JP2012162460A - Nitrogen-containing heteroaryl derivative and germicide for agriculture and horticulture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new nitrogen-containing heteroaryl derivative applicable to a surely-effective and safely-usable germicide for agriculture and horticulture, a salt thereof, and N-oxide thereof, and to provide a germicide for agriculture and horticulture containing at least one kind of these compounds as an active ingredient.SOLUTION: This invention relates to a nitrogen-containing heteroaryl derivative represented by formula (1), a salt thereof or N-oxide thereof, and a germicide for agriculture and horticulture containing at least one kind of these compounds as an active ingredient.

Description

  The present invention relates to a novel nitrogen-containing heteroaryl derivative, a salt thereof, or an N-oxide, and an agricultural and horticultural fungicide containing at least one of these compounds as an active ingredient.

Many agricultural and horticultural fungicides have been proposed for diseases and the like of agricultural and horticultural crops.
For example, Patent Document 1 discloses a carbamate derivative represented by the formula (A) and an agricultural and horticultural fungicide containing it as an active ingredient.

（式（Ａ）中、Ｘ”はハロゲン原子、Ｃ１〜Ｃ６アルキル基等であり、ｎは０から４の整数であり、Ｒ^a1はＣ１〜Ｃ６アルキル基であり、Ｒ^a2は水素原子、Ｃ１〜Ｃ６アルキル基等であり、Ｒ^a3水素原子またはＣ１〜Ｃ６アルキル基であり、Ｇは酸素原子、硫黄原子等であり、Ｙ”は水素原子、Ｃ１〜Ｃ１０アルキル基、Ｃ２〜Ｃ１０アルケニル基等であり、Ｑ”は水素原子、Ｃ１〜Ｃ６ハロアルキル基、フェニル基等である。）

(In formula (A), X ″ is a halogen atom, a C1 to C6 alkyl group, n is an integer of 0 to 4, R ^a1 is a C1 to C6 alkyl group, R ^a2 is a hydrogen atom, C1 A C3 alkyl group, a ^Ra3 hydrogen atom or a C1-C6 alkyl group, G is an oxygen atom, a sulfur atom, etc., Y "is a hydrogen atom, a C1-C10 alkyl group, a C2-C10 alkenyl group, etc. Q ″ is a hydrogen atom, a C1-C6 haloalkyl group, a phenyl group, etc.)

  Patent Document 2 discloses an iminooxymethylpyridine compound represented by the formula (B) and an agricultural and horticultural fungicide containing the compound as an active ingredient.

（式（Ｂ）中、Ｘ’は酸素原子あるいは結合であり、Ｙ’およびＺ’は、それぞれ独立にフェニル基、または酸素原子、硫黄原子および窒素原子からなる群から選ばれた１個または２個以上の原子を含有する複素環である。）

(In the formula (B), X ′ is an oxygen atom or a bond, and Y ′ and Z ′ are each independently one or two selected from the group consisting of a phenyl group, an oxygen atom, a sulfur atom and a nitrogen atom. A heterocycle containing more than one atom.)

  Patent Document 3 discloses an oxyamine derivative represented by the formula (C) and an agricultural and horticultural fungicide containing it as an active ingredient.

［式（Ｃ）中、Ｒ^c1は水素原子、Ｃ１〜６アルキル基、Ｃ１〜６アルキルカルボニル基、またはＣ１〜６アルキルスルホニル基である。Ｒ^c2はＣ１〜６アルキル基、またはＣ１〜６アルコキシ基である。Ｒ^c3はハロゲン原子、Ｃ１〜６アルキル基、またはＣ１〜６アルコキシ基である。Ａ^cは分岐してもよいＣ１〜６アルキレン基、または結合である。Ｑ^cは、Ｇで置換されてもよいフェニル基、式（ｐ１）で表わされる基、または式（ｐ２）で表わされる基である。ｍは０〜４の整数である。

[In the formula (C), R ^c1 represents a hydrogen atom, a C1-6 alkyl group, a C1-6 alkylcarbonyl group, or a C1-6 alkylsulfonyl group. R ^c2 is a C1-6 alkyl group or a C1-6 alkoxy group. R ^c3 is a halogen atom, a C1-6 alkyl group, or a C1-6 alkoxy group. A ^c is a branched or may be C1~6 alkylene group or a bond. Q ^c is a phenyl group which may be substituted with G, a group represented by the formula (p1), or a group represented by the formula (p2). m is an integer of 0-4.

（式（ｐ１）中、Ｒ^c4は水素原子、Ｃ１〜６アルキル基、Ｃ２〜６アルケニル基、またはＳｉＲ^c5Ｒ^c6Ｒ^c7である。Ｒ^c5〜Ｒ^c7はそれぞれ独立して、Ｃ１〜６アルキル基である。式（ｐ２）中、Ｒ^c8は水素原子、Ｃ１〜６アルキル基、Ｃ１〜６ハロアルキル基、またはＧで置換されてもよいフェニル基である。Ｙは水素原子、Ｃ１〜６アルキル基、Ｃ３〜６シクロアルキル基、Ｃ３〜６シクロアルキル−Ｃ１〜６アルキル基、Ｃ２〜６アルケニル基、Ｃ２〜６アルキニル基、またはＧで置換されてもよいフェニルＣ１〜６アルキル基である。
Ｇはハロゲン原子、Ｃ１〜６アルキル基、Ｃ１〜６アルコキシ基、Ｃ１〜６ハロアルキル基、Ｃ１〜６ハロアルコキシ基を表わし、これらＧは同一または相異なって２個から５個置換してもよい。］

(In formula (p1), R ^c4 is a hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, or SiR ^c5 R ^c6 R ^c7 . R ^{c5 to} R ^c7 are each independently C1-6 alkyl. In formula (p2), R ^c8 is a hydrogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, or a phenyl group optionally substituted with G. Y is a hydrogen atom, C1-6 alkyl. Group, a C3-6 cycloalkyl group, a C3-6 cycloalkyl-C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, or a phenyl C1-6 alkyl group optionally substituted by G.
G represents a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a C1-6 haloalkyl group, or a C1-6 haloalkoxy group, and these G may be the same or different and may be substituted by 2 to 5 . ]

  Patent Document 4 discloses an aryl heterocyclic derivative represented by the formula (D) and an agricultural and horticultural fungicide containing it as an active ingredient.

［式中、Ｒ^d1はＣ１〜６アルキル基等を、Ｒ^d2はハロゲン原子等を、ｍは０〜４の整数であり、Ｔは式（ｐ３）、式（ｐ４）、式（ｐ５）で表される基であり、

[Wherein R ^d1 represents a C1-6 alkyl group, R ^d2 represents a halogen atom, etc., m represents an integer of 0 to 4, and T represents a formula (p3), a formula (p4), or a formula (p5). A group represented by

（式中、Ｒ^d3、Ｒ^d4、Ｒ^d5、Ｒ^d6は水素原子等であり、ｎは、１〜４の整数である。）、Ｑ^dは、式（ｐ６）、式（ｐ７）、式（ｐ８）、式（ｐ９）、式（ｐ１０）で表される基である。

(Wherein R ^d3 , R ^d4 , R ^d5 and R ^d6 are hydrogen atoms and the like, n is an integer of 1 to 4), Q ^d is a formula (p6), a formula (p7), a formula It is a group represented by (p8), formula (p9), and formula (p10).

（式（ｐ６）、式（ｐ７）、式（ｐ８）、式（ｐ９）および式（ｐ１０）中、Ｒ^d7はＣ５〜１２アルキル基等を、Ｒ^d8、Ｒ^d9、Ｒ^d10、Ｒ^d11は水素原子等を、Ｘは酸素原子または硫黄原子を、ｋは０または１〜３の整数である。）］

(In formula (p6), formula (p7), formula (p8), formula (p9) and formula (p10), R ^d7 represents a C5-12 alkyl group, etc., R ^d8 , R ^d9 , R ^d10 and R ^d11 are A hydrogen atom, X is an oxygen atom or a sulfur atom, and k is an integer of 0 or 1)]

  Patent Document 5 discloses a phenoxyamine derivative represented by the formula (E) and an agricultural and horticultural fungicide containing it as an active ingredient.

（式（Ｅ）中、Ｒ^e1およびＲ^e2はそれぞれ独立して水素原子等であり；ＶはＮＲ^e3等であり；Ｒ^e3は水素原子等であり；Ｒ^e4はＣ１〜６アルコキシ基等であり；Ｗは酸素原子等であり；Ｑ^e2は酸素原子等であり；ＹはＣ１〜５ハロアルコキシ基等で置換され、さらにハロゲン原子等で置換されていてもよいフェニル基等である。）

(In formula (E), R ^e1 and R ^e2 are each independently a hydrogen atom, etc .; V is NR ^e3, etc .; R ^e3 is a hydrogen atom, etc .; R ^e4 is a C1-6 alkoxy group, etc. Yes; W is an oxygen atom or the like; Q ^e2 is an oxygen atom or the like; Y is a phenyl group or the like which is substituted with a C1-5 haloalkoxy group or the like, and further substituted with a halogen atom or the like.

  However, conventional agricultural and horticultural fungicides have insufficient efficacy against existing pathogens, have no effect on new pathogens with drug resistance even if effective against existing pathogens, and plant bodies However, there were not many things that were satisfactory enough, such as causing phytotoxicity and pollution, or toxic to human livestock and environmental effects.

JP 2001-106666 A JP 2007-137852 A JP 2004-168683 A WO2005 / 051932 WO2008 / 124092

  The present invention has been made in view of such circumstances, a novel nitrogen-containing heteroaryl derivative that can be produced industrially advantageously, can be used safely and safely for agricultural and horticultural use, and its It is an object of the present invention to provide a fungicide for agriculture and horticulture containing a salt or N-oxide and at least one of these compounds as an active ingredient.

  As a result of intensive studies to solve the above problems, the present inventors have found a novel nitrogen-containing heteroaryl derivative, a salt thereof or N-oxide. And it discovered that this novel compound could become an active ingredient of agricultural and horticultural fungicides. The present invention has been further studied and completed based on these findings.

  The first aspect of the present invention is a nitrogen-containing heteroaryl derivative represented by the formula (1), a salt thereof or an N-oxide.

〔式（１）中、Ｒ¹は、無置換の若しくは置換基を有するＣ１〜６アルキル基である。

In [Equation (1), R ¹ is a C1~6 alkyl group having unsubstituted or substituted.

R ² is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, Formula: COR ²¹ (wherein R ²¹ is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, An unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted C2-6 alkynyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted group; A C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted heteroaryl group. A group represented by the formula: CO ₂ R ²² (wherein, R ²² has the unsubstituted or C1~6 alkyl group having a substituent, C2-6 alkenyl groups having an unsubstituted or substituted, unsubstituted or substituted A 2-6 alkynyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, Or an unsubstituted or substituted heteroaryl group.) Or a group represented by the formula: CON (R ²¹ ) ₂ (wherein R ²¹ has the same meaning as above; R ²¹ is the same or They may be different.).

A ¹ is an oxygen atom, a sulfur atom, or a formula: NR ³ (wherein R ³ is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 2- 6 alkenyl groups, unsubstituted or substituted C2-6 alkynyl groups, unsubstituted or substituted C3-8 cycloalkyl groups, unsubstituted or substituted C4-8 cycloalkenyl groups, unsubstituted Or a C6-10 aryl group having a substituent or an unsubstituted or substituted heteroaryl group.

A ² is an oxygen atom, Formula: NR ⁴ (wherein R ⁴ is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, or Formula: COR ²¹ , Formula: CO ₂ R ²² , or A group represented by the formula: CON (R ²¹ ) ₂ (wherein R ²¹ and R ²² have the same meaning as described above. R ²¹ may be the same or different). A group represented by the formula: CR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently a hydrogen atom, an unsubstituted or substituted C ^1-6 alkyl group or a halogen atom). Group.

  J is an oxygen atom or a sulfur atom.

X is Cl to 6 alkyl groups having an unsubstituted or substituted group of the formula: OR ²³ (wherein, R ²³ represents a hydrogen atom, Cl to 6 alkyl groups having an unsubstituted or substituted, unsubstituted or Substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 A cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted heteroaryl group, or a formula: COR ²¹ , a formula: CO ₂ R ²² , or a formula: CON (R ²¹ ) ₂ (wherein R ²¹ and R ²² have the same meanings as described above. R ²¹ may be the same or different.)), A group represented by the formula: SR ^{twenty three} Or a group represented by the formula: N (R ²³ ) ₂ (wherein R ²³ has the same meaning as described above. R ²³ may be the same or different), a cyano group, a nitro group, or a halogen Is an atom.

  n represents the number of X and is an integer of 0-3. When n is 2 or more, Xs may be the same or different.

B ^{1 to} B ⁴ are each independently a nitrogen atom or a carbon atom.
However, all of B ^{1 to} B ³ are not nitrogen atoms, and all of B ^{1 to} B ⁴ are not carbon atoms.

（式（２）〜式（５）中、Ｑ¹は、無置換の若しくは置換基を有するＣ１〜６アルキル基、無置換の若しくは置換基を有するＣ２〜６アルケニル基、無置換の若しくは置換基を有するＣ２〜６アルキニル基、無置換の若しくは置換基を有するＣ３〜８シクロアルキル基、無置換の若しくは置換基を有するＣ４〜８シクロアルケニル基、無置換の若しくは置換基を有するＣ６〜１０アリール基、無置換の若しくは置換基を有するヘテロアリール基、無置換の若しくは置換基を有するアラルキル基、無置換の若しくは置換基を有するヘテロアラルキル基、またはトリ置換シリル基である。 D is any group represented by Formula (2) to Formula (5).

(In the formulas (2) to (5), Q ¹ represents an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted group. A C2-6 alkynyl group having an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl A group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted heteroaralkyl group, or a trisubstituted silyl group.

In the formula (2), R ⁷ is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 2-6 alkenyl group, an unsubstituted or substituted C 2 An -6 alkynyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or It is an unsubstituted or substituted heteroaryl group.

In formula (3), R ⁸ is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 2-6 alkenyl group, an unsubstituted or substituted C 2 -6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 cycloalkenyl group, unsubstituted or substituted C6-10 aryl group, none A substituted or substituted C7-12 aralkyl group, an unsubstituted or substituted heteroaryl group, or an unsubstituted or substituted heteroaralkyl group.

In formula (3), R ⁹ is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 2-6 alkenyl group, an unsubstituted or substituted C 2 -6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 cycloalkenyl group, unsubstituted or substituted C6-10 aryl group, none A substituted or substituted C7-12 aralkyl group, an unsubstituted or substituted heteroaryl group, or an unsubstituted or substituted heteroaralkyl group.

In formula (5), Q ⁴¹ is a C6-10 aryl group or heteroaryl group.

In formula (5), Q ² is represented by formula: OR ²³ , formula: SR ²³ , formula: N (R ²³ ) ₂ , formula: COR ²¹ , formula: CO ₂ R ²² , formula: CON (R ²¹ ) ₂ , Or the formula: SO ₂ R ²² (wherein R ²¹ , R ²² and R ²³ have the same meaning as above. R ²¹ may be the same or different. R ²³ may be the same or different.) Or a cyano group, a nitro group, or a halogen atom.

m1 represents the number of Q ¹ and is an integer of 0 to 7.
m2 represents the number of Q ² and is an integer of 0 to 7.
However, the sum of m1 and m2 is 7 or less.
When m1 is 2 or more, Q ¹ may be the same or different. When m2 is 2 or more, Q ² may be the same or different. Further, Q ¹ , Q ² , or Q ¹ and Q ² that are adjacently substituted on Q ⁴¹ may be bonded to each other to form a 5- to 8-membered ring. )]

（式（６）中、Ｒ¹、Ｒ²、Ａ¹、Ａ²、Ｊ、Ｘ、ｎ、およびＤは、前記と同様の意味である。） Secondly, the present invention is a nitrogen-containing heteroaryl derivative represented by the formula (6), a salt thereof or an N-oxide.

(In the formula (6), R ¹ , R ² , A ¹ , A ² , J, X, n, and D have the same meaning as described above.)

  Thirdly, the present invention is an agricultural and horticultural fungicide containing as an active ingredient at least one of the nitrogen-containing heteroaryl derivative of the present invention, a salt thereof, or an N-oxide.

The nitrogen-containing heteroaryl derivative of the present invention, a salt thereof, or N-oxide is a novel compound, and can be produced advantageously industrially, and is useful as an active ingredient of an agricultural and horticultural fungicide that can be used safely and effectively. is there.
The agricultural and horticultural fungicide of the present invention is an agent that has an excellent control effect, does not cause phytotoxicity or contamination on the plant body, and has little toxicity to human fish and environmental impact.

