JP4970255B2 - New insecticide, acaricide - Google Patents

Description

  The present invention relates to a novel insecticidal and acaricidal composition.

  So far, the insecticidal and acaricidal activity of nicotinic acid anilide derivatives has been disclosed in US2004 / 0249164, JP-A-6-321903, WO2002096882, etc., but any compound has a substituent structure on nicotinic acid or anilide, Different from the compounds of the present invention.

WO2002066470, WO2001023347, WO2001014339, WO2001005769, WO9924404, and DE19629828 disclose similar nicotinic acid anilide derivatives, but the compounds of the present invention are not disclosed, and there is no description of insecticidal and acaricidal activity. Absent.
US2004 / 0249164 JP-A-6-321903 WO2002096882 WO2002066470 WO2001023347 WO2001014339 WO2001005769 WO9924404 DE19629828

  A large number of insecticides and acaricides have been reported so far, but low-sensitivity insect species and difficult-to-control insect species are recognized, and new agents are desired.

  An object of the present invention is to provide a derivative having excellent insecticidal and acaricidal activity, and further to provide an insecticidal and acaricidal composition which can be used safely and reliably with the effect of containing the derivative.

  The first aspect of the present invention provides an insecticidal and acaricidal composition containing a compound represented by the following formula (1) or an agriculturally and horticulturally acceptable acid addition salt as an active ingredient.

（１）
[式中、R₁は、水素原子、水酸基、ハロゲン原子、ハロゲン原子で置換されてもよいC_1〜6アルキル基または、ハロゲン原子で置換されてもよいC_1〜6アルコキシ基を表し、R₂は、水素原子、ハロゲン原子、OR₂’、OC OR₂’、NR₂’R₂”、 SR₂’、SC OR₂’（R₂’、R₂”は同一または異なって、水素原子かまたは、ハロゲン原子、C_1〜4アルコキシ基、またはC_1〜4アルキルカルボニル基で置換されていてもよいC_1〜6アルキル基を表す）、またはC_1〜6アルコキシ-C_1〜6アルコキシ- C_1〜6アルキルオキシ基を表し、
R₃またはR₄は、同一または異なって水素原子、水酸基、ハロゲン原子、ハロゲン原子で置換されてもよいC_1〜6アルコキシ基、置換されてもよいフェニル基、置換されてもよいフェニルオキシ基、ハロゲン原子で置換されてもよいC_1〜6アルキルチオ基、ハロゲン原子で置換されてもよいC_1〜6アルキルスルフィニル基、ハロゲン原子で置換されてもよいC_1〜6アルキルスルフォニル基、シアノ基、ホルミル基、C_1〜6アルキルオキシカルボニル基、C_1〜6アルキルカルボニルオキシ基、ハロゲン原子またはC_1〜4アルコキシで置換されていてもよく部分不飽和であってもよい直鎖または分岐のC_1〜6アルキル基を表すかまたは、
R₃とR₄とが一緒になって5-7員の飽和環状アルキルまたは飽和ヘテロ環を形成してもよく、
Rは、水素原子または、C_1〜6アルキル基を表し、
Wは、基−Y−W’を表し、W’は、置換されていてもよいフェニル基（ここで置換基はハロゲン原子、ハロゲン原子で置換されていてもよいC_1〜6アルキル基、ハロゲン原子で置換されていてもよいC_1〜6アルコキシ基、モノまたはジC_1〜6アルキル置換アミノ基、シアノ基、ニトロ基、ハロゲン原子で置換されていてもよいC_1〜6アルキルチオ基、ハロゲン原子で置換されていてもよいC_1〜6アルキルスルフィニル基、ハロゲン原子で置換されていてもよいC_1〜6アルキルスルフォニル基、ホルミル基、C_1〜6アルキルオキシカルボニル基、C_1〜6アルキルカルボニルオキシ基を表すかまたは、フェニル基上の隣り合う2つの基が一緒になって形成される、ハロゲン原子で置換されていてもよい−O−（CH₂）_ｐ−O−（ここでｐは1または2を表す）を表す）または、置換されていてもよい飽和または不飽和の5、6員複素環を表し、Yは、(CH₂)_ｌ、O(CH₂)_ｌ、S(CH₂)_ｌ、(CH₂)_ｌO、(CH₂)_ｌS、NR_y(CH₂)_ｌまたは、(CH₂)_ｌNR_y（R_yは水素原子、C_1〜6アルキル基を表す）を表し、ｌは0〜4の整数を表し、
Xは、水酸基、ハロゲン原子、ハロゲン原子で置換されていてもよいC_1〜6アルキル基、ハロゲン原子で置換されていてもよいC_1〜6アルコキシ基、モノまたはジC_1〜6アルキル置換アミノ基、シアノ基、ニトロ基、ハロゲン原子で置換されていてもよいC_1〜6アルキルチオ基、ハロゲン原子で置換されていてもよいC_1〜6アルキルスルフィニル基、ハロゲン原子で置換されていてもよいC_1〜6アルキルスルフォニル基、ホルミル基、C_1〜6アルキルオキシカルボニル基または、C_1〜6アルキルカルボニルオキシ基を表し、
nは、0〜4の整数を表し、
mは、0〜4の整数を表すがただし、
R₂〜R₄またはR₁、R₃とR₄が全て同一に水素原子を表すことはない。]
特に、（１）式中、R ₁ が、水素原子、C _1〜6 アルキル基またはハロゲン原子であり、
R ₂ が、水酸基またはC _1〜6 アルキルカルボニルオキシ基であり、
R ₃ およびR ₄ が、C _1〜6 アルコキシ基であり、
Rが、水素原子であり、
Wが、置換されていてもよいフェニルオキシ基（置換基はハロゲン原子、ハロゲン原子で置換されていてもよいC _1〜6 アルキル基、ハロゲン原子で置換されていてもよいC _1〜6 アルコキシ基、シアノ基、ハロゲン原子で置換されていてもよいC _1〜6 アルキルチオ基または、ハロゲン原子で置換されていてもよいC _1〜6 アルキルスルフィニル基であるかまたは、フェニル基上の隣り合う2つの基が一緒になって形成される、ハロゲン原子で置換されていてもよい−O−（CH ₂ ） _ｐ −O−（ここでｐは1または2である）である）、フェニル基、ベンジルオキシ基または、置換されていてもよいフェニルチオ基（置換基はハロゲン原子、ハロゲン原子で置換されていてもよいC _1〜6 アルキル基）であり、
Xが、ハロゲン原子、ハロゲン原子で置換されていてもよいC _1〜6 アルキル基または、C _1〜6 アルコキシ基であり、
nが、0または1の整数であり、
mが、0または1の整数である。

(1)
[Wherein, R ₁ represents a hydrogen atom, a hydroxyl group, a halogen atom, a C _1-6 alkyl group that may be substituted with a halogen atom, or a C _1-6 alkoxy group that may be substituted with a halogen atom; ₂ is a hydrogen atom, a halogen _{atom, oR 2 ', OC oR 2} ', NR 2 'R 2 ", SR 2', SC oR 2 '(R 2', R 2" are the same or different and each a hydrogen atom Or a halogen atom, a C _1-4 alkoxy group, or a C _1-6 alkyl group optionally substituted with a C _1-4 alkylcarbonyl group), or C _1-6 alkoxy-C _1-6 alkoxy- _{Represents a} C _1-6 alkyloxy group,
R ₃ or R ₄ is the same or different and each represents a hydrogen atom, a hydroxyl group, a halogen atom, a C _1-6 alkoxy group that may be substituted with a halogen atom, a phenyl group that may be substituted, or a phenyloxy group that may be substituted , optionally C _{1 to 6} alkylthio group optionally substituted by a halogen atom, by C _{1 to 6} may be alkylsulfinyl group substituted with a halogen atom, a substituted C _{1 to 6} may be an alkylsulfonyl group with a halogen atom, a cyano group , A formyl group, a C _1-6 alkyloxycarbonyl group, a C _1-6 alkylcarbonyloxy group, a halogen atom, or a linear or branched chain that may be partially unsaturated with a C _1-4 alkoxy Represents a C _1-6 alkyl group, or
R ₃ and R ₄ together may form a 5-7 membered saturated cyclic alkyl or saturated heterocycle,
R represents a hydrogen atom or a C _1-6 alkyl group,
W represents a group —Y—W ′, and W ′ represents an optionally substituted phenyl group (wherein the substituent is a halogen atom, a C _1-6 alkyl group _optionally substituted with a halogen atom, a halogen atom) C _1-6 alkoxy group optionally substituted with an atom, mono or di C _1-6 alkyl substituted amino group, cyano group, nitro group, C _1-6 alkylthio group optionally substituted with a halogen atom, halogen optionally substituted with atoms C _{1 to 6} alkylsulfinyl group, an optionally C _{1 to 6} alkylsulfonyl group optionally substituted with a halogen atom, formyl group, C _{1 to 6} alkyloxycarbonyl group, C _{1 to 6} alkyl —O— (CH ₂ ) _p —O— (where p represents an carbonyloxy group or is formed by combining two adjacent groups on the phenyl group together) Represents 1 or 2) Represents a 5-membered or 6-membered heterocyclic ring may be saturated or unsaturated optionally substituted, Y _{is, (CH 2) l, O} (CH 2) l, S (CH 2) l, (CH 2) l O, (CH ₂ ) ₁ S, NR _y (CH ₂ ) ₁ or (CH ₂ ) ₁ NR _y (R _y represents a hydrogen atom, a C _1-6 alkyl group), and l is 0-4 Represents an integer,
X is a hydroxyl group, a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, a C _1-6 alkoxy group which may be substituted with a halogen atom, a mono or di C _1-6 alkyl substituted amino group Group, cyano group, nitro group, C _1-6 alkylthio group optionally substituted with a halogen atom, C _1-6 alkylsulfinyl group optionally substituted with a halogen atom, optionally substituted with a halogen atom C _1-6 alkylsulfonyl group, formyl group, C _1-6 alkyloxycarbonyl group or C _1-6 alkylcarbonyloxy group,
n represents an integer of 0 to 4,
m represents an integer of 0 to 4, provided that
R _{2 to} R ₄ or R ₁ , R ₃ and R ₄ do not all represent the same hydrogen atom. ]
Particularly, in the formula (1), R ₁ is a hydrogen atom, a C _1-6 alkyl group or a halogen atom,
R ₂ is a hydroxyl group or a C _1-6 alkylcarbonyloxy group,
R ₃ and R ₄ are C _1-6 alkoxy groups,
R is a hydrogen atom,
W is an optionally substituted phenyloxy group (the substituent is a halogen atom, a C _1-6 alkyl group that may be substituted with a halogen atom, a C _1-6 alkoxy group that may be substituted with a halogen atom) , A cyano group, a C _1-6 alkylthio group optionally substituted with a halogen atom, a C _1-6 alkylsulfinyl group optionally substituted with a halogen atom, or two adjacent groups on the phenyl group A group formed together, which is —O— (CH ₂ ) _p —O— (where p is 1 or 2) optionally substituted with a halogen atom, a phenyl group, benzyloxy Or a phenylthio group which may be substituted (the substituent is a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom ),
X is a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, or a C _1-6 alkoxy group,
n is an integer of 0 or 1,
m is an integer of 0 or 1.

