WO2021060240A1 - 7-オキサ-3,4-ジアザビシクロ[4.1.0]ヘプタ-4-エン-2-オン化合物および除草剤 - Google Patents
7-オキサ-3,4-ジアザビシクロ[4.1.0]ヘプタ-4-エン-2-オン化合物および除草剤 Download PDFInfo
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- WO2021060240A1 WO2021060240A1 PCT/JP2020/035689 JP2020035689W WO2021060240A1 WO 2021060240 A1 WO2021060240 A1 WO 2021060240A1 JP 2020035689 W JP2020035689 W JP 2020035689W WO 2021060240 A1 WO2021060240 A1 WO 2021060240A1
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- GXHFUVWIGNLZSC-UHFFFAOYSA-N CC(C)(OC(C1)=O)OC1=O Chemical compound CC(C)(OC(C1)=O)OC1=O GXHFUVWIGNLZSC-UHFFFAOYSA-N 0.000 description 1
- WEMMKWCCQNHYIO-UHFFFAOYSA-N O=Cc(c(F)c(C(F)(F)F)cc1)c1Br Chemical compound O=Cc(c(F)c(C(F)(F)F)cc1)c1Br WEMMKWCCQNHYIO-UHFFFAOYSA-N 0.000 description 1
- GKLDGAVHIFOIMF-UHFFFAOYSA-N OC(CCc(c(Br)ccc1C(F)(F)F)c1F)=O Chemical compound OC(CCc(c(Br)ccc1C(F)(F)F)c1F)=O GKLDGAVHIFOIMF-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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
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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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P13/00—Herbicides; Algicides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P13/00—Herbicides; Algicides
- A01P13/02—Herbicides; Algicides selective
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
Definitions
- the present invention relates to a 7-oxa-3,4-diazabicyclo [4.1.0] hepta-4-en-2-one compound and a herbicide containing the same as an active ingredient.
- the present application claims priority based on Japanese Patent Application No. 2019-174531 filed in Japan on September 25, 2019, the contents of which are incorporated herein by reference.
- herbicides may be used to control weeds.
- Various compounds have been proposed as active ingredients of herbicides.
- Patent Document 1 discloses a compound represented by the formula (A).
- Herbicides are required not only to have an excellent weed control effect, but also to have less phytotoxicity on crops, to be less likely to remain in the environment, and to not pollute the environment.
- the subject of the present invention is a novel 7-oxa-3,4-, which is useful as an active ingredient of a herbicide, which has a reliable weed control effect even at a low dose, has less phytotoxicity to crops, and is highly safe for the environment.
- R 1 is a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C2-6 alkenyl group, a substituted or unsubstituted C2-6 alkynyl group, a substituted or unsubstituted C3-6 cycloalkyl group, or Shows a 5- to 6-membered cyclic ether group
- R 2 represents a substituted or unsubstituted C1 ⁇ 6 alkyl group, a substituted or unsubstituted C2 ⁇ 6 alkenyl group or a substituted or unsubstituted C2 ⁇ 6 alkynyl group
- R 3 is a hydrogen atom, a substituted or unsubstituted C1 to 6 alkyl group, a substituted or unsubstituted C2 to 6 alkenyl group, a substituted or unsubstituted C
- R 1 , R 2 , and R 3 are the same as their definitions in claim 1.
- X is a halogeno group, a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C2-6 alkenyl group, a substituted or unsubstituted C2-6 alkynyl group, a hydroxyl group, a substituted or unsubstituted C1-6 alkoxy.
- R-S (O) 2- NH-
- R independently represent a substituted or unsubstituted C1-6 alkyl group or a substituted or unsubstituted C3-6 cycloalkyl group, respectively.
- R a each independently represent a hydrogen atom, a substituted or unsubstituted C1 ⁇ 6 alkyl group or a substituted or unsubstituted C1 ⁇ 6 alkoxy group
- R b represents a substituted or unsubstituted C1-6 alkyl group or a substituted or unsubstituted phenyl group
- R c represents a hydrogen atom or a substituted or unsubstituted C1-6 alkyl group;
- R and R may be bonded to form a 4- to 6-membered ring together with the nitrogen atom to which they are bonded;
- R 2 S (O) N-, R and R may be bonded to form a 5- to 6-membered ring together with the sulfur atom to which they are bonded;
- n represents an integer of 0 to 5, and when n is 2 or more, X may be the same or different, and when n is 2 or more, two Xs thereof are combined to be divalent.
- Organic groups may be formed.
- R 1 , R 2 , and R 3 are the same as their definitions in claim 1, where X 1 is a halogeno group, a substituted or unsubstituted C1-6 alkyl group, substituted.
- an unsubstituted C2 to 6 alkenyl group a substituted or unsubstituted C2 to 6 alkynyl group, a substituted or unsubstituted C1 to 6 alkoxy group, a substituted or unsubstituted C1 to 6 alkylthio group, a substituted or unsubstituted C1 to 6 Alkyl sulfinyl groups, substituted or unsubstituted C1-6 alkylsulfonyl groups, substituted or unsubstituted C3-6 cycloalkyl groups, substituted or unsubstituted phenyl groups, substituted or unsubstituted 5-6-membered heterocyclyl groups, nitro Indicates a group or cyano group; m represents an integer of 0 to 3, and when m is 2 or more, X 1 may be the same or different.
- Substituents on the C1 to 6 alkyl groups in R 2 are halogeno groups, hydroxyl groups, C1 to 6 alkoxy groups, C1 to 6 alkoxy C1 to 6 alkoxy groups, C1 to 6 haloalkoxy groups, and C1 to 6 alkylthio groups.
- a method for controlling monocotyledonous and / or dicotyledonous weeds in a useful plant which contains the compound according to any one of [1] to [4], a salt thereof, or the compound.
- a method comprising the step of applying a herbicide to the weed and / or the plant and / or its location.
- the 7-oxa-3,4-diazabicyclo [4.1.0] hepta-4-en-2-one compound of the present invention exerts a reliable weed control effect even at a low dose, has less phytotoxicity to crops, and has less phytotoxicity. Since it is highly safe for the environment, it is useful as an active ingredient of herbicides.
- the herbicide of the present invention can be safely used for controlling weeds in the cultivation of agricultural and horticultural crops.
- the 7-oxa-3,4-diazabicyclo [4.1.0] hepta-4-en-2-one compound of the present invention (hereinafter, may be referred to as “the compound of the present invention” for simplicity) is of the formula. It is a compound represented by (I) (sometimes referred to as compound (I)) or a salt of compound (I). Compound (I) also includes hydrates, various solvates, polymorphs of crystals, and the like. Compound (I) may have a stereoisomer based on an asymmetric carbon, a double bond, or a tautomer. All such isomers and mixtures thereof are within the technical scope of the present invention.
- the term "unsubstituted” means that it is only a parent group. When there is no description of "substitution” and only the name of the parent group is described, it means “unsubstituted” unless otherwise specified.
- substituted means that any hydrogen atom of the parent group is substituted with a group (substituent) having the same or different structure as the mother nucleus. Therefore, a “substituent” is another group attached to a parent group.
- the substituent may be one or two or more.
- the two or more substituents may be the same or different.
- Terms such as "C1 to 6" indicate that the number of carbon atoms of the parent group is 1 to 6 or the like. This number of carbon atoms does not include the number of carbon atoms in the substituent. For example, a butyl group having an ethoxy group as a substituent is classified as a C2 alkoxy C4 alkyl group.
- the "substituent” is chemically acceptable and is not particularly limited as long as it has the effect of the present invention.
- the groups that can be “substituents” are illustrated below. C1-6 such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc.
- Alkyl group Vinyl group, 1-propenyl group, 2-propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, etc.
- C2-6 alkenyl groups C2-6 alkynyl groups such as ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group;
- C3-6 cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; Phenyl group, naphthyl group; Phenyl C1-6 alkyl groups such as benzyl group and phenethyl group; 3-6 member heterocyclyl group; 3-6 member heterocyclyl C1-6 alkyl group;
- Hydroxy group C1-6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group; C2-6 alkenyloxy groups such as vinyloxy group, allyloxy group, propenyloxy group, butenyloxy group; C2-6 alkynyloxy groups such as ethynyloxy group and propargyloxy group; Phenoxy group, naphthoxy group; Benzyloxy group, phenethyloxy group; 5- to 6-membered heteroaryloxy groups such as thiazolyloxy groups and pyridyloxy groups; 5- to 6-membered heteroaryl C1 to 6 alkyloxy groups such as thiazolylmethyloxy group and pyridylmethyloxy group;
- Holmil group C1-6 alkylcarbonyl groups such as acetyl group, propionyl group; Formyloxy group; C1-6 alkylcarbonyloxy groups such as acetyloxy group, propionyloxy group; Benzoyl group; C1-6 alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group; C1-6 alkoxycarbonyloxy groups such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group; Carboxyl group;
- Halogeno groups such as fluoro group, chloro group, bromo group, iod group; C1 to chloromethyl group, chloroethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,2-dichloro-n-propyl group, 1-fluoro-n-butyl group, etc.
- C2-6 haloalkyl groups such as 2-chloro-1-propenyl group, 2-fluoro-1-butenyl group; C2-6 haloalkynyl groups such as 4,4-dichloro-1-butynyl group, 4-fluoro-1-pentynyl group, 5-bromo-2-pentynyl group; C1-6 haloalkoxy groups such as difluoromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,3-dichlorobutoxy group; C2-6 haloalkenyloxy groups such as 2-chloropropenyloxy group, 3-bromobutenyloxy group; C1-6 haloalkylcarbonyl groups such as chloroacetyl group, trifluoroacetyl group, trichloroacetyl group;
- Amino group C1-6 alkyl-substituted amino groups such as methylamino group, dimethylamino group, diethylamino group; Anilino group, naphthylamino group; Phenyl C1-6 alkylamino groups such as benzylamino group, phenethylamino group; Formylamino group; C1-6 alkylcarbonylamino groups such as acetylamino group, propanoylamino group, butyrylamino group, i-propylcarbonylamino group; C1-6 alkoxycarbonylamino groups such as methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group; Aminocarbonyl group having an unsubstituted or substituent such as an aminocarbonyl group, a dimethylaminocarbonyl group, a phenylaminocarbony
- C1-6 alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group; C1-6 haloalkylthio groups such as trifluoromethylthio group, 2,2,2-trifluoroethylthio group; Phenylthio group; 5- to 6-membered heteroarylthio groups such as thiazolylthio groups and pyridylthio groups;
- C1-6 alkylsulfinyl groups such as methylsulfinyl group, ethylsulfinyl group, t-butylsulfinyl group; C1-6 haloalkylsulfinyl groups such as trifluoromethylsulfinyl groups, 2,2,2-trifluoroethylsulfinyl groups; Phenylsulfinyl group; 5- to 6-membered heteroarylsulfinyl groups such as thiazolylsulfinyl groups, pyridylsulfinyl groups; C1-6 alkylsulfonyl groups such as methylsulfonyl groups, ethylsulfonyl groups, t-butylsulfonyl groups; C1-6 haloalkylsulfonyl groups such as trifluoromethylsulfonyl groups, 2,2,2-trifluoroethylsulfony
- Tri-C1-6 alkyl-substituted silyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group; Triphenylsilyl group; Pentafluorosulfanil group; Cyan group; Nitro group;
- any hydrogen atom in the substituent may be substituted with a group having a different structure.
- the "substituent” in this case include a C1 to 6 alkyl group, a C1 to 6 haloalkyl group, a C1 to 6 alkoxy group, a C1 to 6 haloalkoxy group, a halogeno group, a cyano group, a nitro group and the like.
- the above-mentioned "3- to 6-membered heterocyclyl group” is a 3-membered ring or 4-membered ring containing 1 to 4 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom as ring constituent atoms.
- the heterocyclyl group may be monocyclic or polycyclic.
- the polycyclic heterocyclyl group may have any of a saturated alicyclic ring, an unsaturated alicyclic ring, and an aromatic ring as long as at least one ring is a heterocyclic ring.
- Examples of the "3- to 6-membered heterocyclyl group” include a 3- to 6-membered saturated heterocyclyl group, a 5- to 6-membered unsaturated heterocyclyl group, and a 5- to 6-membered heteroaryl group.
- Examples of the 3- to 6-membered saturated heterocyclyl group include an aziridinyl group, an epoxy group, an azetidinyl group, a pyrrolidinyl group, a tetrahydrofuranyl group, a dioxolanyl group, a tetrahydropyranyl group, a piperidyl group, a piperazinyl group, a morpholinyl group and a dioxanyl group. it can.
- the 5- to 6-membered unsaturated heterocyclyl group includes a pyrrolinyl group, a dihydrofuranyl group, an imidazolinyl group, a pyrazolinyl group, an oxazolinyl group, an isooxazolinyl group, a thiazolinyl group, an isothiazolinyl group, a dihydropyranyl group and a dihydrooxadinyl group. And so on.
- Examples of the 5-membered heteroaryl group include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isooxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, an oxadiazolyl group, a thiadiazolyl group and a tetrazolyl group. Can be done.
- 6-membered heteroaryl group examples include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridadinyl group, a triazinyl group and the like.
- R 1 is a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C2-6 alkenyl group, a substituted or unsubstituted C2-6 alkynyl group, a substituted or unsubstituted C3-6 cycloalkyl group, or It shows a 5- to 6-membered cyclic ether group.
- the "C1 to 6 alkyl group” in R 1 may be a straight chain or a branched chain.
- C1 ⁇ 6 alkyl group” in R 1 include methyl group, ethyl group, n- propyl group, n- butyl group, n- pentyl group, n- hexyl, i- propyl, i- butyl, s -Butyl group, t-butyl group, i-pentyl group, neopentyl group, 2-methylbutyl group, i-hexyl group and the like can be mentioned.
- the "C2-6 alkenyl group" in R 1 includes a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-2-propenyl group, and the like.
- 2-Methyl-2-propenyl group 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl Examples thereof include a group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group and the like.
- the "C2-6 alkynyl group" in R 1 includes an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-methyl-2-propynyl group, and the like.
- C1 ⁇ 6 alkyl group in R 1, the substituent on the "C2 ⁇ 6 alkenyl group", or “C2 ⁇ 6 alkynyl group” refers to fluoro, chloro, bromo group, a halogeno group such as iodo groups; hydroxyl C1-6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group; 2,3-dichlorobutoxy C1-6 haloalkoxy groups such as groups, trifluoromethoxy groups, 2,2,2-trifluoroethoxy groups; methylthio groups, ethylthio groups, n-propylthio groups, i-propylthio groups, n-butylthio groups, i-butylthio groups C1-6 alkylthio groups such as groups, s-butylthi
- Examples of the "C3 to 6 cycloalkyl group" in R 1 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
- Examples of the "5- to 6-membered cyclic ether group" in R 1 include a tetrahydrofuranyl group and a tetrahydropyranyl group.
- Substituent on "C3 ⁇ 8 cycloalkyl group" in R 1 is fluoro, chloro, bromo group, a halogeno group such as iodo groups; methyl, ethyl, n- propyl, i- propyl radical, n C1-6 alkyl groups such as -butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group; difluoromethyl group, trifluoromethyl group, 1,2-dichloro C1-6 haloalkyl groups such as -n-propyl group, 1-fluoro-n-butyl group; hydroxyl groups; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, C1-6 alkoxy groups such as i-butoxy group, t-butoxy group; C
- R 1 is preferably a substituted or unsubstituted C1 to 6 alkyl group or a 5 to 6 member cyclic ether group.
- Substituents on the "C1-6 alkyl group" in R 1 are a halogeno group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a C1-6 alkylthio group, a C1-6 alkylsulfinyl group, a C1-6 alkylsulfonyl group. Groups or C3-6 cycloalkyl groups are preferred.
- R 2 represents a substituted or unsubstituted C1 ⁇ 6 alkyl group, a substituted or unsubstituted C2 ⁇ 6 alkenyl group or a substituted or unsubstituted C2 ⁇ 6 alkynyl group,.
- "Unsubstituted C1 ⁇ 6 alkyl group” in R 2 specific examples of the "substituted or unsubstituted C2 ⁇ 6 alkenyl group", or “substituted or unsubstituted C2 ⁇ 6 alkynyl group”, exemplified in R 1 You can list the same things that you did.
- Substituent on "C1 ⁇ 6 alkyl group" in R 2 is fluoro, chloro, bromo group, a halogeno group such as iodo group; methoxy group, ethoxy group, n- propoxy group, i- propoxy, n- C1-6 alkoxy groups such as butoxy group, s-butoxy group, i-butoxy group, t-butoxy group; C1-6 alkoxy C1-6 alkoxy groups such as methoxyethoxy group; 2,3-dichlorobutoxy group, trifluoro C1-6 haloalkoxy groups such as methoxy group, 2,2,2-trifluoroethoxy group; methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s- C1-6 alkylthio groups such as butylthio group, t-butyl
- the nitrogen atom, 1 to 4 hetero atoms selected from the group consisting of an oxygen atom and a sulfur atom Is a group of a 5-membered aromatic ring containing as a constituent atom of the ring.