Hereinafter, the present invention will be described in detail.
1) Nitrogen-containing heteroaryl derivative The nitrogen-containing heteroaryl derivative of the present invention is a compound represented by the formula (1).

First, the meanings of “unsubstituted” and “having a substituent” will be described.
The term “unsubstituted” means that the group is only the parent group. In addition, when there is no description of “having a substituent” and only the name of the group serving as a mother nucleus is described, it means “unsubstituted” unless otherwise specified.
On the other hand, the term “having a substituent” means that any hydrogen atom of a group serving as a mother nucleus is substituted with a group having a structure different from that of the mother nucleus. Therefore, the “substituent” is another group substituted with a group serving as a mother nucleus. The number of substituents may be one, or two or more. Two or more substituents may be the same or different. For example, in a C1-6 alkyl group having a substituent, a group serving as a mother nucleus is a C1-6 alkyl group, and any of these hydrogen atoms is substituted with a group having a different structure ("substituent") It is.

Examples of the group that can be a “substituent” include C1-6 alkyl group, C2-6 alkenyl group, C2-6 alkynyl group, C3-8 cycloalkyl group, C4-8 cycloalkenyl group, C6-10 aryl group, heteroaryl Group, formula: COR ³¹ , formula: CO ₂ R ³¹ , formula: CON (R ³¹ ) ₂ , or formula: SO ₂ R ³¹ (wherein R ³¹ independently represents a hydrogen atom or a C 1-6 alkyl group) A C2-6 alkenyl group, a C2-6 alkynyl group, a C3-8 cycloalkyl group, a C4-8 cycloalkenyl group, a C6-10 aryl group, or a heteroaryl group. ³² , Formula: SR ³² , or Formula: N (R ³² ) ₂ (wherein R ³² independently represents a hydrogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, C 3 ~ 8 sq A loalkyl group, a C4-8 cycloalkenyl group, a C6-10 aryl group, a heteroaryl group, a group represented by the formula: COR ³¹ , a group represented by the formula: CO ₂ R ³¹ , or a formula: CON (R ³¹ ) . ₂ in a group represented), a group represented by oxo, thio, formula: = NR ³³ (wherein, R ³³ represents a hydrogen atom, Cl to 6 alkyl, C2-6 alkenyl, A C2-6 alkynyl group, a C3-8 cycloalkyl group, a C4-8 cycloalkenyl group, a C6-10 aryl group, a heteroaryl group, or a group represented by the formula: OR ³² ). A cyano group, a nitro group, and a halogen atom can be mentioned.

A C1-6 alkyl group is a saturated aliphatic hydrocarbon group having 1-6 carbon atoms. The C1-6 alkyl group may be a straight chain or a branched chain.
Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, s-butyl group, t-butyl group, An isopentyl group, a neopentyl group, a 2-methylbutyl group, a 2,2-dimethylpropyl group, an isohexyl group, and the like can be given.

A C2-6 alkenyl group is an aliphatic hydrocarbon group having 2-6 carbon atoms and having at least one carbon-carbon double bond. The C2-6 alkenyl group may be linear or branched.
Specifically, vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-methyl-2- A butenyl group, 2-methyl-2-butenyl group, etc. can be mentioned.

A C2-6 alkynyl group is an aliphatic hydrocarbon group having 2-6 carbon atoms and having at least one carbon-carbon triple bond. The C2-6 alkynyl group may be linear or branched.
Specifically, ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group 1-hexynyl group, 1-methyl-2-propynyl group, 2-methyl-3-butynyl group, 1-methyl-2-butynyl group, 2-methyl-3-pentynyl group, 1,1-dimethyl-2- A butynyl group etc. can be mentioned.

A C3-8 cycloalkyl group is a saturated alicyclic hydrocarbon group having 3-8 carbon atoms.
Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

A C4-8 cycloalkenyl group is an alicyclic hydrocarbon group having 4-8 carbon atoms and having at least one carbon-carbon double bond.
Specific examples include 1-cyclobutenyl group, 1-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 3-cyclohexenyl group, 3-cycloheptenyl group, 4-cyclooctenyl group and the like.

A C6-10 aryl group is an aromatic hydrocarbon group having 6-10 carbon atoms. The C6-10 aryl group may have one ring or two or more rings. In the aryl group having two or more rings, as long as at least one ring is an aromatic ring, the remaining ring may be a hetero ring, a saturated alicyclic ring, an unsaturated alicyclic ring, or an aromatic ring.
Specifically, phenyl group, naphthyl group, azulenyl group, indenyl group, indanyl group, tetralinyl group, 1,2,3,4-tetrahydro-naphthalen-1-yl group, 5,6,7,8-tetrahydro- And a naphthalen-2-yl group.

A heteroaryl group is a 5- to 10-membered aromatic group containing at least one nitrogen atom, oxygen atom or sulfur atom as the atoms constituting the ring.
Specifically, pyrrol-1-yl group, pyrrol-2-yl group, pyrrol-3-yl group, furan-2-yl group, furan-3-yl group, thiophen-2-yl Yl group, thiophen-3-yl group, imidazol-1-yl group, imidazol-2-yl group, imidazol-4-yl group, imidazol-5-yl group, pyrazol-1-yl group, pyrazol-3-yl Group, pyrazol-4-yl group, pyrazol-5-yl group, oxazol-2-yl group, oxazol-4-yl group, oxazol-5-yl group, thiazol-2-yl group, thiazol-4-yl group , Thiazol-5-yl group, isoxazol-3-yl group, isoxazol-4-yl group, isoxazol-5-yl group, isothiazol-3-yl group, isothiazol-4-yl group, Azol-5-yl group, 1,2,3-triazol-1-yl group, 1,2,3-triazol-4-yl group, 1,2,3-triazol-5-yl group, 1,2, 4-triazol-1-yl group, 1,2,4-triazol-3-yl group, 1,2,4-triazol-5-yl group, 1,3,4-oxadiazol-2-yl group, 1,2,4-oxadiazol-3-yl group, 1,3,4-thiadiazol-2-yl group, 1,2,4-thiadiazol-3-yl group, tetrazol-1-yl group, tetrazole- A 5-membered heteroaryl group such as a 2-yl group;

  Pyridin-2-yl group, Pyridin-3-yl group, Pyridin-4-yl group, Pyrazin-2-yl group, Pyrimidin-2-yl group, Pyrimidin-4-yl group, Pyrimidin-5-yl group, Pyridazine A 6-membered heteroaryl group such as a 3-yl group, a pyridazin-4-yl group, or a triazinyl group;

  Indol-1-yl group, indol-2-yl group, indol-3-yl group, indol-4-yl group, indol-5-yl group, indol-6-yl group, indol-7-yl group, benzofuran 2-yl group, benzofuran-3-yl group, benzofuran-4-yl group, benzofuran-5-yl group, benzofuran-6-yl group, benzofuran-7-yl group, benzothiophen-2-yl group, benzo Thiophen-3-yl group, benzothiophen-4-yl group, benzothiophen-5-yl group, benzothiophen-6-yl group, benzothiophen-7-yl group, isoindol-1-yl group, isoindole- 2-yl group, isoindol-4-yl group, isoindol-5-yl group, isoindol-6-yl group, isoindol-7-i Group, isobenzofuran-1-yl group, isobenzofuran-4-yl group, isobenzofuran-5-yl group, isobenzofuran-6-yl group, isobenzofuran-7-yl group, benzimidazol-1-yl group, Benzimidazol-2-yl group, benzimidazol-4-yl group, benzimidazol-5-yl group, benzoxazol-2-yl group, benzoxazol-4-yl group, benzoxazol-5-yl group, benzothiazole 2-yl group, benzothiazol-4-yl group, benzothiazol-5-yl group, quinolin-2-yl group, quinolin-3-yl group, quinolin-4-yl group, quinolin-5-yl group, Quinolin-6-yl group, quinolin-7-yl group, quinolin-8-yl group, isoquinolin-1-yl group, isoquinoline-3 Yl group, isoquinolin-4-yl group, isoquinolin-5-yl group, isoquinolin-6-yl group, isoquinolin-7-yl group, condensed heteroaryl group such as isoquinolin-8-yl group;

  2-oxo-2H-pyran-3-yl group, 2-oxo-2H-pyran-4-yl group, 6-oxo-6H-pyran-3-yl group, 6-oxo-6H-pyran-2-yl Group, 2-oxo-2H-pyridin-1-yl group, 1-alkyl-2-oxo-1,2-dihydro-pyridin-3-yl group, 1-alkyl-2-oxo-1,2-dihydro- Pyridin-4-yl group, 1-alkyl-6-oxo-1,6-dihydro-pyridin-3-yl group, 1-alkyl-6-oxo-1,6-dihydro-pyridin-2-yl group, chromene Oxo such as 2-yl group, chromen-3-yl group, chromen-4-yl group, chromen-5-yl group, chromen-6-yl group, chromen-7-yl group, chromen-8-yl group A heteroaryl group having a group; .

As the group represented by the formula: COR ³¹ , formyl group, acetyl group, propionyl group, n-propylcarbonyl group, n-butylcarbonyl group, pentanoyl group, valeryl group, i-propylcarbonyl group, i-butylcarbonyl group Alkylcarbonyl groups such as pivaloyl group and isovaleryl group; alkenylcarbonyl groups such as acryloyl group and methacryloyl group; alkynylcarbonyl groups such as propioyl group; arylcarbonyl groups such as benzoyl group and naphthylcarbonyl group; pyridin-2-ylcarbonyl group And heteroarylcarbonyl groups such as thienylcarbonyl group; benzylcarbonyl group, phenethylcarbonyl group, pyridin-2-ylmethylcarbonyl group and the like.

Examples of the group represented by the formula: CO ₂ R ³¹ include a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, and an i-butoxycarbonyl group. T-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, vinyloxycarbonyl group, cyclopropylmethyloxycarbonyl group, 2-cyclopentylethyloxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, A benzyloxycarbonyl group, 2-pyridylmethyloxycarbonyl group, etc. can be mentioned.

Examples of the group represented by the formula: CON (R ³¹ ) ₂ include mono C1-6 alkylcarbamoyl groups such as carbamoyl group, methylcarbamoyl group, and ethylcarbamoyl group; vinylcarbamoyl group, 1-propenylcarbamoyl group, 1- Mono C2-6 alkenylcarbamoyl groups such as hexenylcarbamoyl group; monoC2-6 alkynylcarbamoyl groups such as ethynylcarbamoyl group, propynylcarbamoyl group, propargylcarbamoyl group; mono such as cyclopropylcarbamoyl group, cyclobutylcarbamoyl group, cyclohexylcarbamoyl group C3-8 cycloalkylcarbamoyl group; mono C4-8 cycloalkenylcarbamoyl group such as cyclobut-2-enylcarbamoyl group, cyclohex-2-enylcarbamoyl group; phenylcarbamoyl Group, mono C6-10 arylcarbamoyl group such as 1-naphthylcarbamoyl group; pyridin-2-ylcarbamoyl group, pyridin-3-ylcarbamoyl group, pyridin-4-ylcarbamoyl group, pyrazin-2-ylcarbamoyl group, pyrimidine A heteroarylcarbamoyl group such as a 2-ylcarbamoyl group; a disubstituted carbamoyl group such as a dimethylcarbamoyl group, a diethylcarbamoyl group, and a methyl-phenyl-carbamoyl group.

Examples of the group represented by the formula: SO ₂ R ³¹ include a methanesulfonyl group, an ethanesulfonyl group, a benzenesulfonyl group, and the like.

Examples of the group represented by the formula: OR ³² include a hydroxyl group; a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an i-propoxy group, i -Butoxy group, s-butoxy group, t-butoxy group, 1-ethylpropoxy group, isohexyloxy group, 4-methylpentoxy group, 3-methylpentoxy group, 2-methylpentoxy group, 1-methylpent Toxi group, 3,3-dimethylbutoxy group, 2,2-dimethylbutoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,3-dimethylbutoxy group C1-6 alkoxy groups such as 1-ethylbutoxy group and 2-ethylbutoxy group; vinyloxy group, 1-propenyloxy group, 2-propenyloxy group, 1-butyl Nyloxy group, 2-butenyloxy group, 3-butenyloxy group, 1-pentenyloxy group, 2-pentenyloxy group, 3-pentenyloxy group, 4-pentenyloxy group, 1-hexenyloxy group, 2-hexenyloxy group, 3 -Hexenyloxy group, 4-hexenyloxy group, 5-hexenyloxy group, 1-methyl-2-propenyloxy group, 2-methyl-2-propenyloxy group, 1-methyl-2-butenyloxy group, 2-methyl- C2-6 alkenyloxy group such as 2-butenyloxy group; ethynyloxy group, propynyloxy group, propargyloxy group, 1-butynyloxy group, 2-butynyloxy group, 3-butynyloxy group, 1-pentynyloxy group, 2-pentyl Nyloxy group, 3-pentynyloxy group, 4-pentynyloxy group 1-hexynyloxy group, 1-methyl-2-propynyloxy group, 2-methyl-3-butynyloxy group, 1-methyl-2-butynyloxy group, 2-methyl-3-pentynyloxy group, 1,1-dimethyl- C2-6 alkynyloxy groups such as 2-butynyloxy group; C3-8 cycloalkoxy groups such as cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group; cyclobut-2-enyloxy group, cyclohex-2-yl C4-8 cycloalkenyloxy groups such as an phenyloxy group; C6-10 aryloxy groups such as a phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group; pyridin-2-yloxy group, pyridin-3-yloxy group, Pyridin-4-yloxy group, pyrazin-2-yloxy group Heteroaryloxy groups such as pyrimidin-2-yloxy group; formyloxy group, acetyloxy group, propionyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butylcarbonyl C1-7 acyloxy groups such as oxy group, pentanoyloxy group, pivaloyloxy group, benzoyloxy group, 2-pyridylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, n-butoxycarbonyl C1-7 carboxyoxy groups such as oxy group, t-butoxycarbonyloxy group, vinyloxycarbonyloxy group, phenoxycarbonyloxy group, pyridyloxycarbonyloxy group; carbamoyloxy group, methyl Examples thereof include a mono-substituted carbamoyloxy group such as a rucarbamoyloxy group, an ethylcarbamoyloxy group, a dimethylcarbamoyloxy group, a diethylcarbamoyloxy group, and a phenylcarbamoyloxy group, or a disubstituted carbamoyloxy group.

Formula: The group represented by SR ^32, for example, mercapto group; methylsulfanyl group, ethylsulfanyl group, Cl to 6 alkylsulfanyl group such as n- hexylsulfanyl group; vinyl sulfanyl group, 1-propenyl Nils Alpha group, 1 -C2-6 alkenylsulfanyl group such as hexenylsulfanyl group; C2-6 alkynylsulfanyl group such as ethynylsulfanyl group, propynylsulfanyl group, propargylsulfanyl group; C3-6 such as cyclopropylsulfanyl group, cyclobutylsulfanyl group, cyclohexylsulfanyl group 8 cycloalkylsulfanyl group; C4-8 cycloalkenylsulfanyl group such as cyclobut-2-enylsulfanyl group, cyclohex-2-enylsulfanyl group; phenylsulfanyl group C6-10 arylsulfanyl groups such as 1-naphthylsulfanyl group and 2-naphthylsulfanyl group; pyridin-2-ylsulfanyl group, pyridin-3-ylsulfanyl group, pyridin-4-ylsulfanyl group, pyrazin-2-ylsulfanyl Group, heteroarylsulfanyl group such as pyrimidin-2-ylsulfanyl group; C1-7 acylsulfanyl group such as formylsulfanyl group, acetylsulfanyl group, benzoylsulfanyl group, 2-pyridylcarbonylsulfanyl group; methoxycarbonylsulfanyl group, ethoxycarbonyl Such as sulfanyl group, t-butoxycarbonylsulfanyl group, vinyloxycarbonylsulfanyl group, phenoxycarbonylsulfanyl group, pyridyloxycarbonylsulfanyl group, etc. 1-7 carboxysulfanyl groups; carbamoylsulfanyl groups, methylcarbamoylsulfanyl groups, ethylcarbamoylsulfanyl groups, dimethylcarbamoylsulfanyl groups, diethylcarbamoylsulfanyl groups, phenylcarbamoylsulfanyl groups, etc. monosubstituted carbamoylsulfanyl groups or disubstituted carbamoylsulfanyl groups Can be mentioned.

