in methanol (20 ml), a 15% aqueous sodium hydroxide solution (5 ml) was added, and the mixture was heated under reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate. This was washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was isolated on a silica gel column (Wakogel C-200, eluted with toluene: ethyl acetate = 9: 1) to give 1.74 g of the target compound as a colorless oil.

¹ H-NMR (CDCl ₃ , δ ppm) 1.72 to 2.13 (4H, m), 3.89 to 4.08
(1H, m), 4.12 (2H, t, J = 7 Hz),
4.34 to 4.58 (2H, m), 6.78 to 7.44
(8H, m)

(4) 2- (2,6-difluorophenyl)
-4- [2- (4-phenoxyphenoxy) ethyl]-
Synthesis of 2-oxazoline (Compound 13) N- [1-Chloromethyl-3- (4-phenoxyphenoxy) -propyl] -2,6-difluorobenzamide (3.02 g) was dissolved in methanol (20 ml), and 1
A 5% aqueous sodium hydroxide solution (3.5 ml) was added, and 1
Heated to reflux for an hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate. This was washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by a silica gel column (Wakogel C-200, toluene: ethyl acetate = 2).
(0: 1 elution) to give 1.97 g of the desired compound as a pale yellow oil.

¹ H-NMR (CDCl ₃ , δ ppm) 2.04 to 2.35 (2H, m), 4.17 (2H,
t, J = 3.5 Hz), 4.22 to 4.30 (1H,
m), 4.50 to 4.68 (2H, m), 6.70 to
7.46 (12H, m)

(5) 2- (2,6-difluorophenyl)
Synthesis of -4- {2- [4- (2-ethoxyethyl) phenoxy] ethyl} -2-oxazoline (Compound 17) N- {1-chloromethyl-3- [4- (ethoxyethyl) phenoxy] -propyl ｝ -2,6-difluorobenzamide (2.06 g) is dissolved in methanol (20 ml), and a 15% aqueous sodium hydroxide solution (2.5 ml)
Was added and heated under reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate. This was washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was isolated on a silica gel column (Wakogel C-200, eluted with toluene: ethyl acetate = 9: 1) to give 1.14 g of the target compound as a colorless oil.

¹ H-NMR (CDCl ₃ , δ ppm) 1.20 (3 H, t, J = 7 Hz), 2.02 to 2.3
1 (2H, m), 2.83 (2H, t, J = 7 Hz),
3.50 (2H, q, J = 7 Hz), 3.59 (2H, q, J = 7 Hz)
t, J = 7 Hz), 4.16 (2H, t, J = 3.5H)
z), 4.20-4.31 (1H, m), 4.47-
4.63 (2H, m), 6.75-7.44 (7H,
m)

(6) 2- (2,6-difluorophenyl)
-4- {2- [4- (3-Chloro-5-trifluoromethylpyridin-2-yloxy) phenoxy] ethyl}
Synthesis of 2-oxazoline (compound 19) N- {1-chloromethyl-3- [4- (3-chloro-5
-Trifluoromethylpyrid-2-yloxy) phenoxy-propyl] {-2,6-difluorobenzamide (2.68 g) in methanol (20 ml).
A 5% aqueous sodium hydroxide solution (2.5 ml) was added, and 1
Heated to reflux for an hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate. This was washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by a silica gel column (Wakogel C-200, toluene: ethyl acetate = 2).
(0: 1 elution) to give 1.09 g of the target compound as a colorless viscous oil.

¹ H-NMR (CDCl ₃ , δ ppm) 2.03 to 2.32 (2H, m), 4.14 to 4.31
(3H, m), 4.50-4.63 (2H, m), 6.
78 to 7.45 (7H, m), 7.97 (1H, s),
8.28 (1H, s)

(7) 2- (2,6-difluorophenyl)
-4- [2- (4-trifluoromethoxyphenoxy)
Synthesis of ethyl] -2-oxazoline (compound 11) N- [1-chloromethyl-3- (4-trifluoromethoxyphenoxy) propyl] -2,6-difluorobenzamide (1.27 g) was added to methanol (20 ml). After dissolution, a 15% aqueous sodium hydroxide solution (1.5 ml) was added, and the mixture was heated under reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate. This was washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was isolated on a silica gel column (Wakogel C-200, eluted with toluene: ethyl acetate = 9: 1) to give 0.87 g of the target compound as colorless crystals.

