WO1997012875A1

WO1997012875A1 - α-ALKOXYIMINOBENZYL HETEROCYCLIC DERIVATIVES, INTERMEDIATES FOR PREPARING THE SAME, AND AGRICULTURAL CHEMICALS CONTAINING THE SAME AS ACTIVE INGREDIENT

Info

Publication number: WO1997012875A1
Application number: PCT/JP1996/002766
Authority: WO
Inventors: Akira Takase; Hiroyuki Kai
Original assignee: Shionogi & Co., Ltd.
Priority date: 1995-09-29
Filing date: 1996-09-25
Publication date: 1997-04-10
Also published as: AU7095196A

Abstract

Compounds represented by general formula (I) wherein R1 represents an optionally substituted heterocyclic group; R2 represents an optionally substituted aryl or optionally substituted heterocyclic group; R3 represents an alkyl; R4 represents a hydrogen atom, an alkyl, an alkoxy, a halogen atom, nitro, cyano, or haloalkyl; M represents -N=C(R5)- or -A-(CR6R7)n-; and the wavy line (∩) represents any configuration of E, Z or a mixture thereof; intermediates for preparing the same; and agricultural chemicals containing the same as the active ingredient.

Description

Description α-Alkoxymino-benzyl heterocyclic derivatives, intermediates for their production and chyles containing them as active ingredients

The present invention relates to a novel α-alkoxyimino benzyl heterocyclic derivative, an intermediate for producing the same, and a drug containing the same as an active ingredient. Background art

As α-alkoxyminobenzylheterocyclic derivatives, there have been known benzohydroximoylazole derivatives having an insecticidal action (Japanese Patent Application Laid-Open Nos. Hei 13-28026 and Hei 5-1046). Japanese Patent Application Laid-Open No. Hei 5 — 3 3 0 11 1, Japanese Patent Application Laid-Open No. Hei 5 — 331 01 2, Japanese Patent Application Laid-open No. Hei 6 — 410 8 6 Kaihei 6 — 3 4 5 7 3 8, Japanese Unexamined Patent Application Publication No. 7-17531, WO 92 Z095 581), oxime derivatives having insecticidal action (Japanese Patent Application Laid-Open No. 3-68555) No. 9), 1-azolyl-substituted oxime ethers having fungicidal and fungicidal activity (Japanese Patent Laid-Open No. 60-87269), pyrimid having herbicidal and fungicidal activity Gin derivatives (JP-A-6-4939, JP-A-7-48359, WO94Z089975), oxazolyl and oxaziazolyl derivatives having a bactericidal action (W094 / 2 2 8 4 4 issue) Also, azadioxacycloalkene derivatives (W095 / 047558) and oxoazacycloalkene derivatives (W095Z21833) having a bactericidal action are known.

However, in these inventions, compounds having a substituent similar to that of the present invention in the ortho substituent of the α-alkoxyiminobenzyl heterocycle are specifically described. Not disclosed.

An object of the present invention is to provide a compound having utility such as better bactericidal activity and insecticidal activity. Disclosure of the invention

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the α-alkoxyimino benzyl heterocyclic derivative described below has excellent bactericidal and insecticidal activities. Was completed.

That is, the present invention provides a compound represented by the following general formula (I):

[Wherein, R ′ is a substituted or unsubstituted heterocyclic group; R ² is a substituted or unsubstituted or substituted heterocyclic group; R ³ is a substituted or unsubstituted heterocyclic group; alkyl; R 'is a hydrogen atom, an alkyl, alkoxy, b Gen atom, two Bok port, Shiano or b plasminogen reduction Anorekiru; Micromax one ^{Ν = C (R 5) -} [R s is a hydrogen atom, an alkyl, halogenated It represents an alkyl or a cycloalkyl, indicating that the form of the R ² and R gar cord of connexion, adjacent carbon atoms to the monitor hetero atoms may be included monocyclic or condensed polycyclic ] or an ^{^{A- (CR P R:) n}} - and R ⁷ are each independently hydrogen atom, alkyl, Xia Roh or halogenation alkyl; A is an oxygen atom or NR ^H

(R ^κ is a hydrogen atom, alkyl or acyl), η is 01 or 2.]; Wavy lines (~) indicate Ε, Ζ or a mixture of these. The compound represented by the formula:

The term “lower” as used herein, unless otherwise specified, refers to a group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Represent.

The optionally substituted heterocyclic group represented by R ¹ includes a substituted heterocyclic group in addition to an unsubstituted heterocyclic group. These heterocyclic groups include, for example, a 5- to 7-membered heterocyclic group containing 1 to 4 heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom in the ring, specifically For example, a pyridyl (eg, pyridin-2-yl, pyridin-13-yl, etc.), a pyrimidell (eg, pyrimidine-12-yl, pyridyl) Lisodin azoline, etc.), isosozozoline (e.g., isosozozoru 3-yl, isosozozororu 4-jinore, isosozozororu 5-yl), isosozozolinil (e.g. For example, 2-isoxazolin-1-yl, 2-isoxazolin-5-yl, etc., isothiazolyl (eg, isothiazol-5-yl, etc.), thiadiazolinol [example, 1, 3, 4 —thiadiazole (eg, 1,3,4 —thiadiazole 2—inole, etc.), 1, 2, 3—thiadiazolinole, etc.), pyridazinyl (eg, pyridazine-1-3-yl, etc.), virazolinole (eg, pyrazol-1—yl, pyrazol- 5 — yl), frills (eg, franc 1-yl), chenil (eg, typhoen 1-yl), imidazoril (eg, imidazo — roux) 2-oxyl), oxazolyl (eg, oxazole-2-yl, oxazolyl-5-yl, etc.), thiazolyl (eg, thiazolyl-2-yl, etc.), thiazolidinyl (eg. , Thiazolidin-1-yl, etc.), oxaziaziryl [eg, 1, 3, 4-oxaziaziolinol (eg, 1, 3, 4-oxaziazol-2-yl, etc.), 1,, 2,4—oxaziazione (eg, 1,2,4 And triazoles (eg, 1, 2, 4 — triazolinoles (eg, 1H—1, 2, 4, 4_ triazols) Noreichi 1 Or 4H—1,2,4-triazole 4—yl, 1H—1,2,4—triazole 5—yl), or pyramid Which

These heterocyclic groups may form a condensed ring with a carbocyclic ring or another heterocyclic ring.

Examples of the condensed ring include benzoxazolyl (eg, benzoxazole-2-yl), benzothiazole (eg, benzothiazol-2-yl), benzoisoxazolinole (eg, Benzoi soxazolu 3-yl, etc., tetramethylenisoxazolyl (for example, 3, 4-1 テイ — — — — —, 4, 5 テ tetra) Methylene dioxoxazole-1 -yl).

These heterocyclic groups and their condensed rings may be located at any position where a bond is possible, _c

Examples of the substituent of the substituted heterocyclic group represented by R ¹ include lower alkyl (eg, methyl, ethyl, propyl, butyl, etc.) and lower alkenyl (eg, butyl, aryl) Alkynyl (e.g., ethur, 2 -probyl, 3 -butur, etc.), cycloalkyl (e.g., cyclopropinole, cyclobenchinole, cyclohexinole, etc.), Cyclo anole kenyl (eg, cycloventur, cyclohexenyl, etc.), halogenated lower alkyl (eg, trifluoromethyl, trichloromethyl, difluoromethyltinole, chloromethylinole) , 2—bromoethyl, 1,2—dichlorobenzene pill, etc.), halogen atoms (eg, fluorine, chlorine, bromine, iodine), nitrite , Xia Bruno, lower alkylthio (e.g., main Chiruchio, Echiru Chio, etc. off b Biruchio), one OR [wherein, R ⁹ is a hydrogen atom, a lower § alkyl (e.g., methylation, Echiru, full b arsenide Le ), Lower alkenyl (eg, vinyl, aryl, 2-butyr, etc.), lower alkynyl (eg, ethur, 2—Probul, 3—Butyl, etc.)] and lower alkylsulfonyl (eg, mesyl). Of these, lower alkyl or halogenated lower alkyl is preferred, and methyl is particularly preferred.

R ¹ is preferably an optionally substituted isosoxazole 13-yl, isosoxazole 4-inole, isosoxazoline 1-5-yl, 2—isosoxazoline 13-inole , 2 — Isosoxazoline 1 5 — Ill, Imidazol 1 2 — Ill, Franc 1 2 — Ignore, 1, 2, 2, 4 — Oxaziazolo 3 — Ignore, 1 , 3, 4 — oxaziazolou 2 — yl.

R 'is more preferably 3'-yl, 5'-methyl-isoxazo-l- 3'-inole, 3_-methyl-isoxazole-l--5-yl, 2--isoxazoline-l-3 — It ’s an ill.

Is a substituted good § Li Lumpur also be § Li Lumpur represented by R ^2, 6 to 1 4 § Li Lumpur carbon, for example phenyl, naphthyl (e.g., 1 over Na off chill , 2-naphthyl).

The optionally substituted heterocyclic group represented by R ² includes a substituted heterocyclic group in addition to an unsubstituted heterocyclic group. Examples of these heterocyclic groups include, for example, a 5- to 7-membered heterocyclic group containing 1 to 4 heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom in a ring; Include pyridyl (eg, pyridin-2-yl, pyridin-13-yl, pyridin-14-yl), pyrimidinyl (eg, pyrimidine-12-yl) , Pyrimidine, 14-yl, pyrimidine, 1-5-yl), isosozozo-linole (ex. , Thiadiazol (eg, 1,3,4—thiadiazol-2-yl, 1,2,3—thiadiazol5—yl, etc.), pyridazinyl (pyridazin-13-yl, etc.) ), Pyrrolinole, virazolinenole, furil (e.g., francoline 2-finole, furan一 3-）), chenil (eg ォ 1 — 2-ノノ, 、ォ 1 3 3 —）), Imida Zolyl, oxazolyl, thiazolinole (eg, thiazol-2-yl), oxaziaziolinol (eg, 1,3,4_oxaziazol 1-2-2,4,2,4) —Oxaziazol-5-yl, etc.), pyrajur, quinolinol (eg, quinolin-2-yl) or indrill. These heterocyclic groups may form a condensed ring with a carbocycle or another heterocycle. In addition, these heterocyclic groups may have a bond capable of bonding to M at any position.

