WO1997009302A1 - α-ALKOXYPHENYLACETIC ACID DERIVATIVES, INTERMEDIATE FOR PRODUCING THE SAME, AND PESTICIDE CONTAINING THE SAME - Google Patents
α-ALKOXYPHENYLACETIC ACID DERIVATIVES, INTERMEDIATE FOR PRODUCING THE SAME, AND PESTICIDE CONTAINING THE SAME Download PDFInfo
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- WO1997009302A1 WO1997009302A1 PCT/JP1996/002443 JP9602443W WO9709302A1 WO 1997009302 A1 WO1997009302 A1 WO 1997009302A1 JP 9602443 W JP9602443 W JP 9602443W WO 9709302 A1 WO9709302 A1 WO 9709302A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/36—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/40—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
- C07C251/52—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
- C07C251/54—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by singly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/38—Amides of thiocarboxylic acids
- C07C327/40—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C327/44—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/58—Derivatives of thiocarboxylic acids, the doubly-bound oxygen atoms being replaced by nitrogen atoms, e.g. imino-thio ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to a novel monoalkoxyphenylacetic acid derivative, an intermediate for producing the same, and an agricultural chemical containing the same as an active ingredient.
- An object of the present invention is to provide a novel compound that is useful as a fungicide, especially as a fungicide for agriculture.
- the present inventors have conducted intensive studies to obtain a compound having an excellent bactericidal activity, and as a result, have found that a novel ⁇ -alkoxyphenyl in which the methoxyimino group of the methoxyiminoacetic acid derivative is converted to an anorecoxy group.
- the inventors have found that an acetic acid derivative has a strong bactericidal activity, and completed the present invention.
- R is a hydrogen atom or an optionally substituted alkyl group
- Y is an optionally substituted amino group
- Z is an oxygen atom or an iodine atom
- Q is —O—CR 1 R 2 -A r (wherein, R 1 and R 2 are each independently a hydrogen atom, an alkyl group, or a cycloalkyl group
- Ar is an optionally substituted polyaryl group or an optionally substituted Or a heterocyclic group) or
- N CR 3 R ′ (wherein, R 3 and R 1 are each independently an alkyl group, an alkylthio group, an optionally substituted aryl group or a substituted R 1 and R ′ are bonded together with adjacent carbon atoms to form a monocyclic or condensed polycyclic ring which may contain a hetero atom.
- U is a hydrogen atom, a halogen atom, an alkyl group which may be substituted or substituted
- alkyl group of the optionally substituted alkyl group represented by R examples include alkyl groups having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, specifically, methyl, ethyl, and propyl. , Isopropyl, butyl, isobutyl, t-butyl, pentynole, hexyl and the like. Of these, methyl, ethyl and propyl are preferred, and methyl is particularly preferred.
- substituted alkyl group examples include, for example, a haloalkyl group having a halogen atom (eg, fluorine, chlorine, bromine, iodine) as a substituent (eg, difluoromethyl, trifluoromethylinole, chloromethinole, 2 — Bromoethynole, 2,3-dichloropropyl, etc .; an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms as a substituent (eg, methoxy, ethoxy, propoxy, butoxy) Etc.) (eg, methoxymethyl, ethoxymethyl, 2-methoxethyl, etc.).
- a halogen atom eg, fluorine, chlorine, bromine, iodine
- a substituent eg, difluoromethyl, trifluoromethylinole, chloromethinole, 2 — Bromoethy
- Examples of the optionally substituted amino group represented by Y include, for example, And alkylamino, dialkylamino and the like.
- Examples of the alkyl group of the alkylamino and dialkylamino include the groups exemplified as the alkyl group represented by R above.
- Y is preferably methylamino, ethylamino, or dimethylamino, and particularly preferably methylamino.
- Examples of the alkyl group represented by R 1 , R 2 , R 3 and R 4 include the groups exemplified as the alkyl group represented by R above.
