DK174963B1 - Fungicide, insekticide og miticide forbindelser, fremgangsmåde til fremstilling deraf, midler indeholdende dem og fremgangsmåde til anvendelse heraf - Google Patents

Fungicide, insekticide og miticide forbindelser, fremgangsmåde til fremstilling deraf, midler indeholdende dem og fremgangsmåde til anvendelse heraf Download PDF

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Publication number
DK174963B1
DK174963B1 DK198905847A DK584789A DK174963B1 DK 174963 B1 DK174963 B1 DK 174963B1 DK 198905847 A DK198905847 A DK 198905847A DK 584789 A DK584789 A DK 584789A DK 174963 B1 DK174963 B1 DK 174963B1
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Prior art keywords
alkyl
phenyl
alkoxy
halogen
cyano
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DK198905847A
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English (en)
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DK584789A (da
DK584789D0 (da
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Paul John De Fraine
Anne Martin
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Syngenta Ltd
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26294646&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=DK174963(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from GB888827149A external-priority patent/GB8827149D0/en
Priority claimed from GB898905383A external-priority patent/GB8905383D0/en
Application filed by Syngenta Ltd filed Critical Syngenta Ltd
Publication of DK584789D0 publication Critical patent/DK584789D0/da
Publication of DK584789A publication Critical patent/DK584789A/da
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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 with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/335—Radicals substituted by nitrogen atoms not forming part of a nitro radical
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
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    • 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
    • A01N37/36—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 singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • 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
    • A01N37/36—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 singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—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 singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
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    • A01N37/38—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 singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—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 singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
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    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
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    • 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
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
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    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

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Description

DK 174963 B1
Den foreliggende opfindelse angår derivater af propensyre, der er nyttige som fungicider.· insekticider og miticider, fremgangsmåde til deres fremstilling, midler indeholdende dem og fremgangsmåder til anvendelse af dem til bekæmpelse af svampe, isar svampeinfektioner i planter, og til at dråbe eller bekæm-5 pe insekter og mider.
Ifølge opfindelsen angives en forbindelse med formlen (l); rv.
R \ /°\ / c=ir ch2 I (i)
Rl CH302CT CH.OCHj og stereoisomerer deraf, hvor A, R1 og R2 har de i krav 1 angivne betydninger.
Forbindelserne ifølge opfindelsen indeholder mindst en carbon-1Q nitrogendobbeltbinding og mindst en carbon-carbondobbeltbin-ding og fås sommetider i form af blandinger af geometriske ; i sornerer. Disse blandinger kan dog adskilles i individuelle isomerer, og opfindelsen omfatter sådanne i somerer og blandinger deraf i alle mængdeforhold.
2 DK 174963 B1
De individuelle isomerer, der fremkommer som følge af den usymmetrisk substituerede dobbeltbinding i propenoatgruppen og oximen identificeres med de sædvanligt anvendte udtryk "E" og "Z". Disse udtryk er defineret ifølge Cahn-Ingold-Prelog-sy-stemet, der fuldt ud er beskrevet i litteraturen (se f.eks. J 5 March, "Advanced Organic Chemistry", 3. udgave, Wiley-Inter-science, side 109).
For carbon-carbon-dobbeltbi ndi ngen i propenoatgruppen er den ene isomer i reglen mere aktivt fungicidt end den anden, og den mest aktive isomer er i reglen den, hvori gruppen -CO2CH3 og -OCH3 er på modsatte sider af den olefiniske binding i propenoatgruppen ((E)-isomeren). Disse (E)-isomerer udgør en fo-retrukken udførelsesform ifølge opfindelsen.
Halogen indbefatter fluor, chlor, brom og jod.
15 Alkyl og alkyldele i alkoxy, aralkyl og aryloxyalkyl kan være i form af en lige eller forgrenet kæde, og med mindre andet er anført indeholder de hensigtsmæssigt fra 1 til 6 carbonatomer. Eksempler er methyl, ethyl, isopropyl og tertiær butyl. Eventuelle substituenter indbefatter halogen, især chlor og fluor), hydroxy og Ci~C4-alkoxy. Eksempler på substitueret 20 alkyl og substitueret alkoxy er trif 1 uormethyl og trifluor- '.
methoxy.
Cykloalkyl er hensigtsmæssigt C3-Cg-cykloalkyl, f.eks. cyklo-propyl og cyklohexyl, og cykloalkylalkyl er hensigtsmæssigt 25 C3-C6-cykloalkyl (C1-C4)alkyl, f.eks. cyklopropylethyl.
3 DK 174963 B1
Alkenyl og alkynyl indeholder hensigtsmæssigt fra 2 til 6 car* bonatomer, typisk 2 til 4 car bona tomer i form af lige eller foregrenede kæder. Eksempler er ethenyl, allyl og propargyl. Substituerede alkenyl og alkynylgrupper indbefatter eventuelt 5 substitueret arylalkenyl (især eventuelt substitueret phenyl-ethenyl) og arylalkynyl.
Aryl og aryldele i aralkyl, arylalkenyl, arylalkynyl, aryloxy og aryloxyalkyl indbefatter phenyl og naphthyl.
10
Det carbocykli ske eller heterocykliske ringsystem, som R* og R2 kan danne sammen, er hensigtsmæssigt en C5-C10 alifatisk, aromatisk eller blandet al ifatisk/aromatisk carbocyklisk ring, f.eks. cyklopentyl, cyklohexyl, cyklohexadienony1 og sådanne 15 grupper, der bærer en kondenseret benzenring og/eller substi-tuenter, såsom methyl, eller det kan være et 5- til 10-leddet heterocykli skringsystem, f.eks. tetrahydropyranyl.
Udtrykket heteroaryl anvendes til at beskrive aromatiske 20 heterocykliske grupper. Heteroaryl og heterocyklyl og heteroaryl og heterocyklyldele i andre grupper, såsom heteroaryloxyalkyl og heterocykloalky1, er typisk 5- eller 6-leddede ringe indeholdende et eller flere O, N eller S heteroatomer, der kan være kondenseret med en eller flere 25 andre aromatiske heteroaromati ske eller heterocykliske ringe, såsom en benzenring. Eksempler er thienyl, furyl, pyrrolyl, triazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyrida-zinyl, triazinyl, quinolinyl og qui noxal inylgrupper og li-oxider deraf.
30
Substituenter, der kan findes i eventuelt substituerede aryl og heteroarylde le, indbefatter en eller flere af følgende: halogen, hydroxy, mercapto, Cj-C^alkyl (især methyl og ethyl)» C2~C4-alkeny1 (især allyl), ¢2-04-81kynyl (især propar-35 gyl), Ci-C4~alkoxy (især methoxy), C2-C4~alkenyloxy (især allyloxy), C2~C4-alkynyloxy (især propargyloxy), halogen-(Ci-C4)al kyl (især trifluormethyl), halogen(C1-C4)alkoxy (især 4 DK 174963 B1 trif 1 uormethoxy), C^-C^-alkylthio (især methyl thi o), hydroxy-(Cj-C4) a 1ky1, ci“C4-alkoxy(Cj-C4) a 1ky 1, C3-C6-cykloalky1, C3-Cg-cyk1oalkyl(C1-C4Jalkyl, eventuelt substitueret aryl (især eventuelt substitueret phenyl), eventuelt substitueret 5 heteroaryl (især eventuelt substitueret pyridyl eller pyrimi-dinyl), eventuelt substitueret aryloxy (især eventuelt substitueret phenoxy), eventuelt substitueret heteroaryloxy (især eventuelt substitueret pyridyloxy eller pyrimidinyloxy), eventuelt substitueret aryl(Ci-C4)alkyl (især eventuelt substitue-10 ret benzyl, eventuelt substitueret phenethyl og eventuelt substitueret phenyl-n-propyl), hvori alkyldelen eventuelt er substitueret med hydroxy, eventuelt substitueret heteroaryl (C1-C4)alkyl (især eventuelt substitueret pyridyl- eller pyri-midinyl(Cj-C4)alkyl), eventuelt substitueret aryl(¢2-04)alke-15 nyl (især eventuelt substitueret phenyletheny1), eventuelt substitueret heteroaryl (C2-C4Jalkenyl (især eventuelt substitueret pyridylethenyl eller pyrimidinylethenyl), eventuelt substitueret aryl(Ci-C4)alkoxy (især eventuelt substitueret benzyloxy), eventuelt substitueret heteroaryl(Ci“C4)alkoxy 20 (især eventuelt substitueret pyridyl- eller pyrimidinyl-((^-C^alkoxy), eventuelt substitueret aryloxy(Ci~C4)alkyl (især phenoxymethy1), eventuelt substitueret heteroaryloxy-(C1-C4)al kyl (især eventuelt substitueret pyridyloxy- eller pyrimidinyloxy(Cj-C4)alkyl), acyloxy, herunder C1-C4-alkanoyl-25 oxy (især acetyloxy) og benzoyloxy, cyano, thiocyanato, nitro, -NR'R", -NHC0R', -NHCONR'R", -CONR'R”, -COOR’, -0S02R'. -S02R’. -C0R', -CR'=NR” eller -N=CR'R", hvori R’ og R" uafhængigt af hinanden er hydrogen, C^-C4-alkyl, Ci-C4-alkoxy, C1-C4-alkylthio, C3-C5-cykloalky1, C3-Cg--cykloalkyl (Ci-C4)al-30 kyl, phenyl eller benzyl, hvor phenyl og benzylgrupperne eventuelt er substitueret »ed halogen, Cj-C4-alkyl eller C^-C4-alkoxy.
Substituenter, der kan findes i aryl eller heteroarylringene i 35 enhver af de foregående substituenter, indbefatter en eller flere af følgende: halogen, hydroxy, mercapto, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkyny1, C1-C4-alkoxy, C2-C4-alkeny1oxy, 5 DK 174963 B1 C2-C4-alkynyloxy, halogen(Ci~C4)alkyl, halogen(C1-C4)alkoxy, Ci-C4-alkylthio, hydroxy(Ci~C4)alkyl, C1-C4-alkoxy(C!-C4)al-kyl, C3»C6-cyk1oalkyl, C3-C6-cykloalkyl(Cj-C4)al kyl, alkanoyl-oxy, benzoyloxy, cyano, thiocyanato, nitro, -NR * R", -NHCOR’, 5 -NHCONR’R", -CONR'R", -COOR’, -SC^R', -OSi^R’, -COR', -CR1 =NR" eller -N=CR'R", hvori R' og R" har de ovennævnte betydninger.
