JP5122640B2 - Nitrogen-containing heterocyclic compounds and agricultural and horticultural fungicides - Google Patents

Description

The present invention relates to a novel nitrogen-containing heterocyclic compound and a salt thereof, and an agricultural and horticultural fungicide containing at least one of these compounds as an active ingredient.
This application claims priority based on Japanese Patent Application No. 2008-049112 filed in Japan on March 27, 2008, and Japanese Patent Application No. 2008-278819 filed in Japan on October 29, 2008, and its contents Is hereby incorporated by reference.

  In the cultivation of agricultural and horticultural crops, many control agents are used against crop diseases, but their control efficacy is insufficient, their use is restricted by the emergence of drug-resistant pathogens, and From the viewpoints of causing phytotoxicity and pollution to plants, or toxicity to human and livestock fish and impact on the environment, there are many things that are not necessarily satisfactory control agents. Accordingly, there is a strong demand for the emergence of such a drug that can be safely used with few defects.

In relation to the present invention, Patent Documents 1 and 2 disclose a quinoline derivative having a chemical structure similar to that of the compound of the present invention and an agricultural and horticultural fungicide containing it as an active ingredient. However, the compounds of the present invention are not described.
WO2005 / 0700917 pamphlet WO2007 / 011022 pamphlet

  The present invention relates to a novel nitrogen-containing heterocyclic compound and a salt thereof, which can be an active ingredient of an agricultural and horticultural fungicide that is reliable and can be used safely, and contains at least one of these compounds as an active ingredient. It is an object to provide a disinfectant.

  In order to solve the above problems, the present invention provides a nitrogen-containing heterocyclic compound represented by the following formula (I) or a salt thereof.

Wherein R ¹ and R ² are each independently a hydrogen atom, halogen atom, C1-20 alkyl group, C1-20 haloalkyl group, C2-20 alkenyl group, C2-20 haloalkenyl group, C2-20 Alkynyl group, C2-20 haloalkynyl group, C1-20 alkoxy group, C1-20 haloalkoxy group, C3-20 cycloalkyl group, C4-20 cycloalkenyl group, C8-20 cycloalkynyl group, C1-20 acyl group, .R ¹ and ^{R 2} showing a C1~20 alkoxycarbonyl group together may form a 5- to 8-membered ring an unsubstituted or substituted group.
R ^{3 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 haloalkyl group, a C2-20 alkenyl group, a C2-20 haloalkenyl group, a C2-20 alkynyl group, C2 -20 haloalkynyl group, C1-20 alkoxy group, C1-20 haloalkoxy group, C3-20 cycloalkyl group, C3-20 cycloalkoxy group, C2-20 alkenyloxy group, C2-20 alkynyloxy group, C1-20 An alkylthio group, a cyano group, a nitro group, an unsubstituted or substituted amino group, an unsubstituted or substituted phenyl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted aryloxy group, Or an unsubstituted or substituted heterocyclic group; R ⁴ and R ⁵ , and R ⁵ and R ⁶ may be combined to form a 5- to 8-membered ring having no substituent or a substituent. R ⁵ and R ⁶ are not simultaneously hydrogen atoms.
X represents a halogen atom, a nitro group, an unsubstituted or substituted amino group, a hydroxyl group, or an organic group.
n represents an integer of 0 to 4.
Z represents an oxygen atom or a sulfur atom. )
In the nitrogen-containing heterocyclic compound and the salt thereof of the present invention, it is preferable that R ⁵ and R ⁶ together form an aromatic ring.
The present invention also provides an agricultural and horticultural fungicide containing as an active ingredient at least one compound of the present invention or a salt thereof.

The nitrogen-containing heterocyclic compound and salts thereof of the present invention are novel compounds and are useful as active ingredients of agricultural and horticultural fungicides that can be used safely and reliably.
The agricultural and horticultural fungicide of the present invention is an agent that has an excellent control effect, does not cause phytotoxicity to plants, and has little toxicity to human and livestock fish and environmental impact.

  Hereinafter, the present invention will be described in detail by dividing into 1) a nitrogen-containing heterocyclic compound represented by the formula (I) or a salt thereof, and 2) an agricultural and horticultural fungicide.

1) Nitrogen-containing heterocyclic compound represented by formula (I) or a salt thereof The compound of the present invention is a nitrogen-containing heterocyclic compound represented by formula (I) or a salt thereof. The compound of the present invention or a salt thereof includes hydrates, various solvates and crystal polymorphs.
In formula (I), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 haloalkyl group, a C2-20 alkenyl group, a C2-20 haloalkenyl group, C2 -20 alkynyl group, C2-20 haloalkynyl group, C1-20 alkoxy group, C1-20 haloalkoxy group, C3-20 cycloalkyl group, C4-20 cycloalkenyl group, C8-20 cycloalkynyl group, C1-20 acyl Group, a C1-20 alkoxycarbonyl group. R ¹ and R ² may be combined to form an unsubstituted or substituted 5- to 8-membered ring.

Examples of the “halogen atom” for R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The “C1-20 alkyl group” of R ¹ and R ² means a linear or branched alkyl group having 1 to 20 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, 2 -Methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, nonyl group, isononyl group, n-decyl group, 2-ethyloctyl group, 3-ethyl Octyl group, 2,3-dimethyloctyl group, 4-propyloctyl group, dodecyl group, 4-ethyldecyl group, 6-ethyldodecyl group, 3,5-dimethyldecyl group, 2,5-dimethyldecyl group, 6-propyl Nonyl group, 4-butyloctyl group, tridecyl group, tetradecyl group, 2,4,6,8-tetramethyldecyl group, 2,2-diethyldecyl group, 2,5-die Rudeshiru group, 4-Buchirudeshiru group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, 2,4,6,8-tetraethyl-decyl group, nonadecyl group, eicosyl group and the like. Of these, C1-6 alkyl groups are preferred.

The “C1-20 haloalkyl group” for R ¹ and R ² means a group in which a hydrogen atom of a C1-20 alkyl group is substituted with a halogen atom. For example, fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, pentafluoroethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 3,3,3-trifluoropropyl group, 2,2,2-trifluoro-1-trifluoro Methylethyl group, perfluorohexyl group, perchlorohexyl group, perfluorooctyl group, perchlorooctyl group, 2,4,6-trichlorohexyl group, perfluorodecyl group, 2,2,4,4,6,6 -Hexachlorooctyl group, 2,2,4,4,6,6-hexachloro-3-propyl-octyl group, etc. . Of these, C1-6 haloalkyl groups are preferred.

The “C2-20 alkenyl group” of R ¹ and R ² means a linear or branched alkenyl group having 2 to 20 carbon atoms having a carbon-carbon double bond at any one or more of alkyl groups. . For example, vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 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, 1-heptenyl group, 6-heptenyl group, 1-octenyl group, 7-octenyl group, 1-decenyl group, 9-decenyl group, 1-dodecenyl group, 4-dodecenyl group, 1 -An octadecenyl group, 2-ethyl-1-octadecenyl group, etc. are mentioned. Of these, C2-6 alkenyl groups are preferred.

The “C2-20 haloalkenyl group” of R ¹ and R ² means a linear or branched alkenyl group having 2 to 20 carbon atoms having a carbon-carbon double bond at any one or more of the haloalkyl groups. To do. For example, 3-chloro-2-propenyl group, 4-chloro-2-butenyl group, 4,4-dichloro-3-butenyl group, 4,4-difluoro-3-butenyl group, 3,3-dichloro-2- Propenyl group, 2,3-dichloro-2-propenyl group, 3,3-difluoro-2-propenyl group, 2,4,6-trichloro-2-hexenyl group, 3-ethyl-2,4,6-trifluoro -2-hexenyl group and the like. Of these, C2-6 haloalkenyl groups are preferred.

The “C2-20 alkynyl group” of R ¹ and R ² means a linear or branched alkynyl group having 2 to 20 carbon atoms having a carbon-carbon triple bond at one or more of alkyl groups. For example, ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 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, Examples include dodecinyl group, butadecynyl group, heptadecynyl group, 4-ethylhexadecynyl group and the like. Of these, C2-6 alkynyl groups are preferred.

The “C2-20 haloalkynyl group” of R ¹ and R ² means a linear or branched alkynyl group having 2 to 20 carbon atoms having a carbon-carbon double bond at any one or more of the haloalkyl groups. To do. For example, 3-chloro-1-propynyl group, 3-chloro-1-butynyl group, 3-bromo-1-butynyl group, 3-bromo-2-propynyl group, 3-iodo-2-propynyl group, 5, 5 -Dichloro-2-methyl-3-pentynyl group, 3-bromo-1-hexynyl group, 4-chloro-1,1-dimethyl-2-butynyl group, 4,4,6,6-tetrafluoro-1-dodecynyl group Etc. Of these, C2-6 haloalkynyl groups are preferred.

The “C1-20 alkoxy group” of R ¹ and R ² means a group in which a linear or branched alkyl group having 1 to 20 carbon atoms is bonded to an oxygen atom. For example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, 1-ethylpropoxy group, n-hexyloxy group, isohexyloxy group, 4-methylpentoxy group, 3-methylpentoxy group, 2-methylpentoxy group, 1-methylpentoxy group, 3,3-dimethylbutoxy group, 2,2 -Dimethylbutoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1-ethylbutoxy group, 2-ethylbutoxy group, decyloxy Group, dodecyloxy group, 2-ethyldecyloxy group, lauryloxy group and the like. Of these, C1-6 alkoxy groups are preferred.

The “C1-20 haloalkoxy group” for R ¹ and R ² means a group in which a linear or branched haloalkyl group having 1 to 20 carbon atoms is bonded to an oxygen atom. For example, chloromethoxy group, dichloromethoxy group, trichloromethoxy group, trifluoromethoxy group, 1-fluoroethoxy group, 1,1-difluoroethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group, 4 , 5-dichloro-3-methylpentoxy group, 2-fluoro-2-ethyldecyloxy group, 1-chlorolauryloxy group and the like. Of these, C1-6 haloalkoxy groups are preferred.

