JP2009161511A - Plant disease control agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plant disease control agent having excellent plant disease control effects. <P>SOLUTION: The plant disease control agent containing an amide compound represented by formula (I) as an effective ingredient has excellent plant disease control effects. In formula (I), B represents a group represented by formula (B1), (B2) or (B3), R<SP>1</SP>represents a hydrogen atom or a 1-4C alkyl group, R<SP>2</SP>and R<SP>3</SP>each represent a halogen atom, a 1-4C alkyl group which may be substituted with a halogen atom, a 1-4C alkoxy group which may be substituted with a halogen atom or a cyano group. Z represents an oxygen atom or a sulfur atom; p represents any one of integers 0 to 6; q represents any one of integers 0 to 5; r represents any one of integers 0 to 4; and n represents any one of integers 0 to 3. A<SP>1</SP>-A<SP>2</SP>may be incorporated as hetero atoms as at least one atom selected from the group consisting of oxygen atom, nitrogen atom and sulfur atom for constituting a ring, by joining with two carbon atoms forming a benzene ring structure to which each of A<SP>1</SP>and A<SP>2</SP>is bonded, and represents a five- to eight-membered ring which may be substituted with at least one group selected from a group (a-1): a halogen atom, hydroxyl group, carboxyl group, etc. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a plant disease control agent.

  Conventionally, many plant disease control agents have been developed and put into practical use.

Shibuya Narumi, Kawamata Hiroshi, Kawamata Mariko, Shimazaki Isao, “SHIBUYA INDEX” -2005- (10th Edition), SHIBUYA INDEX Study Group

  This invention makes it a subject to provide the plant disease control agent which has the outstanding plant disease control effect.

〔式中、Bは下記式（Ｂ１）、（Ｂ２）又は（Ｂ３）で示される基を表し、

Ｒ¹は水素原子又はＣ１−Ｃ４アルキル基を表し、
Ｒ²及びＲ³は各々、ハロゲン原子、ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基、ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルコキシ基又はシアノ基を表し、
Ｚは酸素原子又は硫黄原子を表し、
ｐは、０〜６の整数のいずれかを表し、
ｑは、０〜５の整数のいずれかを表し、
ｒは、０〜４の整数のいずれかを表し、
ｎは、０〜３の整数のいずれかを表し、
Ａ¹−Ａ²は、Ａ¹及びＡ²の各々が結合するベンゼン環構造を形成する２つの炭素原子と一緒になり、酸素原子、窒素原子及び硫黄原子からなる群より選ばれる少なくとも１種の原子が環を構成する複素原子として含有されていてもよく、且つ、下記群〔ａ−１〕より選ばれる１種以上の基で置換されていてもよい５〜８員環を表す。
但し、ｐが２〜６の整数のいずれかである場合、Ｒ²は互いに同一でも相異なっていてもよく、ｑが２〜５の整数のいずれかである場合、Ｒ²は互いに同一でも相異なっていてもよく、ｒが２〜４の整数のいずれかである場合、Ｒ²は互いに同一でも相異なっていてもよく、
また、ｎが２又は３である場合、Ｒ³は互いに同一でも相異なっていてもよい。
群〔ａ−１〕
ハロゲン原子、ヒドロキシル基、カルボキシル基、アミノ基、カルバモイル基、ホルミル基、ニトロ基、シアノ基、Ｑ¹⁰、Ｑ¹¹Ｏ、Ｑ¹²Ｓ、Ｑ¹³Ｓ（Ｏ）、Ｑ¹⁴Ｓ（Ｏ）₂、Ｑ¹⁵ＮＨ、Ｑ¹⁶Ｑ¹⁷Ｎ、Ｑ¹⁸Ｃ（Ｏ）、Ｑ¹⁹ＯＣ（Ｏ）、Ｑ²⁰ＮＨＣ（Ｏ）、Ｑ²¹Ｑ²²ＮＣ（Ｏ）、Ｑ²³Ｃ（Ｏ）Ｏ、Ｑ²⁴ＯＣ（Ｏ）Ｏ、Ｑ²⁵ＮＨＣ（Ｏ）Ｏ、Ｑ²⁶Ｑ²⁷ＮＣ（Ｏ）Ｏ、Ｑ²⁸Ｃ（Ｏ）ＮＨ、Ｑ²⁹ＯＣ（Ｏ）ＮＨ、Ｑ³⁰ＮＨＣ（Ｏ）ＮＨ、Ｑ³¹Ｑ³²ＮＣ（Ｏ）ＮＨ、及び、Ｑ³³Ｓ（Ｏ）₂Ｏ；
〔但し、Ｑ¹⁰は下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよいＣ１−Ｃ６アルキル基、下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよいＣ２−Ｃ６アルケニル基、下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよいＣ２−Ｃ６アルキニル基、下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよいＣ３−Ｃ８シクロアルキル基、下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよいフェニル基、下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよい５〜６員芳香族へテロ環式基又は下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよい５〜６脂肪族へテロ環式基を表し、
Ｑ¹¹、Ｑ¹²、Ｑ¹³、Ｑ¹⁴、Ｑ¹⁵、Ｑ¹⁶、Ｑ¹⁷、Ｑ¹⁸、Ｑ¹⁹、Ｑ²⁰、Ｑ²¹、Ｑ²²、Ｑ²³、Ｑ²⁴、Ｑ²⁵、Ｑ²⁶、Ｑ²⁷、Ｑ²⁸、Ｑ²⁹、Ｑ³⁰、Ｑ³¹、Ｑ³²及びＱ³³は独立して、下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよいＣ１−Ｃ６アルキル基、下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよいＣ３−Ｃ６アルケニル基、下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよいＣ３−Ｃ６アルキニル基、下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよいＣ３−Ｃ８シクロアルキル基、下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよいフェニル基、下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよい５〜６員芳香族へテロ環式基又は下記群〔ｂ−１〕より選ばれる１種以上の基で置換されていてもよい５〜６脂肪族へテロ環式基を表す。
群〔ｂ−１〕
ハロゲン原子、ヒドロキシル基、カルボキシル基、アミノ基、カルバモイル基、ホルミル基、ニトロ基、シアノ基、ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基、及び、ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルコキシ基；
〕〕で示されるアミド化合物（以下、本化合物と記す場合もある。）を有効成分として含有する植物病害防除剤（以下、本発明防除剤と記す。）及び本化合物の有効量を植物又は土壌に施用する工程を有してなる植物病害の防除方法を提供する。 As a result of intensive studies to find a plant disease control agent having an excellent plant disease control effect, the present inventors have found that a plant disease control agent containing an amide compound represented by the following formula (I) has an excellent plant disease control effect. The present invention was completed.
That is, the present invention relates to the formula (I)

[In the formula, B represents a group represented by the following formula (B1), (B2) or (B3);

R ¹ represents a hydrogen atom or a C1-C4 alkyl group,
R ² and R ³ each represent a halogen atom, a C1-C4 alkyl group that may be substituted with a halogen atom, a C1-C4 alkoxy group that may be substituted with a halogen atom, or a cyano group,
Z represents an oxygen atom or a sulfur atom,
p represents any integer of 0 to 6,
q represents any integer of 0 to 5;
r represents any integer of 0 to 4;
n represents any integer of 0 to 3,
A ¹ -A ² is combined with two carbon atoms that form a benzene ring structure to which each of A ¹ and A ² is bonded, and is at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. It represents a 5- to 8-membered ring which may be contained as a hetero atom constituting the ring and optionally substituted with one or more groups selected from the following group [a-1].
However, when p is any integer of 2 to 6, R ² may be the same as or different from each other, and when q is any integer of 2 to 5, R ² is the same or different from each other. R ² may be the same or different from each other when r is any integer of 2 to 4,
When n is 2 or 3, R ³ may be the same or different from each other.
Group [a-1]
Halogen atom, hydroxyl group, carboxyl group, amino group, carbamoyl group, formyl group, nitro group, cyano group, Q ¹⁰ , Q ¹¹ O, Q ¹² S, Q ¹³ S (O), Q ¹⁴ S (O) ₂ , Q ¹⁵ NH, Q ¹⁶ Q ¹⁷ N, Q ¹⁸ C (O), Q ¹⁹ OC (O), Q ²⁰ NHC (O), Q ²¹ Q ²² NC (O), Q ²³ C (O) O, Q ²⁴ OC (O) O, Q ²⁵ NHC (O) O, Q ²⁶ Q ²⁷ NC (O) O, Q ²⁸ C (O) NH, Q ²⁹ OC (O) NH, Q ³⁰ NHC (O) NH, Q ³¹ Q ³² NC (O) NH and Q ³³ S (O) ₂ O;
[However, Q ¹⁰ is the following group [b-1] from one or more optionally substituted C1-C6 alkyl group with a group selected, with one or more groups selected from the following group [b-1] C2-C6 alkenyl group which may be substituted, C2-C6 alkynyl group which may be substituted with one or more groups selected from the following group [b-1], selected from the following group [b-1] A C3-C8 cycloalkyl group optionally substituted with one or more groups, a phenyl group optionally substituted with one or more groups selected from the following group [b-1], and the following group [b-1 A 5- or 6-membered aromatic heterocyclic group which may be substituted with one or more groups selected from the above group or a group selected from the following group [b-1]. Represents a 5-6 aliphatic heterocyclic group,
^{Q 11, Q 12, Q 13} , Q 14, Q 15, Q 16, Q 17, Q 18, Q 19, Q 20, Q 21, Q 22, Q 23, Q 24, Q 25, Q 26, Q 27 , Q ²⁸ , Q ²⁹ , Q ³⁰ , Q ³¹ , Q ³² and Q ³³ are each independently a C1-C6 alkyl group optionally substituted with one or more groups selected from the following group [b-1]. A C3-C6 alkenyl group optionally substituted with one or more groups selected from the following group [b-1], or a substituent substituted with one or more groups selected from the following group [b-1]. A good C3-C6 alkynyl group, a C3-C8 cycloalkyl group optionally substituted with one or more groups selected from the following group [b-1], one or more kinds selected from the following group [b-1] A phenyl group which may be substituted with a group, or a 5- to 6-membered aromatic heteroalkyl group which may be substituted with one or more groups selected from the following group [b-1] Shikimoto or the following group [b-1] from the one or more may also be 5-6 aliphatic optionally substituted by a group selected represents a heterocyclic group.
Group [b-1]
A halogen atom, a hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a formyl group, a nitro group, a cyano group, an optionally substituted C1-C4 alkyl group, and an optionally substituted halogen atom A C1-C4 alkoxy group;
] An amide compound (hereinafter sometimes referred to as the present compound) represented by the following formula: as an active ingredient, a plant disease control agent (hereinafter referred to as the present invention control agent) and an effective amount of the present compound in a plant or soil The present invention provides a method for controlling plant diseases comprising the step of applying to a plant.

  Since the control agent of the present invention has an excellent plant disease control effect, it is useful for controlling plant diseases.

The present control agent contains an amide compound represented by the formula (I) as an active ingredient.
In the present invention, specific examples of each substituent described in formula (I) include the following.
Examples of the C1-C4 alkyl group represented by R ¹ include a methyl group.
Examples of the halogen atom represented by R ² and R ³ include a fluorine atom, a chlorine atom and a bromine atom,
Examples of the C1-C4 alkyl group optionally substituted with a halogen atom include a methyl group, an ethyl group, and a trifluoromethyl group.
Examples of the C1-C4 alkoxy group that may be substituted with a halogen atom include a methoxy group, an ethoxy group, and a trifluoromethoxy group.
A ¹ -A ² is taken together with two carbon atoms forming a benzene ring structure to which each of A ¹ and A ² is bonded, and is at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom In a 5- to 8-membered ring, the atom may be contained as a hetero atom constituting the ring, and may be substituted with one or more groups selected from the following group [a-1].
As a 5- to 8-membered ring,
Cyclopentene, cyclohexene, cycloheptene, cyclooctene, 2,3-dihydrofuran, 2,5-dihydrofuran, [1,3] dioxole, furan, pyrrole, thiophene, oxazole, imidazole, thiazole, isoxazole, pyrazole, isothiazole, Benzene, [1,4] dioxin, [1,3] dioxin, 2,3-dihydro-2H- [1,5] dioxepin, pyridine, pyridazine, pyrimidine, pyrazine and the like,

In group [a-1],
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
^{Q 10, Q 11, Q 12} , Q 13, Q 14, Q 14, Q 15, Q 16, Q 17, Q 18, Q 19, Q 20, Q 21, Q 22, Q 23, Q 24, Q 25 , Q ²⁶ , Q ²⁷ , Q ²⁸ , Q ²⁹ , Q ³⁰ , Q ³¹ , Q ³² and Q ³³ , respectively.
The C1-C6 alkyl group in the C1-C6 alkyl group optionally substituted with one or more groups selected from the group [b-1] is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group. Hexyl group, isopropyl group and tert-butyl group,
Examples of the C3-C8 cycloalkyl group in the C3-C8 cycloalkyl group optionally substituted with one or more groups selected from the group [b-1] include a cyclopropyl group and a cyclohexyl group.
As the 5- to 6-membered aromatic heterocyclic group in the 5- to 6-membered aromatic heterocyclic group which may be substituted with one or more groups selected from the group [b-1], an N-pyrazolyl group And 2-pyridyl group, etc.
The 5- to 6-membered aliphatic heterocyclic group in the 5- to 6-membered aliphatic heterocyclic group optionally substituted with one or more groups selected from the group [b-1] is 2-tetrahydrofuryl. Group, N-piperidinyl group and N-morpholinyl group, etc.

Indicated by Q ¹⁰ ,
Examples of the C2-C6 alkenyl group in the C2-C6 alkenyl group optionally substituted with one or more groups selected from the group [b-1] include a vinyl group and an allyl group.
Examples of the C2-C6 alkynyl group in the C2-C6 alkynyl group optionally substituted with one or more groups selected from the group [b-1] include an ethynyl group and a propargyl group.
^{Q 11, Q 12, Q 13} , Q 14, Q 14, Q 15, Q 16, Q 17, Q 18, Q 19, Q 20, Q 21, Q 22, Q 23, Q 24, Q 25, Q 26 , Q ²⁷ , Q ²⁸ , Q ²⁹ , Q ³⁰ , Q ³¹ , Q ³² and Q ³³
The C3-C6 alkenyl group in the C3-C6 alkenyl group optionally substituted with one or more groups selected from the group [b-1] includes an allyl group, and the like.
Examples of the C3-C6 alkynyl group in the C3-C6 alkynyl group optionally substituted with one or more groups selected from the group [b-1] include a propargyl group,
In group [b-1],
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the C1-C4 alkyl group which may be substituted with a halogen atom include a methyl group and a trifluoromethyl group.
Examples of the C1-C4 alkoxy group which may be substituted with a halogen atom include a methoxy group and a trifluoromethoxy group.

As an aspect of this compound, the following are mentioned, for example.
An amide compound in which R ¹ is a hydrogen atom in formula (I);
An amide compound represented by formula (I), wherein R ¹ is a C1-C4 alkyl group;
An amide compound represented by formula (I), wherein B is a quinolin-6-yl group, a [1,5] naphthyridin-2-yl group or a benzothiazol-6-yl group;
An amide compound in which n is 0 in formula (I);
An amide compound represented by formula (I), wherein R ³ is a halogen atom;
An amide compound represented by formula (I), wherein Z is an oxygen atom;
An amide compound in which B is quinolin-6-yl group, [1,5] naphthyridin-2-yl group or benzothiazol-6-yl group and n is 0 in formula (I);
In formula (I), B is a quinolin-6-yl group, [1,5] naphthyridin-2-yl group or benzothiazol-6-yl group, n is 0, Z is an oxygen atom, An amide compound in which R ¹ is a hydrogen atom;

In formula (I), A ¹ -A ² is
E ¹ -E ² -E ³ , E ²¹ = E ²² -E ⁴ , E ⁵ -E ²³ = E ²⁴ , E ⁶ -E ⁷ -E ⁸ -E ⁹ , E ²⁵ = E ²⁶ -E ²⁷ = E ²⁸ Or E ¹⁰ -E ¹¹ -E ¹² -E ¹³ -E ¹⁴
[However, E ¹ , E ² , E ³ , E ⁴ , E ⁵ , E ⁶ , E ⁷ , E ⁸ , E ⁹ , E ¹⁰ , E ¹¹ , E ¹² , E ¹³ and E ¹⁴ are independently CX ^{1 represents} X ² , NX ³ , oxygen atom or sulfur atom,
E ²¹ , E ²² , E ²³ , E ²⁴ , E ²⁵ , E ²⁶ , E ²⁷ and E ²⁸ independently represent CX ⁴ or a nitrogen atom;
X ¹ , X ² , X ³ and X ⁴ independently represent any group selected from the following group [a-2].
Group [a-2]
Hydrogen atom, halogen atom, hydroxyl group, carboxyl group, amino group, carbamoyl group, formyl group, nitro group, cyano group, G ¹⁰ , G ¹¹ O, G ¹² S, G ¹³ S (O), G ¹⁴ S (O ) ₂ , G ¹⁵ NH, G ¹⁶ G ¹⁷ N, G ¹⁸ C (O), G ¹⁹ OC (O), G ²⁰ NHC (O), G ²¹ G ²² NC (O), G ²³ C (O) O , G ²⁴ OC (O) O, G ²⁵ NHC (O) O, G ²⁶ G ²⁷ NC (O) O, G ²⁸ C (O) NH, G ²⁹ OC (O) NH, G ³⁰ NHC (O) NH G ³¹ G ³² NC (O) NH and G ³³ S (O) ₂ O;
[However, G ¹⁰ is a C1-C6 alkyl group optionally substituted with one or more groups selected from the following group [b-1], or one or more groups selected from the following group [b-1]. C2-C6 alkenyl group which may be substituted, C2-C6 alkynyl group which may be substituted with one or more groups selected from the following group [b-1], selected from the following group [b-1] A C3-C8 cycloalkyl group optionally substituted with one or more groups, a phenyl group optionally substituted with one or more groups selected from the following group [b-1],
^{G 11, G 12, G 13} , G 14, G 14, G 15, G 16, G 17, G 18, G 19, G 20, G 21, G 22, G 23, G 24, G 25, G 26 , G ²⁷ , G ²⁸ , G ²⁹ , G ³⁰ , G ³¹ , G ^32, and G ³³ are each independently C1- which may be substituted with one or more groups selected from the following group [b-2]. C6-alkyl group, C3-C6 alkenyl group optionally substituted with one or more groups selected from the following group [b-2], substituted with one or more groups selected from the following group [b-2] An optionally substituted C2-C6 alkynyl group, a C3-C8 cycloalkyl group optionally substituted with one or more groups selected from the following group [b-2], 1 selected from the following group [b-2] The phenyl group which may be substituted by the group more than a seed | species is represented.
Group [b-2]
A halogen atom, a hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a formyl group, a nitro group, a cyano group, an optionally substituted C1-C4 alkyl group, and an optionally substituted halogen atom A C1-C4 alkoxy group;
] An amide compound;

In formula (I), A ¹ -A ² is
E ¹ -E ² -E ³ , E ²¹ = E ²² -E ⁴ , E ⁵ -E ²³ = E ²⁴ , E ⁶ -E ⁷ -E ⁸ -E ⁹ , E ²⁵ = E ²⁶ -E ²⁷ = E ²⁸ Or E ¹⁰ -E ¹¹ -E ¹² -E ¹³ -E ¹⁴
[However, E ¹ , E ² , E ³ , E ⁴ , E ⁵ , E ⁶ , E ⁷ , E ⁸ , E ⁹ , E ¹⁰ , E ¹¹ , E ¹² , E ¹³ and E ¹⁴ are independently CX ^{1 represents} X ² , NX ³ , oxygen atom or sulfur atom,
E ²¹ , E ²² , E ²³ , E ²⁴ , E ²⁵ , E ²⁶ , E ²⁷ and E ²⁸ independently represent CX ⁴ or a nitrogen atom;
X ¹ , X ² , X ³ and X ⁴ independently represent any group selected from the following group [a-2].
Group [a-2]
Hydrogen atom, halogen atom, hydroxyl group, carboxyl group, amino group, carbamoyl group, formyl group, nitro group, cyano group, G ¹⁰ , G ¹¹ O, G ¹² S, G ¹³ S (O), G ¹⁴ S (O ) ₂ , G ¹⁵ NH, G ¹⁶ G ¹⁷ N, G ¹⁸ C (O), G ¹⁹ OC (O), G ²⁰ NHC (O), G ²¹ G ²² NC (O), G ²³ C (O) O , G ²⁴ OC (O) O, G ²⁵ NHC (O) O, G ²⁶ G ²⁷ NC (O) O, G ²⁸ C (O) NH, G ²⁹ OC (O) NH, G ³⁰ NHC (O) NH G ³¹ G ³² NC (O) NH and G ³³ S (O) ₂ O;
[However, G ¹⁰ is a C1-C6 alkyl group optionally substituted with one or more groups selected from the following group [b-22], or one or more groups selected from the following group [b-22]. A C2-C6 alkenyl group which may be substituted, a C2-C6 alkynyl group which may be substituted with one or more groups selected from the following group [b-22], and a group selected from the following group [b-22]. A C3-C8 cycloalkyl group optionally substituted with one or more groups, a phenyl group optionally substituted with one or more groups selected from the following group [b-22],
^{G 11, G 12, G 13} , G 14, G 14, G 15, G 16, G 17, G 18, G 19, G 20, G 21, G 22, G 23, G 24, G 25, G 26 , G ²⁷ , G ²⁸ , G ²⁹ , G ³⁰ , G ³¹ , G ³² and G ³³ are each independently C1-C1 which may be substituted with one or more groups selected from the following group [b-22]. C6-alkyl group, C3-C6 alkenyl group optionally substituted with one or more groups selected from the following group [b-22], substituted with one or more groups selected from the following group [b-22] An optionally substituted C2-C6 alkynyl group, a C3-C8 cycloalkyl group optionally substituted with one or more groups selected from the following group [b-22], 1 selected from the following group [b-22] The phenyl group which may be substituted by the group more than a seed | species is represented.
Group [b-22]
A halogen atom, a cyano group, a C1-C4 alkyl group optionally substituted with a halogen atom, and a C1-C4 alkoxy group optionally substituted with a halogen atom;
] An amide compound;

In the formula (I), A ¹ -A ² is E ¹ -E ² -E ³ [where E ¹ , E ² and E ³ represent the same meaning as described above. An amide compound;
In the formula (I), A ¹ -A ² is E ²¹ = E ²² -E ⁴ [where E ²¹ , E ²² and E ⁴ represent the same meaning as described above. An amide compound;
In the formula (I), A ¹ -A ² is E ⁵ -E ²³ = E ²⁴ (where E ⁵ , E ²³ and E ²⁴ represent the same meaning as described above). An amide compound;
In the formula (I), A ¹ -A ² is E ⁶ -E ⁷ -E ⁸ -E ⁹ (where E ⁶ , E ⁷ , E ⁸ and E ⁹ represent the same meaning as described above). An amide compound;
In formula (I), A ¹ -A ² is E ¹⁰ -E ¹¹ -E ¹² -E ¹³ -E ¹⁴ [provided that E ¹⁰ , E ¹¹ , E ¹² , E ¹³ and E ¹⁴ represent the same meaning as described above. . An amide compound;

An amide compound represented by formula (I), wherein A ¹ -A ² is O—CH (X ¹ ) —O, and X ¹ is a C1-C6 alkyl group optionally substituted by a halogen atom;
An amide compound represented by formula (I), wherein A ¹ -A ² is O—CH (X ¹ ) —O, and X ¹ is a phenyl group optionally substituted by a halogen atom;
An amide compound in which A ¹ -A ² is O—CH (CH ₂ CH ₂ CH ₃ ) —O in formula (I);
An amide compound represented by formula (I), wherein A ¹ -A ² is O—CH (C ₆ H ₅ ) —O;
An amide compound represented by formula (I), wherein A ¹ -A ² is CH ₂ —CH ₂ —O;
An amide compound represented by formula (I), wherein A ¹ -A ² is O—CH ₂ —O;
An amide compound represented by formula (I), wherein A ¹ -A ² is O—CH ₂ —CH ₂ ;
An amide compound in which A ¹ -A ² is CH ₂ —CH ₂ —CH ₂ in formula (I);
An amide compound in which A ¹ -A ² is CH═CH—O in formula (I);
An amide compound in which A ¹ -A ² is O—CH═CH in formula (I);
An amide compound represented by formula (I), wherein A ¹ -A ² is O—CH ₂ —CH ₂ —O;
An amide compound represented by formula (I), wherein A ¹ -A ² is O—CH ₂ —CH ₂ —CH ₂ —O.

