JP2009051735A - Benzoxazole derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new benzoxazole compound useful as an insecticide. <P>SOLUTION: The benzoxazole compound is represented by formula (1) (wherein R<SP>1</SP>-R<SP>9</SP>are each H, a halogen atom, a 1-4C alkyl group, a 1-4C alkoxy group, a 1-4C haloalkyl group, a 1-4C haloalkoxy group, NO<SB>2</SB>, CN, CHO, Ph, OPh or the like, or R<SP>5</SP>and R<SP>6</SP>or R<SP>6</SP>and R<SP>7</SP>are combined together to form a 1-4C polymethylenedioxy group; and R<SP>10</SP>and R<SP>11</SP>are each independently a hydrogen atom, a 1-4C straight-chain or branched-chain hydrocarbon group optionally containing an unsaturated bond, a 1-4C haloalkyl group, R<SP>12</SP>S(O)<SB>n</SB>, a 2-7C alkanoyl group, a 2-7C haloalkanoyl group, or a 3-6C cycloalkyl group, or R<SP>10</SP>and R<SP>11</SP>are combined together to form a 2-6C polymethylene group). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a benzoxazole compound, a production method thereof, and use as an insecticide / acaricide.

  It is known that certain benzoxazole derivatives are effective as herbicides (see, for example, Patent Document 1). However, it has not been known so far that the benzoxazole derivatives have insecticidal / miticidal activity.

PCT International Publication WO2006 / 004215 Pamphlet

  An object of the present invention is to provide a novel benzoxazole compound useful as an insecticide / acaricide.

  The present inventors have now found that a novel benzoxazole compound represented by the following formula (1) is effective as an insecticide / acaricide, and has completed the present invention.

  Thus, the present invention provides the following formula (1):

式中、
Ｒ^１は水素原子、ハロゲン原子又は炭素数１〜４のアルキル基を表わし、
Ｒ^２及びＲ^３はそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のハロアルキル基、炭素数１〜４のアルコキシ基、炭素数１〜４のハロアルコキシ基、ニトロ基、シアノ基、ホルミル基、フェニル基、フェノキシ基、Ｒ^１2Ｓ(Ｏ)ｎ、炭素数２〜５のアルコキシカルボニル基、カルボキシル基又はＲ^１３Ｒ^１４ＮＣＯを表わし、ここで、Ｒ^１２は炭素数１〜４のアルキル基を表わし、ｎは０〜２の整数であり、Ｒ^１３及びＲ^１４はそれぞれ独立して炭素数１〜４のアルキル基を表わし、
Ｒ^４は水素原子、ハロゲン原子又は炭素数１〜４のアルキル基を表わし、
Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９はそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のハロアルキル基、炭素数１〜１０のアルコキシ基、炭素数１〜４のハロアルコキシ基、ニトロ基、シアノ基、ホルミル基、フェニル基、フェノキシ基、Ｒ^１２Ｓ(Ｏ)ｎ、Ｒ^１５Ｒ^１６Ｎ、Ｃ(Ｏ)ＸＲ^１７又はカルボキシル基を表わし、ここで、Ｒ^１５及びＲ^１６はそれぞれ独立して水素原子又は炭素数１〜４のアルキル基を表わし、Ｒ^１７は不飽和結合を含んでいてもよい炭素数１〜１０の直鎖状もしくは分枝鎖状の炭化水素基、不飽和結合を含んでいてもよい炭素数１〜１０の直鎖状もしくは分枝鎖状のハロゲン化炭化水素基、炭素数１〜４のアルコキシ−炭素数１〜４のアルキル基
又は炭素数３〜６のシクロアルキル基を表わし、Ｘは酸素原子又は硫黄原子を表わすか、或いはＲ^５及びＲ^６又はＲ^６及びＲ^７は一緒になって、それぞれ炭素数１〜４のポリメチレンジオキシ基を表わし、
Ｒ^１０及びＲ^１１はそれぞれ独立して水素原子、不飽和結合を含んでいてもよい炭素数１〜４の直鎖状もしくは分枝鎖状の炭化水素基、炭素数１〜４のハロアルキル基、Ｒ^１２Ｓ(Ｏ)ｎ、炭素数２〜７のアルカノイル基、炭素数２〜７のハロアルカノイル基又は炭素数３〜６のシクロアルキル基を表わすか、或いはＲ^１０及びＲ^１１は一緒になって炭素数２〜６のポリメチレン基を表わす、
で示されるベンゾオキサゾール化合物を提供するものである。

