WO2010137302A1

WO2010137302A1 - Nitrogen-containing heteroaryl derivatives and fungicides for agricultural and horticultural use

Info

Publication number: WO2010137302A1
Application number: PCT/JP2010/003500
Authority: WO
Inventors: 古川裕紀; 清水一彌; ▲桑▼原頼人; 荻野智和; 大沢陽子
Original assignee: 日本曹達株式会社
Priority date: 2009-05-27
Filing date: 2010-05-25
Publication date: 2010-12-02
Also published as: JP2012162460A

Abstract

Disclosed are nitrogen-containing heteroaryl derivatives represented by formula (1), salts and N-oxides thereof, and fungicides for agricultural and horticultural use which contain at least one of these compounds as the active ingredient. In formula (1), R¹ represents an optionally substituted C_1-6 alkyl group; R² represents a hydrogen atom or a group such as an optionally substituted C_1-6 alkyl group; A¹ and A² represent an oxygen atom or the like; J represents an oxygen atom or the like; X represents an optionally substituted C_1-6 alkyl group, a halogen atom or the like; n, which stands for the number of X's, represents an integer of 0 to 3, provided that when n is 2 or greater, X's may be either the same or different; B¹ to B⁴ independently represent a nitrogen atom or a carbon atom, provided that all of B¹ to B³ are not nitrogen atoms at the same time and all of B¹ to B⁴ are not carbon atoms at the same time; and D represents a group represented by formula (2), formula (3) or the like [in formulae (2) and (3), Q¹ represents an optionally substituted C_6-10 aryl group or the like; and R⁷ and R⁸ represent a hydrogen atom, an optionally substituted C_1-6 alkyl group or the like].

Description

Nitrogen-containing heteroaryl derivatives and agricultural and horticultural fungicides

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.
This application claims priority based on Japanese Patent Application No. 2009-127375 filed in Japan on May 27, 2009, the contents of which are incorporated herein by reference.

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.

(In the formula (A), X ″ is a halogen atom, a C1-C6 alkyl group, etc., n is an integer from 0 to 4, R ^a1 is a C1-C6 alkyl group, R ^a2 is a hydrogen atom, C1 ~ a C6 alkyl group, a R ^a3 hydrogen atom or C1-C6 alkyl group, G is an oxygen atom, a sulfur atom, etc., Y "is hydrogen, C1-C10 alkyl group, C2-C10 alkenyl group 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.

(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.

[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 also 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.

(In the 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, where R ^c5 -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 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 Gs 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.

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

(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).

(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 represent A hydrogen atom, X is an oxygen atom or a sulfur atom, k is 0 or an integer of 1 to 3)]

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

(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 which is substituted with a C1-5 haloalkoxy group or the like, and may be 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 Japanese Patent Laid-Open No. 2004-166863 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 An object of the present invention is 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, its salt, 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.

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

In the formula (1), R ¹ is an unsubstituted or substituted C1-6 alkyl group.
In formula (1), R ² is a hydrogen atom, C1 ~ 6 alkyl group having an unsubstituted or substituted group of the formula: COR ²¹ (wherein, R ²¹ has a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, A substituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted heteroaryl group. formula: CO ₂ R ²² (wherein, R ²² is, C1 ~ 6 alkyl group having an unsubstituted or substituted group, C2 ~ 6 alkenyl groups having an unsubstituted or substituted, unsubstituted or location 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 An 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 described above; R ²¹ May be the same or different.

In the formula (1), 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 C1-6 alkyl group, an 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.

In Formula (1), A ² is an oxygen atom, Formula: NR ⁴ (wherein R ⁴ is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, 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 meanings as described above, and R ²¹ may be the same or different). Or 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) It is a group represented by.

In formula (1), J is an oxygen atom or a sulfur atom.

In formula (1), X, C1 ~ 6 alkyl group having an unsubstituted or substituted group of the formula: OR ²³ (wherein, R ²³ represents a hydrogen atom, C1 ~ 6 alkyl having unsubstituted or substituted Group, unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted A C4-8 cycloalkenyl group having a group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted heteroaryl group, a formula: COR ²¹ , a formula: CO ₂ R ²² , or a formula : CON (R ²¹ ) ₂ (in the formula, R ²¹ and R ²² have the same meanings as described above. R ²¹ may be the same or different.) Formula: SR ²³ ^{_{Formula: N (R 23) 2 (}} . Wherein, R ²³ is .R ²³ is the same meaning as above, which may be the same or different) a group represented by a cyano group, a nitro group or a halogen atom, is there.
In the formula (1), n represents the number of X and is an integer from 0 to 3. When n is 2 or more, Xs may be the same or different.

In formula (1), B ¹ to B ⁴ are each independently a nitrogen atom or a carbon atom.
However, B ¹ to B ³ are not all nitrogen atoms, and B ¹ to B ⁴ are not all carbon atoms.

In the formula (1), D is any group represented by the formulas (2) to (6).

In the formulas (2) to (6), 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.

In formula (2), formula (3), and formula (6), R ⁷ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an 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 cycloalkenyl group, unsubstituted or A C6-10 aryl group having a substituent, or an unsubstituted or substituted heteroaryl group.

In formulas (3) and (6), R ⁸ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted group Or a substituted C2-6 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 unsubstituted or substituted heteroaryl group. R ⁸ may further be bonded to a carbon atom on Q ¹ or a nitrogen atom.

In the formula (5), Q ⁴¹ is a C6-10 aryl group or a 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 , Formula: SO ₂ R ²² (wherein R ²¹ , R ²² , and R ²³ have the same meaning as described above. R ²¹ may be the same or different. R ²³ may be the same or different. ) Group, a cyano group, a nitro group, or a halogen atom.

In formula (5), m1 represents the number of Q ¹ and is an integer of 0 to 7.
In the formula (5), 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 second aspect of the present invention is a nitrogen-containing heteroaryl derivative represented by the formula (7), a salt thereof, or an N-oxide.

In the formula (7), R ¹ , R ² , A ¹ , A ² , J, X, n, and D have the same meaning as in the formula (1).

The third aspect of the present invention is a nitrogen-containing heteroaryl derivative represented by the formula (8), a salt thereof, or an N-oxide.

In formula (8), R ¹ , R ² , A ¹ , A ² , J, X, n, R ⁷ , and Q ¹ have the same meaning as in formula (1).

Fourthly, 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 N-oxide. That is, it is an agricultural and horticultural fungicide containing at least one of the nitrogen-containing heteroaryl derivative represented by the formula (1), a salt thereof, or N-oxide as an active ingredient. Preferably, it is an agricultural and horticultural fungicide containing as an active ingredient at least one of a nitrogen-containing heteroaryl derivative represented by the formula (7), a salt thereof, or an N-oxide. More preferred is an agricultural and horticultural fungicide containing as an active ingredient at least one of a nitrogen-containing heteroaryl derivative represented by the formula (8), a salt thereof, or an N-oxide.

The fifth aspect of the present invention is a production intermediate used for the production of the nitrogen-containing heteroaryl derivative of the present invention, a salt thereof, or N-oxide. That is, it is a nitrogen-containing heteroaryl derivative represented by the formula (9).

In the formula (9), R ¹ is an unsubstituted or substituted C1-6 alkyl group.
In the formula (9), R ² is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, a formula: COR ²¹ (wherein R ²¹ has a hydrogen atom, an unsubstituted or substituted group) C1-6 alkyl group, unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, A substituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted heteroaryl group. formula: CO ₂ R ²² (wherein, R ²² is, C1 ~ 6 alkyl group having an unsubstituted or substituted group, C2 ~ 6 alkenyl groups having an unsubstituted or substituted, unsubstituted or location 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 An 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 described above; R ²¹ May be the same or different.

In the formula (9), 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 C1-6 alkyl group, an 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.

In Formula (9), A ² is an oxygen atom, Formula: NR ⁴ (wherein R ⁴ is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, 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 meanings as described above, and R ²¹ may be the same or different). Or 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) It is a group represented by.

In formula (9), J is an oxygen atom or a sulfur atom.

Wherein (9), X is C1 ~ 6 alkyl group having an unsubstituted or substituted group of the formula: OR ²³ (wherein, R ²³ represents a hydrogen atom, C1 ~ 6 alkyl having unsubstituted or substituted Group, unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted A C4-8 cycloalkenyl group having a group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted heteroaryl group, a formula: COR ²¹ , a formula: CO ₂ R ²² , or a formula : CON (R ²¹ ) ₂ (in the formula, R ²¹ and R ²² have the same meanings as described above. R ²¹ may be the same or different.) Formula: SR ²³ ^{_{Formula: N (R 23) 2 (}} . Wherein, R ²³ is .R ²³ is the same meaning as above, which may be the same or different) a group represented by a cyano group, a nitro group or a halogen atom, is there.
In the formula (9), n represents the number of X and is an integer of 0 to 3. When n is 2 or more, Xs may be the same or different.

In formula (9), B ¹ to B ⁴ are each independently a nitrogen atom or a carbon atom.
However, B ¹ to B ³ are not all nitrogen atoms, and B ¹ to B ⁴ are not all carbon atoms.

In the formula (9), R ⁷ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted C2 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.

A preferred production intermediate is a nitrogen-containing heteroaryl derivative represented by the formula (10), a salt thereof, or N-oxide.

In formula (10), R ¹ , R ² , A ¹ , A ² , J, X, n, and R ⁷ have the same meaning as in formula (9).

The sixth aspect of the present invention is a production intermediate used for the production of the nitrogen-containing heteroaryl derivative of the present invention, a salt thereof, or N-oxide. That is, it is a nitrogen-containing heteroaryl derivative represented by the formula (11).

In the formula (11), R ¹ is an unsubstituted or substituted C1-6 alkyl group.
In the formula (11), R ² is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, a formula: COR ²¹ (wherein R ²¹ has a hydrogen atom, an unsubstituted or substituted group) C1-6 alkyl group, unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, A substituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted heteroaryl group. formula: CO ₂ R ²² (wherein, R ²² is, C1 ~ 6 alkyl group having an unsubstituted or substituted group, C2 ~ 6 alkenyl groups having an unsubstituted or substituted, unsubstituted or A substituted C2-6 alkynyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6 ~ Or a group represented by the formula: CON (R ²¹ ) ₂ (wherein R ²¹ has the same meaning as described above). ²¹ may be the same or different.)

