TW201934007A - N-methoxyamide compound or salt thereof, and agricultural and horticultural fungicide containing same - Google Patents

N-methoxyamide compound or salt thereof, and agricultural and horticultural fungicide containing same Download PDF

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TW201934007A
TW201934007A TW107146386A TW107146386A TW201934007A TW 201934007 A TW201934007 A TW 201934007A TW 107146386 A TW107146386 A TW 107146386A TW 107146386 A TW107146386 A TW 107146386A TW 201934007 A TW201934007 A TW 201934007A
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中村裕治
伏木田地
大北達哉
伊藤智也
岩本拓也
田中薫
西村光子
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日商石原產業股份有限公司
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
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    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/16—Halogen atoms or nitro radicals
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    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/06—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Pyridine Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

Provided is an agricultural and horticultural fungicide exhibiting a high control effect against a wide range of plant pathogens. A compound represented by formula (1) or a salt thereof (in the formula, each symbol is as defined in the description).

Description

Ｎ－甲氧基醯胺化合物或其鹽及含有該等之農園藝用殺菌劑N-methoxypyramine compound or salt thereof and agricultural and horticultural fungicide containing the same

本發明係關於N-甲氧基醯胺化合物或其鹽及含有該等之農園藝用殺菌劑。The present invention relates to an N-methoxylamine compound or a salt thereof, and an agricultural and horticultural fungicide containing the same.

具有一定之苯甲醯甲基醯胺構造的化合物，已知對各式各樣之有害生物的防除有用。例如，分別於專利文獻1及2中，記載具有作為殺蟲劑、殺蟎劑或殺線蟲劑有用之苯甲醯甲基醯胺構造的化合物，專利文獻3及4中記載具有作為農園藝用殺菌劑有用之苯甲醯甲基醯胺構造的化合物。然而，此等文獻中，後述式(1)之化合物，亦即具有醯胺之氮原子以甲氧基修飾之N-甲氧基醯胺構造的化合物，並未伴隨具體例而記載。Compounds having a certain benzamidine methylamidamine structure are known to be useful for controlling various pests. For example, Patent Documents 1 and 2 each describe a compound having a benzamidine methylamidine structure useful as an insecticide, acaricide, or nematicide, and Patent Documents 3 and 4 describe a compound having an agricultural and horticultural application. The fungicide is useful as a benzamidine methylamidine compound. However, in these documents, a compound of the formula (1) described later, that is, a compound having a methoxy-modified N-methoxyamidine structure in which the nitrogen atom of amidine is not described with a specific example.

又，專利文獻5中雖記載具有N-甲氧基醯胺構造之農園藝用殺菌劑，但不具有後述式(1)之
「-C(O)-C(Me)2 -」構造。進而，專利文獻6中雖揭示具有醯胺之氮原子以甲基修飾之N-甲基醯胺構造的化合物，但具有後述式(1)之「-C(O)-C(Me)2 -N(OMe)-C(O)-」構造之化合物，並未伴隨具體例而記載。

[先前技術文獻]
[專利文獻]Further, Patent Document 5 describes an agricultural and horticultural fungicide having an N-methoxyamidamine structure, but does not have a "-C (O) -C (Me) 2- " structure of formula (1) described later. Furthermore, Patent Document 6 discloses a compound having an N-methylamidamine structure in which a nitrogen atom of amidine is modified with a methyl group, but has "-C (O) -C (Me) 2- The compound of N (OMe) -C (O)-"structure is not described with specific examples.

[Prior technical literature]
[Patent Literature]

[專利文獻1] 國際公開公報WO01/60783
[專利文獻2] 國際公開公報WO03/27059
[專利文獻3] 國際公開公報WO2006/016708
[專利文獻4] 國際公開公報WO2007/069777
[專利文獻5] 國際公開公報WO2010/063700
[專利文獻6] 國際公開公報WO2011/151369[Patent Document 1] International Publication WO01 / 60783
[Patent Document 2] International Publication WO03 / 27059
[Patent Document 3] International Publication WO2006 / 016708
[Patent Document 4] International Publication WO2007 / 069777
[Patent Document 5] International Publication WO2010 / 063700
[Patent Document 6] International Publication WO2011 / 151369

[發明欲解決之課題][Questions to be Solved by the Invention]

自以往，為了防除植物病害所提供之多數農園藝用殺菌劑，各自在其光譜或植物病原菌防除效果具有特徵。然而，有對於特定之植物病害，效果不夠充分，或是與預防效果相比較，治療效果稍微劣化，或耐雨性劣化之殘效性比較上較短，藉由施用場面，對於植物病原菌，僅顯示實用上不夠充分之防除效果的情況。據此，正尋求不因施用場面，且對於範圍廣泛之植物病原菌，發揮高度防除效果之農園藝用殺菌劑的創製。

[用以解決課題之手段]Since the past, most agricultural and horticultural fungicides provided to prevent plant diseases have their own characteristics in their spectrum or plant pathogen control effect. However, for certain plant diseases, the effect is insufficient, or the treatment effect is slightly deteriorated compared with the preventive effect, or the residual effect of the deterioration of rain resistance is relatively short. According to the application scene, only the plant pathogenic bacteria are displayed as practical Insufficient control effect. Accordingly, there is a need to create agricultural and horticultural fungicides that exhibit a high degree of control against a wide range of plant pathogenic bacteria regardless of the application scene.

[Means to solve the problem]

本發明者們為了解決前述之問題點而研究的結果，發現後述式(1)表示之化合物或其鹽對於各種植物病害，表現優異之防除效果的卓見，而完成本發明。As a result of studies conducted by the present inventors in order to solve the aforementioned problems, they have found that the compound represented by the formula (1) or a salt thereof described below exhibits excellent control effects against various plant diseases, and completed the present invention.

亦即，本發明係關於式(1)表示之化合物或其鹽(以下，亦稱為本發明化合物)，將本發明化合物作為有效成分含有之農園藝用殺菌劑及將本發明化合物施用在植物或土壤之防除植物病害之方法。That is, the present invention relates to a compound represented by formula (1) or a salt thereof (hereinafter, also referred to as a compound of the present invention), an agricultural and horticultural fungicide containing the compound of the present invention as an active ingredient, and applying the compound of the present invention to plants Or soil control of plant diseases.

[式中，A為被RA 取代之苯基或被取代之吡啶基，
B為被RB 取代之雜環基，
RA 可相同或相異為鹵素原子、可被G1 取代之烷基、烯基、可被G2 取代之炔基、環狀基、硝基、氰基或-LA -YA ，或可鍵結2個RA ，形成可被Z1 取代之環，
RB 可相同或相異為鹵素原子、烷基、烯基、鹵烷基、烷氧基烷基、環烷基或氰基，
LA 為O、S、C(=O)、C(=O)O、C(=O)N(R1 )、
OC(=O)、N(R1 )、N(R1 )C(=O)、N(R1 )C(=O)O、C(=NR2 )、SO、SO2 或SO2 N(R1 )，
YA 為氫原子、可被Z2 取代之烷基、烯基或可被Z3 取代之環狀基，
R1 為氫原子或烷基，
R2 為氫原子、烷基或烷氧基，
G1 為鹵素原子或烷氧基，
G2 為環烷基或鹵素原子，
Z1 為鹵素原子、烷基、烷氧基或環烷基，
Z2 為鹵素原子、氰基、環烷基或烷氧基，
Z3 為鹵素原子或鹵烷基]。

[發明效果][Wherein A is phenyl substituted by R A or substituted pyridyl,
B is a heterocyclic group substituted with R B ,
R A may be the same or different as a halogen atom, an alkyl group which may be substituted by G 1 , an alkenyl group, an alkynyl group which may be substituted by G 2 , a cyclic group, a nitro group, a cyano group, or -L A -Y A , or Can bond 2 R A to form a ring which can be replaced by Z 1 ,
R B may be the same or different and is a halogen atom, an alkyl group, an alkenyl group, a haloalkyl group, an alkoxyalkyl group, a cycloalkyl group or a cyano group,
L A is O, S, C (= O), C (= O) O, C (= O) N (R 1 ),
OC (= O), N (R 1 ), N (R 1 ) C (= O), N (R 1 ) C (= O) O, C (= NR 2 ), SO, SO 2 or SO 2 N (R 1 ),
Y A is a hydrogen atom, an alkyl group which may be substituted by Z 2 , an alkenyl group or a cyclic group which may be substituted by Z 3 ,
R 1 is a hydrogen atom or an alkyl group,
R 2 is a hydrogen atom, an alkyl group or an alkoxy group,
G 1 is a halogen atom or an alkoxy group,
G 2 is a cycloalkyl or halogen atom,
Z 1 is a halogen atom, an alkyl group, an alkoxy group or a cycloalkyl group,
Z 2 is a halogen atom, a cyano group, a cycloalkyl group or an alkoxy group,
Z 3 is a halogen atom or a haloalkyl group].

[Inventive effect]

本發明化合物與類似之以往化合物比較，由於可發揮優異之植物病害的防除效果及滲透傳遞性，故作為農園藝用殺菌劑有用。Compared with similar conventional compounds, the compound of the present invention can exhibit excellent plant disease control effects and osmotic transmission properties, and thus is useful as an agricultural and horticultural fungicide.

在本說明書，在A之苯基或吡啶基的取代基即RA 之數可為1個，亦可為2個以上(例如2個、3個、4個等)。為2個以上時，RA 可分別相同亦可相異。
又，在B之雜環基的取代基即RB 之數可為1個，亦可為2個以上(例如2個、3個、4個等)。為2個以上時，RB 可分別相同亦可相異。In the present specification, the number of R A which is a substituent of phenyl or pyridyl in A may be one or two or more (for example, two, three, four, etc.). When there are two or more, R A may be the same or different.
The number of R B which is a substituent of the heterocyclic group of B may be one or two or more (for example, two, three, four, etc.). When there are two or more, R B may be the same or different.

在本說明書，作為鹵素原子或作為取代基之鹵素原子，可列舉氟、氯、溴或碘之各原子。作為取代基之鹵素原子之數可為1或2以上，為2個以上時，各鹵素原子可分別相同亦可相異。
又，鹵素原子之取代位置可為任一位置。In this specification, as a halogen atom or a halogen atom as a substituent, each atom of fluorine, chlorine, bromine, or iodine is mentioned. The number of halogen atoms as a substituent may be one or two or more, and when two or more, each halogen atom may be the same or different.
The substitution position of the halogen atom may be any position.

在本說明書，作為烷基或烷基部分，例如可列舉如甲基、乙基、丙基、異丙基、n-丁基、異丁基、s-丁基、t-丁基、n-戊基、新戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基之直鏈或分枝鏈狀的C1 -C12 之基。In the present specification, examples of the alkyl group or the alkyl moiety include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, and n- Amyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, straight or branched C 1 -C 12 radicals.

在本說明書，作為烯基或烯基部分，例如可列舉如乙烯基、1-丙烯基、2-丙烯基、異丙烯基、2-甲基-1-丙烯基、1-甲基-1-丙烯基、2-甲基-2-丙烯基、1-甲基-2-丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-戊烯基、2-戊烯基、2-甲基-2-丁烯基、3-甲基-2-丁烯基、1-己烯基、2,3-二甲基-2-丁烯基之直鏈或分枝鏈狀的C2 -C6 之基。In the present specification, examples of the alkenyl or alkenyl moiety include vinyl, 1-propenyl, 2-propenyl, isopropenyl, 2-methyl-1-propenyl, and 1-methyl-1- Propenyl, 2-methyl-2-propenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl Linear or branched chain of alkenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-hexenyl, 2,3-dimethyl-2-butenyl Chain C 2 -C 6 group.

在本說明書，作為炔基或炔基部分，例如可列舉如乙炔基、1-丙炔基、2-丙炔基、1-丁炔基、2-丁炔基、3-丁炔基、1-甲基-2-丙炔基、2-甲基-3-丁炔基、1-己炔基、2-己炔基、3-己炔基、4-己炔基、5-己炔基、3,3-二甲基-1-丁炔基之直鏈或分枝鏈狀的C2 -C6 之基。In the present specification, examples of the alkynyl or alkynyl moiety include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and 1 -Methyl-2-propynyl, 2-methyl-3-butynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl , 3,3-dimethyl-1-butynyl is a linear or branched C 2 -C 6 group.

在本說明書，作為環烷基或環烷基部分，例如可列舉如環丙基、環丁基、環戊基、環己基、環庚基、金剛烷基、雙環[1,1,1]戊基之C3 -C10 之基。In the present specification, examples of the cycloalkyl or cycloalkyl moiety include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and bicyclo [1,1,1] pentane. C 3 -C 10 base.

在本說明書，作為環狀基，係意指飽和或不飽和之碳環基或雜環基。所謂碳環基，係作為環原子僅包含碳原子之環狀基，可列舉如環烷基(例如環丙基、環丁基、環戊基、環己基、環庚基、金剛烷基、雙環[1,1,1]戊基等)及芳基(例如苯基、萘基、茚基、二氫茚基等)之C3 -C10 之基。作為雜環基，可列舉含有1～4個選自由O、S及N所成之群組中之至少1種的原子之3～6員之單環式的雜環基(例如如環氧乙烷基、噻喃基(thiiranyl)、氮呾基(azetidinyl)之3員雜環基；如氧呾基(oxetanyl)、硫呾基(thietanyl)、氮呾基之4員雜環基；呋喃基、四氫呋喃基、噻吩基、吡咯基、唑啉基、咯啶基、二氧戊環基、噁唑基、異噁唑基、噻唑基、異噻唑基、咪唑基、咪唑啉基、咪唑啶基、吡唑基、吡唑啉基、吡唑啶基、***基、噁二唑基、噻二唑基、四唑基等之5員雜環基；吡喃基、吡啶基、哌啶基、二噁烷基、噁嗪基、嗎啉基、噻嗪基、噠嗪基、嘧啶基、吡嗪基、哌嗪基、三嗪基、噻喃基、二氫噻喃基、氧硫雜環己烯基(oxathiinyl)等之6員雜環基)，以及含有1～4個選自由O、S及N所成之群組中之至少1種的原子之縮合雜環基(例如苯并呋喃基、異苯并呋喃基、二氫苯并呋喃基、二氫異苯并呋喃基、苯并噻吩基、異苯并噻吩基、二氫苯并噻吩基、二氫異苯并噻吩基、四氫苯并噻吩基、吲哚基、異吲哚基、苯并噁唑基、苯并噻唑基、吲唑基、苯并咪唑基、苯并二氧環戊基(benzodioxolanyl)、苯并二噁烷基、苯并哌喃基、苯并二氫哌喃基、異苯并二氫哌喃基、色酮基(chromonyl)、色滿酮基(chromanonyl)、喹啉基、異喹啉基、噌啉基、酞嗪基、喹唑啉基、喹喔啉基、吲嗪基(indolizinyl)、喹嗪基、咪唑并吡啶基、萘啶基、蝶啶基、二氫苯并惡嗪基、二氫苯并噁唑酮基、二氫苯并噁嗪酮基(benzoxazinonyl)、苯并硫氧雜環己基(Benzothioxanyl)等)。In the present specification, a cyclic group means a saturated or unsaturated carbocyclic group or a heterocyclic group. The so-called carbocyclyl is a cyclic group containing only carbon atoms as a ring atom, and examples include cycloalkyl (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, bicyclic [1,1,1] pentyl, etc.) and C 3 -C 10 radicals of aryl (eg, phenyl, naphthyl, indenyl, dihydroindenyl, etc.). Examples of the heterocyclic group include a monocyclic heterocyclic group containing 3 to 6 members of at least one atom selected from the group consisting of O, S, and N (for example, ethylene oxide). 3-membered heterocyclic group of alkyl, thiiranyl, azetidinyl; such as oxetanyl, thietanyl, and 4-membered heterocyclic group of azetidinyl; furanyl , Tetrahydrofuryl, thienyl, pyrrolyl, oxazolyl, pyridyl, dioxolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, imidazolinyl, imidazolyl 5-membered heterocyclyl, pyrazolyl, pyrazolyl, pyrazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, etc .; pyranyl, pyridyl, piperidinyl , Dioxanyl, oxazinyl, morpholinyl, thiazinyl, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl, triazinyl, thianyl, dihydrothianyl, oxathiazine 6-membered heterocyclic groups such as oxathiinyl), and condensed heterocyclic groups containing at least one atom selected from the group consisting of O, S, and N (e.g., benzo Furanyl, isobenzofuranyl, dihydrobenzofuran Group, dihydroisobenzofuranyl, benzothienyl, isobenzothienyl, dihydrobenzothienyl, dihydroisobenzothienyl, tetrahydrobenzothienyl, indolyl, isoindole Base, benzoxazolyl, benzothiazolyl, indazolyl, benzimidazolyl, benzodioxolanyl, benzodioxoyl, benzopiperanyl, benzodihydro Piperanyl, isobenzodihydropiperanyl, chromonyl, chromanonyl, quinolinyl, isoquinolinyl, perylene, phthalazinyl, quinazolinyl, Quinoxalinyl, indolizinyl, quinazinyl, imidazopyridyl, naphthyridinyl, pteridinyl, dihydrobenzoxazinyl, dihydrobenzoxazolone, dihydrobenzo Benzoxazinonyl, Benzothioxanyl, etc.).

作為式(1)中之B表示之雜環基，可使用與作為前述環狀基例示之雜環基相同者。較佳為含有1～4個選自由O、S及N所成之群組中之至少1種的原子之5～6員之雜環基，更具體而言，可列舉以下。
選自由式(B-1)～式(B-18)：As the heterocyclic group represented by B in formula (1), the same ones as the heterocyclic groups exemplified as the aforementioned cyclic group can be used. A heterocyclic group having 5 to 6 members containing 1 to 4 atoms of at least one selected from the group consisting of O, S, and N is preferable, and more specifically, the following are listed.
From formula (B-1) to formula (B-18):

[式中，RB1 ～RB20 可相同或相異為鹵素原子、烷基、烯基、鹵烷基、烷氧基烷基、環烷基或氰基，＊表示鍵結位置]表示之5員雜環基及
式(B-101)～式(B-128)：[In the formula, R B1 to R B20 may be the same or different, and are halogen atom, alkyl group, alkenyl group, haloalkyl group, alkoxyalkyl group, cycloalkyl group, or cyano group. * Indicates a bonding position.] Member heterocyclic group and formula (B-101) to formula (B-128):


[式中，RB101 ～RB114 可相同或相異為鹵素原子、烷基、烯基、鹵烷基、烷氧基烷基、環烷基或氰基，＊表示鍵結位置]表示之6員雜環基所成之群組中之雜環基。
[ Wherein , R B101 to R B114 may be the same or different from each other as a halogen atom, an alkyl group, an alkenyl group, a haloalkyl group, an alkoxyalkyl group, a cycloalkyl group, or a cyano group, and * indicates a bonding position] A heterocyclic group in a group formed by a membered heterocyclic group.

作為B表示之雜環基，有於與「＊」鍵結之原子相鄰的原子上具有取代基較佳的情況。As the heterocyclic group represented by B, it is preferable to have a substituent on an atom adjacent to the "*" bonded atom.

在式(1)，作為在鍵結2個RA 形成環的態樣之A，可列舉可被Z1 取代之苯并二氧環戊基、苯并二噁烷基、苯并噻唑基、二氫苯并氧硫雜環己烯基(benzoxathiinyl)等。於此，與同一碳原子鍵結之2個Z1 可鍵結形成螺環，作為形成螺環時之A的例，可列舉螺環[苯并[d][1,3]二氧雜環戊烯(Dioxol)-2,1’-環戊烷]-5-基、螺環[苯并[d][1,3]二氧雜環戊烯(Dioxol)-2,1’-環丁烷]-5-基等。In formula (1), is formed as aspects of the A ring in R & lt bonded 2 A, Z 1 may be substituted include the benzo-dioxolan-yl, benzodioxan-alkyl, benzothiazolyl, Dihydrobenzoxathiinyl and the like. Here, two Z 1 bonded to the same carbon atom may be bonded to form a spiro ring. Examples of A when forming a spiro ring include a spiro ring [benzo [d] [1,3] dioxane Dioxol-2,1'-cyclopentane] -5-yl, Spiro [benzo [d] [1,3] Dioxol-2,1'-cyclobutane Alk] -5-yl and the like.

作為式(1)之化合物之鹽，若為農業上所容許者，雖都包含，但例如可列舉如鈉鹽、鉀鹽之鹼金屬鹽；如鎂鹽、鈣鹽之鹼土類金屬鹽；如鹽酸鹽、過氯酸鹽、硫酸鹽、硝酸鹽之無機酸鹽；如乙酸鹽、甲烷磺酸鹽之有機酸鹽等。As the salt of the compound of formula (1), if it is allowed in agriculture, although it is included, for example, alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; Inorganic acid salts of hydrochloride, perchlorate, sulfate, nitrate; such as organic acid salts of acetate, methanesulfonate, etc.

本發明化合物中，雖存在各種同分異構物、例如光學同分異構物、幾何同分異構物等，但本發明中包含各同分異構物及同分異構物混合物雙方。尚，本發明化合物中，在該技術領域之技術常識的範圍內，亦包含前述者以外之各種同分異構物。Although various isomers such as optical isomers and geometric isomers exist in the compounds of the present invention, the present invention includes both the isomers and the isomer mixtures. However, the compounds of the present invention also include various isomers other than the foregoing within the scope of technical common sense in the technical field.

又，雖有因同分異構物的種類，導致成為與記載之構造式不同之化學構造的情況，但若為本發明領域具有通常知識者，由於該等為同分異構物的關係有充分認識，故非常清楚為本發明的範圍內。In addition, although there are cases where the chemical structure is different from the recorded structural formula depending on the type of the isomer, if the person has ordinary knowledge in the field of the present invention, it is because the relationship between these isomers is Fully recognized, it is very clear within the scope of the present invention.

本發明化合物雖可依以下所示知反應A～I及通常之鹽的製造方法製造，但得到本發明化合物之方法，並不限定於此等之方法。例如，本發明化合物亦可藉由於在A之苯基或吡啶基上之取代基及/或在B之雜環基上之取代基，在本領域，適用周知之各種取代基變換反應(例如水解、氧化、還原、酯化、醯胺化、烷基化等)來製造。又，在本發明化合物之製造，在本領域，如有必要可適用通常所使用之保護及脫保護反應。Although the compound of the present invention can be produced by the production methods of the reactions A to I and ordinary salts shown below, the method of obtaining the compound of the present invention is not limited to these methods. For example, the compounds of the present invention can also be applied in the art by various substituent conversion reactions (such as hydrolysis, for example) due to substituents on the phenyl or pyridyl group of A and / or substituents on the heterocyclic group of B. , Oxidation, reduction, esterification, amidation, alkylation, etc.). In addition, in the production of the compound of the present invention, in the art, if necessary, protection and deprotection reactions generally used can be applied.

反應A
反應A係藉由甲基化式(2)之化合物，得到式(1)之化合物之方法。Reaction A
Reaction A is a method of methylating a compound of formula (2) to obtain a compound of formula (1).

式中之記號係如前述。The symbols in the formula are as described above.

反應A可依一般的甲基化的反應條件進行，通常可於甲基化劑、鹼及溶媒的存在下進行。Reaction A can be carried out under general methylation reaction conditions, and usually can be carried out in the presence of a methylating agent, a base, and a solvent.

作為甲基化劑，例如可列舉碘化甲烷、溴化甲烷、硫酸二甲酯、三甲基矽烷基重氮甲烷等。甲基化劑相對於式(2)之化合物1當量(當量為莫耳當量，以下相同)，可使用1～20當量，期望為1～10當量。
作為鹼，例如可從如鈉、鉀之鹼金屬；如甲醇鈉、乙醇鈉、第3級丁醇鉀之鹼金屬醇鹽；如碳酸鈉、碳酸鉀之碳酸鹽；如碳酸氫鈉、碳酸氫鉀之碳酸氫鹽；如氫氧化鈉、氫氧化鉀之金屬氫氧化物；如氫化鈉、氫化鉀之金屬氫化物；如單甲基胺、二甲基胺、三乙基胺、二異丙基乙基胺之胺類；如吡啶、4-二甲基胺基吡啶之吡啶類；如甲基鋰、n-丁基鋰、鋰二異丙基醯胺、六甲基二矽氮烷鋰之有機鋰化合物等適當選擇1種或2種以上。鹼相對於式(2)之化合物1當量，可使用1～3當量，期望為1～2當量。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如乙酸甲酯、乙酸乙酯之酯類；如甲醇、乙醇、丙醇、tert-丁醇之醇類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒；如丙酮、甲基乙基酮之酮類；水等中適當選擇1種或2種以上。Examples of the methylating agent include methyl iodide, methyl bromide, dimethyl sulfate, and trimethylsilyldiazomethane. The methylating agent may be used in an amount of 1 to 20 equivalents with respect to 1 equivalent of the compound of the formula (2) (equivalent is Moore equivalent, the same applies hereinafter), and desirably is 1 to 10 equivalents.
Examples of the base include alkali metals such as sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium butoxide of the third order; carbonates such as sodium carbonate and potassium carbonate; such as sodium bicarbonate and hydrogen carbonate Potassium bicarbonate; such as sodium hydroxide, potassium hydroxide metal hydroxide; such as sodium hydride, potassium hydride metal hydride; such as monomethylamine, dimethylamine, triethylamine, diisopropyl Amines based on ethylethylamine; such as pyridine, 4-dimethylaminopyridine; such as methyllithium, n-butyllithium, lithium diisopropylamidamine, lithium hexamethyldisilazane One or more organic lithium compounds are appropriately selected. The base can be used in an amount of 1 to 3 equivalents with respect to 1 equivalent of the compound of the formula (2), and is preferably 1 to 2 equivalents.
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent may be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; for example, carbon tetrachloride, methylene chloride, chloroform, methylene chloride, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as methyl acetate, acetic acid Ester of ethyl esters; alcohols such as methanol, ethanol, propanol, tert-butanol; such as dimethylmethylene, cyclobutylammonium, dimethylacetamide, N, N-dimethylformamide , N-methylpyrrolidone, pyridine, acetonitrile, propionitrile polar aprotic solvents; such as acetone, methyl ethyl ketones; water, etc., one or more than one kind is appropriately selected.

反應溫度通常為-78～100℃，期望為0～80℃，反應時間通常為0.1～48小時左右，期望為0.1～24小時左右。The reaction temperature is usually -78 to 100 ° C, preferably 0 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 0.1 to 24 hours.

反應A所使用之式(2)之化合物可依後述之反應1-1製造。The compound of the formula (2) used in the reaction A can be produced by the reaction 1-1 described later.

反應B
反應B係將式(3)之化合物與式(4)之化合物進行反應，得到式(1)之化合物之方法。Reaction B
Reaction B is a method of reacting a compound of formula (3) with a compound of formula (4) to obtain a compound of formula (1).

式中，T為羥基、烷氧基、芳氧基或鹵素，其他記號係如前述。In the formula, T is a hydroxyl group, an alkoxy group, an aryloxy group, or a halogen, and other symbols are as described above.

反應B通常可於鹼及溶媒的存在下進行。式(4)之化合物相對於式(3)之化合物1當量，可使用1～3當量，期望為1～2當量。Reaction B can usually be performed in the presence of a base and a solvent. The compound of the formula (4) can be used in an amount of 1 to 3 equivalents to the compound of the formula (3), and is preferably 1 to 2 equivalents.

鹼例如可從如鈉、鉀之鹼金屬；如甲醇鈉、乙醇鈉、第3級丁醇鉀之鹼金屬醇鹽；如碳酸鈉、碳酸鉀之碳酸鹽；如碳酸氫鈉、碳酸氫鉀之碳酸氫鹽；如氫氧化鈉、氫氧化鉀之金屬氫氧化物；如氫化鈉、氫化鉀之金屬氫化物；如單甲基胺、二甲基胺、三乙基胺、二異丙基乙基胺之胺類；如吡啶、4-二甲基胺基吡啶之吡啶類；如甲基鋰、n-丁基鋰、鋰二異丙基醯胺之有機鋰化合物等中適當選擇1種或2種以上。鹼相對於式(3)之化合物1當量，可使用1～3當量，期望為1～2當量。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如乙酸甲酯、乙酸乙酯之酯類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒；如丙酮、甲基乙基酮之酮類等中適當選擇1種或2種以上。Examples of the base include alkali metals such as sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium butoxide of the third order; carbonates such as sodium carbonate and potassium carbonate; such as sodium bicarbonate and potassium bicarbonate. Bicarbonates; metal hydroxides such as sodium hydroxide and potassium hydroxide; metal hydrides such as sodium hydride and potassium hydride; such as monomethylamine, dimethylamine, triethylamine, diisopropylethyl Amines such as pyridine, pyridine of 4-dimethylaminopyridine; organic lithium compounds such as methyllithium, n-butyllithium, lithium diisopropylamidine, etc. 2 or more. The base can be used in an amount of 1 to 3 equivalents, and desirably 1 to 2 equivalents based on 1 equivalent of the compound of formula (3).
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent may be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; for example, carbon tetrachloride, methylene chloride, chloroform, methylene chloride, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as methyl acetate, acetic acid Ester of ethyl esters; such as dimethylmethylene, cyclobutane, dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, and propionitrile. Protonic solvents; such as acetone, ketones of methyl ethyl ketone, etc. are appropriately selected from one or two or more.

反應B如有必要可於脫水縮合劑的存在下進行。作為脫水縮合劑，可列舉N,N’-二環己基碳二亞胺、氯磺醯基異氰酸酯、N,N’-羰基二咪唑、三氟乙酸酐等。脫水縮合劑相對於式(3)之化合物1當量，可使用1～5當量，期望為1～2當量。Reaction B can be carried out in the presence of a dehydrating condensation agent if necessary. Examples of the dehydrating condensation agent include N, N'-dicyclohexylcarbodiimide, chlorosulfonyl isocyanate, N, N'-carbonyldiimidazole, and trifluoroacetic anhydride. The dehydration condensing agent can be used in an amount of 1 to 5 equivalents with respect to 1 equivalent of the compound of formula (3), and is desirably 1 to 2 equivalents.

反應溫度通常為0～100℃，期望為0～50℃，反應時間通常為0.5～48小時左右，期望為1～24小時左右。The reaction temperature is usually 0 to 100 ° C, preferably 0 to 50 ° C, and the reaction time is usually about 0.5 to 48 hours, and preferably 1 to 24 hours.

反應B所使用之式(3)之化合物可依後述之反應1-2或反應1-3製造。式(4)之化合物可依以下之反應2-1或公知之方法製造，或可使用市售品。The compound of the formula (3) used in the reaction B can be produced according to the following reaction 1-2 or reaction 1-3. The compound of formula (4) can be produced according to the following reaction 2-1 or a known method, or a commercially available product can be used.

反應C
反應C係將式(5)之化合物與式(6)之化合物進行反應，得到式(1)之化合物之方法。Reaction C
Reaction C is a method of reacting a compound of formula (5) with a compound of formula (6) to obtain a compound of formula (1).

式中，X為氯原子、溴原子或碘原子，其他記號係如前述。In the formula, X is a chlorine atom, a bromine atom, or an iodine atom, and other symbols are as described above.

反應C通常可於鹼及溶媒的存在下進行。式(6)之化合物相對於式(5)之化合物1當量，可使用1～3當量，期望為1～2當量。Reaction C can usually be performed in the presence of a base and a solvent. The compound of formula (6) can be used in an amount of 1 to 3 equivalents with respect to 1 equivalent of the compound of formula (5), and is desirably 1 to 2 equivalents.

作為鹼，例如可從如鈉、鉀之鹼金屬；如甲醇鈉、乙醇鈉、第3級丁醇鉀之鹼金屬醇鹽；如碳酸鈉、碳酸鉀之碳酸鹽；如碳酸氫鈉、碳酸氫鉀之碳酸氫鹽；如氫氧化鈉、氫氧化鉀之金屬氫氧化物；如氫化鈉、氫化鉀之金屬氫化物；如單甲基胺、二甲基胺、三乙基胺、二異丙基乙基胺之胺類等中適當選擇1種或2種以上。鹼相對於式(5)之化合物，可使用1～3當量，期望為1～2當量。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如乙酸甲酯、乙酸乙酯之酯類；如甲醇、乙醇、丙醇、tert-丁醇之醇類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒；如丙酮、甲基乙基酮之酮類；水等中適當選擇1種或2種以上。Examples of the base include alkali metals such as sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium butoxide of the third order; carbonates such as sodium carbonate and potassium carbonate; such as sodium bicarbonate and hydrogen carbonate Potassium bicarbonate; such as sodium hydroxide, potassium hydroxide metal hydroxide; such as sodium hydride, potassium hydride metal hydride; such as monomethylamine, dimethylamine, triethylamine, diisopropyl One or two or more of the amines of ethylethylamine are appropriately selected. The base can be used in an amount of 1 to 3 equivalents to the compound of the formula (5), and is preferably 1 to 2 equivalents.
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent may be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; for example, carbon tetrachloride, methylene chloride, chloroform, methylene chloride, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as methyl acetate, acetic acid Ester of ethyl esters; alcohols such as methanol, ethanol, propanol, tert-butanol; such as dimethylmethylene, cyclobutylammonium, dimethylacetamide, N, N-dimethylformamide , N-methylpyrrolidone, pyridine, acetonitrile, propionitrile polar aprotic solvents; such as acetone, methyl ethyl ketones; water, etc., one or more than one kind is appropriately selected.

反應溫度通常為0～100℃，期望為20～80℃，反應時間通常為0.1～48小時左右，期望為1～24小時左右。The reaction temperature is usually 0 to 100 ° C, preferably 20 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 1 to 24 hours.

反應C所使用之式(5)之化合物可依後述之反應1-9製造。式(6)之化合物可依公知之方法製造，或可使用市售品。The compound of the formula (5) used in the reaction C can be produced according to the reactions 1-9 described later. The compound of formula (6) can be produced by a known method, or a commercially available product can be used.

反應D
反應D係使用式(7)之化合物，從A1 之RA 為氟之式(1-1)之化合物，變換成A2 之RA 為羥基之式(1-2)之化合物之方法。Reaction D
Reaction D is a method of using a compound of formula (7) to convert a compound of formula (1-1) in which R A of A 1 is fluorine to a compound of formula (1-2) in which R A of A 2 is hydroxy.

式中，A1 為被氟取代之苯基或被氟取代之吡啶基，A2 為被羥基取代之苯基或被羥基取代之吡啶基，其他記號係如前述。In the formula, A 1 is a phenyl group substituted with fluorine or a pyridyl group substituted with fluorine, and A 2 is a phenyl group substituted with a hydroxyl group or a pyridyl group substituted with a hydroxyl group. Other symbols are as described above.