  The second aspect of the present invention provides a compound represented by the following formula (A) or an agriculturally and horticulturally acceptable acid addition salt thereof.

（Ａ）
[式中、R₁₀₁は、水素原子、フッ素原子、塩素原子または、メチル基を表し、
R₁₀₂は、OR₂’または、OC OR₂’（R₂’は同一または異なって、水素原子かまたは、ハロゲン原子、C_1〜4アルコキシ基、またはC_1〜4アルキルカルボニル基で置換されていてもよいC_1〜6アルキル基を表す）を表し、
Yは、(CH₂)_ｌ、O(CH₂)_ｌ、S(CH₂)_ｌ、(CH₂)_ｌO、(CH₂)_ｌS、NR_y(CH₂)_ｌまたは、(CH₂)_ｌNR_y（R_yは水素原子、C_1〜6アルキル基を表す）を表し、ｌは0〜4の整数を表し、
W₁₀₁、W₁₀₂は、同一または異なってハロゲン原子、ハロゲン原子で置換されていてもよいC_1〜6アルキル基、ハロゲン原子で置換されていてもよいC_1〜6アルコキシ基、ハロゲン原子で置換されていてもよいC_1〜6アルキルチオ基を表すかまたは、W₁₀₁とW₁₀₂が隣り合ってかつ、2つの基が一緒になって形成される、ハロゲン原子で置換されていてもよい−O−（CH₂）_ｐ−O−（ここでｐは1または2を表す）を表し、
W₁₀₃は、水素原子、ハロゲン原子、ハロゲン原子で置換されていてもよいC_1〜6アルキル基、ハロゲン原子で置換されていてもよいC_1〜6アルコキシ基、モノまたはジC_1〜6アルキル置換アミノ基、シアノ基、ニトロ基、ハロゲン原子で置換されていてもよいC_1〜6アルキルチオ基、ハロゲン原子で置換されていてもよいC_1〜6アルキルスルフィニル基、ハロゲン原子で置換されていてもよいC_1〜6アルキルスルフォニル基、ホルミル基、C_1〜6アルキルオキシカルボニル基または、C_1〜6アルキルカルボニルオキシ基を表し、
Xは、水酸基、ハロゲン原子、ハロゲン原子で置換されていてもよいC_1〜6アルキル基、ハロゲン原子で置換されていてもよいC_1〜6アルコキシ基、モノまたはジC_1〜6アルキル置換アミノ基、シアノ基、ニトロ基、ハロゲン原子で置換されていてもよいC_1〜6アルキルチオ基、ハロゲン原子で置換されていてもよいC_1〜6アルキルスルフィニル基、ハロゲン原子で置換されていてもよいC_1〜6アルキルスルフォニル基、ホルミル基、C_1〜6アルキルオキシカルボニル基または、C_1〜6アルキルカルボニルオキシ基を表し、
mは、0〜4の整数を表す。]

(A)
[Wherein R ₁₀₁ represents a hydrogen atom, a fluorine atom, a chlorine atom or a methyl group,
R ₁₀₂ is OR ₂ ′ or OC OR ₂ ′ (R ₂ ′ is the same or different and is substituted with a hydrogen atom, a halogen atom, a C _1-4 alkoxy group, or a C _1-4 alkylcarbonyl group. Represents an _{optionally substituted} C _1-6 alkyl group),
Y is (CH ₂ ) ₁ , O (CH ₂ ) ₁ , S (CH ₂ ) _1, (CH ₂ ) ₁ O, (CH ₂ ) ₁ S, NR _y (CH ₂ ) ₁ or (CH ₂ ) _l NR _y (R _y represents a hydrogen atom, a C _1-6 alkyl group), l represents an integer of 0-4,
W ₁₀₁ and W ₁₀₂ are the same or different and are substituted with a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, a C _1-6 alkoxy group which may be substituted with a halogen atom, or a halogen atom. -O represents an optionally substituted C _1-6 alkylthio group, or W ₁₀₁ and W ₁₀₂ are adjacent to each other and the two groups are formed together, -O optionally substituted with a halogen atom - (CH _{2) p} -O- (wherein p is 1 or 2) represents,
W ₁₀₃ represents a hydrogen atom, a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, a C _1-6 alkoxy group which may be substituted with a halogen atom, mono- or di-C _1-6 alkyl A substituted amino group, a cyano group, a nitro group, a C _1-6 alkylthio group optionally substituted with a halogen atom, a C _1-6 alkylsulfinyl group optionally substituted with a halogen atom, and a halogen atom substituted May represent a C _1-6 alkylsulfonyl group, a formyl group, a C _1-6 alkyloxycarbonyl group, or a C _1-6 alkylcarbonyloxy group,
X is a hydroxyl group, a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, a C _1-6 alkoxy group which may be substituted with a halogen atom, a mono or di C _1-6 alkyl substituted amino group Group, cyano group, nitro group, C _1-6 alkylthio group optionally substituted with a halogen atom, C _1-6 alkylsulfinyl group optionally substituted with a halogen atom, optionally substituted with a halogen atom C _1-6 alkylsulfonyl group, formyl group, C _1-6 alkyloxycarbonyl group or C _1-6 alkylcarbonyloxy group,
m represents an integer of 0 to 4. ]

  The compound of the present invention exhibits an excellent control effect against harmful insects and mites, and is useful as a novel insecticide and acaricide.

  In the present specification, “halogen” refers to fluorine, chlorine, bromine and iodine, and the halogen atom in formula (1) is preferably a fluorine atom or a chlorine atom.

The “alkyl group” is a saturated or unsaturated linear or branched C _1-6 alkyl group.

In the formula (1), R ₁ is preferably a hydrogen atom, a hydroxyl group, a halogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, more preferably a hydrogen atom, a halogen atom, C _1-6 alkyl. It is a group.

R ₂ is preferably a hydrogen atom, a hydroxyl group, a halogen atom, a C _1-6 alkoxy group, a C _1-6 alkylcarbonyloxy group or a C _1-6 alkoxy-C _1-6 alkoxy-C _1-6 alkyloxy group. More preferably a hydroxyl group or a C _1-6 alkylcarbonyloxy group.

A hydrogen atom on the phenyl group of “phenyl group” or “phenyloxy group” that R ₃ and R ₄ may represent may be substituted, and the substituent may be a halogen atom or a halogen atom. a C _1-6 alkoxy group, optionally substituted by halogen C _1-6 alkyl, optionally substituted C _1-6 alkylcarbonyl group with a halogen, optionally substituted by halogen C _{1- 6} alkylcarbonyloxy group, C _1-6 alkylcarbonylamino group optionally substituted with halogen, C _1-6 alkylaminocarbonyloxy group optionally substituted with halogen, C _optionally substituted with halogen _1-6 alkylaminocarbonyl group, C _1-6 alkylsulfonyloxy group optionally substituted with halogen, C _1-6 alkylthio group optionally substituted with halogen, substituted with halogen A C _1-6 alkylsulfinyl group, a halogen optionally substituted C _1-6 alkylsulfonyl group, a cyano group, and a formyl group.

R ₃ is preferably a hydrogen atom, a hydroxyl group, a C _1-6 alkoxy group, a phenyl group, a phenyloxy group, or a C _1-6 alkyl group, and more preferably a C _1-6 alkoxy group.

R ₄ is preferably a hydrogen atom, a hydroxyl group, a C _1-6 alkoxy group, a phenyl group, a phenyloxy group, or a C _1-6 alkyl group, and more preferably a C _1-6 alkoxy group.

  R is preferably a hydrogen atom.

The saturated or unsaturated 5- or 6-membered heterocyclic ring represented by W ′ is the same or different and has 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur. As thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, isothiazolyl, isoxazolyl, thiazolyl, oxazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, preferably pyridazinyl is there. In addition, the heterocyclic ring may be substituted, and examples of the substituent include a halogen atom, a C _1-4 alkyl group, a C _1-4 alkyloxy group, a nitro group, a cyano group, a formyl group, a trifluoromethyl group, Examples thereof include a trifluoromethoxy group, a trifluoromethylthio group, a trifluoromethylsulfinyl group, a trifluoromethylsulfonyl group, an acetyl group, and an acetyloxy group, and a halogen atom is preferable.

W is preferably a phenyl group which may be substituted with W ′ (wherein the substituent is a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, or a halogen atom which may be substituted with a halogen atom) Good C _1-6 alkoxy group, mono or di C _1-6 alkyl-substituted amino group, cyano group, C _1-6 alkylthio group optionally substituted with a halogen atom, or C optionally substituted with a halogen atom —O— (CH ₂ ) _p —O— (which is a _1-6 alkylsulfinyl group or is formed by combining two adjacent groups on a phenyl group together. Where p is 1 or 2) or an optionally substituted pyridyl group (wherein the substituent is a halogen atom) and Y is a bond, an oxygen atom, a sulfur atom, or- OCH ₂ - is a is based on -Y-W ', more Phenyl group also has Mashiku substituted (substituent is a halogen atom, optionally substituted by a halogen atom C _{1 to 6} alkyl groups, optionally C _{1 to 6} alkoxy group optionally substituted by a halogen atom , A cyano group, a C _1-6 alkylthio group optionally substituted with a halogen atom, a C _1-6 alkylsulfinyl group optionally substituted with a halogen atom, or two adjacent groups on the phenyl group groups are formed together, are optionally may -O- (CH _{2) p} -O- substituted by a halogen atom (here p is 1 or 2)), a phenyl group, a benzyl group or , An optionally substituted phenylthio group (the substituent is a halogen atom, a C _1-6 alkyl group _optionally substituted with a halogen atom).

X is preferably a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, or a C _1-6 alkoxy group.

  n is preferably an integer of 0 or 1.

  m is preferably an integer of 0 or 1.

In the formula (A), R ₁₀₁ is preferably a hydrogen atom, a chlorine atom or a methyl group.

R ₁₀₂ is preferably a hydroxyl group or OC OR ₂ ′ (R ₂ ′ represents a C _1-6 alkyl group).
Y is preferably a bond, an oxygen atom or a sulfur atom.
W ₁₀₁ and W ₁₀₂ are preferably the same or different and are a halogen atom, a C _1-6 alkyl group substituted with a halogen atom, a C _1-6 alkoxy group substituted with a halogen atom, or W ₁₀₁ And W ₁₀₂ are adjacent to each other and are formed by combining two groups together with a halogen atom, —O— (CH ₂ ) _p —O— (where p represents 1 or 2) It is.
W ₁₀₃ is preferably a hydrogen atom.
X is preferably a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, or a C _1-6 alkoxy group.
m is preferably an integer of 0 or 1.

