WO2018190321A1 - ピリドン化合物を有効成分とする寄生性有害生物駆除剤およびその使用方法 - Google Patents
ピリドン化合物を有効成分とする寄生性有害生物駆除剤およびその使用方法 Download PDFInfo
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- WO2018190321A1 WO2018190321A1 PCT/JP2018/015003 JP2018015003W WO2018190321A1 WO 2018190321 A1 WO2018190321 A1 WO 2018190321A1 JP 2018015003 W JP2018015003 W JP 2018015003W WO 2018190321 A1 WO2018190321 A1 WO 2018190321A1
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- 0 *CN(C(C=C1)=O)C(c(c(F)ccc2)c2F)=C1c(cc(*)cc1)c1Cl Chemical compound *CN(C(C=C1)=O)C(c(c(F)ccc2)c2F)=C1c(cc(*)cc1)c1Cl 0.000 description 2
- XYYWZIKFDFWNAG-UHFFFAOYSA-N CCN(C(C=C1)=O)C(c(c(F)ccc2)c2F)=C1c(cc(cc1)O)c1Cl Chemical compound CCN(C(C=C1)=O)C(c(c(F)ccc2)c2F)=C1c(cc(cc1)O)c1Cl XYYWZIKFDFWNAG-UHFFFAOYSA-N 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
- A61K31/44—Non condensed pyridines; Hydrogenated derivatives thereof
- A61K31/4412—Non condensed pyridines; Hydrogenated derivatives thereof having oxo groups directly attached to the heterocyclic ring
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
- A61K31/44—Non condensed pyridines; Hydrogenated derivatives thereof
- A61K31/4427—Non condensed pyridines; Hydrogenated derivatives thereof containing further heterocyclic ring systems
- A61K31/444—Non condensed pyridines; Hydrogenated derivatives thereof containing further heterocyclic ring systems containing a six-membered ring with nitrogen as a ring heteroatom, e.g. amrinone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P33/00—Antiparasitic agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D211/74—Oxygen atoms
- C07D211/76—Oxygen atoms attached in position 2 or 6
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
Definitions
- parasitic pests cause various serious problems by infesting animals and plants.
- Parasitic diseases caused by animal parasitic pests are caused by parasitic infection of animal hosts, such as parasites, unicellular protozoa (protozoa), multicellular helminths or arthropods.
- animal hosts such as parasites, unicellular protozoa (protozoa), multicellular helminths or arthropods.
- parasite-infected animals can cause significant anemia, malnutrition, weakness, weight loss, severe damage to the intestinal wall and tissues, organs, and contribute to reduced feed efficiency and productivity.
- Problems caused by plant parasitic pests include a significant economic loss in agriculture and forestry, such as significant inhibition of the growth of crops parasitic on pests.
- parasitic pesticides have been used against these parasitic pests.
- Some of the conventional parasitic pesticides have excellent properties such as immediate effect, osmotic transfer, and gas effect, but they have anti-parasitic pest spectrum, residual effects, toxicity to human and fish, and environmental pollution. Not all are satisfactory in terms of reduction.
- the emergence of parasitic pests exhibiting strong resistance to existing parasitic pesticides has recently become a problem. In such a background, development of a novel parasitic pest control agent that is safer and has a low parasitic dose and excellent parasitic pest control activity is always desired.
- 1,3,5,6-substituted-2-pyridone compounds for example, 1,3,5,6-substituted-2-pyridone having an aryl group or heteroaryl group at the 3-position as a GABA alpha-2 / 3 ligand Compounds have been disclosed (see eg WO 98/55480).
- 1,3,5,6-substituted-2-pyridone compounds having a carboxyl group at the 3-position have been disclosed as therapeutic agents for bacterial infections (see, for example, European Patent No. 0308020).
- An object of the present invention is to provide a novel parasitic pest control agent having excellent parasitic pest control activity.
- R1 is a hydroxyl group, A cyano group, A C1-C6 alkyl group optionally substituted with substituent A, A C1-C6 haloalkyl group, A C3-C8 cycloalkyl group optionally substituted with the substituent A, A C2-C6 alkenyl group optionally substituted with the substituent A, A C2-C6 haloalkenyl group, A C2-C6 alkynyl group optionally substituted with substituent A, A C2-C6 haloalkynyl group, A C1-C6 alkoxy group optionally substituted with the substituent A, A C1-C6 haloalkoxy group, A C3-C8 cycloalkoxy group optionally substituted with the substituent A, A C2-C6 alkenyloxy group optionally substituted with the substituent A, A C2-C6 haloalkenyloxy group, A C3
- R20C ( ⁇ O) O— (wherein R20 has the same meaning as above), A 3- to 6-membered group containing 1 to 2 oxygen atoms, R23-L2- (wherein, R23 represents a C1 alkyl group ⁇ C6 or C1 ⁇ C6 haloalkyl group,, L2 represents S, SO, or SO 2.), R21R22N- (wherein R21 and R22 are as defined above), Or R24C ( ⁇ O) N (R25) — (wherein R24 is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, C1-C6 haloalkoxy group, C3-C8 cycloalkoxy group, or R21R22N— (wherein R21 and R22 have the same meanings as described above), and R25 is optional
- Substituent B1 is At least one selected from the group consisting of a cyano group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, and a C3-C8 cycloalkoxy group
- Substituent C is Hydroxyl group, cyano group, C3-C8 cycloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C3-C8 cycloalkoxy group, R31R32N- (wherein R31 and R32 are the same as R21 And R22), and R30-L3- (wherein R30 has the same meaning as R14 and L3 has the same meaning as L1), and at least one selected from the group consisting of Seeds
- Substituent D is At least one selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C
- R1 represents a C1-C6 alkyl group or a C1-C6 haloalkyl group optionally substituted with the substituent A
- R2 represents a halogen atom, a C1-C6 alkyl group optionally substituted with the substituent B, or a C1-C6 alkoxy group optionally substituted with the substituent B
- R3 represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group optionally substituted with a substituent C.
- a parasitic pest control agent comprising the compound or salt thereof according to [2] as an active ingredient
- the parasitic pests can be efficiently controlled by the novel pyridone compound of the present invention.
- DMF N, N-dimethylformamide
- THF tetrahydrofuran
- Me methyl group
- Et ethyl group
- Pr propyl group
- Bu butyl group
- Pentyl pentyl group
- Hexyl hexyl group
- Ac acetyl group
- Ph Phenyl group
- Py pyridyl group
- i iso
- sec secondary
- ⁇ triple bond.
- a single “-” means no substitution
- Pr, Bu, Pentyl, and Hexyl means normal when there is no prefix.
- Cx-Cy has x to y carbon atoms.
- optionally substituted means substituted or unsubstituted. When this term is used, the number of substituents is 1 when the number of substituents is not specified.
- the C1-C6 alkyl group may be linear or branched, and is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl.
- the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like.
- the C1-C6 haloalkyl group represents a group in which the hydrogen in the C1-C6 alkyl group is optionally substituted with one or more halogen atoms.
- the halogen atoms may be the same or different, and the number of substitutions is not particularly limited as long as it can be present as a substituent.
- C1-C6 haloalkyl group examples include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monochloromethyl group, a monobromomethyl group, a monoiodomethyl group, a chlorodifluoromethyl group, a bromodifluoromethyl group, 1 -Fluoroethyl group, 2-fluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group , Pentafluoroethyl group, 2,2,2-trichloroethyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, heptafluoropropyl group, heptafluoroisopropyl group, 2,2,2
- the C3-C8 cycloalkyl group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.
- the C2-C6 alkenyl group represents an unsaturated hydrocarbon group which has one or more double bonds and is linear or branched.
- C2 to C6 alkenyl groups include vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, and 3-pentenyl.
- the C2-C6 haloalkenyl group represents a group in which the hydrogen atom in the C2-C6 alkenyl group is optionally substituted with one or more halogen atoms.
- the halogen atoms may be the same or different, and the number of substitutions is not particularly limited as long as it can be present as a substituent.
- C2-C6 haloalkenyl group examples include 2-fluorovinyl group, 2,2-difluorovinyl group, 2,2-dichlorovinyl group, 3-fluoroallyl group, 3,3-difluoroallyl group, 3, Examples include 3-dichloroallyl group, 4,4-difluoro-3-butenyl group, 5,5-difluoro-4-pentenyl group, 6,6-difluoro-5-hexenyl group and the like.
- the C2-C6 haloalkynyl group represents a group in which the hydrogen atom in the C2-C6 alkynyl group is optionally substituted with one or more halogen atoms.
- the halogen atoms may be the same or different, and the number of substitutions is not particularly limited as long as it can be present as a substituent.
- C2-C6 haloalkynyl group examples include 2-fluoroethynyl group, 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3,3-difluoro-1-propynyl group, 3-chloro -3,3-difluoro-1-propynyl group, 3-bromo-3,3-difluoro-1-propynyl group, 3,3,3-trifluoro-1-propynyl group, 4,4-difluoro-1-butynyl Group, 4,4-difluoro-2-butynyl group, 4-chloro-4,4-difluoro-1-butynyl group, 4-chloro-4,4-difluoro-2-butynyl group, 4-bromo-4,4 -Difluoro-1-butynyl group, 4-bromo-4,4-Di
- the C1-C6 alkoxy group represents a group in which the C1-C6 alkyl group is bonded via an oxygen atom.
- Specific examples of the C1-C6 alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a pentyloxy group, and an isopentyloxy group.
- the C1-C6 haloalkoxy group represents a group in which the hydrogen atom in the C1-C6 alkoxy group is optionally substituted with one or more halogen atoms.
- the halogen atoms may be the same or different, and the number of substitutions is not particularly limited as long as it can be present as a substituent.
- C1-C6 haloalkoxy group examples include difluoromethoxy group, trifluoromethoxy group, chlorodifluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2,2-difluoroethoxy group, 2,2,2 -Trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, pentafluoroethoxy group, 2,2,2-trichloroethoxy group, 3,3-difluoropropyloxy group, 3,3,3-tri Fluoropropyloxy group, heptafluoropropyloxy group, heptafluoroisopropyloxy group, 2,2,2-trifluoro-1- (trifluoromethyl) -ethoxy group, nonafluorobutoxy group, nonafluoro-sec-butoxy group, 3 , 3,4,4,5,5,5-heptafluoropentyloxy group Undecafluoro pent
- the C3-C8 cycloalkoxy group represents a group in which the C3-C8 cycloalkyl group is bonded via an oxygen atom.
- Specific examples of the C3-C8 cycloalkoxy group include a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.
- the C2-C6 alkenyloxy group is a group in which the C2-C6 alkenyl group is bonded through an oxygen atom.
- E-form and Z-form or a mixture of E-form and Z-form in an arbitrary ratio, is not particularly limited as long as it is within the specified carbon number range. None happen.
- C2-C6 alkenyloxy group examples include vinyloxy group, 1-propenyloxy group, allyloxy group, 1-butenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 1-pentenyloxy group, 2-pentenyloxy group 3-pentenyloxy group, 4-pentenyloxy group, 3-methyl-2-butenyloxy group, 1-hexenyloxy group, 2-hexenyloxy group, 3-hexenyloxy group, 4-hexenyloxy group, 5-hexenyloxy group Group, 4-methyl-3-pentenyloxy group, 3-methyl-2-pentenyloxy group and the like.
- the C2-C6 haloalkenyloxy group represents a group in which the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted with one or more halogen atoms. When substituted with two or more halogen atoms, the halogen atoms may be the same or different, and the number of substitutions is not particularly limited as long as it can be present as a substituent.
- Specific examples of the C2-C6 haloalkenyloxy group include 2-fluorovinyloxy group, 2,2-difluorovinyloxy group, 2,2-dichlorovinyloxy group, 3-fluoroallyloxy group, 3,3-difluoro.
- the C3-C6 alkynyloxy group represents a group in which the C3-C6 alkynyl group is bonded via an oxygen atom among the C2-C6 alkynyl groups.
- Specific examples of the C3-C6 alkynyloxy group include propargyloxy group, 2-butynyloxy group, 3-butynyloxy group, 2-pentynyloxy group, 3-pentynyloxy group, 4-pentynyloxy group, 1,1 -Dimethyl-2-propynyloxy group, 2-hexynyloxy group, 3-hexynyloxy group, 4-hexynyloxy group, 5-hexynyloxy group and the like.
- the C3-C6 haloalkynyloxy group represents a group in which the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted with one or more halogen atoms.
- the halogen atoms may be the same or different, and the number of substitutions is not particularly limited as long as it can be present as a substituent.
- C3-C6 haloalkynyloxy group examples include 1,1-difluoro-2-propynyloxy group, 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro-2-butynyloxy group 4-bromo-4,4-difluoro-2-butynyloxy group, 4,4,4-trifluoro-2-butynyloxy group, 5,5-difluoro-3-pentynyloxy group, 5-chloro-5,5 -Difluoro-3-pentynyloxy group, 5-bromo-5,5-difluoro-3-pentynyloxy group, 5,5,5-trifluoro-3-pentynyloxy group, 6,6-difluoro-4 -Hexynyloxy group, 6-chloro-6,6-difluoro-4-hexynyloxy group, 6-bromo-6
- the C2-C6 alkoxyalkoxy group is a group in which the hydrogen atom in the C1-C5 alkoxy group in the C1-C6 alkoxy group is optionally substituted with one or more C1-C5 alkoxy groups Represents. There is no particular limitation as long as the total number of carbon atoms is within the specified carbon number range.
- C2-C6 alkoxyalkoxy groups include methoxymethoxy, ethoxymethoxy, propyloxymethoxy, isopropyloxymethoxy, methoxyethoxy, ethoxyethoxy, propyloxyethoxy, isopropyloxyethoxy, methoxypropyl Examples thereof include an oxy group, an ethoxypropyloxy group, a propyloxypropyloxy group, and an isopropyloxypropyloxy group.
- 3- to 6-membered ring group containing 1 to 2 oxygen atoms include 1,2-epoxyethanyl group, oxetanyl group, oxolanyl group, oxanyl group, 1,3-dioxolanyl group, 1,3- Examples thereof include a dioxanyl group and a 1,4-dioxanyl group.
- the parasitic pest control agent of the present invention includes a pyridone compound represented by the following formula (1) or a salt thereof (hereinafter simply referred to as a compound represented by the formula (1) or the present compound). To do.
- R1 in the formula (1) is a hydroxyl group, a cyano group, a C1-C6 alkyl group optionally substituted with a substituent A, a C1-C6 haloalkyl group, or a C3-C8 optionally substituted with a substituent A.
- a hydrogen atom or an alkyl group C1 ⁇ C6,) represents a.
- R1 is a cyano group, a C1-C6 alkyl group optionally substituted with the substituent A, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group optionally substituted with the substituent A, a substituted group.
- a C1-C6 alkyl group or a C1-C6 haloalkyl group which may be optionally substituted with the substituent A is preferable.
- R12 and R13 are each independently a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a C3-C8 cycloalkyl group, or R12 and R13 are , Together with the nitrogen atom to which it is attached, represents an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, a homopiperidinyl group, or an azocanyl group), and R14-L1- (where R14 is represents a C1 alkyl group ⁇ C6 or C1 ⁇ C6 haloalkyl group,, L1 is, S, SO, or SO 2 Represents at least one selected from the group consisting of:
- the substituent A is preferably a cyano group, a C1-C6 alkoxy group, or R14-L1- (wherein R14 and L1 are as defined above), In particular, a cyano group or a C1-C6 alkoxy group is preferable.
- substituent A examples include a hydroxyl group; a cyano group; As a C3-C8 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; A methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group as the C1-C6 alkoxy group; C1-C6 haloalkoxy groups include difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 3,3-difluoropropyloxy, and 3,3 , 3-trifluoropropyloxy group; As a C3-C8 cycloalkoxy group, a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclo
- substituent A a hydroxyl group; a cyano group; A cyclopropyl group and a cyclobutyl group as the C3-C8 cycloalkyl group; A methoxy group and an ethoxy group as the C1-C6 alkoxy group; A difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, and a 2,2,2-trifluoroethoxy group as the C1-C6 haloalkoxy group; A cyclopropyloxy group and a cyclobutoxy group as a C3-C8 cycloalkoxy group; R12R13N- (wherein R12 and R13 have the same meanings as described above), dimethylamino group, ethylmethylamino group, and diethylamino group; And R14-L1- (wherein R14 and L1 are as defined above) include a methylthio
- R1 in the formula (1) includes a hydroxyl group and a cyano group.
- the C1-C6 alkyl group of the “C1-C6 alkyl group optionally substituted with the substituent A” in R1 of the formula (1) has the same definition as above, preferably a methyl group, an ethyl group , A propyl group, an isopropyl group, a butyl group, or an isobutyl group, and more preferably a methyl group or an ethyl group.
- the hydrogen atom in the C1-C6 alkyl group is optionally substituted by the substituent A.
- the “C1-C6 haloalkyl group” in R1 of the formula (1) has the same definition as described above, preferably a 2-fluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoro group.
- the C3-C8 cycloalkyl group in the “C3-C8 cycloalkyl group optionally substituted with the substituent A” in R1 of the formula (1) has the same definition as above, preferably a cyclopropyl group , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group.
- the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent A.
- the C2-C6 alkenyl group of the “C2-C6 alkenyl group optionally substituted with the substituent A” in R1 of the formula (1) has the same definition as above, preferably a vinyl group, 1- It is a propenyl group or an allyl group, more preferably a vinyl group or an allyl group.
- the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent A.
- the C2-C6 alkynyl group of the “C2-C6 alkynyl group optionally substituted with the substituent A” in R1 of the formula (1) has the same meaning as defined above, preferably a propargyl group, 2- It is a butynyl group or a 3-butynyl group, more preferably a propargyl group.
- the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent A.
- the “C2-C6 haloalkynyl group” in R1 of the formula (1) has the same definition as above, and is preferably a 4,4-difluoro-2-butynyl group, 4-chloro-4,4-difluoro- 2-butynyl group, 4-bromo-4,4-difluoro-2-butynyl group or 4,4,4-trifluoro-2-butynyl group, more preferably 4,4-difluoro-2-butynyl Or a 4,4,4-trifluoro-2-butynyl group.
- the C1-C6 alkoxy group of the “C1-C6 alkoxy group optionally substituted with the substituent A” in R1 of the formula (1) has the same definition as above, preferably a methoxy group, an ethoxy group , A propyloxy group, an isopropyloxy group, a butoxy group, or an isobutoxy group, and more preferably a methoxy group or an ethoxy group.
- the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent A.
- the “C1-C6 haloalkoxy group” in R1 of the formula (1) has the same definition as above, preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2, 2-trifluoroethoxy group, 3,3-difluoropropyloxy group, or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.
- the C3-C8 cycloalkoxy group in the “C3-C8 cycloalkoxy group optionally substituted with the substituent A” in R1 of the formula (1) has the same definition as described above, preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group.
- the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted with the substituent A.
- the C2-C6 alkenyloxy group of “C2-C6 alkenyloxy group optionally substituted with substituent A” in R1 of formula (1) has the same definition as above, preferably a vinyloxy group, It is a 1-propenyloxy group or an allyloxy group, and more preferably a vinyloxy group.
- the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent A.
- the C3-C6 alkynyloxy group of “C3-C6 alkynyloxy group optionally substituted with substituent A” in R1 of formula (1) has the same definition as above, preferably a propargyloxy group , 2-butynyloxy group, or 3-butynyloxy group, and more preferably a propargyloxy group.
- the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent A.
- R10R11N— The C1-C6 alkyl group of “R10R11N—” in R1 of the formula (1) (wherein R10 and R11 are each independently a hydrogen atom or a C1-C6 alkyl group) Synonymous with definition.
- R10R11N— is preferably an amino group, a dimethylamino group, an ethylmethylamino group, and a diethylamino group, more preferably an amino group and a dimethylamino group.
- R2 is a halogen atom, a hydroxyl group, a cyano group, a nitro group, a C1-C6 alkyl group that may be optionally substituted with a substituent B, a C1-C6 haloalkyl group, and a C3-optionally substituted C3- A C8 cycloalkyl group, a C2-C6 alkenyl group optionally substituted with substituent B, a C2-C6 haloalkenyl group, a C2-C6 alkynyl group optionally substituted with substituent B, C2- C6 haloalkynyl group, C1-C6 alkoxy group optionally substituted with substituent B, C1-C6 haloalkoxy group, C3-C8 cycloalkoxy group optionally substituted with substituent B, substituted C2-C6 alkenyloxy group optionally substituted with group B, C2-C6 haloalkenyloxy group, C3-
- R24C ( ⁇ O) N (R25) (wherein R24 is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group) , A C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, or R21R22N— (wherein R21 and R22 have the same meanings as described above), and R25 is a hydrogen atom or a substituent B1. Place Which may be C1 ⁇ C6 alkyl group, a cycloalkyl group of haloalkyl group having C1 ⁇ C6 or C3 ⁇ C8,. ).
- R2 is a halogen atom, a hydroxyl group, a cyano group, a C1-C6 alkyl group optionally substituted with a substituent B, a C1-C6 haloalkyl group, or a C1-C6 optionally substituted with a substituent B.
- Substituent B in formula (1) is a hydroxyl group, a cyano group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, a C2 To C6 alkoxyalkoxy groups, R21R22N- (wherein R21 and R22 are as defined above), R23-L2- (wherein R23 and L2 are as defined above), R26R27R28Si- ( Here, R26, R27, and R28 are each independently a C1-C6 alkyl group.), R26R27R28Si— (CH 2 ) s—O— (wherein s is an integer of 1 to 3) R26, R27, and R28 are as defined above, R20C ( ⁇ O) — (wherein R20 is as defined above for R20), and ⁇ Represents at least one member selected from the group consist
- the substituent B is a cyano group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, a C2-C6 alkoxyalkoxy group, R23-L2- (wherein R23 and L2 are as defined above).
- Preferred specific examples of the substituent B include a hydroxyl group; a cyano group; As a C3-C8 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; A C1-C6 alkoxy group as a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, and an isobutoxy group; C1-C6 haloalkoxy groups include difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 3,3-difluoropropyloxy, and 3,3 , 3-trifluoropropyloxy group; As a C3-C8 cycloalkoxy group, a cyclopropyloxy group, a cyclobutoxy group, a
- Examples of the 3- to 6-membered ring group containing 1 to 2 oxygen atoms include a 1,3-dioxolanyl group and a 1,3-dioxanyl group.
- the “substituent B1” in the formula (1) is at least one selected from the group consisting of a cyano group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, and a C3-C8 cycloalkoxy group.
- the substituent B1 is preferably a cyano group or a C1-C6 alkoxy group.
- substituent B1 examples include a cyano group;
- a C1-C6 alkoxy group as a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, and an isobutoxy group;
- C1-C6 haloalkoxy groups include difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 3,3-difluoropropyloxy, and 3,3 , 3-trifluoropropyloxy group;
- examples of the C3-C8 cycloalkoxy group include a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
- substituent B1 a cyano group; A methoxy group and an ethoxy group as the C1-C6 alkoxy group; A difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, and a 2,2,2-trifluoroethoxy group as the C1-C6 haloalkoxy group; As the C3-C8 cycloalkoxy group, a cyclopropyloxy group and a cyclobutoxy group can be mentioned.
- the halogen atom in R2 of the formula (1) has the same definition as described above, and is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
- R2 in the formula (1) includes a hydroxyl group, a cyano group, and a nitro group.
- the “C1-C6 haloalkyl group” in R2 of the formula (1) has the same definition as above, and is preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, 2,2,2 A trifluoroethyl group, a 3,3-difluoropropyl group, or a 3,3,3-trifluoropropyl group, more preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, or 2,2,2-trifluoroethyl group.