I en udføre!sesform indbefatter opfindelsen en forbindelse af formlen (I), hvori A er hydrogen, halogen, hydroxy, methyl, 10 methoxy, trif1uormethyl, trif1uormethoxy, Ci-C2~alkylcarbonyl, Ci-C2-alkoxycarbonyl, phenoxy, nitro eller cyano, R1 er C1-C4-alkyl, halogen(Cj-C4)alkyl, Cj-C4-alkoxy, halogen(Cj-C4)alk-oxy, Ci-C4-alkyl carbonyl, Ci-C4-alkoxycarbonyl, cyano, phenyl-(C1-C4)alkyl, phenyl, en 5- eller 6-leddet aromatisk hetero-15 cyklisk ring indeholdende et eller flere 0-, N- eller S-atomer og eventuelt kondenseret med en benzenring, idet de aromatiske og heteroaromatiske alkyldele af enhver af de foregående eventuelt er substitueret med en eller flere af halogen, hydroxy, Ci~C4-alkyl, halogen(Cj-C4)alkyl, Cj-C4-alkoxy, halogen- 20 (Ci~C4)alkoxy, C^-C4-alkylcarbony1, C^-C4-alkoxycarbony1, nitro, cyano, phenyl, phenoxy, benzyl eller benzyloxy, og R2 er hydrogen, halogen, Cj-C4-alky1, halogen(Cj-C4)alky1, Cj-C4-al-kylcarbonyl, Ci-C4-alkoxycarbonyl, cyano eller phenyl, eller R1 og R2 er forbundne til dannelse af et Cs-Cjo'carbocyklisk 25 ringsystem.
en anden udførelsesform indbefatter opfindelsen en forbindelse med formlen (I), hvori A er hydrogen eller halogen, Rl er Ci-C4-alkyl, benzyl, Cj-C4-alkylcarbonyl, Cj-C4-alkoxycar-30 bonyl, cyano, phenyl, thienyl, triazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl eller quinoxalinyl, hvor den aromatiske eller heteroaromatiske molekyldel i enhver af de foregående eventuelt er substitueret med en eller flere af halogen, Cj-C4-alkyl, trifluormethyl, 35 Ci~C4-alkoxy, trifluormethoxy, nitro, cyano, phenyl eller ben 2 zyloxy, og R2 er hydrogen, Cl-C4-alkyl, Cx-C4-alkylcarbonyl, Ci~C4-alkoxycarbonyl, cyano eller phenyl, eller Rl og R2 DK 174963 B1 6 tilsammen danner en cyklopentyl eller cyklohexy1ring, hvortil der eventuelt er kondenseret en benzenring.
Opfindelsen illustreres af forbindelser anført i følgende ta-5 bel I. Overalt i tabel I har methyl-3-methoxypropenoatgruppen (E)-konfiguration.
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f>H I I ** Ξ3 cn o S ·** ·»* **H n-H I
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TABEL II: UDVALGTE PROTON NMR-DATA
DK 174963 B1 25
Tabel II viser udvalgte proton NMR-data for visse forbindelser beskrevet i tabel I. Kemiske forskydninger er målt i ppm fra 5 tetramethy1 s i 1 an og deuterochloroform blev anvendt som opløsningsmiddel overalt. Kolonnen med overskriften “frekvens" refererer til driftsfrekvensen af NMR-spektrometeret. Der anvendes følgende forkortelser: 10 br * bred s = singlet d * dublet t = triplet q = kvartet 15 m - multiplet forbindelse frekvens 20 NR. MHS__ 1 270 3,69(33,s), 3,82(3H,s), 3,83(3H,s), 5,12(23,s), 6,84-6,99(2H,m), 7,11-7,2( IH,m), 25 7,25-7,4(33,m), 7,5-7,62(lH,m), 7,60(IH,s), 7,74-7,8(IH,m), 8,50(IH,s) ppm.
2 400 3.70(3H,s), 3,80(3H,s), 30 * f 3,81(3H,s), 5,13(23,s), 6 j 9-7,54(8H,m), 7,60(1H,s) ppm.
35
I FORBIN- FREKVENS
5 I DELSE MHz NR.
DK 174963 B1 26 TABEL II (fortsat) 6 270 (større isomer) 2,36(311,3)/ 3,68(3H,s), 3,80(3H,s), 5;10(2H,s), 7,1-7,5(8Hfm), 7,60(lH,s), 10 8,07(IH,s) ppm.
11 270 3,70 (3H, s) , 3,81(3^8), 5,14 (2H,s), 7.15- 7,20(IH,m), 7,24-7,43(5H,m), 7.48- 7,54(IH,m), 7,58-7,62(IH,ra), 15 7j59(IH,s), 8,04(lH,s) ppm.
17 270 3,70(3H,s), 3,84(3H,s), 5,17 (2H,s), 7.16- 7,22(IH,m), 7,32-7,39(2H,m), 7.49- 7,58(2H,m), 7,60(lH,s), 20 7,88(lH,d), 8,14(IH,S), 8.17- 8;23(lH,m), 8,42(lH,m) ppm.
20 270 3,70(3H,s), 3,83(3H,s), 5,16(2H,s), 7,14-7,20( IH,m), 7,31-7,38(2H,m), 2δ 7,46-7,55(2H,m), 7,55-7 ,64(IH,m), 7,60(IH,S), 7,7-7,77(1H,d), 7,83(IH,s), 8,12(IH,s) ppm.
23 270 2,25(3H,s), 3,69(3H,s), 3,81(3H,s), 30 5,16(2^3), 7,13-7,20(IH,m) , 7,3-7,4(5H,m), 7,5-7,55{IH,m), 7,59( IH,s), 7,6-7,66(2H,m) ppm.
35
FORBIN- FREKVENS
5 DELSE KHz NR.
TABEL II (fortsat) DK 174963 B1 27 29 270 3;68(3H,s), 3,80(3H,s), 5,08 (2H,s), 5,13(2H,s), 6,94-7,07(lH,ra), 7.07- 7,56(12Hfm) , 7,60(13,5), 10 8;06{lH,s) ppm.
32 270 3 f 70(3H,s), 3,83(3H,s), 5,14{2H,s), 7 T1-7 ,9(8H,m), 7,60(lH,s), 8,07(IH,s) ppm.
15 37 270 3,69(3H,s), 3,81(3H,s), 5,18(2H,s), 7,16-7, 82(7H,m), 7,60(lH,s), 8,19(lH,s), 8,6(lH,m) ppm.
20 38 270 3f69(3H,s), 3,82(38,s), 5/14(2H/s), 7,14-7,53(58,m), 7,60lH,s), 7f90-7,96(IH,m), 8,10(lH,s), 8,55-8,62(IH,m) , 8,72(18,m> ppm.
25 40 270 2,34(3H,s) , 3,69(38,s), 3,81(38,s), 5 f19(2H, s), 7,1-7,7(6H,m), 7,60(13,5), 7;89(lH,d), 8,59(lH,d) ppm.
3Q 42 270 1,32-1,40(38,t), 3,63(3H,s), 3,77(38,s), 4,33-4,44(2H,q), 5,25(2H,s), 7,13-7,20(IH,m), 7,26-7,42(4H,m), 7,56(18,s), 7.7- 7f77(2H,m), 7,66-7,71(lH,a) ppm.
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DK 174963 B1 28 TABEL II (fortsat) 47 270 2,24(3H,s), 3;69(3H,s), 3,82(3H,s), 5,11(2H,s), 6,9-7,55(78,m), 7.58(3H,s) ppm.
10 49 270 l,3(6H,q), 3,70(3H,s), 3;83(3H,s), 4,36(4H,q), 5,28(28,s) , 7;l-7;5(4H,m), 7,58(18,s) ppm.
15 55 270 2,85-3,12(4H,m), 3fS9(3H,s), 3,82(3H,s)# 5,14(28,s), 7j1-7,7(8H,m), 7,58(18,s) ppm.
65 270 (større isomer) 2,24(311,5), 20 3 { 68 ( 3H, s ) , 3;81(3H,S), S,16(2H,s), 7.1- 7,5(58,m), 7,60(18,s), 7j9(lH,m), 8,57(18,»), 8;83(lH,m) ppm.
25 66 270 1,22(68,d), 3,57(IH,m), 3;69(3H,s), 3,82(3H,s), 5,13(28,s), 7; 1-7,5(4H,m), 7,60(lH,s), 8 f 81(2H,s ), 9,18( IH,s) ppm.
30 67 270 1,14(68,d), 2f33(lH,m), 3;66(3H,s), 3 f 78(3H,s), 5,00(2H,s), 7.1- 7,4(48,m), 7,53(1H,S), 8,66(2H,s), 9,17(IH,s) ppm.
35
FORBIN- FREKVENS
5 ; DELSE juhz NR.
TABEL II ffortsat) DK 174963 B1 29 92 270 2,26(3H,s), 3j68(3H,s), 3/80(3H,s)/ 4,00(3H,s), S;21(3H,s), 7,l-7;6(4H,m), 7,58(18,5), 10 8,08(lH,d), 8,16(IH,d) ppm.
93 270 (større isomer) 2,30{3H,s), 3,69(3H,s), 3,83(38,5), 4,03{3H,s), 5,24(2H,s) , 7,1-7,55(4H,m), 15 7t60(lH,s), 9,20(IH,m), 9,23(lH,m), ( mindre isomer) 2,30(3H,s), 3,64(3H,s), 3,80(3H,s), 4,03(3H,s), 5^12(2H,s), 7,1-7,55(4H,m), 7,57(IH,s), 9,32(lH,m), 9;37(ΐΗ,ιιι) 20 ppm.
102 270 2,22(3H,s), 3,68(38,5)·, 3,83(3H,s), 5,12(2H,s), 7 ,15-7, 55(7H,m), 7,60(lH,s) ppm.
25 108 270 2/20(3H,s), 3,67(3H,s), 3,80(38,5), 3,83(3H,S), 5,14(28,5), 6,37-7,60(8H,m) , 7,57(1^3) ppm.
30 111 270 2,20(3H,s), 2,30(3H,s), 3,68(3H,s), 3,80(3H,s), 5,13(2H,s), 7,15-7f4(7H,m), 7,54(18,m), 7,58(IH,s) ppm.
_______ 35 TABEL II (fortsat)
FORBIN- FREKVENS
DELSE MHz 5 NR.
30 DK 174963 B1 112 270 2,23(3H,s), 2f37{3H,s), 3,68(3H,s), 3,81(3H,s), 5 r16(2H,s), 7.1- 7j55(8H,m), 7,58(13,s) ppm.
10 113 270 2,22(3H,s), 2,35(3H,s), 3,68(3H,s), 3f81(3H,s), 5,13(3H,s), 7.1- 7,5(88,11), 7 f 58 (IH, s) ppm.
114 270 2,26(3H,S), 3,68(3H,s), 3/81(3H,s), 5,16(2H,s), 7,0-7,55(8H,m), 7,59(18,s) ppm.
115 270 2,02(3H,S), 3,68(3H,s), 3,82(38,5), 5,15(2H,s), 7,0-7.55(8H,m), 20 ‘ * * 7,60{IH,s) ppm.
116 270 2,22(3H,s), 3,68(3H,s), 3;82(3H,s), 5 f13(2H,s), 6,99-7,65(8H,m), 7,59(lH,s) ppm.