The substituent of the substituted aryl and the substituted heterocyclic group represented by R ² is the same as the substituent exemplified for the substituted heterocyclic group represented by R ¹ above. And phenyl, phenyl (lower) alkyl (eg, benzyl, phenethyl, etc.) and phenyl. The phenyl, and the phenyl in the phenyl (lower) alkyl and the phenyl include, as an unsubstituted or substituted group, a halogen atom, a lower alkyl, a halogenated lower alkyl, and a lower alkoxy. _C may have 1 to 3 substituents selected from the group

As the substituent for the substituted aryl and the substituted heterocyclic group represented by R ² , a halogen atom, lower alkyl, halogenated lower alkyl, lower alkoxy, phenyl and phenoxy are preferred. New These substituents may be located at any substitutable position of the ring. The substituent is 1 to 5, preferably 1 to 4, and more preferably 1 to 3, and these may be the same or different, _c

R ² preferably has 1 to 3 substituents selected from the group consisting of a halogen atom, lower alkyl, lower alkyl halide, lower alkoxy, phenyl and phenyl. An optional phenyl or heterocyclic group includes:

Preferred examples of R 'include phenyl; lower alkoxy (preferred). Methoxy), lower alkyl halides (preferably trifluoromethyl), halogen atoms (preferably fluorine, chlorine, bromine) and lower alkyls (preferably methyl). A phenyl having 1 to 3 substituents selected from the group consisting of, for example, 2—chlorophenyl, 3—chlorophenol, 41-chlorophenol, 3—bromophenyl; Ninore, 4—Bromo Feninore, 2—Mechinore Feninore, 3—Mechinore Feninore, 4-Methi / Le Feninore, 2, 5—Dimetinore Fenie / , 3, 4-dimethylphenyl, 3-phenolic phenol, 4- phenolic phenolic, 3, 4-chloro mouth Chinole Feninore, 41 Tri-Funole Rome Chinolepheninole, 4-methoxyphenyl, 4-chloro-2-methylphenyl, etc.).

Examples of the alkyl represented by R include alkyl having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and specific examples include methyl, ethyl, propyl, and isopropyl. In particular, methyl is preferred.

Examples of the alkyl represented by R ¹ include the same as those exemplified as the alkyl represented by R ^{: |} .

The alkoxy represented by 'is, for example, an alkoxy having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, specifically, methoxy, ethoxy, propoxy, isopropoxy, butoxy, Isobutoxy, sec-butoxy, tert-butoxy, etc. are available.

Examples of the halogen atom represented by R ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom:

The alkyl halide represented by R ′ is, for example, an alkyl having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and specifically, for example, methyl, ethyl, bropinole, isoflur At least one halogen atom (eg, fluorine, chlorine, bromine, iodine) in alkyls such as pills and butinoles Are substituted. For example, Jifuruoro methyl, Application Benefits Furuo Russia main Chinore, click B B methylation, 1, 2 - Axis B port propyl, etc. Chi cormorants this _c include Bok Li Furuoro methyl favored arbitrariness.

R ¹ is preferably hydrogen.

Examples of the alkyl represented by R ⁵ to R ^H include the same alkyls as those exemplified above for the alkyl represented by R. Of these, methyl or ethyl is preferred, respectively.

Examples of the alkyl halide represented by R ⁵ to R ⁷ include the same ones as those exemplified as the alkyl halide represented by R ′ above. Of these, trifluoromethyl is preferable. .

Is a a cycloalkyl represented by R ^5, for example, cyclohexyl having 3 to 8 carbon atoms, preferred and rather 3-6懾of a cycloalkyl, specifically, consequent lob port pills, sik Robenchiru, the consequent b And the like.

Examples of the acyl represented by R ^κ include, for example, alkanol and arylonole. The alkanol is, for example, an alkanol having an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, specifically, for example, formyl, acetyl, triethyl Examples include phenolic acetyl, propionyl, and butylyl. Of these, acetyl is preferred. As the aryl, for example, an aryl having 7 to 15 carbon atoms, specifically, for example, benzoyl, naphthoyl and the like can be mentioned: Of these, benzoyl is preferred.

VI is one ^{Ν - C (R Λ) -} R L ' and R 5 are bonded to good _c The also form a good monocyclic or condensed polycyclic also include heteroatoms in the case of As a monocyclic ring, a 4- to 8-membered ring which is formed together with R and R5 and the carbon atom to which they are bonded, and which may contain a hetero atom (eg, a nitrogen atom, an oxygen atom, a sulfur atom, etc.) The monocyclic ring is fused with another ring to form a fused polycyclic ring. It may be formed. Specific examples of the monocyclic ring and the condensed polycyclic ring include cyclopentane, cyclohexane, indane, 1,2,3,4—tetrahydronaphtalene, 5,6, 7, 8—Tetrahydroquinoline, 4, 5, 6, 7—Tetrahydrobenzo [b] franc.

Is a preferred correct specific example of M, one N = CH-, - N = C (CH 3) _{one, - N = C (C 2} H 5) one, - N = C (CF: ,) one, — NH—, 1— CH ₂ —, — O—CH (CH ₃ ), 1— O— CH (C ₂ H ₅ ) —, 1— O— C (CH ₂ —, 1— O— CH ₂ CH ₂ — , One O—CH (CF ₃ ) one, or one O—CH (CN) one: In this, one N = C (CH :,) one, one O—CH (CH ₃ ) — Especially preferred, _c

The compound of the present invention has two isomers, E-form and Z-isomer due to the R ^: 'oxymino moiety, and the present invention relates to these isomers and mixtures of these isomers in any ratio. Is included. In this specification, this is indicated by using a wavy line (-) in the general formula.

Specific examples of the compound represented by the general formula (I) of the present invention include the compounds shown in Examples described later. For example, the following compounds are preferable (compound numbers are shown in Examples described later). Is shown in the above).

R ¹ force; 3 — methinolay soxazole-5—yl, R ² force; 41-port phenyl, R: 'is methyl, R ¹ is hydrogen and M is —O—CH (CH ₃ ) — (Compound No. C-17),

R 'force; 3-methyl soxazolu 5-yl, R ² is 4-trifluoromethyl phenyl, R ^{: i is} methyl, R ^j is hydrogen and M is-O — CH (CH, ) A compound, (compound number C-123)

R ¹ force; 3 — methyl thioxolone 5 — di-nore, R ² 3, 4 — dicyclo mouth feninole, R ′ is methyl, R ′ is hydrogen and VI is —O— CH (CH ,) A compound (Compound No. C-130), R ¹ force; 3 — methyl soxazolone 5 — dinole, R ² is 4 — black phenyl, R ^{3 is} methyl, R is hydrogen and M is N = C (CH ₃ ) — A compound (Compound No. C-67),

R 'force; 3 — methyl soxazolu 5 — quinoline, R ² is 3 — trifluoromethyl phenyl, R ^{: | is} methylinole, R ⁴ is hydrogen and M is N = C (CH :,) A compound (compound number C—82),

A compound wherein R ′ is isoxazolyl 3 —inole, R ¹¹ force; 3,4-dichloro phenyl, R is methyl, R ′ is hydrogen and M is N = C (CH ;,) one (Compound No. A—90) or

R ¹ force; 2 — dioxoxazoline 3 — yl, R is 4 — black phenyl, R ^{: i is} methyl, R ¹ is hydrogen and M is —N = C (CHJ— Compound (Compound No. D-67) Compound (I) of the present invention (that is, a compound represented by the general formula (I). Hereinafter, compounds represented by other formulas are similarly abbreviated. Can be produced, for example, by the following synthesis route.

(Reaction formula 1)

II III

[In the formula, Y represents a halogen atom (eg, chlorine atom, bromine atom, iodine atom, etc.) p represents a hydroxyl-protecting group, and other symbols have the same meanings as described above. That is, compound (III) can be produced by protecting the hydroxyl group of compound (II), which is commercially available, with an appropriate protecting group: a group represented by p: This protection of the hydroxyl groups can be, for example, Green (T.W. Green), "Protective Groups-In 'Organic Synthesis"! ~ 113 pages, John 'Willy' and 'Son's (John Willy & Sons) (19981); C.B.R. ) "Protective 'Groups'in' Organic 'Chemistry, JF' Matsukomi. Omie), ed., Pages 95-143, Plenum Breath (Plenum Press) (1973), etc. Can be done.

Specifically, for example, Tetrahydridroviranil, Tetrahydrodrovillaninore, Tetrahydrodrofuranoninore, Tetrahydrodrochiofraninole, 1-etoxyshecil and i-mesh Chilled 1-methoxed compound

(III) can be obtained by reacting the corresponding olefin with compound (II) in the presence of an acid catalyst in a suitable solvent or without solvent.

The corresponding orthofins are 3,4—dihydro 2H—pyran, 2,3—dihydro 4 H—thiine, dihydrofuran, dihydrothiofuran, and ethyl butyl, respectively. Ether, 2-Methoxybopenpene, which can be used commercially or manufactured and used in a known manner.

The amount of O reflex fin is 1-3 equivalents relative to compound (II), and rather is preferred a] to 2 equivalents _c

Examples of the acid catalyst include hydrogen chloride, oxylin chloride, p-toluenesulfonate, p-toluenesulfonic acid pyridine salt, montmorinite, bismethyl sulfate, acetic acid, and the like. p — Polyvinyl pyridinium toluenesulfonate, acetic acid in trifluorene, borane trifluoride (BF, · OE t and acidic ion exchange resins.

If a solvent is used, non-alcoholic solvents can be used. For example, hydrocarbons (eg, benzene, toluene, xylene, etc.), halogenated hydrocarbons (eg, black mouth form, dichloromethane, etc.), ethers (eg, Ter, tetrahydrofuran, dioxane, etc.), esters (eg, ethyl sulphate), N, N-dimethylformamide and mixed solvents thereof _c

The reaction temperature is from 130 to 100: preferably from 0 to 60 °.

The reaction time is usually about 15 minutes to 24 hours.

The silyl ether type compound (III) can be obtained by reacting the compound (II) with an appropriate silylating agent. Generally, it is obtained by reacting compound (II) with a suitable solvent using chlorosilane as a silylating agent in the presence of a base.

Chlorsilane can be used as a commercially available product or produced by a known method.