- Examples of the 5-membered heteroaryl group include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isooxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, an oxadiazolyl group, a thiadiazolyl group and a tetrazolyl group. Can be done.
- R 3 is a hydrogen atom, a substituted or unsubstituted C1 to 6 alkyl group, a substituted or unsubstituted C2 to 6 alkenyl group, a substituted or unsubstituted C2 to 6 alkynyl group, a substituted or unsubstituted C1 to 6 alkoxy group. , Substituted or unsubstituted C3-6 cycloalkyl group, or substituted or unsubstituted phenyl group. Specific examples of these groups in R 3 include the same as those illustrated in R 1.
- the "C1 ⁇ 6 alkoxy group" in R 3 a methoxy group, an ethoxy group, n- propoxy group, n- butoxy group, n- pentyloxy group, n- hexyloxy group, i- propoxy, i- butoxy , S-butoxy group, t-butoxy group, i-hexyloxy group and the like.
- Substituents on the "C1-6 alkoxy group" in R 3 are halogeno groups such as fluoro groups, chloro groups, bromo groups, iodo groups; hydroxyl groups; methoxy groups, ethoxy groups, n-propoxy groups, i-propoxy groups, C1-6 alkoxy groups such as n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group; 2,3-dichlorobutoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group C1-6 haloalkoxy groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group and the like.
- halogeno groups such as fluoro groups, chloro groups, bromo
- C1-6 alkylsulfinyl group such as methylsulfinyl group, ethylsulfinyl group, t-butylsulfinyl group
- C1-6alkylsulfonyl group such as methylsulfonyl group, ethylsulfonyl group, t-butylsulfonyl group
- cyclopropyl group C3-6 cycloalkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group
- phenyl group; C1 such as 4-methylphenyl group, 4-chlorophenyl group, 4-trifluoromethylphenyl group, 4-trifluoromethoxyphenyl group
- Substituent on the "phenyl group" in R 3 is fluoro, chloro, bromo group, a halogeno group such as iodo groups; methyl, ethyl, n- propyl, i- propyl, n- butyl group, C1-6 alkyl groups such as s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group; difluoromethyl group, trifluoromethyl group, 1,2-dichloro-n-propyl Group, C1-6 haloalkyl group such as 1-fluoro-n-butyl group; hydroxyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group , C1-6 alkoxy groups such as t-butoxy group; C1-6 haloalkoxy groups such
- R 3 is a hydrogen atom, a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C2-6 alkenyl group, a substituted or unsubstituted C2-6 alkynyl group, or a substituted or unsubstituted C2-6 alkynyl group. It is preferably a C3 to 6 cycloalkyl group of. "C1 ⁇ 6 alkyl group" in R 3, the substituent on "C2 ⁇ 6 alkenyl group", or “C2 ⁇ 6 alkynyl group", halogeno groups are preferable.
- the substituent on the "C3 to 6 cycloalkyl group” is preferably a halogeno group or a C1 to 6 alkyl group.
- [Q] Q indicates a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.
- the substituent (sometimes referred to as substituent (X)) on the "phenyl group” or “naphthyl group” in Q is a halogeno group, a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C2.
- R independently represents a substituted or unsubstituted C1 to 6 alkyl group or a substituted or unsubstituted C3 to 6 cycloalkyl group, respectively.
- R a each independently represent a hydrogen atom, a substituted or unsubstituted C1 ⁇ 6 alkyl group or a substituted or unsubstituted C1 ⁇ 6 alkoxy group,.
- R b represents a substituted or unsubstituted C1-6 alkyl group or a substituted or unsubstituted phenyl group.
- R c represents a hydrogen atom or a substituted or unsubstituted C1-6 alkyl group.
- R 2 N-CO- the group represented by R 2 N-CO-NH-, the group represented by R 2 N-CO-CO-NH-, or the group represented by R 2 N.
- R and R may be bonded to form a 4- to 6-membered ring together with the nitrogen atom to which they are bonded.
- R and R may be bonded to form a 5- to 6-membered ring together with the sulfur atom to which they are bonded.
- X is a halogeno group, a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C2-6 alkenyl group, a substituted or unsubstituted C2-6 alkynyl group, a hydroxyl group, a substituted or unsubstituted C1-6 alkoxy.
- halogeno group examples include a fluoro group, a chloro group, a bromo group, an iod group and the like.
- the "C1 to 6 alkyl group” in X may be a straight chain or a branched chain.
- the "C1 to 6 alkyl groups” in X include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group and s-. Butyl group, t-butyl group, i-pentyl group, neopentyl group, 2-methylbutyl group, i-hexyl group and the like can be mentioned.
- the "C2-6 alkenyl group" in X includes a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-2-propenyl group, and 2 -Methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group , 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like.
- the "C2-6 alkynyl group" in X includes an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-methyl-2-propynyl group, and 2 -Methyl-3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 2-methyl-3-pentynyl group, 1-hexynyl group , 1,1-dimethyl-2-butynyl group and the like.
- Examples of the "C1 to 6 alkoxy group" in X include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an i-propoxy group, and an i-butoxy group. Examples thereof include an s-butoxy group, a t-butoxy group, and an i-hexyloxy group.
- Examples of the "C2 to 6 alkenyloxy group" in X include a vinyloxy group, an allyloxy group, a propenyloxy group, a butenyloxy group and the like.
- Examples of the "C2 to 6 alkynyloxy group" in X include an ethynyloxy group and a propargyloxy group.
- Examples of the "C1 to 6 alkylthio group" in X include a methylthio group, an ethylthio group, an n-propylthio group, an n-butylthio group, an n-pentylthio group, an n-hexylthio group, and an i-propylthio group.
- Examples of the "C1 to 6 alkylsulfinyl group" in X include a methylsulfinyl group, an ethylsulfinyl group, and a t-butylsulfinyl group.
- Examples of the "C1 to 6 alkylsulfonyl group" in X include a methylsulfonyl group, an ethylsulfonyl group, and a t-butylsulfonyl group.
- Substituents on the "C1-6 alkyl group” or “C1-6 alkoxy group” in X are halogeno groups such as fluoro group, chloro group, bromo group, iodo group; hydroxyl group; methoxy group, ethoxy group, n-propoxy.
- C1-6 alkoxy groups such as groups, i-propoxy groups, n-butoxy groups, s-butoxy groups, i-butoxy groups, t-butoxy groups; C1-6 alkoxy C1-6 alkoxy groups such as methoxyethoxy groups; cyclo C3-6 cycloalkyl C1-6 alkoxy groups such as propylmethoxy group; 2,3-dichlorobutoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 3,3,3-trifluoropropoxy group C1-6 haloalkoxy groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group and the like C1-6 alkylthio Group; C1-6 alkylsulfinyl group such as methylsulfinyl
- C2-6 alkenyl group such as fluoro groups, chloro groups, bromo groups and iodo groups; hydroxyl groups; methoxy groups, ethoxy groups, n-propoxy groups, i-propoxy groups, n-butoxy groups, s- C1-6 alkoxy groups such as butoxy group, i-butoxy group, t-butoxy group; C1-6 haloalkoxy groups such as 2,3-dichlorobutoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group Group; C1-6 alkylsulfonyl group such as methylsulfonyl group, ethylsulf
- Examples of the "C3 to 6 cycloalkyl group” in X include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
- Examples of the "C3 to 6 cycloalkyloxy group” in X include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, and a cycloheptyloxy group.
- the "5- to 6-membered heterocyclyl group" in X is a 5-membered ring or 6-membered ring containing 1, 2, 3 or 4 heteroatoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom as ring constituent atoms. It is the base of the ring. When there are two or more heteroatoms, they may be the same or different.
- Examples of the "5- to 6-membered heterocyclyl group” include a 5- to 6-membered saturated heterocyclyl group, a 5- to 6-membered unsaturated heterocyclyl group, and a 5- to 6-membered heteroaryl group.
- Examples of the 5- to 6-membered saturated heterocyclyl group include a pyrrolidinyl group, a tetrahydrofuranyl group, a dioxolanyl group, a tetrahydropyranyl group, a piperidyl group, a piperazinyl group, a morpholinyl group, and a dioxanyl group.
- the 5- to 6-membered unsaturated heterocyclyl group includes a pyrrolinyl group, a dihydrofuranyl group, an imidazolinyl group, a pyrazolinyl group, an oxazolinyl group, an isooxazolinyl group, a thiazolinyl group, an isothiazolinyl group, a dihydropyranyl group and a dihydrooxadinyl group. And so on.
- Examples of the 5-membered heteroaryl group include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isooxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, an oxadiazolyl group, a thiadiazolyl group and a tetrazolyl group. Can be done.
- 6-membered heteroaryl group examples include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridadinyl group, a triazinyl group and the like.
- the "5- to 6-membered heterocyclyloxy group" in X has a structure in which a 5- to 6-membered heterocyclyl group and an oxy group are bonded. Specific examples include a thiazolyloxy group and a pyridyloxy group.
- the substituent on the "phenylsulfonyl group” is a halogeno group such as a fluoro group, a chloro group, a bromo group, an iodo group; a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, s.
- C1-6 alkyl groups such as -butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group; difluoromethyl group, trifluoromethyl group, 1,2-dichloro-n-propyl group , C1-6 haloalkyl groups such as 1-fluoro-n-butyl group; hydroxyl groups; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, C1-6 alkoxy group such as t-butoxy group; C1-6 haloalkoxy group such as 2,3-dichlorobutoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group; oxo group; or cyano group ; Is preferable.
- R, R a , R b , or R c include the same as illustrated in X.
- R-CO- examples include an acetyl group and a cyclopropylcarbonyl group.
- examples of the "group represented by RO-CO-" in X include a methoxycarbonyl group and the like.
- Examples of the " group represented by R-CONR a- " in X include an acetamide group and a cyclopropanecarboxyamide group. Examples of the "group represented by RNH-CO-" in X include a methylaminocarbonyl group and the like.
- Examples of the "group represented by R 2 N-CO-" in X include a dimethylaminocarbonyl group and the like.
- R and R may be bonded to form a 4- to 6-membered ring together with the nitrogen atom to which they are bonded, and the 4- to 6-membered ring to be formed includes an azetidine ring, a pyrrolidine ring, a piperidine group, and a piperazine. Rings, morpholine rings, etc. can be mentioned.
- Examples of the "group represented by R 2 N-CO-" after forming a 4- to 6-membered ring include an azetidine-1-carbonyl group, a pyrrolidine-1-carbonyl group, and a morpholin-4-carbonyl group. it can.
- Examples of the "group represented by RO-CO-NR a- " in X include a (t-butoxycarbonyl) amino group and a methoxy (t-butoxycarbonyl) amino group.
- Examples of the "group represented by RNH-CO-NH-" in X include methylaminocarboxyamide.
- Examples of the " group represented by R 2 N-CO-NH-" in X include dimethylaminocarboxyamide and the like.
- R and R may be bonded to form a 4- to 6-membered ring together with the nitrogen atom to which they are bonded, and specific examples of the 4- to 6-membered ring to be formed include the above-mentioned "R 2 N-”.
- the same ones as exemplified in "Group represented by CO-" can be mentioned.
- Examples of the "group represented by R 2 N-CO-NH-" after forming a 4- to 6-membered ring include an azetidine-1-carboxyamide group, a pyrrolidine-1-carboxyamide group, and a morpholine-4-carboxyamide. Can be mentioned.
- Examples of the "group represented by RNH-CO-CO-NH-" in X include methylaminocarbonylcarboxyamide and the like.
- Examples of the "group represented by R 2 N-CO-CO-NH-” in X include dimethylaminocarbonylcarboxyamide and the like.
- R and R may be bonded to form a 4- to 6-membered ring together with the nitrogen atom to which they are bonded, and specific examples of the 4- to 6-membered ring to be formed include the above-mentioned "R 2 N-”.
- the same ones as exemplified in "Group represented by CO-" can be mentioned.
- the "group represented by R 2 N-CO-NH-" after forming the 4- to 6-membered ring includes azetidine-1-carbonylcarboxyamide group, pyrrolidine-1-carbonylcarboxyamide group, and morpholin-4-carbonyl. Carboxamide and the like can be mentioned.
- Examples of the " group represented by RS (O) 2- NH-" in X include methyl sulfonamide.
- X - it includes "R 2 N-S (O) 2 group represented by” may be mentioned, methyl sulfonamide.
- R and R may be bonded to form a 4- to 6-membered ring together with the nitrogen atom to which they are bonded, and specific examples of the 4- to 6-membered ring to be formed include the above-mentioned "R 2 N-”.
- the same ones as exemplified in "Group represented by CO-" can be mentioned.
- R and R may be bonded to form a 5- to 6-membered ring together with the sulfur atom to which they are bonded, and the 5 to 6-membered ring to be formed includes a tetrahydrothiophene ring and a tetrahydro-2H-thiopyran ring.
- a "divalent organic group that can be formed by two Xs together" is a substituted or unsubstituted saturated divalent hydrocarbon group having 1 to 4 carbon atoms; or from O, N, and S.
- the divalent organic group that can be formed by two Xs together is a substituted or unsubstituted unsaturated hydrocarbon group having 2 to 3 carbon atoms; or O, N, and S.
- a divalent group consisting of a group containing one or more heteroatoms selected from the group consisting of two or more heteroatoms and a divalent hydrocarbon group having 2 to 3 substituted or unsubstituted unsaturated carbon atoms. Is the basis of.
- saturated divalent hydrocarbon group having 1 to 4 carbon atoms examples include "C1 to 4alkylene groups” such as a methylene group, a dimethylene group, a trimethylene group and a tetramethylene group.
- C2 to 3 alkenylene groups can be mentioned.
- the substituent on the "saturated or unsaturated divalent hydrocarbon group” is preferably a halogen group, a C1 to 6 alkyl group, or a C1 to 6 haloalkyl group.
- Examples of the group containing an oxygen atom (O) include an oxy (-O-) group, a carbonyl (-C (O)-) group, a carboxy (-COO-) group and the like.
- Examples of the divalent group formed by bonding an oxygen atom (O) -containing group and a saturated divalent hydrocarbon group include "oxy C2 to 3" such as an oxydimethylene group (-O-CH 2 CH 2-).
- Alkylene group such as dimethyleneoxy group (-CH 2 CH 2 -O-), "oxy C1-2” such as oxymethyleneoxy group (-O-CH 2-O-) Alkyleneoxy group ”, methyleneoxymethylene group (-CH 2- O-CH 2- ), methyleneoxydimethylene group (-CH 2- O-CH 2 CH 2- ), dimethyleneoxymethylene group (-CH 2 CH)
- alkyleneoxy C1-2 alkylene groups such as 2- O-CH 2-).
- Examples of the group containing a nitrogen atom (N) include an imino (-NH-) group, an N-substituted imino group, an iminooxy (-NH- ⁇ -) group, an N-substituted iminooxy group, and an oxyimino (- ⁇ -NH-).
- Examples of the divalent group formed by bonding a group containing a nitrogen atom (N) and a saturated divalent hydrocarbon group include "imino C2 to 3" such as an iminodimethylene group (-NH-CH 2 CH 2-).
- Alkylene group such as dimethylene imino group (-CH 2 CH 2- NH-), "imino C1-2 such as imimethylene imino group (-NH-CH 2-NH-)" Alkylene imino group ”, methylene imino methylene group (-CH 2- NH-CH 2- ), methylene imino dimethylene group (-CH 2- NH-CH 2 CH 2- ), dimethylene imino methylene group (-CH 2 CH)
- Examples thereof include "C1-2 alkylene imino C1-2 alkylene groups” such as 2- NH-CH 2-).
- Examples of the group containing a sulfur atom (S) include a thio (-S-) group, a sulfinyl (-S (O)-) group, and a sulfonyl (-S (O) 2- ) group.
- the divalent group formed by bonding a group containing a sulfur atom (S) and a saturated divalent hydrocarbon group includes a thiodimethylene group (-S-CH 2 CH 2- ) and a thiotrimethylene group (-S-).
- the "divalent organic group that can be formed by two Xs together" is a substituted or unsubstituted saturated divalent hydrocarbon group having 1 to 4 carbon atoms; or O and A divalent group consisting of a group containing one or more heteroatoms selected from the group consisting of S and a divalent hydrocarbon group having 1 to 4 substituted or unsubstituted saturated carbon atoms. It is preferable that it is a group of.