118 270 2f21(3H,s), 3,69(3H,s), 3,81(3H,s), 5,16(28,5), 7,14-7,66(8H,m), 7,59{lH,s) ppm.
30 121 270 2 f 21(38,s ), 3,69(38,s), 3,82(3H,s), 5,16(2H,s), 7,1-7,55(78,0), 7,59(lH,s), 7,81( IH,m) ppm.
35 DK 174963 B1 31 TABEL II (fortsat) FORBIN- FREKVENS 5 DELSE KHz NR.
127 270 2,26(3H,s), 3,69(3H,s), 3,83(3H,s), 5,18(2H,s), 7;l5-7;92(8H,m), 7,60(IH,s) ppm.
10 131 270 2,22(3H,s), 3,68(38,5), 3,82(3H,s), 5,18(2H,s), 7/l-7/8(8H,m), 7,59( IH,s) ppm.
15 143 270 ( større isomer) 2,28{3H,s), > 2 ^ 53(3H,s), 3,69(3H,s), 3;83(3H,s), 5,22(2H,s), 7,1-7,5(4H,m), I 7,60(IH,s), 7,72(lH,s), 9;06(1Η,5) I PPra· · 20 (mindre isomer) 2,27(3H,s), 2 f 48(3H,s), 37 69( 3H,s), 3;83(3H,s), 5;21(2H,s), 7,1-7,5(4H,m), 7,61(IH,s), 7,77(lH,s), 9,10(lH,s) ppm.
25 j 144 270 ( større isomer) 2,22(3H,s), 2 f 5 0(3 H,s), 3;67(3H,s), 3;81(3H,s), 5,14(2H,s), 7^ 1-7,5 ( 4H, m), 7,58(IH,s), 8,5 3(IH,s), 9,02(lH,s) 30 PPm· ( mindre isomer) 2,17(3H,s), 2,40(3H,S), 3,6 5(3H,s), 3,77(3H,s), 5r00(2H,s), 7,1-7,5(4H,m), 7,52(13,s), 8,37(IH,s), 9,05(18,3) 35 PP®· 32 TABEL II (fortsat)
FORBIN- FREKVENS
DELSE MHz 5 NR.
DK 174963 B1 145 270 2,39(3H,s), 2;57(3H,s), 3r68(3H,s), 3f81(3H,s), 5;33(2H,s), 7,ll(lH,d), 7 {1-7 r 55(4H,m), 7j57(lH,s), 8r64(lH,d) ppm.
10 152 270 2;92(2H,t), 3;68(3H,s), 3;82(3H,s), 4,18(2H,t)/ 5,14(2H,s), 6,8-7.0(2Hfm)/ 7,l-7;5(5H,m), 7> 58(IH,s), 7 j 87(IH,m) ppm.
15 154 270 2,22(3H,s), 3;61(3H,s), 3;75(3H,s), 5,08(2H,s ), 7,0-7,5{7H,m), 7,52(lH,s), 8;12{lH,m) ppm.
20 158 270 2;08{3H,s), 3,67(6H,s), 3,80(3H,s), 5;06(2H,s), 6,08(lH,m), 6,38{lH,m), 6,06(lH,m), 7,l-7,5(4H,a), 7,57{lH,s) ppm.
25 160 270 3;69(3H,s), 3,82(3H,s), 5jl9(2H,s), 5,42(2H,s), 7;l-7,5(7H,m), 7,61(IH,s), 7^ 77 (IH, s ) , 8;05(lH,s) ppm.
30 162 270 2,21(3H,s), 2,46(3H,s), 2,62(3H,s>, 3 f 68(3H,S), 3 f 82(3H,s), 5;10(2H,s), 7 f1-7 r 5(4H,m), 7;58(lH,s) ppm.
35 TABEL II (fortsat 1 DK 174963 B1 i i
FORBIN- FREKVENS
5 DELSE KHz NR.
163 270 2,16( 311,3), 3;68(3H,s), 3,81(3H,s), 5,17(2H,s) , 6,42(lH,m), 6,61(lH,m), 7.1- 7,55(6H,a), 7,58(lH,s) ppm.
10 165 270 3,63 ( 3H,s), 3,76{3H,s), 5,22(2H,s), 7.1- 7,8(10H,m), 7 r 56{IH,s), 8,55(lH,d), 8,70(lH,d) ppm.
15 177 270 2,29(3H,s), 2,51(3H,s), 2;53(3H,s), 3,68(3H,s), 3;81{3H,s), 5,15(2H,s), 7.1- 7,5(4H,m), 7, 59( IH,s), 8,24(IH,s) ppm.
20 183 270 2,24(3H,s), 3,03(3H,s), 3,68(3H,s), 3,82(3H,s), 5,20(2H,s), 7.1- 7,5(4H,m), 7,59(lH,s), 7,8-8,0(4H,m) ppm.
25 184 270 2,18(3H,s), 3,67{3H,s), 3;78(3H,s), j 3,80(2H,bc.s), 5,ll(2H,s), | 6,59(2H,d), 7,1-7,55(6H,m), 7,58(lH,s) ppm.
30 ____ ___— 35
FORBIN- FREKVENS
5 DELSE MHz NR.
DK 174963 B1 34 TABEL II (fortsat) 188 270 ( større isomer) 0,65(2H,m), 0,90(2H,m), 2,32(18,m), 3f67(3H,s), 3,80(38,8), 5,13(2H,S), 10 7,l-7,6(9H,m), 7,57(lH,s) ppm.
(mindre isomer) 0,65(2H,m), 2,32(lH,m), 3,63(3H,s), 3,76(3H,s), 4,97(2H,s), 7,1-7,6(9H,m), 7,77(IH,s) ppm.
15 190 270 1,41(3H,t), 3,64(3H,s), 3/76{3H,s), 4,05(2H,q), 5,18(2H,s), 6,8-7.55(8H,m), 7,55(lH,s) ppm.
20 191 270 2,04(3H,s), 3,66{3H,s), 3,78(3H,s), 5,19(2H,s), 7,1-7,4(8H,m), 7,5-7,6(lH,a), 7/57(18,8) ppm.
194 270 1,10(9H,S), l,81(3H,s), 3,68(3H,s), 25 3,81( 3H,s), 4,99(2H,s) , 7.1- 7,5(4H,m), 7,57(18,s) ppm.
196 270 1,76(38,8), 3,46(28,8), 3,67(38,s), 3,80(3H,s), 5,06(28,s), j 30 7,1-7,5(98,0»), 7,57(lH,s) ppm.
198 270 2,10(38,s), 3,69(3H,s), 3,82(38,5), 5,11(28,s), 6,85(28,8), 7.1- 7,5(9H,m), 7,58(18,s) ppm.
3 5 - 1"........
JABEL II (fortsat) DK 174963 B1 35 -1 FORBIN- FREKVENS 5 DELSE MHz NR.
225 270 3;60{3H,s), 3,70(33,5), 3y78(3H,s), 4,94( 2H,s), 7,1-7,5(7H,m), 7,53(lH, s), 7,77-7,81(2H,ra) ppm.
10 226 270 3,66(3H,s), 3,77(33,s), 3,98(3H,s), 5,04(2H,s), 7,10-7,58(7H,a), 7,58(IH,s), 7,60-7,70(2H,m) ppm.
15 227 270 2;e8(3H,s), 3,67(3H,S), 3,79(33,s), 5,18(2B,dd), 7,1-7,5(73,01), 7,60(IH,s), 7,6-7,7(2H,m) ppm.
228 270 I 3,20(3H,s), 3,67(3H,s), 3,80(33,s), 2o 5,30(2H,s), 7,1-7,6(9H,m), 7,60(13,s) ppm.
t _V_;_ 25 , 30 35 DK 174963 B1 36
Forbindelserne ifølge opfindelsen ned formlen (I) kan fremstilles ved de trin, der er vist i skema 1. Udtrykkene A, R1 og r2 er som ovenfor defineret, og χ er en bortgående gruppe, såsom halogen (chlor, brom eller jod).
5
Skema 1 R2 10
A ^ HO. N = C
SO 'v
--~CH,X
Γ c UII) 15 / % CH3°2C CH.OCH3 (II) i 20
Sfri r2 ^>^^~-CH-O.N===C ^ (I)
2 ^rI
25 ch3o2c nch.och3 30 Forbindelserne med formlen (I) kan fremstilles ved at behandle oximer med den almene formel (III) med en egnet base (såsom natriumhydrid eller natriummethoxid) i et egnet opløsningsmiddel (såsom N,N-dimethylformamid eller tetrahydrofuran), til dannelse af anionen og derpå tilsatte en forbindelse med form-35 len (II).
Oximer med den almene formel (III) er velkendt i den kemiske ......
DK 174963 B1 37 litteratur. Forbindelsen med den almene formel (II), hvor X er brom, og propenoatgruppen har (E )-konfi gurat i on, er beskrevet i EP-A-0203606.
5 Alternativt kan forbindelserne ifølge opfindelsen med formlen (I) fremstilles ved de trin, der er vist i skema 2. Udtrykkene A, Ri, R2 og X er som ovenfor defineret, r5 er hydrogen eller et metal (såsom natrium eller kalium), L er en bortgående gruppe, såsom et halogenid (chlor, brom eller jod), en CH3SO4-10 anion eller en sulfonylanion. Hver omdannelse udføres ved en passende temperatur, og i reglen, omend ikke altid, i et egnet opløsningsmiddel.
Forbindelserne ifølge opfindelsen med formlen (I) kan frem-15 stilles af phenyl acetater med formlen (VI) eller ketoesterne med formlen (X) ved de trin, der er vist i skema 2.
Forbindelserne med formlen (I) kan således fremstilles ved behandling med phenyl acetater med formlen (VI) med en base 20 (såsom natriumhydrid eller natriummethoxid) og methylformiat.
Hvis en forbindelse med formlen CH3L, hvor L er som ovenfor defineret, derpå sættes til reaktionsblandingen, kan der fås forbindelser med formlen (I). Hvis en protisk syre sættes til reaktionsblandingen, fås forbindelser med formlen (IX), hvori 25 R5 er hydrogen. Alternativt kan forbindelser med formlen (IX),
hvori R5 er et metal (såsom natrium) selv isoleres af reak- I
tionsblandingen.
Forbindelser med formlen (IX), hvori R® er et metal, kan om-30 dannes til forbindelser med formlen (I) ved behandling med en forbindelse CH3L, hvor L er som ovenfor defineret. Forbindelser med formlen (IX), hvori R5 er hydrogen, kan omdannes til forbindelser med formlen (I) ved på hinanden følgende behandling med en base (såsom kaliumcarbonat) og en forbindelse med 35 den almene formel CH3L.