反應D通常可於鹼及溶媒的存在下進行。式(7)之化合物相對於式(1-1)之化合物1當量，可使用1～10當量，期望為1～5當量。Reaction D can usually be performed in the presence of a base and a solvent. The compound of the formula (7) can be used in an amount of 1 to 10 equivalents with respect to the compound of the formula (1-1), and is desirably 1 to 5 equivalents.

鹼例如可從如鈉、鉀之鹼金屬；如甲醇鈉、乙醇鈉、第3級丁醇鉀之鹼金屬醇鹽；如碳酸鈉、碳酸鉀之碳酸鹽；如碳酸氫鈉、碳酸氫鉀之碳酸氫鹽；如氫氧化鈉、氫氧化鉀之金屬氫氧化物；如氫化鈉、氫化鉀之金屬氫化物；如單甲基胺、二甲基胺、三乙基胺、二異丙基乙基胺之胺類；如吡啶、4-二甲基胺基吡啶之吡啶類；如甲基鋰、n-丁基鋰、鋰二異丙基醯胺之有機鋰化合物等中適當選擇1種或2種以上。鹼相對於式(1-1)之化合物，可使用1～10當量，期望為1～5當量。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如乙酸甲酯、乙酸乙酯之酯類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒；如丙酮、甲基乙基酮之酮類等中適當選擇1種或2種以上。Examples of the base include alkali metals such as sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium butoxide of the third order; carbonates such as sodium carbonate and potassium carbonate; such as sodium bicarbonate and potassium bicarbonate. Bicarbonates; metal hydroxides such as sodium hydroxide and potassium hydroxide; metal hydrides such as sodium hydride and potassium hydride; such as monomethylamine, dimethylamine, triethylamine, diisopropylethyl Amines such as pyridine, pyridine of 4-dimethylaminopyridine; organic lithium compounds such as methyllithium, n-butyllithium, lithium diisopropylamidine, etc. 2 or more. The base can be used in an amount of 1 to 10 equivalents with respect to the compound of the formula (1-1), and is preferably 1 to 5 equivalents.
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent may be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; for example, carbon tetrachloride, methylene chloride, chloroform, methylene chloride, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as methyl acetate, acetic acid Ester of ethyl esters; such as dimethylmethylene, cyclobutane, dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, and propionitrile. Protonic solvents; such as acetone, ketones of methyl ethyl ketone, etc. are appropriately selected from one or two or more.

反應溫度通常為0～150℃，期望為50～100℃，反應時間通常為1～24小時左右，期望為1～12小時左右。The reaction temperature is usually 0 to 150 ° C, preferably 50 to 100 ° C, and the reaction time is usually about 1 to 24 hours, and preferably about 1 to 12 hours.

反應E
反應E係使用式(8)之化合物或式(9)之化合物，將A2 之RA 為羥基之式(1-2)之化合物變換成A3 之RA 為-O-YA1 之式(1-3)之化合物之方法。Reaction E
Reacting a compound of formula E series (8) or the formula (9), the R A A 2 of the compound of formula (1-2) is converted into the hydroxyl groups of A R A 3 is of formula (1 -OY A1 of -3).

式中，A3 為被-O-YA1 取代之苯基或吡啶基，YA1 為可被Z2 取代之烷基、烯基或可被Z3 取代之環狀基，
其他記號係如前述。Wherein, A 3 is a substituted -OY A1 of phenyl or pyridyl, Y A1 Z 2 which may be substituted with the alkyl group, alkenyl group, or Z 3 may be substituted with the cyclic group,
The other symbols are as described above.

反應E通常可於式(8)之化合物、鹼及溶媒的存在下進行。或依一般的光延反應(Mitsunobu reaction)，可於式(9)之化合物、三苯基膦、偶氮二羧酸二酯及溶媒的存在下進行。式(8)之化合物或式(9)之化合物相對於式(1-2)之化合物1當量，可使用1～3當量，期望為1～2當量。三苯基膦相對於式(1-2)之化合物1當量，可使用1～3當量，期望為1～1.5當量。偶氮二羧酸二酯相對於式(1-2)之化合物1當量，可使用1～3當量，期望為1～1.5當量。Reaction E can usually be carried out in the presence of a compound of formula (8), a base and a solvent. Or according to a general Mitsunobu reaction, it can be carried out in the presence of a compound of formula (9), triphenylphosphine, azodicarboxylic acid diester, and a solvent. The compound of the formula (8) or the compound of the formula (9) can be used in an amount of 1 to 3 equivalents with respect to the compound of the formula (1-2), and is desirably 1 to 2 equivalents. Triphenylphosphine can be used in an amount of 1 to 3 equivalents to 1 equivalent of the compound of formula (1-2), and is desirably 1 to 1.5 equivalents. The azodicarboxylic acid diester may be used in an amount of 1 to 3 equivalents with respect to 1 equivalent of the compound of the formula (1-2), and is desirably 1 to 1.5 equivalents.

鹼例如可從如甲醇鈉、乙醇鈉、第3級丁醇鉀之鹼金屬醇鹽；如碳酸鈉、碳酸鉀之碳酸鹽；如碳酸氫鈉、碳酸氫鉀之碳酸氫鹽；如氫氧化鈉、氫氧化鉀之金屬氫氧化物；如氫化鈉、氫化鉀之金屬氫化物；如單甲基胺、二甲基胺、三乙基胺、二異丙基乙基胺之胺類；如吡啶、4-二甲基胺基吡啶之吡啶類等中適當選擇1種或2種以上。鹼相對於式(1-2)之化合物，可使用1～2當量，期望為1～1.5當量。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如乙酸甲酯、乙酸乙酯之酯類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶之極性非質子性溶媒；如乙腈、丙腈、丙烯腈之腈類；如丙酮、甲基乙基酮之酮類；水等中適當選擇1種或2種以上。
作為偶氮二羧酸二酯，例如可使用偶氮二羧酸二乙酯等。The base may be, for example, an alkali metal alkoxide such as sodium methoxide, sodium ethoxide, or potassium butoxide of the third order; a carbonate such as sodium carbonate or potassium carbonate; a bicarbonate such as sodium bicarbonate or potassium bicarbonate; And potassium hydroxide metal hydroxides; such as sodium hydride, potassium hydride metal hydrides; such as monomethylamine, dimethylamine, triethylamine, diisopropylethylamine amines; such as pyridine And 4-dimethylaminopyridine, pyridines, and the like are appropriately selected from one or two or more. The base can be used in an amount of 1 to 2 equivalents to the compound of the formula (1-2), and is preferably 1 to 1.5 equivalents.
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent may be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; for example, carbon tetrachloride, methylene chloride, chloroform, methylene chloride, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as methyl acetate, acetic acid Ester of ethyl esters; such as dimethylmethylene, cyclamidine, dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, and polar aprotic solvents of pyridine; such as Nitriles such as acetonitrile, propionitrile, and acrylonitrile; ketones such as acetone, methyl ethyl ketone; and water, etc., may be appropriately selected from one or two or more kinds.
Examples of the azodicarboxylic acid diester include diethyl azodicarboxylate.

反應溫度通常為-30～100℃，期望為0～50℃，反應時間通常為0.1～24小時左右，期望為0.1～12小時左右。The reaction temperature is usually -30 to 100 ° C, preferably 0 to 50 ° C, and the reaction time is usually about 0.1 to 24 hours, and preferably about 0.1 to 12 hours.

反應E所使用之式(8)及式(9)之化合物可依公知之方法製造，或可使用市售品。The compounds of the formula (8) and the formula (9) used in the reaction E can be produced by a known method, or a commercially available product can be used.

反應F
反應F係使用式(10)之化合物或式(11)之化合物，將A4 之RA 為X之式(1-4)之化合物變換成A5 之RA 為特定之RA2 之式(1-5)之化合物之方法。Reaction F
Reacting a compound of formula F line (10) or of formula (11), the R A A 4 of the compound of formula (1-4) of the X into A R A 5 R A2 of a particular of the formula ( 1-5).

式中，A4 為被X取代之苯基或被X取代之吡啶基，式中，A5 為被RA2 取代之苯基或被RA2 取代之吡啶基，RA2 為烷基、鹵烷基、烯基、炔基、環狀基、氰基或
-LA1 -YA ，LA1 為O、S、C(=O)、C(=O)O、C(=O)N(R1 )、N(R1 )、N(R1 )C(=O)O、SO、SO2 或SO2 N(R1 )，M為如鎂、鋅之金屬原子或其鹽，或硼酸或其酯之殘基，其他記號係如前述。Wherein, A 4 is a substituent of the phenyl group substituted by X or X pyridinyl, wherein, A 5 is the substituted or unsubstituted phenyl group of R A2 R A2 pyridyl, R A2 is alkyl, haloalkyl Group, alkenyl, alkynyl, cyclic, cyano or
-L A1 -Y A , L A1 is O, S, C (= O), C (= O) O, C (= O) N (R 1 ), N (R 1 ), N (R 1 ) C (= O) O, SO, SO 2 or SO 2 N (R 1 ), M is a metal atom such as magnesium or zinc or a salt thereof, or a residue of boric acid or an ester thereof, and other symbols are as described above.

反應F通常可藉由將式(1-4)之化合物，於過渡金屬觸媒、溶媒及惰性氣體的存在下，如有必要添加鹼，與式(10)之化合物或式(11)之化合物進行反應來進行。Reaction F can usually be carried out by adding a compound of formula (1-4) in the presence of a transition metal catalyst, a solvent and an inert gas, if necessary, with a compound of formula (10) or a compound of formula (11) The reaction proceeds.

作為式(10)之化合物或式(11)之化合物，若能進行反應則並未特別限定，可依公知之方法調製，或可使用市售品。式(10)之化合物或式(11)之化合物相對於式(1-4)之化合物，可使用1～10當量，期望為1～5當量。The compound of the formula (10) or the compound of the formula (11) is not particularly limited as long as it can be reacted, and can be prepared according to a known method, or a commercially available product can be used. The compound of the formula (10) or the compound of the formula (11) can be used in an amount of 1 to 10 equivalents with respect to the compound of the formula (1-4), and is desirably 1 to 5 equivalents.

作為過渡金屬觸媒，可列舉包含鈀、銅、銠、釕、鎳、鈷、鉬等之過渡金屬的觸媒。作為過渡金屬觸媒，可使用有機鹵素化物之交叉偶合反應所使用之公知之各種構造者，於本反應包含鈀之過渡金屬觸媒特別有用。作為包含鈀之過渡金屬觸媒，例如可列舉鈀-碳、氯化鈀、乙酸鈀、二氯雙(乙腈)鈀、雙(二苯亞基(Dibenzylidene)丙酮)鈀、二氯雙(三苯基膦)鈀、肆(三苯基膦)鈀、二氯雙(1,4-雙(二苯基膦基)丁烷)鈀等。又，如有必要可將第3級膦或第3級亞磷酸酯作為配位子使用。作為第3級膦或第3級亞磷酸酯，可列舉三苯基膦、苯基二甲基膦、三-o-甲苯基膦、三-p-甲苯基膦、1,2-雙(二苯基膦基)乙烷、1,3-雙(二苯基膦基)丙烷、1,4-雙(二苯基膦基)丁烷、1,1’-雙(二苯基膦基)二茂鐵、三苯基亞磷酸酯等。過渡金屬觸媒相對於式(1-4)之化合物1當量，可使用0.001～0.5當量，期望為0.05～0.2當量。又，配位子相對於過渡金屬觸媒1當量，通常可使用1～50當量，期望為1～10當量。惟，因反應條件亦可使用此範圍外的量。Examples of the transition metal catalyst include catalysts containing transition metals such as palladium, copper, rhodium, ruthenium, nickel, cobalt, and molybdenum. As the transition metal catalyst, various known structures used in cross-coupling reactions of organic halides can be used. The transition metal catalyst containing palladium in this reaction is particularly useful. Examples of the transition metal catalyst containing palladium include palladium-carbon, palladium chloride, palladium acetate, dichlorobis (acetonitrile) palladium, bis (dibenzylideneacetone) palladium, and dichlorobis (triphenylene) Phosphine) palladium, tris (triphenylphosphine) palladium, dichlorobis (1,4-bis (diphenylphosphino) butane) palladium, and the like. If necessary, a third-stage phosphine or a third-stage phosphite may be used as a ligand. Examples of the tertiary phosphine or tertiary phosphite include triphenylphosphine, phenyldimethylphosphine, tri-o-tolylphosphine, tri-p-tolylphosphine, and 1,2-bis (di Phenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) Ferrocene, triphenyl phosphite, etc. The transition metal catalyst can be used in an amount of 0.001 to 0.5 equivalents, and is desirably 0.05 to 0.2 equivalents relative to 1 equivalent of the compound of the formula (1-4). The ligand is usually 1 to 50 equivalents to the transition metal catalyst, and is preferably 1 to 10 equivalents. However, an amount outside this range may be used due to reaction conditions.

作為鹼，例如可列舉如碳酸鈉、碳酸鉀、碳酸銫之鹼金屬碳酸鹽；如甲醇鈉、乙醇鈉、第3級丁醇鉀之鹼金屬醇鹽；如碳酸氫鈉之鹼金屬的碳酸氫鹽；如碳酸鈣之鹼土類金屬的碳酸鹽；如氫氧化鈉、氫氧化鉀之金屬氫氧化物；如氫化鈉、氫化鉀之金屬氫化物；如三乙基胺、二異丙基乙基胺、吡啶、4-(N,N-二甲基胺基)吡啶、咪唑之有機胺類等。鹼相對於式(1-4)之化合物，可使用1～20當量，期望為1～10當量。Examples of the base include alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and third-order potassium butoxide; and alkali metal hydrogen carbonates such as sodium bicarbonate Salts; carbonates of alkaline earth metals such as calcium carbonate; metal hydroxides such as sodium hydroxide and potassium hydroxide; metal hydrides such as sodium hydride and potassium hydride; such as triethylamine, diisopropylethyl Organic amines such as amines, pyridine, 4- (N, N-dimethylamino) pyridine, and imidazole. The base can be used in an amount of 1 to 20 equivalents with respect to the compound of the formula (1-4), and is desirably 1 to 10 equivalents.

溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如乙酸甲酯、乙酸乙酯之酯類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶之極性非質子性溶媒；如乙腈、丙腈、丙烯腈之腈類；如丙酮、甲基乙基酮之酮類；如甲醇、乙醇、丙醇、tert-丁醇之醇類；水等中適當選擇1種或2種以上。Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent may be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; for example, carbon tetrachloride, methylene chloride, chloroform, methylene chloride, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as methyl acetate, acetic acid Ester of ethyl esters; such as dimethylmethylene, cyclamidine, dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, and polar aprotic solvents of pyridine; such as Nitriles such as acetonitrile, propionitrile, and acrylonitrile; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, propanol, and tert-butanol; and one or two or more selected appropriately from water, etc. .

惰性氣體例如可使用氮氣體、氬氣體等。Examples of the inert gas include nitrogen gas and argon gas.

反應溫度通常為-100～200℃，期望為-78～100℃，反應時間通常為0.5～96小時左右，期望為1～48小時左右。The reaction temperature is usually -100 to 200 ° C, preferably -78 to 100 ° C, and the reaction time is usually about 0.5 to 96 hours, and preferably about 1 to 48 hours.

反應G
反應G係藉由A6 之RA 為胺基之式(1-6)之化合物與(鹵)烷基化劑或醯化劑的反應，或還原的烷基化反應，變換成A7 之RA 為-LA2 -YA1 之式(1-7)之化合物之方法。Reaction G
Alkylation reaction system G A R A 6 by the reaction of a compound of an alkylating agent or acylation agent, (halo) formula (1-6) of the group is, or reduced, it is converted to A 7 A method in which R A is -L A2 -Y A1 of the compound of formula (1-7).

式中，A6 為被胺基取代之苯基或被胺基取代之吡啶基，A7 為被-LA2 -YA1 取代之苯基或被-LA2 -YA1 取代之吡啶基，LA2 為N(R1 )、N(R1 )C(=O)或N(R1 )C(=O)O，其他記號係如前述。In the formula, A 6 is a phenyl group substituted with an amine group or a pyridyl group substituted with an amine group, A 7 is a phenyl group substituted with -L A2 -Y A1 or a pyridyl group substituted with -L A2 -Y A1 , L A2 is N (R 1 ), N (R 1 ) C (= O) or N (R 1 ) C (= O) O, and other symbols are as described above.

反應G當中，(鹵)烷基化劑或醯化劑的反應通常可於鹼及溶媒的存在下進行。(鹵)烷基化劑或醯化劑相對於式(1-6)之化合物1當量，可使用1～3當量，期望為1～2當量。In the reaction G, the reaction of the (halo) alkylating agent or the halogenating agent can usually be performed in the presence of a base and a solvent. The (halogen) alkylating agent or sulfonating agent may be used in an amount of 1 to 3 equivalents, and preferably 1 to 2 equivalents, based on 1 equivalent of the compound of the formula (1-6).

鹼及溶媒可使用前述反應E所列舉者。
作為(鹵)烷基化劑，例如可列舉如碘化甲烷、溴化甲烷之鹵素化烷基；硫酸二甲酯等之硫酸二烷酯；三甲基矽烷基重氮甲烷；氯二氟甲烷、氯二氟乙酸鈉等。
作為醯化劑，可列舉醯基氯等之酸氯化物；乙酸酐等之酸酐等。As the base and the solvent, those listed in the above reaction E can be used.
Examples of the (halogen) alkylating agent include halogenated alkyl groups such as methyl iodide and methyl bromide; dialkyl sulfates such as dimethyl sulfate; trimethylsilyl diazomethane; and chlorodifluoromethane. , Sodium chlorodifluoroacetate, etc.
Examples of the halogenating agent include acid chlorides such as fluorenyl chloride; acid anhydrides such as acetic anhydride and the like.

反應溫度通常為-30～100℃，期望為0～50℃，反應時間通常為0.1～24小時左右，期望為0.1～12小時左右。The reaction temperature is usually -30 to 100 ° C, preferably 0 to 50 ° C, and the reaction time is usually about 0.1 to 24 hours, and preferably about 0.1 to 12 hours.

在反應G之還原的烷基化反應，依一般的還原的烷基化反應，可於醛、還原劑、酸及溶媒的存在下進行。醛相對於式(1-6)之化合物1當量，可使用1～10當量，期望為1～5當量。
作為在還原的烷基化之醛，例如可使用甲醛、乙醛等。
作為還原劑，例如可從氰基氫化硼鈉、氫化三乙醯氧基硼鈉等中適當選擇1種或2種以上。還原劑相對於式(1-6)之化合物1當量，可使用1～5當量，期望為1～2當量。
作為酸，例如可使用乙酸等。酸相對於式(1-6)之化合物1當量，可使用1～30當量，期望為1～10當量。
作為溶媒，溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如乙腈、丙腈之腈類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如甲醇、乙醇、丙醇、tert-丁醇之醇類；水等中適當選擇1種或2種以上。
反應溫度通常為0～80℃，期望為0～50℃，反應時間通常為0.1～48小時左右，期望為0.5～24小時左右。The reduction alkylation reaction of reaction G can be performed in the presence of an aldehyde, a reducing agent, an acid, and a solvent according to a general reduction alkylation reaction. The aldehyde may be used in an amount of 1 to 10 equivalents with respect to 1 equivalent of the compound of the formula (1-6), and is preferably 1 to 5 equivalents.
As the reduced alkylated aldehyde, for example, formaldehyde and acetaldehyde can be used.
As the reducing agent, for example, one or two or more kinds can be appropriately selected from sodium cyanoborohydride, sodium triethoxyalkoxyborohydride, and the like. The reducing agent can be used in an amount of 1 to 5 equivalents to 1 equivalent of the compound of the formula (1-6), and is preferably 1 to 2 equivalents.
As the acid, for example, acetic acid can be used. The acid can be used in an amount of 1 to 30 equivalents with respect to 1 equivalent of the compound of the formula (1-6), and is desirably 1 to 10 equivalents.
As the solvent, if the solvent is a solvent that is inert to the reaction, any solvent may be used. Type; alcohols such as methanol, ethanol, propanol, tert-butanol; water or the like is appropriately selected from one or two or more.
The reaction temperature is usually 0 to 80 ° C, preferably 0 to 50 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 0.5 to 24 hours.

反應H
反應H係將式(1-8)之化合物變換成式(1-9)之化合物之方法。Reaction H
Reaction H is a method of converting a compound of the formula (1-8) into a compound of the formula (1-9).

式中，A8 為被與相鄰之碳原子鍵結的2個羥基取代之苯基，A9 為可被Z1 取代之苯并二氧環戊基，其他記號係如前述。In the formula, A 8 is a phenyl group substituted by two hydroxyl groups bonded to adjacent carbon atoms, A 9 is a benzodioxoyl group which may be substituted by Z 1 , and other symbols are as described above.

反應H通常可於酮、醛或原酸酯、與酸或脫水劑及溶媒的存在下進行。酮、醛或原酸酯相對於式(1-8)之化合物1當量，可使用1～50當量，期望為1～5當量。
或反應H可於1,1-二溴乙烷或二溴二氟甲烷、與鹼及溶媒的存在下進行。1,1-二溴乙烷及二溴二氟甲烷相對於式(1-8)之化合物1當量，可使用1～10當量，期望為1～2當量。Reaction H can usually be carried out in the presence of a ketone, aldehyde or orthoester, with an acid or dehydrating agent and a solvent. The ketone, aldehyde or orthoester may be used in an amount of 1 to 50 equivalents, and desirably 1 to 5 equivalents, based on 1 equivalent of the compound of formula (1-8).
Alternatively, reaction H can be carried out in the presence of 1,1-dibromoethane or dibromodifluoromethane in the presence of a base and a solvent. 1,1-dibromoethane and dibromodifluoromethane may be used in an amount of 1 to 10 equivalents based on 1 equivalent of the compound of formula (1-8), and it is desirable to be 1 to 2 equivalents.

作為酮、醛或原酸酯，雖可因應所期望之Z1 適當選擇，但例如可列舉如丙酮、甲基乙基酮之酮；如乙醛、異丁基醛之醛；如原甲酸乙酯、原乙酸乙酯之原酸酯。
作為酸，例如可列舉鹽酸、硫酸、對甲苯磺酸等。作為脫水劑，例如可列舉五氧化二磷等。作為鹼，例如可列舉如氫氧化鈉、氫氧化鉀之金屬氫氧化物；如碳酸鈉、碳酸鉀、碳酸銫之碳酸鹽等。酸相對於式(1-8)之化合物1當量，可使用0.01～5當量，期望為0.05～1當量。脫水劑或鹼相對於式(1-8)之化合物1當量，可使用1～10當量，期望為1～2當量。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如甲醇、乙醇、丙醇、tert-丁醇之醇類；如乙腈、丙腈、丙烯腈之腈類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮之極性非質子性溶媒等中適當選擇1種或2種以上。As the ketone, aldehyde or orthoester, although it can be appropriately selected according to the desired Z 1 , for example, ketones such as acetone and methyl ethyl ketone; aldehydes such as acetaldehyde and isobutyl aldehyde; and ethyl orthoformate Esters, orthoesters of ethyl orthoacetate.
Examples of the acid include hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid. Examples of the dehydrating agent include phosphorus pentoxide. Examples of the base include metal hydroxides such as sodium hydroxide and potassium hydroxide; and carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate. The acid may be used in an amount of 0.01 to 5 equivalents with respect to 1 equivalent of the compound of the formula (1-8), and is desirably 0.05 to 1 equivalent. The dehydrating agent or base may be used in an amount of 1 to 10 equivalents based on 1 equivalent of the compound of the formula (1-8), and is desirably 1 to 2 equivalents.
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent can be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, and cyclohexane; alcohols such as methanol, ethanol, propanol, tert-butanol; nitriles such as acetonitrile, propionitrile, and acrylonitrile; For example, one or two or more of dimethylmethylene, cyclamidine, dimethylacetamide, N, N-dimethylformamide, and polar aprotic solvents of N-methylpyrrolidone are appropriately selected. .

反應溫度通常為0～150℃，期望為20～100℃，反應時間通常為0.1～48小時左右，期望為1～24小時左右。The reaction temperature is usually 0 to 150 ° C, preferably 20 to 100 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 1 to 24 hours.

反應I
反應I係將式(1-10)之化合物變換成式(1-11)之化合物之方法。Reaction I
Reaction I is a method of converting a compound of the formula (1-10) into a compound of the formula (1-11).

式中，A10 為被烯基或炔基取代之苯基或被烯基或炔基取代之吡啶基，A11 為被烷基取代之苯基或被烷基取代之吡啶基，其他記號係如前述。In the formula, A 10 is phenyl substituted by alkenyl or alkynyl or pyridyl substituted by alkenyl or alkynyl, A 11 is phenyl substituted by alkyl or pyridyl substituted by alkyl. Other symbols are As before.

反應I可依一般的接觸還原，氫環境下，藉由將鉑、氧化鉑、鉑黑、雷尼鎳、鈀、鈀碳、銠、銠-氧化鋁等作為觸媒使用來進行。Reaction I can be reduced by general contact. Under a hydrogen environment, platinum, platinum oxide, platinum black, Raney nickel, palladium, palladium carbon, rhodium, rhodium-alumina, and the like are used as catalysts.

反應I通常可於溶媒的存在下進行。溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯之芳香族烴類；如己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如乙酸甲酯、乙酸乙酯之酯類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒；如丙酮、甲基乙基酮之酮類；如甲醇、乙醇、丙醇、tert-丁醇之醇類；水等中適當選擇1種或2種以上。Reaction I can usually be carried out in the presence of a solvent. Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent can be aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and cyclohexane; and dioxane and tetrahydrofuran. , Diethyl ether, dimethoxyethane ethers; such as methyl acetate, ethyl acetate esters; such as dimethyl sulfene, cyclobutylamidine, dimethylacetamide, N, N- Polar aprotic solvents of dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, and propionitrile; such as ketones of acetone and methyl ethyl ketone; such as methanol, ethanol, propanol, tert-butanol Among alcohols; water, etc., one or more kinds are appropriately selected.

反應溫度通常為0～150℃，期望為0～80℃，反應時間通常為0.5～96小時左右，期望為0.5～48小時左右。The reaction temperature is usually 0 to 150 ° C, preferably 0 to 80 ° C, and the reaction time is usually about 0.5 to 96 hours, and preferably about 0.5 to 48 hours.

雖將反應A～I所使用之化合物的製造方法記載於以下，但並非被限定於此等之方法者，此等之化合物可依公知之方法製造，或可使用市售品。Although the production methods of the compounds used in the reactions A to I are described below, they are not limited to these methods, and these compounds can be produced by a known method or a commercially available product can be used.

反應1-1
反應1-1係將式(100)之化合物與式(4)之化合物進行反應，得到式(2)之化合物之方法。進而，藉由水解與式(2)之化合物一同得到之式(101)之化合物，可得到式(2)之化合物。Reaction 1-1
Reaction 1-1 is a method of reacting a compound of formula (100) with a compound of formula (4) to obtain a compound of formula (2). Furthermore, a compound of formula (101) can be obtained by hydrolyzing a compound of formula (101) together with a compound of formula (2).

式中之記號係如前述。The symbols in the formula are as described above.

在反應1-1，式(100)之化合物與式(4)之化合物的反應通常可於鹼及溶媒的存在下進行，或如有必要可於脫水縮合劑的存在下進行。
作為鹼、溶媒及脫水縮合劑，可使用於前述反應B所列舉者。式(4)之化合物相對於式(100)之化合物1當量，可使用1～3當量，期望為1～2當量。鹼相對於式(100)之化合物1當量，可使用1～3當量，期望為1～2當量。In the reaction 1-1, the reaction of the compound of the formula (100) and the compound of the formula (4) can be usually performed in the presence of a base and a solvent, or if necessary, in the presence of a dehydrating condensation agent.
As a base, a solvent, and a dehydration condensation agent, it can be used for the thing mentioned by the said reaction B. The compound of the formula (4) can be used in an amount of 1 to 3 equivalents to the compound of the formula (100), and is preferably 1 to 2 equivalents. The base can be used in an amount of 1 to 3 equivalents with respect to 1 equivalent of the compound of the formula (100), and is desirably 1 to 2 equivalents.

反應溫度通常為0～100℃，期望為0～50℃，反應時間通常為0.5～48小時左右，期望為1～24小時左右。The reaction temperature is usually 0 to 100 ° C, preferably 0 to 50 ° C, and the reaction time is usually about 0.5 to 48 hours, and preferably 1 to 24 hours.

在反應1-1，可藉由水解與式(2)之化合物一同得到之式(101)之化合物，對式(2)之化合物導入。
水解可依一般的水解的反應條件進行，通常可於酸或鹼及溶媒的存在下進行。In the reaction 1-1, the compound of the formula (101) obtained by hydrolysis with the compound of the formula (2) can be introduced into the compound of the formula (2).
The hydrolysis can be performed according to general hydrolysis reaction conditions, and usually can be performed in the presence of an acid or a base and a solvent.

作為酸，例如可列舉鹽酸、硫酸等。作為鹼，例如可列舉如氫氧化鈉、氫氧化鉀之金屬氫氧化物等。酸或鹼相對於式(100)之化合物1當量，可使用1～10當量，期望為1～5當量。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如甲醇、乙醇、丙醇、tert-丁醇之醇類；如乙腈、丙腈、丙烯腈之腈類；如丙酮、甲基乙基酮之酮類；水等中適當選擇1種或2種以上。Examples of the acid include hydrochloric acid and sulfuric acid. Examples of the base include metal hydroxides such as sodium hydroxide and potassium hydroxide. The acid or base may be used in an amount of 1 to 10 equivalents relative to 1 equivalent of the compound of the formula (100), and is desirably 1 to 5 equivalents.
Any solvent may be used if the solvent is a solvent inert to the reaction, for example, alcohols such as methanol, ethanol, propanol, tert-butanol; nitriles such as acetonitrile, propionitrile, and acrylonitrile; such as acetone, formaldehyde One or two or more ketones of ethyl ethyl ketone are appropriately selected from water and the like.

水解之反應溫度通常為0～100℃，期望為20～80℃，反應時間通常為0.1～12小時左右，期望為0.1～1小時左右。The reaction temperature for hydrolysis is usually from 0 to 100 ° C, preferably from 20 to 80 ° C, and the reaction time is usually from about 0.1 to 12 hours, and preferably from about 0.1 to 1 hour.

反應1-1所使用之式(100)之化合物可依以下之反應1-4或反應1-5製造。式(4)之化合物可依以下之反應2-1或公知之方法製造，或可使用市售品。The compound of formula (100) used in reaction 1-1 can be produced according to the following reaction 1-4 or reaction 1-5. The compound of formula (4) can be produced according to the following reaction 2-1 or a known method, or a commercially available product can be used.

反應1-2
反應1-2係藉由甲基化式(100)之化合物，得到式(3)之化合物之方法。Reaction 1-2
Reaction 1-2 is a method of obtaining a compound of formula (3) by methylating a compound of formula (100).

式中之記號係如前述。The symbols in the formula are as described above.

反應1-2可依前述反應A進行。Reaction 1-2 can be performed according to the aforementioned reaction A.

反應1-3
反應1-3係將式(5)之化合物與O-甲基羥基胺鹽酸鹽進行反應，得到式(3)之化合物之方法。Reaction 1-3
Reaction 1-3 is a method of reacting a compound of formula (5) with O-methylhydroxylamine hydrochloride to obtain a compound of formula (3).

式中之記號係如前述。The symbols in the formula are as described above.

反應1-3可依照反應C進行。O-甲基羥基胺鹽酸鹽相對於式(5)之化合物1當量，可使用1～3當量，期望為1～2當量。Reactions 1-3 can be performed according to Reaction C. O-methylhydroxylamine hydrochloride may be used in an amount of 1 to 3 equivalents with respect to 1 equivalent of the compound of the formula (5), and is desirably 1 to 2 equivalents.

反應1-4
反應1-4係還原式(102)之化合物，得到式(100)之化合物之方法。Reactions 1-4
Reaction 1-4 is a method of reducing a compound of formula (102) to obtain a compound of formula (100).

式中之記號係如前述。The symbols in the formula are as described above.

作為還原反應，例如可於氫環境下藉由將氧化鉑、雷尼鎳、鈀-碳、銠等作為觸媒之接觸還原；於由如鐵、鋅之金屬、與如鹽酸、乙酸、氯化銨之酸所構成之反應系的還原來進行。As a reduction reaction, for example, it can be reduced by contacting platinum oxide, Raney nickel, palladium-carbon, rhodium, etc. as catalysts in a hydrogen environment; and metals such as iron, zinc, and hydrochloric acid, acetic acid, chlorination The reduction of the reaction system consisting of ammonium acid proceeds.

反應1-4通常可於溶媒的存在下進行。溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯之芳香族烴類；如己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如乙酸甲酯、乙酸乙酯之酯類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒；如丙酮、甲基乙基酮之酮類；如甲醇、乙醇、丙醇、tert-丁醇之醇類；水等中適當選擇1種或2種以上。Reactions 1-4 can usually be carried out in the presence of a solvent. Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent can be aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and cyclohexane; and dioxane and tetrahydrofuran. , Diethyl ether, dimethoxyethane ethers; such as methyl acetate, ethyl acetate esters; such as dimethyl sulfene, cyclobutylamidine, dimethylacetamide, N, N- Polar aprotic solvents of dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, and propionitrile; such as ketones of acetone and methyl ethyl ketone; such as methanol, ethanol, propanol, tert-butanol Among alcohols; water, etc., one or more kinds are appropriately selected.

反應溫度通常為0～150℃，期望為0～80℃，反應時間通常為0.5～96小時左右，期望為0.5～48小時左右。The reaction temperature is usually 0 to 150 ° C, preferably 0 to 80 ° C, and the reaction time is usually about 0.5 to 96 hours, and preferably about 0.5 to 48 hours.

前述反應1-4所使用之式(102)之化合物可依以下之反應1-6或反應1-8製造。The compound of formula (102) used in the aforementioned reactions 1-4 can be produced according to the following reactions 1-6 or 1-8.

反應1-5
反應1-5係將式(5)之化合物與羥基胺鹽酸鹽進行反應，得到式(100)之化合物之方法。Reaction 1-5
Reaction 1-5 is a method of reacting a compound of formula (5) with hydroxylamine hydrochloride to obtain a compound of formula (100).

式中之記號係如前述。The symbols in the formula are as described above.

反應1-5可依照反應C進行。羥基胺鹽酸鹽相對於式(5)之化合物1當量，可使用1～3當量，期望為1～2當量。Reactions 1-5 can be performed according to Reaction C. The hydroxylamine hydrochloride may be used in an amount of 1 to 3 equivalents to the compound of formula (5), and is preferably 1 to 2 equivalents.

反應溫度通常為0～100℃，期望為20～80℃，反應時間通常為0.1～48小時左右，期望為1～24小時左右。The reaction temperature is usually 0 to 100 ° C, preferably 20 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 1 to 24 hours.