- the group containing an oxygen atom (O) is preferably an oxy (-O-) group, and the group containing a sulfur atom (S) is a thio (-S-) group or a sulfonyl (-S (O) 2). -) Groups are preferred.
- Q is preferably a substituted or unsubstituted phenyl group.
- the compound (I) when Q is a substituted or unsubstituted phenyl group is shown in the formula (I-1).
- R 1 to R 3 have the same meanings as those in formula (I).
- X indicates the substituent on the phenyl group mentioned above.
- n represents an integer from 0 to 5. When n is 2 or more, X may be the same or different. When n is 2 or more, two Xs thereof may be combined to form a divalent organic group.
- the compound represented by the above formula (I-1) is preferably a compound represented by the following formula (I-3).
- R 1 ⁇ R 3 have the same meanings as those in formula (I).
- X 1 is a halogeno group, a substituted or unsubstituted C1 to 6 alkyl group, a substituted or unsubstituted C2 to 6 alkenyl group, a substituted or unsubstituted C2 to 6 alkynyl group, a substituted or unsubstituted C1 to 6 alkoxy group.
- Substituent or unsubstituted C1-6 alkylthio group substituted or unsubstituted C1-6 alkylsulfinyl group, substituted or unsubstituted C1-6 alkylsulfonyl group, substituted or unsubstituted C3-6 cycloalkyl group, substituted or It represents an unsubstituted phenyl group, a substituted or unsubstituted 5- to 6-membered heterocyclyl group, a nitro group, or a cyano group.
- m represents an integer of 0 to 3. When m is 2 or more, X 1 may be the same or different. Specific examples of these groups in X 1 include the same as illustrated in X.
- C1 ⁇ 6 alkyl group in X 1, "C2 ⁇ 6 alkenyl group”, “C2 ⁇ 6 alkynyl group”, “C1 ⁇ 6 alkoxy group”, “C1 ⁇ 6 alkylthio group”, “C1 ⁇ 6 alkylsulfinyl group ,
- the substituent on the "C1-6 alkylsulfonyl group” is preferably a halogeno group.
- the substituent on the "C3 to 6 cycloalkyl group” is preferably a halogeno group or a C1 to 6 alkyl group.
- Substituents on the "phenyl group” or "5-6-membered heterocyclyl group” are halogeno groups, C1-6 alkyl groups, C1-6 haloalkyl groups, C1-6 alkoxy groups, C1-6 haloalkoxy groups, or cyano groups. Is preferable.
- salt of compound (I) examples include alkali metal salts such as lithium, sodium and potassium; alkaline earth metal salts such as calcium and magnesium; transition metal salts such as iron and copper; ammonium salts; triethylamine and tributylamine. , Salts of organic bases such as pyridine, hydrazine; and the like.
- the structure of compound (I) or the salt of compound (I) can be determined by an NMR spectrum, an IR spectrum, an MS spectrum, or the like.
- Compound (I) is not particularly limited depending on the production method thereof. Further, the salt of compound (I) can be obtained from compound (I) by a known method. Compound (I) can be produced, for example, by using the compound obtained by the production method described in Patent Document 1 as a production intermediate thereof, and by the method described in Examples and the like.
- reaction scheme 1 For example, compound (I) can be prepared from compound of formula (2) as shown in Reaction Scheme 1 below.
- the symbols in formula (2) have the same meaning as those in formula (I).
- the compound of formula (2) is reacted with a halogenating agent to construct an ⁇ -haloketone structure in the molecule, and the compound of formula (2Xa) is prepared, followed by R 2 ONa. It can be prepared by reacting with an alkoxide such as (if R 2 is a methyl group, sodium methoxide is applicable).
- Xa in the formula (2Xa) represents a halogeno group such as a chloro group or a bromo group.
- the compound of formula (2Xa) may be unstable and it is preferable to carry out the subsequent reaction without isolation.
- reaction scheme 2 The compound of formula (2) can be prepared from the compound of formula (3) as shown in Reaction Scheme 2 below.
- the symbols in formula (3) have the same meaning as those in formula (I).
- R x represents a lower alkyl group, such as a methyl group.
- R x has the same meaning.
- the compound of formula (2) can be prepared by heating the compound of formula (3) with morpholine.
- reaction scheme 3 The compound of formula (3) can be prepared by condensing the compound of formula (4) with the compound of formula (5) as shown in the following reaction scheme 3.
- the symbols in formula (4) have the same meaning as those in formula (I).
- R y represents a lower alkyl group such as a methyl group or an ethyl group. Further, R y may be bonded to each other to form a 1,3,2-dioxaborolane ring.
- Q in the formula (5) has the same meaning as Q in the formula (I).
- X b represents a halogeno group.
- the compounds of formula (3) are suitable bases (eg, inorganic bases such as potassium phosphate or cesium fluoride), metal catalysts (eg, palladium catalysts such as Pd (OAc) 2 ) and optionally ligands (eg, phosphine). It can be prepared by reacting the compound of the formula (4) with the compound of the formula (5) in the presence of a ligand). Metal catalysts and ligands are added as preformed complexes (eg, palladium / phosphine complexes such as bis (triphenylphosphine) palladium dichloride or [1,1-bis (diphenylphosphino) ferrocene] palladium dichloride dichloromethane adduct).
- bases eg, inorganic bases such as potassium phosphate or cesium fluoride
- metal catalysts eg, palladium catalysts such as Pd (OAc) 2
- ligands eg, phosphine
- Q in the compound of the formula (5) indicates a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, but the phenyl group and the substituent on the naphthyl group may be appropriately converted after the reaction. ..
- reaction scheme 4 The compound of formula (4) can be prepared from the compound of formula (6) as shown in Reaction Scheme 4 below.
- the symbols in formula (6) have the same meaning as those in formula (I).
- the compound of formula (4) is a suitable base (eg, an inorganic base such as potassium phosphate or cesium fluoride), a metal catalyst (eg, a palladium catalyst such as Pd 2 (dba) 3 , (Pd (OAc) 2 )).
- a metal catalyst eg, a palladium catalyst such as Pd 2 (dba) 3 , (Pd (OAc) 2
- a ligand eg, a phosphine ligand
- it can be prepared by reacting the compound of formula (6) with a boronic acid or ester of boronic acid, eg, bis (pinacolato) diboron.
- Metal catalysts and ligands are added as preformed complexes (eg, palladium / phosphine complexes such as bis (triphenylphosphine) palladium dichloride or [1,1-bis (diphenylphosphino) ferrocene] palladium dichloride dichloromethane adduct).
- palladium / phosphine complexes such as bis (triphenylphosphine) palladium dichloride or [1,1-bis (diphenylphosphino) ferrocene] palladium dichloride dichloromethane adduct.
- palladium / phosphine complexes such as bis (triphenylphosphine) palladium dichloride or [1,1-bis (diphenylphosphino) ferrocene] palladium dichloride dichloromethane adduct.
- reaction scheme 5 The compound of formula (6) can be prepared from the compound of formula (7) as shown in Reaction Scheme 5 below.
- the symbols in formula (7) have the same meaning as those in formula (I).
- the compound of formula (6) can be prepared by reacting the compound of formula (7) with a suitable metal alkoxide, for example sodium methoxide.
- a suitable metal alkoxide for example sodium methoxide.
- the compound of formula (7) can be prepared by a known method.
- reaction scheme 3A The compound of formula (3) can be prepared by condensing the compound of formula (6) with the compound of formula (8) as shown in the following reaction scheme 3A.
- Q in the formula (8) has the same meaning as Q in the formula (I).
- R y represents a lower alkyl group such as a methyl group or an ethyl group. Further, R y may be bonded to each other to form a 1,3,2-dioxaborolane ring.
- the compounds of formula (3) are suitable bases (eg, inorganic bases such as potassium phosphate or cesium fluoride), metal catalysts (eg, palladium catalysts such as Pd (OAc) 2 ) and optionally ligands (eg, phosphine). It can be prepared by reacting the compound of formula (6) with the compound of formula (8) in the presence of a ligand). Metal catalysts and ligands are added as preformed complexes (eg, palladium / phosphine complexes such as bis (triphenylphosphine) palladium dichloride or [1,1-bis (diphenylphosphino) ferrocene] palladium dichloride dichloromethane adduct). Can be.
- inorganic bases such as potassium phosphate or cesium fluoride
- metal catalysts eg, palladium catalysts such as Pd (OAc) 2
- ligands eg, phosphine
- Q in the compound of the formula (8) indicates a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, but the phenyl group and the substituent on the naphthyl group may be appropriately converted after the reaction. ..
- the compound of the present invention exhibits high herbicidal activity in both soil treatment and foliage treatment under upland farming conditions.
- the compound of the present invention is effective for various field weeds and may show selectivity for crops such as corn and wheat.
- the compound of the present invention may exhibit a plant growth regulating effect such as a growth inhibitory effect on useful plants such as crops, ornamental plants, and fruit trees.
- the compound of the present invention has an excellent herbicidal effect on paddy weeds and may show selectivity for rice.
- the herbicide of the present invention contains at least one selected from the group consisting of compound (I) and a salt of compound (I) as an active ingredient. That is, one aspect of the present invention is a herbicide containing at least one selected from the group consisting of compound (I) and a salt thereof as an active ingredient.
- the herbicide of the present invention exhibits high herbicidal activity in both soil treatment and foliage treatment under upland farming conditions.
- the herbicide of the present invention has an excellent herbicidal effect on paddy weeds such as Nobie, Cyperus difformis, Sagittaria trifolia, and Scirpus juncoides, and may show selectivity for rice. Further, the herbicide of the present invention can also be applied to control weeds in orchards, lawns, railroad tracks, vacant lots and the like.
- Useful plants for which the herbicides of the invention can be used include crops such as cereals and wheat, cotton, oilseed rape, sunflower, corn, rice, soybeans, sugar beet, sugar cane and lawn. Crops can also include trees such as fruit trees, palm trees, coconut trees or other nuts. It also includes vines such as vines, fruit shrubs, fruit plants and vegetables.
- the field weeds to be controlled include the following weeds.
- A Monocolobed weeds (1) Weeds of the family Cyperaceae Weeds of the genus Cyperus, such as Cyperus esculentus, Cyperus iria, Cyperus iria, Cyperus microiria rotundus).
- Alopecurus weeds such as Alopecurus aequalis and Blackgrass (Alopecurus myosuroides); Weeds of the genus Silkybent (Apera), such as Silkybent (Apera spica-venti); Weeds of the genus Oat (Avena), such as Enbaku (Avena sativa); Bromes weeds, such as Bromes japonicus, Bromes sterilis; Weeds of the genus Digitaria (Digitaria), such as Digitaria ciliaris, Digitaria sanguinalis; Weeds of the genus Echinochloa, such as Echinochloa crus-galli; Weeds of the genus Goosegrass (Eleusine), such as Goosegrass (Eleusine indica); Ryegrass (Lolium) weeds, such as Italian ryegrass (Lolium multiflorum Lam.); Panicgrass
- (B) Twin leaf weeds (1) Amaranthaceae weeds Amaranthus blitum weeds, such as Amaranthus blitum, Amaranthus palmeri, Amaranthus retroflexus, Amaranthus rudis; Weeds of the genus Goosefoot (Chenopodium), such as white goosefoot (Chenopodium album); Weeds of the genus Bassia, such as Bassia scoparia.
- Asteraceae weeds Weeds of the genus Ragweed (Ambrosia), such as ragweed (Ambrosia artemisiifolia) and giant ragweed (Ambrosia trifida); Weeds of the genus Conyza, such as horseweed (Conyza canadensis) and erigeron sumatren (Conyza sumatrensis); Weeds of the genus Fleabane (Erigeron), such as Erigeron annuus; Weeds of the genus Mayweed (Matricaria), such as Tripleurospermum (Matricaria inodora), Chamomile (Matricaria recutita); Weeds of the genus Xanthium, such as the cocklebur (Xanthium occidentale).
- Ambrosia ragweed
- Weeds of the genus Conyza such as horseweed (Con
- paddy weeds to be controlled include the following weeds.
- A Monocotyledonous weeds
- Echinochloa weeds (so-called nobies) weeds, such as Echinochloa oryzoides, Echinochloa crus-galli; Leersia weeds, such as Leersia japonica; Weeds of the genus Paspalum, such as Paspalum distichum.
- Weeds of the family Pontederiaceae Weeds of the genus Monochoria, such as Monochoria korsakowii, Pontederia vaginalis (Monochoria vaginalis var. Plantaginea).
- the herbicide of the present invention may consist only of the compound of the present invention, or may be in a dosage form generally available as a pesticide, for example, a wettable powder, a granule, a powder, an emulsion, a water solvent, a suspension, or a flowable. It may be a formulation such as.
- one aspect of the invention is a herbicide comprising an agrochemically acceptable solid carrier and / or a liquid carrier.
- a herbicide comprising an agrochemically acceptable solid carrier and / or a liquid carrier.
- solid dosage forms vegetable powders such as soybean flour and wheat flour, diatomaceous earth, ashstone, talc, talc, bentonite, pyrophyllite, clay and other mineral fine powders, sodium benzoate, urea, and sardine.
- Solid carriers such as organic and inorganic compounds such as, etc. can be used.
- liquid dosage forms petroleum fractions such as kerosene, xylene and solventnaphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water Liquid carriers such as can be used.
- a surfactant can be added as needed.
- Surfactants include alkylphenyl ethers with polyoxyethylene added, alkyl ethers with polyoxyethylene added, higher fatty acid esters with polyoxyethylene added, sorbitan higher fatty acid esters with polyoxyethylene added, and polyoxyethylene.
- Nonionic surfactant such as added tristyrylphenyl ether, sulfate ester salt of alkylphenyl ether added with polyoxyethylene, alkylnaphthalene sulfonate, polycarboxylate, lignin sulfonate, alkylnaphthalene sulfonate
- examples of the formaldehyde condensate, isobutylene-maleic anhydride copolymer and the like can be mentioned.
- the concentration of the active ingredient can be appropriately set according to the dosage form.
- the concentration of the active ingredient in the wettable powder is preferably 5 to 90% by weight, more preferably 10 to 85% by weight.
- the concentration of the active ingredient in the emulsion is preferably 3 to 70% by weight, more preferably 5 to 60% by weight.
- the concentration of the active ingredient in the granules is preferably 0.01 to 50% by weight, more preferably 0.05 to 40% by weight.
- the wettable powder or emulsion thus obtained is diluted with water to a predetermined concentration to form a suspension or emulsion, and the granules are directly sprayed or mixed on the soil before or after germination of weeds. be able to.
- an appropriate amount of 0.1 g or more of the active ingredient can be applied per hectare.
- the herbicide of the present invention includes known fungicides, fungicides, insecticides, insecticides, acaricides, acaricides, herbicides, herbicides, plant growth regulators, fertilizers, and chemical damage reduction. It can also be mixed with an agent (safener) or the like. In particular, it is possible to reduce the amount of drug used by using it in combination with a herbicide. In addition to saving labor, a higher effect can be expected due to the synergistic action of the mixed drug. In that case, a combination with a plurality of known herbicides is also possible. That is, one aspect of the present invention is a herbicide containing one or more additional herbicidal active ingredients. In addition, one of the aspects of the present invention is a herbicide containing one or more additional phytotoxicity reducing agents.
- herbicidal active ingredients used in the present invention are not particularly limited, and examples thereof include the following.
- Pyridadinone type is carbamate type such as desmedipham, phenmedipham, swep; chlorobromuron, chlorotoluron, chloroxuron, dimefuron, DCMU ( Diuron), ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, metabenzthiazuron, metobromron Ureas such as metoxuron, monolinuron, neburon, siduron, tebuthiuron, metobenzuron, carbutilate; DCPA (propanil), CMMP (penta) Nocroll Amide system such as (pentanochlor); anilide system such as cypromid; nitrile system such as bromofenoxim, bromoxynil, ioxynil; benzothia dinone system such as bentazone.
- Pyridazines such as pyridate and pyridaf
- Bipyridylium-based substances such as diquat and paraquat; other substances that themselves become free radicals in the plant body and generate active oxygen to exhibit a fast-acting herbicidal effect.
- oxazolidinedione system benzfendizone, butafenacil and other pyrimidinedione system; saflufenacil and other sulfonylamide system; flufenpyr-ethyl and other pyridazine system; Inhibiting chlorophyll biosynthesis in plants such as pyrachlonil, profluazol, tiafenacil, and trifludimoxazin, and abnormal accumulation of photosensitizing peroxides in the plant body. It is said to show herbicidal effect.
- Glyphosates such as glyphosate, glyphosate-ammonium, glyphosate-isopropylamine, glyphosate trimesium (sulfosate); other EPSP synthase inhibitors
- glufosinate h) Glyphosinate
- glufosinate-ammonium phosphinic acid
- phosphinic acid such as bialaphos (bilanafos), etc.