Click Rorushira emissions are 1-5 equivalents relative to compound (II), _c for preferred and rather 1-2 equivalents used

Examples of usable bases include organic bases (eg, N, N-dimethylaniline, pyridine, triethylamine, imidazole, etc.), metal carbonates (eg, carbonate) Sodium, potassium carbonate, etc., metal hydrides (eg, sodium hydride, potassium hydride, etc.), metal bicarbonates (eg, sodium bicarbonate, hydrogen bicarbonate) And one equivalent or more, preferably 1 to 2 equivalents can be used.

Solvents that can be used include hydrocarbons (eg, hexane, benzene, tonolene, xylene, etc.), halogenated hydrocarbons (eg, black form, dichloromethan) Etc.), ethers (eg, getyl ether, tetrahedral) Ketones (eg, acetone, methylethylketone, etc.), nitriles (eg, acetonitrile, etc.), N, N-dimethyl Examples include formamide, dimethyl sulfoxide and a mixed solvent thereof.

The reaction temperature is 120 ° C .: preferably 0.60 t.

The reaction time is 5 minutes to 30 hours, preferably 30 minutes to 15 hours. The compound (III) protected with _c- methoxymethyl or triphenylmethyl and the above-mentioned tetrahydrofuranyl or 1 The compound (III) protected with 1-ethoxyshetyl is obtained by reacting the corresponding halide with the compound (II) in the presence of a base.

The corresponding halogenated compounds are, respectively, /, methyl methyl ether, triphenyl methyl halide, 2-halotetrahydrofuran and 1-hydroxyethyl ether, which are commercially available products. It can be used or manufactured by a known method.

Chloride or bromide can be used as a chromogen. The equivalents of the halogenated compound to be used, the types of base and solvent, and the reaction conditions are the same as in the case of the above _- mentioned reaction of chlorosilane with compound (II) _{= the} above _- mentioned compound protected with methoxymethyl ( III) can be obtained by reacting compound (II) with dimethoxymethane in the presence of a suitable catalyst (eg, phosphorus pentoxide, etc.).

The solvents and reaction conditions that can be used are the same as for the reaction of the above-mentioned olefin with compound (II):

The obtained compound (I I 1) may be used as a reaction mixture or in a crude form, or in a conventional manner.

(Eg, column chromatography, recrystallization, etc.) and can be used in the next step: (Reaction formula 2)

III IV

[In the formula, Z represents a lithium or magnesium halide (eg, one MgBr, —Mgl, etc.), and other symbols have the same meanings as described above. ]

That is, the compound (IV) can be usually produced by reacting the compound (III) with lithium or magnesium in a suitable solvent to give the compound (III). 1-4 equivalents for, rather then favored reacting lithium or magnesium 1-2 equivalents _c

Examples of the solvent to be used include ether solvents such as dried tetrahydrofuran, getyl ether, dibutyl ether and the like. These solvents may be used alone or hydrocarbons (eg, toluene, etc.). ), And amines (eg, triethylamine) may be used as a mixed solvent with other solvents. The reaction temperature is between room temperature and 150 ° C, preferably between 40 and 100 ° C.

The reaction time is from 10 minutes to 48 hours, preferably from 30 minutes to 6 hours. If needed iodine to the reaction of the activating agent, Jiburomuetan, Echirubu b _e the amount of using a small amount of such Mi de is 0.0 0 1 to 0.4 equivalents, it is preferred and rather 0.0 0 5 ~ 0.2 equivalents.

The obtained compound (IV) can be used in the next step as a reaction solution or as a crude product.

(Reverse formula 3)

l 4 [Where L is a halogen atom (eg, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkoxy (eg, a lower alkoxy such as methoxy, ethoxy, propoxy, etc.) It represents Dazoru 1-yl or N-methyl-1-N-methoxyamino, and the other symbols have the same meanings as above. ]

That is, the compound represented by the general formula (VI) can be produced by reacting the compound (IV) with the compound (V) in a suitable solvent (single or mixed).

In this reaction, compound (V) can be used in an amount of 1 equivalent or more, preferably 1 to 3 equivalents, relative to compound (IV).

Solvents that can be used include aromatic hydrocarbons (eg, toluene, benzene, xylene, etc.), saturated hydrocarbons (eg, cyclohexane, hexane, etc.), Examples thereof include ters (eg, tetrahydrofuran, getyl ether, dioxane, etc.), triethylamine, and a mixed solvent thereof.

The reaction temperature is from 100 to 100, preferably from -80 to 40. The reaction time varies depending on the compound, but the reaction may be carried out for 0.5 to 80 hours. The resulting compound (VI) can be purified as a crude product or by a conventional method (eg, column chromatography, recrystallization, etc.) and used in the next step.

(Reaction formula 4)

(In the formula, each symbol has the same meaning as described above.) That is, compound (VII1) can be produced by reacting compound (VI) with a salt of compound (VII) in a suitable solvent in the presence of a base. Compound (VII) is used in 1 to 4 equivalents, preferably 1 to 2.5 equivalents, relative to compound (VI).

Examples of the salt of the compound (VII) include mineral acid salts such as hydrochloride and sulfate. ·

Examples of the base that can be used include amines (triethylamine, pyridine, etc.), and the amount used is based on the amount of the salt of compound (VII). It is 1-3 equivalents, preferably 1-2 equivalents.

Solvents that can be used include, for example, hydrocarbons (eg, benzene, toluene, xylene, etc.) and halogenated hydrocarbons (eg, chloroform, 1,2-dichloroethane) Etc.), ethers (eg, tetrahydrofuran, dioxane, etc.), alcohols (eg, methanol, ethanol, n- lobanol, isopropanol) ), Water and a mixed solvent thereof.

The reaction temperature is from 0 to 150: preferably from 20 to 120 °.

The reaction time is usually about 15 minutes to 24 hours.

The obtained compound (VIII) may be used as is in the next step after purification as a reaction solution or in crude form, or by a conventional method (eg, column chromatography, recrystallization, etc.). It can be.

(Reaction formula 5)

(In the formula, each symbol has the same meaning as described above.)

That is, the benzaldehyde derivative represented by the general formula (IX) can be produced by oxidizing the compound (VIII) with various oxidizing agents.

Oxidizing agents that can be used include, for example, pyridinium chromate, tert-butyl chromate, nickel peroxide, activated dimethyl sulfoxide and the like. No.

Various activated dimethyl sulfoxide oxidation methods using activated dimethyl sulfoxide are known, and when the method is used for production by Swer.n oxidation, dimethyl sulfoxide and dimethyl sulfoxide are required. The oxalyl chloride used as an electronic agent can be used in an amount of 1 equivalent or more, preferably 1 to 4 equivalents, to the compound (VIII), respectively.

Examples of the solvent that can be used include halogenated hydrocarbons such as dichloromethane.

The reaction temperature is from 178 to 120 X :, preferably from 178 to 400 :. The reaction time varies depending on the compound, but it is sufficient to carry out the reaction for 15 minutes to 3 hours. Subsequently, a base such as triethylamine is added to form a sulfodiimide.

The amount of base, one equivalent or more than the relative to compound (VIII), the preferred and rather Ru can and this to 1 to 6 equivalents using _c using

The reaction temperature is between −78 and 50 = €, preferably between 1 and 78 ° -30 °. The reaction time varies depending on the compound, but it is recommended that the reaction be performed for 15 minutes to 3 hours. After the reaction is completed, water is added and the product is extracted with a solvent. The obtained compound (IX) is a novel compound and is included in the present invention. If necessary, compound (IX) can be purified by a conventional method (eg, column chromatography, recrystallization, etc.).

(Reaction formula 6)

(In the formula, each symbol has the same meaning as described above.)

That is, the compound of the present invention represented by the general formula (I) is a compound of the formula (IX), a hydrazone represented by the compound (X), an o-substituted hydroxylamine, a hydrazine derivative and a hydrazine derivative. Can be produced by reacting a salt (eg, hydrochloride, sulfate) in a suitable solvent (single or mixed).

In this reaction, compound (X) can be used in an amount of 1 equivalent or more, preferably 1 to 3 equivalents, relative to compound (IX).

Examples of solvents that can be used include aromatic hydrocarbons (eg, toluene, benzene, xylene, etc.), saturated hydrocarbons (eg, cyclohexane, hexane, etc.), and alcohols. (Eg, methanol, ethanol, etc.), ethers (eg, tetrahydrofuran, dioxane, etc.), water and a mixed solvent thereof.

The reaction temperature is from 0 to 160, preferably from 20 to 130. C. The reaction time varies depending on the compound, but the reaction may be carried out for 0.5 to 90 hours. Five

The desired compound (I) thus obtained can be purified by a conventional method (eg, column chromatography, recrystallization, etc.), if necessary.

The hydrazone derivative represented by the compound (X) used as a raw material in this reaction can be produced by reacting the corresponding ketone derivative with hydrazine.

The o-substituted hydroxylamin derivatives represented by the compound (X) are known in the art, and are known from Houben-Weyl's “Met-Ten-Tenole Onoreganischen”. Mi - (M ethodender O rganischen C hemie ) "XZ l Certificates _c that can have a this to produce Ri by the known method similar to the method described in

The hydrazine derivative represented by the compound (X) is a known hydrazine derivative of H. ouben-Weyl (Methodenender Oranischen Chemie). ) j XZ It can be manufactured by a known method similar to the method described in the second volume.

(Reaction formula 7)

(In the formula, each symbol has the same meaning as described above.)

That is, compound (XI) can be produced by reacting compound (IX) with hydroxylamine or a salt thereof in a suitable solvent. 1-4 equivalents to (IX), preferred Or 1 to 2.5 equivalents can be used.

Examples of the salts of hydroxylaminate include mineral salts such as hydrochloride and sulfate. When the salt is used, it may be neutralized with a base and reacted. Examples of bases that can be used include metal hydroxides (eg, sodium hydroxide, potassium hydroxide, etc.) and metal carbonates (eg, sodium carbonate, carbonate) Potassium, etc.), metal alkoxides (eg, sodium methoxide, sodium ethoxide, etc.), pyridine, etc., and the amount of use is the amount of hydroxylamine salt. 1 to 3 equivalents, preferably 1 to 2 equivalents.

Solvents that can be used include, for example, hydrocarbons (eg, benzene, toluene, xylene, etc.), halogenated hydrocarbons (eg, macro-form, 1,2-dichloroethane, etc.), Ethers (eg, tetrahydrofuran, dioxane, etc.), alcohols (eg, methanol, ethanol, n-propanol, isopropanol, etc.), water and their mixed solvents And so on.