反應1-6
反應1-6係氧化式(103)之化合物，得到式(102)之化合物之方法。Reactions 1-6
Reaction 1-6 is a method of oxidizing a compound of formula (103) to obtain a compound of formula (102).

式中之記號係如前述。The symbols in the formula are as described above.

作為氧化反應，例如可列舉於由鉻酸與硫酸、吡啶、吡啶鎓鹽所構成之反應系的氧化；於由二甲基亞碸與草醯氯所構成之反應系的氧化；於由過釕酸四丙基銨與如N-甲基嗎啉-N-氧化物之共氧化劑所構成之反應系的氧化；藉由戴斯-馬丁氧化劑(Dess-Martin Periodinane)之氧化；藉由二氧化錳之氧化等。Examples of the oxidation reaction include oxidation of a reaction system composed of chromic acid and sulfuric acid, pyridine, and pyridinium salts; oxidation of a reaction system composed of dimethylsulfine and chloramphonium chloride; and ruthenium persulfide. Oxidation of a reaction system composed of a tetrapropylammonium acid and a co-oxidant such as N-methylmorpholine-N-oxide; by oxidation of Dess-Martin Periodinane; by manganese dioxide Of oxidation, etc.

反應1-6通常可於溶媒的存在下進行。溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯之芳香族烴類；如四氯化碳、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如乙酸甲酯、乙酸乙酯之酯類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒；如丙酮、甲基乙基酮之酮類；如甲醇、乙醇、丙醇、tert-丁醇之醇類；水等中適當選擇1種或2種以上。Reactions 1-6 can usually be carried out in the presence of a solvent. Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent can be aromatic hydrocarbons such as benzene, toluene, and xylene; such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, and trichloride. Ethane, hexane, cyclohexane aliphatic hydrocarbons; such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane ethers; such as methyl acetate, ethyl acetate; Polar aprotic solvents of dimethylmethylene, cyclobutane, dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, and propionitrile; such as acetone, Ketones of methyl ethyl ketone; alcohols such as methanol, ethanol, propanol, tert-butanol; water, etc. are appropriately selected from one or two or more.

反應溫度通常為-78～150℃，期望為-50～80℃，反應時間通常為0.5～96小時左右，期望為0.5～48小時左右。The reaction temperature is usually -78 to 150 ° C, preferably -50 to 80 ° C, and the reaction time is usually about 0.5 to 96 hours, and preferably about 0.5 to 48 hours.

反應1-6所使用之式(103)之化合物可依以下之反應1-7製造。The compound of formula (103) used in Reactions 1-6 can be produced according to the following Reactions 1-7.

反應1-7
反應1-7係將式(104)之化合物與2-硝基丙烷進行反應，得到式(103)之化合物之方法。Reaction 1-7
Reaction 1-7 is a method of reacting a compound of formula (104) with 2-nitropropane to obtain a compound of formula (103).

式中之記號係如前述。The symbols in the formula are as described above.

反應1-7可依一般的硝基醇醛反應進行，通常可於鹼的存在下，如有必要可於溶媒的存在下進行。2-硝基丙烷相對於式(104)之化合物1當量，可使用1～30當量，期望為1～10當量。Reactions 1-7 can be carried out according to a general nitroaldol reaction, usually in the presence of a base and, if necessary, in the presence of a solvent. 2-Nitropropane may be used in an amount of 1 to 30 equivalents based on 1 equivalent of the compound of formula (104), and is desirably 1 to 10 equivalents.

作為鹼，例如可從如鈉、鉀之鹼金屬；如甲醇鈉、乙醇鈉、第3級丁醇鉀之鹼金屬醇鹽；如碳酸鈉、碳酸鉀之碳酸鹽；如碳酸氫鈉、碳酸氫鉀之碳酸氫鹽；如氫氧化鈉、氫氧化鉀之金屬氫氧化物；如氫化鈉、氫化鉀之金屬氫化物；如單甲基胺、二甲基胺、三乙基胺、二異丙基乙基胺之胺類；如1,8-二氮雜雙環[5.4.0]十一-7-烯之脒類；如四甲基胍、1,5,7-三氮雜雙環[4.4.0]癸-5-烯之胍類等中適當選擇1種或2種以上。鹼相對於式(104)之化合物，可使用0.1～2當量，期望為0.1～1當量。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如甲醇、乙醇、丙醇、tert-丁醇之醇類；如乙腈、丙腈、丙烯腈之腈類；如丙酮、甲基乙基酮之酮類；如四氯化碳、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶之極性非質子性溶媒；水等中適當選擇1種或2種以上。Examples of the base include alkali metals such as sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium butoxide of the third order; carbonates such as sodium carbonate and potassium carbonate; such as sodium bicarbonate and hydrogen carbonate Potassium bicarbonate; such as sodium hydroxide, potassium hydroxide metal hydroxide; such as sodium hydride, potassium hydride metal hydride; such as monomethylamine, dimethylamine, triethylamine, diisopropyl Ethylamines; such as 1,8-diazabicyclo [5.4.0] Undec-7-enes; such as tetramethylguanidine, 1,5,7-triazabicyclo [4.4 .0] One or more guanidines of dec-5-ene are appropriately selected. The base can be used in an amount of 0.1 to 2 equivalents with respect to the compound of the formula (104), and is desirably 0.1 to 1 equivalent.
Any solvent may be used if the solvent is a solvent inert to the reaction, for example, alcohols such as methanol, ethanol, propanol, tert-butanol; nitriles such as acetonitrile, propionitrile, and acrylonitrile; such as acetone, formaldehyde Ketones of ethyl ethyl ketones; such as aliphatic hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, dioxane Ethers of ethyl ether and dimethoxyethane; such as dimethylmethylene, cyclobutane, dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine It is a polar aprotic solvent; one or two or more kinds are appropriately selected among water and the like.

反應溫度通常為0～100℃，期望為20～50℃，反應時間通常為0.1～168小時左右，期望為1～24小時左右。The reaction temperature is usually 0 to 100 ° C, preferably 20 to 50 ° C, and the reaction time is usually about 0.1 to 168 hours, and preferably about 1 to 24 hours.

反應1-7所使用之式(104)之化合物可依公知之方法製造，或可使用市售品。The compound of formula (104) used in Reactions 1-7 can be produced by a known method, or a commercially available product can be used.

反應1-8
反應1-8係硝基化式(5)之化合物，得到式(102)之化合物之方法。Reaction 1-8
Reaction 1-8 is a method of nitrating a compound of formula (5) to obtain a compound of formula (102).

式中之記號係如前述。The symbols in the formula are as described above.

反應1-8通常可於硝基化劑及溶媒的存在下進行。Reactions 1-8 can usually be performed in the presence of a nitrolating agent and a solvent.

作為硝基化劑，例如可從亞硝酸鈉、亞硝酸鉀等中適當選擇1種或2種以上。硝基化劑相對於式(5)之化合物1當量，可使用1～2當量，期望為1～1.5當量。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如乙酸甲酯、乙酸乙酯之酯類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒；如丙酮、甲基乙基酮之酮類；如甲醇、乙醇、丙醇、tert-丁醇之醇類；水等中適當選擇1種或2種以上。As the nitrating agent, for example, one kind or two or more kinds can be appropriately selected from sodium nitrite, potassium nitrite, and the like. The nitroting agent may be used in an amount of 1 to 2 equivalents, and desirably is 1 to 1.5 equivalents based on 1 equivalent of the compound of formula (5).
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent may be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; such as carbon tetrachloride, chloroform, dichloromethane, and dichloroethane. , Trichloroethane, hexane, cyclohexane aliphatic hydrocarbons; such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane ethers; such as methyl acetate, ethyl acetate esters Classes; such as polar aprotic solvents of dimethylmethane, cyclamidine, dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, and propionitrile; Such as acetone, methyl ethyl ketones; alcohols such as methanol, ethanol, propanol, tert-butanol; water, etc., one or two or more kinds are appropriately selected.

反應溫度通常為0～150℃，期望為20～50℃，反應時間通常為0.1～96小時左右，期望為0.5～24小時左右。The reaction temperature is usually 0 to 150 ° C, preferably 20 to 50 ° C, and the reaction time is usually about 0.1 to 96 hours, and preferably about 0.5 to 24 hours.

反應1-9
反應1-9係鹵素化式(105)之化合物，得到式(5)之化合物之方法。Reaction 1-9
Reaction 1-9 is a method of halogenating a compound of formula (105) to obtain a compound of formula (5).

式中之記號係如前述。The symbols in the formula are as described above.

反應1-9可於鹵素化劑(例如氯化劑、溴化劑或碘化劑)及溶媒的存在下，如有必要可於鹼的存在下進行。鹵素化劑相對於式(105)之化合物1當量，可使用1～2當量，期望為1～1.5當量。Reactions 1-9 can be carried out in the presence of a halogenating agent (such as a chlorinating agent, a brominating agent or an iodinating agent) and a solvent, and if necessary, in the presence of a base. The halogenating agent can be used in an amount of 1 to 2 equivalents to 1 equivalent of the compound of formula (105), and is desirably 1 to 1.5 equivalents.

作為氯化劑，例如可從氯、N-氯琥珀醯亞胺等中適當選擇1種或2種以上，作為溴化劑，例如可從溴、N-溴琥珀醯亞胺、三甲基苯基三溴化銨等中適當選擇1種或2種以上，作為碘化劑，例如可從碘、N-碘琥珀醯亞胺等中適當選擇1種或2種以上。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如乙酸甲酯、乙酸乙酯之酯類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶之極性非質子性溶媒；如乙酸、丙酸之有機酸；水等中適當選擇1種或2種以上。
作為鹼，例如可列舉鋰二異丙基醯胺等。鹼相對於式(105)之化合物，可使用1～2當量，期望為1～1.2當量。
於鹼的存在下進行時，通常溶媒可從如四氫呋喃、二乙基醚之醚類中適當選擇1種或2種以上。
反應1-9如有必要可將如乙酸、丙酸之有機酸或如氯化鋁之路易斯酸作為觸媒使用。又，可藉由過剩使用作為觸媒之有機酸，兼作溶媒。As the chlorinating agent, for example, one or two or more can be appropriately selected from chlorine, N-chlorosuccinimide, and the like. As the brominating agent, for example, bromine, N-bromosuccinimide, and trimethylbenzene can be selected. One or two or more of these are appropriately selected from the group of ammonium tribromide and the like. As the iodinating agent, for example, one or two or more can be appropriately selected from iodine, N-iodosuccinimide, and the like.
Any solvent is acceptable as long as the solvent is inert to the reaction. For example, the solvent can be selected from carbon tetrachloride, methane chloride, chloroform, methylene chloride, dichloroethane, trichloroethane, hexane, and cyclohexane. Aliphatic hydrocarbons; such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane, ethers; such as methyl acetate, ethyl acetate; such as dimethyl sulfene, cyclobutane Aprotic solvents such as dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, and pyridine; organic acids such as acetic acid, propionic acid; water, etc. 2 or more.
Examples of the base include lithium diisopropylamidamine. The base can be used in an amount of 1 to 2 equivalents to the compound of the formula (105), and is desirably 1 to 1.2 equivalents.
When the reaction is performed in the presence of a base, one or two or more solvents may be appropriately selected from ethers such as tetrahydrofuran and diethyl ether.
In reactions 1-9, if necessary, organic acids such as acetic acid, propionic acid, or Lewis acids such as aluminum chloride can be used as catalysts. In addition, the organic acid serving as a catalyst can be used in excess to double as a solvent.

反應溫度通常為-100～150℃，期望為-78～110℃，反應時間通常為0.1～48小時左右，期望為0.5～24小時左右。於鹼的存在下進行時，反應溫度通常為-100～0℃，期望為-78～-20℃，反應時間通常為0.1～12小時左右，期望為0.5～6小時左右，又，於酸的存在下進行時，反應溫度通常為0～150℃，期望為20～110℃，反應時間通常為0.1～48小時左右，期望為1～24小時左右。The reaction temperature is usually -100 to 150 ° C, preferably -78 to 110 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 0.5 to 24 hours. When carried out in the presence of a base, the reaction temperature is usually -100 to 0 ° C, preferably -78 to -20 ° C, and the reaction time is usually about 0.1 to 12 hours, preferably about 0.5 to 6 hours. When carried out in the presence, the reaction temperature is usually 0 to 150 ° C, preferably 20 to 110 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 1 to 24 hours.

反應1-9所使用之式(105)之化合物可依以下之反應1-10～反應1-19製造。The compound of the formula (105) used in the reaction 1-9 can be produced according to the following reactions 1-10 to 1-19.

反應1-10
反應1-10係藉由式(106)之化合物及式(107)之化合物的佛瑞德-克來福特反應，得到式(105)之化合物之方法。Reaction 1-10
Reaction 1-10 is a method of obtaining a compound of formula (105) by a Friedel-Crafts reaction of a compound of formula (106) and a compound of formula (107).

式中，A’係相當於A之環，其他記號係如前述。In the formula, A 'is equivalent to the ring of A, and other symbols are as described above.

反應1-10可依一般的佛瑞德-克來福特反應進行，通常可於酸及溶媒的存在下進行。式(107)之化合物相對於式(106)之化合物1當量，可使用1～3當量，期望為1～2當量。
作為酸，例如可從如鹽酸、硫酸之無機酸；如對甲苯磺酸、三氟甲烷磺酸之有機酸；如氯化鋁、氯化鐵、氯化鋅、***合三氟化硼之路易斯酸等中適當選擇1種或2種以上。酸相對於式(106)之化合物1當量，可使用0.1～3當量，期望為1～2當量。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如乙腈、丙腈、丙烯腈之腈類；如四氯化碳、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶之極性非質子性溶媒等中適當選擇1種或2種以上。Reactions 1-10 can be carried out according to a general Friedel-Crafts reaction, and usually can be carried out in the presence of an acid and a solvent. The compound of the formula (107) can be used in an amount of 1 to 3 equivalents to the compound of the formula (106), and is preferably 1 to 2 equivalents.
As the acid, for example, inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as p-toluenesulfonic acid and trifluoromethanesulfonic acid; such as aluminum chloride, ferric chloride, zinc chloride, and Lewis boron trifluoride One kind or two or more kinds are appropriately selected among the acids and the like. The acid can be used in an amount of 0.1 to 3 equivalents with respect to 1 equivalent of the compound of the formula (106), and is desirably 1 to 2 equivalents.
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, it can be selected from nitriles such as acetonitrile, propionitrile, and acrylonitrile; such as carbon tetrachloride, chloroform, methylene chloride, dichloroethane, and trichloroethyl Aliphatic hydrocarbons such as alkane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as dimethyl sulfene, cyclobutane, and dimethyl Among polar aprotic solvents such as acetoamine, N, N-dimethylformamide, N-methylpyrrolidone, and pyridine, etc., one or two or more are appropriately selected.

反應溫度通常為0～100℃，期望為0～80℃，反應時間通常為0.1～48小時左右，期望為1～24小時左右。The reaction temperature is usually 0 to 100 ° C, preferably 0 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 1 to 24 hours.

反應1-10所使用之式(106)及式(107)之化合物可依公知之方法製造，或可使用市售品。The compounds of the formula (106) and the formula (107) used in the reaction 1-10 can be produced by a known method, or a commercially available product can be used.

反應1-11
反應1-11係包含氯化或醯胺化式(108)之化合物，得到式(109)之化合物之第1步驟，及將式(109)之化合物與式(110)之化合物進行反應，得到式(105)之化合物之第2步驟的方法。Reaction 1-11
Reaction 1-11 is a first step comprising chlorinating or amidating a compound of formula (108) to obtain a compound of formula (109), and reacting a compound of formula (109) with a compound of formula (110) to obtain Method for the second step of the compound of the formula (105).

式中，U為氯原子、二烷基胺基(例如二甲基胺基、二乙基胺基)或N-甲氧基-N-甲基胺基，其他記號係如前述。In the formula, U is a chlorine atom, a dialkylamino group (for example, a dimethylamino group, a diethylamino group), or an N-methoxy-N-methylamino group, and other symbols are as described above.

第1步驟
第1步驟為氯化時，可於氯化劑及溶媒的存在下進行，為醯胺化時，可於二烷基胺(例如二甲基胺)或N-甲氧基-N-甲基胺、脫水縮合劑、鹼及溶媒的存在下進行。Step 1 When the first step is chlorination, it can be performed in the presence of a chlorinating agent and a solvent. When it is amidation, it can be performed on a dialkylamine (such as dimethylamine) or N-methoxy-N. -Carried out in the presence of methylamine, dehydrating condensation agent, base and solvent.

作為氯化劑，例如可從亞硫醯氯、草醯氯、五氯化磷等中適當選擇1種或2種以上。氯化劑相對於式(108)之化合物1當量，可使用1～3當量，期望為1～2當量。
作為脫水縮合劑、鹼及溶媒，可使用於前述反應B所列舉者。脫水縮合劑相對於式(108)之化合物1當量，可使用1～3當量，期望為1～2當量。鹼相對於式(108)之化合物，可使用1～10當量，期望為1～5當量。As the chlorinating agent, for example, one kind or two or more kinds can be appropriately selected from thionyl chloride, chloramphenicol, and phosphorus pentachloride. The chlorinating agent may be used in an amount of 1 to 3 equivalents, and preferably 1 to 2 equivalents, based on 1 equivalent of the compound of formula (108).
As the dehydrating condensation agent, the base, and the solvent, those which can be used in the above reaction B can be used. The dehydration condensing agent can be used in an amount of 1 to 3 equivalents with respect to 1 equivalent of the compound of formula (108), and is desirably 1 to 2 equivalents. The base can be used in an amount of 1 to 10 equivalents with respect to the compound of the formula (108), and is desirably 1 to 5 equivalents.

反應溫度通常為0～100℃，期望為0～80℃，反應時間通常為0.1～48小時左右，期望為1～24小時左右。The reaction temperature is usually 0 to 100 ° C, preferably 0 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 1 to 24 hours.

第2步驟
第2步驟通常可於溶媒的存在下，如有必要可於惰性氣體的存在下進行。式(110)之化合物相對於式(108)或式(109)之化合物，可使用1～3當量，期望為1～1.5當量。Second step The second step can usually be carried out in the presence of a solvent and, if necessary, in the presence of an inert gas. The compound of formula (110) can be used in an amount of 1 to 3 equivalents, and desirably 1 to 1.5 equivalents, with respect to the compound of formula (108) or (109).

溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如二噁烷、四氫呋喃、二乙基醚之醚類等中適當選擇1種或2種以上。惰性氣體，例如可從氮氣體、氬氣體等中適當選擇。Any solvent may be used as long as the solvent is inert to the reaction. For example, one or two or more kinds can be appropriately selected from ethers such as dioxane, tetrahydrofuran, and diethyl ether. The inert gas can be appropriately selected from, for example, a nitrogen gas and an argon gas.

反應溫度通常為-20～100℃，期望為0～50℃，反應時間通常為1～48小時左右，期望為1～20小時左右。The reaction temperature is usually -20 to 100 ° C, preferably 0 to 50 ° C, and the reaction time is usually about 1 to 48 hours, and preferably about 1 to 20 hours.

反應1-11所使用之式(108)及式(110)之化合物可依公知之方法製造，或可使用市售品。The compounds of the formula (108) and the formula (110) used in the reaction 1-11 can be produced by a known method, or a commercially available product can be used.

反應1-12
反應1-12係將式(111)之化合物與式(110)之化合物進行反應，得到式(105)之化合物之方法。Reaction 1-12
Reaction 1-12 is a method of reacting a compound of formula (111) with a compound of formula (110) to obtain a compound of formula (105).

式中之記號係如前述。The symbols in the formula are as described above.

反應1-12通常可於溶媒的存在下，如有必要可於觸媒及惰性氣體的存在下進行。式(110)之化合物相對於式(111)之化合物1當量，可使用1～3當量，期望為1～1.5當量。觸媒相對於式(111)之化合物1當量，可使用0.001～1當量，期望為0.01～0.5當量。Reactions 1-12 can usually be performed in the presence of a solvent, if necessary, in the presence of a catalyst and an inert gas. The compound of the formula (110) can be used in an amount of 1 to 3 equivalents to the compound of the formula (111), and is desirably 1 to 1.5 equivalents. The catalyst can be used in an amount of 0.001 to 1 equivalent to 1 equivalent of the compound of the formula (111), and is preferably 0.01 to 0.5 equivalent.

作為觸媒，例如可列舉碘化銅(I)等。
溶媒及惰性氣體可使用於前述反應1-11之第2步驟所列舉者。Examples of the catalyst include copper (I) iodide.
Solvents and inert gases can be used for those listed in the second step of the aforementioned reactions 1-11.

反應溫度通常為-20～100℃，期望為0～50℃，反應時間通常為1～48小時左右，期望為1～20小時左右。The reaction temperature is usually -20 to 100 ° C, preferably 0 to 50 ° C, and the reaction time is usually about 1 to 48 hours, and preferably about 1 to 20 hours.

反應1-12所使用之式(111)之化合物可依公知之方法製造，或可使用市售品。The compound of the formula (111) used in the reaction 1-12 can be produced by a known method, or a commercially available product can be used.

反應1-13
反應1-13係將式(112)之化合物與式(113)之化合物進行反應，得到式(105)之化合物之方法。Reaction 1-13
Reaction 1-13 is a method of reacting a compound of formula (112) with a compound of formula (113) to obtain a compound of formula (105).

式中，V為溴原子或碘原子，G為脫離基(例如如氯原子、溴原子之鹵素；如甲氧基、環氧基之烷氧基；如二甲基胺基、二乙基胺基之二烷基胺基；可被N-甲氧基-N-甲基胺基或烷基取代之氮丙啶基等)，其他記號係如前述。In the formula, V is a bromine atom or an iodine atom, and G is a leaving group (for example, a halogen atom such as a chlorine atom or a bromine atom; an alkoxy group such as a methoxy group or an epoxy group; such as a dimethylamino group or a diethylamine Dialkylamino group; aziridinyl group which may be substituted by N-methoxy-N-methylamino group or alkyl group, etc.), other symbols are as described above.

反應1-13通常可於有機金屬試藥及溶媒的存在下，或可於金屬鎂、活性化劑及溶媒的存在下，如有必要可於惰性氣體的存在下進行。式(113)之化合物相對於式(112)之化合物1當量，可使用1～3當量，期望為1～1.5當量。
有機金屬試藥可從如甲基鋰、n-丁基鋰之有機鋰化合物；如異丙基氯化鎂之格氏化合物等中適當選擇1種或2種以上。有機金屬試藥相對於式(112)之化合物1當量，可使用1～2當量，期望為1～1.5當量。
金屬鎂相對於式(112)之化合物1當量，可使用1～3當量，期望為1～1.5當量。作為活性化劑，可列舉碘、1,2-二溴乙烷等。活性化劑相對於式(112)之化合物1當量，可使用0.01～1當量，期望為0.05～0.5當量。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚之醚類等中適當選擇1種或2種以上。
惰性氣體例如可從氮氣體、氬氣體等中適當選擇。Reactions 1-13 can usually be carried out in the presence of organometallic reagents and solvents, or in the presence of metallic magnesium, activators and solvents, if necessary, in the presence of inert gases. The compound of the formula (113) can be used in an amount of 1 to 3 equivalents to the compound of the formula (112), and is preferably 1 to 1.5 equivalents.
The organometallic reagent can be appropriately selected from one or more of organic lithium compounds such as methyllithium and n-butyllithium; Grignard compounds such as isopropylmagnesium chloride; and the like. The organometallic reagent can be used in an amount of 1 to 2 equivalents to 1 equivalent of the compound of the formula (112), and is preferably 1 to 1.5 equivalents.
Metal magnesium can be used in an amount of 1 to 3 equivalents, and desirably 1 to 1.5 equivalents, based on 1 equivalent of the compound of formula (112). Examples of the activating agent include iodine and 1,2-dibromoethane. The activator can be used in an amount of 0.01 to 1 equivalent to 1 equivalent of the compound of formula (112), and is desirably 0.05 to 0.5 equivalent.
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, it can be appropriately selected from aliphatic hydrocarbons such as hexane and cyclohexane; ethers such as dioxane, tetrahydrofuran, and diethyl ether. One or two or more.
The inert gas can be appropriately selected from, for example, a nitrogen gas and an argon gas.

反應溫度通常為-100～100℃，期望為-78～80℃，反應時間通常為1～48小時左右，期望為1～20小時左右。The reaction temperature is usually -100 to 100 ° C, preferably -78 to 80 ° C, and the reaction time is usually about 1 to 48 hours, and preferably about 1 to 20 hours.

反應1-13所使用之式(112)及式(113)之化合物可依公知之方法製造，或可使用市售品。The compounds of the formula (112) and the formula (113) used in the reaction 1-13 can be produced by a known method, or a commercially available product can be used.

反應1-14
反應1-14係包含使式(104)之化合物及式(110)之化合物進行反應，得到式(114)之化合物之第1步驟，以及氧化式(114)之化合物，得到式(105)之化合物之第2步驟的方法。Reaction 1-14
Reaction 1-14 includes the first step of reacting a compound of formula (104) and a compound of formula (110) to obtain a compound of formula (114), and oxidizing a compound of formula (114) to obtain a compound of formula (105) Method of compound 2 step.

式中之記號係如前述。The symbols in the formula are as described above.

第1步驟
第1步驟可依前述反應1-11之第2步驟進行。First step The first step can be performed according to the second step of the aforementioned reaction 1-11.

第2步驟
第2步驟可依前述反應1-6進行。Step 2 The second step can be performed according to the aforementioned reactions 1-6.

反應1-15
反應1-15係藉由A12 之RA 為-LA3 -YA2 之式(105-1)之化合物與(鹵)烷基化劑、醯化劑或烷氧基羰基化劑的反應、光延反應或還原的烷基化，變換成A13 之RA 為-LA4 -YA2 之式(105-2)之化合物的方法。Reaction 1-15
Reaction 1-15 is a reaction of a compound of formula (105-1) in which R A is -L A3 -Y A2 of A 12 and a (halo) alkylating agent, a halogenating agent or an alkoxycarbonylating agent, Mitsunobu reaction or reductive alkylation, R a a 13 into the compound of the formula -L A4 -Y A2 (105-2) of the method.

式中，A12 為被-LA3 -YA2 取代之苯基或被
-LA3 -YA2 取代之吡啶基，LA3 為O、S或N(R1 )，A13 為被
-LA4 -YA2 取代之苯基或被-LA4 -YA2 取代之吡啶基，LA4 為O、OC(=O)、S、N(R1 )、N(R1 )C(=O)或N(R1 )C(=O)O，其他記號係如前述。In the formula, A 12 is a phenyl group substituted by -L A3 -Y A2 or
-L A3 -Y A2 substituted pyridyl, L A3 is O, S or N (R 1 ), A 13 is
-L A4 -Y A2 substituted phenyl or -L A4 -Y A2 substituted pyridyl, L A4 is O, OC (= O), S, N (R 1 ), N (R 1 ) C (= O) or N (R 1 ) C (= O) O, and other symbols are as described above.

反應1-15可依反應G進行。Reactions 1-15 can be performed according to Reaction G.

反應1-16
反應1-16係包含藉由式(106)之化合物及式(115)之化合物的佛瑞德-克來福特反應，得到式(116)之化合物之第1步驟，及甲基化式(116)之化合物，得到式(105)之化合物之第2步驟的方法。Reaction 1-16
Reactions 1-16 include the first step of obtaining a compound of formula (116) by a Friedel-Crafts reaction of a compound of formula (106) and a compound of formula (115), and methylation of formula (116) ) To obtain a compound of formula (105) in the second step.

式中之記號係如前述。The symbols in the formula are as described above.

第1步驟可依前述反應1-10進行。The first step can be performed according to the aforementioned reactions 1-10.

第2步驟可依前述反應A進行。The second step can be performed according to the aforementioned reaction A.

反應1-17
反應1-17係包含將式(112)之化合物與(117)之化合物進行反應，得到式(114)之化合物之第1步驟，及氧化式(114)之化合物，得到式(105)之化合物之第2步驟的方法。Reaction 1-17
Reaction 1-17 comprises the first step of reacting a compound of formula (112) with a compound of (117) to obtain a compound of formula (114), and oxidizing a compound of formula (114) to obtain a compound of formula (105) Step 2 of the method.

第1步驟
第1步驟可依前述反應1-13進行。First step The first step can be performed according to the aforementioned reaction 1-13.

第2步驟
第2步驟可依前述反應1-6進行。Step 2 The second step can be performed according to the aforementioned reactions 1-6.

反應1-18
反應1-18係包含使式(104)之化合物及式(118)之化合物進行反應，得到式(119)之化合物之第1步驟，氧化式(119)之化合物，得到式(120)之化合物之第2步驟的方法，以及還原式(120)之化合物，得到式(105)之化合物之第3步驟的方法。Reactions 1-18
Reaction 1-18 is a first step of reacting a compound of formula (104) and a compound of formula (118) to obtain a compound of formula (119), and oxidizing a compound of formula (119) to obtain a compound of formula (120) The method of the second step, and the method of the third step of reducing the compound of the formula (120) to obtain the compound of the formula (105).

式中之記號係如前述。The symbols in the formula are as described above.

第1步驟
第1步驟可依前述反應1-11之第2步驟進行。First step The first step can be performed according to the second step of the aforementioned reaction 1-11.

第2步驟
第2步驟可依前述反應1-6進行。Step 2 The second step can be performed according to the aforementioned reactions 1-6.

第3步驟
第3步驟可依前述反應I進行。Step 3 The third step can be performed according to the aforementioned reaction I.

反應1-19
反應1-19係將A14 之RA 為羥基之式(105-3)之化合物，變換成A15 之RA 為巰基或胺基之式(105-4)之化合物的方法。Reactions 1-19
Reaction 1-19 is a method in which R A of A 14 is a compound of formula (105-3) in which R A is a hydroxyl group, and R A of A 15 is a compound of formula (105-4) in which R A is a mercapto group or an amine group.

式中，A14 為被羥基取代之苯基或被羥基取代之吡啶基，A15 為被巰基或胺基取代之苯基或被巰基或胺基取代之吡啶基，其他記號係如前述。In the formula, A 14 is a phenyl group substituted with a hydroxyl group or a pyridyl group substituted with a hydroxyl group, and A 15 is a phenyl group substituted with a mercapto group or an amino group or a pyridyl group substituted with a mercapto group or an amino group.

反應1-19可依一般的Froberg･Schönberg反應進行。通常可於鹼及溶媒的存在下，將式(105-3)之化合物與二甲基硫代胺甲醯氯進行反應，接著經由重排反應、水解，得到式(105-4)之化合物。二甲基硫代胺甲醯氯相對於式(105-3)之化合物1當量，可使用1～5當量，期望為1～2當量。
或反應1-19可依一般的Smiles重排反應進行。通常可於鹼及溶媒的存在下，將式(105-3)之化合物與2-溴異丁基醯胺進行反應，接著經由重排反應、水解，得到式(105-4)之化合物。2-溴異丁基醯胺相對於式(105-3)之化合物1當量，可使用1～10當量，期望為1～3當量。
重排反應可於溶媒的存在下進行，水解可依前述反應1-1進行。Reactions 1-19 can be performed according to the general Froberg ･ Schönberg reaction. Generally, the compound of formula (105-3) can be reacted with dimethylthioamine formamidine chloride in the presence of a base and a solvent, and then the compound of formula (105-4) can be obtained by rearrangement reaction and hydrolysis. The dimethyl thioamine formamidine chloride can be used in an amount of 1 to 5 equivalents to the compound of the formula (105-3), and is desirably 1 to 2 equivalents.
Or reactions 1-19 can be performed according to the general Smiles rearrangement reaction. Generally, the compound of formula (105-3) can be reacted with 2-bromoisobutylphosphonium amine in the presence of a base and a solvent, followed by a rearrangement reaction and hydrolysis to obtain a compound of formula (105-4). 2-bromoisobutylamidine can be used in an amount of 1 to 10 equivalents, and desirably 1 to 3 equivalents, based on 1 equivalent of the compound of formula (105-3).
The rearrangement reaction can be performed in the presence of a solvent, and the hydrolysis can be performed according to the aforementioned reaction 1-1.

在反應1-19，作為鹼，可使用於前述反應1-7所列舉者。鹼相對於式(105-3)之化合物1當量，可使用1～5當量，期望為1～3當量。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如乙腈、丙腈、丙烯腈之腈類；如四氯化碳、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶之極性非質子性溶媒；N,N-二甲基苯胺等中適當選擇1種或2種以上。In reaction 1-19, as the base, those listed in the above reaction 1-7 can be used. The base may be used in an amount of 1 to 5 equivalents, and desirably is 1 to 3 equivalents based on 1 equivalent of the compound of the formula (105-3).
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, it can be selected from nitriles such as acetonitrile, propionitrile, and acrylonitrile; such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, and trichloroethyl. Aliphatic hydrocarbons such as alkane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as dimethyl sulfene, cyclobutane, and dimethyl A polar aprotic solvent of acetamide, N, N-dimethylformamide, N-methylpyrrolidone, and pyridine; N, N-dimethylaniline, or the like is appropriately selected from one or two or more.

反應溫度通常為0～200℃，期望為20～150℃，反應時間通常為1～48小時左右，期望為1～20小時左右。The reaction temperature is usually 0 to 200 ° C, preferably 20 to 150 ° C, and the reaction time is usually about 1 to 48 hours, and preferably about 1 to 20 hours.

反應2-1
反應2-1係藉由式(4)之化合物當中，溴化或氯化T為羥基之式(4-1)之化合物，得到T為溴原子或氯原子之式(4-2)之化合物的方法。Reaction 2-1
Reaction 2-1 is to obtain a compound of formula (4-2) in which T is a bromine atom or a chlorine atom by brominating or chlorinating a compound of formula (4-1) in which T is a hydroxyl group among the compounds of formula (4) Methods.

式中，T1 為溴原子或氯原子，其他記號係如前述。In the formula, T 1 is a bromine atom or a chlorine atom, and other symbols are as described above.

反應2-1通常可將式(4-1)之化合物於溶媒的存在下，藉由與溴化劑或氯化劑進行反應來進行。Reaction 2-1 can usually be performed by reacting a compound of formula (4-1) with a brominating agent or a chlorinating agent in the presence of a solvent.