- the C3-C8 cycloalkyl group in the “C3-C8 cycloalkyl group optionally substituted with the substituent B” in R2 of the formula (1) is as defined above, and preferably a cyclopropyl group , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group.
- the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent B.
- the “C2-C6 haloalkenyl group” in R2 of the formula (1) has the same definition as above, preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group, a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.
- the C2-C6 alkynyl group of the “C2-C6 alkynyl group optionally substituted with the substituent B” in R2 of the formula (1) has the same definition as above, preferably an ethynyl group, 1- A propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group, and more preferably an ethynyl group, a 1-propynyl group, or a propargyl group.
- the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent B.
- the “C2-C6 haloalkynyl group” in R2 of the formula (1) has the same definition as above, preferably 3,3-difluoro-1-propynyl group, 3,3,3-trifluoro-1 -Propynyl group, 4,4-difluoro-1-butynyl group, 4,4-difluoro-2-butynyl group, 4,4,4-trifluoro-1-butynyl group, or 4,4,4-trifluoro- A 2-butynyl group, more preferably a 3,3-difluoro-1-propynyl group, or a 3,3,3-trifluoro-1-propynyl group.
- the C1-C6 alkoxy group of the “C1-C6 alkoxy group optionally substituted with the substituent B” in R2 of the formula (1) is as defined above, preferably a methoxy group, an ethoxy group Propyloxy group, isopropyloxy group, butoxy group, isobutoxy group or pentyloxy group, more preferably methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group or pentyloxy group.
- the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent B.
- the C3-C8 cycloalkoxy group of the “C3-C8 cycloalkoxy group optionally substituted with the substituent B” in R2 of the formula (1) has the same definition as described above, preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group.
- the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent B.
- the C2-C6 alkenyloxy group of the “C2-C6 alkenyloxy group optionally substituted with the substituent B” in R2 of the formula (1) has the same definition as above, preferably a vinyloxy group, A 1-propenyloxy group, an allyloxy group, a 1-butenyloxy group, a 2-butenyloxy group, or a 3-butenyloxy group, and more preferably a vinyloxy group, a 1-propenyloxy group, or an allyloxy group.
- the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent B.
- the “C2-C6 haloalkenyloxy group” in R2 of the formula (1) has the same definition as above, and preferably a 2-fluorovinyloxy group, a 2,2-difluorovinyloxy group, a 2,2- A dichlorovinyloxy group, a 3-fluoroallyloxy group, a 3,3-difluoroallyloxy group, or a 3,3-dichloroallyloxy group, more preferably a 2-fluorovinyloxy group or 2,2-difluoro It is a vinyloxy group.
- the C3-C6 alkynyloxy group of “C3-C6 alkynyloxy group optionally substituted with substituent B” in R2 of formula (1) is as defined above, preferably a propargyloxy group , 2-butynyloxy group, or 3-butynyloxy group, and more preferably a propargyloxy group.
- the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent B.
- the “C3-C6 haloalkynyloxy group” in R2 of the formula (1) has the same definition as above, and is preferably a 4,4-difluoro-2-butynyloxy group, a 4-chloro-4,4-difluoro group.
- R20C ( ⁇ O) — in R2 of the formula (1) (wherein R20 is a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group) , A C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, or R21R22N— (wherein R21 and R22 are each independently a hydrogen atom or a C1-C6 group optionally substituted with a substituent B1).
- R20C ( ⁇ O) — is preferably an acetyl group, a propionyl group, a difluoroacetyl group, a trifluoroacetyl group, a cyclopropanecarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, cyclopropyloxycarbonyl group, aminocarbonyl group, dimethylaminocarbonyl group, ethylmethylaminocarbonyl group, diethylaminocarbonyl group, pyrrolidinylcarbonyl group, and piperidinylcarbonyl group More preferably, acetyl group, difluoroacetyl group, trifluoroacetyl group, methoxycarbonyl group, ethoxycarbonyl group, aminocarbonyl group, dimethylaminocarbonyl
- R20 of “R20C ( ⁇ O) O—” in R2 of the formula (1) has the same meaning as described above.
- “R20C ( ⁇ O) O—” is preferably an acetyloxy group, a propionyloxy group, a difluoroacetyloxy group, a trifluoroacetyloxy group, a cyclopropanecarbonyloxy group, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, 2 , 2-difluoroethoxycarbonyloxy group, 2,2,2-trifluoroethoxycarbonyloxy group, cyclopropyloxycarbonyloxy group, aminocarbonyloxy group, dimethylaminocarbonyloxy group, ethylmethylaminocarbonyloxy group, diethylaminocarbonyloxy group Group, pyrrolidinylcarbonyloxy group, and piperidinylcarbonyloxy group, more preferably acetyloxy group,
- Shi group methoxycarbonyloxy group, ethoxycarbonyloxy group, aminocarbonyl group, dimethylaminocarbonyl group, ethylmethylamino carbonyloxy groups, and diethylamino carbonyl group.
- the “3- to 6-membered ring group containing 1 to 2 oxygen atoms” in R2 of the formula (1) has the same definition as above, and preferably an oxolanyl group, an oxanyl group, a 1,3-dioxolanyl group Or a 1,3-dioxanyl group, and more preferably a 1,3-dioxolanyl group or a 1,3-dioxanyl group.
- R23-L2- in R2 of Formula (1) (wherein R23 represents a C1-C6 alkyl group or a C1-C6 haloalkyl group, and L2 represents S, SO, or SO 2 ). ) Are as defined above. “R23-L2-” is preferably a methylthio group, a methanesulfinyl group, a methanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, a trifluoromethanesulfonyl group, a (chloromethyl) thio group, or a (chloromethane) sulfinyl group.
- chloromethane sulfonyl group, more preferably, methylthio group, methanesulfinyl group, methanesulfonyl group, (chloromethyl) thio group, (chloromethane) sulfinyl group, and (chloromethane) sulfonyl group. It is done.
- R21 and R22 of “R21R22N-” in R2 of the formula (1) have the same meanings as described above.
- “R21R22N—” preferably includes an amino group, a dimethylamino group, an ethylmethylamino group, a diethylamino group, a pyrrolidinyl group, and a piperidinyl group, and more preferably a dimethylamino group, an ethylmethylamino group, and a diethylamino group. Is mentioned.
- R24C ( ⁇ O) N (R25) — in R2 of the formula (1) (wherein R24 is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group) , C1-C6 alkoxy group, C1-C6 haloalkoxy group, C3-C8 cycloalkoxy group, or R21R22N- (wherein R21 and R22 are as defined above), and R25 represents hydrogen.
- R24 is preferably a hydrogen atom, methyl group, ethyl group, difluoromethyl group, trifluoromethyl group, cyclopropyl group, methoxy group, ethoxy group, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy.
- Group cyclopropyloxy group, amino group, dimethylamino group, ethylmethylamino group, diethylamino group, pyrrolidinyl group, and piperidinyl group, and more preferably a hydrogen atom, a methyl group, a difluoromethyl group, a trifluoromethyl group.
- Group, 2,2,2-trifluoroethyl group, and cyclopropyl group more preferably hydrogen atom, methyl group, ethyl group, methoxymethyl group, ethoxymethyl group, methoxyethyl group, ethoxyethyl group, A cyanomethyl group, a 2,2-difluoroethyl group, and a 2,2,2-trifluoroethyl group can be mentioned.
- N in the formula (1) is an integer of 0 to 5.
- n 2 or more
- two or more R2s each represent an independent substituent, may be the same or different, and can be arbitrarily selected.
- R3 in formula (1) may be optionally substituted with a hydrogen atom, a halogen atom, a nitro group, a C1-C6 alkyl group optionally substituted with a substituent C, a C1-C6 haloalkyl group, or a substituent C.
- R3 is a hydrogen atom, a halogen atom, a C1-C6 alkyl group that may be optionally substituted with a substituent C, a C3-C8 cycloalkyl group that may be optionally substituted with a substituent C, or a substituent C as appropriate.
- a hydrogen atom, a halogen atom, or a C1-C6 alkyl group optionally substituted with a substituent C is preferable.
- the “substituent C” in formula (1) is a hydroxyl group, a cyano group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, R31R32N. -(Wherein R31 and R32 are as defined above for R21 and R22), and R30-L3- (wherein R30 is as defined above for R14, and L3 is as defined above for L1).
- the substituent C is preferably a cyano group, a C1-C6 alkoxy group, or R30-L3- (wherein R30 and L3 are as defined above), In particular, a cyano group or a C1-C6 alkoxy group is preferable.
- substituent C examples include a hydroxyl group; a cyano group; As a C3-C8 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; A C1-C6 alkoxy group as a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, and an isobutoxy group; C1-C6 haloalkoxy groups include difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 3,3-difluoropropyloxy, and 3,3 , 3-trifluoropropyloxy group; As a C3-C8 cycloalkoxy group, a cyclopropyloxy group, a cyclobutoxy group, a
- substituent C a hydroxyl group; a cyano group; A cyclopropyl group and a cyclobutyl group as the C3-C8 cycloalkyl group; A methoxy group and an ethoxy group as the C1-C6 alkoxy group; A difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, and a 2,2,2-trifluoroethoxy group as the C1-C6 haloalkoxy group; A cyclopropyloxy group and a cyclobutoxy group as a C3-C8 cycloalkoxy group; R31R32N— (wherein R31 and R32 have the same meanings as described above), a dimethylamino group, an ethylmethylamino group, and a diethylamino group; And R30-L3- (wherein R30 and L3 are as defined above) include
- R3 in the formula (1) includes a hydrogen atom and a nitro group.
- the “halogen atom” in R3 of the formula (1) has the same definition as described above, and is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
- the C1-C6 alkyl group in the “C1-C6 alkyl group optionally substituted with substituent C” in R3 of the formula (1) has the same definition as described above, preferably a methyl group, an ethyl group , A propyl group, an isopropyl group, a butyl group, or an isobutyl group, and more preferably a methyl group, an ethyl group, or a propyl group.
- the hydrogen atom in the C1-C6 alkyl group is optionally substituted by the substituent C.
- the “C1-C6 haloalkyl group” in R3 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, 2,2,2 A trifluoroethyl group, a 3,3-difluoropropyl group, or a 3,3,3-trifluoropropyl group, more preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, or 2,2,2-trifluoroethyl group.
- the C3-C8 cycloalkyl group in the “C3-C8 cycloalkyl group optionally substituted with the substituent C” in R3 of the formula (1) has the same definition as above, preferably a cyclopropyl group , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group.
- the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent C.
- the C1-C6 alkoxy group of the “C1-C6 alkoxy group optionally substituted with the substituent C” in R3 of the formula (1) has the same definition as above, preferably a methoxy group, an ethoxy group , A propyloxy group, an isopropyloxy group, a butoxy group, or an isobutoxy group, and more preferably a methoxy group, an ethoxy group, a propyloxy group, or an isopropyloxy group.
- the hydrogen atom in the C1-C6 alkoxy group is optionally substituted with the substituent C.
- the “C1-C6 haloalkoxy group” in R3 of the formula (1) has the same definition as above, preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2, 2-trifluoroethoxy group, 3,3-difluoropropyloxy group, or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.
- the C2-C6 alkenyl group of “C2-C6 alkenyl group optionally substituted with substituent C” in R3 of formula (1) is as defined above, preferably a vinyl group, 1- A propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group, more preferably a vinyl group, a 1-propenyl group, or an allyl group.
- the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent C.
- the “C2-C6 haloalkenyl group” in R3 of the formula (1) has the same definition as above, preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group, a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.
- the C2-C6 alkynyl group of the “C2-C6 alkynyl group optionally substituted with the substituent C” in R3 of the formula (1) has the same definition as defined above, preferably an ethynyl group, 1- A propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group, and more preferably an ethynyl group, a 1-propynyl group, or a propargyl group.
- the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent C.
- the “C2-C6 haloalkynyl group” in R3 of the formula (1) has the same definition as described above, and is preferably a 3,3-difluoro-1-propynyl group, 3,3,3-trifluoro-1 -Propynyl group, 4,4-difluoro-1-butynyl group, 4,4-difluoro-2-butynyl group, 4,4,4-trifluoro-1-butynyl group, or 4,4,4-trifluoro- A 2-butynyl group, more preferably a 3,3-difluoro-1-propynyl group, or a 3,3,3-trifluoro-1-propynyl group.
- R30-L3- in R3 of the formula (1), R30 has the same meaning as R23, and L3 has the same meaning as L2.
- R30-L3- preferably includes a methylthio group, a methanesulfinyl group, a methanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, and a trifluoromethanesulfonyl group, and more preferably a methylthio group, a methanesulfinyl group. Groups, and methanesulfonyl groups.
- R31R32N— in R3 of the formula (1) has the same meaning as R21 and R22, and is preferably an amino group, a dimethylamino group, an ethylmethylamino group, a diethylamino group, a pyrrolidinyl group, or A piperidinyl group, more preferably a dimethylamino group, an ethylmethylamino group, or a diethylamino group.
- Y in Formula (1) represents a phenyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, a tetrazinyl group, a thienyl group, a thiazolyl group, an isothiazolyl group, or a thiadiazolyl group.
- the substituent D is substituted at the ortho position, and the substituent D1 is independently independently substituted with 0 to 4 appropriately.
- the substituent D is substituted at the ortho position, and the substituent D1 is independently independently selected from 0 to 3 Replace.
- the substituent D is substituted at the ortho position, and the substituent D1 is independently independently substituted with 0-2.
- “Substituent D” in formula (1) is selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, and a C1-C6 haloalkoxy group Represents at least one kind.
- the substituent D is preferably a halogen atom or a C1-C6 alkyl group, In particular, a halogen atom is preferable.
- examples of the C1-C6 haloalkoxy group include a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, and a 2,2,2-trifluoroethoxy group.
- the “substituent D1” in formula (1) is a hydroxyl group, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, a C1-C6 And at least one selected from the group consisting of C3-C8 cycloalkoxy groups.
- substituent D1 a hydroxyl group;
- a halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom;
- a methyl group, an ethyl group, and a propyl group as the C1-C6 alkyl group;
- a C3-C8 cycloalkyl group a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;
- a C1-C6 alkoxy group as a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group,
- substituent D1 a hydroxyl group; A halogen atom, a fluorine atom, a chlorine atom, and a bromine atom; A methyl group and an ethyl group as the C1-C6 alkyl group; A difluoromethyl group and a trifluoromethyl group as a C1-C6 haloalkyl group; A cyclopropyl group and a cyclobutyl group as the C3-C8 cycloalkyl group; A methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group as the C1-C6 alkoxy group; A difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, and a 2,2,2-trifluoroethoxy group as the C1-C6 haloalkoxy group; As the C3-C8 cycloalkoxy
- Y is a phenyl group
- Y is represented by the formula (a) (Wherein D and D1 are as defined above, and ma represents an integer of 0 to 4).
- ma represents an integer of 0 to 4.
- 2 or more D1s each represent an independent substituent, may be the same or different, and can be arbitrarily selected.
- the ortho position means the position of the phenyl group having the substituent D as shown in the formula (a).
- the phenyl group in which the substituent D is located in the ortho position is a feature of the present invention.
- a preferred combination of the formula (a) is a 2-D-6-D1-phenyl group, a 2-D-4-D1-phenyl group, or a 2-D-4-D1-6-D1-phenyl group.
- 2-D-6-D1-phenyl group means a disubstituted phenyl group having a substituent D at the 2-position and a substituent D1 at the 6-position, and the following description is also the same.
- Y is a group represented by the formula (b) (Wherein D and D1 are as defined above, and mb represents an integer of 0 to 3).
- G1, G2, G3 and G4 in the formula (b) are each independently a carbon atom or a nitrogen atom. However, at least one of G1, G2, G3 and G4 is a nitrogen atom. Preferred G1, G2, G3 and G4 are any one of G1, G2, G3 and G4 being a nitrogen atom. That is, it is a pyridyl group.
- mb represents an integer of 0 to 3. When mb in the formula (b) is 2 or more, 2 or more D1s each represent an independent substituent, may be the same or different, and can be arbitrarily selected.
- the ortho position means a 6-membered ring having a substituent D as shown in the formula (b).
- Means the position of Specific examples of the partial structure of the formula (b) are shown below.
- a pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, or tetrazinyl group in which the substituent D is located in the ortho position is a feature of the present invention.
- Preferred combinations of formula (b) are 3-D-2-pyridyl group, 3-D-5-D1-2-pyridyl group, 2-D-3-pyridyl group, 2-D-4-D1-3- Pyridyl group, 2-D-6-D1-3-pyridyl group, 2-D-4-D1-6-D1-3-pyridyl group, 4-D-3-pyridyl group, 4-D-2-D1- 3-pyridyl group, 4-D-6-D1-3-pyridyl group, 4-D-2-D1-6-D1-3-pyridyl group, 3-D-4-pyridyl group, or 3-D-5 -D1-4-pyridyl group.
- Y is a group represented by the formula (c-1) Formula (c-2) Or the formula (c-3) (Wherein D and D1 are as defined above, and mc represents an integer of 0 to 2).
- G5 and G6 in formula (c-1), formula (c-2) and formula (c-3) are each independently a carbon atom or a nitrogen atom.
- mc represents an integer of 0 to 2.
- D1 in 2 represents an independent substituent, and may be the same or different and arbitrarily selected can do.
- the ortho position is represented by the formula (c-1), the formula (c-2), and the formula (c-3).
- the thienyl group, thiazolyl group, isothiazolyl group, or thiadiazolyl group in which the substituent D is located in the ortho position is a feature of the present invention.
- R3 in the formula (1b) is a substituent other than hydrogen, only one of the R-form and S-form, or a mixture of the R-form and the S-form in an arbitrary ratio.
- the compound represented by formula (1) may have one or two axial asymmetry.
- the isomer ratio is a single or an arbitrary mixing ratio, and is not particularly limited.
- the compound represented by Formula (1) may contain an asymmetric atom.
- the isomer ratio is a single or an arbitrary mixing ratio, and is not particularly limited.
- the compound represented by Formula (1) may contain geometric isomers.
- the isomer ratio is a single or an arbitrary mixing ratio, and is not particularly limited.
- the specific compound of the present invention is represented by a combination of the structural formula shown in Table 1, (R2) n shown in Table 2, and X which is an oxygen atom or a sulfur atom. These compounds are for illustrative purposes, and the present invention is not limited thereto.
- the description “2-F—” in Table 2 means that a fluorine atom is bonded to the 2-position of the phenyl group to which (R2) n is bonded, and “2-F-3”
- the description “—HO—” means that a fluorine atom is bonded to the 2-position and a hydroxyl group is bonded to the 3-position.
- the description of “2,3-di-F” means that the 2-position and 3 This means that a fluorine atom is bonded to the position, and other descriptions are the same.
- R4 is a hydrogen atom, a hydroxyl group, a cyano group, a C1-C6 alkyl group that may be optionally substituted with a substituent A, a C1-C6 haloalkyl group, or a C3-optionally substituted C3- A C8 cycloalkyl group, a C2-C6 alkenyl group optionally substituted with substituent A, a C2-C6 haloalkenyl group, a C2-C6 alkynyl group optionally substituted with substituent A, C2- C6 haloalkynyl group, C1-C6 alkoxy group optionally substituted with substituent A, C1-C6 haloalkoxy group, C3-C8 cycloalkoxy group optionally substituted with substituent A, substituted A C2-C6 alkenyloxy group optionally substituted with the group A, a C2-C6 haloalkenyloxy group, a C3-C8
- Production method A is a method for obtaining a compound represented by the formula (1b-a) containing the compound of the present invention and a production intermediate of the compound of the present invention, wherein the compound represented by formula (3) and R4NH 2 are obtained. , A production method comprising reacting in the presence of an acid.
- R4NH 2 used in this reaction can be produced by obtaining or known manner as a commercially available product.
- R4NH 2 are hydrochloric, may be those forming a salt with an acidic compound such as acetic acid, it is not particularly limited as long as the reaction proceeds to the desired.
- R4NH 2 used in this reaction may if 1 equivalent or more relative to the compound represented by formula (3), but are not particularly limited as long as the reaction proceeds to the desired, preferably, 1 Equivalent to 200 equivalents.
- Examples of the acid used in this reaction include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid, methanesulfonic acid, and p-toluenesulfonic acid, and are particularly limited as long as the target reaction proceeds. Although not preferred, acetic acid is preferred. Further, when using salts with R4NH 2 and the acidic compound, the use of acid is not essential.
- the amount of the acid used in this reaction may if 1 equivalent or more relative to the R4NH 2, is not limited in particular as long as the reaction proceeds to the desired, preferably, one or more equivalents 200 equivalent or less is there.
- the acid to be used is a liquid, it can also be used as a solvent.
- a solvent can be used for this reaction, it is not necessarily essential.
- the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but acidic solvents such as acetic acid and methanesulfonic acid, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxy Ether solvents such as ethane, tetrahydrofuran, dioxane, alcohol solvents such as methanol, ethanol, isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ethyl acetate, isopropyl acetate, butyl acetate, etc.
- Ester solvents such as acetonitrile, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea systems such as 1,3-dimethyl-2-imidazolidinone solvent Dichloromethane, dichloroethane, chloroform, and halogen solvents such as carbon tetrachloride. These solvents can be used alone or in admixture of two or more.
- the solvent is preferably an acidic solvent, more preferably acetic acid.
- the amount of the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by formula (3). is there.
- the temperature at which this reaction is carried out is not particularly limited as long as the target reaction proceeds, but is usually 50 ° C. or higher and 180 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, or an arbitrary aqueous solution is used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl Solvents that are not compatible with water, such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. It is possible to add. Moreover, these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio. The number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield.
- the reaction mixture containing the compound represented by the formula (1b-a) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but is not essential.
- the reaction mixture containing the compound represented by the formula (1b-a) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (1b-a) obtained after distilling off the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- the compound represented by formula (2) which can be produced when R4 represents a hydrogen atom in the compound represented by formula (1b-a), It can be a useful production intermediate for obtaining the compound represented by 1b).
- a specific example of the production intermediate represented by the formula (2) is represented by a combination of the structural formula shown in Table 3, (R2) n shown in Table 2, and X which is an oxygen atom or a sulfur atom. These compounds are for illustrative purposes, and the present invention is not limited thereto.
- Lv represents a methanesulfonyl group, a trifluoromethanesulfonyl group, a p-toluenesulfonyl group, a leaving group such as a halogen atom, and R1, R2, R3, X, Y, and n are as defined above.
- Production method B is a method for obtaining a compound represented by formula (1b), which comprises reacting the production intermediate represented by formula (2) with R1Lv in a solvent in the presence of a base. It is a manufacturing method.
- R1Lv used in this reaction can be obtained as a commercial product or can be produced by a known method.
- Examples of the base used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, and sodium hydride, but are particularly limited as long as the intended reaction proceeds. It will never be done.
- the amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by formula (2), and is not particularly limited as long as the target reaction proceeds. 1 equivalent or more and 10 equivalents or less.
- the temperature at which this reaction is carried out is not particularly limited as long as the intended reaction proceeds, but is usually 0 ° C. or higher and 150 ° C. or lower or the boiling point of the solvent or lower.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl
- Solvents that are not compatible with water such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. It is possible to add.
- these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio.
- the number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield.
- the reaction mixture containing the compound represented by the formula (1b) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but is not essential.
- SR represents a sulfurizing agent
- R1, R2, R3, Y, and n are as defined above.
- sulfurizing agent examples include Lawesson's reagent (2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide).
- the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but ether solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, Examples thereof include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene. These solvents can be used alone or in admixture of two or more.