Where
R ¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms,
R ² and R ³ are each independently 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, or a halo having 1 to 4 carbon atoms. Represents an alkoxy group, a nitro group, a cyano group, a formyl group, a phenyl group, a phenoxy group, R ¹² S (O) n, an alkoxycarbonyl group having 2 to 5 carbon atoms, a carboxyl group or R ¹³ R ¹⁴ NCO, wherein R ¹² represents an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 2, R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 4 carbon atoms,
R ⁴ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms,
R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or an alkoxy having 1 to 10 carbon atoms. Group, C 1-4 haloalkoxy group, nitro group, cyano group, formyl group, phenyl group, phenoxy group, R ¹² S (O) n, R ¹⁵ R ¹⁶ N, C (O) XR ¹⁷ or carboxyl group Wherein R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁷ is a straight chain having 1 to 10 carbon atoms which may contain an unsaturated bond. Or a branched hydrocarbon group, a linear or branched halogenated hydrocarbon group having 1 to 10 carbon atoms which may contain an unsaturated bond, or an alkoxy-carbon having 1 to 4 carbon atoms An alkyl group having 1 to 4 carbon atoms or 3 to 6 carbon atoms Represents a cycloalkyl group, X represents an oxygen atom or a sulfur atom, or R ⁵ and R ⁶ or R ⁶ and R ⁷ together represent a C 1-4 polymethylenedioxy group,
R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms which may contain an unsaturated bond, a haloalkyl group having 1 to 4 carbon atoms, R ¹² S (O) n represents an alkanoyl group having 2 to 7 carbon atoms, a haloalkanoyl group having 2 to 7 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, or R ¹⁰ and R ¹¹ are combined together. Represents a polymethylene group having 2 to 6 carbon atoms,
The benzoxazole compound shown by these is provided.

  The benzoxazole compound represented by the above formula (1) of the present invention has excellent insecticidal / miticidal activity and is useful as an insecticidal / miticidal agent.

Hereinafter, the present invention will be described in more detail.
In the present specification, for example, in the case of the compound of the above formula (1), the compound represented by the chemical formula is indicated as “compound (1)” by the number of the chemical formula.

In this specification,
“Halogen atom” includes fluorine atom, chlorine atom, bromine atom and iodine atom.
An “alkyl group” can be linear or branched, such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, Examples include n-hexyl, n-octyl, 2-ethylhexyl, and n-decyl group.
A “haloalkyl group” is a group in which at least one hydrogen atom of an alkyl group is substituted with a halogen atom. For example, chloromethyl, dichloromethyl, trifluoromethyl, chloroethyl, dichloroethyl, trifluoroethyl, tetrafluoropropyl , Bromoethyl, bromopropyl, chlorobutyl, chlorohexyl, perfluorohexyl groups and the like.
An “alkoxy group” is an alkyl-O— group in which the alkyl moiety has the above-mentioned meaning, such as a methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sec- or tert-butoxy group. Can be mentioned.
The “haloalkoxy group” is a haloalkyl-O— group in which the haloalkyl moiety has the above-mentioned meaning, and examples thereof include a trifluoromethoxy group, a trifluoroethoxy group, a tetrafluoropropoxy group, and a perfluorohexyloxy group.
The “alkoxycarbonyl group” is an alkoxy-CO— group in which an alkoxy moiety has the above meaning, and examples thereof include a methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl group and the like.
“Cycloalkyl group” includes cyclopropyl, cyclopentyl, cyclohexyl group and the like.
The “alkanoyl group” is an alkyl-CO— group in which the alkyl moiety has the above-mentioned meaning, and examples thereof include acetyl, propionyl, butyryl, iso-butyryl, valeryl, iso-valeryl, pivaloyl group and the like.
The “haloalkanoyl group” is a group in which at least one hydrogen atom of an alkanoyl group is substituted with a halogen atom, such as a chloroacetyl, trifluoroacetyl, chloropropionyl, bromopropionyl, chlorohexanoyl, chloroheptanoyl group Etc.
Examples of the “polymethylene group” include —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — and the like.
"Poly methylenedioxy group" is a polymethylene moiety is -O- polymethylene -O- group having the meaning given above, for _{example, -OCH 2 O -, - OCH} 2 CH 2 O- and the like.