作為溶媒，若能進行反應則並未特別限定，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如己烷、庚烷、石油醚、石油醚、環己烷之脂肪族烴類；如氯仿、二氯甲烷、四氯化碳、1,2-二氯乙烷之鹵素化烴類；二乙基醚、四氫呋喃、二噁烷等之醚類及此等之混合溶媒等中適當選擇1種或2種以上。
作為溴化劑，若能進行反應則並未特別限定，可列舉磷醯溴等。作為氯化劑，若能進行反應則並未特別限定，可列舉草醯氯、亞硫醯氯、磷醯氯等。溴化劑或氯化劑相對於式(4-1)之化合物1當量，可以1～10當量，期望為1～3當量的比例使用。The solvent is not particularly limited as long as it can be reacted. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; and fats such as hexane, heptane, petroleum ether, petroleum ether, and cyclohexane can be used. Groups of hydrocarbons; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and 1,2-dichloroethane; ethers such as diethyl ether, tetrahydrofuran, dioxane, and their mixed solvents Among them, one kind or two or more kinds are appropriately selected.
The brominating agent is not particularly limited as long as the reaction can be carried out, and examples thereof include phosphorous bromide and the like. The chlorinating agent is not particularly limited as long as the reaction can be performed, and examples include chlorchloramine, thionyl chloride, and phosphonium chloride. The brominating agent or the chlorinating agent may be used in a ratio of 1 to 10 equivalents, and desirably in a ratio of 1 to 3 equivalents, relative to 1 equivalent of the compound of the formula (4-1).

反應2-1亦可添加N,N-二甲基甲醯胺進行。N,N-二甲基甲醯胺相對於式(4-1)之化合物1當量，可以0.01～3當量，期望為0.05～0.3當量的比例使用。Reaction 2-1 can also be performed by adding N, N-dimethylformamide. N, N-dimethylformamide can be used in an amount of 0.01 to 3 equivalents, preferably 0.05 to 0.3 equivalents, based on 1 equivalent of the compound of formula (4-1).

反應溫度通常為0～200℃，期望為0～100℃，反應時間通常為0.1～12小時左右。The reaction temperature is usually 0 to 200 ° C, preferably 0 to 100 ° C, and the reaction time is usually about 0.1 to 12 hours.

式(4-1)之化合物可依公知之方法或藉由後述之方法製造，或可使用市售品。作為公知之方法，例如雖可列舉國際公開公報WO1993/11117號、美國專利第5,093,347號等，但並非被限定於此等，若為本發明領域具有通常知識者，可將各式各樣之文獻所記載的一般的合成方法或適當組合該等，適用在本發明。The compound of the formula (4-1) can be produced by a known method or by a method described later, or a commercially available product can be used. Examples of known methods include, for example, International Publication No. WO1993 / 11117 and US Patent No. 5,093,347. However, the methods are not limited to these. For those who have ordinary knowledge in the field of the present invention, various documents can be provided. The general synthesis methods described or appropriate combinations thereof are applicable to the present invention.

反應2-2
反應2-2係將T2 為烷氧基或芳氧基之式(4-3)之化合物與酸或鹼進行反應，得到式(4-1)之化合物之方法。Reaction 2-2
Reaction 2-2 is a method of reacting a compound of the formula (4-3) in which T 2 is an alkoxy group or an aryloxy group with an acid or a base to obtain a compound of the formula (4-1).

式中，T2 為烷氧基或芳氧基，其他記號係如前述。In the formula, T 2 is an alkoxy group or an aryloxy group, and other symbols are as described above.

反應2-2通常可藉由將式(4-3)之化合物於溶媒的存在下，與酸或鹼進行反應來進行。Reaction 2-2 can usually be performed by reacting a compound of formula (4-3) with an acid or a base in the presence of a solvent.

作為酸，若能進行反應則並未特別限定，例如可使用鹽酸、硫酸、三氟乙酸、p-甲苯磺酸等。作為鹼，若能進行反應則並未特別限定，例如可列舉如碳酸鈉、碳酸鉀、碳酸銫之鹼金屬碳酸鹽；如碳酸氫鈉之鹼金屬的碳酸氫鹽；如碳酸鈣之鹼土類金屬的碳酸鹽；如氫氧化鈉、氫氧化鉀之金屬氫氧化物等。酸或鹼相對於式(4-3)之化合物1當量，可以0.1～20當量，期望為0.1～10當量的比例使用。
作為溶媒，若能進行反應則並未特別限定，例如可從苯、甲苯等之芳香族烴類；如己烷、庚烷之脂肪族烴類；二乙基醚、四氫呋喃、二噁烷等之醚類；甲醇、乙醇等之醇類；氯仿、二氯乙烷、四氯化碳等之鹵素化烴類；水及此等之混合溶媒等中適當選擇1種或2種以上。The acid is not particularly limited as long as it can react, and for example, hydrochloric acid, sulfuric acid, trifluoroacetic acid, p-toluenesulfonic acid, and the like can be used. The base is not particularly limited as long as it can be reacted, and examples thereof include alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; alkali metal bicarbonates such as sodium bicarbonate; and alkaline earth metals such as calcium carbonate. Carbonates; such as sodium hydroxide, potassium hydroxide, and metal hydroxides. The acid or base may be used in a ratio of 0.1 to 20 equivalents, preferably 0.1 to 10 equivalents, based on 1 equivalent of the compound of formula (4-3).
The solvent is not particularly limited as long as it can be reacted. Examples include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as hexane and heptane; and diethyl ether, tetrahydrofuran, and dioxane. Ethers; Alcohols such as methanol and ethanol; Halogenated hydrocarbons such as chloroform, dichloroethane, carbon tetrachloride; etc. One or two or more kinds are appropriately selected from water and mixed solvents thereof.

反應溫度通常為0～200℃，期望為0～100℃，反應時間通常為1～48小時左右。The reaction temperature is usually 0 to 200 ° C, preferably 0 to 100 ° C, and the reaction time is usually about 1 to 48 hours.

式(4-3)之化合物可依公知之方法或藉由後述之方法製造，或可使用市售品。作為公知之方法，例如雖可列舉國際公開公報WO2001/23358號、Journal of the American Chemical Society、128卷、5310～5311頁(2006年)、美國專利第5,093,347號、美國專利第5,223,526號等，但並非被限定於此等，若為本發明領域具有通常知識者，亦可將各式各樣之文獻所記載的一般的合成方法或適當組合該等，適用在本發明。The compound of the formula (4-3) can be produced by a known method or by a method described later, or a commercially available product can be used. Examples of known methods include International Publication No. WO2001 / 23358, Journal of the American Chemical Society, Volume 128, Pages 5310 to 5311 (2006), US Patent No. 5,093,347, and US Patent No. 5,223,526. It is not limited to these, and if it is a person with ordinary knowledge in the field of the present invention, general synthesis methods described in various documents or appropriate combinations thereof may be used in the present invention.

反應2-3
反應2-3係將式(200)之化合物與酸或鹼進行反應，得到式(4-1)之化合物之方法。Reaction 2-3
Reaction 2-3 is a method of reacting a compound of formula (200) with an acid or a base to obtain a compound of formula (4-1).

式中之記號係如前述。The symbols in the formula are as described above.

反應2-3通常可藉由將式(200)之化合物於溶媒的存在下，與酸或鹼進行反應來進行。Reaction 2-3 can usually be carried out by reacting a compound of formula (200) with an acid or a base in the presence of a solvent.

作為酸、鹼及溶媒，可使用於前述反應2-2所列舉者。酸或鹼相對於式(200)之化合物1當量，可以1～20當量，期望為1～10當量的比例使用。As the acid, the base, and the solvent, those used in the reaction 2-2 can be used. The acid or base may be used in a proportion of 1 to 20 equivalents, and desirably 1 to 10 equivalents, relative to 1 equivalent of the compound of formula (200).

反應溫度通常為0～200℃，期望為0～100℃，反應時間通常為1～48小時左右。The reaction temperature is usually 0 to 200 ° C, preferably 0 to 100 ° C, and the reaction time is usually about 1 to 48 hours.

式(200)之化合物可依公知之方法製造，或可使用市售品。The compound of the formula (200) can be produced by a known method, or a commercially available product can be used.

反應2-4
反應2-4係藉由氧化式(201)之化合物，得到式(4-1)之化合物之方法。Reaction 2-4
Reaction 2-4 is a method of obtaining a compound of formula (4-1) by oxidizing a compound of formula (201).

式中之記號係如前述。The symbols in the formula are as described above.

反應2-4通常可藉由將式(201)之化合物於溶媒的存在下，與氧化劑進行反應來進行。Reactions 2-4 can generally be carried out by reacting a compound of formula (201) with an oxidant in the presence of a solvent.

作為氧化劑，若能進行反應則並未特別限定，例如可列舉亞氯酸鈉、氧化鉻、二鉻酸吡啶鎓、過錳酸鉀等。氧化劑相對於式(201)之化合物1當量，可以0.01～20當量，期望為0.1～10當量的比例使用。
作為溶媒，若能進行反應則並未特別限定，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如己烷、庚烷、石油醚、石油醚、環己烷之脂肪族烴類；如氯仿、二氯甲烷、四氯化碳、1,2-二氯乙烷之鹵素化烴類；如乙醇、甲醇、丁醇之醇類；水及此等之混合溶媒等中適當選擇1種或2種以上。The oxidant is not particularly limited as long as it can react, and examples thereof include sodium chlorite, chromium oxide, pyridinium dichromate, and potassium permanganate. The oxidizing agent may be used in an amount of 0.01 to 20 equivalents, preferably 0.1 to 10 equivalents relative to 1 equivalent of the compound of formula (201).
The solvent is not particularly limited as long as it can be reacted. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; and fats such as hexane, heptane, petroleum ether, petroleum ether, and cyclohexane can be used. Family hydrocarbons; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and 1,2-dichloroethane; alcohols such as ethanol, methanol, butanol; water and mixed solvents Choose one or more as appropriate.

作為反應溫度，通常為-100～100℃，期望為-80～50℃，反應時間通常為1～48小時左右。The reaction temperature is usually -100 to 100 ° C, preferably -80 to 50 ° C, and the reaction time is usually about 1 to 48 hours.

式(201)之化合物可依公知之方法製造，或可使用市售品。The compound of formula (201) can be produced by a known method, or a commercially available product can be used.

反應2-5
反應2-5係將式(202)之化合物變換成式(203)之化合物之方法。Reaction 2-5
Reaction 2-5 is a method of converting a compound of the formula (202) into a compound of the formula (203).

式中，B4 為被X取代之雜環基，B5 為被Q1 取代之雜環基，Q1 為烷基、鹵烷基、氰基或環烷基，RC 為氫原子、烷氧基或芳基烷氧基，其他記號係如前述。Wherein, B 4 is a heterocyclic group substituted by X's, B 5 is substituted with Q 1 of the heterocyclic group, Q 1 is alkyl, haloalkyl, cyano or cycloalkyl, R C is a hydrogen atom, an alkoxy The other symbols are as described above.

反應2-5可依反應F進行。Reactions 2-5 can be performed according to Reaction F.

式(202)之化合物可依公知之方法製造，或可使用市售品。The compound of formula (202) can be produced by a known method, or a commercially available product can be used.

反應2-6
反應2-6係將式(204)之化合物變換成式(205)之化合物之方法。Reaction 2-6
Reactions 2-6 are methods for converting a compound of formula (204) into a compound of formula (205).

式中，B6 為被Q2 取代之雜環基，B7 為被單氟烷基或烷氧基烷基取代之雜環基，Q2 為被Q3 取代之烷基，Q3 為羥基、氯原子、溴原子、碘原子、硝基、烷基磺酸酯或氟磺酸酯，其他記號係如前述。In the formula, B 6 is a heterocyclic group substituted with Q 2 , B 7 is a heterocyclic group substituted with a monofluoroalkyl group or an alkoxyalkyl group, Q 2 is an alkyl group substituted with Q 3 , Q 3 is a hydroxyl group, A chlorine atom, a bromine atom, an iodine atom, a nitro group, an alkyl sulfonate, or a fluorosulfonate, and other symbols are as described above.

反應2-6通常可於鹼及溶媒的存在下，藉由與烷基化劑及氟化劑進行反應來進行。Reactions 2-6 can usually be carried out by reacting with an alkylating agent and a fluorinating agent in the presence of a base and a solvent.

作為烷基化劑，若能進行反應則並未特別限定，例如可列舉如碘化甲烷、溴化甲烷之鹵素化烷基、硫酸二甲酯等之硫酸二烷酯、三甲基矽烷基重氮甲烷等。
作為氟化劑，若能進行反應則並未特別限定，可列舉如氟化銫之氟化物鹽；如氟化四-n-丁基銨等之四級銨鹽；如CRYSTAL FLUOR之脫氧的氟化劑等。
作為鹼，例如可從如甲醇鈉、乙醇鈉、第3級丁醇鉀之鹼金屬醇鹽；如碳酸鈉、碳酸鉀之碳酸鹽；如碳酸氫鈉、碳酸氫鉀之碳酸氫鹽；如氫氧化鈉、氫氧化鉀之金屬氫氧化物；如氫化鈉、氫化鉀之金屬氫化物；如單甲基胺、二甲基胺、三乙基胺、二異丙基乙基胺之胺類；如吡啶、4-二甲基胺基吡啶之吡啶類；如甲基鋰、n-丁基鋰、鋰二異丙基醯胺之有機鋰化合物等中適當選擇1種或2種以上。烷基化劑、氟化劑或鹼相對於式(204)之化合物1當量，可以1～20當量，期望為1～10當量的比例使用。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如甲醇、乙醇、丙醇、tert-丁醇之醇類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒；水及此等之混合溶媒等中適當選擇1種或2種以上。The alkylating agent is not particularly limited as long as the reaction can be performed, and examples thereof include halogenated alkyl groups such as methyl iodide, methyl bromide, dialkyl sulfates such as dimethyl sulfate, and trimethylsilyl groups. Nitrogen methane, etc.
The fluorinating agent is not particularly limited as long as it can be reacted, and examples include fluoride salts of cesium fluoride; quaternary ammonium salts such as tetra-n-butylammonium fluoride; deoxyfluorine such as CRYSTAL FLUOR化 剂 And the like.
As the base, for example, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and third-order potassium butoxide; carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; Metal hydroxides of sodium oxide and potassium hydroxide; metal hydrides of sodium hydride and potassium hydride; amines such as monomethylamine, dimethylamine, triethylamine, and diisopropylethylamine; For example, pyridine and pyridines of 4-dimethylaminopyridine; organic lithium compounds such as methyllithium, n-butyllithium, and lithium diisopropylamidamine are appropriately selected from one or two or more. The alkylating agent, fluorinating agent or base may be used in a proportion of 1 to 20 equivalents, and desirably 1 to 10 equivalents, relative to 1 equivalent of the compound of formula (204).
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent can be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Aliphatic hydrocarbons such as dichloroethane, trichloroethane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as methanol, ethanol, and propane Alcohols, tert-butanol alcohols; such as dimethylmethylene, cyclobutane, dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, propane The polar aprotic solvent of the nitrile; one or two or more kinds are appropriately selected from water and the mixed solvent thereof.

反應溫度通常為0～100℃，期望為0～80℃，反應時間通常為0.1～48小時左右，期望為0.1～24小時左右。The reaction temperature is usually 0 to 100 ° C, preferably 0 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 0.1 to 24 hours.

式(204)之化合物可依公知之方法製造，或可使用市售品。The compound of formula (204) can be produced by a known method, or a commercially available product can be used.

反應2-7
反應2-7係得到具有氟原子之式(207)之化合物的方法。Reaction 2-7
Reaction 2-7 is a method of obtaining a compound of formula (207) having a fluorine atom.

式中，B8 為可被Q5 取代之雜環基，B9 為被氟取代之雜環基，Q5 為脫離基(例如氯、溴、碘、硝基、烷基磺酸酯或氟磺酸酯等)、胺基或羥基，RD 為氫、烷氧基、芳氧基、芳基烷氧基、羥基或鹵素。In the formula, B 8 is a heterocyclic group which may be substituted by Q 5 , B 9 is a heterocyclic group which is substituted by fluorine, and Q 5 is a leaving group (for example, chlorine, bromine, iodine, nitro, alkylsulfonate or fluorine Sulfonate, etc.), amine or hydroxy, and R D is hydrogen, alkoxy, aryloxy, arylalkoxy, hydroxy or halogen.

在反應2-7，Q5 為脫離基時，通常於溶媒的存在下，可藉由將式(206)之化合物與氟化劑進行反應，得到式(207)之化合物。
作為氟化劑，若能進行反應則並未特別限定，可列舉如氟化銫之氟化物鹽；如氟化四甲基銨、氟化四-n-丁基銨等之四級銨鹽等。氟化劑相對於式(206)之化合物1當量，可以1～20當量，期望為1～10當量的比例使用。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒及此等之混合溶媒等中適當選擇1種或2種以上。
反應溫度通常為0～200℃，期望為20～150℃，反應時間通常為0.1～48小時左右，期望為0.1～24小時左右。In reactions 2-7, when Q 5 is a leaving group, the compound of formula (206) can be obtained by reacting the compound of formula (206) with a fluorinating agent in the presence of a solvent.
The fluorinating agent is not particularly limited as long as it can react, and examples include fluoride salts of cesium fluoride; quaternary ammonium salts such as tetramethylammonium fluoride and tetra-n-butylammonium fluoride; . The fluorinating agent may be used in a ratio of 1 to 20 equivalents, and preferably 1 to 10 equivalents, based on 1 equivalent of the compound of formula (206).
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent may be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; for example, carbon tetrachloride, methylene chloride, chloroform, methylene chloride, Aliphatic hydrocarbons such as dichloroethane, trichloroethane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as dimethylsulfine , Aprotic solvents such as cyclobutane, dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, propionitrile, and mixed solvents thereof Choose one or more.
The reaction temperature is usually 0 to 200 ° C, preferably 20 to 150 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 0.1 to 24 hours.

在反應2-7，Q5 為胺基時，可藉由Balz-Seaman反應，得到式(207)之化合物。此情況下，通常於溶媒的存在下，將式(206)之化合物與亞硝酸鈉及四氟硼酸進行反應。亞硝酸鈉及四氟硼酸相對於式(206)之化合物1當量，可以1～20當量，期望為1～10當量的比例使用。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒及此等之混合溶媒等中適當選擇1種或2種以上。
反應溫度通常為0～200℃，期望為20～150℃，反應時間通常為0.1～48小時左右，期望為0.1～24小時左右。In reactions 2-7, when Q 5 is an amine group, a compound of formula (207) can be obtained by Balz-Seaman reaction. In this case, the compound of formula (206) is usually reacted with sodium nitrite and tetrafluoroboric acid in the presence of a solvent. Sodium nitrite and tetrafluoroboric acid can be used in a ratio of 1 to 20 equivalents, and desirably in a ratio of 1 to 10 equivalents, based on 1 equivalent of the compound of formula (206).
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent can be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Aliphatic hydrocarbons such as dichloroethane, trichloroethane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as dimethylsulfine , Aprotic solvents such as cyclobutane, dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, propionitrile, and mixed solvents thereof Choose one or more.
The reaction temperature is usually 0 to 200 ° C, preferably 20 to 150 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 0.1 to 24 hours.

在反應2-7，Q5 為羥基時，於式(206)之化合物，通常於溶媒的存在下，如有必要於氟化物鹽的存在下，可藉由使脫氧的氟化劑進行反應，得到式(207)之化合物。
脫氧的氟化劑若能進行反應則並未特別限定，可列舉PhenoFluor等。脫氧的氟化劑相對於式(206)之化合物1當量，可以1～20當量，期望為1～10當量的比例使用。
氟化物鹽可列舉氟化鉀、氟化銫等。氟化物鹽相對於式(206)之化合物1當量，可以1～10當量，期望為1～5當量的比例使用。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒及此等之混合溶媒等中適當選擇1種或2種以上。
反應溫度通常為0～200℃，期望為20～150℃，反應時間通常為0.1～48小時左右，期望為0.1～24小時左右。In reactions 2-7, when Q 5 is a hydroxyl group, the compound of formula (206) is usually in the presence of a solvent, and if necessary in the presence of a fluoride salt, the reaction can be performed by deoxidizing the fluorinating agent. A compound of formula (207) is obtained.
The deoxyfluorination agent is not particularly limited as long as it can react, and examples thereof include PhenoFluor and the like. The deoxidizing fluorinating agent may be used in a ratio of 1 to 20 equivalents, and desirably in a ratio of 1 to 10 equivalents, relative to 1 equivalent of the compound of formula (206).
Examples of the fluoride salt include potassium fluoride and cesium fluoride. The fluoride salt may be used in a ratio of 1 to 10 equivalents, and desirably in a ratio of 1 to 5 equivalents, based on 1 equivalent of the compound of formula (206).
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent may be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; for example, carbon tetrachloride, methylene chloride, chloroform, methylene chloride, Aliphatic hydrocarbons such as dichloroethane, trichloroethane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as dimethylsulfine , Aprotic solvents such as cyclobutane, dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, propionitrile, and mixed solvents thereof Choose one or more.
The reaction temperature is usually 0 to 200 ° C, preferably 20 to 150 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 0.1 to 24 hours.

在反應2-7，B8 為未被Q5 取代之雜環基時，通常於溶媒的存在下，如有必要於鹼的存在下，可藉由使親電子的氟化劑進行反應，得到式(207)之化合物。
親電子的氟化劑若能進行反應則並未特別限定，可列舉氟試劑(Selectfluor)、N-氟苯磺醯亞胺等。親電子的氟化劑相對於式(206)之化合物1當量，可以1～20當量，期望為1～10當量的比例使用。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒及此等之混合溶媒等中適當選擇1種或2種以上。
鹼可從如鋰二異丙基醯胺、六甲基二矽基胺鋰之鋰醯胺化合物等中適當選擇1種或2種以上。鹼相對於式(206)之化合物1當量，可以1～5當量，期望為1～2當量的比例使用。
反應溫度通常為-100～200℃，期望為-78～150℃，反應時間通常為0.1～48小時左右，期望為0.1～24小時左右。When reactions 2-7, B 8 is a heterocyclic group not substituted by Q 5 , usually in the presence of a solvent, and if necessary in the presence of a base, it can be obtained by reacting an electrophilic fluorinating agent to obtain Compound of formula (207).
The electrophilic fluorinating agent is not particularly limited as long as it can react, and examples thereof include a fluorine reagent (Selectfluor), N-fluorobenzenesulfonimide, and the like. The electrophilic fluorinating agent may be used in a ratio of 1 to 20 equivalents, and desirably in a ratio of 1 to 10 equivalents, relative to 1 equivalent of the compound of formula (206).
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent may be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; for example, carbon tetrachloride, methylene chloride, chloroform, methylene chloride, Aliphatic hydrocarbons such as dichloroethane, trichloroethane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as dimethylsulfine , Aprotic solvents such as cyclobutane, dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, propionitrile, and mixed solvents thereof Choose one or more.
The base can be appropriately selected from one or two or more kinds from lithium diisopropylamidamine and lithium hexamethyldisilazyl lithium amidamine compounds. The base can be used in an amount of 1 to 5 equivalents relative to 1 equivalent of the compound of formula (206), and it is desirable to use 1 to 2 equivalents.
The reaction temperature is usually -100 to 200 ° C, preferably -78 to 150 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 0.1 to 24 hours.

式(206)之化合物可依公知之方法製造，或可使用市售品。又，式(206)之化合物亦可依照例如Journal of the American Chemical Society、139卷、1452～1455頁(2017年)、Journal of Organic Chemistry、80卷、12137～12145頁(2015年)、Organic Process Research & Development、18卷、1041～1044頁(2014年)等所記載之方法，或依該等之方法製造。The compound of the formula (206) can be produced by a known method, or a commercially available product can be used. In addition, the compound of formula (206) can also comply with, for example, Journal of the American Chemical Society, Volume 139, pages 1452 to 1455 (2017), Journal of Organic Chemistry, Volume 80, pages 12137 to 12145 (2015), Organic Process Research & Development, Vol. 18, pages 1041 to 1044 (2014), etc., or manufactured by these methods.

反應2-8
反應2-8係(鹵)烷基化或環烷基化式(208)之化合物，變換成式(209)之化合物之方法。Reaction 2-8
A method of reacting 2-8 series (halo) alkylation or cycloalkylation of a compound of formula (208) and conversion to a compound of formula (209).

式中，B10 為可被RB 取代之具有NH之雜環基，B11 為可被RB 取代，且具有被(鹵)烷基或環烷基取代之N的雜環基，其他記號係如前述。In the formula, B 10 is a heterocyclic group having NH which may be substituted by R B , B 11 is a heterocyclic group which may be substituted by R B and having N substituted by (halo) alkyl or cycloalkyl, and other symbols It is as described above.

反應2-8通常於鹼及溶媒的存在下，可藉由於式(208)之化合物使(鹵)烷基化劑或環烷基化劑進行反應來進行。又，本反應亦可藉由將式(208)之化合物於過渡金屬試藥及溶媒存在下，如有必要添加鹼，與有機金屬試藥進行反應來進行。Reactions 2 to 8 are usually carried out by reacting a (halo) alkylating agent or a cycloalkylating agent with a compound of formula (208) in the presence of a base and a solvent. This reaction can also be carried out by reacting a compound of formula (208) with an organometallic reagent in the presence of a transition metal reagent and a solvent, if necessary, by adding a base.

作為(鹵)烷基化劑，若能進行反應則並未特別限定，例如可列舉如碘化甲烷、溴化甲烷之鹵素化烷基、硫酸二甲酯等之硫酸二烷酯、三甲基矽烷基重氮甲烷；氯二氟甲烷、氯二氟乙酸鈉等。作為環烷基化劑，若能進行反應則並未特別限定，例如可列舉碘化環丙基等。
作為鹼，例如可從如甲醇鈉、乙醇鈉、第3級丁醇鉀之鹼金屬醇鹽；如碳酸鈉、碳酸鉀之碳酸鹽；如碳酸氫鈉、碳酸氫鉀之碳酸氫鹽；如氫氧化鈉、氫氧化鉀之金屬氫氧化物；如氫化鈉、氫化鉀之金屬氫化物；如單甲基胺、二甲基胺、三乙基胺、二異丙基乙基胺之胺類；如吡啶、4-二甲基胺基吡啶之吡啶類；如甲基鋰、n-丁基鋰、鋰二異丙基醯胺之有機鋰化合物等中適當選擇1種或2種以上。(鹵)烷基化劑、環烷基化劑或鹼相對於式(208)之化合物1當量，可以1～20當量，期望為1～10當量的比例使用。
作為有機金屬試藥，若能進行反應則並未特別限定，例如可列舉有機硼化合物等。有機金屬試藥可依公知之方法調製，或可使用市售品。有機金屬試藥相對於式(208)之化合物1當量，可使用1～10當量，期望為1～5當量。
作為過渡金屬試藥，可使用交叉偶合反應所使用之公知之各種構造者，本反應中包含銅之過渡金屬試藥特別有用。例如可列舉乙酸銅(II)等。又，如有必要可將二胺作為配位子使用。作為二胺，可列舉N,N,N’,N’-四甲基乙二胺、2、2’-聯吡啶基等。過渡金屬試藥相對於式(208)之化合物1當量，可使用0.1～5當量，期望為0.5～1.5當量。又，配位子相對於過渡金屬觸媒1當量，通常可使用1～10當量，期望為1～5當量。惟，因反應條件亦可使用此範圍外的量。
溶媒若為對反應為惰性的溶媒則任何溶媒皆可，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如四氯化碳、氯化甲烷、氯仿、二氯甲烷、二氯乙烷、三氯乙烷、己烷、環己烷之脂肪族烴類；如二噁烷、四氫呋喃、二乙基醚、二甲氧基乙烷之醚類；如甲醇、乙醇、丙醇、tert-丁醇之醇類；如二甲基亞碸、環丁碸、二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、吡啶、乙腈、丙腈之極性非質子性溶媒；水及此等之混合溶媒等中適當選擇1種或2種以上。The (halo) alkylating agent is not particularly limited as long as it can react, and examples thereof include dialkyl sulfates such as methyl iodide, methyl bromide, dialkyl sulfates, and trimethyl sulfate. Silyl diazomethane; chlorodifluoromethane, sodium chlorodifluoroacetate, etc. The cycloalkylating agent is not particularly limited as long as it can react, and examples thereof include cyclopropyl iodide and the like.
As the base, for example, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and third-order potassium butoxide; carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; such as hydrogen Metal hydroxides of sodium oxide and potassium hydroxide; metal hydrides of sodium hydride and potassium hydride; amines such as monomethylamine, dimethylamine, triethylamine, and diisopropylethylamine; For example, pyridine and pyridines of 4-dimethylaminopyridine; organic lithium compounds such as methyllithium, n-butyllithium, and lithium diisopropylamidamine are appropriately selected from one or two or more. The (halo) alkylating agent, cycloalkylating agent or base is used in an amount of 1 to 20 equivalents, and desirably 1 to 10 equivalents relative to the compound of formula (208).
The organic metal reagent is not particularly limited as long as it can react, and examples thereof include organic boron compounds. The organometallic reagent can be prepared by a known method, or a commercially available product can be used. The organometallic reagent can be used in an amount of 1 to 10 equivalents with respect to 1 equivalent of the compound of formula (208), and is desirably 1 to 5 equivalents.
As the transition metal reagent, various well-known structures used in the cross-coupling reaction can be used. The transition metal reagent containing copper in this reaction is particularly useful. Examples include copper (II) acetate. If necessary, a diamine can be used as a ligand. Examples of the diamine include N, N, N ', N'-tetramethylethylenediamine, 2,2'-bipyridyl, and the like. The transition metal reagent may be used in an amount of 0.1 to 5 equivalents with respect to 1 equivalent of the compound of formula (208), and is desirably 0.5 to 1.5 equivalents. The ligand is usually 1 to 10 equivalents to the transition metal catalyst, and is preferably 1 to 5 equivalents. However, an amount outside this range may be used due to reaction conditions.
Any solvent is acceptable if the solvent is a solvent inert to the reaction. For example, the solvent may be aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; for example, carbon tetrachloride, methylene chloride, chloroform, methylene chloride, Aliphatic hydrocarbons such as dichloroethane, trichloroethane, hexane, and cyclohexane; such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; such as methanol, ethanol, and propane Alcohols, tert-butanol alcohols; such as dimethylmethylene, cyclobutane, dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, propane The polar aprotic solvent of the nitrile; one or two or more kinds are appropriately selected from water and the mixed solvent thereof.

反應溫度通常為0～100℃，期望為0～80℃，反應時間通常為0.1～48小時左右，期望為0.1～24小時左右。The reaction temperature is usually 0 to 100 ° C, preferably 0 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and preferably about 0.1 to 24 hours.

式(208)之化合物可依公知之方法製造，或可使用市售品。The compound of formula (208) can be produced by a known method, or a commercially available product can be used.

反應2-9
反應2-9係使式(210)之化合物及式(211)之化合物進行反應，得到式(4-4)之化合物之方法。Reaction 2-9
Reaction 2-9 is a method of reacting a compound of formula (210) and a compound of formula (211) to obtain a compound of formula (4-4).

式中，RB1-1 為烷基或鹵烷基，RB2-1 為烷基或環烷基，其他記號係如前述。In the formula, R B1-1 is alkyl or haloalkyl, R B2-1 is alkyl or cycloalkyl, and other symbols are as described above.

反應2-9通常於溶媒的存在下，可藉由將式(210)之化合物及式(211)之化合物，如有必要於鹼的存在下，進行反應來進行。式(211)之化合物相對於式(210)之化合物1當量，可以1～10當量，期望為1～2當量的比例使用。Reaction 2-9 is usually carried out in the presence of a solvent by reacting a compound of formula (210) and a compound of formula (211) in the presence of a base if necessary. The compound of the formula (211) may be used in a ratio of 1 to 10 equivalents, and desirably in a ratio of 1 to 2 equivalents, relative to 1 equivalent of the compound of formula (210).

作為溶媒，若能進行反應則並未特別限定，例如可從如苯、甲苯、二甲苯、氯苯之芳香族烴類；如己烷、庚烷、石油醚、石油醚、環己烷之脂肪族烴類；如氯仿、二氯甲烷、四氯化碳、1,2-二氯乙烷之鹵素化烴類；如二乙基醚、二異丙基醚、二丁基醚、四氫呋喃、二噁烷、乙二醇二甲基醚之醚類；如乙腈、丙腈、丙烯腈之腈類；如乙醇、甲醇、丁醇之醇類；如吡啶之有機胺類；水及此等之混合溶媒等中適當選擇1種或2種以上。The solvent is not particularly limited as long as it can be reacted. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; and fats such as hexane, heptane, petroleum ether, petroleum ether, and cyclohexane can be used. Group hydrocarbons; such as halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and 1,2-dichloroethane; such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dichloromethane Dioxane, ethylene glycol dimethyl ether ethers; such as acetonitrile, propionitrile, acrylonitrile, nitriles; alcohols such as ethanol, methanol, butanol; organic amines such as pyridine; water and mixtures thereof One or two or more kinds are appropriately selected among solvents and the like.

作為鹼，若能進行反應則並未特別限定，例如可列舉如碳酸鈉、碳酸鉀、碳酸銫之鹼金屬碳酸鹽；如甲醇鈉、乙醇鈉、第3級丁醇鉀之鹼金屬醇鹽；如碳酸氫鈉之鹼金屬的碳酸氫鹽；如碳酸鈣之鹼土類金屬的碳酸鹽；如氫氧化鈉、氫氧化鉀之金屬氫氧化物；如氫化鈉、氫化鉀之金屬氫化物；如三乙基胺、二異丙基乙基胺、吡啶、4-(N,N-二甲基胺基)吡啶之有機胺類等。鹼相對於式(210)之化合物1當量，可以0.001～10當量，期望為0.005～5當量的比例使用。The base is not particularly limited as long as it can be reacted, and examples include alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; and alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and third-order potassium butoxide; Such as sodium bicarbonate alkali metal bicarbonate; such as calcium carbonate alkaline earth metal carbonate; such as sodium hydroxide, potassium hydroxide metal hydroxide; such as sodium hydride, potassium hydride metal hydride; such as three Organic amines such as ethylamine, diisopropylethylamine, pyridine, 4- (N, N-dimethylamino) pyridine, and the like. The base can be used in an amount of 0.001 to 10 equivalents, and preferably 0.005 to 5 equivalents, based on 1 equivalent of the compound of formula (210).

反應溫度通常為-30～200℃，期望為0～80℃，反應時間通常為1～48小時左右。The reaction temperature is usually -30 to 200 ° C, preferably 0 to 80 ° C, and the reaction time is usually about 1 to 48 hours.

式(210)之化合物及式(211)之化合物可依公知之方法或藉由後述之方法製造，或可使用市售品。The compound of the formula (210) and the compound of the formula (211) can be produced by a known method or by a method described later, or a commercially available product can be used.

反應2-10
反應2-10係將式(212)之化合物與三氟碘甲烷及過氧化氫進行反應，得到式(210)之化合物之方法。Reaction 2-10
Reaction 2-10 is a method of reacting a compound of formula (212) with trifluoroiodomethane and hydrogen peroxide to obtain a compound of formula (210).