- Examples of the cycloalkyl group represented by R 1 and R 2 include a cycloalkyl group having 3 to 7 carbon atoms, specifically, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclohexyl. C, etc.
- alkylthio group represented by R 3 and R 4 examples include, for example, an alkylthio group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, specifically, methylthio, ethylthio, propylthio, and butylthio. No.
- Examples of the optionally substituted aryl group represented by Ar, R 3 and R 4 include aryl groups having 6 to 14 carbon atoms, such as phenyl and naphthyl (eg, 1-naphthyl) , 2-naphthyl, etc.), fluorenyl and the like. Of these, phenyl is preferred.
- the substituents may be lower (C 1-ti , preferably C l-e , and more preferably C,.,; The same applies to the substituents.
- Alkyl group eg, methyl, ethyl, propyl, butyl, etc.
- lower alkenyl group eg, butyl, aryl, crotyl, etc.
- lower alkynyl group eg, echul, Proparginole, butynyl, etc.
- cycloalkyl groups eg, cyclopropyl, cyclopentyl, cyclohexyl, etc.
- lower alkoxy lower alkyl groups eg, methoxymethyl, ethoxymethyl, 2-methoxyethyl, etc.
- Alkenyl groups eg, cyclopentenyl, cyclohexenyl, etc.
- lower Alkanoyl groups eg, acetyl, propionyl, isobutylyl, etc.
- lower alkylsilyl groups eg, trimethylsilyl, triethylsilyl, tripropy
- substituents may be located at any substitutable position on 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.
- the optionally substituted heterocyclic groups represented by i and R ′ include, for example, 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur as ring-constituting atoms. and the to c specifically include Teroa Li Lumpur group to 5-7 membered containing, respectively optionally substituted pyridyl, pyridinium Dajiniru, Birazo Rinore, pyrimidone Jiniru, off Lil, thienyl, Okisazoriru And oxoxazolyl, benzothiazolyl, quinolyl, quinazolinyl, pyrazur, morpholino, piperazinyl and the like.
- pyridyl eg, pyridin-2-yl, pyridin-3-yl
- pyrimidinyl eg, pyrimidine-12-yl, pyrimidin-14-yl
- Etc. French
- French for example, 2 -French, 3-furyl, etc.
- Chenyl eg, 2-phenyl, 3-phenyl, etc.
- examples of the substituent include the same groups as those exemplified as the substituent of the aryl group represented by Ar.
- R : i and R 1 may be combined with adjacent carbon atoms to form a monocyclic ring or a condensed polycyclic ring which may contain a hetero atom .
- the monocyclic ring may have a heteroatom (eg, oxygen, nitrogen, sulfur, etc.) formed with R : i and R ′ and a carbon atom to which they are bonded, and may have 4 to 8 members.
- the monocyclic ring may be condensed with another ring to form a condensed polycyclic ring.
- ring and the condensed polycyclic ring include cyclopentane, cyclohexane, indane, 1,2,3,4—tetrahydronaphthalene, 5,6,7,8—te Trahydroquinoline, 4,5,6,7—tetrahydrobenzo [b] furan. These rings may have a divalent bond at any possible position.
- R ′ is hydrogen
- R 2 is an alkyl group and phenyl optionally substituted with Ar
- R 1 is a hydrogen atom
- R 2 is methyl or ethyl
- Ar is a halogen atom, an alkyl group, an alkoxy group, a group of 1 to 3 substituents selected from the group consisting of an alkyl group and a haloalkoxy group.
- R : i is an alkyl group or an alkylthio group
- R ′ is an optionally substituted phenyl or heteroaryl group, and more preferably.
- R 3 is methyl, ethyl or methylthio
- R is a halogen atom, an alkyl group, an alkoxy group, or a haloalkyl group.
- phenyl or pyridyl, pyrimidinyl, furyl or phenyl which may be substituted with 1 to 3 substituents selected from the group consisting of haloalkoxy groups.