In the formula (1), preferably,
R ¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms,
R ² and R ³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halo having 1 to 3 carbon atoms. Represents an alkoxy group, a nitro group, a cyano group, a formyl group, a phenyl group, a phenoxy group, R ¹² S (O) n or an alkoxycarbonyl group having 2 to 4 carbon atoms, wherein R ¹² is a group having 1 to 3 carbon atoms. Represents an alkyl group, n is an integer of 0-2,
R ⁴ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms,
R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or an alkoxy having 1 to 8 carbon atoms. Group, haloalkoxy group having 1 to 3 carbon atoms, nitro group, cyano group, formyl group, phenyl group, phenoxy group, R ¹² S (O) n, R ¹⁵ R ¹⁶ N, C (O) XR ¹⁷ or carboxyl group Wherein R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁷ is a straight chain having 1 to 10 carbon atoms that may contain an unsaturated bond. Or a branched hydrocarbon group, a linear or branched halogenated hydrocarbon group having 1 to 10 carbon atoms which may contain an unsaturated bond, or an alkoxy-carbon having 1 to 4 carbon atoms An alkyl group or a cyclohexyl group of formulas 1 to 4 X represents an oxygen atom or a sulfur atom, or R ⁵ and R ⁶ or R ⁶ and R ⁷ together represent a polymethylenedioxy group having 1 to 3 carbon atoms,
R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms which may contain an unsaturated bond, a haloalkyl group having 1 to 3 carbon atoms, R ¹² S (O) n represents an alkanoyl group having 2 to 5 carbon atoms, a haloalkanoyl group having 2 to 5 carbon atoms or a cyclohexyl group, or R ¹⁰ and R ¹¹ together represent 2 to 6 carbon atoms. Represents a polymethylene group.

Particularly preferably,
R ¹ represents a hydrogen atom, a fluorine atom or a chlorine atom,
R ² and R ³ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a trifluoromethoxy group, a nitro group or a cyano group,
R ⁴ represents a hydrogen atom, a fluorine atom or a chlorine atom,
R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. , pentyloxy group, hexyloxy group, heptyloxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, or a nitro group, a cyano group, a methylthio group, an ethylthio group or a C (O) ^{XR 17,} Here, R ¹⁷ is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, sec-pentyl. Group, neo-pentyl group, n-hexyl group, neo-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, ant Group, 2-propynyl group, 2-butenyl group, 3-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 4-methyl-2-pentenyl group, 4-methyl-3- A pentenyl group, a 3-chloro-n-propyl group, a 4-chloro-n-butyl group, a methoxyethyl group, an ethoxymethyl group, or a cyclohexyl group, X represents an oxygen atom or a sulfur atom,
R ¹⁰ and R ¹¹ each independently represents a hydrogen atom, methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group, allyl group or 2-propynyl group.

  Among the compounds (1), the following compounds are particularly preferable from the viewpoint of insecticidal / miticidal activity.

(I) R ¹ , R ² and R ^{4 to} R ⁹ are each a hydrogen atom, R ³ represents a haloalkyl group having 1 to 4 carbon atoms, and R ¹⁰ and R ¹¹ are each independently 1 to 1 carbon atoms. A compound of the formula (1) representing an alkyl group of 4. For example, compounds 68, 69, 70 described in Table 1 below.

(Ii) R ¹ , R ² , R ⁴ , R ⁵ , R ⁸ and R ⁹ are each a hydrogen atom, R ³ represents a haloalkyl group having 1 to 4 carbon atoms, and R ⁶ and / or R ⁷ are halogen. The compound of formula (1), which represents an atom, and R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 4 carbon atoms. For example, compounds 82, 83, 85 described in Table 1 below.

(Iii) R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ and R ⁹ are each a hydrogen atom, R ³ represents a haloalkyl group having 1 to 4 carbon atoms, and R ⁶ and R ⁸ are each independently And a compound of formula (1) wherein R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 4 carbon atoms. For example, compounds 88 and 94 described in Table 1 below.

(Iv) R ¹ , R ² , R ⁴ , R ⁵ , R ⁸ and R ⁹ are each a hydrogen atom, R ³ represents a haloalkyl group having 1 to 4 carbon atoms, and R ⁶ or R ⁷ is 1 carbon atom. The compound of the above formula (1), which represents a haloalkyl group of ˜4, and R ¹⁰ and R ¹¹ each independently represents an alkyl group of 1 to 4 carbon atoms. For example, compounds 150, 151, and 153 described in Table 1 below.

(V) R ¹ , R ² , R ⁴ , R ⁵ , R ⁸ and R ⁹ are each a hydrogen atom, R ³ represents a haloalkyl group having 1 to 4 carbon atoms, and R ⁶ or R ⁷ is 1 carbon atom. The compound of the above formula (1), which represents an alkoxy group of ˜4, and R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 4 carbon atoms. For example, compounds 115, 116, 117 described in Table 1 below.