In formula (I):
Q ¹⁰ in the group [a-1] is a C1-C6 alkyl group optionally substituted with one or more groups selected from the following group [b-11], 1 selected from the following group [b-11] A C2-C6 alkenyl group optionally substituted with one or more groups, a C2-C6 alkynyl group optionally substituted with one or more groups selected from the following group [b-11], and the following group [b- 1] a C3-C8 cycloalkyl group optionally substituted with one or more groups selected from [1], or a phenyl group optionally substituted with one or more groups selected from the following group [b-11]. ,
^{Q 11, Q 12, Q 13} , Q 14, Q 15, Q 16, Q 17, Q 18, Q 19, Q 20, Q 21, Q 22, Q 23, Q 24, Q 25, Q 26, Q 27 , Q ²⁸ , Q ²⁹ , Q ³⁰ , Q ³¹ , Q ³² and Q ³³ are each independently a C1-C6 alkyl group optionally substituted with one or more groups selected from the following group [b-11] A C3-C6 alkenyl group optionally substituted with one or more groups selected from the following group [b-11], or a substituent substituted with one or more groups selected from the following group [b-11]. A good C3-C6 alkynyl group, a C3-C8 cycloalkyl group optionally substituted with one or more groups selected from the following group [b-11], or one or more kinds selected from the following group [b-11] An amide compound which is a phenyl group which may be substituted with a group.
Group [b-11]
A halogen atom, a cyano group, a C1-C4 alkyl group optionally substituted with a halogen atom, and a C1-C4 alkoxy group optionally substituted with a halogen atom;
]]

〔式中、
Ｗは窒素原子又はＣＨ基を表し、
Ｒ¹は水素原子又はＣ１−Ｃ４アルキル基を表し、
Ｒ³は各々、ハロゲン原子、ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基、ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルコキシ基又はシアノ基を表し、
Ｚは酸素原子又は硫黄原子を表し、
ｎは、０〜３の整数のいずれかを表し、
Ａ¹−Ａ²は、
Ｅ¹−Ｅ²−Ｅ³、Ｅ²¹＝Ｅ²²−Ｅ⁴、Ｅ⁵−Ｅ²³＝Ｅ²⁴、Ｅ⁶−Ｅ⁷−Ｅ⁸−Ｅ⁹、Ｅ²⁵＝Ｅ²⁶−Ｅ²⁷＝Ｅ²⁸又はＥ¹⁰−Ｅ¹¹−Ｅ¹²−Ｅ¹³−Ｅ¹⁴〔但し、Ｅ¹、Ｅ²、Ｅ³、Ｅ⁴、Ｅ⁵、Ｅ⁶、Ｅ⁷、Ｅ⁸、Ｅ⁹、Ｅ¹⁰、Ｅ¹¹、Ｅ¹²、Ｅ¹³、Ｅ¹⁴、Ｅ²¹、Ｅ²²、Ｅ²³、Ｅ²⁴、Ｅ²⁵、Ｅ²⁶、Ｅ²⁷及びＥ²⁸は前記と同じ意味を表す。〕を表す。
〕で示されるアミド化合物； In the formula (I), B is quinolin-6-yl group or a [1,5] naphthyridin-2-yl group, A ¹ -A ² is ^{E 1 -E 2 -E 3, E} 21 = E 22 - E ⁴ , E ⁵ -E ²³ = E ²⁴ , E ⁶ -E ⁷ -E ⁸ -E ⁹ , E ²⁵ = E ²⁶ -E ²⁷ = E ²⁸ or E ¹⁰ -E ¹¹ -E ¹² -E ¹³ -E ¹⁴
[However, E ¹ , E ² , E ³ , E ⁴ , E ⁵ , E ⁶ , E ⁷ , E ⁸ , E ⁹ , E ¹⁰ , E ¹¹ , E ¹² , E ¹³ , E ¹⁴ , E ²¹ , E ^22] , E ²³ , E ²⁴ , E ²⁵ , E ²⁶ , E ²⁷ and E ²⁸ represent the same meaning as described above. An amide compound represented by formula (I-1)

[Where,
W represents a nitrogen atom or a CH group,
R ¹ represents a hydrogen atom or a C1-C4 alkyl group,
R ³ represents a halogen atom, a C1-C4 alkyl group optionally substituted with a halogen atom, a C1-C4 alkoxy group optionally substituted with a halogen atom, or a cyano group,
Z represents an oxygen atom or a sulfur atom,
n represents any integer of 0 to 3,
A ¹ -A ² is
^{E 1 -E 2 -E 3, E} 21 = E 22 -E 4, E 5 -E 23 = E 24, E 6 -E 7 -E 8 -E 9, E 25 = E 26 -E 27 = E 28 Or E ¹⁰ -E ¹¹ -E ¹² -E ¹³ -E ¹⁴ [However, E ¹ , E ² , E ³ , E ⁴ , E ⁵ , E ⁶ , E ⁷ , E ⁸ , E ⁹ , E ¹⁰ , E ^11] , E ¹² , E ¹³ , E ¹⁴ , E ²¹ , E ²² , E ²³ , E ²⁴ , E ²⁵ , E ²⁶ , E ²⁷ and E ²⁸ represent the same meaning as described above. ] Is represented.
An amide compound represented by the formula:

An amide compound in which W is a CH group in formula (I-1);
An amide compound in which W is a nitrogen atom in formula (I-1);
An amide compound in which W is a CH group and n is 0 in formula (I-1);
An amide compound in which W is a nitrogen atom and n is 0 in formula (I-1);
In the formula (I-1), n is 0, and A ¹ -A ² is O—C (X ¹ ) (X ² ) —O, O—C (X ¹ ) (X ² ) —CH ₂ or CH _2- C (X ¹ ) (X ² ) —O, wherein X ¹ is a C1-C6 alkyl group optionally substituted with a halogen atom or a phenyl group optionally substituted with a halogen atom, and X ² An amide compound in which is a hydrogen atom;
In the formula (I-1), n is 0, and A ¹ -A ² is O—C (X ¹ ) (X ² ) —O, O—C (X ¹ ) (X ² ) —CH ₂ or CH _An amide compound that is _2- C (X ¹ ) (X ² ) —O, and X ¹ and X ² are hydrogen atoms;
In formula (I-1), amide in which n is 0, A ¹ -A ² is O—C (X ⁴ ) ═CH or CH═C (X ⁴ ) —O, and X ⁴ is a hydrogen atom Compound;
In formula (I-1), n is 0, A ¹ -A ² is O—C (X ⁴ ) ═CH or CH═C (X ⁴ ) —O, and X ⁴ is substituted with a halogen atom. An amide compound which is an optionally substituted C1-C6 alkyl group or a phenyl group optionally substituted with a halogen atom;

In Formula (I-1), W is a CH group, n is 0, A ¹ -A ² is O—C (X ¹ ) (X ² ) —O, O—C (X ¹ ) (X ² ) an amide compound which is —CH ₂ or CH ₂ —C (X ¹ ) (X ² ) —O, wherein X ¹ and X ² are hydrogen atoms;
In Formula (I-1), W is a CH group, n is 0, A ¹ -A ² is O—C (X ⁴ ) ═CH or CH═C (X ⁴ ) —O, and X ^An amide compound in which ⁴ is a hydrogen atom;
In Formula (I-1), W is a CH group, n is 0, A ¹ -A ² is O—C (X ⁴ ) ═CH or CH═C (X ⁴ ) —O, and X ^An amide compound wherein ⁴ is a C1-C6 alkyl group optionally substituted with a halogen atom or a phenyl group optionally substituted with a halogen atom;
In formula (I-1), W is a nitrogen atom, n is 0, A ¹ -A ² is O—C (X ¹ ) (X ² ) —O, O—C (X ¹ ) (X ² ) an amide compound which is —CH ₂ or CH ₂ —C (X ¹ ) (X ² ) —O, wherein X ¹ and X ² are hydrogen atoms;
In Formula (I-1), W is a nitrogen atom, n is 0, A ¹ -A ² is O—C (X ⁴ ) ═CH or CH═C (X ⁴ ) —O, and X ^An amide compound in which ⁴ is a hydrogen atom;
In the formula (I-1), W is a nitrogen atom, n is 0, A ¹ -A ² is ^{O-C (X 4) =} CH or CH = C (X ⁴⁾ is -O, X ^An amide compound in which ⁴ is a C1-C6 alkyl group which may be substituted with a halogen atom or a phenyl group which may be substituted with a halogen atom.

  In the present specification, the structural formula of a compound may represent a certain isomer for convenience, but in the present invention, all active geometric isomers, optical isomers, stereoisomers, It includes isomers such as mutants and isomer mixtures, and is not limited to the description of the formula for convenience, and may be either isomer or mixture. Therefore, there may be an optically active substance and a racemate having an asymmetric carbon atom in the molecule. However, the present invention is not particularly limited and includes any case.

Next, the manufacturing method of this compound is demonstrated.
This compound can be produced, for example, by the following (Production Method A) to (Production Method C).

〔式中、Ｒ¹、Ｒ³、ｎ、Ｂ、Ａ¹及びＡ²は前記と同じ意味を表す。〕
で示される化合物は、式（III）

〔式中、Ｂは前記と同じ意味を表す。〕
で示される化合物と、式（IV）

〔式中、Ｒ¹、Ｒ³、ｎ、Ａ¹及びＡ²は前記と同じ意味を表す。〕
で示される化合物とを、脱水縮合剤の存在下に反応させることにより製造することができる。
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばテトラヒドロフラン、エチレングリコールジメチルエーテル、tert-ブチルメチルエーテル等のエーテル類、ヘキサン、へプタン、オクタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、クロロベンゼン等のハロゲン化炭化水素類、酢酸ブチル、酢酸エチル等のエステル類、アセトニトリル等のニトリル類、N,N-ジメチルホルムアミド等の酸アミド類、ジメチルスルホキシド等のスルホキシド類、ピリジン等のピリジン類及びこれらの混合物が挙げられる。
反応に用いられる脱水縮合剤としては、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド、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及び1,3-ジシクロヘキシルカルボジイミド等のカルボジイミド類、（ベンゾトリアゾール-1-イルオキシトリス(ジメチルアミノ)ホスホニウムヘキサフルオロホスフェート等が挙げられる。
式（III）で示される化合物１モルに対して、式（IV）で示される化合物が通常０．５〜３モルの割合、脱水縮合剤が通常１〜５モルの割合で用いられる。
該反応の反応温度は、通常０〜１５０℃の範囲であり、反応時間は通常１〜２４時間の範囲である。
反応終了後は、反応混合物を濾過した後、濾液を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、式（II）で示される化合物を単離することができる。単離された式（II）で示される化合物は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method A)
Of these compounds, the formula (II) wherein Z is an oxygen atom

[Wherein, R ¹ , R ³ , n, B, A ¹ and A ² represent the same meaning as described above. ]
The compound represented by the formula (III)

[Wherein B represents the same meaning as described above. ]
And a compound of formula (IV)

[Wherein, R ¹ , R ³ , n, A ¹ and A ² represent the same meaning as described above. ]
In the presence of a dehydration condensing agent.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, and tert-butyl methyl ether, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatic hydrocarbons such as toluene and xylene, Halogenated hydrocarbons such as chlorobenzene, esters such as butyl acetate and ethyl acetate, nitriles such as acetonitrile, acid amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, pyridines such as pyridine, and the like These mixtures are mentioned.
Examples of the dehydrating condensing agent used in the reaction include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 1,3-dicyclohexylcarbodiimide. And carbodiimides, (benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, and the like.
The compound represented by the formula (IV) is usually used at a ratio of 0.5 to 3 moles and the dehydrating condensing agent is usually used at a ratio of 1 to 5 moles relative to 1 mole of the compound represented by the formula (III).
The reaction temperature of the reaction is usually in the range of 0 to 150 ° C., and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound represented by the formula (II) is isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction of the filtrate with an organic solvent, and drying and concentration of the organic layer. Can do. The isolated compound represented by the formula (II) can be further purified by chromatography, recrystallization or the like.

〔式中、Ｂは前記と同じ意味を表す。〕
で示される化合物と、前記式（IV）で示される化合物とを、塩基の存在下に反応させることにより製造することができる。
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばテトラヒドロフラン、エチレングリコールジメチルエーテル、tert-ブチルメチルエーテル等のエーテル類、ヘキサン、へプタン、オクタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、クロロベンゼン等のハロゲン化炭化水素類、酢酸ブチル、酢酸エチル等のエステル類、アセトニトリル等のニトリル類及びこれらの混合物が挙げられる。
反応に用いられる塩基としては、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩類、トリエチルアミン、ジイソプロピルエチルアミン等の第3級アミン類及びピリジン、4-ジメチルアミノピリジン等の含窒素芳香族化合物類等が挙げられる。
式（V）で示される化合物１モルに対して、式（IV）で示される化合物が通常０．５〜３モルの割合、塩基が通常１〜５モルの割合で用いられる。
該反応の反応温度は通常−２０〜１００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を濾過した後、濾液を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、式（II）で示される化合物を単離することができる。単離された式（II）で示される化合物は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method B)
Among the compounds, the compound represented by the formula (II) is represented by the formula (V)

[Wherein B represents the same meaning as described above. ]
Can be produced by reacting the compound represented by formula (IV) with the compound represented by formula (IV) in the presence of a base.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, and tert-butyl methyl ether, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatic hydrocarbons such as toluene and xylene, Examples thereof include halogenated hydrocarbons such as chlorobenzene, esters such as butyl acetate and ethyl acetate, nitriles such as acetonitrile, and mixtures thereof.
Examples of the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine. It is done.
The compound represented by the formula (IV) is usually used in a proportion of 0.5 to 3 mol and the base is usually used in a proportion of 1 to 5 mol with respect to 1 mol of the compound represented by the formula (V).
The reaction temperature of the reaction is usually in the range of -20 to 100 ° C, and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound represented by the formula (II) is isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction of the filtrate with an organic solvent, and drying and concentration of the organic layer. Can do. The isolated compound represented by the formula (II) can be further purified by chromatography, recrystallization or the like.

〔式中、Ｒ¹、Ｒ³、ｎ、Ｂ、Ａ¹及びＡ²は前記と同じ意味を表す。〕
で示される化合物は、前記式（II）で示される化合物と、2,4-ビス(4-メトキシフェニル)-1,3-ジチア-2,4-ジフォスフェタン-2,4-ジスルフィド(以下、ローソン試薬と記す。)、五硫化ニリン等のイオウ化剤とを反応させることにより製造することができる。
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばテトラヒドロフラン、エチレングリコールジメチルエーテル、tert-ブチルメチルエーテル等のエーテル類、ヘキサン、へプタン、オクタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、クロロベンゼン等のハロゲン化炭化水素類、アセトニトリル、ブチロニトリル等の有機ニトリル類、ジメチルスルホキシド等のスルホキシド類及びこれらの混合物が挙げられる。
式（II）で示される化合物１モルに対して、イオウ化剤が通常１〜２モルの割合で用いられる。
該反応の反応温度は通常２５〜１５０℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を濾過した後、濾液を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、式（VI）で示される化合物を単離することができる。単離された式（VI）で示される化合物は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method C)
Of the compounds, Z is a sulfur atom (VI)

[Wherein, R ¹ , R ³ , n, B, A ¹ and A ² represent the same meaning as described above. ]
The compound represented by formula (II) and 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (hereinafter referred to as Lawson) It can be produced by reacting with a sulfurizing agent such as niline pentasulfide.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, and tert-butyl methyl ether, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, Examples thereof include halogenated hydrocarbons such as chlorobenzene, organic nitriles such as acetonitrile and butyronitrile, sulfoxides such as dimethyl sulfoxide, and mixtures thereof.
The sulfurizing agent is usually used at a ratio of 1 to 2 moles with respect to 1 mole of the compound represented by the formula (II).
The reaction temperature of the reaction is usually in the range of 25 to 150 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound represented by the formula (VI) is isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction of the filtrate with an organic solvent, and drying and concentration of the organic layer. Can do. The isolated compound represented by the formula (VI) can be further purified by chromatography, recrystallization and the like.

  The compounds represented by formula (III), formula (IV) and formula (V) are commercially available, or those produced by a known method or a method analogous thereto can be used.

  Hereinafter, although the specific example of this compound is shown, this compound is not limited only to these examples.

〔式中、Ｚ、Ｒ¹、Ｒ³、Ｅ¹、Ｅ²及びＥ³の組み合わせは、（表１）に記載される組み合わせを表す。〕で示される化合物； Formula (i)

[Wherein, the combination of Z, R ¹ , R ³ , E ¹ , E ² and E ³ represents a combination described in (Table 1). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ²¹、Ｅ²²及びＥ⁴の組み合わせは、（表２）に記載される組み合わせを表す。〕で示される化合物； Formula (ii)

[Wherein, a combination of Z, R ¹ , E ²¹ , E ²² and E ⁴ represents a combination described in (Table 2). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ⁵、Ｅ²³及びＥ²⁴の組み合わせは、（表３）に記載される組み合わせを表す。〕で示される化合物； Formula (iii)

[Wherein, the combination of Z, R ¹ , E ⁵ , E ²³ and E ²⁴ represents a combination described in (Table 3). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ⁶、Ｅ⁷、Ｅ⁸及びＥ⁹の組み合わせは、（表４）に記載される組み合わせを表す。〕で示される化合物； Formula (iv)

[Wherein, the combination of Z, R ¹ , E ⁶ , E ⁷ , E ⁸ and E ⁹ represents a combination described in (Table 4). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ²⁵、Ｅ²⁶、Ｅ²⁷及びＥ²⁸の組み合わせは、（表５）に記載される組み合わせを表す。〕で示される化合物； Formula (v)

[Wherein, the combination of Z, R ¹ , E ²⁵ , E ²⁶ , E ²⁷ and E ²⁸ represents a combination described in (Table 5). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ¹⁰、Ｅ¹¹、Ｅ¹²、Ｅ¹³及びＥ¹⁴の組み合わせは、（表６）に記載される組合わせを表す。〕で示される化合物； Formula (vi)

[Wherein, the combinations of Z, R ¹ , E ¹⁰ , E ¹¹ , E ¹² , E ¹³ and E ^{14 represent} the combinations described in (Table 6). ] The compound shown by

〔式中、Ｚ、Ｒ¹、Ｒ³、Ｅ¹、Ｅ²及びＥ³の組み合わせは、（表１）に記載される組み合わせを表す。〕で示される化合物； Formula (vii)

[Wherein, the combination of Z, R ¹ , R ³ , E ¹ , E ² and E ³ represents a combination described in (Table 1). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ²¹、Ｅ²²及びＥ⁴の組み合わせは、（表２）に記載される組み合わせを表す。〕で示される化合物； Formula (viii)

[Wherein, a combination of Z, R ¹ , E ²¹ , E ²² and E ⁴ represents a combination described in (Table 2). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ⁵、Ｅ²³及びＥ²⁴の組み合わせは、（表３）に記載される組み合わせを表す。〕で示される化合物； Formula (ix)

[Wherein, the combination of Z, R ¹ , E ⁵ , E ²³ and E ²⁴ represents a combination described in (Table 3). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ⁶、Ｅ⁷、Ｅ⁸及びＥ⁹の組み合わせは、（表４）に記載される組み合わせを表す。〕で示される化合物； Formula (x)

[Wherein, the combination of Z, R ¹ , E ⁶ , E ⁷ , E ⁸ and E ⁹ represents a combination described in (Table 4). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ²⁵、Ｅ²⁶、Ｅ²⁷及びＥ²⁸の組み合わせは、（表５）に記載される組み合わせを表す。〕で示される化合物； Formula (xi)

[Wherein, the combination of Z, R ¹ , E ²⁵ , E ²⁶ , E ²⁷ and E ²⁸ represents a combination described in (Table 5). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ¹⁰、Ｅ¹¹、Ｅ¹²、Ｅ¹³及びＥ¹⁴の組み合わせは、（表６）に記載される組合わせを表す。〕で示される化合物； Formula (xii)

[Wherein, the combinations of Z, R ¹ , E ¹⁰ , E ¹¹ , E ¹² , E ¹³ and E ^{14 represent} the combinations described in (Table 6). ] The compound shown by

〔式中、Ｚ、Ｒ¹、Ｒ³、Ｅ¹、Ｅ²及びＥ³の組み合わせは、（表１）に記載される組み合わせを表す。〕で示される化合物； Formula (xiii)

[Wherein, the combination of Z, R ¹ , R ³ , E ¹ , E ² and E ³ represents a combination described in (Table 1). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ²¹、Ｅ²²及びＥ⁴の組み合わせは、（表２）に記載される組み合わせを表す。〕で示される化合物； Formula (xiv)

[Wherein, a combination of Z, R ¹ , E ²¹ , E ²² and E ⁴ represents a combination described in (Table 2). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ⁵、Ｅ²³及びＥ²⁴の組み合わせは、（表３）に記載される組み合わせを表す。〕で示される化合物； Formula (xv)

[Wherein, the combination of Z, R ¹ , E ⁵ , E ²³ and E ²⁴ represents a combination described in (Table 3). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ⁶、Ｅ⁷、Ｅ⁸及びＥ⁹の組み合わせは、（表４）に記載される組み合わせを表す。〕で示される化合物； Formula (xvi)

[Wherein, the combination of Z, R ¹ , E ⁶ , E ⁷ , E ⁸ and E ⁹ represents a combination described in (Table 4). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ²⁵、Ｅ²⁶、Ｅ²⁷及びＥ²⁸の組み合わせは、（表５）に記載される組み合わせを表す。〕で示される化合物； Formula (xvii)

[Wherein, the combination of Z, R ¹ , E ²⁵ , E ²⁶ , E ²⁷ and E ²⁸ represents a combination described in (Table 5). ] The compound shown by

〔式中、Ｚ、R¹、Ｅ¹⁰、Ｅ¹¹、Ｅ¹²、Ｅ¹³及びＥ¹⁴の組み合わせは、（表６）に記載される組合わせを表す。〕で示される化合物； Formula (xviii)

[Wherein, the combinations of Z, R ¹ , E ¹⁰ , E ¹¹ , E ¹² , E ¹³ and E ^{14 represent} the combinations described in (Table 6). ] The compound shown by

  The control agent of the present invention may be composed only of the present compound, but usually the present compound is mixed with a solid carrier, a liquid carrier, a gas carrier, a surfactant, etc., and if necessary, a fixing agent, a dispersant, Additives for formulation such as stabilizers, etc., wettable powder, granular wettable powder, flowable powder, granule, dry flowable liquid, emulsion, aqueous liquid, oil, smoke, aerosol, microcapsule, etc. It is formulated and used. These preparations usually contain the present compound in a weight ratio of 0.1 to 99%, preferably 0.2 to 90%.

