WO2010137302A1 - Dérivés hétéroaryles contenant de l'azote et fongicides pour utilisation agricole et horticole - Google Patents

Dérivés hétéroaryles contenant de l'azote et fongicides pour utilisation agricole et horticole Download PDF

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WO2010137302A1
WO2010137302A1 PCT/JP2010/003500 JP2010003500W WO2010137302A1 WO 2010137302 A1 WO2010137302 A1 WO 2010137302A1 JP 2010003500 W JP2010003500 W JP 2010003500W WO 2010137302 A1 WO2010137302 A1 WO 2010137302A1
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古川裕紀
清水一彌
▲桑▼原頼人
荻野智和
大沢陽子
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日本曹達株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/68—One oxygen atom attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D401/04—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 directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to a novel nitrogen-containing heteroaryl derivative, a salt thereof, or an N-oxide, and an agricultural and horticultural fungicide containing at least one of these compounds as an active ingredient.
  • Patent Document 1 discloses a carbamate derivative represented by the formula (A) and an agricultural and horticultural fungicide containing it as an active ingredient.
  • X ′′ is a halogen atom, a C1-C6 alkyl group, etc.
  • n is an integer from 0 to 4
  • R a1 is a C1-C6 alkyl group
  • R a2 is a hydrogen atom, C1 ⁇ a C6 alkyl group, a R a3 hydrogen atom or C1-C6 alkyl group
  • G is an oxygen atom, a sulfur atom, etc.
  • Y "is hydrogen, C1-C10 alkyl group, C2-C10 alkenyl group Q ′′ is a hydrogen atom, a C1-C6 haloalkyl group, a phenyl group, etc.
  • Patent Document 2 discloses an iminooxymethylpyridine compound represented by the formula (B) and an agricultural and horticultural fungicide containing the compound as an active ingredient.
  • X ′ is an oxygen atom or a bond
  • Y ′ and Z ′ are each independently one or two selected from the group consisting of a phenyl group, an oxygen atom, a sulfur atom and a nitrogen atom.
  • Patent Document 3 discloses an oxyamine derivative represented by the formula (C) and an agricultural and horticultural fungicide containing it as an active ingredient.
  • R c1 represents a hydrogen atom, a C1-6 alkyl group, a C1-6 alkylcarbonyl group, or a C1-6 alkylsulfonyl group.
  • R c2 is a C1-6 alkyl group or a C1-6 alkoxy group.
  • R c3 is a halogen atom, a C1-6 alkyl group, or a C1-6 alkoxy group.
  • a c is a branched also be C1 ⁇ 6 alkylene group or a bond.
  • Q c is a phenyl group which may be substituted with G, a group represented by the formula (p1), or a group represented by the formula (p2).
  • m is an integer of 0-4.
  • R c4 is a hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, or SiR c5 R c6 R c7, where R c5 -R c7 are each independently C1-6 alkyl
  • R c8 is a hydrogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, or a phenyl group optionally substituted with G.
  • Y is a hydrogen atom, C1-6 alkyl A C3-6 cycloalkyl group, a C3-6 cycloalkyl-C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, or a phenyl C1-6 alkyl group optionally substituted by G.
  • G represents a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a C1-6 haloalkyl group, or a C1-6 haloalkoxy group, and these Gs may be the same or different and may be substituted by 2 to 5 .
  • Patent Document 4 discloses an aryl heterocyclic derivative represented by the formula (D) and an agricultural and horticultural fungicide containing it as an active ingredient.
  • R d1 is a C1-6 alkyl group
  • R d2 is a halogen atom, etc.
  • m is an integer of 0-4
  • T is a formula (p3), a formula (p4), a formula (p5)
  • R d3 , R d4 , R d5 and R d6 are hydrogen atoms and the like, n is an integer of 1 to 4
  • Q d is a formula (p6), a formula (p7), a formula It is a group represented by (p8), formula (p9), and formula (p10).
  • R d7 represents a C5-12 alkyl group, etc.
  • R d8 , R d9 , R d10 and R d11 represent A hydrogen atom
  • X is an oxygen atom or a sulfur atom
  • k is 0 or an integer of 1 to 3)
  • Patent Document 5 discloses a phenoxyamine derivative represented by the formula (E) and an agricultural and horticultural fungicide containing it as an active ingredient.
  • R e1 and R e2 are each independently a hydrogen atom, etc .; V is NR e3, etc .; R e3 is a hydrogen atom, etc .; R e4 is a C1-6 alkoxy group, etc. Yes; W is an oxygen atom or the like; Q e2 is an oxygen atom or the like; Y is a phenyl group which is substituted with a C1-5 haloalkoxy group or the like, and may be further substituted with a halogen atom or the like.
  • JP 2001-106666 A JP 2007-137852 A Japanese Patent Laid-Open No. 2004-166863 WO2005 / 051932 WO2008 / 124092
  • the present invention has been made in view of such circumstances, a novel nitrogen-containing heteroaryl derivative that can be produced industrially advantageously, can be used safely and safely for agricultural and horticultural use, and its An object of the present invention is to provide a fungicide for agriculture and horticulture containing a salt or N-oxide and at least one of these compounds as an active ingredient.
  • the present invention is a nitrogen-containing heteroaryl derivative represented by the formula (1), a salt thereof, or an N-oxide.
  • R 1 is an unsubstituted or substituted C1-6 alkyl group.
  • R 2 is a hydrogen atom, C1 ⁇ 6 alkyl group having an unsubstituted or substituted group of the formula: COR 21 (wherein, R 21 has a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, A substituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted heteroaryl group.
  • R 22 is, C1 ⁇ 6 alkyl group having an unsubstituted or substituted group, C2 ⁇ 6 alkenyl groups having an unsubstituted or substituted, unsubstituted or location Group having C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 cycloalkenyl group, unsubstituted or substituted C6-10 An aryl group, or an unsubstituted or substituted heteroaryl group.
  • CON (R 21 ) 2 wherein R 21 has the same meaning as described above; R 21 May be the same or different.
  • a 1 is an oxygen atom, a sulfur atom, or a formula: NR 3 (wherein R 3 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or Substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 A cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted heteroaryl group.
  • R 3 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or Substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalky
  • a 2 is an oxygen atom
  • Formula: NR 4 (wherein R 4 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, Formula: COR 21 , Formula: CO 2 R 22 , or a group represented by the formula: CON (R 21 ) 2 (wherein R 21 and R 22 have the same meanings as described above, and R 21 may be the same or different).
  • a group represented by the formula: CR 5 R 6 (wherein R 5 and R 6 are each independently a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, or a halogen atom) It is a group represented by.
  • J is an oxygen atom or a sulfur atom.
  • X C1 ⁇ 6 alkyl group having an unsubstituted or substituted group of the formula: OR 23 (wherein, R 23 represents a hydrogen atom, C1 ⁇ 6 alkyl having unsubstituted or substituted Group, unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted A C4-8 cycloalkenyl group having a group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted heteroaryl group, a formula: COR 21 , a formula: CO 2 R 22 , or a formula : CON (R 21 ) 2 (in the formula, R 21 and R 22 have the same meanings as described above.
  • R 21 may be the same or different.
  • Formula: SR 23 Formula: N (R 23) 2 ( . Wherein, R 23 is .R 23 is the same meaning as above, which may be the same or different) a group represented by a cyano group, a nitro group or a halogen atom, is there.
  • n represents the number of X and is an integer from 0 to 3. When n is 2 or more, Xs may be the same or different.
  • B 1 to B 4 are each independently a nitrogen atom or a carbon atom. However, B 1 to B 3 are not all nitrogen atoms, and B 1 to B 4 are not all carbon atoms.
  • D is any group represented by the formulas (2) to (6).
  • Q 1 represents an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted group. Having C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 cycloalkenyl group, unsubstituted or substituted C6-10 aryl group An unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted heteroaralkyl group, or a trisubstituted silyl group.
  • R 7 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl.
  • R 8 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted group Or a substituted C2-6 alkynyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6 ⁇ 10 aryl group, or unsubstituted or substituted heteroaryl group.
  • R 8 may further be bonded to a carbon atom on Q 1 or a nitrogen atom.
  • Q 41 is a C6-10 aryl group or a heteroaryl group.
  • Q 2 is represented by formula: OR 23 , formula: SR 23 , formula: N (R 23 ) 2 , formula: COR 21 , formula: CO 2 R 22 , formula: CON (R 21 ) 2 , Formula: SO 2 R 22 (wherein R 21 , R 22 , and R 23 have the same meaning as described above.
  • R 21 may be the same or different.
  • R 23 may be the same or different.
  • m1 represents the number of Q 1 and is an integer of 0 to 7.
  • m2 represents the number of Q 2 and is an integer of 0 to 7. However, the sum of m1 and m2 is 7 or less.
  • Q 1 may be the same or different.
  • Q 2 may be the same or different.
  • Q 1 , Q 2 , or Q 1 and Q 2 that are adjacently substituted on Q 41 may be bonded to each other to form a 5- to 8-membered ring.
  • the second aspect of the present invention is a nitrogen-containing heteroaryl derivative represented by the formula (7), a salt thereof, or an N-oxide.
  • R 1 , R 2 , A 1 , A 2 , J, X, n, and D have the same meaning as in the formula (1).
  • the third aspect of the present invention is a nitrogen-containing heteroaryl derivative represented by the formula (8), a salt thereof, or an N-oxide.
  • R 1 , R 2 , A 1 , A 2 , J, X, n, R 7 , and Q 1 have the same meaning as in formula (1).
  • the present invention is an agricultural and horticultural fungicide containing, as an active ingredient, at least one of the nitrogen-containing heteroaryl derivative of the present invention, a salt thereof, or N-oxide. That is, it is an agricultural and horticultural fungicide containing at least one of the nitrogen-containing heteroaryl derivative represented by the formula (1), a salt thereof, or N-oxide as an active ingredient. Preferably, it is an agricultural and horticultural fungicide containing as an active ingredient at least one of a nitrogen-containing heteroaryl derivative represented by the formula (7), a salt thereof, or an N-oxide. More preferred is an agricultural and horticultural fungicide containing as an active ingredient at least one of a nitrogen-containing heteroaryl derivative represented by the formula (8), a salt thereof, or an N-oxide.
  • the fifth aspect of the present invention is a production intermediate used for the production of the nitrogen-containing heteroaryl derivative of the present invention, a salt thereof, or N-oxide. That is, it is a nitrogen-containing heteroaryl derivative represented by the formula (9).
  • R 1 is an unsubstituted or substituted C1-6 alkyl group.
  • R 2 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, a formula: COR 21 (wherein R 21 has a hydrogen atom, an unsubstituted or substituted group) C1-6 alkyl group, unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, A substituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted heteroaryl group.