The reaction temperature is from 0 to 150 °: preferably from 20 to 100 °. The reaction time is usually about 15 minutes to 24 hours.

The resulting compound (XI) can be used as is in the reaction mixture or in crude form, or purified by a conventional method (eg, column chromatography, recrystallization, etc.) and used in the next step. You.

(Reaction formula 8)

XI la

(In the formula, each symbol has the same meaning as described above.)

That is, the compound of the present invention represented by the general formula (Ia) is produced by reacting compound (XI) and compound (XII) in the presence of a base without solvent or in a suitable solvent (single or mixed). can do.

In this reaction, compound (XII) can be used in an equivalent amount or more to compound (XI).

Examples of bases that can be used include metal hydrides (eg, sodium hydride, potassium hydride, etc.), metal hydroxides (eg, sodium hydroxide, potassium hydroxide). Metal carbonates (eg, sodium carbonate, potassium carbonate, etc.), metal alkoxides (eg, sodium methoxide, sodium ethoxide, potassium tert-) Butoxide, etc., and one or more equivalents, preferably one to two equivalents, of compound (XI) can be used.

Examples of usable solvents include N, N-dimethylformamide, dimethylsulfoxide, aromatic hydrocarbons (eg, toluene, benzene, xylene, etc.), and saturated hydrocarbons (eg, cyclohexane Hexane, hexane, etc.), halogenated hydrocarbons (eg, dichloromethane, 1,2-dichloroethane, etc.), ethers (eg, tetrahydrofuran, dioxane, etc.), ketone (Eg, acetone, methylethylketone, etc.), nitriles (eg, acetonitrile, etc.), water and a mixed solvent thereof. The reaction temperature is from 130 to 120, preferably from 0 to 90. The reaction time varies depending on the compound, but the reaction may be carried out for 0.5 to 90 hours.

The desired compound (Ia) thus obtained can be purified by a conventional method (eg, column chromatography, recrystallization, etc.), if necessary.

(Reaction formula 9)

XIII XIV

(In the formula, each symbol has the same meaning as described above.)

That is, the compound represented by the general formula (XIV) can be produced by halogenating the methyl group of the benzene ring of the compound (XIV) by a known method.

For example, in an inert solvent (eg, carbon tetrachloride, cyclohexane, benzene, benzene benzene, etc.), chlorine, bromine, N-methyl succinate imido, N-bromo The ability to react with halogenating agents, such as succinic acid, if necessary, using a mercury lamp under light irradiation, or a, Q'-azoisopeptylyl nitrile, a radical initiator such as dibenzoyl peroxide, etc. It can be produced by reacting in the presence of In this reaction, the halogenating agent can be used in one or more equivalents, preferably 1 to 1.5 equivalents, relative to compound (XIII). The radical initiator can be used in an amount of 0.01 equivalent or more, preferably 0.05 to 0.5 equivalent, relative to the compound (XIII):

The reaction temperature is from 20 to 120 ° C, preferably from 50 to 90 ° C.

The reaction time varies depending on the compound, but the reaction may be performed for 5 minutes to 3 hours: The desired compound (XIV) thus obtained is used as it is in the next step after being purified as it is or in the form of a crude reaction solution, or by a conventional method (eg, column chromatography, recrystallization, etc.). can do.

The compound (XIII) used as a starting material in this reaction can be produced according to Example 2 using 2-bromotoluene as a starting material.

(Reaction formula 10)

XIV XVI

(In the formula, each symbol has the same meaning as described above.)

That is, the compound represented by the general formula (XVI) can be obtained by benzoyloxylation of the compound (XIV) without solvent or in an appropriate solvent (single or mixed) (even if the phenyl group in the benzoyloxy group is substituted). Good) or alkanoyloxylation (the alkyl group in the alkanoyloxy group may be substituted).

Benzoyloxylation and alkanoyloxylation can be carried out by reacting compound (XIV) with the general formula (XV):

R ¹⁰ COOH (XV)

(Wherein, R ′ represents an optionally substituted alkyl group or an optionally substituted phenyl group:) a metal salt of a carboxylic acid represented by (eg, lithium, sodium, The reaction is carried out by reacting the carboxylic acid in the presence of a force for reacting an alkali metal such as calcium; an alkaline earth metal such as magnesium or potassium, or in the presence of a base. The carboxylic acid The metal salt is preferably sodium phosphate, potassium acetate, sodium benzoate, potassium benzoate. The amount of the metal salt of the carboxylic acid or the carboxylic acid to be used is 1 equivalent or more, preferably 1 to 3 equivalents, relative to compound (XIV).

Examples of the base include metal hydroxides (eg, sodium hydroxide, potassium hydroxide, etc.) and gold hydrides (eg, sodium hydride, lithium hydride, etc.) , Metal carbonates (eg, sodium carbonate, potassium carbonate, etc.), gold bicarbonates (eg, sodium hydrogen carbonate, potassium hydrogen carbonate, etc.), and the like. XIV) 1 or more equivalents relative to, the rather to preferred 1 ~ 1. 5 _c that we can have a this to equivalents used

Examples of usable solvents include N, N-dimethylformamide, dimethylsulfoxide, aromatic hydrocarbons (eg, toluene, benzene, xylene, etc.), and saturated hydrocarbons (eg, , Cyclohexane, hexane, etc.), halogenated hydrocarbons (eg, dichloromethane, 1,2-dichloroethane, etc.), ethers (eg, tetrahydrofuran, dioxane, etc.) ), Ketones (eg, acetone, methylethyl ketone, etc.), nitriles (eg, acetonitril, etc.), water and mixed solvents thereof. The reaction temperature is from 130 to 120 :, preferably from 0 to 90 :. The reaction time varies depending on the compound, but the reaction may be carried out for 0.5 to 90 hours.

The desired compound (XVI) obtained may be used as is in the next step, either as a reaction mixture or as a crude product, or purified by a conventional method (eg, column chromatography, recrystallization, etc.). It can be.

(Reaction formula 11)

XVI XVII

(In the formula, each symbol has the same meaning as described above.)

That is, compound (XVII) can be produced by reacting compound (XVI) with a salt of compound (VII) in a suitable solvent in the presence of a base. Compound (VII) is used in 1 to 4 equivalents, preferably 1 to 2.5 equivalents, relative to compound (XVI).

Examples of the salt of the compound (VII) include mineral acid salts such as hydrochloride and sulfate. When using the salt, neutralize with a base and react

Examples of the base that can be used include, for example, amines (eg, pyridine), and the amount of the base to be used is 1 to 3 equivalents, preferably 1 equivalent to the salt of the compound (VII). Or 1-2 equivalents.

Solvents that can be used include, for example, hydrocarbons (eg, benzene, toluene, xylene, etc.), halogenated hydrocarbons (eg, chloroform, 1,2-dichlorobenzene) Etc.), ethers (eg, tetrahydrofuran, dioxane, etc.), alcohols (eg, methanol, ethanol, n-probanol, i And water and a mixed solvent thereof.

The reaction temperature is from 0 to 150, preferably from 20 to 120 °.

The reaction time is usually about 15 minutes to 24 hours:

The obtained compound (XVII) can be used as it is in the form of a reaction mixture or a crude product, or purified by a conventional method (eg, column chromatography, recrystallization, etc.) and used in the next step. it can. (Reaction formula 1 2)

XVII VIII

(In the formula, each symbol has the same meaning as described above.)

That is, the compound (VIII) can be produced by reacting the compound (XVII) in a suitable solvent in the presence of a base.

Bases that can be used include, for example, metal hydroxides (eg, sodium hydroxide, potassium hydroxide, etc.), metal carbonates (eg, sodium carbonate) , Potassium carbonate, etc.), metal alkoxides (eg, sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), and the compound (XVII) 0.01 equivalents or more, preferably 0.05 to 0.5 equivalents can be used.

Solvents that can be used include, for example, hydrocarbons (eg, benzene, toluene, xylene, etc.), and halogenated hydrocarbons (eg, chloroform, 1,2-dichloroethane, etc.) ), Ethers (eg, tetrahydrofuran, dioxane, etc.), alcohols (eg, methanol, ethanol, _n- propanol, isopropanol) ), Water and their mixed solvents, etc.

The reaction temperature is from 0 to 150, preferably from 20 to 120.

Reaction times are typically on the order of 5 minutes to 24 hours:

The obtained compound (VIII) may be used as is in the next step after purification as it is, in crude form, or by a conventional method (eg, column chromatography, recrystallization, etc.). You can: (Reaction formula 13)

XVI VIII

(In the formula, each symbol has the same meaning as described above.)

That is, compound (VIII) can be produced by reacting compound (XVI) with a salt of compound (VII) in a suitable solvent. Compound (VII) is from 1 to 4 equivalents relative to compound (XVI), and preferred rather is 1 to 2.5 equivalents using _c

Examples of the salt of the compound (VII) include mineral acid salts such as hydrochloride and sulfate.

Solvents that can be used include, for example, hydrocarbons (eg, benzene, toluene, xylene, etc.), halogenated hydrocarbons (eg, black form, 1,2-dichloroethane) ), Ethers (eg, tetrahydrofuran, dioxane, etc.), alcohols (eg, methanol, ethanol, _n -propanol, isopropanol, etc.), Examples thereof include water and a mixed solvent thereof.

The reaction temperature is from 0 to 150, preferably from 20 to: 120.

The reaction time is usually about 15 minutes to 24 hours.

The obtained compound (VIII) can be used as is in the reaction solution or in crude form, or purified by a conventional method (eg, column chromatography, recrystallization, etc.) and used in the next step. it can. The compound (I) of the present invention may be a cultivated plant or a seed thereof, for example, rice, wheat, rye, rye, corn, millet, buckwheat, soybean, soybean, and soybean.

Two Pathogens (fungi) and soil that affect beans, peanuts, etc. or fruit trees, eg, citrus, bud, lingo, pear, peach, or vegetables, eg, cucumber, eggplant, tomato, cabochia, or green beans It is effective against pathogens originating from germs. The compound of the present invention is particularly useful for rice blast fungus (Pyricularia oryzae), rice sheath blight fungus (Rhizoc toni a so1ani), and wheat powdery mildew fungus.