The “C3-20 cycloalkyl group” of R ¹ and R ² means an alkyl group having 3 to 20 carbon atoms having a cyclic portion. For example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclopropylmethyl group, 2-cyclopropylethyl group, 2,3,3-trimethylcyclobutyl group, cyclopentylmethyl group, 2-cyclohexylethyl group, 2-cyclooctylethyl group, 4,4,6,6-tetramethylcyclohexyl group, 1,3-dibutylcyclohexyl group, norbornyl group, bicyclo [2.2.2] octyl group, adamantyl group Etc. Of these, C3-6 cycloalkyl groups are preferred.

The “C4-20 cycloalkenyl group” for R ¹ and R ² means an alkenyl group having 4 to 20 carbon atoms having a cyclic portion. For example, 1-cyclobutenyl group, 1-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 3-cyclohexenyl group, 3-cycloheptenyl group, 4-cyclooctenyl group, 2-methyl-3-cyclohexacenyl Group, 3,4-dimethyl-3-cyclohexenyl group, cyclopentenylmethyl group, 3-cyclopentenylmethyl group, 3-cyclohexenylmethyl group, 2- (3-cyclohexenyl) ethyl group and the like. Of these, C4-8 cycloalkenyl groups are preferred.
The “C8-20 cycloalkynyl group” of R ¹ and R ² means an alkynyl group having 8 to 20 carbon atoms having a cyclic portion. For example, 5-cyclooctynyl group, 6-cyclodecynyl group, 7-cyclododecynyl group, 2,3-diethyl-4-cyclodecynyl group, 5-cyclooctynylmethyl group and the like can be mentioned. Of these, C8-12 cycloalkynyl groups are preferred.

The “C1-20 acyl group” for R ¹ and R ² is a hydrogen atom or a group in which a linear or branched alkyl group having 1 to 19 carbon atoms, an aryl group, or a heteroaryl group is bonded to a carbonyl group. means. For example, formyl group, acetyl group, propionyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group, pentanoyl group, pivaloyl group, valeryl group, isovaleryl group, octanoyl group, Nonanoyl group, decanoyl group, 3-methylnonanoyl group, 8-methylnonanoyl group, 3-ethyloctanoyl group, 3,7-dimethyloctanoyl group, undecanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group , Hexadecanoyl group, 1-methylpentadecanoyl group, 14-methylpentadecanoyl group, 13,13-dimethyltetradecanoyl group, heptadecanoyl group, 15-methylhexadecanoyl group, octadecanoyl group, 1- Methylheptadecanoy Group, Nonadekanoiru group, Aikosanoiru group and Henaikosanoiru group, a benzoyl group, naphthyl carbonyl group, biphenyl carbonyl group, anthranyl group, 2-pyridylcarbonyl group, and a thienylcarbonyl group. Of these, C1-7 acyl groups are preferred.

The “C1-20 alkoxycarbonyl group” of R ¹ and R ² means a group in which a linear or branched alkoxy group having 1 to 20 carbon atoms is bonded to a carbonyl group. For example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyl Examples thereof include an oxycarbonyl group, a decyloxycarbonyl group, a dodecyloxycarbonyl group, a 2-ethyldecyloxycarbonyl group, and a lauryloxycarbonyl group. Of these, C1-6 alkoxycarbonyl groups are preferred.

R ¹ and R ² may be combined to form an unsubstituted or substituted 5- to 8-membered ring.
Examples of the 5- to 8-membered ring include an aliphatic hydrocarbon ring and a heterocycle. A heterocycle means a 5- to 8-membered saturated or unsaturated heterocycle containing 1 to 3 heteroatoms selected from a nitrogen atom, oxygen atom and sulfur atom in addition to carbon atoms.
Specifically, the aliphatic hydrocarbon ring includes a cycloalkane ring and a cycloalkene ring, the cycloalkane ring includes a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and the like, and the cycloalkene ring includes a cyclopentene ring, Examples include a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, and the like. Heterocycle includes tetrahydro-2H-pyran ring, tetrahydro-2H-thiopyran ring, piperidine ring, dioxane ring, oxathian ring, morpholine ring, thiomorpholine ring, dithiane ring, piperazine ring, pyrrolidine ring, tetrahydrothiophene ring, Tetrahydrofuran ring, 1,3-oxazolane ring, dithiolane ring, oxathiolane ring, dioxolane ring and the like can be mentioned. Of these, aliphatic hydrocarbon rings are preferred.
Examples of the substituent include R ^{3 to} R ⁶ described later, “an unsubstituted or substituted amino group”, “an unsubstituted or substituted phenyl group”, “an unsubstituted or substituted aryloxy group”, “ Examples thereof include those similar to the “substituent” of “unsubstituted or substituted aralkyl group” and “unsubstituted or substituted heterocyclic group”.

Among these, R ¹ and R ² are preferably each independently an alkyl group or a haloalkyl group.

R ^{3 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 haloalkyl group, a C2-20 alkenyl group, a C2-20 haloalkenyl group, a C2-20 alkynyl group, C2 -20 haloalkynyl group, C1-20 alkoxy group, C1-20 haloalkoxy group, C3-20 cycloalkyl group, C3-20 cycloalkoxy group, C2-20 alkenyloxy group, C2-20 alkynyloxy group, C1-20 An alkylthio group, a cyano group, a nitro group, an unsubstituted or substituted amino group, an unsubstituted or substituted phenyl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted aryloxy group, An unsubstituted or substituted heterocyclic group is shown. R ⁵ and R ⁶ , and R ⁴ and R ⁵ may be combined to form a 5- to 8-membered ring having no substituent or a substituent. R ⁵ and R ⁶ are not simultaneously hydrogen atoms.

R ^{3 to} R ⁶ , halogen atom, C1-20 alkyl group, C1-20 haloalkyl group, C2-20 alkenyl group, C2-20 haloalkenyl group, C2-20 alkynyl group, C2-20 haloalkynyl group, C1 Specific examples of the 20 alkoxy group, C1-20 haloalkoxy group, and C3-20 cycloalkyl group include the same as those listed as specific examples of R ¹ and R ² .

The “C3-20 cycloalkoxy group” of R ^{3 to} R ⁶ is a group in which a C 3-20 cycloalkyl group and an oxygen atom are bonded, and the cycloalkyl group means an alkyl group having a cyclic portion. For example, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclopropylmethyloxy group, 2-cyclopentylethyloxy group, 2-methylcyclopropyloxy group 2-ethylcyclopropyloxy group, 2,3,3-trimethylcyclobutyloxy group, 2-methylcyclopentyloxy group, 2-ethylcyclohexyloxy group, 2-ethylcyclooctyloxy group, 4,4,6,6 -Tetramethylcyclohexyloxy group, 1,3-dibutylcyclohexyloxy group, etc. are mentioned. Of these, C3-6 cycloalkoxy groups are preferred.

The “C2-20 alkenyloxy group” of R ^{3 to} R ⁶ means a group in which an alkenyl group having 2 to 20 carbon atoms and an oxygen atom are bonded. For example, vinyloxy group, 1-propenyloxy group, 2-propenyloxy group, 1-butenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 1-methyl-2-propenyloxy group, 2-methyl-2-propenyloxy Group, 1-pentenyloxy group, 2-pentenyloxy group, 3-pentenyloxy group, 4-pentenyloxy group, 1-methyl-2-butenyloxy group, 2-methyl-2-butenyloxy group, 1-hexenyloxy group, 2-hexenyloxy group, 3-hexenyloxy group, 4-hexenyloxy group, 5-hexenyloxy group, 1-heptenyloxy group, 6-heptenyloxy group, 1-octenyloxy group, 7-octenyloxy group, 1- Decenyloxy group, 9-decenyloxy group, 1-dodecenyloxy group, 4-dode Niruokishi group, 1-octadecenyl group, 2-ethyl-1-octadecenyl group, and the like. Of these, C2-6 alkenyloxy groups are preferred.

The “C2-20 alkynyloxy group” of R ^{3 to} R ⁶ means a group in which an alkynyl group having 2 to 20 carbon atoms and an oxygen atom are bonded. For example, ethynyloxy group, propynyloxy group, propargyloxy group, 1-butynyloxy group, 2-butynyloxy group, 3-butynyloxy group, 1-methyl-2-propynyloxy group, 2-methyl-3-butynyloxy group, 1- Pentynyloxy group, 2-pentynyloxy group, 3-pentynyloxy group, 4-pentynyloxy group, 1-methyl-2-butynyloxy group, 2-methyl-3-pentynyloxy group, 1-hexynyloxy group 1,1-dimethyl-2-butynyloxy group, dodecynyloxy group, butadecynyloxy group, heptadecynyloxy group, 4-ethylhexadecynyloxy group and the like. Of these, C2-6 alkynyloxy groups are preferred.

The “C1-20 alkylthio group” of R ^{3 to} R ⁶ means a group in which a C 1-20 alkyl group and a sulfur atom are bonded. For example, methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, t-butylthio group, pentylthio group, isopentylthio group, 2-methylbutylthio group, neopentylthio group, 1- Ethylpropylthio group, hexylthio group, isohexylthio group, 4-methylpentylthio group, 3-methylpentylthio group, 2-methylpentylthio group, 1-methylpentylthio group, 3,3-dimethylbutylthio group, 2,2-dimethylbutylthio group, 1,1-dimethylbutylthio group, 1,2-dimethylbutylthio group, 1,3-dimethylbutylthio group, 2,3-dimethylbutylthio group, 2-ethylbutylthio group Group, 3-ethyloctylthio group, 2,3-dimethyloctylthio group, 4-propyloctylthio group, dodecylthio group, 4 Ethyldecylthio group, 6-ethyldodecylthio group, 3,5-dimethyldecylthio group, 2,5-dimethyldecylthio group, 6-propylnonylthio group, 4-butyloctylthio group, tridecylthio group, tetradecylthio group Group, 2,4,6,8-tetramethyldecylthio group, 2,2-diethyldecylthio group, 2,5-diethyldecylthio group, 4-butyldecylthio group, pentadecylthio group, hexadecylthio group, heptadecylthio group, Examples include octadecylthio group, 2,4,6,8-tetraethyldecylthio group, nonadecylthio group, icosylthio group and the like. Of these, C1-6 alkylthio groups are preferred.

