Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
  • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P33/00—Antiparasitic agents
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P33/00—Antiparasitic agents
  • A61P33/14—Ectoparasiticides, e.g. scabicides
• • 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
  • 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
  • C07D401/14—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 three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
  • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
  • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
• • 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
• • 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
  • C07D417/14—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 three or more hetero rings

Definitions

• the present invention relates to a novel pyrazole or thiazole derivative or a salt thereof, and a pest control agent characterized by containing the compound as an active ingredient.
• the pest control agent in the present invention refers to the field of agriculture and horticulture or the field of livestock and hygiene (endoparasites / external parasites for mammals or birds as domestic animals and pets, hygiene pests and unpleasant pests for household and commercial use) It means a pest control agent for harmful arthropods such as
• the agrochemical in the present invention means an insecticide / acaricide, nematicide, herbicide, fungicide, etc. in the field of agriculture and horticulture.
• Patent Documents 1 to 9 and Patent Documents 13 to 14 disclose pyrazole and thiazole derivatives, but do not disclose any pyrazole and thiazole derivatives according to the present invention. Furthermore, its usefulness as a pest control agent, particularly an insecticide / acaricide, and an internal or ectoparasite control agent for mammals or birds is not known at all.
• Patent Documents 10 to 12 disclose that pyrazole and thiazole derivatives are useful as insecticides, but do not disclose any pyrazole and thiazole compounds according to the present invention.
• An object of the present invention is to provide a novel pesticide having high activity, low toxicity, and low persistence.
• the present inventors have found that the novel pyrazole and thiazole derivatives represented by the following formula (1) according to the present invention have excellent pest control activity, particularly insecticide /
• the present invention was completed by discovering that it is a very useful compound that exhibits acaricidal activity and has almost no adverse effect on non-target organisms such as mammals, fish and beneficial insects. That is, the present invention relates to the following [1] to [104].
• a 1 is, -N (-O) m2 or represents -CR 1
• R 1 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, cyano, nitro, —OH, —SH, —NH 2 , —CHO, —C (O) OH, —C (O) NH 2 , —C (S) NH 2 , —S (O) 2 NH 2 , C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 28a , C 3 -C 8 cycloalkyl , optionally substituted with R 28a (C 3 ⁇ C 8 ) cycloalkyl, C 2 ⁇ C 6 alkenyl, optionally substituted with R 28a (C 2 ⁇ C 6 ) alkenyl, C 3 ⁇ C 8 cycloalkyl
• R 2 represents a halogen atom, cyano, nitro, —OH, —SH, —NH 2 , —CHO, —C (O) OH, —C (O) NH 2 , —C (S) NH 2 , —S ( O) 2 NH 2, C 1 ⁇ C 6 alkyl, substituted optionally substituted with R 28a (C 1 ⁇ C 6 ) alkyl, C 3 ⁇ C 8 cycloalkyl, optionally with R 28a (C 3 ⁇ C 8) cycloalkyl, C 2 ⁇ C 6 alkenyl, which is optionally substituted with R 28a (C 2 ⁇ C 6 ) alkenyl, C 3 ⁇ C 8 cycloalkenyl, which is optionally substituted with R 28a (C 3 ⁇ C 8 ) cycloalkenyl, C 2 -C 6 alkynyl, (C 2 -C 6 ) alkynyl optionally substituted with R 28a
• B represents a ring represented by either B-1 or B-2.
• “*” represents the bonding position with the substituent “—N (R a ) R b ”, and “**” represents the bonding position with the substituent shown below.
• R a is a hydrogen atom, C 1 ⁇ C 6 alkyl, optionally substituted with R 5a (C 1 ⁇ C 6 ) alkyl, C 2 ⁇ C 6 alkenyl, optionally substituted with R 5a (C 2 ⁇ C 6) alkenyl, C 2 ⁇ C 6 alkynyl, optionally substituted with R 5a (C 2 ⁇ C 6 ) alkynyl, C 3 ⁇ C 8 cycloalkyl, optionally substituted with R 5a (C 3 ⁇ C 8 ) Cycloalkyl, C 3 -C 8 cycloalkenyl, (C 3 -C 8 ) cycloalkenyl optionally substituted with R 5a , —OR 6a , —S (O) r 2 R 6a , —C (O) OR 6a , -C (O) SR6a , -C (S) OR6a , -C (S) SR6a , -C
• the alkylene chain or alkenylene chain may contain one or two oxygen atoms, sulfur atoms or nitrogen atoms, and is a halogen atom, cyano, nitro, C 1 -C 6 alkyl, —OH, —OR 11a , -SH, S (O) r R 11a, which may be optionally substituted by oxo or thioxo group.
• R 6a , R 8a and R 9a are each independently a hydrogen atom, C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 10a , C 2 -C 6 alkenyl, R 10a in optionally substituted (C 2 ⁇ C 6) alkenyl, C 2 ⁇ C 6 alkynyl, optionally substituted with R 10a (C 2 ⁇ C 6) alkynyl, C 3 ⁇ C 8 cycloalkyl, with R 10a Optionally substituted (C 3 -C 8 ) cycloalkyl, C 3 -C 8 cycloalkenyl, (C 3 -C 8 ) cycloalkenyl optionally substituted with R 10a , —S (O) r2 R 11a , -C (O) OR 11a , -C (O) SR 11a , -C (S) OR 11a , -C (S) SR 11a
• R 10a is a halogen atom, cyano, nitro, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, —OH, —OR 11a , —SH, —S (O) r 2 R 11a
• R 11a and R 12a are each independently a hydrogen atom, C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 15a , C 2 -C 6 alkenyl, optionally with R 15a substituted (C 2 ⁇ C 6) alkenyl, C 3 ⁇ C 8 cycloalkenyl, optionally substituted with R 15a (C 3 ⁇ C 8 ) cycloalkenyl, C 2 ⁇ C 6 alkynyl, optionally with R 15a Substituted (C 2 -C 6 ) alkynyl, C 3 -C 8 cycloalkyl, (C 3 -C 8 ) cycloalkyl optionally substituted with R 15a , —S (O) r 2 R 16a , —C ( O) OR 16a , -C (O) SR 16a , -C (S) OR 16a , -C (S) SR 16a
• R 11b is substituted C 1 ⁇ C 10 alkyl, optionally with R 15b (C 1 ⁇ C 6 ) alkyl, optionally substituted with C 2 ⁇ C 6 alkenyl, R 15b (C 2 ⁇ C 6) alkenyl, C 3 ⁇ C 8 cycloalkenyl, optionally substituted with R 15b (C 3 ⁇ C 8 ) cycloalkenyl, optionally substituted with C 2 ⁇ C 6 alkynyl, R 15b (C 2 ⁇ C 6) Alkynyl, C 3 -C 8 cycloalkyl, (C 3 -C 8 ) cycloalkyl optionally substituted with R 15b , —S (O) r 3 R 16b , —C (O) OR 16b , —C (O) SR 16b , -C (S) OR 16b , -C (S) SR 16b , -C (O) R 17b , -C (S
• R 12b is a hydrogen atom, a halogen atom, substituted cyano, C 1 ⁇ C 6 alkyl, optionally substituted with R 15c (C 1 ⁇ C 6 ) alkyl, C 2 ⁇ C 6 alkenyl, the R 15c optionally (C 2 ⁇ C 6) alkenyl, C 3 ⁇ C 8 cycloalkenyl, substituted is optionally substituted with R 15c (C 3 ⁇ C 8 ) cycloalkenyl, C 2 ⁇ C 6 alkynyl, optionally with R 15c (C 2 -C 6 ) alkynyl, C 3 -C 8 cycloalkyl, (C 3 -C 8 ) cycloalkyl optionally substituted with R 15c , —OR 16c , —S (O) r R 16c , —C (O) OR 16c , -C (O) SR 16c , -C (S) OR 16c , -
• R 13a and R 14a each independently represent a hydrogen atom or C 1 -C 6 alkyl, or R 13a together with R 14a is a C 2 -C 7 alkylene chain or C 2 -C 7. To form a 3- to 8-membered ring together with the nitrogen atom to which R 13a and R 14a are bonded.
• the alkylene chain or alkenylene chain has an oxygen atom, a sulfur atom or a nitrogen atom.
• One may be included, and optionally substituted by a (C 1 -C 6 ) alkyl, oxo group or thioxo group optionally substituted with R 42 , R 15a .
• R 13b is a hydrogen atom, cyano, substituted nitro, C 1 ⁇ C 6 alkyl, optionally substituted with R 15b (C 1 ⁇ C 6 ) alkyl, C 2 ⁇ C 6 alkenyl, optionally with R 15b (C 2 ⁇ C 6) alkenyl, C 3 ⁇ C 8 cycloalkenyl, substituted is optionally substituted with R 15b (C 3 ⁇ C 8 ) cycloalkenyl, C 2 ⁇ C 6 alkynyl, optionally with R 15b (C 2 -C 6 ) alkynyl, C 3 -C 8 cycloalkyl, (C 3 -C 8 ) cycloalkyl optionally substituted with R 15b , —OR 16b , —S (O) r3 R 16b , —C (O) OR 16b , -C (O) SR 16b , -C (S) OR 16b , -C (S)
• the alkylene chain or alkenylene chain may contain one or two oxygen atoms, sulfur atoms or nitrogen atoms, and is optionally substituted with R 42 or R 15b (C 1 ⁇ C 6 Alkyl may be optionally substituted by oxo or thioxo group.
• R 14b is a hydrogen atom, cyano, substituted nitro, C 1 ⁇ C 6 alkyl, optionally substituted with R 15d (C 1 ⁇ C 6 ) alkyl, C 2 ⁇ C 6 alkenyl, optionally with R 15d (C 2 ⁇ C 6) alkenyl, C 3 ⁇ C 8 cycloalkenyl, substituted is optionally substituted with R 15d (C 3 ⁇ C 8 ) cycloalkenyl, C 2 ⁇ C 6 alkynyl, optionally with R 15d (C 2 -C 6 ) alkynyl, C 3 -C 8 cycloalkyl, (C 3 -C 8 ) cycloalkyl optionally substituted with R 15d , —OR 16d , —S (O) r3 R 16d , —C (O) OR 16d , -C (O) SR 16d , -C (S) OR 16d , -C (S)
• R 14e and R 14f are each independently a hydrogen atom, cyano, nitro, C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 15b , C 2 -C 6 alkenyl, R optionally substituted with 15b (C 2 ⁇ C 6) alkenyl, C 3 ⁇ C 8 cycloalkenyl, optionally substituted with R 15b (C 3 ⁇ C 8 ) cycloalkenyl, C 2 ⁇ C 6 alkynyl, R optionally substituted with 15b (C 2 ⁇ C 6) alkynyl, C 3 ⁇ C 8 cycloalkyl, optionally substituted with R 15b (C 3 ⁇ C 8 ) cycloalkyl, -OR 16b, -S (O ) r3 R 16b, -C (O ) OR 16b, -C (O) SR 16b, -C (S) OR 16b, -C (S
• a 3- to 8-membered ring may be formed together with the carbon atom, and this alkylene chain or alkenylene chain may contain 1, 2 or 3 oxygen atoms, sulfur atoms or nitrogen atoms, and R 42 , R 15b At Substituted in (C 1 ⁇ C 6) alkyl, it may be optionally substituted by oxo or thioxo group.
• R 15a is a halogen atom, cyano, nitro, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, —OH, —OR 16a , —SH, —S (O) r 2 R 16a , —S ( ⁇ NR 18a ) R 16a , —S (O) ( ⁇ NR 18a ) R 16a , —P (O) (OR 41 ) 2 , —P (S) (OR 41 ) 2 , phenyl, (Z) q A substituted phenyl, naphthyl, naphthyl substituted by (Z) q , any group of D1-1 to D1-99 or —Si (R 40a ) (R 40b ) R 40 , or two R When 15a is substituted on the same carbon, the two R 5a together are oxo, thioxo, imino, C 1 -C 6 alkylim
• R 18a and R 19a each independently represents a hydrogen atom, cyano or C 1 -C 6 alkyl
• R 18b , R 19b , R 18d and R 19d are each independently a hydrogen atom, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl , C 3 ⁇ C 8 cycloalkenyl, optionally substituted optionally substituted with R 20 (C 1 ⁇ C 6 ) alkyl, optionally substituted with R 20 (C 2 ⁇ C 6 ) alkenyl, optionally with R 20 and (C 2 ⁇ C 6) alkynyl, optionally substituted with R 20 (C 3 ⁇ C 8 ) cycloalkyl, optionally substituted with R 20 (C 3 ⁇ C 8 ) cycloalkenyl, phenyl, (Z ) Phenyl substituted by q ,
• the alkenylene chain may contain one or two oxygen atoms, sulfur atoms or nitrogen atoms, and is optionally substituted with (C 1 -C 6 ) alkyl, oxo group or thioxo group optionally substituted with R 42 , R 20 May be.
• R 18c and R 19c are each independently a hydrogen atom, cyano, C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 20 , —OR 21 , —S (O) r R 21 , —C (O) OR 21 , —C (O) R 22 , —C (S) R 22 , phenyl or phenyl substituted by (Z) q ;
• R 20 is a halogen atom, cyano, nitro, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkenyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, —C (O) OR 21 , phenyl or phenyl substituted by (Z) q , or when two R 20 are
• X 1 and X 1b are each independently a halogen atom, cyano, nitro, —OH, —SH, —NH 2 , —CHO, —C (O) OH, —C (O) NH 2 , —C (S ) NH 2 , —S (O) 2 NH 2 , C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 28 , C 2 -C 6 alkenyl, C 2 -C 6 alkynyl C 3 -C 8 cycloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 8 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 ⁇ C 6 alkylthio, C 1 ⁇ C 6 haloalkylthio, C 1 ⁇ C 6
• X 1a is a hydrogen atom, cyano, —OH, —NH 2 , —CHO, —C (O) NH 2 , —C (S) NH 2 , —S (O) 2 NH 2 , C 1 -C 6 alkyl.
• adjacent X 1a and X 1 are —CH 2 CH 2 CH 2 CH 2 —, —CH ⁇ CHCH ⁇ CH—, —N ⁇ CHCH ⁇ CH— , —CH ⁇ N—CH ⁇ CH—, —CH ⁇ CH—N ⁇ CH—, or —CH ⁇ CH—CH ⁇ N— to form a six-membered atom together with the atoms to which each of X 1a and X 1 is attached.
• a hydrogen atom bonded to each carbon atom forming the ring may be a halogen atom, cyano, nitro, C 1 -C 6 alkyl group, C 1 -C 6 haloalkyl group, C 1 It may be optionally substituted with a 1 to C 6 alkoxy group, a C 1 to C 6 alkylthio group, a C 1 to C 6 alkylsulfinyl group or a C 1 to C 6 alkylsulfonyl group.
• Z represents a halogen atom, cyano, nitro, —OH, —SH, —NH 2 , —CHO, —C (O) OH, —C (O) NH 2 , —C (S) NH 2 , —S (O ) 2 NH 2 , C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl optionally substituted with R 28 , C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 8 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfiny
• each Z may be the same as or different from each other.
• the hydrogen atom bonded to the carbon atom is a halogen atom, cyano, nitro, C 1 -C 6 alkyl group, C 1 -C 6 haloalkyl group, C 1 -C 6 alkoxy group, C 1 -C 6 alkylthio group, C 1 it may be optionally substituted by ⁇ C 6 alkylsulfinyl group or a C 1 ⁇ C 6 alkylsulfonyl group.
• R 28 , R 28a , R 31 and R 32 are each independently a halogen atom, —OH, —SH, —NH 2 , —CHO, —C (O) OH, —C (O) NH 2 , —C (S) NH 2, -S ( O) 2 NH 2, -Si (R 40a) (R 40b) R 40, C 1 ⁇ C 6 alkoxy, C 1 ⁇ C 6 haloalkoxy, C 1 ⁇ C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylcarbonyl, C 3 -C 8 cycloalkylcarbonyl, C 1 -C 6
• R 29 and R 29a are each independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkenyl, R 31 (C 1 -C 6 ) alkyl optionally substituted with R 31 , (C 2 -C 6 ) alkenyl optionally substituted with R 31 , (C 2 -C 6 ) alkynyl optionally substituted with R 31 , R optionally substituted with 31 representing the (C 3 ⁇ C 8) optionally substituted cycloalkyl, or R 31 (C 3 ⁇ C 8 ) cycloalkenyl.
• R 30 and R 30a are each independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkenyl, R 32 (C 1 -C 6 ) alkyl optionally substituted with R 32 , (C 2 -C 6 ) alkenyl optionally substituted with R 32 , (C 2 -C 6 ) alkynyl optionally substituted with R 32 , R optionally substituted with 32 (C 3 ⁇ C 8) cycloalkyl, optionally substituted with R 32 (C 3 ⁇ C 8 ) cycloalkenyl, phenyl, phenyl optionally substituted with C 1 ⁇ C 6 alkyl Alternatively, it represents phenyl optionally substituted with a halogen atom.
• R 40, R 40a and R 40b are each independently C 1 to ⁇ C 6 alkyl, C 1 ⁇ C 6 alkoxy or phenyl, R 41 represents C 1 -C 6 alkyl, R 42 represents a halogen atom, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C Represents 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, phenyl or phenyl substituted by (Z) q .
