JP2013112618A - 1,5-naphthyridine derivative, and insecticide containing the same as active ingredient - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound having excellent agricultural/horticultural pest control power.SOLUTION: This naphthyridine compound is represented by formula (III). [In the formula, Rrepresents an alkyl group, a cyclic alkyl group or an alkyloxy group; Xand Xeach represents a hydrogen atom or an alkyl group, or represent an alkylene group as one; Xand Xeach represents a hydrogen atom, a halogen atom, an alkyl group or an alkyloxy group; Yto Yeach represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkyloxy group, an alkylthio group or an alkylenedioxy group; and Zrepresents a halogen atom].

Description

 The present invention relates to a 1,5-naphthyridine derivative, a production method thereof, and an agricultural and horticultural insecticide comprising the same as an active ingredient.

  Searches for new compounds relating to agricultural and horticultural insecticides and development of new insecticides containing them as active ingredients have been actively pursued. However, when these new insecticides are used, there are problems such as expression of low-sensitivity insect species and presence of difficult-to-control insect species. For this reason, continuous development of agricultural and horticultural insecticides with a novel chemical structure having excellent insecticidal activity is still desired. 1,5-naphthyridine derivatives are useful as pharmaceuticals and intermediates thereof, and many compounds are known. For example, Patent Documents 1 to 6 disclose 4,6-disubstituted-1,5-naphthyridine derivatives as antibiotics or antibacterial active substances. In these patent documents, the substituent at the 4-position is an alkyl, alkenyl group, amide group or ketone group, and the substituent at the 6-position is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a cyano group. is there. In addition, there is no description on the presence or absence of insecticidal activity of these derivatives. Furthermore, the compounds described in these patent documents do not describe a 6-aryloxy-1,5-naphthyridine derivative in which the substituent at the 6-position is substituted phenyloxy.

International Publication No. WO2009 / 077989 International publication WO2009 / 034546 International Publication WO 2008/026172 International Publication WO 2008/126034 International Publication WO2007 / 105154 International Publication WO2006 / 081289

  In recent years, development of a novel agricultural and horticultural insecticide having excellent insecticidal activity has been desired due to problems such as the presence of low-sensitive insect species and difficult-to-control insect species. Therefore, an object of the present invention is to provide a novel 1,5-naphthyridine derivative having an excellent pest control effect.

  As a result of intensive studies to solve the above problems, the present inventors have found that a novel 1,5-naphthyridine derivative represented by the following general formula (I) has a remarkable insecticidal activity, and completes the present invention. It came to.

［式中、Ｒは水素原子、または−ＣＯＲ_１を表し、
ここでＲ_１は、Ｃ１−４のアルキル基（ここで前記Ｃ１−４アルキル基は、同一または異なる一以上のハロゲン原子及び／または同一または異なる一以上のハロゲン原子により置換されていてもよいＣ１−４アルキルオキシ基により置換されていてもよく）、
Ｃ３−６の環状アルキル基（ここで前記Ｃ３−６環状アルキル基は、同一または異なる一以上のハロゲン原子及び／または同一または異なる一以上のハロゲン原子により置換されていてもよいＣ１−４アルキルオキシ基により置換されていてもよく）、
Ｃ１−４のアルキルオキシ基（ここで前記Ｃ１−４アルキルオキシ基は、同一または異なる一以上のハロゲン原子及び／または同一または異なる一以上のハロゲン原子により置換されていてもよいＣ１−４アルキルオキシ基により置換されていてもよく）を表わし、
Ｘ_１およびＸ_２は、互いに独立して、
水素原子、
Ｃ１−４のアルキル基（ここで前記Ｃ１−４アルキル基は、同一または異なる一以上のハロゲン原子及び／または同一または異なる一以上のハロゲン原子により置換されていてもよいＣ１−４アルキルオキシ基により置換されていてもよく）を表わし、
若しくは、Ｘ_１とＸ_２は一緒になって−（ＣＨ_２）ｍ−基（ここで前記−（ＣＨ_２）ｍ−基は、同一または異なる一以上のハロゲン原子及び／または同一または異なる一以上のハロゲン原子により置換されていてもよいＣ１−４アルキルオキシ基により置換されていてもよく、ｍは３または４である）を表わし、
Ｘ_３およびＸ_４は、互いに独立して、
水素原子、ハロゲン原子、
Ｃ１−４のアルキル基（ここで前記Ｃ１−４アルキル基は、同一または異なる一以上のハロゲン原子及び／または同一または異なる一以上のハロゲン原子により置換されていてもよいＣ１−４アルキルオキシ基により置換されていてもよく）、
Ｃ１−４アルキルオキシ基（ここで前記Ｃ１−４アルキルオキシ基は、同一または異なる一以上のハロゲン原子及び／または同一または異なる一以上のハロゲン原子により置換されていてもよいＣ１−４アルキルオキシ基により置換されていてもよく）を表わし、
Ｙ_１、Ｙ_２、Ｙ_３、Ｙ_４およびＹ_５は、互いに独立して、
水素原子、ハロゲン原子、シアノ基、
Ｃ１−４のアルキル基（ここで前記Ｃ１−４アルキル基は、同一または異なる一以上のハロゲン原子及び／または同一または異なる一以上のハロゲン原子により置換されていてもよいＣ１−４アルキルオキシ基により置換されていてもよく）、
Ｃ１−４アルキルオキシ基（ここで前記Ｃ１−４アルキルオキシ基は、同一または異なる一以上のハロゲン原子、及び／または同一または異なる一以上のハロゲン原子により置換されていてもよいＣ１−４アルキルオキシ基により置換されていてもよく）、
Ｃ1−４アルキルチオ基（ここで前記Ｃ１−４アルキルチオ基は、同一または異なる一以上のハロゲン原子及び／または同一または異なる一以上のハロゲン原子により置換されていてもよいＣ１−４アルキルオキシ基により置換されていてもよく）を表わし、
若しくはＹ_１、Ｙ_２、Ｙ_３、Ｙ_４およびＹ_５は、隣り合う２つの基が一緒になって、−Ｏ−（ＣＨ_２）ｎ−Ｏ−基（ここで前記−Ｏ−（ＣＨ_２）ｎ−Ｏ−基は同一または異なる一以上のハロゲン原子及び／または同一または異なる一以上のハロゲン原子により置換されていてもよいＣ１−４アルキルオキシ基により置換されていてもよく、ｎは１または２を表す）を表わす］で表される１，５−ナフチリジン誘導体を要旨とする。 That is, the present invention relates to the following general formula (I),

[Wherein, R represents a hydrogen atom or —COR ₁ ;
Here, R ₁ represents a C1-4 alkyl group (wherein the C1-4 alkyl group is optionally substituted by one or more halogen atoms and / or one or more halogen atoms that are the same or different. -4 alkyloxy group may be substituted),
A C3-6 cyclic alkyl group (wherein the C3-6 cyclic alkyl group is the same or different one or more halogen atoms and / or C1-4 alkyloxy optionally substituted by one or more halogen atoms) Optionally substituted by a group),
A C1-4 alkyloxy group (wherein the C1-4 alkyloxy group is the same or different one or more halogen atoms and / or the same or different one or more halogen atoms). Which may be substituted by a group)
X ₁ and X ₂ are independently of each other
Hydrogen atom,
A C1-4 alkyl group (wherein the C1-4 alkyl group is the same or different one or more halogen atoms and / or a C1-4 alkyloxy group optionally substituted by one or more halogen atoms). Which may be substituted)
Alternatively, X ₁ and X ₂ are taken together to form a — (CH ₂ ) m — group (wherein the — (CH ₂ ) m — group is the same or different one or more halogen atoms and / or the same or different one or more And optionally substituted by a C1-4 alkyloxy group which may be substituted by a halogen atom, and m is 3 or 4.
X ₃ and X ₄ are independent of each other
Hydrogen atom, halogen atom,
A C1-4 alkyl group (wherein the C1-4 alkyl group is the same or different one or more halogen atoms and / or a C1-4 alkyloxy group optionally substituted by one or more halogen atoms). May be substituted),
C1-4 alkyloxy group (wherein the C1-4 alkyloxy group is the same or different one or more halogen atoms and / or the same or different one or more halogen atoms may be substituted) Which may be substituted by
Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ are independently of each other,
Hydrogen atom, halogen atom, cyano group,
A C1-4 alkyl group (wherein the C1-4 alkyl group is the same or different one or more halogen atoms and / or a C1-4 alkyloxy group optionally substituted by one or more halogen atoms). May be substituted),
C1-4 alkyloxy group (wherein the C1-4 alkyloxy group is the same or different one or more halogen atoms, and / or C1-4 alkyloxy group optionally substituted by one or more halogen atoms) Optionally substituted by a group),
A C1-4 alkylthio group (wherein the C1-4 alkylthio group is substituted by one or more halogen atoms and / or one or more C1-4 alkyloxy groups optionally substituted by one or more halogen atoms). May be)
Alternatively, Y ₁ , Y ₂ , Y ₃ , Y _4, and Y ₅ may be a group in which two adjacent groups are combined to form an —O— (CH ₂ ) n—O— group (wherein the above —O— (CH ₂ ) The n-O- group may be substituted by one or more halogen atoms that are the same or different and / or a C1-4 alkyloxy group that may be substituted by one or more halogen atoms that are the same or different, and n is 1 Or represents 2)] is a gist.