Examples of the group represented by the formula: N (R ³² ) ₂ include mono-C 1-6 alkylamino groups such as methylamino group, ethylmethyl group, n-hexylamino group; vinylamino group, 1-propenylamino group Mono-C2-6 alkenylamino groups such as 1-hexenylamino group; mono-C2-6 alkynylamino groups such as ethynylamino group, propynylamino group, propargylamino group; cyclopropylamino group, cyclobutylamino group, cyclohexylamino group Mono C3-8 cycloalkylamino groups such as; mono C4-8 cycloalkenylamino groups such as cyclobut-2-enylamino group and cyclohex-2-enylamino group; mono C6-10 such as phenylamino group and 1-naphthylamino group Arylamino group; pyridin-2-ylamino group, pyridin-3-ylamino Groups, heteroarylamino groups such as pyridin-4-ylamino group, pyrazin-2-ylamino group, pyrimidin-2-ylamino group; formylsulfamino group, acetylamino group, benzoylamino group, 2-pyridylcarbonylamino group, etc. C1-7 acylamino group; C1-7 carboxyamino group such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, vinyloxycarbonylamino group, phenoxycarbonylamino group, pyridyloxycarbonylamino group; carbamoylamino Group, methylcarbamoylamino group, ethylcarbamoylamino group, dimethylcarbamoylamino group, diethylcarbamoylamino group, phenylcarbamoylamino group, monosubstituted carbamoylamino group or disubstituted Moiruamino group or the like;

  Dimethylamino group, diethylmethyl group, methyl-vinyl-amino group, methyl-ethynyl-amino group, methyl-cyclopropyl-amino group, methyl-cyclobut-2-enyl-amino group, methyl-phenyl-amino group, methyl- Examples include pyridin-2-yl-amino group, methyl-acetyl-amino group, methyl-methoxycarbonyl-amino group; methylideneamino group, ethylideneamino group, and the like.

Formula: = The group represented by NR ^33, for example, methylimino group, Cl to 6 alkylimino group such ethylimino group; Biniruimino group, C2-6 alkenylimino group such as 1-Puropeniruimino group; Echiniruimino group C2-6 alkynylimino group of C3-8 cycloalkylimino group such as cyclopropylimino group and cyclobutylimino group; C4-8 cycloalkenylimino group such as cyclobut-2-enylimino group; phenylimino group, 1-naphthylimino group C6-10 arylimino groups such as a group; heteroarylimino groups such as pyridine-2-ylimino group, pyridine-3-ylimino group, pyridine-4-ylimino group, pyrazin-2-ylimino group, pyrimidine-2-ylimino group ; Hydroxyimino group; methoxyimino group, ethoxyimino group A C6-10 alkoxyimino group such as a phenoxyimino group; a heteroarylimino group such as a pyridin-2-yloxyimino group; a C1-7 acyloxy such as an acetyloxyimino group or a benzoyloxyimino group Imino group; C1-7 carboxyoxyimino group such as methoxycarbonyloxyimino group, ethoxycarbonyloxyimino group, t-butoxycarbonyloxyimino group, and the like can be exemplified.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[R ¹ ]
R ¹ in formula (1) is an unsubstituted or substituted C 1-6 alkyl group. The “C 1-6 alkyl group” serving as the mother nucleus is as described above.
Suitable groups that can be the substituent of C1~6 alkyl group, a halogen atom, the formula: can be mentioned groups represented by OR ^32, C6-10 aryl group, and a heteroaryl group.

  Examples of the C1-6 alkyl group having a substituent include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a trifluoromethyl group, a trichloromethyl group, and a tribromomethyl group. 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, pentafluoroethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 3,3,3-trifluoropropyl group, 2 , 2,2-trifluoro-1-trifluoromethylethyl group, perfluorohexyl group, perchlorohexyl group, halogen substituted C1-6 alkyl group such as 2,4,6-trichlorohexyl group; hydroxymethyl group, hydroxy Hydroxy C1-6 alkyl groups such as ethyl and hydroxypropyl; methoxymethyl Group, ethoxymethyl group, methoxyethyl group, ethoxyethyl group, methoxy n-propyl group, ethoxymethyl group, ethoxyethyl group, n-propoxymethyl group, i-propoxyethyl group, s-butoxymethyl group, t-butoxy C1-6 alkoxy C1-6 alkyl group such as ethyl group, 1,2-dimethoxyethyl group, 2,2-dimethoxyethyl group; formyloxymethyl group, acetoxymethyl group, 2-acetoxyethyl group, propionyloxymethyl group, Acyloxy C1-6 alkyl groups such as propionyloxyethyl group; aralkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group; furan-2-ylmethyl group, furan-2-ylethyl group, furan 2-ylpropyl group, furan-3-ylmethyl group, thio Nen-2-ylmethyl group, thiophen-2-ylethyl group, thiophen-3-ylmethyl group, pyridin-2-ylmethyl group, pyridin-2-ylethyl group, pyridin-2-ylpropyl group, pyridin-3-ylmethyl group , Pyridin-4-ylmethyl group, pyrazin-2-ylmethyl group, pyrazin-2-ylethyl group, pyrimidin-2-ylmethyl group, pyrimidin-2-ylethyl group, pyrimidin-4-ylmethyl group, pyrimidin-5-ylmethyl group, etc. A heteroaralkyl group of

R ¹ can be any of the groups described above, but particularly preferred R ¹ is a methyl group.

[R ² ]
R ² in formula (1) is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, a group represented by formula: COR ²¹ , a group represented by formula: CO ₂ R ²² , or A group represented by the formula: CON (R ²¹ ) ₂ .

R ²¹ represents a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 2-6 alkenyl group, an unsubstituted or substituted C 2-6 alkynyl group, A substituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted group Is a heteroaryl group having

An unsubstituted or substituted C2-6 alkenyl group has a "C2-6 alkenyl group" as a mother nucleus. The “C2-6 alkenyl group” serving as a mother nucleus is as described above. A suitable group that can be a substituent of the C2-6 alkenyl group is a halogen atom.
Examples of the C2-6 alkenyl group having a substituent include 3-chloro-2-propenyl group, 4-chloro-2-butenyl group, 4,4-dichloro-3-butenyl group, and 4,4-difluoro-3. -Butenyl group, 3,3-dichloro-2-propenyl group, 2,3-dichloro-2-propenyl group, 3,3-difluoro-2-propenyl group, 2,4,6-trichloro-2-hexenyl group, etc. And a C2-6 haloalkenyl group.

An unsubstituted or substituted C2-6 alkynyl group has a "C2-6 alkynyl group" as a mother nucleus. The “C2-6 alkynyl group” serving as a mother nucleus is as described above. A suitable group that can be a substituent of the C2-6 alkynyl group is a halogen atom.
Examples of the C2-6 alkynyl group having a substituent include a 3-chloro-1-propynyl group, a 3-chloro-1-butynyl group, a 3-bromo-1-butynyl group, a 3-bromo-2-propynyl group, Halo such as 3-iodo-2-propynyl group, 3-bromo-1-hexynyl group, 5,5-dichloro-2-methyl-3-pentynyl group, 4-chloro-1,1-dimethyl-2-butynyl group An alkynyl group etc. can be mentioned.

  An unsubstituted or substituted C 3-8 cycloalkyl group has a “C 3-8 cycloalkyl group” as a mother nucleus. The “C 3-8 cycloalkyl group” serving as a mother nucleus is as described above.

  An unsubstituted or substituted C4-8 cycloalkenyl group has a "C4-8 cycloalkenyl group" as a mother nucleus. The “C4-8 cycloalkenyl group” serving as a mother nucleus is as described above.

  An unsubstituted or substituted C6-10 aryl group has a "C6-10 aryl group" as a mother nucleus. The C6-10 aryl group serving as a mother nucleus is as described above.

  An unsubstituted or substituted heteroaryl group has a “heteroaryl group” as a mother nucleus. The heteroaryl group serving as a mother nucleus is as described above.

Examples of the group represented by the formula: COR ²¹ include formyl group, acetyl group, propionyl group, n-propylcarbonyl group, n-butylcarbonyl group, pentanoyl group, valeryl group, i-propylcarbonyl group, i-butyl. Alkylcarbonyl groups such as carbonyl group, pivaloyl group and isovaleryl group; alkenylcarbonyl groups such as acryloyl group and methacryloyl group; alkynylcarbonyl groups such as propioroyl group; arylcarbonyl groups such as benzoyl group and naphthylcarbonyl group; 2-pyridylcarbonyl group , Heteroarylcarbonyl groups such as thienylcarbonyl group; benzylcarbonyl group, phenethylcarbonyl group, 2-pyridylmethylcarbonyl group; monofluoroacetyl group, monochloroacetyl group, monobromoacetyl group, difluoro Cetyl group, dichloroacetyl group, dibromoacetyl group, trifluoroacetyl group, trichloroacetyl group, tribromoacetyl group, 3,3,3-trifluoropropionyl group, 3,3,3-trichloropropionyl group, 2,2, Examples thereof include haloacyl groups such as 3,3,3-pentafluoropropionyl group.

R ²² is an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted C2-6 alkynyl group, unsubstituted or A substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted hetero An aryl group.

Examples of the group represented by the formula: CO ₂ R ²² include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, t- Butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, vinyloxycarbonyl group, cyclopropylmethyloxycarbonyl group, 2-cyclopentylethyloxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, benzyloxycarbonyl Group, 2-pyridylmethyloxycarbonyl group and the like.

Wherein: R ²¹ of CON (R ²¹⁾ ₂ is the same as described above. Note that two R ²¹ may be the same or different.

Examples of the group represented by the formula: CON (R ²¹ ) ₂ include mono C1-6 alkylcarbamoyl groups such as carbamoyl group, methylcarbamoyl group, and ethylcarbamoyl group; vinylcarbamoyl group, 1-propenylcarbamoyl group, 1- Mono C2-6 alkenylcarbamoyl groups such as hexenylcarbamoyl group; monoC2-6 alkynylcarbamoyl groups such as ethynylcarbamoyl group, propynylcarbamoyl group, propargylcarbamoyl group; mono such as cyclopropylcarbamoyl group, cyclobutylcarbamoyl group, cyclohexylcarbamoyl group C3-8 cycloalkylcarbamoyl group; mono C4-8 cycloalkenylcarbamoyl group such as cyclobut-2-enylcarbamoyl group, cyclohex-2-enylcarbamoyl group; phenylcarbamoyl Group, mono C6-10 arylcarbamoyl group such as 1-naphthylcarbamoyl group; pyridin-2-ylcarbamoyl group, pyridin-3-ylcarbamoyl group, pyridin-4-ylcarbamoyl group, pyrazin-2-ylcarbamoyl group, pyrimidine A heteroarylcarbamoyl group such as a 2-ylcarbamoyl group; a disubstituted carbamoyl group such as a dimethylcarbamoyl group, a diethylcarbamoyl group, and a methyl-phenyl-carbamoyl group.

R ² can be any of the groups described above, but particularly preferred R ² is a hydrogen atom.

[A ¹ ]
A ¹ in the formula (1) is an oxygen atom, a sulfur atom, or a group represented by the formula: NR ³ .
R ³ represents a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 2-6 alkenyl group, an unsubstituted or substituted C 2-6 alkynyl group, A substituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted group Is a heteroaryl group having
Of these, A ¹ is preferably an oxygen atom.

[A ² ]
A ² in Formula (1) is an oxygen atom, a group represented by the formula: NR ⁴ , or a group represented by the formula: CR ⁵ R ⁶ . R ⁴ represents a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, a group represented by the formula: COR ²¹ , a group represented by the formula: CO ₂ R ²² , or a formula: CON ( R ²¹ ) is a group represented by ₂ . R ⁵ and R ⁶ are each independently a hydrogen atom, an unsubstituted or substituted C ^1-6 alkyl group, or a halogen atom.
Of these, A ² is preferably an oxygen atom.

[J]
J in Formula (1) is an oxygen atom or a sulfur atom.

[X]
X in the formula (1) is an unsubstituted or substituted C1-6 alkyl group, a formula: a group represented by OR ²³ , a formula: a group represented by SR ²³ , a formula: N (R ²³ ) ₂ is a group represented by ₂ , a cyano group, a nitro group or a halogen atom.
The subscript n of X represents the number of X and is an integer of 0-3. When n is 2 or more, Xs may be the same or different.

R ²³ represents a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 2-6 alkenyl group, an unsubstituted or substituted C 2-6 alkynyl group, A substituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted group A heteroaryl group having the formula: COR ²¹ , formula CO ₂ R ²² , or formula CON (R ²¹ ) ₂ .

Examples of the group represented by the formula: OR ²³ include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an i-propoxy group, and an i-butoxy. Group, s-butoxy group, t-butoxy group, 1-ethylpropoxy group, isohexyloxy group, 4-methylpentoxy group, 3-methylpentoxy group, 2-methylpentoxy group, 1-methylpentoxy group 3,3-dimethylbutoxy group, 2,2-dimethylbutoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1 -C1-6 alkoxy groups such as ethylbutoxy group and 2-ethylbutoxy group; vinyloxy group, 1-propenyloxy group, 2-propenyloxy group, 1-butenyloxy Si group, 2-butenyloxy group, 3-butenyloxy group, 1-pentenyloxy group, 2-pentenyloxy group, 3-pentenyloxy group, 4-pentenyloxy group, 1-hexenyloxy group, 2-hexenyloxy group, 3 -Hexenyloxy group, 4-hexenyloxy group, 5-hexenyloxy group, 1-methyl-2-propenyloxy group, 2-methyl-2-propenyloxy group, 1-methyl-2-butenyloxy group, 2-methyl- C2-6 alkenyloxy group such as 2-butenyloxy group; ethynyloxy group, propynyloxy group, propargyloxy group, 1-butynyloxy group, 2-butynyloxy group, 3-butynyloxy group, 1-pentynyloxy group, 2-pentyl Nyloxy, 3-pentynyloxy, 4-pentynyloxy, 1-hex Sinyloxy group, 1-methyl-2-propynyloxy group, 2-methyl-3-butynyloxy group, 1-methyl-2-butynyloxy group, 2-methyl-3-pentynyloxy group, 1,1-dimethyl-2- C2-6 alkynyloxy group such as butynyloxy group; C3-8 cycloalkoxy group such as cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group; cyclobut-2-enyloxy group, cyclohex-2-enyloxy group A C4-8 cycloalkenyloxy group such as phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group and the like C6-10 aryloxy group; pyridin-2-yloxy group, pyridin-3-yloxy group, pyridine- 4-yloxy group, pyrazin-2-yloxy group, pyrimid Heteroaryloxy groups such as n-2-yloxy group; formyloxy group, acetyloxy group, propionyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butylcarbonyl C1-7 acyloxy groups such as oxy group, pentanoyloxy group, pivaloyloxy group, benzoyloxy group, 2-pyridylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, n-butoxycarbonyl C1-7 carboxyoxy groups such as oxy group, t-butoxycarbonyloxy group, vinyloxycarbonyloxy group, phenoxycarbonyloxy group, pyridyloxycarbonyloxy group; carbamoyloxy group, methylcarba Mono-substituted carbamoyloxy group such as yloxy group, ethylcarbamoyloxy group, dimethylcarbamoyloxy group, diethylcarbamoyloxy group, phenylcarbamoyloxy group or disubstituted carbamoyloxy group; chloromethoxy group, dichloromethoxy group, trichloromethoxy group, tri A fluoromethoxy group, 1-fluoroethoxy group, 1,1-difluoroethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group and the like can be mentioned.

Examples of the group represented by the formula: SR ²³ include C1-6 alkylsulfanyl groups such as methylsulfanyl group, ethylsulfanyl group, n-hexylsulfanyl group; vinylsulfanyl group, 1-propenylsulfanyl group, 1-hexenylsulfanyl. C2-6 alkenylsulfanyl group such as ethynylsulfanyl group, propynylsulfanyl group, C2-6 alkynylsulfanyl group such as propargylsulfanyl group; C3-8 cycloalkyl such as cyclopropylsulfanyl group, cyclobutylsulfanyl group, cyclohexylsulfanyl group Sulfanyl group; C4-8 cycloalkenylsulfanyl group such as cyclobut-2-enylsulfanyl group, cyclohex-2-enylsulfanyl group; phenylsulfanyl group, 1-naphthyl C6-10 arylsulfanyl groups such as sulfanyl group and 2-naphthylsulfanyl group; pyridin-2-ylsulfanyl group, pyridin-3-ylsulfanyl group, pyridin-4-ylsulfanyl group, pyrazin-2-ylsulfanyl group, pyrimidine Heteroarylsulfanyl groups such as 2-ylsulfanyl group; C1-7 acylsulfanyl groups such as formylsulfanyl group, acetylsulfanyl group, benzoylsulfanyl group, 2-pyridylcarbonylsulfanyl group; methoxycarbonylsulfanyl group, ethoxycarbonylsulfanyl group, C1-7 carboxy such as t-butoxycarbonylsulfanyl group, vinyloxycarbonylsulfanyl group, phenoxycarbonylsulfanyl group, pyridyloxycarbonylsulfanyl group, etc. Cisulfanyl group; monosubstituted carbamoylsulfanyl group or disubstituted carbamoylsulfanyl group such as carbamoylsulfanyl group, methylcarbamoylsulfanyl group, ethylcarbamoylsulfanyl group, dimethylcarbamoylsulfanyl group, diethylcarbamoylsulfanyl group, phenylcarbamoylsulfanyl group, etc. it can.