(Vi) R ¹ , R ² , R ⁴ , R ⁵ , R ⁸ and R ⁹ are each a hydrogen atom, R ³ represents a haloalkyl group having 1 to 4 carbon atoms, and R ⁶ or R ⁷ is 1 carbon atom. The compound of the above formula (1), which represents a haloalkoxy group having ˜4 and R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 4 carbon atoms. For example, compounds 136, 137, and 138 described in Table 1 below.

(Vii) R ¹ , R ² , R ⁴ , R ⁵ , R ⁸ and R ⁹ are each a hydrogen atom, R ³ represents a haloalkyl group having 1 to 4 carbon atoms, and R ⁶ or R ⁷ is 1 carbon atom. A compound of the above formula (1) which represents an alkylthio group of ˜4, and R ¹⁰ and R ¹¹ each independently represents an alkyl group of 1 to 4 carbon atoms. For example, compounds 127 and 128 described in Table 1 below.

(Viii) R ¹ , R ² , R ⁴ , R ⁵ , R ⁸ and R ⁹ are each a hydrogen atom, R ³ represents a haloalkyl group having 1 to 4 carbon atoms, and R ⁶ and / or R ⁷ is C (O) XR ¹⁵ , wherein R ¹⁵ may contain an unsaturated bond, a linear or branched hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 4 carbon atoms The compound of the above formula (1), which represents an alkyl group having 1 to 4 carbon atoms, X represents an oxygen atom or a sulfur atom, and R ¹⁰ or R ¹¹ represents an alkyl group having 1 to 4 carbon atoms. For example, compounds 171, 172, 174 described in Table 1 below.

(Ix) R ¹ , R ² , R ⁴ , R ⁵ , R ⁸ and R ⁹ are each a hydrogen atom, R ³ represents a haloalkyl group having 1 to 4 carbon atoms, and R ⁶ or R ⁷ represents a cyano group. And the compound of formula (1), wherein R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 4 carbon atoms. For example, compounds 167 and 168 described in Table 1 below.

(X) R ¹ , R ² , R ⁴ , R ⁵ , R ⁸ and R ⁹ are each a hydrogen atom, R ³ represents a haloalkyl group having 1 to 4 carbon atoms, and R ⁶ or R ⁷ represents a nitro group. And the compound of formula (1), wherein R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 4 carbon atoms. For example, compounds 142 and 143 described in Table 1 below.

(Xi) R ¹ , R ² , R ⁴ , R ⁵ , R ⁸ and R ⁹ are each a hydrogen atom, R ³ represents a haloalkyl group having 1 to 4 carbon atoms, and R ⁶ and / or R ⁸ is a halogen atom. The compound of formula (1), which represents an atom, R ⁷ represents an alkoxy group having 1 to 4 carbon atoms, and R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 4 carbon atoms. For example, compounds 104, 105, 108 described in Table 1 below.

(Xii) R ¹ , R ² , R ⁴ , R ⁵ and R ^{7 to} R ⁹ are each a hydrogen atom, R ³ represents a haloalkyl group having 1 to 4 carbon atoms, R ⁶ represents a halogen atom, R ⁷ represents C (O) XR ¹⁵ , wherein R ¹⁵ is a linear or branched hydrocarbon group having 1 to 10 carbon atoms which may contain an unsaturated bond, or 1 to 4 carbon atoms. A compound of formula (1) wherein X represents an alkyl group having 1 to 4 carbon atoms, X represents an oxygen atom or a sulfur atom, and R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 4 carbon atoms . For example, compounds 195, 196, and 197 described in Table 1 below.

(Xiii) R ¹ , R ² , R ⁴ , R ⁵ and R ^{7 to} R ⁹ are each a hydrogen atom, R ³ represents a haloalkyl group having 1 to 4 carbon atoms, and R ⁶ has 1 to 4 carbon atoms. Represents an alkoxy group, R ⁷ represents C (O) XR ¹⁵ , wherein R ¹⁵ may have an unsaturated bond, and the C 1-10 linear or branched hydrocarbon group Or an alkoxy group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms, X represents an oxygen atom or a sulfur atom, and R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 4 carbon atoms. Compound of formula (1). For example, compounds 199, 200, 201 described in Table 1 below.

  The compound (1) provided by the present invention can be produced, for example, by the production method described below.

式中、Ｒ^１〜Ｒ^４は前記と同義であり、Ｙはハロゲン原子を表わす、
で示される化合物を次式（３）：

式中、Ｒ^１０及びＲ^１１は前記と同義である、
で示される化合物と塩基触媒の存在下に反応させることを特徴とする次式（１）：

式中、Ｒ^１〜Ｒ^１１は前記と同義である、
で示される化合物の製造法。 Manufacturing method:
Formula (2):

In the formula, R ^{1 to} R ⁴ are as defined above, and Y represents a halogen atom.
A compound represented by the following formula (3):

^{Wherein, R 10} and ^{R 11} are as defined above,
The compound represented by formula (1) is reacted in the presence of a base catalyst:

In the formula, R ^{1 to} R ¹¹ are as defined above.
The manufacturing method of the compound shown by these.