  The 1,5-naphthyridine derivative according to the present invention exhibits an excellent control effect against agricultural and horticultural pests and is useful as an agricultural and horticultural insecticide.

Said general formula (I) provides a general definition of the compounds according to the invention. The ranges of suitable substituents mentioned in the above general formula are specifically described below.
In the present invention, the halogen atom means fluorine, chlorine, bromine or iodine.
The C1-4 alkyl group represented by R ₁ , X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ may be either linear or branched. Refers to a C1-4 alkyl group. The C1-4 alkyl group may have a substituent, and the substituent may be the same or different one or more halogen atoms, a linear or branched C1-4 alkyloxy group, the same or different one or more. And a linear or branched C1-4 alkyloxy group which may be substituted with a halogen atom.
Specific examples of the C1-4 alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, t-butyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1- or 2-chloroethyl group, 2,2,2-trifluoroethyl group, 1 , 1,2,2-tetrafluoroethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, 2-trifluoromethoxyethyl group, 1,1,1,3,3,3-hexafluoro-2- Examples include methoxy-2-propyl group, 1,1-dimethoxymethyl group, 2-methoxyethyl group, trifluoromethoxyethyl group, 2-trifluoromethoxyethyl group, and the like. It is.

The C3-6 cyclic alkyl group represented by R ₁ includes a C3-6 cyclic alkyl group having a substituent. The substituent is one or more halogen atoms that are the same or different and / or a linear or branched C1-4 alkyloxy group that may be substituted by one or more halogen atoms that are the same or different.
Specific examples of the C3-6 cyclic alkyl group represented by R ₁ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 2,2-dichlorocyclopropyl group, a pentafluorocyclohexyl group, and the like. Of these, a cyclopropyl group and a cyclohexyl group are preferable.

The alkyloxy group of C1-4 represented by R ₁ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ is a linear or branched C 1 which may have a substituent. -4 alkyloxy group. Examples of the substituent include one or more halogen atoms that are the same or different and / or a linear or branched C1-4 alkyloxy group that may be substituted with one or more halogen atoms that are the same or different.
Specific examples of the alkyloxy group of C1-4 represented by R ₁ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ include a methoxy group, an ethoxy group, and an n-propyloxy group. I-propyloxy group, n-butyloxy group, t-butyloxy group, methoxymethyloxy group, ethoxymethyloxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, difluoromethoxy group, trifluoromethoxy group, chlorodifluoro Methoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, 1,1,1,3,3,3-hexafluoro-2-propyloxy group, etc. Can be mentioned.

The C1-4 alkylthio group represented by Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ is a linear or branched C1-4 alkylthio group which may have a substituent. Examples of the substituent include one or more halogen atoms that are the same or different and / or a C1-4 alkyloxy group that may be substituted with one or more halogen atoms that are the same or different.
Specific examples of the C1-4 alkylthio group represented by Y ₁ , Y ₂ , Y ₃ , Y ₄ , and Y ₅ include a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, Methoxymethylthio group, ethoxymethylthio group, 2-methoxyethylthio group, 2-ethoxyethylthio group, difluoromethylthio group, trifluoromethylthio group, 2,2,2-trifluoroethylthio group, 1,1,2,2 -Tetrafluoroethylthio group etc. are mentioned.

X ₁ and X ₂ may be taken together to form a — (CH ₂ ) m — group. Here, X ₁ and X ₂ are a — (CH ₂ ) m— group which may have a substituent. Examples of the substituent include one or more halogen atoms which are the same or different and / or a linear or branched C1-4 alkyloxy group which may be substituted with one or more halogen atoms which are the same or different. M represents 3 or 4. That is, it may be a compound in which a saturated carbon 5-membered ring or a saturated carbon 6-membered ring is joined to a 1,5-naphthyridine ring by X ₁ and X ₂ . Preferably, X ₁ and X ₂ are taken together to form a — (CH ₂ ) ₃ — group or a — (CH ₂ ) ₄ — group.

In Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ , two adjacent groups can be taken together to form an —O— (CH ₂ ) n —O— group. This is an —O— (CH ₂ ) n—O— group which may have a substituent. Examples of the substituent include one or more halogen atoms which are the same or different and / or a linear or branched C1-4 alkyloxy group which may be substituted with one or more halogen atoms which are the same or different. N represents 1 or 2. That is, the phenyloxy group at the 6-position in the 1,5-naphthyridine compound is a methylenedioxy which may have a substituent due to two adjacent groups of Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y _5. A compound in which an ethylenedioxy ring which may have a ring or a substituent may be bonded. Preferably, in Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , two adjacent groups are combined to form an —O— (CH ₂ ) —O— group, —O— (CH ₂ ) _2. -O- group, -O- _(CF 2) -O- group, or -O- and the like it is _{(CF 2)} 2 -O- group. Particularly preferred is a —O— (CF ₂ ) ₂ —O— group.

According to a preferred embodiment of the present invention, R is a -COR ₁ group, and R ₁ is one or more halogen atoms which are the same or different and / or one or more halogen atoms which are the same or different. A C1-4 alkyl group which may be substituted by 4 alkyloxy groups, or a C1-4 alkyloxy group which may be substituted by one or more halogen atoms and / or one or more halogen atoms which are the same or different A C 1-4 alkyloxy group which may be substituted by
When R is -COR ₁ group, and R ₁ is the C1-4 alkyl group, more preferably, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group , S-butyl group, t-butyl group, trichloromethyl group, trifluoromethyl group. When the R ₁ group is the C1-4 alkyloxy group, more preferably a methoxy group, an ethoxy group, an i-propyloxy group, a t-butyloxy group, a trifluoromethoxy group, 2,2,2-trifluoro. An ethoxy group and a 1,1,2,2-tetrafluoroethoxy group.

According to another preferred embodiment of the present invention, X ₁ and X ₂ , independently of one another, are optionally substituted by one or more halogen atoms and / or one or more halogen atoms that are the same or different. A C1-4 alkyl group optionally substituted by a -4 alkyloxy group. X ₁ or X ₂ is particularly preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a trichloromethyl group, or a trifluoromethyl group, independently of each other.
In another preferred embodiment of the present invention, X ₃ and X ₄ are each independently substituted by a hydrogen atom, a halogen atom, one or more halogen atoms that are the same or different and / or one or more halogen atoms that are the same or different. A C1-4 alkyl group which may be substituted by an optionally substituted C1-4 alkyloxy group. Particularly preferably as X ₃ or X ₄ , independently of each other, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a trichloromethyl group, A trifluoromethyl group.

In still another preferred embodiment of the present invention, Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ are independently of each other a hydrogen atom, a halogen atom, one or more halogen atoms which are the same or different, and / or the same Or a C1-4 alkyl group that may be substituted by a C1-4 alkyloxy group that may be substituted by one or more different halogen atoms, or one or more halogen atoms that are the same or different, and / or one that is the same or different A C1-4 alkyloxy group which may be substituted with a C1-4 alkyloxy group which may be substituted with the above halogen atoms. Alternatively, in addition to the substituent, _two adjacent groups of Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ are combined to form an —O— (CH ₂ ) n—O— group (wherein The —O— (CH ₂ ) n—O— group is substituted by one or more halogen atoms and / or C1-4 alkyloxy groups which may be substituted by one or more halogen atoms. N may represent 1 or 2.