- Glutamine synthase inhibition and other plant amino acid biosynthesis are said to show herbicidal effect. ..
- Oxyacetamides such as flufenacet and mefenacet; fentrazami Tetrazolinones such as fentrazamide; other anilofos, indanofan, cafenstrole, piperophos, methiozolin, fenoxasulfone, pyroxasulfone, ip
- the herbicidal effect is shown by inhibiting microtubule polymerization, microtubule formation, and cell division of plants such as fenoxasulfone, or by inhibiting very long chain fatty acid (VLCFA) biosynthesis. What has been done.
- Nitrile type such as DBN (dichlobenil), DCBN (chlorthiamid); benzamide type such as isoxaben; triazolocarboxamide type such as flupoxam; quinclorac etc.
- Quinoline carboxylic acid system Others It is said to show herbicidal effect by inhibiting cell wall (cellulose) synthesis such as triaziflam and indaziflam.
- Thiocarbamates such as prosulfocarb, benthiocarb (thiobencarb), tiocarbazil, triallate, vernolate, diallate
- phosphorodithio such
- Phenoxycarboxylic acids such as clomeprop, 2,4-PA (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPB, MCPP (mecoprop) System: Benzoic acid system such as chloramben, MDBA (dicamba), TCBA (2,3,6-TBA); clopyralid, aminopyralid, fluroxypyr, picloram , Triclopyr, halauxifen and other pyridinecarboxylic acid systems; quinclorac, quinmerac and other quinoline carboxylic acid systems; NPA (naptalam), diflufenzopyr ( Phthalamate semicarbazones such as diflufenzopyr; others Benazolin, diflufenzopyr, fluroxypyr, chlorflurenol, aminocyclopyrachlor, DAS534, etc. It is said to show herbicidal effect by disturbing the hormonal action of plants.
- Benzoic acid system such as chloramben, MDBA (dicamba),
- Arylaminopropionic acid type such as flamprop-isopropyl; pyrazolium type such as difenzoquat; organic arsenic type such as DSMA and MSMA; other bromobutide, (chlor)- Flurenol, cinmethylin, cumyluron, dazomet, daimuron, methyl-dymron, etobenzanid, hosamine, oxaziclomefone, oxaziclomefone (Oleic acid), pelargonic acid, pyributicarb, endothall, sodiumchlorate, metam, quinoclamine, cyclopyrimorate, tridiphan (Tridiphane), clacyfos and other herbicides.
- Arylaminopropionic acid type such as flamprop-isopropyl
- pyrazolium type such as difenzoquat
- organic arsenic type such as DSMA
- Examples of the phytotoxicity reducing agent (safener) that can be used in the present invention include benoxacor, cloquintocet, cloquintocet-mexyl, cyometrinil, and cyprosulfamide.
- Cyprosulfamide dichlormid, dicyclonon, dietholate, fenchlorazole, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim , Furilazole, isoxadifen, isoxadifen-ethyl, mefenpyr, mefenpyr-diethyl, mephenate, naphthalic anhydride. ), Oxabetrinil and the like.
- formulation example Although some examples of formulations relating to the herbicide of the present invention are shown, the compounds (active ingredients), additives and addition ratios of the present invention are not limited to the present examples and can be changed in a wide range.
- the part in the formulation example indicates the part by weight.
- Wettable powder 20 parts of the compound of the present invention 20 parts of white carbon 20 parts of diatomaceous earth 52 parts of sodium alkyl sulfate 8 parts or more are uniformly mixed and finely pulverized to obtain a wettable powder having 20% of the active ingredient.
- Step 2 Synthesis of 3- (6-bromo-2-fluoro-3- (trifluoromethyl) phenyl) propanol-1-ol
- the obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure. The obtained crystals were dried to obtain 1.6 g of the target product.
- Table 1 shows an example of the compound of the present invention produced by the same method as in the above synthesis example.
- Table 1 shows the substituents in the compound represented by the formula (I-2).
- the melting point is also shown as a physical characteristic value.
- Me represents a methyl group
- Et represents an ethyl group
- n Pr represents an n-propyl group
- i Pr represents an i-propyl group
- c Pr represents a cyclopropyl group
- t Bu represents a t-butyl group.
- N Hex represents an n-hexyl group
- Ph represents a phenyl group.
- Table 2 shows an example of the compound of the present invention produced by the same method.
- Table 3 shows an example of the compound of the present invention produced by the same method.
- Table 3 shows the substituents in the compound represented by the formula (I-4).
- Compound A-26 1 H-NMR (400MHz, CDCl 3 ): ⁇ 3.14 (s, 3H), 3.53 (s, 3H), 3.79 (s, 3H), 7.42-7.53 (m, 4H), 7.63- 7.65 (m, 2H), 7.89 (d, 1H), 7.95 (dd, 1H), 8.22 (d, 1H).
- Compound A-28 1 H-NMR (400MHz, CDCl 3 ): ⁇ 3.10 (s, 3H), 3.49 (s, 3H), 3.51 (s, 3H), 3.74 (s, 3H), 4.56 (s, 2H), 7.20 (s, 1H), 7.71 (dd, 1H), 7.81 (d, 1H), 7.98 (d, 1H).
- Compound A-31 1 H-NMR (400MHz, CDCl 3 ): ⁇ 3.50 (s, 3H), 3.68-3.77 (m, 10H), 4.01-4.14 (m, 4H), 7.20 (s, 1H), 7.61-7.63 (m, 2H), 8.97 (s, 1H).
- Compound A-32 1 H-NMR (400MHz, CDCl 3 ): ⁇ 2.10 (s, 3H), 3.42-3.50 (m, 7H), 3.66-3.74 (m, 7H), 6.28 (s, 1H), 7.23 (s, 3H), 7.52-7.58 (m, 2H).
- Compound A-41 1 H-NMR (400MHz, CDCl 3 ): ⁇ 2.05 (br, 3H), 2.11 (s, 3H), 2.28 (s, 3H), 3.51 (s, 3H), 3.68 (s, 3H), 3.96 (s, 3H), 7.13 (br, 1H), 7.19 (s, 1H), 7.39 (br, 1H).
- Compound A-42 1 H-NMR (400MHz, CDCl 3 ): ⁇ 3.34 (s, 3H), 3.49 (s, 3H), 3.74 (s, 3H), 7.21 (s, 1H), 7.90 (d, 1H), 8.05 (d, 1H).
- Compound A-43 1 H-NMR (400MHz, CDCl 3 ): ⁇ 2.55-2.68 (m, 6H), 3.15 (s, 3H), 3.65-3.67 (m, 6H), 7.28 (s, 1H), 7.60 (d, 1H), 7.96 (d, 1H).
- Compound A-45 1 H-NMR (400MHz, CDCl 3 ): ⁇ 1.78 (s, 3H), 1.80 (s, 3H), 3.33 (s, 3H), 3.51 (s, 3H), 3.66 (s, 3H), 5.62 (d, 1H), 5.72 (d, 1H), 7.25 (s, 1H), 7.73 (d, 1H), 8.15 (d, 1H).
- Compound A-52 1 H-NMR (400MHz, CDCl 3 ): ⁇ 3.54 (s, 3H), 3.71 (s, 3H), 7.31 (s, 1H), 7.68-7.75 (m, 2H), 7.85- 7.89 (m, 1H), 8.14 (s, 1H), 8.61 (s, 1H).
- Compound A-53 1 H-NMR (400 MHz, CDCl 3 ): ⁇ 3.30 (s, 3H), 3.43 (s, 3H), 3.80 (s, 3H), 7.36 (dd, 1H), 7.49 (s) , 1H), 7.54-7.60 (m, 1H), 7.91 (dd, 1H).
- Compound A-54 1 H-NMR (400 MHz, CDCl 3 ): ⁇ 0.70 (t, 3H), 1.45-1.54 (m, 2H), 3.10 (s, 3H), 3.38 (s, 3H), 3.77 (s, 3H), 3.93 (t, 2H), 7.90-7.97 (m, 2H), 8.21 (s, 1H).
- Compound A-56 1 H-NMR (400MHz, CDCl 3 ): ⁇ 3.54 (s, 3H), 3.69 (s, 3H), 7.30 (s, 1H), 7.60-7.70 (m, 3H), 7.81 ( d, 1H), 7.94 (s, 1H).
- Compound A-70 1 H-NMR (400MHz, CDCl 3 ): ⁇ 3.02 (s, 3H), 3.54 (s, 3H), 3.76 (s, 3H), 6.86-6.96 (m, 1H), 7.15 ( s, 1H), 7.50-7.82 (m, 4H).
- Compound A-71 1 H-NMR (400MHz, CDCl 3 ): ⁇ 1.45 (t, 3H), 3.20 (q, 2H), 3.35 (s, 3H), 3.48 (s, 3H), 3.65 (s, 3H), 4.98-5.85 (m, 1H), 7.25 (s, 1H), 7.79 (d, 1H), 8.12 (d, 1H).
- Compound A-74 1 H-NMR (400MHz, CDCl 3 ): ⁇ 3.19-3.30 (m, 4H), 3.52 (s, 3H), 3.69-3.79 (m, 7H), 7.25 (s, 1H), 7.92-8.09 (m, 3H).
- Compound A-75 1 H-NMR (400MHz, CDCl 3 ): ⁇ 3.13 (s, 3H), 3.51 (s, 3H), 3.78 (s, 3H), 7.20 (s, 1H), 7.59 (dd, 1H), 7.86 (d, 1H), 7.89 (d, 1H).
- Compound B-2 1 H-NMR (400MHz, CDCl 3 ): ⁇ 2.49-2.63 (m, 2H), 2.80-2.89 (m, 1H), 3.09-3.18 (m, 1H), 3.35-3.40 (m, 1H), 3.55 (s, 3H), 3.69-3.73 (m, 1H), 4.07-4.16 (m, 2H), 4.29-4.34 (m, 1H), 4.61-4.68 (m, 1H), 7.19 (s, 1H), 7.60-7.99 (m, 6H).
- Compound B-9 1 H-NMR (400MHz, CDCl 3 ): ⁇ 1.79 (m, 2H), 2.09-2.23 (m, 2H), 3.30-3.45 (m, 4H), 3.54 (s, 3H), 3.74 (s, 3H), 7.16 (s, 1H), 7.89 (s, 2H).
- Compound B-11 1 H-NMR (400MHz, CDCl 3 ): ⁇ 2.15 (s, 3H), 2.50-2.78 (m, 5H), 3.41-3.56 (m, 5H), 3.69 (s, 3H), 4.12-4.28 (m, 4H), 7.13 (s, 1H), 7.49 (s, 1H).
- Compound B-12 1 H-NMR (400MHz, CDCl 3 ): ⁇ 1.41 (s, 6H), 2.22-2.40 (m, 4H), 2.56 (s, 3H), 3.39-3.45 (m, 2H), 3.51 (s, 3H), 3.68 (s, 3H), 7.15 (s, 1H), 7.36 (d, 1H), 7.62 (d, 1H).
- Compound B-13 1 H-NMR (400MHz, CDCl 3 ): ⁇ 3.51 (s, 3H), 3.59 (dt, 2H), 3.73 (s, 3H), 4.83-4.95 (m, 2H), 7.18 ( s, 1H), 7.56 (d, 1H), 7.76 (d, 1H).
- Test Example 1 (1) Preparation of test emulsion POA allylphenyl ether (4.1 parts by weight), POE-POP glycol (1 part by weight), POE sorbitan laurate (0.8 parts by weight), glycerin (2.6 parts by weight) , Dimethylformamide (65.9 parts by weight), N-methylpyrrolidone (5.1 parts by weight), cyclohexanone (15.4 parts by weight), and aromatic hydrocarbon (5.1 parts by weight) were mixed and dissolved. , Emulsion was prepared.
- a 150 cm 2 pot is filled with soil, and the surface layer is covered with Enbaku (Avena sativa), Chamomile (Matricaria chamomilla), Setaria faberi (Setaria faberi), Digitaria ciliaris (Digitaria ciliaris), and Amaranthus retroflexus (Abutilon theophrasti). Amaranthus retroflexus) seeds were sown and lightly covered with soil.
- A-1, A-2, A-3, A-4, A-5, A-6, A-9, A-10, and B-1 compounds should be applied in an amount of 1000 g per hectare. It was sprayed. As a result, all the compounds had a herbicidal rate of 80% or more with respect to velvetleaf.
- the compounds of A-1, A-2, A-3, A-4, A-5, A-6, A-10, and B-1 were sprayed in an amount of 1000 g per hectare. As a result, all the compounds had a herbicidal rate of 80% or more with respect to chamomile.
- the compounds shown in Table 5 were sprayed so as to have a spraying amount of 250 g per hectare. As a result, all the compounds showed 80% or more herbicidal activity against velvetleaf.
- the compounds shown in Table 7 were sprayed so as to have a spraying amount of 250 g per hectare. As a result, all the compounds showed 80% or more herbicidal activity against chamomile.
- the compounds shown in Table 9 were sprayed so as to have a spraying amount of 250 g per hectare. As a result, all the compounds showed 80% or more herbicidal activity against embaku.
- the compounds shown in Table 11 were sprayed so as to have a spraying amount of 250 g per hectare. As a result, all the compounds showed 80% or more herbicidal activity against Setaria faberi.
- the compounds shown in Table 13 were sprayed so as to have a spraying amount of 250 g per hectare. As a result, all the compounds showed 80% or more herbicidal activity against crabgrass.
- the compounds shown in Table 15 were sprayed so as to have a spraying amount of 250 g per hectare. As a result, all the compounds showed 80% or more herbicidal activity against Amaranthus retroflexa.
- the compounds of the present invention may be compounds having a high herbicidal effect, including compounds that could not be exemplified. It can be understood.
- New 7-oxa-3,4-diazabicyclo [4.1.] Useful as an active ingredient of herbicides, which has a reliable weed control effect even at a low dose, has less phytotoxicity to crops, and is highly safe for the environment. 0] Hepta-4-en-2-one compounds and herbicides can be provided.