In the formula (11), 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 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.

In Formula (11), A ² is an oxygen atom, Formula: NR ⁴ (wherein R ⁴ is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, 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 meanings as described above, and R ²¹ may be the same or different). Or 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) It is a group represented by.

In formula (11), J is an oxygen atom or a sulfur atom.

Wherein (11), X is C1 ~ 6 alkyl group having an unsubstituted or substituted group of the formula: OR ²³ (wherein, R ²³ represents a hydrogen atom, C1 ~ 6 alkyl having unsubstituted or substituted Group, unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted A C4-8 cycloalkenyl group having a group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted heteroaryl group, a formula: COR ²¹ , a formula: CO ₂ R ²² , or a formula : CON (R ²¹ ) ₂ (in the formula, R ²¹ and R ²² have the same meanings as described above. R ²¹ may be the same or different.) Formula: SR ²³ ^{_{Formula: N (R 23) 2 (}} . Wherein, R ²³ is .R ²³ is as defined above, which may be the same or different) a group represented by a cyano group, a nitro group or a halogen atom, It is.
In the formula (11), n represents the number of X and is an integer from 0 to 3. When n is 2 or more, Xs may be the same or different.

In formula (11), B ¹ to B ⁴ are each independently a nitrogen atom or a carbon atom.
However, B ¹ to B ³ are not all nitrogen atoms, and B ¹ to B ⁴ are not all carbon atoms.

In the formula (11), R ⁷ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted C2 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 (11), each R ⁹ is independently a hydrogen atom or a group represented by the formula: COR ²¹ (wherein R ²¹ has the same meaning as described above). R ⁹ may be the same or different. R ⁹ may be together.

A preferred production intermediate is a nitrogen-containing heteroaryl derivative represented by the formula (12), a salt thereof, or N-oxide.

In formula (12), R ¹ , R ² , A ¹ , A ² , J, X, n, R ⁷ , and R ⁹ have the same meaning as in formula (11).

The nitrogen-containing heteroaryl derivative of the present invention, a salt thereof, or N-oxide is a novel compound, and can be produced industrially advantageously, and is useful as an active ingredient in agricultural and horticultural fungicides that can be used safely and reliably. 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).

[Substituent]
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.

As a group that can be a “substituent”,
A C1-6 alkyl group, a halogen-substituted C1-6 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, a heteroaryl group;
Formula: COR ^31, wherein: CO ₂ R ^31, wherein: CON (R ³¹⁾ _2, wherein: SO ₂ R ³¹ (wherein, R ³¹ each independently represent a hydrogen atom, C1 ~ 6 alkyl group, C2 ~ A 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);
Formula: OR ³² , Formula: SR ³² , Formula: N (R ³² ) ₂ (wherein R ³² independently represents a hydrogen atom, a C1-6 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, a heteroaryl group, a group represented by the formula: COR ³¹ , a group represented by the formula: CO ₂ R ³¹ , or a formula: A group represented by CON (R ³¹ ) ₂ );
Oxo group, thio group, formula: = NR ³³ (wherein R ³³ is a hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C3-8 cycloalkyl group, a C4-8) A 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 linear or branched.
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, Examples include isopentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, isohexyl group and the like.

A halogen-substituted C1-6 alkyl group is a C1-6 alkyl group substituted with 1-13 halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Specifically, fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2,2,2-trifluoro Ethyl 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, 2,4,6-trichlorohexyl group and the like can be mentioned.

A C2-6 alkenyl group is an aliphatic hydrocarbon group having from 2 to 6 carbon atoms and having at least one carbon-carbon double bond. The C2-6 alkenyl group may be a straight chain or a branched chain.
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- Examples thereof include a butenyl group and a 2-methyl-2-butenyl group.

A C2-6 alkynyl group is an aliphatic hydrocarbon group having from 2 to 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 saturated alicyclic ring, an unsaturated alicyclic ring, or an aromatic ring.
Specific examples include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and the like. In addition, 1,2,3,4-tetrahydro-naphthalen-1-yl group, 1,2,3,4-tetrahydro-naphthalen-2-yl group, 5,6,7,8-tetrahydro-naphthalene-1- And tetralinyl groups such as an yl group and a 5,6,7,8-tetrahydro-naphthalen-2-yl group.

The heteroaryl group is a 5- to 10-membered aryl group containing 1 to 4 heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom in addition to carbon atoms as atoms constituting the ring. In this case, it may be a single ring or a polycyclic ring condensed.
Specific examples of the heteroaryl group include the following groups.
(1) 5-membered heteroaryl group pyrrolyl group such as pyrrol-1-yl group, pyrrol-2-yl group and pyrrol-3-yl group;
Furyl groups such as a furan-2-yl group and a furan-3-yl group;
Thienyl groups such as a thiophen-2-yl group and a thiophen-3-yl group;
Imidazolyl groups such as imidazol-1-yl group, imidazol-2-yl group, imidazol-4-yl group, imidazol-5-yl group;
Pyrazolyl groups such as a pyrazol-1-yl group, a pyrazol-3-yl group, a pyrazol-4-yl group, a pyrazol-5-yl group;
An oxazolyl group such as an oxazol-2-yl group, an oxazol-4-yl group, an oxazol-5-yl group;
Isoxazolyl groups such as isoxazol-3-yl group, isoxazol-4-yl group and isoxazol-5-yl group;
Thiazolyl groups such as thiazol-2-yl group, thiazol-4-yl group, thiazol-5-yl group;
Isothiazolyl groups such as isothiazol-3-yl group, isothiazol-4-yl group, isothiazol-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 A triazolyl group such as a group, 1,2,4-triazol-3-yl group, 1,2,4-triazol-5-yl group;
Oxadiazolyl groups such as 1,2,4-oxadiazol-3-yl group, 1,2,4-oxadiazol-5-yl group, 1,3,4-oxadiazol-2-yl group;
Thiadiazolyl groups such as 1,2,4-thiadiazol-3-yl group, 1,2,4-thiadiazol-5-yl group, 1,3,4-thiadiazol-2-yl group;
Tetrazolyl groups such as a tetrazol-1-yl group and a tetrazol-2-yl group;

(2) pyridyl groups such as a 6-membered heteroaryl group pyridin-2-yl group, pyridin-3-yl group and pyridin-4-yl group;
Pyrazinyl groups such as a pyrazin-2-yl group and a pyrazin-3-yl group;
Pyrimidyl groups such as a pyrimidin-2-yl group, a pyrimidin-4-yl group, and a pyrimidin-5-yl group;
Pyridazinyl groups such as a pyridazin-3-yl group and a pyridazin-4-yl group;
A triazinyl group;

(3) Heteroaryl group of fused ring 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, benzothiophen-3-yl group, benzothiophen-4-yl group, benzothiophen-5-yl group, benzothiophen-6-yl group, benzothiophen-7-yl group;
Benzimidazol-1-yl group, benzimidazol-2-yl group, benzimidazol-4-yl group, benzimidazol-5-yl group, benzooxazol-2-yl group, benzooxazol-4-yl group, benzoxazole -5-yl group, benzothiazol-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;

(4) Heteroaryl group having an oxo 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, chromen-2-yl, chromen-3-yl, chromen-4-yl, chromen-5-yl, chromen-6-yl, chromen-7-yl A chromen-8-yl group.

Examples of the group represented by the formula: COR ³¹ 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 propioyl group; arylcarbonyl groups such as benzoyl group and naphthylcarbonyl group; pyridin-2-yl Examples thereof include heteroarylcarbonyl groups such as carbonyl group and 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, Examples thereof include a benzyloxycarbonyl group and a 2-pyridylmethyloxycarbonyl group.

Examples of the group represented by the formula: CON (R ³¹ ) ₂ include a mono C1-6 alkylcarbamoyl group such as a carbamoyl group, a methylcarbamoyl group, and an ethylcarbamoyl group; a vinylcarbamoyl group, a 1-propenylcarbamoyl group, 1- Mono-C2-6 alkenylcarbamoyl groups such as hexenylcarbamoyl group; mono-C2-6 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 Groups, mono C6-10 arylcarbamoyl groups 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; and 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, s-butoxy, t-butoxy, 1-ethylpropoxy, isohexyloxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 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 A C1-6 alkoxy group such as 1-ethylbutoxy group, 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 groups such as 2-butenyloxy group; ethynyloxy group, propynyloxy group, propargyloxy group, 1-butynyloxy group, 2-butynyloxy group, 3-butynyloxy group, 1-pentynyloxy group, 2-pentynyl group 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- A C4-8 cycloalkenyloxy group such as an enyloxy group; a C6-10 aryloxy group such as a phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group; pyridine-2-yloxy group, pyridine-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, C1 ~ 6 alkylsulfanyl group such as n- hexylsulfanyl group; vinyl sulfanyl group, 1-propenyl Nils Alpha group, 1 A C2-6 alkenylsulfanyl group such as a hexenylsulfanyl group; a C2-6 alkynylsulfanyl group such as an ethynylsulfanyl group, a propynylsulfanyl group, a propargylsulfanyl group; 8 cycloalkylsulfanyl groups; C4-8 cycloalkenylsulfanyl groups such as cyclobut-2-enylsulfanyl groups and cyclohex-2-enylsulfanyl groups; phenylsulfanyl groups C6-10 arylsulfanyl groups such as 1-naphthylsulfanyl group, 2-naphthylsulfanyl group; pyridin-2-ylsulfanyl group, pyridin-3-ylsulfanyl group, pyridin-4-ylsulfanyl group, pyrazin-2-ylsulfanyl Groups, heteroarylsulfanyl groups such as pyrimidin-2-ylsulfanyl group; C1-7 acylsulfanyl groups 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 C1-6 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, cyclohex-2-enylamino group; mono C6-10 such as phenylamino group, 1-naphthylamino group, etc. 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.