  • R 22 is, C1 ⁇ 6 alkyl group having an unsubstituted or substituted group, C2 ⁇ 6 alkenyl groups having an unsubstituted or substituted, unsubstituted or location Group having C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 cycloalkenyl group, unsubstituted or substituted C6-10 An aryl group, or an unsubstituted or substituted heteroaryl group.
  • CON (R 21 ) 2 wherein R 21 has the same meaning as described above; R 21 May be the same or different.
  • a 1 is an oxygen atom, a sulfur atom, or a formula: NR 3 (wherein R 3 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or Substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 A cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted heteroaryl group.
  • R 3 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or Substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalky
  • a 2 is an oxygen atom
  • Formula: NR 4 (wherein R 4 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, Formula: COR 21 , Formula: CO 2 R 22 , or a group represented by the formula: CON (R 21 ) 2 (wherein R 21 and R 22 have the same meanings as described above, and R 21 may be the same or different).
  • a group represented by the formula: CR 5 R 6 (wherein R 5 and R 6 are each independently a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, or a halogen atom) It is a group represented by.
  • J is an oxygen atom or a sulfur atom.
  • X is C1 ⁇ 6 alkyl group having an unsubstituted or substituted group of the formula: OR 23 (wherein, R 23 represents a hydrogen atom, C1 ⁇ 6 alkyl having unsubstituted or substituted Group, unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted A C4-8 cycloalkenyl group having a group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted heteroaryl group, a formula: COR 21 , a formula: CO 2 R 22 , or a formula : CON (R 21 ) 2 (in the formula, R 21 and R 22 have the same meanings as described above.
  • R 21 may be the same or different.
  • Formula: SR 23 Formula: N (R 23) 2 ( . Wherein, R 23 is .R 23 is the same meaning as above, which may be the same or different) a group represented by a cyano group, a nitro group or a halogen atom, is there.
  • n represents the number of X and is an integer of 0 to 3. When n is 2 or more, Xs may be the same or different.
  • B 1 to B 4 are each independently a nitrogen atom or a carbon atom. However, B 1 to B 3 are not all nitrogen atoms, and B 1 to B 4 are not all carbon atoms.
  • R 7 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted C2 An -6 alkynyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or It is an unsubstituted or substituted heteroaryl group.
  • a preferred production intermediate is a nitrogen-containing heteroaryl derivative represented by the formula (10), a salt thereof, or N-oxide.
  • R 1 , R 2 , A 1 , A 2 , J, X, n, and R 7 have the same meaning as in formula (9).
  • the sixth aspect of the present invention is a production intermediate used for the production of the nitrogen-containing heteroaryl derivative of the present invention, a salt thereof, or N-oxide. That is, it is a nitrogen-containing heteroaryl derivative represented by the formula (11).
  • R 1 is an unsubstituted or substituted C1-6 alkyl group.
  • R 2 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, a formula: COR 21 (wherein R 21 has a hydrogen atom, an unsubstituted or substituted group) C1-6 alkyl group, unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, A substituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted heteroaryl group.
  • R 22 is, C1 ⁇ 6 alkyl group having an unsubstituted or substituted group, C2 ⁇ 6 alkenyl groups having an unsubstituted or substituted, unsubstituted or A substituted C2-6 alkynyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6 ⁇ Or a group represented by the formula: CON (R 21 ) 2 (wherein R 21 has the same meaning as described above). 21 may be the same or different.)
  • a 1 is an oxygen atom, a sulfur atom, or a formula: NR 3 (wherein R 3 is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or Substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 A cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted heteroaryl group.
  • R 3 is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or Substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cyclo
  • a 2 is an oxygen atom
  • Formula: NR 4 (wherein R 4 is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, Formula: COR 21 , Formula: CO 2 R 22 , or a group represented by the formula: CON (R 21 ) 2 (wherein R 21 and R 22 have the same meanings as described above, and R 21 may be the same or different).
  • a group represented by the formula: CR 5 R 6 (wherein R 5 and R 6 are each independently a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, or a halogen atom) It is a group represented by.
  • J is an oxygen atom or a sulfur atom.
  • X is C1 ⁇ 6 alkyl group having an unsubstituted or substituted group of the formula: OR 23 (wherein, R 23 represents a hydrogen atom, C1 ⁇ 6 alkyl having unsubstituted or substituted Group, unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted A C4-8 cycloalkenyl group having a group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted heteroaryl group, a formula: COR 21 , a formula: CO 2 R 22 , or a formula : CON (R 21 ) 2 (in the formula, R 21 and R 22 have the same meanings as described above.
  • R 21 may be the same or different.
  • Formula: SR 23 Formula: N (R 23) 2 ( . Wherein, R 23 is .R 23 is as defined above, which may be the same or different) a group represented by a cyano group, a nitro group or a halogen atom, It is.
  • n represents the number of X and is an integer from 0 to 3. When n is 2 or more, Xs may be the same or different.
  • B 1 to B 4 are each independently a nitrogen atom or a carbon atom. However, B 1 to B 3 are not all nitrogen atoms, and B 1 to B 4 are not all carbon atoms.
  • R 7 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted C2 An -6 alkynyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or It is an unsubstituted or substituted heteroaryl group.
  • each R 9 is independently a hydrogen atom or a group represented by the formula: COR 21 (wherein R 21 has the same meaning as described above). R 9 may be the same or different. R 9 may be together.
  • a preferred production intermediate is a nitrogen-containing heteroaryl derivative represented by the formula (12), a salt thereof, or N-oxide.
  • R 1 , R 2 , A 1 , A 2 , J, X, n, R 7 , and R 9 have the same meaning as in formula (11).
  • the nitrogen-containing heteroaryl derivative of the present invention, a salt thereof, or N-oxide is a novel compound, and can be produced industrially advantageously, and is useful as an active ingredient in agricultural and horticultural fungicides that can be used safely and reliably. is there.
  • the agricultural and horticultural fungicide of the present invention is an agent that has an excellent control effect, does not cause phytotoxicity or contamination on the plant body, and has little toxicity to human fish and environmental impact.
  • Nitrogen-containing heteroaryl derivative of the present invention is a compound represented by the formula (1).
  • the number of substituents may be one, or two or more. Two or more substituents may be the same or different.
  • a group serving as a mother nucleus is a C1-6 alkyl group, and any of these hydrogen atoms is substituted with a group having a different structure ("substituent") It is.
  • a C1-6 alkyl group is a saturated aliphatic hydrocarbon group having 1-6 carbon atoms.
  • the C1-6 alkyl group may be linear or branched. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, s-butyl group, t-butyl group, Examples include isopentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, isohexyl group and the like.
  • a halogen-substituted C1-6 alkyl group is a C1-6 alkyl group substituted with 1-13 halogen atoms.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • fluoromethyl group chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2,2,2-trifluoro Ethyl group, 2,2,2-trichloroethyl group, pentafluoroethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 3,3,3-trifluoropropyl group, 2,2,2-trifluoro-1 -Trifluoromethylethyl group, perfluorohexyl group, perchlorohexyl group, 2,4,6-trichlorohexyl group and the like can be mentioned.
  • a C2-6 alkenyl group is an aliphatic hydrocarbon group having from 2 to 6 carbon atoms and having at least one carbon-carbon double bond.
  • the C2-6 alkenyl group may be a straight chain or a branched chain.
  • a C2-6 alkynyl group is an aliphatic hydrocarbon group having from 2 to 6 carbon atoms and having at least one carbon-carbon triple bond.
  • the C2-6 alkynyl group may be linear or branched. Specifically, ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group 1-hexynyl group, 1-methyl-2-propynyl group, 2-methyl-3-butynyl group, 1-methyl-2-butynyl group, 2-methyl-3-pentynyl group, 1,1-dimethyl-2- A butynyl group etc. can be mentioned.
  • a C3-8 cycloalkyl group is a saturated alicyclic hydrocarbon group having 3-8 carbon atoms. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • a C4-8 cycloalkenyl group is an alicyclic hydrocarbon group having 4-8 carbon atoms and having at least one carbon-carbon double bond. Specific examples include 1-cyclobutenyl group, 1-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 3-cyclohexenyl group, 3-cycloheptenyl group, 4-cyclooctenyl group and the like.
  • a C6-10 aryl group is an aromatic hydrocarbon group having 6-10 carbon atoms.
  • the C6-10 aryl group may have one ring or two or more rings.
  • the remaining ring may be a saturated alicyclic ring, an unsaturated alicyclic ring, or an aromatic ring.
  • Specific examples include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and the like.
  • 1,2,3,4-tetrahydro-naphthalen-1-yl group 1,2,3,4-tetrahydro-naphthalen-2-yl group, 5,6,7,8-tetrahydro-naphthalene-1- And tetralinyl groups such as an yl group and a 5,6,7,8-tetrahydro-naphthalen-2-yl group.
  • the heteroaryl group is a 5- to 10-membered aryl group containing 1 to 4 heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom in addition to carbon atoms as atoms constituting the ring. In this case, it may be a single ring or a polycyclic ring condensed. Specific examples of the heteroaryl group include the following groups.
  • 5-membered heteroaryl group pyrrolyl group such as pyrrol-1-yl group, pyrrol-2-yl group and pyrrol-3-yl group; Furyl groups such as a furan-2-yl group and a furan-3-yl group; Thienyl groups such as a thiophen-2-yl group and a thiophen-3-yl group; Imidazolyl groups such as imidazol-1-yl group, imidazol-2-yl group, imidazol-4-yl group, imidazol-5-yl group; Pyrazolyl groups such as a pyrazol-1-yl group, a pyrazol-3-yl group, a pyrazol-4-yl group, a pyrazol-5-yl group; An oxazolyl group such as an oxazol-2-yl group, an oxazol-4-yl group, an oxazol-5-yl group; Isoxazo
  • pyridyl groups such as a 6-membered heteroaryl group pyridin-2-yl group, pyridin-3-yl group and pyridin-4-yl group; Pyrazinyl groups such as a pyrazin-2-yl group and a pyrazin-3-yl group; Pyrimidyl groups such as a pyrimidin-2-yl group, a pyrimidin-4-yl group, and a pyrimidin-5-yl group; Pyridazinyl groups such as a pyridazin-3-yl group and a pyridazin-4-yl group; A triazinyl group;
  • Examples of the group represented by the formula: COR 31 include formyl group, acetyl group, propionyl group, n-propylcarbonyl group, n-butylcarbonyl group, pentanoyl group, valeryl group, i-propylcarbonyl group, i-butyl.
  • Alkylcarbonyl groups such as carbonyl group, pivaloyl group and isovaleryl group; alkenylcarbonyl groups such as acryloyl group and methacryloyl group; alkynylcarbonyl groups such as propioyl group; arylcarbonyl groups such as benzoyl group and naphthylcarbonyl group; pyridin-2-yl Examples thereof include heteroarylcarbonyl groups such as carbonyl group and thienylcarbonyl group; benzylcarbonyl group, phenethylcarbonyl group, pyridin-2-ylmethylcarbonyl group and the like.