(Erysiphe graminis), Spruce Powdery Mildew (Sphaerotheca ful iginea), Yuno ヽ 'Ko Powdery Mildew (Erysiphe cic oracearum), Z ヽ *

(Phy 1 oph thora inf es tans), Cucumber bee and disease (Pseudoperonospora cubens is), Soybean and Blight (Peronospora manshurica), Budo bee and disease (Plasaopara viticola), or vegetables, Budo, etc. Sclerot inia sclerot iorum (Sclerot inia sclerot iorum), soybean, azuki bean, porridge, etc. It shows strong in-bacterial activity against white silk rot fungi such as peanuts (Corlicium rolfsi i) and wheat eye spot disease (Pseudocercospore 1 la herpotrichoides). Therefore, the compound (I) of the present invention is useful as an agricultural chemical, particularly as a fungicide.

Further, the compound (I) of the present invention has excellent insecticidal activity against plant pests. In particular, it shows an excellent control effect on insects such as Myzus persicae which damage various plants. Therefore, the compound (I) of the present invention is also useful as a biocide.

When the compound (I) of the present invention is used as a fungicide, the compound is applied by spraying, spraying, or applying an active substance to the plant, or by treating the plant seed, or the soil around the plant, or the seed. This can be achieved by treating the soil, rice paddy, and water for hydroponic cultivation with active substances. The application can be made before or after the plant is infected with the pathogen.

When the compound (I) of the present invention is used as an insecticide, it is applied to insects. On the other hand, the active substance is treated by spraying, spraying, or applying. It is applied to plants by fogging, spraying, and application to prevent pest damage. Alternatively, it may be applied to plant seeds, soil around the plant, soil to sow seeds, and paddy fields.

The compound may be used in the usual pharmaceutical form, for example, liquid, wettable powder, emulsifier, suspension, liquid concentrate, tablet, granule, aerosol, powder, paste, smoker, etc. It can be used as a chemical suitable for widespread disinfection and pesticides.

Such embodiments may be useful for improving at least one compound of the present invention and suitable solid or liquid carriers and, if desired, the dispersibility of the active substance and other properties. It can be obtained by usual methods of mixing with suitable auxiliaries (eg surfactants, spreading agents, dispersants, stabilizers).

Examples of solid carriers or diluents include botanicals such as cereal flour, tobacco stalk flour, soy flour, walnut husk flour, vegetable flour, canna flour, bran, bark flour, fiber flour, Vegetable extract residue), fibrous substances (eg, paper, cardboard, rags), artificial plastic powders, clay (eg, kaolin, bentonite, clay), talc and inorganic substances (leaf leaves) Examples include calcite, sericite, pumice, sulfur powder and activated carbon), and chemical fertilizers (eg, ammonium sulfate, ammonium phosphate, ammonium usate, urea, ammonium chloride).

Liquid carriers and diluents include water, alcohols (eg, methanol, ethanol), ketones (eg, acetate, methylethylketone), ethers (eg, , Getyl ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (eg, benzene, toluene, xylene, methyl naphthalene), aliphatic hydrocarbons (eg, gasoline) Lin, kerosene, kerosene), esters, nitriles, acid amides (eg, N, N-dimethylformamide, N, N-dimethylacetamide), halogenation Hydrocarbons (eg For example, dichloroethane, carbon tetrachloride).

Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkynoleyl sulfonates, polyethylene glycols, and polyhydric alcohol esters. Examples of spreading or dispersing agents include casein, gelatin, starch powder, carboxymethyl cellulose, arabia gum, alginic acid, lignin, bentonite, molasses, poly (vinyl alcohol), pine oil and agar. And so on. Stabilizers include PAP (isopropyl pyrinate mixture), tricresyl phosphate (TCP), tall oil, epoxy oil, surfactants, fatty acids and their esters. Is mentioned.

In addition to the above components, the formulations of the present invention can be used in admixture with other fungicides, insecticides, herbicides, or fertilizers.

In general, the above-mentioned preparations contain at least one compound represented by the general formula (I) of the present invention in an amount of 0.1 to 95% by weight, preferably 1.0 to 80% by weight. These preparations can be used alone or in a diluted form. The compound of the present invention, about 1 g to 5.0 Kg / hectare, preferably about 10 g to 1.0 Kg / h. Hector is usually used at a concentration of about 1 to 5,000 ppm, preferably about 100 to 1,000 ppm. Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples, but the present invention is not limited thereto. 'H-NMR (CDC 1 value was measured at 270 or 400 MHz, and the δ value was determined in a double-mouthed form using tetramethylsilyl silane as an internal standard. (Ppm) Coupling constant (J) is indicated by H z In the data, s is a singlet, d is a doublet, t is a triplet, q is a quadruple, and m is a multiplet. Isomer A, 97/1275

B indicates that it is either an E-body or a Z-body. Example 1

Preparation of 1-bromo-2— (1—ethoxystyl) oxymethylbenzene 2—bromobenzinole alcohol 18.70 g (0.1mol), chloromethane 150 ml and etylbininole ether 14 To a mixture of 4 2 g (0.2 mol) was added 0.5 g (0.002 mo 1) of pyridinum p-tonolene snorreona under ice-cooling and 3 hours at room temperature. Stirred. After the reaction, 300 ml of a half-saturated aqueous solution of sodium hydrogencarbonate was added, and the mixture was extracted twice with 100 ml of dichloromethane. The extract is dried over anhydrous magnesium sulfate, and then decompressed under reduced pressure to give 1-promo 2- (1-ethoxyethoxy) oxymethylbenzene 25.44 g (yield 98.2%) as a colorless oil. I got it as a thing.

¹ H-NMR (CDC 1:,) δ ppm: 1.22 (3H, t, J = 7.3), 1.41 (3H, t, J = 5.5), 3.49-3.77 (2H, m), 4.59 (1H, d, J = 12.8), 4.70 (1H, d, J = 12.8), 4.87 (1H, q, J = 5.5), 7.11-7.55 (4H, m).

2 — (1 — ethoxyxyl) oximetyl phenyl 2 — isoxazoline 1 3 — Production of inoleketone

Under a nitrogen gas atmosphere, 1-bromo-2-(-) was added to a suspension of 2.63 g (0.108 mo1) of magnesium, 0.2 ml of bromoethane and 5 ml of tetrahydrofuran. 1 Add a mixture of 18.6 g (0.072 mo1) of ethoxymethylbenzene and 67 ml of tetrahydrofuran at 50-55 over 30 minutes. The mixture was stirred at 50-55 for 1 hour to prepare a Grignard reagent: the Grignard reagent was added to the N-meth Xy N—Methyl 1—2—Sosoxazoline 1—3-Rubonic acid amide 7.59 g (0.048 mol) and a mixture of 70 ml of tetrahydrofuran The solution was dropped at a rate of 16 or less. After the dropwise addition, the mixture was stirred for 1.5 hours at −50 to 10 ° C. After adding 200 ml of water, a saturated aqueous solution of ammonium chloride was added until the insoluble material was dissolved, and the mixture was extracted twice with 100 ml of ether. did. The extract was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue obtained was purified by silica gel chromatography (ethyl acetate Zn-hexane) to give 2 — (1-d). Toxityl) oximetyl phenyl 2 -isoxazoline 13 -ylketone 13.0 g (yield 97.7%) was obtained as a colorless oil.

¹ H-NMR (CDC 1;,) δ ppm: 1.17 (3H, t, J = 7.3), 1.28 (3Η, d, J = 5.5), 3.34 (2H, t, J = l 1.0), 3.41-3.65 (2H, m), 4.56 (2H, t, J = ll.0), 4.65-4.89 (3H, m), 7.33-7.52 (3H, m), 7.71 (1H, d, J = 7.3). Three

3— (2—Hydroxymethyl-1-α-methoxymino-benzyl) -1-2-oxoxazoline

2- (1Ethoxyshethyl) oximetylphenyl 2-isosazozolin-3 —inoleketone 6.66 g (0.024 mo1) and methanol 4 8 ml, 4.08 ml (0.0504 mol) of pyridin and 4.01 g (0.048 mo1) of methoxyamine hydrochloride were added, and the mixture was stirred under reflux for 1 hour. . After the reaction, 200 ml of water was added, the pH was adjusted to 3 or less with concentrated hydrochloric acid, and the mixture was extracted twice with 150 ml of dichloromethane. The extract was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and 3-(2-hydroxymethyl-1-Q-methoxyoximino benzyl)-1-2-isoxazoline 5.59 g (yield 9 9. _c to 4%) as a colorless oil

¹ H-NMR (CDC 1:,) δ ppm: 2.16 (1Η, t, J = 6.1), 3.34 (2H, t, J = l 1.0), 3.96 (3H, s), 4.45-4.58 (4H, m), 7.13-7.56 (4H, m)

Preparation of 3-(2-holminole ct-methoxyminobenzyl) 1-2-isooxosazoline (compound No. IX-4)

0.95 ml (12 mmo 1) of dimethyl sulfoxide in 30 ml of dichloromethane solution containing 0.98 ml (11.2 mmol) of oxalyl chloride at -6 or less was added dropwise for 3 minutes, after dropping one 7 0 6 0 1 0 min stirring L was _e then 3 - (2 - arsenate mud Kishime Chiru alpha - main Tokishii Mi Roh benzyl) one 2 - Lee Sookisazo Li down 0. A solution prepared by dissolving 94 g (4 mm 01) in dichloromethane 1 O m 1 is added dropwise at 16 or less over 5 minutes.After the dropwise addition, it is added at 170 to 160 for 20 minutes. Stirred. To the reaction solution, 2.79 ml (20 mmol) of triethylamine was added dropwise at −60 ° C. or less over 5 minutes, and the mixture was stirred from 170 to 1 lOt for 0.5 hour. After the reaction, a half-saturated aqueous solution of ammonium chloride (150 ml) was added, and the mixture was extracted twice with 80 ml of dichloromethane. The dichloromethane layer is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue obtained is purified by silica gel chromatography (ethyl ethyl hexane) to give 3 — (2 — formyl α — 0.887 g (yield 93.6%) of 1- 2-isoxazoline was obtained as colorless crystals.

¹ H-NMR (CDC 1) δ ppm: 3.39 (2H, t, J = ll.0), 3.93 (3H, s), 4.49 (2H, t, J = 10.4), 7.32 (1H, dd, J) = 7.3, 1.2), 7.57 (1H, td, J = 7.3, 1.8), 7.67 (1H, td, J = 7.3, 1.8), 7.96 (1H, dd, J = 7.9, 1.8), 9.85 (1H, s In the same manner as in the synthesis of the intermediate in Example 4, the compound (I) was prepared. Various compounds represented by the general formula (IX) of the present invention, which are intermediates, were synthesized. Table 1 shows the obtained compounds and their physical property values. In the table, physical properties of the compound (IX-4) obtained in Example 4 are also shown.

table 1 .