Compound of Formula (1) According to a preferred embodiment of the present invention, R ₁ represents a hydrogen atom, a hydroxyl group, a halogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group,
R ₂ represents a hydrogen atom, a hydroxyl group, a halogen atom, a C _1-6 alkoxy group, a C _1-6 alkylcarbonyloxy group, or a C _1-6 alkoxy-C _1-6 alkoxy-C _1-6 alkyloxy group. ,
R ₃ or R ₄ are the same or different and each represents a hydrogen atom, a hydroxyl group, a C _1-6 alkoxy group, a phenyl group, a phenyloxy group, or a C _1-6 alkyl group,
R represents a hydrogen atom,
W is a group -Y-W ', and W' is a phenyl group which may be substituted (wherein the substituent is a halogen atom, a _C1-6 alkyl group which may be substituted with a halogen atom, C _1-6 alkoxy group optionally substituted with a halogen atom, mono or di C _1-6 alkyl substituted amino group, cyano group, C _1-6 alkylthio group optionally substituted with a halogen atom, or halogen atom Or a C _1-6 alkylsulfinyl group which may be substituted with —, or two adjacent groups on the phenyl group may be combined and substituted with a halogen atom —O— (CH ₂ ) _p— O— (wherein p is 1 or 2) or an optionally substituted pyridyl group (wherein the substituent is a halogen atom), and Y is a bond, an oxygen atom, sulfur atom or, -OCH ₂ - represents,
X represents a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, or a C _1-6 alkoxy group,
n represents an integer of 0 or 1,
m represents an integer of 0 or 1.

According to a further preferred embodiment of the present invention, R ₁ represents a hydrogen atom, a C _1-6 alkyl group or a halogen atom,
R ₂ represents a hydroxyl group or a C _1-6 alkylcarbonyloxy group,
R ₃ and R ₄ represent a C _1-6 alkoxy group,
R represents a hydrogen atom,
W is an optionally substituted phenyloxy group (the substituent is a halogen atom, a C _1-6 alkyl group that may be substituted with a halogen atom, a C _1-6 alkoxy group that may be substituted with a halogen atom) , A cyano group, a C _1-6 alkylthio group optionally substituted with a halogen atom, a C _1-6 alkylsulfinyl group optionally substituted with a halogen atom, or two adjacent groups on the phenyl group groups are formed together, are optionally may -O- (CH _{2) p} -O- substituted by a halogen atom (here p is 1 or 2)), a phenyl group, a benzyl group or , Represents an optionally substituted phenylthio group (the substituent is a halogen atom, a C _1-6 alkyl group _optionally substituted with a halogen atom),
X is a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, or a C _1-6 alkoxy group,
n represents an integer of 0 or 1,
m represents an integer of 0 or 1.

Compound of Formula (A) According to a preferred embodiment of the present invention,
R ₁₀₁ is a hydrogen atom, a chlorine atom or a methyl group,
R ₁₀₂ is a hydroxyl group or OC OR ₂ ′ (R ₂ ′ represents a C _1-6 alkyl group),
Y is a bond, an oxygen atom or a sulfur atom,
W ₁₀₁ and W ₁₀₂ are the same or different and are a halogen atom, a C _1-6 alkyl group substituted with a halogen atom, a C _1-6 alkoxy group substituted with a halogen atom, or W ₁₀₁ and W ₁₀₂ and it is adjacent, the two groups are formed together, be -O- substituted by halogen atom (here p represents 1 or 2) (CH _{2) p} -O- ,
W ₁₀₃ is a hydrogen atom,
X is a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, or a C _1-6 alkoxy group,
A compound in which m is an integer of 0 or 1 or an agricultural and horticulturally acceptable acid addition salt thereof is provided.

  According to a preferred embodiment of the present invention, there is provided an insecticidal and acaricidal composition comprising as an active ingredient a compound of formula (A) or an agriculturally and horticulturally acceptable acid addition salt thereof.

  Representative examples of the compound represented by formula (1) or formula (A) of the present invention are shown in Tables 1 to 5.

  Examples of the agriculturally and horticulturally acceptable acid addition salt of the compound represented by the formula (1) or the formula (A) of the present invention include hydrochloride, nitrate, sulfate, phosphate, acetate and the like.

The compound of the present invention represented by the formula (1a) can be produced by the method shown in the following scheme 1.
Scheme 1

［式中、R₁、R₂、R₃、R₄、X、W、m、nが、式（１）に記載のとおりであり、Zが水酸基、またはC_1-6アルキルオキシ基である。］
すなわち置換ニコチン酸誘導体（２）とアニリンまたはフェニルアルキルアミン（３）を縮合することにより製造することができる。また、必要に応じて縮合後化合物（１a）のW,Xを別の適当な置換基に変換して製造することもできる。
縮合に用いる縮合剤としては三塩化リン、三臭化リン、五塩化リン、オキシ塩化リン、塩化チオニル等の酸ハロゲン化合物生成剤、クロロギ酸エチル、塩化メタンスルホニル等の混合酸無水物生成剤、N,N’-ジシクロヘキシルカルボジイミド（DCC）、1-エチル-3-（3-ジメチルアミノプロピル）カルボジイミド塩酸塩（WSCI-HCl）、N,N-カルボジイミダゾール、2-エトキシ-N-エトキシカルボニル-1,2-ジヒドロキノリン（EEDQ）、トリフェニルホスフィン-四塩化炭素(錯体)等が挙げられる。また、1-ヒドロキシベンゾトリアゾール(HOBt)または１-ヒドロキシ-７-アザベンゾトリアゾール（HOAt）、N-ヒドロキシコハク酸イミド等の活性エステル化剤や、酸補足剤、例えばN−メチルモルホリン（NMM）、トリエチルアミン、４−（ジメチルアミノ）ピリジン（DMAP）またはジイソプロピルエチルアミンなどの存在下で縮合剤を用いて反応させることにより式（１a）の化合物を合成することができる。溶媒としては、ベンゼン、トルエン、キシレンなどの芳香族炭化水素類、クロロベンゼン、ジクロロベンゼン等のハロゲン化芳香族炭化水素類、ヘキサン、シクロヘキサン、石油エーテル等の脂肪族炭化水素類、ジクロロメタン、1,2-クロロエタン、クロロホルム、四塩化炭素等の脂肪族ハロゲン化炭化水素類、ジエチルエーテル、ジイソプロピルエーテル、ジオキサン、テトラヒドロフラン等のエーテル類、アセトン、2-ブタノン等のケトン類、アセトニトリル、プロピオニルニトリル等のニトリル類、N,N-ジメチルホルムアミド、ヘキサメチルホスソリックトリアミド（HMPA）等のアミド類、ジメチルスルホキシド等のスルホキシド類またはこれらの混合溶媒等が挙げられる。

[Wherein, R ₁ , R ₂ , R ₃ , R ₄ , X, W, m, n are as described in formula (1), and Z is a hydroxyl group or a C _1-6 alkyloxy group . ]
That is, it can be produced by condensing the substituted nicotinic acid derivative (2) with aniline or phenylalkylamine (3). Moreover, it can also manufacture by converting W and X of the compound (1a) after condensation into another suitable substituent as needed.
As the condensing agent used for the condensation, acid halogen compound generators such as phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride, mixed acid anhydride generators such as ethyl chloroformate and methanesulfonyl chloride, N, N'-dicyclohexylcarbodiimide (DCC), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSCI-HCl), N, N-carbodiimidazole, 2-ethoxy-N-ethoxycarbonyl- Examples include 1,2-dihydroquinoline (EEDQ), triphenylphosphine-carbon tetrachloride (complex), and the like. In addition, active esterifying agents such as 1-hydroxybenzotriazole (HOBt) or 1-hydroxy-7-azabenzotriazole (HOAt), N-hydroxysuccinimide, acid supplements such as N-methylmorpholine (NMM) , Triethylamine, 4- (dimethylamino) pyridine (DMAP), diisopropylethylamine and the like can be reacted with a condensing agent to synthesize the compound of formula (1a). Solvents include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, aliphatic hydrocarbons such as hexane, cyclohexane and petroleum ether, dichloromethane, 1,2 -Aliphatic halogenated hydrocarbons such as chloroethane, chloroform and carbon tetrachloride, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone and 2-butanone, and nitriles such as acetonitrile and propionylnitrile Amides such as N, N-dimethylformamide and hexamethylphosphoric triamide (HMPA), sulfoxides such as dimethyl sulfoxide, and mixed solvents thereof.

Next, as shown in Scheme 2, the compound represented by the formula (1b) is obtained by reacting the compound of the formula (1a) with an alkyl halide in the presence of a base or in the absence of a base, and converting the substituent as necessary. Can be synthesized.
Scheme 2

［式中、Rが、C_1-6アルキル基であり、R₁、R₂、R₃、R₄、X、W、m、nが、式（１）に記載のとおりである。］
ここで塩基としては、例えばトリエチルアミン、ピリジン等の有機アミン、炭酸カリウム、炭酸ナトリウム、水素化ナトリウム等の無機アルカリが挙げられる。

[Wherein R is a C _1-6 alkyl group, and R ₁ , R ₂ , R ₃ , R ₄ , X, W, m, and n are as described in formula (1). ]
Examples of the base include organic amines such as triethylamine and pyridine, and inorganic alkalis such as potassium carbonate, sodium carbonate, and sodium hydride.

As shown in Scheme 3, the compound of formula (1c) is a compound of formula (1 ′) in which R ₂ in formula (1) is OH, in the presence or absence of a base, an alkylating agent, acyl It can also be synthesized by reacting with an agent.
Scheme 3

［式中、R₂がOR₂’、OC OR₂’（R₂’が式（１）に記載のとおりである）であり、R₁、R₃、R₄、R、X、W、m、nが、式（１）に記載のとおりである。］
用いるアルキル化剤としては、ハロゲン化アルキル、ジアゾメタン、ジメチル硫酸、ジエチル硫酸が挙げられる。アシル化剤としては、カルボン酸、酸無水物、ハロゲン化アシルが挙げられる。塩基としては、例えばトリエチルアミン、ピリジン等の有機アミン、炭酸カリウム、炭酸ナトリウム、水素化ナトリウム等の無機アルカリが挙げられる。

[Wherein R ₂ is OR ₂ ′, OC OR ₂ ′ (R ₂ ′ is as described in Formula (1)), and R ₁ , R ₃ , R ₄ , R, X, W, m , N are as described in formula (1). ]
Examples of the alkylating agent used include alkyl halides, diazomethane, dimethyl sulfate, and diethyl sulfate. Examples of the acylating agent include carboxylic acid, acid anhydride, and acyl halide. Examples of the base include organic amines such as triethylamine and pyridine, and inorganic alkalis such as potassium carbonate, sodium carbonate, and sodium hydride.