  Examples of the solid carrier include clays (for example, kaolin, diatomaceous earth, synthetic hydrous silicon oxide, fusami clay, bentonite, acidic clay), talc, and other inorganic minerals (for example, sericite, quartz powder, sulfur powder, activated carbon, Examples of the liquid carrier include water, alcohols (eg, methanol, ethanol), ketones (eg, acetone, methyl ethyl ketone), aromatic carbonization, and the like. Hydrogens (eg, benzene, toluene, xylene, ethylbenzene, methylnaphthalene), aliphatic hydrocarbons (eg, n-hexane, cyclohexanone, kerosene), esters (eg, ethyl acetate, butyl acetate), nitriles (eg, , Acetonitrile, isobutylnitrile), ethers (eg , Dioxane, diisopropyl ether), acid amides (e.g., dimethylformamide, dimethylacetamide), halogenated hydrocarbons (e.g., dichloroethane, trichlorethylene, and carbon tetrachloride), and the like.

  Surfactants include, for example, alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and their polyoxyethylene compounds, polyoxyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives. Etc.

  Other formulation adjuvants include, for example, fixing agents and dispersants, specifically casein, gelatin, polysaccharides (eg starch, arabic gum, cellulose derivatives, alginic acid), lignin derivatives, bentonite, saccharides, synthetic water-soluble high Molecules (for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert-butyl-4) -Mixtures of methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, fatty acids or esters thereof.

  The method of applying the present control agent is not particularly limited as long as the method of the present invention can be applied substantially, but for example, treatment to plant bodies such as foliage spraying, plant such as soil treatment, etc. And the like, and the treatment of seeds such as seed disinfection.

In addition, the present control agent may be used simultaneously with or without mixing with other fungicides, insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers or soil conditioners. You can also.
Such other fungicides include, for example, propiconazole, prothioconazole, triazimenol, prochloraz, penconazole, tebuconazole, flusilazole, diniconazole, bromconazole, epoxiconazole, difenoconazole, cyproconazole, metconazole, triflumi Azole fungicides such as sol, tetraconazole, microbutanyl, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, vitertanol, imazalyl, flutriahol; fenpropimorph, tridemorph, fenpropidin, etc. Cyclic amine bactericidal compounds: benzimidazole bactericidal compounds such as carbendazim, benomyl, thiabendazole, thiophanate methyl; procymidone; ciprodini Pyrimethanyl; Dietofencarb; Thiuram; Fluazinam; Mancozeb; Iprodione; Vinclozoline; Chlorotalonyl; Captan; Mepanipyrim; Fenpiclonyl; Fludioxonil; Xylostrobin; pyraclostrobin; dimoxystrobin; pyribencarb; spiroxamine; quinoxyphene; fenhexamide; famoxadone; fenamidone; zoxamide; ethaboxam; Metolaphenone; fluopyran; bixafen; cyflufenamide and Kinajido and the like.

  The application amount of the control agent of the present invention varies depending on weather conditions, formulation form, application time, application method, application location, target disease, target crop, etc. 1 to 500 g, preferably 2 to 200 g. Emulsions, wettable powders, suspensions and the like are usually diluted with water and applied. In this case, the concentration of the compound after dilution is usually 0.0005 to 2% by weight, preferably 0.005 to 1% by weight. The powder, granules and the like are usually applied as they are without dilution. In the treatment of seeds, the amount of the present compound in the control agent of the present invention is usually 0.001 to 100 g, preferably 0.01 to 50 g per 1 kg seed.

  The control agent of the present invention can be used as a plant disease control agent in agricultural land such as fields, paddy fields, lawns, orchards. The control agent of the present invention can control diseases of the farmland in the farmland where the following “crop” and the like are cultivated.

Agricultural crops: corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybeans, peanuts, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, tobacco, vegetables, solanaceous vegetables (eggplant, tomato, pepper, pepper, potato) Cucumber, pumpkin, zucchini, watermelon, melon, etc., cruciferous vegetables (radish, turnip, horseradish, kohlrabi, cabbage, cabbage, mustard, broccoli, cauliflower, etc.), asteraceae (burdock, Shungiku, artichokes, lettuce, etc.), liliaceae vegetables (leek, onion, garlic, asparagus), celeryaceae vegetables (carrot, parsley, celery, red pepper, etc.), red crustacean vegetables (spinach, chard, etc.) (Perilla, mint, basil ), Strawberry, sweet potato, yam, taro, etc.,
Bridegroom,
Foliage plant,
Fruit trees; pears (apples, pears, Japanese pears, quince, quince, etc.), nuclear fruits (peaches, plums, nectarines, ume, sweet cherry, apricots, prunes, etc.), citrus (satsuma mandarin, orange, lemon, lime, grapefruit) ), Nuts (chestnut, walnut, hazel, almond, pistachio, cashew nut, macadamia nut, etc.), berries (blueberry, cranberry, blackberry, raspberry, etc.), grape, oyster, olive, loquat, banana, coffee, Date palm, coconut palm, etc.
Trees other than fruit trees: Cha, mulberry, flowering trees, street trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak, poplar, redwood, fu, sycamore, zelkova, black bean, peach tree, Tsuga, rat, pine, Spruce, yew) etc.

  The above `` crop '' is resistant to HPPD inhibitors such as isoxaflutol, ALS inhibitors such as imazetapyr and thifensulfuron methyl, EPSP synthase inhibitors, glutamine synthase inhibitors, herbicides such as bromoxynil, This includes crops granted by classical breeding methods or genetic engineering techniques.

  As an example of a “crop” to which resistance has been imparted by a classic breeding method, imidazolinone herbicide-resistant Clearfield (registered trademark) canola, such as imazetapil, and sulfonylurea-based ALS-inhibiting herbicide resistance such as thifensulfuron methyl There are STS soybeans. In addition, examples of “crop” to which tolerance has been imparted by genetic engineering techniques include glyphosate and glufosinate-resistant corn varieties that have already been sold under trade names such as RoundupReady (registered trademark) and LibertyLink (registered trademark). Yes.

The “crop” includes, for example, a crop that can synthesize selective toxins known in the genus Bacillus by using genetic recombination technology.
Toxins expressed in such genetically modified plants include insecticidal proteins from Bacillus cereus and Bacillus popirie; Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C from Bacillus thuringiensis Insecticidal protein such as δ-endotoxin, VIP1, VIP2, VIP3 or VIP3A; nematode-derived insecticidal protein; toxin produced by animals such as scorpion toxin, spider toxin, bee toxin or insect-specific neurotoxin; filamentous fungal toxin; plant Lectin; agglutinin; protease inhibitor such as trypsin inhibitor, serine protease inhibitor, patatin, cystatin, papain inhibitor; ribosome inactivating protein (RIP) such as lysine, corn-RIP, abrin, ruffin, saporin, bryodin; 3-hydroxysteroid oxidase, ecdysteroid Steroid metabolic enzymes such as UDP-glucosyltransferase and cholesterol oxidase; ecdysone inhibitor; HMG-COA reductase; ion channel inhibitor such as sodium channel and calcium channel inhibitor; juvenile hormone esterase; diuretic hormone receptor; stilbene synthase; Benzyl synthase; chitinase; glucanase and the like.

In addition, as toxins expressed in such genetically modified crops, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, δ-endotoxin proteins such as Cry3Bb1 or Cry9C, and insecticidal protein hybrids such as VIP1, VIP2, VIP3 or VIP3A Toxins, partially defective toxins, modified toxins are also included. Hybrid toxins are produced by new combinations of different domains of these proteins using recombinant techniques. As a toxin lacking a part, Cry1Ab lacking a part of the amino acid sequence is known. In the modified toxin, one or more amino acids of the natural toxin are substituted.
Examples of these toxins and recombinant plants capable of synthesizing these toxins are EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878. , WO 03/052073 and the like.
The toxins contained in these recombinant plants particularly confer resistance to Coleoptera pests, Diptera pests, and Lepidoptera pests.

  Also, genetically modified plants that contain one or more insecticidal pest resistance genes and express one or more toxins are already known, and some are commercially available. Examples of these transgenic plants include YieldGard® (a corn variety expressing Cry1Ab toxin), YieldGard Rootworm® (a corn variety expressing Cry3Bb1 toxin), YieldGard Plus® (Cry1Ab and Cry3Bb1 Corn varieties expressing toxins), Herculex I® (corn varieties expressing phosphinotricin N-astilyltransferase (PAT) to confer resistance to Cry1Fa2 toxin and glufosinate), NuCOTN33B (Cry1Ac toxin) Cotton varieties expressing), Bollgard I (registered trademark) (cotton varieties expressing Cry1Ac toxin), Bollgard II (registered trademark) (cotton varieties expressing Cry1Ac and Cry2Ab toxin), VIPCOT (registered trademark) (VIP toxin) Cotton varieties), NewLeaf (registered trademark) (potato varieties expressing Cry3A toxin), NatureGard (registered trademark) Agrisure (registered trademark) GT Advant Examples include age (GA21 glyphosate resistance trait), Agrisure (registered trademark) CB Advantage (Bt11 corn borer (CB) trait), Protecta (registered trademark), and the like.

The above “crop” includes those given the ability to produce an anti-pathogenic substance having a selective action using genetic recombination technology.
PR proteins and the like are known as examples of anti-pathogenic substances (PRPs, EP-A-0 392 225). Such anti-pathogenic substances and genetically modified plants that produce them are described in EP-A-0 392 225, WO 95/33818, EP-A-0 353 191 and the like.
Examples of anti-pathogenic substances expressed in such genetically modified plants include, for example, sodium channel inhibitors and calcium channel inhibitors (KP1, KP4, KP6 toxins produced by viruses, etc.) are known. Ion channel inhibitors; stilbene synthase; bibenzyl synthase; chitinase; glucanase; PR protein; peptide antibiotics, heterocyclic antibiotics, protein factors involved in plant disease resistance (called plant disease resistance genes, WO 03/000906)) and other anti-pathogenic substances produced by microorganisms.

Examples of plant diseases that can be controlled by the present invention include filamentous fungi and the like, and more specifically, the following diseases can be mentioned, but are not limited thereto.
Usually, this invention control method is performed by using this invention control agent by the method of applying this invention control agent mentioned above.

Rice blast (Magnaporthe grisea), sesame leaf blight (Cochliobolus miyabeanus), blight (Rhizoctonia solani), idiot seedling (Gibberella fujikuroi);
Wheat powdery mildew (Erysiphe graminis), red mold (Fusarium graminearum, F. avenacerum, F. culmorum, Microdochium nivale), rust (Puccinia striiformis, P. graminis, P. recondita, P. hordei), snow Rot (Typhula sp., Micronectriella nivalis), Bare Scarf (Ustilago tritici, U. nuda), Namahusa scab (Tilletia caries), Eye ailment (Pseudocercosporella herpotrichoides), Cloud disease (Rhynchosporium secalis), Leaf blight ( Septoria tritici), blight (Leptosphaeria nodorum), net blotch (Pyrenophora teres Drechsler), blight (Gaeumannomyces graminis);
Citrus spot disease (Diaporthe citri), scab (Elsinoe fawcetti), fruit rot (Penicillium digitatum, P. italicum);
Monilinia mali, apple rot (Valsa ceratosperma), powdery mildew (Podosphaera leucotricha), spotted leaf (Alternaria alternata apple pathotype), black rot (Venturia inaequalis), anthracnose (Glomerella cingulata);
Pear black spot disease (Venturia nashicola, V. pirina), black spot disease (Alternaria alternata Japanese pear pathotype), red star disease (Gymnosporangium haraeanum);
Peach ash scab (Monilinia fructicola), black scab (Cladosporium carpophilum), Phomopsis sp. (Phomopsis sp.);

Grapes black rot (Elsinoe ampelina), late rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black lot disease (Guignardia bidwellii), downy mildew (Plasmopara viticola);
Oyster anthracnose (Gloeosporium kaki), deciduous leaf disease (Cercospora kaki, Mycosphaerella nawae);
Colletotrichum lagenarium, powdery mildew (Sphaerotheca fuliginea), vine blight (Mycosphaerella melonis), vine split (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), plague (Phytophthora sp.) Seedling blight (Pythium sp.);
Tomato ring disease (Alternaria solani), leaf mold (Cladosporium fulvum), plague (Phytophthora infestans);
Eggplant brown spot (Phomopsis vexans), powdery mildew (Erysiphe cichoracearum);
Brassicaceae vegetable black spot (Alternaria japonica), white spot (Cercosporella brassicae);
Leek rust (Puccinia allii), soybean purpura (Cercospora kikuchii), black scab (Elsinoe glycines), black spot (Diaporthe phaseolorum var. Sojae), rust (Phakopsora pachyrhizi)
Green Bean Anthracnose (Colletotrichum lindemthianum)
Groundnut black astringency (Cercospora personata), brown spot (Cercospora arachidicola), white silkworm (Sclerotium rolfsii);
Pea powdery mildew (Erysiphe pisi);
Potato summer plague (Alternaria solani), plague (Phytophthora infestans), half body wilt (Verticillium albo-atrum, V. dahliae, V. nigrescens);
Strawberry powdery mildew (Sphaerotheca humuli);
Tea net blast (Exobasidium reticulatum); white spot (Elsinoe leucospila), ring spot (Pestalotiopsis sp.), Anthracnose (Colletotrichum theae-sinensis)
Tobacco red blight (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), plague (Phytophthora nicotianae);

Sugar beet brown spot (Cercospora beticola), leaf rot (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris);
Rose scab (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa);
Chrysanthemum brown spot (Septoria chrysanthemi-indici), white rust (Puccinia horiana);
Onion leaf blight (Botrytis cinerea, B. byssoidea, B. squamosa), gray rot (Botrytis alli), sclerotia rot (Botrytis squamosa);
Various crops of gray mold (Botrytis cinerea), mycorrhizal disease (Sclerotinia sclerotiorum); radish black soot (Alternaria brassicicola);
Shiva dollar spot disease (Sclerotinia homeocarpa), Shiva brown patch disease and Rhizoctonia solani; and banana Sigatoka disease (Mycosphaerella fijiensis, Mycosphaerella musicola, Pseudocercospora musae).

  Hereinafter, although this invention is demonstrated in more detail by a manufacture example, a formulation example, a test example, etc., this invention is not limited only to these examples.

About manufacture of this compound and the manufacturing intermediate of this compound, it shows in a manufacture example and a reference manufacture example. Unless otherwise specified, the reaction was carried out under a nitrogen atmosphere, and ¹ H-NMR measurement was carried out using tetramethylsilane (TMS) as an internal standard (0 [ppm]).

ディーンスターク蒸留装置をつけたナスフラスコ内で、3,4‐ジヒドロキシベンゾニトリル1.35g、ベンズアルデヒド1.06g、p-トルエンスルホン酸1水和物0.19g及びトルエン40mlの混合物を生成した水を除去しながら１０時間加熱還流した。反応混合液を室温まで冷却した反応混合物を減圧下濃縮し、残渣に水を加え、酢酸エチルで抽出した。得られた有機層を水酸化ナトリウム水溶液、水及び飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥し、減圧下濃縮した。残渣をシリカゲルクロマトグラフィーに付し、粗5‐シアノ‐2フェニルベンゾ[1,3]ジオキソールを得た。
得られた粗5‐シアノ‐2‐フェニルベンゾ[1,3]ジオキソールをテトラヒドロフラン5mlに溶解し、それを水素化リチウムアルミニウム0.14gのテトラヒドロフラン15ml溶液に氷冷下で加え、加熱還流下で4時間攪拌した。0℃に冷却した反応混合物に水酸化ナトリウム水溶液を加え、セライト濾過して、濾液を減圧下濃縮した。残渣にクロロホルムを加え、無水硫酸ナトリウムで乾燥し、減圧下濃縮した。
得られた残渣にキノリン-6-カルボン酸0.35g、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0.46g及びピリジン10mlを加えて室温で20時間攪拌した。反応混合物に水を加え、酢酸エチルで抽出した。得られた有機層を水酸化ナトリウム水溶液、水及び飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥し、減圧下濃縮した。残渣をシリカゲルクロマトグラフィーに付し、 N-(2-フェニルベンゾ[1,3]ジオキソール-5‐イルメチル) -6-キノリンカルボン酸アミド（以下、本化合物１と記す。）を得た。
本化合物１
¹H-NMR (CDCl₃) δ: 4.63-4.66 (2H, m), 6.51 (1H, s), 6.82-6.93 (3H, m), 6.99 (1H, br s), 7.43-7.49 (4H, m), 7.55-7.58 (2H, m), 8.04-8.08 (1H, m), 8.15-8.18 (1H, m), 8.24-8.26 (1H, m), 8.33-8.35 (1H, m), 8.98-9.00 (1H, m) Production Example 1

In an eggplant flask equipped with a Dean-Stark distillation apparatus, while removing water that produced a mixture of 1.35 g of 3,4-dihydroxybenzonitrile, 1.06 g of benzaldehyde, 0.19 g of p-toluenesulfonic acid monohydrate and 40 ml of toluene. The mixture was heated to reflux for 10 hours. The reaction mixture was cooled to room temperature, concentrated under reduced pressure, water was added to the residue, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed successively with aqueous sodium hydroxide solution, water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to obtain crude 5-cyano-2-phenylbenzo [1,3] dioxole.
The obtained crude 5-cyano-2-phenylbenzo [1,3] dioxole was dissolved in 5 ml of tetrahydrofuran and added to a solution of 0.14 g of lithium aluminum hydride in 15 ml of tetrahydrofuran under ice-cooling, and heated for 4 hours under reflux. Stir. To the reaction mixture cooled to 0 ° C., an aqueous sodium hydroxide solution was added, filtered through celite, and the filtrate was concentrated under reduced pressure. Chloroform was added to the residue, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
To the obtained residue, 0.35 g of quinoline-6-carboxylic acid, 0.46 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 10 ml of pyridine were added and stirred at room temperature for 20 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed successively with aqueous sodium hydroxide solution, water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to obtain N- (2-phenylbenzo [1,3] dioxol-5-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as the present compound 1).
Compound 1
¹ H-NMR (CDCl ₃ ) δ: 4.63-4.66 (2H, m), 6.51 (1H, s), 6.82-6.93 (3H, m), 6.99 (1H, br s), 7.43-7.49 (4H, m ), 7.55-7.58 (2H, m), 8.04-8.08 (1H, m), 8.15-8.18 (1H, m), 8.24-8.26 (1H, m), 8.33-8.35 (1H, m), 8.98-9.00 (1H, m)

3,4‐ジヒドロキシベンゾニトリル1.35g、五酸化リン2.13g及びトルエン20mlの混合物を75℃で攪拌し、アセトン1.16gを加えて1時間攪拌した。室温まで冷却した反応混合物に水酸化ナトリウム水溶液を加え、酢酸エチルで抽出した。得られた有機層を水及び飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥し、減圧下濃縮した。残渣をシリカゲルクロマトグラフィーに付し、粗5‐シアノ‐2,2‐ジメチルべンゾ[1,3] ジオキソールを得た。
得られた粗5‐シアノ‐2,2-ジメチルベンゾ[1,3] ジオキソールをテトラヒドロフラン5mlに溶解し、それを水素化リチウムアルミニウム0.23gのテトラヒドロフラン15ml溶液に氷冷下で加え、加熱還流下で4時間攪拌した。0℃に冷却した反応混合物に水酸化ナトリウム水溶液を加え、セライト濾過し、濾液を減圧下濃縮した。残渣にクロロホルムを加え、無水硫酸ナトリウムで乾燥し、減圧下濃縮した。
得られた残渣にキノリン-6-カルボン酸0.17g、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0.23g及びピリジン2mlを加えて室温で20時間攪拌した。反応混合物に水を加え、酢酸エチルで抽出した。得られた有機層を水酸化ナトリウム水溶液、水及び飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥し、減圧下濃縮した。残渣をシリカゲルクロマトグラフィーに付し、N- (2,2-ジメチルベンゾ[1,3]ジオキソール‐5‐イルメチル) - 6-キノリンカルボン酸アミド（以下、本化合物２と記す。）を得た。
本化合物２
¹H-NMR (CDCl₃) δ: 1.68 (6H, s), 4.60 (2H, d, J = 5.4 Hz), 6.48 (1H, s), 6.67-6.72 (1H, m), 6.80-6.82 (2H, m), 7.45-7.49 (1H, m), 8.04-8.07 (1H, m), 8.14-8.17 (1H, m), 8.23-8.25 (1H, m), 8.32-8.34 (1H, m), 8.98-9.01 (1H, m). Production Example 2

A mixture of 1.35 g of 3,4-dihydroxybenzonitrile, 2.13 g of phosphorus pentoxide and 20 ml of toluene was stirred at 75 ° C., 1.16 g of acetone was added, and the mixture was stirred for 1 hour. An aqueous sodium hydroxide solution was added to the reaction mixture cooled to room temperature, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed successively with water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to obtain crude 5-cyano-2,2-dimethylbenzo [1,3] dioxole.
The obtained crude 5-cyano-2,2-dimethylbenzo [1,3] dioxole was dissolved in 5 ml of tetrahydrofuran, added to a solution of 0.23 g of lithium aluminum hydride in 15 ml of tetrahydrofuran under ice-cooling, and heated under reflux. Stir for 4 hours. A sodium hydroxide aqueous solution was added to the reaction mixture cooled to 0 ° C., and the mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. Chloroform was added to the residue, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
To the obtained residue, 0.17 g of quinoline-6-carboxylic acid, 0.23 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 2 ml of pyridine were added and stirred at room temperature for 20 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed successively with aqueous sodium hydroxide solution, water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to obtain N- (2,2-dimethylbenzo [1,3] dioxol-5-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as the present compound 2).
Compound 2
¹ H-NMR (CDCl ₃ ) δ: 1.68 (6H, s), 4.60 (2H, d, J = 5.4 Hz), 6.48 (1H, s), 6.67-6.72 (1H, m), 6.80-6.82 (2H , m), 7.45-7.49 (1H, m), 8.04-8.07 (1H, m), 8.14-8.17 (1H, m), 8.23-8.25 (1H, m), 8.32-8.34 (1H, m), 8.98 -9.01 (1H, m).