More preferably, at least one substituent of Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ is substituted by a halogen atom, one or more halogen atoms which are the same or different and / or one or more halogen atoms which are the same or different. A C1-4 alkyl group that may be substituted by an optionally substituted C1-4 alkyloxy group, one or more halogen atoms that are the same or different, and / or one or more halogen atoms that are the same or different A C1-4 alkyloxy group which may be substituted by a good C1-4 alkyloxy group, or C1- which may be substituted by one or more halogen atoms which are the same or different and / or one or more halogen atoms which are the same or different A C1-4 alkylthio group optionally substituted by a 4 alkyloxy group, or Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ are combined together to form an —O— (CH ₂ ) n—O— group (wherein the —O— (CH ₂ ) n—O— group). Are optionally substituted by one or more halogen atoms and / or C1-4 alkyloxy groups optionally substituted by one or more halogen atoms, and n represents 1 or 2) And the residue is a hydrogen atom.
Y ₁ , Y ₂ , Y ₃ , Y ₄ or Y ₅ is particularly preferably a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, a propyl group, an i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1- or 2- Chloroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, 2-trifluoromethoxyethyl group, 1, 1,1,3,3,3-hexafluoro-2-methoxy-2-propyl group, 1,1-dimethoxymethyl group, 2-methoxyethyl group, trifluoromethoate Siethyl group, 2-trifluoromethoxyethyl group, methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, n-butyloxy group, t-butyloxy group, methoxymethyloxy group, ethoxymethyloxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, difluoromethoxy group, trifluoromethoxy group, chlorodifluoromethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, 1,1,1,3,3,3-hexafluoro-2-propyloxy group, methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, methoxymethylthio group, ethoxymethylthio group, 2-methoxyethylthio group, 2-ethoxyethylthio group, difluoromethylthio Group, trifluoromethylthio group, 2,2,2-trifluoroethylthio group, 1,1,2,2-tetrafluoroethylthio group. Two adjacent groups are combined to form an —O—CH ₂ —O— group, an —O—CF ₂ —O— group, an —O— (CH ₂ ) ₂ —O— group, an —O— ( CF ₂ ) ₂ —O— group, —O—CH (OMe) —O— group, —O—C (OMe) ₂ —O— group, and the like.

More preferably in the present invention, Y ₁ , Y ₃ and Y ₅ are each independently replaced by a hydrogen atom, a halogen atom, one or more halogen atoms which are the same or different and / or one or more halogen atoms which are the same or different. A C1-4 alkyl group which may be substituted by an optionally substituted C1-4 alkyloxy group, or one or more halogen atoms which are the same or different and / or one or more halogen atoms which are the same or different A C1-4 alkyloxy group which may be substituted by an optionally substituted C1-4 alkyloxy group, or C1 which may be substituted by one or more halogen atoms which are the same or different and / or one or more halogen atoms which are the same or different A C1-4 alkylthio group which may be substituted by a -4 alkyloxy group, Y ₂ , Y ₄ is a hydrogen atom, and at least one of Y ₁ , Y ₃ , and Y ₅ is the halogen atom, the C1-4 alkyl group, the C1-4 alkyloxy group, or the C1-4 It is an alkylthio group, and the residue is a hydrogen atom.
In another preferred embodiment of the present invention, Y ₃ is a halogen atom, one or more halogen atoms that are the same or different, and / or a C1-4 alkyloxy group that may be substituted with one or more halogen atoms that are the same or different. C1-4 alkyl group which may be substituted, or C1-4 alkyloxy group which may be substituted with the same or different one or more halogen atoms and / or one or more halogen atoms which are the same or different A good C1-4 alkyloxy group or a C1-alkyloxy group optionally substituted by one or more halogen atoms and / or a C1-4 alkyloxy group optionally substituted by one or more halogen atoms. 4 is one selected from alkylthio _{group, Y 1, Y 2, Y} 4 Contact Fine _{Y 5} is hydrogen atom.

In a more preferred first aspect of the present invention, R is a —COR ₁ group, and R ₁ is _one selected from a methyl group, a trifluoromethyl group, a methoxy group, and a trifluoromethoxy group, ₁ and X ₂ are each independently a methyl group or an ethyl group, X ₃ and X ₄ are each independently a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, and Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ are each independently selected from the group consisting of at least one of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a trifluoromethyl group, and t-butyl. Group, methoxy group, trifluoromethoxy group, chlorodifluoromethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, methylthio group Is at least one selected from the trifluoromethylthio group, residue is a hydrogen atom.
In a more preferred second aspect of the present invention, R is a —COR ₁ group, and R ₁ is _one selected from a methyl group, a trifluoromethyl group, a methoxy group, and a trifluoromethoxy group, ₁ and X ₂ are each independently a methyl group or an ethyl group, X ₃ and X ₄ are each independently a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, and Y ₁ , In Y ₂ , Y ₃ , Y ₄ and Y ₅ , two adjacent groups are combined to form an —O—CH ₂ —O— group, an —O—CF ₂ —O— group, —O— (CH ₂ ) ₂ —O— group or —O— (CF ₂ ) ₂ —O— group, and the residue is a hydrogen atom.

In a particularly preferred third aspect of the present invention, R is a —COR ₁ group, and R ₁ is _one selected from a methyl group, a trifluoromethyl group, a methoxy group, and a trifluoromethoxy group, ₁ and X ₂ are each independently a methyl group or an ethyl group, X ₃ and X ₄ are each independently a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, and Y ₁ , Y ₃ and Y ₅ each independently represent at least one group selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a trifluoromethyl group, a t-butyl group, a methoxy group, Trifluoromethoxy group, chlorodifluoromethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, methylthio group, trifluoro Is at least one selected from methylthio, residue is hydrogen atom, Y _2, Y ₄ is a hydrogen atom.
In a particularly preferred fourth aspect of the present invention, R is a —COR ₁ group, and R ₁ is _one selected from a methyl group, a trifluoromethyl group, a methoxy group, and a trifluoromethoxy group, ₁ and X ₂ are each independently a methyl group or an ethyl group, X ₃ and X ₄ are each independently a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, and Y ₃ is , Fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, trifluoromethyl group, t-butyl group, methoxy group, trifluoromethoxy group, chlorodifluoromethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, a methylthio group, a one selected from trifluoromethylthio _group, Y _1, Y 2, _{Y 4,} and Y Is a hydrogen atom.

  The 1,5-naphthyridine derivative of the present invention may be a free base (free form), or includes an acid addition salt form with an appropriate acid acceptable for agriculture and horticulture. Specific acid addition salts include inorganic acids such as hydrochloride, sulfate, nitrate, phosphate, formic acid, acetic acid, oxalic acid, citric acid, succinic acid, maleic acid, fumaric acid, tartaric acid, lactic acid, benzoic acid Examples thereof include carboxylic acids such as acid and phthalic acid, and sulfonic acids such as mesylic acid, tosylic acid, and benzenesulfonic acid.

Furthermore, although the example of the specific combination of the substituent of the compound of the following general formula (I) is shown to Tables 1-29, this invention is not limited to these. In the following table, Me represents a methyl group, Et represents an ethyl group, c-Pr represents a cyclopropyl group, and t-Bu represents a tert-butyl group.

The compound (I) of the present invention can be produced by various methods. As a specific example of the production method, the compound (I) of the present invention can be produced by a method according to the following scheme. In the following scheme, R ₁ , X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ are as defined above.

[Step 1] A compound of general formula (X-III) is produced by reacting a nitropyridine compound of general formula (X-II) with a phenol compound of general formula (XI) in the presence of a base. be able to. In the general formula (X-II), Z ₁ represents a general leaving substituent in organic synthesis. Specific examples of the leaving substituent include chlorine, fluorine, bromine, iodine halogen, methanesulfonyloxy group, trifluoromethanesulfonyloxy group, and toluenesulfonyloxy group.

[Step 2] Reduction of the compound of the general formula (X-III) by a general method such as reduction with a metal powder such as iron powder under acidic conditions or hydrogenation in the presence of a metal catalyst such as palladium. Can produce a compound of general formula (X-IV).

[Step 3] The compound of general formula (X-IV) and the 3-oxocarboxylic acid compound of general formula (XV) (R ₂ represents a hydrogen atom or an alkyl group) are converted into an acid such as paratoluenesulfonic acid. By reacting in the presence of a catalyst, the compound of the general formula (II) can be produced. It can be efficiently produced by performing a dehydration reaction by heating and refluxing using a water-insoluble solvent such as xylene as a reaction solvent. The compound of the general formula (II) is a compound in which R is a hydrogen atom in the compound of the general formula (I), and is included in the present invention.

[Step 4] A compound of general formula (III) can be produced by carbonylation of the 4-position hydroxyl group of the compound of general formula (II). That is, it can be produced by reacting the compound of the general formula (II) with a halogen compound (Z ₂ is a halogen atom) represented by the general formula (X-VI) under basic conditions. Or, instead halogen compound represented by the general formula (X-VI), acid _anhydride; (R 1 _CO) using ₂ O, can be prepared by reacting in the same manner. In addition, the compound of general formula (III) is a compound of this invention in which R is a compound of -COR _{1 in} the compound of general formula (I) of this invention.