式中之記號係如前述。
反應2-10例如可依照Tetrahedron、68卷、2636～2649頁(2012年)等所記載之方法，或依照該等之方法，製造式(210)之化合物。式(212)之化合物可依公知之方法製造，或可使用市售品。The symbols in the formula are as described above.
Reaction 2-10 can produce the compound of Formula (210) according to the method described in Tetrahedron, Vol. 68, pages 2636-2649 (2012), or the like. The compound of formula (212) can be produced by a known method, or a commercially available product can be used.

本發明化合物作為以低藥量可防除有害菌類之農園藝用殺菌劑的有效成分有用。作為農園藝用殺菌劑使用時，本發明化合物，例如可防除屬於卵菌類(Oomycetes)、子嚢菌類(Ascomycetes)、担子菌類(Basidiomycetes)、不完全菌類(Deuteromycetes)等之有害菌類，其中，對屬於子嚢菌類(Ascomycetes)、不完全菌類(Deuteromycetes)等之有害菌類的防除特別有效。The compound of the present invention is useful as an active ingredient of an agricultural and horticultural fungicide capable of controlling harmful bacteria at a low drug amount. When used as a fungicide for agriculture and horticulture, the compounds of the present invention can prevent harmful fungi such as Oomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes, etc., among which The control of harmful fungi belonging to Ascomycetes and Deuteromycetes is particularly effective.

作為前述有害菌類更具體之例，例如可列舉如以下者等。
作為卵菌類，可列舉如馬鈴薯或番茄疫病菌(Phytophthora infestans)、番茄灰色疫病菌(Phytophthora capsici)之疫病菌(Phytophthora)屬；如黃瓜霜霉病(
Pseudoperonospora cubensis)之露菌病菌(
Pseudoperonospora)屬；如葡萄霜霉病(Plasmopara viticola)之單軸黴菌(Plasmopara)屬；如稻苗立枯病菌(
Pythium graminicola)、小麥褐色雪腐病菌(Pythium
iwayamai)之腐霉菌(Pythium)屬等。More specific examples of the harmful fungi include, for example, the following.
Examples of the oomycetes include potato or Phytophthora infestans, Phytophthora capsici, Phytophthora, and cucumber downy mildew (
Pseudoperonospora cubensis)
Pseudoperonospora); such as Plasmopara viticola; Plasmopara;
Pythium graminicola), wheat brown snow rot fungus (Pythium
iwayamai), Pythium and the like.

作為子嚢菌類，可列舉如小麥白粉病菌(
Erysiphe graminis)之白粉菌(Erysiphe)屬；如黃瓜白粉病菌(Sphaerotheca fuliginea)、草莓白粉病菌(Sphaerotheca humuli)之草單囊殼(Sphaerotheca)屬；如葡萄白粉病菌(Uncinula necator)之鈎絲殼(Uncinula)屬；如蘋果白粉病菌(Podosphaera leucotricha)之絲單囊殼(Podosphaera)屬；如豌豆褐紋病菌(Mycosphaerella pinodes)、蘋果黑點病菌(Mycosphaerella pomi)、香蕉香蕉葉斑病菌(
Mycosphaerella musicola)、柿子圓星落葉病菌(
Mycosphaerella nawae)、草莓蛇紋石病菌(Mycosphaerella fragariae)之球腔菌(Mycosphaerella)屬；如蘋果黑星病菌(Venturia inaequalis)、梨黑星病菌(Venturia nashicola)之黑星菌(Venturia)屬；如大麥網斑病菌(Pyrenophora teres)、大麥斑葉病菌(Pyrenophora graminea)之核腔菌(
Pyrenophora)屬；如綠豆菌核病菌、黃瓜菌核病菌、甘藍菌核病菌、白菜菌核病菌、胡椒菌核病菌、青椒菌核病菌或洋蔥菌核病菌之各種菌核病菌(Sclerotinia sclerotiorum)、如小麥雪腐大粒菌核病菌(Sclerotinia borealis)、番茄小粒菌核病菌(Sclerotinia minor)、苜蓿菌核病菌(Sclerotinia trifoliorum)之核盤菌(Sclerotinia)屬；如花生小菌核病菌(Botryolinia arachidis)之孢盤菌(Botryolinia)屬；如稻芝麻斑病菌(Cochliobolus miyabeanus)之旋孢腔菌(
Cochliobolus)屬；如黃瓜藤枯病菌(Didymella bryoniae)之亞隔孢殼(Didymella)屬；如稻馬鹿苗病菌(Gibberella fujikuroi)之赤黴菌(Gibberella)屬；如葡萄黑痘病菌(Elsinoe ampelina)、柑橘瘡痂病菌(Elsinoe fawcettii)之痂囊腔菌(Elsinoe)屬；如柑橘黑點病菌(Diaporthe citri)、葡萄科膨病菌(Diaporthe sp.)之間座殼菌(Diaporthe)屬；如蘋果念珠菌病菌(Monilinia mali)、桃灰色病菌(Monilinia fructicola)之鏈核盤菌(Monilinia)屬；如葡萄晩腐病菌(Glomerella cingulata)之炭疽刺盤孢菌(Glomerella)屬等。Examples of the fungus fungus include wheat powdery mildew (
Erysiphe graminis); such as Sphaerotheca fuliginea, Sphaerotheca humuli; Sphaerotheca; such as Uncinula necator Uncinula); such as the genus Podosphaera of Podosphaera leucotricha; such as Mycosphaerella pinodes, Mycosphaerella pomi, banana leaf spot
Mycosphaerella musicola)
Mycosphaerella nawae, Mycosphaerella fragariae, Mycosphaerella; such as Venturia inaequalis, Venturia nashicola, Venturia; such as barley Pyrenophora teres and Pyrenophora graminea
Pyrenophora); such as Sclerotinia sclerotiorum (Sclerotinia sclerotiorum) Sclerotinia borealis, Sclerotinia minor, Sclerotinia trifoliorum, and Sclerotinia; such as Botryolinia arachidis Botryolinia; for example, Cochliobolus miyabeanus (Cochliobolus miyabeanus)
Cochliobolus); such as Didymella genus Didymella bryoniae; Gibberella fujikuroi; Gibberella; Elsinoe ampelina; Elsinoe genus of citrus scab (Elsinoe fawcettii); such as Diaporthe citri, Diaporthe sp. (Diaporthe sp.); Such as Candida apple Monilinia mali, Monilinia fructicola (Monilinia) genus; such as grape rot fungus (Glomerella cingulata) anthracnose thorn spore (Glomerella) genus and so on.

作為担子菌類，可列舉如稻紋枯病菌(
Rhizoctonia solani)之絲核菌(Rhizoctonia)屬；如小麥裸黑穂病菌(Ustilago nuda)之黑粉菌(Ustilago)屬；如燕麥冠銹病菌(Puccinia coronata)、小麥葉銹病菌(Puccinia recondita)、小麥黃銹病菌(Puccinia striiformis)之柄銹菌(Puccinia)屬；如大豆銹病菌(Phakopsora pachyrhizi)之層銹菌(Phakopsora)屬；如小麥或大麥雪腐小粒菌核病菌(Typhula incarnata, Typhula ishikariensisis)之雪腐菌核菌(Typhula)屬等。Examples of Basidiomycetes include Rhizoctonia solani
Rhizoctonia solani), such as Rhizoctonia; Ustilago nuda; Ustilago; Puccinia coronata; Puccinia recondita; Puccinia genus of Puccinia striiformis; such as Phakopsora of Phakopsora pachyrhizi; typhula incarnata, Typhula ishikariensisis of wheat or barley snow rot ) Of the genus Snow rot sclerotia (Typhula) and the like.

作為不完全菌類，可列舉如小麥穎枯病菌(Septoria nodorum)、小麥葉枯病菌(Septoria tritici)之殼針孢菌(Septoria)屬；如葡萄灰黴病菌、柑橘灰黴病菌、黃瓜灰黴病菌、番茄灰黴病菌、草莓灰黴病菌、茄子灰黴病菌、綠豆灰黴病菌、紅豆灰黴病菌、豌豆灰黴病菌、花生灰黴病菌、胡椒灰黴病菌、青椒灰黴病菌、萵苣灰黴病菌、洋蔥灰黴病菌、星辰花灰黴病菌、康乃馨灰黴病菌、玫瑰灰黴病菌、三色堇灰黴病菌或向日葵灰黴病菌之各種灰黴病菌(Botrytis cinerea)、如洋蔥灰腐病菌(Botrytis allii)、引起因洋蔥之葡萄孢屬菌導致之葉枯病的病原菌(Botrytis squamosa, Botrytis byssoidea, Botrytis tulipae)之葡萄孢菌(Botrytis)屬；如小麥赤黴病菌(Fusarium graminearum)、黃瓜鶴見病菌(Fusarium oxysporum)之鐮孢菌(Fusarium)屬、如稻瘟病菌(Pyricularia oryzae)之梨孢(Pyricularia)屬；如甜菜褐斑病菌(Cercospora beticola)、柿子角斑病菌(Cercospora kakivola)之尾孢菌(Cercospora)屬；如黃瓜炭疽病菌(Colletotrichum orbiculare)之炭疽刺盤孢菌(Colletotrichum)屬；如蘋果斑點落葉病菌(
Alternaria alternata apple pathotype)、梨黑斑病菌(
Alternaria alternata Japanese pear pathotype)、馬鈴薯早疫或番茄輪紋病菌(Alternaria solani)、甘藍或白菜黑斑病菌(Alternaria brassicae)、甘藍黑煙病菌(Alternaria
brassicola)、洋蔥或蔥黑斑病菌(Alternaria porri)之鏈隔孢菌(Alternaria)屬；如甘藍根朽病菌(Phoma lingam)之莖點霉(Phoma)屬；如小麥眼紋病菌(Pseudocercosporella herpotrichoides)之假小尾孢黴(Pseudocercosporella)屬；如葡萄褐斑病菌(Pseudocercospora vitis)之假尾孢菌(
Pseudocercospora)屬；如大麥雲形病菌(Rhynchosporium secalis)之雲紋菌(Rhynchosporium)屬；如桃黑星病菌(
Cladosporium carpophilum)之枝孢菌(Cladosporium)屬；如桃擬莖點黴腐敗病菌(Phomopsis sp.)之擬莖點黴(
Phomopsis)屬；如柿子炭疽病菌(Gloeosporium kaki)之盤長孢黴(Gloeosporium)屬；如番茄葉黴病菌(Fulvia fulva)之葉黴病菌(Fulvia)屬；如黃瓜褐斑病菌(Corynespora cassiicola)之棒狀桿孢菌(Corynespora)屬等。Examples of incomplete fungi include Septoria nodorum, Septoria tritici, Septoria, and Botrytis cinerea, Botrytis citrus, Botrytis cinerea Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis pea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea Botrytis cinerea, onion botrytis, star flower botrytis, carnation botrytis, rose botrytis, pansy botrytis, or sunflower botrytis (Botrytis cinerea), such as onion grey rot (Botrytis allii), Botrytis genus that causes leaf blight caused by Botrytis squamosa, Botrytis byssoidea, Botrytis tulipae; such as Fusarium graminearum, cucumber Tsurumi (Fusarium oxysporum) Fusarium, such as Pyricularia oryzae Pyricularia; such as Cercospora betico la). Cercospora genus of Cercospora kakivola; for example, Colletotrichum of Colletotrichum orbiculare; for example, apple leaf deciduous fungus (Colletotrichum)
Alternaria alternata apple pathotype)
Alternaria alternata Japanese pear pathotype), early potato blight or Alternaria solani, cabbage or cabbage black spot (Alternaria brassicae), cabbage black smoke (Alternaria
brassicola), onion or Alternaria porri, Alternaria genus; for example, Phoma lingam, Phoma genus; for example, Pseudocercosporella herpotrichoides Pseudocercosporella; such as Pseudocercospora vitis (Pseudocercospora vitis)
Pseudocercospora); such as Rhynchosporium secalis; Rhynchosporium;
Cladosporium carpophilum); genus Cladosporium; such as Phomopsis sp.
Phomopsis); such as Gloeosporium kaki, Gloeosporium; Fulvia fulva; Fulvia; Corynespora cassiicola Corynespora and the like.

本發明化合物由於可防除前述之各種有害菌類，故可預防性或治療性防除各種病害。尤其是本發明化合物對於農園藝領域成為問題的各種病害，例如對梨孢菌導致之稻瘟病、鐮孢菌導致之馬鹿苗病、旋孢腔菌導致之芝麻斑病、絲核菌導致之紋枯病等之稻之病害；白粉菌導致之白粉病、鐮孢菌導致之赤黴病或冠腐病、柄銹菌導致之銹病、腐霉菌導致之褐色雪腐病、黑粉菌導致之裸黑穂病、假小尾孢黴菌導致之眼紋病、殼針孢菌導致之葉枯病或穎枯病等之麥類之病害；鐮孢菌導致之赤黴病、暗球腔菌導致之斑點病、柄銹菌導致之銹病、Setosphaeria菌導致之煤紋病、旋孢腔菌導致之芝麻斑病、腐霉菌導致之根腐病、黑粉菌導致之黑穂病等之玉米之病害；黑粉菌導致之黑穂病、殼多孢菌導致之葉燒病、柄銹菌導致之銹病、赤黴菌導致之梢頭腐敗病、Caldariomyces菌導致之煙塵病、假尾孢菌導致之葉枯病等之甘蔗之病害等之稻科作物之病害；卵黴菌導致之白粉病、層銹菌導致之銹病、墓蔔露菌病菌導致之霜霉病、疫病菌導致之疫病、炭疽刺盤孢菌導致之炭疽病、核盤菌導致之菌核病、葡萄孢菌導致之灰黴病、鐮孢菌導致之根腐病或立枯病等之豆科作物之病害；鐮孢菌導致之枯萎病、墓蔔露菌病菌導致之霜霉病、鏈隔孢菌導致之黑斑病、莖點霉菌導致之根朽病等之十字花科作物之病害；盤梗黴菌導致之霜霉病、疫病菌導致之疫病、葡萄孢菌導致之灰黴病、核盤菌導致之菌核病、銹孢銹菌導致之銹病等之菊科作物之病害；鏈隔孢菌導致之輪紋病、葉黴病菌導致之葉黴病、疫病菌導致之疫病、葡萄孢菌導致之灰黴病、卵黴菌導致之白粉病、鐮孢菌導致之萎凋病、假尾孢菌導致之煤鰴病等之番茄之病害；鏈隔孢菌導致之早疫病、疫病菌導致之疫病、核盤菌導致之菌核病、鐮孢菌導致之乾腐病等之馬鈴薯之病害等之茄科作物之病害；炭疽刺盤孢菌導致之炭疽病、草單囊殼菌導致之白粉病、亞隔孢殼(Didymella)菌導致之藤枯病、露菌病菌導致之霜霉病、疫病菌導致之疫病、棒狀桿孢菌導致之褐斑病、鐮孢菌導致之鶴見病等之葫蘆科作物之病害；墓蔔露菌病菌導致之霜霉病、疫病菌導致之疫病、葡萄孢菌導致之灰黴病、核盤菌導致之菌核病、柄銹菌導致之銹病等之蔥科作物之病害；鏈隔孢菌導致之黑葉枯病或黑斑病、葡萄孢菌導致之灰黴病、核盤菌導致之菌核病、白粉菌導致之白粉病、尾孢菌導致之斑點病等之繖形科作物之病害；葡萄孢菌導致之葉枯病、疫病菌導致之疫病、擬莖點黴菌導致之莖枯病等之百合科作物之病害；墓蔔露菌病菌導致之霜霉病、白粉菌導致之白粉病、絲核菌導致之立枯病等之蓼科作物之病害；鐮孢菌導致之鶴見病、長喙黴菌導致之黑斑病、鏈黴菌導致之立枯病等之旋花科作物之病害；墓蔔露菌病菌導致之霜霉病、疫病菌導致之疫病、葡萄孢菌導致之灰黴病、核盤菌導致之菌核病、卵黴菌導致之白粉病、尾孢菌導致之褐斑病等之藜科作物之病害；痂囊腔菌導致之黑痘病、炭疽刺盤孢菌導致之晩腐病、白粉菌導致之白粉病、單軸黴菌導致之霜霉病、葡萄孢菌導致之灰黴病、假尾孢菌導致之褐斑病、胴枯病菌導致之科膨病等之葡萄科作物之病害；草單囊殼菌導致之白粉病、葡萄孢菌導致之灰黴病、炭疽刺盤孢菌導致之炭疽病、鐮孢菌導致之乾腐病等之草莓之病害；鏈核盤菌導致之念珠菌病、絲單囊殼菌導致之白粉病、鏈隔孢菌導致之斑點落葉病、黑星菌導致之黑星病、炭疽刺盤孢菌導致之炭疽病、褐斑病菌導致之褐斑病、葡萄座腔菌導致之輪紋病、接瓶黴菌導致之煤點病、黏孢殼菌(Gloeodes)導致之煤斑病、球腔菌導致之黑點病等之蘋果之病害；黑星菌導致之黑星病、鏈隔孢菌導致之黑斑病、球針殼菌導致之白粉病、疫病菌導致之疫病、鐮孢菌導致之果實腐敗病等之梨類之病害；鏈核盤菌導致之灰色病、枝孢菌導致之黑星病、擬莖點黴菌導致之擬莖點黴腐敗病等之桃之病害等之薔薇科作物之病害；胴枯病菌導致之黑點病、痂囊腔菌導致之瘡痂病、鐮孢菌導致之鐮孢立枯病等之柑橘之病害等之芸香科作物之病害；盤長孢黴菌導致之炭疽病、尾孢菌導致之落葉病、球針殼菌導致之白粉病、接瓶黴菌導致之煤點病等之柿樹科作物之病害；炭疽刺盤孢菌導致之炭疽病、擬盤多毛孢菌導致之輪斑病、假單胞菌導致之赤燒病、山茶菌導致之餅病等之山茶花科作物之病害；等之植物病害的防除為有效。
又，對鐮孢菌導致之赤黴病或冠腐病、炭疽刺盤孢菌導致之炭疽病、腥黑粉菌導致之腥黑粉病、黑粉菌導致之裸黑穂病、頭芽胞菌導致之條斑病、殼針孢菌導致之穎枯病等之麥類之病害；
雙孔孢菌導致之芝麻斑病、炭疽刺盤孢菌導致之炭疽病、鐮孢菌導致之苗立枯病等之玉米之病害；炭疽刺盤孢菌導致之赤腐病、長喙黴菌導致之黑腐病、指梗黴菌導致之霜霉病等之甘蔗之病害等之稻科作物之病害；尾孢菌導致之紫斑病、墓蔔露菌病菌導致之霜霉病、鐮孢菌導致之立枯病、殼針孢菌導致之褐紋病、胴枯病菌導致之黑點病、炭疽刺盤孢菌導致之炭疽病、Septogloeum菌導致之昏睡病等之大豆之病害等之豆科作物之病害；鏈隔孢 蕓苔屬真菌導致之黑斑病、鏈隔孢鏈隔孢菌導致之黑煙病、墓蔔露菌病菌導致之霜霉病、假單胞菌導致之黑斑細菌病、黃單胞菌導致之黑腐病、莖點霉菌導致之根朽病等之甘藍之病害；鏈隔孢菌導致之黑斑病、鐮孢菌導致之枯萎病、黃單胞菌導致之黑腐病等之蘿蔔之病害；鏈隔孢菌導致之黑斑病、黃單胞菌導致之黑腐病、輪黴菌導致之黃化病等之白菜之病害等之十字花科作物之病害；鏈隔孢菌導致之輪紋病、棒桿菌導致之潰瘍病、黃單胞菌導致之斑點細菌病等之番茄之病害；鏈隔孢菌導致之褐斑病、擬莖點黴菌導致之褐紋病等之茄子之病害；鏈黴菌導致之瘡痂病、長蠕孢黴菌導致之銀痂病、馬鈴薯粉痂菌(
Spongospora)導致之粉狀瘡痂病等之馬鈴薯之病害等茄科作物之病害；鏈隔孢菌導致之黑斑病、假單胞菌導致之斑點細菌病、黃單胞菌導致之褐斑細菌病等之黃瓜之病害等之葫蘆科作物之病害；鏈隔孢菌導致之黑斑病、葡萄孢菌導致之灰腐病或菌絲性腐敗病、鐮孢菌導致之乾腐病、墓蔔露菌病菌導致之霜霉病等之洋蔥之病害等之蔥科作物之病害；鏈隔孢菌導致之黑葉枯病或黑斑病、黃單胞菌導致之斑點細菌病；芹菜之殼針孢菌導致之葉枯病、核盤菌導致之菌核病、假單胞菌導致之葉枯細菌病等之紅蘿蔔之病害等之繖形科作物之病害；墓蔔露菌病菌導致之霜霉病、鐮孢菌導致之萎凋病、炭疽刺盤孢菌導致之炭疽病等之菠菜之病害等之藜科作物之病害；等之種子傳染性病害亦有效。
進而，對因鐮孢菌、腐霉菌、絲核菌、輪黴菌、根腫菌、根串珠黴菌等之有害菌類所引起之土壤病害的防除亦有效。Since the compound of the present invention can prevent various harmful fungi mentioned above, it can prevent various diseases preventively or therapeutically. In particular, the compounds of the present invention have various diseases that have become problems in the field of agriculture and horticulture, such as rice blast caused by pear spore, red deer disease caused by Fusarium, sesame spot disease caused by Coccidioides, and streaks caused by Rhizoctonia Diseases of rice such as blight; powdery mildew caused by powdery mildew, scab caused by Fusarium or crown rot, rust caused by Puccinia sclerotiorum, brown snow rot caused by Pythium, naked by powdery mildew Black streak disease, eye streak caused by Pseudocercospora, leaf blight caused by Fusarium sp Disease, corn rust caused by Puccinia sclerotiorum, coal streak caused by Setosphaeria fungus, sesame spot disease caused by Sporocystis spp., Root rot caused by Pythium fungus, black scab caused by black fungus, etc. Black fungus caused by powdery mildew, leaf burn caused by polycystic spores, rust caused by Puccinia sclerotiorum, tip rot caused by Gibberella, fume caused by Caldariomyces, leaf blight caused by Pseudocercospora, etc. Diseases of rice plants, such as sugarcane; eggs Powdery mildew caused by bacteria, rust caused by layer rust fungus, downy mildew caused by phytophthora blight fungus, blight caused by phytophthora blight, anthracnose caused by discobacterium anthracis, sclerotinia caused by sclerotinia sclerotiorum, grapes Botrytis cinerea caused by Botrytis cinerea, root rot caused by Fusarium or blight, etc .; Fusarium caused by Fusarium, downy mildew caused by Fusarium spp., Alternaria spp. Diseases of cruciferous crops such as black spot caused by fungi, root rot caused by stem mold, etc .; downy mildew caused by Sclerotinia spp., Blight caused by Phytophthora blight, gray mold caused by Botrytis spp., Nuclear disc Sclerotinia sclerotiorum caused by fungi, rust caused by Puccinia sclerotiorum and other chrysanthemum crops; rotariae caused by Streptomyces, leaf mold caused by leaf mold, blight caused by Phytophthora blight, grape spores Diseases of tomato caused by gray mold, powdery mildew caused by oomycetes, Fusarium wilt, coal blight caused by pseudocercospora, etc .; early blight caused by Streptomyces, blight caused by Phytophthora Sclerotinia caused by Sclerotinia sclerotiorum, dry rot caused by Fusarium Diseases of solanaceous crops such as diseases of boll potato; anthracnose caused by anthracnose spores, powdery mildew caused by monocystis spp., Vine blight caused by Didymella spp. And exposed bacteria Downy mildew, blight caused by Phytophthora blight, brown spot disease caused by Corynebacterium spp., Disease of cucurbitaceous crops caused by Fusarium spp. Diseases caused by Phytophthora, gray mold caused by Botrytis, sclerotinia caused by Sclerotinia sclerotiorum, rust caused by Puccinia sclerotiorum, etc .; black leaf blight or black spot caused by Streptomyces Botrytis cinerea caused by Botrytis cinerea caused by Botrytis cinerea, Sclerotinia sclerotiorum caused by Sclerotinia sclerotiorum, powdery mildew caused by powdery mildew, spot disease caused by Cercospora, and leaf blight caused by Botrytis Diseases of Liliaceae crops caused by Phytophthora infestans, Phytophthora blight caused by Phytophthora spp .; Downy mildew caused by Tombgrass fungus, Powdery mildew caused by powdery mildew, Rhizoctonia solani caused by Rhizoctonia solani Diseases of Polygonaceae crops; Tsurumi disease caused by Fusarium Diseases of convolvulaceous crops caused by black spot disease caused by fungi, bacterial blight caused by streptomyces; downy mildew caused by grave fungus, blight caused by Phytophthora blight, gray mold caused by Botrytis, nucleus Sclerotinia sclerotiorum caused by Sclerotinia sclerotiorum, powdery mildew caused by Oomycetes, brown spot disease caused by Cercospora and other diseases of Chenopodiaceae; black pox caused by Saccharomyces sp. Disease, powdery mildew caused by powdery mildew, downy mildew caused by uniaxial mold, gray mold caused by botrytis, brown spot disease caused by pseudocercospora, phytophthora caused by bacterial wilt, etc. Diseases; powdery mildew caused by Phytophthora gracilis, gray mold caused by Botrytis spp., Anthracnose caused by Anthracnose anthracnose, dry rot caused by Fusarium, etc. Streptomyces sclerotiorum Candidiasis, powdery mildew caused by Phytophthora capsici, spotted leaf disease caused by Alternaria spp., Black spot disease caused by Aspergillus niger, anthracnose caused by discobacterium anthracis, brown caused by brown spot disease Leaf spot disease 、 Apple disease caused by coal spot disease caused by Gloeodes, black spot disease caused by coccus spp .; black spot disease caused by sphaerotheca, black spot disease caused by streptomyces, and needle shell Powdery mildew caused by fungi, blight caused by Phytophthora infestans, pear spoilage caused by Fusarium, etc .; gray disease caused by Streptococcus sclerotiorum, black spot disease caused by Cladosporium sp Diseases of the Rosaceae crops, such as P. spp., Which are caused by Pythium sp., Etc .; black spot disease caused by Fusarium oxysporum, scab caused by Saccharomyces, Fusarium solani caused by Fusarium, etc. Diseases of rutae crops such as citrus diseases; anthracnose caused by Phytophthora spp., Defoliation caused by Cercospora, powdery mildew caused by Sphaerothecium, coal spot disease caused by bottle mold, etc. Diseases of crops; diseases caused by anthracnose caused by anthracnose, sclerotinia sclerotiorum, red spot disease caused by pseudomonas, red fever caused by Pseudomonas, cake disease caused by camellia, etc .; etc. The prevention of plant diseases is effective.
Also, for Fusarium oxysporum or crown rot, anthracnose caused by anthracnose spores, anthracnose caused by black fungus, black smut caused by black fungus, naked black scab caused by black fungus, cephalosporin Diseases of wheat caused by streak spot disease, gracilaria blight, etc.
Diseases of corn caused by sesame spot disease caused by diammonae, anthracnose caused by anthracnose anthracnose, bacterial blight caused by Fusarium, and red rot caused by anthracnose anthracnose Black rot, refers to diseases such as sugarcane caused by downy mildew caused by P. spp., And diseases of rice crops; purple spot disease caused by Cercospora, downy mildew caused by Fusarium spp., And Fusarium Leguminous blight, brown spot disease caused by needle fungus, black spot disease caused by Fusarium oxysporum, anthracnose caused by anthrax anthracnose, lethargy caused by septogloeum, etc. Diseases; black spot disease caused by Alternaria brassicae fungus, black smoke disease caused by Alternaria alternariae, downy mildew caused by Grave blight fungus, black spot disease caused by Pseudomonas, Black rot caused by Xanthomonas, root rot caused by Phytophthora sp .; black spot caused by Streptomyces, fusarium caused by Fusarium, black rot caused by Xanthomonas Diseases such as radish; black spot caused by Streptomyces and black rot caused by Xanthomonas Diseases of Brassicaceae crops such as yellow disease caused by Rotter mold, diseases of Brassicaceae crops caused by Streptomyces, ulcer disease caused by Streptomyces, ulcer disease caused by Corynebacterium, spotted bacterial disease caused by Xanthomonas Diseases of tomato; brown spot disease caused by Alternaria spp., Brown egg disease caused by Phytophthora sp., Eggplant disease, etc .; scab caused by Streptomyces, silver scab caused by Helminthosporium sp., Potato fungus (
Spongospora), powdery scab and other potato diseases; diseases of solanaceous crops; black spot disease caused by Streptomyces, spot bacterial disease caused by Pseudomonas, brown spot disease caused by Xanthomonas Diseases of cucumbers and other cucurbits; diseases of black spot caused by Streptomyces, gray rot or mycelial rot caused by Fusarium, dry rot caused by Fusarium, grave Diseases of onion crops such as downy mildew caused by fungal diseases; black leaf blight or black spot caused by Alternaria spp. And spotted bacterial disease caused by Xanthomonas; Diseases of umbelliferous crops such as leaf blight caused by bacteria, sclerotinia caused by Sclerotinia sclerotiorum, leaf blight caused by Pseudomonas, and diseases of umbelliferous crops, etc. Diseases, Fusarium wilt, Spinal diseases such as anthracnose caused by Anthracnose caused by Anthracnose, and other diseases of Chenopodiaceae crops; Infectious diseases of seeds are also effective.
Furthermore, it is also effective in controlling soil diseases caused by harmful fungi such as Fusarium, Pythium, Rhizoctonia, Rotter mold, Rhizobium, Leuconostoc, etc.

作為可從各種有害菌類藉由本發明來保護之植物，若為農業上有用者，雖並未特別限制，但例如可列舉稻科作物(稻、小麥、大麥、燕麥、黑麥、玉米、甘蔗等)、豆科作物(大豆、菜豆、紅豆等)、十字花科作物(甘藍、白菜、蘿蔔、蕪菁、青花菜、花椰菜、油菜花、油菜等)、菊科作物(萵苣、牛蒡、春菊等)、茄科作物(馬鈴薯、茄子、番茄、青椒、煙草等)、葫蘆科作物(黃瓜、南瓜、甜瓜、西瓜等)、蔥科作物(蔥、韭菜、薤、大蒜等)、繖形科作物(芹菜、紅蘿蔔、香菜等)、百合科作物(百合、鬱金香、蘆筍等)、蓼科(蕎麥等)、旋花科(甘藷等)、藜科作物(菠菜、甜菜等)、葡萄科作物(葡萄等)、薔薇科作物(玫瑰、草莓、蘋果、梨、桃、枇杷、杏仁等)、芸香科作物(蜜柑、檸檬、橙等)、柿樹科作物(柿子等)、山茶花科作物(茶等)、木犀科作物(橄欖、茉莉花等)、錦葵科作物(棉花、可可、秋葵等)、芭蕉科作物(香蕉等)、薑科作物(薑等)、茜草科作物(咖啡樹等)或鳳梨科作物(鳳梨、鳳梨(Ananas)等)。As a plant that can be protected from various harmful fungi by the present invention, if it is agriculturally useful, although it is not particularly limited, examples thereof include rice plants (rice, wheat, barley, oats, rye, corn, sugar cane, etc.) ), Leguminous crops (soybeans, kidney beans, red beans, etc.), cruciferous crops (cabbage, cabbage, radish, turnip, broccoli, broccoli, rapeseed, rapeseed, etc.), compositae crops (lettuce, burdock, chamomile, etc.) , Solanaceous crops (potato, eggplant, tomato, green pepper, tobacco, etc.), Cucurbitaceous crops (cucumber, pumpkin, melon, watermelon, etc.), Allium crops (onion, leek, coriander, garlic, etc.), Umbelliferous crops ( Celery, carrot, coriander, etc.), Liliaceae (lily, tulip, asparagus, etc.), Polygonaceae (buckwheat, etc.), Convolvulaceae (sweet potato, etc.), Chenopodiaceae (spinach, beet, etc.), Grape crops ( Grapes, etc.), Rosaceae crops (rose, strawberry, apple, pear, peach, loquat, almond, etc.), rutae crops (mandarin, lemon, orange, etc.), persimmon crops (persimmon, etc.), camellia crops (tea Etc.), Osmanthus crops (olive, jasmine, etc.), Aquilaceae crops (cotton, cocoa, okra, etc.), Musa crops (bananas, etc.), ginger crops (ginger, etc.), madder crops (coffee trees, etc.), or pineapple crops (Bromeliad, Ananas, etc.) .

又，本發明化合物相對於苯并咪唑、甲氧基丙烯酸酯(Strobilurin)、二甲醯亞胺、苯基醯胺、麥角固醇生合成阻害劑等之藥劑的各種抵抗性有害菌類的防除亦有效。In addition, the compound of the present invention is effective in controlling various harmful harmful fungi such as benzimidazole, strobilurin, dimethylimine, phenylamidine, and ergosterol biosynthesis inhibitors. Also effective.

進而，本發明化合物由於具有優異之滲透傳遞性，故可藉由將含有本發明化合物之農園藝用殺菌劑施用在土壤，與土壤中之有害菌類的防除同時，亦防除莖葉部之有害菌類。Furthermore, since the compound of the present invention has excellent osmotic transmission properties, the agricultural and horticultural fungicide containing the compound of the present invention can be applied to the soil to prevent harmful fungi in the soil and prevent harmful fungi in the stem and leaf. .