¹ H-NMR (CDCl ₃ , δ ppm) 2.07 to 2.29 (2H, m), 4.06 to 4.38
(3H, m), 4.47 to 4.70 (2H, m), 6.
78-7.46 (7H, m)

(8) 2- (2,6-difluorophenyl)
Synthesis of -4- [2- (4-chlorophenoxyphenoxy) ethyl] -2-oxazoline (Compound 21) N- [1-Chloromethyl-3- (4-chlorophenoxyphenoxy) propyl] -2,6-difluoro Benzamide (1.40 g) was dissolved in methanol (20 ml), a 15% aqueous sodium hydroxide solution (1.5 ml) was added, and the mixture was heated under reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate. This was washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by a silica gel column (Wakogel C-200, toluene: ethyl acetate =
(9: 1 elution) to give 0.98 g of the desired compound as a pale yellow oil.

¹ H-NMR (CDCl ₃ , δ ppm) 2.11 to 2.30 (2H, m), 4.14 to 4.30
(3H, m), 4.55-4.65 (2H, m), 6.
80-7.45 (11H, m)

(9) 2- (2,6-difluorophenyl)
-4- {2- [4- (1,1,2,3,3,3-hexafluoro-1-propoxy) phenoxy] ethyl} -2
Synthesis of -oxazoline (compound 43) N- {1-chloromethyl-3- [4- (1,1,2,2
3,3,3-Hexafluoro-1-propoxy) phenoxy] propyl} -2,6-difluorobenzamide (1.52 g) was dissolved in methanol (20 ml).
A 5% aqueous sodium hydroxide solution (1.5 ml) was added, and 1
Heated to reflux for an hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate. This was washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by a silica gel column (Wakogel C-200, toluene: ethyl acetate = 9:
1.02 g of the target compound as a pale yellow viscous oil.

¹ H-NMR (CDCl ₃ , δ ppm) 1.97 to 2.31 (2H, m), 4.05 to 4.30
(3H, m), 4.43 to 4.67 (2H, m);
80 to 5.12 (1H, m), 6.68 to 7.52 (7
H, m)

(10) 2- (2,6-difluorophenyl)
Synthesis of -4- {2- [4- (4-trifluoromethylphenyl) phenoxy] ethyl} -2-oxazoline (Compound 63) N- {1-chloromethyl-3- [4- (4-trifluoromethyl) Phenyl) phenoxy] propyl} -2,6-
Difluorobenzamide (0.97 g) was dissolved in methanol (15 ml), a 15% aqueous sodium hydroxide solution (1.0 ml) was added, and the mixture was heated under reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate. This was washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was isolated on a silica gel column (Wakogel C-200, eluted with toluene: ethyl acetate = 9: 1) to give 0.59 g of the target compound as colorless crystals.

¹ H-NMR (CDCl ₃ , δ ppm) 2.08 to 2.35 (2H, m), 4.10 to 4.38
(3H, m), 4.47 to 4.71 (2H, m), 6.
78 to 7.78 (11H, m)

(11) 2- (2,6-difluorophenyl)
Synthesis of -4- {2- [4- (4-trifluoromethoxyphenyl) phenoxy] ethyl} -2-oxazoline (Compound 65) N- {1-chloromethyl-3- [4- (4-trifluoromethoxy) Phenyl) phenoxy] propyl} -2,6
-Difluorobenzamide (1.00 g) was dissolved in methanol (15 ml), a 15% aqueous sodium hydroxide solution (1.0 ml) was added, and the mixture was heated under reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate. This was washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was isolated on a silica gel column (Wakogel C-200, eluted with toluene: ethyl acetate = 9: 1) to give 0.54 g of the target compound as colorless crystals.