The compound represented by the general formula (I) exhibits excellent control effects against agricultural and horticultural harmful insect pests as shown in the following examples. Therefore, according to this invention, the agricultural and horticultural insecticide which contains the compound represented by general formula (I) as an active ingredient is provided. Moreover, the agricultural and horticultural insecticide according to the present invention may contain an agriculturally and horticulturally acceptable acid addition salt of these compounds as an active ingredient.
Specific acid addition salts include, for example, inorganic acids such as hydrochloride, sulfate, nitrate, phosphate, formic acid, acetic acid, oxalic acid, citric acid, succinic acid, maleic acid, fumaric acid, tartaric acid, lactic acid And carboxylic acids such as benzoic acid and phthalic acid, and sulfonic acids such as mesylic acid, tosylic acid, and benzenesulfonic acid.

  In the present invention, the insect species to be controlled (the insect species in which the compound represented by the general formula (I) exhibits a controlling effect) is not particularly limited, and is used for controlling harmful pests in a wide range of agriculture and horticulture. Can do. Preferable insect species to be controlled include, for example, lepidoptera pests (for example, moths such as Spodoptera litura, Scotch moth moth, Ayayoto, Yotsuga, Tamanaga, Trichopulsia, Heliothis spp, Helicocovera spp, etc .; Common moths such as Japanese corn borer, European corn borer, Hydra corn borer, Shibatatsuga, Watanogaiga, Noshimemadaranoga, white butterflies, such as white butterflies; Species: Limantria, Euprocutis, etc .; Suga, etc .; Cottontail, such as cotton beetle; ), Hemiptera pests (for example, aphids such as peach aphid, cotton aphid, etc .; planthoppers such as Japanese brown planthopper, brown planthopper, white-tailed planthopper; leafhoppers such as leafhopper leafhopper; red-bellied leafy beetle, chabanaeokamemushi, minamiaokameshi Stink bugs such as the stag beetle; whitefly, silverleaf whitefly, etc .; scale insects such as stag beetles; humorbirds; pheasants, etc .; crustacean pests (eg, maizewevil, rice weevil, azuki beetle, etc.) Weevil; moth beetle such as white beetle; beetle such as scallop and scallop; kiss beetle, cucumber potato beetle, Colorado potato potato beetle, western corn rootwa Potato beetles such as rice and southern corn rootworms; epilacunas such as rice beetles, green-spotted beetles, beetles, staghorn beetles, beetles, etc .; pests of insects (for example, nymph mites, kanzawa spider mites, citrus mites, apple spider mites, apple spider mites, genus Oligonicus) Spider mites such as tomato rustic mites, citrus mite mites, tea rust mites, dust mites such as chano mite mites; acarid mites, etc., Hymenoptera pests (eg, bees such as wasps), straight insects (eg, Grasshoppers, etc.), Diptera pests (eg, house flies; house mosquitoes; anopheles; chironomids; black flies; moth flies; sand flies; sand flies; wing flies; Flies; fleas; Drosophila; butterflies; flyfish; aphids; flies; Etc.), plant parasitic nematodes (for example, root-knot nematodes; neptune nematodes; cyst nematodes; aferencoides such as rice scented nematodes; pine wood nematodes and the like). More preferred are lepidopterous insects, semilepidopterous insects, Coleoptera insects, mite insects, diptera insects, thrips insects, or plant parasitic nematodes.

  The compound represented by formula (I) of the present invention or an agriculturally and horticulturally acceptable acid addition salt thereof is provided for use as an active ingredient of an agricultural and horticultural insecticide.

  When the compound represented by the general formula (I) is used as an agricultural and horticultural insecticide, the compound represented by the general formula (I) may be used as it is, but an appropriate solid carrier, liquid carrier, gaseous carrier, etc. Agrochemical formulations may be prepared by mixing with surfactants, dispersants, other formulation adjuvants, and the like. As the agrochemical formulation, preferably, emulsion, EW agent, solution, suspension, wettable powder, wettable powder, powder, DL powder, powder, granule, tablet, oil, aerosol, flowable, dry A flowable agent, a microcapsule agent, etc. can be mentioned. It can be used as a dosage form arbitrarily selected as these agricultural chemical preparations.

Examples of the solid carrier include talc, bennite, clay, kaolin, diatomaceous earth, vermiculite, white carbon, calcium carbonate, acid clay, silica sand, silica, zeolite, perlite, attapulgite, pumice, ammonium sulfate, sodium sulfate, urea, and the like. It is done.
Examples of the liquid carrier include alcohols such as methanol, ethanol, n-hexanol, ethylene glycol, and propylene glycol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; and aliphatic hydrocarbons such as n-hexane, kerosene, and kerosene. , Aromatic hydrocarbons such as toluene, xylene and methylnaphthalene, ethers such as diethyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, nitriles such as acetonitrile and isobutyronitrile, dimethylformamide, dimethylacetamide and the like Acid amides, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, water and the like.
Examples of the gaseous carrier include LPG, air, nitrogen, carbon dioxide gas, dimethyl ether and the like.
Examples of the surfactant and the dispersant include alkyl sulfates, alkyl (aryl) sulfonates, polyoxyalkylene alkyl (aryl) ethers, polyhydric alcohol esters, lignin sulfonates, and alkyl sulfosuccinic acids. Salt, formalin condensate of alkyl naphthalene sulfonate, polycarboxylate, POE polystyryl phenyl ether sulfate and phosphate, POE / POP block polymer, and the like.
Furthermore, examples of the adjuvant for preparation include carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, xanthan gum, pregelatinized starch, gum arabic, polyethylene glycol, liquid paraffin, calcium stearate, and antifoaming agent, preservative and the like. It is done.
The above-mentioned various carriers, surfactants, dispersants, and formulation adjuvants can be used alone or in combination as necessary.

  The content of the compound represented by the general formula (I), which is an active ingredient in the agrochemical formulation, is not particularly limited. It is 1-90% by weight for wettable powders and 0.5-10% by weight for granules.

  The agricultural and horticultural insecticide according to the present invention can be used as it is or after dilution. The agricultural and horticultural insecticide according to the present invention can be mixed or used in combination with other insecticides, fungicides, acaricides, herbicides, plant growth regulators, fertilizers and the like. Examples of drugs that can be mixed or used in combination include, for example, the Pesticide Manual (13th edition published by The British Crop Protection Council) and Shibuya Index (SHIBUYA INDEX 13th edition, 2008, published by SHIBUYA INDEX RESEARCH GROUP; and SHIBUYA INDEX 14th). Edition, 2009, published by SHIBUYA INDEX RESEARCH GROUP).

  Specifically, the insecticides include, for example, acephate, dichlorvos, EPN, fenitrothion, fenamifos, prothiofos, profenfos, pyraclofos, chlorpyrifosmethyl (chlorpyrifos-methyl), organophosphate compounds such as diazinon; methomyl, thiodicarb, aldicarb, oxamyl, propoxur, carbaryl, Carbamate compounds such as fenobucarb, ethiofencarb, fenothiocarb, pirimicarb, carbofuran, benfuracarb; nelices such as cartap, thiocyclam Toxin derivatives; Zicoho organochlorine compounds such as (dicofol), tetradifon; permethrin, tefluthrin, cypermethrin, deltamethrin, cyhalothrin, fenvalerate, fullvalinate pyrethroids such as (fluvalinate), etofenprox, silafluofen; benzoyls such as diflubenzuron, teflubenzuron, flufenoxuron, chlorfluazuron Urea compounds; or juvenile hormone-like compounds such as metoprene. Other insecticides include buprofezin, hexythiazox, amitraz, chlordimeform, pyridaben, fenpyroxymate, pyrimidifen, tebufenpyrad tebufenpyrad fluacrypyrim), acequinocyl, fipronyl, etoxazole, imidacloprid, chlothianidin, sulfoxaflor, pyoxatrozine, bifenazate, bifenazate, bifenazate Spirotetramat, chlorfenapyr, pyriproxyfene, indoxacarb, pyridalyl, spinosad, avermectin, milbema Of milbemycin, pyrifluquinazon, flubendiamide, chlorantraniliprole, organometallic compounds, dinitro compounds, organosulfur compounds, urea compounds, triazine compounds, hydrazine compounds Such a compound is mentioned. Furthermore, the agricultural and horticultural insecticide according to the present invention can be used in combination or in combination with microbial pesticides such as BT agents and entomopathogenic virus agents.