本發明化合物通常雖可混合本發明化合物與各種農業上之輔助劑，製劑成粉劑、粒劑、顆粒可濕性粉劑、可濕性粉劑、水性懸濁劑、油性懸濁劑、水溶劑、乳劑、液劑、糊劑、氣霧劑、微量散布劑等之各種形態使用，但只要能適合本發明的目的，可成為於通常之該領域使用之所有製劑形態。作為製劑所使用之輔助劑，可列舉矽藻土、熟石灰、碳酸鈣、滑石、白碳、高嶺土、膨潤土、高嶺石及絹雲母之混合物、黏土、碳酸鈉、碳酸氫鈉、芒硝、沸石、澱粉等之固型載體；水、甲苯、二甲苯、溶劑石腦油、二噁烷、丙酮、異佛爾酮、甲基異丁基酮、氯苯、環己烷、二甲基亞碸、N,N-二甲基甲醯胺、二甲基乙醯胺、N-甲基-2-吡咯烷酮、醇等之溶劑；如脂肪酸鹽、苯甲酸鹽、烷基磺基琥珀酸鹽、二烷基磺基琥珀酸鹽、聚羧酸鹽、烷基硫酸酯鹽、烷基硫酸鹽、烷基芳基硫酸鹽、烷基二甘醇醚硫酸鹽、醇硫酸酯鹽、烷基磺酸鹽、烷基芳基磺酸鹽、芳基磺酸鹽、木質素磺酸鹽、烷基二苯基醚二磺酸鹽、聚苯乙烯磺酸鹽、烷基磷酸酯鹽、烷基芳基磷酸鹽、苯乙烯基芳基磷酸鹽、聚氧乙烯烷基醚硫酸酯鹽、聚氧乙烯烷基芳基醚硫酸鹽、聚氧乙烯烷基芳基醚硫酸酯鹽、聚氧乙烯烷基醚磷酸鹽、聚氧乙烯烷基芳基磷酸酯鹽、萘磺酸福爾馬林縮合物的鹽之陰離子系的界面活性劑或展著劑；如山梨糖醇脂肪酸酯、甘油脂肪酸酯、脂肪酸聚甘油酯、脂肪酸醇聚甘醇醚、乙炔二醇、乙炔醇、氧化烯嵌段聚合物、聚氧乙烯烷基醚、聚氧乙烯烷基芳基醚、聚氧乙烯苯乙烯基芳基醚、聚氧乙二醇烷基醚、聚乙二醇、聚氧乙烯脂肪酸酯、聚氧乙烯山梨糖醇脂肪酸酯、聚氧乙烯甘油脂肪酸酯、聚氧乙烯硬化蓖麻油、聚氧丙烯脂肪酸酯之非離子系的界面活性劑或展著劑；橄欖油、木棉油、蓖麻油、棕櫚油、山茶油、椰子油、芝麻油、玉米油、米糠油、花生油、棉籽油、大豆油、菜子油、亞麻子油、桐油、液狀石蠟等之植物油或礦物油等。此等輔助劑之各成分只要不偏離本發明的目的，可適當選擇1種或2種以上使用。又，除了前述之輔助劑以外，亦可從於該領域所知悉者當中適當選擇使用，例如亦可使用增量劑、增黏劑、防止沉澱劑、防凍劑、分散安定劑、防護劑、防黴劑等通常所使用之各種輔助劑。本發明化合物與各種輔助劑的摻合比例為0.001:99.999～95:5，期望為0.005:99.995～90:10。於此等製劑實際之使用時，可直接使用，或以水等之稀釋劑稀釋成指定濃度，如有必要可添加各種展著劑(界面活性劑、植物油、礦物油等)使用。Although the compound of the present invention can usually be mixed with the compound of the present invention and various agricultural auxiliary agents, it can be formulated into powders, granules, granular wettable powders, wettable powders, aqueous suspension agents, oily suspension agents, water solvents, emulsions. , Liquid, paste, aerosol, micro-dispersion, etc., but as long as it is suitable for the purpose of the present invention, it can be used in all forms of preparations commonly used in this field. Examples of auxiliary agents used in the preparation include diatomite, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, a mixture of kaolinite and sericite, clay, sodium carbonate, sodium bicarbonate, mirabilite, zeolite, starch Other solid carriers; water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfene, N , N-dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, alcohols, etc .; such as fatty acid salts, benzoates, alkyl sulfosuccinates, dioxane Sulfosuccinate, polycarboxylate, alkyl sulfate, alkyl sulfate, alkyl aryl sulfate, alkyl diethylene glycol ether sulfate, alcohol sulfate, alkyl sulfonate, Alkyl aryl sulfonate, aryl sulfonate, lignin sulfonate, alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate salt, alkyl aryl phosphate , Styrylaryl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylaryl ether sulfate, polyoxyethylene alkylaryl Anionic surfactants or extenders of sulfate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylaryl phosphates, salts of formalin naphthalenesulfonic acid; such as sorbose Alcohol fatty acid esters, glycerol fatty acid esters, fatty acid polyglycerol esters, fatty acid alcohol polyglycol ethers, acetylene glycols, acetylene alcohols, alkylene oxide block polymers, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl groups Ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyethylene glycol, polyoxyethylene fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glyceryl fatty acid ester , Polyoxyethylene hardened castor oil, non-ionic surfactant or spreading agent of polyoxypropylene fatty acid esters; olive oil, kapok oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, Rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, liquid paraffin, and other vegetable or mineral oils. As long as each component of these auxiliary agents does not deviate from the purpose of the present invention, one or two or more kinds may be appropriately selected and used. In addition, in addition to the aforementioned adjuvants, it can also be appropriately selected and used from those skilled in the art. For example, extenders, thickeners, anti-settling agents, antifreeze agents, dispersion stabilizers, protective agents, anti- Various adjuvants such as molds. The blending ratio of the compound of the present invention and various adjuvants is 0.001: 99.999 to 95: 5, and it is desirable to be 0.005: 99.995 to 90:10. When these preparations are actually used, they can be used directly, or diluted to the specified concentration with a diluent such as water. If necessary, various spreading agents (surfactants, vegetable oils, mineral oils, etc.) can be added for use.

本發明化合物之施用雖因氣象條件、製劑形態、對象作物、施用時期、施用場所、有害菌類的種類或發生狀況、病害的種類或發生狀況等之不同，無法一概規定，但一般而言，於莖葉處理的情況可以0.1～10,000 ppm，期望為1～2,000ppm的有效成分濃度施用，其施用適量每1公頃之本發明化合物可成為0.1～50,000g，期望為1～30,000g左右。土壤處理的情況，一般而言，可將每1公頃之本發明化合物施用10～100,000g，期望為200～20,000g。種子處理的情況，一般而言，可將種子每1kg之本發明化合物施用0.001～10g，期望為0.01～1g。Although the application of the compound of the present invention cannot be generally defined due to differences in meteorological conditions, preparation forms, target crops, application period, application site, types or occurrence of harmful bacteria, types or occurrence of diseases, etc., in general, In the case of stem and leaf treatment, it can be applied at an effective ingredient concentration of 0.1 to 10,000 ppm, desirably 1 to 2,000 ppm, and an appropriate amount of the compound of the present invention per 0.1 ha can be 0.1 to 50,000 g, and desirably is about 1 to 30,000 g. In the case of soil treatment, in general, 10 to 100,000 g, and preferably 200 to 20,000 g, can be applied to the compound of the present invention per hectare. In the case of seed treatment, in general, 0.001 to 10 g, and preferably 0.01 to 1 g, can be applied per 1 kg of the seed of the compound of the present invention.

本發明化合物之各種製劑或其稀釋物的施用，通常為一般所進行之施用方法，亦即，可藉由散布(例如散布、噴霧、墨霧(Misting)、霧化(Atomizing)、散粒、水面施用等)、土壤施用(混入、灌注等)、表面施用(塗布、粉衣、被覆等)等進行。又，亦可藉由所謂超高濃度少量散布法(ultra low volume)施用。在此方法，可含有100%之活性成分。The various formulations of the compounds of the present invention or their dilutions are generally applied in the usual manner, i.e., by spreading (e.g., spreading, spraying, misting, atomizing, scattering, Water surface application, etc.), soil application (mixing, pouring, etc.), surface application (coating, powder coating, coating, etc.) are performed. It can also be applied by a so-called ultra low volume method. In this method, it can contain 100% of active ingredients.

本發明化合物可與其他農藥、肥料、防護劑等混用或併用，此情況下有時會顯示更為優異之效果、作用性。作為其他農藥，可列舉除草劑、殺蟲劑、殺蟎劑、殺線蟲劑、殺土壤害蟲劑、殺菌劑、抗病毒劑、引誘劑、抗生物質、植物激素、植物成長調整劑等。尤其是混用或併用本發明化合物、與其他殺菌性有效成分化合物之1種或2種以上的混合殺菌性組成物，有將適用範圍、藥劑處理之時期、防除活性等往較佳之方向改良的情況。尚，本發明化合物與其他殺菌劑的有效成分化合物，即使每個分別製劑者於散布時混合進行使用，亦可將兩者一起製劑來使用。本發明中亦包含這般之混合殺菌性組成物。The compound of the present invention may be used in combination with other pesticides, fertilizers, protective agents, etc., or in combination. In this case, it may show more excellent effects and functions. Examples of other pesticides include herbicides, insecticides, acaricides, nematicides, soil insecticides, fungicides, antivirals, attractants, antibiotics, plant hormones, and plant growth regulators. In particular, when the compound of the present invention is mixed or used in combination with one or two or more bactericidal active ingredient compounds, the bactericidal composition may be improved in a better direction, such as the scope of application, the period of chemical treatment, and the control activity. . The compound of the present invention and the active ingredient compound of other fungicides can be used together even if they are mixed and used by each of the individual preparations when they are dispersed. The present invention also includes such a mixed bactericidal composition.

本發明化合物與其他殺菌性有效成分化合物的混合比，雖因氣象條件、製劑形態、對象作物、施用時期、施用場所、有害菌類的種類或發生狀況、病害的種類或發生狀況等之不同無法一概規定，但一般而言可成為1:300～300:1，期望為1:100～100:1。又，作為施用適量每1公頃之總有效成分化合物量，可成為0.1～70,000g，期望為1～30,000g。本發明中，亦包含藉由這般之混合殺菌性組成物的施用之植物病害的防除方法。Although the mixing ratio of the compound of the present invention and other bactericidal active ingredient compounds cannot be generalized due to differences in meteorological conditions, preparation forms, target crops, application period, application place, types or occurrence of harmful bacteria, types of occurrence or occurrence of diseases, etc. It is stipulated, but generally it can be 1: 300 to 300: 1, and it is expected to be 1: 100 to 100: 1. The amount of the total active ingredient compound applied per hectare may be 0.1 to 70,000 g, and preferably 1 to 30,000 g. The present invention also includes a method for controlling plant diseases by applying such a mixed fungicidal composition.

通過本發明化合物的施用，亦可進一步合併其他農藥例如殺菌劑、殺蟲劑、殺蟎劑、殺線蟲劑、殺土壤害蟲劑、抗病毒劑、引誘劑、除草劑、植物生長調整劑等來處理。Through the application of the compound of the present invention, other pesticides such as fungicides, insecticides, acaricides, nematicides, soil insecticides, antivirals, attractants, herbicides, plant growth regulators, etc. can be further combined. deal with.

作為上述其他農藥中之殺菌劑的有效成分化合物(一般名或日本植物防疫協會試驗代碼)，例如可從下述之化合物群組中適當選擇。即使是並未特別記載的情況，於此等化合物存在如鹽、烷基酯、光學同分異構物之各種構造同分異構物等時，當然亦包含該等。
如嘧菌胺(mepanipyrim)、嘧黴胺(pyrimethanil)、嘧菌環胺(cyprodinil)之苯胺基嘧啶系化合物；
如滅脫定(ametoctradin)之***并嘧啶(
Triazolopyrimidine)系化合物；
如氰啶胺(fluazinam)之吡啶胺系化合物；
如三泰芬(triadimefon)、比多農(bitertanol)、氟菌唑(triflumizole)、乙環唑(etaconazole)、丙環唑(
propiconazole)、戊菌唑(penconazole)、氟矽唑(
flusilazole)、邁克尼(myclobutanil)、環克唑(
cyproconazole)、戊唑醇(tebuconazole)、己唑醇(
hexaconazole)、順呋醚唑(furconazole-cis)、咪鮮安(
prochloraz)、滅特唑(metconazole)、氟環唑(
epoxiconazole)、氟醚唑(tetraconazole)、反丁烯二酸噁咪唑(oxpoconazole fumarate)、丙硫菌唑(prothioconazole)、***醇(triadimenol)、粉唑醇(flutriafol)、苯醚甲環唑(
difenoconazole)、氟喹唑(fluquinconazole)、腈苯唑(
fenbuconazole)、糠菌唑(bromuconazole)、烯唑醇(
diniconazole)、三環唑(tricyclazole)、矽氟唑(
simeconazole)、稻瘟酯(pefurazoate)、種菌唑(ipconazole)、醯胺唑(imibenconazole)、阿扎康唑(azaconazole)、環菌唑(triticonazole)、依滅列(imazalil)、ipfentrifluconazole、氯氟醚菌唑(mefentrifluconazole)之唑系化合物；
如灰蟎猛(quinomethionate)之喹喔啉系化合物；
如代森猛(maneb)、代森鋅(zineb)、代森錳鋅(
mancozeb)、聚胺基甲酸酯(polycarbamate)、代森聯(metiram)、丙森鋅(propineb)、福美雙(thiram)之二硫代胺基甲酸酯系化合物；
如四氯苯酞(fthalide)、四氯異苯(chlorothalonil)、五氯硝基苯(quintozene)之有機氯系化合物；
如苯菌靈(benomyl)、甲基硫菌靈(thiophanate-
methyl)、多菌靈(carbendazim)、噻菌靈(thiabendazole)、弗貝唑(fuberiazole)之咪唑系化合物；
如霜脲氰(cymoxanil)之氰基乙醯胺系化合物；
如甲霜靈(metalaxyl)、甲霜靈-M(metalaxyl-M；別名精甲霜靈(mefenoxam))、悉霜靈(oxadixyl)、甲呋醯胺(ofurace)、苯霜靈(benalaxyl)、精苯霜靈(benalaxyl-M、別名可瑞西(kiralaxyl、chiralaxyl))、呋霜靈(furalaxyl)、伐利芬(valifenalate)之醯基胺基酸系化合物；
如酯菌胺(cyprofuram)、萎銹靈(carboxin)、氧化萎銹靈(oxycarboxin)、噻呋醯胺(thifluzamide)、啶醯菌胺(boscalid)、環醯菌胺(fenhexamid)、異噻菌胺(isotianil)、噻醯菌胺(tiadinil)、吡瑞氟密得(Pyraziflumid)之苯胺系化合物；
如苯氟醯胺(dichlofluanid)之磺醯胺系化合物；
如氫氧化銅(cupric hydroxide)、有機銅(oxine copper)、無水硫酸銅、壬基酚磺酸銅、8-羥基喹啉銅、十二烷基苯磺酸雙乙二胺銅絡鹽(II)(別名DBEDC)之銅系化合物；
如疫霜靈鋁(fosetyl-Al)、甲基立枯磷(tolclofos-methyl)、護粒松(edifenphos)、異稻瘟淨(iprobenfos)之有機磷系化合物；
如克菌丹(captan)、四氯丹(captafol)及滅菌丹(folpet)之鄰苯二甲醯亞胺系化合物；
如二甲菌核利(procymidone)、異菌脲(iprodione)、乙烯菌核利(vinclozolin)之二碳二亞胺系化合物；
如福多寧(flutolanil)、滅普寧(mepronil)、麥鏽靈(benodanil)之苯甲醯苯胺系化合物；
環丙醯菌胺(carpropamid)、雙氯氰菌胺(diclocymet)、矽噻菌胺(silthiopham)、氰菌胺(fenoxanil)之醯胺系化合物；
如苯并烯氟菌唑(benzovindiflupyr)、比沙吩(bixafen)、氟茚唑菌胺(fluindapyr)、氟唑菌醯胺(fluxapyroxad)、福拉比(furametpyr)、吡唑萘菌胺(isopyrazam)、戊苯吡菌胺(penflufen)、吡噻菌胺(penthiopyrad)、氟唑菌醯羥胺（pydiflumetofen)、環丙吡菌胺(sedaxane)、isoflucypram、inpyrfluxam、吡瑞普尼(pyrapropoyne)之吡唑羧醯胺系化合物；
如氟吡菌胺(fluopicolide)、氟吡菌醯胺(fluopyram)、座賽胺(zoxamide)、fluopimomide之苯并醯胺系化合物；
如甲呋醯胺(fenfuram)之糠苯胺(furanilide)系化合物；
如艾索非他滅(isofetamid)之噻吩醯胺系化合物；
如賽福寧(triforine)之哌嗪系化合物；
如比芬諾(pyrifenox)、啶菌唑(pyrisoxazole)、
aminopyrifen之吡啶系化合物；
如氯苯嘧啶醇(fenarimol)、富米綜(ferimzone)、尼瑞莫(nuarimol)之嘧啶系化合物；
如苯銹啶(fenpropidin)之哌啶系化合物；
如丁基嗎啉(fenpropimorph)、十三嗎啉(tridemorph)之嗎啉系化合物；
如三苯基氫氧化錫(fentin hydroxide)、三苯基乙酸錫(fentin acetate)之有機錫系化合；
如戊菌隆(pencycuron)之脲系化合物；
如烯醯嗎啉(dimethomorph)、氟嗎啉(flumorph)、丁吡嗎啉(pyrimorph)、丙森鋅(iprovalicarb)、苯噻菌胺(benthiavalicarb-isopropyl)、曼普胺(mandipropamid)之羧酸醯胺系化合物；
如乙黴威(diethofencarb)之苯基胺基甲酸酯(
Carbamate)系化合物；
如咯菌腈(fludioxonil)、拌種咯(fenpiclonil)之氰基吡咯系化合物；
如嘧菌酯(azoxystrobin)、克收欣(kresoxim-methyl)、苯氧菌胺(metominostrobin)、三氟敏(trifloxystrobin)、啶氧菌酯(picoxystrobin)、肟醚菌胺(oryzastrobin)、嘧菌胺(dimoxystrobin)、百克敏(pyraclostrobin)、氟嘧菌酯(
fluoxastrobin)、烯肟菌酯(Enestroburin)、唑菌酯(
Pyraoxystrobin)、唑胺菌酯(Pyrametostrobin)、丁香菌酯(
coumoxystrobin)、亞托敏(enoxastrobin)、烯肟菌胺(
fenaminstrobin)、氟菌蟎酯(flufenoxystrobin)、氯啶菌酯(
triclopyricarb)、滿得賓(mandestrobin)之甲氧基丙烯酸酯(Strobilurin)系化合物；
如噁唑菌酮(famoxadone)、奧賽普林(oxathiapiprolin)之噁唑啶酮系化合物；
如噻唑菌胺(ethaboxam)之噻唑羧醯胺系化合物；
如咪唑菌酮(fenamidone)之咪唑啉酮系化合物；
如磺菌胺(flusulfamide)之苯磺醯胺系化合物；
如環氟菌胺(cyflufenamid)之肟醚系化合物；
如腈硫醌(dithianon)之蒽醌系化合物；
如美啶卡(meptyldinocap)之巴豆酸系化合物；
如井岡黴素(validamycin)、嘉賜徵素(kasugamycin)、鏈黴素(streptomycin)、保粒黴素(polyoxins)之抗生物質；
如雙胍辛胺(iminoctadine)、多果定(dodine)之胍系化合物；
如特布弗喹(tebufloquin)、快諾芬(quinoxyfen)、
quinofumelin、ipflufenoquin之喹啉系化合物；
如氟噻菌淨(flutianil)之四氫噻唑系化合物；
如鹽酸霜黴威(propamocarb hydrochloride)、吡本卡(
pyribencarb)、托普洛卡(tolprocarb)胺基甲酸酯(
Carbamate)系化合物；
如皮卡布西(picarbutrazox)、metyltetraprole之四唑系化合物；
如唑磺菌胺(amisulbrom)、氰唑磺菌胺(cyazofamiid)之磺醯胺系化合物；
如苯菌酮(metrafenone)、哌瑞芬酮(pyriofenone)之烯丙基苯基酮系化合物；
如烯丙苯噻唑(probenazole)、二氯苯泰(
dichlobentiazox)之苯并噻唑系化合物；
如胺苯吡菌酮(fenpyrazamine)之苯基吡唑系化合物；
如亞賜圃(isoprothiolane)之二硫戊環系化合物；
如fenpicoxamid、florylpicoxamid之甲吡啶醯胺系化合物；
如硫(Sulfur)、石灰硫劑之硫系化合物；
作為其他化合物，如咯喹酮(pyroquilon)、達菌清(
diclomezine)、氯化苦(chloropicrin)、棉隆(dazomet)、威百畝(metam-sodium)、丙氧喹啉(proquinazid)、螺環菌胺(spiroxamine)、大芬滅替松(dipymetitrone)等；
如Bacillus amyloliqefaciens strain QST713、Bacillus amyloliqefaciens strain FZB24、Bacillus amyloliqefaciens strain MBI600、Bacillus amyloliqefaciens strain D747、Pseudomonas fluorescens、Bacillus subtilis、Trichoderma atroviride SKT-1之微生物殺菌劑；及如茶樹油(Tea tree oil)之植物萃取物。The compound (general name or test code of the Japanese Plant Epidemic Prevention Association) as an active ingredient of the fungicide in the above-mentioned other pesticides can be appropriately selected from the following compound groups, for example. Even if it is not specifically described, it is a matter of course that these compounds are also included when these compounds include various structural isomers such as salts, alkyl esters, and optical isomers.
Such as mepanipyrim, pirimethanil, cyprodinil aniline pyrimidine-based compounds;
Such as triazolopyrimidine (ametoctradin) (
Triazolopyrimidine) compounds;
For example, pyrazimine compounds of fluazinam;
Such as triadimefon, bitertanol, triflumizole, etaconazole, propiconazole (
propiconazole), penconazole, flusilazole (
flusilazole), myclobutanil,
cyproconazole), tebuconazole, hexaconazole (
hexaconazole), furconazole-cis, midazolam (
prochloraz), metconazole, fluconazole (
epoxiconazole), tetraconazole, oxpoconazole fumarate, prothioconazole, triadimenol, flutriafol, anisoleconazole
difenoconazole), fluquinconazole,
fenbuconazole), bromuconazole, enazol (
diniconazole), tricyclazole,
simeconazole, pefurazoate, ipconazole, imibenconazole, azaconazole, triticonazole, imazalil, ipfentrifluconazole, chlorofluoroether Azole compounds of mefentrifluconazole;
Such as quinomethionate quinoxaline compounds;
Such as maneb, zineb, manganese zinc (
mancozeb), polycarbamate, metiram, propineb, thiram dithiocarbamate compounds;
For example, organochlorine compounds of fthalide, chlorothalonil, and quintozene;
Such as benomyl, thiophanate-
methyl), carbendazim, thiabendazole, fuberiazole, and imidazole compounds;
Such as cymoxanil cyanoacetamide compounds;
Such as metalaxyl (metalaxyl), metalaxyl-M (metalaxyl-M; alias mefenoxam), oxadixyl, ofurace, benalaxyl, Benzoxyl-M (alias kiralaxyl, chiralaxyl), furalaxyl, valifenalate, amido amino acid compounds;
Such as cyprofuram, carboxin, oxycarboxin, thifluzamide, boscalid, fenhexamid, isothiazide Aniline compounds of isotianil, tiadinil, and Pyraziflumid;
Such as difluxant (dichlofluanid) sulfonamide compounds;
Such as cupric hydroxide, organic copper (oxine copper), anhydrous copper sulfate, copper nonylphenol sulfonate, copper 8-hydroxyquinoline, copper dodecylbenzenesulfonate diethylenediamine complex salt (II ) (Alias DBEDC) copper compounds;
Organophosphorus compounds such as episetyl-Al, tolclofos-methyl, edifenphos, and iprobenfos;
For example, phthalimidine compounds of captan, captafol and folpet;
For example, dicarbamidine (procymidone), iprodione, vinclozolin dicarbodiimide compounds;
Such as flutolanil, mepronil, benodanil benzamidine aniline compounds;
Carboxamid, diclocymet, silthiopham, and fenoxanil are amidine compounds;
Such as benzovindiflupyr, bixafen, fludapyr, fluapyroxad, furametpyr, isopyrazam , Pyrflufen, penthiopyrad, pydiflumetofen, sedaxane, isoflucypram, inpyrfluxam, pyrapropoyne, pyrazole Carboxamide compound
Such as fluopicolide, fluopyram, zoxamide, fluopimomide benzopyramine-based compounds;
For example, furanilide compounds of fenfuram;
Such as isofetamid (thiophene amide) compounds;
Such as piperazine compounds of triforine;
Such as pyrifenox, pyrizoxazole,
pyridine compounds of aminopyrifen;
Such as fenarimol, ferimzone, nuarimol pyrimidine compounds;
Such as piperidine compounds of fenpropidin;
For example, morpholine compounds of fenpropimorph and tridemorph;
For example, the organotin compounds of fentin hydroxide and fentin acetate;
Urea compounds such as pencycuron;
Such as dimethomorph, flumorph, pirimorph, iprovalicarb, benthiavalicarb-isopropyl, and mandipropamid carboxylic acids Amidine compounds
For example, phenylcarbamate (diethofencarb)
Carbamate) compounds;
Such as fludioxonil, fenpiclonil cyanopyrrole compounds;
Such as azoxystrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, picoxystrobin, oryzastrobin, azoxystrobin Amine (dimoxystrobin), pyraclostrobin, fluoxastrobin (
fluoxastrobin), enestroburin, pyraclostrobin (
Pyraoxystrobin), Pyrametostrobin, Syringaprol (
coumoxystrobin), suboxamine (enoxastrobin), enoxastrobin (
fenaminstrobin), flufenoxystrobin, fluoxanil (flufenoxystrobin),
triclopyricarb), mandestrobin (Strobilurin) -based compounds;
Such as famoxadone, oxathiapiprolin oxazolidone compounds;
Such as thiazolamide (ethaboxam) thiazolamide compounds;
Such as imidazolinone (fenamidone) imidazolinone compounds;
Such as flusulfamide, benzsulfonamide compounds;
For example, the oxime ether compounds of cyflufenamid;
Anthraquinone compounds such as dithianon;
Crotonic acid-based compounds such as meptyldinocap;
Antibiotics such as validamycin, kasugamycin, streptomycin, and polyoxins;
For example, guanidine compounds of iminoctadine and dodine;
Such as tebufloquin, quinoxyfen,
quinofumelin, ipflufenoquin quinoline compounds;
Such as flutianil tetrahydrothiazole compounds;
Such as propamocarb hydrochloride, pirbenka (
pyribencarb), tolprocarb carbamate (
Carbamate) compounds;
For example, tetrazolium compounds of picarbutrazox and metyltetraprole;
Such as amisulbrom, cyazofamiid sulfonamide compounds;
For example, allyl phenone compounds such as metrafenone and pyriofenone;
E.g., probenazole, dichlorobenzidine (
dichlobentiazox) benzothiazole compounds;
Such as fenpyrazamine phenylpyrazole compounds;
Such as dipropane compounds of isoprothiolane;
Such as fenpicoxamid, florylpicoxamid, pyridinium compounds;
Such as sulfur (Sulfur), sulfur compounds of lime sulfur agent;
As other compounds, such as pyroquilon,
diclomezine, chloropicrin, dazomet, metam-sodium, proquinazid, spiroxamine, dipymetitrone, etc. ;
Such as Bacillus amyloliqefaciens strain QST713, Bacillus amyloliqefaciens strain FZB24, Bacillus amyloliqefaciens strain MBI600, Bacillus amyloliqefaciens strain D747, Pseudomonas fluorescens, Bacillus subtilis, Trichoderma atrovira tea microbial oil .