Example 5

3 — [α — methoxyminino 2 — {4-(4-trifluoromethyl phenyl) 1 2, 3 — diaza 1, 1, 3 — pentadenyl} benzil] 1 2 1 isoxoxazo Production of Lin (Compound No. D-83)

3 — (2 — Hormyl-α-methoxymino-benzyl) 1-2 — Isoxosazolin 0.19 g (0.8 mmol) was dissolved in 2 ml of methanol, and 4 '-(Trifrenoleolomethyl) acetophenone hydrazone (0.22 g, 0.88 mmo 1) was added, and the mixture was stirred at room temperature for 4 hours. After the reaction, METHANOL - Le vacuo澳縮after purification obtained residue was re Kageruku Loma preparative graph I by chromatography (acetic acid Echiruzu _n-hexane), performs recrystallization (acetic Echiru / hexa down), 3 — [α — methoxyminino 2 — {4-(4-trifluoromethyltinolepheninole) 1 2, 3 — diaza 1 13 — pentageninole) benzil] 1 2 — i 0.23 g of soxazoline (yield: 75.0%) was obtained as colorless crystals.

m p 1 3 4 to 1 3 5

_{'H - NR (CDC 1 3} ) δ ppm: 2.49 (3H, s), 3.35 (2H, t, J = 10.4), 3.94 (3H, s), 4.47 (2H, t, J = 10.4), 7.23- 7.55 (3H, m), 7.68 (2H, d,] = 7.9), 8.00 (2H, d, J = 7.9), 8.14-8.19 (1H, m), 8.21 (1H, s).

3— (2—Hydroxyminomethyl-1α-Methoxyxyminobenzyl) -1-2—Dioxoxazoline

3 — (2 — holminole α — methoxyminobenzyl) 1-2 — isooxosazolin 0.46 g (2 mmo1) was dissolved in 4 ml of methanol, and 0.28 g (4 mmol) of roxylamine hydrochloride and 0.35 g (4.4 mmol) of pyridine were added, and the mixture was stirred under reflux for 1 hour. After the reaction, 0. 100 ml of IN aqueous hydrochloric acid solution was added, and the mixture was extracted twice with 50 ml of dichloromethane. The dichloromethane layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 3-(2-hydroxyiminomethyl-methoximinobenzyl)-1-2-isoxazoline 0.50 g (100% yield). ) Was obtained as an oil.

_{1 H - NMR (CDC 1 3} ) δ ppm: 3.33 (2H, t, J = 10.4), 3.94

(3H, s), 4.48 (2Η, t, J = 10.4), 7.19-7.22 (1H.m), 7.38-7.47

(3H, m), 7.83-7.86 (1H, m), 7.93 (1H, s).

3 — [α — methoxymino 2 — — {4-(4 1-chlorophenyl) 1 2 1 aza 3 — oxa 1 1 1 pentenyl} benzyl] 1 2 — isoxazoline (compound N o Production of D-7)

3 — (2 — Hydroxyminomethyl-α-Methoxyminobenzyl) 1-2-isoxazoline 0.17 g (1 mmo1), N, N-dimethylformamide 2 m1 and 4-chloroー α-Methylbenzyl bromide 0.29 g (1.34 mmol) of 60% sodium hydride 0.04 g (1.3 mmo 1) on ice And stirred at room temperature for 2 hours. After the reaction, 100 ml of ether was added, and the mixture was washed twice with 80 ml of a saline solution. The ether layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue obtained was purified by silica gel chromatography (ethyl acetate / n-hexane) to give 3 — [Hexoximino. 2 — {4-(4 1-mouth phenyl) 1-2 -aza 3-oxa 1-1-pentenyl] benzyl] 1-2-isooxosazolin 0.32 g (yield 91.3%) Was obtained as a colorless oil.

^{_{1 H - NMR (CDC 1 3}} ) δ ppm: 1.56 (3H, d, 6.7), 3. 12-3.30 (. 2Η m), 3.89 (3H, s), 4.32-4.47 (2H, q), 5.26 ( 1H, mq.) = 6.7), 7.14-7.42 (7H.m), 7.76 (1H, dd, J = 7.9, 2.5), 7.98 (1H.s). Example 8

Production of 3- (2-bromomethylbenzoyl) isoxazole

3 — (2—Methylbenzoyl) isoxazolyl 0.56 g (3 mmo 1) in 6 ml of benzene, N-bromosuccinic imid 0.59 g (3.3 mmo 1) and 2 Then, 0.05 g (0.3 mmo 1) of 2,2′-azobisisobutyrylonitrile was added, and the mixture was stirred under heating and reflux for 1 hour. After the reaction, the insolubles were removed, and the residue obtained by concentration under reduced pressure was purified by silica gel chromatography (ethyl acetate / n-hexane) to give 3- (2-bromomethylbenzoyl) isoxazole. 0.50 g (yield 62.6%) was obtained as a pale brown oil.

_{'H - NMR (CDC 1 3} ) δ ppm: 4.80 (2Η, s), 6.95 (. 1H d, J = l.02), 7.42-7.57 (3H, m), 7.93 (1H, d, J = 7.3 ), 8.56 (1H, d, J = l.8).

3 — (2—Acetoxymethyl benzoyl) isoxoxapur 3 — (2—Bromomethylbenzoyl) isoxoxazole 1.68 g (6.3 mm o 1) in N, N — 1 ml of dimethylformamide and 1.24 g (12.6 mmo 1) of acetic acid-rich lithium were added, followed by stirring at room temperature for 17 hours. After the reaction, 150 ml of ether was added, and the mixture was washed twice with 100 ml of saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue obtained was subjected to silica gel chromatography (ethyl acetate / ethyl acetate). Purification with n-hexane) provided 1.23 g (yield: 79.5%) of 3— (2-acetoxymethylbenzoyl) isoxazole as an oil.

^{_{1 H- NMR (CDC 1 3)}} δ ppm: 2.04 (3H, s), .28 (2H, s), 6.92 (1H, d, J = 1.8), 7.43-7.63 (. 3H m), 7.96 (1H d.) = 7.3), 8.55 (1H.d.J = l.8). Example 10

Production of 3- (2-acetoxymethyl-a-methoximeminobenzyl) isoxoxazole

3 — (2-acetoxymethylbenzoinole) 0.49 g (2 mmo 1) of isoxazole, 4 ml of methanol and 0.34 ml of pyridine (4.2 mmo 1) and main Tokishia Mi emissions hydrochloride 0. 3 3 g (4 mmo 1 ) after _t reaction was stirred for 6 hours at heritage falling adding water 1 0 0 ml was added, it was adjusted to p H 3 below with concentrated hydrochloric acid, Extracted with 120 ml of ether. The extract is dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue obtained is purified by silica gel gel chromatography (ethyl acetate Zn—hexane) to obtain 3 — (2-acetate). 0.52 g (yield 94.8%) of toximetyl-α-methoxyminobenzyl) isoxazole was obtained as a colorless oil _c

_{'H - NR (CDC 1 3} ) δ ρ ρ m: 1.98 (1.93) (3Η, s), 4. 11 (4.00) (3H, s), 5. 11 (5.00) (2H, s), 7.04 ( 6.78) (1H, d, J = l.8), 7.38-7.52 (4H, m), 8.50 (8.40) (1H, d, J = 1.8).

3— (2—Hydroxymethyl-α-methoxymethoxy) Production of iso-oxazole

3-(2-acetoxymethyl-α-methoxyminobenzyl) isoxazole 0.25 g (1 mmo1) in 2 ml of methanol and 28% sodium methoxide Then, 0.02 g (0.1 mmol) was added and the mixture was stirred for 10 minutes under a flow. After the reaction, 8 O ml of saturated aqueous sodium hydrogencarbonate was added, and the mixture was extracted with 10 O ml of ether. After drying over magnesium sulfate and concentrating under reduced pressure, the residue obtained is purified by silica gel chromatography (ethyl acetate n-hexane) to give 3 — (2 — hydroxymethyl ethyl acetate). Mexican Nonbenzyl) isoxazole 0.22 g (yield 94.7) was obtained as a colorless oil.

^{_{1 H - NMR (CDC 1 3}} ) δ ppm: 2.28 (3.07) (1 H, t, J = 6.7), 4.01 (4. 12) (3Η, s), 4.48 (4.59) (2Η, d, J = 6.7), 6.81 (6.99) (1H, d, i 1.8), 7.20-7.61 (4H, m), 8.41 (8.53) (1H, d, i 1.80).

3— (2—Hydroxymethyl-α-methoxyminobenzyl)

3 — (2—acetoxymethyl benzoyl) isoxazole 0.25 g (1 mm o 1) in methanol 2 ml and methoxyamine hydrochloride 0.17 g (2 mm o 1 ) Was added and the mixture was stirred for 2 hours under reflux with heating. After the reaction, 100 mL of ether was added, washed with 80 mL of brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue obtained was purified by silica gel chromatography (ethyl acetate / ethyl acetate). Purification with n-hexane) gave 0.09 g of 3-((2-hydroxymethyl-α-methoxymethoxybenzyl) isoxazole) (yield 38.8) as an oil. Example 1 3

3 — (2 — Formyl α- methoxyminobenzyl) isoxazole

2.77 ml (39 mmo 1) of dimethylsulfoxide was added to 65 ml of a dichloromethane solution containing 3.12 ml (36.4 mmol) of oxalyl chloride. Then, the mixture was stirred at 170 to 160 for 16 minutes. Next, 3.0 2 g (13 mmo 1) of 3-(2-hydroxymethyl-α-methoxyminobenzyl) isoxazole is added to dichloromethane. A solution dissolved in 26 ml of tan was added dropwise at a temperature of 160 ° C or less for 25 minutes, and the mixture was stirred at −70 to 16 for 20 minutes. To the reaction solution, 9.06 ml (65 mmol) of triethylamine was added dropwise at 160: below for 25 minutes, and the mixture was stirred from -70 to 1 l Ot for 1.5 hours. After the reaction, a half-saturated aqueous ammonium chloride solution (230 ml) was recovered and extracted twice with dichloromethane (150 ml). The dichloromethane layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue obtained was purified with silica gel chromatography (ethyl acetate Zn—hexane), and 3 — (2 —Formyl-1-α-methoxyminobenzyl) isoxazol (2.38 g, yield 78.9%) was obtained as colorless crystals.