  The fungicides used are, for example, strobilurin compounds such as azoxystrobin, kresoxym-methyl, trifloxystrobin; mepanipyrim, pyrimethanil, cyprodinil Anilinopyrimidine compounds such as triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, microbutanyl (tributimefon) azole compounds such as myclobutanil, cyproconazole, tebuconazole, hexaconazole, prochloraz, simeconazole; quinoxaline compounds such as quinomethionate Dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, propineb; phenyl carbamate compounds such as diethofencarb; chlorothalonil Organochlorine compounds such as quintozene; benzimidazole compounds such as benomyl, thiophanate-methyl and carbendazole; metalaxyl, oxadixyl and ofurase ), Benalaxyl, furalaxyl, cyprofuram and other phenylamide compounds; sulfenic compounds such as dichlofluanid; cupper hydroxide, oxyquinoline Copper-based compounds such as copper (oxine-copper); Isoxazole compounds such as hydroxyisoxazole; organophosphorus compounds such as fosetyl-aluminium and tolclofos-methyl; captan, captafol, folpet N-halogenothioalkyl compounds such as: Procymidone, iprodione, dicarboximide compounds such as vinchlozolin; Benzanilide compounds such as flutolanil, mepronil; Morpholine compounds such as fenpropimorph and dimethomorph; organotin compounds such as fenthin hydroxide and fenthin acetate; fludioxonil; Cyanopics such as fenpiclonil It can be a roll compound. Other fungicides include fthalide, fluazinam, cymoxanil, triforine, pyrifenox, fenarimol, fenpropidin, penticuron. ), Cyazofamid, iprovalicarb, benthiavalicarb-isopropyl and the like.

  In addition, the compound represented by the general formula (I) of the present invention or an acid and pharmaceutically acceptable acid addition salt thereof is used to control agricultural and horticultural pests by applying an effective amount thereof to a plant or soil. be able to. That is, a method for controlling agricultural and horticultural pests is provided. Here, the control method according to the present invention includes a method in which the compound represented by the general formula (I) or an acid-addition salt acceptable in agriculture and horticulture is applied by smoke treatment in a sealed space. .

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples.

Example 1 2-Ethyl-3,7-dimethyl-6- (4- (trifluoromethoxy) phenoxy) -1,5-naphthyridin-4-ylmethyl carbonate (Compound No. 1-105)
[Step 1] 2-chloro-3-methyl-5-nitropyridine (1.03 g, 6 mmol), 4- (trifluoromethoxy) phenol (1.06 g, 6 mmol), dimethylacetamide (3 mL), potassium carbonate (0 .62 g, 4.5 mmol) was reacted at 90 ° C. for 2.5 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer is washed with water and a saturated aqueous sodium chloride solution and then concentrated to precipitate crystals, which are then dried and crude crystals of 3-methyl-5-nitro-2- (4- (trifluoromethoxy) phenoxy) pyridine are obtained. 45 g was obtained.
[Step 2] A mixture of iron powder (2.4 g, 42.9 mmol), ethanol (8.3 mL), water (3.4 mL) and concentrated hydrochloric acid (0.02 mL) was heated to reflux, where 3-methyl- A mixture of 5-nitro-2- (4- (trifluoromethoxy) phenoxy) pyridine (1.88 g, 6 mmol) in ethanol (2.6 mL) was added dropwise, and the mixture was further heated to reflux for 4 hours. Saturated sodium hydrogen carbonate was added, and the mixture was cooled to room temperature and the iron powder was filtered off. The filtrate was concentrated under reduced pressure to obtain solid crystals. The solid crystals are dissolved in ethyl acetate, washed successively with water and a saturated aqueous sodium chloride solution, dried and concentrated to give crude 5-amino-3-methyl-2- (4- (trifluoromethoxy) phenoxy) pyridine. 1.72 g of crystals were obtained.
[Step 3] 5-Amino-3-methyl-2- (4- (trifluoromethoxy) phenoxy) pyridine (1.7 g, 6 mmol), p-toluenesulfonic acid monohydrate (1.2 g, 6 mmol), 2 -A mixture of methyl-3-oxopentanoate (1.82 g, 12.6 mmol) and xylene (61 mL) was heated to reflux for 22 hours while distilling off water, then cooled to 100 ° C and saturated bicarbonate. A sodium aqueous solution was added to precipitate crystals. After cooling to room temperature, the crystals were filtered off, washed with water and n-hexane, dried, and 2-ethyl-3,7-dimethyl-6- (4- (trifluoromethoxy) phenoxy) -1,5- 2.15 g of crude crystals of naphthyridin-1H-4-one were obtained.
[Step 4] 2-ethyl-3,7-dimethyl-6- (4- (trifluoromethoxy) phenoxy) -1,5-naphthyridin-1H-4-one (2.15 g, 5.7 mmol), sodium A mixture of t-butoxide (0.93 g, 9.7 mmol) and dimethylacetamide (11.4 mL) was reacted at 10 ° C. or lower for 30 minutes, and then methyl chlorocarbonate (0.92 g, 9.7 mmol) was added. The reaction was performed for 1 hour. The reaction solution was poured into ice water and extracted with ethyl acetate, and the organic layer was washed and concentrated to obtain crude crystals. The crude crystals were purified by silica gel column chromatography to obtain 1.74 g of 2-ethyl-3,7-dimethyl-6- (4- (trifluoromethoxy) phenoxy) -1,5-naphthyridin-4-ylmethyl carbonate. Obtained.

Example 2 2-Ethyl-3-methyl-6- (4- (trifluoromethoxy) phenoxy) -1,5-naphthyridin-4-yl acetate (Compound No. 1-95)
[Step 1] 2-chloro-5-nitropyridine (1.59 g, 10 mmol), 4- (trifluoromethoxy) phenol (1.96 g, 11 mmol), dimethylacetamide (10 mL), potassium carbonate (1.38 g, 10 mmol) ) Was reacted at 60 ° C. for 2 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and a saturated aqueous sodium chloride solution and then concentrated to precipitate crystals and dried to obtain 3.55 g of crude crystals of 5-nitro-2- (4- (trifluoromethoxy) phenoxy) pyridine. .
[Step 2] Mixture of 5-nitro-2- (4- (trifluoromethoxy) phenoxy) pyridine (3.55 g, 10 mmol), ethanol (32 mL), water (8 mL) and iron powder (2.80 g, 50 mmol) The mixture was heated to reflux, concentrated hydrochloric acid (0.2 mL) was added dropwise thereto, and the mixture was further heated to reflux for 4 hours. Saturated sodium hydrogen carbonate was added, and the mixture was cooled to room temperature and the iron powder was filtered off. The filtrate was concentrated under reduced pressure to obtain solid crystals. The solid crystals are dissolved in ethyl acetate, washed successively with water and a saturated aqueous sodium chloride solution, dried and concentrated to give 2.80 g of crude crystals of 5-amino-2- (4- (trifluoromethoxy) phenoxy) pyridine. Got.
[Step 3] 5-Amino-2- (4- (trifluoromethoxy) phenoxy) pyridine (2.80 g, 10 mmol), p-toluenesulfonic acid monohydrate (1.90 g, 10 mmol), 2-methyl-3 -A mixture of methyl oxopentanoate (2.89 g, 20 mmol) and xylene (50 mL) was heated to reflux for 1 hour while distilling off water. 20 mL of the reflux solution was removed, xylene (20 mL) was added to the reaction solution, and the mixture was further heated to reflux for 3 hours. 20 mL of the reflux solution was removed, xylene (20 mL) was added to the reaction solution, and the mixture was further heated to reflux for 4 hours. After cooling to 100 ° C., a saturated aqueous sodium hydrogen carbonate solution was added to precipitate crystals. After cooling to room temperature, the crystals were filtered off, washed with water and n-hexane, dried, and 2-ethyl-3-methyl-6- (4- (trifluoromethoxy) phenoxy) -1,5-naphthyridine- 3.03 g of crude 1H-4-one crystals were obtained.
[Step 4] 2-ethyl-3-methyl-6- (4- (trifluoromethoxy) phenoxy) -1,5-naphthyridin-1H-4-one (1.09 g, 3 mmol), acetic anhydride (10 mL) The mixture was heated to reflux for 1 hour and then concentrated under reduced pressure to precipitate a solid. The obtained solid was dissolved in ethyl acetate (100 mL) and washed with a saturated aqueous sodium hydrogen carbonate solution, and then the organic layer was dried over magnesium sulfate and concentrated to obtain crude crystals (1.14 g). The crude crystals were purified by silica gel column chromatography to obtain 0.99 g of 2-ethyl-3-methyl-6- (4- (trifluoromethoxy) phenoxy) -1,5-naphthyridin-4-yl acetate.