• g1, f1 and n each independently represent an integer of 0, 1, 2 or 3; g2 and f2 each independently represent an integer of 0, 1 or 2; g3 represents an integer of 0 or 1, g4 and f4 each independently represent an integer of 0, 1, 2, 3 or 4; f5 represents an integer of 0, 1, 2, 3, 4 or 5, f6 represents an integer of 0, 1, 2, 3, 4, 5 or 6, f7 represents an integer of 0, 1, 2, 3, 4, 5, 6 or 7, f8 represents an integer of 0, 1, 2, 3, 4, 5, 6, 7 or 8; f9 represents an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, q represents an integer of 1, 2, 3, 4 or 5; m1, m2 and m3 each independently represent an integer of 0 or 1, r, r2 and r3 each independently represents an integer of 0, 1 or 2. ]
• a 1 represents -CR 1 R 1 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 28a , C 2 -C 6 alkynyl , (C 2 -C 6 ) alkynyl or C 1 -C 6 alkylcarbonyl optionally substituted with R 28a , R 2 represents a halogen atom or C 1 -C 6 alkyl, B is a pyrazole derivative or a salt thereof according to the above [1], wherein B represents B-1.
• a 1 represents -N (-O) m2
• B represents B-1
• R 3 and R 4 each independently represents a hydrogen atom, a halogen atom or C 1 -C 6 alkyl
• R 2 represents a halogen atom or C 1 -C 6 alkyl
• B is a pyrazole derivative or a salt thereof according to the above [1], wherein B represents B-1.
• B represents B-2
• R 12b is a hydrogen atom, cyano, C 1 ⁇ C 6 alkyl, optionally substituted with R 15c (C 1 ⁇ C 6 ) alkyl, substituted C 2 ⁇ C 6 alkenyl, the R 15c optionally (C 2 ⁇ C 6) alkenyl, C 3 ⁇ C 8 cycloalkenyl, substituted is optionally substituted with R 15c (C 3 ⁇ C 8 ) cycloalkenyl, C 2 ⁇ C 6 alkynyl, optionally with R 15c (C 2 —C 6 ) alkynyl, C 3 -C 8 cycloalkyl, (C 3 -C 8 ) cycloalkyl optionally substituted with R 15c , —OR 16c , —S (O) r R 16c , —C (O) OR 16c , —C (O) SR 16c , —C (S) OR 16c , —C (
• R 1 represents a hydrogen atom or a halogen atom
• R 2 represents a halogen atom
• R 3 represents a hydrogen atom, a halogen atom, substituted C 1 ⁇ C 6 alkyl, optionally substituted with R 28a (C 1 ⁇ C 6 ) alkyl, C 2 ⁇ C 6 alkynyl, optionally with R 28a ( C 2 -C 6 ) alkynyl or C 1 -C 6 alkylcarbonyl
• R 4 represents a hydrogen atom, a halogen atom or C 1 -C 6 alkyl
• R a is a hydrogen atom, C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 5a , C 2 -C 6 alkenyl, C 2 -C 6 alkynyl
• —S (O) represents an r2 R 6a, -C (O) oR 6a, -C (O)
• R 10a represents —OR 11a or —S (O) r2 R 11a ;
• R 11a is C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 15a , C 2 -C 6 alkynyl, -C (O) OR 16a , -C (O) R 17a , —C (O) N (R 18a ) R 19a or —Si (R 40a ) (R 40b ) R 40
• R 11b is C 1 -C 7 alkyl, (C 1 -C 6 ) alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, optionally substituted with R 15b , -C (O) OR 16b or Represents -C (O) R 17b
• R 12a represents (C 1 -C 6 ) alkyl optionally substituted with R 15a
• R 12b is a hydrogen atom,
• R 13a and R 14a each independently represents a hydrogen atom or C 1 -C 6 alkyl;
• R 15a represents —OR 16a , —S (O) r2 R 16a , phenyl or —Si (R 40a ) (R 40b ) R 40 ,
• R 15b is a halogen atom, cyano, C 3 -C 8 cycloalkyl, —OH, —OR 16b , —S (O) r3 R 16b , —C (O) OH, —C (O) OR 16b , —C (O) represents N (R 18b ) R 19b , —C ( ⁇ NOR 16b ) R 17b , (Z) q , phenyl substituted by q , D1-33 or D1-84,
• R 15c represents a halogen atom, cyano, —OH, —OR 16c , —S (O) r R 16
• R 16c is C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, (C 1 -C 6 ) alkyl optionally substituted with R 20 , -S (O) r R 21 , (Z) represents phenyl or D1-32 substituted by q ;
• R 17a represents C 1 -C 6 alkyl or phenyl;
• R 17b represents C 1 -C 6 alkyl or (C 1 -C 6 ) alkyl optionally substituted with R 20 ;
• R 17c represents C 1 -C 6 alkyl;
• R 18a and R 19a each independently represent C 1 -C 6 alkyl;
• R 18b represents a hydrogen atom, or R 18b together with R 19b forms a C 5 alkylene chain to form a 6-membered ring with the nitrogen atom to which R 18b and R 19b are
• the alkylene chain may contain one oxygen atom
• R 18c represents C 1 -C 6 alkyl or —C (O) R 22
• R 19b represents (C 1 -C 6 ) alkyl optionally substituted with R 20
• R 19c represents a hydrogen atom
• R 20 represents a halogen atom, C 1 -C 6 alkoxy or C 1 -C 6 alkylthio
• R 21 represents phenyl substituted by (Z) q
• R 22 represents C 1 -C 6 alkyl
• R 23 and R 24 represent a hydrogen atom
• X 1 represents a halogen atom or (C 1 -C 6 ) alkyl optionally substituted with R 28
• R 28 represents a halogen atom
• R 28a represents a halogen atom or —Si (R 40a ) (R 40b ) R 40
• Z represents a halogen atom, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or C 1 -C 6 alkylthio
• R 40 , R 40a and R 40b each independently represent C 1 -C 6 alkyl.
• g1, g4, m1 and n each independently represent an integer of 0 or 1, f5, f7 and m3 represent 0; q represents an integer of 1; r and r3 each independently represents an integer of 0, 1 or 2; r2 represents 0 or an integer of 2; the pyrazole derivative or the salt thereof according to [2] above.
• a 1 represents -CR 1 R 1 and R 3 each independently represents a hydrogen atom, a halogen atom or C 1 -C 6 alkyl;
• R 2 represents a halogen atom or C 1 -C 6 alkyl,
• R 12b is a hydrogen atom, cyano, C 1 ⁇ C 6 alkyl, optionally substituted with R 15c (C 1 ⁇ C 6 ) alkyl, substituted C 2 ⁇ C 6 alkenyl, the R 15c optionally (C 2 ⁇ C 6) alkenyl, C 3 ⁇ C 8 cycloalkenyl, substituted is optionally substituted with R 15c (C 3 ⁇ C 8 ) cycloalkenyl, C 2 ⁇ C 6 alkynyl, optionally with R 15c (C 2 The thiazole derivative or a salt thereof according to the above [4], which represents (C 3 -C 8 ) cycloalkyl optionally substituted with —C 6 ) alkyny
• R a is a hydrogen atom, C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 5a , C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, —C (O) OR 6a , —C (O) R 7a , —C (O) N (R 8a ) R 9a or —C (S) N (R 8a ) R 9a , or R a together with R 3 And forming a C 2 -C 4 alkylene chain to form a 5- to 7-membered ring together with the nitrogen atom to which R a is bonded and the carbon atom to which R 3 is bonded, R b represents —C (O) R 7b or —C (S) R 7b ; R 5a represents a halogen atom, cyano, C 3 -C 8 cycloalkyl, —OH, —OR 11a or —S
• R 11b represents C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl optionally substituted with R 15b
• R 12b is a hydrogen atom, C 1 ⁇ C 6 alkyl, optionally substituted with R 15c (C 1 ⁇ C 6 ) alkyl, C 2 ⁇ C 6 alkenyl, optionally substituted with R 15c (C 2 ⁇ C 6 ) alkenyl, C 2 -C 6 alkynyl or (C 2 -C 6 ) alkynyl optionally substituted with R 15c
• R 13b and R 14b are each independently a hydrogen atom, C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 15b , C 2 -C 6 alkenyl, C 3 -C 8 Cycloalkyl, —S (O) r3 R 16b ,
• R 15b represents a halogen atom or cyano
• R 15c represents —OH, —OR 16c , —SH, —S (O) r R 16c , (Z) q substituted with phenyl, D1-7, D1-87 or D1-98
• R 16a and R 17a each independently represent C 1 -C 6 alkyl
• R 16b represents C 1 -C 6 alkyl, C 2 -C 6 alkenyl or (C 1 -C 6 ) alkyl optionally substituted with R 20
• R 16c is C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 20 , C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, Phenyl, phenyl substituted by (Z) q , D1-32, D1-33, D1-34, D1-36, D1-37 or D1-38, each
• R 20 represents a halogen atom, cyano, C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio or phenyl
• X 1 represents a halogen atom, C 1 -C 6 alkyl or (C 1 -C 6 ) alkyl optionally substituted with R 28
• R 28 represents a halogen atom, C 1 -C 6 alkoxy or C 1 -C 6 alkylthio
• Z represents a halogen atom, cyano, nitro, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkoxy or C 1 -C 6 haloalkylthio, the thiazole derivative according to the above [6] Or a salt thereof.
• R 1 represents a hydrogen atom
• R 3 represents a hydrogen atom, a halogen atom or C 1 -C 6 alkyl
• R a represents a hydrogen atom, C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 5a , C 2 to C 6 alkynyl or —C (O) OR 6a , or R a together with R 3 forms a C 3 alkylene chain to form a nitrogen atom to which R a is attached and R 3 May form a 6-membered ring with the carbon atom to which R b represents —C (O) R 7b ;
• R 5a represents C 3 -C 8 cycloalkyl or —OR 11a
• R 6a represents C 1 -C 6 alkyl
• R 11a represents C 1 -C 6 alkyl or —C (O) R 17a
• R 11b represents C 1 -C 6 alkyl or (C 1 -C
• R 15c represents —OR 16c , —S (O) r R 16c , (Z) q substituted with phenyl, D1-7, D1-87 or D1-98;
• R 16b represents C 1 -C 6 alkyl or (C 1 -C 6 ) alkyl optionally substituted with R 20 ;
• R 16c is, C 1 ⁇ C 6 alkyl, optionally substituted with R 20 (C 1 ⁇ C 6 ) alkyl, C 2 ⁇ C 6 alkenyl, C 3 ⁇ C 8 cycloalkyl, substituted by (Z) q Represents phenyl or D1-32.
• R 17a represents C 1 -C 6 alkyl
• R 17b represents C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 20 , C 3 -C 8 cycloalkyl or phenyl
• R 18b represents C 1 -C 6 alkyl, C 2 -C 6 alkenyl, phenyl or phenyl substituted by (Z) q
• R 19b represents a hydrogen atom.
• R 20 represents a halogen atom, cyano, C 1 -C 6 alkoxy or phenyl
• X 1 represents (C 1 -C 6 ) alkyl optionally substituted with R 28
• R 28 represents a halogen atom
• Z represents a halogen atom, nitro or C 1 -C 6 alkoxy
• g1 and g4 represent an integer of 1
• f5, f7, m1, m3 and n represent 0
• q represents an integer of 1 or 2
• r is a thiazole derivative or a salt thereof according to the above [7], wherein r represents an integer of 0, 1 or 2.
• R a is a hydrogen atom, C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 5a , C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, —C (O) Represents OR 6a or —C (O) R 7a , R b represents —C (O) R 7b or —C (S) R 7b ; R 5a represents a halogen atom, cyano, C 3 -C 8 cycloalkyl, —OH, —OR 11a or —S (O) r2 R 11a , R 6a represents C 1 -C 6 alkyl; R 7a represents C 1 -C 6 alkyl or C 3 -C 8 cycloalkyl, R 11a represents C 1 -C 6 alkyl, —C (O) OR 16a or —C (O) R 17a , R 12b is a hydrogen atom, C
• R 13b is a hydrogen atom, C 1 ⁇ C 6 alkyl, optionally substituted with R 15b (C 1 ⁇ C 6 ) alkyl, C 2 ⁇ C 6 alkenyl, optionally substituted with R 15b (C 2 ⁇ C 6 ) alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, (C 3 -C 8 ) cycloalkyl optionally substituted with R 15b , —S (O) r3 R 16b , —C ( O) OR 16b , —C (S) OR 16b , —C (O) SR 16b , —C (S) SR 16b , —C (O) R 17b , —C (S) R 17b , —C (O) N (R 18b ) R 19b , —C (S) N (R 18b ) R 19b , —C (S) N (R 18b
• X 1 represents a halogen atom, C 1 -C 6 alkyl or (C 1 -C 6 ) alkyl optionally substituted with R 28
• R 28 represents a halogen atom, C 1 -C 6 alkoxy or C 1 -C 6 alkylthio
• Z is a halogen atom, nitro, C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 28 , C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C The pyrazole derivative or the salt thereof according to the above [9], which represents 1 to C 6 alkoxy, C 1 to C 6 haloalkoxy, C 1 to C 6 alkylthio or C 1 to C 6 haloalkylthio.
• R 1 represents a hydrogen atom
• R 2 represents a halogen atom
• R 4 represents a hydrogen atom or C 1 -C 6 alkyl
• R 3 represents a hydrogen atom, a halogen atom or C 1 -C 6 alkyl
• R a represents a hydrogen atom, C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 5a or —C (O) R 7a
• R 5a represents -OR 11a
• R 7a represents C 3 -C 8 cycloalkyl
• R 11a represents C 1 -C 6 alkyl
• R 12b represents a hydrogen atom, C 1 -C 6 alkyl or (C 1 -C 6 ) alkyl optionally substituted with R 15c .
• R 13b is a hydrogen atom, C 1 -C 6 alkyl, (C 1 -C 6 ) alkyl optionally substituted with R 15b , C 2 -C 6 alkenyl, C 3 -C 8 cycloalkyl, —S (O ) r3 R 16b, -C (O ) OR 16b, -C (O) SR 16b, -C (O) R 17b, -C (O) N (R 18b) R 19b, -C (S) N (R 18b ) R 19b , phenyl, phenyl substituted by (Z) q , D1-32 or D1-37, or R 13b together with R 14b forms a C 4 alkylene chain , R 13b and R 14b may form a 5-membered ring with the nitrogen atom to which they are bonded, R 14b represents a hydrogen atom or C 1 -C 6 alkyl, or R 14b together with R 13b may form
• R 14e represents C 1 -C 6 alkyl or —OR 16b
• R 14f represents a hydrogen atom or C 1 -C 6 alkyl
• R 15b represents a halogen atom
• R 15c represents -S (O) r R 16c
• R 16b represents C 1 -C 6 alkyl, C 2 -C 6 alkenyl, (C 1 -C 6 ) alkyl or phenyl optionally substituted with R 20
• R 16c represents C 1 -C 6 alkyl
• R 17b is optionally substituted with a hydrogen atom, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkenyl, R 20 (C 1 -C 6 ) alkyl, —C (O) R 22 , —C ( ⁇ NOR 21 ) R 22 , pheny
• R 19b represents a hydrogen atom
• R 20 represents cyano, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkenyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, -C (O) OR 21 or phenyl
• R 21 represents C 1 -C 6 alkyl
• R 22 represents a hydrogen atom or C 1 -C 6 alkyl
• R 28 represents a halogen atom
• Z represents a halogen atom, (C 1 -C 6 ) alkyl optionally substituted with R 28 , C 3 -C 8 halocycloalkyl, C 1 -C 6 haloalkoxy or C 1 -C 6 haloalkylthio
• g1, g4 and m3 represent 0
• n represents an integer of 0 or 1
• q represents an integer of 1 or 2
• r3 is the pyrazole derivative or the salt
• a 1 represents -CR 1 R 1 and R 4 represent a hydrogen atom, The pyrazole or thiazole derivative or a salt thereof according to any one of [1] to [11], wherein n and m1 represent 0.
• a 1 represents -CR 1 R 1 represents a halogen atom, The pyrazole or thiazole derivative or a salt thereof according to any one of [1] to [11], wherein n and m1 represent 0.
• a 1 represents -CR 1 R 1 represents a hydrogen atom, R 2 represents a halogen atom, n represents an integer of 1; The pyrazole or thiazole derivative or a salt thereof according to any one of [1] to [11], wherein m1 represents 0.
• R 3 is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [15], wherein R 3 represents a hydrogen atom, a halogen atom or C 1 -C 6 alkyl.
• R 3 is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [15], in which R 3 represents a hydrogen atom.
• R 3 represents a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [15], wherein R 3 represents a halogen atom or C 1 -C 6 alkyl.
• R 3 represents a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [15], which represents a halogen atom.
• R 3 is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [15], in which R 3 represents a chlorine atom.
• R 3 represents a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [15], wherein R 3 represents C 1 -C 6 alkyl.
• R 3 represents methyl.
• R a represents (C 1 -C 6 ) alkyl, —C (O) N (R 8a ) R 9a or —C (S) N (R 8a ) R 9a optionally substituted with R 5a
• R 5a represents —OR 11a or —C (O) OH
• R 8a represents a hydrogen atom
• R 9a represents C 1 -C 6 alkyl
• R 11a represents —C (O) OR 16a , —C (O) R 17a or —C (O) N (R 18a ) R 19a
• R 16a represents C 1 -C 6 alkyl or (C 1 -C 6 ) alkyl optionally substituted with R 20
• R 17a represents C 1 -C 6 alkyl or phenyl
• R 18a and R 19a each independently represent C 1 -C 6 alkyl
• R 20 represents a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1
• R a represents C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, the pyrazole or thiazole derivative or salt thereof according to any one of [1] to [22] above.
• R a is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [22], wherein R a represents C 1 -C 6 alkyl.
• R a is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [22], wherein R a represents C 2 -C 6 alkenyl.