¹ H-NMR (CDC 1;,) 6 ppm: 3.99 (3H, s), 6.86 (1H, d, J = l.8),

7.39 (1H, dd, J = 7.3, 1.2), 7.58-7.74 (2H, m), 8.01 (1H, dd, J = 7.3, 1.2),

8.41 (1H, d, J = l.8), 9.88 (1H, s). Example 14

3 — [α — methoxyminino 2 — {4-(3, 4 — dichlorophenyl) — 2,3 — diaza 1, 3 — pentagenenyl} benzyl] isoxoxazole (compound N o. Production of A—90)

3 — (2—Horminole a—Methoxyminobenzyl) Dissolve 0.23 g (lmmol) of isosoxazoline in 2 ml of methanol and add 3 ′, 4′—dichloroacetate 0.22 g (1.1 mmol) of tophenonhydrazone was added, and the mixture was stirred at room temperature for 20 hours. After the reaction, the methanol was decompressed and concentrated, and the obtained residue was purified by silica gel chromatography (ethyl ethyl acetate / n-hexane) and then recrystallized (ethyl acetate). Hexane), and then 3 — [a — methoxyminino 2 — {4-(3,4-cyclohexene) 1, 2, 3 — diaza 1, 1, 3 — pentagenil } Benzyl] isoxazole 0. 26 g (yield 62.7%) were obtained as colorless crystals.

m p l 6 1 to 1 6 2:

'H - NM R (CDC 1 3) δ ppm: 2.38 (3H, s), 3.99 (3H, s), 6.81 (1Η, d, J = l.8), 7.30-7.71 (4H, m), 7.98 (1H, d, J = l.8), 8.13- 8.16 (1H, m), 8.26 (1H, s), 8.39 (1H, d, J = l.8). Compound groups A to I are shown below as examples of the compound represented by the general formula (I), and combinations of the substituents R ² and R \ M of the compound groups A to I are shown in Tables 2 to 16. Shown in The physical properties of these compounds are shown in Tables 17 and 18. In the table, physical properties of the compounds obtained in the above Examples are also shown. No in the table indicates a compound number.

≠

n ϋΐ

ο CD 0Q cn C Γ \ 3 ο CD 0J t z

o

04

m o

6

104 Uru! "* Nj-shi 6 Me H-i N = shi

105 f lithium-2-yl Me H -N = C (Me)

106 HI'RISHIN-3-YL Me H -N = C (Me) ¹

107 Pilisin-4-Me H -N = C (Me)

108 Franc- 2- · (Le Me H — N = C (Me)

109 franc-Me H -N = C (e) ―

110 Thione -2 yl Me H -N = C (Me)

111 Chioff: n -3-ί Me H -N = C (e)

112 2-Naphthyl Me H -N = C (Me)

113 3-Naphthy A Me H -N = C (Me)

114 h 7 -h-2-i Me H -N = C (Me)

Π ί> * Two '-Funo No 2- (Λ> Me H * »NI (Μ ΛΛΘ'

116 5-Me-furan-2- Me H -N = C (, e)

117 5-C totioff I -2-ίΑ Me H -N = C (e)

118 5-Br-thiophene I-2-Fl Me H -N = C (Me) ―

119 3-Pfri soxable Me H-I N = C (Me '

120 5-Me-isoxoxa 'No'-le-3-ίΑ Me H — N = C (Me

121 Me H — OCH (Et)

122 4-FC ₆ H ₄ Me H -OCH (Et)

123 3-FC ₆ H ₄ Me H -OCH (Et)

124 3-CI-C ₆ H ₄ Me H -OCH (Et)

125 4-CI-C ₆ H ₄ Me H one OCH (Et)

126 4-Br-C ₆ H ₄ Me H one OCH (Et ' 00

G3 ω ω G3 ro z

n CO t o CO 03 ^ 4 3 r o o

67 3-Me-C ₆ H ₄ Me H i NH—

168 4-Me-C ₆ H ₄ Me H i NH—

169 3-CF ₃ -CgH ₄ Me H — NH—

160 4-CF ₃ -C ₆ H ₄ Me H i NH—

161 3,4-F ₂ -C ₆ H ₃ Me H i NH—

162 Me H one NH—

163 3,4-Cl ゥ -C ₆ H ₃ Me H -NH-

164 Me H one NH—

165 3,4-Me ₂ -C ₆ H ₃ Me H -NH-

166 4-CI-3-Me-C ₆ H ₃ Me H -NH-

167 5-CF3-I: "Risin -2 Le Me H -NH-

168 5-CF ₃ -3-C ヒ '"/ ン -2-yl Me H -NH-

169 3.5-CI ₂ -Piricin '-2-ίΑ Me H, -NH-

170 3,4,5-CI ₃ -CeH ₂ Me H -NH—

171 —

^C 6 ^H 5 Me H -〇CH ₂

172 4-FC ₆ H ₄ Me H -〇CH ₂ —

173 3-FC ₆ H ₄ Me H -OCH one

174 3-CI-C ₆ H ₄ Me H -OCH

175 4-CI-C ₆ H ₄ Me H one OCH _2-

176 4-Br-C ₆ H ₄ Me H -OCH- 1

No R2 R3 R ⁴ M iff

1 / o A KAa U Me Π 一 UUM y ^{4 tx} ^ 6 4 ΜΘ Π

I ou Me U

I O I * +

Π Π Π Π

Rishuichi

^J then ¹ ^ 3 then 6 ^M 4 ΜΘ Π one u

I o 4 oshi 6 ^M 4 ΜΘ u Π one per π

1 QA

卩卩卩》 ~ ~ 2 6 6 ^M 3 ΜΘ u

103 ^r 2 Π — PeriΡΗ, · ゥ

6 ⁿ 3 ΜΘ u ^ one

186 34-CI -C Me H — 0CH one by one

187 '6 3 Me H —〇CH ₂ —

188 3,4-Me ゥ -〇 _Λ Η Me H -〇CH ₂ —

189 4-CI-3- eC _c H Me H 100 CH ₂ —

190 Me H one 0CH ₂ — u

191 6 ^H 5 Me H

192 4-FC ₆ H ₄ Me H —〇C (Me) ₂ —

193 3-FC ₆ H ₄ Me H 1〇C (Me) ₂ —

194 3-CI-C ₆ H ₄ Me H — 0C (Me) ₂ —

195 4-CI-C ₆ H ₄ Me H -0C (Me) _2-

196 4-Br-C ₆ H ₄ Me H 1 0C (Me) ₂ — 875 2

No R ² R ³ R ⁴ M

1 Q7 Li

IS Π Π WIS} ゥ

1 1 Q ½7A0 M Moe u Π one ΠΠ Ρ ^ one

Mo u Π ri view Λ Mo Π

202 3 6 4 IvltS ク Noku

203 * t 3 ^ 6 4 μ Π — OCfMe

204 '2 6 3 w H — OCiMe) —

205 ^ ^{, j} 2 6 3 H — OCfM, -e * ノ —

206 ^w , 26 3 Me H — 0C (Me) —

207

£. D Me H One C (Me) one

209 — OCiMe —

210 Mp H

— OC (Me) ノ —

211 then 6 ^H 5 Me H — OCHiCFg) —

212 4-FC ₆ H ₄ Me H-1CH (CF ₃ ) —

213 3-FC ₆ H ₄ Me H 100 CH (CF ₃ ) —

214 3-CI-C ₆ H ₄ Me H OCH (CF ₃ ) —

215 4-CI-C ₆ H ₄ Me H OCH (CF ₃ ) —

216 4-Br-C ₆ H ₄ Me H OCH (CF ₃ ) —

9 α 96fc

Next, the bactericidal and insecticidal effects of the compound of the present invention will be described with reference to the following test examples.

I. Various plant disease control tests by foliage application (pot test)

Test method

The test solution was prepared by dissolving the compound in a small amount of NN-dimethylformamide and diluting it to a predetermined concentration with distilled water containing an adhesive. The test liquid was sprayed on the test plant, and 24 hours later, the pathogen was inoculated by the method described below.

The control rate was calculated by the following formula.

Disease incidence in untreated plots 1 Degree of disease development in treated plots · Number of lesions, etc. · Number of lesions, etc. Control rate (%) = X 100

Test degree 1

Effect test for control of powdery mildew of cucumber

The seedlings were sown on plastic cups with a diameter of 9 cm and raised for 2 to 3 weeks. The compound solution or suspension solution was applied to the surface of the first true leaf of the seedlings (variety: Tsukuba Shirobo). The pathogen was inoculated by spraying a conidia suspension of the powdery mildew fungus (Sphaerotheca ful iginea) cultured on the leaves of Cucumber. After inoculation, the plants were kept in 20 greenhouses for 10 days, and the area occupied by the signs that appeared on the inoculated leaves was investigated to determine the control rate.

The results are shown below. Compound No. of 500 ppm against Cucumber powdery mildew Preventive effect by foliage application (control rate)

A-1 7 1 0 0

A-2 2 1 0 0

A-one 2 3 1 0 0

A-1 3 0 1 0 0

A-one 6 7 1 0 0

A-1 8 2 1 0 0

A-1 8 3 1 0 0

A-1 9 0 1 0 0

C-7 B 1 0 0

C-1 2 3 A 1 0 0

C-1 2 3 B 1 0 0

C-1 30 B 1 0 0

C 1 6 7 B 1 0 0

C-1 8 2 A 1 0 0

C-1 8 2 B 1 0 0

C-1 8 3 1 0 0

D 1 1 0 0

D 1 2 3 1 0 0

D-6 7 1 0 0

D-1 8 3 1 0 0

Control agent

Fenarimol 1 0 0 Test example 2

Cucumber and disease control effect test

The seedlings were seeded on a plastic cup with a diameter of 9 cm and raised for 2 to 3 weeks. The compound solution or suspension was sprayed on the surface of the first true leaves of the cucumber (variety: Tsukuba Shirobo). The pathogen was inoculated by spraying a suspension of zoospores of cucumber and Pseudoperonospora cubens is cultivated on green leaves and a solution or suspension of arsenic compound. It was performed by dropping on the surface of the leaves. After inoculation, they were kept for 10 days in the wet room of No. 2 and the extent of lesions appearing around the inoculated area was investigated to determine the control rate.