Example 3 2-Ethyl-3-methyl-6- (4- (trifluoromethyl) phenoxy) -1,5-naphthyridin-4-yl acetate (Compound No. 1-47)
[Step 1] 2-chloro-5-nitropyridine (0.96 g, 6 mmol), 4- (trifluoromethyl) phenol (0.95 g, 6 mmol), dimethylacetamide (12 mL), potassium carbonate (0.83 g, 6 mmol) ) Was reacted at 60 ° C. for 3 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and a saturated aqueous sodium chloride solution and then concentrated to precipitate crystals, which were then dried to obtain 1.68 g of crude crystals of 5-nitro-2- (4- (trifluoromethyl) phenoxy) pyridine. .
[Step 2] Heat a mixture of 5-nitro-2- (4- (trifluoromethyl) phenoxy) pyridine (1.68 g, 6 mmol), ethanol (9.5 mL), and iron powder (1.70 g, 30 mmol). The mixture was refluxed, and a mixture of water (2.5 mL) and concentrated hydrochloric acid (0.5 mL) was added dropwise thereto, and the mixture was further heated to reflux for 4 hours. Saturated sodium hydrogen carbonate was added, and the mixture was cooled to room temperature and the iron powder was filtered off. The filtrate was concentrated under reduced pressure to obtain solid crystals. The solid crystals are dissolved in ethyl acetate, washed successively with water and a saturated aqueous sodium chloride solution, dried and concentrated to give 1.46 g of crude crystals of 5-amino-2- (4- (trifluoromethyl) phenoxy) pyridine. Got.
[Step 3] 5-Amino-2- (4- (trifluoromethyl) phenoxy) pyridine (1.46 g, 6 mmol), p-toluenesulfonic acid monohydrate (1.14 g, 6 mmol), 2-methyl-3 -A mixture of methyl oxopentanoate (1.73 g, 12 mmol) and xylene (30 mL) was heated to reflux for 4 hours while distilling off water. Excluding 20 mL of the refluxing solution, xylene (20 mL) and paratoluenesulfonic acid monohydrate (1.14 g, 6 mmol) were added to the reaction solution, and the mixture was further heated to reflux for 7 hours. 20 mL of the reflux solution was removed, xylene (20 mL) was added to the reaction solution, and the mixture was further heated to reflux for 4 hours. Thereafter, all xylene was concentrated, and the residue was dissolved in ethyl acetate (100 mL), and water (50 mL) and a saturated aqueous sodium hydrogen carbonate solution (50 mL) were added to precipitate crystals. The crystals were filtered off, washed with ethyl acetate, dried, and crude crystals of 2-ethyl-3-methyl-6- (4- (trifluoromethyl) phenoxy) -1,5-naphthyridin-1H-4-one 1.52 g was obtained.
[Step 4] 2-ethyl-3-methyl-6- (4- (trifluoromethyl) phenoxy) -1,5-naphthyridin-1H-4-one (0.70 g, 2 mmol), acetic anhydride (10 mL) The mixture was heated to reflux for 2 hours and then concentrated under reduced pressure to precipitate a solid. The obtained solid was dissolved in ethyl acetate (100 mL) and washed with a saturated aqueous sodium hydrogen carbonate solution, and then the organic layer was dried over magnesium sulfate and concentrated to obtain crude crystals (1.14 g). The crude crystals were purified by silica gel column chromatography to obtain 0.70 g of 2-ethyl-3-methyl-6- (4- (trifluoromethyl) phenoxy) -1,5-naphthyridin-4-yl acetate.

Example 4
2-Ethyl-3-methyl-6- (4-chlorophenoxy) -1,5-naphthyridin-4-ylmethyl carbonate (Compound No. 1-14)
[Step 1] A mixture of 2-chloro-5-nitropyridine (4.76 g, 30 mmol), 4-chlorophenol (4.27 g, 33 mmol), dimethylacetamide (30 mL), potassium carbonate (4.15 g, 30 mmol) was added. And reacted at 60 ° C. for 2.5 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and a saturated aqueous sodium chloride solution and then concentrated to precipitate crystals, which were dried to obtain 7.42 g of 5-nitro-2- (4-chlorophenoxy) pyridine crude crystals.
[Step 2] A mixture of 5-nitro-2- (4-chlorophenoxy) pyridine (7.42 g, 30 mmol), ethanol (48 mL), water (12 mL), and iron powder (8.34 g, 150 mmol) was heated to reflux. Then, a mixed solution of concentrated hydrochloric acid (0.5 mL) was added dropwise thereto, and the mixture was further heated to reflux for 4 hours. Saturated sodium hydrogen carbonate was added, and the mixture was cooled to room temperature and the iron powder was filtered off. The filtrate was concentrated under reduced pressure to obtain solid crystals. The solid crystals were dissolved in ethyl acetate, washed with water and a saturated aqueous sodium chloride solution in this order, dried and concentrated to obtain 6.37 g of crude crystals of 5-amino-2- (4-chlorophenoxy) pyridine.
[Step 3] 5-Amino-2- (4-chlorophenoxy) pyridine (1.99 g, 9 mmol), p-toluenesulfonic acid monohydrate (1.70 g, 9 mmol), 2-methyl-3-oxopentanoic acid A mixture of methyl (2.64 g, 18 mmol) and xylene (45 mL) was heated to reflux for 1.5 hours while distilling off water. 20 mL of the reflux solution was removed, and xylene (20 mL) was added to the reaction solution, followed by further heating to reflux for 2 hours. 20 mL of the reflux solution was removed, and xylene (20 mL) was added to the reaction solution, followed by further heating to reflux for 2.5 hours. Paratoluenesulfonic acid monohydrate (1.72 g, 9 mmol) was added, and the mixture was further heated to reflux for 3.5 hours. 20 mL of the reflux solution was removed, xylene (20 mL) was added to the reaction solution, and the mixture was further heated to reflux for 4 hours. A saturated aqueous sodium hydrogen carbonate solution (50 mL) was added to precipitate crystals, methanol (10 mL) and water (10 mL) were added, and the mixture was heated to reflux for 1 hr. After cooling to room temperature, the crystals were filtered off, washed with 80% aqueous methanol (20 mL), dried, and 2-ethyl-3-methyl-6- (4-chlorophenoxy) -1,5-naphthyridine. 2.53 g of crude crystals of -1H-4-one were obtained.
[Step 4] 2-ethyl-3-methyl-6- (4-chlorophenoxy) -1,5-naphthyridin-1H-4-one (0.70 g, 2 mmol), tetrabutylammonium bromide (2 mg), toluene ( 8 mL) and dimethylacetamide (1 mL) were heated to 30 ° C., added with 48% aqueous sodium hydroxide (1 g), stirred for 30 minutes, and then cooled to 10 ° C. After adding methyl chloroformate (0.41 g, 3.6 mmol) and stirring for 1.5 hours, the reaction solution was poured into ice water. The mixture was extracted with ethyl acetate, and the organic layer was washed with water and a saturated aqueous sodium chloride solution, dried over magnesium sulfate, and concentrated to obtain crude crystals (1.10 g). The crude crystals were purified by silica gel column chromatography to obtain 0.93 g of 2-ethyl-3-methyl-6- (4-chlorophenoxy) -1,5-naphthyridin-4-ylmethyl carbonate.