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Abstract
Description
本願は、2019年9月25日に、日本に出願された特願2019-174531号に基づき優先権を主張し、その内容をここに援用する。
本発明の課題は、低薬量でも確実な雑草防除効果を奏し、作物に対する薬害が少なく、且つ環境への安全性が高い、除草剤の有効成分として有用な新規7-オキサ-3,4-ジアザビシクロ[4.1.0]ヘプタ-4-エン-2-オン化合物および除草剤を提供することである。
R1は、置換若しくは無置換のC1~6アルキル基、置換若しくは無置換のC2~6アルケニル基、置換若しくは無置換のC2~6アルキニル基、置換若しくは無置換のC3~6シクロアルキル基、または5~6員環状エーテル基を示し、
R2は、置換若しくは無置換のC1~6アルキル基、置換若しくは無置換のC2~6アルケニル基、または置換若しくは無置換のC2~6アルキニル基を示し、
R3は、水素原子、置換若しくは無置換のC1~6アルキル基、置換若しくは無置換のC2~6アルケニル基、置換若しくは無置換のC2~6アルキニル基、置換若しくは無置換のC1~6アルコキシ基、置換若しくは無置換のC3~6シクロアルキル基、または置換若しくは無置換のフェニル基を示し、且つ
Qは、置換若しくは無置換のフェニル基、または置換若しくは無置換のナフチル基を示す。
Xは、ハロゲノ基、置換若しくは無置換のC1~6アルキル基、置換若しくは無置換のC2~6アルケニル基、置換若しくは無置換のC2~6アルキニル基、水酸基、置換若しくは無置換のC1~6アルコキシ基、置換若しくは無置換のC2~6アルケニルオキシ基、置換若しくは無置換のC2~6アルキニルオキシ基、置換若しくは無置換のC1~6アルキルチオ基、置換若しくは無置換のC1~6アルキルスルフィニル基、置換若しくは無置換のC1~6アルキルスルホニル基、置換若しくは無置換のC3~6シクロアルキル基、置換若しくは無置換のC3~6シクロアルキルオキシ基、置換若しくは無置換のフェニル基、フェノキシ基、置換若しくは無置換の5~6員ヘテロシクリル基、置換若しくは無置換の5~6員ヘテロシクリルオキシ基、置換若しくは無置換のフェニルスルホニル基、R-CO-で表される基、RO-CO-で表される基、R-CONRa-で表される基、RNH-CO-で表される基、R2N-CO-で表される基、RO-CO-NRa-で表される基、RNH-CO-NH-で表される基、R2N-CO-NH-で表される基、RNH-CO-CO-NH-で表される基、R2N-CO-CO-NH-で表される基、R-S(O)2-NH-で表される基、R2N-S(O)2-で表される基、R2S(O)=N-で表される基、R-S(O)(=N-Rb)-で表される基、RO-N=C(Rc)-で表される基、ニトロ基、またはシアノ基を示し;
Rは、それぞれ独立に、置換若しくは無置換のC1~6アルキル基または置換若しくは無置換のC3~6シクロアルキル基を示し、
Raは、それぞれ独立に、水素原子、置換若しくは無置換のC1~6アルキル基、または置換若しくは無置換のC1~6アルコキシ基を示し、
Rbは、置換若しくは無置換のC1~6アルキル基または置換若しくは無置換のフェニル基を示し、
Rcは、水素原子または置換若しくは無置換のC1~6アルキル基を示し;
上記のR2N-CO-で表される基、R2N-CO-NH-で表される基、R2N-CO-CO-NH-で表される基、またはR2N-S(O)2-で表される基において、RとRとが結合してそれらが結合する窒素原子と共に4~6員環を形成してもよく;
上記のR2S(O)=N-で表される基において、RとRとが結合してそれらが結合する硫黄原子と共に5~6員環を形成してもよく;
nは、0~5の整数を示し、nが2以上である場合Xは同一であっても異なっていてもよく、nが2以上ある場合そのうちの2つのXが一緒になって二価の有機基を形成してもよい。
mは、0~3の整数を示し、mが2以上である場合X1は同一であっても異なっていてもよい。
[4]R2におけるC1~6アルキル基上の置換基が、ハロゲノ基、水酸基、C1~6アルコキシ基、C1~6アルコキシC1~6アルコキシ基、C1~6ハロアルコキシ基、C1~6アルキルチオ基、C1~6アルキルスルフィニル基、C1~6アルキルスルホニル基、C3~6シクロアルキル基、フェニル基、5員ヘテロアリール基、C1~6アルキルカルボニル基、ベンゾイル基、C1~6アルコキシカルボニル基、C1~6アルキルカルボキシアミド基、((1,3-ジオキソイソインドリン-2-イル)オキシ基、トリメチルシリル基、シアノ基からなる群、
並びに、C1~6アルキル基置換、ハロゲノ基置換、C1~6ハロアルキル基置換若しくはC1~6ハロアルコキシ基置換のフェニル基;C1~6アルキル基置換、ハロゲノ基置換、C1~6ハロアルキル基置換若しくはC1~6ハロアルコキシ基置換のフェノキシ基;およびC1~6アルキル基置換、ハロゲノ基置換、C1~6ハロアルキル基置換若しくはC1~6ハロアルコキシ基置換の5員ヘテロアリール基からなる群;
より選択される少なくともひとつである前記[1]に記載の化合物またはその塩。
一方、「置換(substituted)」の用語は、母核となる基のいずれかの水素原子が、母核と同一または異なる構造の基(置換基)で置換されていることを意味する。従って、「置換基」は、母核となる基に結合した他の基である。置換基は1つであってもよいし、2つ以上であってもよい。2つ以上の置換基は同じでもよいし、異なってもよい。
「C1~6」などの用語は、母核となる基の炭素原子数が1~6個などであることを表している。この炭素原子数には、置換基の中にある炭素原子の数を含まない。例えば、置換基としてエトキシ基を有するブチル基は、C2アルコキシC4アルキル基に分類する。
メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、s-ブチル基、i-ブチル基、t-ブチル基、n-ペンチル基、n-ヘキシル基などのC1~6アルキル基;
ビニル基、1-プロペニル基、2-プロペニル基(アリル基)、1-ブテニル基、2-ブテニル基、3-ブテニル基、1-メチル-2-プロペニル基、2-メチル-2-プロペニル基などのC2~6アルケニル基;
エチニル基、1-プロピニル基、2-プロピニル基、1-ブチニル基、2-ブチニル基、3-ブチニル基、1-メチル-2-プロピニル基などのC2~6アルキニル基;
フェニル基、ナフチル基;
ベンジル基、フェネチル基などのフェニルC1~6アルキル基;
3~6員ヘテロシクリル基;
3~6員へテロシクリルC1~6アルキル基;
メトキシ基、エトキシ基、n-プロポキシ基、i-プロポキシ基、n-ブトキシ基、s-ブトキシ基、i-ブトキシ基、t-ブトキシ基などのC1~6アルコキシ基;
ビニルオキシ基、アリルオキシ基、プロペニルオキシ基、ブテニルオキシ基などのC2~6アルケニルオキシ基;
エチニルオキシ基、プロパルギルオキシ基などのC2~6アルキニルオキシ基;
フェノキシ基、ナフトキシ基;
ベンジルオキシ基、フェネチルオキシ基;
チアゾリルオキシ基、ピリジルオキシ基などの5~6員ヘテロアリールオキシ基;
チアゾリルメチルオキシ基、ピリジルメチルオキシ基などの5~6員ヘテロアリールC1~6アルキルオキシ基;
アセチル基、プロピオニル基などのC1~6アルキルカルボニル基;
ホルミルオキシ基;
アセチルオキシ基、プロピオニルオキシ基などのC1~6アルキルカルボニルオキシ基;
ベンゾイル基;
メトキシカルボニル基、エトキシカルボニル基、n-プロポキシカルボニル基、i-プロポキシカルボニル基、n-ブトキシカルボニル基、t-ブトキシカルボニル基などのC1~6アルコキシカルボニル基;
メトキシカルボニルオキシ基、エトキシカルボニルオキシ基、n-プロポキシカルボニルオキシ基、i-プロポキシカルボニルオキシ基、n-ブトキシカルボニルオキシ基、t-ブトキシカルボニルオキシ基などのC1~6アルコキシカルボニルオキシ基;
カルボキシル基;
クロロメチル基、クロロエチル基、ジフルオロメチル基、トリフルオロメチル基、2,2,2-トリフルオロエチル基、1,2-ジクロロ-n-プロピル基、1-フルオロ-n-ブチル基などのC1~6ハロアルキル基;
2-クロロ-1-プロペニル基、2-フルオロ-1-ブテニル基などのC2~6ハロアルケニル基;
4,4-ジクロロ-1-ブチニル基、4-フルオロ-1-ペンチニル基、5-ブロモ-2-ペンチニル基などのC2~6ハロアルキニル基;
ジフルオロメトキシ基、トリフルオロメトキシ基、2,2,2-トリフルオロエトキシ基、2,3-ジクロロブトキシ基などのC1~6ハロアルコキシ基;
2-クロロプロペニルオキシ基、3-ブロモブテニルオキシ基などのC2~6ハロアルケニルオキシ基;
クロロアセチル基、トリフルオロアセチル基、トリクロロアセチル基などのC1~6ハロアルキルカルボニル基;
メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基などのC1~6アルキル置換アミノ基;
アニリノ基、ナフチルアミノ基;
ベンジルアミノ基、フェネチルアミノ基などのフェニルC1~6アルキルアミノ基;
ホルミルアミノ基;
アセチルアミノ基、プロパノイルアミノ基、ブチリルアミノ基、i-プロピルカルボニルアミノ基などのC1~6アルキルカルボニルアミノ基;
メトキシカルボニルアミノ基、エトキシカルボニルアミノ基、n-プロポキシカルボニルアミノ基、i-プロポキシカルボニルアミノ基などのC1~6アルコキシカルボニルアミノ基;
アミノカルボニル基、ジメチルアミノカルボニル基、フェニルアミノカルボニル基、N-フェニル-N-メチルアミノカルボニル基などの無置換若しくは置換基を有するアミノカルボニル基;
イミノメチル基、(1-イミノ)エチル基、(1-イミノ)-n-プロピル基などのイミノC1~6アルキル基;
N-ヒドロキシ-イミノメチル基、(1-(N-ヒドロキシ)-イミノ)エチル基、(1-(N-ヒドロキシ)-イミノ)プロピル基、N-メトキシ-イミノメチル基、(1-(N-メトキシ)-イミノ)エチル基などの置換若しくは無置換のN-ヒドロキシイミノC1~6アルキル基;
アミノカルボニルオキシ基;
エチルアミノカルボニルオキシ基、ジメチルアミノカルボニルオキシ基などのC1~6アルキル置換アミノカルボニルオキシ基;
メチルチオ基、エチルチオ基、n-プロピルチオ基、i-プロピルチオ基、n-ブチルチオ基、i-ブチルチオ基、s-ブチルチオ基、t-ブチルチオ基などのC1~6アルキルチオ基;
トリフルオロメチルチオ基、2,2,2-トリフルオロエチルチオ基などのC1~6ハロアルキルチオ基;
フェニルチオ基;
チアゾリルチオ基、ピリジルチオ基などの5~6員ヘテロアリールチオ基;
トリフルオロメチルスルフィニル基、2,2,2-トリフルオロエチルスルフィニル基などのC1~6ハロアルキルスルフィニル基;
フェニルスルフィニル基;
チアゾリルスルフィニル基、ピリジルスルフィニル基などの5~6員ヘテロアリールスルフィニル基;
メチルスルホニル基、エチルスルホニル基、t-ブチルスルホニル基などのC1~6アルキルスルホニル基;
トリフルオロメチルスルホニル基、2,2,2-トリフルオロエチルスルホニル基などのC1~6ハロアルキルスルホニル基;
フェニルスルホニル基;
チアゾリルスルホニル基、ピリジルスルホニル基などの5~6員ヘテロアリールスルホニル基;
メチルスルホニルオキシ基、エチルスルホニルオキシ基、t-ブチルスルホニルオキシ基などのC1~6アルキルスルホニルオキシ基;
トリフルオロメチルスルホニルオキシ基、2,2,2-トリフルオロエチルスルホニルオキシ基などのC1~6ハロアルキルスルホニルオキシ基;
トリフェニルシリル基;
ペンタフルオロスルファニル基;
シアノ基;ニトロ基;
5~6員不飽和ヘテロシクリル基としては、ピロリニル基、ジヒドロフラニル基、イミダゾリニル基、ピラゾリニル基、オキサゾリニル基、イソオキサゾリニル基、チアゾリニル基、イソチアゾリニル基、ジヒドロピラニル基、ジヒドロオキサジニル基などを挙げることができる。
6員ヘテロアリール基としては、ピリジル基、ピラジニル基、ピリミジニル基、ピリダジニル基、トリアジニル基などを挙げることができる。
R1は、置換若しくは無置換のC1~6アルキル基、置換若しくは無置換のC2~6アルケニル基、置換若しくは無置換のC2~6アルキニル基、置換若しくは無置換のC3~6シクロアルキル基、または5~6員環状エーテル基を示す。
R1における「C1~6アルキル基」上の置換基は、ハロゲノ基、C1~6アルコキシ基、C1~6ハロアルコキシ基、C1~6アルキルチオ基、C1~6アルキルスルフィニル基、C1~6アルキルスルホニル基、またはC3~6シクロアルキル基が好ましい。
R2は、置換若しくは無置換のC1~6アルキル基、置換若しくは無置換のC2~6アルケニル基、または置換若しくは無置換のC2~6アルキニル基を示す。
R2における「無置換のC1~6アルキル基」、「置換若しくは無置換のC2~6アルケニル基」、または「置換若しくは無置換のC2~6アルキニル基」の具体例としては、R1において例示したものと同じものを挙げることができる。
5員ヘテロアリール基としては、ピロリル基、フリル基、チエニル基、イミダゾリル基、ピラゾリル基、オキサゾリル基、イソオキサゾリル基、チアゾリル基、イソチアゾリル基、トリアゾリル基、オキサジアゾリル基、チアジアゾリル基、テトラゾリル基などを挙げることができる。
R3は、水素原子、置換若しくは無置換のC1~6アルキル基、置換若しくは無置換のC2~6アルケニル基、置換若しくは無置換のC2~6アルキニル基、置換若しくは無置換のC1~6アルコキシ基、置換若しくは無置換のC3~6シクロアルキル基、または置換若しくは無置換のフェニル基を示す。
R3におけるこれらの基の具体例としては、R1において例示したものと同じものを挙げることができる。
R3における「C1~6アルキル基」、「C2~6アルケニル基」、または「C2~6アルキニル基」上の置換基は、ハロゲノ基が好ましい。「C3~6シクロアルキル基」上の置換基は、ハロゲノ基またはC1~6アルキル基が好ましい。
Qは、置換若しくは無置換のフェニル基、または置換若しくは無置換のナフチル基を示す。
ここで、Rは、それぞれ独立に、置換若しくは無置換のC1~6アルキル基または置換若しくは無置換のC3~6シクロアルキル基を示す。
Raは、それぞれ独立に、水素原子、置換若しくは無置換のC1~6アルキル基、または置換若しくは無置換のC1~6アルコキシ基を示す。
Rbは、置換若しくは無置換のC1~6アルキル基または置換若しくは無置換のフェニル基を示す。
Rcは、水素原子または置換若しくは無置換のC1~6アルキル基を示す。
また、上記のR2N-CO-で表される基、R2N-CO-NH-で表される基、R2N-CO-CO-NH-で表される基、またはR2N-S(O)2-で表される基において、RとRとが結合してそれらが結合する窒素原子と共に4~6員環を形成してもよい。
また、上記のR2S(O)=N-で表される基において、RとRとが結合してそれらが結合する硫黄原子と共に5~6員環を形成してもよい。
Qにおける「フェニル基」、または「ナフチル基」の置換基(X)は2以上ある場合、そのうちの2つが一緒になって二価の有機基を形成してもよい。
Xは、ハロゲノ基、置換若しくは無置換のC1~6アルキル基、置換若しくは無置換のC2~6アルケニル基、置換若しくは無置換のC2~6アルキニル基、水酸基、置換若しくは無置換のC1~6アルコキシ基、置換若しくは無置換のC2~6アルケニルオキシ基、置換若しくは無置換のC2~6アルキニルオキシ基、置換若しくは無置換のC1~6アルキルチオ基、置換若しくは無置換のC1~6アルキルスルフィニル基、置換若しくは無置換のC1~6アルキルスルホニル基、置換若しくは無置換のC3~6シクロアルキル基、置換若しくは無置換のC3~6シクロアルキルオキシ基、置換若しくは無置換のフェニル基、フェノキシ基、置換若しくは無置換の5~6員ヘテロシクリル基、置換若しくは無置換の5~6員ヘテロシクリルオキシ基、置換若しくは無置換のフェニルスルホニル基、R-CO-で表される基、RO-CO-で表される基、R-CONRa-で表される基、RNH-CO-で表される基、R2N-CO-で表される基、RO-CO-NRa-で表される基、RNH-CO-NH-で表される基、R2N-CO-NH-で表される基、RNH-CO-CO-NH-で表される基、R2N-CO-CO-NH-で表される基、R-S(O)2-NH-で表される基、R2N-S(O)2-で表される基、R2S(O)=N-で表される基、R-S(O)(=N-Rb)-で表される基、RO-N=C(Rc)-で表される基、ニトロ基、またはシアノ基を示す。
Xにおける「C3~6シクロアルキルオキシ基」としては、シクロプロピルオキシ基、シクロブチルオキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基、シクロヘプチルオキシ基などを挙げることができる。
5~6員不飽和ヘテロシクリル基としては、ピロリニル基、ジヒドロフラニル基、イミダゾリニル基、ピラゾリニル基、オキサゾリニル基、イソオキサゾリニル基、チアゾリニル基、イソチアゾリニル基、ジヒドロピラニル基、ジヒドロオキサジニル基などを挙げることができる。
5員ヘテロアリール基としては、ピロリル基、フリル基、チエニル基、イミダゾリル基、ピラゾリル基、オキサゾリル基、イソオキサゾリル基、チアゾリル基、イソチアゾリル基、トリアゾリル基、オキサジアゾリル基、チアジアゾリル基、テトラゾリル基などを挙げることができる。
6員ヘテロアリール基としては、ピリジル基、ピラジニル基、ピリミジニル基、ピリダジニル基、トリアジニル基などを挙げることができる。
Xにおける「R-CO-で表される基」としては、アセチル基、シクロプロピルカルボニル基などを挙げることができる。
Xにおける「RO-CO-で表される基」としては、メトキシカルボニル基などを挙げることができる。
Xにおける「RNH-CO-で表される基」としては、メチルアミノカルボニル基などを挙げることができる。
ここで、RとRとが結合してそれらが結合する窒素原子と共に4~6員環を形成してもよく、形成する4~6員環としては、アゼチジン環、ピロリジン環、ピペリジン基、ピペラジン環、モルホリン環などを挙げることできる。