- U represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group or an optionally substituted hydroxyl group, which is obtained when the phenylene group in the above general formula (I) is unsubstituted ( That is, when X is a hydrogen atom), and the phenylene group is not possible with one to three substituents selected from a halogen atom, an optionally substituted alkyl group and an optionally substituted hydroxyl group. Is intended to include the case where it is substituted at the position. When the number of the substituents is two or three, they may be the same or different.
- Examples of the halogen atom represented by U include fluorine, chlorine, bromine and iodine.
- Examples of the optionally substituted alkyl group represented by U include the same as the optionally substituted alkyl group represented by R.
- Examples of the optionally substituted hydroxyl group represented by U include, for example, a hydroxyl group, an optionally substituted alkoxy group, an optionally substituted alkenyloxy group, an optionally substituted alkynyloxy group, and an alkylcarbonyloxy group.
- Examples of the optionally substituted alkoxy group include, for example, an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, specifically, methoxy, ethoxy, propoxy, isopropoxy, butoxy, a Sobutoxy, t-butoxy, pentyloxy, hexyloxy, etc .; halogen as a substituent A haloalkoxy group having an atom (eg, fluorine, chlorine, bromine, silicon), specifically, difluoromethoxy, trifluoromethoxy, chloromethoxy, etc .; 8.
- an alkoxy group having 1 to 8 carbon atoms preferably 1 to 6 carbon atoms, specifically, methoxy, ethoxy, propoxy, isopropoxy, butoxy, a Sobutoxy, t-butoxy, pentyloxy, hexyloxy, etc .
- halogen as a substituent A haloalkoxy group having an atom (eg, flu
- Alkoxyalkoxy groups preferably having 14 carbon atoms in alkoxy groups (eg, methoxy, ethoxy, propoxy, butoxy, etc.), such as methoxymethoxy, 2-methoxyethoxy, c etc. d Tokishime butoxy, and the like
- alkenyloxy group which may be substituted include, for example, an alkenyloxy group having 38, preferably 36 carbon atoms, for example, aryloxy, propenyloxy, isopropoxy. Nyloxy, butenyloxy, isobuteroxy, penteleoxy, hexeleoxy, hexenoxy, etc .; haloalkenyl having a halogen atom (eg, fluorine, chlorine, bromine, iodine) as a substituent And the like. Specific examples thereof include 33-dichloro-2-propeninoleoxy, 4444-trifrenolelomethyl-12-butyroxy and the like.
- halogen atom eg, fluorine, chlorine, bromine, iodine
- the optionally substituted alkynyloxy group includes, for example, an alkynyloxy group having 38, preferably 34 carbon atoms, specifically propargyloxy, butynyloxy and the like;
- a haloalkynyloxy group having a halogen atom eg, fluorine, chlorine, bromine, iodine
- 3 chloro 2 —propynyloxy
- 4 4 4 trifluoromethyl-2 —Buchuroxy and the like.
- alkylcarbonyloxy group examples include an alkylcarbonyloxy group containing an alkyl group having 18 or 14 carbon atoms, specifically, acetooxy, propionyloxy, and butyryloxy. Is raised
- the (alkylthio) carbonyloxy group preferably has 18 carbon atoms. / JP96 / 02 43 or (alkylthio) carbonyloxy group containing an alkyl group having 1 to 4 carbon atoms, for example, (methylthio) carbonyloxy, (ethylthio) carbonyloxy, (propylthio) ) Carbonyloxy and the like.
- alkylsulfonyloxy group examples include an alkylsulfonyloxy group containing an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and specifically, methanesulfonyloxy and ethane. Sulfonyloxy, propyl sulfonyloxy and the like.
- arylsulfonyloxy group an arylsulfonyloxy group containing an aryl group having 6 to 12 carbon atoms, preferably 6 to 8 carbon atoms, specifically, Examples thereof include benzenesulfonyloxy and p-toluenesulfonyloxy.