Examples of the group represented by the formula: = NR ³³ include C1-6 alkylimino groups such as methylimino group and ethylimino group; C2-6 alkenylimino groups such as vinylimino group and 1-propenylimino group; ethynylimino group and the like A C2-6 alkynylimino group, a cyclopropylimino group, a C3-8 cycloalkylimino group such as a cyclobutylimino group, a C4-8 cycloalkenylimino group such as a cyclobut-2-enylimino group, a phenylimino group, a 1-naphthylimino group C6-10 arylimino groups such as pyridine groups; heteroarylimino groups such as pyridine-2-ylimino group, pyridine-3-ylimino group, pyridine-4-ylimino group, pyrazine-2-ylimino group, pyrimidine-2-ylimino group ; Hydroxyimino group; methoxyimino group, ethoxyimino group C1-6 alkoxyimino groups such as: C6-10 arylimino groups such as phenoxyimino groups; heteroarylimino groups such as pyridin-2-yloxyimino groups; C1-7 acyloxy groups such as acetyloxyimino groups and benzoyloxyimino groups Imino groups; C1-7 carboxyoxyimino groups such as methoxycarbonyloxyimino group, ethoxycarbonyloxyimino group, t-butoxycarbonyloxyimino group, and the like.

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

[R ¹ ]
R ¹ in the formula (1) is an unsubstituted or substituted C1-6 alkyl group. The “C1-6 alkyl group” serving as a mother nucleus is as described above (hereinafter the same for R ² to R ⁸ , R ²¹ to R ²³ , X, and Q ¹ ).
Suitable groups that can be a substituent of the C1-6 alkyl group include a halogen atom, a group represented by the formula: OR ³² , a 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, 2,4,6-trichlorohexyl group and other halogen-substituted C1-6 alkyl groups; hydroxymethyl group, hydroxy Hydroxy C1-6 alkyl groups such as ethyl and hydroxypropyl; methoxy Til, ethoxymethyl, methoxyethyl, ethoxyethyl, methoxy n-propyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, i-propoxyethyl, s-butoxymethyl, t-butoxy C1-6 alkoxy C1-6 alkyl groups 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 Thiophen-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, Such as 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; and the like.

Of these, R ¹ is preferably an unsubstituted C1-6 alkyl 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 .
Suitable groups that can be a substituent of the C1-6 alkyl group include a halogen atom, a group represented by the formula: COR ³¹ , a group represented by the formula: OR ³² , a C6-10 aryl group, and a heteroaryl group. Can be mentioned.
Examples of the C1-6 alkyl group having a substituent include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxy n-propyl group, an ethoxymethyl group, an ethoxyethyl group, an n-propoxymethyl group, a C1-6 alkoxy C1-6 alkyl group such as i-propoxyethyl group, s-butoxymethyl group, t-butoxyethyl group, 1,2-dimethoxyethyl group, 2,2-dimethoxyethyl group; formyloxymethyl group, And C1-7 acyloxy C1-6 alkyl groups such as an acetoxymethyl group, 2-acetoxyethyl group, propionyloxymethyl group, propionyloxyethyl group, and the like.

R ²¹ represents 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, 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 (hereinafter the same in R ³ , R ⁷ , R ⁸ , R ²² , R ²³ , and Q ¹ ).
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, for example, 3-chloro-2-propenyl group, 4-chloro-2-butenyl group, 4,4-dichloro-3-butenyl group, 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 (hereinafter the same for R ³ , R ⁷ , R ⁸ , R ²² , R ²³ , and Q ¹ ).
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, etc. An alkynyl group etc. can be mentioned.

An unsubstituted or substituted C3-8 cycloalkyl group has a “C3-8 cycloalkyl group” as a mother nucleus. The “C3-8 cycloalkyl group” serving as a mother nucleus is as described above (hereinafter the same for R ³ , R ⁷ , R ⁸ , R ²² , R ²³ , and Q ¹ ).

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 (hereinafter the same for R ³ , R ⁷ , R ⁸ , R ²² , R ²³ , and Q ¹ ).

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 (hereinafter the same for R ³ , R ⁷ , R ⁸ , R ²² , R ²³ , and Q ⁴¹ ).

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 (hereinafter the same in R ³ , R ⁷ , R ⁸ , R ²² , R ²³ , and Q ⁴¹ ).

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 propioloyl group; arylcarbonyl groups such as benzoyl group and naphthylcarbonyl group; 2-pyridylcarbonyl group A heteroarylcarbonyl group 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, And 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 And 2-pyridylmethyloxycarbonyl group.

In the formula: CON (R ²¹ ) ₂ , R ²¹ has the same meaning 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, ethylcarbamoyl group; vinylcarbamoyl group, 1-propenylcarbamoyl group, 1- Mono-C2-6 alkenylcarbamoyl groups such as hexenylcarbamoyl group; mono-C2-6 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 Groups, mono C6-10 arylcarbamoyl groups 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; and a disubstituted carbamoyl group such as a dimethylcarbamoyl group, a diethylcarbamoyl group, and a methyl-phenyl-carbamoyl group.

Of these, R ² is preferably 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 C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted C2-6 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 the 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 C1-6 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 formula (1) is an unsubstituted or substituted C1-6 alkyl group, formula: a group represented by OR ²³ , formula: a group represented by SR ²³ , 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 from 0 to 3. When n is 2 or more, Xs may be the same or different.

R ²³ represents 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, 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 methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, i-propoxy, and 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, 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 groups such as 2-butenyloxy group; ethynyloxy group, propynyloxy group, propargyloxy group, 1-butynyloxy group, 2-butynyloxy group, 3-butynyloxy group, 1-pentynyloxy group, 2-pentynyl group Nyloxy, 3-pentynyloxy, 4-pentynyloxy, 1-hex Sinyloxy, 1-methyl-2-propynyloxy, 2-methyl-3-butynyloxy, 1-methyl-2-butynyloxy, 2-methyl-3-pentynyloxy, 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; 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 group 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 Examples thereof include a fluoromethoxy group, a 1-fluoroethoxy group, a 1,1-difluoroethoxy group, a 2,2,2-trifluoroethoxy group, and a pentafluoroethoxy group.

Formula: The group represented by SR ^23, for example, methylsulfanyl group, ethylsulfanyl group, C1 ~ 6 alkylsulfanyl group such as n- hexylsulfanyl group; vinyl sulfanyl group, 1-propenyl Nils Alpha group, 1-hexenyl sulfanyl C2-6 alkenylsulfanyl groups such as ethynylsulfanyl groups, C2-6 alkynylsulfanyl groups such as ethynylsulfanyl group, propynylsulfanyl group, 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 group such as sulfanyl group, 2-naphthylsulfanyl group; pyridin-2-ylsulfanyl group, pyridin-3-ylsulfanyl group, pyridin-4-ylsulfanyl group, pyrazin-2-ylsulfanyl group, pyrimidine A heteroarylsulfanyl group such as -2-ylsulfanyl group; a C1-7 acylsulfanyl group 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. A carbamoylsulfanyl group; a mono-carbamoylsulfanyl group such as a carbamoylsulfanyl group, a methylcarbamoylsulfanyl group, an ethylcarbamoylsulfanyl group, a dimethylcarbamoylsulfanyl group, a diethylcarbamoylsulfanyl group, or a phenylcarbamoylsulfanyl group; it can.

Examples of the group represented by the formula: N (R ²³ ) ₂ include mono C1-6 alkylamino groups such as a methylamino group, an ethylmethyl group, and an n-hexylamino group; a vinylamino group, a 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, cyclohex-2-enylamino group; mono C6-10 such as phenylamino group, 1-naphthylamino group, etc. 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, 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.

Of these, X is preferably an unsubstituted or substituted C1-6 alkyl group or a halogen atom. A suitable group that can be a substituent is a halogen atom.

[B ¹ to B ⁴ ]
B ¹ to B ⁴ are each independently a nitrogen atom or a carbon atom. However, B ¹ to B ³ are not all nitrogen atoms, and B ¹ to B ⁴ are not all carbon atoms. As a combination mode of B ¹ to B ⁴ , for example, structures of the formulas (A-1) to (A-6) (structures below the double and X is omitted). Things can be mentioned.
The structure represented by the formula (A-1) is a structure in which B ¹ , B ² , B ³ , and B ⁴ are each composed of a nitrogen atom, a carbon atom, a carbon atom, and a carbon atom. In addition, the structure represented by the formula (A-4) is a structure in which B ¹ , B ² , B ³ , and B ⁴ are each composed of a carbon atom, a carbon atom, a nitrogen atom, and a carbon atom. The structure represented by the formula (A-5) is a structure in which B ¹ , B ² , B ³ , and B ⁴ are each composed of a carbon atom, a carbon atom, a carbon atom, and a nitrogen atom. Of these structures, the structure of the formula (A-1) is preferable.

[D]
D is any group represented by the formulas (2) to (6).

The carbon nitrogen double bond in the formula (2) represents any of geometric isomers (E / Z isomers) or a mixture thereof.
Each of the two carbon nitrogen double bonds in the formula (3) represents one of geometric isomers (E / Z isomer) or a mixture thereof.
The carbon nitrogen double bond in the formula (6) represents any of geometric isomers (E / Z isomers) or a mixture thereof.

In the formulas (2) to (6), 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 trimethylsilyl group, triethylsilyl group, tricyclopropylsilyl group, t-butyldimethylsilyl group and the like.

Preferred Q ¹ in the formula (2) is an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted aralkyl group, or an unsubstituted or substituted heteroaralkyl group. .

An aralkyl group is a C1-6 alkyl group substituted with a C6-10 aryl group.
Specific examples include a benzyl group, a phenethyl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group.

The heteroaralkyl group is a C1-6 alkyl group substituted with a heteroaryl group.

The C1-6 alkyl group substituted with a heteroaryl group is a C1-6 alkyl group substituted with a 5-membered nitrogen-containing heteroaryl group, or a C1-6 substituted with a 6-membered nitrogen-containing heteroaryl group. Alkyl groups are preferred.
Specifically, pyridyl C1-6 alkyl groups such as pyridin-2-ylmethyl group, pyridin-3-ylmethyl group, pyridin-4-ylmethyl group; pyrazol-1-ylmethyl group, pyrazol-3-ylmethyl group, pyrazole- And a pyrazolyl C1-6 alkyl group of a 4-ylmethyl group.