4~6員環を形成後の「R2N-CO-で表される基」としては、アゼチジン-1-カルボニル基、ピロリジン-1-カルボニル基、モルホリン-4-カルボニル基などを挙げることができる。
Xにおける「R2N-CO-NH-で表される基」としては、ジメチルアミノカルボキシアミドなどを挙げることができる。
ここで、RとRとが結合してそれらが結合する窒素原子と共に4~6員環を形成してもよく、形成する4~6員環の具体例としては、上記の「R2N-CO-で表される基」において例示したものと同じものを挙げることができる。
4~6員環を形成後の「R2N-CO-NH-で表される基」としては、アゼチジン-1-カルボキシアミド基、ピロリジン-1-カルボキシアミド基、モルホリン-4-カルボキシアミドなどを挙げることができる。
Xにおける「R2N-CO-CO-NH-で表される基」としては、ジメチルアミノカルボニルカルボキシアミドなどを挙げることができる。
ここで、RとRとが結合してそれらが結合する窒素原子と共に4~6員環を形成してもよく、形成する4~6員環の具体例としては、上記の「R2N-CO-で表される基」において例示したものと同じものを挙げることができる。
4~6員環を形成後の「R2N-CO-NH-で表される基」としては、アゼチジン-1-カルボニルカルボキシアミド基、ピロリジン-1-カルボニルカルボキシアミド基、モルホリン-4-カルボニルカルボキシアミドなどを挙げることができる。
Xにおける「R2N-S(O)2-で表される基」としては、メチルスルホンアミドなどを挙げることができる。
ここで、RとRとが結合してそれらが結合する窒素原子と共に4~6員環を形成してもよく、形成する4~6員環の具体例としては、上記の「R2N-CO-で表される基」において例示したものと同じものを挙げることができる。
4~6員環を形成後の「R2N-S(O)2-で表される基」としては、アゼチジン-1-スルホニル基、ピロリジン-1-スルホニル基、モルホリノスルホニル基などを挙げることができる。
ここで、RとRとが結合してそれらが結合する硫黄原子と共に5~6員環を形成してもよく、形成する5~6員環としては、テトラヒドロチオフェン環、テトラヒドロ-2H-チオピラン環などを挙げることできる。
5~6員環を形成後の「R2S(O)=N-で表される基」としては、(テトラヒドロ-1-オキシド-2H-チオピラン-1-イリデン)アミノ基などを挙げることができる。
さらに、2つのXが一緒になって形成しうる二価の有機基は、置換若しくは無置換の不飽和の炭素原子数が2~3個の二価炭化水素基;またはO、N、およびSからなる群より選択される1または2以上のヘテロ原子を含有する基と、置換若しくは無置換の不飽和の炭素原子数が2~3個の二価炭化水素基とが結合して成る二価の基である。
不飽和の炭素原子数が2~3個の二価炭化水素基としては、ビニレン基(-CH=CH-)、プロペニレン基(-CH=CH-CH2-、-CH2-CH=CH-)などの「C2~3アルケニレン基」を挙げることができる。
「飽和若しくは不飽和の二価炭化水素基」上の置換基は、ハロゲン基、C1~6アルキル基、またはC1~6ハロアルキル基が好ましい。
酸素原子(O)を含有する基と飽和二価炭化水素基とが結合して成る2価の基としては、オキシジメチレン基(-O-CH2CH2-)などの「オキシC2~3アルキレン基」、ジメチレンオキシ基(-CH2CH2-O-)などの「C2~3アルキレンオキシ基」、オキシメチレンオキシ基(-O-CH2-O-)などの「オキシC1~2アルキレンオキシ基」、メチレンオキシメチレン基(-CH2-O-CH2-)、メチレンオキシジメチレン基(-CH2-O-CH2CH2-)、ジメチレンオキシメチレン基(-CH2CH2-O-CH2-)などの「C1~2アルキレンオキシC1~C2アルキレン基」などを挙げることができる。
窒素原子(N)を含有する基と飽和二価炭化水素基とが結合して成る2価の基としては、イミノジメチレン基(-NH-CH2CH2-)などの「イミノC2~3アルキレン基」、ジメチレンイミノ基(-CH2CH2-NH-)などの「C2~3アルキレンイミノ基」、イミノメチレンイミノ基(-NH-CH2-NH-)などの「イミノC1~2アルキレンイミノ基」、メチレンイミノメチレン基(-CH2-NH-CH2-)、メチレンイミノジメチレン基(-CH2-NH-CH2CH2-)、ジメチレンイミノメチレン基(-CH2CH2-NH-CH2-)などの「C1~2アルキレンイミノC1~C2アルキレン基」などを挙げることができる。
硫黄原子(S)を含有する基と飽和二価炭化水素基とが結合して成る2価の基としては、チオジメチレン基(-S-CH2CH2-)、チオトリメチレン基(-S-CH2CH2CH2-)などの「チオC2~4アルキレン基」、ジメチレンチオ基(-CH2CH2-S-)などの「C2~4アルキレンチオ基」、「スルフィニル-C2~4アルキレン基」、「スルホニル-C2~4アルキレン基」、「C2~4アルキレン-スルフィニル基」、「C2~4アルキレン-スルホニル基」などを挙げることができる。
X1は、ハロゲノ基、置換若しくは無置換のC1~6アルキル基、置換若しくは無置換のC2~6アルケニル基、置換若しくは無置換のC2~6アルキニル基、置換若しくは無置換のC1~6アルコキシ基、置換若しくは無置換のC1~6アルキルチオ基、置換若しくは無置換のC1~6アルキルスルフィニル基、置換若しくは無置換のC1~6アルキルスルホニル基、置換若しくは無置換のC3~6シクロアルキル基、置換若しくは無置換のフェニル基、置換若しくは無置換の5~6員ヘテロシクリル基、ニトロ基、またはシアノ基を示す。
mは、0~3の整数を示す。mが2以上である場合、X1は同一であっても異なっていてもよい。
X1におけるこれらの基の具体例としては、Xにおいて例示したものと同じものを挙げることができる。
化合物(I)の塩としては、リチウム、ナトリウム、カリウム等のアルカリ金属の塩;カルシウム、マグネシウム等のアルカリ土類金属の塩;鉄、銅等の遷移金属の塩;アンモニウム塩;トリエチルアミン、トリブチルアミン、ピリジン、ヒドラジン等の有機塩基の塩;等を挙げることができる。
例えば、化合物(I)は、以下の反応スキーム1に示されるように、式(2)の化合物から調製され得る。式(2)中の記号は式(I)中のそれらと同様の意味を示す。
式(2)の化合物は、以下の反応スキーム2に示されるように、式(3)の化合物から調製され得る。式(3)中の記号は式(I)中のそれらと同様の意味を示す。Rxは、低級アルキル基、例えばメチル基を示す。以下Rxは、同じ意味を示す。
式(3)の化合物は、以下の反応スキーム3に示すように、式(4)の化合物と式(5)の化合物を縮合させることで調製され得る。
式(4)中の記号は式(I)中のそれらと同様の意味を示す。Ryは、低級アルキル基、例えばメチル基、エチル基などを示す。また、Ry同士が結合して、1,3,2-ジオキサボロラン環を形成してもよい。式(5)中のQは式(I)中のQと同じ意味を示す。Xbはハロゲノ基を示す。
金属触媒およびリガンドは、予め形成された錯体( 例えば、ビス(トリフェニルホスフィン)パラジウムジクロリドまたは[1,1-ビス(ジフェニルホスフィノ)フェロセン]パラジウムジクロリドジクロロメタン付加物などのパラジウム/ホスフィン錯体) として加えられ得る。
式(5)の化合物中のQは、置換若しくは無置換のフェニル基、または置換若しくは無置換のナフチル基を示すが、フェニル基、ナフチル基上の置換基は反応後も適宜変換してもよい。
式(4)の化合物は、以下の反応スキーム4に示すように、式(6)の化合物から調製され得る。式(6)中の記号は式(I)中のそれらと同様の意味を示す。
金属触媒およびリガンドは、予め形成された錯体( 例えば、ビス(トリフェニルホスフィン)パラジウムジクロリドまたは[1,1-ビス(ジフェニルホスフィノ)フェロセン]パラジウムジクロリドジクロロメタン付加物などのパラジウム/ホスフィン錯体) として加えられ得る。
式(6)の化合物は、以下の反応スキーム5に示すように、式(7)の化合物から調製され得る。式(7)中の記号は式(I)中のそれらと同様の意味を示す。
式(7)の化合物は、公知の方法により調製され得る。
式(3)の化合物は、以下の反応スキーム3Aに示すように、式(6)の化合物と式(8)の化合物を縮合させることで調製され得る。
式(8)中のQは式(I)中のQと同じ意味を示す。Ryは、低級アルキル基、例えばメチル基、エチル基などを示す。また、Ry同士が結合して、1,3,2-ジオキサボロラン環を形成してもよい。
金属触媒およびリガンドは、予め形成された錯体( 例えば、ビス(トリフェニルホスフィン)パラジウムジクロリドまたは[1,1-ビス(ジフェニルホスフィノ)フェロセン]パラジウムジクロリドジクロロメタン付加物などのパラジウム/ホスフィン錯体) として加えられ得る。
式(8)の化合物中のQは、置換若しくは無置換のフェニル基、または置換若しくは無置換のナフチル基を示すが、フェニル基、ナフチル基上の置換基は反応後も適宜変換してもよい。
本発明化合物は、各種畑雑草に有効で、トウモロコシ、コムギ等の作物に選択性を示すことがある。
また、本発明化合物は、作物、観賞用植物、果樹等の有用植物に対し、生育抑制作用等の植物成長調節作用を示すことがある。
また、本発明化合物は、水田雑草に対し、優れた殺草効力を有し、イネに選択性を示すことがある。
すなわち、本発明の態様のひとつは、化合物(I)およびその塩からなる群から選ばれる少なくともひとつを有効成分として含有する除草剤である。
本発明の除草剤は、畑作条件で、土壌処理、茎葉処理のいずれの方法でも高い除草活性を示す。
また、本発明の除草剤は、水田雑草のノビエ、タマガヤツリ、オモダカ、ホタルイ等に対し、優れた殺草効力を有し、イネに選択性を示すことがある。
更に本発明の除草剤は、果樹園、芝生、線路端、空き地等の雑草の防除にも適用することができる。
作物は、果樹、ヤシの木、ココヤシの木または他の木の実などの木も含み得る。ブドウ、果実の低木、果実植物および野菜などのつる植物も含まれる。
(A)単子葉類の雑草
(1)カヤツリグサ科(Cyperaceae)の雑草
カヤツリグサ属(Cyperus)の雑草、例えばショクヨウガヤツリ(Cyperus esculentus)、コゴメガヤツリ(Cyperus iria)、カヤツリグサ(Cyperus microiria)、ハマスゲ(Cyperus rotundus)。
(2)イネ科(Poaceae)の雑草
スズメノテッポウ属(Alopecurus)の雑草、例えばスズメノテッポウ(Alopecurus aequalis)、ブラックグラス(ノスズメノテッポウ(Alopecurus myosuroides));
セイヨウヌカボ属(Apera)の雑草、例えばセイヨウヌカボ(Apera spica-venti);
カラスムギ属(Avena)の雑草、例えばエンバク(Avena sativa);
スズメノチャヒキ属(Bromus)の雑草、例えばスズメノチャヒキ(Bromus japonicus)、アレチノチャヒキ(Bromus sterilis);
メヒシバ属(Digitaria)の雑草、例えばメヒシバ(Digitaria ciliaris)、オニメヒシバ(Digitaria sanguinalis);
ヒエ属(Echinochloa)の雑草、例えばイヌビエ(Echinochloa crus-galli);
オヒシバ属(Eleusine)の雑草、例えばオヒシバ(Eleusine indica);
ドクムギ属(Lolium)の雑草、例えばイタリアンライグラス(ネズミムギ(Lolium multiflorum Lam.));
キビ属(Panicum)の雑草、例えばオオクサキビ(Panicum dichotomiflorum);
イチゴツナギ属(Poa)の雑草、例えばスズメノカタビラ(Poa annua);
エノコログサ属(Setaria)の雑草、例えばアキノエノコログサ(Setaria faberi)、キンエノコロ(Setaria pumila)、エノコログサ(Setaria viridis);
モロコシ属(Sorghum)の雑草、例えばモロコシ(Sorghum bicolor);
ニクキビモドキ属(Urochloa)の雑草、例えばメリケンニクキビ(Urochloa platyphylla)。
(1)ヒユ科(Amaranthaceae)の雑草
ヒユ属(Amaranthus blitum)の雑草、例えばイヌビユ(Amaranthus blitum)、オオホナガアオゲイトウ(Amaranthus palmeri)、アオゲイトウ(Amaranthus retroflexus)、ホソバイヌビユ(Amaranthus rudis);
アカザ属(Chenopodium)の雑草、例えばシロザ(Chenopodium album);
バッシア属(Bassia)の雑草、例えばホウキギ(Bassia scoparia)。
(2)キク科(Asteraceae)の雑草
ブタクサ属(Ambrosia)の雑草、例えばブタクサ(Ambrosia artemisiifolia)、オオブタクサ(Ambrosia trifida);
イズハハコ属(Conyza)の雑草、例えばヒメムカシヨモギ(Conyza canadensis)、オオアレチノギク(Conyza sumatrensis);
ムカシヨモギ属(Erigeron)の雑草、例えばヒメジョオン(Erigeron annuus);
シカギク属(Matricaria)の雑草、例えばイヌカミツレ(Matricaria inodora)、カミツレ(Matricaria recutita);
オナモミ属(Xanthium)の雑草、例えばオオオナモミ(Xanthium occidentale)。
(3)ナデシコ科(Caryophyllaceae)の雑草
ツメクサ属(Sagina)の雑草、例えば ツメクサ(Sagina japonica);
ハコベ属(Stellaria)の雑草、例えばコハコベ(Stellaria media)。
(4)ヒルガオ科(Convolvulaceae)の雑草
ヒルガオ属(Calystegia)の雑草、例えばヒルガオ(Calystegia japonica);
サツマイモ属(Ipomoea)の雑草、例えばマルバルコウ(Ipomoea coccinea)、アメリカアサガオ(Ipomoea hederacea)、マメアサガオ(Ipomoea lacunosa)、ホシアサガオ(Ipomoea triloba)。
(5)シソ科(Lamiaceae)の雑草
オドリコソウ属(Lamium)の雑草、例えばオドリコソウ(Lamium album var. barbatum)、ホトケノザ(Lamium amplexicaule)、ヒメオドリコソウ(Lamium purpureum)。
(6)アオイ科(Malvaceae)の雑草
イチビ属(Abutilon)の雑草、例えばイチビ(Abutilon theophrasti);
キンゴジカ属(Sida)の雑草、例えばアメリカキンゴジカ(Sida spinosa)。
(7)オオバコ科(Plantaginaceae)の雑草
クワガタソウ属(Veronica)の雑草、例えばオオイヌノフグリ(Veronica persica)。
(8)タデ科(Polygonaceae)の雑草
ソバカズラ属(Fallopia)の雑草、例えばソバカズラ(Fallopia convolvulus)。
イヌタデ属(Persicaria)の雑草、例えばオオイヌタデ(Persicaria lapathifolia)、イヌタデ(Persicaria longiseta)。
(9)アカネ科(Rubiaceae)の雑草
ヤエムグラ属(Galium)の雑草、例えばヤエムグラ(Galium spurium var. echinospermon)。
(A)単子葉類の雑草
(1)オモダカ科(Alismataceae)の雑草
オモダカ属(Sagittaria)の雑草、例えばウリカワ(Sagittaria pygmaea Miq.)、オモダカ(Sagittaria trifolia)。
(2)カヤツリグサ科(Cyperaceae)の雑草の雑草
カヤツリグサ属(Cyperus)の雑草、例えばミズガヤツリ(Cyperus serotinus)、タマガヤツリ(Cyperus difforis);
ハリイ属(Eleocharis)の雑草、例えばクログワイ(Eleocharis kuroguwai Ohwi);
ホソガタホタルイ属(Schoenoplectiella)の雑草、例えばホタルイ(Schoenoplectiella hotarui)、イヌホタルイ(Schoenoplectiella juncoides Roxb.)。
アブラガヤ属(Scirpus)の雑草、例えばコウキヤガラ(Scirpus martimus)、シズイ(Scirpus nipponicus)。
(3)イネ科(Poaceae)の雑草
ヒエ属(Echinochloa)の雑草(いわゆるノビエ)の雑草、例えばタイヌビエ(Echinochloa oryzoides)、イヌビエ(Echinochloa crus-galli);
サヤヌカグサ属(Leersia)の雑草、例えばアシカキ(Leersia japonica);
スズメノヒエ属(Paspalum)の雑草、例えばキシュウスズメノヒエ(Paspalum distichum)。
(4)ミズアオイ科(Pontederiaceae)の雑草
ミズアオイ属(Monochoria)の雑草、例えばミズアオイ(Monochoria korsakowii)、
コナギ(Monochoria vaginalis var. plantaginea)。
(1)セリ科(Apiaceae)の雑草
セリ属(Oenanthe)の雑草、例えばセリ(Oenanthe javanica)。
(2)ミゾハコベ科(Elatinaceae)の雑草
ミゾハコベ属(Elatine)の雑草、例えばミゾハコベ(Elatine triandra)。
(3)アゼナ科(Linderniaceae)の雑草
アゼナ属(Lindernia)の雑草、例えば アメリカアゼナ(Lindernia dubia subsp. major)、タケトアゼナ(Lindernia dubia subsp. dubia)、アゼナ(Lindernia procumbens)。
(4)ミソハギ科(Lythraceae)の雑草
キカシグサ属(Rotala)の雑草、例えばキカシグサ(Rotala indica var. uliginosa)。