¹ H-NMR (CDCl ₃ , δ ppm) 2.03 to 2.35 (2H, m), 4.05 to 4.34
(3H, m), 4.48 to 4.72 (2H, m), 6.
78 to 7.69 (11H, m)

(12) 2- (2,6-difluorophenyl)
-4- [2- (2,2-dimethyl-3,4-dihydro-
Synthesis of 2H-chromen-6-yloxy) ethyl] -2-oxazoline (Compound 85) N- [1-Chloromethyl-3- (2,2-dimethyl-
3,4-dihydro-2H-chromen-6-yloxy)
Propyl] -2,6-difluorobenzamide (1.2
7 g) was dissolved in methanol (20 ml), a 15% aqueous sodium hydroxide solution (1.5 ml) was added, and the mixture was heated under reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate. This was washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The resulting oil is purified on a silica gel column (Wakogel C-200, toluene: ethyl acetate = 9: 1).
0.77 g of the target compound as a pale yellow viscous oil was obtained.

¹ H-NMR (CDCl ₃ , δ ppm) 1.31 (6H, s), 1.77 (2H, t, J = 7.
3 Hz), 2.02 to 2.32 (2H, m), 2.74
(2H, t, J = 6.7 Hz), 4.02 to 4.30
(3H, m), 4.48 to 4.63 (2H, m), 6.
58-7.47 (6H, m)

(13) Synthesis of 2- (2-chloro-6-fluorophenyl) -4- [2- (4-trifluoromethoxyphenoxy) ethyl] -2-oxazoline (Compound 98) N- [1-chloro Methyl-3- (4-trifluoromethoxyphenoxy) propyl] -2-chloro-6-fluorobenzamide (1.32 g) in methanol (20 m
l) and dissolved in a 15% aqueous sodium hydroxide solution (1.5%).
ml) and heated to reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate.
This was washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was isolated on a silica gel column (Wakogel C-200, eluted with toluene: ethyl acetate = 9: 1) to give 0.83 g of the target compound as a colorless oil.

¹ H-NMR (CDCl ₃ , δ ppm) 2.18 to 2.25 (2H, m), 4.17 to 4.29
(3H, m), 4.57 to 4.68 (2H, m), 6.
86-7.38 (7H, m)

(14) 2- (2,6-dichlorophenyl)-
Synthesis of 4- [2- (4-trifluoromethoxyphenoxy) ethyl] -2-oxazoline (Compound 99) N- [1-Chloromethyl-3- (4-trifluoromethoxyphenoxy) propyl] -2,6- Dichlorobenzamide (1.37 g) was dissolved in methanol (20 ml), a 15% aqueous sodium hydroxide solution (1.5 ml) was added, and the mixture was heated under reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate. This was washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by a silica gel column (Wakogel C-200, toluene: ethyl acetate =
(9: 1 elution) to give 0.94 g of the desired compound as a pale yellow viscous oil.

¹ H-NMR (CDCl ₃ , δ ppm) 2.07 to 2.29 (2H, m), 4.06 to 4.38
(3H, m), 4.47 to 4.70 (2H, m), 6.
78-7.43 (7H, m)

(15) 2- (2,6-difluorophenyl)
Synthesis of -4- [2- (2-naphthyloxy) ethyl] -2-oxazoline (Compound 105) N- [1-Chloromethyl-3- (2-naphthyloxy)
Propyl] -2,6-difluorobenzamide (1.3
2 g) was dissolved in methanol (20 ml), a 15% aqueous sodium hydroxide solution (1.5 ml) was added, and the mixture was heated under reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the target compound was extracted with ethyl acetate. This was washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The resulting oil is purified on a silica gel column (Wakogel C-200, toluene: ethyl acetate = 9: 1).
0.87 g of the target compound was obtained as a pale yellow oil.

¹ H-NMR (CDCl ₃ , δ ppm) 2.10 to 2.39 (2H, m), 4.14 to 4.39
(3H, m), 4.47 to 4.70 (2H, m), 6.
82 to 7.80 (10H, m)

(16) Other compounds (1) in Tables 1 to 14
According to the methods described in the above (1) to (15), other compounds (1) in Tables 1 to 14 were synthesized. Tables 1 to 15 show the compounds synthesized as described above.