A suitable group that can be a substituent of the aralkyl group or heteroaralkyl group is a C1-6 alkyl group, a halogen-substituted C1-6 alkyl group, or a halogen atom.

Preferred Q ¹ in the 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, an unsubstituted or substituted pyridyl group, and the like. A preferred group that can be a substituent of the aryl group or heteroaryl group is a halogen atom.

Preferred Q ¹ in the formula (4) is an unsubstituted or substituted C1-6 alkyl group.

Preferred Q ¹ in formula (5) is an aralkyl group which is unsubstituted or has a substituent (particularly preferably a C6-10 aryl-substituted C1-6 alkyl group which is unsubstituted or has a substituent) or an 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 pyridylmethyl group, and the like. A preferred group that can be a substituent of the aralkyl group or heteroaralkyl group is a C1-6 alkyl group, a halogen-substituted C1-6 alkyl group, or a halogen atom.

R ⁷ in formula (2), formula (3), and formula (6) is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an 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 cycloalkenyl group, unsubstituted or A C6-10 aryl group having a substituent, or an unsubstituted or substituted heteroaryl group. Preferred R ⁷ is a C1-6 alkyl group.

In formula (3), each R ⁸ independently represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted. A C2-6 alkynyl group having a group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 An aryl group, or an unsubstituted or substituted heteroaryl group. R ⁸ may further be bonded to a carbon atom on Q ¹ or a nitrogen atom. Preferred R ⁸ is a C1-6 alkyl group.

In formula (5), Q ⁴¹ is a C6-10 aryl group or heteroaryl group.
In the aryl group or heteroaryl 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.
A preferred 5-membered heteroaryl group is a 5-membered nitrogen-containing heteroaryl group.
Specifically, pyrazolyl groups such as pyrazol-1-yl group, pyrazol-3-yl group, pyrazol-4-yl group; thiazol-2-yl group, thiazol-4-yl group, thiazol-5-yl group And the like.

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, and a benzenesulfonyl group.

m1 represents the number of Q ¹ and is an integer from 0 to 7. m2 represents the number of Q ^2, is any integer of 0-7. 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.

The nitrogen-containing heteroaryl derivative of the present invention is preferably a compound represented by the formula (7). More preferably, it is a compound represented by Formula (8).

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 agricultural and 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 N-oxides include compounds in which any nitrogen in the partial structures represented by the above formulas (A-1) to (A-6) 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 the formula (B-2) (hereinafter sometimes referred to as “compound (B-2)”) and a ketone compound represented by the formula (B-1) (hereinafter referred to as “compound”). (B-1) ”) may be reacted.

(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 amount of the catalyst to be used is generally 0.0001-1 mol per 1 mol of compound (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 solvents.
The amount of the solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of compound (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) Compound (B-2) can be produced according to a conventionally known method for producing an 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). . This is reacted with Nt-butoxycarbonylhydroxylamine in the presence of a base to give an oxyamine compound represented by the formula (B-2-3) (hereinafter referred to as “compound (B-2-3)”). There are things.) Compound (B-2) can be obtained by reacting this with an acid.

(In the formula, 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) to the compound are added in the same reaction system. Conversion to (B-2) and synthesis of compound (B-3) from compound (B-2) and compound (B-1) produced 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, It can be produced by reaction.

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

First, a dihalogeno compound represented by the formula (C-1) (hereinafter sometimes referred to as “compound (C-1)”) is added to the compound represented by the formula (C-2) in the presence of a base ( Hereinafter, by reacting with “compound (C-2)”), 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 compound (C-2) used for the reaction with compound (C-1) is usually 0.8 to 5 mol, preferably 1 to 3 mol, relative to 1 mol of compound (C-1). .

Examples of the base used for the reaction between the compound (C-1) and the compound (C-2) include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide; 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 And 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;
The amount of the organic solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of compound (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 in the reaction between the compound (C-3) and the compound (C-4) include organolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, and lithium diisopropylamide; sodium metal, 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 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)), R ¹ is a t-butyl group, R ² is a hydrogen atom, and A ¹ and J are oxygen atoms (hereinafter referred to as “compound (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 ′} .

(Wherein 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 compound (B-1-1: (A ² ═O)) is added to a halogenoformate compound represented by the formula (B-1-2) in the presence of a base (hereinafter referred to as “ester compound (B-1)”. -2) ”) and a compound represented by the formula (B-1-3: (A ² ═O)) (hereinafter“ compound (B-1-3: (A ²⁾ = O)) ". Next, an acid is allowed to act on the compound, whereby a compound represented by the formula (B-1-4: (A ² ═O)) (hereinafter referred to as “compound (B-1-4: (A ² ═O))”) Can be obtained.)

Examples of the base used for the reaction of 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 hydroxide such as calcium hydroxide; metal alkoxide 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 is generally 1 to 20 mol per 1 mol of compound (B-1-1: (A ² ═O)).

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 to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of the compound (B-1-1: (A ² ═O)).
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)) into the compound (B-1-4: (A ² ═O)) include inorganic substances 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 to be used is generally 1 to 20 mol per 1 mol of compound (B-1-3: (A ² ═O)).
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. Examples of the solvent that can be used in the reaction of the compound (B-1-1: (A ² ═O)) and the ester compound (B-1-2) are the same as those listed.
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, it can be produced by reacting a hydrazine compound represented by formula (B-5) (hereinafter sometimes referred to as “compound (B-5)”) with compound (B-1). it can.
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-5).

(In the formula, R ¹ , R ² , R ⁷ , R ⁸ , 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-1) 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 amount of the catalyst to be used is generally 0.0001-1 mol per 1 mol of compound (B-5).
Further, 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 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.
The amount of the solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of compound (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.

(Wherein R ⁸ and Q ¹ have the same meaning as described above.)

(III) When D in Formula (1) is Formula (4) and A ² is O a) Compound represented by Formula (B-9: (A ² ═O)) (hereinafter referred to as “compound”) (B-9: (A ² ═O)) ”is sometimes referred to as a halogeno compound represented by the formula (D-1) (hereinafter, referred to as“ compound (D-1) ”). To the compound (C-2) in the presence of a base.

(In the formula, R ¹ , R ² , A ¹ , J, 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.)

As a method of reacting compound (D-1) and compound (C-2), the same method as the method of reacting compound (C-1) and 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 amount of the acetylene compound (D-1-1) to be used is generally 1 to 2 mol per 1 mol of the compound (C-1).

(In the formula, X, n, B ¹ to B ⁴ , and Q ¹ have the same meanings as described above. E ⁶ represents 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 amount of the Pd complex to be used is generally 0.01-0.5 mol per 1 mol of compound (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 amount of copper halide to be used is generally 0.1-1 mol per 1 mol of compound (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.
The amount of the organic solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of compound (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: (A ² ═O)) (hereinafter “compound” (B-12: (A ² ═O)) ”is sometimes referred to as a halogeno compound represented by the formula (E-1) (hereinafter referred to as“ compound (E-1) ”). To the compound (C-2) in the presence of a base.
As a method of reacting compound (E-1) and compound (C-2), the same method as the method of reacting compound (C-1) and compound (C-2) can be used.

(Wherein 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 -1-1) ”. 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.

(Wherein, 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 amount of the Pd catalyst to be used is generally 0.01-0.5 mol per 1 mol of compound (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).

The reaction temperature should be a temperature that is 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.

(V) When D in Formula (1) is Formula (6) a) The compound represented by formula (B-13) (hereinafter sometimes referred to as “compound (B-13)”) is: For example, an oxyamine compound represented by formula (B-14) (hereinafter sometimes referred to as “compound (B-14)”) and a ketone compound represented by formula (F-1) (hereinafter referred to as “compound”). (F-1) ”) may be reacted.

The amount of compound (B-14) to be used is generally 0.5 to 2 mol, preferably 0.7 to 1.5 mol, per 1 mol of compound (F-1).
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 amount of the catalyst to be used is generally 0.0001-1 mol per 1 mol of compound (F-1).
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 solvents.
The amount of the solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of compound (B-14).

b) Among compounds (B-14), a compound in which A ² is O (hereinafter sometimes referred to as “compound (B-14: (A ² ═O))”) is, for example, It can be produced by reaction.

(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 ⁷ is a chlorine atom or a bromine atom.)

First, the compound (B-1: (A ² ═O)) is reduced to a hydroxyl group using a known hydride reducing agent, and then halogenated using a halogenating agent. A compound represented by the formula (B-14-1: (A ² ═O)) (hereinafter sometimes referred to as “compound (B-14-1: (A ² ═O))”) can be obtained. it can.

Examples of the hydride reducing agent used in the reduction reaction include sodium borohydride, sodium cyanoborohydride, lithium triethylborohydride, lithium tri (sec-butyl) borohydride, potassium tri (sec-butyl) borohydride, hydrogen Examples thereof include lithium borohydride, zinc borohydride, sodium acetoxyborohydride, lithium aluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, and the like.
The amount of the hydride reducing agent used for the reduction reaction is usually 0.25 to 2 mol per 1 mol of the compound (B-1: (A ² ═O)).

The reduction reaction can be 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, 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 a mixed solvent composed of two or more of these solvents; and the like.
The amount of the organic solvent used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of the raw material.
The reduction reaction proceeds smoothly in the temperature range from −20 ° C. to the boiling point of the solvent used.

Examples of the halogenating agent used in the halogenation reaction include oxalyl halide, thionyl halide, a mixed reagent of carbon tetrabromide and triphenylphosphine;
The amount of the halogenating agent used in the halogenation reaction is usually 0.8 to 5 mol, preferably 1 to 3 mol, relative to 1 mol of the raw material.