すなわち、本発明の態様のひとつは、農芸化学的に許容できる固体担体、および/または液体担体を含む、除草剤である。
固体の剤形を目的とする場合は、大豆粉、小麦粉等の植物性粉末、珪藻土、燐灰石、石こう、タルク、ベントナイト、パイロフィライト、クレイ等の鉱物性微粉末、安息香酸ソーダ、尿素、芒硝等の有機及び無機化合物などの固体担体を用いることができる。
液体の剤形を目的とする場合は、ケロシン、キシレン及びソルベントナフサ等の石油留分、シクロヘキサン、シクロヘキサノン、ジメチルホルムアミド、ジメチルスルホキシド、アルコール、アセトン、トリクロルエチレン、メチルイソブチルケトン、鉱物油、植物油、水などの液体担体を用いることができる。
すなわち、本発明の態様のひとつは、1つ以上のさらなる除草活性成分を含む除草剤である。
また、本発明の態様のひとつは、1つ以上のさらなる薬害軽減剤を含む除草剤である。
(a) クロジナホッププロパルギル(clodinafop-propargyl)、シハロホップブチル(cyhalofop-butyl)、ジクロホップメチル(diclofop-methyl)、フェノキサプロップ-P-エチル(fenoxaprop-P-ethyl)、フルアジホップP(fluazifop-P)、フルアジホップ-P-ブチル(fluazifop-P-butyl)、ハロキシホップメチル(haloxyfop-methyl)、ピリフェノップナトリウム(pyriphenop-sodium)、プロパキザホップ(propaquizafop)、キザロホップ-P-エチル(quizalofop-P-ethyl)、メタミホップ(metamifop)等のアリ-ルオキシフェノキシプロピオン酸エステル系;アロキシジム(alloxydim)、ブトロキシジム(butroxydim)、クレトジム(clethodim)、シクロキシジム(cycloxydim)、プロホキシジム(profoxydim)、セトキシジム(sethoxydim)、テプラロキシジム(tepraloxydim)、トラルコキシジム(tralkoxydim)等のシクロヘキサンジオン系;ピノキサデン(pinoxaden)等のフェニルピラゾリン系;その他の植物のアセチルCoAカルボキシラーゼを阻害することで除草効力を示すとされているもの。
(h) グルホシネート(glufosinate)、グルホシネートアンモニウム(glufosinate-ammonium)、ビアラホス(ビラナホス(bilanafos))等のホスフィン酸系等のグルタミン合成酵素阻害
その他の植物のアミノ酸生合成を阻害することで除草効力を示すとされているもの。
本発明の除草剤に関する製剤例を若干示すが、本発明化合物(有効成分)、添加物及び添加割合は、本実施例にのみ限定されることなく、広い範囲で変更可能である。製剤実施例中の部は重量部を示す。
本発明化合物 20部
ホワイトカーボン 20部
ケイソウ土 52部
アルキル硫酸ソーダ 8部
以上を均一に混合、微細に粉砕して、有効成分20%の水和剤を得る。
本発明化合物 20部
キシレン 55部
ジメチルホルムアミド 15部
ポリオキシエチレンフェニルエーテル 10部
以上を混合、溶解して有効成分20%の乳剤を得る。
本発明化合物 5部
タルク 40部
クレイ 38部
ベントナイト 10部
アルキル硫酸ソーダ 7部
以上を均一に混合して微細に粉砕後、直径0.5~1.0mmの粒状に造粒して有効成分5%の粒剤を得る。
1-メトキシ-3-メチル-6-(2-(メチルスルホニル)-4-(トリフルオロメチル)フェニル)-7-オキサ-3,4-ジアザビシクロ[4.1.0]ヘプタ-4-エン-2-オン〔1-methoxy-3-methyl-6-(2-(methylsulfonyl)-4-(trifluoromethyl)phenyl)-7-oxa-3,4-diazabicyclo[4.1.0]hept-4-en-2-one〕(化合物番号A-1)の製造
反応溶液を減圧濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーで精製することによって目的化合物0.05gを得た。
1-メトキシ-3-メチル-6-(1,1-ジオキサド-8-(トリフルオロメチル)チオクロマン-5-イル)-7-オキサ-3,4-ジアザビシクロ[4.1.0]ヘプタ-4-エン-2-オン〔1-methoxy-3-methyl-6-(1,1-dioxido-8-(trifluoromethyl)thiochroman-5-yl)-7-oxa-3,4-diazabicyclo[4.1.0]hept-4-en-2-one〕の合成:(化合物番号B-1)
反応溶液を減圧濃縮し、得られた残渣をシリカゲルカラムクロマトグラフィーで精製することによって目的物0.23gを得た。
5-(1,1-ジオキサド-8-(トリフルオロメチル)チオクロマン-5-イル)-4-ヒドロキシ-2-メチルピリダジン-3(2H)-オンの合成
反応溶液を塩酸に注ぎ、次いで酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥させ、ろ過した。ろ液を減圧濃縮することで目的物0.31gを得た。
5-(1,1-ジオキサド-8-(トリフルオロメチル)チオクロマン-5-イル)-4-メトキシ-2-メチルピリダジン-3(2H)-オンの合成
得られた液をろ過した。ろ液を減圧濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーで精製することによって目的化合物0.22gを得た。
得られた化合物のNMRデータを示す。
1H-NMR(400 MHz, CDCl3): δ 2.40-2.48(m, 2H), 2.72-2.80(m, 1H), 2.86-2.95(m, 1H), 3.40(t, 2H), 3.83(s, 3H), 4.12(s, 3H), 7.41(d, 1H), 7.44(s, 1H), 7.84(d, 1H).
5-ブロモ-8-(トリフルオロメチル)チオクロマン 1,1-ジオキシドの合成
(工程1)
3-(6-ブロモ-2-トリフルオロ-3-(トリフルオロメチル)フェニル)プロピオン酸の合成
得られた液に塩酸を加え、析出固形物を濾別した。得られた固形物を乾燥させることによって目的化合物53.8gを得た。
3-(6-ブロモ-2-フルオロ-3-(トリフルオロメチル)フェニル)プロパン-1-オールの合成
得られた液を塩酸に注ぎ、次いで酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥させ、ろ過した。ろ液を減圧濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーで精製することによって目的化合物28.9gを得た。
1-ブロモ-2-(3-クロロプロピル)-3-フルオロ-4-(トリフルオロメチル)ベンゼンの合成
得られた液を減圧濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーで精製することによって目的化合物16.4gを得た。
5-ブロモ-8-(トリフルオロメチル)チオクロマンの合成
得られた液を水に注ぎ、次いで酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥させ、ろ過した。ろ液を減圧濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーで精製することによって目的化合物6.8gを得た。
5-ブロモ-8-(トリフルオロメチル)チオクロマン 1,1-ジオキシドの合成
得られた液をろ過した。ろ液を減圧濃縮した。これに水を注ぎ、次いで酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥させ、ろ過した。ろ液を減圧濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーで精製することによって目的化合物2.0gを得た。
5-(1,1-ジオキサド-8-(トリフルオロメチル)チオクロマン-5-イル)-4-メトキシ-2-メチルピリダジン-3(2H)-オンの合成
(工程1)
5-(8-(トリフルオロメチル)チオクロマン-5-イル)-4-メトキシ-2-メチルピリダジン-3(2H)-オンの合成
これに水を注ぎ、次いで酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥させ、ろ過した。ろ液を減圧濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーで精製することによって目的化合物16.8gを得た。
5-(1,1-ジオキサド-8-(トリフルオロメチル)チオクロマン-5-イル)-4-メトキシ-2-メチルピリダジン-3(2H)-オンの合成
これに、水、チオ酢酸ナトリウム水溶液、飽和重曹水を順次加え、減圧濃縮した。この濃縮液を酢酸エチルで抽出した。得られた有機層を飽和重曹水、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥させ、ろ過した。ろ液を減圧濃縮した。得られた結晶を乾燥させることによって目的物1.6gを得た。
8-(トリフルオロメチル)チオクロマン-5-イル)ボロン酸の合成
これに塩酸を注ぎ、次いで酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥させ、ろ過した。ろ液を減圧濃縮した。析出固形物を濾別し、得られた固形物を乾燥させることによって目的化合物2.8gを得た。
化合物A-10:1H-NMR(400MHz, CDCl3): δ 3.08(s, 3H), 3.50(s, 3H), 3.76(s, 3H), 4.03(s, 3H), 7.97(d, 1H), 7.65-7.68(m, 2H), 7.74(t, 1H), 7.82(d, 1H), 8.01(d, 1H).
化合物A-11:1H-NMR(400MHz,CDCl3): δ1.59 (s, 9H), 3.54(s, 3H), 3.72(s, 3H), 3.91(s, 3H), 7.31(s, 1H), 7.73(m, 2H).
化合物A-15:1H-NMR(400MHz,CDCl3): δ 2.78(s, 3H), 3.14(s, 3H), 3.25(s, 3H), 3.52(s, 3H), 3.70(s, 3H), 7.21(s, 1H), 7.76(d, 1H), 8.07(d, 1H).
化合物A-17:1H-NMR(400MHz,CDCl3): δ 3.28(s, 3H), 3.42(s, 3H), 3.49(s, 3H), 3.66(s, 3H), 3.77-3.81(m, 2H), 4.36-4.40(m, 2H), 7.20(s, 1H), 7.48(d, 1H), 7.93(d, 1H).
化合物A-20:1H-NMR(400MHz,CDCl3): δ2.44-2.56(m, 2H), 3.10(s, 3H), 3.75(s, 3H), 3.79(t, 2H), 4.64(s, 2H), 7.19(s, 1H), 7.72(dd, 1H), 7.82(d, 1H), 7.97(d, 1H).
化合物A-24:1H-NMR(400MHz,CDCl3): δ 2.97(s, 3H), 3.49(s, 3H), 3.72(s, 3H), 6.54(s, 1H), 7.24(s, 1H), 7.72(s, 1H), 7.80(s, 1H), 7.87(d, 1H), 8.21(d, 1H).
化合物A-25:1H-NMR(400MHz,CDCl3): δ2.52-2.63(m, 4H), 3.45-3.67(m, 15H), 7.19(s, 1H), 7.70(d, 1H), 8.16(d, 1H).
化合物A-26:1H-NMR(400MHz,CDCl3): δ3.14(s, 3H), 3.53(s, 3H), 3.79(s, 3H), 7.42-7.53(m, 4H), 7.63-7.65(m, 2H), 7.89(d, 1H), 7.95(dd, 1H), 8.22(d, 1H).
化合物A-28:1H-NMR(400MHz,CDCl3): δ3.10(s, 3H), 3.49(s, 3H), 3.51(s, 3H), 3.74(s, 3H), 4.56(s, 2H), 7.20(s, 1H), 7.71(dd, 1H), 7.81(d, 1H), 7.98(d, 1H).
化合物A-31:1H-NMR(400MHz,CDCl3): δ3.50(s, 3H), 3.68-3.77(m, 10H), 4.01-4.14(m, 4H), 7.20(s, 1H), 7.61-7.63(m, 2H), 8.97(s, 1H).
化合物A-32:1H-NMR(400MHz,CDCl3): δ2.10(s, 3H), 3.42-3.50(m, 7H), 3.66-3.74(m, 7H), 6.28(s, 1H), 7.23(s, 3H), 7.52-7.58(m, 2H).
化合物A-33:1H-NMR(400MHz,CDCl3): δ2.21-2.46(m, 2H), 2.52-2.58(m, 2H), 3.14(s, 3H), 3.50(s, 3H), 3.67-3.88(m, 5H), 7.25(s, 1H), 7.75(d, 1H), 8.06-8.11(m, 1H).
化合物A-35:1H-NMR(400MHz,CDCl3): δ2.28(s, 3H), 3.17(s, 3H), 3.53(s, 3H), 3.71(s, 3H), 3.96-4.05(m, 2H), 5.10-5.31(m, 2H), 7.17(s, 1H), 7.73(d, 1H), 8.08(d, 1H).
化合物A-38:1H-NMR(400MHz,CDCl3): δ2.72(s, 3H), 3.23(s, 3H), 3.50(s, 3H), 3.67(s, 3H), 4.74-4.75(m, 2H), 6.93(s, 1H), 7.20(s, 1H), 7.55(d, 1H), 7.97(d, 1H).
化合物A-40:1H-NMR(400MHz,CDCl3): δ3.52(s, 3H), 3.70(s, 3H), 3.73-3.81(m, 6H), 4.25(dd, 2H), 7.27(s, 1H), 7.51(s, 2H), 9.05(s, 1H).
化合物A-41:1H-NMR(400MHz,CDCl3): δ2.05(br, 3H), 2.11(s, 3H), 2.28(s, 3H), 3.51(s, 3H), 3.68(s, 3H), 3.96(s, 3H), 7.13(br, 1H), 7.19(s, 1H), 7.39(br, 1H).
化合物A-42:1H-NMR(400MHz,CDCl3): δ3.34(s, 3H), 3.49(s, 3H), 3.74(s, 3H), 7.21(s, 1H), 7.90(d, 1H), 8.05(d, 1H).
化合物A-43:1H-NMR(400MHz,CDCl3): δ2.55-2.68(m, 6H), 3.15(s, 3H), 3.65-3.67(m, 6H), 7.28(s, 1H), 7.60(d, 1H), 7.96(d, 1H).
化合物A-45:1H-NMR(400MHz,CDCl3): δ1.78(s, 3H), 1.80(s, 3H), 3.33(s, 3H), 3.51(s, 3H), 3.66(s, 3H), 5.62(d, 1H), 5.72(d, 1H), 7.25(s, 1H), 7.73(d, 1H), 8.15(d, 1H).
化合物A-47:1H-NMR(400MHz,CDCl3): δ3.11(s, 3H), 3.74(s, 3H), 4.15-4.26(m, 1H), 4.70-4.80(m, 1H), 7.25(s, 1H), 7.96-8.03(m, 2H), 8.25(s, 1H).
化合物A-49:1H-NMR(400MHz,CDCl3): δ1.82(s, 3H), 2.69(s, 3H), 3.51(s, 3H), 3.74(s, 3H), 7.18-7.29(m, 3H), 7.45-7.49(m, 2H), 7.75(d, 1H), 8.17(d, 1H).
化合物A-50:1H-NMR(400MHz,CDCl3): δ0.76(t, 3H), 0.87-0.95(m, 2H), 1.02-1.15(m, 4H), 1.36-1.48(m, 2H), 3.17(s, 3H), 3.52(s, 3H), 3.75-3.86(m, 2H), 4.46-4.56(m, 2H), 7.21(s, 1H), 7.98-8.02(m, 2H), 8.29(s, 1H).
化合物A-52:1H-NMR(400MHz,CDCl3): δ3.54(s, 3H), 3.71(s, 3H), 7.31(s, 1H), 7.68-7.75(m, 2H), 7.85-7.89(m, 1H), 8.14(s, 1H), 8.61(s, 1H).
化合物A-53:1H-NMR(400 MHz,CDCl3): δ3.30(s, 3H), 3.43(s, 3H), 3.80(s, 3H), 7.36(dd, 1H), 7.49(s, 1H), 7.54-7.60(m, 1H), 7.91(dd, 1H).
化合物A-54:1H-NMR(400 MHz,CDCl3): δ0.70(t, 3H), 1.45-1.54(m, 2H), 3.10(s, 3H), 3.38(s, 3H), 3.77(s, 3H), 3.93(t, 2H), 7.90-7.97(m, 2H), 8.21(s, 1H).
化合物A-56:1H-NMR(400MHz,CDCl3): δ3.54(s, 3H), 3.69(s, 3H), 7.30(s, 1H), 7.60-7.70(m, 3H), 7.81(d, 1H), 7.94(s, 1H).
化合物A-60:1H-NMR(400MHz,CDCl3): δ1.08(t, 3H), 3.17(s, 3H), 3.52(s, 3H), 3.86-3.94(m, 1H), 4.46-4.54(m, 1H), 5.21(d, 1H), 5.25(d, 1H), 7.20(s, 1H), 7.94-8.03(m, 2H), 8.29(s, 1H).