[0111]

[Table 1]

[0112]

[Table 2]

[0113]

[Table 3]

[0114]

[Table 4]

[0115]

[Table 5]

[0116]

[Table 6]

[0117]

[Table 7]

[0118]

[Table 8]

[0119]

[Table 9]

[0120]

[Table 10]

[0121]

[Table 11]

[0122]

[Table 12]

[0123]

[Table 13]

[0124]

[Table 14]

[0125]

[Table 15]

Example 3 [Preparation of preparation] (1) Preparation of granule 5 parts by weight of compound 1, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of Neoperex powder (trade name; manufactured by Kao Corporation) And 2 parts by weight of sodium ligninsulfonate were uniformly mixed, then kneaded by adding a small amount of water, and then granulated and dried to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound 1, 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of Neoperex powder (trade name, manufactured by Kao Corporation) and Demol (trade name) Name; manufactured by Kao Corporation)
Then, it was ground to obtain a wettable powder.

(3) Preparation of Emulsion To 20 parts by weight of compound 1 and 70 parts by weight of xylene, 10 parts by weight of toxanone (trade name, manufactured by Sanyo Chemical Industries) was added, mixed uniformly, and dissolved to obtain an emulsion. .

(4) Preparation of Dust A powder was obtained by uniformly mixing 5 parts by weight of Compound 1, 50 parts by weight of talc and 45 parts by weight of kaolin.

Example 4 [Efficacy test] (1) Efficacy test for Japanese moth [0130] Each wettable powder of compound (1) shown in Tables 1 to 14 prepared according to Example 3 was added to a surfactant (0.01%) Diluted to 300 ppm, 50 ppm and 10 ppm with water containing
30 pieces of cabbage leaf (5 × 5 cm) are placed in each of these solutions.
After immersion for 2 seconds, each piece was placed in each plastic cup and air-dried. Next, 10 moths (3rd instar larvae) were released into each of these cups, covered, and allowed to stand in a constant temperature room at 25 ° C. After 2 days, the number of live and dead insects in each cup was counted to determine the mortality. I asked. The insecticidal effect was evaluated in four stages (A: 100%, B: less than 100 to 80%, C: less than 80 to 60%, D: less than 60%) according to the range of the mortality. In addition, as a comparative compound, the following JP-A-5-271206 (E
Comparative compounds 1 and 2 described in P-A-553,623) and Comparative compound 3 described in JP-A-2-85268 were diluted to 300 ppm, 50 ppm and 10 ppm, and the mortality was determined in the same manner. Was.

[0131]

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[0132]

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[0133]

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Table 16 shows the results.

[0135]

[Table 16]

(2) Efficacy test for Spodoptera litura The wettable powders of compounds (1) shown in Tables 1 to 14 prepared according to Example 3 were each 500 ppm in water containing a surfactant (0.01%). It was diluted to 100 ppm, soybean leaves were immersed in each of these chemicals for 30 seconds, placed one by one into each plastic cup, and air-dried. In each of these cups, ten cutworm armyworms (2nd instar larvae) were released, covered, left in a constant temperature room at 25 ° C., and two days later, the number of live and dead insects in each cup was counted to determine the insecticidal rate. The above (1)
Were diluted to 500 ppm and 100 ppm, and the mortality was determined in the same manner. The results of the evaluation of these insecticidal effects were
The results are shown in Table 17 by the four-step evaluation method described in the above (1).

[0137]

[Table 17]

(3) Efficacy test on the spider mite egg Either the wettable powder of the compound (1) shown in Tables 1 to 14 prepared according to Example 3 was reduced to 300 ppm with water containing a surfactant (0.01%). After diluting, 15 adult female spider mites were produced and egg-produced for 24 hours in each of these drug solutions, each kidney leaf piece (20 mm in diameter) from which the adult was removed was immersed for 10 seconds. Next, these leaf pieces were allowed to stand in a constant temperature room at 25 ° C., and after 6 days, the number of unhatched eggs in each leaf piece was counted to determine the egg kill rate. The evaluation of the ovicidal effect was performed in four stages (A: 100%, B: less than 100 to 80%,
C: less than 80 to 60%, D: less than 60%). Table 18 shows the results.