  • Examples of the group represented by the formula: CO 2 R 31 include a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, and an i-butoxycarbonyl group.
  • T-butoxycarbonyl group n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, vinyloxycarbonyl group, cyclopropylmethyloxycarbonyl group, 2-cyclopentylethyloxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, Examples thereof include a benzyloxycarbonyl group and a 2-pyridylmethyloxycarbonyl group.
  • Examples of the group represented by the formula: CON (R 31 ) 2 include a mono C1-6 alkylcarbamoyl group such as a carbamoyl group, a methylcarbamoyl group, and an ethylcarbamoyl group; a vinylcarbamoyl group, a 1-propenylcarbamoyl group, 1- Mono-C2-6 alkenylcarbamoyl groups such as hexenylcarbamoyl group; mono-C2-6 alkynylcarbamoyl groups such as ethynylcarbamoyl group, propynylcarbamoyl group, propargylcarbamoyl group; mono- such as cyclopropylcarbamoyl group, cyclobutylcarbamoyl group, cyclohexylcarbamoyl group C3-8 cycloalkylcarbamoyl group; mono C4
  • Examples of the group represented by the formula: SO 2 R 31 include a methanesulfonyl group, an ethanesulfonyl group, a benzenesulfonyl group, and the like.
  • OR 32 examples include a hydroxyl group; a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an i-propoxy group, i -Butoxy, s-butoxy, t-butoxy, 1-ethylpropoxy, isohexyloxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 1-methylpent Toxi group, 3,3-dimethylbutoxy group, 2,2-dimethylbutoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,3-dimethylbutoxy group A C1-6 alkoxy group such as 1-ethylbutoxy group, 2-ethylbutoxy group; vinyloxy group, 1-propenyloxy group, 2-propenyloxy group, 1-butyl Nyloxy group, 2-but
  • the group represented by SR 32 for example, mercapto group; methylsulfanyl group, ethylsulfanyl group, C1 ⁇ 6 alkylsulfanyl group such as n- hexylsulfanyl group; vinyl sulfanyl group, 1-propenyl Nils Alpha group, 1 A C2-6 alkenylsulfanyl group such as a hexenylsulfanyl group; a C2-6 alkynylsulfanyl group such as an ethynylsulfanyl group, a propynylsulfanyl group, a propargylsulfanyl group; 8 cycloalkylsulfanyl groups; C4-8 cycloalkenylsulfanyl groups such as cyclobut-2-enylsulfanyl groups and cyclohex-2-enylsulfanyl groups; phenylsulfanyl groups
  • carboxysulfanyl groups carbamoylsulfanyl groups, methylcarbamoylsulfanyl groups, ethylcarbamoylsulfanyl groups, dimethylcarbamoylsulfanyl groups, diethylcarbamoylsulfanyl groups, phenylcarbamoylsulfanyl groups, etc. monosubstituted carbamoylsulfanyl groups or disubstituted carbamoylsulfanyl groups Can be mentioned.
  • N (R 32 ) 2 examples include mono C1-6 alkylamino groups such as methylamino group, ethylmethyl group, n-hexylamino group; vinylamino group, 1-propenylamino group Mono-C2-6 alkenylamino groups such as 1-hexenylamino group; mono-C2-6 alkynylamino groups such as ethynylamino group, propynylamino group, propargylamino group; cyclopropylamino group, cyclobutylamino group, cyclohexylamino group Mono C3-8 cycloalkylamino groups such as: mono C4-8 cycloalkenylamino groups such as cyclobut-2-enylamino group, cyclohex-2-enylamino group; mono C6-10 such as phenylamino group, 1-naphthylamino group, etc.
  • C1-7 acylamino group C1-7 carboxyamino group such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, vinyloxycarbonylamino group, phenoxycarbonylamino group, pyridyloxycarbonylamino group; carbamoylamino Group, methylcarbamoylamino group, ethylcarbamoylamino group, dimethylcarbamoylamino group, diethylcarbamoylamino group, phenylcarbamoylamino group, monosubstituted carbamoylamino group or disubstituted Moiruamino group or the like;
  • Dimethylamino group diethylmethyl group, methyl-vinyl-amino group, methyl-ethynyl-amino group, methyl-cyclopropyl-amino group, methyl-cyclobut-2-enyl-amino group, methyl-phenyl-amino group, methyl- Examples include pyridin-2-yl-amino group, methyl-acetyl-amino group, methyl-methoxycarbonyl-amino group; methylideneamino group, ethylideneamino group, and the like.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 1 in the formula (1) is an unsubstituted or substituted C1-6 alkyl group.
  • the “C1-6 alkyl group” serving as a mother nucleus is as described above (hereinafter the same for R 2 to R 8 , R 21 to R 23 , X, and Q 1 ).
  • Suitable groups that can be a substituent of the C1-6 alkyl group include a halogen atom, a group represented by the formula: OR 32 , a C6-10 aryl group, and a heteroaryl group.
  • Examples of the C1-6 alkyl group having a substituent include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a trifluoromethyl group, a trichloromethyl group, and a tribromomethyl group.
  • R 1 is preferably an unsubstituted C1-6 alkyl group.
  • R 2 in formula (1) is a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, a group represented by formula: COR 21 , a group represented by formula: CO 2 R 22 , or A group represented by the formula: CON (R 21 ) 2 .
  • Suitable groups that can be a substituent of the C1-6 alkyl group include a halogen atom, a group represented by the formula: COR 31 , a group represented by the formula: OR 32 , a C6-10 aryl group, and a heteroaryl group. Can be mentioned.
  • Examples of the C1-6 alkyl group having a substituent include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxy n-propyl group, an ethoxymethyl group, an ethoxyethyl group, an n-propoxymethyl group, a C1-6 alkoxy C1-6 alkyl group such as i-propoxyethyl group, s-butoxymethyl group, t-butoxyethyl group, 1,2-dimethoxyethyl group, 2,2-dimethoxyethyl group; formyloxymethyl group, And C1-7 acyloxy C1-6 alkyl groups such as an acetoxymethyl group, 2-acetoxyethyl group, propionyloxymethyl group, propionyloxyethyl group, and the like.
  • R 21 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted C2-6 alkynyl group, A substituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted group Is a heteroaryl group having
  • An unsubstituted or substituted C2-6 alkenyl group has a “C2-6 alkenyl group” as a mother nucleus.
  • the “C2-6 alkenyl group” serving as a mother nucleus is as described above (hereinafter the same in R 3 , R 7 , R 8 , R 22 , R 23 , and Q 1 ).
  • a suitable group that can be a substituent of the C2-6 alkenyl group is a halogen atom.
  • Examples of the C2-6 alkenyl group having a substituent include, for example, 3-chloro-2-propenyl group, 4-chloro-2-butenyl group, 4,4-dichloro-3-butenyl group, 4,4-difluoro-3 -Butenyl group, 3,3-dichloro-2-propenyl group, 2,3-dichloro-2-propenyl group, 3,3-difluoro-2-propenyl group, 2,4,6-trichloro-2-hexenyl group, etc.
  • a C2-6 haloalkenyl group a C2-6 haloalkenyl group.
  • An unsubstituted or substituted C2-6 alkynyl group has a “C2-6 alkynyl group” as a mother nucleus.
  • the “C2-6 alkynyl group” serving as a mother nucleus is as described above (hereinafter the same for R 3 , R 7 , R 8 , R 22 , R 23 , and Q 1 ).
  • a suitable group that can be a substituent of the C2-6 alkynyl group is a halogen atom.
  • Examples of the C2-6 alkynyl group having a substituent include a 3-chloro-1-propynyl group, a 3-chloro-1-butynyl group, a 3-bromo-1-butynyl group, a 3-bromo-2-propynyl group, Halo such as 3-iodo-2-propynyl group, 3-bromo-1-hexynyl group, 5,5-dichloro-2-methyl-3-pentynyl group, 4-chloro-1,1-dimethyl-2-butynyl group, etc.
  • An alkynyl group etc. can be mentioned.
  • An unsubstituted or substituted C3-8 cycloalkyl group has a “C3-8 cycloalkyl group” as a mother nucleus.
  • the “C3-8 cycloalkyl group” serving as a mother nucleus is as described above (hereinafter the same for R 3 , R 7 , R 8 , R 22 , R 23 , and Q 1 ).
  • An unsubstituted or substituted C4-8 cycloalkenyl group has a “C4-8 cycloalkenyl group” as a mother nucleus.
  • the “C4-8 cycloalkenyl group” serving as a mother nucleus is as described above (hereinafter the same for R 3 , R 7 , R 8 , R 22 , R 23 , and Q 1 ).
  • An unsubstituted or substituted C6-10 aryl group has a “C6-10 aryl group” as a mother nucleus.
  • the C6-10 aryl group serving as a mother nucleus is as described above (hereinafter the same for R 3 , R 7 , R 8 , R 22 , R 23 , and Q 41 ).
  • An unsubstituted or substituted heteroaryl group has a “heteroaryl group” as a mother nucleus.
  • the heteroaryl group serving as a mother nucleus is as described above (hereinafter the same in R 3 , R 7 , R 8 , R 22 , R 23 , and Q 41 ).
  • Examples of the group represented by the formula: COR 21 include formyl group, acetyl group, propionyl group, n-propylcarbonyl group, n-butylcarbonyl group, pentanoyl group, valeryl group, i-propylcarbonyl group, i-butyl.
  • Alkylcarbonyl groups such as carbonyl group, pivaloyl group and isovaleryl group; alkenylcarbonyl groups such as acryloyl group and methacryloyl group; alkynylcarbonyl groups such as propioloyl group; arylcarbonyl groups such as benzoyl group and naphthylcarbonyl group; 2-pyridylcarbonyl group A heteroarylcarbonyl group such as thienylcarbonyl group; benzylcarbonyl group, phenethylcarbonyl group, 2-pyridylmethylcarbonyl group; monofluoroacetyl group, monochloroacetyl group, monobromoacetyl group, difluoro Cetyl group, dichloroacetyl group, dibromoacetyl group, trifluoroacetyl group, trichloroacetyl group, tribromoacetyl group, 3,3,3-trifluoropro
  • R 22 is an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted C2-6 alkynyl group, unsubstituted or A substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted hetero An aryl group.
  • Examples of the group represented by the formula: CO 2 R 22 include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, t- Butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, vinyloxycarbonyl group, cyclopropylmethyloxycarbonyl group, 2-cyclopentylethyloxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, benzyloxycarbonyl And 2-pyridylmethyloxycarbonyl group.