The “amino group” of the “unsubstituted or substituted amino group” of R ^{3 to} R ⁶ is an amino group; a monoalkylamino group such as a methylamino group or an ethylamino group, preferably a monoC1-6 alkylamino A dialkylamino group such as a dimethylamino group or a diethylamino group, preferably a diC1-6 alkylamino group; a monoarylamino group such as a phenylamino group or a 4-methylphenylamino group, preferably a monoC6-10 arylamino group A diarylamino group such as a di1-naphthylamino group, preferably a diC6-10 arylamino group; an acylamino group such as an acetylamino group or a benzoylamino group, preferably a C1-6 acylamino group;

The “aralkyl group” in the “unsubstituted or substituted aralkyl group” of R ^{3 to} R ⁶ means a group in which an aryl group and an alkyl group are bonded. For example, benzyl group, phenethyl group, 3-phenylpropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like can be mentioned. Of these, C6-10 aryl C1-6 alkyl groups are preferred.
The “aryloxy group” of the “unsubstituted or substituted aryloxy group” of R ^{3 to} R ^{6 is} a group in which an aryl group and an oxygen atom are bonded, and the aryl group is a monocyclic or polycyclic aryl group. means. Here, in the case of a polycyclic aryl group, a partially saturated group is included in addition to the fully unsaturated group. Examples thereof include a phenyloxy group, a naphthyloxy group, an azulenyloxy group, an indenyloxy group, an indanyloxy group, a tetralinyloxy group, and the like. Of these, C6-10 aryloxy groups are preferred.
The “heterocyclic group” of the “unsubstituted or substituted heterocyclic group” of R ^{3 to} R ⁶ is selected from a nitrogen atom, an oxygen atom and a sulfur atom in addition to a carbon atom as an atom constituting the ring. It means a 5- to 7-membered aromatic heterocycle containing 4 heteroatoms, a saturated heterocycle, an unsaturated heterocycle, or a condensed heterocycle obtained by condensing these heterocycles with a benzene ring. For example, furan-2-yl group, furan-3-yl group, thiophen-2-yl group, thiophen-3-yl group, pyrrol-1-yl group, pyrrol-2-yl group, pyrrole Ru-3-yl group, pyridin-2-yl group, pyridin-3-yl group, pyridin-4-yl group, pyrazin-2-yl group, pyrazin-3-yl group, pyrimidin-2-yl group, pyrimidine -4-yl group, pyrimidin-5-yl group, pyridazin-3-yl group, pyridazin-4-yl group, pyrrolidin-2-yl group, pyrrolidin-3-yl group, piperidin-2-yl group, piperidin- 4-yl group, tetrahydrofuran-2-yl group, tetrahydrofuran-3-yl group, morpholin-2-yl group, morpholin-3-yl group, 1,3-benzodioxol-4-yl group, 1,3 -Benzodioxole 5-yl group, 1,4-benzodioxan-5-yl group, 1,4-benzodioxan-6-yl group, 3,4-dihydro-2H-1,5-benzodioxepin-6-yl group 3,4-dihydro-2H-1,5-benzodioxepin-7-yl group, 2,3-dihydrobenzofuran-4-yl group, 2,3-dihydrobenzofuran-5-yl group, 2,3 -Dihydrobenzofuran-6-yl group, 2,3-dihydrobenzofuran-7-yl group, benzofuran-2-yl group, benzofuran-3-yl group, benzofuran-4-yl group, benzofuran-5-yl group, benzofuran -6-yl group, benzofuran-7-yl group, benzothiophen-2-yl group, benzothiophen-3-yl group, benzothiophen-4-yl group, benzothiophen-5-yl group, ben Thiophen-6-yl group, benzothiophen-7-yl group, quinoxalin-2-yl group, quinoxalin-5-yl group, quinoxalin-6-yl group, indol-1-yl group, indol-2-yl group, Indol-3-yl group, indol-4-yl group, indol-5-yl group, indol-6-yl group, indol-7-yl group, isoindol-1-yl group, isoindol-2-yl group , Isoindol-4-yl group, isoindol-5-yl group, isoindol-6-yl group, isoindol-7-yl group, isobenzofuran-1-yl group, isobenzofuran-4-yl group, iso Benzofuran-5-yl group, isobenzofuran-6-yl group, isobenzofuran-7-yl group, chromen-2-yl group, chromen-3-yl group, chrome Men-4-yl group, chromen-5-yl group, chromen-6-yl group, chromen-7-yl group, chromen-8-yl group, imidazol-1-yl group, imidazol-2-yl group, imidazole -4-yl group, imidazol-5-yl group, pyrazol-1-yl group, pyrazol-3-yl group, pyrazol-4-yl group, pyrazol-5-yl group, thiazol-2-yl group, thiazole- 4-yl group, thiazol-5-yl group, oxazol-2-yl group, oxazol-4-yl group, oxazol-5-yl group, isoxazol-3-yl group, isoxazol-4-yl group, iso Oxazol-5-yl group, benzimidazol-1-yl group, benzimidazol-2-yl group, benzimidazol-4-yl group, benzimidazol-5- Group, benzothiazol-2-yl group, benzothiazol-4-yl group, benzothiazol-5-yl group, benzoxazol-2-yl group, benzoxazol-4-yl group, benzoxazol-5-yl group Quinolin-2-yl group, quinolin-3-yl group, quinolin-4-yl group, quinolin-5-yl group, quinolin-6-yl group, quinolin-7-yl group, quinolin-8-yl group, Isoquinolin-1-yl group, isoquinolin-3-yl group, isoquinolin-4-yl group, isoquinolin-5-yl group, isoquinolin-6-yl group, isoquinolin-7-yl group, isoquinolin-8-yl group, 1 , 3,4-thiadiazol-2-yl group, morpholin-4-yl group, 1,2,3-triazol-1-yl group, 1,2,3-triazol-4-yl 1,2,3-triazol-5-yl group, 1,2,4-triazol-1-yl group, 1,2,4-triazol-3-yl group, 1,2,4-triazole-5- An yl group, a tetrazol-1-yl group, a tetrazol-2-yl group, and the like.
Of these, 5- to 10-membered heterocyclic groups are preferred.

R ^{3 to} R ^{6 represent} an “unsubstituted or substituted amino group”, “unsubstituted or substituted phenyl group”, “unsubstituted or substituted aryloxy group”, “unsubstituted or substituted group” As the “substituent” of “aralkyl group having” and “unsubstituted or substituted heterocyclic group”, halogen atom such as fluorine atom, chlorine atom, bromine atom; 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, isopentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, n- Hexyl group, C1-6 alkyl group of isohexyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-buto C1-6 alkoxy groups such as cis group, t-butoxy group, pentyloxy group, hexyloxy group; chloromethoxy group, dichloromethoxy group, trichloromethoxy group, trifluoromethoxy group, 1-fluoroethoxy group, 1,1- C1-6 haloalkoxy groups such as difluoroethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group, 4,5-dichloro-3-methylpentoxy group; methylthio group, ethylthio group, n-propylthio Group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group and other C1-6 alkylthio groups; methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, n- C1-6 alkylsulfonyl groups such as butylsulfonyl group; chloromethyl group, fluoro C1-6 haloalkyl groups such as til group and trifluoromethyl group; C1-6 alkylsulfonyloxy groups such as methylsulfonyloxy group, ethylsulfonyloxy group, n-propylsulfonyloxy group and t-butylsulfonyloxy group; Can be mentioned.

In addition to the above examples, R ⁴ and R ⁵ , and R ⁵ and R ⁶ may be combined together to form a 5- to 8-membered ring having an unsubstituted or substituted group. “R ⁴ and R ⁵ , and R ⁵ and R ⁶ may be combined together to form a ring” means that R ⁴ and R ⁵ and R ⁵ and R ⁶ both form a ring. And when R ⁴ and R ⁵ and any one of R ⁵ and R ⁶ form a ring.
Specific examples of the ring include those similar to the examples in which R ¹ and R ² form a ring, may form an aromatic ring, may be an aromatic hydrocarbon ring, An aromatic heterocyclic ring containing an oxygen atom, a nitrogen atom, and / or a sulfur atom as an atom constituting s may be used.
Examples of the aromatic hydrocarbon ring include a benzene ring, and examples of the aromatic heterocycle include a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an imidazole ring, a pyrazole ring, Examples include a thiazole ring, an oxazole ring, and an isoxazole ring.
Among these, a benzene ring or a substituted benzene ring is preferable, and the substituent is preferably a halogen atom, a C1-4 alkyl group, or a C1-4 alkoxy group.

Among these, as R ^{3 to} R ⁶ , an alkyl group, a halogen atom, a haloalkyl group, a cycloalkyl group, an unsubstituted or substituted heterocyclic group is preferable.

X represents a halogen atom, a nitro group, an unsubstituted or substituted amino group, a hydroxyl group, or an organic group.
Examples of the “halogen atom” are the same as those exemplified for R ¹ and R ² . The “amino group” is an amino group; a monoalkylamino group such as a methylamino group or an ethylamino group, preferably a mono C1-6 alkylamino group; a dialkylamino group such as a dimethylamino group or a diethylamino group, preferably diC1. -6 alkylamino group; monoarylamino group such as phenylamino group and 4-methylphenylamino group, preferably monoC6-10 arylamino group; diarylamino group such as diphenylamino group and di1-naphthylamino group, preferably Are di-C6-10 arylamino groups; acylamino groups such as acetylamino groups and benzoylamino groups, preferably C1-6 acylamino groups; and the like.