アセトンに代えて、ブタナール（butyraldehyde）を用いて、N- (2‐プロピルベンゾ[1,3]ジオキソール‐5‐イルメチル) - 6-キノリンカルボン酸アミド（以下、本化合物３と記す。）を得た。
本化合物３
¹H-NMR (CDCl₃) δ: 1.01 (3H, t, J = 7.4 Hz), 1.51-1.58 (2H, m), 1.91-1.95 (2H, m), 4.60 (2H, d, J = 5.6 Hz), 6.14 (1H, t, J = 4.9 Hz), 6.48 (1H, s), 6.73-6.75 (1H, m), 6.81-6.83 (2H, m), 7.46-7.49 (1H, m), 8.04-8.07 (1H, m), 8.14-8.17 (1H, m), 8.23-8.26 (1H, m), 8.32-8.33 (1H, m), 8.98-9.00 (1H, m). The following compound was obtained according to the method described in Production Example 2.

N- (2-propylbenzo [1,3] dioxol-5-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as the present compound 3) is obtained by using butyraldehyde instead of acetone. It was.
Compound 3
¹ H-NMR (CDCl ₃ ) δ: 1.01 (3H, t, J = 7.4 Hz), 1.51-1.58 (2H, m), 1.91-1.95 (2H, m), 4.60 (2H, d, J = 5.6 Hz ), 6.14 (1H, t, J = 4.9 Hz), 6.48 (1H, s), 6.73-6.75 (1H, m), 6.81-6.83 (2H, m), 7.46-7.49 (1H, m), 8.04- 8.07 (1H, m), 8.14-8.17 (1H, m), 8.23-8.26 (1H, m), 8.32-8.33 (1H, m), 8.98-9.00 (1H, m).

アセトンに代えて、プロパナールを用いて、N-（２‐エチルベンゾ[1,3]ジオキソール‐５‐イルメチル）-６−キノリンカルボン酸アミド（以下、本化合物４と記す。）０．２２ｇを得た。
本化合物４
¹H-NMR (CDCl₃) δ: 1.06 (3H, t, J = 7.4 Hz), 1.94-2.00 (2H, m), 4.59 (2H, d, J = 5.6 Hz), 6.10 (1H, t, J = 4.6 Hz), 6.61 (1H, s), 6.72-6.75 (1H, m), 6.80-6.84 (2H, m), 7.45-7.48 (1H, m), 8.03-8.07 (1H, m), 8.12-8.15 (1H, m), 8.21-8.24 (1H, m), 8.31-8.33 (1H, m), 8.97-8.99 (1H, m).

Using propanal instead of acetone, 0.22 g of N- (2-ethylbenzo [1,3] dioxol-5-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as the present compound 4) is obtained. It was.
Compound 4
¹ H-NMR (CDCl ₃ ) δ: 1.06 (3H, t, J = 7.4 Hz), 1.94-2.00 (2H, m), 4.59 (2H, d, J = 5.6 Hz), 6.10 (1H, t, J = 4.6 Hz), 6.61 (1H, s), 6.72-6.75 (1H, m), 6.80-6.84 (2H, m), 7.45-7.48 (1H, m), 8.03-8.07 (1H, m), 8.12- 8.15 (1H, m), 8.21-8.24 (1H, m), 8.31-8.33 (1H, m), 8.97-8.99 (1H, m).

(5,6,7,8-テトラヒドロナフタレン-2-イルメチル)アミン0.26g、キノリン-6-カルボン酸0.26g、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0.31g及びピリジン10ml混合し、室温で16時間攪拌した。反応混合物に水を加え、酢酸エチルで抽出した。得られた有機層を水酸化ナトリウム水溶液、水及び飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥し、減圧下濃縮した。残渣をヘキサン洗浄して、N- (5,6,7,8-テトラヒドロナフタレン-2-イルメチル) -6-キノリンカルボン酸アミド（以下、本化合物５と記す。）を得た。
本化合物５
¹H-NMR (CDCl₃) δ: 1.78-1.82 (4H, m), 2.75-2.79 (4H, m), 4.63 (2H, d, J = 5.6 Hz), 6.51 (1H, br s), 7.07-7.14 (3H, m), 7.44-7.49 (1H, m), 8.04-8.08 (1H, m), 8.12-8.15 (1H, m), 8.21-8.24 (1H, m), 8.31-8.33 (1H, m), 8.97-8.99 (1H, m) Production Example 3

(5,6,7,8-tetrahydronaphthalen-2-ylmethyl) amine 0.26 g, quinoline-6-carboxylic acid 0.26 g, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 0.31 g and pyridine 10 ml Mix and stir at room temperature for 16 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed successively with aqueous sodium hydroxide solution, water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was washed with hexane to obtain N- (5,6,7,8-tetrahydronaphthalen-2-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as the present compound 5).
Compound 5
¹ H-NMR (CDCl ₃ ) δ: 1.78-1.82 (4H, m), 2.75-2.79 (4H, m), 4.63 (2H, d, J = 5.6 Hz), 6.51 (1H, br s), 7.07- 7.14 (3H, m), 7.44-7.49 (1H, m), 8.04-8.08 (1H, m), 8.12-8.15 (1H, m), 8.21-8.24 (1H, m), 8.31-8.33 (1H, m ), 8.97-8.99 (1H, m)

  The following compounds were obtained according to the method described in Production Example 3.

(5,6,7,8-テトラヒドロナフタレン-2-イルメチル)アミンの代わりに、(インダン-5-イルメチル)アミンを用いて、N- (インダン-5-イルメチル) - 6-キノリンカルボン酸アミド（以下、本化合物６と記す。）を得た。
本化合物６
¹H-NMR (CDCl₃) δ: 2.05-2.12 (2H, m), 2.89-2.94 (4H, m), 4.67 (2H, d, J = 5.4 Hz), 6.54 (1H, br s), 7.15-7.28 (3H, m), 7.45-7.48 (1H, m), 8.04-8.08 (1H, m), 8.12-8.15 (1H, m), 8.21-8.23 (1H, m), 8.31-8.33 (1H, m), 8.97-8.99 (1H, m)

Instead of (5,6,7,8-tetrahydronaphthalen-2-ylmethyl) amine, using (indan-5-ylmethyl) amine, N- (indan-5-ylmethyl) -6-quinolinecarboxylic acid amide ( Hereinafter, this is referred to as the present compound 6.).
Compound 6
¹ H-NMR (CDCl ₃ ) δ: 2.05-2.12 (2H, m), 2.89-2.94 (4H, m), 4.67 (2H, d, J = 5.4 Hz), 6.54 (1H, br s), 7.15- 7.28 (3H, m), 7.45-7.48 (1H, m), 8.04-8.08 (1H, m), 8.12-8.15 (1H, m), 8.21-8.23 (1H, m), 8.31-8.33 (1H, m ), 8.97-8.99 (1H, m)

(5,6,7,8-テトラヒドロナフタレン-2-イルメチル)アミンの代わりに、6-アミノメチル-1-ベンゾ[b]フランを用いて、 N-(ベンゾ[b]フラン-6-イルメチル) -6-キノリンカルボン酸アミド（以下、本化合物７と記す。）を得た。
本化合物７
¹H-NMR (CDCl₃) δ:4.83 (2H, d, J = 5.6 Hz), 6.61 (1H, br s), 6.74 (1H, m), 7.29 (1H, d, J = 7.8 Hz), 7.47 (1H, dd, J = 8.3 Hz, 4.1 Hz), 7.56 (1H, s), 7.60 (1H, d, J = 8.0 Hz), 7.64 (1H, d, J = 2.2 Hz), 8.07 (1H, d, J = 8.8 Hz), 8.16 (1H, d, J = 8.8 Hz), 8.24 (1H, d, J = 8.3 Hz), 8.34 (1H, s), 8.99 (1H, d, J = 4.1 Hz)

Instead of (5,6,7,8-tetrahydronaphthalen-2-ylmethyl) amine, 6-aminomethyl-1-benzo [b] furan is used, and N- (benzo [b] furan-6-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as the present compound 7) was obtained.
Compound 7
¹ H-NMR (CDCl ₃ ) δ: 4.83 (2H, d, J = 5.6 Hz), 6.61 (1H, br s), 6.74 (1H, m), 7.29 (1H, d, J = 7.8 Hz), 7.47 (1H, dd, J = 8.3 Hz, 4.1 Hz), 7.56 (1H, s), 7.60 (1H, d, J = 8.0 Hz), 7.64 (1H, d, J = 2.2 Hz), 8.07 (1H, d , J = 8.8 Hz), 8.16 (1H, d, J = 8.8 Hz), 8.24 (1H, d, J = 8.3 Hz), 8.34 (1H, s), 8.99 (1H, d, J = 4.1 Hz)

(5,6,7,8-テトラヒドロナフタレン-2-イルメチル)アミンの代わりに、(キノリン-7-イル)メチルアミンを用いて、 N-(キノリン-7-イルメチル) -6-キノリンカルボン酸アミド（以下、本化合物８と記す。）を得た。
本化合物８
¹H-NMR (CDCl₃) δ:4.94 (2H, d, J = 5.6 Hz), 6.93 (1H, br s), 7.41 (1H, dd, J = 8.3 Hz, 4.2 Hz), 7.47 (1H, dd, J = 8.3 Hz, 4.2 Hz), 7.61 (1H, dd, J = 8.3 Hz, 1.3 Hz), 7.83 (1H, d, J = 8.3 Hz), 8.09 (1H, s), 8.12 (1H, dd, J = 8.8 Hz, 1.8 Hz), 8.15-8.17 (2H, m), 8.23 (1H, dd, J = 8.2 Hz, 1.6 Hz), 8.38 (1H, d, J = 1.8 Hz), 8.91 (1H, dd, J = 4.2 Hz, 1.3 Hz), 8.99 (1H, dd, J = 4.2 Hz, 1.6 Hz)

Instead of (5,6,7,8-tetrahydronaphthalen-2-ylmethyl) amine, using (quinolin-7-yl) methylamine, N- (quinolin-7-ylmethyl) -6-quinolinecarboxylic acid amide (Hereinafter referred to as the present compound 8).
Compound 8
¹ H-NMR (CDCl ₃ ) δ: 4.94 (2H, d, J = 5.6 Hz), 6.93 (1H, br s), 7.41 (1H, dd, J = 8.3 Hz, 4.2 Hz), 7.47 (1H, dd , J = 8.3 Hz, 4.2 Hz), 7.61 (1H, dd, J = 8.3 Hz, 1.3 Hz), 7.83 (1H, d, J = 8.3 Hz), 8.09 (1H, s), 8.12 (1H, dd, J = 8.8 Hz, 1.8 Hz), 8.15-8.17 (2H, m), 8.23 (1H, dd, J = 8.2 Hz, 1.6 Hz), 8.38 (1H, d, J = 1.8 Hz), 8.91 (1H, dd , J = 4.2 Hz, 1.3 Hz), 8.99 (1H, dd, J = 4.2 Hz, 1.6 Hz)

(5,6,7,8-テトラヒドロナフタレン-2-イルメチル)アミンの代わりに、6-アミノメチルベンゾチアゾールを用いて、N- (ベンゾチアゾール-6-イルメチル) -6-キノリンカルボン酸アミド（以下、本化合物９と記す。）を得た。
本化合物９
¹H-NMR (CDCl₃) δ:4.87 (2H, d, J = 5.8 Hz), 6.80 (1H, br s), 7.47 (1H, dd, J = 8.3 Hz, 4.1 Hz), 7.55 (1H, dd, J = 8.3 Hz, 1.7 Hz), 8.01 (1H, br s), 8.07-8.24 (4H, m), 8.36 (1H, d, J = 2.0 Hz), 8.99 (2H, m)

Instead of (5,6,7,8-tetrahydronaphthalen-2-ylmethyl) amine, N- (benzothiazol-6-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as 6-aminomethylbenzothiazole) is used. And referred to as the present compound 9.).
Compound 9
¹ H-NMR (CDCl ₃ ) δ: 4.87 (2H, d, J = 5.8 Hz), 6.80 (1H, br s), 7.47 (1H, dd, J = 8.3 Hz, 4.1 Hz), 7.55 (1H, dd , J = 8.3 Hz, 1.7 Hz), 8.01 (1H, br s), 8.07-8.24 (4H, m), 8.36 (1H, d, J = 2.0 Hz), 8.99 (2H, m)

(5,6,7,8-テトラヒドロナフタレン-2-イルメチル)アミンの代わりに、(7-アミノメチル)-3,4-ジヒドロ-2H-ベンゾ[1,5]ジオキセピン塩酸塩を用いて、N- (3,4-ジヒドロ-2H-ベンゾ[1,5]ジオキセピン-7-イルメチル) - 6-キノリンカルボン酸アミド（以下、本化合物１０と記す。）を得た。
本化合物１０
¹H-NMR (CDCl₃) δ: 2.20 (2H, m), 4.20-4.25 (4H, m), 4.62 (2H, d, J = 5.6 Hz), 6.50 (1H, br s), 6.94-6.98 (2H, m), 7.01 (1H, s), 7.48 (1H, dd, J = 8.1 Hz, 4.1 Hz), 8.07 (1H, d, J = 8.8 Hz), 8.16 (1H, d, J = 8.8 Hz), 8.25 (1H, d, J = 8.1 Hz), 8.33 (1H, s), 8.99 (1H, dd, J = 4.1 Hz, 1.7 Hz).

Instead of (5,6,7,8-tetrahydronaphthalen-2-ylmethyl) amine, using (7-aminomethyl) -3,4-dihydro-2H-benzo [1,5] dioxepin hydrochloride, N -(3,4-Dihydro-2H-benzo [1,5] dioxepin-7-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as the present compound 10) was obtained.
Compound 10
¹ H-NMR (CDCl ₃ ) δ: 2.20 (2H, m), 4.20-4.25 (4H, m), 4.62 (2H, d, J = 5.6 Hz), 6.50 (1H, br s), 6.94-6.98 ( 2H, m), 7.01 (1H, s), 7.48 (1H, dd, J = 8.1 Hz, 4.1 Hz), 8.07 (1H, d, J = 8.8 Hz), 8.16 (1H, d, J = 8.8 Hz) , 8.25 (1H, d, J = 8.1 Hz), 8.33 (1H, s), 8.99 (1H, dd, J = 4.1 Hz, 1.7 Hz).

6-ホルミル-2,3-ジヒドロベンゾ[b]フラン0.7g、2-プロパノール15ml及びピリジン3gの混合物に、室温でO-メチルヒドロキシルアミン塩酸塩0.7gを加えて１時間攪拌した。反応混合物を減圧下濃縮し、残渣に水を加え、メチルt-ブチルエーテルで抽出した。有機層を硫酸ナトリウムで乾燥し、減圧下濃縮した。
得られた残渣をテトラヒドロフラン20mlに溶解し、ここに室温で水素化リチウムアルミニウム0.12gを加え、15分間撹拌した。反応混合物に硫酸ナトリウム10水和物を加え、セライト上で濾過し、濾液を減圧下濃縮した。
得られた残渣に、6-キノリンカルボン酸0.17g及びピリジン1mlを加えて攪拌し、そこに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0.18gを加え、100℃で2時間撹拌した。室温まで冷却した反応混合物に水を加え、メタノールとクロロホルムとの混合液（混合割合 メタノール:クロロホルム＝1:10）で抽出し、有機層を硫酸ナトリウムで乾燥し、減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィー(クロロホルム:メタノール=20:1)で精製し、N- (2,3-ジヒドロ-1-ベンゾ[b]フラン-6-イルメチル) -6-キノリンカルボン酸アミド（以下、本化合物１１と記す。）を得た。
本化合物１１
¹H-NMR (CDCl₃) δ: 3.21 (2H, t, J = 8.7 Hz), 4.59 (2H, t, J = 8.7 Hz), 4.65 (2H, d), 6.53 (1H, br s), 6.83 (1H, s), 6.88 (1H, d, J = 7.5 Hz), 7.18 (1H, d, J = 7.5 Hz), 7.47 (1H, dd, J = 8.2 Hz, 4.2 Hz), 8.06 (1H, dd, J = 8.8 Hz, 2.0 Hz), 8.15 (1H, d, J = 8.8 Hz), 8.24 (1H, d, J = 8.2 Hz), 8.32 (1H, d, J = 2.0 Hz), 8.99 (1H, d, J = 4.2 Hz) Production Example 4

To a mixture of 0.7 g of 6-formyl-2,3-dihydrobenzo [b] furan, 15 ml of 2-propanol and 3 g of pyridine, 0.7 g of O-methylhydroxylamine hydrochloride was added at room temperature and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure, water was added to the residue, and the mixture was extracted with methyl t-butyl ether. The organic layer was dried over sodium sulfate and concentrated under reduced pressure.
The obtained residue was dissolved in 20 ml of tetrahydrofuran, and 0.12 g of lithium aluminum hydride was added thereto at room temperature, followed by stirring for 15 minutes. To the reaction mixture was added sodium sulfate decahydrate, filtered over celite, and the filtrate was concentrated under reduced pressure.
To the obtained residue, 0.17 g of 6-quinolinecarboxylic acid and 1 ml of pyridine were added and stirred, and 0.18 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added thereto, and the mixture was stirred at 100 ° C. for 2 hours. Stir. Water was added to the reaction mixture cooled to room temperature, and the mixture was extracted with a mixed solution of methanol and chloroform (mixing ratio methanol: chloroform = 1: 10). The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (chloroform: methanol = 20: 1) to give N- (2,3-dihydro-1-benzo [b] furan-6-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter, This is referred to as the present compound 11.).
Compound 11
¹ H-NMR (CDCl ₃ ) δ: 3.21 (2H, t, J = 8.7 Hz), 4.59 (2H, t, J = 8.7 Hz), 4.65 (2H, d), 6.53 (1H, br s), 6.83 (1H, s), 6.88 (1H, d, J = 7.5 Hz), 7.18 (1H, d, J = 7.5 Hz), 7.47 (1H, dd, J = 8.2 Hz, 4.2 Hz), 8.06 (1H, dd , J = 8.8 Hz, 2.0 Hz), 8.15 (1H, d, J = 8.8 Hz), 8.24 (1H, d, J = 8.2 Hz), 8.32 (1H, d, J = 2.0 Hz), 8.99 (1H, d, J = 4.2 Hz)

キノリン-6-カルボン酸0.35g、ベンゾ[1,3]ジオキソール‐5‐イルメチルアミン0.30g及びN,N-ジメチルホルムアミド10mlの混合物に、（ベンゾトリアゾール-1-イルオキシ）トリス(ジメチルアミノ)ホスホニウムヘキサフルオロホスフェート0.88g及びトリエチルアミン0.40gを順次加えて室温で2時間攪拌した。反応混合物に氷及び水を加え、酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥し、減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、N- (ベンゾ[1,3]ジオキソール‐5‐イルメチル) -6-キノリンカルボン酸アミド（以下、本化合物１２と記す。）を得た。
本化合物１２
¹H-NMR (CDCl₃) δ: 4.61 (2H, d, J = 5.6 Hz), 5.98 (2H, s), 6.61 (1H, br s) , 6.79 (1H, d, J = 8.0 Hz), 6.85 (1H, dd, J = 8.0 Hz, 1.5 Hz), 6.89 (1H, d, J = 1.5 Hz), 7.46 (1H, dd, J = 8.3 Hz, 4.2 Hz), 8.05 (1H, dd, J = 8.8 Hz, 2.0 Hz), 8.14 (1H, d, J = 8.8 Hz), 8.22 (1H, d, J = 8.3 Hz), 8.33 (1H, d, J = 2.0 Hz), 8.99 (1H, dd, J = 4.2 Hz, 1.7 Hz) Production Example 5

To a mixture of 0.35 g of quinoline-6-carboxylic acid, 0.30 g of benzo [1,3] dioxol-5-ylmethylamine and 10 ml of N, N-dimethylformamide, (benzotriazol-1-yloxy) tris (dimethylamino) phosphonium Hexafluorophosphate 0.88 g and triethylamine 0.40 g were sequentially added, and the mixture was stirred at room temperature for 2 hours. Ice and water were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain N- (benzo [1,3] dioxol-5-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as the present compound 12).
Compound 12
¹ H-NMR (CDCl ₃ ) δ: 4.61 (2H, d, J = 5.6 Hz), 5.98 (2H, s), 6.61 (1H, br s), 6.79 (1H, d, J = 8.0 Hz), 6.85 (1H, dd, J = 8.0 Hz, 1.5 Hz), 6.89 (1H, d, J = 1.5 Hz), 7.46 (1H, dd, J = 8.3 Hz, 4.2 Hz), 8.05 (1H, dd, J = 8.8 Hz, 2.0 Hz), 8.14 (1H, d, J = 8.8 Hz), 8.22 (1H, d, J = 8.3 Hz), 8.33 (1H, d, J = 2.0 Hz), 8.99 (1H, dd, J = (4.2 Hz, 1.7 Hz)

  The following compounds were obtained according to the method described in Production Example 5.

ベンゾ[1,3]ジオキソール‐5‐イルメチルアミンの代わりに、2,3-ジヒドロ[1,4]ベンゾジオキシン‐6‐イルメチルアミンを用いて、N- (2,3-ジヒドロ[1,4]ベンゾジオキシン‐6‐イルメチル) - 6-キノリンカルボン酸アミド（以下、本化合物１３と記す。）を得た。
本化合物１３
¹H-NMR (CDCl₃) δ: 4.26 (4H, s), 4.59 (2H, d, J = 5.4 Hz), 6.53 (1H, br), 6.86 (2H), 6.91 (1H, s), 7.47 (1H, dd, J = 8.3 Hz, 4.2 Hz), 8.05 (1H, dd, J = 8.8 Hz, 1.9 Hz), 8.14 (1H, d, J = 8.8 Hz), 8.23 (1H, d, J = 8.3 Hz), 8.32 (1H, d, J = 1.7 Hz), 8.98 (1H, dd, J = 4.2 Hz, 1.7 Hz).