• R a is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [22], wherein R a represents C 2 -C 6 alkynyl.
• R a represents (C 1 -C 6 ) alkyl optionally substituted with R 5a , R 5a represents cyano, C 3 -C 8 cycloalkyl, —OH or —OR 11a
• R 11a is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [22], wherein R 11a represents C 1 -C 6 alkyl or C 2 -C 6 alkynyl.
• R a represents (C 1 -C 6 ) alkyl optionally substituted with R 5a
• R 5a is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [22], in which R 5a represents cyano.
• R a represents (C 1 -C 6 ) alkyl optionally substituted with R 5a , R 5a is, pyrazole or thiazole derivative or a salt thereof according to any one of [1] to [22] representing the C 3 - C 8 cycloalkyl.
• R a represents (C 1 -C 6 ) alkyl optionally substituted with R 5a , R 5a represents -OR 11a ;
• R 11a represents a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [22], in which R 11a represents C 1 -C 6 alkyl.
• R a represents (C 1 -C 6 ) alkyl optionally substituted with R 5a
• R 5a represents a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [22], in which —OH represents —OH.
• R a represents (C 1 -C 6 ) alkyl optionally substituted with R 5a
• R 5a represents -OR 11a
• R 11a represents a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [22], wherein R 11a represents C 2 -C 6 alkynyl.
• R a represents —C (O) R 7a ;
• R 7a is a pyrazole or thiazole derivative or a salt thereof according to the above [1] to [22], wherein R 7a represents C 1 -C 6 alkyl or C 3 -C 8 cycloalkyl.
• R a represents —C (O) R 7a ;
• R 7a represents a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [22], wherein R 7a represents C 1 -C 6 alkyl.
• R a represents —C (O) R 7a ;
• R 7a is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [22], wherein R 7a represents C 3 -C 8 cycloalkyl.
• R a represents —C (O) OR 6a
• R 6a represents a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [22], wherein R 6a represents C 1 -C 6 alkyl.
• R b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [38], wherein R b represents —C (O) R 7b or —C (S) R 7b .
• R b represents a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [38], wherein R b represents —C (O) R 7b .
• R b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [38], wherein R b represents —C (S) R 7b .
• R 7b is the pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [41], wherein R 7b represents —C ( ⁇ NOH) R 12b .
• R 7b is the pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [41], wherein R 7b represents —C ( ⁇ NOR 11b ) R 12b .
• R 11b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [45], wherein R 11b represents C 1 -C 10 alkyl or C 2 -C 6 alkenyl.
• R 11b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [45], wherein R 11b represents C 1 -C 10 alkyl.
• R 11b is pyrazole or thiazole derivative or a salt thereof according to any one of [1] to [45] representing the C 1 ⁇ C 6 alkyl.
• R 11b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [45], in which R 11b represents methyl.
• R 11b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [45], in which R 11b represents ethyl.
• R 11b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [45], wherein R 11b represents C 2 -C 6 alkenyl.
• R 11b represents (C 1 -C 6 ) alkyl optionally substituted with R 15b
• R 15b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [45], wherein R 15b represents cyano or C 3 -C 8 cycloalkyl.
• R 11b represents (C 1 -C 6 ) alkyl optionally substituted with R 15b , R 15b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [45], in which R 15b represents cyano.
• R 11b represents (C 1 -C 6 ) alkyl optionally substituted with R 15b , R 15b is pyrazole or thiazole derivative or a salt thereof according to any one of [1] to [45] representing the C 3 - C 8 cycloalkyl.
• R 12b represents cyano, —C (O) OR 16c , —C (O) N (R 18c ) R 19c or —C ⁇ NN (R 18c ) R 19c ⁇ R 17c
• R 16c represents C 1 -C 6 alkyl
• R 17c represents C 1 -C 6 alkyl
• R 18c represents C 1 -C 6 alkyl or —C (O) R 22
• R 19c represents a hydrogen atom
• R 22 represents a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein C 22 represents C 1 -C 6 alkyl.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein R 12b represents a hydrogen atom or C 1 -C 6 alkyl.
• R 12b represents (C 1 -C 6 ) alkyl optionally substituted with R 15c , R 15c represents -S (O) r R 16c ;
• R 16c is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein R 16c represents C 1 -C 6 alkyl.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], which represents a substituent represented by the following structural formula.
• R 12b represents (C 1 -C 6 ) alkyl optionally substituted with R 15c , R 15c represents -S (O) r R 16c ; R 16c is the pyrazole or thiazole derivative or salt thereof according to any one of the above [1] to [54], wherein C 16 represents C 3 -C 8 cycloalkyl.
• R 12b is optionally substituted with R 15c (C 2 ⁇ C 6 ) alkenyl, optionally substituted with optionally substituted with R 15c (C 2 ⁇ C 6 ) alkynyl, or R 15c (C 3 ⁇ C 8 ) represents cycloalkyl, R 15c represents -S (O) r R 16c ; R 16c is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein R 16c represents C 1 -C 6 alkyl.
• R 12b represents (C 2 -C 6 ) alkenyl optionally substituted with R 15c , R 15c represents -S (O) r R 16c ; R 16c is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein R 16c represents C 1 -C 6 alkyl.
• R 12b represents (C 2 -C 6 ) alkynyl optionally substituted with R 15c , R 15c represents -S (O) r R 16c ; R 16c is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein R 16c represents C 1 -C 6 alkyl.
• R 12b represents (C 3 -C 8 ) cycloalkyl optionally substituted with R 15c , R 15c represents -S (O) r R 16c ; R 16c is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein R 16c represents C 1 -C 6 alkyl.
• R 12b represents (C 1 -C 6 ) alkyl optionally substituted with R 15c , R 15c represents -S (O) r R 16c ; R 16c is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein C 16 represents C 2 -C 6 alkenyl.
• R 12b represents (C 1 -C 6 ) alkyl optionally substituted with R 15c
• R 15c represents -S (O) r R 16c
• R 16c represents (C 1 -C 6 ) alkyl optionally substituted with R 20
• R 20c is the pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], in which R 20c represents a halogen atom.
• R 12b represents (C 1 -C 6 ) alkyl optionally substituted with R 15c
• R 15c is the pyrazole or thiazole derivative or salt thereof according to any one of the above [1] to [54], wherein D 15 represents D 1-87 or D 1-98.
• R 12b represents (C 1 -C 6 ) alkyl optionally substituted with R 15c
• R 15c represents a halogen atom or —S (O) r R 16c
• R 16c is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein R 16c represents C 1 -C 6 alkyl.
• R 12b represents (C 1 -C 6 ) alkyl optionally substituted with R 15c , R 15c represents cyano or —S (O) r R 16c , R 16c is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein R 16c represents C 1 -C 6 alkyl.
• R 12b represents (C 1 -C 6 ) alkyl optionally substituted with R 15c
• R 15c is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein R 15c represents —OR 16c or —S (O) r R 16c .
• R 12b represents (C 1 -C 6 ) alkyl optionally substituted with R 15c , R 15c represents -OR 16c or -S (O) r R 16c ; R 16c represents C 1 -C 6 alkyl or —S (O) r R 21 , R 21 represents a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein R 21 represents C 1 -C 6 alkyl.
• R 12b is phenyl, phenyl substituted by (Z) q , D1-2, D1-32 or D1-34, and the pyrazole or thiazole derivative or salt thereof according to any one of [1] to [54] above .
• R 12b is the pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein -S (O) r R 16c is represented.
• R 12b represents -S (O) r R 16c ;
• R 16c is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein R 16c represents C 1 -C 6 alkyl.
• R 12b is the pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [54], wherein -C (O) R 17c is represented.
• R 12b is phenyl, phenyl substituted by (Z) q , D1-2, D1-32 or D1-34, and the pyrazole or thiazole derivative or salt thereof according to any one of [1] to [54] above .
• R 13b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [92], in which R 13b represents a hydrogen atom.
• R 13b represents -S (O) r3 R 16b , R 16b is pyrazole or thiazole derivative or a salt thereof according to any one of [1] to [92], which represents the C 1 ⁇ C 6 alkyl.
• R 13b represents -C (O) OR 16b , R 16b is pyrazole or thiazole derivative or a salt thereof according to any one of [1] to [92], which represents the C 1 ⁇ C 6 alkyl.
• R 13b represents -C (O) R 17b , R 16b is pyrazole or thiazole derivative or a salt thereof according to any one of [1] to [92], which represents the C 1 ⁇ C 6 alkyl.
• R 14b is a pyrazole or thiazole derivative or a salt thereof according to any one of the above [1] to [96], in which R 14b represents a hydrogen atom.
• R 14b is pyrazole or thiazole derivative or a salt thereof according to any one of [1] to [96], which represents the C 1 ⁇ C 6 alkyl.
• a pest control agent comprising one or more selected from the pyrazole or thiazole derivatives or salts thereof according to any one of [1] to [98] as an active ingredient.
• a mammal or avian internal or ectoparasite control agent comprising, as an active ingredient, one or more selected from the pyrazole or thiazole derivative according to any one of [1] to [98] or a salt thereof.
• the soil treatment agent according to [103], wherein the soil treatment method is soil irrigation treatment.
• the compound of the present invention has excellent insecticidal / miticidal activity against internal or ectoparasites of many agricultural pests, spider mites, mammals or birds, and has acquired resistance to existing insecticides. Exhibits a sufficient control effect. Furthermore, it has little adverse effect on mammals, fish and beneficial insects, has low persistence, and has a light environmental impact. Therefore, the present invention can provide a useful novel pest control agent.
• the compounds encompassed by the present invention may have geometrical isomers of E-form and Z-form depending on the type of substituent, but the present invention is not limited to these E-form, Z-form, or E-form. And a mixture containing Z-isomer and Z-isomer in an arbitrary ratio.
• the compounds included in the present invention include optically active substances resulting from the presence of one or more asymmetric carbon atoms, but the present invention includes all optically active substances or racemates.
• those that can be converted into acid addition salts according to a conventional method include, for example, hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and the like.
• Salts inorganic acid salts such as nitric acid, sulfuric acid, phosphoric acid, chloric acid, perchloric acid, sulfonic acid salts such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, Salts of carboxylic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, fumaric acid, tartaric acid, succinic acid, maleic acid, malic acid, succinic acid, benzoic acid, mandelic acid, ascorbic acid, lactic acid, gluconic acid, citric acid, etc.
• carboxylic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, fumaric acid, tartaric acid, succinic acid, maleic acid, malic acid, succinic acid, benzoic acid, man
• a salt of an amino acid such as glutamic acid or aspartic acid can be used.
• those that can be converted into a metal salt according to a conventional method include, for example, alkali metal salts such as lithium, sodium, and potassium, and alkaline earth metals such as calcium, barium, and magnesium. It can be a salt or an aluminum salt.
• n- means normal
• i- means iso
• s- means secondary and tert- means tertiary
• Ph means phenyl.
• halogen atom in the present specification include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• the notation “halo” also represents these halogen atoms.
• C a -C b alkyl represents a linear or branched hydrocarbon group having a carbon number of a to b, for example, a methyl group, an ethyl group, an n-propyl group, Specific examples include i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1,1-dimethylpropyl group, n-hexyl group and the like. Each selected range of carbon atoms is selected.
• C a -C b haloalkyl is a linear or branched chain having a to b carbon atoms, in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom.
• fluoromethyl group chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, dichloromethyl group, trifluoromethyl group, chlorodifluoromethyl group, trichloromethyl group, bromodifluoromethyl group, 2-fluoroethyl group, 2- Chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2,2-trichloroethyl group, 1 , 1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, pentafluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3 , 3-pentafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group
• C a -C b cycloalkyl represents a cyclic hydrocarbon group having a to b carbon atoms, and forms a monocyclic or complex ring structure having 3 to 8 members. I can do it.
• Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms. Specific examples include cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. Selected in a range of numbers.
• C a -C b halocycloalkyl represents a cyclic hydrocarbon group having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom. And can form monocyclic or complex ring structures from 3 to 8 membered rings.
• Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the substitution with a halogen atom may be a ring structure part, a side chain part, They may be both, and when they are substituted by two or more halogen atoms, the halogen atoms may be the same as or different from each other.
• 2,2-difluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dibromocyclopropyl group, 2,2-difluoro-1-methylcyclopropyl group, 2,2-dichloro-1-methyl Specific examples include cyclopropyl group, 2,2-dibromo-1-methylcyclopropyl group, 2,2,3,3-tetrafluorocyclobutyl group, etc., each selected within the range of the designated number of carbon atoms.
• C a -C b alkenyl is a linear or branched chain composed of a to b carbon atoms and has one or more double bonds in the molecule.
• Represents a saturated hydrocarbon group for example, vinyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 2-butenyl group, 2-methyl-2-propenyl group, 3-methyl-2-butenyl group, 1
• Specific examples include 1,2-dimethyl-2-propenyl group and the like, and each is selected within the range of the designated number of carbon atoms.
• C a -C b haloalkenyl is represented by a linear or branched chain having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom. And an unsaturated hydrocarbon group having one or more double bonds in the molecule. At this time, when substituted by two or more halogen atoms, these halogen atoms may be the same as or different from each other.
• C a -C b cycloalkenyl represents a cyclic unsaturated hydrocarbon group having 1 to 2 carbon atoms and having 1 to 2 carbon atoms.
• a monocyclic or complex ring structure from a member ring to a 6-member ring can be formed.
• Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the double bond may be in an endo- or exo- form.
• Specific examples include 1-cyclopenten-1-yl group, 2-cyclopenten-1-yl group, 1-cyclohexen-1-yl group, 2-cyclohexen-1-yl group, and the like. Selected in a range of numbers.
• C a -C b alkylidene represents a linear or branched hydrocarbon group having a carbon number of a to b and bonded by a double bond, for example, a methylidene group, an ethylidene group, Specific examples include a group, a propylidene group, a 1-methylethylidene group, etc., and each is selected within the range of the designated number of carbon atoms.
• C a -C b alkynyl represents a linear or branched chain having a carbon number of a to b and an unsaturated group having one or more triple bonds in the molecule.
• C a -C b haloalkynyl represents a linear or branched chain having a carbon number of a to b in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom. And an unsaturated hydrocarbon group having one or more triple bonds in the molecule. At this time, when substituted by two or more halogen atoms, these halogen atoms may be the same as or different from each other.
• Specific examples include 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 3-iodo-2-propynyl group and the like. Each of which is selected for each specified number of carbon atoms.
• C a -C b alkoxy in the present specification represents an alkyl-O— group having the above-mentioned meaning consisting of a to b carbon atoms, such as methoxy group, ethoxy group, n-propyloxy group, Specific examples include i-propyloxy group, n-butyloxy group, i-butyloxy group, s-butyloxy group, tert-butyloxy group and the like, and each is selected within the range of the designated number of carbon atoms.
• C a -C b haloalkoxy in the present specification represents a haloalkyl-O— group having the above-mentioned meaning consisting of a to b carbon atoms, for example, a difluoromethoxy group, a trifluoromethoxy group, a chlorodifluoro Methoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2, -tetrafluoroethoxy group, 2-chloro-1 Specific examples include 1,2,2-trifluoroethoxy group, 1,1,2,3,3,3-hexafluoropropyloxy group and the like, and each is selected within the range of the designated number of carbon atoms.
• C a -C b alkylthio in the present specification represents an alkyl-S-group having the above-mentioned meaning comprising a to b carbon atoms, for example, methylthio group, ethylthio group, n-propylthio group, i Specific examples include -propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, tert-butylthio group and the like, and each is selected within the range of the designated number of carbon atoms.
• C a -C b haloalkylthio in the present specification represents a haloalkyl-S— group having the above-mentioned meaning consisting of a to b carbon atoms, such as difluoromethylthio group, trifluoromethylthio group, chlorodifluoro Methylthio group, bromodifluoromethylthio group, 2,2,2-trifluoroethylthio group, 1,1,2,2-tetrafluoroethylthio group, 2-chloro-1,1,2-trifluoroethylthio group, Pentafluoroethylthio group, 1,1,2,3,3,3-hexafluoropropylthio group, heptafluoropropylthio group, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethylthio group , Nonafluorobutylthio group and the like are given as specific examples,
• C a -C b alkylsulfinyl in the present specification represents an alkyl-S (O) -group having the above-mentioned meaning consisting of a to b carbon atoms, such as methylsulfinyl group, ethylsulfinyl group, Specific examples include n-propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, i-butylsulfinyl group, s-butylsulfinyl group, tert-butylsulfinyl group and the like. The range is selected.
• C a -C b haloalkylsulfinyl represents a haloalkyl-S (O) — group having the above-mentioned meaning consisting of a to b carbon atoms, for example, difluoromethylsulfinyl group, trifluoromethyl Sulfinyl group, chlorodifluoromethylsulfinyl group, bromodifluoromethylsulfinyl group, 2,2,2-trifluoroethylsulfinyl group, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethylsulfinyl group, nona Specific examples include a fluorobutylsulfinyl group and the like, and each is selected within the range of the designated number of carbon atoms.
• C a -C b alkylsulfonyl in the present specification represents an alkyl-SO 2 — group having the above-mentioned meaning consisting of a to b carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, n- Specific examples include propylsulfonyl group, i-propylsulfonyl group, n-butylsulfonyl group, i-butylsulfonyl group, s-butylsulfonyl group, tert-butylsulfonyl group, etc. Selected.
• C a -C b haloalkylsulfonyl in the present specification represents a haloalkyl-SO 2 — group having the above-mentioned meaning consisting of a to b carbon atoms, such as a difluoromethylsulfonyl group or a trifluoromethylsulfonyl group.