The “organic group” is not particularly limited as long as it is an atomic group containing a carbon atom. For example, the following groups are mentioned.
A cyano group;
C1-7 acyl groups such as formyl group, acetyl group, benzoyl group;
A C1-6 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group;
A C2-6 alkenyl group such as a vinyl group, a propenyl group, an isopropenyl group, a 2-butenyl group;
A C2-6 alkynyl group such as a propargyl group and a 3-butynyl group;
A C1-6 haloalkyl group such as a trifluoromethyl group, a pentafluoroethyl group, or a 3,3,3-trifluoropropyl group;
A C3-8 cycloalkyl group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group;
C3-8 halocycloalkyl groups such as 2-chlorocyclopropyl group, 2,2-dichlorocyclopropyl group, 3-chlorocyclopentyl group, 4-bromocyclohexyl group;
C1-6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group;
A C1-6 haloalkoxy group such as a trichloromethoxy group or a trifluoromethoxy group;

A C1-6 alkylsulfonyl group such as a methylsulfonyl group or an ethylsulfonyl group;
A C1-6 haloalkylsulfonyl group such as a chloromethylsulfonyl group or a trichloromethylsulfonyl group;
A C1-6 alkylsulfonyloxy group such as a methylsulfonyloxy group or an ethylsulfonyloxy group;
An unsubstituted or substituted phenylsulfonyl group such as a phenylsulfonyl group and a 4-methylphenylsulfonyl group;
An unsubstituted or substituted phenylsulfonyloxy group such as a phenylsulfonyloxy group, a 4-methylphenylsulfonyloxy group;
A C1-6 alkylthio group such as a methylthio group or an ethylthio group;
C1-6 haloalkylthio groups such as chloromethylthio group, trichloromethylthio group and trifluoromethylthio group; phenylthio groups having no substituents or substituents such as phenylthio group and 4-methylphenylthio group;
A C1-6 alkylsulfinyl group such as a methylsulfinyl group or an ethylsulfinyl group;
A C1-6 haloalkylsulfinyl group such as a halomethylsulfinyl group and a haloethylsulfinyl group;
An unsubstituted or substituted phenylsulfinyl group such as a phenylsulfinyl group;

_{-N = CHOH, -N = CSH (} OCH 3), - N = C (CF 3) (OcPr) (cPr represents a cyclopropyl group or less the same.), - N = C _[N (CH 2 _CH 3) ₂ ] a group represented by —N═C (R ¹⁰ ) OR ¹¹ , such as OCH ₂ CH ₃ ;
_{-C (= O) N (CH} 3) C 2 H 5, -C (= O) N (CF 3) Ph (Ph represents a phenyl group or less the same..), - C (= O) N (cPr A group represented by —C (═O) N (R ¹⁰ ) (R ¹¹ ) such as C ₂ H ₅ , —C (═O) N (CH═CH ₂ ) OH;
_{-CO 2 CH 3, -CO 2 CCl} 3, -CO 2 Ph, a group represented by _-CO 2 ^{R 10,} such as -CO 2 (cPr);
_{-C (= S) N (CH} 3) C 2 H 5, -C (= S) N (CF 3) Ph, -C (= S) N (cPr) C 2 H 5, -C (= S) A group represented by —C (═S) N (R ¹⁰ ) (R ¹¹ ), such as N (CH═CH ₂ ) OH;
-Si (CH ₃ ) ₃ , -SiPh ₃ , -Si (cPr) ₃ , -Si (CH ₃ ) ₂ (t-Bu) (t-Bu represents a tertiary butyl group; the same shall apply hereinafter). A group represented by Si (R ¹² ) (R ¹³ ) (R ¹⁴ );
An unsubstituted or substituted aryl group such as a phenyl group, 4-methylphenyl group, 2-fluorophenyl group, 2,4-dichlorophenyl group, 2,4,6-trimethylphenyl group; or
An unsubstituted or substituted heterocyclic group similar to the unsubstituted or substituted heterocyclic group of R ^{3 to} R ⁶ ;
Etc. Of these, alkyl groups and haloalkyl groups are preferred.

Among the organic groups, the “substituent” of “unsubstituted or substituted” refers to the “unsubstituted or substituted amino group” or “unsubstituted or substituted phenyl” of R ^{3 to} R ^6. Group "," unsubstituted or substituted aryloxy group "," unsubstituted or substituted aralkyl group "and" unsubstituted or substituted heterocyclic group ". Things.
Among the organic groups, R ^{10 to} R ¹⁴ each independently represent a hydrogen atom; a hydroxyl group; a thiol group; a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, C1-10 alkyl groups such as i-butyl group, s-butyl group, t-butyl group; C1-10 haloalkyl groups such as trifluoromethyl group, pentafluoroethyl group; vinyl group, aryl group, isopropenyl group, 2 -C2-10 alkenyl groups such as butenyl groups; unsubstituted or substituted amino groups, methylamino groups, dimethylamino groups, phenylamino groups, 4-methylphenylamino groups, diphenylamino groups, acetylamino groups, benzoylamino groups, etc. An amino group having a group; C3-10 cycloamino such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, etc. Kill group; a phenyl group, 2-chlorophenyl group, a phenyl group or an unsubstituted or substituted group such as a 4-methylphenyl group.

n represents an integer of 0 to 4.
Z represents an oxygen atom or a sulfur atom. This represents a 2H-1,3-benzoxazine ring or a 2H-1,3-benzothiazine ring.

(Production method)
(Production method 1)
The nitrogen-containing heterocyclic compound of the present invention can be produced, for example, by a known method. For example, it can be produced as follows (Japanese Patent Laid-Open No. 5-97824, Chem. Pharm. Bull. 1996, 44, 734-745, J. Med. Chem. 2007, 50, 2647-2654.).
Formula (II)

(In the formula, X, n, Z, R ¹ and R ² are the same as the definitions of X, n, Z, R ¹ and R ^{2 in} the formula (I). E is halogenated or esterified. And a compound represented by the formula (III)

(Wherein R ^{3 to} R ⁶ are the same as the definitions of R ^{3 to} R ⁶ in formula (I). M represents a leaving group). it can.
In the formula (II), the halogen represented by E is preferably chlorine, bromine or iodine, and the esterified hydroxyl group is preferably a reaction of trifluoromethanesulfonyl, methanesulfonyl, p-toluenesulfonyl or the like. And a hydroxyl group esterified with a functional group.
In the formula (III), the leaving group represented by M is Li, Na, K, Ca (1/2), MgCl, MgBr, MgI, ZnCl, SnCl, Sn (n-Bu) ₃ , CrCl ₂ , CuCl, CuBr, NiCl, PdCl, B (OH) _{2 and the} like can be mentioned.
The reaction is carried out at about −50 ° C. in an inert solvent such as tetrahydrofuran, diethyl ether, dimethoxyethane, hexane, toluene, benzene, methylene chloride, chloroform, 1,2-dichloroethane, DMF, DMSO or a mixed solvent thereof. It is carried out in a temperature range of ˜50 ° C. The reaction is preferably performed in an inert gas atmosphere (for example, nitrogen, argon, etc.). If necessary, tetrakis (triphenylphosphine) palladium (O), tetrakis (triphenylphosphine) nickel (O) or the like can be added as a catalyst to allow the reaction to proceed smoothly.

The compound represented by the formula (II), which is a starting material, can be produced by using a known compound or by the method shown in the examples.
In addition, the compound represented by the formula (III) is, for example, the formula (III ′)

(Wherein R ^{3 to} R ⁶ are as defined above; W represents hydrogen or halogen (Cl, Br, I)) and a compound that is a starting material of the leaving group M Is reacted in the above inert solvent in a temperature range of about -78 ° C to 70 ° C, preferably in an inert gas atmosphere. Usually, the compound of the formula (III) is produced in the reaction system and is isolated from the reaction mixture without reacting with the compound of the formula (II) to produce the compound of the formula (I).

Furthermore, X and R ^{1 to} R ⁶ in the compound represented by the formula (I) can be converted into other substituents by, for example, the following known methods. For example, a hydrogen atom is replaced by a halogen atom by halogenation, or by nitration to a nitro group, and by reduction of the nitro group to an amino group, by acylation or sulfonation of the amino group, to an acylamino group or sulfonylamino group It can also be guided. The cyano group can be converted to a carbamoyl group by treatment with, for example, an aqueous sodium hydroxide solution / 30% hydrogen peroxide, or a thiocarbamoyl group using hydrogen sulfide in pyridine / triethylamine. The cyano group can be converted to a carboxyl group by heating and hydrolysis in an aqueous sodium hydroxide solution, or a formyl group using Raney nickel in water / acetic acid / pyridine in the presence of sodium phosphate. You can also The formyl group can be converted into a vinyl group by a Wittig reaction, a hydroxyiminomethyl group or the like by a reaction with hydroxyamine. A hydroxyl group can be converted to an alkoxy group by alkylation, an acyloxy group by acylation, and an alkyl hydroxyl group can be converted to a nitroxyalkyl group by sulfuric acid / nitric acid.

(Production method 2)
When Z in the formula (I) is an oxygen atom, it can also be produced by the following method (see JP-A-5-97824, etc.).
Formula (IV)

Wherein X and n are as defined above, M ′ represents a leaving group, and Y represents a hydroxyl-protecting group, and a compound represented by formula (V)

(Wherein R ^{3 to} R ⁶ are the same as defined above. M ′ represents a leaving group), and after the reaction, the compound is deprotected by a known method to give a compound represented by the general formula (VI)

(Wherein X, n and R ^{3 to} R ⁶ are the same as defined above), and in the presence of an acid catalyst, the compound of formula (VII) is obtained.

(In the formula, R ¹ and R ² are the same as the definitions of R ¹ and R ² in formula (I). R represents a methyl group or an ethyl group). .

  The imino compound represented by the formula (VI) is represented by the formula (VIII)

(Wherein, X, n, and R ^{3 to} R ⁶ are the same as defined above) can be obtained by reacting with ammonia. Furthermore, the nitrogen-containing heterocyclic compound represented by the formula (I) of the present invention includes a compound represented by the formula (VIII), a compound represented by the formula (VII) and ammonia in the presence of an acid catalyst. It can also be produced by reacting with.

In the formulas (IV) and (V), the leaving group represented by M ′ is preferably Li, Na, K, Ca (1/2), MgCl, MgBr, MgI, ZnCl, SnCl, CrCl ₂ or the like. Is mentioned. In the formula (IV), the hydroxyl-protecting group represented by Y is preferably a known phenolic hydroxyl-protecting group, such as a methoxydimethylmethyl group, a trimethylsilyl group, or a t-butyldimethylsilyl group.

  The condensation reaction of the compound represented by the above formula (IV) and the compound represented by the formula (V) is an inert solvent such as tetrahydrofuran, diethyl ether, dimethoxyethane, hexane, toluene, benzene, methylene chloride, DMF, or the like. Among these mixed solvents, it is carried out at a temperature range of about -70 ° C to 70 ° C. This reaction is preferably performed under an atmosphere of an inert gas (for example, nitrogen, argon, etc.). The subsequent deprotection reaction is carried out by acid hydrolysis or a fluorinated salt reagent such as tetrabutylammonium fluoride or potassium fluoride.