  The compound (2) used as a starting material in the above production method is known per se and / or can be produced by a known method (see PCT International Publication No. WO2006 / 004215). Examples of the compound (2) include (E) -2- (5-trifluorobenzoxazol-2-yl) -1- (3-chloromethylphenyl) -3-bromopropene, (E) -2- ( And 5-trifluoromethylbenzoxazol-2-yl) -1- (3-trifluorophenyl) -3-bromopropene.

  Compound (3) to be reacted with compound (2) is known per se and / or can be prepared by known methods (see, for example, Org. Syn. Coll. Vol. 5, 736). . Examples of compound (3) include amines such as monomethylamine, monoethylamine, dimethylamine, diethylamine, methylethylamine, methylallylamine, methylpropargylamine, pyrrolidine, and piperidine.

  Examples of the base catalyst that can be used in the reaction of the compound (2) and the compound (3) include triethylamine, pyridine, 4-N, N-dimethylaminopyridine, N, N-dimethylaniline, and 1,4-diazabicyclo. [2.2.2] Organic bases such as octane and 1,8-diazabicyclo [5.4.0] undec-7-ene; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide Inorganic bases such as sodium hydride, potassium hydride, sodium amide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate; organic metals such as lithium diisopropylamide, bistrimethylsilyl lithium amide Examples include amides. These base catalysts can be generally used in the range of 0.001 to 1 mole relative to the compound (2).

  The ratio of the compound (3) to the compound (2) is not particularly limited, and the compound (3) is generally in the range of 1 to 6 mol, particularly 1 to 3 mol, relative to 1 mol of the compound (2). Are preferably used.

  The reaction temperature can be changed according to the type of starting material used, the type of catalyst, etc., but is usually set to a temperature not higher than the boiling point of the solvent used, preferably within the range of 0 to 110 ° C. it can.

  The reaction of the compound (2) and the compound (3) can be usually performed in the presence of a solvent inert to the reaction. Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran and dioxane; N, Dipolar aprotic solvents such as N-dimethylformamide and dimethyl sulfoxide; Aromatic hydrocarbons such as benzene, toluene and xylene; Nitriles such as acetonitrile; Ketones such as acetone and methyl ethyl ketone; Mixed solvents thereof It is done.

  The reaction time varies depending on the type of starting material and reaction conditions, but can usually be about 0.5 to 24 hours.

The compound (1) obtained by the above production method can be isolated and purified by a method known per se, for example, by means of recrystallization, chromatography, distillation or the like.
The compound of the formula (1) provided by the present invention has excellent insecticidal / miticidal activity, as is apparent from the results of the insecticidal activity test described in Test Examples 1 to 4 described later, Useful as a pest control agent in the composition.

  The compound (1) of the present invention is useful for various pests parasitic on useful plants, specifically vegetables, fruit trees, flowering plants, garden trees, etc., particularly insects and mites, such as peach aphids, cotton aphids, Aphids such as larval aphids, apple cotton aphids, nasimidori aphids, peach beetles; , Chahamaki, Chonokokakumonhamaki, Kinmonhosoga, Peach-winged moth, Citrus-winged moth, Nasihime-sinkui, Lepidoptera, Nika-meiga, Akanomeiga, etc .; Exhibit outstanding insecticidal and acaricidal effect against spider mites such as two. In addition, the pest control agent of the present invention does not exhibit phytotoxicity that causes problems for useful plants.

  The compound (1) of the present invention can be formulated into various dosage forms when used as a pest control agent, particularly an insecticide / acaricide, such as powders, granules, wettable powders, emulsions, It can be formulated into dosage forms such as flowables, microcapsules, aerosols, fumigants, smokers, poison baits. Such a preparation is usually prepared by mixing the compound (1) with a solid or liquid carrier or diluent, a surfactant, and other auxiliary agents for formulation, and formulating it into a desired dosage form according to a conventional method. can do.

  Examples of solid carriers or diluents that can be used include plant powders such as soybean flour and wheat flour; mineral fine powders such as diatomaceous earth, talc, bentonite, and clay, and liquid carriers or diluents include For example, xylene, toluene, benzene, cyclohexane, acetone, alcohol, mineral oil, petroleum, water and the like can be mentioned. Examples of the surfactant that can be blended as necessary include nonionic polyoxyalkylene alkyl ether, polyoxyalkylene allyl ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester; anionic type Examples thereof include alkyl allyl sulfate ester salts, polyoxyalkylene alkyl allyl sulfate ester salts, and mixtures thereof.