The compound represented by the formula (2) can be produced by the method shown in the following scheme 4.
Scheme 4

［式中、R₁、R₂、R₃、R₄が、式（１）に記載のとおりであり、Zが水酸基、または低級アルキルオキシ基である。また、Qは、式（５a）においてメチル基、ハロゲン化メチル基、ヒドロキシメチル基、低級アルコキシメチル基、ホルミル基、シアノ基、三級アミノメチル基、プロパルギル基、酸ヒドラジドであり、式（５b）においてシアノ基、ニトロ基、エステル基、１，１，１−トリハロゲン化メチル基、酸ハロゲン化物、酸無水物、酸アミド、酸イミド、酸ヒドラジド、アルドオキシムである。］
すなわち、市販または標準的手順で置換基の変換を行って得られる置換ピリジル誘導体（４）に、塩基存在下もしくは塩基非存在下でメチル基、ハロゲン化メチル基、ヒドロキシメチル基、低級アルコキシメチル基、ホルミル基、シアノ基、三級アミノメチル基、プロパルギル基、酸ヒドラジドを導入した誘導体（５a）を合成した後、酸化反応を行うことにより式（２）で示される化合物を合成することができる。好ましくはメチル基、ハロゲン化メチル基、メチルアルコール基、ホルミル基、シアノ基を用いる。または式（２）で示される化合物は化合物（４）を塩基存在下もしくは塩基非存在下でシアノ基、ニトロ基、エステル基、１，１，１−トリハロゲン化メチル基、酸ハロゲン化物、酸無水物、酸アミド、酸イミド、酸ヒドラジド、アルドオキシムを導入した誘導体（５ｂ）を合成した後、加水分解反応を行うことによっても合成することができる。好ましくはシアノ基、エステル基を用いる。さらに、式（２）の化合物は化合物（４）を、塩基存在下で一酸化炭素、二酸化炭素、ギ酸と反応させることによっても合成することができる。用いるメチル化剤としては、ハロゲン化メチル、ジメチル硫酸、ジアゾメタンが挙げられる。ヒドロキシメチル化剤としてはホルムアルデヒド、パラホルムアルデヒドが挙げられる。ハロゲン化メチル化剤としては１，１−ジブロモメタン、１−ブロモ１−クロロメタン、１，１−ジクロロメタンが挙げられる。ホルミル化剤としては、１，１−ジメチルホルムアミド、ギ酸メチル、ギ酸エチルが挙げられる。シアノ化剤としては、シアン化カリウム、シアン化ナトリウム、シアン化銅などの金属シアン化物、臭化シアン、シアン化トルエンスルフォニルが挙げられる。エステル化剤としては、一酸化炭素、二酸化炭素、ハロゲン化炭酸アルキルが挙げられる。

[Wherein R ₁ , R ₂ , R ₃ and R ₄ are as described in formula (1), and Z is a hydroxyl group or a lower alkyloxy group. Q is a methyl group, a halogenated methyl group, a hydroxymethyl group, a lower alkoxymethyl group, a formyl group, a cyano group, a tertiary aminomethyl group, a propargyl group, or an acid hydrazide in the formula (5a). And cyano group, nitro group, ester group, 1,1,1-trihalogenated methyl group, acid halide, acid anhydride, acid amide, acid imide, acid hydrazide, and aldoxime. ]
That is, a substituted pyridyl derivative (4) obtained by converting a substituent by a commercially available or standard procedure, a methyl group, a halogenated methyl group, a hydroxymethyl group, a lower alkoxymethyl group in the presence or absence of a base. Then, after synthesizing the derivative (5a) into which formyl group, cyano group, tertiary aminomethyl group, propargyl group and acid hydrazide are introduced, the compound represented by formula (2) can be synthesized by carrying out an oxidation reaction. . Preferably, a methyl group, a halogenated methyl group, a methyl alcohol group, a formyl group, or a cyano group is used. Alternatively, the compound represented by the formula (2) is obtained by reacting the compound (4) with a cyano group, a nitro group, an ester group, a 1,1,1-trihalogenated methyl group, an acid halide, an acid in the presence or absence of a base. It can also be synthesized by synthesizing a derivative (5b) into which an anhydride, acid amide, acid imide, acid hydrazide, or aldoxime has been introduced, followed by a hydrolysis reaction. Preferably, a cyano group or an ester group is used. Furthermore, the compound of the formula (2) can also be synthesized by reacting the compound (4) with carbon monoxide, carbon dioxide and formic acid in the presence of a base. Examples of the methylating agent used include methyl halide, dimethyl sulfate, and diazomethane. Examples of the hydroxymethylating agent include formaldehyde and paraformaldehyde. Examples of the halogenated methylating agent include 1,1-dibromomethane, 1-bromo1-chloromethane, and 1,1-dichloromethane. Examples of the formylating agent include 1,1-dimethylformamide, methyl formate, and ethyl formate. Examples of the cyanating agent include metal cyanides such as potassium cyanide, sodium cyanide, and copper cyanide, cyanogen bromide, and cyanogen toluenesulfonyl. Examples of the esterifying agent include carbon monoxide, carbon dioxide, and alkyl halide carbonate.

The compound represented by the formula (3) can be produced by the method shown in the following scheme 5.
Scheme 5

［式中、X、W、m、nが、式（１）に記載のとおりである。］
すなわち対応する置換基を有するニトロ化合物（６）におけるニトロ基を還元することにより製造することができる。

[Wherein, X, W, m and n are as described in formula (1). ]
That is, it can be produced by reducing the nitro group in the nitro compound (6) having a corresponding substituent.

Further, as shown in Scheme 6, the compound of the formula (6a) in which W in the formula (6) is —O—W ′ can be produced from the compound of the formula (7) and the compound of the formula (8).
Scheme 6

［式中、X、W’、m、nが、式（１）に記載のとおりである。］
すなわち、一般に入手可能な式（７）のニトロ化合物および式（８）のアルコールを塩基存在下あるいは塩基非存在下で反応させ式（６a）の化合物を合成することができる。ここでHalはフッ素、塩素、臭素、ヨウ素のようなハロゲン原子を示す。

[Wherein, X, W ′, m and n are as described in the formula (1). ]
That is, a compound of formula (6a) can be synthesized by reacting a generally available nitro compound of formula (7) and an alcohol of formula (8) in the presence or absence of a base. Here, Hal represents a halogen atom such as fluorine, chlorine, bromine or iodine.

As shown in Scheme 7, the compound of formula (6b) in which W in formula (6) is —S—W ′ can be prepared from the compound of formula (7) and the compound of formula (9).
Scheme 7

［式中、X、W’、m、nが、式（１）に記載のとおりである。］

[Wherein, X, W ′, m and n are as described in the formula (1). ]

As shown in Scheme 8, the compound of formula (6c) in which W in formula (6) is —NH—W ′ can be prepared from the compound of formula (7) and the compound of formula (10).
Scheme 8

［式中、X、W’、m、nが、式（１）に記載のとおりである。］

[Wherein, X, W ′, m and n are as described in the formula (1). ]

As shown in Scheme 9, the compound of formula (6d) in which W in formula (6) is -W 'can be produced from the compound of formula (7) and the compound of formula (11).
Scheme 9

［式中、X、W’、m、nが、式（１）に記載のとおりである。］

[Wherein, X, W ′, m and n are as described in the formula (1). ]

  The derivative represented by the formula (A) of the present invention can also be synthesized by the same method as that for the compound of the formula (1).

  Representative examples of the insect species in which the derivative represented by the formula (1) or the formula (A) of the present invention exhibits a controlling effect include lepidopterous pests, for example, Spodoptera litura, Scarlet moth, Scots moth, Aomushi, Konaiga, Shirochimojito, Nikaameiga, Knotomeiga, Hemiptera, Thymus moth, Anopheles, Tobacco, etc. Azuki beetle, white-tailed beetle, western corn root worm, southern corn root worm, red squirrel buoy, scallop, kiss beetle, cucumber potato beetle, Colorado potato potato beetle, rice beetle, sink Muscarids, longhorn beetles, etc., Acarina, for example, nymphid mite, black spider mite, kanzawa spider mite, citrus spider mite, apple spider mite, citrus mite, teaspider mite, pterodactyl mite etc. Dipterous pests such as house flies, leafhoppers, thrips pests such as southern thrips, citrus thrips, etc., plant parasitic nematodes such as root-knot nematodes, nesting nematodes, prunus nematodes, pine wood nematodes etc. In particular, it exhibits an excellent effect against hemipod pests, mites, and thrips pests.

  According to another aspect of the present invention, there is provided use of a compound represented by the formula (1) or an agriculturally and horticulturally acceptable acid addition salt for producing an agricultural and horticultural insecticidal or acaricidal composition. The In addition, about the said use, it can implement easily based on the content described above.

  Moreover, according to another aspect of the present invention, use of a compound represented by the formula (A) or an agriculturally and horticulturally acceptable acid addition salt for producing an agricultural and horticultural insecticide or acaricidal composition is possible. Provided. In addition, about the said use, it can implement easily based on the content described above.

  When the compound of formula (1) or formula (A) of the present invention is used as an active ingredient of an agricultural / horticultural insecticidal or acaricidal composition, the derivative may be used as it is, but usually a suitable solid carrier, Emulsions, EW agents, solutions, suspensions, wettable powders, granular wettable powders, powders, DL powders, liquid carriers, gaseous carriers, etc. It is used in any dosage form such as powder, granule, tablet, oil, aerosol, flowable, dry flowable, and microcapsule.

  Examples of the solid support include talc, bentonite, 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. .

  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; aliphatic hydrocarbons such as n-hexane, kerosene and kerosene, toluene , Aromatic hydrocarbons such as xylene and methylnaphthalene, ethers such as diethyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, nitriles such as acetonitrile and isobutyronitrile, acids such as dimethylformamide and dimethylacetamide Examples include amides, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, and water.

  Examples of the gaseous carrier include LPG, air, nitrogen, carbon dioxide gas, dimethyl ether and the like.

  Surfactants and dispersants for emulsification, dispersion, spreading, etc. include, for example, alkyl sulfates, alkyl (aryl) sulfonates, polyoxyalkylene alkyl (aryl) ethers, polyhydric alcohol esters, lignin Formalin condensates of sulfonates, alkylsulfosuccinates, alkylnaphthalenesulfonates, polycarboxylates, POE polystyrylphenyl ether sulfates and phosphates, POE / POP block polymers, and the like are used.

  Further, adjuvants for improving the properties of the preparation include, for example, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, xanthan gum, pregelatinized starch, gum arabic, polyethylene glycol, liquid paraffin, calcium stearate, and antifoaming agent, antiseptic, An agent or the like is used.

  The above carriers, surfactants, dispersants, and adjuvants may be used alone or in combination as necessary.

  The content of active ingredients in these preparations is usually 1-75% by weight for emulsions, usually 0.3-25% by weight for powders, 1-90% by weight for wettable powders, and usually 0.5-% for granules. 10% by weight is suitable.

  These preparations are used as they are or diluted. These preparations can also be used by mixing with other fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers and the like.

  Drugs that can be used in combination are those listed in the Pesticide Manual (issued by The British Crop Protection Council 13th edition) and Shibuya Index (issued by SHIBUYA INDEX 9th edition, 2002, published by SHIBUYA INDEX RESEARCH GROUP). . For example, the insecticide, acaricide or nematicide used may be, for example, acephate, dichlorvos, EPN, fenitrothion, fenamifos, prothiofos, profenofos , Pyraclofos, chlorpyrifos-methyl, organophosphate compounds such as diazinon, metomyl, thiodicarb, aldicarb, oxamyl, propoxyl ( carbamate compounds such as propoxur, carbaryl, fenobucarb, ethiofencarb, fenothiocarb, pirimicarb, carbofuran, benfuracarb, cartap, thiocyclam Ne like (thiocyclam) Istoxin derivatives, organochlorine compounds such as dicofol, tetradifon, permethrin, tefluthrin, cypermethrin, deltamethrin, cyhalothrin, fenvalerate ), Fluvalinate, etofenprox, pyrethroids such as silafluofen, diflubenzuron, teflubenzuron, flufenoxuron, chlorfluazuron Benzoyl urea compounds such as methoprene, juvenile hormone-like compounds such as metoprene, and other compounds such as buprofezin, hexythiazox, amitraz, chlordimeform, pyridaben idaben), fenpyroxymate, pyrimidifen, tebufenpyrad, fluacrypyrim, acequinocyl, cyflumetofen, flubendiamide, profitrol, ethiprol (ethoxazole), imidacloprid, chlothianidin, pymetrozine, bifenazate, spirodiclofen, spirodisifen, spiromesifen, chlorfenapyr, pyriproxyfen (pyri) Alternatively, it may be a compound such as avermectin, milbemycin, organometallic compound, dinitro compound, organosulfur compound, urea compound, triazine compound, hydrazine compound. Furthermore, the compound of the present invention can be used in combination or in combination with a microbial pesticide such as a BT agent, an entomopathogenic virus agent and the like.