  The reaction of the hydroxyketone compound (VIII) with ammonia is carried out in an inert solvent such as ethanol, benzene, toluene, chloroform, dichloromethane, 1,2-dichloroethane, tetrahydrofuran, diethyl ether, or a mixed solvent thereof. It is performed in a temperature range of 0 ° C to 100 ° C. Usually, this reaction is carried out in the presence of a dehydrating agent (for example, molecular sieves, anhydrous calcium sulfate, anhydrous magnesium sulfate, etc.) in a solvent containing 1 to 10 times the molar amount of ammonia with respect to the hydroxyketone compound (VIII). Done in a sealed tube. The imino compound (VI) can also be used in the next reaction without isolation and purification.

  The ring closure reaction between imino compound (VI) and compound (VII) is carried out by using an acid catalyst in a solvent-free or inert solvent such as benzene, toluene, chloroform, dichloromethane, 1,2-dichloroethane, diethyl ether, or a mixed solvent thereof. In the presence of a dehydrating agent, the reaction is performed at a temperature ranging from room temperature to 100 ° C. As the acid catalyst, hydrochloric acid, p-toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, ammonium chloride, ammonium acetate and the like can be used. The amount of the acid catalyst to be used is preferably changed as appropriate depending on the acidity of the catalyst, and is preferably in the range of about 1/100 to 10 times the molar amount of the imino compound (VI). As the dehydrating agent, for example, molecular sieves, anhydrous calcium sulfate, anhydrous magnesium sulfate and the like can be used.

  One-pot reaction of hydroxyketone compound (VIII), ammonia and compound (VII) can be carried out without solvent or inert solvent such as benzene, toluene, chloroform, dichloromethane, 1,2-dichloroethane, diethyl ether, etc. The reaction is performed in a mixed solvent in the temperature range of 0 ° C. to 100 ° C. in the presence of an acid catalyst and a dehydrating agent. Usually, this reaction is carried out in a sealed tube in a solvent containing 1 to 10 times the molar amount of ammonia with respect to the hydroxyketone compound (VIII). As the acid catalyst, those described in the ring-closing reaction of the imino compound (VI) and the compound (VII) can be used, and the amount of the acid catalyst used is 1/20 to 10 times that of the hydroxyketone compound (VIII). It is preferable to be in the range of about a mole. As the dehydrating agent, those described in the ring closure reaction of imino compound (VI) and compound (VII) can be used.

Of the nitrogen-containing heterocyclic compounds represented by the formula (I), basic compounds can be converted into salts using an acid. Suitable acids for this reaction are preferably acids which give an agro-horticulturally acceptable salt. For example, inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, nitric acid or sulfamic acid, organic acids such as acetic acid, tartaric acid, citric acid, fumaric acid, maleic acid, p-toluenesulfonic acid, methanesulfonic acid or glutamic acid Examples include acids.
The salt of the compound represented by the formula (I) can be produced, for example, by allowing an inorganic acid or an organic acid to act on the compound represented by the formula (I).

  In any reaction, after completion of the reaction, if purification of the product is necessary after the usual post-treatment operation, it is purified by a known and conventional purification means such as distillation, recrystallization or column chromatography. The target product can be isolated.

  The structure of the target product can be identified and confirmed by known analytical means such as elemental analysis, NMR spectrum, IR spectrum, and mass spectrum.

  Examples of the nitrogen-containing heterocyclic compound of the present invention obtained as described above are shown in Tables 1 to 4 below. In the following table, Me is a methyl group, Et is an ethyl group, n-Pr is an n-propyl group, c-Pr is a cyclopropyl group, c-Hex is a cyclohexyl group, n-Bu is an n-butyl group, and t-Bu. Represents a t-butyl group, i-Pen represents an i-pentyl group, Py represents a pyridyl group, and Ph represents a phenyl group.

In Tables 1 to 4 above, when R ⁵ and R ⁶ are combined to represent Ph, it represents that a quinoline ring is formed, and when it has a substituent, the substitution position is defined as quinoline. Represent.
In Tables 1 to 4, when R ⁵ and R ⁶ are combined to represent the formula: —CH═CH—S—, a thieno [2,3-b] pyridine ring is formed. Represents that

2) Agricultural / horticultural fungicide The nitrogen-containing heterocyclic compound represented by the formula (I) of the present invention or a salt thereof (hereinafter sometimes referred to as "the present compound") has at least one of them as an active ingredient. It can be used as an agricultural and horticultural fungicide (hereinafter sometimes referred to as “the present invention fungicide”).

  The amount of the active ingredient is not particularly limited, but is usually 0.01 to 90% by weight, preferably 0.05 to 85% by weight, based on the whole fungicide.

  The fungicide of the present invention is excellent against a wide variety of fungi, for example, bacteria belonging to Omycetes, Ascomycetes, Deuteromycetes, and Basidiomycetes. Has sterilizing power.

  The composition containing the fungicide of the present invention as an active ingredient is used by seed treatment, foliage application, soil application, water application, etc., for the control of various diseases that occur during cultivation of agricultural and horticultural crops including flowers, turf, and grass. be able to.

For example,
Sugar beet brown spot (Cercospora beticola)
Peanut brown spot (Mycosphaerella arachidis)
Black astringent disease (Mycosphaerella berkeleyi)
Cucumber powdery mildew (Sphaerotheca furiginea)
Vine Blight (Mycosphaella melonis)
Sclerotinia sclerotiorum
Gray mold disease (Botrytis cinerea)
Black star disease (Cladosporium cucumerinum)
Brown spot disease (Corynespora casiccola)
Seedling Blight (Phythium debaryanam, Rhizoctonia solani Kuhn)
Spotted bacterial disease (Pseudomonas syringae pv. Lecrymans)
Tomato gray mold (Botrytis cinerea)
Leaf mold (Cladosporium fulvum)
Eggplant gray mold (Botrytis cinerea)
Black blight (Corynespora melogenae)
Powdery mildew (Erysiphe cichoracerarum)
Susmolder disease (Mycovelosella natrassii)
Strawberry Gray mold disease (Botrytis cinerea)
Powdery mildew (Sohaerotheca humuli)
Anthracnose (Colletotrichum acutatum, Colletotrichum fragariae)
Onion gray rot (Botrytis allii)
Gray mold disease (Botrytis cinerea)
White spotted leaf blight (Botrytis squamosa)
Cabbage root-knot disease (Plasmodiophora brassicae)
Soft rot (Erwinia carotovora)
Kidney bean sclerotia (Sclerotinia sclerotiorum)
Gray mold disease (Botrytis cinerea)
Apple powdery mildew (Podosphaera leukotricha)
Venturia inaequalis
Moniria disease
Rot rot (Valsa mali)
Spotted leaf fall (Alternaria mary)
Red Star Disease (Gymnosporium yamadae)
Ring-shaped disease (Botryosphaeria berengeriana)
Anthracnose (Colletotrichum gloeosprioides)
Brown spot disease (Diplocarpon mary)
Oyster powdery mildew (Phyllactinia kakicola)
Anthracnose (Gloeosporium kaki)
Spotted leaf disease (Cercospora kaki)

Peach out ash scab (Monilinia fracticola)
Grapes Gray mold (Botrytis cinerea)
Powdery mildew (Uncinula necator)
Late rot (Glomerella cingulata)
Pear black scab (Venturia nashicola)
Red Star Disease (Gymnosporium asiaticum)
Black spot disease (Alternaria kikuchiana)
Cha ring spot disease (Pestaloti theae)
Anthracnose (Colletotrichum theae-sinensis)
Citrus common scab (Elsinoe fawceti)
Blue mold disease (Penicillium italicum)
Green mold (Penicillium digitatum)
Gray mold disease (Botrytis cinerea)
Black spot disease (Diaporthe citri)
Sickness disease (Xanthomonas campestris pv. Citri)
Wheat powdery mildew (Erysiphe graminis f. Sp. Tritici)
Red mold disease (Gibberella zeae)
Red rust (Puccinia recondita)
Brown snow rot (Pythium iwayamai)
Scarlet Snow Rot (Monographella nivalis)
Eye disease (Pseudocercosporella herpotriochoides)
Leaf blight (Septoria tritici)
Blight disease (Leptosphaeria nodorum)
Typhula incarnata (Typhula incarnata)
Snow rot large mycobacterial disease (Myriosclerotinia borealis)
Blight (Gaeumanomyces graminis)

Barley leaf spot disease (Pyrenophora graminia)
Rhynchosporium secalis
Bare Scab (Ustilago tritici, U. nuda)
Rice blast disease (Pyricularia oryzae)
Rhizoctonia solani
Idiot Seedling (Gibberella fujikuroi)
Sesame leaf blight (Cochliobolus niyabeanus)
Tobacco sclerotia (Sclerotinia sclerotiorum)
Powdery mildew (Erysiphe cichoracerarum)
Tulip Gray mold disease (Botrytis cinerea)
Bentgrass (Sclerotinia borealis)
Orchardgrass powdery mildew (Erysiphe graminis)
Soybean Purpura (Cercospora kikuchii)
Potato tomato plague (Phytophthora infestans)
Cucumber downy mildew (Pseudoperonospora cubensis)
It can be used to control grape downy mildew (Plasmopara viticola) and the like.

  In recent years, resistance to benzimidazole fungicides, dicarboximide fungicides, and the like has developed in various pathogenic bacteria, resulting in insufficient efficacy of these drugs, and drugs effective against resistant bacteria are desired. The bactericidal agent of the present invention has an excellent bactericidal effect not only on pathogenic bacteria sensitive to these drugs but also on resistant bacteria.

  For example, gray mold fungus (Botrytis cinerea), sugar beet brown fungus (Cercospora beticola), Venturia inaequalis, Venturia ina ol (Venturia inaequilis), Venturia in ol The fungicides of the present invention are also effective against susceptible bacteria.

  Furthermore, the fungicides of the present invention are also effective against gray mold fungi (Botrytis cinerea) that are resistant to dicarboximide fungicides (for example, vinclozoline, procymidone, iprodione).

  Examples of diseases that can be preferably applied include brown spot of sugar beet, powdery mildew of wheat, rice blast, rice black scab, gray mold of cucumber, and brown spot of peanut. Examples of diseases more preferably applied include various fruit tree diseases.