  • R 21 has the same meaning as described above. Note that two R 21 may be the same or different.
  • Examples of the group represented by the formula: CON (R 21 ) 2 include mono-C1-6 alkylcarbamoyl groups such as carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group; vinylcarbamoyl group, 1-propenylcarbamoyl group, 1- Mono-C2-6 alkenylcarbamoyl groups such as hexenylcarbamoyl group; mono-C2-6 alkynylcarbamoyl groups such as ethynylcarbamoyl group, propynylcarbamoyl group, propargylcarbamoyl group; mono- such as cyclopropylcarbamoyl group, cyclobutylcarbamoyl group, cyclohexylcarbamoyl group C3-8 cycloalkylcarbamoyl group; mono C4-8 cycloalkenylcarbam
  • R 2 is preferably a hydrogen atom.
  • a 1 in the formula (1) is an oxygen atom, a sulfur atom, or a group represented by the formula: NR 3 .
  • R 3 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted C2-6 alkynyl group, A substituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted group Is a heteroaryl group having Of these, A 1 is preferably an oxygen atom.
  • a 2 in the formula (1) is an oxygen atom, a group represented by the formula: NR 4 , or a group represented by the formula: CR 5 R 6 .
  • R 4 represents a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, a group represented by the formula: COR 21 , a group represented by the formula: CO 2 R 22 , or a formula: CON ( R 21 ) is a group represented by 2 .
  • R 5 and R 6 are each independently a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or a halogen atom. Of these, A 2 is preferably an oxygen atom.
  • [J] J in Formula (1) is an oxygen atom or a sulfur atom.
  • [X] X in formula (1) is an unsubstituted or substituted C1-6 alkyl group, formula: a group represented by OR 23 , formula: a group represented by SR 23 , formula: N (R 23 ) 2 is a group represented by 2 , a cyano group, a nitro group, or a halogen atom.
  • the subscript n of X represents the number of X and is an integer from 0 to 3. When n is 2 or more, Xs may be the same or different.
  • R 23 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted C2-6 alkynyl group, A substituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted group A heteroaryl group having the formula: COR 21 , Formula: CO 2 R 22 , or Formula: CON (R 21 ) 2 .
  • OR 23 examples include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, i-propoxy, and i-butoxy.
  • a carbamoylsulfanyl group a mono-carbamoylsulfanyl group such as a carbamoylsulfanyl group, a methylcarbamoylsulfanyl group, an ethylcarbamoylsulfanyl group, a dimethylcarbamoylsulfanyl group, a diethylcarbamoylsulfanyl group, or a phenylcarbamoylsulfanyl group; it can.
  • N (R 23 ) 2 examples include mono C1-6 alkylamino groups such as a methylamino group, an ethylmethyl group, and an n-hexylamino group; a vinylamino group, a 1-propenylamino group Mono-C2-6 alkenylamino groups such as 1-hexenylamino group; mono-C2-6 alkynylamino groups such as ethynylamino group, propynylamino group, propargylamino group; cyclopropylamino group, cyclobutylamino group, cyclohexylamino group Mono C3-8 cycloalkylamino groups such as: mono C4-8 cycloalkenylamino groups such as cyclobut-2-enylamino group, cyclohex-2-enylamino group; mono C6-10 such as phenylamino group, 1-naphthyla
  • C1-7 acylamino group C1-7 carboxyamino group such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, vinyloxycarbonylamino group, phenoxycarbonylamino group, pyridyloxycarbonylamino group; carbamoylamino Group, methylcarbamoylamino group, ethylcarbamoylamino group, dimethylcarbamoylamino group, diethylcarbamoylamino group, phenylcarbamoylamino group, monosubstituted carbamoylamino group or disubstituted Moiruamino group or the like;
  • Dimethylamino group diethylmethyl group, methyl-vinyl-amino group, methyl-ethynyl-amino group, methyl-cyclopropyl-amino group, methyl-cyclobut-2-enyl-amino group, methyl-phenyl-amino group, methyl- Disubstituted amino groups such as pyridin-2-yl-amino group, methyl-acetyl-amino group, methyl-methoxycarbonyl-amino group; amino groups in which nitrogen atoms such as methylideneamino group and ethylideneamino group are bonded to the same carbon atom Etc.
  • X is preferably an unsubstituted or substituted C1-6 alkyl group or a halogen atom.
  • a suitable group that can be a substituent is a halogen atom.
  • B 1 to B 4 are each independently a nitrogen atom or a carbon atom. However, B 1 to B 3 are not all nitrogen atoms, and B 1 to B 4 are not all carbon atoms.
  • B 1 to B 4 are not all nitrogen atoms.
  • structures of the formulas (A-1) to (A-6) structures below the double and X is omitted). Things can be mentioned.
  • the structure represented by the formula (A-1) is a structure in which B 1 , B 2 , B 3 , and B 4 are each composed of a nitrogen atom, a carbon atom, a carbon atom, and a carbon atom.
  • the structure represented by the formula (A-4) is a structure in which B 1 , B 2 , B 3 , and B 4 are each composed of a carbon atom, a carbon atom, a nitrogen atom, and a carbon atom.
  • the structure represented by the formula (A-5) is a structure in which B 1 , B 2 , B 3 , and B 4 are each composed of a carbon atom, a carbon atom, a carbon atom, and a nitrogen atom. Of these structures, the structure of the formula (A-1) is preferable.
  • [D] D is any group represented by the formulas (2) to (6).
  • the carbon nitrogen double bond in the formula (2) represents any of geometric isomers (E / Z isomers) or a mixture thereof.
  • Each of the two carbon nitrogen double bonds in the formula (3) represents one of geometric isomers (E / Z isomer) or a mixture thereof.
  • the carbon nitrogen double bond in the formula (6) represents any of geometric isomers (E / Z isomers) or a mixture thereof.
  • Q 1 represents an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, an unsubstituted or substituted group. Having C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 cycloalkenyl group, unsubstituted or substituted C6-10 aryl group An unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted heteroaralkyl group, or a trisubstituted silyl group. Examples of the tri-substituted silyl group include trimethylsilyl group, triethylsilyl group, tricyclopropylsilyl group, t-butyldimethylsilyl group and the like.
  • Preferred Q 1 in the formula (2) is an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted aralkyl group, or an unsubstituted or substituted heteroaralkyl group.
  • a C6-10 aryl group is an aromatic hydrocarbon group having 6-10 carbon atoms.
  • the C6-10 aryl group may have one ring or two or more rings.
  • the remaining ring may be a saturated alicyclic ring, an unsaturated alicyclic ring, or an aromatic ring.
  • Specific examples include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and the like.
  • 1,2,3,4-tetrahydro-naphthalen-1-yl group 1,2,3,4-tetrahydro-naphthalen-2-yl group, 5,6,7,8-tetrahydro-naphthalene-1- And tetralinyl groups such as an yl group and a 5,6,7,8-tetrahydro-naphthalen-2-yl group.
  • An aralkyl group is a C1-6 alkyl group substituted with a C6-10 aryl group. Specific examples include a benzyl group, a phenethyl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group.
  • the heteroaryl group is a 5- to 10-membered aryl group containing 1 to 4 heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom in addition to carbon atoms as atoms constituting the ring. In this case, it may be a single ring or a polycyclic ring condensed. Specific examples of the heteroaryl group include the following groups.
  • 5-membered heteroaryl group pyrrolyl group such as pyrrol-1-yl group, pyrrol-2-yl group and pyrrol-3-yl group; Furyl groups such as a furan-2-yl group and a furan-3-yl group; Thienyl groups such as a thiophen-2-yl group and a thiophen-3-yl group; Imidazolyl groups such as imidazol-1-yl group, imidazol-2-yl group, imidazol-4-yl group, imidazol-5-yl group; Pyrazolyl groups such as a pyrazol-1-yl group, a pyrazol-3-yl group, a pyrazol-4-yl group, a pyrazol-5-yl group; An oxazolyl group such as an oxazol-2-yl group, an oxazol-4-yl group, an oxazol-5-yl group; Isoxazo
  • pyridyl groups such as a 6-membered heteroaryl group pyridin-2-yl group, pyridin-3-yl group and pyridin-4-yl group; Pyrazinyl groups such as a pyrazin-2-yl group and a pyrazin-3-yl group; Pyrimidyl groups such as a pyrimidin-2-yl group, a pyrimidin-4-yl group, and a pyrimidin-5-yl group; Pyridazinyl groups such as a pyridazin-3-yl group and a pyridazin-4-yl group; A triazinyl group;
  • the heteroaralkyl group is a C1-6 alkyl group substituted with a heteroaryl group.
  • the C1-6 alkyl group substituted with a heteroaryl group is a C1-6 alkyl group substituted with a 5-membered nitrogen-containing heteroaryl group, or a C1-6 substituted with a 6-membered nitrogen-containing heteroaryl group.
  • Alkyl groups are preferred. Specifically, pyridyl C1-6 alkyl groups such as pyridin-2-ylmethyl group, pyridin-3-ylmethyl group, pyridin-4-ylmethyl group; pyrazol-1-ylmethyl group, pyrazol-3-ylmethyl group, pyrazole- And a pyrazolyl C1-6 alkyl group of a 4-ylmethyl group.
  • a suitable group that can be a substituent of the aralkyl group or heteroaralkyl group is a C1-6 alkyl group, a halogen-substituted C1-6 alkyl group, or a halogen atom.
  • Preferred Q 1 in the formula (3) is an unsubstituted or substituted C6-10 aryl group or an unsubstituted or substituted heteroaryl group. Specific examples include an unsubstituted or substituted phenyl group, an unsubstituted or substituted pyridyl group, and the like.
  • a preferred group that can be a substituent of the aryl group or heteroaryl group is a halogen atom.
  • Preferred Q 1 in the formula (4) is an unsubstituted or substituted C1-6 alkyl group.
  • Preferred Q 1 in formula (5) is an aralkyl group which is unsubstituted or has a substituent (particularly preferably a C6-10 aryl-substituted C1-6 alkyl group which is unsubstituted or has a substituent) or an unsubstituted or substituted A heteroaralkyl group having a group (particularly preferably, an unsubstituted or substituted heteroaryl-substituted C1-6 alkyl group). Specific examples include an unsubstituted or substituted benzyl group, an unsubstituted or substituted pyridylmethyl group, and the like.
  • a preferred group that can be a substituent of the aralkyl group or heteroaralkyl group is a C1-6 alkyl group, a halogen-substituted C1-6 alkyl group, or a halogen atom.
  • R 7 in formula (2), formula (3), and formula (6) is a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl Group, unsubstituted or substituted C2-6 alkynyl group, unsubstituted or substituted C3-8 cycloalkyl group, unsubstituted or substituted C4-8 cycloalkenyl group, unsubstituted or A C6-10 aryl group having a substituent, or an unsubstituted or substituted heteroaryl group.