DK 174963 B1 38
Skema 2
R2 A
\ \ χί (I) -fe- ΟίΧ (IV)
/ yCH
k N. V / \ R CH302C CH(OCH3)2 2 \ < i i \ ^CN-O-CHfY \ < /N ir* R·1· C \ _C=N' CH2'^^ (V) / I r1 CH:C(OCH3)(OSiRj) CH3°2C I t ' (XI) /
/ _A
/ < / ΓΊ (I) / J^C=N ΝΟΗ2^Λΐϊγ^ (VI) / R1 CH2C02CH3 / / / t ^χζκ / (III) < /-. Xj C=N/ CH2 (IX) \ ch,o2c/C^chor5 Γ"^ν^Α(νιιι
\ /V
\ xCH2 cij2C°2CH3 \ „ /.
^ /
X\ > J
ch2 i JL J
C (VIII) / % \ 2 \ / 0 °N /'CH2 ch3o2c yX 1 o DK 174963 B1 39
Alternativt kan forbindelser med formlen (I) fremstilles af acetaler med formlen (IV) ved eliminering af ethanol onder enten sure eller basiske betingelser. Eksempler på reagenser eller reagensblandinger, der kan anvendes til denne omdannelse, 5 er 1 ithium-diisopropy1 amid, kaliumhydrogensu1fat (se f.eks. T. Yamada, H. Hagiwara og H. Uda, J. Chera. Soc. Chemical Communications, 1980, 838 og referencerne deri) og triethylamin, ofte i nærværelse af en Lewis-syre, såsom titantetrachlorid (se f.eks. K. Nsunda og l. Heresi, J. Chem. Soc. Chemical Communi-10 cations, 1985, 1000).
Acetaler med formlen (IV kan fremstilles ved behandling af methylsilylketenacetaler med formlen (V), hvor R er en alkyl-gruppe, med trimethylorthoformiat i nærværelse af en Lewis-15 syre, såsom titantetrachlorid (se f.eks. K. Saigo, M. Osaki og T. Mukaiyama, Chemistry Letters, 1976, 769).
Methylsilylketenacetaler med formlen (V) kan fremstilles af phenyl acetater med formlen (VI) ved behandling med en base og 20 trialkylsilylhalogenid med formlen R3SiCl eller R3SiBr, såsom trimethylsilylchlorid, eller en base (såsom triethylamin) og et trialkylsilyltriflat med formlen R3Si-0S02CF3 (se f.eks. C. Ainsworth, F. Chen og Y. Kuo, J. Organometal1ic Chemistry, 1972, 46, 59).
25
Det er ikke altid nødvendigt at isolere mellemprodukterne (IV) og (V). Under passende betingelser kan forbindelser med formlen (I) fremstilles af phenyl acetater med formlen (VI) i "et trin" ved successiv tilsætning af de ovenfor nævnte egnede 30 reagenser.
Phenyl acetater med formlen (VI) kan fremstilles af phenylace-tater med formlen (VII). Hvis således en oxim med den almene formel (III) behandles med en egnet base (såsom natriumhydrid 35 eller natriummethoxid) og phenyl acetaterne med formlen (VII) tilsættes, fås pheny1 acetater med formlen (VI).
DK 174963 B1 40
Phenyl acetater med formlen (VII) fås af isochronanoner med formlen (VIII) ved behandling med HX, hvor X er et halogen (såsom brom) i methanol. Denne omdannelse kan også opnås i to trin, hvis isochromanonen (VIII) behandles med HX i et ikke-5 alkoholisk opløsningsmiddel, og den fremkomne phenyleddikesyre derpå forestres under anvendelse af standardmetoder (se f.eks.
I. Matsumoto og J. Yoshizawa, japansk kokai (Tokkyo Koho) 79 138 536, 27.10.1979, Chem. Abs., 1980, 92, 180829h, og G.M.F.
Lim, Y.G. Perron og R.D. Droghini, Res. Disci., 1979, 188, 10 672, Chem. Abs., 1980, 92, 128526t). Isochromanoner med form len (VIII) er velkendt fra den kemiske litteratur.
Alternativt kan forbindelser med formlen (I) fremstilles ved behandling af ketoestere med formlen (XI) med methoxymethyle-15 neringsmidler, såsom methoxymethy1 entr iphenylphosphoran (se f.eks. W. Steglich, G. Schramm, T. Anke og F. Oberwinkler, EP 0044 448, 4.7.1980).
Ketoestere med formlen (XI) kan fremstilles af ketoestere med 20 formlen (X) ved behandling med anionen af oximer med den almene formel (III) som beskrevet ovenfor. Ketoestere med formlen (X) er beskrevet i EP 0331 061.
Forbindelserne ifølge opfindelsen er aktive fungicider og kan 25 anvendes til bekæmpelse af en eller flere af følgende patogener:
Pyricularia oryzae på ris.
Puccinia recondita, Puccinia striiformis og andre former for 30 rust på hvede, Puccinia hordei, Puccinia striiformis og andre former for rust på byg og rust på andre værter, f.eks. kaffe, pære, æble, jordnød, grøntsager og prydplanter.
Erysiphe graminis (pulvermeldug) på byg og hvede og andre pulvermeldug på forskellige værter, såsom 35 Sphaerotheca macularis på humle, Sphaerotheca fuliginea på cucurbita (f.eks. agurk), Podosphaera leucotricha på æble og Uncinula necator på vin.
^^1^ I·» ' DK 174963 B1 41
Helminthosporium spp., Rhynchosporium spp., Septoria spp., Pyrenophora spp., Pseudocercosporella herpotrichoides og Gaeumannomyces graminis på kornsorter.
Cercospora arachidicola og Cercosporidium personata på jordnød 5 og andre Cercospora-værter på andre værter, f.eks. sukkerroe, banan, sojabønne og ris.
Botrytis cinerea (gråskimmel) på tomat, jordbær, grøntsager, vin og andre værter.
Alternaria spp. på grøntsager (f.eks. agurk), oliefrøraps, 10 æble, tomat og andre værter.
Venturis inaequalis (skurv) på æble.
Plasmopara viticola på vin.
Andre dunede meldug, såsom Bremia lactucae på salat, Perono-spora spp. på sojabønne, tobak, løg og andre værter, Pseudo-15 peronospora humuli på humle og Psedoperonospora cubensis på cucurbi ta.
Phytophthora infestans på kartoffel og tomat og andre Phy-tophthora spp. på grøntsager, jordbær, avocado, peber, prydplanter, tobak, kakao og andre værter.
20 Thanatephorus cucumeris på ris og andre Rhizoctonia-arter på forskellige værter, såsom hvede og byg, grøntsager, bomuld og græstørv.
Nogle af forbindelserne udviser et bredt interval af aktivi-25 teter over for svampe in vitro. De kan også have virkning mod forskellige sygdomme på frugt efter høst (f.eks. Penicillium digitatum og Italicum og Trichoderma viride på appelsin, Gloeosporium musarum på banan og Botrytis cinerea på vindruer) .
30
Endvidere kan nogle af forbindelserne være aktive som frøbehandlingsmidler over for Fusarium spp., Septoria spp., Tille-tia spp., (hvedens stinkbrand, en frøbåren sygdom på hvede), Ustillago spp. og Helmintosporium spp. på kornsorter, Rhizoc-35 tonia solani på bomuld og Pyricularia oryzae på ris.
Forbindelserne kan have systemisk bevægelse i planter. Endvidere kan forbindelserne være flygtige nok til at være aktive i DK 174963 B1 42 dampfase mod svampe på planten.
Opfindelsen angiver derfor en fremgangsmåde til bekæmpelse af svampe ved på en plante, på frø af en plante eller på en plan-5 tes voksested eller et frøs voksested at påføre en fungicidt effektiv mængde af en forbindelse som defineret i det foregå- .
ende eller et middel indeholdende denne.
Nogle af forbindelserne udviser insekticid virkning og kan i 10 passende anvendte mængder benyttes til bekæmpelse af forskellige insekter og mider.
En anden udførelsesform ifølge opfindelsen er derfor en fremgangsmåde til dræbning eller bekæmpelse af insekter eller mi-15 der ved til insektet eller miden eller til dets opholdssted at administrere en insekticidt eller miticidt effektiv mængde af en forbindelse som defineret i det foregående eller et middel indeholdende denne.
20 Forbindelserne kan anvendes direkte til landbrugsmæssige formål, men sammensættes bekvemt til midler under anvendelse af et bærestof eller fortyndingsmiddel. Opfindelsen angiver fungicide, insekticide og miticide midler omfattende en forbindelse som defineret i det foregående og et acceptabelt bærer-25 stof eller fortyndingsmiddel hertil.
Forbindelserne kan anvendes på flere forskellige måder. F.eks. kan de påføres i præparatform eller uden at være i præparat-form direkte på løvet af en plante, på frø eller på andet me-20 dium, hvori planterne vokser eller skal plantes eller sås, eller de kan sprøjtes på, støves på eller påføres som en creme eller pasta, eller de kan påføres som en damp eller som langsomt frigørende korn.
35 Påføringen kan være på enhver del af planten, herunder løvet, stilkene, grene eller rødder, eller på jorden, der omgiver rødderne, eller på frø før det sås, eller på jorden i alminde- DK 174963 B1 43 lighed til overrislingsvand eller til hydroponiske kultursystemer. Forbindelserne ifølge opfindelsen kan også injiceres i planter eller sprøjtes på vegetation under anvendelse af elek-trodynamisk sprøjteteknik eller andre metoder med lavt rum-5 fang.
*
Udtrykket "plante" som anvendt i den foreliggende beskrivelse indbefatter frøplanter, buske og træer. Den fungicide fremgangsmåde ifølge opfindelsen indbefatter endvidere forebyggen-10 de beskyttende profylaktisk og udryddende behandling. Forbindelserne anvendes fortrinsvis til landbrugsmæssige og havebrugsmæssige formål i form af et middel. Den anvendte type middel i et givet tilfælde vil afhænge af det særligt tilstræbte formål.
15
Forbindelserne kan være i form af støvepulvere eller korn omfattende den aktive bestanddel (forbindelsen ifølge opfindelsen) og et fast fortyndingsmiddel eller bærestof, f.eks. fyldstoffer, såsom kaolin, bentonit, kiselgur, dolomit, calcium-20 carbonat, talk, pulveriseret magnesia, fullerjord, gips, diatoméjord og porcelænsler. Sådanne korn kan være foruddannede korn, der er egnede til påføring på jorden uden yderligere behandling. Disse korn kan fremstilles enten ved at imprægnere små kugler af fyldstof med den aktive bestanddel eller ved at 25 pelletere en blanding af den aktive bestanddel og pulveriseret fyldstof. Midler til frøbehandling kan indbefatte et middel (f.eks. en mineralolie) til at understøtte vedhængningen af midlet på frøet. Alternativt kan den aktive bestanddel sammensættes til frøbehandlingsformål under anvendelse af et orga-3° nisk opløsningsmiddel (f.eks. N-methylpyrrolidon, propylen-glycol eller dimethylformamid). Midlerne kan også være i form af befugtelige pulvere eller vanddispergerbare korn omfattende befugtningsmidler eller dispergeringsmidler for at lette dispersionen i væsker. Pulverne og kornene kan også indeholde 35 fyldstoffer og suspenderingsmidler.