Example 5 2-Ethyl-3,7-dimethyl-6- (4-chlorophenoxy) -1,5-naphthyridin-4-ylmethyl carbonate (Compound No. 1-16)
[Step 1] 2-chloro-3-methyl-5-nitropyridine (1.03 g, 6 mmol), 4-chlorophenol (0.8 g, 6 mmol), dimethylacetamide (5 mL), potassium carbonate (0.62 g, 4 .5 mmol) was reacted at 90 ° C. for 2.5 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and a saturated aqueous sodium chloride solution and then concentrated to precipitate crystals, which were then dried to obtain 1.71 g of 3-methyl-5-nitro-2- (4-chlorophenoxy) pyridine crude crystals. .
[Step 2] A mixture of iron powder (2.4 g, 42.9 mmol), ethanol (8.3 mL), water (3.4 mL) and concentrated hydrochloric acid (0.02 mL) was heated to reflux, where 3-methyl- A mixture of 5-nitro-2- (4-chlorophenoxy) pyridine (1.58 g, 6 mmol) in ethanol (2.6 mL) was added dropwise, and the mixture was further heated to reflux for 2 hours. Saturated sodium hydrogen carbonate was added, and the mixture was cooled to room temperature and the iron powder was filtered off. The filtrate was concentrated under reduced pressure to obtain solid crystals. The solid crystals are dissolved in ethyl acetate, washed successively with water and a saturated aqueous sodium chloride solution, dried and concentrated to give 1.4 g of crude crystals of 5-amino-3-methyl-2- (4-chlorophenoxy) pyridine. Got.
[Step 3] 5-Amino-3-methyl-2- (4-chlorophenoxy) pyridine (1.4 g, 6 mmol), p-toluenesulfonic acid monohydrate (1.2 g, 6 mmol), 2-methyl-3 -A mixture of methyl oxopentanoate (1.82 g, 12.6 mmol) and xylene (61 mL) was heated to reflux for 25 hours while distilling off water, then cooled to 100 ° C, and a saturated aqueous sodium bicarbonate solution was added. Crystals were precipitated. After cooling to room temperature, the crystals were filtered off, washed with water and n-hexane, dried, and 2-ethyl-3,7-dimethyl-6- (4-chlorophenoxy) -1,5-naphthyridine-1H- 1.77 g of 4-one crude crystals were obtained.
[Step 4] 2-Ethyl-3,7-dimethyl-6- (4-chlorophenoxy) -1,5-naphthyridin-1H-4-one (1.77 g, 5.4 mmol), sodium-t-butoxide ( 0.88 g, 9.1 mmol) and dimethylacetamide (10.8 mL) were reacted at 10 ° C. or lower for 30 minutes, and then methyl chlorocarbonate (0.87 g, 9.1 mmol) was added and reacted for 1 hour. I let you. The reaction solution was poured into ice water and extracted with ethyl acetate, and the organic layer was washed and concentrated to obtain crude crystals. The crude crystals were purified by silica gel column chromatography to obtain 1.53 g of 2-ethyl-3,7-dimethyl-6- (4-chlorophenoxy) -1,5-naphthyridin-4-ylmethyl carbonate.

Example 6 2-Ethyl-3,7-dimethyl-6- (4- (1,1,2,2-tetrafluoroethoxy) phenoxy) -1,5-naphthyridin-4-ylmethyl carbonate (Compound No. 1) -124)
[Step 1] 2-chloro-3-methyl-5-nitropyridine (1.03 g, 6 mmol), 4- (1,1,2,2-tetrafluoroethoxy) phenol (1.30 g, 6 mmol), dimethylacetamide (4.5 mL) and a mixture of potassium carbonate (0.62 g, 4.5 mmol) were reacted at 90 ° C. for 3.0 hours, and then 4- (1,1,2,2-tetrafluoroethoxy) phenol ( 0.16 g, 0.7 mmol) was added, and the mixture was further reacted for 30 minutes. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer is washed with water and a saturated aqueous sodium chloride solution and then concentrated to precipitate crystals, which are then dried, and 3-methyl-5-nitro-2- (4- (1,1,2,2-tetrafluoroethoxy) 2.45 g of phenoxy) pyridine crude crystals were obtained.
[Step 2] A mixture of iron powder (2.4 g, 42.9 mmol), ethanol (8.3 mL), water (3.4 mL) and concentrated hydrochloric acid (0.02 mL) was heated to reflux, where 3-methyl- A mixture of 5-nitro-2- (4- (1,1,2,2-tetrafluoroethoxy) phenoxy) pyridine (2.08 g, 6 mmol) in ethanol (2.6 mL) was added dropwise and heated for an additional 4 hours. Refluxed. Saturated sodium hydrogen carbonate was added, and the mixture was cooled to room temperature and the iron powder was filtered off. The filtrate was concentrated under reduced pressure to obtain solid crystals. This solid crystal is dissolved in ethyl acetate, washed with water and a saturated aqueous sodium chloride solution in that order, dried and concentrated to give 5-amino-3-methyl-2- (4- (1,1,2,2-tetra). 1.76 g of crude crystals of fluoroethoxy) phenoxy) pyridine were obtained.
[Step 3] 5-Amino-3-methyl-2- (4- (1,1,2,2-tetrafluoroethoxy) phenoxy) pyridine (1.76 g, 5.56 mmol), paratoluenesulfonic acid monohydrate Product (1.06 g, 5.56 mmol), methyl 2-methyl-3-oxopentanoate (1.7 g, 11.67 mmol) and xylene (57 mL) were heated to reflux for 15 hours while distilling off water. After cooling to 100 ° C., saturated aqueous sodium hydrogen carbonate solution was added to precipitate crystals. After cooling to room temperature, the crystals were filtered off, washed with water and n-hexane, dried, and 2-ethyl-3,7-dimethyl-6- (4- (1,1,2,2-tetrafluoroethoxy). ) 1.80 g of crude crystals of phenoxy) -1,5-naphthyridin-1H-4-one were obtained.
[Step 4] 2-ethyl-3,7-dimethyl-6- (4- (1,1,2,2-tetrafluoroethoxy) phenoxy) -1,5-naphthyridin-1H-4-one (1.8 g 4.38 mmol), sodium-t-butoxide (0.72 g, 7.5 mmol), and dimethylacetamide (8.8 mL) were reacted at 10 ° C. or lower for 30 minutes, and then methyl chlorocarbonate (0. 0. 71 g, 7.5 mmol) was added and allowed to react for 1 hour. The reaction solution was poured into ice water and extracted with ethyl acetate, and the organic layer was washed and concentrated to obtain crude crystals. The crude crystals were purified by silica gel column chromatography to give 2-ethyl-3,7-dimethyl-6- (4- (1,1,2,2-tetrafluoroethoxy) phenoxy) -1,5-naphthyridine-4. -1.52 g of ylmethyl carbonate was obtained.

Tables 30 to 35 show proton NMR spectrum data and / or melting points of compounds of the following general formula (I) synthesized according to the same method as described above.

Moreover, the example of an agrochemical formulation which contains the compound represented with general formula (I) based on this invention as an active ingredient is given below.
Formulation Example 1 [wettable powder]
Compound (I) 30% by mass
Clay 30% by mass
Diatomaceous earth 3 5 mass%
Calcium lignin sulfonate 4% by mass
Sodium lauryl sulfate 1% by mass
The above components can be mixed uniformly and pulverized to obtain a wettable powder.

Formulation Example 2 [Dust]
Compound (I) 2% by mass
Clay 60% by mass
Talc 3 7% by mass
Calcium stearate 1% by mass
The said component can be mixed uniformly and a powder agent can be obtained.

Formulation Example 3 [Emulsion]
Compound (I) 20% by mass
N, N-dimethylformamide 20% by mass
Solvesso 1 5 0 (ExxonMobil Co., Ltd.) 5 0% by mass
Polyoxyethylene alkyl aryl ether 10% by mass
The above ingredients can be mixed uniformly and dissolved to obtain an emulsion.

Formulation Example 4 [Granule]
Compound (I) 5% by mass
Bentonite 40% by mass
Talc 10% by mass
Clay 4 3% by mass
Calcium lignin sulfonate 2% by mass
After the above components are uniformly pulverized and mixed, water is added and kneaded well, and then granulated and dried to obtain granules.

Formulation Example 5 [Flowable Agent]
Compound (I) 25% by mass
POE polystyryl phenyl ether sulfate 5% by mass
Propylene glycol 6% by mass
Bentonite 1% by mass
Xanthan gum 1% aqueous solution 3% by mass
PRONALEX-300 (Toho Chemical Co., Ltd.) 0.05% by mass
ADDAC827 (Kay Kasei Co., Ltd.) 0.02% by mass
Water 59.93 mass%
The whole amount of the above formulation except for 1% aqueous xanthan gum solution and an appropriate amount of water was premixed and then pulverized with a wet pulverizer. Thereafter, a 1% aqueous solution of xanthan gum and the remaining water are added to the obtained pulverized product to obtain a 100% by mass flowable agent.

Formulation Example 6 [Emulsion]
Compound (I) 5% by mass
Xylene 42.5% by mass
DMSO 42.5 mass%
New Calgen 900 10.0% by mass
The above ingredients can be mixed uniformly and dissolved to obtain an emulsion.