- the mono- or dialkyl-substituted rubamoyloxy group a mono- or di-alkyl-substituted rubamoyloxy group containing an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, Monomethyl canolebamoyl noreoxy, N, N-dimethinorecanolebamoy noleoxy, N-monoethylcarbamoyloxy and the like.
- aryloxy group an aryloxy group having 6 to 12 carbon atoms, preferably 6 to 8 carbon atoms, specifically, phenoxy, 2-methylphenoxy, and 2,5-dimethylphenoxy And the like.
- U is preferably hydrogen.
- the compound of the present invention represented by the general formula (I) has an asymmetric carbon atom at the 2-position of the phenylacetic acid moiety.
- a mixture thereof is also included in the present invention.
- the compound of the present invention has a salt at the carbon-nitrogen double bond.
- Such salts that may be formed include hydrochlorides, sulfates, oxalates and the like.
- the compound of the present invention may form a hydrate.
- a preferred method for producing the compound of the present invention, which is included in the general formula (I), is exemplified.
- the compound (I) of the present invention can be produced by condensing an aldehyde compound (II) with an amino compound (III).
- reaction solvent for example, a solvent used for a normal oximation reaction such as alcohols such as methanol and ethanol can be used.
- the reaction temperature is a suitable temperature from 0 ° C to the reflux temperature of the solvent, preferably 20 ° C to 50 ° C, and the reaction time is 0.5 hour to 48 hours, preferably 0.5 to 1 hour. 2 hours.
- the obtained compound (I) of the present invention can be separated and purified by a known means (eg, chromatography, recrystallization, etc.).
- A is a hydroxy group or an amino group;
- X is a halogen atom;
- B is an optionally substituted aryl group or an optionally substituted heterocyclic group;
- D is an alkyl group or A cycloalkyl group; other symbols are IPJ
- the compound (I) of the present invention can be produced by condensing the compound (V) with the compound (VII) or the compound (VIII).
- halogen atom represented by X examples include chlorine, bromine, and iodine.
- the optionally substituted aryl group and the optionally substituted heterocyclic group represented by B the optionally substituted aryl group represented by Ar And the same as those exemplified as the optionally substituted heterocyclic group.
- alkyl group and a cycloalkyl group represented by D include the same ones as exemplified as the alkyl group and a cycloalkyl group represented by R 1.
- a of the compound (V) is a hydroxy group.
- the reaction is preferably performed in the presence of a base.
- Examples of the base include potassium butoxide, sodium hydride or potassium hydride, and 1 to 5 equivalents, preferably 1 equivalent, to compound (V).
- Use ⁇ 2 equivalents Compound (VII) is different from compound (V) by: Use up to 5 equivalents, preferably 1 to 2 equivalents.
- the reaction solvent for example, tetrahydrofuran, N, N-dimethylformamide, or dimethyl sulfoxide can be used:
- the reaction temperature is from 0 ° C to the solvent reflux temperature.
- the reaction temperature is preferably 0 ° C to 30 ° C, and the reaction time is 0.5 hour to 48 hours, preferably 1 to 12 hours.
- a of the compound (V) is an amino group.
- the reaction can be carried out in the presence or absence of a base: Examples of the base include sodium carbonate, triethylamine, etc., and 1 to 5 relative to compound (V). Equivalent, preferably 1-2 equivalents are used.
- Compound (VIII) is used in 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to compound (V).
- reaction solvent for example, alcohols such as methanol and ethanol can be used.
- the reaction temperature is a suitable temperature from 0 ° C to the solvent reflux temperature, preferably from 20 ° C to the solvent reflux temperature, and the reaction time is 0.5 hours to 48 hours, preferably 2 to 24 hours. It is.
- the obtained compound (I) of the present invention can be separated and purified by a known means (eg, chromatography, recrystallization, etc.).