- the amount of the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by the formula (1b-b). It is as follows.
- the temperature at which this reaction is carried out is not particularly limited as long as the target reaction proceeds, but is usually 50 ° C. or higher and 180 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, or an arbitrary aqueous solution is used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl
- Solvents that are not compatible with water such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane.
- liquid separation operation is not essential.
- the reaction mixture containing the compound represented by the formula (1b-c) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (1b-c) obtained after the solvent is distilled off can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- R3a is a C1-C6 alkyl group optionally substituted with a substituent C, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group optionally substituted with a substituent C, a substituent C2-C6 alkenyl group optionally substituted with C, C2-C6 haloalkenyl group, C2-C6 alkynyl group optionally substituted with substituent C, or C2-C6 haloalkynyl group , Lv, R1, R2, X, Y, and n are as defined above.
- R3a is optionally substituted with a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a substituent C, which may be optionally substituted with a substituent C.
- R3aLv used in this reaction can be obtained as a commercial product or can be produced by a known method.
- the amount of R3aLv used in this reaction may be 1 equivalent or more with respect to the compound represented by formula (1b-d), and is not particularly limited as long as the target reaction proceeds, but is preferably Is 1 equivalent or more and 1.8 equivalent or less.
- the amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1b-d), and is not particularly limited as long as the target reaction proceeds, but preferably Is 1 equivalent or more and 10 equivalents or less.
- the amount of the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by the formula (1b-d). It is as follows.
- the temperature at which this reaction is carried out is not particularly limited as long as the intended reaction proceeds, but is usually from ⁇ 80 ° C. to 100 ° C. or the boiling point of the solvent.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, sodium thiosulfate, sulfurous acid
- An aqueous solution or a salt solution in which a salt containing sulfur such as sodium is dissolved can be arbitrarily used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl
- a solvent that is not compatible with water such as an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, or chloroform, or a hydrocarbon solvent such as hexane, heptane, cyclohexane, or methylcyclohexane.
- these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio.
- the number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield.
- the reaction mixture containing the compound represented by the formula (1b-e) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but is not essential.
- the reaction mixture containing the compound represented by the formula (1b-e) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (1b-e) obtained after distilling off the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- Ox represents an oxidizing agent
- R1, R2, R3, X, Y, and n are as defined above.
- Production method E is a method for obtaining a compound represented by formula (1a), which comprises reacting a compound represented by formula (1b) with an oxidizing agent (Ox) in a solvent. is there.
- oxidizing agent used in this reaction examples include metal oxides such as manganese dioxide, benzoquinones such as 2,3-dichloro-5,6-dicyano-p-benzoquinone, azobisisobutyronitrile, and benzoyl peroxide.
- the oxidizing agent is a metal oxide.
- the amount of the oxidizing agent used in this reaction is not particularly limited as long as the target reaction proceeds as long as it is 1 equivalent or more with respect to the compound represented by the formula (1b). Equivalent to 200 equivalents.
- the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, dichloromethane, dichloroethane, chloroform, And halogen-based solvents such as carbon tetrachloride. These solvents can be used alone or in admixture of two or more.
- the amount of solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by formula (1b). is there.
- the temperature at which this reaction is carried out is not particularly limited as long as the intended reaction proceeds, but is usually 0 ° C. or higher and 150 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, or an arbitrary aqueous solution is used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl
- Solvents that are not compatible with water such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane.
- liquid separation operation is not essential.
- the reaction mixture containing the compound represented by the formula (1a) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but is not essential.
- the reaction mixture containing the compound represented by the formula (1a) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (1a) obtained after distilling off the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- the oxidizing agent is a benzoquinone.
- the amount of the oxidizing agent used in this reaction is not particularly limited as long as the target reaction proceeds as long as it is 1 equivalent or more with respect to the compound represented by the formula (1b). Equivalent to 20 equivalents.
- the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, dichloromethane, dichloroethane, chloroform, And halogen-based solvents such as carbon tetrachloride. These solvents can be used alone or in admixture of two or more.
- the amount of solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by formula (1b). is there.
- the temperature at which this reaction is carried out is not particularly limited as long as the intended reaction proceeds, but is usually 0 ° C. or higher and 150 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, or an arbitrary aqueous solution is used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl
- Solvents that are not compatible with water such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane.
- liquid separation operation is not essential.
- the reaction mixture containing the compound represented by the formula (1a) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but is not essential.
- the oxidizing agent is a combination of a radical initiator and a halogenating agent. If the amount of the radical initiator and the halogenating agent used in this reaction is 0.01 equivalent or more and 1.0 equivalent or more with respect to the compound represented by the formula (1b), the target reaction proceeds. As long as it does, it will not specifically limit.
- the radical initiator is 0.01 equivalent to 1 equivalent and the halogenating agent is 1 equivalent to 3 equivalent.
- the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but halogenated benzene solvents such as chlorobenzene and dichlorobenzene, and ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate.
- halogenated benzene solvents such as chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate.
- the solvent include halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. These solvents can be used alone or in admixture of two or more.
- the amount of solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by formula (1b). is there.
- the temperature at which this reaction is carried out is not particularly limited as long as the target reaction proceeds, but is usually 20 ° C. or higher and 150 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, sodium thiosulfate, sulfurous acid
- An aqueous solution or a salt solution in which a salt containing sulfur such as sodium is dissolved can be arbitrarily used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl
- a solvent that is not compatible with water such as an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, or chloroform, or a hydrocarbon solvent such as hexane, heptane, cyclohexane, or methylcyclohexane.
- these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio.
- the number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield.
- the reaction mixture containing the compound represented by the formula (1a) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but is not essential.
- the reaction mixture containing the compound represented by the formula (1a) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (1a) obtained after distilling off the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- Production method F is a production method for obtaining a compound represented by formula (1a-b) in which R3b represents a halogen atom among the compounds represented by formula (1a), which is represented by formula (1a-a). And a halogenating agent (HalR) in a solvent.
- selectfluoro N-fluoro-N′-triethylenediamine bis (tetrafluoroborate)
- N-chlorosuccinimide N-bromosuccinimide
- N-iodosuccinimide 1 1,3-Dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, bromine, iodine and the like.
- the amount of the halogenating agent used in this reaction is not particularly limited as long as the target reaction proceeds as long as it is 1 equivalent or more with respect to the compound represented by the formula (1a-a). Preferably, it is 1 equivalent or more and 10 equivalents or less. However, the amount of the halogenating agent containing hydantoin is not particularly limited as long as the target reaction proceeds as long as it is 0.5 equivalent or more, and preferably 1 equivalent or more and 5 equivalents or less.
- the halogenating agent used in this reaction is an iodinating agent
- an acid such as an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as acetic acid, trifluoroacetic acid, methanesulfonic acid, or trifluoromethanesulfonic acid.
- the amount of acid used is 0.01 equivalent or more with respect to the compound represented by formula (1a-a), although it does not restrict
- the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but acidic solvents such as sulfuric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid and trifluoromethanesulfonic acid, diethyl ether , Ether solvents such as diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran and dioxane, alcohol solvents such as methanol, ethanol and isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene Ester solvents such as ethyl acetate, isopropyl acetate, butyl acetate, nitrile solvents such as acetonitrile, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N
- the amount of the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by the formula (1a-a). It is as follows.
- the temperature at which this reaction is carried out is not particularly limited as long as the intended reaction proceeds, but is usually 0 ° C. or higher and 150 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, sodium thiosulfate, sulfurous acid
- An aqueous solution or a salt solution in which a salt containing sulfur such as sodium is dissolved can be arbitrarily used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl
- Solvents that are not compatible with water such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. It is possible to add.
- these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio.
- the number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield.
- the reaction mixture containing the compound represented by the formula (1a-b) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but is not essential.
- the reaction mixture containing the compound represented by the formula (1a-b) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (1a-b) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- R3c is a C1-C6 alkyl group optionally substituted with a substituent C, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group optionally substituted with a substituent C, a substituent C
- J represents an oxygen atom or a sulfur atom
- Q represents a hydrogen atom or a metal
- R1, R2, R3b, X, Y, and n have the same meanings as described above.
- R3c is optionally substituted with a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a substituent C, which may be optionally substituted with a substituent C.
- C3-C8 cycloalkyl group C2-C6 alkenyl group optionally substituted with substituent C, C2-C6 haloalkenyl group, C2-C6 optionally substituted with substituent C Or a haloalkynyl group of C2 to C6, wherein J is an oxygen atom or a sulfur atom, and is a method of synthesizing a compound represented by the formula (1a-b) A compound obtained by a coupling reaction in which R3c-JQ is reacted in the presence of a transition metal.
- R 3b is a chlorine atom, a bromine atom, or an iodine atom.
- R3c-JQ used in this reaction is obtained as a commercial product or can be produced by a known method.
- Preferred Q is a hydrogen atom or an alkali metal such as sodium or potassium.
- the amount of R3c-JQ used in this reaction is not particularly limited as long as the target reaction proceeds as long as it is 1 equivalent or more with respect to the compound represented by the formula (1a-b).
- Q is a hydrogen atom, it can also be used as a solvent.
- the transition metal used in this reaction may have a ligand, such as palladium acetate, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis ( Palladiums such as triphenylphosphine) palladium and bis (triphenylphosphine) palladium dichloride.
- a ligand such as palladium acetate, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis ( Palladiums such as triphenylphosphine) palladium and bis (triphenylphosphine) palladium dichloride.
- the amount of the transition metal used in this reaction is 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (1a-b), but is particularly limited as long as the target reaction proceeds. None happen.
- triphenylphosphine 1,1′-bis (diphenylphosphino) ferrocene, 2-dicyclohexylphosphino-2′4′6′-triisopropylbiphenyl, 2-di-t -A phosphine ligand such as butylphosphino-2'4'6'-triisopropylbiphenyl can be added.
- the amount of the phosphine ligand used in this reaction is 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (1a-b), but is particularly limited as long as the target reaction proceeds. It will never be done.
- the base used in this reaction is an inorganic base such as sodium carbonate, potassium carbonate or cesium carbonate, or an organic base such as triethylamine, tributylamine or diisopropylethylamine.
- the amount of the base used in this reaction is not particularly limited as long as the target reaction proceeds as long as it is 1 equivalent or more with respect to the compound represented by the formula (1a-b). 1 equivalent or more and 50 equivalents or less.
- the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but R3c-JH (wherein R3c has the same meaning as described above and J is an oxygen atom).
- the amount of the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by the formula (1a-b). It is as follows.
- the temperature at which this reaction is carried out is not particularly limited as long as the target reaction proceeds, but is usually 30 ° C. or higher and 200 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, or an arbitrary aqueous solution is used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl
- Solvents that are not compatible with water such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane.
- these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio.
- the number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield. Further, it is possible to remove insoluble matters by performing a filtration operation, but this is not essential.
- the reaction mixture containing the compound represented by the formula (1a-c) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (1a-c) obtained after distilling off the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- R3d is a C1-C6 alkyl group optionally substituted with a substituent C, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group optionally substituted with a substituent C, a substituent C Represents an optionally substituted C2-C6 alkenyl group or C2-C6 haloalkenyl group, R3d-B represents an organic boronic acid, and R1, R2, R3b, X, Y and n are as defined above. It is.
- R3d in the compound represented by the formula (1a) is optionally substituted with a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a substituent C, which may be optionally substituted with a substituent C.
- a compound represented by the formula (1a-d) which may be a C3-C8 cycloalkyl group, a C2-C6 alkenyl group optionally substituted with a substituent C, or a C2-C6 haloalkenyl group.
- a method of synthesis comprising obtaining a compound of formula (1a-b) and an organoboronic acid (R3d-B) by a Suzuki-Miyaura coupling in the presence of a transition metal and a base Is the method.
- R 3b is a chlorine atom, a bromine atom, or an iodine atom.
- R3d-B used in this reaction represents an organic boronic acid such as an organic boronic acid or an organic boronic acid ester, and can be obtained as a commercial product or produced by a known method.
- the amount of R3d-B used in this reaction is not particularly limited as long as the target reaction proceeds as long as it is 1 equivalent or more with respect to the compound represented by the formula (1a-b). Preferably, it is 1 equivalent or more and 10 equivalents or less.
- the amount of the transition metal used in this reaction is 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (1a-b), but is particularly limited as long as the target reaction proceeds. None happen.
- phosphine ligands such as triphenylphosphine and tricyclohexylphosphine can be added.
- the amount of the phosphine ligand used in this reaction is 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (1a-b), but is particularly limited as long as the target reaction proceeds. It will never be done.
- the amount of the base used in this reaction is not particularly limited as long as the target reaction proceeds as long as it is 1 equivalent or more with respect to the compound represented by the formula (1a-b). 1 equivalent or more and 50 equivalents or less.
- the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but an ether such as an aqueous solvent, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, etc.
- benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene. These solvents can be used alone or in admixture of two or more.
- the amount of the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by the formula (1a-b). It is as follows.
- the temperature at which this reaction is carried out is not particularly limited as long as the target reaction proceeds, but is usually 30 ° C. or higher and 200 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, or an arbitrary aqueous solution is used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl
- Solvents that are not compatible with water such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane.
- these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio.
- the number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield. Further, it is possible to remove insoluble matters by performing a filtration operation, but this is not essential.
- reaction mixture containing the compound represented by the formula (1a-d) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- reaction mixture containing the compound represented by formula (1a-d) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- R3e represents a C2-C6 alkynyl group or a C2-C6 haloalkynyl group optionally substituted with a substituent C
- R1, R2, R3b, X, Y and n are as defined above.
- R3e is a C2-C6 alkynyl group or a C2-C6 haloalkynyl group optionally substituted with a substituent C (1a-)
- R 3b is a chlorine atom, a bromine atom, or an iodine atom.
- the terminal alkyne compound used in this reaction can be obtained as a commercial product or produced by a known method. Trimethylsilylacetylene can also be used as the terminal alkyne compound. In this case, it is necessary to perform desilylation after introducing a trimethylsilylethynyl group into the compound represented by the formula (1a-b).
- For the desilylation Journal of the American Chemical Society, Vol. 131, No. 2, pp. 634-643 (2009), Journal of the American Chemical Society. And Journal of Organometallic Chemistry (Vol. 696, No. 25, pages 4039-4045 (2011)), Journal of Organometallic Chemistry (Journal of Organometallic Chemistry). It can carry out with reference to nonpatent literatures, such as.
- the amount of the terminal alkyne compound used in this reaction is not particularly limited as long as the target reaction proceeds as long as it is 1 equivalent or more with respect to the compound represented by the formula (1a-b). Preferably, it is 1 equivalent or more and 10 equivalents or less.
- the transition metal used in this reaction may have a ligand, such as palladium acetate, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis ( Palladiums such as triphenylphosphine) palladium and bis (triphenylphosphine) palladium dichloride.
- a ligand such as palladium acetate, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis ( Palladiums such as triphenylphosphine) palladium and bis (triphenylphosphine) palladium dichloride.
- coppers such as copper chloride, copper bromide and copper iodide are also used at the same time.
- the amount of the transition metal used in this reaction may be 0.001 equivalent or more with respect to the compound represented by the formula (1a-b) for palladium and the like, respectively, and the target reaction proceeds. There is no particular limitation as long as it does. A preferable amount is 0.001 equivalent or more and 1 equivalent or less for both.
- Examples of the base used in this reaction include organic amines such as triethylamine, tributylamine, isopropylamine, diethylamine, diisopropylamine and diisopropylethylamine, and inorganic bases such as sodium carbonate, potassium carbonate and cesium carbonate.
- organic amines such as triethylamine, tributylamine, isopropylamine, diethylamine, diisopropylamine and diisopropylethylamine
- inorganic bases such as sodium carbonate, potassium carbonate and cesium carbonate.
- the amount of the base used in this reaction is not particularly limited as long as the target reaction proceeds as long as it is 1 equivalent or more with respect to the compound represented by the formula (1a-b). 1 equivalent or more and 50 equivalents or less.
- the organic base when it is liquid, it can be used as a solvent.
- a phosphine ligand such as tri-t-butylphosphine or 2-dicyclohexylphosphino-2'4'6'-triisopropylbiphenyl can be added to allow the reaction to proceed efficiently, but it is not essential. .
- the amount of the phosphine ligand used in this reaction is 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (1a-b), but is particularly limited as long as the target reaction proceeds. It will never be done.
- the amount of the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by the formula (1a-b). It is as follows.
- the temperature at which this reaction is carried out is not particularly limited as long as the intended reaction proceeds, but is usually 0 ° C. or higher and 150 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, or an arbitrary aqueous solution is used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl
- Solvents that are not compatible with water such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane.
- these solvents can be used alone, or two or more of them can be mixed in an arbitrary ratio.
- the number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield. Further, it is possible to remove insoluble matters by performing a filtration operation, but this is not essential.
- the reaction mixture containing the compound represented by the formula (1a-e) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (1a-e) obtained after the solvent is distilled off can be purified with an appropriate solvent by washing, reprecipitation, recrystallization, column chromatography or the like. What is necessary is just to set suitably according to the target purity.
- R2a represents a C1 to C6 alkoxy group
- nb represents an integer of 0 to 4 (provided that when nb is 2 or more, each of R2 and 2 represents an independent substituent)
- R1 , R2, R3, X, Y and the broken line part have the same meanings as described above.
- Production method J is a method for synthesizing a compound represented by formula (1-b) having a hydroxyl group among the compounds represented by formula (1), wherein R2a is a C1-C6 alkoxy group ( This is a production method comprising obtaining the compound represented by 1-a) by reacting with an acid.
- the acid used for this reaction includes boron halides such as boron trichloride and boron tribromide.
- the amount of acid used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1-a), and is not particularly limited as long as the target reaction proceeds, but preferably Is 1 equivalent or more and 10 equivalents or less.
- the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, and nitrile solvents such as acetonitrile. And halogen solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane and methylcyclohexane. These solvents can be used alone or in admixture of two or more.
- the amount of the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by the formula (1-a). It is as follows.
- the temperature at which this reaction is carried out is not particularly limited as long as the intended reaction proceeds, but is usually from ⁇ 80 ° C. to 100 ° C. or the boiling point of the solvent.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, or an arbitrary aqueous solution is used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl Solvents that are not compatible with water, such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. It is possible to add. Moreover, these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio. The number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield.
- the reaction mixture containing the compound represented by the formula (1-b) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but is not essential.
- a desiccant such as sodium sulfate or magnesium sulfate
- the reaction mixture containing the compound represented by the formula (1-b) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (1-b) obtained after distilling off the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- R2b—O— may be optionally substituted with a substituent B, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a substituent C3-C8 cycloalkoxy group optionally substituted with B, C2-C6 alkenyloxy group optionally substituted with substituent B, C2-C6 haloalkenyloxy group, optionally substituted with substituent B
- a process for synthesizing a compound represented by formula (1-b) comprising reacting a compound represented by formula (1-b) with R2b-Lv in a solvent in the presence of a base.
- R2b-Lv used in this reaction can be obtained as a commercial product or can be produced by a known method.
- R2b-Lv used in this reaction may be 1 equivalent or more with respect to the compound represented by formula (1-b), and is not particularly limited as long as the target reaction proceeds, but preferably Is 1 equivalent or more and 10 equivalents or less.
- the base used in this reaction may be 1 equivalent or more with respect to the compound represented by formula (1-b), and is not particularly limited as long as the target reaction proceeds. 1 equivalent or more and 10 equivalents or less.
- the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but ether solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, Alcohol solvents such as methanol, ethanol and isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitrile solvents such as acetonitrile, Amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroethane, Ch
- the amount of the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by the formula (1-b). It is as follows.
- the temperature at which this reaction is carried out is not particularly limited as long as the intended reaction proceeds, but is usually ⁇ 20 ° C. or higher and 150 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, sodium thiosulfate, sulfurous acid
- An aqueous solution or a salt solution in which a salt containing sulfur such as sodium is dissolved can be arbitrarily used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl
- Solvents that are not compatible with water such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. It is possible to add.
- these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio.
- the number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield.
- the reaction mixture containing the compound represented by the formula (1-c) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
- the reaction mixture containing the compound represented by the formula (1-c) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (1-c) obtained after distilling off the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- R2c represents a halogen atom
- R2d is a C1-C6 alkyl group optionally substituted with the substituent B, a C1-C6 haloalkyl group, a C3-C8 optionally substituted with the substituent B
- R2d-B represents an organic boronic acid, R1, R2, R3, nb, X, Y, and the broken line are as defined above.
- R2d is optionally substituted with a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a substituent B which may be optionally substituted with a substituent B.
- R2d is optionally substituted with a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a substituent B which may be optionally substituted with a substituent B.
- the compound represented by the formula (1-e) which may be a C3-C8 cycloalkyl group, a C2-C6 alkenyl group optionally substituted with the substituent B, or a C2-C6 haloalkenyl group.
- a synthesis method comprising obtaining by a Suzuki-Miyaura coupling in which a compound represented by the formula (1-d) and an organic boronic acid (R2d-B) are reacted.
- R2c is preferably a chlorine atom, a bromine atom, or an iodine atom.
- production method H By using the compound represented by formula (1a-b) and R3d-B in production method H instead of the compound represented by formula (1-d) and R2d-B, respectively, production method H
- the production method L can be carried out according to the above.
- R2e represents a C2-C6 alkynyl group or a C2-C6 haloalkynyl group which may be optionally substituted with the substituent B, and R1, R2, R2c, R3, nb, X, Y and the broken line part It is synonymous with the above.
- R2e is a C2-C6 alkynyl group or a C2-C6 haloalkynyl group which may be optionally substituted with a substituent B
- a method for synthesizing the compound represented by f which comprises obtaining the compound represented by the formula (1-d) by Sonogashira coupling with a terminal alkyne compound.
- R2c is a chlorine atom, a bromine atom, or an iodine atom.
- the production method M can be carried out according to the production method I. .
- Da represents a halogen atom
- D1a represents a halogen atom
- D1b represents a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, or a C3-C8 cycloalkoxy group
- E represents a halogen atom.
- R 1, R 2, R 3, n, X, Q, and a broken line part are as defined above.
- D1b is a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, or a C3-C8 cycloalkoxy group
- E is a halogen atom.
- D1b-Q used in this reaction can be obtained as a commercial product or can be produced by a known method.
- Preferred Q is a hydrogen atom or an alkali metal such as sodium or potassium.
- the amount of D1b-Q used in this reaction is not particularly limited as long as the target reaction proceeds as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-g). Preferably, it is 1 equivalent or more and 30 equivalent or less. Moreover, when Q represents a hydrogen atom, it can be used as a solvent.
- the base used in this reaction is preferably an inorganic base such as sodium carbonate, potassium carbonate, cesium carbonate or sodium hydride. Further, when Q is an alkali metal, the use of a base is not essential.
- the amount of the base used in this reaction is not particularly limited as long as the target reaction proceeds as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-g). 1 equivalent or more and 30 equivalent or less.
- the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but alcohol solvents represented by D1b-H, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxy Ether solvents such as ethane, tetrahydrofuran and dioxane, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitrile solvents such as acetonitrile, Amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroethane, chloroform, carbon te
- the amount of the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by the formula (1-g). It is as follows.
- the temperature at which this reaction is carried out is not particularly limited as long as the intended reaction proceeds, but is usually 0 ° C. or higher and 150 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, or an arbitrary aqueous solution is used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl Solvents that are not compatible with water, such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. It is possible to add. Moreover, these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio. The number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield.
- the reaction mixture containing the compound represented by the formula (1-h) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
- the reaction mixture containing the compound represented by the formula (1-h) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (1-h) obtained after distilling off the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- R2e represents a C1-C6 alkoxy group that may be optionally substituted with the substituent B
- R2f represents a C1-C6 alkoxy group that may be optionally substituted with the substituent B
- R2g represents a halogen atom.