Examples of the group represented by the formula: N (R ²³ ) ₂ include mono-C 1-6 alkylamino groups such as methylamino group, ethylmethyl group, n-hexylamino group; vinylamino group, 1-propenylamino group Mono-C2-6 alkenylamino groups such as 1-hexenylamino group; mono-C2-6 alkynylamino groups such as ethynylamino group, propynylamino group, propargylamino group; cyclopropylamino group, cyclobutylamino group, cyclohexylamino group Mono C3-8 cycloalkylamino groups such as; mono C4-8 cycloalkenylamino groups such as cyclobut-2-enylamino group and cyclohex-2-enylamino group; mono C6-10 such as phenylamino group and 1-naphthylamino group Arylamino group; pyridin-2-ylamino group, pyridin-3-ylamino Groups, heteroarylamino groups such as pyridin-4-ylamino group, pyrazin-2-ylamino group, pyrimidin-2-ylamino group; formylsulfamino group, acetylamino group, benzoylamino group, 2-pyridylcarbonylamino group, etc. C1-7 acylamino group; C1-7 carboxyamino group such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, vinyloxycarbonylamino group, phenoxycarbonylamino group, pyridyloxycarbonylamino group; carbamoylamino Group, methylcarbamoylamino group, ethylcarbamoylamino group, dimethylcarbamoylamino group, diethylcarbamoylamino group, phenylcarbamoylamino group, monosubstituted carbamoylamino group or disubstituted Moiruamino group or the like;

  Dimethylamino group, diethylmethyl group, methyl-vinyl-amino group, methyl-ethynyl-amino group, methyl-cyclopropyl-amino group, methyl-cyclobut-2-enyl-amino group, methyl-phenyl-amino group, methyl- Disubstituted amino groups such as pyridin-2-yl-amino group, methyl-acetyl-amino group, and methyl-methoxycarbonyl-amino group; amino groups in which nitrogen atoms such as methylideneamino group and ethylideneamino group are bonded to the same carbon atom Etc.

[B ¹ ~B ^4]
B ^{1 to} B ⁴ are each independently a nitrogen atom or a carbon atom. However, all of B ^{1 to} B ³ are not nitrogen atoms, and all of B ^{1 to} B ⁴ are not carbon atoms. As a combination aspect of B ^{1 to} B ⁴ , for example, a structure represented by the formula (A-1), the formula (A-2) or the formula (A-3) (a structure below the double wavy line and X is a notation Are omitted.). Of these structures, the structure of the formula (A-1) is preferable.

[D]
D is any group represented by Formula (2) to Formula (5).

The carbon nitrogen double bond in the formula (2) represents any of geometric isomers (E / Z isomers) or a mixture thereof.
The two carbon nitrogen double bonds in the formula (3) each represent any of geometric isomers (E / Z isomers) or a mixture thereof.

In Formula (2) to Formula (5), Q ¹ represents an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted group. Having C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 cycloalkenyl group, unsubstituted or substituted C6-10 aryl group An unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted heteroaralkyl group, or a trisubstituted silyl group.
Examples of the tri-substituted silyl group include a trimethylsilyl group, a triethylsilyl group, a tricyclopropylsilyl group, and a t-butyldimethylsilyl group.

Preferred Q ¹ in formula (2) is an unsubstituted or substituted aralkyl group (particularly preferably an unsubstituted or substituted C6-10 aryl-substituted C1-6 alkyl group) or unsubstituted or substituted A heteroaralkyl group having a group (particularly preferably, an unsubstituted or substituted heteroaryl-substituted C1-6 alkyl group). Specific examples include an unsubstituted or substituted benzyl group, an unsubstituted or substituted pyridin-2-ylmethyl group, and the like. A preferred group that can be a substituent of the aralkyl group or heteroaralkyl group is a halogen atom.

Preferred Q ¹ in formula (3) is an unsubstituted or substituted C6-10 aryl group or an unsubstituted or substituted heteroaryl group. Specific examples include an unsubstituted or substituted phenyl group and an unsubstituted or substituted pyridin-2-yl group. A preferred group that can be a substituent of the aryl group or heteroaryl group is a halogen atom.

Preferred Q ¹ in formula (4) is an unsubstituted or substituted C 1-6 alkyl group.

Preferred Q ¹ in formula (5) is an unsubstituted or substituted aralkyl group (particularly preferably an unsubstituted or substituted C6-10 aryl-substituted C1-6 alkyl group) or unsubstituted or substituted A heteroaralkyl group having a group (particularly preferably, an unsubstituted or substituted heteroaryl-substituted C1-6 alkyl group). Specific examples include an unsubstituted or substituted benzyl group, an unsubstituted or substituted pyridin-2-ylmethyl group, and the like. A preferred group that can be a substituent of the aralkyl group or heteroaralkyl group is a halogen atom.

R ⁷ in formula (2) is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 2-6 alkenyl group, an unsubstituted or substituted C 2 An -6 alkynyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or It is an unsubstituted or substituted heteroaryl group. Preferred R ⁷ is a C 1-6 alkyl group.

In formula (3), R ⁸ and R ⁹ are each independently a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, and unsubstituted Or substituted or unsubstituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 cycloalkenyl group, unsubstituted or substituted A C6-10 aryl group, an unsubstituted or substituted C7-12 aralkyl group, an unsubstituted or substituted heteroaryl group, or an unsubstituted or substituted heteroaralkyl group. Preferred R ⁸ and R ⁹ are C1-6 alkyl groups.

In formula (5), Q ⁴¹ is a C6-10 aryl group or heteroaryl group.
In the aryl group or heteroalkyl group, Q ¹ and / or Q ² may be substituted as shown in Formula (5). Preferred Q ⁴¹ is a phenyl group or a 5-membered heteroaryl group.

Q ² in the formula (5) is a group represented by the formula: OR ²³ , a group represented by the formula: SR ²³ , a group represented by the formula: N (R ²³ ) ₂ , a formula: COR ²¹ Group represented by the formula: CO ₂ R ²² , group represented by the formula: CON (R ²¹ ) ₂ , group represented by the formula: SO ₂ R ²² , cyano group, nitro group, or halogen Is an atom.
Examples of the group represented by the formula: SO ₂ R ²² include a methanesulfonyl group, an ethanesulfonyl group, a benzenesulfonyl group, and the like.

m1 represents the number of Q ¹ and is an integer of 0 to 7. m2 represents the number of Q ² and is an integer of 0 to 7. However, the sum of m1 and m2 is 7 or less.
When m1 is 2 or more, Q ¹ each other may be the same or different. When m2 is 2 or more, Q ² to each other may be the same or different. Further, Q ¹ , Q ² , or Q ¹ and Q ² that are adjacently substituted on Q ⁴¹ may be bonded to each other to form a 5- to 8-membered ring.
Examples of the 5- to 8-membered ring include an aliphatic hydrocarbon ring and an unsaturated heterocyclic ring.
Examples of the aliphatic hydrocarbon ring include a cycloalkene ring, and examples of the cycloalkene ring include a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring.
Examples of the unsaturated heterocycle include a dihydro-2H-pyran ring, a dihydro-2H-thiopyran ring, and a tetrahydropyridine ring.

2) Salt of nitrogen-containing heteroaryl derivative or N-oxide The present invention includes a salt of nitrogen-containing heteroaryl derivative represented by the formula (1) and N-oxide. Nitrogen-containing heteroaryl derivatives, salts of nitrogen-containing heteroaryl derivatives and N-oxides are sometimes collectively referred to as “the present compound”.
The salt is not particularly limited as long as it is an agro-horticulturally acceptable salt. Examples thereof include salts of inorganic acids such as hydrochloric acid and sulfuric acid; salts of organic acids such as acetic acid and lactic acid.
Examples of the N-oxide include compounds in which any nitrogen in the partial structures represented by the above formulas (A-1) to (A-3) is oxidized.

3) Manufacturing method Next, the manufacturing method of this invention compound is demonstrated.
(I) When D in Formula (1) is Formula (2) a) The compound represented by formula (B-3) (hereinafter sometimes referred to as “compound (B-3)”) is: For example, an oxyamine compound represented by formula (B-2) (hereinafter sometimes referred to as “compound (B-2)”) and a ketone compound represented by formula (B-1) (hereinafter referred to as “compound”). (B-1) ") may be reacted.

（式中、Ｒ¹、Ｒ²、Ｒ⁷、Ａ¹、Ａ²、J、Ｘ、ｎ、Ｂ¹〜Ｂ⁴、及びＱ¹は前記と同じ意味である。）

(In the formula, R ¹ , R ² , R ⁷ , A ¹ , A ² , J, X, n, B ^{1 to} B ⁴ , and Q ¹ have the same meanings as described above.)

The amount of compound (B-1) to be used is generally 0.5 to 2 mol, preferably 0.7 to 1.5 mol, per 1 mol of compound (B-2).
Although this reaction can be performed in the absence of a catalyst, it is preferably performed in the presence of an acid catalyst or a base catalyst, and more preferably in the presence of an acid catalyst.

Examples of the acid catalyst include trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, pyridinium p-toluenesulfonate, hydrochloric acid, sulfuric acid, and the like.
Examples of the base catalyst include pyridine, triethylamine, potassium hydroxide and the like.
The usage-amount of a catalyst is 0.0001-1 mol normally with respect to 1 mol of compounds (B-2).
Further, a dehydrating agent such as anhydrous sodium sulfate or molecular sieve may be added to the reaction system.

This reaction can be carried out in a solvent. The solvent is not particularly limited as long as it is inert to the reaction. For example, ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, benzene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvent; Halogenated hydrocarbon solvent such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane; Amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; Examples thereof include nitrile solvents such as acetonitrile and benzonitrile; alcohol solvents such as methanol, ethanol and n-propanol; and mixed solvents composed of two or more of these.
Although the usage-amount of a solvent is not specifically limited, It is 1-100 ml normally with respect to 1 g of compounds (B-2).

  The reaction temperature is a temperature range from room temperature to the boiling point of the solvent used. The reaction time is usually several minutes to several tens of hours depending on the reaction scale.

  b) A compound (B-2) can be manufactured according to the manufacturing method of a conventionally well-known oxyamine compound. For example, as shown below, the compound represented by the formula (B-2-1) is reacted with carbon tetrabromide and triphenylphosphine to obtain the compound represented by the formula (B-2-2). . By reacting this with Nt-butoxycarbonylhydroxylamine in the presence of a base, an oxyamine compound represented by the formula (B-2-3) (hereinafter referred to as “compound (B-2-3)”) There are things.) The compound (B-2) can be obtained by allowing an acid to act on this.

（式中、Ｑ¹は前記と同じ意味である。）

(Wherein Q ¹ has the same meaning as described above.)

  Further, after mixing the compound (B-1) and the compound (B-2-3), an acid such as trifluoroacetic acid is added, and the compound (B-2-3) is converted to the compound in the same reaction system. Chemical conversion to (B-2) and chemical conversion from compound (B-1) and compound (B-2) to compound (B-3) may be performed.

c) Among the compounds (B-1), a compound in which A ² is O (hereinafter sometimes referred to as “compound (B-1: (A ² ═O))”) is, for example, as follows: It can be produced by reaction.

（式中、Ｒ¹、Ｒ²、Ｒ⁷、Ａ¹、J、Ｘ、ｎ、及びＢ¹〜Ｂ⁴は前記と同じ意味である。Ｅ⁶は、フッ素原子または塩素原子である。）

(In the formula, R ¹ , R ² , R ⁷ , A ¹ , J, X, n, and B ^{1 to} B ⁴ have the same meaning as above. E ⁶ is a fluorine atom or a chlorine atom.)

First, a compound represented by formula (C-2) in the presence of a base is added to a dihalogeno compound represented by formula (C-1) (hereinafter sometimes referred to as “compound (C-1)”) ( Hereinafter, the compound may be referred to as “compound (C-2)”) to react with the hydroxycarbamic acid compound represented by formula (C-3) (hereinafter referred to as “compound (C-3)”). There is.) Next, by reacting the compound (C-3) with an amide compound represented by the formula (C-4) (hereinafter sometimes referred to as “compound (C-4)”) in the presence of a base, The target compound (B-1: (A ² ═O)) can be obtained.
The amount of the compound (C-2) used for the reaction with the compound (C-1) is usually 0.8 to 5 mol, preferably 1 to 3 mol, relative to 1 mol of the compound (C-1). .

  Examples of the base used for the reaction between the compound (C-1) and the compound (C-2) include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and other metal hydroxides; sodium methoxy Metal alkoxides such as sodium ethoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide; metal hydrides such as sodium hydride, potassium hydride, calcium hydride; triethylamine, diisopropylethylamine, pyridine, 1,8 -Organic bases such as diazabicyclo [5.4.0] undec-7-ene (DBU) and 1,4-diazabicyclo [2.2.2] octane. The amount of the base used for the reaction between the compound (C-1) and the compound (C-2) is usually 1 to 20 mol with respect to 1 mol of the compound (C-1).

The reaction of compound (C-1) and compound (C-2) can be carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as it is inert to the reaction. For example, sulfur-containing solvents such as dimethyl sulfoxide and diethyl sulfoxide; ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, benzene and xylene; n-pentane, n- Aliphatic hydrocarbon solvents such as hexane and n-heptane; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; nitrile solvents such as acetonitrile and benzonitrile; And a mixed solvent composed of two or more of these;
Although the usage-amount of an organic solvent is not specifically limited, It is 1-100 ml normally with respect to 1 g of compounds (C-1).
The reaction between the compound (C-1) and the compound (C-2) proceeds smoothly in a temperature range from 0 ° C. to the boiling point of the solvent used.

Examples of the compound (C-4) used for the reaction with the compound (C-3) include N, N-dimethylacetamide, N, N-dimethylpropionamide and the like.
The amount of compound (C-4) to be used is generally 0.8 to 5 mol, preferably 1 to 3 mol, per 1 mol of compound (C-3).

Examples of the base used for the reaction between the compound (C-3) and the compound (C-4) include organic lithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, lithium diisopropylamide; metal sodium, metal Examples thereof include alkali metals such as potassium; metal hydrides such as sodium hydride, potassium hydride and calcium hydride;
The amount of the base used for the reaction between the compound (C-3) and the compound (C-4) is usually 1 to 20 mol with respect to 1 mol of the compound (C-3).

The reaction of compound (C-3) and compound (C-4) can be carried out in an organic solvent. The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, benzene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvent; and the like.
The reaction between the compound (C-3) and the compound (C-4) proceeds smoothly in a temperature range from −100 ° C. to the boiling point of the solvent used.

d) Among the compounds (B-1: (A ² ═O)), a compound in which R ¹ is a t-butyl group, R ² is a hydrogen atom, and A ¹ and J are oxygen atoms (formula (B-1 -1: (A ² ═O)) can be obtained by converting R ¹ by the method shown below. The following formula shows a reaction in which a t-butyl group is converted to another group R ^{1 ′} .

（式中、Ｒ¹、Ｒ⁷、Ｘ、ｎ、及びＢ¹〜Ｂ⁴は前記と同じ意味である。Ｒ^1'は、ｔ−ブチル基を除くＲ¹である。））

(In the formula, R ¹ , R ⁷ , X, n, and B ^{1 to} B ⁴ have the same meaning as described above. R ^{1 ′} is R ¹ excluding the t-butyl group.)

First, a carbamic acid t-butyl ester compound represented by the formula (B-1-1: (A ² ═O)) (hereinafter referred to as “compound (B-1-1: (A ² ═O))”. Is reacted with a halogenoformate compound represented by the formula (B-1-2) (hereinafter sometimes referred to as “ester compound (B-1-2)”) in the presence of a base. Thus, a compound represented by the formula (B-1-3: (A ² ═O)) (hereinafter sometimes referred to as “compound (B-1-3: (A ² ═O))”) is obtained. . Next, an acid is allowed to act on the compound, whereby the compound represented by the formula (B-1-4: (A ² ═O)) (hereinafter “compound (B-1-4: (A ² ═O))” is expressed. Can be obtained.)

Examples of the base used for the reaction between the compound (B-1-1: (A ² ═O)) and the ester compound (B-1-2) include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, Metal hydroxides such as calcium hydroxide; metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide; metal hydrogen such as sodium hydride, potassium hydride, calcium hydride Organic bases such as triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,4-diazabicyclo [2.2.2] octane; be able to.
The amount of the base to be used, the compound ^{(B-1-1: (A 2} = O)) with respect to 1 mol, usually 1 to 20 mol.