  • Preferred R 7 is a C1-6 alkyl group.
  • each R 8 independently represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C2-6 alkenyl group, unsubstituted or substituted.
  • R 8 may further be bonded to a carbon atom on Q 1 or a nitrogen atom.
  • Preferred R 8 is a C1-6 alkyl group.
  • Q 41 is a C6-10 aryl group or heteroaryl group.
  • Q 1 and / or Q 2 may be substituted as shown in Formula (5).
  • Preferred Q 41 is a phenyl group or a 5-membered heteroaryl group.
  • a preferred 5-membered heteroaryl group is a 5-membered nitrogen-containing heteroaryl group.
  • pyrazolyl groups such as pyrazol-1-yl group, pyrazol-3-yl group, pyrazol-4-yl group; thiazol-2-yl group, thiazol-4-yl group, thiazol-5-yl group And the like.
  • Q 2 in the formula (5) is a group represented by the formula: OR 23 , a group represented by the formula: SR 23 , a group represented by the formula: N (R 23 ) 2 , a formula: COR 21
  • Group represented by the formula: CO 2 R 22 group represented by the formula: CON (R 21 ) 2
  • group represented by the formula: SO 2 R 22 cyano group, nitro group, or halogen Is an atom.
  • Examples of the group represented by the formula: SO 2 R 22 include a methanesulfonyl group, an ethanesulfonyl group, and a benzenesulfonyl group.
  • m1 represents the number of Q 1 and is an integer from 0 to 7.
  • m2 represents the number of Q 2, is any integer of 0-7. However, the sum of m1 and m2 is 7 or less.
  • Q 1 each other may be the same or different.
  • Q 2 to each other may be the same or different.
  • Q 1 , Q 2 , or Q 1 and Q 2 that are adjacently substituted on Q 41 may be bonded to each other to form a 5- to 8-membered ring.
  • the 5- to 8-membered ring include an aliphatic hydrocarbon ring and an unsaturated heterocyclic ring.
  • Examples of the aliphatic hydrocarbon ring include a cycloalkene ring, and examples of the cycloalkene ring include a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring.
  • Examples of the unsaturated heterocycle include a dihydro-2H-pyran ring, a dihydro-2H-thiopyran ring, and a tetrahydropyridine ring.
  • the nitrogen-containing heteroaryl derivative of the present invention is preferably a compound represented by the formula (7). More preferably, it is a compound represented by Formula (8).
  • the present invention includes a salt of nitrogen-containing heteroaryl derivative represented by the formula (1) and N-oxide.
  • Nitrogen-containing heteroaryl derivatives, salts of nitrogen-containing heteroaryl derivatives and N-oxides are sometimes collectively referred to as “the present compound”.
  • the salt is not particularly limited as long as it is an agricultural and horticulturally acceptable salt. Examples thereof include salts of inorganic acids such as hydrochloric acid and sulfuric acid; salts of organic acids such as acetic acid and lactic acid.
  • Examples of N-oxides include compounds in which any nitrogen in the partial structures represented by the above formulas (A-1) to (A-6) is oxidized.
  • R 1 , R 2 , R 7 , A 1 , A 2 , J, X, n, B 1 to B 4 , and Q 1 have the same meanings as described above.
  • the amount of compound (B-1) to be used is generally 0.5 to 2 mol, preferably 0.7 to 1.5 mol, per 1 mol of compound (B-2). Although this reaction can be performed in the absence of a catalyst, it is preferably performed in the presence of an acid catalyst or a base catalyst, and more preferably in the presence of an acid catalyst.
  • the acid catalyst examples include trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, pyridinium p-toluenesulfonate, hydrochloric acid, sulfuric acid, and the like.
  • the base catalyst examples include pyridine, triethylamine, potassium hydroxide and the like.
  • the amount of the catalyst to be used is generally 0.0001-1 mol per 1 mol of compound (B-2).
  • a dehydrating agent such as anhydrous sodium sulfate or molecular sieve may be added to the reaction system.
  • This reaction can be carried out in a solvent.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane
  • Solvent Halogenated hydrocarbon solvent such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane
  • Amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone
  • nitrile solvents such as acetonitrile and benzonitrile
  • alcohol solvents such as methanol, ethanol and n-propanol
  • mixed solvents composed of two or more of these solvents
  • the reaction temperature is a temperature range from room temperature to the boiling point of the solvent used.
  • the reaction time is usually several minutes to several tens of hours depending on the reaction scale.
  • Compound (B-2) can be produced according to a conventionally known method for producing an oxyamine compound. For example, as shown below, the compound represented by the formula (B-2-1) is reacted with carbon tetrabromide and triphenylphosphine to obtain the compound represented by the formula (B-2-2). . This is reacted with Nt-butoxycarbonylhydroxylamine in the presence of a base to give an oxyamine compound represented by the formula (B-2-3) (hereinafter referred to as “compound (B-2-3)”). There are things.) Compound (B-2) can be obtained by reacting this with an acid.
  • compound (B-1: (A 2 ⁇ O)) is, for example, It can be produced by reaction.
  • R 1 , R 2 , R 7 , A 1 , J, X, n, and B 1 to B 4 have the same meanings as described above.
  • E 6 is a fluorine atom or a chlorine atom.
  • a dihalogeno compound represented by the formula (C-1) (hereinafter sometimes referred to as “compound (C-1)”) is added to the compound represented by the formula (C-2) in the presence of a base (
  • compound (C-2) the hydroxycarbamic acid compound represented by formula (C-3) (hereinafter referred to as “compound (C-3)”).
  • compound (C-3) the hydroxycarbamic acid compound represented by formula (C-3)
  • compound (C-3) hereinafter referred to as “compound (C-3)”.
  • the target compound (B-1: (A 2 ⁇ O)) can be obtained.
  • the amount of compound (C-2) used for the reaction with compound (C-1) is usually 0.8 to 5 mol, preferably 1 to 3 mol, relative to 1 mol of compound (C-1). .
  • Examples of the base used for the reaction between the compound (C-1) and the compound (C-2) include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide; sodium methoxy Metal alkoxides such as sodium ethoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide; metal hydrides such as sodium hydride, potassium hydride, calcium hydride; triethylamine, diisopropylethylamine, pyridine, 1,8 And organic bases such as diazabicyclo [5.4.0] undec-7-ene (DBU) and 1,4-diazabicyclo [2.2.2] octane.
  • the amount of the base used for the reaction between the compound (C-1) and the compound (C-2) is usually 1 to 20 mol with respect to 1 mol of the compound (C-1).
  • the reaction of compound (C-1) and compound (C-2) can be carried out in an organic solvent.
  • the organic solvent to be used is not particularly limited as long as it is inert to the reaction.
  • sulfur-containing solvents such as dimethyl sulfoxide and diethyl sulfoxide
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • n-pentane n- Aliphatic hydrocarbon solvents such as hexane and n-heptane
  • amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone
  • nitrile solvents such as acetonitrile and benzonitrile
  • the amount of the organic solvent to be used is not particularly limited, but is usually
  • Examples of the compound (C-4) used for the reaction with the compound (C-3) include N, N-dimethylacetamide, N, N-dimethylpropionamide and the like.
  • the amount of compound (C-4) to be used is generally 0.8 to 5 mol, preferably 1 to 3 mol, per 1 mol of compound (C-3).
  • Examples of the base used in the reaction between the compound (C-3) and the compound (C-4) include organolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, and lithium diisopropylamide; sodium metal, metal Examples thereof include alkali metals such as potassium; metal hydrides such as sodium hydride, potassium hydride and calcium hydride;
  • the amount of the base used for the reaction between the compound (C-3) and the compound (C-4) is usually 1 to 20 mol with respect to 1 mol of the compound (C-3).
  • the reaction of compound (C-3) and compound (C-4) can be carried out in an organic solvent.
  • the solvent used is not particularly limited as long as it is inert to the reaction.
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvent; and the like.
  • R 1 is a t-butyl group
  • R 2 is a hydrogen atom
  • a 1 and J are oxygen atoms
  • compound (B -1-1: (A 2 ⁇ O)) can be obtained by converting R 1 by the method shown below.
  • the following formula shows a reaction in which a t-butyl group is converted to another group R 1 ′ .
  • R 1 ′ is R 1 excluding the t-butyl group.
  • an acid is allowed to act on the compound, whereby a compound represented by the formula (B-1-4: (A 2 ⁇ O)) (hereinafter referred to as “compound (B-1-4: (A 2 ⁇ O))”) Can be obtained.)
  • Examples of the base used for the reaction of the compound (B-1-1: (A 2 ⁇ O)) and the ester compound (B-1-2) include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, Metal hydroxide such as calcium hydroxide; metal alkoxide such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide; metal hydrogen such as sodium hydride, potassium hydride, calcium hydride
  • Organic bases such as triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,4-diazabicyclo [2.2.2] octane; be able to.
  • the amount of the base to be used is generally 1 to 20 mol per 1 mol of compound (B-1-1: (A 2 ⁇ O)).
  • the reaction of the compound (B-1-1: (A 2 ⁇ O)) and the ester compound (B-1-2) is performed in an organic solvent.
  • the organic solvent to be used is not particularly limited as long as it is inert to the reaction.
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and 1,2-dichloroethane
  • sulfur-containing solvents such as dimethyl sulfoxide and diethyl sulfoxide
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • Aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane
  • Amide solvents such as N-methylpyrrolidone
  • the amount of the organic solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of the compound (B-1-1: (A 2 ⁇ O)).
  • the reaction proceeds smoothly in a temperature range from ⁇ 20 ° C. to the boiling point of the solvent used.
  • the reaction time depends on the reaction scale, it is usually from several minutes to several tens of hours.
  • Examples of the acid used in the reaction for converting the compound (B-1-3: (A 2 ⁇ O)) into the compound (B-1-4: (A 2 ⁇ O)) include inorganic substances such as hydrochloric acid, sulfuric acid, and nitric acid.
  • Examples of the acid include acetic acid, trifluoroacetic acid, methanesulfonic acid, and p-toluenesulfonic acid.
  • the amount of the acid to be used is generally 1 to 20 mol per 1 mol of compound (B-1-3: (A 2 ⁇ O)).
  • This reaction is performed in an organic solvent.
  • the organic solvent to be used is not particularly limited as long as it is inert to the reaction.
  • Examples of the solvent that can be used in the reaction of the compound (B-1-1: (A 2 ⁇ O)) and the ester compound (B-1-2) are the same as those listed.
  • the reaction for converting the compound (B-1-3: (A 2 ⁇ O)) to the compound (B-1-4: (A 2 ⁇ O)) is performed at a temperature range from ⁇ 20 ° C. to the boiling point of the solvent used. Proceed smoothly. Although the reaction time depends on the reaction scale, it is usually from several minutes to several tens of hours.