- HalR, R1, R3, X, Y and the broken line part are as defined above.
- R2e is a C1-C6 alkoxy group which may be appropriately substituted with the substituent B
- R2f may be appropriately substituted with the substituent B.
- selectfluoro N-fluoro-N′-triethylenediamine bis (tetrafluoroborate)
- N-chlorosuccinimide N-bromosuccinimide
- N-iodosuccinimide 1 1,3-Dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, bromine, iodine and the like.
- the amount of the halogenating agent used in this reaction is not particularly limited as long as the target reaction proceeds as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-i). Preferably, it is 1 equivalent or more and 10 equivalents or less. However, the amount of the halogenating agent containing hydantoin is not particularly limited as long as the target reaction proceeds as long as it is 0.5 equivalent or more, and preferably 1 equivalent or more and 5 equivalents or less.
- the halogenating agent used in this reaction is an iodinating agent
- an acid such as an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as acetic acid, trifluoroacetic acid, methanesulfonic acid, or trifluoromethanesulfonic acid.
- the halogenating agent used in this reaction is an iodinating agent
- the amount of acid used is 0.01 equivalent or more with respect to the compound represented by formula (1-i), and the target reaction
- it is 0.1 equivalent or more and 3 equivalent or less.
- the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but acidic solvents such as sulfuric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid and trifluoromethanesulfonic acid, diethyl ether , Ether solvents such as diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran and dioxane, alcohol solvents such as methanol, ethanol and isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene Ester solvents such as ethyl acetate, isopropyl acetate, butyl acetate, nitrile solvents such as acetonitrile, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N
- the amount of the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but usually 3 to 200 times by weight with respect to the compound represented by the formula (1-i). It is as follows.
- the temperature at which this reaction is carried out is not particularly limited as long as the intended reaction proceeds, but is usually 0 ° C. or higher and 150 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, sodium thiosulfate, sulfurous acid
- An aqueous solution or a salt solution in which a salt containing sulfur such as sodium is dissolved can be arbitrarily used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl
- Solvents that are not compatible with water such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. It is possible to add.
- these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio.
- the number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield.
- the reaction mixture containing the compound represented by the formula (1-j) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but is not essential.
- the reaction mixture containing the compound represented by the formula (1-j) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (1-j) obtained after distilling off the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- La represents S
- Lb represents SO or SO 2
- Ox ′ represents an oxidizing agent
- Production method P during the compound represented by formula (1) a process for the preparation of a compound represented by R1, Lb contained in R2 and R3 is SO or SO 2 wherein (Lb), the formula ( In 1), it is a production method comprising reacting a compound represented by the formula (La) in which La contained in R1, R2 or R3 is S with an oxidizing agent (Ox ′) in a solvent.
- oxidizing agent used in this reaction examples include peroxides such as hydrogen peroxide and meta-chloroperbenzoic acid.
- transition metals such as sodium tungstate can be added.
- the amount of the oxidizing agent used in this reaction is usually 1.0 equivalent or more and 1.2 equivalent or less with respect to the compound represented by the formula (La) when producing SO, and produces SO 2 . When doing, it is usually 2 equivalents or more and 10 equivalents or less. Moreover, when adding transition metals, it is 0.001 equivalent or more and 1 equivalent or less normally.
- the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but an aqueous solvent, an acidic solvent such as acetic acid, benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc.
- an acidic solvent such as acetic acid, benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc.
- examples thereof include benzene solvents, nitrile solvents such as acetonitrile, and halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride. These solvents can be used alone or in admixture of two or more.
- the temperature at which this reaction is carried out is not particularly limited as long as the intended reaction proceeds, but is usually ⁇ 10 ° C. or higher and 120 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, sodium thiosulfate, sulfurous acid
- An aqueous solution or a salt solution in which a salt containing sulfur such as sodium is dissolved can be arbitrarily used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl
- Solvents that are not compatible with water such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. It is possible to add.
- these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio.
- the number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield.
- the reaction mixture containing the compound represented by the formula (Lb) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but is not essential.
- the reaction mixture containing the compound represented by the formula (Lb) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (Lb) obtained after distilling off the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- R2, R3, R5, n, X and Y have the same meanings as described above.
- Production method Q is a production method of a production intermediate represented by formula (3), in which a compound represented by formula (4) and a compound represented by formula (5) are mixed in a solvent in the presence of a base. It is a manufacturing method including making it react with.
- the compound represented by the formula (4) used in this reaction is, for example, Green Chemistry, Vol. 41, pages 580-585, The Journal of Organic Chemistry, No. 65, No. 20, pages 6458-6461 (2000). Etc. can be synthesized by reference.
- the base used in this reaction includes inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, and tripotassium phosphate, and metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.
- inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, and tripotassium phosphate
- metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.
- the base used in this reaction can be carried out in a catalytic amount, and is not particularly limited as long as the target reaction proceeds, but preferably the compound represented by formula (4) is used. On the other hand, it is 0.01 equivalent or more and 3 equivalent or less.
- Solvents used in this reaction are ether solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran and dioxane, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, Ester solvents such as ethyl acetate, isopropyl acetate, butyl acetate, nitrile solvents such as acetonitrile, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl -2-Urea solvents such as imidazolidinone, halogen solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, sulfur solvents such as dimethyl sulfox
- the amount of solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by formula (4). is there.
- the temperature at which this reaction is carried out is not particularly limited as long as the intended reaction proceeds, but is usually ⁇ 50 ° C. or higher and 150 ° C. or lower or the boiling point of the solvent or lower.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, or an arbitrary aqueous solution is used.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl Solvents that are not compatible with water, such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. It is possible to add. Moreover, these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio. The number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield.
- the reaction mixture containing the compound represented by the formula (3) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but is not essential.
- the reaction mixture containing the compound represented by the formula (3) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by the formula (3) obtained after distilling off the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography or the like with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- R5a represents a C1 to C6 alkyl group
- R2, R3, n, X, and Y are as defined above.
- Production method R is a production method of a production intermediate represented by formula (3b) among the compounds represented by formula (3), wherein the compound represented by formula (3a) is subjected to acidic conditions or a base. It is a manufacturing method including making it react in a solvent on sexual conditions.
- the reaction under acidic conditions will be described.
- the acid used in this reaction include inorganic acids such as hydrochloric acid, hydrobromic acid, and phosphoric acid, and organic acids such as acetic acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid.
- inorganic acids such as hydrochloric acid, hydrobromic acid, and phosphoric acid
- organic acids such as acetic acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid.
- the amount of the acid used in this reaction may be a catalytic amount, and is not particularly limited as long as the target reaction proceeds.
- the amount of the acid is 0. 0 with respect to the compound represented by the formula (3a). 01 equivalents or more.
- liquid acids can be used as solvents.
- the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but is not limited to an aqueous solvent, an acidic solvent such as acetic acid or methanesulfonic acid, diethyl ether, diisopropyl ether, methyl-t- Ether solvents such as butyl ether, dimethoxyethane, tetrahydrofuran and dioxane, alcohol solvents such as methanol, ethanol and isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ethyl acetate, isopropyl acetate and acetic acid Ester solvents such as butyl, nitrile solvents such as acetonitrile, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-d
- the amount of the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by formula (3a). is there.
- the temperature at which this reaction is carried out is not particularly limited as long as the target reaction proceeds, but is usually 0 ° C. or higher and 180 ° C. or lower or the boiling point of the solvent or lower.
- Examples of the base used in this reaction include inorganic bases such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, but are not particularly limited as long as the target reaction proceeds.
- the base used in this reaction is not particularly limited as long as the target reaction proceeds as long as it is 1 equivalent or more with respect to the compound represented by formula (3a), but preferably 1 equivalent or more. 30 equivalents or less,
- the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but an ether such as an aqueous solvent, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, etc.
- an ether such as an aqueous solvent, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, etc.
- Solvents alcohol solvents such as methanol, ethanol and isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitriles such as acetonitrile Solvents, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroethane Down, chloroform, and halogen solvents such as carbon tetrachloride. These solvents can be used alone or in admixture of two or more.
- the amount of the solvent used in this reaction is not particularly limited as long as the target reaction proceeds, but it is usually 3 to 200 times by weight with respect to the compound represented by formula (3a). is there.
- the temperature at which this reaction is carried out is not particularly limited as long as the intended reaction proceeds, but is usually ⁇ 20 ° C. or higher and 180 ° C. or lower or the boiling point of the solvent or lower.
- reaction under acidic conditions and the reaction under basic conditions can be performed by a common method.
- a liquid separation operation can be performed by adding water or an appropriate aqueous solution to the reaction mixture.
- an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, etc. are dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. are dissolved, saline, etc. are optional.
- benzene solvents such as toluene, xylene, benzene, chlorobenzene and dichlorobenzene
- ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, diethyl ether, diisopropyl ether, methyl Solvents that are not compatible with water, such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. It is possible to add. Moreover, these solvents can be used alone, or two or more kinds can be mixed in an arbitrary ratio. The number of times of liquid separation is not particularly limited, and can be carried out according to the target purity and yield.
- the reaction mixture containing the compound represented by the formula (3b) obtained above can remove moisture with a desiccant such as sodium sulfate or magnesium sulfate, but is not essential.
- the reaction mixture containing the compound represented by the formula (3b) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.
- the reaction mixture containing the compound represented by formula (3b) obtained after distilling off the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography, etc. with an appropriate solvent. What is necessary is just to set suitably according to the target purity.
- the compound represented by the formula (3b) is represented by the formula (3b ′) (Wherein R2, R3, n, X and Y are as defined above.)
- the compound represented by the formula (1) can be produced by arbitrarily combining the production methods A to R shown above. Alternatively, the compound represented by the formula (1) can also be produced by arbitrarily combining known methods and production methods A to R.
- the compound of the present invention exhibits an excellent anti-parasitic pest effect and exerts a precise control effect against parasitic pests.
- Parasitic pests in the present invention refer to those parasitic on the outside of the animal body, the inside of the animal body or the plant.
- the animals to which the compound of the present invention can be applied for the purpose of controlling parasitic pests include domestic animals such as horses, cows, pigs, sheep, goats, sharks, frogs, buffalos, deer, minks, chinchillas, etc .; chickens, ducks, geese, turkeys And the like; and pets such as dogs, cats, small birds, monkeys; and laboratory animals such as rats, mice, golden hamsters, guinea pigs, etc., but the present invention is not limited thereto. However, it is preferable to remove humans from animals.
- Agricultural crops Eggplant vegetables (eggplants, tomatoes, peppers, peppers, potatoes, etc.), cucurbits vegetables (cucumbers, pumpkins, zucchini, watermelons, melons, etc.), cruciferous vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage) , Cabbage, mustard, broccoli, cauliflower, etc.), asteraceae vegetables (burdock, garlic, artichoke, lettuce, etc.), liliaceae vegetables (leek, onion, garlic, asparagus, etc.), celery family vegetables (carrot, parsley, celery, American redfish, etc.) Vegetables such as spinach, chard, etc., vegetables such as perilla, mint, basil, etc .; vegetables such as strawberries, sweet potatoes, yam and taro; berries (apples, pears, Japanese pears, quince, quince, etc.), fruits Peaches, plums, nectarines, ume, sweet cherry, apricots, prunes, etc.), citrus (such
- Parasitic pests that parasitize outside the animal's body include cat fleas (Ctenocephalides felis), dog fleas (Ctenocephalides canis), Xenopsylla cheopes, chicken fleas (Echinophaga gallina), Pests, Haemaphyxalislongicornis, Haephysalis japonica, Rhipipephalus sanguineus, Boophilus ect.
- Tick (Dermacentor taiwanensis), Tick tick (Haemphysalis flava), Tick tick (Ixodes ovaticus), Mt. , West Coast Tick (Dermacentor ocidentalis), American Dog Tick (Dermacentor variabilis), Thorny Tick Tick (Haemaphysalis campulanata), Haematophysalis meg ticks such as aspinosa, Ixodes nipponensis, western mite (Ixodes pacifcus), ticks (Ixodes ricinus), mites (Citrus), ticks (Demodex canis), mite mites (Demodex cati), mite mites (Psoroptes ovis), mite mites (Sarcoptes scabiei), catfish mites (Knemidocoptes spp.
- Acarina pests mites and the like such as, Noiebae (Musca hervei), Kuroiebae (Musca bezzii), the horn fly (Haematobia irritans), stable fly (Stomoxys calcitrans), Kisujiushibae (Hypoderma lineatum), Hitsujibae (Oestrus ovis), keds (Melophagus ovinus), bullflies (Hypoderma bovis), tsetse flies (Glossina palpalis, Glossina morsitans), smutium iwatans (Simulus iwatans) (Curicoides oxytaurususususususususususususususususususususususususususususuususususususususususususususususususususususususususususususususus
- Examples of parasitic pests that parasitize the interior of an animal are nematodes (Dioctophyma renale), ringed hairy nematodes (Capillaria annulata), torsional hairy nematodes (Capillaria contoura), hepatic hairy nematodes (Capillaria hepatica), Nematode (Capillaria perforans), Philippine capillary nematode (Capillaria philippinensis), pig hairy nematode (Capillaria suis), bull whipworm (Trichuris discor), Trichuris ovis (Trichuris ovis) Trichuris trichura, Trichuris vulpis, Trichinus (Trichin) lla spiralis) Enopurusu eyes such as (Enoplida) nematodes, Niplopods nematodes (Strongyloides pacificus), Strongyloides lannepis (Strongloides ranso
- Trichostromylus rubidus Trichostromylus axei, Serpentine-like ciliate nematode (Trichostrongylus columbriformis), Trichostrogeniforma (Trichostrostrogen) nchus contortus, cattle torsion gastroworm (Meistocirrus digitatus), Ostertag gastroworm (Osttagiaoluslidia), pulmonary worm (Dictyocaulus filiform), cattle Metastromylus elongatus, Canine pneumoniae (Firaroides hirthii), Lungo nematode (Crenosoma aerophila), Fox pulmonary nematode (Crenosoma violetstros) Girasu genus (Protostrongylus spp.
- Etc. (Strongylida) nematodes, Oxyurida nematodes such as Oxyuris equi, Passarurus ambiguus, and Enterobius vermicularis, Ascaris suum, Parascaris equorum, Toxascaris leonina, Toxocara canis, Toxocara sapiens, Toxocaracum saporum.
- Ascaridida nematodes such as Pseudoterranova spp., Heterakis gallinarum, Ascaridaria galli, etc., Medicinal insects (Dracunculus medinensis), Dolores jaw-and-mouth bugs (Gnathostoma hispidum), Japanese jaw-and-mouth beetles (Gnatostoma nipponicum), spiny-mouthed jaw-worms canis), catastrophic catfish (Physaloptera felidis), larva gastroworm (Physaloptera rara), oriental eyeworm (Thelazia callipaeda), rodentia ophthalmic bug (Telazia moradoma) Insect (Habronema microstoma) Haboryma muscae, Gonylonema pulchrum, Ascarops stranylina, Bovine parafilaria, Parafilaria papula , Bancroft filamentous worms (Wuchereria bancrofti),
- Pharygostotom cordomim Schistosoma haematobium, Schistosoma jachonicum, Ascitica mushroom , Fasciola gigantica, Fasciola hepatica, Fasciolopsis buski, Homologaster paloniae, D.
- Amoeba such as Entamoeba histolytica (E. invadens), Futago Babesia (Babesia bigis), Cattle Babesia (Babesia cavalli), Dog Babesia (Babesia canis), Cats Babe (Besia felis), Gibson Dog Babesia ), Cytauxzoon felis, tropical piroplasmosis Theileria anthelata, pseudocoastal fever Theileria mutans, small piroplasma Theilia orientalis Proteus Mansoni (Haemopro) eus mansoni), chicken leucocytozone (Leucocytozoon caulleryi), Plasmodium falciparum, Plasmodium malariae, Plasmodium variala (Plasmodium malariae) , Caryospora spp., Eimeria acervulina, Eimeria bovis, iimeria bruneti
- Eimeria ovinoidalis rabbit liver coccidium (Eimeria steidae), chicken caecum (Eimeria tenella), canopy isospois (sosopis), cat isospo alleni), Tyzeria anceris, Tyzeria perniciosa, Wenyonella anatis, Wenonella cratopolito, and Wenionella sp.
- cat cryptosporidium felis cat cryptosporidium felis
- human cryptosporidium hominis turkey cryptosporidium melripidium (Cryptosporidium melripidium)
- Sarcocystis cruzi Sarcocystis felis, Sarcocystis hominis, Sarcocystis michaelis (Sarco) ystis miescheriana), Sarukoshisuchisu-Nyurona (Sarcocystis neurona), Sarukoshisuchisu tenella (Sarcocystis tenella), Sarukoshisuchisu-ovalis (Sarcocystis ovalis), Toxoplasma (Toxoplasma gondii), dog Hepatozon (Hepatozoon canis), cat Hepatozon (Hepatozoon felis) spores, etc.
- Pepper leaf beetle (Arboridia apicalis), Green leafhopper (Balcrutha saltuella), Pepper leaf beetle (Epicaanthus stamineus), Potato leaf abalone (Empoasca pea) , Peanut leafhopper (Empoasaka sakaii), leafhopper leafhopper (Macrosteles striifrons), leafhopper leafhopper (Nephotettix multiplinceps), cotton-free hopper (Psuedatomososerissera tossera tossera serisser seraistosera serissertosera tossera serasto elphax striatella), brown planthopper (Nilaparvata lugens), Sejirounka (Sogatella furcifera), Diaphorina citri (Diaphorina citri), Nashikijirami (Psylla pyrisuga), mandarin orange spiny whitefly (Aleurocanthus spiniferus), silverleaf whitefly (B
- Hirazuhanaazamiuma (Frankliniella intonsa), Yellow Hana thrips (Thrips flavus), western flower thrips (Frankliniella occidentalis), Croton thrips (Heliothrips haemorrhoidalis), yellow tea thrips (Scirtothrips dorsalis), southern thrips (Thrips palmi), green onion thrips (Thrips tabaci ), Coleoptera thrips (Ponticulotrips diospyrosi), etc.
- Soybean pod gall midge (Asphondylia yushimai), wheat red gall midge (Sitodiplosis mosellana), melon fly (Bactrocera cucurbitae), oriental fruit fly (Bactrocera dorsalis), the Mediterranean fruit fly (Ceratitis capitata), rice Hime leafminer (Hydrellia griseola), cherry fruit fly (Drosophila suzukii), rice Leafhopper (Agromyza oryzae), Leafworm (Chromatomyia horticola), Eggplant leaffly (Liriomyza bryoniae), Leafhopper fly (Liriomyza chinensis), Tomato leafworm D (Liriomyza sativae), legume leafminer (Liriomyza trifolii), seedcorn maggot (Delia platura), onion maggot (Delia antique), sugar beet diving Hana fly (Pegomya cunicularia), Apple Maggot (Rhago
- Bumblebee (Aphethymus kuri), Bumblebee (Athalia rosae), Bumblebee (Age paganas), Bumblebee (Neodipion sertifer), Drosophila (Dryocosmus kuris), etc.
- Tuna cricket (Teleoglyllus emma), Kera (Gryllotalpa orientalis), Tosama grasshopper (Locusta migratoria), Oba yezoensis, etc.
- Coleopterous insects such as Onychiurus folsomi, Siberian white beetle (Onychiurus sibiricus), Bourletiella hortensis, Termite insects such as the termites (Coptothermes formosanus), the Yamato termites (Reticulitermes speratus), the Taiwan termites (Odontotermes formosanus),
- Sweet potato root-knot nematode (Meloidogyne incognita), Java root-knot nematode (Meloidogyne javanica), northern root-knot nematode (Meloidogyne hapla), Arena rear root-knot nematode (Meloidogyne arenaria), Columbia root-knot nematode (Meloidogyne chitwoodi), root-knot nematodes such as Thames root-knot nematode (Meloidogyne thamesi), Imogusaresenchuu (Ditylenchus destructors), Namikiki nematodes (Ditylenchus dipsaci), rice nematodes (Ditylenchus angustus), etc.
- Nemoglycenchus (Radophorus similis), Negroglycenchus (Radophorus citrophilus), Root-knot nematodes (Nacobus aberenus), Aphlenchus avenus Nematodes such as nematodes (Xifinema index), chapin nematodes (Paratilenchus curvitatus), Cyclamen dust mite (Phytonemus pallidus), Chanohokoridani (Polyphagotarsonemus latus), streaks but-dust mite (Tarsonemus bilobatus) dust mite such as, Hakusaidani (Penthaleus erythrocephalus), Hashiridani such as Mugidani (Penthaleus major), Inehadani (Oligonychus shinkajii), citrus red mite (Panonychus citri ), Spider mites such as Panonychus mori, Panonychus ulmi, Tetranychus kanzawa
- Crustaceans such as armadillium vulgare, Pomacea canalicula, Achatina falica, slugs (Megemiatum bimineatum), Chacuranam entrum (L) And gastropods such as Euhadra peliomphala).
- Said parasitic pest is preferably an acarid pest or nematode, more preferably a plant parasitic mite pest, an animal parasitic nematode or a plant parasitic nematode, even more preferably Spider mites, Spirurida nematodes, or root-knot nematodes, most preferably spider mites, canine finch or sweet potato nematodes.
- the compound of the present invention can be used for plants that have acquired characteristics such as pest resistance, disease resistance, herbicide resistance by genetic recombination, artificial mating, etc., and further, organophosphorus compounds, carbamate compounds, synthetic pyrethroids It is also effective against parasitic pests that are resistant to existing insecticides, acaricides and nematicides such as compounds and acylurea compounds.
- the present invention also relates to a method for controlling parasitic pests comprising applying an effective amount of a compound of the present invention or a salt thereof to a subject in need thereof.
- the object refers to the aforementioned animals and plants
- the application refers to, for example, the following administration to animals and application to plants.
- the method of using the compounds of the present invention for controlling parasitic pests can be administered orally or parenterally to animals.
- For oral administration by blending into capsules, tablets, pills, powders, granules, fine granules, powders, syrups, intestinal solvents, suspensions, pastes or animal liquid drinks or feeds, It is possible to use.
- mucous membranes or infusions For parenteral administration, mucous membranes or infusions, drops, suppositories, emulsions, suspensions, drops, ointments, creams, solutions, lotions, sprays, aerosols, poultices, tapes Used in a dosage form that maintains percutaneous absorption.
- wettable powder, water solvent, flowable powder, wettable powder, powder, emulsion, granule, powder, liquid, oil, aerosol, paste, microcapsule, smoke, fumigation In addition to spraying various preparations on the foliage, various soil preparations, soil full-layer treatment, crop application, floor soil mixing, cell seedling treatment, planting hole treatment, plant base treatment, top dressing
- the root part can be protected by absorbing it from the root part by treating it in soil or the like, such as a seedling box treatment of paddy rice, water surface application, and the like.
- it can be used for nutrient solution in nutrient solution (hydroponics) cultivation, smoke, or trunk injection.
- the parasitic pest control agent of the present invention can be in the above dosage form.
- the compounds of the present invention not only combat parasitic pests inside and outside living organisms of plants and animals, but also prevent infection of parasitic pests prophylactically by being applied in an environment that is an infection route.
- an infection route for example, soil-borne infection from fields, park soils, transdermal infections from rivers, lakes, wetlands, paddy fields and other water systems, oral infections from feces of animals such as dogs and cats, saltwater fish, freshwater fish, crustaceans
- the active ingredient ranges from about 0.0001 mg / kg to 10,000 mg / kg body weight, preferably about 0.001 mg / kg to 1000 mg / day. kg body weight range.