Emulgerbare koncentrater eller emulsioner kan fremstilles ved at opløse den aktive bestanddel i et organisk opløsningsmid DK 174963 B1 44 del, der eventuelt indeholder et befugtningsmiddel eller emulger ingsmiddel , og derpå sætte blandingen til vand, der også kan indeholde et befugtningsmiddel eller emulgeringsmiddel.
Egnede organiske opløsningsmidler er aromatiske op løsningsmid-5 ler, såsom alkyl benzener og alkylnaphthalener, ketoner, såsom isophoron, cyklohexanon og methylcyk1ohexanon, chlorerede hy-drocarboner, såsom chlorbenzen og trichlorethan, og alkoholer, såsom benzylalkohol, furfurylalkohol, butanol og glycolethere.
10 Suspensionskoncentrater af stort set uopløselige faste stoffer kan fremstilles ved kuglemøl leformaling eller per lemøl leforma-ling med et dispergeringsmiddel og et suspenderingsmiddel inkluderet for at forhindre det faste stof i udfældning.
15 Midler, der skal anvendes som sprøjtevæsker, kan være i form af aerosoler, hvori præparatet holdes i en beholder under tryk af et drivmiddel, f.eks. f1uortrichlormethan eller dichlordi-fluormethan.
20 Forbindelserne ifølge opfindelsen kan blandes i tør tilstand med en pyroteknisk blanding til dannelse af et middel, der er egnet til i lukkede rum at udvikle en røg indeholdende forbindelserne .
25 Alternativt kan forbindelserne anvendes i mikroindkapslet form. De kan også sammensættes til bionedbrydelige præparater for at opnå en langsom reguleret frigørelse af det aktive stof.
30 Ved at inkludere egnede additiver, f.eks. additiver til forbedring af fordelingen, klæbeevnen og modstandsevnen mod regn på behandlede overflader, kan de forskellige midler gøres bedre egnede til forskellige formål.
35 Forbindelserne ifølge opfindelsen kan anvendes som blandinger sammen med gødningsstoffer (f.eks. nitrogen, kalium eller phosphorholdige gødninger). Midler, der kun omfatter korn af DK 174963 B1 45 gødningsstoffer, der inkorporerer forbindelsen, f.eks. er belagt dermed, foretrækkes. Sådanne korn indeholder hensigtsmæssigt op til 25 vægt% af forbindelsen. Opfindelsen angiver derfor også et gødningsmiddel omfattende et gødningsstof og for-5 bindeisen med den almene formel (I) eller et salt eller metalkompleks deraf.
Befugtelige pulvere, emulgerbare koncentrater og suspensionskoncentrater vil normalt indeholde overfladeaktive stoffer, 10 f.eks. et befugtningsmiddel, dispergeringsmiddel, emulgeringsmiddel eller suspenderingsmiddel. Disse midler kan være kat-ioniske, anioniske eller ikke-ioniske midler.
Egnede kationiske midler er kvaternære ammoniumforbindelser, 15 f.eks. cetyltrimethylammoniumbromid. Egnede anioniske midler er sæber, salte af alifatiske monoestere af svovlsyre (f.eks. natriumlaurylsulfat) og salte af sulfonerede aromatiske forbindelser (f.eks. natriumdodecylbenzensulfonat, natrium, calcium eller ammoniumlignosulfonat, butyl naphthalensul fonat, og 20 en blanding af natriumdi isopropyl- og triisopropylnaphthalen-sulfonat).
Egnede ikke-ioniske midler er kondensationsprodukterne af et-hylenoxid med fedtalkoholer, såsom oleyl eller cetylalkohol, 25 eller med alkylphenoler, såsom octyl eller nonylphenol og oc-tylcresol. Andre ikke-ioniske midler er partialesterne afledt af langkædede fedtsyrer og hexitanhydrider, kondensationsprodukterne af disse partialestere med ethylenoxid og lecithiner-ne. Egnede suspenderingsmidler er hydrofile kolloider (f.eks.
30 polyvinylpyrrolidon og natriumcarboxymethylcel1ulose) og kvældende lerarter såsom bentonit eller attapulgit.
Midler til brug som vandige dispersioner eller emulsioner leveres normalt i form af et koncentrat indeholdende en høj 35 mængde af den aktive bestanddel, hvilket koncentrat fortyndes med vand før brugen. Disse koncentrater skal fortrinsvis kunne tåle lagring i længere tid og efter denne lagring kunne for- DK 174963 B1 46 tyndes med vand til dannelse af vandige præparater, der forbliver homogene i tilstrækkelig tid til, at de kan påføres med sædvanligt sprøjteudstyr. Koncentraterne kan bekvemt indeholde op til 95%, hensigtsmæssigt 10-85%, f.eks. 25-60 vægt% af den 5 aktive bestanddel. Efter fortynding til dannelse af vandige præparater kan disse indeholde varierende mængder af den aktive bestanddel afhængende af det tilstræbte formål, men et vandigt præparat indeholdende 0,0005% eller 0,01 til 10 vægt% aktiv bestanddel kan anvendes. Midlerne ifølge opfindelsen kan 10 indeholde andre forbindelser, der har biologisk aktivitet, f.eks, forbindelser der har en lignende eller komplementær fungicid aktivitet, eller som har plantevækstregulerende her-bicidellerinsekticidvirkning.
15 En fungicid forbindelse, der kan findes i midlet ifølge opfindelsen, kan være et, som er i stand til at bekæmpe akssygdomme hos kornsorter (f.eks. hvede), såsom Septoria, Gibberella og Helminthosporium ssp., frøbårne og jordbårne sygdomme og dunet meldug og pul vermel dug på vindruer og pulvermeldug og skurv på 20 æble osv. Ved at indeholde et andet fungicid kan midlet have et bredere aktivitetsspektrum end forbindelsen med den almene formel (I) alene. Endvidere kan det andet fungicid have en sy-nergistisk virkning på den fungicide virkning af forbindelsen med den almene formel (I); Eksempler på fungicide forbindel-25 ser, der kan være indeholdt i midlet ifølge opfindelsen, er (i)-2-(,4-dichlorphenyl)-3-(lH-l,2,4-triazol-l-yl) propyl-1,1,2,2-tetraf1 uorethyl ether, (RS)-l-aminopropylphosphonsyre, (RS)-4-(4-chlorphenyl)-2-pheny1-2-(1H-1,2,4-triazol-l-ylmethyl )butyronitri 1, (RS)-4-chlor-N-(cyano(ethoxy)methyl)benzamid, 30 (Z)-N-but-2-enyloxymethyl-2-chlor-2',6'-diethylacetani1 id, l-(2-cyano-2-methoxyiminoacetyl)-3-ethyluri nstof, l-[2RS,4RS,2RS,4R$)-4-brom-2-(2,4-dichlorphenyl)tetrahydrofur-furyl]-lH-l,2,4-triazol, 3-(2,4-dichlorphenyl)-2-(1H-1,2,4- triazol-l-ylJquinazolin-4-(3H)-on, 3-chlor-4-[4-methy1-2-(1H-35 1,2,4-tri azol-1-methyl)-1,3-dioxolan-2-y1Iphenyl-4-chlorphe-nylether, 4-brom-2-cyano-N,N-dimethy1-6-tri f1uormethy1benz im i -dazol-l-sulfonamid, 4-chlorbenzyl-N-(2,4-dichlorphenyl)-2-(lH- DK 174963 B1 47 l,2,4-triazol-l-yl)thioacetamidat, 5-ethyl-5,8-di hydro-8-oxo-(l,3)-dioxolo(4,5-g)quir.olin-7-carboxylsyre, a-[N-(3-chlor- 2,6-xylyl)-2-methoxyacetamido]-γ-butyrolacton, anilazin, BAS 454, benalaxyl, benomyl, biloxazol, binapacryl, bitertanol, 5 blasticidin S, bupirimat, buthiobat, captafol, captan, carben-dazim, carboxin, ch1orbenzthiazol, chloroneb, chlorthaloni1, chlorzolinat, kobberhol dige forbindelser, såsom kobberoxych1o-rid, kobbersulfat og Bordeaux-væske, cykloheximid, cymoxanil, cyproconazol, cyprofuram, di-2-pyri dy1 di sulfid-1,11-dioxid, 10 dichlofluanid, dichlon, diclobutrazol, diclomezin, dicloran, dimethamorph, dimethirimol, diniconazol, dinocap, ditalimfos, dithianon, dodemorph, dodin, edifenphos, etaconazol, ethiri-mol, ethyl-(Z)-N-benzyl-N-([methyl{methylthioethylidenamino-oxycarbonyl)amino]thio)-ø-a1aninat, etridazol, fenapanil, 15 fenarimol, fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fenti nacetat, fentinhydroxid, flutolanil, flutrifol, fluzil-azol, folpet, fosetyl-aluminium, fuberidazol, furalaxyl, fur-conazol-cis, guazatin, hexaconazol, hydroxyisoxazol, imazalil, iprobenfos, iprodion, isoprothiolan, kasugamycin, mancozeb, 20 maneb, mepronil, metalaxyl, methfuroxam, metsulfovax, myclobu-tanil, neoasozin, nikkeldimethyldithiocarbamat, nitrothal-iso-propyl, nuarimol, ofurace, organiske kviksølvforbindelser, oxadixyl, oxycarboxin, penconazol, pencycuron, pent-4-enyl-M-furfury1-N-imidazol-l-ylcarbonyl-DL-homoalaninat, phenazin-25 oxid, phthalid, polyoxin D, polyram, probenazol, prochloraz, procymidon, propamocarb, propiconazol, propineb, prothiocarb, pyrazophos, pyrifenox, pyroquilon, pyroxyfur, pyrrylnitrin, quinomethionat, quintozen, streptomycin, svovl, techlofthaiam, tecnazen, tebuconazol, thiabendazol, thiophanat-methyl, thi-30 ram, tolclofos-methyl, tri acetatsa 11 af 1,1'-i minodi(octameth-ylen)diguanidin, triadimefon, triadimenol, triazbutyl, tri-cyklazol, tridemorph, triforin, validamycin A, vinclozolin og zineb. Forbindelserne med den almene formel (I) kan blandes med jord, tørv eller andre roddannende medier til beskyttelse 35 af planterne mod frøbårne, jordbårne eller løvbårne svampesygdomme.
DK 174963 B1 48
Egnede insekticider, der kan inkorporeres i midlet ifølge opfindelsen indbefatter buprofezin, carbaryl, carbofuran, car-bosulfan, chlorpyri fos, cykloprothrin, demeton-s-methyl, dia-zinon, dimethoat, ethofenprox, fenitrothion, fenobucarb, fen-5 thion, formothion, isoprocarb, isoxathion, øonocrotophos, phenthoat, pirimicarb, propaphos og XMC.
Plantevækstregulerende forbindelser er forbindelser, der regulerer ukrudt eller dannelse af frøstand eller selektivt regu-10 lerer væksten af mindre ønskelige planter (f.eks. græsarter).