  • D in Formula (1) is Formula (3) a)
  • the compound represented by formula (B-6) (hereinafter sometimes referred to as “compound (B-6)”) is: For example, it can be produced by reacting a hydrazine compound represented by formula (B-5) (hereinafter sometimes referred to as “compound (B-5)”) with compound (B-1). it can.
  • the amount of compound (B-1) to be used is generally 0.5 to 2 mol, preferably 0.7 to 1.5 mol, per 1 mol of compound (B-5).
  • R 1 , R 2 , R 7 , R 8 , A 1 , A 2 , J, X, n, B 1 to B 4 , and Q 1 have the same meanings as described above.
  • the reaction between the compound (B-1) and the compound (B-5) is preferably performed in the presence of an acid catalyst or a base catalyst, and more preferably performed in the presence of an acid catalyst.
  • the acid catalyst used include benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, pyridinium p-toluenesulfonate, hydrochloric acid, sulfuric acid and the like.
  • the base catalyst include pyridine, triethylamine, potassium hydroxide and the like.
  • the amount of the catalyst to be used is generally 0.0001-1 mol per 1 mol of compound (B-5).
  • a dehydrating agent such as anhydrous sodium sulfate may be added to the reaction system.
  • This reaction can be carried out in a solvent.
  • the solvent used is not particularly limited as long as it is inert to the reaction.
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane
  • Solvent Halogenated hydrocarbon solvent such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane
  • Amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone
  • nitrile solvents such as acetonitrile and benzonitrile
  • alcohol solvents such as methanol, ethanol and n-propanol
  • the amount of the solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of compound (B-5).
  • the reaction temperature is a temperature range from room temperature to the boiling point of the solvent used.
  • the reaction time is usually several minutes to several tens of hours.
  • Compound (B-5) is obtained, for example, by reacting a ketone compound represented by formula (B-5-1) with hydrazine (or hydrazine monohydrate) as shown below. be able to.
  • R 1 , R 2 , A 1 , J, X, n, B 1 to B 4 , and Q 1 have the same meanings as described above.
  • E 6 is a fluorine atom or a chlorine atom.
  • Compound (D-1) includes, for example, compound (C-1) and an acetylene compound represented by formula (D-1-1) (hereinafter referred to as “acetylene compound (D-1)” as shown below. -1) ").) Can be obtained.
  • the amount of the acetylene compound (D-1-1) to be used is generally 1 to 2 mol per 1 mol of the compound (C-1).
  • E 6 represents a fluorine atom or a chlorine atom.
  • This reaction is a coupling reaction called the Sonogashira reaction.
  • a Pd complex is usually used for this reaction.
  • the Pd complex include palladium (II) acetate, dichlorobis (triphenylphosphine) palladium (II), tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), and the like.
  • the amount of the Pd complex to be used is generally 0.01-0.5 mol per 1 mol of compound (C-1).
  • copper halide is further used as a catalyst.
  • the copper halide include monovalent copper halides such as cuprous fluoride, cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, Examples thereof include divalent copper halides such as cupric iodide.
  • the amount of copper halide to be used is generally 0.1-1 mol per 1 mol of compound (C-1).
  • a base is further used.
  • the base include sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, cesium carbonate, potassium phosphate and other inorganic bases, or triethylamine, pyridine, Examples include amines such as piperidine.
  • the amount of the base to be used is generally 1 to 10 mol per 1 mol of compound (C-1).
  • the organic solvent to be used is not particularly limited as long as it is inert to the reaction.
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvents
  • Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone
  • Nitrile solvents such as acetonitrile and benzonitrile
  • the amount of the organic solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of compound (C-1).
  • the reaction temperature should be a temperature sufficient to complete the coupling reaction, and is usually room temperature to 100 ° C.
  • the reaction time is usually several minutes to several tens of hours.
  • the reaction is preferably carried out in an inert gas atmosphere.
  • R 1 , R 2 , A 1 , J, X, n, B 1 to B 4 , Q 41 , Q 1 , m 1, Q 2 , and m 2 have the same meanings as described above.
  • E 6 represents , Fluorine atom or chlorine atom.
  • the compound (E-1) is obtained by adding a boronic acid compound represented by the formula (E-1-1) to the compound (C-1) (hereinafter referred to as “boronic acid compound (E -1-1) ”.
  • the amount of the boronic acid compound (E-1-1) used is usually 1 with respect to 1 mol of the compound (C-1). ⁇ 2 moles.
  • E 6 is a fluorine atom or a chlorine atom.
  • the reaction between the compound (C-1) and the boronic acid compound (E-1-1) is a coupling reaction called the Suzuki-Miyaura reaction.
  • a Pd catalyst is used for this reaction.
  • the Pd catalyst used in the reaction include tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium dichloride (II), “1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris ( Pd catalysts such as dibenzylideneacetone) dipalladium (0), palladium (II) acetate, palladium chloride, palladium carbon and the like can be mentioned.
  • the amount of the Pd catalyst to be used is generally 0.01-0.5 mol per 1 mol of compound (C-1).
  • a base is further used.
  • the base include hydrated or non-aqueous bases such as sodium carbonate, potassium carbonate, sodium hydroxide and cesium fluoride.
  • the amount of the base to be used is generally 1 to 10 mol per 1 mol of compound (C-1).
  • the organic solvent to be used is not particularly limited as long as it is inert to the reaction.
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvents
  • Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone
  • Nitrile solvents such as acetonitrile and benzonitrile
  • the amount of the organic solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of compound (C-1).
  • the reaction temperature should be a temperature that is sufficient to complete the coupling reaction, and is room temperature to 150 ° C.
  • the reaction time is usually several minutes to several tens of hours.
  • the reaction is preferably carried out in an inert gas atmosphere.
  • R 1 , R 2 , R 7 , R 8 , A 1 , A 2 , J, X, n, B 1 to B 4 , and Q 1 have the same meanings as described above.
  • the amount of compound (B-14) to be used is generally 0.5 to 2 mol, preferably 0.7 to 1.5 mol, per 1 mol of compound (F-1). Although this reaction can be performed in the absence of a catalyst, it is preferably performed in the presence of an acid catalyst or a base catalyst, and more preferably in the presence of an acid catalyst.
  • the acid catalyst examples include trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, pyridinium p-toluenesulfonate, hydrochloric acid, sulfuric acid, and the like.
  • the base catalyst examples include pyridine, triethylamine, potassium hydroxide and the like.
  • the amount of the catalyst to be used is generally 0.0001-1 mol per 1 mol of compound (F-1).
  • a dehydrating agent such as anhydrous sodium sulfate or molecular sieve may be added to the reaction system.
  • This reaction can be carried out in a solvent.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane
  • Solvent Halogenated hydrocarbon solvent such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane
  • Amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone
  • nitrile solvents such as acetonitrile and benzonitrile
  • alcohol solvents such as methanol, ethanol and n-propanol
  • mixed solvents composed of two or more of these solvents
  • the reaction temperature is a temperature range from room temperature to the boiling point of the solvent used.
  • the reaction time is usually several minutes to several tens of hours depending on the reaction scale.
  • compound (B-14: (A 2 ⁇ O)) is, for example, It can be produced by reaction.
  • R 1 , R 2 , R 7 , A 1 , J, X, n, and B 1 to B 4 have the same meaning as above.
  • E 7 is a chlorine atom or a bromine atom.
  • the compound (B-1: (A 2 ⁇ O)) is reduced to a hydroxyl group using a known hydride reducing agent, and then halogenated using a halogenating agent.
  • a compound represented by the formula (B-14-1: (A 2 ⁇ O)) (hereinafter sometimes referred to as “compound (B-14-1: (A 2 ⁇ O))”) can be obtained. it can.
  • Examples of the hydride reducing agent used in the reduction reaction include sodium borohydride, sodium cyanoborohydride, lithium triethylborohydride, lithium tri (sec-butyl) borohydride, potassium tri (sec-butyl) borohydride, hydrogen Examples thereof include lithium borohydride, zinc borohydride, sodium acetoxyborohydride, lithium aluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, and the like.
  • the amount of the hydride reducing agent used for the reduction reaction is usually 0.25 to 2 mol per 1 mol of the compound (B-1: (A 2 ⁇ O)).
  • the reduction reaction can be performed in an organic solvent.
  • the organic solvent to be used is not particularly limited as long as it is inert to the reaction.
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvent
  • a mixed solvent composed of two or more of these solvents and the like.
  • the amount of the organic solvent used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of the raw material.
  • the reduction reaction proceeds smoothly in the temperature range from ⁇ 20 ° C. to the boiling point of the solvent used.
  • halogenating agent used in the halogenation reaction examples include oxalyl halide, thionyl halide, a mixed reagent of carbon tetrabromide and triphenylphosphine;
  • the amount of the halogenating agent used in the halogenation reaction is usually 0.8 to 5 mol, preferably 1 to 3 mol, relative to 1 mol of the raw material.
  • the halogenation reaction can be performed in an organic solvent.
  • the organic solvent to be used is not particularly limited as long as it is inert to the reaction.
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvent
  • the amount of the organic solvent used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of the raw material.
  • the halogenation reaction proceeds smoothly in a temperature range from room temperature to the boiling point of the solvent used.
  • Examples of the base used in the reaction include alkali metals such as metal sodium and metal potassium; metal hydrides such as sodium hydride, potassium hydride and calcium hydride;
  • the amount of N-hydroxyphthalimide to be used is usually 1 to 5 mol with respect to 1 mol of the compound (B-14-1: (A 2 ⁇ O)).
  • the amount of the base used is usually 1 to 20 mol with respect to 1 mol of the compound (B-14-1: (A 2 ⁇ O)).
  • the reaction of the compound (B-14-1: (A 2 ⁇ O)) and N-hydroxyphthalimide can be carried out in an organic solvent.
  • the solvent used is not particularly limited as long as it is inert to the reaction.
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and 1,2-dichloroethane
  • sulfur-containing solvents such as dimethyl sulfoxide and diethyl sulfoxide
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • Aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane
  • Amide solvents such as N-methylpyrrolidone
  • the amount of hydrazine to be used is usually 1 to 10 mol per 1 mol of compound (B-14-2: (A 2 ⁇ O)).
  • the deprotection reaction of compound (B-14-2: (A 2 ⁇ O)) is carried out in an organic solvent.
  • the organic solvent to be used is not particularly limited as long as it is inert to the reaction.
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and 1,2-dichloroethane
  • sulfur-containing solvents such as dimethyl sulfoxide and diethyl sulfoxide
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • Aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane
  • Amide solvents such as N-methylpyrrolidone
  • the amount of the organic solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of the compound (B-14-2: (A 2 ⁇ O)).