- the active ingredient is in the range of about 0.0001 mg / kg to 10,000 mg / kg body weight per day, preferably in the range of about 0.001 mg / kg to 1000 mg / kg body weight per day.
- Oral and parenteral administration are performed in a single dose or divided.
- the optimum amount used is various factors such as purpose, target pests, crop growth status, pest occurrence tendency, weather, environmental conditions, although it varies depending on the dosage form, application method, application location, application time, etc., it is usually selected from the range of 0.1 g to 10000 g as an active ingredient per 1 are, and is preferably in the range of 1 g to 1000 g. .
- the concentration of the active ingredient in the parasitic pesticide of the present invention is generally 0.0001 to 100% by weight, preferably 0.001 to 99% by weight, more preferably 0.005 to 80% by weight. It is.
- the pest control agent can generally be provided as a high-concentration composition that is diluted to an appropriate concentration at the time of use.
- aqueous agent is obtained by sufficiently mixing 5 parts of the pyridone compound of the present invention, 20 parts of a surfactant and 75 parts of ion-exchanged water.
- a method for controlling parasitic pests can be provided using the pyridone compound of the present invention or a salt thereof, or a parasitic pest control agent containing the same as an active ingredient.
- the parasitic pest is a nematode or a method for controlling a parasitic pest that is an Acarina pest. More preferably, it is a method for controlling a parasitic pest in which the nematode is a dog filamentous or sweet potato nematode, or the mite pest is a spider mite.
- Step 2 Synthesis of 5- (2-chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -1-ethyl-3,4-dihydropyridin-2 (1H) -one (Compound No. 52)
- the obtained organic layer was washed successively with aqueous sodium thiosulfate solution and saturated brine, and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 109 mg off-white solid.
- the resulting white solid was the title compound, 2.24 g. Further, the filtrate produced when the precipitate was washed was evaporated under reduced pressure, and the resulting residue was purified by silica gel column chromatography. The white solid obtained from the filtrate was also the title compound, 0.46 g. 1 H-NMR (CDCl 3 ) ⁇ : 7.28-7.26 (1H, m), 7.18 (1H, br s), 6.86-6.83 (1H, m), 6.74- 6.72 (1H, m), 6.61-6.59 (2H, br m), 2.85-2.74 (4H, br m).
- Step 2 Synthesis of 5- (2-chloro-5-fluorophenyl) -1-ethyl-6- (2,4,6-trifluorophenyl) -3,4-dihydropyridin-2 (1H) -one (compound Number 320)
- Step 2 Synthesis of ethyl 4- (2-chloro-5-methoxyphenyl) -5- (2,6-difluorophenyl) -5-oxopentanoate
- Step 3 Synthesis of 4- (2-chloro-5-methoxyphenyl) -5- (2,6-difluorophenyl) -5-oxopentanoic acid
- Step 1 Synthesis of N ′-(2-chloro-5-fluorobenzylidene) -4-methylbenzenesulfonyl hydrazide
- Step 2 Synthesis of 2- (2-chloro-5-fluorophenyl) -1- (2,4,6-trifluorophenyl) ethanone
- Step 4 Synthesis of 4- (2-chloro-5-fluorophenyl) -5-oxo-5- (2,4,6-trifluorophenyl) pentanoic acid
- Step 2 Synthesis of 2- (3,5-dimethoxyphenyl) -1- (2,4,6-trifluorophenyl) ethanone
- Step 3 Synthesis of ethyl 4- (3,5-dimethoxyphenyl) -5-oxo-5- (2,4,6-trifluorophenyl) pentanoate
- Step 4 Synthesis of 4- (3,5-dimethoxyphenyl) -5-oxo-5- (2,4,6-trifluorophenyl) pentanoic acid
- Structure B represents the following:
- Structure C represents:
- Structure D represents:
- the parasitic pest control agent of the present invention is specifically shown to be effective against parasitic pests, but is not limited to these examples.
- Dog filamentous worm Compound No. 32, 53, 54, or 55 was dissolved in dimethyl sulfoxide to a concentration of 10 mg / ml. These dimethyl sulfoxide solutions were diluted 100 times with a culture solution containing canine filamentous microfilariae collected from dogs infected with canine filamentous insects so that the final concentration would be 100 ⁇ g / ml. After 7 days of culturing, the mortality of dog filamentous microfilariae was investigated. As a result, the death rate was 100% in any of the treatment sections.
- novel pyridone compound of the present invention can control pests parasitic on animals and plants, it has utility as a parasitic pest control agent.
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Abstract
Description
動物寄生性有害生物による寄生虫症は、寄生虫、即ち単細胞の原生動物(原虫類)、多細胞の蠕虫類あるいは節足動物等が動物宿主に寄生感染することにより引き起こされるものであり、豚、馬、牛、羊、犬、猫および家禽等の家畜動物に於いて、その感染は重大な問題となりうる。即ち、寄生虫が感染した動物は、貧血、栄養失調、衰弱、体重損失、腸管壁および組織、器官の重大な損傷を起こし、飼料効率の低下や生産性低下の一因となるため、大きな経済的損失を生ずる。
植物寄生性有害生物による問題としては、有害生物に寄生された作物の生育が著しく阻害される等の農業、林業における顕著な経済的損失の原因になることがあげられる。
これら寄生性有害生物に対しては、従来多数の寄生性有害生物駆除剤が使用されている。従来の寄生性有害生物駆除剤は、即効性、浸透移行性、ガス効果等優れた特性を持つものがあるが、抗寄生性有害生物スペクトル、残効性、人畜魚類への毒性、環境汚染の低減等の点で全てに満足のいくものではない。さらに、昨今では既存の寄生性有害生物駆除剤に対し強い抵抗性を示す寄生性有害生物の出現も問題となっている。このような背景で、より安全で、且つ低薬量で優れた寄生性有害生物防除活性を有する新規な寄生性有害生物駆除剤の開発が常に望まれている。
本発明は、優れた寄生性有害生物駆除活性を有する新規な寄生性有害生物駆除剤を提供することを課題とする。
[1]
式(1)
[式中、R1は、水酸基、
シアノ基、
置換基Aで適宜置換されてもよいC1~C6のアルキル基、
C1~C6のハロアルキル基、
置換基Aで適宜置換されてもよいC3~C8のシクロアルキル基、
置換基Aで適宜置換されてもよいC2~C6のアルケニル基、
C2~C6のハロアルケニル基、
置換基Aで適宜置換されてもよいC2~C6のアルキニル基、
C2~C6のハロアルキニル基、
置換基Aで適宜置換されてもよいC1~C6のアルコキシ基、
C1~C6のハロアルコキシ基、
置換基Aで適宜置換されてもよいC3~C8のシクロアルコキシ基、
置換基Aで適宜置換されてもよいC2~C6のアルケニルオキシ基、
C2~C6のハロアルケニルオキシ基、
置換基Aで適宜置換されてもよいC3~C6のアルキニルオキシ基、
C3~C6のハロアルキニルオキシ基、
またはR10R11N-(ここで、R10およびR11は、それぞれ独立していて、水素原子、またはC1~C6のアルキル基を表す。)を表し;
R2は、ハロゲン原子、
水酸基、
シアノ基、
ニトロ基、
置換基Bで適宜置換されてもよいC1~C6のアルキル基、
C1~C6のハロアルキル基、
置換基Bで適宜置換されてもよいC3~C8のシクロアルキル基、
置換基Bで適宜置換されてもよいC2~C6のアルケニル基、
C2~C6のハロアルケニル基、
置換基Bで適宜置換されてもよいC2~C6のアルキニル基、
C2~C6のハロアルキニル基、
置換基Bで適宜置換されてもよいC1~C6のアルコキシ基、
C1~C6のハロアルコキシ基、
置換基Bで適宜置換されてもよいC3~C8のシクロアルコキシ基、
置換基Bで適宜置換されてもよいC2~C6のアルケニルオキシ基、
C2~C6のハロアルケニルオキシ基、
置換基Bで適宜置換されてもよいC3~C6のアルキニルオキシ基、
C3~C6のハロアルキニルオキシ基、
R20C(=O)-(ここで、R20は、C1~C6のアルキル基、C1~C6のハロアルキル基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、C3~C8のシクロアルコキシ基、またはR21R22N-(ここで、R21およびR22は、それぞれ独立していて、水素原子、置換基B1で適宜置換されてもよいC1~C6のアルキル基、C1~C6のハロアルキル基、またはC3~C8のシクロアルキル基を表すか、あるいはR21およびR22は、結合する窒素原子と一緒になって、アジリジニル基、アゼチジニル基、ピロリジニル基、ピペリジニル基、ホモピペリジニル基、またはアゾカニル基を形成するものを表す。)を表す。)、
R20C(=O)O-(ここで、R20は、前記と同義である。)、
1~2個の酸素原子を含む3~6員環の基、
R23-L2-(ここで、R23は、C1~C6のアルキル基、またはC1~C6のハロアルキル基を表し、L2は、S、SO、またはSO2を表す。)、
R21R22N-(ここで、R21およびR22は、前記と同義である。)、
またはR24C(=O)N(R25)-(ここで、R24は、水素原子、C1~C6のアルキル基、C1~C6のハロアルキル基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、C3~C8のシクロアルコキシ基、またはR21R22N-(ここで、R21およびR22は、前記と同義である。)を表し、R25は、水素原子、置換基B1で適宜置換されてもよいC1~C6のアルキル基、C1~C6のハロアルキル基、またはC3~C8のシクロアルキル基を表す。)を表し;
R3は、水素原子、
ハロゲン原子、
ニトロ基、
置換基Cで適宜置換されてもよいC1~C6のアルキル基、
C1~C6のハロアルキル基、
置換基Cで適宜置換されてもよいC3~C8のシクロアルキル基、
置換基Cで適宜置換されてもよいC1~C6のアルコキシ基、
C1~C6のハロアルコキシ基、
置換基Cで適宜置換されてもよいC2~C6のアルケニル基、
C2~C6のハロアルケニル基、
置換基Cで適宜置換されてもよいC2~C6のアルキニル基、
C2~C6のハロアルキニル基、
R30-L3-(ここで、R30は、前記のR23と同義であり、L3は、前記のL2と同義である。)、
R31R32N-(ここで、R31およびR32は、前記のR21およびR22と同義である。)、
またはR33C(=O)-(ここで、R33は、C1~C6のアルキル基、C1~C6のハロアルキル基、またはC3~C8のシクロアルキル基を表す。)を表し;
nは、0~5の整数(ただし、nが2以上のとき、2以上のR2は、それぞれ独立した置換基を表す。)を表し;
Xは、酸素原子、または硫黄原子を表し;
Yは、フェニル基、ピリジル基、ピリダジニル基、ピリミジニル基、ピラジニル基、トリアジニル基、テトラジニル基、チエニル基、チアゾリル基、イソチアゾリル基、またはチアジアゾリル基を表し、
該フェニル基は、置換基Dがオルト位に置換し、さらに置換基D1が、それぞれ独立して適宜0~4置換し、
該ピリジル基、該ピラジニル基、該ピリミジニル基、該ピリダジニル基、該トリアジニル基、または該テトラジニル基は、置換基Dがオルト位に置換し、さらに置換基D1が、それぞれ独立して適宜0~3置換し、
該チエニル基、該チアゾリル基、該イソチアゾリル基、または該チアジアゾリル基は、置換基Dがオルト位に置換し、さらに置換基D1が、それぞれ独立して適宜0~2置換し;
破線部を含む結合は、二重結合、または単結合を表し、
そして、置換基Aは、
水酸基、シアノ基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、C3~C8のシクロアルコキシ基、R12R13N-(ここで、R12およびR13は、それぞれ独立していて、水素原子、C1~C6のアルキル基、C1~C6のハロアルキル基、またはC3~C8のシクロアルキル基を表すか、あるいはR12およびR13は、結合する窒素原子と一緒になって、アジリジニル基、アゼチジニル基、ピロリジニル基、ピペリジニル基、ホモピペリジニル基、またはアゾカニル基を形成するものを表す。)、およびR14-L1-(ここで、R14は、C1~C6のアルキル基、またはC1~C6のハロアルキル基を表し、L1は、S、SO、またはSO2を表す。)からなる群から選択される少なくとも1種であり;
置換基Bは、
水酸基、シアノ基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、C3~C8のシクロアルコキシ基、C2~C6のアルコキシアルコキシ基、R21R22N-(ここで、R21およびR22は、前記と同義である。)、R23-L2-(ここで、R23およびL2は、前記と同義である。)、R26R27R28Si-(ここで、R26、R27およびR28は、それぞれ独立していてC1~C6のアルキル基を表す。)、R26R27R28Si-(CH2)s-O-(ここで、sは、1~3の整数を表し、R26、R27およびR28は、前記と同義である。)、R20C(=O)-(ここで、R20は、前記と同義である。)、および1~2個の酸素原子を含む3~6員環の基からなる群から選択される少なくとも1種であり;
置換基B1は、
シアノ基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、およびC3~C8のシクロアルコキシ基からなる群から選択される少なくとも1種であり;
置換基Cは、
水酸基、シアノ基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、C3~C8のシクロアルコキシ基、R31R32N-(ここで、R31およびR32は、前記のR21およびR22と同義である。)、およびR30-L3-(ここで、R30は、前記のR14と同義であり、L3は、前記のL1と同義である。)からなる群から選択される少なくとも1種であり;
置換基Dは、
ハロゲン原子、C1~C6のアルキル基、C1~C6のハロアルキル基、C1~C6のアルコキシ基、およびC1~C6のハロアルコキシ基からなる群から選択される少なくとも1種であり;
置換基D1は、
水酸基、ハロゲン原子、C1~C6のアルキル基、C1~C6のハロアルキル基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、およびC3~C8のシクロアルコキシ基からなる群から選択される少なくとも1種である。]で表される化合物またはその塩を有効成分として含有する寄生性有害生物駆除剤であり、
R1は、シアノ基、
置換基Aで適宜置換されてもよいC1~C6のアルキル基、
C1~C6のハロアルキル基、
置換基Aで適宜置換されてもよいC3~C8のシクロアルキル基、
置換基Aで適宜置換されてもよいC2~C6のアルケニル基、
C2~C6のハロアルケニル基、
置換基Aで適宜置換されてもよいC2~C6のアルキニル基、
またはR10R11N-(ここで、R10およびR11は、それぞれ独立していて、水素原子、またはC1~C6のアルキル基を表す。)を表し;
R2は、ハロゲン原子、
水酸基、
シアノ基、
置換基Bで適宜置換されてもよいC1~C6のアルキル基、
C1~C6のハロアルキル基、
置換基Bで適宜置換されてもよいC1~C6のアルコキシ基、
C1~C6のハロアルコキシ基、
置換基Bで適宜置換されてもよいC3~C8のシクロアルコキシ基、
置換基Bで適宜置換されてもよいC2~C6のアルケニルオキシ基、
置換基Bで適宜置換されてもよいC3~C6のアルキニルオキシ基、
R20C(=O)O-(ここで、R20は、C1~C6のアルキル基、C1~C6のハロアルキル基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、C3~C8のシクロアルコキシ基、またはR21R22N-(ここで、R21およびR22は、それぞれ独立していて、水素原子、置換基B1で適宜置換されてもよいC1~C6のアルキル基、C1~C6のハロアルキル基、またはC3~C8のシクロアルキル基を表すか、あるいはR21およびR22は、結合する窒素原子と一緒になって、アジリジニル基、アゼチジニル基、ピロリジニル基、ピペリジニル基、ホモピペリジニル基、またはアゾカニル基を形成するものを表す。)、
またはR23-L2-(ここで、R23は、C1~C6のアルキル基、またはC1~C6のハロアルキル基を表し、L2は、S、SO、またはSO2を表す。)を表し;
R3は、水素原子、
ハロゲン原子、
置換基Cで適宜置換されてもよいC1~C6のアルキル基、
置換基Cで適宜置換されてもよいC3~C8のシクロアルキル基、
置換基Cで適宜置換されてもよいC1~C6のアルコキシ基、
置換基Cで適宜置換されてもよいC2~C6のアルキニル基、
またはR30-L3-(ここで、R30は、前記のR23と同義であり、L3は、前記のL2と同義である。)を表し;
Yは、フェニル基、またはピリジル基を表し、
該フェニル基は、置換基Dがオルト位に置換し、さらに置換基D1が、それぞれ独立して適宜0~4置換し、
該ピリジル基は、置換基Dがオルト位に置換し、さらに置換基D1が、それぞれ独立して適宜0~3置換する、
[1]に記載の化合物またはその塩を有効成分として含有する寄生性有害生物駆除剤であり、
R1は、置換基Aで適宜置換されてもよいC1~C6のアルキル基、またはC1~C6のハロアルキル基を表し;
R2は、ハロゲン原子、置換基Bで適宜置換されてもよいC1~C6のアルキル基、または置換基Bで適宜置換されてもよいC1~C6のアルコキシ基を表し;
R3は、水素原子、ハロゲン原子、または置換基Cで適宜置換されてもよいC1~C6のアルキル基を表す、
[2]に記載の化合物またはその塩を有効成分として含有する寄生性有害生物駆除剤であり、
寄生性有害生物がダニ目害虫または線虫類である[1]に記載の寄生性有害生物駆除剤であり、
[5]
寄生性有害生物が植物寄生性ダニ目害虫、動物寄生性線虫類または植物寄生性線虫類である[1]に記載の寄生性有害生物駆除剤であり、
[6]
寄生性有害生物がハダニ類、旋尾線虫目(Spirurida)線虫類またはネコブセンチュウ類である[1]に記載の寄生性有害生物駆除剤であり、
[7]
寄生性有害生物がナミハダニ、犬糸状虫またはサツマイモネコブセンチュウである[1]に記載の寄生性有害生物駆除剤であり、
[8]
[1]に記載の寄生性有害生物駆除剤を用いた寄生性有害生物を駆除する方法であり、
[9]
寄生性有害生物を駆除する方法であって、それを必要とする対象に[1]に記載の化合物またはその塩の有効量を適用することを含む方法であり、
[10]
寄生性有害生物駆除剤としての[1]に記載の化合物またはその塩の植物への使用であり、
[11]
寄生性有害生物駆除剤として動物に使用するための[1]に記載の化合物またはその塩である。
なお、特許請求の範囲および明細書中において用いられる各用語は、特に断らない限り、当該技術分野において一般的に用いられる定義によるものとする。
本明細書において、使用する略号を以下に説明する。
DMF:N,N-ジメチルホルムアミド、THF:テトラヒドロフラン、Me:メチル基、Et:エチル基、Pr:プロピル基、Bu:ブチル基、Pentyl:ペンチル基、Hexyl:ヘキシル基、Ac:アセチル基、Ph:フェニル基、Py:ピリジル基、i:イソ、sec:セカンダリ、t:ターシャリ、c:シクロ、=:二重結合、≡:三重結合を表す。表のカラム中、単独の“-”は無置換を意味し、Pr、Bu、Pentyl、Hexylに関しては、接頭辞がない場合は、ノルマルを意味する。
Cx~Cyとの記載は、x個からy個の炭素原子を有することを表す。
用語「適宜置換されてもよい」とは、置換または無置換であることを意味する。この用語を用いる際、置換基の数が明示されていないときは、置換基の数は1であることを表す。
C1~C6のアルキル基とは、直鎖状または分岐状でよく、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、ペンチル基、イソペンチル基、2-メチルブチル基、ネオペンチル基、1-エチルプロピル基、ヘキシル基、4-メチルペンチル基、3-メチルペンチル基、2-メチルペンチル基、1-メチルペンチル基、3,3-ジメチルブチル基、2,2-ジメチルブチル基、1,1-ジメチルブチル基、1,2-ジメチルブチル基、1,3-ジメチルブチル基、2,3-ジメチルブチル基、または2-エチルブチル基等である。
式(1)のR1は、水酸基、シアノ基、置換基Aで適宜置換されてもよいC1~C6のアルキル基、C1~C6のハロアルキル基、置換基Aで適宜置換されてもよいC3~C8のシクロアルキル基、置換基Aで適宜置換されてもよいC2~C6のアルケニル基、C2~C6のハロアルケニル基、置換基Aで適宜置換されてもよいC2~C6のアルキニル基、C2~C6のハロアルキニル基、置換基Aで適宜置換されてもよいC1~C6のアルコキシ基、C1~C6のハロアルコキシ基、置換基Aで適宜置換されてもよいC3~C8のシクロアルコキシ基、置換基Aで適宜置換されてもよいC2~C6のアルケニルオキシ基、C2~C6のハロアルケニルオキシ基、置換基Aで適宜置換されてもよいC3~C6のアルキニルオキシ基、C3~C6のハロアルキニルオキシ基、またはR10R11N-(ここで、R10およびR11は、それぞれ独立していて、水素原子、またはC1~C6のアルキル基を表す。)を表す。
特に、置換基Aで適宜置換されてもよいC1~C6のアルキル基、またはC1~C6のハロアルキル基が好ましい。
特に、シアノ基、またはC1~C6のアルコキシ基が好ましい。
C3~C8のシクロアルキル基として、シクロプロピル基、シクロブチル基、シクロペンチル基、およびシクロヘキシル基;
C1~C6のアルコキシ基として、メトキシ基、エトキシ基、プロピルオキシ基、およびイソプロピルオキシ基;
C1~C6のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、2,2-ジフルオロエトキシ基、2,2,2-トリフルオロエトキシ基、3,3-ジフルオロプロピルオキシ基、および3,3,3-トリフルオロプロピルオキシ基;
C3~C8のシクロアルコキシ基として、シクロプロピルオキシ基、シクロブトキシ基、シクロペンチルオキシ基、およびシクロヘキシルオキシ基;
R12R13N-(ここで、R12およびR13は、前記と同義である。)として、アミノ基、ジメチルアミノ基、エチルメチルアミノ基、およびジエチルアミノ基;
ならびにR14-L1-(ここで、R14およびL1は、前記と同義である。)として、メチルチオ基、メタンスルフィニル基、メタンスルホニル基、トリフルオロメチルチオ基、トリフルオロメタンスルフィニル基、およびトリフルオロメタンスルホニル基が挙げられる。
C3~C8のシクロアルキル基として、シクロプロピル基、およびシクロブチル基;
C1~C6のアルコキシ基として、メトキシ基、およびエトキシ基;