化合物A-61:1H-NMR(400MHz,CDCl3): δ0.32-0.37(m, 2H), 0.50-0.56(m, 2H), 1.19-1.25(m, 1H), 3.14(s, 3H), 3.66-3.87(m, 5H), 7.20(s, 1H), 7.97-8.01(m, 2H), 8.27(s, 1H).
化合物A-62:1H-NMR(400MHz,CDCl3): δ3.13(s, 3H), 3.58(s, 3H), 4.23-4.32(m, 1H), 4.81-4.90(m, 1H), 7.24(s, 1H), 7.95-8.05(m, 2H), 8.28(s, 1H).
化合物A-63:1H-NMR(400MHz,CDCl3): δ1.08(t, 3H), 3.18(s, 3H), 3.43(s, 3H), 3.87-3.95(m, 1H), 4.46-4.54(m, 1H), 5.21(d, 1H), 5.25(d, 1H), 7.26(s, 1H), 7.98-8.04(m, 2H), 8.29(s, 1H).
化合物A-64:1H-NMR(400MHz,CDCl3): δ3.16(s, 3H), 3.43(s, 3H), 3.80(s, 3H), 5.20(d, 1H), 5.27(d, 1H), 7.27(s, 1H), 7.99-8.07(m, 2H), 8.29(s, 1H).
化合物A-69:1H-NMR(400MHz,CDCl3): δ2.86-3.02(m, 3H), 3.10-3.44(m, 4H), 3.53(s, 3H), 3.76(s, 3H), 7.21(s, 1H), 7.55-7.74(m, 3H).
化合物A-70:1H-NMR(400MHz,CDCl3): δ3.02(s, 3H), 3.54(s, 3H), 3.76(s, 3H), 6.86-6.96(m, 1H), 7.15(s, 1H), 7.50-7.82(m, 4H).
化合物A-71:1H-NMR(400MHz,CDCl3): δ1.45(t, 3H), 3.20(q, 2H), 3.35(s, 3H), 3.48(s, 3H), 3.65(s, 3H), 4.98-5.85(m, 1H), 7.25(s, 1H), 7.79(d, 1H), 8.12(d, 1H).
化合物A-74:1H-NMR(400MHz,CDCl3): δ3.19-3.30(m, 4H), 3.52(s, 3H), 3.69-3.79(m, 7H), 7.25(s, 1H), 7.92-8.09(m, 3H).
化合物A-75:1H-NMR(400MHz,CDCl3): δ3.13(s, 3H), 3.51(s, 3H), 3.78(s, 3H), 7.20(s, 1H), 7.59(dd, 1H), 7.86(d, 1H), 7.89(d, 1H).
化合物B-2:1H-NMR(400MHz,CDCl3): δ 2.49-2.63(m, 2H), 2.80-2.89(m, 1H), 3.09-3.18(m, 1H), 3.35-3.40(m, 1H), 3.55(s, 3H), 3.69-3.73(m, 1H), 4.07-4.16(m, 2H), 4.29-4.34(m, 1H), 4.61-4.68(m, 1H), 7.19(s, 1H), 7.60-7.99(m, 6H).
化合物B-9:1H-NMR(400MHz,CDCl3): δ1.79(m, 2H), 2.09-2.23(m, 2H), 3.30-3.45(m, 4H), 3.54(s, 3H), 3.74(s, 3H), 7.16(s, 1H), 7.89(s, 2H).
化合物B-11:1H-NMR(400MHz,CDCl3): δ2.15(s, 3H), 2.50-2.78(m, 5H), 3.41-3.56(m, 5H), 3.69(s, 3H), 4.12-4.28(m, 4H), 7.13(s, 1H), 7.49(s, 1H).
化合物B-12:1H-NMR(400MHz,CDCl3): δ1.41(s, 6H), 2.22-2.40(m, 4H), 2.56(s, 3H), 3.39-3.45(m, 2H), 3.51(s, 3H), 3.68(s, 3H), 7.15(s, 1H), 7.36(d, 1H), 7.62(d, 1H).
化合物B-13:1H-NMR(400MHz,CDCl3): δ3.51(s, 3H), 3.59(dt, 2H), 3.73(s, 3H), 4.83-4.95(m, 2H), 7.18(s, 1H), 7.56(d, 1H), 7.76(d, 1H).
化合物B-15:1H-NMR(400MHz,CDCl3): δ2.46-2.49(m, 3H), 3.45-3.46(m, 3H), 3.78-3.79(m, 3H), 4.10-4.13(m, 3H), 6.76-6.80(m, 2H), 7.00-7.05(m, 3H), 7.38-7.44(m, 1H), 7.85-7.95(m, 1H).
化合物C-6:1H-NMR(400MHz,CDCl3): δ1.67-1.86(m, 4H), 1.97(s, 3H), 2.52-2.61(m, 2H), 2.80-2.84(m, 2H), 3.40-3.47(m, 2H), 3.53(s, 3H), 3.79-3.82(m, 1H), 4.35-4.39(m, 1H), 7.15(s, 1H), 7.85-7.88(m, 2H).
化合物C-11:1H-NMR(400MHz,CDCl3): δ2.49-2.52(m, 2H), 2.82-2.88(m, 2H), 3.12(s, 3H), 3.21(s, 3H), 3.36-3.46(m, 2H), 3.54(s, 3H), 3.78-3.82(m, 1H), 4.15-4.30(m, 2H), 7.16(s, 1H), 7.89(s, 2H).
化合物C-12:1H-NMR(400MHz,CDCl3): δ2.50-2.55(m, 2H), 2.83-2.96(m, 2H), 3.36-3.43(m, 2H), 3.54(s, 3H), 3.66(s, 3H), 4.74(s, 2H), 7.17(s, 1H), 7.86-7.91(m, 2H).
化合物C-23:1H-NMR(400MHz,CDCl3): δ1.52(s, 9H), 2.46-2.50(m, 2H), 2.74-2.88(m, 2H), 3.34-3.37(m, 2H), 3.67(s, 3H), 7.05(s, 1H), 7.83-7.86(m, 2H).
化合物C-26:1H-NMR(400MHz,CDCl3): δ2.37-2.42(m, 2H), 2.62-2.78(m, 2H), 2.80(s, 3H), 3.37-3.40(m, 2H), 3.52(s, 3H), 3.70(s, 3H), 7.14(s, 1H), 7.28(d, 1H), 7.58(d, 1H).
化合物C-30:1H-NMR(400MHz,CDCl3): δ1.87(s, 3H), 2.44-2.65(m, 2H), 3.06-3.15(m, 2H), 3.38-3.53(m, 5H), 3.72(s, 3H), 7.38(d, 1H), 7.80(d, 1H).
化合物C-31:1H-NMR(400MHz,CDCl3): δ2.48-2.98(m, 4H), 3.36-3.45(m, 5H), 3.74(s, 3H), 5.10(d, 1H), 5.34(d, 1H), 7.21(d, 1H), 7.83-7.90(m, 2H).
化合物C-35:1H-NMR(400MHz,CDCl3): δ2.45-2.52(m, 2H), 2.67-2.83(m, 2H), 3.29-3.42(m, 2H), 3.54(s, 3H), 4.31(dt, 1H), 4.86-4.95(m, 1H), 7.21(s, 1H), 7.79-7.96(m, 2H).
化合物C-36:1H-NMR(400MHz,CDCl3): δ2.49-2.51(m, 2H), 2.79-2.83(m, 1H), 2.93-2.99(m, 1H), 3.32-3.37(m, 2H), 3.54(s, 3H), 5.01-5.17(m, 1H), 5.47-5.53(m, 1H), 7.16(s, 1H), 7.30-7.36(m, 2H), 7.51-7.77(m, 5H).
次に本発明化合物が除草剤の有効成分として有用であることを以下の試験例で示す。
(試験例1)
(1)試験用乳剤の調製
POAアリルフェニルエーテル(4.1重量部)、POE-POPグリコール(1重量部)、POEソルビタンラウレート(0.8重量部)、グリセリン(2.6重量部)、ジメチルホルムアミド(65.9重量部)、N-メチルピロリドン(5.1重量部)、シクロヘキサノン(15.4重量部)、および芳香族炭化水素(5.1重量部)を混合し溶解させて、乳剤を調製した。この乳剤(100μL)に対し、本発明化合物(4mg)を溶解させて、試験用乳剤を調製した。POAは「ポリオキシアルキレン」を、POEは「ポリオキシエチレン」を、POPは「ポリオキシプロピレン」を意味する。
(2)茎葉散布処理
150cm2のポットに土壌を充填し、表層にエンバク(Avena sativa)、カミツレ(Matricaria chamomilla)、アキノエノコログサ(Setaria faberi)、メヒシバ(Digitaria ciliaris)、イチビ(Abutilon theophrasti)およびアオゲイトウ(Amaranthus retroflexus)の種子を播き、軽く覆土した。その後、温室内で生育させた。各植物が2~4cmの草丈に生育した時点で、所定の有効成分量になるように上記の試験用乳剤を希釈し、ヘクタール当たり250Lの散布水量にて小型噴霧器で茎葉部に散布した。
(3)評価
3週間後、雑草ごとに無処理区および処理区の地上部生草重を測定し、下記の算出式によって殺草率を算出した。
(4)殺草率の算出式
殺草率 (%) = 〔(無処理区の地上部生草重 - 処理区の地上部生草重) /(無処理区の地上部生草重)〕×100
A-1、A-2、A-3、A-4、A-5、A-6、A-10、およびB-1の化合物を、ヘクタール当たり1000gの散布量になるように散布した。結果、いずれの化合物もカミツレに対し、殺草率が80%以上であった。
(a)イチビ
第4表に示す化合物を、ヘクタール当たり1000gの散布量になるように散布した。結果、いずれの化合物もイチビに対し、80%以上の殺草活性を示した。
第6表に示す化合物を、ヘクタール当たり1000gの散布量になるように散布した。結果、いずれの化合物もカミツレに対し、80%以上の殺草活性を示した。
第8表に示す化合物を、ヘクタール当たり1000gの散布量になるように散布した。結果、いずれの化合物もエンバクに対し、80%以上の殺草活性を示した。
第10表に示す化合物を、ヘクタール当たり1000gの散布量になるように散布した。結果、いずれの化合物もアキノエノコログサに対し、80%以上の殺草活性を示した。
第12表に示す化合物を、ヘクタール当たり1000gの散布量になるように散布した。結果、いずれの化合物もメヒシバに対し、80%以上の殺草活性を示した。
第14表に示す化合物を、ヘクタール当たり1000gの散布量になるように散布した。結果、いずれの化合物もアオゲイトウに対し、80%以上の殺草活性を示した。
Claims (6)
- 式(I)で表される化合物またはその塩。
R1は、置換若しくは無置換のC1~6アルキル基、置換若しくは無置換のC2~6アルケニル基、置換若しくは無置換のC2~6アルキニル基、置換若しくは無置換のC3~6シクロアルキル基、または5~6員環状エーテル基を示し、
R2は、置換若しくは無置換のC1~6アルキル基、置換若しくは無置換のC2~6アルケニル基、または置換若しくは無置換のC2~6アルキニル基を示し、
R3は、水素原子、置換若しくは無置換のC1~6アルキル基、置換若しくは無置換のC2~6アルケニル基、置換若しくは無置換のC2~6アルキニル基、置換若しくは無置換のC1~6アルコキシ基、置換若しくは無置換のC3~6シクロアルキル基、または置換若しくは無置換のフェニル基を示し、且つ
Qは、置換若しくは無置換のフェニル基、または置換若しくは無置換のナフチル基を示す。 - 式(I-1)で表される、請求項1に記載の式(I)で表される化合物またはその塩。
Xは、ハロゲノ基、置換若しくは無置換のC1~6アルキル基、置換若しくは無置換のC2~6アルケニル基、置換若しくは無置換のC2~6アルキニル基、水酸基、置換若しくは無置換のC1~6アルコキシ基、置換若しくは無置換のC2~6アルケニルオキシ基、置換若しくは無置換のC2~6アルキニルオキシ基、置換若しくは無置換のC1~6アルキルチオ基、置換若しくは無置換のC1~6アルキルスルフィニル基、置換若しくは無置換のC1~6アルキルスルホニル基、置換若しくは無置換のC3~6シクロアルキル基、置換若しくは無置換のC3~6シクロアルキルオキシ基、置換若しくは無置換のフェニル基、フェノキシ基、置換若しくは無置換の5~6員ヘテロシクリル基、置換若しくは無置換の5~6員ヘテロシクリルオキシ基、置換若しくは無置換のフェニルスルホニル基、R-CO-で表される基、RO-CO-で表される基、R-CONRa-で表される基、RNH-CO-で表される基、R2N-CO-で表される基、RO-CO-NRa-で表される基、RNH-CO-NH-で表される基、R2N-CO-NH-で表される基、RNH-CO-CO-NH-で表される基、R2N-CO-CO-NH-で表される基、R-S(O)2-NH-で表される基、R2N-S(O)2-で表される基、R2S(O)=N-で表される基、R-S(O)(=N-Rb)-で表される基、RO-N=C(Rc)-で表される基、ニトロ基、またはシアノ基を示し;
Rは、それぞれ独立に、置換若しくは無置換のC1~6アルキル基または置換若しくは無置換のC3~6シクロアルキル基を示し、
Raは、それぞれ独立に、水素原子、置換若しくは無置換のC1~6アルキル基、または置換若しくは無置換のC1~6アルコキシ基を示し、
Rbは、置換若しくは無置換のC1~6アルキル基または置換若しくは無置換のフェニル基を示し、
Rcは、水素原子または置換若しくは無置換のC1~6アルキル基を示し;
上記のR2N-CO-で表される基、R2N-CO-NH-で表される基、R2N-CO-CO-NH-で表される基、またはR2N-S(O)2-で表される基において、RとRとが結合してそれらが結合する窒素原子と共に4~6員環を形成してもよく;
上記のR2S(O)=N-で表される基において、RとRとが結合してそれらが結合する硫黄原子と共に5~6員環を形成してもよく;
nは、0~5の整数を示し、nが2以上である場合Xは同一であっても異なっていてもよく、nが2以上ある場合そのうちの2つのXが一緒になって二価の有機基を形成してもよい。 - 式(I-3)で表される、請求項1に記載の式(I)で表される化合物またはその塩。
mは、0~3の整数を示し、mが2以上である場合X1は同一であっても異なっていてもよい。 - R2におけるC1~6アルキル基上の置換基が、ハロゲノ基、水酸基、C1~6アルコキシ基、C1~6アルコキシC1~6アルコキシ基、C1~6ハロアルコキシ基、C1~6アルキルチオ基、C1~6アルキルスルフィニル基、C1~6アルキルスルホニル基、C3~6シクロアルキル基、フェニル基、5員ヘテロアリール基、C1~6アルキルカルボニル基、ベンゾイル基、C1~6アルコキシカルボニル基、C1~6アルキルカルボキシアミド基、((1,3-ジオキソイソインドリン-2-イル)オキシ基、トリメチルシリル基、シアノ基からなる群、
並びに、C1~6アルキル基置換、ハロゲノ基置換、C1~6ハロアルキル基置換若しくはC1~6ハロアルコキシ基置換のフェニル基;C1~6アルキル基置換、ハロゲノ基置換、C1~6ハロアルキル基置換若しくはC1~6ハロアルコキシ基置換のフェノキシ基;およびC1~6アルキル基置換、ハロゲノ基置換、C1~6ハロアルキル基置換若しくはC1~6ハロアルコキシ基置換の5員ヘテロアリール基からなる群;
より選択される少なくともひとつである請求項1に記載の化合物またはその塩。 - 請求項1~4のいずれかに記載の化合物およびその塩からなる群から選ばれる少なくともひとつを有効成分として含有する除草剤。
- 有用植物における単子葉類および/または双子葉類の雑草を防除する方法であって、請求項1~4のいずれかに記載の化合物若しくはその塩、または前記化合物を含有する除草剤を、前記雑草および/または前記植物および/またはその場所に施用する工程を含む、方法。
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CN202080063624.1A CN114375292A (zh) | 2019-09-25 | 2020-09-23 | 7-氧杂-3,4-二氮杂双环[4.1.0]庚-4-烯-2-酮化合物和除草剂 |
US17/636,710 US20220289758A1 (en) | 2019-09-25 | 2020-09-23 | 7-oxa-3,4-diazabicyclo [4.1.0] hept-4-en-2-one compound and herbicide |
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MX2022002898A MX2022002898A (es) | 2019-09-25 | 2020-09-23 | Compuesto de 7-oxa-3,4-diazabiciclo-[4.1.0]-4-hepten-2-ona y herbicida. |
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