• Chlorodifluoromethylsulfonyl group bromodifluoromethylsulfonyl group, 2,2,2-trifluoroethylsulfonyl group, 1,1,2,2-tetrafluoroethylsulfonyl group, 2-chloro-1,1,2-trimethyl
• Specific examples include a fluoroethylsulfonyl group and the like, and each is selected within the range of the designated number of carbon atoms.
• C a -C b alkylamino in the present specification represents an amino group in which one of the hydrogen atoms is substituted with an alkyl group having the above-mentioned meaning consisting of a to b carbon atoms, for example, a methylamino group , Ethylamino group, n-propylamino group, i-propylamino group, n-butylamino group, i-butylamino group, tert-butylamino group and the like. Selected by range.
• di (C a -C b alkyl) amino in the present specification has the above-mentioned meaning that the number of carbon atoms, which may be the same or different from each other, is ab.
• Specific examples include an amino group, a di (n-butyl) amino group, and the like, and each is selected within the range of the designated number of carbon atoms.
• Specific examples include an oxyimino group, an i-propyloxyimino group, an n-butyloxyimino group, and the like, and each is selected within the range of the designated number of carbon atoms.
• C a -C b alkylcarbonyl in the present specification represents an alkyl-C (O) — group having the above-mentioned meaning comprising a to b carbon atoms, for example, an acetyl group, a propionyl group, a butyryl group.
• Specific examples thereof include isobutyryl group, valeryl group, isovaleryl group, 2-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group and the like, and each is selected in the range of the designated number of carbon atoms.
• C a -C b haloalkylcarbonyl in the present specification represents a haloalkyl-C (O) — group having the above-mentioned meaning consisting of a to b carbon atoms, such as a fluoroacetyl group, a chloroacetyl group, Difluoroacetyl group, dichloroacetyl group, trifluoroacetyl group, chlorodifluoroacetyl group, bromodifluoroacetyl group, trichloroacetyl group, pentafluoropropionyl group, heptafluorobutanoyl group, 3-chloro-2,2-dimethylpropanoyl group Etc.
• a fluoroacetyl group such as a fluoroacetyl group, a chloroacetyl group, Difluoroacetyl group, dichloroacetyl group, trifluoroacety
• C a -C b cycloalkylcarbonyl in the present specification represents a cycloalkyl-C (O) -group having the above-mentioned meaning consisting of a to b carbon atoms, such as cyclopropylcarbonyl group, 2 Specific examples include -methylcyclopropylcarbonyl group, cyclobutylcarbonyl group and the like, each selected within the range of the designated number of carbon atoms.
• C a -C b halocycloalkylcarbonyl represents a halocycloalkyl-C (O) — group having the above-mentioned meaning consisting of a to b carbon atoms, for example 2,2- Specific examples include a dichlorocyclopropylcarbonyl group, a 2,2-dichloro-1-methylcyclopropylcarbonyl group, etc., and each is selected within the range of the designated number of carbon atoms.
• C a -C b alkoxycarbonyl represents an alkyl-O—C (O) — group having the above-mentioned meanings consisting of a to b carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl Specific examples include a group, n-propyloxycarbonyl group, i-propyloxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, tert-butoxycarbonyl group and the like. Selected.
• C a -C b haloalkoxycarbonyl represents a haloalkyl-O—C (O) — group having the above-mentioned meaning of a to b carbon atoms, such as a chloromethoxycarbonyl group, Specific examples include 2-chloroethoxycarbonyl group, 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, and the like. Selected in the range of the number of carbon atoms.
• C a -C b alkylaminocarbonyl represents a carbamoyl group in which one of the hydrogen atoms is substituted with an alkyl group having the above-mentioned meaning consisting of a to b carbon atoms, for example methylcarbamoyl
• Specific examples include a group, ethylcarbamoyl group, n-propylcarbamoyl group, i-propylcarbamoyl group, n-butylcarbamoyl group, i-butylcarbamoyl group, s-butylcarbamoyl group, tert-butylcarbamoyl group, etc.
• C a -C b haloalkylaminocarbonyl in this specification represents a carbamoyl group in which one of the hydrogen atoms is substituted with a haloalkyl group as defined above consisting of a to b carbon atoms, for example 2-fluoro Specific examples include an ethylcarbamoyl group, a 2-chloroethylcarbamoyl group, a 2,2-difluoroethylcarbamoyl group, a 2,2,2-trifluoroethylcarbamoyl group, and the like, each selected within the specified number of carbon atoms. Is done.
• the notation of di (C a -C b alkyl) aminocarbonyl means in the above meaning that the number of carbon atoms, which may be the same or different from each other, is ab.
• Specific examples include a group, an N, N-di (n-butyl) carbamoyl group, and the like, and each is selected within the range of the designated number of carbon atoms.
• C a -C b alkylaminosulfonyl represents a sulfamoyl group in which one of the hydrogen atoms is substituted with an alkyl group having the above-mentioned meaning consisting of a to b carbon atoms.
• Famoyl group ethylsulfamoyl group, n-propylsulfamoyl group, i-propylsulfamoyl group, n-butylsulfamoyl group, i-butylsulfamoyl group, s-butylsulfamoyl group, Specific examples include a tert-butylsulfamoyl group and the like, and each is selected within the range of the designated number of carbon atoms.
• di (C a -C b alkyl) aminosulfonyl means in the above meaning that the number of carbon atoms in which both hydrogen atoms may be the same or different from each other consists of a to b.
• R 5a (C a ⁇ C b ) alkyl optionally substituted with R 10a (C a ⁇ C b ) alkyl, optionally substituted with R 15a (C a ⁇ C b) alkyl, optionally substituted with R 15b (C a ⁇ C b ) alkyl, optionally substituted with R 15c (C a ⁇ C b ) alkyl, optionally substituted with R 15d (C a ⁇ C b) alkyl, optionally substituted with R 20 (C a ⁇ C b ) alkyl, optionally substituted with R 28 (C a ⁇ C b ) alkyl, optionally substituted with R 28a (C a ⁇ C b) alkyl, optionally substituted with R 31 (C a ⁇ C b ) alkyl or optionally substituted with R 32 (C a ⁇ C b ) notation alkyl or the like, any of
• R 5a , R 10a , R 15a , R 15b , R 15c , R 15d , R 20 , R 28 , R 28a , R 31, or R 32 may be the same or different. .
• R 5a C a ⁇ C b cycloalkyl
• R 10a C a ⁇ C b cycloalkyl
• R 15a C a ⁇ C b
• R 15b C a ⁇ C b
• R 15c C a ⁇ C b
• R 15d been (C a ⁇ C b) cycloalkyl
• R 20 C a ⁇ C b
• R 28 optionally substituted in (C a ⁇ C b) cycloalkyl
• each R 5a , R 10a , R 15a , R 15b , R 15c , R 15d , R 20 , R 28a , R 31 or R 32 may be the same or different from each other;
• the substitution position may be a ring structure moiety, a side chain moiety, or both.
• R 5a (C a ⁇ C b ) alkenyl optionally substituted with R 10a (C a ⁇ C b ) alkenyl, optionally substituted with R 15a (C a ⁇ C b) alkenyl, optionally substituted with R 15b (C a ⁇ C b ) alkenyl, optionally substituted with R 15c (C a ⁇ C b ) alkenyl, optionally substituted with R 15d (C a ⁇ C b) alkenyl, optionally substituted with R 20 (C a ⁇ C b ) alkenyl, optionally substituted with R 28 (C a ⁇ C b ) alkenyl, optionally substituted with R 28a (C a ⁇ C b) alkenyl, which is optionally substituted with R 31 (C a ⁇ C b ) alkenyl or optionally substituted with R 32 (C a ⁇ C b ) alkenyl, which
• R 5a , R 10a , R 15a , R 15b , R 15c , R 15d , R 20 , R 28 , R 28a , R 31, or R 32 may be the same or different. .
• R 5a (C a ⁇ C b ) cycloalkenyl, optionally substituted with R 10a (C a ⁇ C b ) cycloalkenyl, optionally substituted with R 15a (C a ⁇ C b ) cycloalkenyl, optionally substituted with R 15b (C a ⁇ C b ) cycloalkenyl, optionally substituted with R 15c (C a ⁇ C b ) cycloalkenyl, optionally substituted with R 15d (C a ⁇ C b) cycloalkenyl, substituted optionally substituted with R 20 (C a ⁇ C b ) cycloalkenyl, optionally substituted with R 28 (C a ⁇ C b ) cycloalkenyl, optionally with R 28a been (C a ⁇ C b) cycloalkenyl, optionally substituted with R 31 (C a ⁇ C b) cycl
• Is represented by any R 5a , R 10a , R 15a , R 15b , R 15c , R 15d , R 20 , R 28 , R 28a , R 31 or R 32 , and a hydrogen atom bonded to a carbon atom is arbitrarily It represents a cycloalkenyl group having the above meaning consisting of a to b substituted carbon atoms, and is selected in the range of each designated number of carbon atoms.
• each R 5a , R 10a , R 15a , R 15b , R 15c , R 15d , R 20 , R 28 , R 28a , R 31 or R 32 may be the same or different from each other.
• the substitution position may be a ring structure part, a side chain part, or both.
• R 5a (C a ⁇ C b ) alkynyl optionally substituted with R 10a (C a ⁇ C b ) alkynyl, optionally substituted with R 15a (C a ⁇ C b) alkynyl, optionally substituted with R 15b (C a ⁇ C b ) alkynyl, optionally substituted with R 15c (C a ⁇ C b ) alkynyl, optionally substituted with R 15d (C a (C b ) alkynyl, optionally substituted with R 20 (C a -C b ) alkynyl, optionally substituted with R 28 (C a -C b ) alkynyl, optionally substituted with R 28a (C a ⁇ C b) alkynyl, which is optionally substituted with R 31 (C a ⁇ C b ) alkynyl or optionally substituted with R 32
• R 5a , R 10a , R 15a , R 15b , R 15c , R 15d , R 20 , R 28 , R 28a , R 31, or R 32 may be the same or different. .
• [R 8a is by forming alkenylene chain alkylene chain or C 2 ⁇ C 7 of C 2 ⁇ C 7 together with R 9a, 3 ⁇ 8-membered ring together with the nitrogen atom to which R 8a and R 9a are bonded
• the alkylene chain or alkenylene chain may contain one oxygen atom, sulfur atom or nitrogen atom
• [R 13a is by forming alkenylene chain alkylene chain or C 2 ⁇ C 7 of C 2 ⁇ C 7 together with R 14a, 3 ⁇ 8-membered ring together with the nitrogen atom to which R 13a and R 14a are attached
• the alkylene chain or alkenylene chain may contain one oxygen atom, sulfur atom or nitrogen atom
• [R 13b is by forming alkenylene chain alkylene chain or C 2 ⁇ C 7 of C 2 ⁇ C 7 together with R 14b, 3 ⁇ 8-membered ring together with the nitrogen atom to which R 13b and R 14b are bonded
• R 14e herein by forming the alkenylene chain alkylene chain or C 2 ⁇ C 7 of C 2 ⁇ C 7 together with R 14f, 3 together with the carbon atom to which R 14e and R 14f are bonded May form an ⁇ 8-membered ring, and this alkylene chain or alkenylene chain may contain 1, 2 or 3 oxygen atoms, sulfur atoms or nitrogen atoms.
• Specific examples of the notation include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, oxetane-3-ylidene, thietan-3-ylidene, dihydrofuran-3-ylidene, dihydrothiophene-3-ylidene, Dihydropyran-3-ylidene, dihydropyran-4-ylidene, dihydrothiopyran-3-ylidene, dihydrothiopyran-4-ylid
• the compound of the present invention can be produced by the following method. Manufacturing method A Formula (6) [wherein A 1 , R 2 , R 3 , R 4 , R 6b , R a and n represent the same meaning as described above. And a compound represented by the formula (7) [wherein A 1 , R 2 , R 3 , R 4 , R a and n represent the same meaning as described above]. The compound represented by this can be obtained.
• hydrochloric acid hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, trifluoroacetic acid and the like can be used.
• base potassium carbonate, sodium hydroxide or the like can be used. This reaction may be carried out without solvent, but a solvent may be used.
• polar solvents such as acetonitrile and water, alcohols such as methanol, ethanol, propanol, 2-propanol and ethylene glycol, ethers such as diethyl ether, tetrahydrofuran and diphenyl ether, and aromatic hydrocarbons such as benzene, toluene and xylene Halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, and aliphatic hydrocarbons such as pentane and n-hexane. These solvents may be used alone or as a mixture of two or more thereof.
• the reaction temperature can be set to any temperature from ⁇ 60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary within the range of 5 minutes to 100 hours. Can be set.
• the compound represented by the formula (7) thus obtained is represented by the formula (8-1) [wherein R 7b represents the same meaning as described above. And a compound represented by formula (9) [wherein A 1 , R 2 , R 3 , R 4 , R 7b , R a and n represent the same meaning as described above].
• This invention compound represented by this can be synthesize
• the compound represented by formula (8-1) is used in the range of 0.5 to 50 equivalents, preferably 0.8 to 2 equivalents, relative to 1 equivalent of the compound represented by formula (7). be able to.
• a base such as potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine can be used.
• This reaction may be carried out without a solvent, but a solvent may be used, for example, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2- Polar solvents such as imidazolinone, alcohols such as methanol, ethanol, propanol, 2-propanol and ethylene glycol, ethers such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride Halogenated hydrocarbons such as chloroform and carbon tetrachloride, and aliphatic hydrocarbons such as pentane and n-hexane.
• a solvent may be used, for example, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3
• the reaction temperature can be set to any temperature from ⁇ 60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary within the range of 5 minutes to 100 hours. Can be set.
• the compounds represented by formula (8-1) are known compounds, and some of them are commercially available. Others can be synthesized according to known methods described in the literature. Further, the compound represented by the formula (7) is converted into the formula (8-2) using a condensing agent, wherein R 7b represents the same meaning as described above.
• the compound of the present invention represented by formula (9) can also be synthesized by reacting with the compound represented by formula (9). In this reaction, 1 to 4 equivalents of WSC ⁇ 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride ⁇ , CDI (carbonyldiimidazole) per 1 equivalent of the compound represented by formula (8-2) ) And the like can be used.
• the compound represented by the formula (8-2) is used in the range of 0.5 to 50 equivalents, preferably 0.8 to 2 equivalents with respect to 1 equivalent of the compound represented by the formula (7).
• a base such as potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine can be used.
• This reaction may be carried out without a solvent, but a solvent may be used, for example, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2- Polar solvents such as imidazolinone, alcohols such as methanol, ethanol, propanol, 2-propanol and ethylene glycol, ethers such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride Halogenated hydrocarbons such as chloroform and carbon tetrachloride, and aliphatic hydrocarbons such as pentane and n-hexane.
• a solvent may be used, for example, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3
• the reaction temperature can be set to any temperature from ⁇ 60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary within the range of 5 minutes to 100 hours. Can be set.
• Some of the compounds represented by formula (8-2) are known compounds, and some of them are commercially available. Others can be synthesized according to known methods described in the literature.
• the amount of the compound represented by the formula (2-2) can be used in the range of 0.8 to 5 equivalents relative to 1 equivalent of the compound represented by the formula (2-12).
• Some of the compounds represented by the formula (2-2) used here are known compounds, and some of them are commercially available. Others can be synthesized according to the methods described in the literature.
• Examples of the catalyst that can be used in this reaction include palladium catalysts such as palladium-carbon, palladium chloride, palladium acetate, bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, copper metal, and copper (I) acetate.
• copper catalysts such as copper (II) acetate, copper (I) oxide, copper (II) oxide and copper iodide.
• the amount of the catalyst to be used is 0.001 to 1.0 equivalent, preferably 0.01 to 0.5 equivalent, more preferably 0.05 to 1 equivalent relative to 1 equivalent of the compound represented by formula (2-12). It can be used in the range of 0.2 equivalents.
• the base used include tertiary amine compounds such as pyridine, diisopropylethylamine, and triethylamine, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, and sodium bicarbonate. .
• the amount of the base used can be 0.1 to 10.0 equivalents, preferably 0.5 to 3 equivalents, relative to 1 equivalent of the compound represented by formula (2-12).
• This reaction can be carried out without solvent, but a solvent may be used.
• a solvent may be used.
• the reaction temperature can be set to any temperature from ⁇ 60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary within the range of 5 minutes to 100 hours. Can be set.
• Manufacturing method C A compound represented by the formula (9), diphosphorus pentasulfide, diphosphorus pentasulfide-HMDO (hexamethyldisiloxane), Lawesson's Reagent; 2,4-bis (4-methoxyphenyl) -1 , 3,2,4-dithiadiphosphetane-2,4-disulfide) and the like to react with a compound represented by the formula (35) [wherein A 1 , R 2 , R 3 , R 4 , R 7b , R a and n represent the same meaning as described above. This invention compound represented by this can be obtained.
• the sulfurizing agent used in this reaction can be used in the range of 0.5 to 50 equivalents, preferably 0.5 to 2 equivalents, relative to 1 equivalent of the compound represented by formula (9). If necessary, a base such as potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine can be used. This reaction can be carried out without solvent, but a solvent may be used.
• the reaction temperature can be set to any temperature from ⁇ 60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary within the range of 5 minutes to 100 hours. Can be set.
• Manufacturing method D Formula (13) [wherein A 1 , R 2 , R 3 , R 4 and n represent the same meaning as described above.
• the compound represented by the formula (8-1) or the compound represented by the formula (8-2) is reacted with the compound represented by the formula (8-1) using the same method as the production method A. 41) [wherein A 1 , R 2 , R 3 , R 4 , R 7b and n represent the same meaning as described above.