The halogenation reaction can be 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, 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 a mixed solvent composed of two or more of these solvents; and the like.
The amount of the organic solvent used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of the raw material. The halogenation reaction proceeds smoothly in a temperature range from room temperature to the boiling point of the solvent used.

c) Next, the compound (B-14-1: (A ² ═O)) is reacted with N-hydroxyphthalimide in the presence of a base to obtain a compound of formula (B-14-2: (A ² ═O)). ) (Hereinafter sometimes referred to as “compound (B-14-2: (A ² ═O))”).

Examples of the base used in the reaction include alkali metals such as metal sodium and metal potassium; metal hydrides such as sodium hydride, potassium hydride and calcium hydride;
The amount of N-hydroxyphthalimide to be used is usually 1 to 5 mol with respect to 1 mol of the compound (B-14-1: (A ² ═O)). The amount of the base used is usually 1 to 20 mol with respect to 1 mol of the compound (B-14-1: (A ² ═O)).

The reaction of the compound (B-14-1: (A ² ═O)) and N-hydroxyphthalimide can be carried out in an organic solvent. The solvent 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 used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of the raw material. The reaction proceeds smoothly in a temperature range from −20 ° C. to the boiling point of the solvent used.

d) Next, the target compound (B-14: (A ² = O)) is obtained by deprotecting the phthaloyl group from the compound (B-14-2: (A ² = O)). Can do. Deprotection is performed by a known method. For example, the method of adding hydrazines is mentioned.

The amount of hydrazine to be used is usually 1 to 10 mol per 1 mol of compound (B-14-2: (A ² ═O)).

The deprotection reaction of compound (B-14-2: (A ² ═O)) is 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, 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 to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of the compound (B-14-2: (A ² ═O)).
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.

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 agricultural and horticulturally acceptable salt. For example, salts of inorganic acids such as hydrochloric acid and sulfuric acid; salts of organic acids such as acetic acid and lactic acid;
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, column chromatography and the like.
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) Production Intermediate Next, the production intermediate used for producing the nitrogen-containing heteroaryl derivative of the present invention, a salt thereof, or N-oxide will be described.
The nitrogen-containing heteroaryl derivative represented by the formula (9) is a compound represented by the above formula (1), wherein D represents a compound represented by the formula (2) or the formula (3). Useful production intermediate. In the formula (9), R ¹ , R ² , A ¹ , A ² , J, X, n, and R ⁷ have the same meaning as described above. The production intermediate is preferably a compound represented by the formula (10).

The nitrogen-containing heteroaryl derivative represented by the formula (11) is a compound represented by the above formula (1), wherein D is a production intermediate useful for the production of the compound represented by the formula (6) It is. In the formula (11), R ¹ , R ² , A ¹ , A ² , J, X, n, and R ⁷ have the same meaning as described above.
R ⁹ are each independently hydrogen atom or the formula,: COR ²¹ (wherein, R ²¹ is as defined above.) Is a group represented by. R ⁹ may be the same or different. R ⁹ may be together.
Examples of R ⁹ include formyl group, acetyl group, methoxycarbonyl group and the like.
Examples of R ^{9 taken} together include a phthaloyl group.
The production intermediate is preferably a compound represented by the formula (12).

5) Agricultural and horticultural fungicide The agricultural and horticultural fungicide of the present invention contains at least one of a nitrogen-containing heteroaryl derivative represented by the above formula (1), a salt thereof, or an N-oxide thereof as an active ingredient. It is an agricultural and horticultural fungicide (hereinafter sometimes referred to as “the present invention fungicide”).

The fungicide of the present invention is used for 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 (Cercospora beticola)
Black root disease (Aphanomyces cochlloides)
Root rot (Thanatephorus cucumeris)
Leaf rot (Thanatephorus cucumeris)
Peanut Brown Spot (Mycosphaerella arachidis)
Black astringency (Mycosphaerella berkeleyi)
Cucumber powdery mildew (Sphaerotheca fuliginea)
Downy mildew (Pseudoperonospora cubensis)
Vine Blight (Mycosphaerella melonis)
Vine split disease (Fusarium oxysporum)
Sclerotinia sclerotiorum
Gray mold (Botrytis cinerea)
Anthracnose (Colletotrichum orbiculare)
Black star disease (Cladosporium cucumerinum)
Brown spot disease (Corynespora cassicola)
Seedling blight (Pythium debaryanam, Rhizoctonia solani Kuhn)
Spotted bacterial disease (Pseudomonas syringae pv. Lecrymans)
Tomato gray mold (Botrytis cinerea)
Leaf mold (Cladosporium fulvum)
Plague (Phytophthora infestans)
Eggplant gray mold (Botrytis cinerea)
Black blight (Corynespora melongenae)
Powdery mildew (Erysiphe cichoracearum)
Susmolder disease (Mycovellosiella nattrassii)
Strawberry Gray mold disease (Botrytis cinerea)
Powdery mildew (Sohaerotheca humuli)
Anthracnose (Colletotrichum acutatum, Colletotrichum fragariae)
Plague (Phytophthora cactorum)
Onion Gray rot (Botrytis allii)
Gray mold (Botrytis cinerea)
Botrytis squamosa
Downy mildew (Peronospora destructor)
Cabbage root-knot disease (Plasmodiophora brassicae)
Soft rot (Erwinia carotovora)
Downy mildew (Peronospora parasitica)
Kidney sclerotia (Sclerotinia sclerotiorum)
Gray mold (Botrytis cinerea)

Apple powdery mildew (Podosphaera leucotricha)
Black star disease (Venturia inaequalis)
Monilinia mali
Sunspot disease (Mycosphaerella pomi)
Rot (Valsa mali)
Spotted leaf fall (Alternaria mali)
Red Star Disease (Gymnosporangium yamadae)
Ring-shaped disease (Botryosphaeria berengeriana)
Anthracnose (Glomerella cingulata, Colletotrichum acutatum)
Brown spot disease (Diplocarpon mali)
Soot spot disease (Zygophiala jamaicensis)
Soot spot (Gloeodes pomigena)
Oyster powdery mildew (Phyllactinia kakicola)
Anthracnose (Gloeosporium kaki)
Spotted leaf disease (Cercospora kaki)
Peach (Assassin Disease) (Monilinia fructicola)
Black star disease (Cladosporium carpophilum)
Homopsis spoilage (Phomopsis sp.)
Sweet cherry blight (Monilinia fructicola)
Grapes Gray mold (Botrytis cinerea)
Powdery mildew (Uncinula necator)
Late rot (Glomerella cingulata, Colletotrichum acutatum)
Downy mildew (Plasmopara viticola)
Black depression (Elsinoe ampelina)
Brown spot disease (Pseudocercospora vitis)
Black rot (Guignardia bidwellii)
Pear black star disease (Venturia nashicola)
Red Star Disease (Gymnosporangium asiaticum)
Black spot disease (Alternaria kikuchiana)
Ring-shaped disease (Botryosphaeria berengeriana)
Powdery mildew (Phyllactinia mali)
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)
Black spot disease (Diaporthe citri)
Sickness (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)
Eye disease (Pseudocercosporella herpotrichoides)
Leaf blight (Septoria tritici)
Dry blight (Leptosphaeria nodorum)
Snowy rot granule nuclear disease (Typhula incarnata)
Myriosclerotinia borealis
Blight disease (Gaeumanomyces graminis)
Barley Leafy spot disease (Pyrenophora graminea)
Cloud shape disease (Rhynchosporium secalis)
Bare Scab (Ustilago tritici, U.nuda)
Rice blast (Pyricularia oryzae)
Rhizoctonia solani
Idiot Seedling (Gibberella fujikuroi)
Sesame leaf blight (Cochliobolus niyabeanus)
Seedling blight (Pythium graminicolum)
White leaf blight (Xanthomonas oryzae)
Burkholderia plantarii
Brown stripe disease (Acidovorax avenae)
Burkholderia glumae
Tobacco sclerotia (Sclerotinia sclerotiorum)
Powdery mildew (Erysiphe cichoracearum)
Tulip gray mold (Botrytis cinerea)
Bentgrass Snow Rot Large Bacterial Nuclear Disease (Sclerotinia borealis)
Red fire (Pythium aphanidermatum)
Orchardgrass powdery mildew (Erysiphe graminis)
Soybean Purpura (Cercospora kikuchii)
Downy mildew (Peronospora Manshurica)
Phytophthora sojae
Potato and tomato plague (Phytophthora infestans)
It can be used for the control of etc.

Moreover, this fungicide has an excellent bactericidal effect against various resistant bacteria.
Such resistant bacteria include, for example, gray mold fungus (Botrytis cinerea), sugar beet brown fungus (Cercospora beticola), apple black rot (Venturia inaequalis), Examples include Venturia nashicola; Botrytis cinerea which is resistant to dicarboximide fungicides such as vinclozolin, procymidone and 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 fungicide of the present invention is a highly safe drug with little phytotoxicity, low toxicity to fish and warm-blooded animals.

When actually applying the fungicide of the present invention, it can be used without particularly adding other components to the compound of the present invention, and forms that can be taken by general agricultural chemicals, that is, wettable powder, granules, powders, It can also be used in the form of an emulsion, aqueous solvent, suspension, granule wettable powder or the like.

Additives and carriers used in formulation into 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 and clay 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-based 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 Acid salt, formaldehyde condensate of alkyl naphthalene sulfonate, isobutylene-maleic anhydride copolymer, and the like.

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., but is usually 1 to 1000 g in terms of the amount of active ingredient compound per hectare. It is 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 to 1000 ppm, preferably 10 to 250 ppm.

In addition to the compounds of the present invention, one or two or more of various fungicides, insecticides, acaricides and the like can be mixed with the fungicides of the present invention.