The fungicide of the present invention is a highly safe drug with little phytotoxicity, low toxicity to fish and warm-blooded animals.
The fungicide of the present invention can be used in a pure form without adding other components, but using additives and carriers, wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, You may use with the form which general agricultural chemicals, such as a granule wettable powder, can take.

  Additives and carriers that can be added to the agrochemical formulation include vegetable powders such as soybean flour and wheat flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, Mineral fine powders such as clay, organic and inorganic compounds such as sodium benzoate, urea, and mirabilite are used.

  For liquid dosage forms, kerosene, xylene and petroleum aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil Water or the like can be used as a solvent.

Furthermore, in order to take a uniform and stable form in these preparations, a surfactant may be added as necessary.
The surfactant to be used is not particularly limited. For example, alkylphenyl ether added with polyoxyethylene, alkyl ether added with polyoxyethylene, higher fatty acid ester added with polyoxyethylene, sorbitan added with polyoxyethylene Higher fatty acid esters, nonionic surfactants such as tristyryl phenyl ether added with polyoxyethylene, sulfates of alkylphenyl ethers added with polyoxyethylene, alkylbenzene sulfonates, sulfates of higher alcohols, alkyls Examples thereof include naphthalene sulfonate, polycarboxylate, lignin sulfonate, formaldehyde condensate of alkyl naphthalene sulfonate, and isobutylene-maleic anhydride copolymer.

  The wettable powder, emulsion, flowable, aqueous solvent and granular wettable powder thus obtained are diluted with water to a predetermined concentration to obtain a solution, suspension or emulsion, and the powder and granules are left as they are. Used in a method of spraying on plants.

  The formulated bactericidal agent of the present invention is applied as it is or diluted with water or the like to a plant body, seeds, water surface or soil. The application amount varies depending on weather conditions, formulation form, application magnetism, application method, application location, disease to be controlled, target crop, etc., but is usually 1 to 1,000 g, preferably 10 to 10 g of active ingredient compound per hectare. 100 g.

  When a wettable powder, emulsion, suspension, aqueous solvent, granular wettable powder and the like are diluted with water and applied, the applied concentration is 1-1000 ppm, preferably 10-250 ppm. In this case, it can be applied as it is without dilution.

  In addition to the compound of the present invention, one or two or more of various fungicides, insecticides / acaricides, or synergists can be mixed with the fungicide of the present invention.

  Typical examples of fungicides, insecticides, acaricides, and plant growth regulators that can be used in combination with the compounds of the present invention are shown below.

Fungicide:
Captan, phorpet, thiuram, ziram, dinebu, manneb, mancozeb, propineb, polycarbamate, chlorothalonil, quintozen, captaphor, iprodione, prosaimidin, vinclozolin, fluoroimide, thymoxanyl, mepronil, flutolanil, pencyclon, oxycarboxyl, fosetyl aluminum, Propamocurve, triadimephone, triadimenol, propiconazole, diclobutrazole, viteltanol, hexaconazole, microbutanyl, flusilazole, metconazole, etaconazole, fluotrimazole, cyproconazole, epoxyconazole, flutriaphene, beconazole , Diniconazole, cyproconazole, phenalimol, triflumizole, prochlor , Imazalyl, pefrazoate, tridemorph, fenpropimorph, triphorin, butiobate, pyrifenox, anilazine, polyoxin, metalaxyl, oxadixyl, furaxyl, isoprothiolane, probenazole, pyrrolnitrin, blasticidin S, kasugamycin, validamycin, dihydrostreptomycin sulfate , Benomyl, carbendazim, thiophanatemethyl, hymexazole, basic copper chloride, basic copper sulfate, fentin acetate, triphenyltin hydroxide, dietofencarb, metasulfocarb, quinomethionate, binapacryl, lecithin, baking soda, dithianone, dinocup, phenaminosulfur, Dichromemedin, Guazatine, Dodin, IBP, Edifenphos, Mepanipyrim, Fermzo , Trichlamide, methasulfocarb, fluazinam, Etokinorakku, dimethomorph, pyroquilon, tecloftalam, fthalide, phenazine oxide, thiabendazole, tricyclazole, vinclozolin, cymoxanil, cyclobutanyl, guazatine, propamocarb hydrochloride, oxolinic acid, hydroxy isoxazole, iminoctadine acetate, and the like.

Insecticides and acaricides:
Organophosphorus and carbamate insecticides:
Fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, bamidthione, phentoate, dimethoate, formothione, marathon, trichlorfone, thiometone, phosmet, dichlorvos, acephate, EPBP, methyl parathion, oxydimethone methyl, ethion, salicione, cyanophos, isoxathione, cyanophos, isoxathione Methidathion, sulfophos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, ethylthiomethone, propenofos, pyracrofos, monocrotophos, azinephosmethyl, aldicarb, mesomil, thiodicarb, carbofuran, carbosulfan, benfracarb, furiocarb, Propoxur, BPMC, M MC, MIPC, carbaryl, pirimicarb, ethiofencarb, fenoxycarb, EDDP, and the like.
Pyrethroid insecticides:
Permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatoline, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propraslin, phenothrin, protorin, fulvalinate, cyfluthrin, cyhalothrin, flucitrinate, etofenprox, cycloprotorin, thoramethrin , Silafluophene, brofenprox, aclinasrin, etc.
Benzoylurea and other insecticides:
Diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, metoprene, benzoepin, diafenthiuron, acetamiprid, imidacloprid, nitenpyram, fipronil, cartap Thiocyclam, bensultap, nicotine sulfate, rotenone, metaldehyde, machine oil, microbial pesticides such as BT and entomopathogenic viruses.

Nematicides:
Phenamifos, phostiazates, etc.
Acaricide:
Chlorbenzilate, phenisobromolate, dicofol, amitraz, BPPS, benzomate, hexithiazox, fenbutazin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentedin, cihexatin, pyridaben, fenpyroximate, tebufenpyrad, thiomidibene Dienochlor etc.
Plant growth regulator:
Gibberellins (eg, gibberellin A3, gibberellin A4, gibberellin A7), IAA, NAA.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.

[Example 1]
2,2-dimethyl-4- (3-quinolyl) -2H-1,3-benzoxazine (Compound No. 1a-1)
To a solution of 3-bromoquinoline (1.29 g, 6.20 mmol) in diethyl ether (20 mL) was added 1.7 M t-butyllithium solution (3.83 mL, 6.51 mmol) at −78 ° C. Stir for 5 hours. To this solution was added 1.0 M zinc chloride in tetrahydrofuran (6.82 mL, 6.82 mmol) at −78 ° C., and the temperature was raised to 0 ° C. over 20 minutes. Diethyl ether solution (5 mL) of tetrakistriphenylphosphine palladium (0.36 g, 0.31 mmol) and Trifluoromethanesulfonic acid 2,2-dimethyl-2H-1,3-benzoxazin-4-yl ester (3.10 mmol) was added to this solution. And stirred at room temperature for 18 hours. Thereafter, the reaction solution was poured into ethyl acetate (60 mL), water (100 mL) and saturated aqueous sodium hydrogen carbonate (50 mL), and the aqueous layer was extracted with ethyl acetate (100 mL). The combined organic layers were washed with brine (50 mL) and dried over magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 0.71 g (79%) of the desired product.
Physical property: mp93-95 ° C
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.71 (s, 6H), 6.90-6.98 (m, 2H), 7.20 (m, 1H), 7.42 (m, 1H), 7.60 (m, 1H), 7.79 ( m, 1H), 7.89 (dd, 1H, J = 1.5, 8.4 Hz), 8.17 (d, 1H, J = 8.4 Hz), 8.37 (dd, 1H, J = 0.6, 2.1 Hz), 9.11 (d, 1H , J = 2.1 Hz); MS (APCI, m / z) 289 ([M + 1] ⁺ )
The following compounds were synthesized by the same method.

[Example 2]
2,2-dimethyl-8-fluoro-4- (3-quinolyl) -2H-1,3-benzoxazine (Compound No. 1b-1)
Physical property: mp107-109 ° C
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.76 (s, 6H), 6.87 (m, 1H), 7.01 (m, 1H), 7.23 (m, 1H), 7.62 (m, 1H), 7.80 (m, 1H), 7.89 (dd, 1H, J = 1.5, 8.1 Hz), 8.18 (d, 1H, J = 8.1 Hz), 8.36 (dd, 1H, J = 0.6, 2.1 Hz), 9.10 (d, 1H, J = 2.1 Hz); MS (APCI, m / z) 307 ([M + 1] ⁺ )

[Example 3]
2,2-diethyl-4- (3-quinolyl) -2H-1,3-benzoxazine (Compound No. 1a-51)
Physical properties: amorphous
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.04 (t, 6H, J = 7.5 Hz), 2.00 (q, 4H, 1.76 J = 7.5 Hz), 6.85-6.94 (m, 2H), 7.18 (dd, 1H, J = 1.5, 7.5 Hz), 7.39 (m, 1H), 7.61 (m, 1H), 7.79 (m, 1H), 7.89 (d, 1H, J = 8.1 Hz), 8.17 (d, 1H, J = 8.1 Hz), 8.36 (d, 1H, J = 1.8 Hz), 9.12 (d, 1H, J = 1.8 Hz); MS (APCI, m / z) 317 ([M + 1] ⁺ )

[Example 4]
2,2-dimethyl-4- (3-quinolyl) -2H-1,3-benzothiazine (Compound No. 1c-1)
(Process 1)
2,2-dimethyl-2H-1,3-benzothiazin-4-one (0.50 g, 2.58 mmol) in benzene (10 mL) was added to phosphorus oxychloride (0.40 g, 2.58 mmol) and N, N- Dimethylaniline (0.63 g, 5.16 mmol) was added and heated to reflux for 14 hours. Further, 2,6-lutidine (0.50 g, 4.65 mmol) was added and stirred in an ice bath for 30 minutes. Thereafter, the reaction solution was cooled to 0 ° C., water (10 mL) was added, and the mixture was stirred at 0 ° C. for 20 minutes. The solution was poured into diethyl ether (100 mL) and water (100 mL), and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed with brine (50 mL) and dried over magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure to obtain 0.82 g of 4-chloro-2,2-dimethyl-2H-1,3-benzothiazine as a blue-black oily substance. This product was used in the next reaction without further purification.
(Process 2)
A dimethylformamide solution (10 mL) of 3-quinolineboronic acid (0.33 g, 1.94 mmol) and 2M aqueous cesium carbonate solution (1.94 mL, 3.87 mol) was substituted with nitrogen, and then tetrakistriphenylphosphine palladium (0 30 g, 0.26 mmol) and 4-chloro-2,2-dimethyl-2H-1,3-benzothiazine (1.29 mmol) were added. This solution was stirred at 80 ° C. for 2 days. Thereafter, the reaction solution was cooled to room temperature, poured into ethyl acetate (100 mL) and water (100 mL), and the aqueous layer was extracted with ethyl acetate (100 mL). The combined organic layers were washed with brine (60 mL) and dried over magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 0.05 g (13%) of the desired product.
Physical property: mp140-142 ° C
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.70 (s, 6H), 7.13 (m, 1H), 7.27 (m, 1H), 7.36-7.44 (m, 2H), 7.59 (m, 1H), 7.77 ( m, 1H), 7.86 (d, 1H, J = 8.41 Hz), 8.16 (d, 1H, J = 8.4 Hz), 8.30 (d, 1H, J = 2.1 Hz), 9.05 (d, 1H, J = 2.1 Hz); MS (APCI, m / z) 305 ([M + 1] ⁺ )
The following compounds were synthesized by the same method.