C1~C6のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、2,2-ジフルオロエトキシ基、および2,2,2-トリフルオロエトキシ基;
C3~C8のシクロアルコキシ基として、シクロプロピルオキシ基、およびシクロブトキシ基;
R12R13N-(ここで、R12およびR13は、前記と同義である。)として、ジメチルアミノ基、エチルメチルアミノ基、およびジエチルアミノ基;
ならびにR14-L1-(ここで、R14およびL1は、前記と同義である。)として、メチルチオ基、メタンスルフィニル基、およびメタンスルホニル基が挙げられる。
式(1)のR1における「置換基Aで適宜置換されてもよいC1~C6のアルキル基」のC1~C6のアルキル基は、前記の定義と同義であり、好ましくは、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、またはイソブチル基であり、さらに好ましくは、メチル基、またはエチル基である。置換基Aを有する場合、C1~C6のアルキル基における水素原子が、置換基Aによって任意に置換される。
特に、ハロゲン原子、置換基Bで適宜置換されてもよいC1~C6のアルキル基、または置換基Bで適宜置換されてもよいC1~C6のアルコキシ基が好ましい。
特に、シアノ基、またはC1~C6のアルコキシ基が好ましい。
C3~C8のシクロアルキル基として、シクロプロピル基、シクロブチル基、シクロペンチル基、およびシクロヘキシル基;
C1~C6のアルコキシ基として、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基、およびイソブトキシ基;
C1~C6のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、2,2-ジフルオロエトキシ基、2,2,2-トリフルオロエトキシ基、3,3-ジフルオロプロピルオキシ基、および3,3,3-トリフルオロプロピルオキシ基;
C3~C8のシクロアルコキシ基として、シクロプロピルオキシ基、シクロブトキシ基、シクロペンチルオキシ基、およびシクロヘキシルオキシ基;
C2~C6のアルコキシアルコキシ基として、メトキシメトキシ基、エトキシメトキシ基、メトキシエトキシ基、エトキシエトキシ基、およびメトキシプロピルオキシ基;
R21R22N-(ここで、R21およびR22は、前記のと同義である。)として、アミノ基、ジメチルアミノ基、エチルメチルアミノ基、ジエチルアミノ基、ピロリジニル基、およびピペリジニル基;
R23-L2-(ここで、R23およびL2は、前記と同義である。)として、メチルチオ基、メタンスルフィニル基、メタンスルホニル基、トリフルオロメチルチオ基、トリフルオロメタンスルフィニル基、およびトリフルオロメタンスルホニル基;
R26R27R28Si-(ここで、R26、R27、およびR28は、前記と同義である。)として、トリメチルシリル基、およびトリエチルシリル基;
R26R27R28Si-(CH2)s-O-(ここで、s、R26、R27、およびR28は、前記と同義である。)として、2-(トリメチルシリル)エトキシ基、および2-(トリエチルシリル)エトキシ基;
R20C(=O)-(ここで、R20は、前記と同義である。)として、アセチル基、プロピオニル基、ジフルオロアセチル基、トリフルオロアセチル基、シクロプロパンカルボニル基、メトキシカルボニル基、エトキシカルボニル基、2,2-ジフルオロエトキシカルボニル基、3,3,3-トリフルオロプロピルオキシカルボニル基、シクロプロピルオキシカルボニル基、アミノカルボニル基、ジメチルアミノカルボニル基、エチルメチルアミノカルボニル基、ジエチルアミノカルボニル基、ピロリジニルカルボニル基、およびピペリジニルカルボニル基;
ならびに1~2個の酸素原子を含む3~6員環の基として、オキソラニル基、オキサニル基、1,3-ジオキソラニル基、および1,3-ジオキサニル基が挙げられる。
C3~C8のシクロアルキル基として、シクロプロピル基、およびシクロブチル基;
C1~C6のアルコキシ基として、メトキシ基、およびエトキシ基;
C1~C6のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、2,2-ジフルオロエトキシ基、および2,2,2-トリフルオロエトキシ基;
C3~C8のシクロアルコキシ基として、シクロプロピルオキシ基、およびシクロブトキシ基;
C2~C6のアルコキシアルコキシ基として、メトキシメトキシ基、エトキシメトキシ基、メトキシエトキシ基、およびエトキシエトキシ基;
R21R22N-(ここで、R21およびR22は、前記と同義である。)として、ジメチルアミノ基、エチルメチルアミノ基、およびジエチルアミノ基;
R23-L2-(ここで、R23およびL2は、前記と同義である。)として、メチルチオ基、メタンスルフィニル基、およびメタンスルホニル基;
R26R27R28Si-(ここで、R26、R27、およびR28は、前記と同義である。)として、トリメチルシリル基;
R26R27R28Si-(CH2)s-O-(ここで、s、R26、R27、およびR28は、前記と同義である。)として、2-(トリメチルシリル)エトキシ基;
R20C(=O)-(ここで、R20は、前記と同義である。)として、アセチル基、ジフルオロアセチル基、トリフルオロアセチル基、メトキシカルボニル基、エトキシカルボニル基、アミノカルボニル基、ジメチルアミノカルボニル基、エチルメチルアミノカルボニル基、およびジエチルアミノカルボニル基;
ならびに1~2個の酸素原子を含む3~6員環の基として、1,3-ジオキソラニル基、および1,3-ジオキサニル基が挙げられる。
C1~C6のアルコキシ基として、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基、およびイソブトキシ基;
C1~C6のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、2,2-ジフルオロエトキシ基、2,2,2-トリフルオロエトキシ基、3,3-ジフルオロプロピルオキシ基、および3,3,3-トリフルオロプロピルオキシ基;
ならびにC3~C8のシクロアルコキシ基として、シクロプロピルオキシ基、シクロブトキシ基、シクロペンチルオキシ基、およびシクロヘキシルオキシ基が挙げられる。
C1~C6のアルコキシ基として、メトキシ基、およびエトキシ基;
C1~C6のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、2,2-ジフルオロエトキシ基、および2,2,2-トリフルオロエトキシ基;
ならびにC3~C8のシクロアルコキシ基として、シクロプロピルオキシ基、およびシクロブトキシ基が挙げられる。
式(1)のR2には、水酸基、シアノ基、およびニトロ基が含まれる。
特に、水素原子、ハロゲン原子、または置換基Cで適宜置換されてもよいC1~C6のアルキル基が好ましい。
特に、シアノ基、またはC1~C6のアルコキシ基が好ましい。
C3~C8のシクロアルキル基として、シクロプロピル基、シクロブチル基、シクロペンチル基、およびシクロヘキシル基;
C1~C6のアルコキシ基として、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基、およびイソブトキシ基;
C1~C6のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、2,2-ジフルオロエトキシ基、2,2,2-トリフルオロエトキシ基、3,3-ジフルオロプロピルオキシ基、および3,3,3-トリフルオロプロピルオキシ基;
C3~C8のシクロアルコキシ基として、シクロプロピルオキシ基、シクロブトキシ基、シクロペンチルオキシ基、およびシクロヘキシルオキシ基;
R31R32N-(ここで、R31およびR32は、前記のR21およびR22と同義である。)として、アミノ基、ジメチルアミノ基、エチルメチルアミノ基、ジエチルアミノ基、ピロリジニル基、およびピペリジニル基;
ならびにR30-L3-(ここで、R30は、前記のR14と同義であり、L3は、前記のL1と同義である。)として、メチルチオ基、メタンスルフィニル基、メタンスルホニル基、トリフルオロメチルチオ基、トリフルオロメタンスルフィニル基、およびトリフルオロメタンスルホニル基が挙げられる。
C3~C8のシクロアルキル基として、シクロプロピル基、およびシクロブチル基;
C1~C6のアルコキシ基として、メトキシ基、およびエトキシ基;
C1~C6のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、2,2-ジフルオロエトキシ基、および2,2,2-トリフルオロエトキシ基;
C3~C8のシクロアルコキシ基として、シクロプロピルオキシ基、およびシクロブトキシ基;
R31R32N-(ここで、R31およびR32は、前記と同義である。)として、ジメチルアミノ基、エチルメチルアミノ基、およびジエチルアミノ基;
ならびにR30-L3-(ここで、R30およびL3は、前記と同義である。)として、メチルチオ基、メタンスルフィニル基、およびメタンスルホニル基が挙げられる。
式(1)のR3における「ハロゲン原子」は、前記の定義と同義であり、好ましくはフッ素原子、塩素原子、臭素原子、またはヨウ素原子である。
該フェニル基は、置換基Dがオルト位に置換し、さらに置換基D1が、それぞれ独立して適宜0~4置換する。
該ピリジル基、該ピリダジニル基、該ピリミジニル基、該ピラジニル基、該トリアジニル基、または該テトラジニル基は、置換基Dがオルト位に置換し、さらに置換基D1が、それぞれ独立して適宜0~3置換する。
該チエニル基、該チアゾリル基、該イソチアゾリル基、または該チアジアゾリル基は、置換基Dがオルト位に置換し、さらに置換基D1が、それぞれ独立して適宜0~2置換する。
中でも置換基Dは、ハロゲン原子、またはC1~C6のアルキル基が好ましく、
特に、ハロゲン原子が好ましい。
ハロゲン原子として、フッ素原子、塩素原子、臭素原子、およびヨウ素原子;
C1~C6のアルキル基として、メチル基、エチル基、およびプロピル基;
C1~C6のハロアルキル基として、ジフルオロメチル基、トリフルオロメチル基、2,2-ジフルオロエチル基、および2,2,2-トリフルオロエチル基;
C1~C6のアルコキシ基として、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基、イソブトキシ基、およびt-ブトキシ基;
ならびにC1~C6のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、2,2-ジフルオロエトキシ基、2,2,2-トリフルオロエトキシ基、3,3-ジフルオロプロピルオキシ基、および3,3,3-トリフルオロプロピルオキシ基が挙げられる。
ハロゲン原子として、フッ素原子、塩素原子、および臭素原子;
C1~C6のアルキル基として、メチル基、およびエチル基;
C1~C6のアルコキシ基として、メトキシ基、エトキシ基、プロピルオキシ基、およびイソプロピルオキシ基;
ならびにC1~C6のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、2,2-ジフルオロエトキシ基、および2,2,2-トリフルオロエトキシ基が挙げられる。
中でも置換基D1は、水酸基、ハロゲン原子、C1~C6のアルキル基、C1~C6のアルコキシ基、またはC1~C6のハロアルキル基が好ましく、
さらに好ましくは、ハロゲン原子、C1~C6のアルキル基、C1~C6のアルコキシ基、またはC1~C6のハロアルコキシ基が好ましい。
ハロゲン原子として、フッ素原子、塩素原子、臭素原子、およびヨウ素原子;
C1~C6のアルキル基として、メチル基、エチル基、およびプロピル基;
C1~C6のハロアルキル基として、ジフルオロメチル基、トリフルオロメチル基、2,2-ジフルオロエチル基、および2,2,2-トリフルオロエチル基;
C3~C8のシクロアルキル基として、シクロプロピル基、シクロブチル基、シクロペンチル基、およびシクロヘキシル基;
C1~C6のアルコキシ基として、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基、イソブトキシ基、およびt-ブトキシ基;
C1~C6のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、2,2-ジフルオロエトキシ基、2,2,2-トリフルオロエトキシ基、3,3-ジフルオロプロピルオキシ基、および3,3,3-トリフルオロプロピルオキシ基;
ならびにC3~C8のシクロアルコキシ基として、シクロプロピルオキシ基、シクロブトキシ基、シクロペンチルオキシ基、およびシクロヘキシルオキシ基が挙げられる。
ハロゲン原子として、フッ素原子、塩素原子、および臭素原子;
C1~C6のアルキル基として、メチル基、およびエチル基;
C1~C6のハロアルキル基として、ジフルオロメチル基、およびトリフルオロメチル基;
C3~C8のシクロアルキル基として、シクロプロピル基、およびシクロブチル基;
C1~C6のアルコキシ基として、メトキシ基、エトキシ基、プロピルオキシ基、およびイソプロピルオキシ基;
C1~C6のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、2,2-ジフルオロエトキシ基、および2,2,2-トリフルオロエトキシ基;
ならびにC3~C8のシクロアルコキシ基として、シクロプロピルオキシ基、およびシクロブトキシ基が挙げられる。
式(a)のmaが2以上の場合、2以上のD1は、それぞれ独立した置換基を表し、同一または異なっていてよく、任意に選択することができる。
本明細書においてYがフェニル基の場合、オルト位とは、式(a)に示されるように、置換基Dがあるフェニル基の位置を意味する。
置換基Dがオルト位に位置したフェニル基は、本発明の特徴をなしている。
で表される部分構造(ここで、DおよびD1は前記と同義であり、mbは0~3の整数を表す。)を表す。
式(b)のmbは、0~3の整数を表す。
式(b)のmbが2以上の場合、2以上のD1は、それぞれ独立した置換基を表し、同一、または異なっていてよく、任意に選択することができる。
式(b)の部分構造の具体例を以下に示す。
式(c-2)
または、式(c-3)
で表される部分構造(ここで、DおよびD1は前記と同義であり、mcは0~2の整数を表す。)を表す。
式(c-1)、式(c-2)および式(c-3)のmcは、0~2の整数を表す。
式(c-1)、式(c-2)および式(c-3)のmcが2の場合、2のD1は、それぞれ独立した置換基を表し、同一または異なっていてよく、任意に選択することができる。
式(c-1)の部分構造の具体例を以下に示す。
式(1)で表される化合物は、不斉原子を含むことがある。この際の異性体比は、単独または任意の割合の混合比であり、特に限定されることはない。
式(1)で表される化合物は、幾何異性体を含むことがある。この際の異性体比は、単独または任意の割合の混合比であり、特に限定されることはない。
[製造方法A]
本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、酢酸、メタンスルホン酸等の酸性系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル-t-ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、メタノール、エタノール、イソプロパノール等のアルコール系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、アセトニトリル等のニトリル系溶媒、N-メチルピロリドン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等のアミド系溶媒、1,3-ジメチル-2-イミダゾリジノン等のウレア系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒等が挙げられる。これらの溶媒は、単独または2種類以上を任意の割合で混合して使用することができる。溶媒として、好ましくは、酸性系溶媒が挙げられ、さらに好ましくは、酢酸が挙げられる。
溶媒留去後に得られた式(1b-a)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
溶媒留去後に得られた式(1b)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
溶媒留去後に得られた式(1b-c)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
本反応に使用するR3aLvの量は、式(1b-d)で表される化合物に対して1当量以上あればよく、目的とする反応が進行する限りにおいて特に制限されることはないが、好ましくは、1当量以上1.8当量以下である。
溶媒留去後に得られた式(1b-e)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
本反応に使用する酸化剤の量は、式(1b)に表される化合物に対して1当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、1当量以上200当量以下である。
溶媒留去後に得られた式(1a)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
本反応に使用する酸化剤の量は、式(1b)で表される化合物に対して1当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、1当量以上20当量以下である。
溶媒留去後に得られた式(1a)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
本反応に使用するラジカル開始剤とハロゲン化剤の量は、それぞれ、式(1b)で表される化合物に対して0.01当量以上と1.0当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはない。好ましくは、ラジカル開始剤が0.01当量以上1当量以下であり、ハロゲン化剤が1当量以上3当量以下である。
溶媒留去後に得られた式(1a)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
本反応に使用するハロゲン化剤がヨウ素化剤である場合に使用する酸の量は、式(1a-a)で表される化合物に対して0.01当量以上あれば、目的とする反応が進行する限りにおいて特に制限されることはないが、好ましくは、0.1当量以上3当量以下である。
溶媒留去後に得られた式(1a-b)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
本反応に使用するR3c-J-Qの量は、式(1a-b)で表される化合物に対して1当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはない。Qが水素原子のときは、溶媒としても使用可能である。
溶媒留去後に得られた式(1a-c)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
本反応に使用するR3d-Bの量は、式(1a-b)で表される化合物に対して、1当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、好ましくは、1当量以上10当量以下である。
本反応に使用するホスフィン配位子の量は、式(1a-b)で表される化合物に対して0.001当量以上1当量以下であるが、目的とする反応が進行する限りにおいて特に限定されることはない。
溶媒留去後に得られた式(1a-e)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
溶媒留去後に得られた式(1-b)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
本反応に使用するR2b-Lvは、式(1-b)で表される化合物に対して1当量以上あればよく、目的とする反応が進行する限りにおいて特に制限されることはないが、好ましくは、1当量以上10当量以下である。
溶媒留去後に得られた式(1-c)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
溶媒留去後に得られた式(1-h)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
本反応に使用するハロゲン化剤がヨウ素化剤である場合に使用する酸の量は、式(1-i)で表される化合物に対して0.01当量以上あれば、目的とする反応が進行する限りにおいて特に制限されることはないが、好ましくは、0.1当量以上3当量以下である。
溶媒留去後に得られた式(1-j)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
溶媒留去後に得られた式(Lb)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
本反応に使用する式(5)で表される化合物の量は、式(4)で表される化合物に対して1当量以上あれば、目的とする反応が進行する限りにおいて特に制限されることはないが、好ましくは1当量以上3当量以下である。
溶媒留去後に得られた式(3)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
本反応に使用する酸は、塩酸、臭化水素酸、リン酸等の無機酸類や、酢酸、メタンスルホン酸、p-トルエンスルホン酸、トリフルオロ酢酸等の有機酸類が例示される。目的とする反応が進行する限り特に制限されることはない。
本反応に使用する塩基は、水酸化リチウム、水酸化ナトリウム、水酸化カリウム等の無機塩基類が例示されるが、目的とする反応が進行する限りにおいて特に限定されることはない。
溶媒留去後に得られた式(3b)で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
本発明化合物を寄生性有害生物駆除の目的で適用できる動物とは、馬、牛、豚、羊、山羊、兎、駱駝、水牛、鹿、ミンク、チンチラ等の家畜;鶏、アヒル、ガチョウ、七面鳥等の家禽;犬、猫、小鳥、猿等のペット;並びにラット、マウス、ゴールデンハムスター、モルモット等の実験動物;等が挙げられるが、本発明はこれらに限定されるものではない。但し、動物からヒトを除くことが好ましい。
本発明化合物を寄生性有害生物駆除の目的で適用できる植物とは、トウモロコシ、イネ、コムギ、オオムギ、ライムギ、エンバク、ソルガム、ワタ、ダイズ、ピーナッツ、ソバ、テンサイ、ナタネ、ヒマワリ、サトウキビおよびタバコ等の農作物類;ナス科野菜(ナス、トマト、ピーマン、トウガラシ、ジャガイモ等)、ウリ科野菜(キュウリ、カボチャ、ズッキーニ、スイカ、メロン等)、アブラナ科野菜(ダイコン、カブ、セイヨウワサビ、コールラビ、ハクサイ、キャベツ、カラシナ、ブロッコリー、カリフラワー等)、キク科野菜(ゴボウ、シュンギク、アーティチョーク、レタス等)、ユリ科野菜(ネギ、タマネギ、ニンニク、アスパラガス等)、セリ科野菜(ニンジン、パセリ、セロリ、アメリカボウフウ等)、アカザ科野菜(ホウレンソウ、フダンソウ等)、シソ科野菜(シソ、ミント、バジル等)、イチゴ、サツマイモ、ヤマノイモおよびサトイモ等の野菜類;仁果類(リンゴ、セイヨウナシ、ニホンナシ、カリン、マルメロ等)、核果類(モモ、スモモ、ネクタリン、ウメ、オウトウ、アンズ、プルーン等)、カンキツ類(ウンシュウミカン、オレンジ、レモン、ライム、グレープフルーツ等)、堅果類(クリ、クルミ、ハシバミ、アーモンド、ピスタチオ、カシューナッツ、マカダミアナッツ等)、液果類(ブルーベリー、クランベリー、ブラックベリー、ラズベリー等)、ブドウ、カキ、オリーブ、ビワ、バナナ、コーヒー、ナツメヤシ、ココヤシおよびアブラヤシ等の果実類;チャ、クワ、街路樹(トネリコ、カバノキ、ハナミズキ、ユーカリ、イチョウ、ライラック、カエデ、カシ、ポプラ、ハナズオウ、フウ、プラタナス、ケヤキ、クロベ、モミノキ、ツガ、ネズ、マツ、トウヒ、イチイ、ニレ、トチノキ等)、サンゴジュ、イヌマキ、スギ、ヒノキ、クロトン、マサキおよびカナメモチ等の果樹以外の樹木類;シバ類(ノシバ、コウライシバ等)、バミューダグラス類(ギョウギシバ等)、ベントグラス類(コヌカグサ、ハイコヌカグサ、イトコヌカグサ等)、ブルーグラス類(ナガハグサ、オオスズメノカタビラ等)、フェスク類(オニウシノケグサ、イトウシノケグサ、ハイウシノケグサ等)、ライグラス類(ネズミムギ、ホソムギ等)、カモガヤおよびオオアワガエリ等の芝生類;オイルパームおよびナンヨウアブラギリ等の油糧作物類;花卉類(バラ、カーネーション、キク、トルコギキョウ、カスミソウ、ガーベラ、マリーゴールド、サルビア、ペチュニア、バーベナ、チューリップ、アスター、リンドウ、ユリ、パンジー、シクラメン、ラン、スズラン、ラベンダー、ストック、ハボタン、プリムラ、ポインセチア、グラジオラス、カトレア、デージー、バーベナ、シンビジューム、ベゴニア等);観葉植物等が挙げられるが、本発明はこれらに限定されるものではない。
動物の生体外部に寄生する寄生性有害生物として、ネコノミ(Ctenocephalides felis)、イヌノミ(Ctenocephalides canis)、ケオプスネズミノミ(Xenopsylla cheopis)、ニワトリノミ(Echidnophaga gallinacea)、ヒトノミ(Pulex irritans)等のノミ目害虫、フタトゲチマダニ(Haemaphyxalislongicornis)、ヤマトチマダニ(Haemaphysalis japonica)、クリイロコイタマダニ(Rhipicephalus sanguineus)、オウシマダニ(Boophilus microplus)、アミメカクマダニ(Dermacentor recticulatus)、タイワンカクマダニ(Dermacentor taiwanensis)、キチマダニ(Haemaphysalis flava)、ヤマトマダニ(Ixodes ovatus)、シュルツェマダニ(Ixodes persulcatus)、ローン・スターマダニ(Amblyomma americanum)、メキシコ湾岸マダニ(Amblyomma maculatum)、ロッキー山脈森林マダニ(Dermacentor andersoni)、西海岸マダニ(Dermacentor occidentalis)、アメリカンドッグティック(Dermacentor variabilis)、ツリガネチマダニ(Haemaphysalis campanulata)、オオトゲチマダニ(Haemaphysalis megaspinosa)、タネガタマダニ(Ixodes nipponensis)、西部クロアシダニ(Ixodes pacifcus)、ヒツジダニ(Ixodes ricinus)、クロアシダニ(Ixodes scapularis)等のマダニ類、イヌツメダニ(Cheyletiella yasguri)、ネコツメダニ(Cheyletiella blakei)等のツメダニ類、イヌニキビダニ(Demodex canis)、ネコニキビダニ(Demodex cati)等のニキビダニ類、ヒツジキュウセンダニ(Psoroptes ovis)等のキュウセンダニ類、センコウヒゼンダニ(Sarcoptes scabiei)、ネコショウセンコウヒゼンダニ(Notoedres cati)、ニワトリヒゼンダニ(Knemidocoptes spp.)等のヒゼンダニ類等のダニ目害虫、ノイエバエ(Musca hervei)、クロイエバエ(Musca bezzii)、ノサシバエ(Haematobia irritans)、サシバエ(Stomoxys calcitrans)、キスジウシバエ(Hypoderma lineatum)、ヒツジバエ(Oestrus ovis)、ヒツジシラミバエ(Melophagus ovinus)、ウシバエ(Hypoderma bovis)、ツェツェバエ(Glossina palpalis, Glossina morsitans)、ツメトゲブユ(Simulium iwatens)、ウシヌカカ(Culicoides oxystoma)、ウシアブ(Tabanus chrysurus)、アカイエカ(Culex pipiens)、ヒトスジシマカ(Aedes albopictus)、ネッタイシマカ(Aedes aegypti)、シナハマダラカ(Anopheles hyracanus sinesis)、チカイエカ(Culex pipiens molestus)、キアシオオブユ(Prosimulium yezoensis)等の双翅目害虫、ニワトリオオハジラミ(Menacanthus stramineus)、ウシハジラミ(Bovicola bovis)、ウシジラミ(Haematopinus eurysternus)、ヒツジジラミ(Damalinia ovis)、ブタジラミ(Haematopinus suis)、ウシホソジラミ(Linognathus vituli)、ケブカウシジラミ(Solenopotes capillatus)等のシラミ目害虫等が挙げられる。