  The compound (1) of the present invention is prepared by using the above-described ingredients and according to a known agricultural chemical formulation method, wettable powder, granule, powder, emulsion, flowable, microcapsule, aerosol, fumigation. It can be formulated into a dosage form such as an agent, smoke agent, poison bait.

The compounding ratio of compound (1) in these preparations can be varied over a wide range depending on the type and dosage form of compound (1), but generally within the range of 0.01 to 80% by weight. More specifically, depending on the individual dosage form, for example, in the case of emulsions, wettable powders and flowables, the compound (1) is usually 0.01 to 50% by weight, preferably Can be contained at a concentration in the range of 0.1 to 20% by weight, and in the case of powders and granules, the compound (1) is usually 0.01 to 20% by weight, preferably 0.8. It can be included at a concentration in the range of 1-10% by weight. The wettable powder, emulsion and flowable can be sprayed as a suspension or emulsion by diluting with water to a predetermined concentration, and the powder and granules can be sprayed as they are. In addition, the insecticide / acaricide of the present invention may be mixed or used in combination with other agricultural chemicals, for example, insecticides, acaricides, fungicides, plant growth regulators and the like.

  The preparation containing the compound (1) of the present invention is applied to an insect, a tick adult, a larva or an egg harmful to agricultural and horticultural crops, or by spraying to a place where the adult, larva or egg lives, And / or can be used to control ticks. The amount of compound (1) applied at that time can be appropriately changed according to the type of active compound, dosage form, occurrence of pests, etc., and is generally 1 to 10,000 g, preferably 10 to 1 per hectare. More specifically, for example, in the case of the aforementioned emulsion, wettable powder and flowable agent, they are usually diluted 1,000 to 10,000 times, It can be sprayed at a rate of 1,000 to 10,000 l per hectare, and in the case of powders and granules, it is usually appropriate to spray these at a rate of 2 to 40 kg per hectare. is there.

  Hereinafter, the present invention will be described more specifically with reference to examples. These examples are not intended to limit the scope of the present invention.

Example 1 Synthesis of (E) -2- (5-trifluoromethylbenzoxazol-2-yl) -3-phenylprop-2-enyl) tert-butylamine (Compound 72):
(E) -2- (5-trifluorobenzooxazol-2-yl) -1-phenyl-3-bromopropene (2.0 g, 5.2 mmol) and tert-butylamine (1.5 g, 20.9 mmol) in THF (5 ml) The mixture was further stirred at room temperature for 2 hours. 25 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Ethyl acetate was distilled off under reduced pressure, and the resulting residue was isolated by column chromatography (Wakogel C-300, manufactured by Wako Pure Chemical Industries, eluting with n-hexane: ethyl acetate = 10: 1) to give the target compound 72 as white crystals. 0.8 g was obtained (yield 41.1%).

Example 2 Synthesis of (E) -2- (5-trifluoromethylbenzoxazol-2-yl) -3-phenylprop-2-enyl) n-butylmethylamine (Compound 75):
(E) -2- (5-trifluorobenzooxazol-2-yl) -1-phenyl-3-bromopropene 1.0 g (2.6 mmol) and N-methyl-n-butylamine 0.7 g (7.9 mmol) ) Was added to 5 ml of THF and stirred at room temperature for 2 hours. 25 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Ethyl acetate was distilled off under reduced pressure, and the resulting residue was isolated by column chromatography (Wakogel C-300, manufactured by Wako Pure Chemical Industries, eluting with n-hexane: ethyl acetate = 10: 1) to give the target compound 75 as white crystals. 0.7 g was obtained (yield 73.3%).

Example 3 Synthesis of (E) -2- (5-trifluoromethylbenzoxazol-2-yl) -3- (3,4-dichlorophenyl) prop-2-enyl) dimethylamine (Compound 85):
(E) -2- (5-trifluoromethylbenzoxazol-2-yl) -1- (3,4-dichlorophenyl) -3-bromopropene (9.9 g, 22 mmol) and 50% aqueous dimethylamine solution (5.9 g) 66 mmol) was added to 25 ml of THF and stirred at room temperature for 2 hours. 100 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Ethyl acetate was distilled off under reduced pressure, and the resulting residue was isolated by column chromatography (Wakogel C-300, manufactured by Wako Pure Chemical Industries, eluting with n-hexane: ethyl acetate = 9: 1) to give the target compound 85 as white crystals. 5.5 g was obtained (yield 60.1%).