The reaction of the compound (B-1-1: (A ² ═O)) and the ester compound (B-1-2) is performed in an organic solvent. The organic solvent to be used is not particularly limited as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and 1,2-dichloroethane; sulfur-containing solvents such as dimethyl sulfoxide and diethyl sulfoxide; ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran Aromatic hydrocarbon solvents such as toluene, benzene and xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; N, N-dimethylformamide, N, N-dimethylacetamide Amide solvents such as N-methylpyrrolidone; nitrile solvents such as acetonitrile and benzonitrile; and mixed solvents composed of two or more of these solvents.
The amount of the organic solvent is not particularly limited, Compound: For ^{(B-1-1 (A 2 =} O)) 1g, usually 1 to 100 ml.
The reaction proceeds smoothly in a temperature range from −20 ° C. to the boiling point of the solvent used. Although the reaction time depends on the reaction scale, it is usually from several minutes to several tens of hours.

Examples of the acid used in the reaction for converting the compound (B-1-3: (A ² ═O)) to the compound (B-1-4: (A ² ═O)) include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid. Examples of the acid include acetic acid, trifluoroacetic acid, methanesulfonic acid, and p-toluenesulfonic acid.
The amount of the acid compound ^{(B-1-3: (A 2} = O)) with respect to 1 mol, usually 1 to 20 mol.
This reaction is performed in an organic solvent. The organic solvent to be used is not particularly limited as long as it is inert to the reaction. The compound ^{(B-1-1: (A 2} = O)) and can be the same as the those listed as the solvent which can be used for the reaction with the ester compound (B-1-2).
The reaction for converting the compound (B-1-3: (A ² ═O)) to the compound (B-1-4: (A ² ═O)) is performed at a temperature range from −20 ° C. to the boiling point of the solvent used. Proceed smoothly. Although the reaction time depends on the reaction scale, it is usually from several minutes to several tens of hours.

(II) When D in Formula (1) is Formula (3) a) The compound represented by formula (B-6) (hereinafter sometimes referred to as “compound (B-6)”) is: For example, a hydrazine compound represented by formula (B-5) (hereinafter sometimes referred to as “compound (B-5)”) and a ketone compound represented by formula (B-4) (hereinafter referred to as “compound”). (B-4) ") may be reacted.
The amount of compound (B-4) to be used is generally 0.5 to 2 mol, preferably 0.7 to 1.5 mol, per 1 mol of compound (B-5).

（式中、Ｒ¹、Ｒ²、Ｒ⁸、Ｒ⁹、Ａ¹、Ａ²、J、Ｘ、ｎ、Ｂ¹〜Ｂ⁴、及びＱ¹は前記と同じ意味である。）

(In the formula, R ¹ , R ² , R ⁸ , R ⁹ , A ¹ , A ² , J, X, n, B ^{1 to} B ⁴ , and Q ¹ have the same meanings as described above.)

The reaction between the compound (B-4) and the compound (B-5) is preferably performed in the presence of an acid catalyst or a base catalyst, and more preferably performed in the presence of an acid catalyst.
Examples of the acid catalyst used include benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, pyridinium p-toluenesulfonate, hydrochloric acid, sulfuric acid and the like.
Examples of the base catalyst include pyridine, triethylamine, potassium hydroxide and the like.
The usage-amount of a catalyst is 0.0001-1 mol normally with respect to 1 mol of compounds (B-5).
A dehydrating agent such as anhydrous sodium sulfate may be added to the reaction system.

This reaction can be carried out in a solvent. The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, benzene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvent; Halogenated hydrocarbon solvent such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane; Amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; Examples thereof include nitrile solvents such as acetonitrile and benzonitrile; alcohol solvents such as methanol, ethanol and n-propanol; and mixed solvents composed of two or more of these.
Although the usage-amount of a solvent is not specifically limited, It is 1-100 ml normally with respect to 1 g of compounds (B-5).
The reaction temperature is a temperature range from room temperature to the boiling point of the solvent used. The reaction time is usually several minutes to several tens of hours.

  b) Compound (B-5) is obtained, for example, by reacting a ketone compound represented by formula (B-5-1) with hydrazine (or hydrazine monohydrate) as shown below. be able to.

（式中、Ｒ⁹、及びＱ¹は前記と同じ意味である。）

(In the formula, R ⁹ and Q ¹ have the same meaning as described above.)

c) Among the compounds (B-4), a compound in which A ² is O can be produced by the same method as the compound (B-1: (A ² ═O)).

(III) When D in Formula (1) is Formula (4) and A ² is O a) A compound represented by Formula (B-9) (hereinafter referred to as “Compound (B-9: (A ² ═O)) ”is sometimes present in the halogeno compound represented by the formula (D-1) (hereinafter sometimes referred to as“ compound (D-1) ”). It can manufacture by making a compound (C-2) react under.

（式中、Ｒ¹、Ｒ²、Ａ¹、J、Ｘ、ｎ、Ｂ¹〜Ｂ⁴、及びＱ¹は前記と同じ意味である。
Ｅ⁶は、フッ素原子または塩素原子である。）

(In the formula, R ¹ , R ² , A ¹ , J, X, n, B ^{1 to} B ⁴ , and Q ¹ have the same meaning as described above.
E ⁶ is a fluorine atom or a chlorine atom. )

  As a method of reacting the compound (D-1) and the compound (C-2), the same method as the method of reacting the compound (C-1) and the compound (C-2) can be used.

b) Compound (D-1) includes, for example, compound (C-1) and an acetylene compound represented by formula (D-1-1) (hereinafter referred to as “acetylene compound (D-1)” as shown below. -1) ").) Can be obtained.
The usage-amount of an acetylene compound (D-1-1) is 1-2 mol normally with respect to 1 mol of compounds (C-1).

（式中、Ｘ、ｎ、Ｂ¹〜Ｂ⁴、及びＱ¹は前記と同じ意味である。Ｅ⁶は、フッ素原子または塩素原子である。）

(In the formula, X, n, B ^{1 to} B ⁴ , and Q ¹ have the same meanings as described above. E ⁶ is a fluorine atom or a chlorine atom.)

This reaction is a coupling reaction called the Sonogashira reaction. A Pd complex is usually used for this reaction.
Examples of the Pd complex include palladium (II) acetate, dichlorobis (triphenylphosphine) palladium (II), tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), and the like. .
The usage-amount of Pd complex is 0.01-0.5 mol normally with respect to 1 mol of compounds (C-1).

In the reaction, copper halide is further used as a catalyst. Examples of the copper halide include monovalent copper halides such as cuprous fluoride, cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, Examples thereof include divalent copper halides such as cupric iodide.
The usage-amount of a copper halide is 0.1-1 mol normally with respect to 1 mol of compounds (C-1).

In the reaction, a base is further used. Examples of the base include sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, cesium carbonate, potassium phosphate and other inorganic bases, or triethylamine, pyridine, Examples include amines such as piperidine.
The amount of the base to be used is generally 1 to 10 mol per 1 mol of compound (C-1).

This reaction can be carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as it is inert to the reaction. For example, ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, benzene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvents; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; Nitrile solvents such as acetonitrile and benzonitrile; and mixed solvents composed of two or more of these; etc. Can be mentioned.
Although the usage-amount of an organic solvent is not specifically limited, It is 1-100 ml normally with respect to 1 g of compounds (C-1).

  The reaction temperature should be a temperature sufficient to complete the coupling reaction, and is usually room temperature to 100 ° C. The reaction time is usually several minutes to several tens of hours. The reaction is preferably carried out in an inert gas atmosphere.

(IV) When D in Formula (1) is Formula (5) and A ² is O a) Compound represented by Formula (B-12) (hereinafter referred to as “Compound (B-12: (A ² ═O)) ”is sometimes present in the halogeno compound represented by the formula (E-1) (hereinafter sometimes referred to as“ compound (E-1) ”). It can manufacture by making a compound (C-2) react under.
As a method of reacting the compound (E-1) and the compound (C-2), a method similar to the method of reacting the compound (C-1) and the compound (C-2) can be used.

（式中、Ｒ¹、Ｒ²、Ａ¹、J、Ｘ、ｎ、Ｂ¹〜Ｂ⁴、Ｑ⁴¹、Ｑ¹、ｍ１、Ｑ²、及びｍ２は、前記と同じ意味である。Ｅ⁶は、フッ素原子または塩素原子である。）

(In the formula, R ¹ , R ² , A ¹ , J, X, n, B ^{1 to} B ⁴ , Q ⁴¹ , Q ¹ , m 1, Q ² , and m ² have the same meanings as described above. E ⁶ represents , Fluorine atom or chlorine atom.)

  b) For example, as shown below, the compound (E-1) is obtained by adding a boronic acid compound represented by the formula (E-1-1) to the compound (C-1) (hereinafter referred to as “boronic acid compound (E The amount of the boronic acid compound (E-1-1) used is usually 1 with respect to 1 mol of the compound (C-1). ~ 2 moles.

（式中、Ｘ、ｎ、Ｂ¹〜Ｂ⁴、Ｑ⁴¹、Ｑ¹、ｍ１、Ｑ²、及びｍ２は、前記と同じ意味である。
Ｅ⁶は、フッ素原子または塩素原子である。）

(In the formula, X, n, B ^{1 to} B ⁴ , Q ⁴¹ , Q ¹ , m 1, Q ² , and m ² have the same meaning as described above.
E ⁶ is a fluorine atom or a chlorine atom. )

The reaction between the compound (C-1) and the boronic acid compound (E-1-1) is a coupling reaction called the Suzuki-Miyaura reaction. A Pd catalyst is used for this reaction.
Examples of the Pd catalyst used in the reaction include tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium dichloride (II), “1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris ( Pd catalysts such as dibenzylideneacetone) dipalladium (0), palladium (II) acetate, palladium chloride, palladium carbon and the like can be mentioned.
The usage-amount of Pd catalyst is 0.01-0.5 mol normally with respect to 1 mol of compounds (C-1).

In this reaction, a base is further used. Examples of the base include hydrated or non-aqueous bases such as sodium carbonate, potassium carbonate, sodium hydroxide and cesium fluoride.
The amount of the base to be used is generally 1 to 10 mol per 1 mol of compound (C-1).

This reaction can be carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as it is inert to the reaction. For example, ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, benzene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvents; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; Nitrile solvents such as acetonitrile and benzonitrile; and mixed solvents composed of two or more of these; etc. Can be mentioned.
Although the usage-amount of an organic solvent is not specifically limited, It is 1-100 ml normally with respect to 1 g of compounds (C-1).

  The reaction temperature should be a temperature sufficient to complete the coupling reaction, and is room temperature to 150 ° C. The reaction time is usually several minutes to several tens of hours. The reaction is preferably carried out in an inert gas atmosphere.

The nitrogen-containing heteroaryl derivative of the present invention obtained by the above production method can be further converted into a salt. The salt is not particularly limited as long as it is an agro-horticulturally acceptable salt. Examples thereof include salts of inorganic acids such as hydrochloric acid and sulfuric acid; salts of organic acids such as acetic acid and lactic acid; and the like.
These salts can be produced by a conventionally known method using an acid corresponding to the compound of the present invention.

In any reaction, after completion of the reaction, the desired product can be isolated by purifying by a conventional post-treatment operation and, if desired, known and conventional purification means such as distillation, recrystallization and column chromatography.
The structure of the target product can be identified and confirmed by known analytical means such as IR spectrum, NMR spectrum, mass spectrum, and elemental analysis.

  In the nitrogen-containing heteroaryl derivative of the present invention, geometric isomers based on carbon-nitrogen double bonds (cis-trans isomers) may exist, and all of these isomers are included in the present invention.

4) Agricultural and horticultural fungicide The second aspect of the present invention is an agricultural product containing, as an active ingredient, at least one of a nitrogen-containing heteroaryl derivative represented by the formula (I) of the present invention, a salt thereof, or an N-oxide thereof. It is a horticultural fungicide (hereinafter sometimes referred to as "the present invention fungicide").

The fungicide of the present invention is effective against a wide variety of fungi, for example, bacteria belonging to algae (Oomycetes), Ascomycetes, Deuteromycetes, and Basidiomycetes. Excellent sterilizing power.
The disinfectant of the present invention can be used by seed treatment, foliage application, soil application, water application, etc., for the control of various diseases that occur during cultivation of agricultural and horticultural crops including flowers, turf, and grass.

For example, sugar beet: brown spot disease (Cercospora beticola), black root disease (Aphanomyces cochlloides);
Peanut: brown spot (Mycosphaerella arachidis), black astringency (Mycosphaerella berkeleyi);
Cucumber: powdery mildew (Sphaerotheca fuliginea), vine blight (Mycosphaerella melonis), mycorrhizal disease (Sclerotinia sclerotiorum), gray mold disease (Botrytis cinerea), black spot disease (Cladosporium cucumerinum), brown spot disease (Corynespora cassicola), seedling Blight disease (Pythium debaryanam, Rhizoctonia solani Kuhn), spotted bacterial disease (Pseudomonas syringae pv. Lecrymans), downy mildew (Pseudoperonospora cubensis);
Tomato: gray mold (Botrytis cinerea), leaf mold (Cladosporium fulvum);
Eggplant: gray mold disease (Botrytis cinerea), black blight disease (Corynespora melongenae), powdery mildew (Erysiphe cichoracearum), subtilis disease (Mycovellosiella nattrassii);
Strawberry: Gray mold disease (Botrytis cinerea), powdery mildew (Sohaerotheca humuli), anthracnose (Colletotrichum acutatum, Colletotrichum fragariae);
Onion: gray rot (Botrytis allii), gray mold (Botrytis cinerea), white spotted blight (Botrytis squamosa);
Cabbage: clubroot (Plasmodiophora brassicae), soft rot (Erwinia carotovora);
Kidney bean: Sclerotinia sclerotiorum, gray mold (Botrytis cinerea);

Apple: powdery mildew (Podosphaera leucotricha), black spot disease (Venturia inaequalis), monilia disease (Monilinia mali), rot disease (Valsa mali), spotted leaf disease (Alternaria mali), red star disease (Gymnosporangium yamadae), ring-shaped disease ( Botryosphaeria berengeriana), anthracnose (Colletotrichum gloeosprioides), brown spot (Diplocarpon mali);
Oysters: powdery mildew (Phyllactinia kakicola), anthracnose (Gloeosporium kaki), deciduous leaf spot (Cercospora kaki);
Momo cherry: Monilinia fructicola;
Grapes: gray mold (Botrytis cinerea), powdery mildew (Uncinula necator), late rot (Glomerella cingulata), downy mildew (Plasmopara viticola);
Pear: Black star disease (Venturia nashicola), Red star disease (Gymnosporangium asiaticum), Black spot disease (Alternaria kikuchiana);
Tea: Ring spot disease (Pestalotia theae), anthracnose (Colletotrichum theae-sinensis);
Citrus: common scab (Elsinoe fawcetti), blue mold (Penicillium italicum), green mold (Penicillium digitatum), gray mold (Botrytis cinerea), sunspot (Diaporthe citri), scab (Xanthomonas campestris pv.Citri);

Wheat: powdery mildew (Erysiphe graminis f.sp.tritici), red mold (Gibberella zeae), red rust (Puccinia recondita), brown snow rot (Pythium iwayamai), red snow rot (Monographella nivalis), eyeprint Disease (Pseudocercosporella herpotrichoides), leaf blight (Septoria tritici), blight (Leptosphaeria nodorum), snow rot microbe nuclei (Typhula incarnata), snow rot large bacilli (Myriosclerotinia borealis), blight (Gaeumanomyces graminis) );
Barley: leafy leaf disease (Pyrenophora graminea), cloud shape disease (Rhynchosporium secalis), naked smut (Ustilago tritici, U.nuda);
Rice: Rice blast (Pyricularia oryzae), Rhizoctonia solani, idiot seedling (Gibberella fujikuroi), sesame leaf blight (Cochliobolus niyabeanus), seedling blight (Pythium graminicolum);
Tobacco: Sclerotinia sclerotiorum, powdery mildew (Erysiphe cichoracearum);
Tulip: Gray mold disease (Botrytis cinerea);
Bentgrass: Sclerotinia borealis, Pythium aphanidermatum;
Orchardgrass: powdery mildew (Erysiphe graminis);
Soybean: Purpura (Cercospora kikuchii), downy mildew (Peronospora Manshurica), stem rot (Phytophthora sojae);
It can be used to control potato-tomato infestans (Phytophthora infestans);

In addition, the bactericidal agent of the present invention has an excellent bactericidal effect against a new bacterium that exhibits resistance to benzimidazole fungicides, dicarboximide fungicides, and the like, that is, resistant fungi.
Examples of such resistant bacteria include gray mold fungus (Botrytis cinerea), sugar beet brown blight fungus (Cercospora beticola), apple black rot fungus (Venturia inaequalis), Pear black rot (Venturia nashicola);
Examples include Botrytis cinerea, which is resistant to dicarboximide fungicides (for example, vinclozolin, procymidone, iprodione).