Eksempler på egnede plantevækstregulerende forbindelser til brug sammen med forbindelserne ifølge opfindelsen er 3,6-di-chlorpicolinsyre, 1-(4-chlorpheny1)-4,6-dimethy1-2-oxo-l,2-di -15 hydropyridin-3-carboxylsyre, methyl-3,6-dichloranisat, absci-sinsyre, asulam, benzoylprop-ethy1, carbetamid, aminozid, di-fenzoquat, dikegulac, ethephon, fenpentezol, fluoridamid, gly-phosat, glyphosin, hydroxybenzonitriler (f.eks. bromoxynil), inabenfid, isopyrimol, langkædede fedtalkoholer og syrer, ma-20 leinsyrehydrazid, mefluidid, morphactiner (f.eks. chlorfluor-ecol), paclobutrazol, phenoxyeddikesyre (f.eks. 2,4-D eller MCPA), substitueret benzosyre (f.eks. trijodbenzosyre), substituerede kvaternære ammonium og phosphoniumforbindelser (f.eks. chlormequat, chlorphonium eller mepiquatchlorid), tec-25 nazen, auxinerne (f.eks. indoleddikesyre, indolsmørsyre, naphthyleddikesyre eller naphthoxyeddikesyre), cytokininerne (f.eks. benzimidazol, benzyladenin, benzylaminopurin, dipheny-lurinstof eller kinetin), gibberellinerne (f.eks. GA3, GA4 eller GA7) og triapenthenol.
30
De følgende eksempler illustrerer opfindelsen. Overalt i eksemplerne referer udtrykket "ether" til diethylether, magniumsulfat blev anvendt til at tørre opløsninger, og opløsninger blev koncentreret under reduceret tryk. Reaktioner, der inde-35 bærer vandfølsomme eller luftfølsomme mellemprodukter blev udført under en atmosfære af nitrogen, og opløsningsmidler blev tørret før brugen, hvor det var nødvendigt. Med mindre andet DK 174963 B1 49 er anført blev kromatografi udført på en søjle af silicagel som den stationære fase. Hvor de er vist, er infrarøde data og NMR-data selektive. Der er ikke gjort noget forsøg på at anføre enhver absorption i alle tilfælde. *Η NMR-spektre blev re-5 gistreret under anvendelse af CDCl3~op1øsninger med mindre andet er anført. Der anvendes følgende forkortelser: THF = tetrahydrofuran s = singlet DMF = Ν,Ν-dimethylformamid d = dublet 10 NMR = kernemagnetisk resonans t * triplet IR = infrarød m = multiplet
Smp. s smeltepunkt br = bred HPLC a højtydende væskekromatografi 15 EKSEMPEL 1
Dette eksempel illustrerer fremstillingen af (E),(E)-methyl-3-methoxy-2-[2-(3-methylbenzaldoximinomethyl) phenyl]propenoat (forbindelse nr. 5 i tabel I).
20
En opløsning af (E)-3-methylbenzaldoxim (0,23 g) i DMF (5 ml) blev sat dråbevis til en omrørt suspension af natriumhydrid (0,051 g) i DMF (5 ml) ved stuetemperatur. Efter en halv time blev en opløsning af (E)-methy1-2-[2-(brommethy1)pheny1]-3-25 methoxypropenoat (0,5 g, fremstillet ved fremgangsmåden beskrevet i EP-A-0203606) i DMF (5 ml) sat til reaktionsblandingen, som så blev omrørt ved stuetemperatur i 4 timer. Blandingen blev hældt i vand og ekstraheret to gange med ether. De forenede ekstrakter blev vasket med vand, derpå tørret, kon-30 centreret og kromatograferet under anvendelse af ether som eluant til dannelse af titelforbi ndel sen (0,132 g, 23% udbytte) som en bleggul olie.
IR maxima (film) : 1709, 1631 cm”l.
lH NMR (270 MHz) δ : 2,35 (3H, s); 3,69 (3H, s); 3,80 (3H, S); 5,12 (2H, S); 7,1-7,55 (8H, ro); 7,59 (IH, S); 8,05 (s) ppm.
35 EKSEMPEL 2 DK 174963 B1 50
Dette eksempel illustrerer fremstillingen af (E),(E)- og (Z),(E)-blandingen af methy1-2-[2-(3,5-dimethy1pyrazin-2-y1 -5 acetoximinomethyl)phenyl]-3-methoxypropenoat (forbindelse nr.
176 i tabel I).
Til en blanding af 2,6-dimethylpyrazin (3,24 g) svovlsyre (15 ml af en 3,4 M opløsning) og acetaldehyd (10 ml) omrørt ved 10 0eC, blev der samtidigt sat en opløsning af ferrosulfat (50,1 g i 150 ml vand) og t-butylhydroperoxid (16,2 ml af en 70¾ vandig opløsning). Temperaturen under tilsætningen blev holdt under 3°C. Efter tilsætningen blev reaktionsblandingen omrørt ved 0°C i 1 time. Natri ummetabi sulf it blev tilsat, indtil 15 blandingen gav en negativ stivelse-jodprøve. Reaktionen blev ekstraheret med dichlormethan, de forenede ekstrakter blev vasket med vand, derpå tørret, koncentreret og kromatograferet under anvendelse af en blanding af ether og 60-80°C benzin (4:1) som eluant til dannelse af 2-acetyl-3,5-dimethylpyrazin 20 (2,65 g, 59% udbytte) som en bleggul olie.
IR maxima (film) : 1694, 1551, 1262, 1175 cm-1.
*H NMR (270 MHZ) δ : 2,62 (3H, s); 2,70 (3H, s); 2,80 (3H, s); 25 8,36 (IH, S) ppm.
2-acetyl-3,5-dimethy1pyrazin (2,65 g), hydroxylaminhydrochlo-rid (2,5 g) og natriumacetattrihydrat (3,5 g) blev tilbagesva-let i methanol (50 ml) i 1 time. Reaktionsblandingen blev kon-30 centreret, fortyndet med vand (75 ml) og ekstraheret med et-hylacetat. De forenede ekstrakter blev tørret og koncentreret til dannelse af en olie, der blev tritureret med ether og 60 til 80°C benzin til dannelse af 3,5-dimethy1-2-(1-hydroxyi mi -noethyl)pyrazin (2,54 g, 87% udbytte) som et hvidt fast stof 35 (smp. 85-89eC) og som en 1:1 blanding af (E/Z)-isomerer.
IR maxima (film) : 2925, 1465, 1376, 1086, 930 cm-*.
DK 174963 B1 51
Ih NMR (270 MHZ) δ : 2,23 (3H, s); 2,33 (3H, S); 2,53 (3H, s); 2,56 ( 3H , s); 2,58 (3H, S); 2,68 (3H, S); 8,32 (IH, s); 8,35 (IH, s); 9,45 (IH, br.s); 9,85 (IH, br.s) ppm.
5 En 1:1 blanding af (E/Z)-3,5-dimethy1-2-(1-hydroxyi minoethy1) -pyrazin (0,87 g) blev sat portionsvis til en omrørt suspension af natriumhydrid (0,25 g) i DMF (20 ml) ved ca. 5eC. Efter 1 time blev en opløsning af (E)-methyl-2-[2-(brommethylJphenyl)- 3-methoxypropenoat (1,5 g) i DMF (5 ml) sat til reaktionsblan-10 dingen ved °C. Efter IH time blev blandingen hældt i vand og ekstraheret to gange med ether. De forenede ekstrakter blev vasket med saltvand, derpå tørret, koncentreret og kromatogra-feret under anvendelse af ether:hexan 1:1 som eluant til dannelse af titelforbindelsen, en blanding af oximisomerer (stør-15 re:mindre 7:3) som et blegt lysrødt fast stof (0,57 g, 30% udbytte) smp. 56-60°C.
IR maxima (film) : 1707, 1624, 1132 cm-1.
20 Ih NMR (270 MHz) større isomer - 6 2,39 (3H, s); 2,54 (3H, S); 2,57 (3Η, s); 3,67 (3H, s); 3,82 (3H, s); 5,15 (2Η, s); 7,1-7,9 (4H, m); 7,59 (IH, s); 8,27 (IH, s) ppm. Mindre isomer - δ : 2,22 (3H, s); 2,51 (3H, s); 2,57 (3H, S); 3,67 (3H, s); 3,82 (3, HS); 5,27 (2H, s); 7,1-7,9 (4H, m); 7,76 (IH, s); 25 8,33 (IH, s) ppm.
EKSEMPEL 3
Dette eksempel illustrerer fremstillingen af (E),(E)-methyl-3-30 methoxy-2-[2-(phenylacetoxyiminomethyl)-phenyl]propenoat (forbindelse nr. 23 i tabel I).
En opløsning af acetophenonoxim (1,23 g) i DMF (5 ml) blev sat dråbevis til en omrørt suspension af natriumhydrid (0,367 g) i 35 DMF (25 ml). Efter 1 time blev en opløsning af (E)-methyl-2-[2-(brommethyl) phenyl]-3-methoxypropenoat (2,0 g) i DMF (15 ml) sat til reaktionsblandingen, som så blev omrørt ved stue- DK 174963 B1 52 temperatur i 16 timer. Blandingen blev hældt i vand og ekstraheret to gange med ether. De forenede ekstrakter blev vasket med vand, derpå tørret, koncentreret og kromatograferet under anvendelse af ether*. 40-60 petroleum 3:2 til dannelse af en rå 5 olie. HPLC under anvendelse af ether: 40-60 petroleum 1:1 gav titelforbindelsen (0,55 g, 23% udbytte) som en bleggul olie.
IR maxima (film) : 1708, 1631 cm"*.
10 Ih NMR er anført i tabel II.
EKSEMPEL 4
Dette eksempel illustrerer fremstillingen og adskillelsen af 15 de (E),(E)- og (Z),(E)-isomerer af methyl-3-methoxy-2-{2-[(py-ridin-5-yli sopropyloxyi mi no)-0-methyl]phenyl}propenoat (forbindelserne nr. 66 og 67 i tabel I).
En opløsning af oximet af isopropy1pyrimidin-5-y1 keton (0,29 g 20 af en 3:2 blanding af de (E)- (Z) - i somerer) i DMF (5 ml) blev sat til en omrørt suspension af natriumhydrid (0,09 g) i DMF (10 ml). Efter 2 timer blev blandingen afkølet til 0eC, og en opløsning af (E)-methy1-2-[2-(brommethy1)pheny1J-3-methoxy-propenoat (0,5 g) i DMF (5 ml) blev sat til reaktionsblandin-25 gen, som så blev omrørt i 3 timer. Blandingen blev hældt i vand og ekstraheret i ether. De forenede ekstrakter blev vasket med vand, derpå tørret og koncentreret til dannelse af en olie, den rå blanding af (E),(E)- og (Z),(E)-isomerer. HPLC under anvendelse af ether som eluant blev anvendt til at ad-30 skille disse isomerer i deres to komponenter: 1. Den hurtigt eluerende fraktion - (Z)-oximetheren, (E)-pro-penoat. (0,115 g, 18% udbytte). En klar olie. (Forbindelse nr. 67 i tabel I).