乳頭糞線虫(Strongyloides papillosus)、猫糞線虫(Strongyloides planiceps)、豚糞線虫(Strongyloides ransomi)、ヒト糞線虫(Strongyloides stercoralis)、ミクロネマ属(Micronema spp.)等の桿線虫目(Rhabditida)線虫類、
ブラジル鉤虫(Ancylostoma braziliense)、犬鉤虫(Ancylostoma caninum)、ズビニ鉤虫(Ancylostoma duodenale)、猫鉤虫(Ancylostoma tubaeforme)、狭頭鉤虫(Uncinaria stenocephala)、牛鉤虫(Bunostomum phlebotomum)、羊鉤虫(Bunostomum trigonocephalum)、アメリカ鉤虫(Necator americanus)、シアトストーマム属(Cyathostomum spp.)、シリコシクラス属(Cylicocyclus spp.)、シリコドントフォラス属(Cylicodontophorus spp.)、シリコステファナス属(Cylicostephanus spp.)、ロバ円虫(Strongylus asini)、無歯円虫(Strongylus edentatus)、馬円虫(Strongylus equinus)、普通円虫(Strongylus vulgaris)、羊縮小線虫(Chabertia ovina)、インド腸結節虫(Oesophagostomum brevicaudatum)、コロンビア腸結節虫(Oesophagostomum columbianum)、豚腸結節虫(Oesophagostomum dentatum)、アメリカ腸結節虫(Oesophagostomum georgianum)、腸結節虫(Oesophagostomum maplestonei)、豚盲結虫(Oesophagostomum quadrispinulatum)、牛腸結節虫(Oesophagostomum radiatum)、山羊腸結節虫(Oesophagostomum venulosum)、スクリジャビン開嘴虫(Syngamus skrjabinomorpha)、鶏開嘴虫(Syngamus trachea)、豚腎虫(Stephanurus dentatus)、クーペリア(Cooperia oncophora)、紅色毛様線虫(Hyostrongylus rubidus)、皺胃毛様線虫(Trichostrongylus axei)、蛇状毛様線虫(Trichostrongylus colubriformis)、東洋毛様線虫(Trichostrongylus orientalis)、捻転胃虫(Haemonchus contortus)、牛捻転胃虫(Mecistocirrus digitatus)、オステルターグ胃虫(Ostertagia ostertagi)、糸状肺虫(Dictyocaulus filaria)、牛肺虫(Dictyocaulus viviparus)、細頸毛円虫(Nematodirusfilicollis)、豚肺虫(Metastrongylus elongatus)、犬肺虫(Filaroides hirthi)、肺毛細線虫(Crenosoma aerophila)、キツネ肺虫(Crenosoma vulpis)、広東住血線虫(Angiostrongylus cantonensis)、住血線虫(Angiostrongylus vasorum)、プロトストロンギラス属(Protostrongylus spp.)等の円虫目(Strongylida)線虫類、
馬蟯虫(Oxyuris equi)、ウサギ蟯虫(Passalurus ambiguus)、ヒト蟯虫(Enterobius vermicularis)等の蟯虫目(Oxyurida)線虫類、
豚回虫(Ascaris suum)、馬回虫(Parascaris equorum)、犬小回虫(Toxascaris leonina)、犬回虫(Toxocara canis)、猫回虫(Toxocara cati)、牛回虫(Toxocara vitulorum)、アニサキス属(Anisakis spp.)、シュードテラノーバ属(Pseudoterranova spp.)、鶏盲腸虫(Heterakis gallinarum)、鶏回虫(Ascaridia galli)等の回虫目(Ascaridida)線虫類、
メジナ虫(Dracunculus medinensis)、ドロレス顎口虫(Gnathostoma doloresi)、剛棘顎口虫(Gnathostoma hispidum)、日本顎口虫(Gnathostoma nipponicum)、有棘顎口虫(Gnathostoma spinigerum)、犬胃虫(Physaloptera canis)、猫胃虫(Physaloptera felidis, P. praeputialis)、ラーラ胃虫(Physaloptera rara)、東洋眼虫(Thelazia callipaeda)、ロデシア眼虫(Thelazia rhodesi)、大口馬胃虫(Draschia megastoma)、小口胃虫(Habronema microstoma)、ハエ胃虫(Habronema muscae)、美麗食道虫(Gongylonema pulchrum)、類円豚胃虫(Ascarops strongylina)、牛パラフィラリア(Parafilaria bovicola)、多乳頭糸状虫(Parafilaria multipapillosa)、沖縄糸状虫(Stephanofilaria okinawaensis)、バンクロフト糸状虫(Wuchereria bancrofti)、マレー糸状虫(Brugiamalayi)、頸部糸状虫(Onchocerca cervicalis)、ギブソン糸状虫(Onchocerca gibsoni)、咽頭糸状虫(Onchocerca gutturosa)、回旋糸状虫(Onchocerca volvulus)、指状糸状虫(Setaria digitata)、馬糸状虫(Setaria equina)、唇乳頭糸状虫(Setaria labiatopapillosa)、マーシャル糸状虫(Setaria marshalli)、犬糸状虫(Dirofilaria immitis)、ロア糸状虫(Loa loa)等の旋尾線虫目(Spirurida)線虫類等の線虫類、
鎖状鉤頭虫(Moniliformis moniliformis)、大鉤頭虫(Macracanthorhynchus hirudinaceus)等の鉤頭虫類、
広節裂頭条虫(Diphyllobothrium latum)、日本海裂頭条虫(Diphyllobothrium nihonkaiense)、マンソン裂頭条虫(Spirometra erinaceieuropaei)、大複殖門条虫(Diplogonoporus grandis)、有線条虫(Mesocestoides lineatus)、有輪条虫(Raillietina cesticillus)、棘溝条虫(Raillietina echinobothrida)、方形条虫(Raillietina tetragona)、胞状条虫(Taenia hydatigena)、多頭条虫(Taenia multiceps)、羊条虫(Taenia ovis)、豆状条虫(Taenia pisiformis)、無鉤条虫(Taenia saginata)、連節条虫(Taenia serialis)、有鉤条虫(Taenia solium)、猫条虫(Taenia taeniaeformis)、単包条虫(Echinococcus granulosus)、多包条虫(Echinococcus multilocularis)、ヤマネコ包条虫(Echinococcus oligarthrus)、フォーゲル包条虫(Echinococcusvogeli)、縮小条虫(Hymenolepis diminuta)、小型条虫(Hymenolepis nana)、瓜実条虫(Dipylidium caninum)、楔状条虫(Amoebotaenia sphenoides)、漏斗状条虫(Choanotaenia infundibulum)、ウズラ条虫(Metroliasthes coturnix)、大条虫(Anoplocephala magna)、葉状条虫(Anoplocephala perfoliata)、乳頭条虫(Paranoplocephala mamillana)、ベネデン条虫(Moniezia benedeni)、拡張条虫(Moniezia expansa)、スティレシア属(Stilesia spp.)等の条虫類、
赤痢アメーバ(Entamoeba histolytica, E. invadens)等のアメーバ類、
フタゴバベシア(Babesia bigemina)、牛バベシア(Babesia bovis)、大形馬バベシア(Babesia caballi)、犬バベシア(Babesia canis)、猫バベシア(Babesia felis)、ギブソン犬バベシア(Babesia gibsoni)、大型ピロプラズマ(Babesia ovata)、サイタウクスゾーン・フェリス(Cytauxzoon felis)、熱帯ピロプラズマ病タイレリア(Theileria annulata)、仮性沿岸熱タイレリア(Theileria mutans)、小型ピロプラズマ(Theileria orientalis)、東沿岸熱タイレリア(Theileria parva)、ヘモプロテウス・マンソニ(Haemoproteus mansoni)、鶏ロイコチトゾーン(Leucocytozoon caulleryi)、熱帯熱マラリア原虫(Plasmodium falciparum)、四日熱マラリア原虫(Plasmodium malariae)、卵形マラリア原虫(Plasmodium ovale)、三日熱マラリア原虫(Plasmodium vivax)、カリオスポラ属(Caryospora spp.)、エイメリア・アセルブリナ(Eimeria acervulina)、エイメリア・ボビス(Eimeria bovis)、エイメリア・ブルネッチ(Eimeria brunetti)、エイメリア・マクシマ(Eimeria maxima)、エイメリア・ネカトリクス(Eimerianecatrix)、エイメリア・オビノイダリス(Eimeria ovinoidalis)、ウサギ肝コクシジウム(Eimeria stiedae)、鶏盲腸コクシジウム(Eimeria tenella)、犬イソスポーラ(Isospora canis)、猫イソスポーラ(Isospora felis)、豚イソスポーラ(Isospora suis)、ティゼリア・アレニ(Tyzzeria alleni)、ティゼリア・アンセリス(Tyzzeria anseris)、ティゼリア・パーニシオサ(Tyzzeria perniciosa)、ウェニョネラ・アナティス(Wenyonella anatis)、ウェニョネラ・ガガリ(Wenyonella gagari)、犬クリプトスポリジウム(Cryptosporidium canis)、猫クリプトスポリジウム(Cryptosporidium felis)、ヒトクリプトスポリジウム(Cryptosporidium hominis)、シチメンチョウクリプトスポリジウム(Cryptosporidium meleagridis)、ネズミクリプトスポリジウム(Cryptosporidium muris)、小形クリプトスポリジウム(Cryptosporidium parvum)、サルコシスチス・カニス(Sarcocystis canis)、クルーズ肉胞子虫(Sarcocystis cruzi)、サルコシスチス・フェリス(Sarcocystis felis)、ヒト肉胞子虫(Sarcocystis hominis)、サルコシスチス・ミーシェリアナ(Sarcocystis miescheriana)、サルコシスチス・ニューロナ(Sarcocystis neurona)、サルコシスチス・テネラ(Sarcocystis tenella)、サルコシスチス・オバリス(Sarcocystis ovalis)、トキソプラズマ(Toxoplasma gondii)、犬ヘパトゾーン(Hepatozoon canis)、猫ヘパトゾーン(Hepatozoon felis)等の胞子虫類、
ヒストモナス(Histomanas meleagridis)、腸トリコモナス(Pentatrichomonas hominis)、口腔トリコモナス(Trichomonas tenax)、ランブル鞭毛虫(Giardia intestinalis)、ジアルディア・ムリス(Giardia muris)、シチメンチョウヘキサミタ(Hexamita meleagridis)、ヘキサミタ・パルバ(Hexamitaparva)、ドノバンリーシュマニア(Leishmania donovani)、幼児リーシュマニア(Leishmaniainfantum)、大形リーシュマニア(Leishmania major)、熱帯リーシュマニア(Leishmania tropica)、ガンビアトリパノソーマ(Trypanosoma brucei gambiense)、ローデシアトリパノソーマ(Trypanosoma brucei rhodesiense)、クルーズトリパノソーマ(Trypanosoma cruzi)、媾疫トリパノソーマ(Trypanosoma equiperdum)、エバンストリパノソーマ(Trypanosoma evansi)等の鞭毛虫類、
大腸バランチジウム(Balantidium coli)等の繊毛虫類等が挙げられる。
ダイズサヤタマバエ(Asphondylia yushimai)、ムギアカタマバエ(Sitodiplosis mosellana)、ウリミバエ(Bactrocera cucurbitae)、ミカンコミバエ(Bactrocera dorsalis)、チチュウカイミバエ(Ceratitis capitata)、イネヒメハモグリバエ(Hydrellia griseola)、オウトウショウジョウバエ(Drosophila suzukii)、イネハモグリバエ(Agromyza oryzae)、ナモグリバエ(Chromatomyia horticola)、ナスハモグリバエ(Liriomyza bryoniae)、ネギハモグリバエ(Liriomyza chinensis)、トマトハモグリバエ(Liriomyza sativae)、マメハモグリバエ(Liriomyza trifolii)、タネバエ(Delia platura)、タマネギバエ(Delia antique)、テンサイモグリハナバエ(Pegomya cunicularia)、アップルマゴット(Rhagoletis pomonella)、ヘシアンフライ(Mayetiola destructor)等の双翅目昆虫、
エンマコオロギ(Teleogryllus emma)、ケラ(Gryllotalpa orientalis)、トノサマバッタ(Locusta migratoria)、コバネイナゴ(Oxya yezoensis)、サバクワタリバッタ(Schistocerca gregaria)等の直翅目昆虫、
トゲナシシロトビムシ(Onychiurus folsomi)、シベリアシロトビムシ(Onychiurus sibiricus)、キボシマルトビムシ(Bourletiella hortensis)等の粘管目昆虫、
イエシロアリ(Coptotermes formosanus)、ヤマトシロアリ(Reticulitermes speratus)、タイワンシロアリ(Odontotermes formosanus)等のシロアリ目昆虫、
シクラメンホコリダニ(Phytonemus pallidus)、チャノホコリダニ(Polyphagotarsonemus latus)、スジブトホコリダニ(Tarsonemus bilobatus)等のホコリダニ類、ハクサイダニ(Penthaleus erythrocephalus)、ムギダニ(Penthaleus major)等のハシリダニ類、イネハダニ(Oligonychus shinkajii)、ミカンハダニ(Panonychus citri)、クワオオハダニ(Panonychus mori)、リンゴハダニ(Panonychus ulmi)、カンザワハダニ(Tetranychus kanzawai)、ナミハダニ(Tetranychus urticae)等のハダニ類、チャノナガサビダニ(Acaphylla theavagrans)、チューリップサビダニ(Aceria tulipae)、トマトサビダニ(Aculops lycopersici)、ミカンサビダニ(Aculops pelekassi)、リンゴサビダニ(Aculus schlechtendali)、ニセナシサビダニ(Eriophyes chibaensis)、シトラスラストマイト(Phyllocoptruta oleivora)等のフシダニ類、ロビンネダニ(Rhizoglyphus robini)、ケナガコナダニ(Tyrophagus putrescentiae)、ホウレンソウケナガコナダニ(Tyrophagus similis)等のコナダニ類等のダニ目害虫、
寄生性有害生物駆除のための本発明化合物の使用方法は、動物に対しては経口投与または非経口投与のいずれも可能である。経口投与の場合は、カプセル剤、錠剤、丸剤、粉剤、顆粒剤、細粒剤、散剤、シロップ、腸溶剤、懸濁剤、ペーストまたは動物用の液体飲料もしくは飼料中に配合することにより、使用することが可能である。非経口投与の場合は、注射剤、点滴剤、座薬、乳剤、懸濁剤、滴下剤、軟膏剤、クリーム剤、液剤、ローション剤、スプレー剤、エアゾル剤、パップ剤、テープ剤として、粘膜または経皮吸収が維持できるような剤型で使用される。植物に対しては、水和剤、水溶剤、フロアブル剤、顆粒水和剤、粉剤、乳剤、粒剤、粉粒剤、液剤、油剤、エアゾル、ペースト剤、マイクロカプセル剤、燻煙剤、燻蒸剤、塗布剤等があり、各種製剤を茎葉部に散布する他に、土壌全面処理、土壌全層処理、作条施用、床土混和、セル苗処理、植え穴処理、株元処理、トップドレッシング、水稲の育苗箱処理、水面施用等、土壌等に処理することで根部を保護し、または根部から吸収させて使用することもできる。加えて、養液(水耕)栽培における養液への施用、くん煙あるいは樹幹注入等による使用もできる。
本発明の寄生性有害生物駆除剤は上記の剤型であることができる。
本発明化合物を植物の寄生性有害生物駆除のために使用する場合、用いられる最適量は種々の因子、例えば目的、対象有害生物、作物の生育状況、有害生物の発生傾向、天候、環境条件、剤型、施用方法、施用場所、施用時期等により変動するが、通常1アール当たり有効成分として0.1g~10000gの範囲から適宜選択して施用すれば良く、好ましくは1g~1000gの範囲である。
本発明の寄生性有害生物駆除剤中の有効成分の濃度は、一般に0.0001~100重量%であり、好ましくは0.001~99重量%であり、さらに好ましくは0.005~80重量%である。有害生物駆除剤は、一般に、使用時に適当な濃度に希釈して使用される高濃度な組成物として提供しうる。
本発明の寄生性有害生物駆除剤は、本発明化合物や上記の殺虫成分以外に慣用の添加剤を含んでいてもよい。
本発明のピリドン化合物を10部、ポリオキシエチレンスチリルフェニルエーテル6部、ソルベントナフサ84部、以上を均一に攪拌混合して乳剤を得る。
本発明のピリドン化合物を1部、サラシミツロウ50部、白色ワセリン49部を十分混合し軟膏剤を得る。
本発明のピリドン化合物を2部、植物油(オリーブ油)10部、結晶セルローズ3部、ホワイトカーボン20部、カオリン65部を十分混合し、打錠し錠剤を得る。
本発明のピリドン化合物を10部、食品添加物用プロピレングリコール10部、植物油(コーンオイル)80部を混合し注射液を得る。
本発明のピリドン化合物を5部、界面活性剤20部、イオン交換水75部を十分混合し水性剤を得る。
本発明のピリドン化合物を10部、ジオクチルスルホサクシネート0.5部、酵素変性デキストリン3部、タルク15部、クレー71.5部を混合し、加水した後押出し造粒機で成型する。得られた成型物を乾燥したのち、整粒して粒剤を得る。
本発明のピリドン化合物を10部、ナフタレンスルホン酸のホルムアルデヒド縮合物ナトリウム塩5部、ポリオキシエチレンアリールフェニルエーテル1部、プロピレングリコール5部、シリコン系消泡剤0.1部、キサンタンガム0.2部、イオン交換水78.7部を混合してスラリーとなし、さらにダイノミルKDLで直径1.0mmのガラスビーズを用いて湿式粉砕しフロアブル剤を得る。
本発明のピリドン化合物を10部、ホワイトカーボン10部、ポリビニルアルコール2部、ジオクチルスルホコハク酸ナトリウム塩0.5部、アルキルベンゼンスルホン酸ナトリウム塩5部、焼成珪藻土10部およびカオリナイトクレー62.5部を充分に混合し、エアーミルで粉砕し、水和剤を得る。
また、前述の他の殺虫成分を併用してもよい。
ステップ1:5-(2-クロロ-5-メトキシフェニル)-6-(2,6-ジフルオロフェニル)-3,4-ジヒドロピリジン-2(1H)-オンの合成
1H-NMR (CDCl3) δ: 7.25-7.21 (1H, m), 7.19 (1H, d, J = 8.8 Hz), 6.83-6.76 (3H, m), 6.65 (1H, dd, J = 8.8, 3.4 Hz), 6.53 (1H, d, J = 3.4 Hz), 3.61 (3H, s), 2.91-2.76 (4H, m).
5-(2-クロロ-5-メトキシフェニル)-6-(2,6-ジフルオロフェニル)-1-エチルピリジン-2(1H)-オンの合成(化合物番号53)
3-クロロ-5-(2-クロロ-5-メトキシフェニル)-6-(2,6-ジフルオロフェニル)-1-エチルピリジン-2(1H)-オンの合成(化合物番号54)
5-(2-クロロ-5-ヒドロキシフェニル)-6-(2,6-ジフルオロフェニル)-1-エチルピリジン-2(1H)-オンの合成(化合物番号234)
5-(2-クロロ-5-(メトキシメトキシ)フェニル)-6-(2,6-ジフルオロフェニル)-1-エチルピリジン-2(1H)-オンの合成(化合物番号97)
3-クロロ-5-(2-クロロ-5-(メトキシメトキシ)フェニル)-6-(2,6-ジフルオロフェニル)-1-エチルピリジン-2(1H)-オンの合成(化合物番号127)
5-(2-クロロ-5-メトキシフェニル)-1-(2,2-ジフルオロエチル)-6-(2,6-ジフルオロフェニル)-3,4-ジヒドロピリジン-2(1H)-オンの合成(化合物番号192)
5-(2-クロロ-5-メトキシフェニル)-1-(2,2-ジフルオロエチル)-6-(2,6-ジフルオロフェニル)ピリジン-2(1H)-オンの合成(化合物番号194)
3-ブロモ-5-(2-クロロ-5-メトキシフェニル)-1-(2,2-ジフルオロエチル)-6-(2,6-ジフルオロフェニル)ピリジン-2(1H)-オンの合成(化合物番号198)
5-(2-クロロ-5-メトキシフェニル)-6-(2,6-ジフルオロフェニル)-1-エチル-3-メチル-3,4-ジヒドロピリジン-2(1H)-オンの合成
1H-NMR (CDCl3) δ: 7.24-7.17 (1H, m:mixture), 7.15-7.13 (1H, m:mixture), 6.87-6.71 (2H, m:mixture), 6.57-6.49 (2H, m:mixture), 3.70-3.14 (2H, m:mixture), 3.65 (3H, s:major), 3.58 (3H, s:minor), 2.98-2.70 (2H, m:mixture), 2.46-2.37 (1H, m:mixture), 1.35 (3H, d, J = 6.7 Hz:minor), 1.33 (3H, d, J = 7.0 Hz:major), 1.00-0.96 (3H, m).
立体異性混合物比:約57:43
5-(2-クロロ-5-メトキシフェニル)-6-(2,6-ジフルオロフェニル)-1-エチル-3-メチルピリジン-2(1H)-オンの合成(化合物番号329)
ステップ1:5-(2-クロロ-5-フルオロフェニル)-6-(2,4,6-トリフルオロフェニル)-3,4-ジヒドロピリジン-2(1H)-オンの合成
1H-NMR (CDCl3) δ: 7.28-7.26 (1H, m), 7.18 (1H, br s), 6.86-6.83 (1H, m), 6.74-6.72 (1H, m), 6.61-6.59 (2H, br m), 2.85-2.74 (4H, br m).
5-(2-クロロ-5-フルオロフェニル)-1-エチル-6-(2,4,6-トリフルオロフェニル)ピリジン-2(1H)-オンの合成(化合物番号321)
3-ブロモ-5-(2-クロロ-5-フルオロフェニル)-1-エチル-6-(2,4,6-トリフルオロフェニル)ピリジン-2(1H)-オンの合成(化合物番号381)
5-(2-クロロ-5-フルオロフェニル)-1-エチル-3-メチル-6-(2,4,6-トリフルオロフェニル)ピリジン-2(1H)-オンの合成(化合物番号461)
3-ブロモ-5-(2-クロロ-5-フルオロフェニル)-6-(2,6-ジフルオロ-4-メトキシフェニル)-1-エチルピリジン-2(1H)-オンの合成(化合物番号476)
ステップ1:5-(3,5-ジメトキシフェニル)-6-(2,4,6-トリフルオロフェニル)-3,4-ジヒドロピリジン-2(1H)-オンの合成
1H-NMR (CDCl3) δ: 6.68 (1H, s), 6.62 (2H, td, J = 8.7, 1.4 Hz), 6.26 (1H, t, J = 2.1 Hz), 6.16 (2H, d, J = 2.1 Hz), 3.65 (6H, s), 2.87-2.86 (2H, m), 2.73-2.71 (2H, m).
1H-NMR (CDCl3) δ: 6.62-6.60 (2H, m), 6.23 (1H, t, J = 2.1 Hz), 6.13 (2H, d, J = 2.1 Hz), 3.65 (6H, s), 2.87 (3H, s), 2.76-2.74 (4H, m).
5-(3,5-ジメトキシフェニル)-1-メチル-6-(2,4,6-トリフルオロフェニル)ピリジン-2(1H)-オンの合成(化合物番号134)
5-(2-クロロ-3,5-ジメトキシフェニル)-1-メチル-6-(2,4,6-トリフルオロフェニル)ピリジン-2(1H)-オンの合成(化合物番号136)
ステップ1:2-(2-クロロ-5-メトキシフェニル)-1-(2,6-ジフルオロフェニル)エタノンの合成
1H-NMR (CDCl3) δ: 7.40-7.38 (1H, m), 7.28-7.27 (1H, m), 6.96-6.94 (2H, m), 6.83 (1H, d, J = 3.1 Hz), 6.78 (1H, dd, J = 8.9, 3.1 Hz), 4.27 (2H, s), 3.79 (3H, s).