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

Fungicide:
1) benzimidazole series: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate methyl, etc .;
2) Dicarboximide type: Clozolinate, iprodione, procymidone, vinclozolin and the like;
3) DMI-bactericidal system: imazalyl, oxpoconazole, pefazoate, prochloraz, triflumizole, triphorin, pyrifenox, phenarimol, nuarimol, azaconazole, viteltanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxy Conazole, fenbuconazole, fluquinconazole, flusilazole, flutriaol, hexaconazole, imibenconazole, ipconazole, metconazole, microbutanyl, penconazole, propiconazole, prothioconazole, cimeconazole, tebuconazole, tetraconazole, triazimephone, tri Azimenol, triticonazole, etaconazole, farconazole cis and the like;
4) Phenylamide series: Benalaxyl, furaxyl, metalaxyl, metalaxyl-M, oxadixyl, oflase, etc .;
5) Amine-based: aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidine, piperalin, spiroxamine, etc .;
6) Phosphorothiolate system: EDDP, iprobenphos, pyrazophos, etc .;
7) Dithiolane type: isoprothiolane and the like;
8) Carboxamide: benodanyl, boscalid, carboxin, fenfuran, flutolanil, furamethopyl, mepronil, oxycarboxin, pentiopyrad, tifluzamide, etc .;
9) Hydroxy- (2-amino) pyrimidine series: bupyrimeto, dimethylolmol, ethylimol, etc .;
10) AP fungicide (anilinopyrimidine) type: cyprodinil, mepanipyrim, pyrimethanil, etc .;
11) N-phenyl carbamate type: dietofencarb and the like;
12) QoI-bactericidal (Qo inhibitor) system: azoxystrobin, picoxystrobin, pyraclostrobin, cresoxime-methyl, trifloxystrobin, dimoxystrobin, metminostrobin, orizastrobin, famoxadone , Fluoxastrobin, phenamidon, metminophen, etc .;
13) PP fungicide (phenylpyrrole) type: fenpiconyl, fludioxonil, etc .;
14) Quinoline series: quinoxyphene, etc .;
15) AH fungicide (aromatic hydrocarbon) series: biphenyl, chloronebu, dichlorane, kintozen, technazen, tortofos-methyl, etc .;
16) MBI-R series: fusaride, pyrokilone, tricyclazole, etc .;
17) MBI-D system: carpropamide, diclocimet, phenoxanyl, etc .;
18) SBI agent: Fenhexamide, Pyributicarb, Turbinafine, etc .;
19) Phenylurea: pencyclon, etc .;
20) QiI-bactericide (Qi inhibitor): cyazofamide and the like;
21) benzamide type: zoxamide and the like;
22) Enopyranuron series: blastcidin, mildiomycin, etc .;
23) Hexopyranosyl system: Kasugamycin and the like;
24) Glucopyranosyl: streptomycin, validamycin and the like;
25) Cyanoacetamide series: Simoxanyl and the like;
26) Carbamate series: idcarb, propamocarb, prothiocarb, polycarbamate, etc .;
27) Uncouplers: Vinapacryl, Zinocup, Ferimzone, Fluazinam, etc .;
28) Organotin compounds: triphenyltin acetate, triphenyltin chloride, triphenyltin hydroxide, etc .;
29) Phosphate ester: phosphorous acid, tolcrofosmethyl, fosetyl and the like;
30) Phthalamic acid type: Teclophthalam, etc .;
31) Benzotriazine series: triazoxide and the like;
32) Benzenesulfonamide series: fullsulfamide and the like;
33) Pyridazinone: Dichromedin and the like;
34) CAA disinfectant (carboxylic amide) type: dimethomorph, fulmorph, benchavaricarb, iprovaricarb, mandipropamide, etc .;
35) Tetracycline: oxytetracycline and the like;
36) Thiocarbamate type: metasulfocarb, etc.
37) Other compounds: etridiazole, polyoxin, oxolinic acid, hydroxyisoxazole, octinoline, silthiofam, diflumetrim, acibenzoral S methyl, probenazole, thiazinyl, ethaboxam, cyflufenamide, proquinazide, metolaphenone, fluopicolide, cupric hydroxide, organic copper , Sulfur, Farbum, Manzeb, Mannebu, Methylum, Propineb, Thiuram, Dinebu, Diram, Captan, Captahol, Folpet, Chlorothalonil, Diclofluuride, Tolylfluanid, Dodine, Guazatine, Iminocazine Acetate, Iminocazine Dodecylbenzenesulfonate , Anilazine, dithianone, chloropicrin, dazomet, metham sodium salt, quinomethionate, ciprofram, Chiofamu, Agrobacterium, Furuoruimido) and the like;

Insecticides, acaricides, nematicides, soil insecticides:
1) Organic (thio) phosphates: acephate, azamethiphos, azinephosmethyl, chlorpyrifos, chlorpyrifosmethyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfotone, ethion, EPN, phenamiphos, fenitrothion, fenthion, isoxathione, metathione, metaxamide, , Methidathion, methylparathion, mevinphos, monocrotophos, oxydemetonmethyl, paraoxon, parathion, phentoate, hosalon, phosmet, phosphamidone, folate, oxime, pirimiphosmethyl, propenophos, prothiophos, sulfophos, tetrachlorbinphos, terbufos, triazophos, trichlorphone, Phosphiazate, Phosphocarb, Kazusafos, Dis Photon, demeton -S - methyl, BRP, CYAP, ethoprophos, quinalphos, dimethyl bottle phosphite, vamidothion, pyraclofos;
2) Carbamate series: alanic carb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, phenoxycarb, phenothiocarb, methiocarb, mesomil, oxamyl, pirimicarb, propoxyl, thiodicarb, triazamate, etiofencarb, MPC, MPC MTMC, pyridafenthione, furthiocarb, XMC;
3) Pyrethroid: Allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha cypermethrin, beta cypermethrin, zetacypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropatoline, fenvalerate, imiprotorin, Lambda cihalothrin, permethrin, praretrin, pyrethrin I and II, resmethrin, silafluophene, taufluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimeflutrin, acrinathrin, cycloprotorin, halfenprox, flucitrinate;
4) Growth regulator:
a) Chitin synthesis inhibitors: chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, nobarulone, teflubenzuron, triflumuron;
Bistrifluron, nobiflumuron, buprofezin, diophenolane, hexythiazox, etoxazole, clofentadine;
b) ecdysone antagonists: halofenozide, methoxyphenozide, tebufenozide, azadirachtin;
Chromafenozide;
c) Juvenile hormone-like substances: pyriproxyfen, metoprene, phenoxycarb;
d) Lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
5) Nicotine receptor agonist / antagonist compounds: acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam;
6) GABA antagonist compounds: acetoprole, endosulfan, ethipyrrole, fipronil, vaniliprole, pyrafluprolol, pyriprol;
7) Macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad;
Ivermectin;
8) METI I compounds: phenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
9) METI II and III compounds: acequinosyl, fluacyprim, hydramethylnon;
10) Uncoupler compound: chlorfenapyr;
11) Oxidative phosphorylation inhibitor compounds: cyhexatin, diafenthiuron, phenbutatin oxide, propargite;
12) Molting compound: cyromazine;
13) Mixed function oxidase inhibitor compound: piperonyl butoxide;
14) Sodium channel blocker compounds: indoxacarb, metaflumizone;
15) Microbial pesticides: BT agents, entomopathogenic virus agents, entomopathogenic fungi agents, nematode pathogenic fungi agents;
16) Others: Benclothiaz, Bifenazate, Cartap, Flonicamid, Pyridalyl, Pymetrozine, Sulfur, Thiocyclam, Flubendiamide, Sienopyrafen, Flupirazophos, Cyflumethofene, Amidoflumet, Bensultap, Dicophor, Tetradiphone, Fenpyroximate, Amitraz, Chlordimetform, Triza Pyrimidifen, 1,3-dichloropropene, clofentezin, fluacrylpyrim, rotenone, DCIP, phenisobromolate, benzomate, metaldehyde, chlorantraniliprole spinetoram, pyrifluquinazone;

Plant growth regulator:
Abscisic acid, indole butyric acid, uniconazole, etiquelozate, etephone, cloxiphonac, chlormecote, chlorella extract, calcium peroxide, cyanamide, dichlorprop, gibberellin, daminozide, decyl alcohol, trinexapac ethyl, mepicoat chloride, pack Lobutrazole, paraffin wax, piperonyl butoxide, pyraflufenethyl, flurprimidol, prohydrojasmon, prohexadione calcium salt, benzylaminopurine, pendimethalin, forchlorphenuron, potassium maleate hydrazide, 1-naphthyl Acetamide, 4-CPA, MCPB, choline, oxyquinoline sulfate, ethiclozeate, butorualine, 1-methylcyclopropene, abiglycine hydrochloride.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

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 added 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 was added 3.81 g of dimethylacetamide, and the mixture was 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 (Compound No. 6-a-2)
To a solution obtained by dissolving 3.85 g of 2-acetyl-4-chloro-5-methylpyridine and 4.54 g of N-Boc-hydroxylamine in 50 ml of dimethyl sulfoxide, 4.50 g of potassium hydroxide was added, and the mixture was stirred at room temperature for 1 hour. Stir. 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 (Compound No. 6-a-1)
4.37 g of t-butyl N- (2-acetyl-5-methylpyridin-4-yloxy) carbamate was dissolved in 50 ml of methylene chloride. 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. To this was added an aqueous ammonium chloride solution 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, 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 hydrogen carbonate 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 (Compound No. 1-a-10)
0.25 g of methyl N- (2-acetyl-5-methylpyridin-4-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) to obtain the target N- {5-methyl-2- [1- (2-trifluoromethylbenzyloxy). 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 (Compound No. 2-b- 7)
0.35 g of methyl N- (2-acetyl-5-methylpyridin-4-yloxy) carbamate was dissolved in 10 ml of THF. To this solution was added 0.29 g of [1- (6-chloropyridin-2-yl) ethylidene] hydrazine, and the mixture was 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] There was obtained 0.35 g (yield 59%, melting point 172 ° -174 ° C.) of -yl) ethylidene] hydrazono} ethyl) -5-methylpyridin-4-yloxy] carbamate.

(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 was added 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, 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 obtain 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 (Compound No. 3-a-20)
To a solution of 0.85 g of 4-chloro-2- (3,3-dimethyl-1-butynyl) -5-methylpyridine and 2.60 g of N-Boc-hydroxylamine in 20 ml of dimethyl sulfoxide, potassium hydroxide was added. 2.60 g was added and 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 target N- [2- (3,3-dimethyl-1-butynyl) -5-methyl. 0.81 g (yield 65%, melting point 166-167 ° C.) of t-butyl pyridine-4-yloxy) carbamate was obtained.