  More preferable diseases to which the fungicide of the present invention is applied include sugar beet brown spot, wheat powdery mildew, rice blast, apple scab, cucumber gray mold, peanut brown etc. it can.

  The disinfectant of the present invention is a highly safe drug with little phytotoxicity, low toxicity to fish and warm-blooded animals.

  When the fungicide of the present invention is actually applied, the compound of the present invention can be used as it is without adding other components, and the form that can be taken by general agricultural chemicals, that is, wettable powder, granules It can also be used in the form of a preparation, powder, emulsion, aqueous solvent, suspension, granule wettable powder and the like.

  Additives and carriers used in the preparation of solid dosage forms include vegetable powders such as soybean flour and wheat flour, mineral fine powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay, etc. And organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate.

  Solvents used in formulating liquid dosage forms include kerosene, xylene and petroleum aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil , Vegetable oil, water and the like.

  In order to take a uniform and stable form in the preparation, a surfactant can be added as necessary. The surfactant that can be added is not particularly limited. For example, alkyl phenyl ether added with polyoxyethylene, alkyl ether added with polyoxyethylene, higher fatty acid ester added with polyoxyethylene, sorbitan higher fatty acid ester added with polyoxyethylene, tristyryl added with polyoxyethylene Nonionic surfactants such as phenyl ether, sulfates of alkylphenyl ethers added with polyoxyethylene, alkylbenzene sulfonates, sulfates of higher alcohols, alkylnaphthalene sulfonates, polycarboxylates, lignin sulfones Examples thereof include acid salts, formaldehyde condensates of alkyl naphthalene sulfonates, and isobutylene-maleic anhydride copolymers.

  The wettable powder, emulsion, flowable powder, aqueous solvent, and granular wettable powder thus obtained are diluted with water to a predetermined concentration to obtain a solution, suspension or emulsion. Granules can be sprayed on plants as they are.

  The amount of the active ingredient in the fungicide of the present invention is usually preferably 0.01 to 90% by weight, more preferably 0.05 to 85% by weight, based on the entire composition (formulation).

The application amount of the fungicide of the present invention varies depending on weather conditions, formulation form, application time, application method, application place, disease to be controlled, target crop, etc. , Preferably 10 to 100 g.
When a wettable powder, emulsion, suspension, aqueous solvent, granular wettable powder or the like is diluted with water and applied, the applied concentration is 1-1000 ppm, preferably 10-250 ppm.

  In addition to the compound of the present invention, one or two or more of various fungicides, insecticides / acaricides, and synergists can be mixed in the present fungicide.

  Typical examples of fungicides, insecticides, acaricides, and plant growth regulators that can be used in combination with the compounds of the present invention are shown below.

Fungicide:
Captan, phorpet, thiuram, ziram, dinebu, manneb, mancozeb, propineb, polycarbamate, chlorothalonil, quintozen, captaphor, iprodione, prosaimidin, vinclozolin, fluoroimide, thymoxanyl, mepronil, flutolanil, pencyclon, oxycarboxyl, fosetyl aluminum, Propamocurve, triadimephone, triadimenol, propiconazole, diclobutrazole, viteltanol, hexaconazole, microbutanyl, flusilazole, metconazole, etaconazole, fluotrimazole, cyproconazole, epoxyconazole, flutriaphene, beconazole , Diniconazole, cyproconazole, phenalimol, triflumizole, prochlor , Imazalyl, pefrazoate, tridemorph, fenpropimorph, triphorin, butiobate, pyrifenox, anilazine, polyoxin, metalaxyl, oxadixyl, furaxyl, isoprothiolane, probenazole, pyrrolnitrin, blasticidin S, kasugamycin, validamycin, dihydrostreptomycin sulfate , Benomyl, carbendazim, thiophanatemethyl, hymexazole, basic copper chloride, basic copper sulfate, fentin acetate, triphenyltin hydroxide, dietofencarb, metasulfocarb, quinomethionate, binapacryl, lecithin, baking soda, dithianone, dinocup, phenaminosulfur, Dichromemedin, Guazatine, Dodin, IBP, Edifenphos, Mepanipyrim, Fermzo , Trichlamide, methasulfocarb, fluazinam, Etokinorakku, dimethomorph, pyroquilon, tecloftalam, fthalide, phenazine oxide, thiabendazole, tricyclazole, vinclozolin, cymoxanil, cyclobutanyl, guazatine, propamocarb hydrochloride, oxolinic acid, hydroxy isoxazole, iminoctadine acetate, and the like.

Insecticides and acaricides:
Organophosphorus and carbamate insecticides:
Fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, bamidthione, phentoate, dimethoate, formothione, marathon, trichlorfone, thiometone, phosmet, dichlorvos, acephate, EPBP, methyl parathion, oxydimethone methyl, ethion, salicione, cyanophos, isoxathione, cyanophos, isoxathione Methidathione, Sulprophos, Chlorfenvinphos, Tetrachlorbinphos, Dimethylvinphos, Propafos, Isophenphos, Ethylthiomethone, Profenofos, Piracrofos, Monocrotophos, Adinfosmethyl, Aldicarb, Mesomil, Thiodicarb, Carbofuran, Carbosulfan, Benhracarb, Furatiocarb Propoxur, BPMC, M MC, MIPC, carbaryl, pirimicarb, ethiofencarb, fenoxycarb, EDDP, and the like.
Pyrethroid insecticides:
Permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatoline, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propraslin, phenothrin, protorin, fulvalinate, cyfluthrin, cyhalothrin, flucitrinate, etofenprox, cycloprotorin, thoramethrin , Silafluophene, brofenprox, aclinasrin, etc.
Benzoylurea and other insecticides:
Diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, metoprene, benzoepin, diafenthiuron, acetamiprid, imidacloprid, nitenpyram, fipronil, cartap Thiocyclam, bensultap, nicotine sulfate, rotenone, metaldehyde, machine oil, microbial pesticides such as BT and entomopathogenic viruses.

Nematicides:
Phenamifos, phostiazates, etc.
Acaricide:
Chlorbenzilate, phenisobromolate, dicofol, amitraz, BPPS, benzomate, hexithiazox, fenbutazin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentedin, cihexatin, pyridaben, fenpyroximate, tebufenpyrad, thiomidibene Dienochlor etc.
Plant growth regulator:
Gibberellins (eg, gibberellin A3, gibberellin A4, gibberellin A7), IAA, NAA and the like.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited at all by the following example.

Example 1
a) Preparation of 2-acetyl-4-chloro-5-methylpyridine Under nitrogen atmosphere, 6.00 g of 2-bromo-4-chloro-5-methylpyridine was dissolved in 100 ml of toluene, and n-butyl was dissolved at -78 ° C. 13 ml of lithium (2.69 mol / L) was added dropwise. After completion of dropping, the mixture was aged by stirring for 20 minutes. To this, 3.81 g of dimethylacetamide was added and stirred at -78 ° C for 1 hour. To this, an aqueous ammonium chloride solution was added at −78 ° C., followed by extraction with ethyl acetate. Magnesium sulfate was added to the obtained organic layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 5: 1) to give 2.59 g of the desired 2-acetyl-4-chloro-5-methylpyridine (yield 53%). )
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.49 (s, 1H), 8.01 (s, 1H), 2.70 (s, 3H), 2.44 (s, 1H)

b) Preparation of t-butyl N- (2-acetyl-5-methylpyridin-4-yloxy) carbamate 3.85 g of 2-acetyl-4-chloro-5-methylpyridine and N-Boc-hydroxylamine To a solution in which 54 g was dissolved in 50 ml of dimethyl sulfoxide, 4.50 g of potassium hydroxide was added and stirred at room temperature for 1 hour. The solution was poured into ice water and then extracted with ethyl acetate. The obtained organic layer was washed with water three times. Magnesium sulfate was added to this, dried, filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 7: 3), and the target N- (2-acetyl-5-methylpyridin-4-yloxy) carbamic acid t- 4.37 g (72% yield) of butyl was obtained.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.34 (s, 1H), 7.89 (s, 1H), 7.70 (bs, 1H), 2.69 (s, 3H) , 2.30 (s, 3H), 1.51 (s, 9H)

c) Preparation of methyl N- (2-acetyl-5-methylpyridin-4-yloxy) carbamate 4.37 g of N- (2-acetyl-5-methylpyridin-4-yloxy) carbamate 4.37 g of methylene chloride Dissolved in 50 ml. To this, 3.32 g of triethylamine was added under ice cooling, and then 1.86 g of methyl chloroformate was added dropwise. It stirred for 1 hour after completion | finish of dripping. An aqueous ammonium chloride solution was added thereto, and the methylene chloride layer was separated. Magnesium sulfate was added to this, dried, filtered, and then the solvent was distilled off under reduced pressure.
To the obtained residue, 30 ml of methylene chloride was added, and 10 ml of trifluoroacetic acid was added dropwise under ice cooling. After completion of the addition, the mixture was stirred at room temperature for 5 hours. The obtained liquid was poured into a saturated aqueous sodium hydrogencarbonate solution, and methylene chloride was added thereto for extraction. Magnesium sulfate was added to the resulting methylene chloride layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained crystals were washed with hexane to obtain 3.45 g (yield 94%) of the target methyl N- (2-acetyl-5-methylpyridin-4-yloxy) carbamate.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.35 (s, 1H), 8.07 (s, 1H), 7.88 (bs, 1H), 3.84 (s, 3H) , 2.69 (s, 3H), 2.29 (s, 3H)

d) Preparation of methyl N- {5-methyl-2- [1- (2-trifluoromethylbenzyloxyimino) ethyl] pyridin-4-yloxy} carbamate N- (2-acetyl-5-methylpyridine-4) -0.25 g of methyl yloxy) carbamate was dissolved in 15 ml of methanol. To this, 0.30 g of O- (2-trifluoromethylbenzyl) hydroxylamine hydrochloride was added and refluxed for 2 hours. To this was added ethyl acetate and then washed with saturated aqueous sodium bicarbonate. The organic layer was dried over magnesium sulfate, filtered, and then the solvent was removed under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1), and the desired N- {5-methyl-2- [1- (2-trifluoromethylbenzyloxy) was obtained. 0.37 g of methyl (imino) ethyl] pyridin-4-yloxy} carbamate (yield 84%, melting point: 110-111 ° C.) was obtained.

(Example 2)
Preparation of methyl N- [2- (1-{[1- (6-chloropyridin-2-yl) ethylidene] hydrazono} ethyl) -5-methylpyridin-4-yloxy] carbamate N- (2-acetyl- 0.35 g of methyl 5-methylpyridin-4-yloxy) carbamate was dissolved in 10 ml of THF. To this solution, 0.29 g of [1- (6-chloropyridin-2-yl) ethylidene] hydrazine was added and refluxed for 24 hours. The solvent was distilled off from the resulting liquid under reduced pressure. The obtained residue was purified by NH gel column chromatography (developing solvent; benzene: ethyl acetate = 3: 1), and the desired N- [2- (1-{[1- (6-chloropyridine-2] -Il) ethylidene] hydrazono} ethyl) -5-methylpyridin-4-yloxy] carbamate 0.35 g (yield 59%, mp 172 ° -174 ° C.) was obtained.

(Example 3)
a) Preparation of 4-chloro-2- (3,3-dimethyl-1-butynyl) -5-methylpyridine 1.05 g of 2-bromo-4-chloro-5-methylpyridine was dissolved in 30 ml of ethyl acetate. To this, 0.79 g of 3,3-dimethyl-1-butyne, 2.43 g of triethylamine, 0.05 g of copper iodide and 0.17 g of dichlorobistriphenylphosphine palladium were added, and the mixture was stirred at 50 ° C. for 2 hours under a nitrogen atmosphere. did. The resulting liquid was filtered through Celite, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 9: 1) to give the desired 4-chloro-2- (3,3-dimethyl-1-butynyl) -5-methylpyridine 1 0.04 g (98% yield) was obtained.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.35 (s, 1H), 7.37 (s, 1H), 2.34 (s, 3H), 1.37 (s, 9H)

b) Preparation of t-butyl N- [2- (3,3-dimethyl-1-butynyl) -5-methylpyridin-4-yloxy] carbamate 4-chloro-2- (3,3-dimethyl-1- 2.60 g of potassium hydroxide was added to a solution prepared by dissolving 0.85 g of butynyl) -5-methylpyridine and 2.60 g of N-Boc-hydroxylamine in 20 ml of dimethyl sulfoxide, and the mixture was stirred at 50 ° C. for 15 hours. The resulting solution was poured into ice water and then extracted with ethyl acetate. The obtained organic layer was washed with water three times. Magnesium sulfate was added and dried, filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1) to obtain the desired N- [2- (3,3-dimethyl-1-butynyl) -5-methyl. 0.81 g (yield 65%, melting point 166 to 167 ° C.) of t-butyl pyridine-4-yloxy) carbamate was obtained.

Example 4
Preparation of methyl N- [2- (3,3-dimethyl-1-butynyl) -5-methylpyridin-4-yloxy] carbamate N- [2- (3,3-dimethyl-1-butynyl) -5 0.64 g of methylpyridin-4-yloxy) carbamate was dissolved in 20 ml of methylene chloride. To this, 0.42 g of triethylamine was added under ice cooling, and then 0.30 g of methyl chloroformate was added dropwise. It stirred for 1 hour after completion | finish of dripping. Aqueous ammonium chloride was added and the methylene chloride layer was separated. Magnesium sulfate was added to this, dried, filtered, and then the solvent was distilled off under reduced pressure.
To the obtained residue, 12 ml of methylene chloride was added, and 4 ml of trifluoroacetic acid was added dropwise under ice cooling. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The obtained liquid was poured into a saturated aqueous sodium hydrogencarbonate solution, and methylene chloride was added thereto for extraction. Magnesium sulfate was added to the resulting methylene chloride layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1) to obtain the desired N- [2- (3,3-dimethyl-1-butynyl) -5-methyl. 0.37 g of methyl pyridin-4-yloxy] carbamate (yield 67%, melting point 120-121 ° C.) was obtained.

(Example 5)
a) Preparation of 4-chloro-5-methyl-2- (3-trifluoromethoxyphenyl) pyridine 0.61 g of 2-bromo-4-chloro-5-methylpyridine and 3-trifluoromethoxyphenylboronic acid 13 g was dissolved in 20 ml of dimethylformamide. 4 ml of water, 1.12 g of potassium carbonate, and 0.11 g of Pd (dppf) Cl ₂ .CH ₂ Cl ₂ were added thereto, and the mixture was stirred at 60 ° C. for 2 hours under a nitrogen atmosphere. Ethyl acetate was added thereto, and then washed with an aqueous ammonium chloride solution. The obtained organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 20: 1 to 10: 1) to obtain the desired 4-chloro-5-methyl-2- (3-trifluoromethoxy). 0.51 g (60% yield) of phenyl) pyridine was obtained.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.51 (s, 1H), 7.89 to 7.84 (m, 2H), 7.70 (s, 1H), 7.48 ( t, 1H), 7.29-7.24 (m, 1H), 2.41 (s, 3H)

b) Preparation of t-butyl N- [5-methyl-2- (3-trifluoromethoxyphenyl) pyridin-4-yloxy] carbamate 4-chloro-5-methyl-2- (3-trifluoromethoxyphenyl) To a solution prepared by dissolving 0.51 g of pyridine and 1.44 g of N-Boc-hydroxylamine in 20 ml of dimethyl sulfoxide, 1.42 g of potassium hydroxide was added and stirred at 40 ° C. for 15 hours. The resulting liquid was poured into ice water and then extracted with ethyl acetate. The obtained organic layer was washed with water three times. Magnesium sulfate was added and dried, filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 3: 1) to obtain the desired N- [5-methyl-2- (3-trifluoromethoxyphenyl) pyridine-4. 0.60 g (yield 65%) of t-butyl carbamate was obtained.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.36 (s, 1H), 7.87 to 7.82 (m, 2H), 7.62 (s, 1H), 7.53 ( s, 1H), 7.46 (t, 3H), 7.26-7.24 (m, 1H), 2.27 (s, 3H), 1.53 (s, 9H)

(Example 6)
Preparation of methyl N- [5-methyl-2- (3-trifluoromethoxyphenyl) pyridin-4-yloxy] carbamate N- [5-methyl-2- (3-trifluoromethoxyphenyl) pyridin-4-yloxy ] 0.50 g of t-butyl carbamate was dissolved in 20 ml of methylene chloride. To this, 0.26 g of triethylamine was added under ice cooling, and then 0.16 g of methyl chloroformate was added dropwise. It stirred for 1 hour after completion | finish of dripping. Aqueous ammonium chloride was added to separate the methylene chloride layer. Magnesium sulfate was added to this, dried, filtered, and then the solvent was distilled off under reduced pressure.
To the obtained residue, 12 ml of methylene chloride was added, and 4 ml of trifluoroacetic acid was added dropwise under ice cooling. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The resulting liquid was poured into a saturated aqueous sodium hydrogen carbonate solution, and then extracted by adding methylene chloride. Magnesium sulfate was added to the resulting methylene chloride layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1) to obtain the desired N- [5-methyl-2- (3-trifluoromethoxyphenyl) pyridine-4. There was obtained 0.35 g (yield 78%, melting point 130-132 ° C.) of methyl -yloxy] carbamate.