[0139]

[Table 18]

(4) Test for controlling efficacy against cucumber downy mildew (preventive effect) One cucumber (cultivar: Sagamihanjiro) per pot was grown in a plastic flowerpot having a diameter of 6 cm, and a 1.5-leaf seedling was planted. Example 3 was obtained from the compound (1) shown in Tables 1 to 14
Each wettable powder prepared in accordance with
%) To 500 ppm with water containing
Sprayed at 0 ml. After spraying, cultivate in a glass greenhouse for 2 days, and then cucumber downy mildew (Pseudoperonospora cu
zoospores were prepared from diseased leaves and sprayed evenly on the underside of plant leaves. 2 days after inoculation for 2 days
After being kept in the dark at 0 ° C., they were grown in a glass greenhouse for 5 days, and the degree of cucumber downy spots appearing on the first leaves was examined. The evaluation of the bactericidal effect was performed in six stages (0: the whole diseased, 1: the lesion area was about 60%, 2: the lesion area was about 40%, and 3: Lesion area is 20%
(4: Lesion area is 10% or less, 5: No lesion). Table 19 shows the results.

[0141]

[Table 19]

[0142]

The novel oxazoline derivative of the present invention is
It has excellent effects such as insecticide, miticide, and sterilization.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // (C07D 413/12 213: 04 263: 14) (C07D 413/12 263: 14 311: 72) (56) References JP-A-5-271206 (JP, A) JP-A-6-48907 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 263/14 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. The following formula (1): (Wherein, R ¹ is a halogen atom, a hydrogen atom, a carbon number of 1 to 1)
0 alkyl groups, C1-C8 alkoxy groups, C1-C4 haloalkyl groups, C1-C4 haloalkoxy groups, unsubstituted or substituted halogen atoms,
Haloalkyl group having 1 to 4 carbon atoms, or 1 to carbon atoms
A phenyl group having 4 haloalkoxy groups, an unsubstituted or substituted halogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a phenoxy group having a haloalkoxy group having 1 to 4 carbon atoms, unsubstituted or substituted A benzyl group having a halogen atom as a group, a benzyloxy group having a halogen atom as an unsubstituted or substituted group, a haloalkyl group having 1 to 4 carbon atoms as an unsubstituted or substituted group, or a pyridyloxy group having a halogen atom, unsubstituted Or a pyridylmethyloxy group having a halogen atom as a substituent, an alkyl group having 1 to 4 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyanomethyloxy group, and having 1 to 4 carbon atoms Haloalkylsulfonyloxy group, alkylsulfonyloxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms It represents an alkylthio group. R ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or Represents a haloalkoxy group having 1 to 4 carbon atoms. R ¹
And R ² form a saturated or unsaturated 6-membered ring which may have an oxygen atom, and 1 or 2
May have one methyl group. R ³ is a hydrogen atom,
Represents a halogen atom or an alkoxy group having 1 to 4 carbon atoms. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. R ⁵ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms. X ¹ is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or 1
Represents up to 4 alkoxy groups. X ² is a halogen atom,
Represents a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms. X ³ represents a hydrogen atom or a halogen atom.
n represents an integer of 2 to 5. An oxazoline derivative represented by the formula: 2. The following formula (2): (Wherein, R ^{1 to} R ⁴ , X ^{1 to} X ³ and n have the same meanings as in claim 1. Y represents a halogen atom.) An amide ethyl halide derivative represented by the formula: 3. An oxazoline derivative represented by the formula (1) according to claim 1, wherein the amide ethyl halide derivative represented by the formula (2) according to the claim 2 is cyclized by treating with an alkali. Recipe. 4. A pest control agent for agricultural and horticultural use, comprising the oxazoline derivative represented by the formula (1) according to claim 1 as an active ingredient.