• This invention compound represented by this can be obtained.
• the compound represented by the formula (41) is represented by the formula (5) [wherein R a represents the same meaning as described above, J b represents a halogen atom, —OH, —OSO 2 CH 3 , —OSO 2 CF 3 Represents a leaving group.
• the compound of the present invention represented by the formula (9) can also be obtained by reacting with the compound represented by formula (9).
• the compound represented by formula (5) is used in the range of 0.5 to 50 equivalents, preferably 0.5 to 2 equivalents, relative to 1 equivalent of the compound represented by formula (41). Can do.
• bases such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, etc., potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine, sodium hydride, sodium hydroxide, potassium hydroxide, or diethyl Mitsunobu reaction using azodicarboxylate and triphenylphosphine can be used.
• This reaction can be carried out without solvent, but a solvent may be used.
• the reaction temperature can be set to any temperature from ⁇ 60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary within the range of 5 minutes to 100 hours. Can be set.
• Some of the compounds represented by formula (5) are known compounds, and some of them are commercially available. Others can be synthesized according to known methods described in the literature.
• Manufacturing method F Formula (9-4) [wherein A 1 , R 2 , R 3 , R 4 , R 12b , R a and n represent the same meaning as described above.
• the compound represented by formula (9-5) which is a geometric isomer of the oxime moiety, is prepared in the same manner as in Production Method E, wherein A 1 , R 2 , R 3 , R 4 , R 12b , R a and n represent the same meaning as described above.
• This invention compound represented by this can be obtained.
• the compound of the present invention represented by the formula (9-4) can also be obtained from the compound represented by the formula (9-5).
• J a is a hydrogen atom, a halogen atom, —OH, —OSO 2 CH 3 , —OSO 2 CF 3 , — It represents a leaving group such as C (O) OH, —C (O) OR 52 , and R 52 represents C 1 -C 6 alkyl, phenyl or the like.
• the compound of the present invention represented by the formula (9-T) can be obtained by reacting the compound represented by formula (9-T) in the presence of a catalyst and a base.
• the amount of the compound represented by the formula (2-2) is in the range of 0.8 to 5 equivalents, preferably 0.8 to 2 equivalents with respect to 1 equivalent of the compound represented by the formula (17-T). Can be used.
• Some of the compounds represented by the formula (2-2) used here are known compounds, and some of them are commercially available. Others can be synthesized according to the methods described in the literature.
• Examples of the catalyst that can be used in this reaction include palladium catalysts such as palladium-carbon, palladium chloride, palladium acetate, bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, copper metal, and copper (I) acetate.
• palladium catalysts such as palladium-carbon, palladium chloride, palladium acetate, bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, copper metal, and copper (I) acetate.
• Copper catalysts such as copper acetate (II), copper oxide (I), copper oxide (II) and copper iodide
• nickel catalysts such as bis (1,5-cyclooctadiene) nickel and nickel (II) acetylacetonate Is mentioned.
• the amount of the catalyst used is 0.001 to 1.0 equivalent, preferably 0.01 to 0.5 equivalent, more preferably 0.05 to 1 equivalent, relative to 1 equivalent of the compound represented by the formula (17-T). It can be used in the range of 0.2 equivalents.
• the base used include tertiary amine compounds such as pyridine, diisopropylethylamine, and triethylamine, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, and sodium bicarbonate. .
• the amount of the base used can be 0.1 to 10.0 equivalents, preferably 0.5 to 3 equivalents, relative to 1 equivalent of the compound represented by the formula (17-T).
• This reaction can be carried out without solvent, but a solvent may be used.
• a solvent for example, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water and other polar solvents, methanol, ethanol, propanol, 2-propanol, ethylene glycol Alcohols such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, pentane and n-hexane And aliphatic hydrocarbons.
• the reaction temperature can be set to any temperature from ⁇ 60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary within the range of 5 minutes to 100 hours. Can be set.
• the compound of the present invention represented by the formula (41-T) can be obtained by reacting the compound represented by the formula (2-2) with the compound represented by the formula (2-2) in the same manner as in Production Method J. .
• the reaction from production method A to production method K may be carried out in an inert gas atmosphere such as nitrogen or argon if necessary.
• the reaction mixture after completion of the reaction is directly concentrated, or dissolved in an organic solvent, concentrated after washing with water, or poured into ice water, and subjected to usual post-treatment such as concentration after extraction with an organic solvent.
• the objective compound of the present invention can be obtained.
• it can be separated and purified by any purification method such as recrystallization, column chromatograph, thin layer chromatograph, liquid chromatographic fractionation and the like.
• reaction formula 1 The compound represented by the formula (6) used in the production method A can be synthesized, for example, according to the following reaction formulas 1 and 2. Reaction formula 1
• Formula (2-1) [wherein R 3 and R 4 represent the same meaning as described above, and R 50 represents a C 1 -C 6 alkyl group. ] Can be synthesized by a known method such as Sinlet 2004, Vol. 4, 703. The compound represented by the formula (2-1) is converted into a known formula (2-2) according to a known method known in the literature, for example, the method described in Journal of Organic Chemistry 2004, 69, 5578.
• R 51 represents a hydrogen atom or C 1 to C 6 alkyl which may be the same or different, or two R 51 together represent —CH 2 CH 2 — or —C (CH 3 ) 2.
• C (CH 3 ) 2 — may be formed).
• the compound represented by the formula (2-3) is represented by the formula (2-4) [wherein R 3 , R 4 and R 50 represent the same meaning as described above, and R 51 represents a methoxy group, an ethoxy group, a dimethyl group, Represents a leaving group such as an amino group.
• a compound represented by formula (2-5) [wherein A 1 , R 2 and n represent the same meaning as described above. Can be synthesized according to a method known in the literature, for example, the method described in Journal of Heterocyclic Chemistry 1987, Vol. 24, page 1669.
• the compound represented by the formula (2-4) can be obtained by a known method such as Journal of Heterocyclic Chemistry 1987, 24, 693, etc., and the compound represented by the formula (2-5) can be obtained by using a journal of medicinal. Chemistry 2002, 45, 5397, etc. can be synthesized. Further, the compound represented by the formula (2-3) is hydrolyzed according to a known method known in the literature to obtain a compound represented by the formula (2) [wherein A 1 , R 2 , R 3 , R 4 and n Represents the same meaning as described above. The compound represented by this can be manufactured.
• Reaction formula 2 The compound represented by formula (2) is diphenylphosphoryl azide (DPPA) and formula (3) [wherein R 6b represents the same meaning as described above.
• DPPA diphenylphosphoryl azide
• formula (3) [wherein R 6b represents the same meaning as described above.
• a 1 , R 2 , R 3 , R 4 , R 6b and n have the same meaning as described above. The compound represented by this can be obtained.
• DPPA can be used in the range of 0.5 to 50 equivalents, preferably 0.5 to 2 equivalents, relative to 1 equivalent of the compound represented by formula (2).
• the compound to be used can be used in the range of 1 equivalent to a solvent amount with respect to 1 equivalent of the compound represented by the formula (2).
• a base such as potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine can be used. This reaction can be carried out without solvent, but a solvent may be used.
• the reaction temperature can be set to any temperature from ⁇ 60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary within the range of 5 minutes to 100 hours. Can be set.
• Some of the compounds represented by formula (3) are known compounds, and some of them are commercially available. Others can be synthesized according to known methods described in the literature.
• Formula (2-6) [wherein R 3 , R 4 and R 50 represent the same meaning as described above, and P 1 represents tertiary butyl, benzyl, 4-methoxybenzyl, acetyl, benzoyl, benzenesulfonyl, p-toluenesulfonyl. Represents a protecting group such as methanesulfonyl, methoxymethyl or methylthiomethyl. ] Can be synthesized by known methods such as Journal of Heterocyclic Chemistry 1987, 24, 693.
• the compound represented by the formula (7) used in the production method A can be synthesized, for example, as follows.
• Reaction formula 4 Formula (2-13) [wherein R 3, R 4 and R a are as defined above. ] Can be synthesized by a known method such as International Publication No. 2011/048082.
• the compound represented by formula (7) is synthesized by reacting the compound represented by formula (2-13) with the compound represented by formula (2-2) in the same manner as in Production Method B. be able to.
• the formula (2-14) [wherein A 1 , R 2 , R 3 , R 4 and n are the same as defined above] Represents meaning. ] Can be synthesized.
• the compound represented by the formula (2-14) is obtained by converting the compound represented by the formula (2-15) into a method known in the literature, for example, Journal of Heterocyclic Chemistry 1981, Vol. 18, p. According to the method described, it can be synthesized by reacting.
• the compound represented by the formula (2-15) can be synthesized by a known method such as European Journal of Organic Chemistry 2004, No. 4, page 695.
• the compound represented by the formula (2-14) is obtained by reacting the compound represented by the formula (2-16) and the compound represented by the formula (2-2) in the same manner as in Production Method B. Can be synthesized. Some of the compounds represented by formula (2-16) are known compounds, and some of them are commercially available. Others can be synthesized according to known methods described in the literature. Subsequently, the compound represented by the formula (2-14) is converted into the formula (13) by the known nitro group reduction method, wherein A 1 , R 2 , R 3 , R 4 and n have the same meaning as described above. To express. ] Can be synthesized.
• the compound represented by the formula (13) is obtained by converting the compound represented by the formula (2) into a diphenyl phosphate according to a method known in the literature, for example, the method described in Pharmaceutical Journal 1990, 110, 457, etc. It can be synthesized by reacting with azide (DPPA).
• DPPA azide
• the compound represented by the formula (2-14b) can be further synthesized by reacting according to a method known in the literature, for example, the method described in Tetrahedron 2013, 69, 395.
• Reaction formula 6 The compound represented by the formula (2-7) is reacted according to a method known in the literature, for example, the method described in Tetrahedron Letters 2003, 44, 7629, etc. [Wherein R 3 , R 4 and P 1 represent the same meaning as described above. ] Can be synthesized. Subsequently, the compound represented by the formula (2-17) is converted into a method known in the literature, for example, according to the method described in Experimental Chemistry Course 5th Edition (Edited by The Chemical Society of Japan) 2005, Vol. 14, p. Formula (2-18) [wherein M represents an alkali metal such as sodium or potassium. Or a compound represented by formula (2-19) [wherein M represents the same meaning as described above.
• Reaction formula 7 Formula (8-3) [wherein R 11b , R 50 and J b represent the same meaning as described above, and R 60 and R 61 each independently represent a hydrogen atom, a C 1 -C 6 alkyl group or R 15c. Represents a (C 1 -C 6 ) alkyl group optionally substituted with, R 15c represents the same meaning as described above, and t represents an integer of 0 to 6. ]
• R 15c represents the same meaning as described above, and t represents an integer of 0 to 6.
• Formula (8-4) [wherein R 16c represents the same meaning as described above. Some of the compounds represented by] are known compounds, and some of them are commercially available. Others can be synthesized according to known methods described in the literature.
• bases such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, etc., potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine, sodium hydride, sodium hydroxide, potassium hydroxide, or diethyl Mitsunobu reaction using azodicarboxylate and triphenylphosphine can be used.
• This reaction can be carried out without solvent, but a solvent may be used.
• a solvent for example, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water and other polar solvents, methanol, ethanol, propanol, 2-propanol, ethylene glycol Alcohols such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, pentane and n-hexane And aliphatic hydrocarbons.
• the reaction temperature can be set to any temperature from ⁇ 60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary within the range of 5 minutes to 100 hours. Can be set.
• formula (8-8) [wherein R 16c , R 50 , R 60 , R 61 and t represent the same meaning as described above.
• the compound represented by formula (8-9) [wherein R 11b represents the same meaning as described above] according to the method described in International Publication No. 2007/026221.
• the compound represented by formula (8-5) can also be obtained by reacting with the compound represented by formula (8).
• the compound represented by the formula (8-5) is subjected to a hydrolysis reaction according to a known method known in the literature to obtain a compound represented by the formula (8-6) [wherein R 11b , R 16c , R 60 , R 61 and t represent the same meaning as described above.
• the compound represented by this can be obtained.
• a compound represented by the formula (8-6) by reacting the compound represented by the formula (8-6) with a halogenating agent such as thionyl chloride or oxalyl chloride according to a known method known in the literature, a compound represented by the formula (8-7) [in the formula, 11b , R 16c , R 60 , R 61 and t have the same meaning as described above.
• the compound represented by this can be obtained.
• Reaction formula 8 Formula (8-8) [wherein R 16c , R 50 , R 60 , R 61 and t represent the same meaning as described above.
• the compound represented by formula (8-10) [wherein R 13b and R 14b represent the same meaning as described above, according to the method described in International Publication No. 2009/102997 and the like.
• R 13b , R 14b , R 16c , R 50 , R 60 , R 61 and t have the same meaning as described above.
• the compound represented by this can be obtained.
• Some of the compounds represented by formula (8-10) are known compounds, and some of them are commercially available. Others can be synthesized according to known methods described in the literature.
• Formula (8-11) which can be synthesized by a known method described in Journal of the Chemical Society Parkin Transactions 1 1981, Vol. 18, p. 9, etc. [wherein R 13b , R 14b , R 50 , R 60 , R 61 , J b and t represent the same meaning as described above.
• the compound represented by the formula (8-12) may be synthesized by reacting the compound represented by the formula (8-4) with the compound represented by the formula (8-4) by the same method as the reaction formula 7. I can do it.
• Reaction formula 9 Formula (14-T) [wherein R 3 , R 6b and J a represent the same meaning as described above.
• the compound represented by formula (5) is reacted with the compound represented by formula (5) using the same method as in Production Method B, thereby producing a compound represented by formula (15-T) [wherein R 3 , R a , R 6b and J a represent the same meaning as described above.
• the compound represented by this can be obtained.
• the compound represented by the formula (14-T) can be easily produced according to a known method known in the literature, for example, a method described in Bioorganic Medicinal Chemistry Letters 2010, 20th, 1559, etc.
• the compound represented by the formula (15-T) is reacted with an acid or a base using the same method as in Production Method A to obtain a compound represented by the formula (16-T) [wherein R 3 , R a and J a Represents the same meaning as described above. The compound represented by this can be obtained. Further, the compound represented by the formula (16-T) is reacted with the compound represented by the formula (8-1) or the compound represented by the formula (8-2) by using the same method as in Production Method A. To obtain a compound represented by the formula (17-T).
• the compound represented by the formula (14-T) is reacted with an acid or a base in the same manner as in the reaction formula 1, and the formula (18-T) [wherein R 3 and J a represent the same meaning as described above. .
• the compound represented by this can be obtained.
• the compound represented by the formula (18-T) is reacted with the compound represented by the formula (8-1) or the compound represented by the formula (8-2) by using the same method as in Production Method A. By doing so, a compound represented by the formula (19-T) can be obtained.
• the compound represented by the formula (19-T) is represented.
• the compound represented by the formula (17-T) is represented. Can be obtained.
• the active compound included in the present invention include compounds shown in Tables 1 to 4.
• the compounds in Tables 1 to 4 are for illustrative purposes, and the present invention is not limited thereto.
• a substituent described as Me represents a methyl group, hereinafter, Et represents an ethyl group, n-Pr and Pr-n represent normal propyl groups, i-Pr and Pr-i Is an isopropyl group, c-Pr and Pr-c are cyclopropyl groups, n-Bu and Bu-n are normal butyl groups, s-Bu and Bu-s are secondary butyl groups, i-Bu and Bu--- i is an isobutyl group, t-Bu and Bu-t are tertiary butyl groups, c-Bu and Bu-c are cyclobutyl groups, n-Pen and Pen-n are normal pentyl groups, c-Pen and Pen -C is a cyclopentyl
• D1-7b D1-32a, D1-32b, D1-32c, D1-33a, D1-34a, D1-37a, D1-79a, D1-79b, D1-80a, D1-80b , D1-80c, D1-80d, D1-80e, D1-80f, D1-87a, D1-98a, D1-103m, D1-103o, D1-103p, D1-103q, D1-108a, D1-108b, D1 -108c, D1-104a, D1-104b, and structures represented by D1-104c represents the following structures, D1-7b, and structure number marked on the type D1-32b the substitution position of X 1 Represents the substitution position of X 1b , and the number written in the structural formula of D1-108b represents the substitution position of Z.
• the compounds of the present invention are stored in warehouses, so-called agricultural pests that harm agricultural and horticultural crops and trees, so-called livestock pests that parasitize livestock and poultry, so-called sanitary pests that cause various adverse effects in the human living environment such as houses. It is possible to effectively control insects such as so-called stored grain pests that harm cereals and the like, and pests such as mites, crustaceans, molluscs, and nematodes that occur and harm in similar situations at low concentrations.
• insects, mites, crustaceans, mollusks and nematodes that can be controlled using the compounds of the present invention include, for example, the wasp chestnut gall wasp (Dryocosmus kuriphilus), the Argentine ant Argentine ant (Linepithema humile), Gunmy ant Army ant (Eciton burchelli, E.