Instead of benzo [1,3] dioxol-5-ylmethylamine, using 2,3-dihydro [1,4] benzodioxin-6-ylmethylamine, N- (2,3-dihydro [1, 4] benzodioxin-6-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as the present compound 13) was obtained.
Compound 13
¹ H-NMR (CDCl ₃ ) δ: 4.26 (4H, s), 4.59 (2H, d, J = 5.4 Hz), 6.53 (1H, br), 6.86 (2H), 6.91 (1H, s), 7.47 ( 1H, dd, J = 8.3 Hz, 4.2 Hz), 8.05 (1H, dd, J = 8.8 Hz, 1.9 Hz), 8.14 (1H, d, J = 8.8 Hz), 8.23 (1H, d, J = 8.3 Hz ), 8.32 (1H, d, J = 1.7 Hz), 8.98 (1H, dd, J = 4.2 Hz, 1.7 Hz).

ベンゾ[1,3]ジオキソール‐5‐イルメチルアミンの代わりに、2,3-ジヒドロベンゾ[b]フラン‐5‐イルメチルアミンを用いて、 N-(2,3-ジヒドロベンゾ[b]フラン‐5‐イルメチル) -6-キノリンカルボン酸アミド（以下、本化合物１４と記す。）を得た。
本化合物１４
¹H-NMR (CDCl₃) δ: 3.21 (2H, t, J = 8.8 Hz), 4.58 (2H, t, J = 8.8 Hz), 4.62 (2H, d, J = 5.4 Hz), 6.48 (1H, br), 6.78 (1H, d, J = 8.3 Hz), 7.14 (1H, d, J = 8.1 Hz), 7.28 (1H, s), 7.47 (1H, dd, J = 8.3 Hz, 4.1 Hz), 8.05 (1H, dd, J = 8.8 Hz, 2.0 Hz), 8.15 (1H, d, J = 8.8 Hz), 8.24 (1H, d, J = 8.3 Hz), 8.32 (1H, d, J = 2.0 Hz), 8.99 (1H, dd, J = 4.1 Hz, 1.7 Hz).

Instead of benzo [1,3] dioxol-5-ylmethylamine, using 2,3-dihydrobenzo [b] furan-5-ylmethylamine, N- (2,3-dihydrobenzo [b] furan -5-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as the present compound 14) was obtained.
Compound 14
¹ H-NMR (CDCl ₃ ) δ: 3.21 (2H, t, J = 8.8 Hz), 4.58 (2H, t, J = 8.8 Hz), 4.62 (2H, d, J = 5.4 Hz), 6.48 (1H, br), 6.78 (1H, d, J = 8.3 Hz), 7.14 (1H, d, J = 8.1 Hz), 7.28 (1H, s), 7.47 (1H, dd, J = 8.3 Hz, 4.1 Hz), 8.05 (1H, dd, J = 8.8 Hz, 2.0 Hz), 8.15 (1H, d, J = 8.8 Hz), 8.24 (1H, d, J = 8.3 Hz), 8.32 (1H, d, J = 2.0 Hz), 8.99 (1H, dd, J = 4.1 Hz, 1.7 Hz).

ベンゾ[1,3]ジオキソール‐5‐イルメチルアミンの代わりに、ベンゾ[b]フラン‐5‐イルメチルアミンを用いて、 N-(ベンゾ[b]フラン‐5‐イルメチル) -6-キノリンカルボン酸アミド（以下、本化合物１５と記す。）を得た。
本化合物１５
¹H-NMR (CDCl₃) δ: 4.80 (2H, d, J = 5.4 Hz), 6.58 (1H, br) , 6.77 (1H, dd, J = 2.2 Hz, 1.0 Hz), 7.34 (1H, dd, J = 8.5 Hz, 1.7 Hz), 7.45-7.52 (2H), 7.65 (2H, d, J = 2.2 Hz), 8.07 (1H, dd, J = 8.8 Hz, 2.0 Hz), 8.16 (1H, d, J = 8.8 Hz), 8.24 (1H, d, J = 8.3 Hz), 8.34 (1H, d, J = 2.0 Hz), 8.99 (1H, dd, J = 4.1 Hz, 1.7 Hz).

Using benzo [b] furan-5-ylmethylamine instead of benzo [1,3] dioxol-5-ylmethylamine, N- (benzo [b] furan-5-ylmethyl) -6-quinolinecarbon An acid amide (hereinafter referred to as the present compound 15) was obtained.
Compound 15
¹ H-NMR (CDCl ₃ ) δ: 4.80 (2H, d, J = 5.4 Hz), 6.58 (1H, br), 6.77 (1H, dd, J = 2.2 Hz, 1.0 Hz), 7.34 (1H, dd, J = 8.5 Hz, 1.7 Hz), 7.45-7.52 (2H), 7.65 (2H, d, J = 2.2 Hz), 8.07 (1H, dd, J = 8.8 Hz, 2.0 Hz), 8.16 (1H, d, J = 8.8 Hz), 8.24 (1H, d, J = 8.3 Hz), 8.34 (1H, d, J = 2.0 Hz), 8.99 (1H, dd, J = 4.1 Hz, 1.7 Hz).

ベンゾ[1,3]ジオキソール‐5‐イルメチルアミンの代わりに、ベンゾ[b]チオフェン‐5‐イルメチルアミンを用いて、N- (ベンゾ[b]チオフェン‐5‐イルメチル) -6-キノリンカルボン酸アミド（以下、本化合物１６と記す。）を得た。
本化合物１６
¹H-NMR (DMSO-d₆) δ: 4.65 (2H, d, J = 5.8 Hz), 7.39 (1H, d, J = 8.0 Hz), 7.44 (1H, d, J = 5.4 Hz), 7.60 (1H, dd, J = 8.3 Hz, 4.4 Hz), 7.73 (1H, d, J = 5.4 Hz), 7.85 (1H, s), 7.95 (1H, d, J = 8.6 Hz) ,8.08 (1H, d, J = 8.8 Hz), 8.22 (1H, dd, J = 8.8 Hz, 2.0 Hz), 8.47 (1H, d, J = 8.0 Hz), 8.55 (1H, d, J = 1.7 Hz), 8.97 (1H, dd, J = 4.1 Hz, 1.7 Hz), 9.3-9.4(1H, m)

Using benzo [b] thiophen-5-ylmethylamine instead of benzo [1,3] dioxol-5-ylmethylamine, N- (benzo [b] thiophen-5-ylmethyl) -6-quinolinecarbon An acid amide (hereinafter referred to as the present compound 16) was obtained.
Compound 16
¹ H-NMR (DMSO-d ₆ ) δ: 4.65 (2H, d, J = 5.8 Hz), 7.39 (1H, d, J = 8.0 Hz), 7.44 (1H, d, J = 5.4 Hz), 7.60 ( 1H, dd, J = 8.3 Hz, 4.4 Hz), 7.73 (1H, d, J = 5.4 Hz), 7.85 (1H, s), 7.95 (1H, d, J = 8.6 Hz), 8.08 (1H, d, J = 8.8 Hz), 8.22 (1H, dd, J = 8.8 Hz, 2.0 Hz), 8.47 (1H, d, J = 8.0 Hz), 8.55 (1H, d, J = 1.7 Hz), 8.97 (1H, dd , J = 4.1 Hz, 1.7 Hz), 9.3-9.4 (1H, m)

ベンゾ[1,3]ジオキソール‐5‐イルメチルアミンの代わりに、1,3-ジヒドロ-5-イソベンゾフランメタンアミンを用いて、N-1,3-ジヒドロ-5-イソベンゾフランメタン-6-キノリンカルボン酸アミド（以下、本化合物１７と記す。）を得た。
本化合物１７
¹H-NMR (CDCl₃) δ: 4.72 (2H, d, J = 5.7 Hz), 5.10 (4H, s), 6.66 (1H, br s), 7.23-7.31 (3H, m), 7.48 (1H, dd, J = 8.3 Hz, 4.2 Hz), 8.07 (1H, dd, J = 8.8 Hz, 2.0 Hz), 8.18 (1H, d, J = 8.8 Hz), 8.32 (1H, dd, J = 2.0 Hz), 8.39 (1H, s), 8.99 (1H, dd, J = 4.2 Hz, 1.7 Hz).

Instead of benzo [1,3] dioxol-5-ylmethylamine, 1,3-dihydro-5-isobenzofuranmethanamine is used, and N-1,3-dihydro-5-isobenzofuranmethane-6-quinoline is used. Carboxylic acid amide (hereinafter referred to as the present compound 17) was obtained.
Compound 17
¹ H-NMR (CDCl ₃ ) δ: 4.72 (2H, d, J = 5.7 Hz), 5.10 (4H, s), 6.66 (1H, br s), 7.23-7.31 (3H, m), 7.48 (1H, dd, J = 8.3 Hz, 4.2 Hz), 8.07 (1H, dd, J = 8.8 Hz, 2.0 Hz), 8.18 (1H, d, J = 8.8 Hz), 8.32 (1H, dd, J = 2.0 Hz), 8.39 (1H, s), 8.99 (1H, dd, J = 4.2 Hz, 1.7 Hz).

ベンゾ[1,3]ジオキソール‐5‐イルメチルアミンの代わりに、2-ナフチルメチルアミン塩酸塩を用いて、N- (2-ナフチルメチル) -6-キノリンカルボン酸アミド（以下、本化合物１８と記す。）を得た。
本化合物１８
¹H-NMR (CDCl₃) δ: 4.88 (2H, d, J = 5.6 Hz), 6.64 (1H, br) , 7.46-7.53 (4H), 7.84-7.88 (4H), 8.09 (1H, d, J = 8.8 Hz), 8.17 (1H, d, J = 9.0 Hz), 8.23 (1H, d, J = 8.3 Hz), 8.35 (1H, s), 8.99 (1H, d, J = 4.1 Hz).

Using 2-naphthylmethylamine hydrochloride instead of benzo [1,3] dioxol-5-ylmethylamine, N- (2-naphthylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as this compound 18) I wrote.)
Compound 18
¹ H-NMR (CDCl ₃ ) δ: 4.88 (2H, d, J = 5.6 Hz), 6.64 (1H, br), 7.46-7.53 (4H), 7.84-7.88 (4H), 8.09 (1H, d, J = 8.8 Hz), 8.17 (1H, d, J = 9.0 Hz), 8.23 (1H, d, J = 8.3 Hz), 8.35 (1H, s), 8.99 (1H, d, J = 4.1 Hz).

テトラヒドロフラン5mlに、6-キノリンカルボン酸塩化物塩酸塩0.34g、2,2-ジフルオロベンゾ[1,3]ジオキソール‐5‐イルメチルアミン0.28g及びトリエチルアミン0.6mlを加え、該混合物を室温で12時間攪拌した。反応混合物に水を加え、酢酸エチルで抽出した。得られた有機層を飽和炭酸水素ナトリウム水溶液及び飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥し、減圧下濃縮した。残渣をヘキサン洗浄して、N- (2,2-ジフルオロ‐ベンゾ[1,3]ジオキソール‐5‐イルメチル) -6-キノリンカルボン酸アミド（以下、本化合物１９と記す。）を得た。
本化合物１９
¹H-NMR (CDCl₃) δ: 4.69 (2H, d, J = 5.9 Hz), 6.64 (1H, br s), 7.03-7.15 (3H, m), 7.49 (1H, dd, J = 7.9 Hz, 4.3 Hz), 8.06 (1H, d, J = 8.7 Hz), 8.17 (1H, d, J = 8.7 Hz), 8.24-8.26 (1H, m), 8.34-8.34 (1H, m), 8.99-9.01 (1H, m). Production Example 6

To 5 ml of tetrahydrofuran are added 0.34 g of 6-quinolinecarboxylic acid chloride hydrochloride, 0.28 g of 2,2-difluorobenzo [1,3] dioxol-5-ylmethylamine and 0.6 ml of triethylamine, and the mixture is stirred at room temperature for 12 hours. Stir. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was washed with hexane to obtain N- (2,2-difluoro-benzo [1,3] dioxol-5-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as the present compound 19).
Compound 19
¹ H-NMR (CDCl ₃ ) δ: 4.69 (2H, d, J = 5.9 Hz), 6.64 (1H, br s), 7.03-7.15 (3H, m), 7.49 (1H, dd, J = 7.9 Hz, 4.3 Hz), 8.06 (1H, d, J = 8.7 Hz), 8.17 (1H, d, J = 8.7 Hz), 8.24-8.26 (1H, m), 8.34-8.34 (1H, m), 8.99-9.01 ( 1H, m).

¹H-NMR (CDCl₃) δ: 4.69 (2H, d, J = 5.9 Hz), 6.03 (2H, s), 6.62-6.67 (2H, m), 6.91-6.95 (1H, m), 7.45-7.49 (1H, m), 8.03-8.06 (1H, m), 8.13-8.16 (1H, m), 8.22-8.25 (1H, m), 8.30-8.31 (1H, m), 8.97-9.00 (1H, m). Production Example 7
0.34-g of (4-fluorobenzo [1,3] dioxol-5-yl) methylamine, 0.35 g of quinoline-6-carboxylic acid, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 50 g and 5 ml of pyridine were added and stirred at room temperature. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed successively with aqueous sodium hydroxide solution, water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was washed with hexane to obtain 0.35 g of N- (4-fluorobenzo [1,3] dioxol-5-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter referred to as the present compound 20).
Compound 20

¹ H-NMR (CDCl ₃ ) δ: 4.69 (2H, d, J = 5.9 Hz), 6.03 (2H, s), 6.62-6.67 (2H, m), 6.91-6.95 (1H, m), 7.45-7.49 (1H, m), 8.03-8.06 (1H, m), 8.13-8.16 (1H, m), 8.22-8.25 (1H, m), 8.30-8.31 (1H, m), 8.97-9.00 (1H, m) .

¹H-NMR (CDCl₃) δ: 0.93-0.97 (3H, m), 1.37-1.47 (2H, m), 1.69-1.76 (2H, m), 2.75-2.79 (2H, m), 4.76 (2H, d, J = 5.8 Hz), 6.36 (1H, s) , 6.56 (1H, br) , 7.24 (1H, d, J = 8.3 Hz), 7.39 (1H, d, J = 8.3 Hz), 7.45-7.48 (1H, m), 7.51 (1H, s) , 8.05-8.08 (1H, m), 8.15 (1H, d, J = 8.8 Hz), 8.22 (1H, d, J = 8.3 Hz), 8.33 (1H, s), 8.98 (1H, d, J = 2.9 Hz). Production Example 8
To a mixture of 0.17 g of quinoline-6-carboxylic acid, 0.23 g of 2-butylbenzo [b] furan-5-ylmethylamine and 3 ml of N, N-dimethylformamide, (benzotriazol-1-yloxy) tris (dimethylamino) phosphonium Hexafluorophosphate (0.50 g) and triethylamine (0.30 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture and stirred for a while. The resulting precipitate was collected by filtration, washed successively with water and tert-butyl methyl ether, dried, and dried to give N- (2-butylbenzo [b] furan-5-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter, This is referred to as the present compound 21.) 0.33 g was obtained.
Compound 21

¹ H-NMR (CDCl ₃ ) δ: 0.93-0.97 (3H, m), 1.37-1.47 (2H, m), 1.69-1.76 (2H, m), 2.75-2.79 (2H, m), 4.76 (2H, d, J = 5.8 Hz), 6.36 (1H, s), 6.56 (1H, br), 7.24 (1H, d, J = 8.3 Hz), 7.39 (1H, d, J = 8.3 Hz), 7.45-7.48 ( 1H, m), 7.51 (1H, s), 8.05-8.08 (1H, m), 8.15 (1H, d, J = 8.8 Hz), 8.22 (1H, d, J = 8.3 Hz), 8.33 (1H, s ), 8.98 (1H, d, J = 2.9 Hz).

¹H-NMR (CDCl₃) δ: 0.95 (3H, t, J = 7.3 Hz), 1.37-1.44 (2H, m), 1.69-1.76 (2H, m), 2.75-2.78 (2H, m), 4.79 (2H, d, J = 5.4 Hz), 6.37 (1H, s) , 6.56 (1H, br) , 7.22 (1H, d, J = 7.8 Hz), 7.46-7.48 (3H), 8.07 (1H, d, J = 8.7 Hz), 8.15 (1H, d, J = 8.7 Hz), 8.23 (1H, d, J = 8.0 Hz), 8.33 (1H, s), 8.98 (1H, d, J = 1.5 Hz). Production Example 9
To a mixture of 0.17 g of quinoline-6-carboxylic acid, 0.23 g of 2-butylbenzo [b] furan-6-ylmethylamine and 3 ml of N, N-dimethylformamide, (benzotriazol-1-yloxy) tris (dimethylamino) phosphonium Hexafluorophosphate (0.50 g) and triethylamine (0.30 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture and stirred for a while. The resulting precipitate was collected by filtration, washed successively with water and tert-butyl methyl ether, dried, and dried to give N- (2-butylbenzo [b] furan-6-ylmethyl) -6-quinolinecarboxylic acid amide (hereinafter, This is referred to as the present compound 22.) 0.29 g was obtained.
Compound 22

¹ H-NMR (CDCl ₃ ) δ: 0.95 (3H, t, J = 7.3 Hz), 1.37-1.44 (2H, m), 1.69-1.76 (2H, m), 2.75-2.78 (2H, m), 4.79 (2H, d, J = 5.4 Hz), 6.37 (1H, s), 6.56 (1H, br), 7.22 (1H, d, J = 7.8 Hz), 7.46-7.48 (3H), 8.07 (1H, d, J = 8.7 Hz), 8.15 (1H, d, J = 8.7 Hz), 8.23 (1H, d, J = 8.0 Hz), 8.33 (1H, s), 8.98 (1H, d, J = 1.5 Hz).

¹H-NMR (CDCl₃)δ: 4.65 (2H, d, J = 6.0 Hz), 5.96 (2H, s), 6.80 (1H, d, J = 8.0 Hz), 6.89 (1H, d, J = 8.0 Hz), 6.91 (1H, s), 7.69 (1H, dd, J = 8.5, 4.1 Hz), 8.37-8.40 (1H, m), 8.44 (1H, s), 8.56 (1H, d, J = 8.7 Hz), 8.58 (1H, d, J = 8.7 Hz), 9.05 (1H, dd, J = 4.0, 1.3 Hz). Production Example 10
0.25 g of [1,5] naphthyridine-2-carboxylic acid, 0.21 g of benzo [1,3] dioxol-5-ylmethylamine, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 29 g, 0.5 ml of pyridine and 3 ml of N, N-dimethylformamide were mixed and stirred at 50 ° C. for 4 hours. Thereafter, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, and N- (benzo [1,3] dioxol-5-ylmethyl)-[1,5] naphthyridine-2-carboxylic acid amide (hereinafter referred to as the present compound 23). ) 0.064 g was obtained.
Compound 23

¹ H-NMR (CDCl ₃ ) δ: 4.65 (2H, d, J = 6.0 Hz), 5.96 (2H, s), 6.80 (1H, d, J = 8.0 Hz), 6.89 (1H, d, J = 8.0 Hz), 6.91 (1H, s), 7.69 (1H, dd, J = 8.5, 4.1 Hz), 8.37-8.40 (1H, m), 8.44 (1H, s), 8.56 (1H, d, J = 8.7 Hz ), 8.58 (1H, d, J = 8.7 Hz), 9.05 (1H, dd, J = 4.0, 1.3 Hz).

¹H-NMR (CDCl₃) δ: 0.95 (3H, t, J = 7.3 Hz), 1.37-1.46 (2H, m), 1.68-1.76 (2H, m), 2.74-2.78 (2H, m), 4.79 (2H, d, J = 5.8 Hz), 6.35 (1H, s) , 7.25 (1H, d, J = 8.6 Hz), 7.39 (1H, d, J = 8.6 Hz), 7.53 (1H, s) , 7.65-7.68 (1H, m), 8.36 (1H, d, J = 8.3 Hz), 8.48 (1H, br), 8.54-8.60 (2H), 9.04 (1H, d, J = 3.9 Hz). Production Example 11
To a mixture of 0.17 g of [1,5] naphthyridine-2-carboxylic acid, 0.23 g of 2-butylbenzo [b] furan-5-ylmethylamine and 3 ml of N, N-dimethylformamide, (benzotriazol-1-yloxy) tris (Dimethylamino) phosphonium hexafluorophosphate (0.50 g) and triethylamine (0.30 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture and stirred for a while. The resulting precipitate was collected by filtration, washed sequentially with water and tert-butyl methyl ether, then dried and N- (2-butylbenzo [b] furan-5-ylmethyl)-[1,5] naphthyridine-2- 0.17 g of carboxylic acid amide (hereinafter referred to as the present compound 24) was obtained.
Compound 24

¹ H-NMR (CDCl ₃ ) δ: 0.95 (3H, t, J = 7.3 Hz), 1.37-1.46 (2H, m), 1.68-1.76 (2H, m), 2.74-2.78 (2H, m), 4.79 (2H, d, J = 5.8 Hz), 6.35 (1H, s), 7.25 (1H, d, J = 8.6 Hz), 7.39 (1H, d, J = 8.6 Hz), 7.53 (1H, s), 7.65 -7.68 (1H, m), 8.36 (1H, d, J = 8.3 Hz), 8.48 (1H, br), 8.54-8.60 (2H), 9.04 (1H, d, J = 3.9 Hz).

¹H-NMR (CDCl₃) δ: 0.92-0.96 (3H, m), 1.38-1.45 (2H, m), 1.67-1.75 (2H, m), 2.75 (2H, t, J = 7.3 Hz), 4.82 (2H, d, J = 6.1 Hz), 6.36 (1H, d J = 0.76 Hz) , 7.22-7.25 (1H, m), 7.44-7.46 (2H), 7.64-7.67 (1H, m), 8.33-8.36 (1H, m), 8.53 (1H, br), 8.53-8.58 (2H), 9.02-9.04 (1H, m). Production Example 12
To a mixture of 0.17 g of [1,5] naphthyridine-2-carboxylic acid, 0.23 g of 2-butylbenzo [b] furan-6-ylmethylamine and 3 ml of N, N-dimethylformamide, (benzotriazol-1-yloxy) tris (Dimethylamino) phosphonium hexafluorophosphate (0.50 g) and triethylamine (0.30 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture and stirred for a while. The resulting precipitate was collected by filtration, washed successively with water and tert-butyl methyl ether and dried. 0.30 g of the obtained residue was subjected to silica gel column chromatography, and N- (2-butylbenzo [b] furan-6-ylmethyl)-[1,5] naphthyridine-2-carboxylic acid amide (hereinafter referred to as Compound 25) 0.23g was obtained.
Compound 25

¹ H-NMR (CDCl ₃ ) δ: 0.92-0.96 (3H, m), 1.38-1.45 (2H, m), 1.67-1.75 (2H, m), 2.75 (2H, t, J = 7.3 Hz), 4.82 (2H, d, J = 6.1 Hz), 6.36 (1H, d J = 0.76 Hz), 7.22-7.25 (1H, m), 7.44-7.46 (2H), 7.64-7.67 (1H, m), 8.33-8.36 (1H, m), 8.53 (1H, br), 8.53-8.58 (2H), 9.02-9.04 (1H, m).