(Example 7)
a) Preparation of 4-chloro-5-methylpyridine-2-carbonitrile 1.50 g of 2-bromo-4-chloro-5-methylpyridine was dissolved in 20 ml of DMF. To this, 0.43 g of zinc cyanide and 0.43 g of tetrakistriphenylphosphine palladium were added and stirred at 80 ° C. for 1 hour. Water was added thereto, followed by extraction with ethyl acetate. The obtained organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 9: 1), and 0.68 g of the desired 4-chloro-5-methylpyridine-2-carbonitrile (yield 61). %).
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.54 (s, 1H), 7.68 (s, 1H), 2.46 (s, 3H)

b) Production of 4-chloro-5-methylpyridine-2-thiocarboxamide To 0.94 g of sodium hydrosulfide, 15 ml of DMF and 1.20 g of magnesium chloride hexahydrate were added, and the mixture was stirred at room temperature for 30 minutes. To this was added 0.68 g of 4-chloro-5-methylpyridine-2-carbonitrile, and the mixture was stirred at room temperature for 3 hours. The resulting liquid was poured into an aqueous ammonium chloride solution and then extracted with ethyl acetate. The obtained organic layer was washed with an aqueous ammonium chloride solution three times. Magnesium sulfate was added to this, dried, filtered, and then the solvent was distilled off under reduced pressure. The obtained crystals were washed with hexane to obtain 0.83 g (yield 72%) of the target methyl N- (2-chloro-5-thiocarbamoylphenoxy) carbamate.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 9.38 (bs, 1H), 8.67 (s, 1H), 8.33 (s, 1H), 7.70 (bs, 1H) , 2.43 (s, 3H)

c) Preparation of 4-chloro-2- [4- (2-chloro-6-fluorobenzyl) thiazol-2-yl] -5-methylpyridine 0.83 g of 4-chloro-5-methylpyridine-2-thiocarboxamide Was dissolved in 30 ml of ethanol. To this, 1.41 g of 1-bromo-3- (2-chloro-6-fluorophenyl) -2-propanone was added and refluxed for 6 hours. To this was added a saturated aqueous sodium hydrogen carbonate solution, followed by extraction with ethyl acetate. The obtained organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 9: 1) to obtain the desired 4-chloro-2- [4- (2-chloro-6-fluorobenzyl) thiazole. -2-yl] -5-methylpyridine (1.32 g, yield 84%) was obtained.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.38 (s, 1H), 8.17 (s, 1H), 7.28-7.17 (m, 2H), 7.08- 7.01 (m, 1H), 6.82 (s, 1H), 4.37 (s, 2H), 2.39 (s, 3H)

d) Preparation of t-butyl N- {2- [4- (2-chloro-6-fluorobenzyl) thiazol-2-yl] -5-methylpyridin-4-yloxy} carbamate 4-chloro-2- [ To a solution of 1.32 g of 4- (2-chloro-6-fluorobenzyl) thiazol-2-yl] -5-methylpyridine and 1.48 g of N-Boc-hydroxylamine in 30 ml of dimethyl sulfoxide, 1.47 g of potassium was added and stirred at 40 ° C. for 15 hours. The resulting solution was poured into ice water and then extracted with ethyl acetate. The obtained organic layer was washed with water three times. Magnesium sulfate was added and dried, filtered, and then the solvent was distilled off under reduced pressure. The obtained crystals were washed with hexane, and the desired N- {2- [4- (2-chloro-6-fluorobenzyl) thiazol-2-yl] -5-methylpyridin-4-yloxy} carbamic acid t 0.93 g of butyl (yield 55%, melting point 140-143 ° C.) was obtained.

(Example 8)
Preparation of methyl N- {2- [4- (2-chloro-6-fluorobenzyl) thiazol-2-yl] -5-methylpyridin-4-yloxy} carbamate N- {2- [4- (2- 0.80 g of chloro-6-fluorobenzyl) thiazol-2-yl] -5-methylpyridin-4-yloxy} carbamate was dissolved in 20 ml of methylene chloride. To this, 0.36 g of triethylamine was added under ice cooling, and then 0.22 g of methyl chloroformate was added dropwise. It stirred for 1 hour after completion | finish of dripping. An aqueous ammonium chloride solution was added thereto, and the methylene chloride layer was separated. Magnesium sulfate was added to this, dried, filtered, and then the solvent was distilled off under reduced pressure.
To the obtained residue, 9 ml of methylene chloride was added, and 3 ml of trifluoroacetic acid was added dropwise under ice cooling. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The obtained liquid was poured into a saturated aqueous sodium hydrogencarbonate solution, and methylene chloride was added thereto for extraction. Magnesium sulfate was added to the resulting methylene chloride layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1), and the target N- {2- [4- (2-chloro-6-fluorobenzyl) thiazole- 0.68 g of methyl 2-yl] -5-methylpyridin-4-yloxy} carbamate (yield 93%, melting point 175 to 177 ° C.) was obtained.

Example 9
Preparation of methyl N- {2- [4- (2-chloro-6-fluorobenzyl) thiazol-2-yl] -5-methylpyridin-4-yloxy} -N-acetoxymethylcarbamate N- {2- [4 0.36 g of methyl-(2-chloro-6-fluorobenzyl) thiazol-2-yl] -5-methylpyridin-4-yloxy} carbamate was dissolved in 15 ml of acetonitrile. To this, 1.22 g of potassium carbonate and 0.20 g of bromomethyl acetate were added and stirred at room temperature for 2 hours. The resulting solution was filtered and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent; benzene: ethyl acetate = 20: 1), and the desired N- {2- [4- (2-chloro-6-fluorobenzyl) thiazol-2-yl ] 0.32 g of methyl methyl-5-methylpyridin-4-yloxy} -N-acetoxymethylcarbamate (yield 76%, melting point 104-106 ° C.) was obtained.

(Example 10)
a) Preparation of 4-chloro-5-methyl-2- (1H-pyrazol-3-yl) pyridine 8 ml of dimethylformamide dimethylacetal was added to 2.49 g of 2-acetyl-4-chloro-5-methylpyridine for 18 hours. Heated to reflux. This was then concentrated under reduced pressure. The obtained crude product was dissolved in 20 ml of methanol. To this, 0.74 g of hydrazine hydrate was added and stirred at 50 ° C. for 6 hours. To this was added a saturated aqueous ammonium chloride solution, followed by extraction with ethyl acetate. The organic layer was dried over magnesium sulfate, filtered, and then the solvent was removed under reduced pressure. The obtained crystals were washed with hexane, and 2.56 g (yield 90%, melting point 98 to 101 ° C.) of the desired 4-chloro-5-methyl-2- (1H-pyrazol-3-yl) pyridine was obtained. Obtained.

b) Preparation of 4-chloro-2- [1- (2-chloro-6-fluorobenzyl) -1H-pyrazol-3-yl] -5-methylpyridine 4-chloro-5-methyl-2- (1H- 0.70 g of pyrazol-3-yl) pyridine was dissolved in 20 ml of DMF. Under ice cooling, 0.19 g of sodium hydride and 0.77 g of 2-chloro-6-fluorobenzyl chloride were added thereto, and the mixture was stirred at room temperature for 3 hours. A saturated aqueous ammonium chloride solution was added to the obtained liquid, and then extracted with ethyl acetate. The obtained organic layer was washed 3 times with saturated brine. Magnesium sulfate was added to this, dried, filtered, and then the solvent was distilled off under reduced pressure. The obtained crystals were washed with hexane, and 0.97 g of the desired 4-chloro-2- [1- (2-chloro-6-fluorobenzyl) -1H-pyrazol-3-yl] -5-methylpyridine ( Yield 80%, melting point 118-120 ° C.).

c) Preparation of t-butyl N- {2- [1- (2-chloro-6-fluorobenzyl) -1H-pyrazol-3-yl] -5-methylpyridin-4-yloxy} carbamate 4-chloro- 2- [1- (2-Chloro-6-fluorobenzyl) -1H-pyrazol-3-yl] -5-methylpyridine (0.78 g) and N-Boc-hydroxylamine (3.20 g) were dissolved in 30 ml of dimethyl sulfoxide. To the solution, 3.20 g of potassium hydroxide was added and stirred at 50 ° C. for 15 hours. After returning to room temperature, the solution was poured into ice water and then extracted with ethyl acetate. The obtained organic layer was washed with water three times. Magnesium sulfate was added and dried, filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 3: 1) to obtain the target N- {2- [1- (2-chloro-6-fluorobenzyl) -1H. -Pyrazol-3-yl] -5-methylpyridin-4-yloxy} carbamate t-butyl 0.24 g (yield 24%) was obtained.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.41 (s, 1H), 8.40 (s, 1H), 7.88 (s, 1H), 7.48 (d, 1H) , 7.31 to 7.25 (m, 2H), 7.15 (dd, 1H), 6.75 (d, 1H), 5.60 (s, 2H), 2.35 (s, 3H), 1.50 (s, 9H)

(Example 11)
Preparation of methyl N- {2- [1- (2-chloro-6-fluorobenzyl) -1H-pyrazol-3-yl] -5-methylpyridin-4-yloxy} carbamate N- {2- [1- 0.24 g of (2-chloro-6-fluorobenzyl) -1H-pyrazol-3-yl] -5-methylpyridin-4-yloxy} carbamate was dissolved in 20 ml of methylene chloride. To this, 0.11 g of triethylamine was added under ice cooling, and then 0.07 g of methyl chloroformate was added dropwise. It stirred for 1 hour after completion | finish of dripping. An aqueous ammonium chloride solution was added thereto, and the methylene chloride layer was separated. Magnesium sulfate was added to this, dried, filtered, and then the solvent was distilled off under reduced pressure.
To the obtained residue, 9 ml of methylene chloride was added, and 3 ml of trifluoroacetic acid was added dropwise under ice cooling. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The resulting liquid was poured into a saturated aqueous sodium hydrogen carbonate solution, and then extracted by adding methylene chloride. Magnesium sulfate was added to the resulting methylene chloride layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained crystals were washed with hexane, and the desired N- {2- [1- (2-chloro-6-fluorobenzyl) -1H-pyrazol-3-yl] -5-methylpyridin-4-yloxy} 0.22 g of methyl carbamate (yield 100%, melting point 152-155 ° C.) was obtained.

(Example 12)
a) Preparation of 6-acetyl-2-bromo-3-methylpyridine 1.26 g of 2-bromo-6-cyano-3-methylpyridine was dissolved in 100 ml of THF under a nitrogen atmosphere. To this, 4.5 ml of methylmagnesium iodide (3.0 mol / L) was added dropwise at -78 ° C. After completion of dropping, the mixture was stirred at 0 ° C. for 3 hours. After completion of the reaction, an aqueous ammonium chloride solution was added at 0 ° C., followed by extraction with ethyl acetate. Magnesium sulfate was added to the obtained organic layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 1: 1) to obtain 0.88 g of the intended 6-acetyl-2-bromo-3-methylpyridine (yield 64%). )
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.90 (d, 1H), 7.64 (d, 1H), 2.69 (s, 3H), 2.47 (s, 3H)

b) Preparation of t-butyl N- (6-acetyl-3-methylpyridin-2-yloxy) carbamate To a solution of 1.48 g (26.3 mmol) of potassium hydroxide in dimethyl sulfoxide (20 ml), 6-acetyl-2 -1.88 g of bromo-3-methylpyridine and 1.52 g of N-Boc-hydroxylamine were added, and the mixture was stirred at room temperature for 24 hours. The resulting solution was poured into ice water and then extracted with ethyl acetate. The obtained organic layer was washed with water three times. Magnesium sulfate was added and dried, filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1), and the target N- (6-acetyl-3-methylpyridin-2-yloxy) carbamic acid t- 0.75 g (36% yield) of butyl was obtained.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.20 (s, 1H), 7.71 (d, 1H), 7.61 (d, 1H), 2.64 (s, 3H) , 2.38 (s, 3H), 1.48 (s, 9H)

c) Preparation of methyl N- (6-acetyl-3-methylpyridin-2-yloxy) carbamate 0.75 g of N- (6-acetyl-3-methylpyridin-2-yloxy) carbamate 0.75 g of methylene chloride Dissolved in 10 ml. To this, 0.67 ml of triethylamine was added under ice cooling, and then 0.32 ml of methyl chloroformate was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 24 hours. The resulting solution was poured into ice water and then extracted with ethyl acetate. Magnesium sulfate was added to the obtained organic layer, dried and filtered, and then the solvent was distilled off under reduced pressure.
To the obtained residue, 10 ml of methylene chloride was added, and 3.3 ml of trifluoroacetic acid was added dropwise under ice cooling. After completion of dropping, the mixture was stirred at 0 ° C. for 4 hours. Ethyl acetate and aqueous sodium hydroxide solution (4 mol / l) were added to the resulting liquid to adjust the pH to about 10. It was then extracted with ethyl acetate. Magnesium sulfate was added to the obtained organic layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 1: 1) to obtain the desired methyl N- (6-acetyl-3-methylpyridin-2-yloxy) carbamate. Obtained .44 g (61% yield).
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.33 (bs, 1H), 7.71 (d, 1H), 7.62 (d, 1H), 3.83 (s, 3H) 2.61 (s, 3H), 2.38 (s, 3H)

d) Preparation of methyl N- [6- (1-{[1- (6-bromopyridin-2-yl) ethylidene] hydrazono} ethyl) -3-methylpyridin-2-yloxy] carbamate 2-acetyl-6 -0.40 g of bromopyridine was dissolved in 10 ml of methanol. To this solution, 0.15 ml of hydrazine hydrate was added and stirred at 50 ° C. Water was added to this at room temperature, followed by extraction with ethyl acetate. Magnesium sulfate was added to the obtained organic layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was dissolved in 10 ml of 1,4-dioxane. To this solution was added 0.22 g of methyl N- (6-acetyl-3-methylpyridin-2-yloxy) carbamate, an excess amount of anhydrous sodium sulfate and a catalytic amount of p-toluenesulfonic acid monohydrate. For 10 minutes. The obtained liquid was poured into a saturated aqueous sodium hydrogen carbonate solution, and then extracted by adding ethyl acetate. Magnesium sulfate was added to the obtained organic layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by NH gel column chromatography (developing solvent; hexane: ethyl acetate = 3: 1), and the desired N- [6- (1-{[1- (6-bromopyridine-2] -Il) ethylidene] hydrazono} ethyl) -3-methylpyridin-2-yloxy] carbamate 0.12 g (yield 32%, melting point 136-140 ° C.).