  Examples of the bactericides used include azoxystrobin, kresoxym-methyl, trifloxystrobin and other strobilurin compounds, mepanipyrim, pyrimethanil, cyprodinil ) Anilinopyrimidine-based compounds such as triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, microbutanyl azole compounds such as myclobutanil, cyproconazole, tebuconazole, hexaconazole, prochloraz, simeconazole, and quinoxalines such as quinomethionate Compounds, maneb, zineb, mancozeb, dicarbamate compounds such as polycarbamate, propineb, phenyl carbamate compounds such as dietofencarb, chlorothalonil ), Organochlorine compounds such as quintozene, benomyl, thiophanate-methyl, benzimidazole compounds such as carbendazole, metalaxyl, oxadixyl, and olase ( ofurace), benalaxyl, furalaxyl, phenylamide compounds such as cyprofuram, sulfenic compounds such as dichlofluanid, cupric hydroxide, oxy Copper-based compounds such as oxine-copper, Isoxazole compounds such as hydroxyisoxazole, organophosphorus compounds such as fosetyl-aluminium, tolclofos-methyl, captan, captafol, N-halogenothioalkyl compounds such as folpet, procymidone, iprodione, dicarboximide compounds such as vinchlozolin, flutolanil, mepronil, etc. Benzanilide compounds, morpholine compounds such as fenpropimorph, dimethomorph, phenthin hydroxide, organotin compounds such as fenthin acetate, fludioxonil (fludioxonil), fenpiclonil Anopirole compounds, other fthalide, fluazinam, cymoxanil, triforine, pyrifenox, fenarimol, fenpropidin, pencicuron, cyazofamide ( cyazofamid), iprovalicarb, and benchthiavalicarb-isopropyl.

  According to another aspect of the present invention, an effective amount of the compound represented by the formula (1) or an agriculturally and horticulturally acceptable acid addition salt thereof is applied to various application targets, particularly plants or soils. There is provided a method for controlling agricultural and horticultural pests, especially mites. Therefore, when carrying out the control method according to the present invention, at least an effective amount of the compound represented by the formula (1) or an acid and pharmaceutically acceptable acid addition salt thereof is applied to various applications. What is necessary is just to include one or more well-known pre-treatments or post-treatments used for controlling other agricultural and horticultural pests. In addition, about the compound represented by the said Formula (1), or its acid-acceptable acid addition salt, it is as having described above.

  The effective amount of the compound represented by the formula (1) described above or an acid addition salt acceptable in agriculture and horticulture is not particularly limited, but preferably 1 to 75% by weight when an emulsion is selected as the dosage form. Preferably 0.3 to 25% by weight when powder is selected, preferably 1 to 90% by weight when wettable powder is selected, and preferably 0.5 to 10% by weight when granule is selected. .

  Furthermore, according to another aspect of the present invention, an effective amount of the compound represented by the formula (A) or an agriculturally and horticulturally acceptable acid addition salt thereof is applied to various applications, particularly plants or soils. There is provided a method for controlling agricultural and horticultural pests, especially mites. Therefore, when the control method according to the present invention is carried out, it includes at least applying an effective amount of the compound represented by the formula (A) or an acid-addition salt acceptable in agriculture and horticulture to various applications. What is necessary is just to include one or more well-known pre-treatments or post-treatments used for controlling other agricultural and horticultural pests. In addition, the compound represented by the formula (A) or the acid addition salt acceptable in agriculture and horticulture is as described above.

  The effective amount of the compound represented by the formula (A) described above or an acid addition salt acceptable in agriculture and horticulture is not particularly limited, but preferably 1 to 75% by weight when an emulsion is selected as the dosage form. Preferably 0.3 to 25% by weight when powder is selected, preferably 1 to 90% by weight when wettable powder is selected, and preferably 0.5 to 10% by weight when granule is selected. .

  Here, in the control method according to the present invention, the compound represented by the formula (1), the compound represented by the formula (A), or an acid addition salt acceptable in agriculture and horticulture is applied in a sealed manner. Application by a known method that can be developed in the future, such as application by smoke treatment in a closed space, is also included.

Specific examples of the present invention are shown below, but the present invention is not limited thereto.
[Synthesis example]
Reference Example 1 Synthesis Example of Compound of Formula (2)
Synthesis of 2-chloro-4-hydroxy-5,6-dimethoxynicotinic acid (intermediate 2-1)
Dissolve 634 mg of 6-chloro-2,3-dimethoxy-4-pyridyl N, N-diisopropylcarbamate in 50 ml of tetrahydrofuran, cool to -78 ° C under argon atmosphere, and add 3.75 ml of 1.6 M normal butyl lithium hexane solution. After stirring for 1 hour, 1.88 g of methyl chlorocarbonate was added and stirred for 4 hours. To the reaction solution, 8 ml of a solution of acetic acid / EtOH / THF (2/2/4) was added, and the temperature was raised to room temperature. Further, 20 ml of a saturated aqueous potassium carbonate solution was added, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give 2-chloro-5 A crude product of methyl 6-dimethoxy-4- (N, N-diisopropylamino) carbonyloxynicotinate was obtained. The obtained crude product was added to 4N potassium hydroxide solution (80% aqueous methanol solution) under ice cooling, and the mixture was stirred at 75 ° C. for 6 hours. After allowing to cool, methanol was distilled off under reduced pressure, and the resulting solution was extracted with diethyl ether. The aqueous layer was adjusted to pH 2 or less with 4N hydrochloric acid, and extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 428 mg of 2-chloro-4-hydroxy-5,6-dimethoxynicotinic acid (intermediate 2-1).

Reference Example 2 Synthesis example of compound of formula (2)
Synthesis of 2,4-dihydroxy-5,6-dimethoxynicotinic acid (intermediate 2-2)
0.67 g of 2,3-dimethoxy-6- [2- (trimethylsilyl) ethoxy] methoxy-4-pyridyl N, N-diisopropylcarbamate was dissolved in 40 ml of tetrahydrofuran, cooled to −78 ° C. under an argon atmosphere, and 1.6 M After adding 3.1 ml of normal butyl lithium hexane solution and stirring for 1 hour, 1.2 g of methyl chlorocarbonate was added and stirred for 4 hours. To the reaction solution was added 8 ml of a solution of acetic acid / EtOH / THF (2/2/4), and the temperature was raised to room temperature. Further, 20 ml of a saturated aqueous potassium carbonate solution was added, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give 2- [2- A crude product of methyl (trimethylsilyl) ethoxy] methoxy-5,6-dimethoxy-4- (N, N-diisopropylamino) carbonyloxynicotinate was obtained. The obtained crude product was added to 30 ml of 4N potassium hydroxide solution (80% aqueous methanol solution) under ice-cooling, and the mixture was stirred at 75 ° C. for 14 hours. After allowing to cool, methanol was distilled off under reduced pressure, and the resulting solution was extracted with diethyl ether. The aqueous layer was adjusted to pH 2 or less with 4N hydrochloric acid, and extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 120 mg of 2,4-dihydroxy-5,6-dimethoxynicotinic acid (intermediate 2-2).

Reference Example 3 Synthesis Example of Compound of Formula (2)
Synthesis of 4-hydroxy-5,6-dimethoxy-2-methylnicotinic acid (intermediate 2-3) 25 ml of tetrahydrofuran was cooled to −78 ° C. under an argon atmosphere, and 950 μL of a 2.35 M normal butyllithium hexane solution was added. added. 2 ml of tetrahydrofuran in which 360 mg of 6-bromo-2,3-dimethoxy-4-pyridyl N, N-diisopropylcarbamate was dissolved was quickly added and stirred at the same temperature for 5 minutes, followed by tetrahydrofuran in which 1.42 g of methyl iodide was dissolved. 2 ml of the solution was added and stirred at −78 ° C. for 2 hours. To the reaction solution was added 8 ml of an acetic acid / EtOH / THF (2/2/4) solution, and the mixture was brought to room temperature and 20 ml of a saturated aqueous potassium carbonate solution was added. Tetrahydrofuran was distilled off under reduced pressure, followed by extraction with ethyl acetate. The organic layer was dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off. Purification with a silica gel column (hexane / ethyl acetate: 8/1) gave 6-methyl-2,3-dimethoxy-4-pyridyl N, N-diisopropylcarbamate. Dissolve 190 mg of 6-methyl-2,3-dimethoxy-4-pyridyl N, N-diisopropylcarbamate obtained in 20 mL of tetrahydrofuran, cool to −78 ° C. under argon atmosphere, and add 2.35 M normal butyl lithium hexane. 870 μL of the solution was gradually added dropwise. After stirring at the same temperature for 1 hour, 2 mL of a tetrahydrofuran solution in which 660 mg of methyl chloroformate was dissolved was added, and the mixture was stirred at -78 ° C for 1 hour. After adding 8 ml of a solution of acetic acid / EtOH / THF (2/2/4), the mixture was brought to room temperature and 20 ml of saturated aqueous potassium carbonate solution was added. Tetrahydrofuran was distilled off under reduced pressure, followed by extraction with ethyl acetate. The organic layer was dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off to obtain crude 2-methyl-5,6-dimethoxy-4- (N, N Methyl -diisopropylamino) carbonyloxynicotinate was obtained. Dissolve 243 mg of crude methyl 2-methyl-5,6-dimethoxy-4- (N, N-diisopropylamino) carbonyloxynicotinate in 12 mL of 5N sodium hydroxide solution (80% aqueous methanol) for 72 hours. Refluxed. After allowing to cool, methanol was distilled off under reduced pressure, and the resulting solution was extracted with ethyl acetate. The aqueous layer was acidified with 4N hydrochloric acid, extracted with diethyl ether, the organic layer was dehydrated with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give 4-hydroxy-5,6-dimethoxy-2-methylnicotine. The acid (intermediate 2-3) (113 mg) was obtained.

Reference Example 4 Synthesis Example of Compound of Formula (3)
2- [2- (Trifluoromethyl) phenoxy] aniline
Add potassium carbonate (2.6 g), 18-crown-6 (4.0 g), and 2-fluoronitrobenzene (0.5 g) to a dimethyl sulfoxide solution (30 ml) of 2- (trifluoromethyl) phenol (0.6 g) at room temperature. It was. After stirring at the same temperature for 15 hours, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1) to obtain 2- [2- (trifluoromethyl) phenoxy] nitrobenzene (1.0 g). The obtained 2- [2- (trifluoromethyl) phenoxy] nitrobenzene (0.6 g) was dissolved in methanol (15 ml), 10% palladium carbon (60 mg) was added, and the mixture was stirred at room temperature for 5 hours under a hydrogen atmosphere. did. The reaction mixture was filtered to remove the catalyst, and the solvent was distilled off under reduced pressure to obtain 2- [2- (trifluoromethyl) phenoxy] aniline (580 mg).