- Compound (V) which is a raw material of Reaction Scheme 2, is a novel compound and is included in the present invention.
- Compound (V) can be produced by the method of Reaction Scheme 3 below.
- Compound (V) can be produced by condensing compound (II) and amino compound (VI).
- reaction solvent for example, alcohols such as methanol and ethanol can be used.
- the reaction temperature is a suitable temperature from 0 ° C to the reflux temperature of the solvent, preferably 20 ° C to 50 ° C, and the reaction time is 0.5 to 48 hours, preferably 0.5 to 50 hours. 12 hours.
- the obtained compound (V) can be used in the next step after being purified as a reaction solution or a crude product, or by a conventional method (eg, chromatography, recrystallization, etc.).
- the compound (II) used as a starting material in Reaction Schemes 1 and 3 is obtained by oxidizing an alcohol (IV) by a usual method as shown in Reaction Scheme 4 below. Can be manufactured.
- Compound (IV) used as a starting material in Reaction Scheme 4 protects the hydroxyl group of 2-bromobenzyl alcohol (commercially available, Aldrich), and then reacts with magnesium to prepare a Grignard reagent to form oxalic acid. It can be produced by condensing with a dialkyl form to obtain a keto ester form, reducing it, alkylating the obtained hydroxy ester form, amidating, and then deprotecting. Compound (IV) can also be produced by amidating the above-mentioned hydroxyester, followed by alkylation and deprotection.
- the substituent when a substituent in the compound interferes with the reaction, the substituent may be protected in advance by a conventional method and deprotected at an appropriate stage.
- the compound represented by the general formula (I) of the present invention is a cultivated plant or a seed thereof, for example, rice, wheat, rye, corn, millet, millet, buckwheat, soybean, red bean, peanut or the like, or fruit tree, for example, cucumber It is effective against pathogens (fungi) that affect, eggplant, tomato, capocia, or kidney beans and pathogens derived from soil.
- the compound of the present invention is particularly useful for rice blast (Pyricu 1 aria oryzae), rice thread or Bacillus bacillus (Rhi zoc tonia ia solani), wheat powdery mildew (Erysiphe graminis), cucumber udon Disease
- the application of the compound represented by the general formula (I) of the present invention may be carried out by spraying, spraying, applying, or the like on a plant, or by sowing a plant seed or a soil or a seed around the plant. It can be achieved by treating the soil, paddy and hydroponic water with active substances. Application can be made before or after the plant is infected with the pathogen.
- the compound is in the form of usual preparations, such as solutions, wettable powders, emulsions, suspensions, liquid concentrates, tablets, granules, aerosols, powders, pastes, smokers, fumigants, flowables, etc. It can be used as an agent suitable for agricultural germicides such as Such forms may contain at least one compound of the present invention and suitable solid or liquid carriers and, if desired, suitable adjuvants for improving the dispersibility or other properties of the active substance. (For example, a surfactant, a spreading agent, a dispersing agent, and a stabilizer).
- solid carriers or diluents include botanicals (e.g., cereal flour, tobacco stem flour, soy flour, walnut husk flour, vegetable flour, canna flour, bran, bark flour, fiber flour, vegetable extract residue) ), Fibrous substances (eg, paper, corrugated cardboard, rags), artificial plastic powder, clay (eg, kaolin, bentonite, clay), talc and inorganic substances (pyroxene, sericite, pumice stone) , Sulfur powder, activated carbon), fertilizers (eg, ammonium sulfate, ammonium phosphate, nitric acid) Ammonium, urea, and ammonium chloride).
- botanicals e.g., cereal flour, tobacco stem flour, soy flour, walnut husk flour, vegetable flour, canna flour, bran, bark flour, fiber flour, vegetable extract residue
- Fibrous substances eg, paper, corrugated cardboard, rags
- artificial plastic powder eg, clay (e
- liquid carriers and diluents examples include water, alcohols (eg, methanol, ethanol), ketones (eg, acetone, methylethylketone), ethers (eg, getyl ether, dioxane, cellosol).