[Example 5]
2-ethyl-2-methyl-4- (3-quinolyl) -2H-1,3-benzoxazine (Compound No. 1a-2)
Physical properties: amorphous
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.08 (t, 3H, J = 7.5 Hz), 1.64 (s, 3H), 2.03 (q, 2H, J = 7.5 Hz), 6.88-6.96 (m, 2 H ), 7.19 (dd, 1H, J = 1.5, 7.8 Hz), 7.40 (m, 1H), 7.60 (m, 1H), 7.79 (m, 1H), 7.89 (d, 1H, J = 8.4 Hz), 8.17 (d, 1H, J = 8.4 Hz), 8.36 (d, 1H, J = 2.1 Hz), 9.11 (d, 1H, J = 2.1 Hz)

[Example 6]
4- (3-quinolyl) -2H-spiro [1,3-benzoxazine-2,1'-cyclohexane] (Compound No. 1a-47)
Physical property: mp 117-119 ° C
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.51 (m, 1H), 1.63-1.79 (m, 5H), 1.91-2.09 (m, 4H), 6.93 (m, 1H), 6.99 (m, 1H), 7.20 (m, 1H), 7.41 (m.1H), 7.60 (m, 1H), 7.78 (m, 1H), 7.89 (dd, 1H, J = 1.5, 8.4 Hz), 8.17 (dd, 1H, J = 0.9, 8.4 Hz), 8.37 (dd, 1H, J = 0.6, 2.1 Hz), 9.13 (d, 1H, J = 2.1 Hz); MS (APCI, m / z) 329 ([M + 1] ⁺ )

[Example 7]
4- (3-quinolyl) -2H-spiro [1,3-benzoxazine-2,1'-cyclopentane] (Compound No. 1a-52)
Physical properties: amorphous
¹ H NMR (300 MHz, CDCl ₃ ) δ1.92-1.95 (m, 4H), 2.04-2.17 (m, 2H), 2.23-2.30 (m, 2H), 6.91-6.99 (m, 2H), 7.20 ( dd, 1H, J = 1.5, 7.8 Hz), 7.41 (m, 1H), 7.60 (m, 1H), 7.79 (m, 1H), 7.89 (m, 1H), 8.17 (m, 1H), 8.38 (d , 1H, J = 2.1 Hz), 9.13 (d, 1H, J = 2.1 Hz); MS (APCI, m / z) 315 ([M + 1] ⁺ )

[Example 8]
2,2-dimethyl-8-fluoro-4- (3-quinolyl) -2H-1,3-benzothiazine (Compound No. 1b-33)
Physical property: mp162-163 ° C
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.72 (s, 6H), 7.10-7.25 (m, 3H), 7.60 (m, 1H), 7.79 (m, 1H), 7.87 (d, 1H, J = 8Hz ), 8.16 (d, 1H, J = 8 Hz), 8.30 (d, 1H, J = 2.1 Hz), 9.05 (d, 1H, J = 2.1 Hz)

[Example 9]
2,2-dimethyl-8-fluoro-4- (8-fluoroquinolin-3-yl) -2H-1,3-benzoxazine (Compound No. 1b-23)
Physical property: mp 127-128 ° C
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.76 (s, 6H), 6.88 (m, 1H), 6.98 (m, 1H), 7.24 (m, 1H), 7.45-7.60 (m, 2H), 7.70 ( d, 1H, J = 7.4 Hz), 8.40 (t, 1H, J = 1.9 Hz), 9.14 (d, 1H, J = 1.8 Hz)

[Example 10]
2,2-dimethyl-8-methyl-4- (3-quinolyl) -2H-1,3-benzoxazine (Compound No. 1b-70)
Physical property: mp110-112 ° C
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.71 (s, 6H), 2.27 (s, 3H), 6.82 (t, 1H, J = 7.7 Hz), 7.0-7.9 (m, 5H), 8.17 (d, 1H, J = 8.4 Hz), 8.36 d, 1H, J = 2.1 Hz), 9.10 (d, 1H, J = 2.1 Hz)

[Example 11]
8-chloro-2,2-dimethyl-4- (3-quinolyl) -2H-1,3-benzoxazine (Compound No. 1b-67)
Physical property: mp118-120 ° C
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.76 (s, 6H), 6.88 (t, 1H, J = 7.9 Hz), 7.1-8.0 (m, 5H), 8.18 (d, 1H, J = 8.6 Hz) , 8.36 d, 1H, J = 1.8 Hz), 9.10 (bs, 1H)

[Example 12]
2-Ethyl-8-fluoro-2-methyl-4- (3-quinolyl) -2H-1,3-benzoxazine (Compound No. 1b-2)
Physical properties: amorphous
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.10 (t, 3H, J = 7.4 Hz), 1.69 (s, 3H), 2.07 (q, 2H, J = 7.4 Hz), 6.8-8.0 (m, 6H) , 8.17 (d, 1H, J = 8.4 Hz), 8.36 (d, 1H, J = 2.0 Hz), 9.11 (d, 1H, J = 2.0 Hz)

[Example 13]
2-cyclopropyl-2-methyl-4- (3-quinolyl) -2H-1,3-benzoxazine (Compound No. 1a-53)
Physical properties: amorphous
¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.5-0.8 (m, 4H), 1.4-1.5 (m, 1H), 1.66 (s, 3H), 6.8-7.0 (m, 2H), 7.15-8.0 ( m, 5H), 8.17 (d, 1H, J = 8.6 Hz), 8.35 (d, 1H, J = 2.4 Hz), 9.10 (d, 1H, J = 2.4 Hz)

[Example 14]
2-Ethyl-8-fluoro-2-methyl-4- (3-quinolyl) -2H-1,3-benzothiazine (Compound No. 1b-68)
Physical property: mp123-125 ° C
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.12 (t, 3H, J = 7.4 Hz), 1.64 (s, 3H), 2.02 (q, 2H, J = 7.4 Hz), 7.0-7.9 (m, 6H) , 8.17 (d, 1H, J = 8.9 Hz), 8.29 (bs, 1H), 9.06 (bs, 1H)

[Example 15]
2,2-dimethyl-8-fluoro-4- (8-fluoroquinolin-3-yl) -2H-1,3-benzothiazine (Compound No. 1b-69)
Physical property: mp172-174 ° C
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.72 (s, 6H), 7.0-7.3 (m, 3H), 7.4-7.6 (m, 2H), 7.67 (d, 1H, J = 7.4Hz), 8.34 ( d, 1H, J = 2.0 Hz), 9.07 (d, 1H, J = 2.0 Hz)
[Example 16]
2-Methyl-2- (1-propyl) -4- (3-quinolyl) -2H-1,3-benzoxazine (Compound No. 1a-3)
Physical property: amorphous
¹ H-NMR (300 MHz, CDCl ₃ ) δ0.95 (t, 3H), 1.55 (m, 2H), 1.64 (s, 3H), 1.97 (t, 2H), 6.92 (t, 1H), 7.16 ( d, 1H), 7.42 (t, 1H), 7.56-7.59 (m, 2H), 7.72 (t, 1H), 7.88 (d, 1H), 8.18 (d, 1H), 8.35 (s, 1H), 9.20 (s, 1H)
[Example 17]
2-Ethyl-8-fluoro-2-methyl-4- (8-fluoroquinolin-3-yl) -2H-1,3-benzothiazine (Compound No. 1b-72)
Physical property: mp144-146 ° C
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.12 (t, 3H, J = 7.4 Hz), 1.63 (s, 3H), 2.0-2.1 (m, 2H), 7.0-7.7 (m, 6H), 8.32 ( m, 1H), 9.09 (d, 1H, J = 2.1 Hz)
[Example 18]
4- (3-quinolyl) -2H-spiro [1,3-benzoxazine-2,1'-cyclobutane] (Compound No. 1a-60)
Physical properties: amorphous
¹ H-NMR (300 MHz, CDCl ₃ ) a1.98-2.08 (m, 2H), 2.54-2.66 (m, 4H), 6.93-7.92 (m, 7H), 8.17 (d, 1H, J = 8.4 Hz ), 8.40 (d, 1H, J = 2.0 Hz), 9.15 (d, 1H, J = 2.0 Hz)
[Example 19]
2-tert-Butyl-4- (3-quinolyl) -2H-1,3-benzoxazine (Compound No. 1a-61)
Physical properties: amorphous
¹ H-NMR (300 MHz, CDCl ₃ ) δ1.17 (s, 9H), 4.94 (s, 1H), 6.94-7.04 (m, 2H), 7.25-7.46 (m, 2H), 7.57-7.63 (m , 1H), 7.75-7.82 (m, 1H), 7.87-7.91 (m, 1H), 8.38 (d, 1H, J = 2.1 Hz), 9.21 (d, 1H, J = 2.1 Hz)
[Example 20]
2,2-Dimethyl-4- (6-chloropyridine-3-yl) -2H-1,3-benzoxazine (Compound No. 1a-63)
Physical properties: amorphous
¹ H NMR (300 MHz, CDCl ₃ ) a1.59 (s, 6H), 6.85-6.96 (m, 2H), 7.05-7.15 (m, 1H), 7.35-7.45 (m, 2H), 7.87 (dd, 1H, J = 8.6, 2.7Hz), 8.60 (dd, 1H, J = 2.4, 0.6Hz)
[Example 21]
2-Ethyl-8-fluoro-2-methyl-4- (6-chloropyridine-3-yl) -2H-1,3-benzothiazine (Compound No. 1c-66)
Physical properties: amorphous
¹ H NMR (300 MHz, CDCl ₃ ) δ1.07 (t, 3H, J = 7.4 Hz), 1.57 (s, 3H), 1.9-2.0 (m, 2H), 7.0-7.5 (m, 3H), 7.79 -7.84 (m, 1H), 8.52 (d, 1H, J = 2.7Hz)