Reference Example 5 Synthesis Example of Compound of Formula (3)
To 15 ml of 2- [3- (trifluoromethyl) phenoxy] aniline dimethyl sulfoxide, add 3- (trifluoromethyl) phenol (0.48 g), 2-bromonitrobenzene (0.60 g) and potassium carbonate (0.32 g). After heating up to 120 ° C., the mixture was stirred at the same temperature for 6 hours. After allowing to cool, the reaction mixture was poured into water and extracted with ethyl acetate. The obtained ethyl acetate layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1) to obtain 2- [3- (trifluoromethyl) phenoxy] nitrobenzene (560 mg). Add iron powder (0.78 g) to a mixed solvent of ethanol (3 ml), water (5 ml), and concentrated hydrochloric acid (30 μl) and stir at 63 ° C with 2- [3- (trifluoromethyl) phenoxy] nitrobenzene. (560 mg) was added. After raising the temperature to 83 ° C., the mixture was stirred for 2 hours. After allowing to cool, an aqueous sodium hydrogen carbonate solution was added, and the mixture was filtered through celite and washed with ethanol. The solvent was concentrated under reduced pressure, and the resulting aqueous layer was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure to obtain a crude 2- [3- (trifluoromethyl) phenoxy] aniline (510 mg).

Reference Example 6 Synthesis Example of Compound of Formula (3)
To 50 ml of 2- [4- (trifluoromethyl) phenoxy] aniline dimethyl sulfoxide, 4- (trifluoromethyl) phenol (1.62 g), 2-bromonitrobenzene (2.02 g) and potassium carbonate (1.04 g) were added. After heating up to 120 ° C., the mixture was stirred at the same temperature for 12 hours. After allowing to cool, the reaction mixture was poured into water and extracted with ethyl acetate. The obtained ethyl acetate layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1) to obtain 2- [4- (trifluoromethyl) phenoxy] nitrobenzene (320 mg). 2- (4-Trifluoromethyl) phenoxynitrobenzene (300 mg) was dissolved in methanol (5 ml), 10% palladium carbon (30 mg) was added, and the mixture was stirred at room temperature for 6 hours in a hydrogen atmosphere. The reaction mixture was filtered to remove the catalyst, and the solvent was distilled off under reduced pressure to obtain 2- [4- (trifluoromethyl) phenoxy] aniline (274 mg).

Reference Example 7 Synthesis Example of Compound of Formula (3)
2- [3,5-Bis (trifluoromethyl) phenoxy] aniline
Potassium carbonate (7.2 g), 18-crown-6 (11.5 g), 2-fluoronitrobenzene (0.3 g) in dimethyl sulfoxide solution (85 ml) of 3,5-bis (trifluoromethyl) phenol (2.0 g) at room temperature ) Was added. After stirring at the same temperature for 15 hours, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1) to obtain 2- [3,5-bis (trifluoromethyl) phenoxy] nitrobenzene (0.9 g). 2- [3,5-bis (trifluoromethyl) phenoxy] nitrobenzene (1.68 g) is dissolved in methanol (30 ml), 10% palladium on carbon (100 mg) is added, and the mixture is stirred at room temperature for 4 hours under a hydrogen atmosphere. did. The reaction mixture was filtered to remove the catalyst, and the solvent was distilled off under reduced pressure to obtain 2- [3,5-bis (trifluoromethyl) phenoxy] aniline (1.50 g).

Reference Example 8 Synthesis Example of Compound of Formula (3)
2- [3-Fluoro-5- (trifluoromethyl) phenoxy] aniline
To a solution of 3-fluoro-5- (trifluoromethyl) phenol (1.0 g) in dimethyl sulfoxide (50 ml) at room temperature is potassium carbonate (4.6 g), 18-crown-6 (7.3 g), 2-fluoronitrobenzene (0.3 g). g) was added. After stirring at the same temperature for 15 hours, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1) to obtain 2- [3-fluoro-5- (trifluoromethyl) phenoxy] nitrobenzene (0.8 g). Iron powder (1.0 g) was added to a mixed solvent of ethanol (12 ml), water (5 ml) and concentrated hydrochloric acid (0.1 ml), and the intermediate (0.8 g) was added with stirring at 63 ° C. After raising the temperature to 83 ° C., the mixture was stirred for 2 hours. After allowing to cool, an aqueous sodium hydrogen carbonate solution was added, and the mixture was filtered through celite and washed with ethanol. The solvent was concentrated under reduced pressure, and the resulting aqueous layer was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure to give a crude 2- [3-fluoro-5- (trifluoromethyl) phenoxy] aniline product (200 mg). Obtained.

Reference Example 9 Synthesis Example of Compound of Formula (3)
4-Methoxy-2- [3,5-bis (trifluoromethyl) phenoxy] aniline
A solution of 3,5-bis (trifluoromethyl) phenol (1.0 g) in dimethyl sulfoxide (45 ml) at room temperature with potassium carbonate (3.6 g), 18-crown-6 (5.8 g), 2-fluoro-4-methoxy Nitrobenzene (0.2 g) was added. After stirring at the same temperature for 15 hours, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1) to give 4-methoxy-2- [3,5-bis (trifluoromethyl) phenoxy] nitrobenzene (1.1 g). Obtained. Add iron (1.2 g) to a mixed solvent of ethanol (10 ml), water (6 ml), and concentrated hydrochloric acid (0.1 ml) and stir at 63 ° C with 4-methoxy-2- [3,5-bis (tri Fluoromethyl) phenoxy] nitrobenzene (1.1 g) was added. After raising the temperature to 83 ° C., the mixture was stirred for 2 hours. After allowing to cool, an aqueous sodium hydrogen carbonate solution was added, and the mixture was filtered through celite and washed with ethanol. The solvent was concentrated under reduced pressure, and the resulting aqueous layer was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure to give a crude product of 4-methoxy-2- [3,5-bis (trifluoromethyl) phenoxy] aniline ( 600 mg) was obtained.

Reference Example 10 Synthesis Example of Compound of Formula (3)
2- [3,5-Bis (trifluoromethyl) phenylthio] aniline
3,5-Bis (trifluoromethyl) thiophenol (1.2 g) was added to a 60% sodium hydride (0.2 g) solution in dimethylformamide (5 ml) under ice cooling. After stirring at room temperature for 1 hour, 2-bromonitrobenzene (0.5 g) was added and heated to reflux. After 21 hours, the mixture was cooled at room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1) to obtain 2- [3,5-bis (trifluoromethyl) phenylthio] nitrobenzene (1.1 g). 2- [3,5-bis (trifluoromethyl) phenylthio] nitrobenzene (0.3 g) is dissolved in a mixed solvent of ethanol (0.5 ml) and water (0.5 ml), iron (2.9 g) is added, and the mixture is stirred at 100 ° C. did. A mixed solution of concentrated hydrochloric acid (0.2 ml), ethanol (0.4 ml) and water (0.4 ml) was added to the reaction solution, followed by heating under reflux for 2 hours. After allowing to cool, sodium hydroxide was added, and the mixture was filtered through celite and washed with ethanol. The solvent was concentrated under reduced pressure, and the resulting aqueous layer was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure to give a crude product of 2- [3,5-bis (trifluoromethyl) phenylthio] aniline (0.1 g). Obtained.

Reference Example 11 Synthesis Example of Compound of Formula (3)
2,5-bis (trifluoromethyl) phenylboric acid (0.9 g), 2-bromonitrobenzene (0.5 g), carbonic acid in 2- [3,5-bis (trifluoromethyl) phenyl] aniline acetone (25 ml) Potassium (1.0 g), triethylenediamine (17 mg), and palladium acetate (17 mg) were added, and the mixture was sealed and stirred at 110 ° C. for 2 hours. After cooling to room temperature, water was added, the solvent was concentrated under reduced pressure, and the resulting aqueous layer was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1) to obtain 2- [3,5-bis (trifluoromethyl) phenyl] nitrobenzene (0.23 g). 2- [3,5-bis (trifluoromethyl) phenyl] nitrobenzene (0.23 g) is dissolved in methanol (5 ml), 10% palladium on carbon (catalytic amount) is added, and the mixture is stirred at room temperature for 3 hours in a hydrogen atmosphere. did. The reaction mixture was filtered to remove the catalyst, and the solvent was distilled off under reduced pressure to obtain 2- [3,5-bis (trifluoromethyl) phenyl] aniline (0.10 g).

Reference Example 12 Synthesis Example of Compound of Formula (3)
2- [3-Fluoro-5- (trifluoromethyl) phenylthio] aniline potassium carbonate (2.5 g) in N, N-dimethylformamide solution (50 ml) was added to 3-fluoro-5- (trifluoromethyl) thiophenol. (3.3 g) and 2-fluoronitrobenzene (2.4 g) were added. The mixture was stirred at 90 ° C. for 5 hours, cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate, and then the solvent was concentrated under reduced pressure to obtain a crude product (5.0 g). This crude product (1.0 g) was dissolved in a mixed solvent of ethanol (5.0 ml) and concentrated hydrochloric acid (2.4 ml), tin chloride (2.1 g) was added, and the mixture was stirred at room temperature for 36 hours. The reaction mixture was poured into water (200 ml) and extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure to give a crude product of 2- [3-fluoro-5- (trifluoromethyl) phenylthio] aniline (0.29 g) Got.

Synthesis example 1
<Compound 15> 15 mg of 4-hydroxy-5,6-dimethoxy-2-methyl-3′-phenoxynicotinic acid anilide intermediate (2-3) and 10.4 mg of 1-hydroxybenzotriazole (HOBt) in 1 ml of tetrahydrofuran Dissolved. To this was added 0.4 ml of a tetrahydrofuran solution in which 15.9 mg of N, N′-dicyclohexylcarbodiimide (DCC) was dissolved. After stirring at 0 ° C. for 1 hour and at room temperature for 45 minutes, 0.4 ml of a tetrahydrofuran solution in which 65 mg of 3-phenoxyaniline was dissolved was added, and the mixture was stirred at room temperature for 3 hours. The solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate and washed with a saturated aqueous sodium hydrogen carbonate solution. The organic layer was washed with pH 2 hydrochloric acid and dehydrated with anhydrous sodium sulfate. After the solvent was distilled off, purification by preparative TLC gave 4.2 mg of compound 15.
Mass spectrometry data (ESI ⁺ ); 761 (2M + H) ⁺ , 381 (M + H) ⁺

<Compound 29> 2,4-dihydroxy-5,6-dimethoxy-2′-phenylnicotinic acid anilide intermediate (2-2) 15 mg and 1-hydroxybenzotriazole (HOBt) 10.4 mg were dissolved in tetrahydrofuran 1 ml. . To this was added 0.4 ml of a tetrahydrofuran solution in which 15.9 mg of N, N′-dicyclohexylcarbodiimide (DCC) was dissolved. After stirring at 0 ° C. for 1 hour and at room temperature for 45 minutes, 0.4 ml of a tetrahydrofuran solution in which 58 mg of 2-phenylaniline was dissolved was added, and the mixture was stirred at room temperature for 3 hours. The solvent was distilled off, and after dissolving in ethyl acetate, a saturated aqueous sodium hydrogen carbonate solution was added and partitioned. The organic layer was washed with pH 2 aqueous hydrochloric acid and dried over anhydrous sodium sulfate. After the solvent was distilled off, purification by preparative TLC gave 5.5 mg of compound 29.
Mass spectrometry data (ESI ⁺ ); 733 (2M + H) ⁺ , 367 (M + H) ⁺