Example 4
Production of methyl N- [2- (3,3-dimethyl-1-butynyl) -5-methylpyridin-4-yloxy] carbamate (Compound No. 3-a-1)
0.64 g of t-butyl N- [2- (3,3-dimethyl-1-butynyl) -5-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 hydrogen carbonate 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 target 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 (Compound No. 4-a-13)
To a solution of 0.51 g of 4-chloro-5-methyl-2- (3-trifluoromethoxyphenyl) 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 target N- [5-methyl-2- (3-trifluoromethoxyphenyl) pyridine-4. There was obtained 0.60 g (yield: 65%) of t-butyl carbamate.
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)
Production of methyl N- [5-methyl-2- (3-trifluoromethoxyphenyl) pyridin-4-yloxy] carbamate (Compound No. 4-a-4)
0.50 g of t-butyl N- [5-methyl-2- (3-trifluoromethoxyphenyl) pyridin-4-yloxy] 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. An aqueous ammonium chloride solution 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 with 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 to 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) to obtain 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 15 ml of DMF and 1.20 g of magnesium chloride hexahydrate were added to 0.94 g of sodium hydrosulfide, 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 desired 4-chloro-5-methylpyridine-2-thiocarboxamide.
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. A saturated aqueous sodium hydrogen carbonate solution was added thereto, and the mixture was extracted 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 (Compound No. 4-a- 23)
Dissolve 1.32 g of 4-chloro-2- [4- (2-chloro-6-fluorobenzyl) thiazol-2-yl] -5-methylpyridine and 1.48 g of N-Boc-hydroxylamine in 30 ml of dimethyl sulfoxide To the solution was added 1.47 g of potassium hydroxide, and the mixture was 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)
Production of methyl N- {2- [4- (2-chloro-6-fluorobenzyl) thiazol-2-yl] -5-methylpyridin-4-yloxy} carbamate (Compound No. 4-a-16)
0.80 g of t-butyl N- {2- [4- (2-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. To this was added an aqueous ammonium chloride solution 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, 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 hydrogen carbonate 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 (Compound No. 4-a- 19)
0.36 g of methyl N- {2- [4- (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 5-5-pyridin-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 dimethyl acetal 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 of the desired 4-chloro-5-methyl-2- (1H-pyrazol-3-yl) pyridine was obtained (yield 90%, melting point 98-101 ° C.). Obtained.

b) Preparation of 4-chloro-2- [1- (2-chloro-6-fluorobenzyl) -1H-pyrazol-3-yl] -5-methylpyridine 4-chloro-5-methyl-2- (1H- Pyrazol-3-yl) pyridine (0.70 g) 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 (Compound No. 4) -A-33)
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 added to dimethyl sulfoxide. To the solution dissolved in 30 ml, 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), and the desired 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) , 7.31-7.25 (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 (Compound No. 4-a-26 )
0.24 g of t-butyl N- {2- [1- (2-chloro-6-fluorobenzyl) -1H-pyrazol-3-yl] -5-methylpyridin-4-yloxy} carbamate is added to 20 ml of methylene chloride. Dissolved. 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. To this was added an aqueous ammonium chloride solution 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, 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 with 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 desired 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) Production of t-butyl N- (6-acetyl-3-methylpyridin-2-yloxy) carbamate (Compound No. 6-b-8)
To a solution of 1.48 g (26.3 mmol) of potassium hydroxide in dimethyl sulfoxide (20 ml) was added 1.88 g of 6-acetyl-2-bromo-3-methylpyridine and 1.52 g of N-Boc-hydroxylamine. 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 (Compound No. 6-b-7)
0.75 g of t-butyl N- (6-acetyl-3-methylpyridin-2-yloxy) carbamate was dissolved in 10 ml of methylene chloride. 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 target 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 (Compound No. 2- b-18)
0.40 g of 2-acetyl-6-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 thereto 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, 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 were added, and the mixture was stirred at 50 ° C. 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 (Compound No. 6-b-2)
To a solution of 5.41 g (96.4 mmol) of potassium hydroxide in dimethyl sulfoxide (80 ml) was added 5.00 g of 4-acetyl-2-chloropyridine and 5.57 g of N-Boc-hydroxylamine, and the mixture was stirred at room temperature for 24 hours. did. The resulting solution was poured into a saturated aqueous ammonium chloride solution 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 (Compound No. 6-b-1)
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 with 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) to give 2.19 g (recovery) of the target methyl N- (4-acetylpyridin-2-yloxy) carbamate. 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 (Compound No. 1-b-4)
0.23 g of methyl N- (4-acetylpyridin-2-yloxy) carbamate was dissolved in 10 ml of methanol. To this, 0.21 g of O- (2-trifluoromethylbenzyl) hydroxylamine hydrochloride was added and 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)
Production of methyl N- {4- [1- (6-chloropyridin-2-ylmethoxyimino) ethyl] pyridin-2-yloxy} carbamate (Compound No. 1-b-11)
0.23 g of methyl N- (4-acetylpyridin-2-yloxy) carbamate 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 a method similar to the above production method are shown in Tables 1 to 10 including the compounds obtained in the above Examples. Further, production intermediates are shown in Tables 11 to 14.
In the table, Me is a methyl group, Et is an ethyl group, ⁱ Pr is an isopropyl group, ^t Bu is a tertiary butyl group, Ac is an acetyl group, Ph is a phenyl group, and ^c Pr is cyclopropyl. ^C Pen represents a cyclopentyl group, ^c Hex represents a cyclohexyl group, and Py-2-yl represents a pyridin-2-yl group. Table 1 is a compound represented by formula (1-a), Table 2 is a compound represented by formula (1-b), Table 3 is a compound represented by formula (2-a), Table 4 Table is a compound represented by Formula (2-b), Table 5 is a compound represented by Formula (3-a), Table 6 is a compound represented by Formula (3-b), Table 7 is The compounds represented by formula (4-a) and Table 8 show the compounds represented by formula (4-b), respectively. Table 9 shows the compound represented by the formula (5-a), and Table 10 shows the compound represented by the formula (5-b). Table 11 shows production intermediates represented by formula (6-a), and Table 12 shows production intermediates represented by formula (6-b). Table 13 shows the production intermediate represented by the formula (7-a), and Table 14 shows the production intermediate represented by the formula (7-b).

Further, physical properties such as ¹ H-NMR of the compounds shown in the above table were measured. Some of them are shown below.
<Compound No. 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)
<Compound No. 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), 2.28-2 .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) )
<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)
<Compound No. 1-a-56>
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.69 (s, 1H), 7.55 (t, 1H), 7.48 (s, 1H), 7.15 (d, 1H) 7.02 (d, 1H), 5.47 (q, 1H), 3.80 (s, 3H), 3.05 (sep, 1H), 2.49 (s, 3H), 2.40 ( s, 3H), 2.15 (s, 3H), 1.63 (d, 3H), 1.29 (d, 6H)
<Compound No. 1-a-65>
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.69 (s, 1H), 7.61 (s, 1H), 7.49 to 7.46 (m, 1H), 7.23 to 7.12 (m, 3H), 5.35 (t, 1H), 3.85 (s, 3H), 2.91 to 2.70 (m, 2H), 2.51 (s, 3H), 2 .28 (s, 3H), 2.24 to 2.20 (m, 1H), 2.18 (s, 3H), 2.06 to 1.94 (m, 2H), 1.84 to 1.73 (M, 1H)
<Compound No. 1-a-70>
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.25 (s, 1H), 7.87 (s, 1H), 7.74 (s, 1H), 7.51 (d, 1H) 7.29-7.18 (m, 3H), 5.82 (dd, 1H), 3.86 (s, 3H), 3.18-3.08 (m, 1H), 2.93-2 .83 (m, 1H), 2.56 to 2.44 (m, 1H), 2.33 to 2.24 (m, 1H), 2.25 (s, 3H), 2.23 (s, 3H )

<Compound No. 1-a-75>
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.24 (s, 1H), 7.89 (s, 1H), 7.62 (s, 1H), 7.57 (t, 1H) , 7.16 (d, 1H), 7.03 (d, 1H), 5.48 (q, 1H), 3.81 (s, 3H), 3.05 (sep, 1H), 2.40 ( s, 3H), 2.20 (s, 3H), 1.64 (d, 3H), 1.29 (d, 6H)
<Compound No. 1-a-77>
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.27 (s, 1H), 7.78 (s, 1H), 7.75 (s, 1H), 7.40 (d, 1H) , 7.34 (dd, 1H), 7.12 (t, 1H), 5.33 (t, 1H), 3.86 (s, 3H), 3.03 (dt, 1H), 2.80- 2.70 (m, 1H), 2.27 (s, 3H), 2.24 (s, 3H), 2.23 to 2.17 (m, 1H), 2.10 (s, 3H), 2 .02 to 1.95 (m, 2H), 1.87 to 1.79 (m, 1H)
<Compound No. 1-a-83>
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.74 (s, 1H), 7.63 (s, 1H), 7.48 (d, 1H), 7.35 to 7.19 ( m, 3H), 5.81 (dd, 1H), 3.85 (s, 3H), 2.51 (s, 3H), 2.37 (dd, 1H), 2.27 (s, 3H), 2.18 (s, 3H), 2.18 to 2.13 (m, 1H), 1.34 (s, 3H), 1.31 (s, 3H)
<Compound No. 1-a-85>
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.14 (s, 1H), 7.73 (s, 1H), 7.42 (d, 1H), 6.20 (d, 1H) , 5.34 (q, 1H), 3.95 (d, 2H), 3.80 (s, 3H), 2.49 (s, 3H), 2.25 (s, 3H), 2.18 ( s, 3H), 1.56 (d, 3H), 1.29 to 1.24 (m, 1H), 0.65 to 0.59 (m, 2H), 0.37 to 0.31 (m, 2H)
<Compound No. 1-a-87>
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.91 (s, 1H), 7.55 (s, 1H), 7.46 (d, 1H), 6.42 (d, 1H) , 5.26 (s, 2H), 4.95 to 4.81 (m, 1H), 3.83 (s, 3H), 2.49 (s, 3H), 2.30 (s, 3H), 2.15 (s, 3H), 1.75 (d, 3H)