[Example 22]
2,2-Dimethyl-8-fluoro-4- (thieno [2,3-b] pyridine-5-yl) -2H-1,3-benzoxazine (Compound No. 1b-71)
To a 50 mL flask purged with nitrogen gas was added anhydrous THF (5 mL) with a syringe, and the reaction vessel was cooled with a salt-ice bath. Then, a THF solution of 0.91 M n-BuMgCl (1.1 mL, 1.0 mmol) and a hexane solution of 2.69 M n-BuLi (0.8 mL, 2.15 mmol) were sequentially added, and the mixture was stirred at this temperature for 30 minutes. A solution of 5-Bromothieno [2,3-b] pyridine (0.6 g, 2.8 mmol) dissolved in 5 mL of dehydrated THF was added to this solution and stirred at the same temperature for 1.5 hours, and then B (OMe) 3 (0.38 mL, 3.4 mmol) was added, and the mixture was further stirred for 1 hour. H2O (5 mL) was added to the reaction solution, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was concentrated to dryness under reduced pressure. To the resulting residue, 20 mL of toluene was added, followed by cesium carbonate (2.0 g, 6.1 mmol) and tetrakistriphenylphosphine palladium (0.65 g, 0.56 mmol).
To this solution, 4-chloro-2,2-dimethyl-8-fluoro- prepared by the method of Example 2 from 2,2-dimethyl-2H-1,3-benzoxazin-4-one (0.50 g, 2.58 mmol). A solution of 2H-1,3-benzoxazine (2.56 mmol) in 5 mL of toluene was added, and the mixture was heated to reflux for 15 hours with stirring under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, water and ethyl acetate were added in 50 mL portions, insolubles were removed by celite filtration, liquid separation was performed, and the organic layer was washed with brine (60 mL) and dried over magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1) to obtain 0.07 g (9%) of the desired product.
Physical properties: amorphous
¹ H NMR (300 MHz, CDCl ₃ ) δ1.73 (s, 6H), 6.8-6.9 (m, 1H), 6.98 (d, 1H, J = 7.7 Hz), 7.21 (m, 1H), 7.32 (d , 1H, J = 6.0 Hz), 7.60 (d, 1H, J = 6.0 Hz), 8.27 (d, 1H, J = 2.1 Hz), 8.75 (d, 1H, J = 2.1 Hz)
The following compounds were synthesized by the same method.
[Example 23]
2,2-Dimethyl-8-fluoro-4- (thieno [2,3-b] pyridine-3-yl) -2H-1,3-benzothiazine (Compound No. 1c-67)
Physical property: mp186-188 ℃
¹ H NMR (300 MHz, CDCl ₃ ) δ1.71 (s, 6H), 7.05-7.27 (m, 3H), 7.32 (d, 1H, J = 6.0 Hz), 7.61 (d, 1H, J = 6.0 Hz ), 8.23 (d, 1H, J = 2.1 Hz), 8.70 (d, 1H, J = 2.1 Hz)
[Example 24]
2,2-Dimethyl-8-fluoro-4- (5,6,7,8-tetrahydroquinoline-3-yl) -2H-1,3-
benzothiazine (Compound No. 1c-65)
Physical property: amorphous
¹ H NMR (300 MHz, CDCl ₃ ) δ1.66 (s, 6H), 1.79-1.97 (m, 4H), 2.81 (t, 2H, J = 6.3 Hz), 2.97 (t, 2H, J = 6.3 Hz ), 7.05-7.22 (m, 3H), 7.52 (d, 1H, J = 2.1 Hz), 8.40 (d, 1H, J = 2.1 Hz)
[Example 25]
2,2-Dimethyl-4- (5,6,7,8-tetrahydroquinoline-3-yl) -2H-1,3-benzoxazine (Compound No. 1a-62)
Physical properties: amorphous
¹ H NMR (300 MHz, CDCl ₃ ) δ1.65 (s, 6H), 1.79-2.00 (m, 4H), 2.83 (t, 2H, J = 6.2 Hz), 2.98 (t, 2H, J = 6.2 Hz ), 6.85-6.95 (m, 2H), 7.15-7.27 (m, 1H), 7.35-7.42 (m, 1H), 7.57 (d, 1H, J = 2.1 Hz), 8.51 (d, 1H, J = 2.1 Hz)

  Next, formulation examples of the bactericidal agent of the present invention will be shown. However, the additives and addition ratios are not limited to these examples, and can be changed in a wide range. The part in a formulation example shows a weight part.

Formulation Example 1 Wetting agent Compound of the present invention 40 parts Clay 48 parts Dioctylsulfosuccinate sodium salt 4 parts Lignin sulfonic acid sodium salt 8 parts or more are uniformly mixed and finely pulverized, and 40% active ingredient wettable powder Get.

Formulation Example 2 Emulsion Compound of the present invention 10 parts Solvesso 200 53 parts Cyclohexanone 26 parts Calcium dodecylbenzenesulfonate 1 part Polyoxyethylene alkylallyl ether 10 parts or more are mixed and dissolved to obtain an emulsion containing 10% active ingredient.

Formulation Example 3 Powder A compound of the present invention 10 parts Clay 90 parts or more are mixed uniformly and finely pulverized to obtain a powder of 10% active ingredient.

Formulation Example 4 Granules Compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctyl sulfosuccinate sodium salt 1 part Potassium phosphate 1 part or more is pulverized and mixed well, and after adding water and kneading well, granulation drying As a result, granules containing 5% of the active ingredient are obtained.

Formulation Example 5 Suspension Compound of the present invention 10 parts Polyoxyethylene alkyl allyl ether 4 parts Polycarboxylic acid sodium salt 2 parts Glycerin 10 parts Xanthan gum 0.2 parts Water 73.8 parts or more are mixed and the particle size is 3 microns or less The suspension is wet-pulverized until a suspension of 10% active ingredient is obtained.

Formulation Example 6 Granule wettable powder Compound of the present invention 40 parts Clay 36 parts Potassium chloride 10 parts Alkylbenzenesulfonic acid sodium salt 1 part Ligninsulfonic acid sodium salt 8 parts Formaldehyde condensate of alkylbenzenesulfonic acid sodium salt
Mix 5 parts or more uniformly and pulverize finely, add an appropriate amount of water and knead to make clay. The clay-like product is granulated and then dried to obtain a granule wettable powder containing 40% of the active ingredient.

(Test Example 1) Apple black spot disease control test An apple seedling (cultivar "Kunimitsu", 3-4 leaf stage) cultivated in an unglazed pot with a fungicide emulsion containing the following compound as an active ingredient at a concentration of 100 ppm active ingredient Scattered. After natural drying at room temperature, conidia spores of Venturia inaequalis were inoculated and kept in a room of 20 ° C. and high humidity for 2 weeks, repeating light and dark every 12 hours. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.

As a result, an excellent control value of 75% or more was shown.
Compound numbers (corresponding to the compound numbers in Tables 1 to 4): 1a-1, 1a-47, 1a-53, 1a-60, 1a-62, 1b-1, 1b-2, 1b-23, 1b -33, 1b-67, 1b-68, 1b-69, 1b-70, 1b-71, 1b-72, 1c-1, 1c-65, 1c-67

  The nitrogen-containing heterocyclic compound and the salt thereof of the present invention are useful as an active ingredient of an agricultural and horticultural fungicide that can be used safely and reliably. In addition, the agricultural and horticultural fungicide of the present invention has an excellent control effect, does not cause phytotoxicity to plants, has little toxicity to human livestock and environmental impact, and is industrially useful.

Claims (3)

Formula (I)
Wherein R ¹ and R ² are each independently a hydrogen atom, halogen atom, C1-20 alkyl group, C1-20 haloalkyl group, C2-20 alkenyl group, C2-20 haloalkenyl group, C2-20 Alkynyl group, C2-20 haloalkynyl group, C1-20 alkoxy group, C1-20 haloalkoxy group, C3-20 cycloalkyl group, C4-20 cycloalkenyl group, C8-20 cycloalkynyl group, C1-20 acyl group, .R ¹ and ^{R 2} showing a C1~20 alkoxycarbonyl group together may form a 5- to 8-membered ring an unsubstituted or substituted group.
R ^{3 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 haloalkyl group, a C2-20 alkenyl group, a C2-20 haloalkenyl group, a C2-20 alkynyl group, C2 -20 haloalkynyl group, C1-20 alkoxy group, C1-20 haloalkoxy group, C3-20 cycloalkyl group, C3-20 cycloalkoxy group, C2-20 alkenyloxy group, C2-20 alkynyloxy group, C1-20 An alkylthio group, a cyano group, a nitro group, an unsubstituted or substituted amino group, an unsubstituted or substituted phenyl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted aryloxy group, Or an unsubstituted or substituted heterocyclic group. R ⁴ and R ⁵ , and R ⁵ and R ⁶ may be taken together to form a 5- to 8-membered ring having no substituent or a substituent. R ⁵ and R ⁶ are not simultaneously hydrogen atoms.
X represents a halogen atom, a nitro group, an unsubstituted or substituted amino group, a hydroxyl group, or an organic group.
n represents an integer of 0 to 4.
Z represents an oxygen atom or a sulfur atom. )
Or a salt thereof. The nitrogen-containing heterocyclic compound or a salt thereof according to claim 1, wherein R ⁵ and R ⁶ are combined to form an aromatic ring. An agricultural and horticultural fungicide containing as an active ingredient at least one of the compounds represented by claim 1 or 2 or a salt thereof.