• Desert locust (Schistocerca gregaria), Australian platypus locust Australian plague locust (Chortoicetes terminifera), locust grasshopper Migratory locust (Locusta migratoria), red-eye locust Lesser paddy grasshopper (Oxya japonica), red-eye grass oxen (Teleogryllus emma), Kela Oriental mole cricket (Gryllotalpa orientalis), etc., Orthoptera insects, German cockroach (Blattella germanica), American cockroach (Periplaneta americana), Black cockroach Smoky-brown cockroach (Periplaneta jafonica), Japanese cockroach (Periplaneta japonica), Daikokuus tomato (America) Termite Western dry-wood termite (Incisitermes minor), Common termite Formosan subterranean termite (Coptotermes formosanus), Japanese termite Japanese subterranean termit
• Isopoda crustaceans such as Pill bug (Armadillidium vulgare), common rough woodlouse (Porcellio scaber), Butterflyfish (Arguloida) crustaceans such as butterfly (Argulus coregoni), butterfly Japanese fishlouse (Argulus japonicus), sea butterfly (Argulus scutiformis) Sea louse (Caligus curtus, C.
• Tick American cattle tick (Rhipicephalus annulatus), Brown dog tick (Rhipicephalus sanguineus) and other ticks (Metastigmata) ticks, Red mite (Dermanyssus gallinae), house dust mite Tropical rat mite (Ornithonyssus bacoti), northern fowl mite (Ornithonyssus sylviarum), honey bee mite Honeybee mite (Varroa destructor), honeybee mite Varroa mite Varroa mite (Mesostigmata) mites, Pancreas (Architaenioglossa) gastropod, such as Apple snail (Pomacea canaliculata) Giant African snail (Achatina fulica), terrestrial slug (Limax marginatus), slug slug (Meghimatium bilineatum), Korean round snail (Acusta despecta sieboldiana), Miss maimai Land snio (Euha
• Rice white nematode (Aphelenchoides besseyi), Pine wood nematode (Bursaphelenchus xylophilus) nematode (Aphelenchida) nematode, Potato cyst nematode (Globodera rostochiensis), wheat cyst nematode Cereal cyst nematode (Heterodera avenae), soybean cyst nematode (Seterbean cyst nematode (Heterodera glycines)), arenaria root nematode (Peterut root-Menot nematode) -knot nematode (Meloidogyne hapla), Southern root-knot nematode (Meloidogyne incognita), Java root-knot nematode (Meloidogyne javanica), Southern root-kion nematode Coffee root-lesion nem
• lenchida nematode
• Oxyurida nematodes such as human worm Pinworm (Enterobius vermicularis), horse worm Equine pinworm (Oxyuris equi), rabbit worm Rabbit pinworm (Passalurus ambiguus), Pig roundworm (Ascaris suum), Horse roundworm Horse roundworm (Parascaris equorum), Dog roundworm Dog roundworm (Toxascaris leonina), Dog roundworm Dog intestinal roundworm (Toxocara canis), Cat roundworm Feline roundworm (Toxocara cati), Cattle roundworm Large cattle roundworm (Toxocara vitulorum), Anisakis spp., Pseudoterranova spp., chicken caecal caecal worm (Heterakis gallinarum), chicken roundworm (Ascaridia galli) and other roundworms (Ascaridida) Nematode, Medinaworm Guinea worm (Dracunculus medinens
• Striated insects (Pharyngostomum cordatum), Schistosoma haematobium, Schistosoma haematobium, Schistosoma japonicum, Schistosoma japonicum, Schistosoma mansoni, etc.
• Echinostoma cinetorchis Echinostoma hortense, Giant liver fluke (Fasciola gigantica), Liver common liver fluke (Fasciola hepatica), Fasciolopsis buski, Flat belly twin Echinostomida, such as Homalogaster paloniae, Continental flukes (Dicrocoelium chinensis), moth-type flukes Lancet liver fluke (Dicrocoelium dendriticum), African moth-type flukes African lancet fluke (Dicrocoelium hospes), small pancreatic folds (Eurytrema coelomaticum), pancreatic folds Pancreatic fluke (Eurytrema pancreaticum) Paragonimus miyazakii, Paragonimus ohirai, Westermann Lung fluke (Paragonimus westermani), etc.
• Platimorchiida Amphimerus spp., Liver fluke Chinese liver fluke (Clonorchis sinensis), Cat liver fluke Cat liver fluke (Opisthorchis felineus), Thai liver fluke Southeast Aasian liver fluke (Opisthorchis viverrini), Pseudamphistom spp .), Metrochis spp., Parametorchis spp., Malformed fluke (Heterophyes heterophyes), Metagonimus yokokawai, foregut fluke (Pygidiopsis summa), etc. Opisthorchiida) fluke, Amoeba such as Entamoeba histolytica, E.
• cidiorida spores
• Vestibuliferida ciliates such as large intestine barantidium coli, Histomanas meleagridis, Pentatrichomonas hominis, Trichomonas tenax and other Trichomonadida flagellates, Dipromonads (Vaccinonadida) flagellates such as Giardia intestinalis, Giardia muris, turkey hexamita (Hexamita meleagridis), Hexamita parva, Leishmania donovani, Leishmania infantum, Leishmania major, Leishmania tropica, Trypanosoma brucei gambiense, Trypanosoma brucei cruise, Trypanosoma brucei rhodesi Examples include Trypanosoma cruzi, Trypanosoma equiperdum, Trypanosoma evansi, and Kinetoplastida flagellates, which can be controlled using the compounds of the present invention
• the compound of the present invention is also effective against pests having developed resistance against existing insecticides such as organophosphorus compounds, carbamate compounds or pyrethroid compounds. That is, the compound of the present invention is composed of the order of mucous (Coleoptera); Eyes), Lepidoptera (Lepidoptera), Coleoptera (Coleoptera), Hymenoptera (Hymenoptera), Diptera (Flyes), etc.
• pests belonging to gastropods and nematodes can be effectively controlled at low concentrations.
• the compound of the present invention has extremely no adverse effect on mammals, fish, crustaceans and beneficial insects (beneficial insects such as honeybees, bumblebees, natural enemies such as honeybees, wasps, mistletoe, spider mites, burdock mites). Has useful features.
• the compound of the present invention When using the compound of the present invention, it is usually mixed with a suitable solid carrier or liquid carrier, and if desired, a surfactant, penetrant, spreading agent, thickener, antifreezing agent, binder, anti-caking agent. , Disintegrating agents, antifoaming agents, antiseptics, anti-degradation agents, etc., adding liquid (soluble concentrate), emulsion (emulsifiable concentrate), wettable powder (wettable powder), water solvent (water soluble powder) Water dispersible granule, water soluble granule, suspension ⁇ concentrate, emulsion ⁇ concentrated ⁇ suspoemulsion, microemulsion, microemulsion, dustable powder ), Granules, tablets, emulsifiable gels, etc., can be put to practical use.
• the preparations of any of the above dosage forms can be provided by being enclosed in a water-soluble package such as a water-soluble capsule or a water-soluble film bag.
• solid carrier examples include quartz, calcite, gypsum, dolomite, chalk, kaolinite, pyrophyllite, sericite, halosite, metahalosite, kibushi clay, glazed clay, porcelain stone, nostirite, and allophane.
• Sugars eg polysaccharides such as starch, powdered cellulose, dextrin, organic substances such as urea, urea derivatives, benzoic acid, benzoic acid salts, plants such as wood flour, cork flour, corn cob, walnut shell, tobacco stem , Fly ash, white carbon (for example, hydrous synthetic silica, anhydrous synthetic silica, hydrous synthetic silicate, etc.), fertilizer and the like.
• liquid carrier examples include xylene, alkyl (C 9 or C 10 etc.) benzene, phenyl xylyl ethane, alkyl (C 1 or C 3 etc.) naphthalene and other aromatic hydrocarbons, machine oil, normal paraffin, isoparaffin, Aliphatic hydrocarbons such as naphthene, mixtures of aromatic and aliphatic hydrocarbons such as kerosene, alcohols such as ethanol, isopropanol, cyclohexanol, phenoxyethanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, hexylene glycol , Polyhydric alcohols such as polyethylene glycol and polypropylene glycol, propyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl Ethers, ethers such as propylene glycol monopropyl
• surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl (mono or di) phenyl ether, polyoxyethylene (mono, di or tri) styryl phenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene Ethylene fatty acid (mono or di) ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, acetylene glycol, acetylene alcohol, ethylene oxide adduct of acetylene glycol, ethylene oxide adduct of acetylene alcohol, alkyl Nonionic surfactants such as glycosides, alkyl sulfate esters, alkylbenzene sulfonates, lignin sulfonates, alkyl sulfates Succinate, naphthalene sulfonate, alkyl naphthalene
• the content of these surfactants is not particularly limited, but is usually in the range of 0.05 to 20 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the preparation of the present invention. . These surfactants may be used alone or in combination of two or more.
• the application amount of the compound of the present invention varies depending on the application scene, application time, application method, cultivated crops, etc., but generally the active ingredient amount is about 0.005 to 50 kg per hectare (ha), preferably 0.01. ⁇ 5 kg is suitable.
• an effective amount of the compound of the present invention is administered orally, and injected (muscles) together with pharmaceutical additives.
• Parenteral administration such as internal, subcutaneous, intravenous, intraperitoneal
• transdermal administration such as immersion, spraying, bathing, washing, pouring-on, spotting-on, dusting
• Administration can be by nasal administration.
• the compounds of the present invention can be administered by molded products using strips, plates, bands, collars, ear marks, limb bands, labeling devices and the like. In administration, the compound of the present invention can be in any dosage form suitable for the administration route.
• Arbitrary dosage forms to be prepared include powders, granules, wettable powders, pellets, tablets, large pills, capsules, solid preparations such as molded products containing active compounds; injection solutions; oral solutions; skin Liquid preparations used above or in body cavities; Solution preparations such as Pour-on agents, Spot-on agents, flowable agents, and emulsions; Semi-solid preparations such as ointments and gels.
• the solid preparation can be mainly used for oral administration or transdermal administration after dilution with water or environmental treatment.
• Solid preparations can be prepared by adding the active compound, if necessary, with adjuncts and mixing with appropriate excipients to give the desired shape.
• Suitable excipients include, for example, inorganic substances such as carbonates, bicarbonates, phosphates, aluminum oxides, silicas, clays, and organic substances such as sugars, celluloses, ground grains, and starches.
• Injection solutions can be administered intravenously, intramuscularly and subcutaneously.
• Injection solutions can be prepared by dissolving the active compound in a suitable solvent and adding additives such as solubilizers, acids, bases, buffer salts, antioxidants, protective agents, etc., if necessary.
• suitable solvents include water, ethanol, butanol, benzyl alcohol, glycerin, propylene glycol, polyethylene glycol, N-methylpyrrolidone and mixtures thereof, physiologically acceptable vegetable oils, synthetic oils suitable for injection, and the like.
• the solubilizer include polyvinyl pyrrolidone, polyoxyethylated castor oil, polyoxyethylated sorbitan ester, and the like.
• Examples of the protective agent include benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid ester, n-butanol and the like.
• Oral solutions can be administered directly or diluted. It can be prepared in the same manner as an injectable solution. Flowables, emulsions and the like can be administered directly or diluted transdermally or by environmental treatment.
• Solutions used on the skin can be administered by dripping, spreading, rubbing, spraying, spraying or applying by dipping (immersion, bathing or washing). These solutions can be prepared in the same manner as injection solutions. Pour-on and spot-on agents can be dripped or sprayed onto a limited area of the skin, so that the active compound is immersed in the skin and acts systemically. it can. Drops and drop preparations can be prepared by dissolving, suspending or emulsifying the active ingredient in suitable skin-compatible solvents or solvent mixtures. If necessary, auxiliary agents such as surfactants, colorants, absorption promoting substances, antioxidants, light stabilizers, and adhesives may be added.
• auxiliary agents such as surfactants, colorants, absorption promoting substances, antioxidants, light stabilizers, and adhesives may be added.
• Suitable solvents include water, alkanol, glycol, polyethylene glycol, polypropylene glycol, glycerin, benzyl alcohol, phenylethanol, phenoxyethanol, ethyl acetate, butyl acetate, benzyl benzoate, dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether, acetone, Methyl ethyl ketone, aromatic and / or aliphatic hydrocarbons, vegetable or synthetic oil, DMF, liquid paraffin, light liquid paraffin, silicone, dimethylacetamide, N-methylpyrrolidone or 2,2-dimethyl-4-oxy-methylene-1, 3-dioxolane is mentioned.
• Absorption promoting substances include DMSO, isopropyl myristate, dipropylene glycol pelargonate, silicone oil, aliphatic esters, triglycerides, fatty alcohols and the like.
• Antioxidants include sulfites, metabisulfites, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol and the like.
• the emulsion can be administered orally, transdermally or as an injection.
• the active ingredient is dissolved in a hydrophobic phase or a hydrophilic phase, and this is further added with a suitable emulsifier, and if necessary, a colorant, an absorption promoting substance, a protective agent, an antioxidant, a light-shielding agent, a thickening substance, etc.
• a suitable emulsifier and if necessary, a colorant, an absorption promoting substance, a protective agent, an antioxidant, a light-shielding agent, a thickening substance, etc.
• hydrophobic phase paraffin oil, silicone oil, sesame oil, almond oil, castor oil, synthetic triglyceride, ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol pelargonate, branched chain Of a short fatty acid having a chain length and a saturated fatty acid having a chain length of C16 to C18, isopropyl myristate, isopropyl palmitate, capryl / caprate of a saturated fatty alcohol having a chain length of C12 to C18, isopropyl stearate, oleyl oleate Decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid ester, dibutyl phthalate, diisopropyl adipate, isotridecyl alcohol, 2-octyldodecanol, cetyl stearate,
• hydrophilic phase examples include water, propylene glycol, glycerin, sorbitol and the like.
• nonionic interfaces such as polyoxyethylated castor oil, polyoxyethylated sorbitan monoolefin acid, sorbitan monostearate, glyceryl monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether, etc.
• amphoteric surfactants such as disodium N-lauryl- ⁇ -iminodipropionate and lecithin
• anions such as sodium lauryl sulfate, fatty alcohol sulfate ether, monoethanolamine salt of mono / dialkyl polyglycol orthophosphate
• Surfactants cationic surfactants such as cetyltrimethylammonium chloride.
• Other adjuvants include carboxymethyl cellulose, methyl cellulose, polyacrylate, alginate, gelatin, gum arabic, polyvinyl pyrrolidone, polyvinyl alcohol, methyl vinyl ether, maleic anhydride copolymer, polyethylene glycol, wax, colloidal silica and the like.
• Semi-solid preparations can be administered by application on the skin or spreading or introduction into body cavities. Gels can be prepared by adding sufficient thickener to a solution prepared as described above for an injectable solution to produce a clear material having an ointment-like consistency.
• [Wettable powder] Compound of the present invention 0.1 to 80 parts Solid carrier 5 to 98.9 parts Surfactant 1 to 10 parts Others 0 to 5 parts Others include, for example, anti-caking agent, decomposition inhibitor and the like.
• ⁇ emulsion ⁇ Compound of the present invention 0.1 to 30 parts Liquid carrier 45 to 95 parts Surfactant 4.9 to 15 parts Others 0 to 10 parts Others include, for example, spreading agents, decomposition inhibitors and the like.
• Liquid Compound of the present invention 0.01 to 70 parts Liquid carrier 20 to 99.99 parts Others 0 to 10 parts Others include, for example, antifreezing agents and spreading agents.
• wettable powder Compound No. 1-001 of the present invention 20 parts Pyrophyllite 74 parts Solpol 5039 4 parts (mixture of nonionic surfactant and anionic surfactant: manufactured by Toho Chemical Co., Ltd., Product name) Carplex # 80D 2 parts (Synthetic hydrous silicic acid: manufactured by Shionogi & Co., Ltd., trade name) The above is uniformly mixed and ground to obtain a wettable powder.
• Suspension Agent Compound No.1-001 25 parts Agrisol S-710 10 parts (Nonionic Surfactant: Kao Corporation, trade name) LUNOX 1000C 0.5 part (anionic surfactant: Toho Chemical Industries, trade name) Xanthan gum 0.2 parts water 64.3 parts After uniformly mixing the above, wet pulverize to make a suspension.
• Granule wettable powder Compound No. 1-1001 of the present invention 75 parts Hytenol NE-15 5 parts (anionic surfactant: trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Vanillex N 10 parts (anionic surfactant: Nippon Paper Industries Co., Ltd. trade name) Carplex # 80D 10 parts (Synthetic hydrous silicic acid: manufactured by Shionogi & Co., Ltd., trade name) After uniformly mixing and pulverizing the above, a small amount of water is added, stirred and mixed, granulated with an extrusion granulator, and dried to obtain a granulated wettable powder.
• anionic surfactant trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
• Vanillex N 10 parts anionic surfactant: Nippon Paper Industries Co., Ltd. trade name
• Carplex # 80D 10 parts Synthetic hydrous silicic acid: manufactured by Shion
• composition Example 6 Powder Compound of the present invention No.1-001 3 parts Carplex # 80D 0.5 part (Synthetic hydrous silicic acid: Shionogi & Co., trade name) Kaolinite 95 parts Diisopropyl phosphate 1.5 parts The above is uniformly mixed and ground to obtain a powder. In use, the formulation is diluted 1 to 10,000 times with water or sprayed directly without dilution.
• wettable powder preparation Compound No. 1-001 of the present invention 25 parts sodium diisobutylnaphthalenesulfonate 1 part calcium n-dodecylbenzenesulfonate 10 parts alkylaryl polyglycol ether 12 parts naphthalenesulfonic acid formalin condensate Sodium salt 3 parts Emulsion type silicone 1 part Silicon dioxide 3 parts Kaolin 45 parts
• the compound of the present invention when used as an agrochemical, other types of herbicides, various insecticides, acaricides, nematicides, fungicides, plant growth regulators, if necessary, at the time of formulation or spraying Alternatively, it may be mixed with a synergist, a fertilizer, a soil conditioner and the like. In particular, by applying it in combination with other agricultural chemicals or plant hormones, it can be expected to reduce costs by reducing the amount of applied medicine, expand the insecticidal spectrum due to the synergistic action of the mixed drugs, and achieve higher pest control effects. At this time, a combination with a plurality of known agricultural chemicals is also possible. Examples of the type of agricultural chemical used in combination with the compound of the present invention include compounds described in The Pesticide Manual 15th edition, 2009, and the like. Specific examples of common names are as follows, but the general names are not necessarily limited to these.