作為上述其他農藥中之殺蟲劑、殺蟎劑、殺線蟲劑或殺土壤害蟲劑，亦即殺害蟲劑的有效成分化合物(一般名或日本植物防疫協會試驗代碼)，例如可從下述之化合物群組中適當選擇。即使是並未特別記載的情況，於此等化合物存在如鹽、烷基酯、光學同分異構物之各種構造同分異構物等時，當然亦包含該等。
如佈飛松(profenofos)、二氯松(dichlorvos)、芬滅松(fenamiphos)、撲滅松(fenitrothion)、EPN((RS)-(O-ethyl O-4-nitrophenyl phenylphosphonothioate))、大利松(
diazinon)、陶斯松(chlorpyrifos)、甲基毒死蜱(
chlorpyrifos‐methyl)、歐殺松(acephate)、普硫松(
prothiofos)、福賽絕(fosthiazate)、硫線磷(cadusafos)、二硫松(disulfoton)、加福松(isoxathion)、亞芬松(isofenphos)、乙硫磷(ethion)、益多松(etrimfos)、拜裕松(quinalphos)、二甲基乙烯磷(dimethylvinphos)、大滅松(dimethoate)、硫丙磷(sulprofos)、二甲硫吸磷(thiometon)、繁類松(vamidothion)、白克松(pyraclofos)、必芬松(
pyridaphenthion)、嘧啶磷甲酯(pirimiphos-methyl)、丙蟲磷(propaphos)、裕必松(phosalone)、褔木松(formothion)、馬拉松(malathion)、四氯乙烯磷(tetrachlorvinphos)、克芬松(chlorfenvinphos)、殺螟腈(cyanophos)、三氯松(trichlorfon)、滅大松(methidathion)、賽達松(phenthoate)、異亞碸磷(oxydeprofos、別名ESP)、谷速松(azinphos-methyl)、芬殺松(fenthion)、庚烯磷(heptenophos)、氯化甲醇(methoxychlor)、帕若提(parathion)、磷蟲威(
phosphocarb)、滅多松-S-甲酯(demeton-S-methyl)、亞速靈(monocrotophos)、達馬松(methamidophos)、依米塞松(imicyafos)、帕若提-甲酯(parathion-methyl)、托褔松(terbufos)、福賜米松(phosphamidon)、益滅松(phosmet)、褔瑞松(phorate)之有機磷酸酯系化合物；
如加保利(carbaryl)、安丹(propoxur)、得滅克(
aldicarb)、加保扶(carbofuran)、硫敵克(thiodicarb)、納乃得(methomyl)、歐殺滅(oxamyl)、乙硫苯威(ethiofencarb)、比加普(pirimicarb)、丁基滅必蝨(fenobucarb)、丁基加保扶(carbosulfan)、免扶克(benfuracarb)、免敵克(
bendiocarb)、呋線威(furathiocarb)、異丙威(isoprocarb)、治滅蝨(metolcarb)、滅爾蝨(xylylcarb)、XMC(3,5-xylyl methylcarbamate)、芬硫克(fenothiocarb)之胺基甲酸酯(Carbamate)系化合物；
如培丹(cartap)、硫賜安(thiocyclam)、硫賜安草酸鹽(thiocyclam oxalate)、硫賜安鹽酸鹽(thiocyclam
hydrochloride)、免速達(bensultap)、殺蟲雙(thiosultap)、殺蟲單(monosultap；別名殺蟲雙單鈉(thiosultap-
monosodium)、殺蟲雙(bisultap；別名殺蟲雙二鈉(thiosultap-disodium)、多噻烷(polythialan)之沙蠶毒素衍生物；
如大克蟎(dicofol)、四氯殺蟎碸(tetradifon)、安殺番(endosulufan)、得氯蟎(dienochlor)、特地靈(dieldrin)之有機氯系化合物；
如芬佈賜(fenbutatin oxide)、三環錫(cyhexatin)之有機金屬系化合物；
如芬化利(fenvalerate)、百滅靈(permethrin)、賽滅寧(cypermethrin)、α-賽滅寧(alpha-cypermethrin)、ζ-賽滅寧(zeta-cypermethrin)、θ-賽滅寧(theta-cypermethrin)、β-賽滅寧(beta-cypermethrin)、第滅靈(deltamethrin)、三氟氯氰菊酯(cyhalothrin)、γ-三氟氯氰菊酯(gamma-cyhalothrin)、λ-三氟氯氰菊酯(lambda-cyhalothrin)、七氟菊酯(tefluthrin)、κ-汰福寧(kappa-tefluthrin)、依芬寧(ethofenprox)、三氟醚菊酯(flufenprox)、氟氯氰菊酯(cyfluthrin)、β-氟氯氰菊酯(beta-cyfluthrin)、甲氰菊酯(
fenpropathrin)、氟氰戊菊酯(flucythrinate)、氟氰胺菊酯(
fluvalinate)、乙氰菊酯(cycloprothrin)、除蟲菊素(
pyrethrins)、氰戊菊酯(esfenvalerate)、胺菊酯(
tetramethrin)、苄呋菊酯(resmethrin)、普提芬布(
protrifenbute)、畢芬寧(bifenthrin)、κ-畢芬寧(kappa-bifenthrin)、氟丙菊酯(acrinathrin)、丙烯菊酯(allethrin)、氟胺氰戊菊酯(tau-fluvalinate)、四溴菊酯(tralomethrin)、丙氟菊酯(profluthrin)、甲氧苄氟甲酯(metofluthrin)、甲氧苄氟菊酯單體(epsilon-metofluthrin)、七福司靈(
heptafluthrin)、酚丁滅寧(phenothrin)、氯苯菊酯(
flumethrin)、沒氟菊酯(momfluorothrin)、甲氧苄氟菊酯單體(epsilon-momfluorothrin)、氟矽菊酯(silafluofen)、右旋反式氯丙炔菊酯(chloroprallethrin)之除蟲菊酯系化合物；
如二福隆(diflubenzuron)、克福隆(chlorfluazuron)、得福隆(teflubenzuron)、氟芬隆(flufenoxuron)、祿芬隆(lufenuron)、諾伐隆(novaluron)、三褔隆(triflumuron)、六褔隆(hexaflumuron)、雙三氟蟲脲(bistrifluron)、諾唯褔隆(noviflumuron)、氟札隆(fluazuron)之苯甲醯基脲系化合物；
如美賜平(methoprene)、百利普芬(pyriproxyfen)、芬諾克(fenoxycarb)、二苯丙醚(diofenolan)之幼年激素類化合物；
如嗒蟎酮(pyridaben)之嗒嗪酮系化合物；
如芬普蟎(fenpyroximate)、芬普尼(fipronil)、乙蟲腈(ethiprole)、乙醯蟲腈(acetoprole)、吡蟲腈(pyrafluprole)、吡瑞蟲腈(pyriprole)、塞比芬(cyenopyrafen)、丁烯氟蟲腈(flufiprole)之吡唑系化合物；
如氟蟲雙醯胺(pyflubumide)、吡蟎胺(tebufenpyrad)、唑蟲醯胺(tolfenpyrad)之吡唑羧醯胺系化合物；
如氯蟲醯胺(chlorantraniliprole)、氰蟲醯胺(
cyantraniliprole)、環溴蟲醯胺(cyclaniliprole)、氟氰蟲醯胺(tetraniliprole)、tyclopyrazoflor之吡啶基吡唑系化合物；
如益達胺(imidacloprid)、烯啶蟲胺(nitenpyram)、亞滅培(acetamiprid)、噻蟲啉(thiacloprid)、噻蟲嗪(
thiamethoxam)、可尼丁(clothianidin)、尼啶替弗(
nidinotefuran)、達特南(dinotefuran)、硝蟲噻嗪(
nithiazine)之新菸鹼系化合物；
如得芬諾(tebufenozide)、美芬諾(methoxyfenozide)、可芬諾(chromafenozide)、氯蟲醯肼(halofenozide)之胼系化合物；
如三氟甲吡醚(pyridalyl)、氟尼胺(flonicamid)之吡啶系化合物；
如賜派芬(spirodiclofen)、螺甲蟎酯(spiromesifen)之特窗酸(tetronic acid)系化合物；
如螺蟲乙酯(spirotetramat)、spiropidion之吡咯酮酸(tetramic acid)系化合物；
如嘧蟎酯(fluacrypyrim)、嘧蟎胺(pyriminostrobin)之甲氧基丙烯酸酯(strobilurin)系化合物；
如氟芬林(flufenerim)、嘧蟎醚(pyrimidifen)之吡啶胺系化合物；
如馬拉松(malathion)之有機硫化合物；
如氟芬隆(flufenoxuron)之脲系化合物；
如賽滅淨(cyromazine)之三嗪系化合物；
如愛美松(hydramethylnon)之腙系化合物；
如氟蟲胺(flubendiamide)、溴氟苯胺(broflanilide)、氯氟氰蟲醯胺(cyhalodiamide)之二醯胺系化合物；
如殺蟎隆(diafenthiuron)、滅蟲隆(chloromethiuron)之硫脲系化合物；
如三亞蟎(amitraz)、殺蟲脒(chlordimeform)、伊托明(chloromebuform)之甲脒系化合物；
如吡蚜酮(pymetrozine)、pyrifluquinazone之吡啶偶氮甲鹼(Azomethine)系化合物；
如afoxolaner、氟拉內(fluralaner)、氟米塔麥(
fluxametamide)、寵愛食剋(sarolaner)之異噁唑啉系化合物；
又，作為其他化合物，如布酚淨(buprofezin)、噻蟎酮(hexythiazox)、唑蚜威(triazamate)、蟲蟎腈(
chlorfenapyr)、茚蟲威(indoxacarb)、亞醌蟎(acequinocyl)、依殺蟎(etoxazole)、1,3-二氯丙烯(1,3-dichloropropene)、苯克提(benclothiaz)、聯苯肼(bifenazate)、毆蟎多(
propargite)、克芬蟎(clofentezine)、氰氟蟲腙(
metaflumizone)、丁氟蟎酯(cyflumetofen)、芬殺蟎(
fenazaquin)、醯胺氟美(amidoflumet)、氟蟲胺(
sulfluramid)、愛美松(hydramethylnon)、介乙醛(
metaldehyde)、速殺氟(sulfoxaflor)、氟速芬(fluensulfone)、唯布汀(verbutin)、二克滅(dicloromezotiaz)、三氟苯嘧啶(triflumezopyrim)、fluhexafon、替奧沙芬(tioxazafen)、雙丙環蟲酯(afidopyropen)、氟米克(flometoquin)、氟哌二福隆(flupyradifurone)、氯氟氰蟲醯胺(fluazaindolizine)、acynonapyr、benzpyrimoxan、flupyrimin、oxazosulfyl之化合物等。
又，本發明化合可與下述化合物組合施用。
如Bacillus thuringiensis aizawai、Bacillus
thuringiensis kurstaki、Bacillus thuringiensis israelensis、Bacillus thuringiensis japonensis、Bacillus thuringiensis tenebrionis或Bacillus thuringiensis所生成之結晶蛋白毒素、昆蟲病原病毒劑、昆蟲病原絲狀菌劑、線蟲病原絲狀菌劑等之微生物農藥；
如阿巴汀(abamectin)、因滅汀(emamectin benzoate)、伊維菌素(ivermectin)、密滅汀(milbemectin)、倍脈心(milbemycin oxime)、列比美汀(lepimectin)、賜諾殺(spinosad)、司平托列(spinetoram)之抗生物質及半合成抗生物質；
如印楝素(azadirachtin)、毒魚藤素(rotenone)、瑞諾啶(ryanodine)之天然物；
如待乙妥(deet)之忌避劑；
如石蠟油、礦物油(mineral oil)之物理性防除劑。As an insecticide, acaricide, nematicide, or soil insecticide in the above-mentioned other pesticides, that is, an active ingredient compound of the insecticide (common name or Japanese Plant Epidemic Prevention Association test code), for example, from the following The compound group is appropriately selected. Even if it is not specifically described, it is a matter of course that these compounds are also included when these compounds include various structural isomers such as salts, alkyl esters, and optical isomers.
Such as profenofos, dichlorvos, fenamiphos, fenitrothion, EPN ((RS)-(O-ethyl O-4-nitrophenyl phenylphosphonothioate)), and darpine (
diazinon), chlorpyrifos, chlorpyrifos (
chlorpyrifos-methyl), acephate, thiophasone (
prothiofos, fosthiazate, cadusafos, disulfoton, isoxathion, isofenphos, ethion, etrimfos , Quinalphos, dimethylvinphos, dimethoate, sulprofos, thiometon, vamidothion, pyraclofos ), Bifensone (
pyridaphenthion, pirimiphos-methyl, propaphos, phosalone, formosion, malathion, tetrachlorvinphos, clofensone (chlorfenvinphos), cyanophos, trichlorfon, metidathion, phenthoate, oxydeprofos (alias ESP), azonphos-methyl , Fenthion, heptenophos, methoxychlor, parathion,
phosphocarb), demeton-S-methyl, monocrotophos, methamidophos, imicyafos, parathion-methyl ), Organophosphate compounds of terbufos, phosphamidon, phosmet, and phorate;
Such as carbaryl, propoxur, and demex (
aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, butylfenb Lice (fenobucarb), butyl plus carbosulfan, benfuracarb, dienol (
bendiocarb), furathiocarb, isoprocarb, metolcarb, xylylcarb, XMC (3,5-xylyl methylcarbamate), amine groups of fenothiocarb Carbamate compounds;
Such as cartap, thiocyclam, thiocyclam oxalate, thiocyclam
hydrochloride), bensultap, thiosultap, monosultap; alias thiosultap-
monosodium), bisultap; thiasultap-disodium and polythialan derivatives;
For example, organochlorine compounds of dicofol, tetradifon, endosulufan, dienochlor, and dieldrin;
Organometallic compounds such as fenbutatin oxide and cyhexatin;
Such as fenvalerate, permethrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, θ-cypermethrin theta-cypermethrin), beta-cypermethrin, deltamethrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin ), Tefluthrin, kappa-tefluthrin, ethofenprox, flufenprox, cyfluthrin, β-cyfluthrin (beta- cyfluthrin), fenvalerate (
fenpropathrin), flucythrinate, flucythrinate (fluprothrinate)
fluvalinate), cycloprothrin, pyrethrin (
pyrethrins), esfenvalerate, fenvalerate (
tetramethrin), resmethrin, protefenb (
protrifenbute, bifenthrin, kappa-bifenthrin, acrithrin, allethrin, tau-fluvalinate, tralomethrin ), Profluthrin, metofluthrin, epsilon-metofluthrin, heptofirin (
heptafluthrin), phenothrin, permethrin (
flumethrin), momfluorothrin, epsilon-momfluorothrin, silafluofen, and chloroprallethrin Department of compounds
Such as diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, lufenuron, novaluron, triflumuron, Benzamyl urea-based compounds of hexaflumuron, bistrifluron, noviflumuron, and fluazuron;
For example, juvenile hormones such as metoprene, pyriproxyfen, fenoxycarb, and diofenolan;
Pyrazinone compounds such as pyridaben;
Such as fenpyroximate, fipronil, ethiprole, acetoprole, pyrafluprole, pyriprole, cyenopyrafen ), Pyrazole compounds of flufiprole;
Such as pyraclopamide (pyflubumide), tebufenpyrad, tolfenpyrad, pyracloscarboxamide compounds;
Such as chlorantraniliprole
cyantraniliprole), cyclaniliprole, tetraniliprole, tyclopyrazoflor, pyridylpyrazole-based compounds;
Such as imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam (
thiamethoxam), clothianidin, and niridin (
nidinotefuran), dinotefuran, nitrate
nithiazine);
Such as tebufenozide, methoxyfenozide, chromafenozide, halofenozide actinide compounds;
For example, pyridalyl and flonicamid pyridine compounds;
For example, tetronic acid compounds of spirodiclofen and spiromesifen;
Such as spirotetramat, spiropidion, and tetramic acid;
Such as fluacrypyrim, pyriminostrobin, strobilurin-based compounds;
For example, flufenerim, pyrimidifen, pyridine amine compounds;
Organic sulfur compounds such as malathion;
For example, urea compounds of flufenoxuron;
Triazine compounds such as cyromazine;
For example, the actinides of hydramethylnon;
Such as flubendiamide, broflanilide, cyhalodiamide diamidide compounds;
Such as diafenthiuron and chloromethiuron thiourea compounds;
For example, the formazan compounds of amitraz, chlordimeform, and chloromebuform;
Such as pymetrozine, pyrizfluquinazone, pyrazosine (Azomethine) compounds;
E.g. afoxolaner, fluralaner, flumeta (
fluxametamide), isoxazoline-based compounds of sarolaner;
In addition, as other compounds, for example, bufofezin, hexythiazox, triazamate, and acetonitrile (
chlorfenapyr), indoxacarb, acequinocyl, etoxazole, 1,3-dichloropropene, benclothiaz, biphenylhydrazine ( bifenazate), and more mites (
propargite), clofentezine, cyanfludizone (
metaflumizone), cyflumetofen, fenflumizone (
fenazaquin), amidoflumet, fipronil (
sulfluramid), hydramethylnon, acetaldehyde (
metaldehyde), sulfoxaflor, fluensulfone, verbutin, dicloromezotiaz, triflumezopyrim, fluhexafon, tioxazafen, dioxazafen Afidopyropen, flometoquin, flupyradifurone, fluazaindolizine, acynonapyr, benzpyrimoxan, flupyrimin, oxazosulfyl and the like.
The compounds of the present invention can be applied in combination with the following compounds.
Such as Bacillus thuringiensis aizawai, Bacillus
microbial pesticides produced by thuringiensis kurstaki, Bacillus thuringiensis israelensis, Bacillus thuringiensis japonensis, Bacillus thuringiensis tenebrionis or Bacillus thuringiensis, crystalline protein toxins, insect pathogenic virus agents, insect pathogenic filamentous agents, nematode pathogenic filamentous agents, etc
Such as abamectin, emamectin benzoate, ivermectin, milbemectin, milbemycin oxime, lepimectin, and sirolimus spinosad), spinetoram and semi-synthetic antibiotics;
Natural products such as azadirachtin, rotenone, and ryanodine;
As a repellent for deet;
Such as paraffin oil, mineral oil (mineral oil) physical control agents.

本發明期望的態樣係如以下。惟，本發明並非被限定於此等者。
[1]一種式(1)表示之化合物或其鹽。
[2]如前述[1]所記載之化合物或其鹽，其中，B為選自由式(B-1)～式(B-18)及式(B-101)～式(B-128)表示之基所成之群組中之雜環基。
[3]如前述[1]所記載之化合物或其鹽，其中，B為選自由式(B-1)～式(B-4)表示之基所成之群組中之雜環基。
[4]如前述[1]所記載之化合物或其鹽，其中，B為式(B-1)或式(B-2)表示之基。
[5]如前述[4]所記載之化合物或其鹽，其中，RB1 為鹵素原子、烷基、烯基、鹵烷基、烷氧基烷基或氰基；RB2 為烷基、鹵烷基或環烷基；RB3 為鹵素原子。
[6]如前述[1]～[5]所記載之化合物或其鹽，其中，[式中，A為被RA 取代之苯基或被取代之吡啶基，
B為被RB 取代之雜環基，
RA 可相同或相異為鹵素原子、烷基、鹵烷基、烯基、炔基、環狀基、硝基、氰基或-LA -YA ，或可鍵結2個RA ，形成可被Z1 取代之環，
RB 可相同或相異為鹵素原子、烷基、鹵烷基、烷氧基烷基、環烷基或氰基，
LA 為O、S、C(=O)、C(=O)O、C(=O)N(R1 )、
OC(=O)、N(R1 )、N(R1 )C(=O)、N(R1 )C(=O)O、C(=NR2 )、SO、SO2 或SO2 N(R1 )，
YA 為氫原子、可被Z2 取代之烷基、烯基或可被Z3 取代之環狀基，
R1 為氫原子或烷基，
R2 為氫原子、烷基或烷氧基，
Z1 為鹵素原子，Z2 為鹵素原子、氰基、環烷基或烷氧基，
Z3 為鹵素原子或鹵烷基。
[7]如前述[6]所記載之化合物或其鹽，其中，RB1 為鹵素原子、烷基、鹵烷基、烷氧基烷基或氰基；RB2 為烷基、鹵烷基或環烷基；RB3 為鹵素原子。
[8]如前述[1]～[7]所記載之化合物或其鹽，其中，A為被RA 取代之苯基。
[9]如前述[1]～[7]所記載之化合物或其鹽，其中，A為被相同或相異之2～3個RA 取代之苯基。
[10]如前述[1]～[7]所記載之化合物或其鹽，其中，A為2位及4位之至少一者被RA 取代之苯基。
[11]如前述[1]～[7]所記載之化合物或其鹽，其中，A為可被Z1 取代之苯并二氧環戊基。
[12]如前述[1]～[11]所記載之化合物或其鹽，其中，RA 為鹵素原子、烷基、鹵烷基或-LA -YA 。The desirable aspects of the present invention are as follows. However, the present invention is not limited to these.
[1] A compound represented by formula (1) or a salt thereof.
[2] The compound or a salt thereof according to the above [1], wherein B is selected from the group consisting of formulae (B-1) to (B-18) and formulae (B-101) to (B-128) Heterocyclyl in the group formed by the
[3] The compound or a salt thereof according to the above [1], wherein B is a heterocyclic group selected from the group consisting of a group represented by formula (B-1) to formula (B-4).
[4] The compound or a salt thereof according to the above [1], wherein B is a group represented by the formula (B-1) or the formula (B-2).
[5] The compound or the salt thereof according to the above [4], wherein R B1 is a halogen atom, an alkyl group, an alkenyl group, a haloalkyl group, an alkoxyalkyl group, or a cyano group; and R B2 is an alkyl group or a halogen Alkyl or cycloalkyl; R B3 is a halogen atom.
[6] The compound or a salt thereof according to the above [1] to [5], wherein [in the formula, A is a phenyl group substituted by R A or a substituted pyridyl group,
B is a heterocyclic group substituted with R B ,
R A may be the same or different from each other as a halogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, a cyclic group, a nitro group, a cyano group, or -L A -Y A , or two R A may be bonded, Forming a ring which can be replaced by Z 1 ,
R B may be the same or different and is a halogen atom, an alkyl group, a haloalkyl group, an alkoxyalkyl group, a cycloalkyl group or a cyano group,
L A is O, S, C (= O), C (= O) O, C (= O) N (R 1 ),
OC (= O), N (R 1 ), N (R 1 ) C (= O), N (R 1 ) C (= O) O, C (= NR 2 ), SO, SO 2 or SO 2 N (R 1 ),
Y A is a hydrogen atom, an alkyl group which may be substituted by Z 2 , an alkenyl group or a cyclic group which may be substituted by Z 3 ,
R 1 is a hydrogen atom or an alkyl group,
R 2 is a hydrogen atom, an alkyl group or an alkoxy group,
Z 1 is a halogen atom, Z 2 is a halogen atom, cyano, cycloalkyl or alkoxy,
Z 3 is a halogen atom or a haloalkyl group.
[7] The compound or a salt thereof according to the aforementioned [6], wherein R B1 is a halogen atom, an alkyl group, a haloalkyl group, an alkoxyalkyl group, or a cyano group; and R B2 is an alkyl group, a haloalkyl group, or Cycloalkyl; R B3 is a halogen atom.
[8] The compound or a salt thereof according to the above [1] to [7], wherein A is a phenyl group substituted with R A.
[9] The compound or a salt thereof according to the above [1] to [7], wherein A is a phenyl group substituted with 2 to 3 R A which are the same or different.
[10] The compound or a salt thereof according to the above [1] to [7], wherein A is a phenyl group in which at least one of the 2-position and the 4-position is substituted with R A.
[11] The compound or a salt thereof according to the aforementioned [1] to [7], wherein A is a benzodioxoyl group which may be substituted by Z 1 .
[12] The compound or a salt thereof according to the above [1] to [11], wherein R A is a halogen atom, an alkyl group, a haloalkyl group, or -L A -Y A.

[13]一種農園藝用殺菌劑，其係將如前述[1]～[12]所記載之化合物或其鹽作為有效成分含有。
[14]一種防除植物病害之方法，其係將如前述[1]～[13]所記載之化合物或其鹽施用在植物或土壤。

[實施例][13] A fungicide for agriculture and horticulture comprising the compound or a salt thereof as described in the above [1] to [12] as an active ingredient.
[14] A method for controlling plant diseases, which comprises applying the compound or a salt thereof according to the above [1] to [13] to a plant or soil.

[Example]

其次，雖記載本發明的實施例，但本發明並非被限定於此等者。Next, although examples of the present invention are described, the present invention is not limited to these.

合成例1：N-(1-(3,4-二氯苯基)-2-甲基-1-氧代丙烷-2-基)-N-甲氧基-2,5-二甲基呋喃-3-羧醯胺(化合物No.202)之合成
(1)1-(3,4-二氯苯基)-2-甲基-2-硝基丙烷-1-醇的合成
於3,4-二氯苯并醛(5g)與2-硝基丙烷(10.26ml)之混合物，加入1,5,7-三氮雜雙環[4.4.0]癸-5-烯(TBD、1.19g)，在室溫攪拌。24小時後，將反應混合物投入水中，在乙酸乙酯萃取。將有機層以水洗淨，再以無水硫酸鎂乾燥、過濾後，減壓下進行濃縮。將所得之殘渣以管柱層析(溶離液：乙酸乙酯/庚烷)純化，而得到固體之目的物(0.97g)。
1 H NMR (CDCl3 /500MHz)：δ(ppm)= 7.50 (d, J=2.0 Hz, 1H), 7.45 (d, J = 8.0 Hz, 1H), 7.21 (dd, J = 8.0, 2.0 Hz, 1H), 5.28 (s, 1H), 2.73 (brs, 1H), 1.57 (s, 3H), 1.46 (s, 3H).Synthesis Example 1: N- (1- (3,4-dichlorophenyl) -2-methyl-1-oxopropane-2-yl) -N-methoxy-2,5-dimethylfuran Synthesis of -3-carboxamide (Compound No. 202)
(1) Synthesis of 1- (3,4-dichlorophenyl) -2-methyl-2-nitropropane-1-ol from 3,4-dichlorobenzoaldehyde (5g) and 2-nitro A mixture of propane (10.26 ml) was added with 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD, 1.19 g), and the mixture was stirred at room temperature. After 24 hours, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and then concentrated under reduced pressure. The obtained residue was purified by column chromatography (eluent: ethyl acetate / heptane) to obtain the desired compound (0.97 g) as a solid.
1 H NMR (CDCl 3 / 500MHz): δ (ppm) = 7.50 (d, J = 2.0 Hz, 1H), 7.45 (d, J = 8.0 Hz, 1H), 7.21 (dd, J = 8.0, 2.0 Hz, 1H), 5.28 (s, 1H), 2.73 (brs, 1H), 1.57 (s, 3H), 1.46 (s, 3H).

(2)1-(3,4-二氯苯基)-2-甲基-2-硝基丙烷-1-酮的合成
於1-(3,4-二氯苯基)-2-甲基-2-硝基丙烷-1-醇(0.97g)之二氯甲烷(20mL)溶液，加入戴斯-馬丁氧化劑(DMP、1.64g)，在室溫攪拌一晩。將反應混合物投入水中，以碳酸氫鈉水溶液中和，濾出不溶物。將濾液在乙酸乙酯萃取，將有機層以水洗淨。以無水硫酸鎂乾燥、過濾後，減壓下進行濃縮。將所得之殘渣以管柱層析(溶離液：乙酸乙酯/庚烷)純化，而得到油狀之目的物(0.78g)。
1 H NMR (CDCl3 /500MHz)：δ(ppm)=7.90 (d, J= 1.5Hz, 1H)、7.53-7.49 (m, 2H)、1.92 (s, 6H).(2) Synthesis of 1- (3,4-dichlorophenyl) -2-methyl-2-nitropropane-1-one in 1- (3,4-dichlorophenyl) -2-methyl A solution of 2-nitropropane-1-ol (0.97 g) in dichloromethane (20 mL) was added to Dess-Martin periodinane (DMP, 1.64 g), and the mixture was stirred at room temperature for a while. The reaction mixture was poured into water, neutralized with an aqueous sodium hydrogen carbonate solution, and insoluble matters were filtered off. The filtrate was extracted with ethyl acetate, and the organic layer was washed with water. It was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was purified by column chromatography (eluent: ethyl acetate / heptane) to obtain the object product (0.78 g) as an oil.
1 H NMR (CDCl 3 / 500MHz): δ (ppm) = 7.90 (d, J = 1.5Hz, 1H), 7.53-7.49 (m, 2H), 1.92 (s, 6H).

(3)1-(3,4-二氯苯基)-2-(羥基胺基)-2-甲基丙烷-1-酮的合成
於1-(3,4-二氯苯基)-2-甲基-2-硝基丙烷-1-酮(0.76g)與氯化銨(1.55g)之四氫呋喃(10mL)、水(5mL)、乙醇(5mL)之混合溶液，冰水下劃分鋅(0.95g)加入並攪拌。15分鐘後，將反應混合物使用矽鈣石過濾，將所得之濾液投入水中，在乙酸乙酯萃取。將有機層以水洗淨，再以無水硫酸鎂乾燥、過濾後，減壓下進行濃縮。將所得之殘渣以管柱層析(庚烷：乙酸乙酯)純化，而得到固體之目的物(0.48g)。(3) Synthesis of 1- (3,4-dichlorophenyl) -2- (hydroxyamino) -2-methylpropane-1-one in 1- (3,4-dichlorophenyl) -2 -A mixed solution of methyl-2-nitropropane-1-one (0.76g) and ammonium chloride (1.55g) in tetrahydrofuran (10mL), water (5mL), and ethanol (5mL). 0.95 g) was added and stirred. After 15 minutes, the reaction mixture was filtered through wollastonite, and the obtained filtrate was poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and then concentrated under reduced pressure. The obtained residue was purified by column chromatography (heptane: ethyl acetate) to obtain the objective substance (0.48 g) as a solid.

(4)N-(1-(3,4-二氯苯基)-2-甲基-1-氧代丙烷-2-基)-N-羥基-2,5-二甲基呋喃-3-羧醯胺的合成
於1-(3,4-二氯苯基)-2-(羥基胺基)-2-甲基丙烷-1-酮(0.3g)與三乙基胺(TEA、0.37g)之四氫呋喃溶液(10ml)，加入2,5-二甲基呋喃-3-碳醯氯(0.4g)，以室溫攪拌一晩。將反應混合物投入水中，在乙酸乙酯萃取。
將有機層以水洗淨，再以無水硫酸鎂乾燥、過濾後，減壓下進行濃縮。將所得之殘渣以管柱層析(庚烷：乙酸乙酯)純化，而得到糖果狀之N-(1-(3,4-二氯苯基)-2-甲基丙烷-1-氧代丙烷-2-基)-N-((2,5-二甲基呋喃-3-羰基)氧基)-2,5-二甲基呋喃-3-羧醯胺(0.53g)。將此溶解於乙醇(10ml)、四氫呋喃(5ml)及水(5ml)之混合溶媒，加入氫氧化鈉(0.22g)，在室溫攪拌。1小時後，將反應混合物投入水中，在乙酸乙酯萃取。將有機層以水洗淨，再以無水硫酸鎂乾燥、過濾後，減壓下進行濃縮，而得到糖果狀之目的物(0.38g)。
1 H NMR (CDCl3 /500MHz)：δ(ppm)= 8.15 (d, J=1.5Hz, 1H), 7.88 (dd, J=8.5, 2.5 Hz, 1H), 7.41 (d, J=8.5 Hz, 1H), 6.21 (s, 1H), 2.24 (s, 3H), 2.20 (s, 3H), 1.60 (s, 6H).(4) N- (1- (3,4-dichlorophenyl) -2-methyl-1-oxopropane-2-yl) -N-hydroxy-2,5-dimethylfuran-3- Carboxamide is synthesized from 1- (3,4-dichlorophenyl) -2- (hydroxyamino) -2-methylpropane-1-one (0.3g) and triethylamine (TEA, 0.37g ) Tetrahydrofuran solution (10 ml), 2,5-dimethylfuran-3-carboxamidine chloride (0.4 g) was added, and the mixture was stirred at room temperature for one night. The reaction mixture was poured into water and extracted with ethyl acetate.
The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and then concentrated under reduced pressure. The obtained residue was purified by column chromatography (heptane: ethyl acetate) to obtain N- (1- (3,4-dichlorophenyl) -2-methylpropane-1-oxo as a candy. Propane-2-yl) -N-((2,5-dimethylfuran-3-carbonyl) oxy) -2,5-dimethylfuran-3-carboxamide (0.53 g). This was dissolved in a mixed solvent of ethanol (10 ml), tetrahydrofuran (5 ml) and water (5 ml), sodium hydroxide (0.22 g) was added, and the mixture was stirred at room temperature. After 1 hour, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and then concentrated under reduced pressure to obtain a candy-like object (0.38 g).
1 H NMR (CDCl 3 / 500MHz): δ (ppm) = 8.15 (d, J = 1.5Hz, 1H), 7.88 (dd, J = 8.5, 2.5 Hz, 1H), 7.41 (d, J = 8.5 Hz, 1H), 6.21 (s, 1H), 2.24 (s, 3H), 2.20 (s, 3H), 1.60 (s, 6H).

(5)N-(1-(3,4-二氯苯基)-2-甲基-1-氧代丙烷-2-基)-N-甲氧基-2,5-二甲基呋喃-3-羧醯胺(化合物No.202)之合成
於N-(1-(3,4-二氯苯基)-2-甲基-1-氧代丙烷-2-基)-N-羥基-2,5-二甲基呋喃-3-羧醯胺(0.218g)之N,N-二甲基甲醯胺溶液(7ml)，冰冷下加入氫化鈉(0.03g、60%)並攪拌。15分鐘後，以同溫加入碘化甲烷(0.21g)並攪拌。1小時後，將反應混合物投入水中，加入鹽酸而成為酸性。將混合物在乙酸乙酯萃取。將有機層以水洗淨，再以無水硫酸鎂乾燥、過濾後，減壓下進行濃縮。將所得之殘渣以管柱層析(庚烷：乙酸乙酯)純化，而得到固體之目的物(0.21g)。
1 H NMR (CDCl3 /500MHz)：δ(ppm)= 8.16 (d, J=2.5Hz, 1H), 7.88 (dd, J=8.5, 2.5 Hz, 1H), 7.42 (d, J=8.5 Hz, 1H), 6.28 (s, 1H), 3.85 (s, 3H), 2.31 (s, 3H), 2.24 (s, 3H), 1.68 (brs, 6H).(5) N- (1- (3,4-dichlorophenyl) -2-methyl-1-oxopropane-2-yl) -N-methoxy-2,5-dimethylfuran- Synthesis of 3-carboxamide (Compound No. 202) from N- (1- (3,4-dichlorophenyl) -2-methyl-1-oxopropane-2-yl) -N-hydroxy- A solution of 2,5-dimethylfuran-3-carboxamide (0.218 g) in N, N-dimethylformamide (7 ml), sodium hydride (0.03 g, 60%) was added under ice cooling, and the mixture was stirred. After 15 minutes, methyl iodide (0.21 g) was added at the same temperature and stirred. After 1 hour, the reaction mixture was poured into water, and hydrochloric acid was added to make it acidic. The mixture was extracted in ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and then concentrated under reduced pressure. The obtained residue was purified by column chromatography (heptane: ethyl acetate) to obtain the intended product (0.21 g) as a solid.
1 H NMR (CDCl 3 / 500MHz): δ (ppm) = 8.16 (d, J = 2.5Hz, 1H), 7.88 (dd, J = 8.5, 2.5 Hz, 1H), 7.42 (d, J = 8.5 Hz, 1H), 6.28 (s, 1H), 3.85 (s, 3H), 2.31 (s, 3H), 2.24 (s, 3H), 1.68 (brs, 6H).

合成例2：3-(二氟甲基)-N-(1-(4-異丙氧基-2-甲基苯基)-2-甲基-1-氧代丙烷-2-基)-N-甲氧基-1-甲基-1H-吡唑-4-羧醯胺(化合物No.8)之合成Synthesis Example 2: 3- (difluoromethyl) -N- (1- (4-isopropoxy-2-methylphenyl) -2-methyl-1-oxopropane-2-yl)- Synthesis of N-methoxy-1-methyl-1H-pyrazole-4-carboxamide (Compound No. 8)

(1)2-溴-1-(4-異丙氧基-2-甲基苯基)-2-甲基丙烷-1-酮的合成
於根據日本特開2016-108332號合成之1-(4-異丙氧基-2-甲基苯基)-2-甲基丙烷-1-酮(14.41g)之四氫呋喃(100mL)溶液，加入三甲基苯基三溴化銨(28.87g)，以室溫攪拌5小時。反應結束後，過濾反應混合物，將所得之濾液減壓下進行濃縮。將所得之殘渣以管柱層析(溶離液：乙酸乙酯/庚烷)純化，而得到目的物(20.4g)。(1) Synthesis of 2-bromo-1- (4-isopropoxy-2-methylphenyl) -2-methylpropane-1-one was synthesized in accordance with Japanese Patent Application Laid-Open No. 2016-108332 1- ( A solution of 4-isopropoxy-2-methylphenyl) -2-methylpropane-1-one (14.41g) in tetrahydrofuran (100mL), and trimethylphenylammonium tribromide (28.87g), Stir at room temperature for 5 hours. After completion of the reaction, the reaction mixture was filtered, and the obtained filtrate was concentrated under reduced pressure. The obtained residue was purified by column chromatography (eluent: ethyl acetate / heptane) to obtain the target compound (20.4 g).

(2)1-(4-異丙氧基-2-甲基苯基)-2-甲基-2-硝基丙烷-1-酮的合成
於2-溴-1-(4-異丙氧基-2-甲基苯基)-2-甲基丙烷-1-酮(20.4g)之二甲基亞碸(100mL)溶液，加入亞硝酸鈉(7.6g)，在室溫攪拌4小時使其反應。加入二甲基亞碸(40mL)在40℃攪拌2小時使其反應。反應結束後，冷卻至室溫加入水，以乙酸乙酯萃取。將合併之有機層以飽和食鹽水洗淨，再以硫酸鈉乾燥，減壓下進行濃縮。將所得之殘渣以管柱層析(庚烷：乙酸乙酯)純化，而得到目的物(19.5g)。
1 H NMR (CDCl3 /300MHz)：δ(ppm)=7.31(d, J=8.7 Hz, 1H), 6.76(d, J=2.4 Hz, 1H), 6.64(dd, J=9.0, 2.7 Hz, 1H), 4.63-4.55(m, 1H), 2.45(s, 3H), 1.92(s, 6H), 1.34(d, J=6.0 Hz, 6H).(2) Synthesis of 1- (4-isopropoxy-2-methylphenyl) -2-methyl-2-nitropropane-1-one in 2-bromo-1- (4-isopropoxy A solution of dimethyl-2-methylphenyl) -2-methylpropane-1-one (20.4 g) in dimethylsulfinium (100 mL), and sodium nitrite (7.6 g) was added, followed by stirring at room temperature for 4 hours to Its response. Dimethyl sulfene (40 mL) was added and the mixture was stirred at 40 ° C for 2 hours for reaction. After the reaction was completed, the mixture was cooled to room temperature, and water was added thereto, followed by extraction with ethyl acetate. The combined organic layers were washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by column chromatography (heptane: ethyl acetate) to obtain the target compound (19.5 g).
1 H NMR (CDCl 3 / 300MHz): δ (ppm) = 7.31 (d, J = 8.7 Hz, 1H), 6.76 (d, J = 2.4 Hz, 1H), 6.64 (dd, J = 9.0, 2.7 Hz, 1H), 4.63-4.55 (m, 1H), 2.45 (s, 3H), 1.92 (s, 6H), 1.34 (d, J = 6.0 Hz, 6H).

(3)2-(羥基胺基)-1-(4-異丙氧基-2-甲基苯基)-2-甲基丙烷-1-酮的合成
以與合成例1(3)同樣的方法，從1-(4-異丙氧基-2-甲基苯基)-2-甲基-2-硝基丙烷-1-酮(1.0g)得到目的物(0.5g)。
1 H NMR (CDCl3 /300MHz)：δ(ppm)= 7.35(d, J=8.4 Hz, 1H), 6.73(d, J=2.4 Hz,1H), 6.67(dd, J=8.7, 2.7 Hz, 1H), 4.60-4.52(m, 1H), 2.38(s, 3H), 1.36(s, 6H), 1.32(d, J=6.0 Hz, 6H).(3) Synthesis of 2- (hydroxyamino) -1- (4-isopropoxy-2-methylphenyl) -2-methylpropane-1-one The same procedures as in Synthesis Example 1 (3) were performed. Method: The target compound (0.5 g) was obtained from 1- (4-isopropoxy-2-methylphenyl) -2-methyl-2-nitropropane-1-one (1.0 g).
1 H NMR (CDCl 3 / 300MHz): δ (ppm) = 7.35 (d, J = 8.4 Hz, 1H), 6.73 (d, J = 2.4 Hz, 1H), 6.67 (dd, J = 8.7, 2.7 Hz, 1H), 4.60-4.52 (m, 1H), 2.38 (s, 3H), 1.36 (s, 6H), 1.32 (d, J = 6.0 Hz, 6H).