¹H-NMR (CDCl₃) δ:4.65-4.67 (2H, m), 6.83 (1H, d J = 8.1 Hz) , 6.90-6.94 (2H), 6.98 (1H, s), 7.43-7.45 (3H), 7.55-7.57 (2H, m), 7.68-7.71 (1H, m), 8.39 (1H, d, J = 8.5 Hz), 8.46 (1H, br), 8.55-8.60 (2H), 9.05-9.06 (1H, m). Production Example 13
To a mixture of 0.17 g of [1,5] naphthyridine-2-carboxylic acid, 0.23 g of 2-phenylbenzo [1,3] dioxol-5-ylmethylamine and 3 ml of N, N-dimethylformamide, (benzotriazole-1- Iroxy) tris (dimethylamino) phosphonium hexafluorophosphate (0.50 g) and triethylamine (0.30 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine (3 times), dried over magnesium sulfate, and concentrated under reduced pressure. 0.39 g of the obtained residue was subjected to silica gel column chromatography, and N- (2-phenylbenzo [1,3] dioxol-5-ylmethyl)-[1,5] naphthyridine-2-carboxylic acid amide (hereinafter referred to as the present product). This is referred to as compound 26.) 0.32 g was obtained.
Compound 26

¹ H-NMR (CDCl ₃ ) δ: 4.65-4.67 (2H, m), 6.83 (1H, d J = 8.1 Hz), 6.90-6.94 (2H), 6.98 (1H, s), 7.43-7.45 (3H) , 7.55-7.57 (2H, m), 7.68-7.71 (1H, m), 8.39 (1H, d, J = 8.5 Hz), 8.46 (1H, br), 8.55-8.60 (2H), 9.05-9.06 (1H , m).

¹H-NMR (CDCl₃) δ:1.00 (3H, t, J = 7.6 Hz), 1.54-1.56 (2H, m), 1.90-1.94 (2H, m), 4.62 (2H, d, J = 6.0 Hz), 6.12 (1H, t J = 4.8 Hz) , 6.73 (1H, d J = 8.4 Hz) , 6.83-6.85 (2H), 7.67-7.70 (1H, m), 8.37-8.39 (1H, m), 8.43 (1H, br), 8.55-8.60 (2H), 9.04-9.05 (1H, m). Production Example 14
To a mixture of 13.51 g of 3,4-dihydroxybenzonitrile and 400 ml of toluene, 21.3 g of phosphorus pentoxide was added and stirred at a bath temperature of 75 ° C. Then 14.4 g of butanal was added thereto and stirred at a bath temperature of 75 ° C. for 2 hours. To the ice-cooled reaction mixture was added 500 ml of 10% aqueous sodium carbonate solution, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. 15.39 g of the residue was subjected to silica gel chromatography to obtain 1.8 g of crude 5-cyano-2-propylbenzo [1,3] dioxole.
To a mixture of 0.36 g of lithium aluminum hydride and 20 ml of tetrahydrofuran was added dropwise a solution of 1.8 g of crude 5-cyano-2-propylbenzo [1,3] dioxole in 30 ml of tetrahydrofuran while cooling with water, and at room temperature for 4 hours. Stir. Next, an aqueous sodium potassium tartrate solution was added dropwise with cooling with ice in a nitrogen atmosphere, and then it was extracted with tert-butyl methyl ether. The organic layer was washed with saturated brine, dried and concentrated under reduced pressure to give 1.65 g of crude 2-propylbenzo [1,3] dioxol-5-ylmethylamine.
To a mixture of 0.17 g of [1,5] naphthyridine-2-carboxylic acid, 0.28 g of 2-propylbenzo [1,3] dioxol-5-ylmethylamine and 3 ml of N, N-dimethylformamide, (benzotriazole-1- Iroxy) tris (dimethylamino) phosphonium hexafluorophosphate (0.50 g) and triethylamine (0.30 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine (3 times), dried over magnesium sulfate, and concentrated under reduced pressure. 0.48 g of the obtained residue was subjected to silica gel column chromatography, and N- (2-propylbenzo [1,3] dioxol-5-ylmethyl)-[1,5] naphthyridine-2-carboxylic acid amide (hereinafter referred to as the present product). This is referred to as Compound 27.) 0.35 g was obtained.
Compound 27

¹ H-NMR (CDCl ₃ ) δ: 1.00 (3H, t, J = 7.6 Hz), 1.54-1.56 (2H, m), 1.90-1.94 (2H, m), 4.62 (2H, d, J = 6.0 Hz ), 6.12 (1H, t J = 4.8 Hz), 6.73 (1H, d J = 8.4 Hz), 6.83-6.85 (2H), 7.67-7.70 (1H, m), 8.37-8.39 (1H, m), 8.43 (1H, br), 8.55-8.60 (2H), 9.04-9.05 (1H, m).

¹H-NMR (CDCl₃) δ:4.26 (4H, s), 4.63 (2H, d, J = 6.1 Hz), 6.85-6.93 (3H), 7.69 (1H, dd, J = 8.8, 4.2 Hz), 8.37-8.39 (1H, m), 8.43 (1H, br), 8.55 (1H, d, J = 8.8 Hz), 8.58 (1H, d, J = 8.8 Hz), 9.05 (1H, dd, J = 4.2, 1.7 Hz). Production Example 15
To a mixture of 0.17 g of [1,5] naphthyridine-2-carboxylic acid, 0.17 g of 2,3-dihydro-1,4-benzodioxin-6-ylmethylamine and 3 ml of N, N-dimethylformamide, (benzotriazole-1 -Iloxy) tris (dimethylamino) phosphonium hexafluorophosphate (0.44 g) and triethylamine (0.20 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine (3 times), dried over magnesium sulfate, and concentrated under reduced pressure. The resulting residue was cooled by adding 5 ml of tert-butyl methyl ether. The resulting solid was collected by filtration, and N- (2,3-dihydro-1,4-benzodioxin6-ylmethyl)-[1,5] naphthyridine-2-carboxylic acid amide (hereinafter referred to as the present compound 28). 0.25 g was obtained.
Compound 28

¹ H-NMR (CDCl ₃ ) δ: 4.26 (4H, s), 4.63 (2H, d, J = 6.1 Hz), 6.85-6.93 (3H), 7.69 (1H, dd, J = 8.8, 4.2 Hz), 8.37-8.39 (1H, m), 8.43 (1H, br), 8.55 (1H, d, J = 8.8 Hz), 8.58 (1H, d, J = 8.8 Hz), 9.05 (1H, dd, J = 4.2, 1.7 Hz).

¹H-NMR (CDCl₃) δ: 4.83 (2H, d, J = 6.1 Hz), 6.76 (1H, d, J = 1.2 Hz) , 7.35-7.38 (1H, m), 7.51 (1H, d, J = 8.5 Hz), 7.64-7.70 (3H), 8.37 (1H, d, J = 8.8 Hz), 8.52 (1H, br), 8.55-8.61 (2H), 9.04-9.06 (1H, m). Production Example 16
To a mixture of 0.17 g of [1,5] naphthyridine-2-carboxylic acid, 0.17 g of benzo [b] furan-5-ylmethylamine and 3 ml of N, N-dimethylformamide, (benzotriazol-1-yloxy) tris (dimethyl Amino) phosphonium hexafluorophosphate (0.50 g) and triethylamine (0.30 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture and stirred for a while. The resulting precipitate was collected by filtration, washed successively with water and tert-butyl methyl ether, then dried and N- (benzo [b] furan-5-ylmethyl)-[1,5] naphthyridine-2-carboxylic acid 0.23 g of amide (hereinafter referred to as the present compound 29) was obtained.
Compound 29

¹ H-NMR (CDCl ₃ ) δ: 4.83 (2H, d, J = 6.1 Hz), 6.76 (1H, d, J = 1.2 Hz), 7.35-7.38 (1H, m), 7.51 (1H, d, J = 8.5 Hz), 7.64-7.70 (3H), 8.37 (1H, d, J = 8.8 Hz), 8.52 (1H, br), 8.55-8.61 (2H), 9.04-9.06 (1H, m).

¹H-NMR (CDCl₃) δ: 3.19-3.23 (2H, m), 4.55-4.60 (2H, m), 4.65 (2H, d, J = 6.1 Hz), 6.78 (1H, d, J = 8.2 Hz) , 7.16 (1H, d, J = 8.2 Hz) , 7.27 (1H, s), 7.67-7.70 (1H, m), 8.36-8.39 (1H, m), 8.42 (1H, br), 8.54-8.60 (2H), 9.04-9.05 (1H, m). Production Example 17
To a mixture of 0.17 g of [1,5] naphthyridine-2-carboxylic acid, 0.17 g of 2,3-dihydro-benzo [b] furan-5-ylmethylamine and 3 ml of N, N-dimethylformamide, (benzotriazole-1 -Iloxy) tris (dimethylamino) phosphonium hexafluorophosphate (0.50 g) and triethylamine (0.30 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture and stirred for a while. The resulting precipitate was collected by filtration, washed sequentially with water and tert-butyl methyl ether, then dried to give N- (2,3-dihydro-benzo [b] furan-5-ylmethyl)-[1,5] 0.25 g of naphthyridine-2-carboxylic acid amide (hereinafter referred to as the present compound 30) was obtained.
Compound 30

¹ H-NMR (CDCl ₃ ) δ: 3.19-3.23 (2H, m), 4.55-4.60 (2H, m), 4.65 (2H, d, J = 6.1 Hz), 6.78 (1H, d, J = 8.2 Hz ), 7.16 (1H, d, J = 8.2 Hz), 7.27 (1H, s), 7.67-7.70 (1H, m), 8.36-8.39 (1H, m), 8.42 (1H, br), 8.54-8.60 ( 2H), 9.04-9.05 (1H, m).

¹H-NMR (DMSO-d6)δ: 4.42 (2H, d, J = 5.7 Hz), 5.99 (2H, s), 6.83 (1H, d, J = 7.8 Hz), 6.87 (1H, d, J = 7.8 Hz), 6.93 (1H, s), 8.04 (1H, dd, J = 8.6, 1.5 Hz), 8.16 (1H, d, J = 8.6 Hz), 8.70 (1H, d, J = 0.72 Hz), 9.12-9.15 (1H, br m), 9.54 (1H,s). Production Example 18
To a mixture of 0.36 g of benzothiazole-6-carboxylic acid, 0.30 g of benzo [1,3] dioxol-5-ylmethylamine and 7 ml of N, N-dimethylformamide, (benzotriazol-1-yloxy) tris (dimethylamino) Phosphonium hexafluorophosphate 0.88 g and triethylamine 0.40 g were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine (3 times), dried over magnesium sulfate, and concentrated under reduced pressure. 0.81 g of the obtained residue was subjected to silica gel column chromatography, and N- (benzo [1,3] dioxol-5-ylmethyl) -benzothiazole-6-carboxylic acid amide (hereinafter referred to as the present compound 31) 0.57 g was obtained.
Compound 31

¹ H-NMR (DMSO-d6) δ: 4.42 (2H, d, J = 5.7 Hz), 5.99 (2H, s), 6.83 (1H, d, J = 7.8 Hz), 6.87 (1H, d, J = 7.8 Hz), 6.93 (1H, s), 8.04 (1H, dd, J = 8.6, 1.5 Hz), 8.16 (1H, d, J = 8.6 Hz), 8.70 (1H, d, J = 0.72 Hz), 9.12 -9.15 (1H, br m), 9.54 (1H, s).

¹H-NMR (CDCl₃) δ: 0.93-0.97 (3H, m), 1.37-1.47 (2H, m), 1.69-1.76 (2H, m), 2.75-2.79 (2H, m), 4.74 (2H, d, J = 5.6 Hz), 6.36 (1H, s) , 6.47 (1H, br), 7.22 (1H, d, J = 8.3 Hz), 7.39 (1H, d, J = 8.3 Hz), 7.50 (1H, s) , 7.88 (1H, d, J = 8.3 Hz), 8.16 (1H, d, J = 8.3 Hz), 8.50 (1H, s), 9.11 (1H, s). Production Example 19
To a mixture of 0.18 g of benzothiazole-6-carboxylic acid, 0.23 g of 2-butylbenzo [b] furan-5-ylmethylamine and 3 ml of N, N-dimethylformamide, (benzotriazol-1-yloxy) tris (dimethylamino) Phosphonium hexafluorophosphate (0.50 g) and triethylamine (0.30 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture and stirred for a while. The resulting precipitate was collected by filtration, washed successively with water and tert-butyl methyl ether, then dried to give N- (2-butylbenzo [b] furan-5-ylmethyl) -benzothiazole-6-carboxylic acid amide ( Hereinafter referred to as the present compound 32.) 0.29 g was obtained.
Compound 32

¹ H-NMR (CDCl ₃ ) δ: 0.93-0.97 (3H, m), 1.37-1.47 (2H, m), 1.69-1.76 (2H, m), 2.75-2.79 (2H, m), 4.74 (2H, d, J = 5.6 Hz), 6.36 (1H, s), 6.47 (1H, br), 7.22 (1H, d, J = 8.3 Hz), 7.39 (1H, d, J = 8.3 Hz), 7.50 (1H, s), 7.88 (1H, d, J = 8.3 Hz), 8.16 (1H, d, J = 8.3 Hz), 8.50 (1H, s), 9.11 (1H, s).

¹H-NMR (CDCl₃) δ: 0.95 (3H, t, J = 7.3 Hz), 1.39-1.42 (2H, m), 1.70-1.74 (2H, m), 2.74-2.78 (2H, m), 4.77 (2H, d, J = 5.1 Hz), 6.36 (1H,s) , 6.51 (1H, br), 7.20 (1H, d, J = 8.0 Hz), 7.44-7.47 (2H), 7.88 (1H, d, J = 8.1 Hz), 8.15 (1H, d, J = 8.1 Hz), 8.50 (1H, s) , 9.11 (1H, s). Production Example 20
To a mixture of 0.18 g of benzothiazole-6-carboxylic acid, 0.23 g of 2-butylbenzo [b] furan-6-ylmethylamine and 3 ml of N, N-dimethylformamide, (benzotriazol-1-yloxy) tris (dimethylamino) Phosphonium hexafluorophosphate (0.50 g) and triethylamine (0.30 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture and stirred for a while. The resulting precipitate was collected by filtration, washed successively with water and tert-butyl methyl ether and then dried to give N- (2-butylbenzo [b] furan-6-ylmethyl) -benzothiazole-6-carboxylic acid amide ( Hereinafter referred to as the present compound 33.) 0.33 g was obtained.
Compound 33

¹ H-NMR (CDCl ₃ ) δ: 0.95 (3H, t, J = 7.3 Hz), 1.39-1.42 (2H, m), 1.70-1.74 (2H, m), 2.74-2.78 (2H, m), 4.77 (2H, d, J = 5.1 Hz), 6.36 (1H, s), 6.51 (1H, br), 7.20 (1H, d, J = 8.0 Hz), 7.44-7.47 (2H), 7.88 (1H, d, J = 8.1 Hz), 8.15 (1H, d, J = 8.1 Hz), 8.50 (1H, s), 9.11 (1H, s).

¹H-NMR (CDCl₃) δ:4.58-4.62 (2H, m), 644 (1H, br) , 6.82-6.91 (3H), 6.99 (1H, s), 7.43-7.45 (3H), 7.55-7.58 (2H, m), 7.88 (1H, dd, J = 8.6, 1.6 Hz), 8.17 (1H, d, J = 8.6 Hz), 8.50 (1H, d, J = 1.6 Hz), ), 9.11 (1H, s). Production Example 21
To a mixture of 0.18 g of benzothiazole-6-carboxylic acid, 0.30 g of 5-aminomethyl-2-phenylbenzo [1,3] dioxole and 3 ml of N, N-dimethylformamide was added N- (benzotriazol-1-yloxy) tris. (Dimethylamino) phosphonium hexafluorophosphate (0.50 g) and triethylamine (0.30 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture and stirred for a while. The resulting precipitate was collected by filtration, washed successively with water and tert-butyl methyl ether, then dried to give (2-phenylbenzo [1,3] dioxol-5-ylmethyl) -benzothiazole-6-carboxylic acid amide (Hereinafter referred to as the present compound 34.) 0.35 g was obtained.
Compound 34

¹ H-NMR (CDCl ₃ ) δ: 4.58-4.62 (2H, m), 644 (1H, br), 6.82-6.91 (3H), 6.99 (1H, s), 7.43-7.45 (3H), 7.55-7.58 (2H, m), 7.88 (1H, dd, J = 8.6, 1.6 Hz), 8.17 (1H, d, J = 8.6 Hz), 8.50 (1H, d, J = 1.6 Hz),), 9.11 (1H, s).

¹H-NMR (CDCl₃) δ:0.99-1.02 (3H, m), 1.51-1.59 (2H, m), 1.87-1.95 (2H, m), 4.57-4.60 (2H, m), 6.12-6.14 (1H, m) , 6.42 (1H, br) , 6.72-6.74 (1H, m), 6.79-6.81 (2H), 7.87 (1H, dd, J = 8.6, 1.6 Hz), 8.16 (1H, d, J = 8.6 Hz), 8.49 (1H, d, J = 1.6 Hz), 9.11 (1H, s). Production Example 22
To a mixture of 0.18 g of benzothiazole-6-carboxylic acid, 0.28 g of crude 2-propylbenzo [1,3] dioxol-5-ylmethylamine and 3 ml of N, N-dimethylformamide, (benzotriazol-1-yloxy) tris ( Dimethylamino) phosphonium hexafluorophosphate (0.50 g) and triethylamine (0.30 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine (3 times), dried over magnesium sulfate, and concentrated under reduced pressure. 0.46 g of the obtained residue was subjected to silica gel column chromatography, and N- (2-propylbenzo [1,3] dioxol-5-ylmethyl) -benzothiazole-6-carboxylic acid amide (hereinafter referred to as the present compound 35). .) 0.24 g was obtained.
Compound 35

¹ H-NMR (CDCl ₃ ) δ: 0.99-1.02 (3H, m), 1.51-1.59 (2H, m), 1.87-1.95 (2H, m), 4.57-4.60 (2H, m), 6.12-6.14 ( 1H, m), 6.42 (1H, br), 6.72-6.74 (1H, m), 6.79-6.81 (2H), 7.87 (1H, dd, J = 8.6, 1.6 Hz), 8.16 (1H, d, J = 8.6 Hz), 8.49 (1H, d, J = 1.6 Hz), 9.11 (1H, s).

¹H-NMR (CDCl₃) δ:4.26 (4H, s), 4.57 (2H, d, J = 5.6 Hz), 6.42 (1H, br), 6.86 (2H, s), 6.90 (1H, s), 7.87 (1H, dd, J = 8.6, 1.7 Hz), 8.16 (1H, d, J = 8,6 Hz), 8.49 (1H, s), 9.11 (1H, s). Production Example 23
To a mixture of 0.18 g of benzothiazole-6-carboxylic acid, 0.17 g of 2,3-dihydro-1,4-benzodioxin-6-ylmethylamine and 3 ml of N, N-dimethylformamide was added (benzotriazol-1-yloxy) tris. (Dimethylamino) phosphonium hexafluorophosphate (0.44 g) and triethylamine (0.20 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture and stirred for a while. The resulting precipitate was collected by filtration, washed successively with water and tert-butyl methyl ether and then dried to give N- (2,3-dihydro-1,4-benzodioxin6-ylmethyl) -benzothiazole-6- 0.31 g of carboxylic acid amide (hereinafter referred to as the present compound 36) was obtained.
Compound 36

¹ H-NMR (CDCl ₃ ) δ: 4.26 (4H, s), 4.57 (2H, d, J = 5.6 Hz), 6.42 (1H, br), 6.86 (2H, s), 6.90 (1H, s), 7.87 (1H, dd, J = 8.6, 1.7 Hz), 8.16 (1H, d, J = 8,6 Hz), 8.49 (1H, s), 9.11 (1H, s).

¹H-NMR (CDCl₃) δ: 4.78 (2H, d, J = 5.6 Hz), 6.52 (1H, br) , 6.76 (1H, m), 7.32 (1H, m), 7.50 (1H, d, J = 8.5 Hz), 7.62-7.65 (2H, m), 7.89 (1H, dd, J = 8.5, 1.6 Hz), 8.16 (1H, d, J = 8.5 Hz), 8.50 (1H, d, J = 1.6 Hz), 9.11 (1H, s). Production Example 24
To a mixture of 0.18 g of benzothiazole-6-carboxylic acid, 0.17 g of benzo [b] furan-5-ylmethylamine and 3 ml of N, N-dimethylformamide, (benzotriazol-1-yloxy) tris (dimethylamino) phosphonium hexa 0.50 g of fluorophosphate and 0.30 g of triethylamine were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture and stirred for a while. The resulting precipitate was collected by filtration, washed successively with water and tert-butyl methyl ether, then dried to give N- (benzo [b] furan-5-ylmethyl) -benzothiazole-6-carboxylic acid amide (hereinafter, This is referred to as the present compound 37.) 0.27 g was obtained.
Compound 37

¹ H-NMR (CDCl ₃ ) δ: 4.78 (2H, d, J = 5.6 Hz), 6.52 (1H, br), 6.76 (1H, m), 7.32 (1H, m), 7.50 (1H, d, J = 8.5 Hz), 7.62-7.65 (2H, m), 7.89 (1H, dd, J = 8.5, 1.6 Hz), 8.16 (1H, d, J = 8.5 Hz), 8.50 (1H, d, J = 1.6 Hz) ), 9.11 (1H, s).

¹H-NMR (CDCl₃) δ: 3.19-3.23 (2H, m), 4.56-4.61 (4H), 6.40 (1H, br) , 6.77 (1H, d, J = 8.2 Hz) , 7.12 (1H, d, J = 8.2 Hz) , 7.24 (1H, s), 7.87 (1H, d, J = 8.3 Hz) , 8.16 (1H, d, J = 8.3 Hz), 8.49 (1H, s), 9.11 (1H, s). Production Example 25
To a mixture of 0.18 g of benzothiazole-6-carboxylic acid, 0.17 g of 2,3-dihydro-benzo [b] furan-5-ylmethylamine and 3 ml of N, N-dimethylformamide was added (benzotriazol-1-yloxy) tris. (Dimethylamino) phosphonium hexafluorophosphate (0.50 g) and triethylamine (0.30 g) were sequentially added, and the mixture was stirred at room temperature for 4 hours. Ice and water were added to the reaction mixture and stirred for a while. The resulting precipitate was collected by filtration, washed sequentially with water and tert-butyl methyl ether and then dried to give N- (2,3-dihydro-benzo [b] furan-5-ylmethyl) -benzothiazole-6- 0.28 g of carboxylic acid amide (hereinafter referred to as the present compound 38) was obtained.
Compound 38

¹ H-NMR (CDCl ₃ ) δ: 3.19-3.23 (2H, m), 4.56-4.61 (4H), 6.40 (1H, br), 6.77 (1H, d, J = 8.2 Hz), 7.12 (1H, d , J = 8.2 Hz), 7.24 (1H, s), 7.87 (1H, d, J = 8.3 Hz), 8.16 (1H, d, J = 8.3 Hz), 8.49 (1H, s), 9.11 (1H, s ).