• Bactericides acibenzolar-S-methyl, acylaminobenzamide, acypetacs, aldimorph, ametoctradin, amisulbrom, amobam, ampropyl Phos (ampropyfos), anilazine, azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M (Benodanil), benomyl, benquinox, bentaluron, benthiavalicarb, benthiazole, benzamacril, benzamorf, bethoxazine, Binapacryl ), Biphenyl, bitertanol, blasticidin-S, bixafen, bordeaux mixture, boscalid, bromoconazole, bupirimate , Buthiobate, calcium polysulfide, calcium polysulfide, captafol, captan,
• Bactericides (continued): diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole-, diniconazole-M M), dinobuton, dinocap, dinocap-4, dinocap-6, dinoton, dinosulfon, dinoterbon, diphenylamine ), Dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon, edifenphos, epoxiconazole, ethaconazole, etaconazole Boxaam, etem, etirimol, ethoxyquin, etridiazole, famoxadone, fenarimol, febuconazole, fenamidone, sulfaminosulfen ), Fenapanil, fendazo
• Fungicide (continued): kasugamycin, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid , Mepanipyrim, mepronil, metalaxyl, metalaxyl-M, metam, metazoxolon, metconazole, methasulfocarb, metoxafloxam ), Methylisothiocyanate, metiram, metinominostrobin, metrafenone, metsulfovax, milneb, microbutanil, microzoline (myc) lozolin, nabam, natamycin, nickel bis (dimethyldithiocarbamate), nitrostyrene, nitrothal-isopropyl, nuarimol, OH (OCH), octhilinone, offurace, orysastrobin, oxadixyl, organic copper (oxi
• Bactericides (continued): sodium azide, sodium hydrogen carbonate, sodium hypochlorite, sulfur, spiroxamine, salicylanilide, silthiofam (Silthiofam), simeconazole, tebuconazole, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide thifluzamide, thiochlorfenphim, thiophanate, thiophanate-methyl, thioquinox, thiram, thiadinyl, tioxymid, tolcrofos -Tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triamiphos, triarimol, triazoxide, triazbutil, tributyltin oxide oxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin,
• Bactericides benzalkonium chloride, bithionol, bronopol, cresol, formaldehyde, nitrapyrin, oxolinic acid, oxyterracycline , Streptomycin and tecloftalam.
• Nematicides aldoxycarb, cadusafos, DCP, DBCH, dichlofenthion, DSP (DSP), etoprophos, fenamiphos, fensulfothion, fluene Sulfone (fluensulfone), fosthiazate (fosthiazate), fosthietan (fosthietan), imisiafos (imicyafos), isamidofos (isamidofos), isazofos (isazofos), oxamyl (oxamyl) and thionazin (thionazin) and the like.
• Acaricides acequinocyl, acrinathrin, amitraz, BCI-033 (test name), bifenazate, bromopropylate, chinomethionat, chlorobezilate , Clofentezine, cyenopyrafen, cyflumetofen, cyhexatine, dicofol, dienochlor, denochlor (DNOC), etoxazole, quinazaquin (fenaza) Fenbutatin oxide, fenothiocarb, fenpropathrin, fenpyroximate, fluacrypyrim, halfenprox (halfenpro) x), hexythiazox, milbemectin, propargite, pyflubumide, pyridaben, pyrimidifen, S-1870 (test name), spirodiclofen , Spyromesifen, CL900167 (test name), tebuf
• Insecticides abamectin, acephate, acetamipirid afidopyropen, alanidocarb, aldicarb, allethrin, azaphos-methyl, azine-methyl- ), Bacillus thuringiensis, bendiocarb, benfluthrin, benfuracarb, bensultap, bifenthrin, bioallethrin, violesmethrin, bioresmethrin (bistrifluron), buprofezin, butocarboxim, carbaryl, carbofuran, carbosulfan, cartap, chloranthra Chlorantraniliprole, chlorethxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos-methyl ), Chromafenozide, clothianidin, cyantraniliprole,
• Insecticides (continued): halofenozide, hexaflumuron, hydramethylnon, imidacloprid, isofenphos, indoxacarb, isoprocarb, isoxathion ), Lepimectin, lufenuron, malathion, meperfluthrin, metaflumizone, metalaldehyde, methamidophos, methidathion, methidathion, methacrifos (methacrifos) ), Metalcarb, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromi de), monocrotophos, muscalure, nitenpyram, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeproton Phos (oxydeprofos), parathion, parathion-methyl
• the medium pressure preparative liquid chromatography described in the synthesis example used an intermediate pressure preparative device manufactured by Yamazen Co., Ltd .; YFLC-Wprep (flow rate 18 ml / min, silica gel 40 ⁇ m column).
• the high performance preparative liquid chromatography used Shimadzu Corporation 10AVP system on the following conditions. Oven temperature: 40 ° C
• Mobile phase acetonitrile 7 ml / min., Water 4 ml / min.
• Step 2 Preparation of tert-butyl 3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl (ethyl) carbamate 60 wt% sodium hydride (dispersed in mineral oil) 0.15 g N , N-dimethylformamide (10 ml) was mixed with 0.95 g of tert-butyl 3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-ylcarbamate under ice-cooling. After completion of the addition, the temperature was raised to room temperature and stirred at the same temperature for 30 minutes.
• Step 3 Preparation of 3-chloro-N-ethyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine dihydrochloride tert-butyl 3-chloro-1- (pyridin-3-yl)-
• a 20 ml 1,4-dioxane solution of 1.0 g of 1H-pyrazol-4-yl (ethyl) carbamate was added 8.1 ml of a 1,4-dioxane solution of about 4M hydrogen chloride. After completion of the addition, the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the solid precipitated in the reaction solution was removed by filtration under reduced pressure.
• Step 4 Preparation of 3-chloro-N-ethyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine To 7.4 ml of 1N aqueous sodium hydroxide solution, 3-chloro-N-ethyl-1- 1 g of (pyridin-3-yl) -1H-pyrazol-4-amine dihydrochloride was added. After completion of the addition, the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the reaction mixture was extracted with 20 ml (x3) of dichloromethane.
• Step 5 Preparation of N- ⁇ 3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl ⁇ -N-ethyl-2-oxopropanamide 3-Chloro-N-ethyl-1-
• To a solution of 1 g of (pyridin-3-yl) -1H-pyrazol-4-amine in 10 ml of dichloromethane at room temperature is 0.59 g of pyruvic acid and 1.7 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. And 3 mg of 4-dimethylaminopyridine was added sequentially.
• Step 6 Preparation of N- ⁇ 3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl ⁇ -N-ethyl-2- (hydroxyimino) propanamide N- ⁇ 3-Chloro- To a solution of 400 mg of 1- (pyridin-3-yl) -1H-pyrazol-4-yl ⁇ -N-ethyl-2-oxopropanamide in 5 ml of ethanol was added 179 mg of triethylamine and 123 mg of hydroxylammonium chloride. After completion of the addition, the mixture was stirred for 1 hour while refluxing ethanol.
• the obtained residue was added to a separately prepared solution of 0.46 g of 3-chloro-N-ethyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine and 0.41 g of pyridine in 5 ml of dichloromethane. . After completion of the addition, stirring was continued at room temperature for 30 minutes. After completion of the reaction, the reaction solution was washed with 10 ml of water. The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
• Step 3 Preparation of 2- (ethylthio) -2- (methoxyimino) acetic acid 4.1 ml of 1N aqueous sodium hydroxide solution was added to a solution of 0.66 g of ethyl 2- (ethylthio) -2- (methoxyimino) acetate in 5 ml of ethanol. Added. After completion of the addition, the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, ethanol was distilled off from the reaction solution under reduced pressure. The resulting residue was adjusted to pH 2 by adding a 1N aqueous hydrochloric acid solution.
• Step 2 Preparation of 3-chloro-N- (prop-2-yn-1-yl) -1- (pyridin-3-yl) -1H-pyrazol-4-amine tert-butyl 3-chloro-1- ( Pyridine-3-yl) -1H-pyrazol-4-yl (prop-2-yn-1-yl) carbamate 9.4 g in 1,4-dioxane 15 ml solution and about 4 M hydrogen chloride in 1,4-dioxane solution 50 ml was added and stir
• Step 3 N- ⁇ 3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl ⁇ -2- (methoxyimino) -3- (methylthio) -N- (prop-2-yne
• 1-yl) propanamide 2- (methoxyimino) -3- (methylthio) propanoic acid 0.84 g in dichloromethane 10 ml solution at room temperature 0.65 g oxalyl chloride, then N, N-dimethylformamide 0. Added in order of 1 ml. After completion of the addition, the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure.
• the obtained residue was separated from 1.0 g of 3-chloro-N- (prop-2-yn-1-yl) -1- (pyridin-3-yl) -1H-pyrazol-4-amine prepared separately and pyridine. 0.51 g of dichloromethane in 10 ml solution was added. After the addition was complete, stirring was continued overnight at room temperature. After completion of the reaction, the reaction solution was added to 20 ml of water and extracted with 20 ml of chloroform ( ⁇ 2). The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
• the obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (gradient 9: 1 to 1: 1) to obtain 1.67 g of the desired product as a yellow oil. Obtained.
• the obtained target product was a mixture of two geometric isomers, and the isomer ratio was 7: 1.
• the reaction solution was added to water and extracted with 4 ml (x3) of ethyl acetate, and then the solvent was distilled off under reduced pressure.
• the obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (gradient 4: 1 to 1: 3) to obtain 65 mg of the desired product as a colorless oil.
• the obtained target product was a mixture of two geometric isomers, and the isomer ratio was 5: 1.
• reaction solution was stirred overnight at room temperature.
• solvent was distilled off from the reaction solution under reduced pressure, and the resulting solid was added to 30 ml of 2N aqueous sodium hydroxide solution.
• insoluble matter precipitated in the solution was removed by filtration.
• the obtained filtrate was adjusted to pH 3 with concentrated hydrochloric acid, and the precipitated solid was removed by filtration.
• the obtained solid was washed with water and dried under reduced pressure to obtain 2.5 g of the desired product as a white solid.
• Step 2 2- [2-[ ⁇ 3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl ⁇ amino] -2-oxoethylidene] -N- (2,6-dichlorophenyl)
• 2- [2- ⁇ (2,6-dichlorophenyl) carbamoyl ⁇ hydrazono] acetic acid in a solution of 235 mg of dichloromethane in 4 ml of dichloromethane was mixed with 3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-amine 150 mg and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 223 mg were sequentially added.
• reaction solution was stirred at room temperature for 2 hours. After completion of the reaction, 4 ml of water was added to the reaction solution. After completion of the addition, the solid precipitated in the solution was taken out by filtration. The obtained solid was washed with water and then with isopropyl ether, and then dried under reduced pressure to obtain 280 mg of the desired product as a white solid. Melting point: 211-214 ° C
• reaction mixture was heated to 80 ° C. and stirring was continued for 1 hour at the same temperature.
• 30 ml of water was added to the reaction mixture and extracted with 50 ml of ethyl acetate.
• the obtained organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution, washed with saturated brine, and then dried over anhydrous sodium sulfate in that order.
• the solvent was distilled off under reduced pressure to obtain 2 g of the desired product as a pale yellow oil.
• Step 3 Production of N- ⁇ 4-methyl-2- (pyridin-3-yl) thiazol-5-yl ⁇ -2- (methoxyimino) -3- (methylthio) propanamide 2- (methoxyimino) -3 -360 mg of oxalyl chloride and then 10 mg of N, N-dimethylformamide were added to a solution of 370 mg of (methylthio) propanoic acid in 3 ml of dichloromethane. After the addition was complete, the reaction mixture was stirred at room temperature for 2 hours.
• reaction mixture was added dropwise to a separately prepared solution of 4-methyl-2- (pyridin-3-yl) thiazol-5-amine dihydrochloride (500 mg) and pyridine (747 mg) in ethylene dichloride (5 ml). After completion of the dropwise addition, the reaction mixture was stirred at room temperature for 30 minutes. After completion of the reaction, the reaction mixture was washed with 10 ml of water and then with 10 ml of a saturated aqueous sodium hydrogen carbonate solution, and then the organic layer was separated by a liquid separation operation. The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
• the reaction mixture was added dropwise to a separately prepared solution of 150 mg of 4-chloro-N-ethyl-2- (pyridin-3-yl) thiazol-5-amine and 198 mg of pyridine in 5 ml of ethylene dichloride at room temperature. . After completion of dropping, the mixture was stirred overnight at the same temperature. After completion of the reaction, the reaction mixture was washed with 10 ml of water and then with 10 ml of a saturated aqueous sodium hydrogen carbonate solution, and then the organic layer was separated by a liquid separation operation. The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
• Step 2 Preparation of N- (2-bromo-4-methylthiazol-5-yl) -2- (methoxyimino) -3- (methylthio) butanamide 2- (methoxyimino) -3- (methylthio) butanoic acid 0
• dichloromethane 0.65 g of oxalyl chloride and then 10 mg of N, N-dimethylformamide were added in this order. After completion of the addition, the mixture was stirred at room temperature for 1 hour.
• Step 3 Preparation of 2- (methoxyimino) -N- ⁇ 4-methyl-2- (pyridin-3-yl) thiazol-5-yl ⁇ -3- (methylthio) butanamide N- (2-Bromo-4-
• a solution of 0.1 g of methylthiazol-5-yl) -2- (methoxyimino) -3- (methylthio) butanamide and 0.05 g of 3-pyridylboronic acid in 5 ml of 1,4-dioxane and 3 ml of water 0. 2 g and bis (triphenylphosphine) palladium (II) dichloride 0.06 g were added and stirred at 90 ° C. for 1 hour.
• the solvent was distilled off from the reaction solution under reduced pressure, the resulting solid was added to 30 ml of 2N aqueous sodium hydroxide solution, and insoluble matters were removed by filtration.
• the obtained filtrate was adjusted to pH 3 with concentrated hydrochloric acid, and the precipitated solid was removed by filtration.
• the obtained solid was washed with water and dried under reduced pressure to obtain 2.5 g of the desired product as a white solid.
• Step 2 N- (2,6-Dichlorophenyl) -2- [2-[ ⁇ 4-methyl-2- (pyridin-3-yl) thiazol-5-yl ⁇ amino] -2-oxoethylidene] hydrazinecarboxamide
• Preparation of Preparation 2- [2- ⁇ (2,6-dichlorophenyl) carbamoyl ⁇ hydrazono] acetic acid in 160 mg of dichloromethane in 4 ml solution was added 4-methyl-2- (pyridin-3-yl) thiazol-5-amine 100 mg, 1- Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 131 mg was sequentially added, and the mixture was stirred at room temperature for 1 hour.
• reaction mixture was cooled to 0 ° C., neutralized with an aqueous sodium hydroxide solution, and extracted with 100 ml of ethyl acetate.
• the obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
• the obtained solid was washed with n-hexane to obtain 6.28 g of the desired product as a white solid.
• Step 2 Preparation of ethyl 3-chloro-1- (pyridin-3-yl) -1H-pyrazole-4-carboxylate 10.3-g N, N-dimethyl ethyl 3-chloro-1H-pyrazole-4-carboxylate To a 150 ml formamide solution, 15.6 g of 3-iodopyridine, 2.23 g of copper iodide (monovalent) and 33.0 g of cesium carbonate were sequentially added.
• reaction vessel was replaced with nitrogen gas, followed by stirring at 130 ° C. for 5 hours.
• reaction mixture was allowed to cool to room temperature and 100 ml of 1N aqueous sodium hydroxide solution was added. Impurities in the reaction mixture were removed by Celite filtration under reduced pressure, and the obtained filtrate was extracted with 100 ml of ethyl acetate. The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
• Step 3 Preparation of 3-chloro-1- (pyridin-3-yl) -1H-pyrazole-4-carboxylic acid
• Ethyl 3-chloro-1- (pyridin-3-yl) -1H-pyrazole-4-carboxylate 5.6 g of potassium hydroxide and 130 ml of water were sequentially added to a solution of 16.75 g of ethanol in 130 ml. After the addition was complete, the mixture was stirred overnight at room temperature. After completion of the reaction, 2N hydrochloric acid aqueous solution was added to adjust the pH of the reaction mixture to 4. Then, the precipitated solid was removed by filtration, and the removed solid was washed with water.
• Step 4 Preparation of 3- (3-chloro-4-nitro-1H-pyrazol-1-yl) pyridine 1.72 ml of acetic anhydride was added dropwise to a solution of concentrated hydrochloric acid 9 ml and fuming nitric acid 3.1 ml at a temperature of 40 ° C or lower. did.
• reaction mixture was stirred at room temperature for 30 minutes. After stirring, the reaction mixture was heated to 60 ° C. After completion of heating, 5 g of 3-chloro-1- (pyridin-3-yl) -1H-pyrazole-4-carboxylic acid was added to the reaction mixture in 5 portions while maintaining 60 ° C. After completion of the addition, stirring was continued at 65 ° C. for 2 hours. After completion of the reaction, the reaction mixture was poured into ice water and neutralized with 1N aqueous sodium hydroxide solution. The precipitated solid was filtered, washed with water, and dried to obtain 4.2 g of the desired product as a pale yellow solid.