(Example 13)
a) Preparation of t-butyl N- (4-acetylpyridin-2-yloxy) carbamate To a solution of 5.41 g (96.4 mmol) of potassium hydroxide in dimethyl sulfoxide (80 ml), 4-acetyl-2-chloropyridine 5 0.000 g and N-Boc-hydroxylamine 5.57 g were added and stirred at room temperature for 24 hours. The resulting solution was poured into saturated aqueous ammonium chloride and then extracted with ethyl acetate. The obtained organic layer was washed with water three times. Magnesium sulfate was added to this, dried, filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 1: 1) to obtain 5.92 g of the target t-butyl N- (4-acetylpyridin-2-yloxy) carbamate. (Yield 73%) was obtained.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.33 (d, 1H), 8.25 (bs, 1H), 7.46 (dd, 1H), 7.41-7.40 ( m, 1H), 2.61 (s, 3H), 1.49 (s, 9H)

b) Production of methyl N- (4-acetylpyridin-2-yloxy) carbamate 5.92 g of t-butyl N- (4-acetylpyridin-2-yloxy) carbamate was dissolved in 100 ml of methylene chloride. To this was added 5.0 ml of triethylamine under ice cooling, and then 2.4 ml of methyl chloroformate was added dropwise. After completion of dropping, the mixture was stirred at 0 ° C. for 3 hours. The resulting solution was poured into ice water and then extracted with ethyl acetate. Magnesium sulfate was added to the obtained organic layer, dried and filtered, and then the solvent was distilled off under reduced pressure.
100 ml of methylene chloride was added to the resulting residue, and 15 ml of trifluoroacetic acid was added dropwise under ice cooling. After completion of dropping, the mixture was stirred at room temperature for 2 hours. The resulting liquid was poured into a saturated aqueous sodium hydrogen carbonate solution, and then extracted by adding methylene chloride. Magnesium sulfate was added to the resulting methylene chloride layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; benzene: ethyl acetate = 5: 1), and 2.19 g of the target methyl N- (4-acetylpyridin-2-yloxy) carbamate was obtained. 44%).
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.44 (bs, 1H), 8.33 (d, 1H), 7.48 (d, 1H), 7.42 (bs, 1H) , 3.82 (s, 3H), 2.62 (s, 3H)

c) Preparation of methyl N- {4- [1- (2-trifluoromethylbenzyloxyimino) ethyl] pyridin-2-yloxy} carbamate Methyl N- (4-acetylpyridin-2-yloxy) carbamate 23 g was dissolved in 10 ml of methanol. To this was added 0.21 g of O- (2-trifluoromethylbenzyl) hydroxylamine hydrochloride, and the mixture was stirred at 50 ° C. for 1 hour. To this was added ethyl acetate and then washed with saturated aqueous sodium bicarbonate. The organic layer was dried over magnesium sulfate, filtered, and then the solvent was removed under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; benzene: ethyl acetate = 5: 1), and the desired N- {4- [1- (2-trifluoromethylbenzyloxyimino) ethyl] 0.29 g (yield 76%) of methyl pyridin-2-yloxy} carbamate was obtained.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.46 (s, 1H), 8.12 (d, 1H), 7.68 (d, 1H), 7.60 to 7.53 ( m, 2H), 7.44-7.39 (m, 1H), 7.32 (d, 1H), 7.16 (s, 1H), 5.47 (s, 2H), 3.81 (s) , 3H), 2.26 (s, 3H)

(Example 14)
Preparation of methyl N- {4- [1- (6-chloropyridin-2-ylmethoxyimino) ethyl] pyridin-2-yloxy} carbamate Methyl N- (4-acetylpyridin-2-yloxy) carbamate 23 g was dissolved in 10 ml of 1,2-dichloroethane. To this were added 0.25 g of O- (6-chloropyridin-2-ylmethyl) hydroxylamine hydrochloride and 1 ml of trifluoroacetic acid, and the mixture was stirred at 50 ° C. for 1 hour. To this was added ethyl acetate and then washed with saturated aqueous sodium bicarbonate. The organic layer was dried over magnesium sulfate, filtered, and then the solvent was removed under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; benzene: ethyl acetate = 5: 1) to obtain the target N- {4- [1- (6-chloropyridin-2-ylmethoxyimino). 0.46 g (82% yield) of methyl] ethyl] pyridin-2-yloxy} carbamate was obtained.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.50 (s, 1H), 8.13 (d, 1H), 7.66 (t, 1H), 7.32 to 7.24 ( m, 3H), 7.16 (s, 1H), 5.34 (s, 2H), 3.81 (s, 3H), 2.29 (s, 3H)

(Examples of compounds)
Other examples of the nitrogen-containing heteroaryl derivative of the present invention obtained by the same method as the production method as described above are shown in Tables 1 to 5 including the compounds obtained in the above Examples. In the table, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, tBu represents a tertiary butyl group, Ac represents an acetyl group, Bn represents a benzyl group, Ph represents a phenyl group, c -Pr represents a cyclopropyl group, c-Pen represents a cyclopentyl group, and c-Hex represents a cyclohexyl group. Table 1 is a compound represented by the formula (1-a), Table 2 is a compound represented by the formula (1-b), Table 3 is a compound represented by the formula (2-a), and Table 4 is a formula (2- 2-b), Table 5 is a compound represented by formula (3-a), Table 6 is a compound represented by formula (3-b), and Table 7 is a formula (4-a). Table 8 shows compounds represented by formula (4-b).

Further, physical properties such as ¹ H-NMR were measured for the compounds shown in the above table. Some of them are shown below.
Compound No. 4-a-13: ¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.36 (s, 1H), 7.87 to 7.82 (m, 2H), 7.62 ( s, 1H), 7.53 (s, 1H), 7.46 (t, 3H), 7.26-7.24 (m, 1H), 2.27 (s, 3H), 1.53 (s , 9H); Viscous Oil

Compound of number 1-a-13: ¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.27 (s, 1H), 7.80 (s, 1H), 7.76 (s, 1H) 7.47 (d, 1H), 7.25-7.12 (m, 3H), 5.36 (t, 1H), 3.86 (s, 3H), 2.92-2.73 (m , 2H), 2.28 to 2.17 (m, 1H), 2.28 (s, 3H), 2.23 (s, 3H), 2.04 to 1.95 (m, 2H), 1. 85 to 1.74 (m, 1H); Amorphous

Compound of number 1-a-11: ¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.23 (s, 1H), 7.97 (bs, 1H), 7.61 (s, 1H) , 7.57 (t, 1H), 7.16 (d, 1H), 7.02 (d, 1H), 5.47 (q, 1H), 3.81 (s, 3H), 2.82 ( q, 1H), 2.39 (s, 3H), 2.20 (s, 3H), 1.63 (d, 3H), 1.30 (t, 3H); Viscous Oil

Compound No. 1-a-24: ¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.26 (s, 1H), 7.57 (t, 1H), 7.44 (s, 1H) 7.16 (d, 1H), 7.03 (d, 1H), 5.63 (s, 2H), 5.47 (q, 1H), 3.82 (s, 3H), 2.82 ( q, 2H), 2.40 (s, 3H), 2.25 (s, 3H), 2.01 (s, 3H), 1.64 (d, 3H), 1.30 (t, 3H); Viscous Oil

Compound number 1-a-4: melting point 110-111 ° C.
Compound number 1-a-5: melting point 109-111 ° C.
Compound number 1-a-6: melting point 101-103 ° C.
Compound number 1-a-7: melting point 144-146 ° C.
Compound number 1-a-8: melting point 133-134 ° C.
Compound number 1-a-9: melting point 77-78 ° C.
Compound number 1-a-10: melting point 135-137 ° C.
Compound number 1-a-12: melting point 149-150 ° C.
Compound number 1-a-21: melting point 91-93 ° C.
Compound number 1-a-22: melting point 99-100 ° C.
Compound number 1-a-23: melting point 66-68 ° C.
Compound number 1-b-4: Amorphous
Compound number 1-b-11: Amorphous
Compound No. 2-a-7: melting point 172-174 ° C.
Compound No. 2-b-7: melting point 142-144 ° C.
Compound No. 2-b-10: melting point 101-103 ° C.
Compound No. 2-b-18: melting point 136-140 ° C.
Compound No. 3-a-1: Melting point 120-121 ° C.
Compound No. 3-a-20: melting point 166-167 ° C.
Compound No. 4-a-4: melting point 130-132 ° C.
Compound No. 4-a-16: melting point 175-177 ° C.
Compound No. 4-a-23: melting point 140-143 ° C.
Compound No. 4-a-26: Melting point: 152-155 ° C.

  Next, formulation examples of the bactericide of the present invention will be shown slightly. However, additives and addition ratios are not limited to these examples, and can be changed in a wide range. Moreover, the part in a formulation Example shows a weight part.

Formulation Example 1 wettable powder Compound of the present invention 40 parts Clay 48 parts Dioctylsulfosuccinate sodium salt 4 parts Lignin sulfonic acid sodium salt 8 parts The above is uniformly mixed and finely pulverized, and a wettable powder with 40% active ingredient. Get.

Formulation Example 2 Emulsion Compound of the present invention 10 parts Solvesso 200 53 parts Cyclohexanone 26 parts Calcium dodecylbenzenesulfonate 1 part Polyoxyethylene alkylallyl ether 10 parts The above components are mixed and dissolved to obtain an emulsion containing 10% active ingredient.

Formulation Example 3 Powder The present compound 10 parts Clay 90 parts The above is uniformly mixed and finely pulverized to obtain a powder of 10% active ingredient.

Formulation Example 4 Granules Compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctylsulfosuccinate sodium salt 1 part Potassium phosphate 1 part After pulverizing and mixing well, adding water and kneading well, granulation drying As a result, granules containing 5% of the active ingredient are obtained.

Formulation Example 5 Suspension Compound of the present invention 10 parts Polyoxyethylene alkyl allyl ether 4 parts Polycarboxylic acid sodium salt 2 parts Glycerin 10 parts Xanthan gum 0.2 parts Water 73.8 parts The above is mixed and the particle size is 3 microns or less The suspension is wet-pulverized until a suspension of 10% active ingredient is obtained.

Formulation Example 6 Granule wettable powder Compound of the present invention 40 parts Clay 36 parts Potassium chloride 10 parts Alkylbenzenesulfonic acid sodium salt 1 part Ligninsulfonic acid sodium salt 8 parts Formaldehyde condensate of alkylbenzenesulfonic acid sodium salt
Mix 5 parts or more uniformly and pulverize finely, add an appropriate amount of water and knead to make clay. The clay-like product is granulated and then dried to obtain a granule wettable powder containing 40% of the active ingredient.

Test examples of the fungicide of the present invention obtained as described above are shown below.
(Test example 1) Apple black spot disease control test An emulsion of the compound of the present invention was sprayed at a concentration of 100 ppm of the active ingredient on apple seedlings (variety "Kunimitsu", 3-4 leaf stage) cultivated in an unglazed pot. After natural drying at room temperature, conidia of Venturia inaequalis were inoculated, and the light and darkness was repeated every 12 hours, and kept in a room of high humidity at 20 ° C. for 2 weeks. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
1-a-4, 1-a-5, 1-a-6, 1-a-7, 1-a-8, 1-a-9, 1-a-10, 1-a-11, 1 -A-12, 1-a-13, 1-a-21, 1-a-22, 1-a-23, 1-a-24, 1-b-4, 2-a-7, 2-b When the compounds of -7, 2-b-10, 2-b-18, 3-a-1, 4-a-4, 4-a-16, and 4-a-23 were examined, all of them were 75. The control value of% or more was shown.

(Test Example 2) Wheat powdery mildew control test The wettable powder of the compound of the present invention was sprayed at a concentration of 100 ppm on wheat seedlings (variety “Chihoku”, 1.0-1.2 leaf stage) cultivated in an unglazed pot. After the leaves were air-dried, conidia spores of wheat powdery mildew (Erysiphe graminis f.sp.tritici) were shaken off and inoculated in a greenhouse at 22 to 25 ° C. for 7 days. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
1-a-4, 1-a-5, 1-a-6, 1-a-9, 1-a-10, 1-a-11, 1-a-13, 1-a-21, 1 When the compounds -a-23, 1-a-24, and 4-a-13 were examined, all showed a control value of 75% or more.

(Test Example 3) Wheat red rust control test A wheat seedling (cultivar “Noribayashi No. 61”, 1.0-1.2 leaves) cultivated in an unglazed pot was sprayed with a wettable powder of the compound of the present invention at a concentration of 100 ppm. . After the leaves were air-dried, summer spores of wheat rust (Puccinia recondita) were shaken off and inoculated in a greenhouse at 22 to 25 ° C. for 10 days. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
1-a-4, 1-a-5, 1-a-6, 1-a-8, 1-a-9, 1-a-11, 1-a-13, 1-a-21, 1 When the compounds -a-23, 1-a-24, 2-a-7, 4-a-4, and 4-a-16 were examined, all showed a control value of 75% or more.

  From the above, the nitrogen-containing heteroaryl derivative of the present invention, its salt, or N-oxide is a novel compound, and can be produced industrially advantageously, and the active ingredient of an agricultural and horticultural fungicide that can be used safely and effectively. It turns out that it is useful.

Claims (3)

A nitrogen-containing heteroaryl derivative represented by the formula (1), a salt thereof or an N-oxide.

(1)
In [Equation (1), R ¹ is a C1~6 alkyl group having unsubstituted or substituted.

R ² is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, Formula: COR ²¹ (wherein R ²¹ is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, An unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted C2-6 alkynyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted group; A C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted heteroaryl group. A group represented by the formula: CO ₂ R ²² (wherein, R ²² has the unsubstituted or C1~6 alkyl group having a substituent, C2-6 alkenyl groups having an unsubstituted or substituted, unsubstituted or substituted A 2-6 alkynyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, Or an unsubstituted or substituted heteroaryl group.) Or a group represented by the formula: CON (R ²¹ ) ₂ (wherein R ²¹ has the same meaning as above; R ²¹ is the same or They may be different.).

A ¹ is an oxygen atom, a sulfur atom, or a formula: NR ³ (wherein R ³ is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 2- 6 alkenyl groups, unsubstituted or substituted C2-6 alkynyl groups, unsubstituted or substituted C3-8 cycloalkyl groups, unsubstituted or substituted C4-8 cycloalkenyl groups, unsubstituted Or a C6-10 aryl group having a substituent or an unsubstituted or substituted heteroaryl group.

A ² is an oxygen atom, Formula: NR ⁴ (wherein R ⁴ is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, or Formula: COR ²¹ , Formula: CO ₂ R ²² , or A group represented by the formula: CON (R ²¹ ) ₂ (wherein R ²¹ and R ²² have the same meaning as described above. R ²¹ may be the same or different). A group represented by the formula: CR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently a hydrogen atom, an unsubstituted or substituted C ^1-6 alkyl group or a halogen atom). Group.

J is an oxygen atom or a sulfur atom.

X is Cl to 6 alkyl groups having an unsubstituted or substituted group of the formula: OR ²³ (wherein, R ²³ represents a hydrogen atom, Cl to 6 alkyl groups having an unsubstituted or substituted, unsubstituted or Substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 A cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted heteroaryl group, or a formula: COR ²¹ , a formula: CO ₂ R ²² , or a formula: CON (R ²¹ ) ₂ (wherein R ²¹ and R ²² have the same meanings as described above. R ²¹ may be the same or different.)), A group represented by the formula: SR ^{twenty three} Or a group represented by the formula: N (R ²³ ) ₂ (wherein R ²³ has the same meaning as above. R ²³ may be the same or different), a cyano group, a nitro group, or a halogen Is an atom.

n represents the number of X and is an integer of 0-3. When n is 2 or more, Xs may be the same or different.

B ^{1 to} B ⁴ are each independently a nitrogen atom or a carbon atom.
However, all of B ^{1 to} B ³ are not nitrogen atoms, and all of B ^{1 to} B ⁴ are not carbon atoms.

D is any group represented by Formula (2) to Formula (5).

(In the formulas (2) to (5), Q ¹ represents an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted group. A C2-6 alkynyl group having an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl A group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted heteroaralkyl group, or a trisubstituted silyl group.

In the formula (2), R ⁷ is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 2-6 alkenyl group, an unsubstituted or substituted C 2 An -6 alkynyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or It is an unsubstituted or substituted heteroaryl group.

In formula (3), R ⁸ is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 2-6 alkenyl group, an unsubstituted or substituted C 2 -6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 cycloalkenyl group, unsubstituted or substituted C6-10 aryl group, none A substituted or substituted C7-12 aralkyl group, an unsubstituted or substituted heteroaryl group, or an unsubstituted or substituted heteroaralkyl group.

In formula (3), R ⁹ is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 2-6 alkenyl group, an unsubstituted or substituted C 2 -6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 cycloalkenyl group, unsubstituted or substituted C6-10 aryl group, none A substituted or substituted C7-12 aralkyl group, an unsubstituted or substituted heteroaryl group, or an unsubstituted or substituted heteroaralkyl group.

In formula (5), Q ⁴¹ is a C6-10 aryl group or heteroaryl group.

In formula (5), Q ² is represented by formula: OR ²³ , formula: SR ²³ , formula: N (R ²³ ) ₂ , formula: COR ²¹ , formula: CO ₂ R ²² , formula: CON (R ²¹ ) ₂ , Or the formula: SO ₂ R ²² (wherein R ²¹ , R ²² and R ²³ have the same meaning as above. R ²¹ may be the same or different. R ²³ may be the same or different.) Or a cyano group, a nitro group, or a halogen atom.

m1 represents the number of Q ¹ and is an integer of 0 to 7.
m2 represents the number of Q ² and is an integer of 0 to 7.
However, the sum of m1 and m2 is 7 or less.
When m1 is 2 or more, Q ¹ may be the same or different. When m2 is 2 or more, Q ² may be the same or different. Further, Q ¹ , Q ² , or Q ¹ and Q ² that are adjacently substituted on Q ⁴¹ may be bonded to each other to form a 5- to 8-membered ring. )] The nitrogen-containing heteroaryl derivative of Claim 1 represented by Formula (6), its salt, or N-oxide.

(In the formula (6), R ¹ , R ² , A ¹ , A ² , J, X, n, and D have the same meaning as described above.)   An agricultural and horticultural fungicide containing, as an active ingredient, at least one of the nitrogen-containing heteroaryl derivative according to claim 1 or 2, a salt thereof or N-oxide.