  Next, reference production examples are shown for the production of the production intermediate of the present compound.

文献（Organic Letters 2001, 3(21), 3357-3360）に記載の方法に従って製造した6-ブロモ-2,3-ジヒドロベンゾフラン1.30g、N,N,N',N'-テトラメチルエチレンジアミン0.75g及びテトラヒドロフラン40mlの混合物に、-78℃でn-ブチルリチウム(1.6Mのヘキサン溶液)8.3mlを滴下し、１５分間撹拌した。次いでジメチルホルムアミド7mlを加え、30分間攪拌した。反応混合物に希塩酸を加えた後に室温まで昇温し、酢酸エチルで抽出した。有機層を硫酸ナトリウムで乾燥し、減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィー(ヘキサン:酢酸エチル=2:1)で精製し、6-ホルミル-2,3-ジヒドロベンゾ[b]フランを得た。
6-ホルミル-2,3-ジヒドロベンゾ[b]フラン
¹H-NMR (CDCl₃) δ: 3.29 (2H, t, J = 8.9 Hz), 4.65 (2H, t, J = 8.9 Hz), 7.33-7.40 (3H, m), 9.92 (1H, s) Reference production example 1

1.30 g of 6-bromo-2,3-dihydrobenzofuran prepared according to the method described in the literature (Organic Letters 2001, 3 (21), 3357-3360), 0.75 g of N, N, N ′, N′-tetramethylethylenediamine Then, 8.3 ml of n-butyllithium (1.6M hexane solution) was added dropwise at -78 ° C. to a mixture of 40 ml of tetrahydrofuran and stirred for 15 minutes. Subsequently, 7 ml of dimethylformamide was added and stirred for 30 minutes. Dilute hydrochloric acid was added to the reaction mixture, and the mixture was warmed to room temperature and extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to give 6-formyl-2,3-dihydrobenzo [b] furan.
6-Formyl-2,3-dihydrobenzo [b] furan
¹ H-NMR (CDCl ₃ ) δ: 3.29 (2H, t, J = 8.9 Hz), 4.65 (2H, t, J = 8.9 Hz), 7.33-7.40 (3H, m), 9.92 (1H, s)

文献（WO96/06095）に記載の方法に従って製造した4-ブロモベンゾ[b]フランと6-ブロモベンゾ[b]フランとの混合物（混合比 1:1）6.9gをジメチルスルホキシド35mlに溶解し、青酸銅(I)4.8gを加え、180℃で6時間攪拌した。室温まで冷却した反応混合物に水を加え、酢酸エチルで抽出した。有機層をアンモニア水で洗浄後、硫酸ナトリウムで乾燥し、減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィー(ヘキサン:酢酸エチル=10:1)で精製し、6-シアノベンゾ[b]フランを得た。
6-シアノベンゾ[b]フラン
¹H-NMR (CDCl₃) δ:6.87 (1H, d, J = 2.2 Hz), 7.52 (1H, dd, J = 8.0 Hz, 1.2 Hz), 7.69 (1H, d, J = 8.0 Hz), 7.81 (1H, d, J = 2.2 Hz), 7.83 (1H, d, J = 1.2 Hz) Reference production example 2

6.9 g of a mixture of 4-bromobenzo [b] furan and 6-bromobenzo [b] furan produced according to the method described in the literature (WO96 / 06095) (mixing ratio 1: 1) was dissolved in 35 ml of dimethyl sulfoxide, and copper cyanide (I) 4.8g was added and it stirred at 180 degreeC for 6 hours. Water was added to the reaction mixture cooled to room temperature, and the mixture was extracted with ethyl acetate. The organic layer was washed with aqueous ammonia, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1) to give 6-cyanobenzo [b] furan.
6-Cyanobenzo [b] furan
¹ H-NMR (CDCl ₃ ) δ: 6.87 (1H, d, J = 2.2 Hz), 7.52 (1H, dd, J = 8.0 Hz, 1.2 Hz), 7.69 (1H, d, J = 8.0 Hz), 7.81 (1H, d, J = 2.2 Hz), 7.83 (1H, d, J = 1.2 Hz)

6-シアノベンゾ[b]フラン0.35gをテトラヒドロフラン15mlに溶解し、ここに水素化リチウムアルミニウム0.4gを加え、15分間撹拌した。次いで、硫酸ナトリウム10水和物を加えて攪拌し、セライト上で濾過した。濾液を減圧下濃縮し、6-アミノメチルベンゾ[b]フランを得た。
6-アミノメチルベンゾ[b]フラン
¹H-NMR (CDCl₃) δ:3.98 (2H, d, J = 2.0 Hz), 6.74 (1H, d, J = 2.0 Hz), 7.19 (1H, d, J = 7.8 Hz), 7.47 (1H, s), 7.55 (1H, d, J = 7.8 Hz), 7.60 (1H, d, J = 2.0 Hz). Reference production example 3

0.35 g of 6-cyanobenzo [b] furan was dissolved in 15 ml of tetrahydrofuran, and 0.4 g of lithium aluminum hydride was added thereto, followed by stirring for 15 minutes. Then, sodium sulfate decahydrate was added and stirred, and filtered over celite. The filtrate was concentrated under reduced pressure to obtain 6-aminomethylbenzo [b] furan.
6-Aminomethylbenzo [b] furan
¹ H-NMR (CDCl ₃ ) δ: 3.98 (2H, d, J = 2.0 Hz), 6.74 (1H, d, J = 2.0 Hz), 7.19 (1H, d, J = 7.8 Hz), 7.47 (1H, s), 7.55 (1H, d, J = 7.8 Hz), 7.60 (1H, d, J = 2.0 Hz).

３−フルオロカテコール１．９２ｇ、１，１−ジブロモメタン３．９１ｇ、炭酸セシウム７．３２ｇ及びＤＭＦ２５ｍｌの混合物を１１０℃で１時間攪拌した。室温まで冷却した反応混合物に水を加え、酢酸エチルで抽出した。得られた有機層を水酸化ナトリウム水溶液、水及び飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥し、減圧下濃縮した。残渣をシリカゲルクロマトグラフィーに付し、４−フルオロベンゾ[1,3]ジオキソールを得た。
４−フルオロベンゾ[1,3]ジオキソール
¹H-NMR (CDCl₃) δ:6.01 (2H, s), 6.63-6.69 (2H, m), 6.74-6.79 (1H, m). Reference production example 4

A mixture of 1.92 g of 3-fluorocatechol, 3.91 g of 1,1-dibromomethane, 7.32 g of cesium carbonate, and 25 ml of DMF was stirred at 110 ° C. for 1 hour. Water was added to the reaction mixture cooled to room temperature, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed successively with aqueous sodium hydroxide solution, water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to obtain 4-fluorobenzo [1,3] dioxole.
4-Fluorobenzo [1,3] dioxole
¹ H-NMR (CDCl ₃ ) δ: 6.01 (2H, s), 6.63-6.69 (2H, m), 6.74-6.79 (1H, m).

ヘキサメチレンテトラミン２．６４ｇ及びトリフルオロ酢酸１０ｍｌの混合物を、８０℃で攪拌し、ここに４−フルオロベンゾ[1,3]ジオキソール１．３２ｇ及びトリフルオロ酢酸１０ｍｌの混合溶液を少しずつ滴下した。４時間後、室温まで冷却した反応混合物に水を加え、中性になるまで飽和炭酸水素ナトリウム水溶液を加え、酢酸エチルで抽出した。得られた有機層を水及び飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥し、減圧下濃縮した。残渣をシリカゲルクロマトグラフィーに付し、４−フルオロ−５−ホルミルベンゾ[1,3]ジオキソールを得た。
４−フルオロ−５−ホルミルベンゾ[1,３]ジオキソール
¹H-NMR (CDCl₃) δ:6.15 (2H, s), 6.76 (1H, d, J = 8.3 Hz), 7.46 (1H, dd, J = 8.3 Hz, 6.1 Hz), 10.14 (1H, s). Reference production example 5

A mixture of 2.64 g of hexamethylenetetramine and 10 ml of trifluoroacetic acid was stirred at 80 ° C., and a mixed solution of 1.32 g of 4-fluorobenzo [1,3] dioxole and 10 ml of trifluoroacetic acid was added dropwise little by little. After 4 hours, water was added to the reaction mixture cooled to room temperature, saturated aqueous sodium hydrogen carbonate solution was added until neutrality, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed successively with water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to obtain 4-fluoro-5-formylbenzo [1,3] dioxole.
4-Fluoro-5-formylbenzo [1,3] dioxole
¹ H-NMR (CDCl ₃ ) δ: 6.15 (2H, s), 6.76 (1H, d, J = 8.3 Hz), 7.46 (1H, dd, J = 8.3 Hz, 6.1 Hz), 10.14 (1H, s) .

４−フルオロ−５−ホルミルベンゾ[1,3]ジオキソール０．５８ｇ及びメタノール１０ｍｌの混合液を氷冷下で攪拌し、そこに水素化ホウ素ナトリウム６５ｍｇを加え、室温で１５分間攪拌した。反応混合物に水を加え、減圧下濃縮し、濃縮液を酢酸エチルで抽出した。得られた有機層を水及び飽和食塩水で順次洗浄し、無水硫酸ナトリウムで乾燥し、減圧下濃縮した。次いで硫酸マグネシウムで乾燥し、減圧下濃縮した。残渣をシリカゲルクロマトグラフィーに付し、４−フルオロ−５−ヒドロキシメチルベンゾ[1,3]ジオキソールを得た。
４−フルオロ−５−ヒドロキシメチル−ベンゾ[1,3]ジオキソール
¹H-NMR (CDCl₃) δ:1.76 (1H, br s), 4.68 (2H, s), 6.03 (2H, s), 6.62-6.64 (1H, m), 6.83-6.87 (1H, m). Reference production example 6

A mixture of 0.58 g of 4-fluoro-5-formylbenzo [1,3] dioxole and 10 ml of methanol was stirred under ice cooling, 65 mg of sodium borohydride was added thereto, and the mixture was stirred at room temperature for 15 minutes. Water was added to the reaction mixture, the mixture was concentrated under reduced pressure, and the concentrated solution was extracted with ethyl acetate. The obtained organic layer was washed successively with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Subsequently, it dried with magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to obtain 4-fluoro-5-hydroxymethylbenzo [1,3] dioxole.
4-Fluoro-5-hydroxymethyl-benzo [1,3] dioxole
¹ H-NMR (CDCl ₃ ) δ: 1.76 (1H, br s), 4.68 (2H, s), 6.03 (2H, s), 6.62-6.64 (1H, m), 6.83-6.87 (1H, m).

４−フルオロ−５−ヒドロキシメチルベンゾ[1,3]ジオキソール０．５６ｇ、フタルイミド０．５３ｇ、トリフェニルホスフィン０．９５ｇ及びトルエン５ｍｌの混合物を８０℃で攪拌し、アゾジカルボン酸ジエチル(２．２Ｍｏｌ／Ｌのトルエン溶液、１．６５ｍｌ)を加え、1時間撹拌した。室温まで冷却した反応混合物を減圧下濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付し、Ｎ−（４−フルオロ−ベンゾ[1,3]ジオキソール−５−イルメチル）フタルイミド０．５６ｇを得た。
Ｎ−（４−フルオロ−ベンゾ[1,3]ジオキソール−５−イルメチル）フタルイミド
¹H-NMR (CDCl₃) δ:4.86 (2H, d, J = 0.5 Hz), 6.00 (2H, s), 6.56-6.59 (1H, m), 6.85-6.88 (1H, m), 7.70-7.75 (2H, m), 7.84-7.87 (2H, m). Reference production example 7

A mixture of 0.56 g of 4-fluoro-5-hydroxymethylbenzo [1,3] dioxole, 0.53 g of phthalimide, 0.95 g of triphenylphosphine and 5 ml of toluene was stirred at 80 ° C., and diethyl azodicarboxylate (2.2 mol) / L toluene solution, 1.65 ml) was added and stirred for 1 hour. The reaction mixture cooled to room temperature was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 0.56 g of N- (4-fluoro-benzo [1,3] dioxol-5-ylmethyl) phthalimide.
N- (4-Fluoro-benzo [1,3] dioxol-5-ylmethyl) phthalimide
¹ H-NMR (CDCl ₃ ) δ: 4.86 (2H, d, J = 0.5 Hz), 6.00 (2H, s), 6.56-6.59 (1H, m), 6.85-6.88 (1H, m), 7.70-7.75 (2H, m), 7.84-7.87 (2H, m).

Ｎ−（４−フルオロ−ベンゾ[1,3]ジオキソール−５−イルメチル）フタルイミド０．５６ｇ及びメタノール１０ｍｌの混合物を加熱還流下で攪拌し、ヒドラジン１水和物０．１７ｇを加え、３時間撹拌した。室温まで冷却した反応混合物に水を加え、減圧下濃縮した。残渣に希塩酸を加え酸性にした後、セライト上で濾過した。濾液に水酸化ナトリウム水溶液を加えてアルカリ性にし、クロロホルムで抽出した。得られた有機層を水及び飽和食塩水で順次洗浄し、無水硫酸ナトリウムで乾燥し、減圧下濃縮して、（４−フルオロ−ベンゾ[1,3]ジオキソール−５−イル）メチルアミンを得た。
（４−フルオロ−ベンゾ[1,3]ジオキソール−５−イル）メチルアミン
¹H-NMR (CDCl₃) δ:1.57 (2H, s), 3.83 (2H, s), 6.01 (2H, s), 6.58-6.61 (1H, m), 6.72-6.77 (1H, m). Reference production example 8

A mixture of 0.56 g of N- (4-fluoro-benzo [1,3] dioxol-5-ylmethyl) phthalimide and 10 ml of methanol was stirred with heating under reflux, 0.17 g of hydrazine monohydrate was added, and the mixture was stirred for 3 hours. did. Water was added to the reaction mixture cooled to room temperature, and the mixture was concentrated under reduced pressure. The residue was acidified with dilute hydrochloric acid, and then filtered over celite. The filtrate was made alkaline by adding an aqueous sodium hydroxide solution and extracted with chloroform. The obtained organic layer was washed successively with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain (4-fluoro-benzo [1,3] dioxol-5-yl) methylamine. It was.
(4-Fluoro-benzo [1,3] dioxol-5-yl) methylamine
¹ H-NMR (CDCl ₃ ) δ: 1.57 (2H, s), 3.83 (2H, s), 6.01 (2H, s), 6.58-6.61 (1H, m), 6.72-6.77 (1H, m).

3,4‐ジヒドロキシベンゾニトリル18.78g、ベンズアルデヒドジエチルアセタール25.14g及びトルエン55mlの混合物にシュウ酸0.40gを加えて、生じるエタノールを除きながらバス温130℃で３時間攪拌した。室温まで冷却した反応混合物に１０％炭酸ナトリウム水溶液500mlを加え、トルエンで抽出した。得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥し、減圧下濃縮した。残渣29.59gをシリカゲルクロマトグラフィーに付し、5‐シアノ‐2-フェニルべンゾ[1,3] ジオキソール5.75gを得た。
5‐シアノ‐2-フェニルべンゾ[1,3] ジオキソール
¹H-NMR (CDCl₃) δ: 6.90 (1H, d, J = 8.1 Hz), 7.08-7.09 (2H), 7.29 (1H, s), 7.44-7.49 (3H), 7.51-7.55 (2H, m). Reference production example 9

To a mixture of 18.78 g of 3,4-dihydroxybenzonitrile, 25.14 g of benzaldehyde diethyl acetal and 55 ml of toluene, 0.40 g of oxalic acid was added and stirred at a bath temperature of 130 ° C. for 3 hours while removing the resulting ethanol. To the reaction mixture cooled to room temperature, 500 ml of 10% aqueous sodium carbonate solution was added and extracted with toluene. The obtained organic layer was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. 29.59 g of the residue was subjected to silica gel chromatography to obtain 5.75 g of 5-cyano-2-phenylbenzo [1,3] dioxole.
5-Cyano-2-phenylbenzo [1,3] dioxole
¹ H-NMR (CDCl ₃ ) δ: 6.90 (1H, d, J = 8.1 Hz), 7.08-7.09 (2H), 7.29 (1H, s), 7.44-7.49 (3H), 7.51-7.55 (2H, m ).

水素化リチウムアルミニウム0.60gとテトラヒドロフラン40mlの混合物に、水冷しながら、5-シアノ2-フェニルべンゾ[1,3] ジオキソール3.57gをテトラヒドロフラン60mlに溶解した溶液を滴下し、室温で４時間撹拌した。次いで、窒素雰囲気下、氷冷しながら酒石酸ナトリウムカリウム水溶液を滴下した。残渣をtert-ブチルメチルエーテルで抽出し、有機層を飽和食塩水で洗浄した後、乾燥し、減圧下濃縮して、3.39gを得た。
2-フェニルベンゾ[1,3]ジオキソール-5-イルメチルアミン
¹H-NMR (CDCl₃) δ: 3.78 (2H, s), 6.76-6.80 (2H), 6.84 (1H, s), 6.94 (1H, s), 7.41-7.44 (3H), 7.55-7.58 (2H, m). Reference production example 10

To a mixture of 0.60 g of lithium aluminum hydride and 40 ml of tetrahydrofuran, a solution of 3.57 g of 5-cyano-2-phenylbenzo [1,3] dioxole dissolved in 60 ml of tetrahydrofuran was added dropwise with water cooling and stirred at room temperature for 4 hours. did. Next, an aqueous sodium potassium tartrate solution was added dropwise with cooling with ice in a nitrogen atmosphere. The residue was extracted with tert-butyl methyl ether, and the organic layer was washed with saturated brine, dried, and concentrated under reduced pressure to give 3.39 g.
2-Phenylbenzo [1,3] dioxol-5-ylmethylamine
¹ H-NMR (CDCl ₃ ) δ: 3.78 (2H, s), 6.76-6.80 (2H), 6.84 (1H, s), 6.94 (1H, s), 7.41-7.44 (3H), 7.55-7.58 (2H , m).

酸化銅(I) (Cu₂O) 0.86gおよびピリジン40mlの混合物に、１−ヘキシン0.82gおよび2-ヨード-4-シアノフェノール2.01gを加えて、バス温130℃で10時間攪拌した。室温まで冷却した反応混合物をセライトろ過した後、ろ液を濃縮した。得られた残渣4.93gをシリカゲルカラムクロマトグラフィーに付し、2-ブチル-5-シアノベンゾ[b]フラン1.72gを得た。
2-ブチル-5-シアノベンゾ[b]フラン
¹H-NMR (CDCl₃) δ: 0.94-0.98 (3H, m), 1.42-1.50 (2H, m), 1.70-1.78 (2H, m), 2.77-2.81 (2H, m), 6.44 (1H, d, J = 0.48 Hz), 7.45-7.50 (2H), 7.80 (1H, d, J = 0.72 Hz) Reference production example 11

To a mixture of 0.86 g of copper (I) oxide (Cu ₂ O) and 40 ml of pyridine, 0.82 g of 1-hexyne and 2.01 g of 2-iodo-4-cyanophenol were added and stirred at a bath temperature of 130 ° C. for 10 hours. The reaction mixture cooled to room temperature was filtered through celite, and then the filtrate was concentrated. The obtained residue (4.93 g) was subjected to silica gel column chromatography to obtain 1.72 g of 2-butyl-5-cyanobenzo [b] furan.
2-Butyl-5-cyanobenzo [b] furan
¹ H-NMR (CDCl ₃ ) δ: 0.94-0.98 (3H, m), 1.42-1.50 (2H, m), 1.70-1.78 (2H, m), 2.77-2.81 (2H, m), 6.44 (1H, d, J = 0.48 Hz), 7.45-7.50 (2H), 7.80 (1H, d, J = 0.72 Hz)

水素化リチウムアルミニウム0.30gとテトラヒドロフラン20mlの混合物に、水冷しながら、2-ブチル-5-シアノベンゾ[b]フラン1.59gをテトラヒドロフラン30mlに溶解した溶液を滴下し、室温で４時間撹拌した。次いで、窒素雰囲気下、氷冷しながら酒石酸ナトリウムカリウム水溶液を滴下した。残渣をtert-ブチルメチルエーテルで抽出し、有機層を飽和食塩水で洗浄した後、乾燥し、減圧下濃縮して、5-アミノメチル2-ブチルベンゾ[b]フラン1.54gを得た。
5-アミノメチル-2-ブチルベンゾ[b]フラン
¹H-NMR (CDCl₃) δ: 0.93-0.97 (3H, m), 1.37-1.46 (2H, m), 1.70-1.76 (2H, m), 2.73-2.77 (2H, m), 3.92 (2H, s), 6.33 (1H, d, J = 0.96 Hz), 7.13 (1H, dd, J = 8.3, 1.7 Hz) 7.35 (1H, d, J = 8.3 Hz) 740 (1H, d, J = 1.2 Hz) Reference production example 12

A solution of 1.59 g of 2-butyl-5-cyanobenzo [b] furan in 30 ml of tetrahydrofuran was added dropwise to a mixture of 0.30 g of lithium aluminum hydride and 20 ml of tetrahydrofuran while cooling with water, followed by stirring at room temperature for 4 hours. Next, an aqueous sodium potassium tartrate solution was added dropwise with cooling with ice in a nitrogen atmosphere. The residue was extracted with tert-butyl methyl ether, and the organic layer was washed with saturated brine, dried and concentrated under reduced pressure to obtain 1.54 g of 5-aminomethyl 2-butylbenzo [b] furan.
5-Aminomethyl-2-butylbenzo [b] furan
¹ H-NMR (CDCl ₃ ) δ: 0.93-0.97 (3H, m), 1.37-1.46 (2H, m), 1.70-1.76 (2H, m), 2.73-2.77 (2H, m), 3.92 (2H, s), 6.33 (1H, d, J = 0.96 Hz), 7.13 (1H, dd, J = 8.3, 1.7 Hz) 7.35 (1H, d, J = 8.3 Hz) 740 (1H, d, J = 1.2 Hz)

酸化銅(I) (Cu₂O) 0.81gおよびピリジン35mlの混合物に、１−ヘキシン0.77gおよび2-ヨード-5-シアノフェノール1.90gを加えて、バス温130℃で9時間攪拌した。室温まで冷却した反応混合物をセライトろ過した後、ろ液を濃縮した。得られた残渣4.29gをシリカゲルカラムクロマトグラフィーに付し、2-ブチル-6-シアノベンゾ[b]フラン1.53gを得た。
2-ブチル-6-シアノベンゾ[b]フラン
¹H-NMR (CDCl₃) δ: 0.95-0.98 (3H, m), 1.38-1.47 (2H, m), 1.71-1.78 (2H, m), 2.81 (2H, t, J = 7.6 Hz), 6.46 (1H, d, J = 1.0 Hz), 7.46-7.48 (1H, m), 7.53 (1H, d, J = 8.0 Hz), 7.69 (1H, d, J = 0.72 Hz) Reference production example 13