• Step 5 Preparation of 3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-amine 3- (3-Chloro-4-nitro-1H-pyrazol-1-yl) pyridine 4 g of ethyl acetate A solution of 20 ml, 10 ml of acetic acid and 10 ml of water was heated to 65 ° C., and 2.5 g of reduced iron was added little by little. After completion of the addition, the mixture was stirred at 70 ° C. for 2 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, 50 ml of water was added, and the pH of the reaction solution was adjusted to 10 with sodium bicarbonate.
• Step 2 Preparation of 2- (methoxyimino) -3- (methylthio) propanoic acid To a mixed solution of 1.84 g of ethyl 2- (methoxyimino) -3- (methylthio) propanoate in 10 ml of water and 10 ml of ethanol, sodium hydroxide 430 mg was added. After completion of the addition, the mixture was stirred at room temperature for 2 days.
• reaction mixture was stirred overnight at room temperature.
• 20 ml of saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution, and the mixture was extracted with 30 ml of ethyl acetate.
• the obtained organic layer was washed with water, then washed and dried with saturated brine and then anhydrous sodium sulfate in this order, and the solvent was distilled off under reduced pressure.
• the obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (5: 1) to obtain 0.8 g of the desired product as a yellow oil.
• Step 2 Preparation of ethyl 2- (methoxyimino) -3- (methylthio) butanoate (Compound E-001) To a solution of 0.8 g of ethyl 2- (methoxyimino) -3- (tosyloxy) butanoate in 5 ml of N, N-dimethylformamide was added 0.2 g of sodium methyl mercaptan at 0 ° C. After completion of the addition, the mixture was stirred at the same temperature for 30 minutes. After completion of the reaction, 10 ml of water was added to the reaction solution and extracted with 10 ml of ethyl acetate.
• reaction solution was cooled to 0 ° C., 10 ml of acetone, 5.2 g of potassium carbonate, and 2.5 g of sodium ethyl mercaptan were sequentially added, followed by stirring at room temperature for 1 hour. After completion of the reaction, 30 ml of hexane and 30 ml of water were added to the reaction solution, and the aqueous layer was taken out by a liquid separation operation. To the obtained aqueous layer, 10 ml of concentrated hydrochloric acid was added, followed by extraction with 50 ml of ethyl acetate.
• Step 2 Production of 3- (ethylthio) -2- (methoxyimino) butanoic acid (Compound F-004) To a solution of 1 g of 3- (ethylthio) -2-oxobutanoic acid in 10 ml of methanol and 5 ml of water, 1 g of O-methylhydroxylamine hydrochloride was added and stirred at room temperature for 15 hours. After completion of the reaction, 2 g of sodium hydroxide, 10 ml of water and 10 ml of hexane were sequentially added to the reaction solution, and the aqueous layer was taken out by a liquid separation operation.
• the solvent of the reaction solution was distilled off under reduced pressure, 50 ml of water was added to the residue, and the mixture was washed with 50 ml of ethyl acetate.
• Concentrated hydrochloric acid was added to the obtained aqueous layer to adjust the pH to 1, and the solid deposited in the aqueous layer was taken out by filtration and washed with water.
• the obtained solid was dried under reduced pressure to obtain 9.0 g of the objective product as a white solid.
• Step 2 Preparation of 1- (tert-butyl) -5-methyl-1H-pyrazole-4-carboxamide 1 g of 1- (tert-butyl) -5-methyl-1H-pyrazole-4-carboxylic acid was added to a 10 ml solution of dichloromethane. At room temperature, 0.84 g of oxalyl chloride and then 0.1 ml of N, N-dimethylformamide were added in this order. After completion of the addition, the mixture was stirred at the same temperature for 30 minutes. After completion of the reaction, the solvent was distilled off under reduced pressure. Tetrahydrofuran (15 ml) was added to the obtained residue, and added at 0 ° C.
• Step 3 Preparation of 1- (tert-butyl) -5-methyl-1H-pyrazol-4-amine 5.2 g of 8 wt% aqueous sodium hypochlorite solution in 0.5 ml of water of 0.64 g of sodium hydroxide And 2 ml of water were added and cooled to 0 ° C. To the reaction solution, 0.48 g of 1- (tert-butyl) -5-methyl-1H-pyrazole-4-carboxamide was added and stirred at 70 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with 10 ml of ethyl acetate.
• Step 5 Preparation of 2- (methoxyimino) -N- (3-methyl-1H-pyrazol-4-yl) -3- (methylthio) butanamide N- ⁇ 1- (tert-butyl) -5-methyl-1H
• a solution of 0.34 g of -pyrazol-4-yl ⁇ -2- (methoxyimino) -3- (methylthio) butanamide in 5 ml of formic acid was stirred at the reflux temperature of formic acid for 5 hours. After completion of the reaction, 5 ml of water was added to the reaction solution and extracted with 5 ml of ethyl acetate.
• the obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
• the obtained residue was purified by medium pressure preparative liquid chromatography eluting with ethyl acetate to obtain 86 mg of the desired product as a pale yellow oil.
• the obtained residue was added at room temperature to a separately prepared solution of 0.9 g of 3-chloro-1H-pyrazol-4-amine and 1.4 g of pyridine in 20 ml of dichloromethane. After the addition was complete, stirring was continued overnight. After completion of the reaction, the solvent was distilled off from the reaction solution under reduced pressure. To the obtained residue was added 20 ml of 1N aqueous hydrochloric acid, and the mixture was extracted with 20 ml of ethyl acetate. The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain 1.2 g of the desired product as a yellow oil.
• the obtained target product was a mixture of two geometric isomers, and the isomer ratio was 2: 1.
• Isomer ratio 2 1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) ⁇ 9.52 (brs, 1H), 8.26 (s, 1H), 4.37-4.31 (m, 1H) 4.07 (s, 3H ), 2.14 (s, 3H), 1.62 (d, J 7.5 Hz, 3H)
• Isomer ratio 1 1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) ⁇ 9.52 (brs, 1H), 8.50 (s, 1H), 4.37-4.31 (m, 1H) 4.07 (s, 3H ), 2.17 (s, 3H), 1.58 (d, J 7.5 Hz, 3H)
• Step 2 Preparation of 3-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine 3-methyl-1- (pyridin-3-yl) -1H-pyrazole-4-carbonyl azide 120 mg
• the toluene 2.5 ml solution was stirred at 100 ° C. for 30 minutes. After completion of the stirring, the reaction solution was cooled to room temperature, and 1 ml of concentrated hydrochloric acid was added.
• reaction solution was continuously stirred at room temperature for 10 minutes.
• 10% by weight aqueous sodium hydroxide solution was added to the reaction solution to adjust the pH of the reaction solution to 11, and then extracted twice with 10 ml of ethyl acetate.
• the obtained organic layer was washed and dried in the order of saturated brine and anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 85 mg of the desired product as a white solid. Melting point: 133-135 ° C
• the solvent of the reaction solution was distilled off under reduced pressure, and then 40 ml of tetrahydrofuran was added to the obtained residue to dissolve it.
• the obtained solution was added at 0 ° C. to 300 ml of a 1.5 M aqueous potassium hydroxide solution prepared separately. After completion of the addition, the reaction solution was stirred at room temperature for 3 hours. After completion of the stirring, the reaction solution was washed with 200 ml of diethyl ether, adjusted to pH 1 with concentrated hydrochloric acid, and extracted with 300 ml of ethyl acetate.
• Step 2 Preparation of (+)-2- (methoxyimino) -3- (methylthio) pentanoic acid To a solution of 96 g of 2- (methoxyimino) -3- (methylthio) pentanoic acid synthesized in Step 1 in 288 ml of acetonitrile, quinidine 155 g and 768 ml of diisopropyl ether were added sequentially.
• reaction solution was stirred at 65 ° C. for 5 minutes. After completion of the stirring, the reaction solution was continuously stirred at room temperature for 3 hours. After completion of the stirring, the solid precipitated in the reaction solution was filtered, and 405 ml of acetonitrile and 576 ml of diisopropyl ether were added to the obtained solid. After stirring at 65 ° C. for 5 minutes, stirring was continued at room temperature for 15 hours. The precipitated solid was filtered, 300 ml of 1M aqueous hydrochloric acid solution was added to the obtained solid, and the mixture was extracted with 300 ml of ethyl acetate.
• Step 2 Preparation of 3-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine 3-methyl-1H-pyrazol-4-amine 0.61 g of dimethyl sulfoxide in 10 ml of solution 1 g of bromopyridine, 0.24 g of copper iodide (monovalent), 3.1 g of cesium carbonate, and 0.36 g of trans-N, N′-dimethylcyclohexane-1,2-diamine were sequentially added.
• the inside of the reaction vessel was replaced with nitrogen gas and then stirred at 140 ° C. for 14 hours.
• the solid precipitated in the reaction mixture was filtered off.
• 50 ml of water was added to the obtained filtrate and extracted with 100 ml of chloroform.
• the obtained organic layer was washed with 50 ml of a 7 wt% aqueous ammonia solution and then with saturated saline, and then dehydrated and dried over anhydrous sodium sulfate.
• the solvent was distilled off under reduced pressure.
• the obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (gradient 3: 1 to 0: 1) to obtain the desired product and its isomer 5- 276 mg of a mixture of methyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine was obtained. This mixture was washed with diisopropyl ether to obtain the desired product (134 mg) as a brown solid. Melting point: 125-127 ° C
• the obtained organic layer was washed with water and then dehydrated and dried in the order of saturated brine and anhydrous sodium sulfate.
• the solvent was distilled off under reduced pressure.
• the obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (gradient 3: 1 to 0: 1) to obtain 114 mg of the desired product as a yellow solid. Melting point: 131-133 ° C
• the obtained organic layer was dehydrated and dried in the order of saturated saline and anhydrous sodium sulfate.
• the solvent was distilled off under reduced pressure to obtain 0.8 g of the objective product as a brown oil.
• the obtained target product was a mixture of two kinds of geometric isomers, and the isomer ratio was 3: 2.
• Step 2 Preparation of ethyl 3- (1,3-dithian-2-yl) -2- (methoxyimino) propanoate
• Ethyl 3- (1,3-dithian-2-yl) -2-oxopropanoate To a 20 ml solution of ethanol, 0.86 g of O-methylhydroxylamine hydrochloride was added and stirred at room temperature for 2 hours. After completion of the reaction, the solvent was distilled off from the reaction solution under reduced pressure, and 30 ml of water was added to the residue, followed by extraction with 50 ml of ethyl acetate.
• the obtained organic layer was dehydrated and dried in the order of saturated brine and anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.
• the obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (gradient 20: 1 to 4: 1) to give 2.1 g of the desired product as a pale yellow oil.
• Gradient 20: 1 to 4: 1 grade 20: 1 to 4: 1
• Step 3 Preparation of 3- (1,3-dithian-2-yl) -2- (methoxyimino) propanoic acid 2 g of ethyl 3- (1,3-dithian-2-yl) -2- (methoxyimino) propanoate 25 ml of water and 0.36 g of sodium hydroxide were added to a 20 ml ethanol solution and stirred at room temperature for 2 hours. After completion of the reaction, ethanol was distilled off from the reaction solution under reduced pressure.
• This invention compound can be manufactured according to the said manufacturing method and an Example.
• Examples of the compounds of the present invention produced in the same manner as in Synthesis Examples 1 to 22 are shown in Tables 5 to 11 and their physical properties are shown in Table 12.
• the present invention is not limited to these. .
• c-Pr and Pr-c represent cyclopropyl groups
• c-Pen and Pen-c represent cyclopentyl groups
• c-Hex and Hex-c represent cyclohexyl groups
• the structures represented by ⁇ 103n, D1 ⁇ 103o, D1 ⁇ 103p, D1 ⁇ 103q, D1 ⁇ 108a, and D1 ⁇ 108b represent the following structures, and are described in the structural formulas of D1-7b, D1 ⁇ 32b, and D1 ⁇ 33b.
• the proton nuclear magnetic resonance chemical shift values in Table 12 were measured at 300 MHz using Me 4 Si (tetramethylsilane) as a reference substance.
• a part of the optically active form of the compound of the present invention was separated into the optically active form using high performance liquid chromatography having an optically active column. The method will be described in detail, but the present invention is not limited to these.
• (A) Separation of optically active substance High performance liquid chromatography was manufactured by Shimadzu Corporation; 10AVP system was used. The optically active substance was separated according to the conditions described below. Flow rate: 7.0 ml / min.
• Test Example 1 Insecticidal test against brown planthopper A 10% emulsion of the compound of the present invention (depending on the compound, 10% wettable powder) was diluted with water containing a spreading agent to prepare a chemical solution having a concentration of 500 ppm. Rice leaf sheaths are immersed in this chemical solution for about 10 seconds, air-dried and placed in a test tube, and 5 second-instar larvae of the green planthopper (Nilaparvata lugens) are released per test tube and covered with a sponge. Housed in a constant temperature room.
• the number of dead insects after 6 days was investigated, and the death rate (%) (number of dead insects ⁇ number of test insects ⁇ 100) was calculated.
• the test was performed by 2 continuous systems. As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
• Test Example 2 Insecticidal test against silver leaf whitefly A moist filter paper was laid on a 7 cm inner diameter styrol cup, and a green leaf cut into 3 cm was placed thereon. A 10% emulsion of a compound of the present invention (depending on the compound, 10% wettable powder) is diluted with water containing a spreading agent to prepare a chemical solution with a concentration of 500 ppm, and the chemical solution is prepared using a rotary spray tower. 2.5 ml was sprayed per styrene cup (2.5 mg / cm 2 ). After the leaves were air-dried, adults of silver leaf whiteflies (Bemisia argentifolii) were released, covered, and housed in a thermostatic chamber at 25 ° C. The number of dead insects after 5 days was investigated, and the dead insect rate was calculated from the same calculation formula as in Test Example 1. In addition, the test was performed by 2 continuous systems. As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
• Test Example 3 Insecticidal test against peach aphid A moist absorbent cotton was laid on a glass petri dish with an inner diameter of 3 cm, and kanran leaves cut out to the same diameter were placed on it. did. One day later, a 10% emulsion of the compound of the present invention (depending on the compound, 10% wettable powder was tested) was diluted with water containing a spreading agent to prepare a chemical solution with a concentration of 500 ppm. The chemical solution was sprayed (2.5 mg / cm 2 ), covered, and stored in a constant temperature room at 25 ° C. The number of dead insects after 6 days was investigated, and the death rate was calculated from the same calculation formula as in Test Example 1. In addition, the test was performed by 2 continuous systems. As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
• Test Example 4 Insecticidal test against cotton aphids Wet cotton wool with a 3 cm inner diameter petri dish, and a cucumber leaf cut to the same diameter was placed on it, and four cotton aphids (Aphis gossypii) adults were released.
• a 10% emulsion of the compound of the present invention (depending on the compound, 10% wettable powder was tested) was diluted with water containing a spreading agent to prepare a chemical solution with a concentration of 100 ppm.
• the chemical solution was sprayed (2.5 mg / cm 2 ), covered, and stored in a constant temperature room at 25 ° C.
• the number of dead insects after 6 days was investigated, and the death rate was calculated from the same calculation formula as in Test Example 1.
• the test was performed by 2 continuous systems. As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
• Test Example 5 Soil irrigation treatment test for peach aphid A 10% emulsion of the compound of the present invention was diluted with tap water to prepare a chemical solution having a concentration of 100 ppm. 10 ml of the chemical solution was irrigated to the stock soil portion of the plastic cup planted cabbage seedling (2.5 true leaf stage) and left in the greenhouse. One day after the irrigation treatment, 20 mosquitoes / strain of adult peach aphid (Myzus persicae) were released and then left in the greenhouse. The number of surviving insects 6 days after the release was examined, and a control value was calculated from the following formula.
• Control value (%) ⁇ 1 ⁇ (Cb ⁇ Tai) / (Cai ⁇ Tb) ⁇ ⁇ 100
• the characters in the formula represent the following: Cb: Number of insects before treatment in the untreated group Cai: Number of live insects at the time of final survey in the untreated group Tb: Number of insects before treatment in the treated group Tai: Number of live insects at the time of final survey in the treated group Results Among the compounds tested, the following compounds showed a control value of 90% or more.
• Test Example 6 Effect test on cat fleas 3.5 mg of the compound of the present invention was dissolved in 3.5 ml of acetone to prepare a chemical solution having a concentration of 1000 ppm. After 350 ⁇ l of this chemical solution was applied to the bottom and side surfaces of a glass container having an inner wall surface area of 35 cm 2 , acetone was volatilized to form a pyrazole and thiazole derivative thin film on the inner wall of the glass container. Since the inner wall of the used glass container is 35 cm 2 , the treatment dose is 10 ⁇ g / cm 2 .
• Test Example 7 Effect test on tick (American dog tick) 3.5 mg of the compound of the present invention was dissolved in 3.5 ml of acetone to prepare a chemical solution having a concentration of 1000 ppm. After 350 ⁇ l of this chemical solution was applied to the bottom and side surfaces of a glass container having an inner wall surface area of 35 cm 2 , acetone was volatilized to form a pyrazole and thiazole derivative thin film on the inner wall of the glass container. Since the inner wall of the used glass container is 35 cm 2 , the treatment dose is 10 ⁇ g / cm 2 .
• novel pyrazole and thiazole derivatives in the present invention exhibit excellent pest control activity, particularly insecticidal / miticidal activity, and have almost no adverse effects on non-target organisms such as mammals, fish and beneficial insects. It is a useful compound.

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