35 2. Den langsomt eluerende fraktion - (E)-oximetheren, (E) — propenoat. (0,098 g, 15% udbytte). En klar olie (forbindelse nr. 66 i tabel I).
1 —— EKSEMPEL 5 DK 174963 B1 53 *H NMR er anført i tabel II.
5 Dette eksempel illustrerer fremstillingen af en stereoisomer af methyl-2-[2-{phenyl[methylthio]oximinomethyl) phenyl]-3- methoxypropenoat (forbindelse nr. 191 i tabel I).
En opløsning af chlor (1,5 g) i carbontetrachlorid (42 ml) 10 blev sat portionsvis til en omrørt delvis opløsning af benz-aldehydoxim [2,5; *H NMR: δ 8,18 (IH, s), 9,40 (IH, brs) ppm] i carbontetrachlorid (20 ml) ved stuetemperatur. Efter tilsætningen blev reaktionsblandingen omrørt ved stuetemperatur i 3 timer og derpå hældt i vand. Det organiske lag blev fraskilt, 15 tørret og koncentreret til dannelse af næsten ren a-chlorbenz-aldehydoxim (3,2 g) som en gul væske. En opløsning af natrium-methanthiolat (0,68 g) i methanol (15 ml) blev sat dråbevis til en isafkølet og omrørt opløsning af en del af denne a-chlorbenzaldehydoxim (1,5 g) i methanol (15 ml). Efter tilsæt-20 ningen blev reaktionsblandingen omrørt i 2 timer under fortsat afkøling i isvand. Methanolen blev fjernet under reduceret tryk, og remanensen blev kromatograferet under anvendelse af dichlormethan som eluant til dannelse af en enkelt stereoisomer af a-methylthiobenzaldehydoxim (0,670 g, 42% udbytte) som 25 et hvidt krystallinsk fast stof, smp. 76-78eC, *H NMR: δ 2,08 (3H, s), 9,12 (IH, s) ppm.
En opløsning af o-methylthiobenzaldehydoxim (0,575 g) i DMF (10 ml) blev sat dråbevis til en omrørt suspension af natrium-30 hydrid (85 mg) i DMF (15 ml) ved stuetemperatur. En time senere blev en opløsning af (E)-methyl-2-[2-(brommethyl)phenyl]- 3-methoxypropenoat (0,990 g) i DMF tilsat dråbevis og efter yderligere 3 timer blev blandingen hældt i vand og ekstraheret med ethylacetat. De organiske ekstrakter blev vasket med vand, 35 tørret, koncentreret og kromatograferet under anvendelse af stigende mængder ethylacetat i hexan som eluant til dannelse af titelforbindelsen (1,05 g, 83%) som en farveløs olie, IR : 1706 cm"l.
DK 174963 B1 54 EKSEMPEL 6 *H NMR er anført i tabel II.
5 Dette eksempel illustrerer fremstillingen af enkelte i somerer af me thy 1-2-[2-(pheny1[methy1su1fi ny 1]oximinomethy1)pheny1]- 3-methoxypropenoat og methy1-2-[2-(pheny1[methy1su1fony 1]oxi -minomethy1)pheny1]-3-methoxypropenoat (forbindelse nr. 227 og 228 i tabel I).
10 m-chlorperbenzosyre (0,250 g, indeholdende 45% m-chlorbenzo-syre) blev sat portionsvis i løbet af 30 minutter til en om-rcrt opløsning af methyl-2-[2-(pheny1[methylthio]oximinomethy 1)pheny1]-3-methoxypropenoat (0,300 g, fremstillet som 15 beskrevet i eksempel 5) i dichlormethan (20 ml) afkølet i isvand. Efter yderligere 15 minutter blev reaktionsblandingen vasket i rækkefølge med vandig natriumbicarbonat og vand, derpå tørret, koncentreret og kromatograferet under anvendelse af en 1:1 blanding af ethylacetat og hexan som eluant til dannel-20 se af titelforbindelserne: (i) sul fonen, elueret først som en gummi (0,090 g, 28% udbytte) og (ii) sulfoxidet, også en gummi (0,150 g, 48% udbytte).
*H NMR er anført i tabel II.
25 EKSEMPEL 7
Dette eksempel illustrerer fremstillingen af to stereoisomerer af methyl-2-[2-(phenyl[methoxy]oximinomethyl)phenyl]-3-roeth-30 oxypropenoat (forbindelse nr. 225 og 226 i tabel I).
En blanding af stereoisomerer af α-methoxybenza1dehydoxim blev fremstillet i to trin af methylbenzoat ved behandling i rækkefølge med Lawessons reagens og hydroxylamin (se f.eks. EP 35 0 299 382). De stereo i somere blev adskilt ved kromatografi under anvendelse af dichlormethan som eluant-.
——11 —-- - DK 174963 B1 55 (i) Isomer A, elueret først, et bleggult fast stof, smp.
55-57eC, Ih NMR: 6 3,83 (3H, s), 7, 72 (IH, s) ppm. og (ii) Isomer B, en farveløs gummi, *H NMR: 6 3,96 (3H, s), 5 8,84 (IH, s) ppm.
Disse to stereoisomere oximer blev omdannet hver for sig til titelforbindelserne ved fremgangsmåden beskrevet i eksempel 5, dvs. ved behandling i rækkefølge med natriumhydrid og (E)-10 methyl-2-[2-(brommethyl) phenyl]-3-methoxypropenoat. Isomer A gav titelforbi ndel sen nr. 225 i tabel I som en gummi, og isomer B gav t i tel forbindelsen nr. 226 i tabel I, også som en gummi.
15 *H NMR er anført i tabel II.
De følgende er eksempler på midler egnede til landbrugsmsssige og havebrugsmæssige formål, der kan sammensættes af forbindelserne ifølge opfindelsen. Sådanne midler udgør en anden side 20 af opfindelsen. Procenterne er efter vægt.
EKSEMPEL 8
Et emulgerbart koncentrat fremstilles ved at blande og omrøre 25 bestanddelene, indtil alt er opløst.
Forbindelse nr. 45 i tabel I 10%
Benzylalkohol 30%
Calciumdodecylbenzensulfonat 5% 30 Nonylphenolethoxylat (13 mol ethylenoxid) 10%
Alkylbenzener 45% EKSEMPEL 9 35 Den aktive bestanddel opløses i methy1endich1 or id, og den fremkomne væske sprøjtes på korn af attapulgitler. Opløsningsmidlet får så lov at afdampe til dannelse af et kornet middel.
DK 174963 B1 56
Forbindelse nr. 45 i tabel I 45%
Attapulgi tkorn 95% EKSEMPEL 10 5
Et middel egnet til brug som frøbehandlingsmiddel fremstilles ved at formale og blande de tre bestanddele.
Forbi ndel se nr. 45 i tabel I 50% 10 Mineralolie 2%
Porcelænsler 48% EKSEMPEL 11 15 Et støvepulver fremstilles ved at formale og blande den aktive bestanddel med talk.
Forbindelse nr. 45 i tabel I 5%
Talk 95% 20 EKSEMPEL 12
Et suspensionskoncentrat fremstilles ved kuglemøl leformaling af bestanddelene til dannelse af en vandig suspension af den 25 formalede blanding med vand.
Forbindelse nr. 45 i tabel I 40%
Natriumlignosu1fonat 10%
Bentonitler 1% 30 Vand 49%
Dette præparat kan anvendes som en sprøjtevæske ved fortynding i vand eller påføres direkte på frø.
35 EKSEMPEL 13 DK 174963 B1 57
Et befugteligt pulverpræparat fremstilles ved sammen at blande og formale bestanddelene, indtil alt er grundigt blandet.
5
Forbindelse nr. 45 i tabel I 25%
Natriumlaurylsulfat 2%
Natri umiignosulfonat 5%
Si 1 i c iumdioxid 25% 10 Porcelænsler 43% EKSEMPEL 14
Forbindelserne blev afprøvet over for forskellige løvbårne 15 svampesygdomme på planter. Den anvendte teknik var som følger.
Planterne blev dyrket i John Innes pottekompost (nr. 1 eller 2) i minipotter med en diameter på 4 cm. Forsøgsforbindelserne blev sammensat enten ved perlemølleformaling med vandig Dis-20 persol T eller som en opløsning i acetone eller acetone/etha-nol, der blev fortyndet til den ønskede koncentration umiddelbart før brugen. Til løvbårne sygdomme blev præparaterne (100 ppm aktiv bestanddel) sprøjtet på løvet og påført på planternes rødder i jorden. Sprøjtevæskerne blev påført til maksimal 25 tilbageholdelse, og rodvædevæskerne til en slutkoncentration ækvivalent med ca. 40 ppm aktiv bestanddel i tør jord. Tween 20 til en endelig koncentration på 0,05% blev tilsat, når sprøjtevæskerne blev påført på kornsorter.
30 Til de fleste af prøverne blev forbindelsen påført på jorden (rødderne) og løvet (ved sprøjtning) en eller to dage, før planten blev podet med sygdommen. En undtagelse var prøven på Erysiphe graminis, hvor planterne blev podet 24 timer før behandlingén. Løvpatogener blev påført ved sprøjtning som spore-35 suspensioner på forsøgsplanternes blade. Efter podning blev planterne anbragt i passende omgivelser for at lade infektionen forløbe og blev så inkuberet, indtil sygdommen var parat DK 174963 B1 58 til bedømmelse. Perioden mellem podning og bedømmelse varierede fra 4 til 14 dage afhængende af sygdommen og omgivelserne.
Sygdomsbekæmpelse blev registreret efter følgende skala: 5 4 = ingen sygdom 3 = spor - 5% sygdom på ubehandlede planter 2 = 6-25% sygdom på ubehandlede planter 1 = 26-59% sygdom på ubehandlede planter 10 0 - 60-100% sygdom på ubehandlede planter 15 20 25 30 35 _ r —i DK 174963 B1 59 o s w Λ
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De insekticide egenskaber af forbindelsen med formlen (I) blev påvist som følger: 5
Aktiviteten af forbindelsen blev bestemt under anvendelse af forskellige insekter, mider og nematoder. Med undtagelse af knockdown-akti vi teten over for Musca domistica, hvor forsøgsmetoden er beskrevet senere, blev forbindelsen anvendt i form 10 af flydende præparater indeholdende fra 12,5 til 1000 dele per million (ppm) efter vægt af forbindelsen. Præparaterne blev fremstillet ved at opløse forbindelsen i acetone og fortynde opløsningerne med vand indeholdende 0,01 vægt% af et befugt-ningsmiddel forhandlet under handelsnavnet "SYNPERONIC" NX, 15 indtil væskepræparaterne indeholdt den ønskede koncentration af produktet. "SYNPERONIC" er et registreret varemærke.