Biological Test Example 1: Cotton Aphid (Aphis gossypi) Control Test Cucumber leaves were cut to a diameter of 2.8 cm and placed on absorbent cotton moistened with water. Two adult cotton aphids were released here and allowed to lay for 24 hours, and then the adults were removed. In this cucumber leaf, a diluted solution (xylene 0.17 mass%, DMSO 0.17 mass%, New Calgen 900 0) diluted to 200 ppm as a test compound with some compounds of Tables 31 to 34 and Table 35 was used. 2 mL) (containing .04 mass% and water) was sprayed using a spray tower. After air drying, they were put in a plastic cup together with absorbent cotton, covered and kept in a constant temperature room at 25 ° C. After 5 days of treatment, the survival rate was observed and the death rate was calculated.
As a result, no. 1-11, 1-14, 1-24, 1-33, 1-41, 1-44, 1-46, 1-47, 1-48, 1-56, 1-58, 1-59, 1- 61, 1-62, 1-64, 1-66, 1-68, 1-70, 1-74, 1-80, 1-84, 1-85, 1-86, 1-89, 1-91, 1-92, 1-94, 1-95, 1-96, 1-101, 1-105, 1-108, 1-109, 1-113, 1-114, 1-116, 1-120, 1- 122, 1-126, 1-130, 1-134, 1-142, 1-146, 1-148, 1-149, 1-151, 2-74, 2-92, 2-98 are dead insects. The rate was 100%.

Biological Test Example 2: Tobacco Whitefly (Bemisia tabaci Genn.) Control Test Cucumber leaves were cut to a diameter of 6.0 cm and placed on absorbent cotton moistened with water. In this cucumber leaf, a diluted solution (xylene 0.17 mass%, DMSO 0.17 mass%, New Calgen 900 0) diluted to 200 ppm as a test compound with some compounds of Tables 31 to 34 and Table 35 was used. 2 mL) (containing .04 mass% and water) was sprayed using a spray tower. After air drying, this cucumber leaf was put in a plastic cup, 20 silver leaf whitefly female adults were released, and placed upside down in a thermostatic chamber at 25 ° C. Five days after the treatment, the number of live and dead insects was examined, and the death rate was calculated.
As a result, no. 1-7, 1-14, 1-16, 1-24, 1-33, 1-38, 1-47, 1-56, 1-61, 1-62, 1-64, 1-66, 1- 68, 1-74, 1-80, 1-85, 1-86, 1-88, 1-95, 1-96, 1-105, 1-108, 1-109, 1-113, 1-116, The compounds of 1-120, 1-124, 1-126, 1-128, 1-134, 1-142, 1-148, 1-149, 1-151 showed a mortality rate of 100%.

Biological Test Example 3: Plutella xylostella Control Test A test compound solution (xylene 0) obtained by diluting cabbage leaves having a diameter of 5 cm to 200 ppm with some compounds shown in Tables 31 to 34 and Table 35 as test compounds. .17 mass%, DMSO 0.17 mass%, Neucargen 900 0.04 mass% and water). After air-drying, the cabbage leaves were put in a cup, and 10 third-ordered longhorn larvae were released, covered and kept in a constant temperature room at 25 ° C. Five days after the treatment, the mortality of the larvae was observed and the mortality rate was calculated.
As a result, no. 1-24, 1-48, 1-56, 1-58, 1-64, 1-74, 1-80, 1-84, 1-97, 1-105, 1-106, 1-108, 1- 109, 1-110, 1-116, 1-120, 1-124, 1-126, 1-128, 1-130, 1-134, 1-142, 1-146, 1-151 are dead insects. The rate was 100%.

Biological test example 4: Nite spider mite (Tetranychus urticae) control test A 2 cm diameter kidney leaf disc was placed on absorbent cotton moistened with water, and 5 adult mite spider mites were inoculated. The female adults were removed after laying eggs in a constant temperature room at 25 ° C. for 24 hours, and a test compound solution (xylene 0.17) was prepared by diluting some compounds in Tables 31 to 34 and Table 35 to 200 ppm as test compounds. (Mass%, DMSO 0.17 mass%, New Calgen 900 0.04 mass% and water). After air drying, the leaves were placed in a plastic cup together with absorbent cotton and the leaf discs were stored in a constant temperature room at 25 ° C. Seven days after the treatment, the hatching status of the eggs and the viability of the larvae and nymphs were observed, the unhatched egg rate and the larval mortality rate were calculated, and the sum of these was used as the insecticidal rate.
As a result, no. 1-10, 1-46, 1-47, 1-64, 1-66, 1-86, 1-95, 1-96, 1-116, 1-122, 1-126, 1-130, 1- The compounds of 134, 1-142, 1-148, 1-149 showed a mortality rate of 100%.

Claims (5)

A compound represented by the following formula (I) or an agriculturally and horticulturally acceptable acid addition salt thereof;

[Wherein, R represents a hydrogen atom or —COR ₁ ;
R ₁ represents a C1-4 alkyl group (wherein the C1-4 alkyl group is optionally substituted by one or more halogen atoms and / or one or more halogen atoms that are the same or different. Optionally substituted by an alkyloxy group),
A C3-6 cyclic alkyl group (wherein the C3-6 cyclic alkyl group is the same or different one or more halogen atoms and / or C1-4 alkyloxy optionally substituted by one or more halogen atoms) Optionally substituted by a group),
A C1-4 alkyloxy group (wherein the C1-4 alkyloxy group is the same or different one or more halogen atoms and / or the same or different one or more halogen atoms). Which may be substituted by a group)
X ₁ and X ₂ are independently of each other
Hydrogen atom,
A C1-4 alkyl group (wherein the C1-4 alkyl group is the same or different one or more halogen atoms and / or a C1-4 alkyloxy group optionally substituted by one or more halogen atoms). Which may be substituted)
Alternatively, X ₁ and X ₂ are taken together to form a — (CH ₂ ) m — group (wherein the — (CH ₂ ) m — group is the same or different one or more halogen atoms and / or the same or different one or more And optionally substituted by a C1-4 alkyloxy group which may be substituted by a halogen atom, and m is 3 or 4.
X ₃ and X ₄ are independent of each other
Hydrogen atom,
Halogen atoms,
A C1-4 alkyl group (wherein the C1-4 alkyl group is the same or different one or more halogen atoms and / or a C1-4 alkyloxy group optionally substituted by one or more halogen atoms). May be substituted),
C1-4 alkyloxy group (wherein the C1-4 alkyloxy group is the same or different one or more halogen atoms and / or the same or different one or more halogen atoms may be substituted) Which may be substituted by
Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ are independently of each other,
Hydrogen atom, halogen atom, cyano group,
A C1-4 alkyl group (wherein the C1-4 alkyl group is the same or different one or more halogen atoms and / or a C1-4 alkyloxy group optionally substituted by one or more halogen atoms). May be substituted),
C1-4 alkyloxy group (wherein the C1-4 alkyloxy group is the same or different one or more halogen atoms, and / or C1-4 alkyloxy group optionally substituted by one or more halogen atoms) Optionally substituted by a group),
C1-4 alkylthio group (wherein the C1-4 alkylthio group is substituted with one or more halogen atoms and / or one or more C1-4 alkyloxy groups optionally substituted with one or more halogen atoms). May be)
Alternatively, Y ₁ , Y ₂ , Y ₃ , Y _4, and Y ₅ can be formed by combining two adjacent groups together to form an —O— (CH ₂ ) n—O— group (wherein the —O— (CH ₂ ) The n-O- group may be substituted with one or more halogen atoms that are the same or different and / or a C1-4 alkyloxy group that may be substituted with one or more halogen atoms that are the same or different. Represents 1 or 2). X ₁ and X ₂ are each independently a C 1-4 alkyl group (wherein the C 1-4 alkyl group is substituted with one or more halogen atoms that are the same or different and / or one or more halogen atoms that are the same or different). The compound according to claim 1, which may be substituted with an optionally substituted C1-4 alkyloxy group, or an agriculturally and horticulturally acceptable acid addition salt thereof. In Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ , at least one substituent is
Halogen atoms,
A C1-4 alkyl group (wherein the C1-4 alkyl group is the same or different one or more halogen atoms and / or a C1-4 alkyloxy group optionally substituted by one or more halogen atoms). May be substituted),
C1-4 alkyloxy group (wherein the C1-4 alkyloxy group is the same or different one or more halogen atoms, and / or C1-4 alkyloxy group optionally substituted by one or more halogen atoms) Optionally substituted by a group),
C1-4 alkylthio group (wherein the C1-4 alkylthio group is substituted with one or more halogen atoms and / or one or more C1-4 alkyloxy groups optionally substituted with one or more halogen atoms). May be)
The compound according to claim 1 or 2, wherein the residue is a hydrogen atom, or an agriculturally and horticulturally acceptable acid addition salt thereof.   An agricultural and horticultural insecticide comprising the compound according to any one of claims 1 to 3 or an agriculturally and horticulturally acceptable acid addition salt as an active ingredient.   Claim 4 for the control of lepidopterous insects, semilepidopterous insects, coleopterous insects, mite insects, hymenopteran insects, straight moth insects, diptera insects, thrips insects, or plant parasitic nematodes The agricultural and horticultural insecticide described in 1.