<Compound No. 1-b-4>
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.46 (s, 1H), 8.12 (d, 1H), 7.68 (d, 1H), 7.60-7.53 ( 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)
<Compound No. 1-b-11>
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)
<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)
<Compound No. 6-a-1>
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)
<Compound No. 6-a-2>
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)
<Compound No. 6-a-4>
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.53 (s, 1H), 7.99 (bs, 1H), 7.98 (s, 1H), 3.86 (s, 3H) , 2.70 (s, 3H)

<Compound No. 6-b-1>
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)
<Compound No. 6-b-2>
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)
<Compound No. 6-b-5>
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.73 (d, 1H), 8.01 (d, 1H), 7.99 (s, 1H), 3.85 (s, 3H) 2.62 (s, 3H), 2.58 (s, 3H)
<Compound No. 6-b-7>
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)
<Compound No. 6-b-8>
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)

Next, some preparation examples of the bactericidal agent of the present invention are shown. However, the additives and the addition ratio 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 Lignin sulfonic acid sodium salt 8 parts Formaldehyde condensate of alkylbenzenesulfonic acid sodium salt 5 parts After finely pulverizing, 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 “Kokumitsu”, 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.
Compound Nos. 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-16, 1-a-21, 1-a-22, 1-a-23, 1-a-24, 1-a-55, 1- a-56, 1-a-61, 1-a-63, 1-a-64, 1-a-65, 1-a-66, 1-a-67, 1-a-69, 1-a- 70, 1-a-74, 1-a-75, 1-a-76, 1-a-77, 1-a-78, 1-a-79, 1-a-80, 1-a-81, 1-a-83, 1-a-84, 1-a-85, 1-a-86, 1-a-97, 1-b-4, 1-b-15, 2-a-7, 2- b-7, 2-b-10, 2-b-18, 3-a-1, 4-a-4, 4-a-16, 4-a-19, 4-a 23, and were examined respectively for compounds of 5-a-14, all showed more than 75% of control value.

(Test Example 2) Wheat powdery mildew control test A wet seedling 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 of wheat powdery mildew (Erysiphe graminis f.sp.tritici) were sprinkled off and inoculated in a greenhouse at 22-25 ° C. for 7 days. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
Compound Nos. 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-a-23, 1-a-24, 1-a-56, 1-a-63, 1-a-65, 1-a-66, 1-a-67, 1-a-70, 1- a-74, 1-a-75, 1-a-76, 1-a-78, 1-a-81, 1-a-83, 1-a-85, 1-a-86, 4-a- When the compounds 13 and 4-a-16 were examined, both showed a control value of 75% or more.

(Test Example 3) Wheat red rust control test Wheat seedlings grown in an unglazed pot (variety “Noribayashi No. 61”, 1.0 to 1.2 leaves) were sprayed with a wettable powder of the compound of the present invention at a concentration of 100 ppm. . After the leaves were air-dried, they were inoculated with summer spores of wheat rust (Puccinia recondita) and kept in a greenhouse at 22-25 ° C. for 10 days. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
Compound Nos. 1-a-4, 1-a-5, 1-a-6, 1-a-8, 1-a-9, 1-a-11, 1-a-13, 1-a-16, 1-a-21, 1-a-23, 1-a-24, 1-a-55, 1-a-56, 1-a-61, 1-a-63, 1-a-64, 1- a-65, 1-a-67, 1-a-69, 1-a-70, 1-a-74, 1-a-75, 1-a-76, 1-a-81, 1-a- 83, 1-a-84, 1-a-85, 1-a-86, 1-a-97, 2-a-7, 4-a-4, 4-a-16, 4-a-19, When the compounds of 5- and 14-a-14 were examined, both 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, which can be produced industrially advantageously, has an effect, and can be used safely and safely. It turns out that it is useful.

Claims

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

[In the formula (1), R 1 is an unsubstituted or substituted C1-6 alkyl group.
R 2 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, a 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 2-6 alkynyl groups, unsubstituted or substituted C3-8 cycloalkyl groups, unsubstituted or substituted C4-8 cycloalkenyl groups, unsubstituted or substituted C6-10 aryl groups, 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 described 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 C1-6 alkyl group, an unsubstituted or substituted C2˜ 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 a heteroaryl group having no substituent or a substituent.
A 2 is an oxygen atom, Formula: NR 4 (wherein R 4 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, Formula: COR 21 , Formula: CO 2 R 22 , or 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.) Or the formula: CR 5 R 6 (wherein R 5 and R 6 are each independently a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or a halogen atom). Group.
J is an oxygen atom or a sulfur atom.
X is an unsubstituted or substituted C1-6 alkyl group, Formula: OR 23 (wherein R 23 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, 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, an unsubstituted or substituted heteroaryl group, formula: COR 21 , formula: CO 2 R 22 , or 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. The group represented by the formula: SR 23 , Formula: N (R 2 3 ) 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 atom.
n represents the number of X and is an integer from 0 to 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, B 1 to B 3 are not all nitrogen atoms, and B 1 to B 4 are not all carbon atoms.
D is any group represented by the formulas (2) to (6).

(In the formulas (2) to (6), 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 formula (2), formula (3), and formula (6), R 7 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an 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 cycloalkenyl group, unsubstituted or A C6-10 aryl group having a substituent, or an unsubstituted or substituted heteroaryl group.
In formulas (3) and (6), R 8 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted group Or a substituted C2-6 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 unsubstituted or substituted heteroaryl group. R 8 may further be bonded to a carbon atom on Q 1 or a nitrogen atom.
In the formula (5), Q 41 is a C6-10 aryl group or a 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 , Formula: SO 2 R 22 (wherein R 21 , R 22 , and R 23 have the same meanings as described above. R 21 may be the same or different. R 23 may be the same or different. ) Group, a cyano group, a nitro group, or a halogen atom.
In formula (5), m1 represents the number of Q 1 and is an integer of 0 to 7.
In the formula (5), 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 according to claim 1, represented by formula (7), a salt thereof, or N-oxide.

(In formula (7), R 1 , R 2 , A 1 , A 2 , J, X, n, and D have the same meaning as in formula (1).)
The nitrogen-containing heteroaryl derivative according to claim 1, represented by formula (8), a salt thereof, or N-oxide.

(In formula (8), R 1 , R 2 , A 1 , A 2 , J, X, n, R 7 , and Q 1 have the same meaning as in formula (1).)
An agricultural and horticultural fungicide containing as an active ingredient at least one of the nitrogen-containing heteroaryl derivative according to claims 1 to 3, a salt thereof, or an N-oxide.
The nitrogen-containing heteroaryl derivative represented by Formula (9).

[In Formula (9), R 1 represents an unsubstituted or substituted C1-6 alkyl group.
R 2 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, a 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 2-6 alkynyl groups, unsubstituted or substituted C3-8 cycloalkyl groups, unsubstituted or substituted C4-8 cycloalkenyl groups, unsubstituted or substituted C6-10 aryl groups, 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 described 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 C1-6 alkyl group, an unsubstituted or substituted C2˜ 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 a heteroaryl group having no substituent or a substituent.
A 2 is an oxygen atom, Formula: NR 4 (wherein R 4 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, Formula: COR 21 , Formula: CO 2 R 22 , or 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.) Or the formula: CR 5 R 6 (wherein R 5 and R 6 are each independently a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or a halogen atom). Group.
J is an oxygen atom or a sulfur atom.
X is an unsubstituted or substituted C1-6 alkyl group, Formula: OR 23 (wherein R 23 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, 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, an unsubstituted or substituted heteroaryl group, formula: COR 21 , formula: CO 2 R 22 , or 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. The group represented by the formula: SR 23 , Formula: N (R 2 3 ) 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 atom.
n represents the number of X and is an integer from 0 to 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, B 1 to B 3 are not all nitrogen atoms, and B 1 to B 4 are not all carbon atoms.
R 7 represents 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, 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 ]
The nitrogen-containing heteroaryl derivative represented by the formula (10), a salt thereof, or an N-oxide according to claim 5.

(In formula (10), R 1 , R 2 , A 1 , A 2 , J, X, n, and R 7 have the same meaning as in formula (9).)
The nitrogen-containing heteroaryl derivative represented by Formula (11).

[In Formula (11), R 1 represents an unsubstituted or substituted C1-6 alkyl group.
R 2 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, a 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 2-6 alkynyl groups, unsubstituted or substituted C3-8 cycloalkyl groups, unsubstituted or substituted C4-8 cycloalkenyl groups, unsubstituted or substituted C6-10 aryl groups, 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 described 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 C1-6 alkyl group, an unsubstituted or substituted C2˜ 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 a heteroaryl group having no substituent or a substituent.
A 2 is an oxygen atom, Formula: NR 4 (wherein R 4 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, Formula: COR 21 , Formula: CO 2 R 22 , or 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.) Or the formula: CR 5 R 6 (wherein R 5 and R 6 are each independently a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or a halogen atom). Group.
J is an oxygen atom or a sulfur atom.
X is an unsubstituted or substituted C1-6 alkyl group, Formula: OR 23 (wherein R 23 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, 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, an unsubstituted or substituted heteroaryl group, formula: COR 21 , formula: CO 2 R 22 , or 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. The group represented by the formula: SR 23 , Formula: N (R 2 3 ) 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 atom.
n represents the number of X and is an integer from 0 to 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, B 1 to B 3 are not all nitrogen atoms, and B 1 to B 4 are not all carbon atoms.
R 7 represents 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, 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
R 9 is each independently a hydrogen atom or a group represented by the formula: COR 21 (wherein R 21 has the same meaning as described above). R 9 may be the same or different. R 9 may be together. ]
The nitrogen-containing heteroaryl derivative according to claim 7, represented by formula (12), a salt thereof, or N-oxide.

(In formula (12), R 1 , R 2 , A 1 , A 2 , J, X, n, R 7 , and R 9 have the same meaning as in formula (11).)