<Compound 2> 16.5 mg of 2 -chloro-4-hydroxy-5,6-dimethoxy-4'-phenoxynicotinic acid anilide intermediate (2-1) and 10.4 mg of 1-hydroxybenzotriazole (HOBt) in 0.8 ml of tetrahydrofuran Dissolved. To this was added 0.8 ml of a dichloromethane solution in which 14.7 mg of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSCI-HCl) and 7.7 mg of triethylamine were dissolved. After stirring at 0 ° C. for 20 minutes and at room temperature for 50 minutes, 0.8 ml of a tetrahydrofuran solution in which 65 mg of 4-phenoxyaniline was dissolved was added, and the mixture was stirred at room temperature for 3.5 hours. A saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with a 1 mol / L aqueous citric acid solution and a saturated aqueous sodium chloride solution. The organic layer was dehydrated with anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by preparative TLC to obtain 4.8 mg of compound 2.
Mass spectrometry data (ESI ⁺ ); 403 (M + H) ⁺ , 401 (M + H) ⁺

<Compound 16>2-chloro-4-hydroxy-5,6-dimethoxy-3'-benzyloxynicotinic acid anilide intermediate (2-1) 16.5 mg and 1-hydroxybenzotriazole (HOBt) 10.4 mg Dissolved in 0.8 ml. To this was added 0.8 ml of a dichloromethane solution in which 14.7 mg of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSCI-HCl) and 7.7 mg of triethylamine were dissolved. After stirring at 0 ° C. for 20 minutes and at room temperature for 50 minutes, 0.8 ml of a tetrahydrofuran solution in which 70 mg of 3-benzyloxyaniline was dissolved was added, and the mixture was stirred at room temperature for 3.5 hours. A saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with a 1 mol / L aqueous citric acid solution and a saturated aqueous sodium chloride solution. The organic layer was dehydrated with anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by preparative TLC to obtain 6.6 mg of compound 16.
Mass spectrometry data (ESI ⁺ ); 417 (M + H) ⁺ , 415 (M + H) ⁺

<Compound 3> 16.5 mg of 2-chloro-4-hydroxy-5,6-dimethoxy-N- (4′-phenoxyphenyl) methylnicotinic acid amide intermediate (2-1) and 1-hydroxybenzotriazole (HOBt) Was dissolved in 0.8 ml of tetrahydrofuran. To this was added 0.8 ml of a dichloromethane solution in which 14.7 mg of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSCI-HCl) and 7.7 mg of triethylamine were dissolved. After stirring at 0 ° C. for 20 minutes and at room temperature for 50 minutes, 0.8 ml of a tetrahydrofuran solution in which 70 mg of 4-phenoxybenzylamine was dissolved was added and stirred at room temperature for 3.5 hours. A saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with a 1 mol / L aqueous citric acid solution and a saturated aqueous sodium chloride solution. The organic layer was dehydrated with anhydrous sodium sulfate and the solvent was distilled off, followed by purification by preparative TLC to obtain 4.3 mg of compound 3.
Mass spectrometry data (ESI ⁺ ); 417 (M + H) ⁺ , 415 (M + H) ⁺

<Compound 40> 16.5 mg of 2-chloro-4-hydroxy-5,6-dimethoxy-2 ′-(4 ″ -tertbutylphenoxy) nicotinic acid anilide intermediate (2-1) and 1-hydroxybenzotriazole (HOBt ) Was dissolved in 0.8 ml of tetrahydrofuran, 0.8 ml of a dichloromethane solution in which 14.7 mg of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSCI-HCl) and 7.7 mg of triethylamine were dissolved. After stirring at 0 ° C. for 45 minutes and at room temperature for 45 minutes, a tetrahydrofuran solution in which 59 mg of 2- (4-tertbutylphenoxy) aniline was dissolved was added, followed by stirring at room temperature for 3 hours. The organic layer was washed with 1 mol / L citric acid aqueous solution and saturated aqueous sodium chloride solution, and the organic layer was dehydrated with anhydrous sodium sulfate and the solvent was distilled off. Purification , Compound 40 was obtained 10 mg.
Mass spectrometry data (ESI ⁺ ); 459 (M + H) ⁺ , 457 (M + H) ⁺

<Compound 124> 16.5 mg of 2-chloro-4-hydroxy-5,6-dimethoxy-2 ′-(3 ″ -chlorophenoxy) nicotinic acid anilide intermediate (2-1) and 1-hydroxybenzotriazole (HOBt) Was dissolved in 0.8 ml of tetrahydrofuran, and 0.8 ml of a dichloromethane solution containing 14.7 mg of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSCI-HCl) and 7.7 mg of triethylamine was dissolved therein. After stirring at 0 ° C. for 45 minutes and at room temperature for 45 minutes, 0.8 ml of a tetrahydrofuran solution in which 66 mg of 2- (3-chlorophenoxy) aniline was dissolved was added, followed by stirring at room temperature for 3 hours. The organic layer was washed with 1 mol / L citric acid aqueous solution and saturated aqueous sodium chloride solution, and the organic layer was dehydrated with anhydrous sodium sulfate and the solvent was distilled off. Purify 8.7 mg of compound 124 was obtained.
Mass spectrometry data (ESI ⁺ ); 437 (M + H) ⁺ , 435 (M + H) ⁺

<Compound 152> 2-chloro-4-hydroxy-5,6-dimethoxy-2 ′-[3 ″, 5 ″ -bis (trifluoromethyl) phenoxy] nicotinic acid anilide intermediate (2-1) 16.5 mg and 1 -10.4 mg of hydroxybenzotriazole (HOBt) was dissolved in 0.8 ml of tetrahydrofuran. To this was added 0.8 ml of a dichloromethane solution in which 14.7 mg of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSCI-HCl) and 7.7 mg of triethylamine were dissolved. After stirring at 0 ° C. for 45 minutes and at room temperature for 45 minutes, 0.8 ml of a tetrahydrofuran solution in which 98 mg of 2- [3,5-bis (trifluoromethyl) phenoxy] aniline was dissolved was added and stirred at room temperature for 3 hours. A saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with a 1 mol / L aqueous citric acid solution and a saturated aqueous sodium chloride solution. The organic layer was dehydrated with anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by preparative TLC to obtain 1.5 mg of compound 152.
Mass spectrometry data (ESI ⁺ ); 539 (M + H) ⁺ , 537 (M + H) ⁺

<Compound 155> 4-Hydroxy-5,6-dimethoxy-2-methyl-2 ′-[3 ”, 5” -bis (trifluoromethyl) phenoxy] nicotinic acid anilide
60 mg of 4-hydroxy-5,6-dimethoxy-2-methylnicotinic acid and 38.2 mg of 1-hydroxybenzotriazole (HOBt) were dissolved in 4 ml of tetrahydrofuran. To this was added 2 ml of a dichloromethane solution in which 54.2 mg of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSCI-HCl) and 28.6 mg of triethylamine were dissolved. After stirring at 0 ° C. for 45 minutes and at room temperature for 45 minutes, 1 ml of tetrahydrofuran solution in which 104 mg of 2- [3 ′, 5′-bis (trifluoromethyl) phenoxy] aniline was dissolved was added and stirred at room temperature for 18 hours. . A saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with a 1 mol / L aqueous citric acid solution and a saturated aqueous sodium chloride solution. The organic layer was dehydrated with anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 30: 1) to obtain 6.2 mg of compound 155.
Mass spectrometry data (ESI +); 517 (M + H) ⁺

<Compound 39> 2-Chloro-4-hydroxy-5,6-dimethoxy-2 ′-[3 ″ -fluoro-5 ″-(trifluoromethyl) phenoxy] nicotinic acid anilide intermediate (2-1) 60 mg and 38.2 mg of 1-hydroxybenzotriazole (HOBt) was dissolved in 4 ml of tetrahydrofuran. To this was added 2 ml of a dichloromethane solution in which 54.2 mg of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSCI-HCl) and 28.6 mg of triethylamine were dissolved. After stirring at 0 ° C. for 45 minutes and at room temperature for 45 minutes, 1 ml of tetrahydrofuran solution in which 104 mg of 2- [3′-fluoro-, 5 ′-(trifluoromethyl) phenoxy] aniline was dissolved was added, and the mixture was stirred at room temperature for 18 hours. Stir. A saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with a 1 mol / L aqueous citric acid solution and a saturated aqueous sodium chloride solution. The organic layer was dehydrated with anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by preparative TLC to obtain 23.6 mg of compound 39.
Mass spectrometry data (EI ⁺ ); 486 (M) ⁺

<Compound 24> 2-chloro-4-hydroxy-5,6-dimethoxy-2 ′-[3 ″, 5 ″ -bis (trifluoromethyl) phenylthio] nicotinic acid anilide intermediate (2-1) 60.0 mg and 1 38.2 mg of -hydroxybenzotriazole (HOBt) was dissolved in 4 ml of tetrahydrofuran. To this was added 2 ml of a dichloromethane solution in which 54.2 mg of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSCI-HCl) and 28.6 mg of triethylamine were dissolved. After stirring at 0 ° C. for 45 minutes and at room temperature for 45 minutes, 1 ml of a tetrahydrofuran solution in which 124 mg of 2- [3 ′, 5′-bis (trifluoromethyl) phenylthio] aniline was dissolved was added and stirred at room temperature for 43 hours. . A saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with a 1 mol / L aqueous citric acid solution and a saturated aqueous sodium chloride solution. The organic layer was dehydrated with anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by preparative TLC to obtain 13 mg of compound 24.
Mass spectrometry data (EI ⁺ ); 552 (M) ⁺

<Compound 187> 2-chloro-4-hydroxy-5,6-dimethoxy-2 ′-[3 ″ -fluoro-5 ″-(trifluoromethyl) phenylthio] nicotinic acid anilide intermediate (2-1) 100.0 mg and 63.7 mg of 1-hydroxybenzotriazole (HOBt) was dissolved in 4 ml of tetrahydrofuran. To this was added 2 ml of a dichloromethane solution in which 90.3 mg of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSCI-HCl) and 47.7 mg of triethylamine were dissolved. After stirring at 0 ° C. for 45 minutes and at room temperature for 45 minutes, 1 ml of a tetrahydrofuran solution in which 123 mg of 2- [3′-fluoro-5 ′-(trifluoromethyl) phenylthio] aniline was dissolved was added and stirred at room temperature for 5 hours. did. A saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with a 1 mol / L aqueous citric acid solution and a saturated aqueous sodium chloride solution. The organic layer was dehydrated with anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by preparative TLC to obtain 4.2 mg of compound 187.
Mass spectrometry data (FAB ⁺ ); 505 (M + H) ⁺ , 503 (M + H) ⁺

  Tables 6 to 9 show the compounds of the formula (1) synthesized by the same method and their physical properties.