1H-NMR (CDCl3) δ: 7.36-7.25 (1H, m), 7.19 (1H, d, J = 8.9 Hz), 6.83 (2H, t, J = 8.1 Hz), 6.74-6.71 (2H, m), 4.91 (1H, t, J = 7.2 Hz), 4.13 (2H, q, J = 7.1 Hz), 3.76 (3H, s), 2.57-2.53 (1H, m), 2.42-2.29 (2H, m), 2.16-2.07 (1H, m), 1.25 (3H, t, J = 7.1 Hz).
1H-NMR (CDCl3) δ: 7.28-7.27 (1H, m), 7.19 (1H, d, J = 8.6 Hz), 6.83 (2H, t, J = 8.3 Hz), 6.75-6.74 (1H, m), 6.71 (1H, dd, J = 8.6, 3.1 Hz), 4.92 (1H, t, J = 7.3 Hz), 3.75 (3H, s), 2.60-2.34 (3H, m), 2.15-2.12 (1H, m).
ステップ1:N’-(2-クロロ-5-フルオロベンジリデン)-4-メチルベンゼンスルホニルヒドラジドの合成
1H-NMR (CDCl3) δ: 8.27 (1H, s), 8.10 (1H, d, J = 1.8 Hz), 7.88 (2H, d, J = 8.2 Hz), 7.58 (1H, dd, J = 9.2, 3.1 Hz), 7.34 (2H, d, J = 8.2 Hz), 7.30-7.28 (1H, m), 7.02-6.99 (1H, m), 2.43 (3H, s).
1H-NMR (CDCl3) δ: 7.36-7.34 (1H, m), 7.04-7.02 (1H, m), 6.98-6.96 (1H, m), 6.76-6.72 (2H, m) 4.26 (2H, s).
1H-NMR (CDCl3) δ: 7.32-7.29 (1H, m), 7.00-6.97 (1H, m), 6.94-6.89 (1H, m), 6.64-6.60 (2H, m), 4.89 (1H, t, J = 7.2 Hz), 2.58-2.06 (4H, m).
ステップ1:N’-(3,5-ジメトキシベンジリデン)-4-メチルベンゼンスルホニルヒドラジドの合成
1H-NMR (CDCl3) δ: 8.13 (1H, s), 7.87 (2H, d, J = 7.8 Hz), 7.68 (1H, s), 7.30 (2H, d, J = 7.8 Hz), 6.72 (2H, d, J = 2.4 Hz), 6.46 (1H, t, J = 2.4 Hz), 3.79 (6H, s), 2.40 (3H, s).
1H-NMR (CDCl3) δ: 6.68-6.66 (2H, m), 6.35 (3H, s),4.06 (2H,s), 3.75 (6H, s).
1H-NMR (CDCl3) δ: 6.61-6.57 (2H, m), 6.31-6.29 (3H, m), 4.19 (1H, t, J = 7.3 Hz), 4.13 (2H, q, J = 7.1 Hz), 3.73 (6H, s), 2.49-2.47 (1H, m), 2.30 (2H, t, J = 7.5 Hz), 2.09-2.07 (1H, m), 1.25 (3H, t, J = 7.1 Hz)
構造Aは以下を表す。
化合物番号32、53、54、あるいは55の化合物を、ジメチルスルホキシドで10mg/mlとなるように溶解した。それらのジメチルスルホキシド溶液を、終濃度が100μg/mlとなるように、犬糸状虫に感染したイヌより採集した犬糸状虫ミクロフィラリアを含む培養液で100倍希釈した。培養7日後に犬糸状虫ミクロフィラリアの死虫率を調査した。
結果、いずれの処理区でも死虫率100%となった。
化合物番号340、362、427、428、432、438、439、486、487、488、491、500、543、553、554、559、566、577、584、585、586、649、720、753、800、812、813、814、815、816あるいは817の化合物を25000ppmのジメチルスルホキシド溶液とし、サツマイモネコブセンチュウ2期幼虫懸濁水と混和して20ppmの溶液を調製した。これらの調製液を暗所で一晩静置した後、1株当たり90mlの0.5%寒天上で育苗したキュウリ幼苗の株元に2ml/株で処理し、処理7日後に根に形成された根こぶ数をカウントして無処理区の根こぶ数と比較した。
結果、いずれの処理区でも根こぶ数の対無処理比が30以下となった。
9cmシャーレ内に水を入れてスポンジを置きろ紙を敷いて、その上にササゲのリーフディスクを乗せた。ナミハダニ雌成虫をリーフディスク上に4頭放して1晩産卵させ、試験前に成虫を取り除き、産卵された卵数をカウントした。
化合物番号428、430、455、513、577、583、584、585、587、593、607、622、624、649、668、679、683、689、715、733、812、813、814あるいは820の化合物を25000ppmのジメチルスルホキシド溶液とし、グラミンS(三井化学アグロ製)を加えた蒸留水で500ppmの溶液を調製し、これらの調製液をシャーレあたり1mlで散布した。9日後に実体顕微鏡下で観察し、卵および孵化した幼虫の死虫率を調査した。未孵化卵は死虫としてカウントした。
結果、いずれの処理区でも死虫率が70%以上となった。
Claims (11)
- 式(1)
[式中、R1は、水酸基、
シアノ基、
置換基Aで適宜置換されてもよいC1~C6のアルキル基、
C1~C6のハロアルキル基、
置換基Aで適宜置換されてもよいC3~C8のシクロアルキル基、
置換基Aで適宜置換されてもよいC2~C6のアルケニル基、
C2~C6のハロアルケニル基、
置換基Aで適宜置換されてもよいC2~C6のアルキニル基、
C2~C6のハロアルキニル基、
置換基Aで適宜置換されてもよいC1~C6のアルコキシ基、
C1~C6のハロアルコキシ基、
置換基Aで適宜置換されてもよいC3~C8のシクロアルコキシ基、
置換基Aで適宜置換されてもよいC2~C6のアルケニルオキシ基、
C2~C6のハロアルケニルオキシ基、
置換基Aで適宜置換されてもよいC3~C6のアルキニルオキシ基、
C3~C6のハロアルキニルオキシ基、
またはR10R11N-(ここで、R10およびR11は、それぞれ独立していて、水素原子、またはC1~C6のアルキル基を表す。)を表し;
R2は、ハロゲン原子、
水酸基、
シアノ基、
ニトロ基、
置換基Bで適宜置換されてもよいC1~C6のアルキル基、
C1~C6のハロアルキル基、
置換基Bで適宜置換されてもよいC3~C8のシクロアルキル基、
置換基Bで適宜置換されてもよいC2~C6のアルケニル基、
C2~C6のハロアルケニル基、
置換基Bで適宜置換されてもよいC2~C6のアルキニル基、
C2~C6のハロアルキニル基、
置換基Bで適宜置換されてもよいC1~C6のアルコキシ基、
C1~C6のハロアルコキシ基、
置換基Bで適宜置換されてもよいC3~C8のシクロアルコキシ基、
置換基Bで適宜置換されてもよいC2~C6のアルケニルオキシ基、
C2~C6のハロアルケニルオキシ基、
置換基Bで適宜置換されてもよいC3~C6のアルキニルオキシ基、
C3~C6のハロアルキニルオキシ基、
R20C(=O)-(ここで、R20は、C1~C6のアルキル基、C1~C6のハロアルキル基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、C3~C8のシクロアルコキシ基、またはR21R22N-(ここで、R21およびR22は、それぞれ独立していて、水素原子、置換基B1で適宜置換されてもよいC1~C6のアルキル基、C1~C6のハロアルキル基、またはC3~C8のシクロアルキル基を表すか、あるいはR21およびR22は、結合する窒素原子と一緒になって、アジリジニル基、アゼチジニル基、ピロリジニル基、ピペリジニル基、ホモピペリジニル基、またはアゾカニル基を形成するものを表す。)を表す。)、
R20C(=O)O-(ここで、R20は、前記と同義である。)、
1~2個の酸素原子を含む3~6員環の基、
R23-L2-(ここで、R23は、C1~C6のアルキル基、またはC1~C6のハロアルキル基を表し、L2は、S、SO、またはSO2を表す。)、
R21R22N-(ここで、R21およびR22は、前記と同義である。)、
またはR24C(=O)N(R25)-(ここで、R24は、水素原子、C1~C6のアルキル基、C1~C6のハロアルキル基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、C3~C8のシクロアルコキシ基、またはR21R22N-(ここで、R21およびR22は、前記と同義である。)を表し、R25は、水素原子、置換基B1で適宜置換されてもよいC1~C6のアルキル基、C1~C6のハロアルキル基、またはC3~C8のシクロアルキル基を表す。)を表し;
R3は、水素原子、
ハロゲン原子、
ニトロ基、
置換基Cで適宜置換されてもよいC1~C6のアルキル基、
C1~C6のハロアルキル基、
置換基Cで適宜置換されてもよいC3~C8のシクロアルキル基、
置換基Cで適宜置換されてもよいC1~C6のアルコキシ基、
C1~C6のハロアルコキシ基、
置換基Cで適宜置換されてもよいC2~C6のアルケニル基、
C2~C6のハロアルケニル基、
置換基Cで適宜置換されてもよいC2~C6のアルキニル基、
C2~C6のハロアルキニル基、
R30-L3-(ここで、R30は、前記のR23と同義であり、L3は、前記のL2と同義である。)、
R31R32N-(ここで、R31およびR32は、前記のR21およびR22と同義である。)、
またはR33C(=O)-(ここで、R33は、C1~C6のアルキル基、C1~C6のハロアルキル基、またはC3~C8のシクロアルキル基を表す。)を表し;
nは、0~5の整数(ただし、nが2以上のとき、2以上のR2は、それぞれ独立した置換基を表す。)を表し;
Xは、酸素原子、または硫黄原子を表し;
Yは、フェニル基、ピリジル基、ピリダジニル基、ピリミジニル基、ピラジニル基、トリアジニル基、テトラジニル基、チエニル基、チアゾリル基、イソチアゾリル基、またはチアジアゾリル基を表し、
該フェニル基は、置換基Dがオルト位に置換し、さらに置換基D1が、それぞれ独立して適宜0~4置換し、
該ピリジル基、該ピラジニル基、該ピリミジニル基、該ピリダジニル基、該トリアジニル基、または該テトラジニル基は、置換基Dがオルト位に置換し、さらに置換基D1が、それぞれ独立して適宜0~3置換し、
該チエニル基、該チアゾリル基、該イソチアゾリル基、または該チアジアゾリル基は、置換基Dがオルト位に置換し、さらに置換基D1が、それぞれ独立して適宜0~2置換し;
破線部を含む結合は、二重結合、または単結合を表し、
そして、置換基Aは、
水酸基、シアノ基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、C3~C8のシクロアルコキシ基、R12R13N-(ここで、R12およびR13は、それぞれ独立していて、水素原子、C1~C6のアルキル基、C1~C6のハロアルキル基、またはC3~C8のシクロアルキル基を表すか、あるいはR12およびR13は、結合する窒素原子と一緒になって、アジリジニル基、アゼチジニル基、ピロリジニル基、ピペリジニル基、ホモピペリジニル基、またはアゾカニル基を形成するものを表す。)、およびR14-L1-(ここで、R14は、C1~C6のアルキル基、またはC1~C6のハロアルキル基を表し、L1は、S、SO、またはSO2を表す。)からなる群から選択される少なくとも1種であり;
置換基Bは、
水酸基、シアノ基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、C3~C8のシクロアルコキシ基、C2~C6のアルコキシアルコキシ基、R21R22N-(ここで、R21およびR22は、前記と同義である。)、R23-L2-(ここで、R23およびL2は、前記と同義である。)、R26R27R28Si-(ここで、R26、R27およびR28は、それぞれ独立していてC1~C6のアルキル基を表す。)、R26R27R28Si-(CH2)s-O-(ここで、sは、1~3の整数を表し、R26、R27およびR28は、前記と同義である。)、R20C(=O)-(ここで、R20は、前記と同義である。)、および1~2個の酸素原子を含む3~6員環の基からなる群から選択される少なくとも1種であり;
置換基B1は、
シアノ基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、およびC3~C8のシクロアルコキシ基からなる群から選択される少なくとも1種であり;
置換基Cは、
水酸基、シアノ基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、C3~C8のシクロアルコキシ基、R31R32N-(ここで、R31およびR32は、前記のR21およびR22と同義である。)、およびR30-L3-(ここで、R30は、前記のR14と同義であり、L3は、前記のL1と同義である。)からなる群から選択される少なくとも1種であり;
置換基Dは、
ハロゲン原子、C1~C6のアルキル基、C1~C6のハロアルキル基、C1~C6のアルコキシ基、およびC1~C6のハロアルコキシ基からなる群から選択される少なくとも1種であり;
置換基D1は、
水酸基、ハロゲン原子、C1~C6のアルキル基、C1~C6のハロアルキル基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、およびC3~C8のシクロアルコキシ基からなる群から選択される少なくとも1種である。]で表される化合物またはその塩を有効成分として含有する寄生性有害生物駆除剤。 - R1は、シアノ基、
置換基Aで適宜置換されてもよいC1~C6のアルキル基、
C1~C6のハロアルキル基、
置換基Aで適宜置換されてもよいC3~C8のシクロアルキル基、
置換基Aで適宜置換されてもよいC2~C6のアルケニル基、
C2~C6のハロアルケニル基、
置換基Aで適宜置換されてもよいC2~C6のアルキニル基、
またはR10R11N-(ここで、R10およびR11は、それぞれ独立していて、水素原子、またはC1~C6のアルキル基を表す。)を表し;
R2は、ハロゲン原子、
水酸基、
シアノ基、
置換基Bで適宜置換されてもよいC1~C6のアルキル基、
C1~C6のハロアルキル基、
置換基Bで適宜置換されてもよいC1~C6のアルコキシ基、
C1~C6のハロアルコキシ基、
置換基Bで適宜置換されてもよいC3~C8のシクロアルコキシ基、
置換基Bで適宜置換されてもよいC2~C6のアルケニルオキシ基、
置換基Bで適宜置換されてもよいC3~C6のアルキニルオキシ基、
R20C(=O)O-(ここで、R20は、C1~C6のアルキル基、C1~C6のハロアルキル基、C3~C8のシクロアルキル基、C1~C6のアルコキシ基、C1~C6のハロアルコキシ基、C3~C8のシクロアルコキシ基、またはR21R22N-(ここで、R21およびR22は、それぞれ独立していて、水素原子、置換基B1で適宜置換されてもよいC1~C6のアルキル基、C1~C6のハロアルキル基、またはC3~C8のシクロアルキル基を表すか、あるいはR21およびR22は、結合する窒素原子と一緒になって、アジリジニル基、アゼチジニル基、ピロリジニル基、ピペリジニル基、ホモピペリジニル基、またはアゾカニル基を形成するものを表す。)、
またはR23-L2-(ここで、R23は、C1~C6のアルキル基、またはC1~C6のハロアルキル基を表し、L2は、S、SO、またはSO2を表す。)を表し;
R3は、水素原子、
ハロゲン原子、
置換基Cで適宜置換されてもよいC1~C6のアルキル基、
置換基Cで適宜置換されてもよいC3~C8のシクロアルキル基、
置換基Cで適宜置換されてもよいC1~C6のアルコキシ基、
置換基Cで適宜置換されてもよいC2~C6のアルキニル基、
またはR30-L3-(ここで、R30は、前記のR23と同義であり、L3は、前記のL2と同義である。)を表し;
Yは、フェニル基、またはピリジル基を表し、
該フェニル基は、置換基Dがオルト位に置換し、さらに置換基D1が、それぞれ独立して適宜0~4置換し、
該ピリジル基は、置換基Dがオルト位に置換し、さらに置換基D1が、それぞれ独立して適宜0~3置換する、
請求項1に記載の化合物、またはその塩を有効成分として含有する寄生性有害生物駆除剤。 - R1は、置換基Aで適宜置換されてもよいC1~C6のアルキル基、またはC1~C6のハロアルキル基を表し;
R2は、ハロゲン原子、置換基Bで適宜置換されてもよいC1~C6のアルキル基、または置換基Bで適宜置換されてもよいC1~C6のアルコキシ基を表し;
R3は、水素原子、ハロゲン原子、または置換基Cで適宜置換されてもよいC1~C6のアルキル基を表す、
請求項2に記載の化合物、またはその塩を有効成分として含有する寄生性有害生物駆除剤。 - 寄生性有害生物がダニ目害虫または線虫類である請求項1に記載の寄生性有害生物駆除剤。
- 寄生性有害生物が植物寄生性ダニ目害虫、動物寄生性線虫類または植物寄生性線虫類である請求項1に記載の寄生性有害生物駆除剤。
- 寄生性有害生物がハダニ類、旋尾線虫目(Spirurida)線虫類またはネコブセンチュウ類である請求項1に記載の寄生性有害生物駆除剤。
- 寄生性有害生物がナミハダニ、犬糸状虫またはサツマイモネコブセンチュウである請求項1に記載の寄生性有害生物駆除剤。
- 請求項1に記載の寄生性有害生物駆除剤を用いた寄生性有害生物を駆除する方法。
- 寄生性有害生物を駆除する方法であって、それを必要とする対象に請求項1に記載の化合物またはその塩の有効量を適用することを含む方法。
- 寄生性有害生物駆除剤としての請求項1に記載の化合物またはその塩の植物への使用。
- 寄生性有害生物駆除剤として動物に使用するための請求項1に記載の化合物またはその塩。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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EP18784834.6A EP3610730B1 (en) | 2017-04-10 | 2018-04-10 | Parasitic pest control agent having pyridone compound as active component, and use method thereof |
JP2019512514A JP7134945B2 (ja) | 2017-04-10 | 2018-04-10 | ピリドン化合物を有効成分とする寄生性有害生物駆除剤およびその使用方法 |
BR112019021148-9A BR112019021148B1 (pt) | 2017-04-10 | 2018-04-10 | Agente de controle de pragas parasitárias, método para o controle de pragas parasitárias que infectam plantas, método para o controle de pragas parasitárias e uso de compostos de piridona como ingredientes ativos |
US16/497,575 US11234970B2 (en) | 2017-04-10 | 2018-04-10 | Parasitic pest control agents comprising pyridone compounds as active ingredients and methods for using the same |
ES18784834T ES2969695T3 (es) | 2017-04-10 | 2018-04-10 | Agentes de control de plagas parasitarias que comprenden compuestos de piridona como principios activos y métodos para usar los mismos |
CN201880005982.XA CN110167348B (zh) | 2017-04-10 | 2018-04-10 | 以吡啶酮化合物作为有效成分的寄生性有害生物驱除剂及其使用方法 |
CA3058883A CA3058883A1 (en) | 2017-04-10 | 2018-04-10 | Parasitic pest control agents comprising pyridone compounds as active ingredients and methods for using the same |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0308020A2 (en) | 1987-09-18 | 1989-03-22 | Merck & Co. Inc. | 5-(aryl and heteroaryl)-6-(aryl and heteroaryl)-1,2-dihydro-2-oxo 3-pyridinecarboxylic acids and derivatives thereof |
WO1998055480A1 (en) | 1997-06-06 | 1998-12-10 | Merck Sharp & Dohme Limited | Substituted 1h-pyridinyl-2-ones as gabaaalpha 2/3 ligands |
WO1998055448A2 (de) | 1997-06-03 | 1998-12-10 | Novartis Ag | Fluoralkencarbonsäurederivate, verfahren zu ihrer herstellung und diese enthaltende insektizidemittel |
JP2005531520A (ja) * | 2002-03-28 | 2005-10-20 | メルク エンド カムパニー インコーポレーテッド | 置換2,3−ジフェニルピリジン類 |
JP2014525452A (ja) * | 2011-08-29 | 2014-09-29 | ピーティーシー セラピューティクス, インコーポレイテッド | 抗菌化合物および使用方法 |
WO2017061525A1 (ja) * | 2015-10-09 | 2017-04-13 | 三井化学アグロ株式会社 | ピリドン化合物およびそれを有効成分とする農園芸用殺菌剤 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03178964A (ja) | 1989-12-06 | 1991-08-02 | Sumitomo Chem Co Ltd | ピリジルピリドン誘導体およびその殺虫剤としての用途 |
US20100160385A1 (en) * | 2008-12-19 | 2010-06-24 | E.I. Du Pont De Nemours And Company | Fungicidal triphenyl-substituted pyridones |
WO2010093595A1 (en) * | 2009-02-10 | 2010-08-19 | E. I. Du Pont De Nemours And Company | Fungicidal 2-pyridones |
-
2018
- 2018-04-10 BR BR112019021148-9A patent/BR112019021148B1/pt active IP Right Grant
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0308020A2 (en) | 1987-09-18 | 1989-03-22 | Merck & Co. Inc. | 5-(aryl and heteroaryl)-6-(aryl and heteroaryl)-1,2-dihydro-2-oxo 3-pyridinecarboxylic acids and derivatives thereof |
JPH01128969A (ja) * | 1987-09-18 | 1989-05-22 | Merck & Co Inc | 5−(アリールおよびヘテロアリール)−6−(アリールおよびヘテロアリール)−1,2−ジヒドロ−2−オキソ−3−ピリジンカルボン酸およびその誘導体 |
WO1998055448A2 (de) | 1997-06-03 | 1998-12-10 | Novartis Ag | Fluoralkencarbonsäurederivate, verfahren zu ihrer herstellung und diese enthaltende insektizidemittel |
WO1998055480A1 (en) | 1997-06-06 | 1998-12-10 | Merck Sharp & Dohme Limited | Substituted 1h-pyridinyl-2-ones as gabaaalpha 2/3 ligands |
JP2005531520A (ja) * | 2002-03-28 | 2005-10-20 | メルク エンド カムパニー インコーポレーテッド | 置換2,3−ジフェニルピリジン類 |
JP2014525452A (ja) * | 2011-08-29 | 2014-09-29 | ピーティーシー セラピューティクス, インコーポレイテッド | 抗菌化合物および使用方法 |
WO2017061525A1 (ja) * | 2015-10-09 | 2017-04-13 | 三井化学アグロ株式会社 | ピリドン化合物およびそれを有効成分とする農園芸用殺菌剤 |
Non-Patent Citations (5)
Title |
---|
GREEN CHEMISTRY, vol. 41, pages 580 - 585 |
JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 696, no. 25, 2011, pages 4039 - 4045 |
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 131, no. 2, 2009, pages 634 - 643 |
See also references of EP3610730A4 |
THE JOURNAL OF ORGANIC CHEMISTRY, vol. 65, no. 20, 2000, pages 6458 - 6461 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2021261562A1 (ja) * | 2020-06-26 | 2021-12-30 | 日本農薬株式会社 | アリールテトラヒドロピリジン誘導体又はその塩類及び該化合物を含有する殺虫剤並びにその使用方法 |
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BR112019021148A2 (pt) | 2020-05-12 |
CN110167348B (zh) | 2022-04-15 |
CA3058883A1 (en) | 2018-10-18 |
EP3610730C0 (en) | 2024-01-10 |
EP3610730A4 (en) | 2021-01-13 |
JPWO2018190321A1 (ja) | 2020-03-05 |
JP7134945B2 (ja) | 2022-09-12 |
BR112019021148B1 (pt) | 2023-10-31 |
EP3610730A1 (en) | 2020-02-19 |
EP3610730B1 (en) | 2024-01-10 |
US20210100782A1 (en) | 2021-04-08 |
CN110167348A (zh) | 2019-08-23 |
ES2969695T3 (es) | 2024-05-22 |
US11234970B2 (en) | 2022-02-01 |
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