(4)3-(二氟甲基)-N-羥基-N-(1-(4-異丙氧基-2-甲基苯基)-2-甲基-1-氧代丙烷-2-基)-1-甲基-1H-吡唑-4-羧醯胺的合成
於根據美國專利第5093347號合成之3-(二氟甲基)-1-甲基-1H-吡唑-4-羧酸(7.5g)之甲苯(10mL)溶液，加入草醯氯(12.12g)及N,N-二甲基甲醯胺(0.01g)，在80℃攪拌1小時。將反應混合溶液於減壓下進行濃縮，而得到3-(二氟甲基)-1-甲基-1H-吡唑-4-羧醯氯。使所得之羧醯氯溶解在四氫呋喃(1mL)，調製四氫呋喃溶液。而且，於2-(羥基胺基)-1-(4-異丙氧基-2-甲基苯基)-2-甲基丙烷-1-酮(4.8g)之四氫呋喃(9mL)溶液加入三乙基胺(5.8g)，加入經調製之羧醯氯的四氫呋喃溶液。在室溫攪拌4小時。反應結束後，加入飽和碳酸氫鈉水溶液，以乙酸乙酯萃取。以飽和食鹽水洗淨後，將有機層以硫酸鈉乾燥，減壓下進行濃縮。使所得之殘渣溶解於乙醇(50mL)，於其反應溶液加入2M氫氧化鈉水溶液(50mL)，在室溫攪拌15小時30分鐘。反應結束後，加入水以乙酸乙酯萃取。以飽和食鹽水洗淨後，將有機層以硫酸鈉乾燥，減壓下進行濃縮。得到將所得之殘渣以管柱層析(庚烷：乙酸乙酯)純化之混合物。再度使混合物溶解於乙醇(50mL)，於其乙醇溶液加入2M鈉水溶液(50mL)，在室溫攪拌18小時。反應結束後，加入水以乙酸乙酯萃取。以飽和食鹽水洗淨後，將有機層以硫酸鈉乾燥，減壓下進行濃縮，而得到目的物(5.0g)。
1 H NMR (CDCl3 /300MHz)：δ(ppm)= 7.82(s, 1H), 7.68(d, J=8.7 Hz, 1H), 7.05(t, J=54.5 Hz, 1H), 6.73(d, J=2.4 Hz, 1H), 6.62(dd, J=8.7, 2.7 Hz, 1H)、4.60-4.53(m, 1H)、3.82(s, 3H), 2.38(s, 3H), 1.65(brs, 6H), 1.32(d, J=6.0 Hz, 6H)(4) 3- (difluoromethyl) -N-hydroxy-N- (1- (4-isopropoxy-2-methylphenyl) -2-methyl-1-oxopropane-2- (Synyl) -1-methyl-1H-pyrazole-4-carboxamide is synthesized in 3- (difluoromethyl) -1-methyl-1H-pyrazole-4- synthesized according to U.S. Patent No. 5,093,347. A toluene (10 mL) solution of a carboxylic acid (7.5 g) was added with chlorchloramine (12.12 g) and N, N-dimethylformamide (0.01 g), followed by stirring at 80 ° C for 1 hour. The reaction mixture solution was concentrated under reduced pressure to obtain 3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamidine chloride. The obtained carboxyphosphonium chloride was dissolved in tetrahydrofuran (1 mL) to prepare a tetrahydrofuran solution. Furthermore, to a solution of 2- (hydroxyamino) -1- (4-isopropoxy-2-methylphenyl) -2-methylpropane-1-one (4.8 g) in tetrahydrofuran (9 mL) was added three Ethylamine (5.8 g) was added to a solution of carboxyphosphonium chloride in tetrahydrofuran. Stir at room temperature for 4 hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was added and the mixture was extracted with ethyl acetate. After washing with saturated brine, the organic layer was dried over sodium sulfate and concentrated under reduced pressure. The obtained residue was dissolved in ethanol (50 mL), and a 2M aqueous sodium hydroxide solution (50 mL) was added to the reaction solution, followed by stirring at room temperature for 15 hours and 30 minutes. After the reaction was completed, water was added and the mixture was extracted with ethyl acetate. After washing with saturated brine, the organic layer was dried over sodium sulfate and concentrated under reduced pressure. A mixture was obtained in which the obtained residue was purified by column chromatography (heptane: ethyl acetate). The mixture was dissolved in ethanol (50 mL) again, and a 2M aqueous sodium solution (50 mL) was added to the ethanol solution, followed by stirring at room temperature for 18 hours. After the reaction was completed, water was added and the mixture was extracted with ethyl acetate. After washing with saturated brine, the organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain the desired product (5.0 g).
1 H NMR (CDCl 3 / 300MHz): δ (ppm) = 7.82 (s, 1H), 7.68 (d, J = 8.7 Hz, 1H), 7.05 (t, J = 54.5 Hz, 1H), 6.73 (d, J = 2.4 Hz, 1H), 6.62 (dd, J = 8.7, 2.7 Hz, 1H), 4.60-4.53 (m, 1H), 3.82 (s, 3H), 2.38 (s, 3H), 1.65 (brs, 6H ), 1.32 (d, J = 6.0 Hz, 6H)

(5)3-(二氟甲基)-N-(1-(4-異丙氧基-2-甲基苯基)-2-甲基-1-氧代丙烷-2-基)-N-甲氧基-1-甲基-1H-吡唑-4-羧醯胺(化合物No.8)之合成
於3-(二氟甲基)-N-羥基-N-(1-(4-異丙氧基-2-甲基苯基)-2-甲基-1-氧代丙烷-2-基)-1-甲基-1H-吡唑-4-羧醯胺(0.45g)之N,N-二甲基甲醯胺(15mL)溶液，加入氫化鈉(0.07g、60%)，在冰水浴冷卻並加入碘化甲烷(0.19g)。在冰水浴直接冷卻1小時並攪拌使其反應後，使溫度上昇至室溫，攪拌1小時使其反應。反應結束後，加入水以乙酸乙酯萃取。將合併之有機層以飽和食鹽水洗淨，以硫酸鈉乾燥，減壓下進行濃縮。將所得之殘渣以管柱層析(庚烷：乙酸乙酯)純化，而得到目的物(0.33g)。
1 H NMR (CDCl3 /300MHz)：δ(ppm)= 7.78 (s, 1H), 8.00 (d, J=8.4 Hz, 1H), 7.05 (t, J=54.3 Hz, 1H), 6.71 (d, J=2.4 Hz, 1H), 6.57 (dd, J=8.4, 2.4 Hz, 1H), 4.59-4.51 (m, 1H), 3.94 (s, 3H), 3.80 (s, 3H), 2.41 (s, 3H), 1.74 (brm, 6H), 1.30 (d, J=6.0 Hz, 6H)(5) 3- (difluoromethyl) -N- (1- (4-isopropoxy-2-methylphenyl) -2-methyl-1-oxopropane-2-yl) -N Synthesis of -methoxy-1-methyl-1H-pyrazole-4-carboxamide (Compound No. 8) in 3- (difluoromethyl) -N-hydroxy-N- (1- (4- Isopropoxy-2-methylphenyl) -2-methyl-1-oxopropane-2-yl) -1-methyl-1H-pyrazole-4-carboxamide (0.45 g) N , N-dimethylformamide (15 mL) solution, sodium hydride (0.07 g, 60%) was added, cooled in an ice water bath, and methyl iodide (0.19 g) was added. After cooling directly in an ice-water bath for 1 hour and stirring for reaction, the temperature was raised to room temperature, and the reaction was stirred for 1 hour. After the reaction was completed, water was added and the mixture was extracted with ethyl acetate. The combined organic layers were washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by column chromatography (heptane: ethyl acetate) to obtain the intended product (0.33 g).
1 H NMR (CDCl 3 / 300MHz): δ (ppm) = 7.78 (s, 1H), 8.00 (d, J = 8.4 Hz, 1H), 7.05 (t, J = 54.3 Hz, 1H), 6.71 (d, J = 2.4 Hz, 1H), 6.57 (dd, J = 8.4, 2.4 Hz, 1H), 4.59-4.51 (m, 1H), 3.94 (s, 3H), 3.80 (s, 3H), 2.41 (s, 3H ), 1.74 (brm, 6H), 1.30 (d, J = 6.0 Hz, 6H)

其次，將本發明化合物之代表例具體列舉於第1表。此等化合物可在前述製造方法及前述合成例以及本技術領域，根據公知之方法合成。
表中，No.表示化合物No.。第1表之物性欄所記載之數值為熔點(℃)，記載為NMR之化合物於第2表表示1 H-NMR光譜數據。於第1表中之B欄使用之簡稱分別表示以下之取代基。又，Me表示甲基，Et表示乙基。Next, representative examples of the compounds of the present invention are specifically listed in Table 1. These compounds can be synthesized according to a known method in the aforementioned production method, the aforementioned synthesis examples, and the technical field.
In the table, No. represents a compound No. The numerical values described in the physical properties column of Table 1 are melting points (° C), and the compounds described as NMR show 1 H-NMR spectral data in Table 2. The abbreviations used in column B in Table 1 represent the following substituents, respectively. In addition, Me represents a methyl group, and Et represents an ethyl group.

[表1]
[Table 1]

[表2]
[Table 2]

[表3]
[table 3]

[表4]
[Table 4]

[表5]
[table 5]

[表6]
[TABLE 6]

[表7]
[TABLE 7]

[表8]
[TABLE 8]

[表9]
[TABLE 9]

[表10]
[TABLE 10]

[表11]
[TABLE 11]

[表12]
[TABLE 12]

[表13]
[TABLE 13]

[表14]
[TABLE 14]

[表15]
[Table 15]

[表16]
[TABLE 16]

[表17]
[TABLE 17]

[表18]
[TABLE 18]

[表19]
[TABLE 19]

[表20]
[TABLE 20]

[表21]
[TABLE 21]

[表22]
[TABLE 22]

[表23]
[TABLE 23]

[表24]
[TABLE 24]

[表25]
[TABLE 25]

[表26]
[TABLE 26]

[表27]
[TABLE 27]

[表28]
[TABLE 28]

試驗例1：對於小麥葉枯病之殺菌效果試驗
於包含以二甲基亞碸溶解之本發明化合物的YBG(酵母萃取物、蛋白腖(Bacto Peptone)、甘油)介質，接種小麥葉枯病菌(Septoria tritici)之胞子懸濁液，於室溫培養7天調查生育程度。
將化合物No.2～11、13～22、24～40、42～45、52～57、65、69～89、93～97、105～108、110～117、119～124、126～134、138～155、157～161、171、181～184、192～195、197～209、213～218、224～235、237～239、243、248～250、252、253、257～259、261、266～272、274、276、278～292、296、312、338、339、341～344、347、353、356、379、392、394、404、407、410、434、436、459～479、483～487、491、496～506、511、513、520～522、524、530、532、533、541～545、557、577、579、582、585～588、591、836以30ppm將小麥葉枯病菌的生育抑制70%以上。Test Example 1: Bactericidal effect test against wheat leaf blight The YBG (yeast extract, Bacto Peptone, glycerol) medium containing the compound of the present invention dissolved in dimethylarsine was inoculated with wheat leaf blight (Septoria Tritici) cell suspension was cultured at room temperature for 7 days to investigate fertility.
Compound Nos. 2 to 11, 13 to 22, 24 to 40, 42 to 45, 52 to 57, 65, 69 to 89, 93 to 97, 105 to 108, 110 to 117, 119 to 124, 126 to 134, 138-155, 157-161, 171, 181-184, 192-195, 197-209, 213-218, 224-235, 237-239, 243, 248-250, 252, 253, 257-259, 261, 266 to 272, 274, 276, 278 to 292, 296, 312, 338, 339, 341 to 344, 347, 353, 356, 379, 392, 394, 404, 407, 410, 434, 436, 459 to 479, 483 to 487, 491, 496 to 506, 511, 513, 520 to 522, 524, 530, 532, 533, 541 to 545, 557, 577, 579, 582, 585 to 588, 591, 836 wheat leaves at 30 ppm The growth of Fusarium oxysporum was suppressed by more than 70%.

試驗例2：對於小麥赤黴病之殺菌效果試驗
於包含以二甲基亞碸溶解之本發明化合物的YBA(酵母萃取物、蛋白腖(Bacto Peptone)、乙酸鈉)介質，接種小麥赤黴病菌(Fusarium graminearum)之胞子懸濁液，以室溫培養3天調查生育程度。
將化合物No.3、5、6、8、10、11、13、15～18、20～22、24、26、27、29～32、35～40、42～45、55～57、65、69、70、72～74、76～79、81、82、86、88、89、93、96、97、105～108、110～117、122～124、126、129、130、133、134、140、143～145、153、155、157～160、171、181～183、192、194、197～209、213、216、225～231、233～239、243、248～250、252、253、257、258、261、266～269、271、272、274、276、278～292、296、344、347、356、379、392、394、404、407、410、412、434、436、459～467、470～473、475～479、483～487、491、495～506、511、513、521、522、525、530、532、533、541～545、557、577、579、582、585～588、591、836以30ppm將小麥赤黴病菌的生育抑制70%以上。Test Example 2: Bactericidal effect against wheat scab In a YBA (yeast extract, Bacto Peptone, sodium acetate) medium containing a compound of the present invention dissolved in dimethylsulfine, inoculation with wheat scab ( Fusarium graminearum) was cultured at room temperature for 3 days to investigate fertility.
Compound No. 3, 5, 6, 8, 10, 11, 13, 15 to 18, 20 to 22, 24, 26, 27, 29 to 32, 35 to 40, 42 to 45, 55 to 57, 65, 69, 70, 72 to 74, 76 to 79, 81, 82, 86, 88, 89, 93, 96, 97, 105 to 108, 110 to 117, 122 to 124, 126, 129, 130, 133, 134, 140, 143 to 145, 153, 155, 157 to 160, 171, 181 to 183, 192, 194, 197 to 209, 213, 216, 225 to 231, 233 to 239, 243, 248 to 250, 252, 253, 257, 258, 261, 266 to 269, 271, 272, 274, 276, 278 to 292, 296, 344, 347, 356, 379, 392, 394, 404, 407, 410, 412, 434, 436, 459 ~ 467,470 ~ 473,475 ~ 479,483 ~ 487,491,495 ~ 506,511,513,521,522,525,530,532,533,541 ~ 545,557,577,579,582,585 ~ 588, 591, 836 inhibited the growth of wheat scab by more than 70% at 30 ppm.

試驗例3：對於小麥白粉病之效果試驗
以直徑6cm之乙烯盆栽培小麥，於到達1.5～2.0葉期時，將本發明化合物調製成指定濃度之藥液10mL在噴槍散布。乾燥藥液後(處理當日)，灑上白粉病菌(Erysiphe graminis)之分生胞子進行接種，保持在20℃之恆溫室內。於接種7天後從胞子形成面積調查防除率。
將化合物No.5、7、8、11、15、16、24、31、32、34、37～40、55、56、74、79、84、105～107、110～112、114、119、122、123、126、130、133、134、138～141、144、145、147、148、154、157～161、171、182、184、193、195～200、202、205～209、216、217、220、224～226、229、231、233、238、239、248～250、253、257～259、266～268、270、278～280、283、289～292、338、339、343、344、365、379、394、404、407、410、434、436、459～463、465、471、472、475～479、483～487、491、498、499、501～503以100ppm將小麥白粉病的發病抑制90%以上。Test Example 3: Effect test on wheat powdery mildew Wheat was cultivated in an ethylene pot with a diameter of 6 cm. When the 1.5-2.0 leaf stage was reached, 10 mL of the chemical solution of the compound of the present invention was prepared to a specified concentration and sprayed on a spray gun. After drying the medicinal solution (on the day of treatment), the conidia of Erysiphe graminis were sprinkled for inoculation and kept in a constant temperature room at 20 ° C. The control rate was investigated from the spore formation area 7 days after the inoculation.
Compound No. 5, 7, 8, 11, 15, 16, 24, 31, 32, 34, 37 to 40, 55, 56, 74, 79, 84, 105 to 107, 110 to 112, 114, 119, 122, 123, 126, 130, 133, 134, 138 to 141, 144, 145, 147, 148, 154, 157 to 161, 171, 182, 184, 193, 195 to 200, 202, 205 to 209, 216, 217, 220, 224 to 226, 229, 231, 233, 238, 239, 248 to 250, 253, 257 to 259, 266 to 268, 270, 278 to 280, 283, 289 to 292, 338, 339, 343, 344, 365, 379, 394, 404, 407, 410, 434, 436, 459-463, 465, 471, 472, 475-479, 483-487, 491, 498, 499, 501-503 at 100 ppm The incidence of the disease is suppressed by more than 90%.

試驗例4：對於綠豆灰黴病之效果試驗
以直徑15cm之聚鉢栽培綠豆，於本葉充分展開時，將本發明化合物調製成指定濃度之藥液5mL在噴槍散布。乾燥藥液後(處理當日或隔天)，接種含浸以PS(馬鈴薯、蔗糖)介質調製之灰黴病菌(Botrytis cinerea)之分生胞子懸濁液的直徑8mm之紙盤，以多濕條件下保持在20℃之恆溫室內。從接種3日後之病斑長度調查防除率。
將化合物No.6、8、15、17、19、20、31～35、42～45、55～57、77、79、83、84、86、93、105、110、115、126、129、130、133、134、140～142、144、147、151、153、154、157、159、182、198、200、207、233、235、238、239、250、257、258、261、276、280、281、283、285、289、290、292、343、347、379、407、434、436、459、461、462、466、471、472、476、477、479、484～487、503、505、521、557以25ppm將綠豆灰黴病之發病抑制90%以上。Test Example 4: Effect test on mung bean gray mold. Mung beans were cultivated in a poly bowl with a diameter of 15 cm. When the leaf was fully expanded, 5 mL of a chemical solution of the compound of the present invention was prepared to a specified concentration and dispersed in a spray gun. After drying the medicinal solution (on the day of treatment or the next day), inoculate a paper tray with a diameter of 8 mm impregnated with conidia suspension of Botrytis cinerea prepared with PS (potato, sucrose) medium, under humid conditions. Keep in a constant temperature room at 20 ° C. The control rate was investigated from the length of the lesions 3 days after the inoculation.
Compound No. 6, 8, 15, 17, 19, 20, 31 to 35, 42 to 45, 55 to 57, 77, 79, 83, 84, 86, 93, 105, 110, 115, 126, 129, 130, 133, 134, 140-142, 144, 147, 151, 153, 154, 157, 159, 182, 198, 200, 207, 233, 235, 238, 239, 250, 257, 258, 261, 276, 280, 281, 283, 285, 289, 290, 292, 343, 347, 379, 407, 434, 436, 459, 461, 462, 466, 471, 472, 476, 477, 479, 484 to 487, 503, 505, 521, 557 inhibited the incidence of mung bean gray mold by more than 90% at 25 ppm.

試驗例5：對於綠豆菌核病之效果試驗
以直徑15cm之聚鉢栽培綠豆，於本葉充分展開時，將本發明化合物調製成指定濃度之藥液5mL在噴槍散布。乾燥藥液後(處理當日或隔天)，預先將以PSA(馬鈴薯、蔗糖、洋菜)介質培養之菌核病菌(Sclerotinia sclerotiorum)之菌叢盤(直徑4mm)之菌叢面從上進行接種，以多濕條件下保持在20℃之恆溫室內。從接種3日後之病斑長度調查防除率。
將化合物No.2、5～9、13～18、20、26、28、29、31～36、38、39、42～45、52～57、70、74～77、79、80、83、84、86～88、93、95～98、105～108、110～112、115～117、119、122、124、126～131、133、134、138～142、145、147、151～155、157～159、171、182、184、193、197、198、200、202、206、207、209、216～218、220、233、235、238、239、248、250、252、257～259、261、269～272、274、276、278、280～283、285～287、289、290、292、296、338、339、343、347、365、379、394、404、407、410、434、436、459～463、465、471～475、477～479、484～487、498、503～506、511、513、530、533、557、602以25ppm將綠豆菌核病的發病抑制90%以上。
又，如第3表所示，本發明化合物之化合物No.75及No.112與醯胺之氮原子未被甲氧基修飾之化合物相比較，於25ppm顯示更為優異之效果。
效果之評估基準=A：防除率 95～100%、B：90～94%、C：50～89%、D：30～49%、E：0～29%Test Example 5: Test for the effect of mung bean sclerotinia disease Mung beans are cultivated in a poly bowl with a diameter of 15 cm. When the leaf is fully expanded, 5 mL of a chemical solution of the compound of the present invention is prepared to a specified concentration and dispersed in a spray gun. After drying the medicinal solution (on the day of treatment or the next day), inoculate the flora surface of the sclerotinia sclerotiorum sclerotiorum (4mm diameter) in a PSA (potato, sucrose, agar) medium and inoculate it from above , Keep in a constant temperature room at 20 ° C under humid conditions. The control rate was investigated from the length of the lesions 3 days after the inoculation.
Compound No. 2, 5 to 9, 13 to 18, 20, 26, 28, 29, 31 to 36, 38, 39, 42 to 45, 52 to 57, 70, 74 to 77, 79, 80, 83, 84, 86 to 88, 93, 95 to 98, 105 to 108, 110 to 112, 115 to 117, 119, 122, 124, 126 to 131, 133, 134, 138 to 142, 145, 147, 151 to 155, 157 to 159, 171, 182, 184, 193, 197, 198, 200, 202, 206, 207, 209, 216 to 218, 220, 233, 235, 238, 239, 248, 250, 252, 257 to 259, 261, 269-272, 274, 276, 278, 280-283, 285-287, 289, 290, 292, 296, 338, 339, 343, 347, 365, 379, 394, 404, 407, 410, 434, 436, 459 to 463, 465, 471 to 475, 477 to 479, 484 to 487, 498, 503 to 506, 511, 513, 530, 533, 557, and 602 inhibit the incidence of mung bean sclerotinia by more than 90% at 25 ppm .
In addition, as shown in Table 3, compounds No. 75 and No. 112 of the compound of the present invention exhibited more excellent effects at 25 ppm as compared with compounds in which the nitrogen atom of amidine was not methoxy modified.
Evaluation criteria of the effect = A: control rate of 95 to 100%, B: 90 to 94%, C: 50 to 89%, D: 30 to 49%, E: 0 to 29%

試驗例6：對於小麥葉枯病之效果試驗
於處理3日前，於噴霧接種葉枯病菌(Septoria tritici)之分生胞子懸濁液之小麥(以直徑6cm之乙烯盆栽培、1.5～2.0葉期)，將本發明化合物調製成指定濃度之藥液10mL在噴槍散布，乾燥藥液後保持在15℃之恆溫室內。於接種24～28日後從病斑形成面積，調查顯示防除率90%以上之最低有效濃度，將與作為對於小麥葉枯病之殺菌劑使用之丙硫菌唑的最低有效濃度的濃度差以5階段評估。
評估基準之計算式=X/Y
X；本發明之化合物的最低有效濃度(ppm)、Y；丙硫菌唑之最低有效濃度(ppm)
評估基準=A：1/128倍以下、B：較1/128更大且為1/32倍以下、C：較1/32更大且為1/8倍以下、D：較1/8更大且為1倍以下、E：較1倍更大
如第4表所示，本發明化合物之化合物No.8，與醯胺之氮原子為甲氧基以外之化合物相比較，顯示更為優異之效果。Test example 6: Effect test on wheat leaf blight Before treatment 3 days, wheat (sprayed in a 6 cm diameter ethylene pot, 1.5-2.0 leaf stage) was spray-inoculated with a conidium suspension of conidia of Septoria tritici ), 10 mL of a chemical solution prepared by the compound of the present invention to a specified concentration is spread in a spray gun, and the chemical solution is dried and kept in a constant temperature room at 15 ° C. The investigation showed that the minimum effective concentration of the prevention rate of 90% or more from the lesion formation area 24 to 28 days after the inoculation will be 5 times lower than the minimum effective concentration of prothioconazole used as a fungicide for wheat leaf blight. Phase evaluation.
Calculation formula for evaluation basis = X / Y
X; minimum effective concentration (ppm) of compounds of the present invention, Y; minimum effective concentration of prothioconazole (ppm)
Evaluation criteria = A: 1/128 times or less, B: 1/128 times or more and 1/32 times or less, C: 1/32 times or more and 1/8 times or less, D: 1/8 or more times It is as large as 1 time or less and E: larger than 1 time. As shown in Table 4, compound No. 8 of the compound of the present invention is more excellent than a compound in which the nitrogen atom of amidine is other than a methoxy group. The effect.

其次，雖記載本發明組成物之製劑例，但摻合比例、劑型等並非僅被限定於記載例者。

製劑例1
(1)式(1)之化合物 20重量份
(2)黏土 72重量份
(3)木質素磺酸蘇打 8重量份
將均一混合以上者作為可濕性粉劑。

製劑例2
(1)式(1)之化合物 5重量份
(2)滑石 95重量份
將均一混合以上者作為粉劑。

製劑例3
(1)式(1)之化合物 20重量份
(2)N,N’-二甲基乙醯胺 20重量份
(3)聚氧乙烯烷基苯基醚 10重量份
(4)二甲苯 50重量份
將均一混合以上者進行溶解作為乳劑。Next, although formulation examples of the composition of the present invention are described, the blending ratio, dosage form, and the like are not limited only to those described.

Preparation Example 1
(1) 20 parts by weight of a compound of formula (1)
(2) 72 parts by weight of clay
(3) 8 parts by weight of lignin sulfonate soda is used as a wettable powder.

Preparation Example 2
(1) 5 parts by weight of a compound of formula (1)
(2) 95 parts by weight of talc is used as a powder by mixing more than one uniformly.

Preparation Example 3
(1) 20 parts by weight of a compound of formula (1)
(2) 20 parts by weight of N, N'-dimethylacetamide
(3) 10 parts by weight of polyoxyethylene alkylphenyl ether
(4) 50 parts by weight of xylene was dissolved as a homogeneous mixture to dissolve it as an emulsion.

製劑例4
(1)黏土 68重量份
(2)木質素磺酸蘇打 2重量份
(3)聚氧乙烯烷基芳基硫酸鹽 5重量份
(4)微粉二氧化矽 25重量份
將以上之各成分的混合物、與式(1)之化合物以4:1之重量比例混合，作為可濕性粉劑。

製劑例5
(1)式(1)之化合物 50重量份
(2)經氧基化(Oxylated)之聚烷基苯基磷酸鹽-三乙醇胺
2重量份
(3)聚矽氧 0.2重量份
(4)水 47.8重量份
將均一混合以上者於經粉碎之原液進一步加入均一混合，
(5)聚羧酸鈉 5重量份
(6)無水硫酸鈉 42.8重量份
進行造粒、乾燥，作為顆粒可濕性粉劑。

製劑例6
(1)式(1)之化合物 5重量份
(2)聚氧乙烯辛基苯基醚 1重量份
(3)聚氧乙烯之燐酸酯 0.1重量份
(4)粒狀碳酸鈣 93.9重量份
預先均一混合(1)～(3)，以適量之丙酮稀釋後，吹附在(4)，去除丙酮作為粒劑。Preparation Example 4
(1) 68 parts by weight of clay
(2) 2 parts by weight of ligninsulfonic acid soda
(3) 5 parts by weight of polyoxyethylene alkylaryl sulfate
(4) 25 parts by weight of finely powdered silicon dioxide The mixture of the above components and the compound of the formula (1) are mixed at a weight ratio of 4: 1 as a wettable powder.

Preparation Example 5
(1) 50 parts by weight of a compound of formula (1)
(2) Oxylated polyalkylphenyl phosphate-triethanolamine
2 parts by weight
(3) 0.2 parts by weight of polysiloxane
(4) 47.8 parts by weight of water is further added to the pulverized stock solution and mixed uniformly,
(5) 5 parts by weight of sodium polycarboxylate
(6) 42.8 parts by weight of anhydrous sodium sulfate is granulated and dried to obtain a granule wettable powder.

Preparation Example 6
(1) 5 parts by weight of a compound of formula (1)
(2) 1 part by weight of polyoxyethylene octylphenyl ether
(3) 0.1 part by weight of polyoxyethylene gallate
(4) 93.9 parts by weight of granular calcium carbonate are uniformly mixed in advance (1) to (3), diluted with an appropriate amount of acetone, and then blown to (4) to remove acetone as a granule.

製劑例7
(1)式(1)之化合物 2.5重量份
(2)N-甲基-2-吡咯烷酮 2.5重量份
(3)大豆油 95.0重量份
將均一混合以上者溶解，作為微量散布劑(ultra low volume formulation)。

製劑例8
(1)式(1)之化合物 20重量份
(2)經氧基化之聚烷基酚磷酸鹽-三乙醇胺
2重量份
(3)聚矽氧 0.2重量份
(4)三仙膠 0.1重量份
(5)乙二醇 5重量份
(6)水 72.7重量份
將均一混合以上者進行粉碎，作為水性懸濁劑。
尚，將2017年12月21日所申請之日本特許出願
2017-244785號之說明書、申請專利範圍及摘要之全內引用於此，作為本發明之說明書的揭示而取入者。Preparation Example 7
(1) 2.5 parts by weight of a compound of formula (1)
(2) 2.5 parts by weight of N-methyl-2-pyrrolidone
(3) 95.0 parts by weight of soybean oil is dissolved in a homogeneous mixture or more, and is used as an ultra low volume formulation.

Preparation Example 8
(1) 20 parts by weight of a compound of formula (1)
(2) Oxidized polyalkylphenol phosphate-triethanolamine
2 parts by weight
(3) 0.2 parts by weight of polysiloxane
(4) 0.1 parts by weight
(5) 5 parts by weight of ethylene glycol
(6) 72.7 parts by weight of water A homogeneous mixture or more is pulverized as an aqueous suspension agent.
Shang, will apply for a Japanese franchise filed on December 21, 2017
The entire description, patent application scope, and abstract of 2017-244785 are incorporated herein by reference, and are incorporated as disclosures of the description of the present invention.

Claims (11)

一種式(1)表示之化合物或其鹽， [式中，A為被RA 取代之苯基或被RA 取代之吡啶基， B為被RB 取代之雜環基， RA 可相同或相異為鹵素原子、可被G1 取代之烷基、烯基、可被G2 取代之炔基、環狀基、硝基、氰基或-LA -YA ，或可鍵結2個RA ，形成可被Z1 取代之環， RB 可相同或相異為鹵素原子、烷基、烯基、鹵烷基、烷氧基烷基、環烷基或氰基， LA 為O、S、C(=O)、C(=O)O、C(=O)N(R1 )、 OC(=O)、N(R1 )、N(R1 )C(=O)、N(R1 )C(=O)O、C(=NR2 )、SO、SO2 或SO2 N(R1 )，YA 為氫原子、可被Z2 取代之烷基、烯基或可被Z3 取代之環狀基， R1 為氫原子或烷基， R2 為氫原子、烷基或烷氧基， G1 為鹵素原子或烷氧基， G2 為環烷基或鹵素原子， Z1 為鹵素原子、烷基或烷氧基， Z2 為鹵素原子、氰基、環烷基或烷氧基， Z3 為鹵素原子或鹵烷基]。A compound represented by formula (1) or a salt thereof, [Wherein, A is the substituted phenyl is substituted with the R A or R A pyridyl group, B is a heterocyclic group substituted with the R B, R A may be the same or different is a halogen atom, may be substituted G 1 of Alkyl, alkenyl, alkynyl, cyclic, nitro, cyano, or -L A -Y A which may be substituted by G 2 , or may bond 2 R A to form a ring which may be substituted by Z 1 , R B may be the same or different and are halogen atom, alkyl, alkenyl, haloalkyl, alkoxyalkyl, cycloalkyl or cyano, and L A is O, S, C (= O), C (= O) O, C (= O) N (R 1 ), OC (= O), N (R 1 ), N (R 1 ) C (= O), N (R 1 ) C (= O) O, C (= NR 2 ), SO, SO 2 or SO 2 N (R 1 ), Y A is a hydrogen atom, an alkyl group which may be substituted by Z 2 , an alkenyl group or a cyclic group which may be substituted by Z 3 , R 1 Is a hydrogen atom or an alkyl group, R 2 is a hydrogen atom, an alkyl group, or an alkoxy group, G 1 is a halogen atom or an alkoxy group, G 2 is a cycloalkyl group or a halogen atom, and Z 1 is a halogen atom, an alkyl group, or an alkoxy group Oxygen, Z 2 is a halogen atom, cyano, cycloalkyl or alkoxy, and Z 3 is a halogen atom or haloalkyl]. 如請求項1之化合物或其鹽，其中， B為選自由式(B-1)～式(B-18)表示之5員雜環基及式(B-101)～式(B-128)表示之6員雜環基所成之群組中之雜環基， [式中，RB1 ～RB20 可相同或相異為鹵素原子、烷基、烯基、鹵烷基、烷氧基烷基、環烷基或氰基，＊表示鍵結位置] [式中，RB101 ～RB114 可相同或相異為鹵素原子、烷基、烯基、鹵烷基、烷氧基烷基、環烷基或氰基，＊表示鍵結位置]。The compound or a salt thereof as claimed in claim 1, wherein B is selected from the group consisting of a 5-membered heterocyclic group represented by formula (B-1) to formula (B-18) and formula (B-101) to formula (B-128) The heterocyclic group in the group formed by the 6-membered heterocyclic group, [ Wherein R B1 to R B20 may be the same or different from each other as a halogen atom, an alkyl group, an alkenyl group, a haloalkyl group, an alkoxyalkyl group, a cycloalkyl group, or a cyano group, and * represents a bonding position] [In the formula, R B101 to R B114 may be the same or different, and are a halogen atom, an alkyl group, an alkenyl group, a haloalkyl group, an alkoxyalkyl group, a cycloalkyl group, or a cyano group, and * represents a bonding position]. 如請求項2之化合物或其鹽，其中，B為選自由下述之式(B-1)～式(B-4)表示之雜環基所成之群組中之雜環基，。The compound or a salt thereof according to claim 2, wherein B is a heterocyclic group selected from the group consisting of heterocyclic groups represented by the following formulae (B-1) to (B-4), . 如請求項2之化合物或其鹽，其中，B為下述之式(B-1)或式(B-2)表示之基，。A compound or a salt thereof according to claim 2, wherein B is a group represented by the following formula (B-1) or (B-2), . 如請求項4之化合物或其鹽，其中，RB1 為鹵素原子、烷基、烯基、鹵烷基、烷氧基烷基或氰基，RB2 為烷基、鹵烷基或環烷基，RB3 為鹵素原子。The compound or a salt thereof according to claim 4, wherein R B1 is a halogen atom, an alkyl group, an alkenyl group, a haloalkyl group, an alkoxyalkyl group, or a cyano group, and R B2 is an alkyl group, a haloalkyl group, or a cycloalkyl group. R B3 is a halogen atom. 如請求項1之化合物或其鹽，其中，A為被RA 取代之苯基。A compound or a salt thereof as claimed in claim 1, wherein A is a phenyl substituted with R A. 如請求項1之化合物或其鹽，其中，A為2位及4位之至少一者被RA 取代之苯基。The compound or a salt thereof according to claim 1, wherein A is a phenyl group in which at least one of the 2-position and the 4-position is substituted with R A. 如請求項1之化合物或其鹽，其中，A為可被Z1 取代之苯并二氧環戊基(benzodioxolanyl)。The compound or salt thereof according to claim 1, wherein A is benzodioxolanyl which may be substituted by Z 1 . 如請求項1之化合物或其鹽，其中，RA 為鹵素原子、烷基、鹵烷基或-LA -YA 。The compound or a salt thereof according to claim 1, wherein R A is a halogen atom, an alkyl group, a haloalkyl group, or -L A -Y A. 一種農園藝用殺菌劑，其係將如請求項1之化合物或其鹽做為有效成分含有。A fungicide for agriculture and horticulture, which contains the compound according to claim 1 or a salt thereof as an active ingredient. 一種防除植物病害之方法，其係將如請求項1之化合物或其鹽施用在植物或土壤。A method for controlling plant diseases, which comprises applying a compound according to claim 1 or a salt thereof to a plant or soil.
TW107146386A 2017-12-21 2018-12-21 N-methoxyamide compound or salt thereof, and agricultural and horticultural fungicide containing same TW201934007A (en)

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