The results are shown below.

Compound number of 500 ppm against cucumber downy mildew Preventive effect of foliar application (control rate)

A-1 7 1 0 0

A-1 2 3 9 7

A-1 3 0 9 7

A-one 6 7 1 0 0

A-1 8 2 1 0 0

A-1 8 3 1 0 0

A-1 9 0 9 9

C-1 7 B 1 0 0

C-1 2 3 A 1 0 0

C 1 2 3 B 1 0 0

C-1 30 B 1 0 0

C-1 6 7 A 1 0 0

C-1 6 7 B 1 0 0

C-1 8 2 A 1 0 0

C-1 8 2 B 1 0 0

C 1 8 3 1 0 0

D-1 7 1 0 0

D-1 2 3 9 7

D-1 6 7 9 0

D-1 8 3 1 0 0

Control agent

Benalaxyl 9 9 Test example 3

Wheat ぅ Powdery mildew control effect test

The seeds were sown on plastic cups with a diameter of 9 cm and seedlings were raised for 2 to 3 weeks. The pathogen was inoculated by removing conidia of the wheat powdery mildew (Erysiphe graminis f. Sp. Tritici) cultured on the wheat leaves from the test plant. After inoculation, the plants were kept in a greenhouse of 20 m2 for 10 days, and then the area occupied by the signs that appeared on the inoculated leaves was investigated to determine the control rate.

The results are shown below.

Table 21 Preventive effect of foliage application at 500 ppm Compound No. against wheat ぅ powdery mildew (control rate)

A-7 9 0

A—2 2 9 0

A— 2 3 9 7

A-3 0 9 0

A 1 6 7 9 0

A-1 8 2 9 0

C-i A 9 7

C 1 7 B 9 0

C 1 2 3 A 9 0

C 1 2 3 B 9 7

C 1 3 0 A 9 7

D—2 3 9 0

D— 6 7 9 0

Control agent

Fenari monole 9 7 Test example 4

Rice blast control effect test

Two weeks after sowing, rice (cultivar: Asahi Aichi) Seedlings were transplanted to 9 cm diameter plastic cups, seedlings were further raised for two weeks, and a compound solution or suspension was sprayed on the foliage. Inoculation was performed by spraying a suspension of conidia of rice blast (Pyricularia oryzae) cultured in an automeal medium. After inoculation, the plants were kept in a wet room (28%, 100% R.H.) for 24 hours and seedlings were grown in a greenhouse for 5 days. Six days after inoculation, the number of lesions appearing on the inoculated leaves was measured to determine the control rate.

The results are shown below. Table 2 _2

Compound number of 500 ppm on rice and rice blast Preventive effect of foliar application (control rate) A-797

A 1 2 2 9 0

A 1 3 0 9 0

A 1 6 7 9 7

A-1 8 2 1 0 0

A-1 9 0 9 7

C 1 7 A 9 0

C 1 7 B 9 7

C 1 2 3 B 9 0

C 1 3 0 A 9 0

C 1 3 0 B 9 0

c-6 7 B 9 7

C 1 8 2 A 9 0

C 1 8 2 B 9 7

D-9 7

Control agent

Fthalide 9 7 W 97/12875

1 I. Insecticidal activity test

Test example 5

Insecticidal activity against peach aphids (Myzus persicae)

Chinese cabbage leaf pieces having a diameter of 3 cm were placed on a 0.3% agar gel with the back side facing up, and inoculated with wingless adults, kept at 25 for 1 day, and the number of litters was counted. Subsequently, the adult was removed, and a test solution at a predetermined level was sprayed on the larvae on the Chinese cabbage leaf pieces.

After 25 and 48 hours, the number of dead insects was counted to determine the effect. The test solution was prepared by dissolving the compound in a small amount of N, N-dimethylformamide and diluting it with distilled water containing a surfactant to a predetermined concentration.

Compound No. A-90 exhibited a mortality of 100% at 62.5 ppm. The invention's effect

INDUSTRIAL APPLICABILITY As described above, the present invention provides a novel α-alkoxyiminobenzyl heterocyclic derivative having excellent bactericidal and insecticidal activities, an intermediate for the production thereof, and an agricultural chemical containing the same as an active ingredient.

Claims

Scope of claim General formula (I)

[Wherein, R ¹ is a substituted or unsubstituted heterocyclic group; R ² is a substituted or unsubstituted heterocyclic group; R ³ is a substituted or unsubstituted heterocyclic group; alkyl; R 'is a hydrogen atom, an alkyl, alkoxy, Bruno, androgenic atom, - DOO port, Shiano or halogenation alkyl; M an N = C (R ⁵⁾ one [R ⁵ is a hydrogen atom, an alkyl, halogenated It represents an alkyl or a cycloalkyl, that you R ² and R ⁵ together such connexion, to form a contiguous good monocyclic or condensed polycyclic also contain carbon atoms and the monitor heteroatom shown] or an ^{^{A- (CR h R 7) n}} - [ each R ⁶ and R ⁷ independently represent a hydrogen atom, an alkyl, Xia Roh or halogenation alkyl; A is an oxygen atom or NR ^H

(R is a hydrogen atom, alkyl or acyl), n is 0, 1 or 2.]; Wavy line (~) indicates the configuration of E-form, Z-form or a mixture of these. Compound.

2.R 'is an optionally substituted pyridyl, pyrimidinyl, isoxazolyl, isoxoxolinyl, isothiazolyl, thiadiazolyl, pyridazinyl, virazolyl, The compound according to claim 1, which is lilyl, chenyl, imidazolyl, oxazolyl, thiazolyl, thiazolidinyl, oxaziaziryl, triazolyl or pyrazul:

3. R ¹ is optionally substituted isosoxazole-3 — inole, isosoxazoline 1-4 inole, isosoxazoline 1 5 — inore, 2 isoxoxolin 1 3 —yl, 2 — Lsoxazoline 1 5 — yl, imidazo 2 — inore, 1, 2, 4 — oxadiazol 1 3 — inore, 1, 3, 4, 4 — oxaziazolu 2 — yl or fran 2 — The compound according to claim 1 wherein the compound is an yl.

4. R ¹ is isosozoazolu 3-yl, 5-methylisosozozo-ru 3-dino, 3-methylisosozozoru 5-dino or 2-diisoxazoline 3-diru The compound according to claim 1, which is:

5. R ² is phenyl or hetero optionally having 1 to 3 substituents selected from the group consisting of halogen atom, lower alkyl, halogenated lower alkyl, lower alkoxy, phenyl and phenoxy. 2. The compound according to claim 1, which is a cyclic group.

6. The optionally substituted heterocyclic group represented by R ² may be substituted, pyridyl, pyrimidinyl, isosoxazolinole, thiadiazolinole, pyridazinyl, Claim 1 or claim which is pyrrolyl, pyrazolyl, furyl, chenyl, imidazolyl, oxazolinole, thiazolyl, oxaziazolyl, pyrazinyl, quinolyl or indolyl Item 6. The compound according to item 5.

7. R ² Power Feninore, 2 — Kuro Exit Feninore, 3 — Kuro Exit Feninole, 4 — Kuro Exit Feninore, 3 — Bromo Fen 2 / Re, 4 1 Brom Fue Ninole, 2—Methyl phenyl, 3—Methyl phenyl, 41 Methyl phenyl, 2,5—Dimethyl phenyl, 3, 4—Dimethyl phenyl, 3—Fluorophenyl, 4-phenyl / Leo phenyl Nole, 3,4-cyclohexyl phenyl, 3—trinoleno methinolephenyl, 4-trimethylol phenyl, 4—methoxyphenyl, 4—methyl-2-phenyl Claim 1 Compound.

8. The compound according to claim 1, wherein R ^{3 is} methyl.

9. The compound according to claim 1, wherein R 'is a hydrogen atom.

1 0. M Gar N = C (CH ₃₎ - or a O- CH (CH ₃₎ compound in the range first claim of claim is one.

1 1. R ¹ power; 3 — methyl soxazono 1-5 — inor, R ² power; 4 — black phenyl, R is methyl, R ¹ is hydrogen and M is — O— CH (CH, ) A compound,

R ¹ force; 3—Metinolei Soxazo 1-5—R, R ² is 41 Trifluoromethyl, R ^{: t is} methyl, R 'is hydrogen and M is O—CH A compound that is (CH,) —

R ¹ force; 3 — methinolay soxazolone 5 — yl, R ² force; 3, 4 — dichloro mouth phenyl, R ^{3 is} methyl, R ¹ is hydrogen and M is 1 O— CH (CH— A compound,

R 'force; 3 — methyl soxazono _ 5 —inole, R ² force; 4 phenyl, R ^{3 is} methyl, R' is hydrogen and M is N = C (CH ₃ ) — Is a compound,

R ¹ force; 3 — methyl soxazolone 1 5 — inole, R ² force; 3 — trif norelo methylphenyl, R ^{3 is} methyl, R ′ is hydrogen and M is N = C (CH: ,) A compound,

R 'Guy Sookisazoru 3 - I le, R ^L' force; 3, 4 - Axis B port phenylalanine, R ¹ turtle chill, compounds wherein R ¹ is an hydrogen and M gar N = C (CH, or

R ¹ force; 2 - Lee Sookisazo Li down one 3 - Inore, R ^L 'force; 4 one click throat phenylene Honoré, R ¹ turtle chill, R' is hydrogen and M is one N = C (CH;, 2. The compound according to claim 1, wherein the compound is one of the following:

1 2. An agricultural chemical containing the compound according to any one of claims 1 to 11 as an active ingredient.

1 3. A fungicide containing the compound according to any one of claims 1 to 11 as an active ingredient.

1 4. An insecticide containing the compound according to any one of claims 1 to 11 as an active ingredient.

1 5. —General formula (I X):

(Wherein each symbol is as defined in claim 1).

1 6. A phytopathogenic bacterium, characterized in that the compound described in claim 1 or a salt or hydrate thereof is applied as an active ingredient to a part affected or susceptible to the phytopathogenic bacterium. Sterilization or prevention method.

1 7. Use of the compound according to claim 1 or a salt or hydrate thereof in the manufacture of a fungicide.