- alcohols eg, methanol, ethanol
- ketones eg, acetone, methylethylketone
- ethers eg, getyl ether, dioxane, cellosol.
- Tetrahydrofuran examples include aromatic hydrocarbons (eg, benzene, toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (eg, gasoline, kerosene, kerosene), esters, nitriles, Examples include acid amides (eg, dimethylformamide, dimethylacetamide) and halogenated hydrocarbons (eg, dichloroethane, carbon tetrachloride).
- aromatic hydrocarbons eg, benzene, toluene, xylene, methylnaphthalene
- aliphatic hydrocarbons eg, gasoline, kerosene, kerosene
- esters eg, nitriles
- acid amides eg, dimethylformamide, dimethylacetamide
- halogenated hydrocarbons eg, dichloroethane, carbon tetrachloride
- surfactants include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, polyethylene glycol ethers, polyhydric alcohol esters, and the like.
- spreading or dispersing agents include casein, gelatin, starch powder, carboxymethylcellulose, arabia gum, alginic acid, lignin, bentonite, molasses, polyvinyl alcohol, pine oil and agar.
- Stabilizers include PAP (isopropylphosphate mixture), tricresyl phosphate (TCP), tall oil, epoxy oil, surfactants, fatty acids and their esters.
- the above-mentioned preparations contain 1 to 95% by weight, preferably 2.0 to 80% by weight, of at least one compound represented by the general formula (I) of the present invention.
- These preparations can be used alone or in a diluted form, and the compound of the present invention, about 1.0 g to 5 kg ha, preferably about 2 g to 100 g / ha, usually about It is used at a concentration of 1 to 500, 000 ppm, preferably about 100 to 5,000 ppm.
- Triethylamine (0.40 g, 3.3 g) was added to a solution of unpurified 2- (2-formylphenyl) -12-methoxy-N-methylacetate amide (0.38 g) in methanol (5 ml). 95 mmO 1) and hydroxylamin hydrochloride (0.20 g, 2.88 mm O 1) were added, and the mixture was stirred at room temperature for 3 hours. After evaporating the solvent, water was added, and the mixture was extracted with ethyl acetate and washed with saturated sodium hydrogen carbonate. After drying with sodium sulfate, the solvent was distilled off.
- Residue gel gel tog Raffy— (n—ethylethyl hexanoacetate 1-3), and the desired product, 2-[[2— (hydroxyminomethyl) phenyl] 1-2—methoxy-1-X—methylacetamide (0. 19 g) was obtained as an oil.
- test solution was sprayed on a test plant, and a pathogen was inoculated 24 hours later.
- the test solution was prepared by dissolving the compound in a small amount of N, N-dimethylformamide and diluting it to 500 ppm with distilled water containing a spreading agent.
- the control rate was determined by the following formula.
- This compound showed a high control rate against rice blast.
- Compound Nos. 2, 11, 12, 23, and 30 showed a control rate of 90% or more at 500 ppm.
- Test example 2 Test of control effect of cucumber powdery mildew
- Cucumbers seeded in plastic cups with a diameter of 9 cm and raised for 2 to 3 weeks (cultivar: Tsukuba Shirobo)
- the pathogen was inoculated by spraying a conidia suspension of Sphaerotheca fuliginea grown on cucumber leaves onto test plants sprayed with the compound solution or suspension. After inoculation, they were kept in a greenhouse at 20 ° C. Ten days after the inoculation, the occupied area of the signs that appeared on the inoculated leaves was investigated to determine the control rate.
- This compound showed a high control rate against Cucumber powdery mildew.
- Compound Nos. 2, 11, 12, 23, and 30 exhibited a control rate of 97% or more at 500 ppm.