To a mixture of 0.81 g of copper (I) oxide (Cu ₂ O) and 35 ml of pyridine, 0.77 g of 1-hexyne and 1.90 g of 2-iodo-5-cyanophenol were added and stirred at a bath temperature of 130 ° C. for 9 hours. The reaction mixture cooled to room temperature was filtered through celite, and then the filtrate was concentrated. The resulting residue 4.29 g was subjected to silica gel column chromatography to obtain 1.53 g of 2-butyl-6-cyanobenzo [b] furan.
2-Butyl-6-cyanobenzo [b] furan
¹ H-NMR (CDCl ₃ ) δ: 0.95-0.98 (3H, m), 1.38-1.47 (2H, m), 1.71-1.78 (2H, m), 2.81 (2H, t, J = 7.6 Hz), 6.46 (1H, d, J = 1.0 Hz), 7.46-7.48 (1H, m), 7.53 (1H, d, J = 8.0 Hz), 7.69 (1H, d, J = 0.72 Hz)

水素化リチウムアルミニウム0.30gとテトラヒドロフラン20mlの混合物に、水冷しながら、2-ブチル-6-シアノベンゾ[b]フラン1.40gをテトラヒドロフラン30mlに溶解した溶液を滴下し、室温で４時間撹拌した。次いで、窒素雰囲気下、氷冷しながら酒石酸ナトリウムカリウム水溶液を滴下した。残渣をtert-ブチルメチルエーテルで抽出し、有機層を飽和食塩水で洗浄した後、乾燥し、減圧下濃縮して、6-アミノメチル2-ブチルベンゾ[b]フラン1.32gを得た。
6-アミノメチル-2-ブチルベンゾ[b]フラン
¹H-NMR (CDCl₃) δ: 0.95 (3H, t, J = 7.3 Hz), 1.37-1.46 (2H, m), 1.68-1.76 (2H, m), 2.75 (2H, t, J = 7.3 Hz), 3.95 (2H, br s), 6.34 (1H, d, J = 0.76 Hz), 7.12 (1H, dd, J = 7.9, 1.2 Hz) 7.36 (1H, s), 742 (1H, d, J = 7.9 Hz) Reference production example 14

A solution of 1.40 g of 2-butyl-6-cyanobenzo [b] furan in 30 ml of tetrahydrofuran was added dropwise to a mixture of 0.30 g of lithium aluminum hydride and 20 ml of tetrahydrofuran while cooling with water, and the mixture was stirred at room temperature for 4 hours. Next, an aqueous sodium potassium tartrate solution was added dropwise with cooling with ice in a nitrogen atmosphere. The residue was extracted with tert-butyl methyl ether, and the organic layer was washed with saturated brine, dried and concentrated under reduced pressure to obtain 1.32 g of 6-aminomethyl 2-butylbenzo [b] furan.
6-Aminomethyl-2-butylbenzo [b] furan
¹ H-NMR (CDCl ₃ ) δ: 0.95 (3H, t, J = 7.3 Hz), 1.37-1.46 (2H, m), 1.68-1.76 (2H, m), 2.75 (2H, t, J = 7.3 Hz ), 3.95 (2H, br s), 6.34 (1H, d, J = 0.76 Hz), 7.12 (1H, dd, J = 7.9, 1.2 Hz) 7.36 (1H, s), 742 (1H, d, J = (7.9 Hz)

  Next, formulation examples are shown. In addition, a part represents a weight part.

Formulation Example 1
Each wettable powder is obtained by thoroughly grinding and mixing 50 parts of each of the present compounds 1 to 38, 3 parts of calcium lignin sulfonate, 2 parts of magnesium lauryl sulfate, and 45 parts of synthetic silicon hydroxide.

Formulation Example 2
20 parts of each of the present compounds 1 to 38 and 1.5 parts of sorbitan trioleate were mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol and finely pulverized by a wet pulverization method, and then 0.05 parts of xanthan gum and aluminum magnesium silicate 40 parts of an aqueous solution containing 0.1 part is added, and further 10 parts of propylene glycol is added and mixed by stirring to obtain each flowable preparation.

Formulation Example 3
2 parts of each of the present compounds 1 to 38, 88 parts of kaolin clay and 10 parts of talc are thoroughly pulverized and mixed to obtain each powder.

Formulation Example 4
Each emulsion is obtained by thoroughly mixing 5 parts of each of the present compounds 1 to 38, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene.

Formulation Example 5
2 parts of each of the present compounds 1-38, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are mixed well, then kneaded well and granulated and dried. Thus, each granule is obtained.

Formulation Example 6
10 parts of each of the present compounds 1 to 38; 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt;

Next, test examples show that the control agent of the present invention is useful for controlling plant diseases.
The control effect is to visually observe the area of the lesion on the test plant at the time of the survey, and to compare the area of the lesion on the plant treated with the present control agent and the area of the lesion on the untreated plant. It was evaluated by.

Test Example 1: Cucumber Bacterial Nuclear Disease Control Effect Test A plastic pot was filled with sand loam, seeded with cucumber (Sagamihanjiro), and grown in a greenhouse for 12 days. Each of the preparations of the present compound obtained according to Formulation Example 6 was diluted with water, and the present compounds 1, 2, 3, 4, 7, 11, 12, 13, 14, 15, 20, 22, 23, The formulations of 25, 26, 27, 28, 29, 30, 31, 34, 35 and 36 were adjusted to 200 ppm, and the formulations of the present compounds 5, 9, 33 and 38 were adjusted to 500 ppm. It was sprayed so as to adhere well to the cucumber leaf surface. After spraying, the plants were air-dried, and a mycelia-containing PDA medium of cucumber sclerotia was placed on the cucumber leaf surface. After the inoculation, the control effect was investigated after being placed under high humidity at 18 ° C for 4 days. As a result, the lesion area on the plant in the compound-treated area was 10% or less of the lesion area in the untreated area.

  The control agent of the present invention has an excellent plant disease control effect and is useful.

Claims (36)

Formula (I)

[In the formula, B represents a group represented by the following formula (B1), (B2) or (B3);

R ¹ represents a hydrogen atom or a C1-C4 alkyl group,
R ² and R ³ each represent a halogen atom, a C1-C4 alkyl group that may be substituted with a halogen atom, a C1-C4 alkoxy group that may be substituted with a halogen atom, or a cyano group,
Z represents an oxygen atom or a sulfur atom,
p represents any integer of 0 to 6,
q represents any integer of 0 to 5;
r represents any integer of 0 to 4;
n represents any integer of 0 to 3,
A ¹ -A ² is combined with two carbon atoms that form a benzene ring structure to which each of A ¹ and A ² is bonded, and is at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. It represents a 5- to 8-membered ring which may be contained as a hetero atom constituting the ring and optionally substituted with one or more groups selected from the following group [a-1].
However, when p is any integer of 2 to 6, R ² may be the same as or different from each other, and when q is any integer of 2 to 5, R ² is the same or different from each other. R ² may be the same or different from each other when r is any integer of 2 to 4,
When n is 2 or 3, R ³ may be the same or different from each other.
Group [a-1]
Halogen atom, hydroxyl group, carboxyl group, amino group, carbamoyl group, formyl group, nitro group, cyano group, Q ¹⁰ , Q ¹¹ O, Q ¹² S, Q ¹³ S (O), Q ¹⁴ S (O) ₂ , Q ¹⁵ NH, Q ¹⁶ Q ¹⁷ N, Q ¹⁸ C (O), Q ¹⁹ OC (O), Q ²⁰ NHC (O), Q ²¹ Q ²² NC (O), Q ²³ C (O) O, Q ²⁴ OC (O) O, Q ²⁵ NHC (O) O, Q ²⁶ Q ²⁷ NC (O) O, Q ²⁸ C (O) NH, Q ²⁹ OC (O) NH, Q ³⁰ NHC (O) NH, Q ³¹ Q ³² NC (O) NH and Q ³³ S (O) ₂ O;
[However, Q ¹⁰ is the following group [b-1] from one or more optionally substituted C1-C6 alkyl group with a group selected, with one or more groups selected from the following group [b-1] C2-C6 alkenyl group which may be substituted, C2-C6 alkynyl group which may be substituted with one or more groups selected from the following group [b-1], selected from the following group [b-1] A C3-C8 cycloalkyl group optionally substituted with one or more groups, a phenyl group optionally substituted with one or more groups selected from the following group [b-1], and the following group [b-1 A 5- or 6-membered aromatic heterocyclic group which may be substituted with one or more groups selected from the above group or a group selected from the following group [b-1]. Represents a 5-6 aliphatic heterocyclic group,
^{Q 11, Q 12, Q 13} , Q 14, Q 15, Q 16, Q 17, Q 18, Q 19, Q 20, Q 21, Q 22, Q 23, Q 24, Q 25, Q 26, Q 27 , Q ²⁸ , Q ²⁹ , Q ³⁰ , Q ³¹ , Q ³² and Q ³³ are each independently a C1-C6 alkyl group optionally substituted with one or more groups selected from the following group [b-1]. A C3-C6 alkenyl group optionally substituted with one or more groups selected from the following group [b-1], or a substituent substituted with one or more groups selected from the following group [b-1]. A good C3-C6 alkynyl group, a C3-C8 cycloalkyl group optionally substituted with one or more groups selected from the following group [b-1], one or more kinds selected from the following group [b-1] A phenyl group which may be substituted with a group, or a 5- to 6-membered aromatic heteroalkyl group which may be substituted with one or more groups selected from the following group [b-1] Shikimoto or the following group [b-1] from the one or more may also be 5-6 aliphatic optionally substituted by a group selected represents a heterocyclic group.
Group [b-1]
A halogen atom, a hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a formyl group, a nitro group, a cyano group, an optionally substituted C1-C4 alkyl group, and an optionally substituted halogen atom A C1-C4 alkoxy group;
]]
The plant disease control agent which contains the amide compound shown by this as an active ingredient. In formula (I), A ¹ -A ² is
E ¹ -E ² -E ³ , E ²¹ = E ²² -E ⁴ , E ⁵ -E ²³ = E ²⁴ , E ⁶ -E ⁷ -E ⁸ -E ⁹ , E ²⁵ = E ²⁶ -E ²⁷ = E ²⁸ Or E ¹⁰ -E ¹¹ -E ¹² -E ¹³ -E ¹⁴
[However, E ¹ , E ² , E ³ , E ⁴ , E ⁵ , E ⁶ , E ⁷ , E ⁸ , E ⁹ , E ¹⁰ , E ¹¹ , E ¹² , E ¹³ and E ¹⁴ are independently CX ^{1 represents} X ² , NX ³ , oxygen atom or sulfur atom,
E ²¹ , E ²² , E ²³ , E ²⁴ , E ²⁵ , E ²⁶ , E ²⁷ and E ²⁸ independently represent CX ⁴ or a nitrogen atom;
X ¹ , X ² , X ³ and X ⁴ independently represent any group selected from the following group [a-2].
Group [a-2]
Hydrogen atom, halogen atom, hydroxyl group, carboxyl group, amino group, carbamoyl group, formyl group, nitro group, cyano group, G ¹⁰ , G ¹¹ O, G ¹² S, G ¹³ S (O), G ¹⁴ S (O ) ₂ , G ¹⁵ NH, G ¹⁶ G ¹⁷ N, G ¹⁸ C (O), G ¹⁹ OC (O), G ²⁰ NHC (O), G ²¹ G ²² NC (O), G ²³ C (O) O , G ²⁴ OC (O) O, G ²⁵ NHC (O) O, G ²⁶ G ²⁷ NC (O) O, G ²⁸ C (O) NH, G ²⁹ OC (O) NH, G ³⁰ NHC (O) NH G ³¹ G ³² NC (O) NH and G ³³ S (O) ₂ O;
[However, G ¹⁰ is a C1-C6 alkyl group optionally substituted with one or more groups selected from the following group [b-2], or one or more groups selected from the following group [b-2]. An optionally substituted C2-C6 alkenyl group, a C2-C6 alkynyl group optionally substituted with one or more groups selected from the following group [b-2], and a group selected from the following group [b-2]. A C3-C8 cycloalkyl group optionally substituted with one or more groups, a phenyl group optionally substituted with one or more groups selected from the following group [b-2],
^{G 11, G 12, G 13} , G 14, G 15, G 16, G 17, G 18, G 19, G 20, G 21, G 22, G 23, G 24, G 25, G 26, G 27 , G ²⁸ , G ²⁹ , G ³⁰ , G ³¹ , G ³² and G ³³ are each independently a C1-C6 alkyl group optionally substituted with one or more groups selected from the following group [b-2]. A C3-C6 alkenyl group optionally substituted with one or more groups selected from the following group [b-2], or a substituent substituted with one or more groups selected from the following group [b-2]. A good C2-C6 alkynyl group, a C3-C8 cycloalkyl group optionally substituted with one or more groups selected from the following group [b-2], one or more kinds selected from the following group [b-2] Represents a phenyl group which may be substituted with a group.
Group [b-2]
A halogen atom, a hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a formyl group, a nitro group, a cyano group, an optionally substituted C1-C4 alkyl group, and an optionally substituted halogen atom A C1-C4 alkoxy group;
]]
The plant disease control agent according to claim 1. In the formula (I), R ¹ is a hydrogen atom, Z is an oxygen atom, R ³ is a halogen atom, B is a quinolin-6-yl group, [1,5] naphthyridin-2-yl group or The plant disease control agent according to claim 1 or 2, which is a benzothiazol-6-yl group. In formula (I), A ¹ -A ² is taken together with two carbon atoms that form a benzene ring structure to which each of A ¹ and A ² is bonded, and at least selected from an oxygen atom, a nitrogen atom and a sulfur atom A 5- to 8-membered ring which may contain one kind of atom as a hetero atom constituting the ring and may be substituted by one or more C1-C6 alkyl groups optionally substituted by a halogen atom The plant disease control agent according to claim 1. In formula (I), A ¹ -A ² is taken together with two carbon atoms that form a benzene ring structure to which each of A ¹ and A ² is bonded, and at least selected from an oxygen atom, a nitrogen atom and a sulfur atom A 5- to 8-membered ring which may be contained as one kind of atom as a hetero atom constituting a ring and which may be substituted by one or more phenyl groups which may be substituted with a halogen atom. The plant disease control agent according to 1. In formula (I), A ¹ -A ² is E ¹ -E ² -E ³ , E ²¹ = E ²² -E ⁴ , E ⁵ -E ²³ = E ²⁴ or E ⁶ -E ⁷ -E ⁸ -E. a ^9, one least the first E ^1, E ^2, E ³ is a CX ¹ X ^2, less the two are claim 2, wherein the CX ¹ X ² of ^{E 6, E 7, E 8} , E 9 Plant disease control agent. The plant disease control agent according to claim ² , wherein A ¹ -A ² in the formula (I) is O-C (X ¹ ) (X ² ) -O. The plant disease control agent according to claim ₂ , wherein A ¹ -A ² in the formula (I) is OC (X ¹ ) (X ² ) -CH ₂ . The plant disease control agent according to claim ² , wherein A ¹ -A ² in formula (I) is CH ₂ -C (X ¹ ) (X ² ) -O. In formula (I), X ¹ is, according to claim 7-9 to any one claim of plants substituted with a halogen atom is a phenyl group which may be substituted by also be C1-C6 alkyl group or a halogen atom Disease control agent. In formula (I), X ¹ is a plant disease control agent as claimed in any one of claims 7 to 9 are hydrogen atoms. In Formula (I), X < ² > is a hydrogen atom, The plant disease control agent as described in any one of Claims 7-11. In the formula (I), X ¹ and X ² are, plant disease control agent as claimed in any one of claims 7 to 9 are hydrogen atoms. The plant disease control agent according to claim ² , wherein A ¹ -A ² in the formula (I) is O-C (X ⁴ ) = CH. In the formula (I), A ¹ -A ² is, CH = C (X ⁴⁾ a plant disease control agent according to claim 2, wherein the -O. The plant disease control agent according to any one of claims 14 and 15, wherein in the formula (I), X ⁴ is a hydrogen atom. The plant disease control agent according to claim 14 or 15, wherein in the formula (I), X ⁴ is a C1-C6 alkyl group optionally substituted with a halogen atom or a phenyl group optionally substituted with a halogen atom. Formula (I-1)

[Where,
W represents a nitrogen atom or a CH group,
R ¹ represents a hydrogen atom or a C1-C4 alkyl group,
R ³ represents a halogen atom, a C1-C4 alkyl group optionally substituted with a halogen atom, a C1-C4 alkoxy group optionally substituted with a halogen atom, or a cyano group,
Z represents an oxygen atom or a sulfur atom,
n represents any integer of 0 to 3,
A ¹ -A ² is
^{E 1 -E 2 -E 3, E} 21 = E 22 -E 4, E 5 -E 23 = E 24, E 6 -E 7 -E 8 -E 9, E 25 = E 26 -E 27 = E 28 or an ^{E 10 -E 11 -E 12 -E 13} -E 14.
[However, E ¹ , E ² , E ³ , E ⁴ , E ⁵ , E ⁶ , E ⁷ , E ⁸ , E ⁹ , E ¹⁰ , E ¹¹ , E ¹² , E ¹³ and E ¹⁴ are independently CX ^{1 represents} X ² , NX ³ , oxygen atom or sulfur atom,
E ²¹ , E ²² , E ²³ , E ²⁴ , E ²⁵ , E ²⁶ , E ²⁷ and E ²⁸ independently represent CX ⁴ or a nitrogen atom;
X ¹ , X ² , X ³ and X ⁴ independently represent any group selected from the following group [a-2].
Group [a-2]
Hydrogen atom, halogen atom, hydroxyl group, carboxyl group, amino group, carbamoyl group, formyl group, nitro group, cyano group, G ¹⁰ , G ¹¹ O, G ¹² S, G ¹³ S (O), G ¹⁴ S (O ) ₂ , G ¹⁵ NH, G ¹⁶ G ¹⁷ N, G ¹⁸ C (O), G ¹⁹ OC (O), G ²⁰ NHC (O), G ²¹ G ²² NC (O), G ²³ C (O) O , G ²⁴ OC (O) O, G ²⁵ NHC (O) O, G ²⁶ G ²⁷ NC (O) O, G ²⁸ C (O) NH, G ²⁹ OC (O) NH, G ³⁰ NHC (O) NH G ³¹ G ³² NC (O) NH and G ³³ S (O) ₂ O;
[However, G ¹⁰ is a C1-C6 alkyl group optionally substituted with one or more groups selected from the following group [b-2], or one or more groups selected from the following group [b-2]. An optionally substituted C2-C6 alkenyl group, a C2-C6 alkynyl group optionally substituted with one or more groups selected from the following group [b-2], and a group selected from the following group [b-2]. A C3-C8 cycloalkyl group optionally substituted with one or more groups, a phenyl group optionally substituted with one or more groups selected from the following group [b-2],
^{G 11, G 12, G 13} , G 14, G 15, G 16, G 17, G 18, G 19, G 20, G 21, G 22, G 23, G 24, G 25, G 26, G 27 , G ²⁸ , G ²⁹ , G ³⁰ , G ³¹ , G ³² and G ³³ are each independently a C1-C6 alkyl group optionally substituted with one or more groups selected from the following group [b-2]. A C3-C6 alkenyl group optionally substituted with one or more groups selected from the following group [b-2], or a substituent substituted with one or more groups selected from the following group [b-2]. A good C2-C6 alkynyl group, a C3-C8 cycloalkyl group optionally substituted with one or more groups selected from the following group [b-2], one or more kinds selected from the following group [b-2] Represents a phenyl group which may be substituted with a group.
Group [b-2]
A halogen atom, a hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a formyl group, a nitro group, a cyano group, an optionally substituted C1-C4 alkyl group, and an optionally substituted halogen atom A C1-C4 alkoxy group;
]]
An amide compound represented by The amide compound according to claim 18, wherein R ¹ is a hydrogen atom, Z is an oxygen atom, and R ³ is a halogen atom. A ¹ -A ² is combined with two carbon atoms forming a benzene ring structure to which each of A ¹ and A ² is bonded, and at least one atom selected from an oxygen atom, a nitrogen atom and a sulfur atom is a ring 19. A 5- to 8-membered ring which may be contained as a heteroatom constituting the ring and which may be substituted one or more by a C1-C6 alkyl group which may be substituted with a halogen atom. Amide compounds. A ¹ -A ² is combined with two carbon atoms forming a benzene ring structure to which each of A ¹ and A ² is bonded, and at least one atom selected from an oxygen atom, a nitrogen atom and a sulfur atom is a ring The amide compound according to claim 18, wherein the amide compound is a 5- to 8-membered ring which may be contained as a hetero atom constituting, and may be substituted one or more by a phenyl group which may be substituted with a halogen atom. A ¹ -A ² is E ¹ -E ² -E ³ , E ²¹ = E ²² -E ⁴ , E ⁵ -E ²³ = E ²⁴ or E ⁶ -E ⁷ -E ⁸ -E ⁹ , E ¹ The amide compound according to claim 18, wherein at least one of E ² , E ³ and C ³ is CX ¹ X ² , and at least ^two of E ⁶ , E ⁷ , E ⁸ and E ⁹ are CX ¹ X ² . The amide compound according to claim 18, wherein A ¹ -A ² is O-C (X ¹ ) (X ² ) -O. The amide compound according to claim 18, wherein A ¹ -A ² is OC (X ¹ ) (X ² ) -CH ₂ . The amide compound according to claim 18, wherein A ¹ -A ² is CH ₂ -C (X ¹ ) (X ² ) -O. The amide compound according to any one of claims 23 to 25, wherein X ¹ is a C1-C6 alkyl group which may be substituted with a halogen atom or a phenyl group which may be substituted with a halogen atom. The amide compound according to any one of claims 23 to 25, wherein X ¹ is a hydrogen atom. The amide compound according to any one of claims 23 to 27, wherein X ² is a hydrogen atom. The amide compound according to any one of claims 23 to 25, wherein X ¹ and X ² are hydrogen atoms. The amide compound according to claim 18, wherein A ¹ -A ² is O-C (X ⁴ ) ═CH. The amide compound according to claim 18, wherein A ¹ -A ² is CH═C (X ⁴ ) —O. 32. The amide compound according to claim 30, wherein X ⁴ is a hydrogen atom. 32. The amide compound according to claim 30, wherein X ⁴ is a C1-C6 alkyl group which may be substituted with a halogen atom or a phenyl group which may be substituted with a halogen atom.   The amide compound according to any one of claims 18 to 33, wherein W is a CH group.   A method for controlling plant diseases comprising a step of applying an effective amount of the amide compound represented by formula (I) according to any one of claims 1 to 17 to a plant or soil.   Use of the amide compound represented by the formula (I) according to any one of claims 1 to 17, which is applied to a plant or soil to control plant diseases.