  • the reaction proceeds smoothly in a temperature range from ⁇ 20 ° C. to the boiling point of the solvent used.
  • the reaction time depends on the reaction scale, it is usually from several minutes to several tens of hours.
  • the nitrogen-containing heteroaryl derivative of the present invention obtained by the above production method can be further converted into a salt.
  • the salt is not particularly limited as long as it is an agricultural and horticulturally acceptable salt.
  • salts of inorganic acids such as hydrochloric acid and sulfuric acid
  • salts of organic acids such as acetic acid and lactic acid
  • These salts can be produced by a conventionally known method using an acid corresponding to the compound of the present invention.
  • the desired product can be isolated by purifying by a conventional post-treatment operation and, if desired, known and conventional purification means such as distillation, recrystallization, column chromatography and the like.
  • known and conventional purification means such as distillation, recrystallization, column chromatography and the like.
  • the structure of the target product can be identified and confirmed by known analytical means such as IR spectrum, NMR spectrum, mass spectrum, and elemental analysis.
  • geometric isomers based on carbon-nitrogen double bonds may exist, and all of these isomers are included in the present invention.
  • the nitrogen-containing heteroaryl derivative represented by the formula (9) is a compound represented by the above formula (1), wherein D represents a compound represented by the formula (2) or the formula (3).
  • R 1 , R 2 , A 1 , A 2 , J, X, n, and R 7 have the same meaning as described above.
  • the production intermediate is preferably a compound represented by the formula (10).
  • the nitrogen-containing heteroaryl derivative represented by the formula (11) is a compound represented by the above formula (1), wherein D is a production intermediate useful for the production of the compound represented by the formula (6) It is.
  • R 1 , R 2 , A 1 , A 2 , J, X, n, and R 7 have the same meaning as described above.
  • R 9 are each independently hydrogen atom or the formula,: COR 21 (wherein, R 21 is as defined above.) Is a group represented by.
  • R 9 may be the same or different.
  • R 9 may be together. Examples of R 9 include formyl group, acetyl group, methoxycarbonyl group and the like. Examples of R 9 taken together include a phthaloyl group.
  • the production intermediate is preferably a compound represented by the formula (12).
  • the agricultural and horticultural fungicide of the present invention contains at least one of a nitrogen-containing heteroaryl derivative represented by the above formula (1), a salt thereof, or an N-oxide thereof as an active ingredient. It is an agricultural and horticultural fungicide (hereinafter sometimes referred to as “the present invention fungicide”).
  • the fungicide of the present invention is used for a wide variety of fungi, for example, bacteria belonging to algae (Oomycetes), Ascomycetes, Deuteromycetes, and basidiomycetes. Excellent sterilizing power.
  • the disinfectant of the present invention can be used by seed treatment, foliage application, soil application, water application, etc., for the control of various diseases that occur during cultivation of agricultural and horticultural crops including flowers, turf, and grass.
  • Sugar beet brown spot (Cercospora beticola) Black root disease (Aphanomyces cochlloides) Root rot (Thanatephorus cucumeris) Leaf rot (Thanatephorus cucumeris) Peanut Brown Spot (Mycosphaerella arachidis) Black astringency (Mycosphaerella berkeleyi) Cucumber powdery mildew (Sphaerotheca fuliginea) Downy mildew (Pseudoperonospora cubensis) Vine Blight (Mycosphaerella melonis) Vine split disease (Fusarium oxysporum) Sclerotinia sclerotiorum Gray mold (Botrytis cinerea) Anthracnose (Colletotrichum orbiculare) Black star disease (Cladosporium cucumerinum) Brown spot disease (Corynespora cassicola) Seedling blight (Pythium debaryanam, Rhizo
  • Tomato gray mold (Botrytis cinerea) Leaf mold (Cladosporium fulvum) Plague (Phytophthora infestans) Eggplant gray mold (Botrytis cinerea) Black blight (Corynespora melongenae) Powdery mildew (Erysiphe cichoracearum) Susmolder disease (Mycovellosiella nattrassii) Strawberry Gray mold disease (Botrytis cinerea) Powdery mildew (Sohaerotheca humuli) Anthracnose (Colletotrichum acutatum, Colletotrichum fragariae) Plague (Phytophthora cactorum) Onion Gray rot (Botrytis allii) Gray mold (Botrytis cinerea) Botrytis squamosa Downy mildew (Peronospora destructor) Cabbage root-knot disease (Plasmodiophora brassicae) Soft rot (Erwini
  • Apple powdery mildew (Podosphaera leucotricha) Black star disease (Venturia inaequalis) Monilinia mali Sunspot disease (Mycosphaerella pomi) Rot (Valsa mali) Spotted leaf fall (Alternaria mali) Red Star Disease (Gymnosporangium yamadae) Ring-shaped disease (Botryosphaeria berengeriana) Anthracnose (Glomerella cingulata, Colletotrichum acutatum) Brown spot disease (Diplocarpon mali) Soot spot disease (Zygophiala jamaicensis) Soot spot (Gloeodes pomigena) Oyster powdery mildew (Phyllactinia kakicola) Anthracnose (Gloeosporium kaki) Spotted leaf disease (Cercospora kaki) Peach (Assassin Disease) (Monilinia fructicola) Black star disease (C
  • this fungicide has an excellent bactericidal effect against various resistant bacteria.
  • resistant bacteria include, for example, gray mold fungus (Botrytis cinerea), sugar beet brown fungus (Cercospora beticola), apple black rot (Venturia inaequalis), Examples include Venturia nashicola; Botrytis cinerea which is resistant to dicarboximide fungicides such as vinclozolin, procymidone and iprodione.
  • More preferable diseases to which the fungicide of the present invention is applied include sugar beet brown spot, wheat powdery mildew, rice blast, apple scab, cucumber gray mold, peanut brown etc. it can.
  • the fungicide of the present invention is a highly safe drug with little phytotoxicity, low toxicity to fish and warm-blooded animals.
  • the fungicide of the present invention When actually applying the fungicide of the present invention, it can be used without particularly adding other components to the compound of the present invention, and forms that can be taken by general agricultural chemicals, that is, wettable powder, granules, powders, It can also be used in the form of an emulsion, aqueous solvent, suspension, granule wettable powder or the like.
  • Additives and carriers used in formulation into solid dosage forms include vegetable powders such as soybean flour and wheat flour, mineral fine powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite and clay And organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate.
  • Solvents used in formulating liquid dosage forms include kerosene, xylene and petroleum-based aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil , Vegetable oil, water and the like.
  • a surfactant can be added as necessary.
  • the surfactant that can be added is not particularly limited.
  • alkyl phenyl ether added with polyoxyethylene alkyl ether added with polyoxyethylene, higher fatty acid ester added with polyoxyethylene, sorbitan higher fatty acid ester added with polyoxyethylene, tristyryl added with polyoxyethylene
  • Nonionic surfactants such as phenyl ether, sulfates of alkylphenyl ethers added with polyoxyethylene, alkylbenzene sulfonates, sulfates of higher alcohols, alkylnaphthalene sulfonates, polycarboxylates, lignin sulfones Acid salt, formaldehyde condensate of alkyl naphthalene sulfonate, isobutylene-maleic anhydride copolymer, and the like.
  • the wettable powder, emulsion, flowable powder, aqueous solvent, and granular wettable powder thus obtained are diluted with water to a predetermined concentration to obtain a solution, suspension or emulsion.
  • Granules can be sprayed on plants as they are.
  • the amount of the active ingredient in the fungicide of the present invention is usually preferably 0.01 to 90% by weight, more preferably 0.05 to 85% by weight, based on the entire composition (formulation).
  • the application amount of the fungicide of the present invention varies depending on weather conditions, formulation form, application time, application method, application place, disease to be controlled, target crop, etc., but is usually 1 to 1000 g in terms of the amount of active ingredient compound per hectare. It is preferably 10 to 100 g.
  • the applied concentration is 1 to 1000 ppm, preferably 10 to 250 ppm.
  • one or two or more of various fungicides, insecticides, acaricides and the like can be mixed with the fungicides of the present invention.
  • fungicides insecticides / acaricides, nematicides, soil pesticides and plant growth regulators that can be used in combination with the compounds of the present invention are shown below.
  • Fungicide 1) benzimidazole series: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate methyl, etc .; 2) Dicarboximide type: Clozolinate, iprodione, procymidone, vinclozolin and the like; 3) DMI-bactericidal system: imazalyl, oxpoconazole, pefazoate, prochloraz, triflumizole, triphorin, pyrifenox, phenarimol, nuarimol, azaconazole, viteltanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxy Conazole, fenbuconazole, fluquinconazole, flusilazole, flutriaol, hexaconazole, imibenconazole, ipconazole, metconazole, microbutanyl, penconazole, propi
  • Insecticides, acaricides, nematicides, soil insecticides 1) Organic (thio) phosphates: acephate, azamethiphos, azinephosmethyl, chlorpyrifos, chlorpyrifosmethyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfotone, ethion, EPN, phenamiphos, fenitrothion, fenthion, isoxathione, metathione, metaxamide, , Methidathion, methylparathion, mevinphos, monocrotophos, oxydemetonmethyl, paraoxon, parathion, phentoate, hosalon, phosmet, phosphamidone, folate, oxime, pirimiphosmethyl, propenophos, prothiophos, sulfophos, tetrachlorbinphos, terbufos
  • Plant growth regulator Abscisic acid, indole butyric acid, uniconazole, etiquelozate, etephone, cloxiphonac, chlormecote, chlorella extract, calcium peroxide, cyanamide, dichlorprop, gibberellin, daminozide, decyl alcohol, trinexapac ethyl, mepicoat chloride, pack Lobutrazole, paraffin wax, piperonyl butoxide, pyraflufenethyl, flurprimidol, prohydrojasmon, prohexadione calcium salt, benzylaminopurine, pendimethalin, forchlorphenuron, potassium maleate hydrazide, 1-naphthyl Acetamide, 4-CPA, MCPB, choline, oxyquinoline sulfate, ethiclozeate, butorualine, 1-methylcyclopropene, abiglycine hydrochloride.
  • Example 3 a) Preparation of 4-chloro-2- (3,3-dimethyl-1-butynyl) -5-methylpyridine 1.05 g of 2-bromo-4-chloro-5-methylpyridine was dissolved in 30 ml of ethyl acetate. To this was added 0.79 g of 3,3-dimethyl-1-butyne, 2.43 g of triethylamine, 0.05 g of copper iodide, and 0.17 g of dichlorobistriphenylphosphine palladium, and the mixture was stirred at 50 ° C. for 2 hours under a nitrogen atmosphere. did. The resulting liquid was filtered through Celite, and then the solvent was distilled off under reduced pressure.