Example 4 (E) -2- (5-trifluoromethylbenzoxazol-2-yl) -3
Synthesis of-(3-fluorophenyl) prop-2-enyl) dimethylamine (Compound 89):
(E) -2- (5-trifluorobenzooxazol-2-yl) -1- (3-fluorophenyl) -3-bromopropene 26.2 g (65.4 mmol) and 17.7 g of 50% aqueous dimethylamine solution ( 196.4 mmol) was added to 70 ml of THF, and the mixture was stirred at room temperature for 2 hours. 150 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Ethyl acetate was distilled off under reduced pressure, and the resulting residue was isolated by column chromatography (Wakogel C-300, manufactured by Wako Pure Chemical Industries, eluting with n-hexane: ethyl acetate = 9: 1) to give the target compound 89 as white crystals. 10.5 g was obtained (yield 44.1%).

Example 5 Synthesis of n-butyl 4-((E) -2- (5-trifluoromethylbenzoxazol-2-yl) -3- (dimethylamino) prop-1-enyl) benzoate (Compound 184):
n-Butyl 4-((E) -2- (5-trifluoromethylbenzoxazol-2-yl) -3-bromoprop-1-enyl) benzoate 2.0 g (4.2 mmol) and 50% aqueous dimethylamine 1 0.1 g (12.6 mmol) was added to 5 ml of THF, and the mixture was stirred at room temperature for 2 hours. 25 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Ethyl acetate was distilled off under reduced pressure, and the resulting residue was isolated by column chromatography (Wakogel C-300, manufactured by Wako Pure Chemical Industries, eluting with n-hexane: ethyl acetate = 10: 1) to give the target compound 184 as white crystals. 0.6 g was obtained (yield 32.0%).

  According to the method described in Examples 1 to 5, another compound (1) of the present invention shown in Table 1 below was synthesized. The synthesized compound (1) including the compounds synthesized in Examples 1 to 5 is shown in Table 1. Table 2 shows the physical properties of representative ones of these compounds.

Formulation Example 1: Emulsion Compound (1) 10 parts by weight, polyoxyethylene nonylphenyl ether 12 parts by weight and xylol 78 parts by weight are uniformly mixed to obtain an emulsion.

Formulation example 2: wettable powder Compound (1) 10 parts by weight, sodium dodecylbenzenesulfonate 5 parts by weight, polyoxyethylene nonylphenyl ether 3 parts by weight, clay 30 parts by weight and diatomaceous earth 52 parts by weight were mixed and pulverized uniformly. Get wettable powder.

Formulation Example 3: Flowable Agent 5 parts by weight of polyoxyethylene styryl phenyl ether sulfate salt, 3 parts by weight of smectite mineral and 62 parts by weight of water were uniformly dissolved, and then 10 parts by weight of Compound (1) was added and stirred well. Thereafter, wet milling is performed in a sand mill, and then 20 parts by weight of a 1% xanthan gum aqueous solution is added and stirred well to obtain a flowable agent.

Test Example 1 Insecticidal test for diamondback radish leaf pieces (5 × 7 cm) cut to a certain size are immersed in a 100 ppm chemical solution (the emulsion of Formulation Example 1 is diluted with water) for about 10 seconds, air-dried, and then a plastic petri dish having a diameter of 9 cm Along with 15 first-instar larvae of the moth, placed in a thermostatic chamber at 25 ° C., 3 days later, the number of survivors in the untreated group and the treated group was investigated, and the corrected mortality rate was determined by the following formula. The test was conducted in 1 district and 2 continuous systems.

Corrected death rate (%) = (Non-treated group survival rate-treated group survival rate) / (Non-treated group survival rate) × 100

The insecticidal effect was evaluated according to the following 6 levels according to the ratio of the corrected death rate (%).
0: 0% to less than 10%,
1: 10% to less than 35%,
2: 35% to less than 60%,
3: 60% to less than 85%,
4: 85% to less than 100%,
5: 100%.

  As a result of the above test, compounds showing an insecticidal effect of 4 or more are 14, 15, 20, 21, 24, 27, 37, 38, 41, 47-50, 68-70, 72, 75, 81, 82, 83-85, 88-98, 106, 107, 110, 114-118, 124-128, 136, 137, 142, 143, 149-153, 156, 158, 160, 161, 163, 167, 168, 177- 190, 195, 197, 200, 203-222.