  Furthermore, reaction conditions and intermediates for compound synthesis in Tables 6 to 9 are shown in Tables 10 to 13.

<Compound 153> 4-acetoxy-2-chloro-5,6-dimethoxy-2 '-[3 ", 5" -bis (trifluoromethyl) phenoxy] nicotinic acid anilide compound 152 32 mg of N, N-dimethylformamide After dissolving in 0.5 ml, potassium carbonate 8.2 mg and acetyl chloride 7 μl were added and stirred at room temperature for 10 hours. The reaction solution was poured into water and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. Obtained. Purification by preparative TLC gave 15.6 mg of compound 153.
Mass spectrometry data (FAB ⁺ ); 579 (M) ⁺

<Compound 154> 2-Chloro-5,6-dimethoxy-4-methoxyethoxymethyloxy-2 '-[3 ", 5" -bis (trifluoromethyl) phenoxy] nicotinic acid anilide compound 152 42 mg N, N -Dissolved in 0.5 ml of dimethylformamide, 16 mg of potassium carbonate and 14 μl of ethoxymethoxymethyl chloride were added, and the mixture was stirred at room temperature for 7.5 hours. The reaction solution was poured into water and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. Purification by preparative TLC gave 26.4 mg of compound 154.
Mass spectrometry data; mass spectrometry data (EI ⁺ ); 624 (M) ⁺

<Compound 55> 2-chloro-4-hydroxy-5,6-dimethoxy-2 '-(3 "-trifluoromethylsulfinylphenoxy) nicotinic acid anilide compound 56 20 mg was dissolved in 1 ml of methylene chloride, and m-chloro 10.6 mg of perbenzoic acid was added, and the mixture was stirred at room temperature for 3.5 hours.The reaction solution was poured into water and extracted with ethyl acetate.The ethyl acetate layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. Distilled off to give crude compound 211. This was purified by preparative TLC to obtain 2 mg of compound 55.
Mass spectrometry data (ESI ⁺ ); 517 (M + H) ⁺

<Compound 188> 2-Chloro-5,6-dimethoxy-4-butyryloxy-2 '-[3 "-fluoro-5"-(trifluoromethyl) phenoxy] nicotinic acid anilide compound 39 25 mg N, N-dimethyl The product was dissolved in 2.0 ml of formamide, 11.1 mg of potassium carbonate and 11.6 μl of butyric chloride were added, and the mixture was stirred at room temperature for 16 hours. The reaction solution was poured into water and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. Purification by preparative TLC gave 21.3 mg of compound 188.
Mass spectrometry data; Mass spectrometry data (FAB ⁺ ); 557 (M + H) ⁺

[Formulation example]
Formulation Example 1 [wettable powder]
30% by weight of the compound of the present invention (Compound No. 24)
30% by weight of clay
Diatomaceous earth 35% by weight
Calcium lignin sulfonate 4% by weight
Sodium lauryl sulfate 1% by weight
The above was mixed uniformly and pulverized to obtain a wettable powder.

Formulation Example 2 [Dust]
Compound of the present invention (Compound No. 39) 2% by weight
60% clay
Talc 37% by weight
Calcium stearate 1% by weight
The above was uniformly mixed to obtain a powder.

Formulation Example 3 [Emulsion]
20% by weight of the compound of the present invention (Compound No. 109)
N, N-dimethylformamide 20% by weight
Solvesso 150 (ExxonMobil Co., Ltd.) 50% by weight
10% by weight of polyoxyethylene alkyl aryl ether
The above was uniformly mixed and dissolved to obtain an emulsion.

Formulation Example 4 [Granule]
5% by weight of the compound of the present invention (Compound No. 152)
Bentonite 40% by weight
Talc 10% by weight
43% by weight of clay
2% by weight calcium lignin sulfonate
The above was pulverized and mixed uniformly, kneaded well with water, and granulated and dried to obtain granules.

Formulation Example 5 [Flowable Agent]
Compound of the present invention (Compound No. 177) 25% by weight
POE polystyryl phenyl ether sulfate 5% by weight
Propylene glycol 6% by weight
Bentonite 1% by weight
Xanthan gum 1% aqueous solution 3% by weight
PRONAL EX-300 (Toho Chemical Co., Ltd.) 0.05% by weight
ADDAC 827 (Kay Kasei Co., Ltd.) 0.02% by weight
100% by weight of water
The total amount excluding the 1% aqueous solution of xanthan gum and an appropriate amount of water from the above blend was premixed and then pulverized with a wet pulverizer. Thereafter, 1% aqueous solution of xanthan gum and the remaining water were added to obtain a flowable agent at 100% by weight.

[Test example]
Test Example 1 Tetranychus cinnabarinus Control Test A small piece of green bean leaf was inoculated with 4 adult females of the spider mite, and allowed to lay eggs in a constant temperature room at 25 ° C. After 24 hours, the female adults were removed from the small pieces, and the small pieces were immersed in a chemical solution adjusted to 500 ppm with 50% acetone water (added with 0.05% tween20). After air drying, the small piece was placed on agar and left in a constant temperature room at 25 ° C. (16 hours light period-8 hours dark period). Six days after the drug treatment, the number of remaining eggs and the number of dead insects were counted, and the egg killing rate was calculated according to the following formula.

  Egg kill rate (%) = {(number of remaining eggs + number of dead insects) / (number of remaining eggs + number of dead insects + number of surviving insects)} × 100

As a result, compound numbers 2, 3, 5, 6, 8, 10, 14, 16, 24, 30, 33, 37, 39, 40, 41, 46, 49, 52, 54, 55, 56, 57, 58 , 60,72,76,82,92,109,124,126,128,131,136,138,142,152,153,155,157,159,163,164,165,169,177,181,182 , 183, 184, 185, 186, 187, and 188 showed 100% ovulation rate.

Claims (9)

An insecticidal and acaricidal composition comprising a compound of the following formula (1) or an acid addition salt acceptable in agriculture and horticulture as an active ingredient.

(1)
[ Wherein R ₁ is a hydrogen atom, a C _1-6 alkyl group or a halogen atom,
R ₂ is a hydroxyl group or a C _1-6 alkylcarbonyloxy group,
R ₃ and R ₄ are C _1-6 alkoxy groups,
R is a hydrogen atom,
W is an optionally substituted phenyloxy group (the substituent is a halogen atom, a C _1-6 alkyl group that may be substituted with a halogen atom, a C _1-6 alkoxy group that may be substituted with a halogen atom) , A cyano group, a C _1-6 alkylthio group optionally substituted with a halogen atom, a C _1-6 alkylsulfinyl group optionally substituted with a halogen atom, or two adjacent groups on the phenyl group A group formed together, which is —O— (CH ₂ ) _p —O— (where p is 1 or 2) optionally substituted with a halogen atom, a phenyl group, benzyloxy Or a phenylthio group which may be substituted (the substituent is a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom),
X is a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, or a C _1-6 alkoxy group,
n is an integer of 0 or 1,
m is an integer of 0 or 1. ] A compound represented by the following formula (A) or an agriculturally and horticulturally acceptable acid addition salt thereof:

(A)
[Wherein R ₁₀₁ represents a hydrogen atom, a fluorine atom, a chlorine atom or a methyl group,
R ₁₀₂ represents OR ₂ ′ or OC OR ₂ ′ (R ₂ ′ represents a hydrogen atom or a C atom optionally substituted by a halogen atom, a C _1-4 alkoxy group, or a C _1-4 alkylcarbonyl group. Represents a _1-6 alkyl group),
Y is (CH ₂ ) ₁ , O (CH ₂ ) ₁ , S (CH ₂ ) _1, (CH ₂ ) ₁ O, (CH ₂ ) ₁ S, NR _y (CH ₂ ) ₁ or (CH ₂ ) _l NR _y (R _y represents a hydrogen atom, a C _1-6 alkyl group), l represents an integer of 0-4,
W ₁₀₁ and W ₁₀₂ are the same or different and are substituted with a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, a C _1-6 alkoxy group which may be substituted with a halogen atom, or a halogen atom. -O represents an optionally substituted C _1-6 alkylthio group, or W ₁₀₁ and W ₁₀₂ are adjacent to each other and the two groups are formed together, -O optionally substituted with a halogen atom - (CH _{2) p} -O- (wherein p is 1 or 2) represents,
W ₁₀₃ represents a hydrogen atom, a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, a C _1-6 alkoxy group which may be substituted with a halogen atom, mono- or di-C _1-6 alkyl A substituted amino group, a cyano group, a nitro group, a C _1-6 alkylthio group optionally substituted with a halogen atom, a C _1-6 alkylsulfinyl group optionally substituted with a halogen atom, and a halogen atom substituted May represent a C _1-6 alkylsulfonyl group, a formyl group, a C _1-6 alkyloxycarbonyl group, or a C _1-6 alkylcarbonyloxy group,
X is a hydroxyl group, a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, a C _1-6 alkoxy group which may be substituted with a halogen atom, a mono or di C _1-6 alkyl substituted amino group Group, cyano group, nitro group, C _1-6 alkylthio group optionally substituted with a halogen atom, C _1-6 alkylsulfinyl group optionally substituted with a halogen atom, optionally substituted with a halogen atom C _1-6 alkylsulfonyl group, formyl group, C _1-6 alkyloxycarbonyl group or C _1-6 alkylcarbonyloxy group,
m represents an integer of 0 to 4. ] R ₁₀₁ is a hydrogen atom, a chlorine atom or a methyl group,
R ₁₀₂ is a hydroxyl group or OC OR ₂ ′ (R ₂ ′ represents a C _1-6 alkyl group),
Y is a bond, an oxygen atom or a sulfur atom,
W ₁₀₁ and W ₁₀₂ are the same or different and are a halogen atom, a C _1-6 alkyl group substituted with a halogen atom, a C _1-6 alkoxy group substituted with a halogen atom, or W ₁₀₁ and W ₁₀₂ and it is adjacent, the two groups are formed together, be -O- substituted by halogen atom (here p represents 1 or 2) (CH _{2) p} -O- ,
W ₁₀₃ is a hydrogen atom,
X is a halogen atom, a C _1-6 alkyl group which may be substituted with a halogen atom, or a C _1-6 alkoxy group,
The compound according to claim 2 , wherein m is an integer of 0 or 1. An insecticidal and acaricidal composition comprising as an active ingredient the compound of formula (A) according to claim 2 or an agriculturally and horticulturally acceptable acid addition salt thereof. Control of agricultural and horticultural pests, comprising applying an effective amount of the compound represented by formula (1) or the agricultural and horticulturally acceptable acid addition salt according to claim 1 to a plant or soil. Method. An agricultural and horticultural pest comprising applying an effective amount of the compound represented by the formula (A) or the agricultural and horticulturally acceptable acid addition salt thereof according to claim 2 or 3 to a plant or soil. Control method. The control method according to claim 5 or 6 , wherein the pest is a mite. Use of the compound represented by the formula (1) according to claim 1 or an agriculturally and horticulturally acceptable acid addition salt for producing an agricultural and horticultural insecticidal or acaricidal composition. Use of the compound represented by the formula (A) according to claim 2 or 3 or an agriculturally and horticulturally acceptable acid addition salt for producing an agricultural and horticultural insecticidal or acaricidal composition.