- Cucumbers seeded in plastic cups with a diameter of 9 cm and raised for 2 to 3 weeks (cultivar: Tsukuba Shirobo)
- the pathogen is inoculated by dropping a suspension of zoospores of cucumber and a bacterium (Pseudoperonospora cubensis) cultured on cucumber leaves onto the surface of the cucumber leaves that have been spray-treated with the compound solution or suspension.
- bacterium Pseudoperonospora cubensis
- This compound showed a high control rate against cucumber and disease.
- Compound Nos. 2, 5, 11, 12, 23, 30, and 34 showed a control rate of 90% or more at 500 ppm.
- it has bactericidal activity and low toxicity
- a novel ⁇ -alkoxyphenylacetic acid derivative, a method for producing the same, an intermediate for the production thereof, and an agricultural chemical containing the same as an active ingredient are provided.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU68381/96A AU6838196A (en) | 1995-09-08 | 1996-08-30 | Alpha-alkoxyphenylacetic acid derivatives, intermediate for producing the same, and pesticide containing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7/257028 | 1995-09-08 | ||
JP25702895 | 1995-09-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997009302A1 true WO1997009302A1 (en) | 1997-03-13 |
Family
ID=17300747
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1996/002443 WO1997009302A1 (en) | 1995-09-08 | 1996-08-30 | α-ALKOXYPHENYLACETIC ACID DERIVATIVES, INTERMEDIATE FOR PRODUCING THE SAME, AND PESTICIDE CONTAINING THE SAME |
Country Status (2)
Country | Link |
---|---|
AU (1) | AU6838196A (ja) |
WO (1) | WO1997009302A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014002105A1 (en) * | 2012-06-25 | 2014-01-03 | Cadila Healthcare Limited | Compounds for the treatment of dyslipidemia and other diseases |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59108742A (ja) * | 1982-11-10 | 1984-06-23 | バイエル・アクチエンゲゼルシヤフト | 害虫防除剤としての置換されたマロン酸誘導体類の使用 |
WO1994027693A1 (en) * | 1993-05-27 | 1994-12-08 | Freilich Daniel S | Endless belt roller skate |
JPH0776564A (ja) * | 1992-10-02 | 1995-03-20 | Mitsubishi Chem Corp | メトキシイミノ酢酸誘導体およびこれを有効成分とする農園芸用殺菌剤 |
JPH0789923A (ja) * | 1993-06-03 | 1995-04-04 | Basf Ag | アジン置換フェニル酢酸誘導体およびこれを含有する殺菌剤 |
WO1996007633A1 (de) * | 1994-09-10 | 1996-03-14 | Basf Aktiengesellschaft | Phenylessigsäurealkylester |
-
1996
- 1996-08-30 WO PCT/JP1996/002443 patent/WO1997009302A1/ja active Application Filing
- 1996-08-30 AU AU68381/96A patent/AU6838196A/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59108742A (ja) * | 1982-11-10 | 1984-06-23 | バイエル・アクチエンゲゼルシヤフト | 害虫防除剤としての置換されたマロン酸誘導体類の使用 |
JPH0776564A (ja) * | 1992-10-02 | 1995-03-20 | Mitsubishi Chem Corp | メトキシイミノ酢酸誘導体およびこれを有効成分とする農園芸用殺菌剤 |
WO1994027693A1 (en) * | 1993-05-27 | 1994-12-08 | Freilich Daniel S | Endless belt roller skate |
JPH0789923A (ja) * | 1993-06-03 | 1995-04-04 | Basf Ag | アジン置換フェニル酢酸誘導体およびこれを含有する殺菌剤 |
WO1996007633A1 (de) * | 1994-09-10 | 1996-03-14 | Basf Aktiengesellschaft | Phenylessigsäurealkylester |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014002105A1 (en) * | 2012-06-25 | 2014-01-03 | Cadila Healthcare Limited | Compounds for the treatment of dyslipidemia and other diseases |
Also Published As
Publication number | Publication date |
---|---|
AU6838196A (en) | 1997-03-27 |
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