  • Example 4 Production of methyl N- [2- (3,3-dimethyl-1-butynyl) -5-methylpyridin-4-yloxy] carbamate (Compound No. 3-a-1) 0.64 g of t-butyl N- [2- (3,3-dimethyl-1-butynyl) -5-methylpyridin-4-yloxy) carbamate was dissolved in 20 ml of methylene chloride. To this, 0.42 g of triethylamine was added under ice cooling, and then 0.30 g of methyl chloroformate was added dropwise. It stirred for 1 hour after completion
  • Example 5 a) Preparation of 4-chloro-5-methyl-2- (3-trifluoromethoxyphenyl) pyridine 0.61 g of 2-bromo-4-chloro-5-methylpyridine and 3-trifluoromethoxyphenylboronic acid 13 g was dissolved in 20 ml of dimethylformamide. 4 ml of water, 1.12 g of potassium carbonate, and 0.11 g of Pd (dppf) Cl 2 .CH 2 Cl 2 were added thereto, and the mixture was stirred at 60 ° C. for 2 hours under a nitrogen atmosphere. Ethyl acetate was added thereto, and then washed with an aqueous ammonium chloride solution.
  • Example 7 a) Preparation of 4-chloro-5-methylpyridine-2-carbonitrile 1.50 g of 2-bromo-4-chloro-5-methylpyridine was dissolved in 20 ml of DMF. To this, 0.43 g of zinc cyanide and 0.43 g of tetrakistriphenylphosphine palladium were added and stirred at 80 ° C. for 1 hour. Water was added thereto, followed by extraction with ethyl acetate. The obtained organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure.
  • Example 9 Preparation of methyl N- ⁇ 2- [4- (2-chloro-6-fluorobenzyl) thiazol-2-yl] -5-methylpyridin-4-yloxy ⁇ -N-acetoxymethylcarbamate (Compound No. 4-a- 19) 0.36 g of methyl N- ⁇ 2- [4- (2-chloro-6-fluorobenzyl) thiazol-2-yl] -5-methylpyridin-4-yloxy ⁇ carbamate was dissolved in 15 ml of acetonitrile. To this, 1.22 g of potassium carbonate and 0.20 g of bromomethyl acetate were added and stirred at room temperature for 2 hours.
  • Example 11 Preparation of methyl N- ⁇ 2- [1- (2-chloro-6-fluorobenzyl) -1H-pyrazol-3-yl] -5-methylpyridin-4-yloxy ⁇ carbamate (Compound No. 4-a-26 ) 0.24 g of t-butyl N- ⁇ 2- [1- (2-chloro-6-fluorobenzyl) -1H-pyrazol-3-yl] -5-methylpyridin-4-yloxy ⁇ carbamate is added to 20 ml of methylene chloride. Dissolved. To this, 0.11 g of triethylamine was added under ice cooling, and then 0.07 g of methyl chloroformate was added dropwise.
  • Magnesium sulfate was added to the obtained organic layer, dried and filtered, and then the solvent was distilled off under reduced pressure. 100 ml of methylene chloride was added to the resulting residue, and 15 ml of trifluoroacetic acid was added dropwise under ice cooling. After completion of dropping, the mixture was stirred at room temperature for 2 hours. The resulting liquid was poured into a saturated aqueous sodium hydrogen carbonate solution, and then extracted with methylene chloride. Magnesium sulfate was added to the resulting methylene chloride layer, dried and filtered, and then the solvent was distilled off under reduced pressure.
  • Examples of compounds Other examples of the nitrogen-containing heteroaryl derivative of the present invention obtained by a method similar to the above production method are shown in Tables 1 to 10 including the compounds obtained in the above Examples. Further, production intermediates are shown in Tables 11 to 14. In the table, Me is a methyl group, Et is an ethyl group, i Pr is an isopropyl group, t Bu is a tertiary butyl group, Ac is an acetyl group, Ph is a phenyl group, and c Pr is cyclopropyl.
  • Table 1 is a compound represented by formula (1-a)
  • Table 2 is a compound represented by formula (1-b)
  • Table 3 is a compound represented by formula (2-a)
  • Table 4 Table is a compound represented by Formula (2-b)
  • Table 5 is a compound represented by Formula (3-a)
  • Table 6 is a compound represented by Formula (3-b)
  • Table 7 is The compounds represented by formula (4-a) and Table 8 show the compounds represented by formula (4-b), respectively.
  • Table 9 shows the compound represented by the formula (5-a)
  • Table 10 shows the compound represented by the formula (5-b).
  • Table 11 shows production intermediates represented by formula (6-a)
  • Table 12 shows production intermediates represented by formula (6-b).
  • Table 13 shows the production intermediate represented by the formula (7-a)
  • Table 14 shows the production intermediate represented by the formula (7-b).
  • Formulation Example 1 wettable powder Compound of the present invention 40 parts Clay 48 parts Dioctylsulfosuccinate sodium salt 4 parts Lignin sulfonic acid sodium salt 8 parts The above is uniformly mixed and finely pulverized, and a wettable powder with 40% active ingredient. Get.
  • Emulsion Compound of the present invention 10 parts Solvesso 200 53 parts Cyclohexanone 26 parts Calcium dodecylbenzenesulfonate 1 part Polyoxyethylene alkylallyl ether 10 parts The above components are mixed and dissolved to obtain an emulsion containing 10% active ingredient.
  • Formulation Example 3 Powder The present compound 10 parts Clay 90 parts The above is uniformly mixed and finely pulverized to obtain a powder of 10% active ingredient.
  • Formulation Example 4 Granules Compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctylsulfosuccinate sodium salt 1 part Potassium phosphate 1 part After pulverizing and mixing well, adding water and kneading well, granulation drying As a result, granules containing 5% of the active ingredient are obtained.
  • Formulation Example 5 Suspension Compound of the present invention 10 parts Polyoxyethylene alkyl allyl ether 4 parts Polycarboxylic acid sodium salt 2 parts Glycerin 10 parts Xanthan gum 0.2 parts Water 73.8 parts The above is mixed and the particle size is 3 microns or less The suspension is wet-pulverized until a suspension of 10% active ingredient is obtained.
  • Granule wettable powder Compound of the present invention 40 parts Clay 36 parts Potassium chloride 10 parts Alkylbenzenesulfonic acid sodium salt 1 part Lignin sulfonic acid sodium salt 8 parts Formaldehyde condensate of alkylbenzenesulfonic acid sodium salt 5 parts After finely pulverizing, add an appropriate amount of water and knead to make clay. The clay-like product is granulated and then dried to obtain a granule wettable powder containing 40% of the active ingredient.
  • Test examples of the fungicide of the present invention obtained as described above are shown below.
  • (Test Example 1) Apple black spot disease control test An emulsion of the compound of the present invention was sprayed at a concentration of 100 ppm of the active ingredient on apple seedlings (variety “Kokumitsu”, 3-4 leaf stage) cultivated in an unglazed pot. After natural drying at room temperature, conidia of Venturia inaequalis were inoculated, and the light and darkness was repeated every 12 hours, and kept in a room of high humidity at 20 ° C. for 2 weeks. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
  • the nitrogen-containing heteroaryl derivative of the present invention is a novel compound, which can be produced industrially advantageously, has an effect, and can be used safely and safely. It turns out that it is useful.

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Abstract

L'invention concerne des dérivés hétéroaryles contenant de l'azote représentés par la formule (1), leurs sels et leurs N-oxydes, et des fongicides pour utilisation agricole et horticole qui contiennent au moins un de ces composés en tant qu'ingrédient actif. Dans la formule (1), R1 représente un groupe alkyle en C1-6 éventuellement substitué ; R2 représente un atome d'hydrogène ou un groupe tel qu'un groupe alkyle en C1-6 éventuellement substitué ; A1 et A2 représentent un atome d'oxygène ou analogue ; J représente un atome d'oxygène ou analogue ; X représente un groupe alkyle en C1-6 éventuellement substitué, un atome d'halogène ou analogue ; n, qui désigne le nombre de X, représente un entier de 0 à 3, à condition que lorsque n vaut 2 ou plus, les X puissent être identiques ou différents ; B1 à B4 représentent indépendamment un atome d'azote ou un atome de carbone, à condition que B1 à B3 ne soient pas tous des atomes d'azote en même temps et que B1 à B4 ne soient pas tous des atomes de carbone en même temps ; et D représente un groupe représenté par la formule (2), la formule (3) ou analogue [dans les formules (2) et (3), Q1 représente un groupe aryle en C6-10 éventuellement substitué ou analogue ; et R7 et R8 représentent un atome d'hydrogène, un groupe alkyle en C1-6 éventuellement substitué ou analogue].
PCT/JP2010/003500 2009-05-27 2010-05-25 Dérivés hétéroaryles contenant de l'azote et fongicides pour utilisation agricole et horticole WO2010137302A1 (fr)

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WO2012028676A1 (fr) * 2010-09-02 2012-03-08 Boehringer Ingelheim International Gmbh Nouveaux composés, compositions pharmaceutiques, et leurs utilisations
WO2012117021A3 (fr) * 2011-03-03 2012-11-08 Syngenta Participations Ag Nouveaux éthers d'oxime microbiocides
JP2015096482A (ja) * 2012-12-21 2015-05-21 石原産業株式会社 有害生物防除剤
WO2015119099A1 (fr) * 2014-02-05 2015-08-13 日本曹達株式会社 Composé de pyridine et son application
KR101728898B1 (ko) * 2010-12-07 2017-04-21 광주과학기술원 신규한 하이드라진 유도체 및 이의 용도
JP6585328B1 (ja) * 2018-04-09 2019-10-02 日本曹達株式会社 フェノキシウレア化合物および有害生物防除剤
CN110590763A (zh) * 2019-09-30 2019-12-20 齐鲁工业大学 2-噻唑甲醛-噻吩席夫碱的结构、制备和用途
US11046658B2 (en) 2018-07-02 2021-06-29 Incyte Corporation Aminopyrazine derivatives as PI3K-γ inhibitors
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WO2012028676A1 (fr) * 2010-09-02 2012-03-08 Boehringer Ingelheim International Gmbh Nouveaux composés, compositions pharmaceutiques, et leurs utilisations
KR101728898B1 (ko) * 2010-12-07 2017-04-21 광주과학기술원 신규한 하이드라진 유도체 및 이의 용도
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JP2015096482A (ja) * 2012-12-21 2015-05-21 石原産業株式会社 有害生物防除剤
WO2015119099A1 (fr) * 2014-02-05 2015-08-13 日本曹達株式会社 Composé de pyridine et son application
JPWO2015119099A1 (ja) * 2014-02-05 2017-03-23 日本曹達株式会社 ピリジン化合物およびその用途
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JP6585328B1 (ja) * 2018-04-09 2019-10-02 日本曹達株式会社 フェノキシウレア化合物および有害生物防除剤
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