Test Example 2 Insecticidal test against Spodoptera litura A radish leaf piece (5 × 7 cm) cut to a certain size is immersed in a 100 ppm chemical solution (the emulsion of Formulation Example 1 is diluted with water) for about 10 seconds, air-dried, and a plastic petri dish having a diameter of 9 cm The sample was placed together with 15 first-instar larvae of Spodoptera litura and placed at a constant temperature of 25 ° C. After 3 days, the corrected mortality was determined in the same manner as in Test Example 1 to evaluate the insecticidal effect. The test was conducted in 1 district and 2 continuous systems.
As a result of the above test, compounds showing 4 or more activities are 83 to 85, 89 to 98, 136, 137, 139, 140, 150, 152, 153, 158, 161, 164, 167, 168, 177 to 180. 182, 184-190, 203-222.

Test Example 3 Insecticidal test against peach aphid Infested radish leaves (diameter 40 mm), infested with 5 adult mosquito aphids infertile females per leaf piece and removed adults after 24 hours of litter Then, it was immersed for about 10 seconds in 100 ppm of a drug (the emulsion of Formulation Example 1 was diluted with water). The treated leaves were placed in a thermostatic chamber at 25 ° C., and after 48 hours, the corrected mortality was determined in the same manner as in Test Example 1 to evaluate the insecticidal effect. The test was conducted in 1 district and 2 continuous systems.
As a result of the above test, compounds showing 4 or more activities are 68-70, 75, 81, 83-85, 89-96, 115, 124, 149, 150, 167, 177, 182-187, 195, 197. 203-222.

Test example 4: Spider mite killing test Put water into a foamed styrene container (diameter 9 cm), make a hole in a part of the lid, insert a piece of filter paper that has been cut into a strip, and the entire filter paper absorbs water Then, it was moistened, and green beans were placed on it. The leaves were immersed for about 10 seconds in 500 ppm of a drug (the emulsion of Formulation Example 1 was diluted with water). After air-drying, the leaves were inoculated with 15 adult female spider mites and left in a thermostatic chamber (25 ° C.). After 48 hours, they were examined under a microscope, and the corrected mortality was determined in the same manner as in Test Example 1 to determine the insecticide. The effect was evaluated. The test was conducted in 1 district and 2 continuous systems.
As a result of the above test, 72, 228 to 240 were compounds showing 4 or more activities.

Claims (4)

The following formula (1):

Where
R ¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms,
R ² and R ³ are each independently 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, or a halo having 1 to 4 carbon atoms. Represents an alkoxy group, a nitro group, a cyano group, a formyl group, a phenyl group, a phenoxy group, R ¹² S (O) n, an alkoxycarbonyl group having 2 to 5 carbon atoms, a carboxyl group or R ¹³ R ¹⁴ NCO, wherein R ¹² represents an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 2, R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 4 carbon atoms,
R ⁴ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms,
R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or an alkoxy having 1 to 10 carbon atoms. Group, C 1-4 haloalkoxy group, nitro group, cyano group, formyl group, phenyl group, phenoxy group, R ¹² S (O) n, R ¹⁵ R ¹⁶ N, C (O) XR ¹⁷ or carboxyl group Wherein R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁷ is a straight chain having 1 to 10 carbon atoms which may contain an unsaturated bond. Or a branched hydrocarbon group, a linear or branched halogenated hydrocarbon group having 1 to 10 carbon atoms which may contain an unsaturated bond, or an alkoxy-carbon having 1 to 4 carbon atoms An alkyl group having 1 to 4 carbon atoms or 3 to 6 carbon atoms Represents a cycloalkyl group, X represents an oxygen atom or a sulfur atom, or R ⁵ and R ⁶ or R ⁶ and R ⁷ together represent a C 1-4 polymethylenedioxy group,
R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms which may contain an unsaturated bond, a haloalkyl group having 1 to 4 carbon atoms, R ¹² S (O) n represents an alkanoyl group having 2 to 7 carbon atoms, a haloalkanoyl group having 2 to 7 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, or R ¹⁰ and R ¹¹ are combined together. Represents a polymethylene group having 2 to 6 carbon atoms,
A benzoxazole compound represented by: Formula (2):

In the formula, R ^{1 to} R ⁹ are as defined in claim 1, Y represents a halogen atom,
A compound represented by the following formula (3):

Wherein R ¹⁰ and R ¹¹ are as defined in claim 1.
The compound represented by the following formula (1) is reacted in the presence of a base catalyst:

Wherein R ^{1 to} R ¹¹ are as defined in claim 1.
The manufacturing method of the compound shown by these.   An insecticide / acaricide containing the compound represented by formula (1) according to claim 1 as an active ingredient.   The agrochemical composition containing the compound shown by Formula (1) of Claim 1.