Prøvemetoden anvendt over for hvert skadedyr var i princippet den samme og bestod i at understøtte et antal af skadedyrene 20 på et medium, som i reglen var en værtsplante eller et foderstof, hvorpå skadedyret levede, og behandle enten det ene eller det andet eller både skadedyret og mediet med præparaterne. Dødeligheden af skadedyrene blev så bedømt med mellemrum varierende fra 1 til 7 dage efter behandlingen.
25
Resultaterne af prøverne er vist i tabel IV for hver af forbindelserne i første kolonne, og i den mængde i dele per million, der er anført i anden kolonne. De er vist som en bedømmelse af dødelighed betegnet som 9, 5 eller 0, hvor 9 viser 80 30 til 100¾ dødelighed (70 til 100% reduktion af rodopsvulmning sammenlignet med ubehandlede planter for Meloidogyne incognita semi in vi tro-prøve) , 5 viser 50 til 79% dødelighed (50 til 69% reduktion af rodopsvulmning af Meloidogyne incognita semi in vitro-prøve) og 0 viser mindre end 50% dødelighed.
35 I tabel IV er skadedyret betegnet med en bogstavkode. Betydningen af koden, understøtningsmediet eller føden og typen og varigheden af prøven er anført i tabel V.
DK 174963 B1 65
Knockdown-egenskaberne over for Musca domestica blev vist som følger.
En prøve af forbindelsen blev fortyndet i 0,1% ethanol/acetone 5 (50:50 blanding) og fyldt op til 1000 ppm opløsning med 0,1% vandig Synperonic NX-opløsning. Opløsningen (1 ml) blev så sprøjtet direkte på 10 stuefluer af blandet køn, der blev holdt i en drikkekop indeholdende en sukkerklump, der også blev sprøjtet.
10
Umiddelbart efter sprøjtningen blev kopperne vendt om og fik lov at tørre. En bedømmelse af knockdown blev foretaget, når kopperne igen blev vendt om 15 minutter senere. Fluerne blev så forsynet med en fugtig vatpude og holdt i 48 timer i et 15 værelse indstillet til 25eC og 65% relativ fugtighed, før der blev foretaget en bedømmelse af dødelighed.
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Claims (8)

75 DK 174963 B1
1. Forbindelser nied formlen (I): /°\ C =N CHj (I) Rl CH302C ch.och3 og stereoisomerer deraf, hvor A er hydrogen, halogen, hydroxy, Ci-C4-alkyl, C|-C4-5 alkoxy, CrC4-halogenalkyl, CrC4-halogenalkoxy, C|-C4-alkylcarbonyl, CrC4alkoxycar-bonyl, phenoxy, nitro eller cyano; R' og R2, som kan være ens eller forskellige, er hydrogen, Cj-Q-alkyl, C3-C6-cycloalkyl, heterocyclyl-CrC4-alkyl, C3-C6-cycloalkyl-CrC4-alkyl, aryl-C,-C4-alkyl, aryloxy-CrC4-alkyl, heteroaiyloxyalkyl, C2-C6-alkenyl, Q-Q-alkynyl, CrC6-alkoxy, aryl, heteroaryl, aryloxy, heteroaryloxy, nitro, halogen, cyano,
10 -NR3R4,-C02R3,-C0NR3R4,-C0R3,-S(0)nR3 eller (CH2)mPO(OR3)2, hvor n er 0,1 eller 2, m er 0 eller 1 og R3 og R4, som er ens eller forskellige, er hydrogen, C|-C6-alkyl, aryl-C,-C6-alkyI, C2-C6-alkenyl, C2-C6-alkynyl, aiyl eller heteroaryl, eller R1 ogR2 er forenede til dannelse afen cyclopentyl-, cyclohexyl- eller cyclohexadienonylgruppe, som eventuelt bærer en kondenseret benzenring og/eller en methylsubstituent, eller R1 og R2 er 15 forenede til dannelse af et tetrahydropyranylringsystem; idet en hvilken som helst af de g ovennævnte alkyldele eventuelt er substitueret med halogen, hydroxy eller C,-C4-alkoxy, idet en hvilken som helst af de ovennævnte alkenyl- eller alkynyldele eventuelt er substitueret med phenyl, og idet en hvilken som helst af de ovennævnte aryldele, som er phenyl eller naphthyl, og en hvilken som helst af de ovennævnte heterocyclyl- eller heteroaryl-20 dele, som er valgt blandt gruppen bestående af thienyl, fiiryl, pyrrolyl, triazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl og quinoxalinyl og N-oxider deraf, eventuelt er substitueret med en eller flere blandt halogen, hydroxy, mercapto, C,-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, CrC4-alkoxy, C2-C4-alkenyloxy, DK 174963 B1 76 C2-C4-alkynyloxy, halogen-CrC4-alkyl, halogen-C,-C4-alkoxy, C,-C4-alkylthio, hydroxy-C,-C4-alkyl, CrC4-aIkoxy-CrC4-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-CrC4-alkyl, phenyl, pyridyl, pyrimidinyl, phenoxy, pyridyloxy, pyrimidinyloxy, phenyl-CrC4-alkyl, hvor alkyldelen eventuelt er substitueret med hydroxy, pyridyl- eller pyrimidinyl-CrC4-5 alkyl, phenyl-C2-C4-alkenyl, pyridyl- eller pyrimidinyl-C2-C4-alkenyl, phenyl-C,-C4-alkoxy, pyridyl- eller pyrimidinyl-C|-C4-alkoxy, phenoxy-C, -C4-alkyl, pyridyloxy- eller pyrimidinyloxy-CrC4-alkyl, C,-C4-alkanoyloxy, benzoyloxy, cyano, thiocyanato, nitro, -NR’R", -NHCOR', -NHCONR'R”, -CONR'R’', -COOR’, -0S02R', -S02R', -COR', -CR-NR” eller -N=CR'R", hvor R' og R" uafhængigt af hinanden er hydrogen, CrC4-10 alkyl, CrC4-alkoxy, C|-C4-alkylthio, C3-(Vcycloalky1, C3-C6-cycloalkyl-C,-C4-alkyl, phenyl eller benzyl, idet phenyl- og benzylgruppeme eventuelt er substitueret med halogen, CrC4-alkyl eller CrC4-alkoxy; og en hvilken som helst af de ovennævnte phenyl-, pyridyl- eller pyrimidinylsubstituenter i sig selv eventuelt er substitueret med en eller flere af halogen, hydroxy, mercapto, CrC4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl,
15 CrC4-alkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, halogen-C,-C4-alkyl, halogen-C,-C4- alkoxy, C|-C4-alkylthio, hydroxy-CrC4-alkyl, Ci-C4-alkoxy-C|-C4-alkyl, C3-C6-cycloal-kyl,C3-C6-cycloalkyl-C|-C4-alkyl, alkanoyloxy, benzoyloxy, cyano, thiocyanato, nitro, -NR’R", -NHCOR’, -NHCONR'R", -CONR'R", -COOR', -S02R’, -0S02R\ -COR’, -CR-NR" eller -N=CR'R", hvor R’ og R" har de ovenfor angivne betydninger.
2. Forbindelse ifølge krav 1, hvor A er hydrogen, halogen, hydroxy, methyl, methoxy, trifluormethyl, trifluormethoxy, C,-C2-alkylcarbonyl, C|-C2-alkoxycarbonyI, phenoxy, nitro eller cyano; og R1 er Q-Q-alkyl, halogen-CrC4-alkyl, C,-C4-alkoxy, halogen-C|-C4-alkoxy, C,-C4-alkylcarbonyl, C,-C4-alkoxycarbonyl, cyano, phenyl-C,-C4-alkyl, phenyl eller en aromatisk heteroring valgt blandt gruppen bestående af thienyl, furyl, 25 pyrrolyl, triazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quino-linyl og quinoxalinyl; idet phenyl- og heteroaromatiske dele af en hvilken som helst af de ovennævnte eventuelt er substitueret med en eller flere af halogen, hydroxy, C,-C4-alkyl, halogen-C,-C4-alkyl, CrC4-alkoxy, halogen-C|-C4-alkoxy, CrC4-alkylcarbonyl, CrC4-alkoxycarbonyl, nitro, cyano, phenyl, phenoxy, benzyl eller benzyloxy; og R2 er DK 174963 B1 77 hydrogen, halogen, CrC4-alkyl, halogen-C,-C4-alkyl, C,-C4-alkylcarbonyl, C,-C4-aIkoxy-carbonyl, cyano eller phenyl.
3. Forbindelse ifølge krav 1, kendetegnet ved, at ' 5 A er hydrogen eller halogen, R* er C^-C^alky!, benzyl, C1-C4- alkylcarbonyl, C^-C4-alkoxycarbonyl, cyano, phenyl, thienyl, triazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyrida-zinyl, triazinyl, quinolinyl eller quinoxalinyl, idet de aromatiske eller heteroaromati ske molekyldele af enhver af de foregående eventuelt er substitueret med en eller flere af 10 halogen, C1-C4-alkyl, trif1uormethy1, C1-C4-alkoxy, trifluor-methoxy, nitro, cyano, phenyl eller benzyloxy, og R2 er hydrogen, Ci~C4-alkyl, Ci~C4-alkylcarbonyl, C1-C4~alkoxycarbpny1 , cyano eller phenyl, eller Ri og R2 er forbundne til dannelse af en cyklopentyl eller cyk1ohexy1ring, hvortil der eventuelt er kondenseret en benzenring.
4. Fremgangsmåde til fremstilling af en forbindelse ifølge krav 1,kendetegnet ved reaktion af en forbindelse med formlen (Π): A—|j (II) \ch2x i CH302C >ch.och3 hvor A har den i krav 1 anførte betydning, og X er en bortgående gruppe, med et salt af en oxim med formlen (III): DK 174963 B1 78 R2 / HO.N=C (III) \ Ri hv°r Ri og R2 har den i krav 1 anførte betydning under basiske I t>etl*ngelser. C * Fremgangsmåde til fremstilling af en forbindelse ifølge ^Γθν i, kendetegnet ved ^ (*) behandling af en forbindelse med formlen (IX): k /x /0“' J> N' CH- (IX) R
/ \ 5 CH3°2C CHOR3 med en forbindelse med formlen CH3L; eller (b) eliminering af grundstofferne i methanol fra en forbindelse med formlen (IV): R\ /\ /V A=n \h2 I (IV) R1 CH ch3o2c under sure eller basiske betingelser; eller (c) behandling af en ketoester med formlen (XI): DK 174963 B1 79 I “rA r2-X /°\ CH, (XI) 1/ 1 R CH302C o med et methoxymethyleneringsreagens; hvor A, rI og R2 har den i krav 1 anførte betydning, L er en bortgående gruppe, og R5 er et metalatom.
6. Fungicidt, insekticidt eller miticidt middel omfattende som aktiv bestanddel en forbindelse ifølge krav 1 og et fungicidt, insekticidt eller miticidt acceptabelt bærestof eller fortyndingsmiddel derfor.
7. Fremgangsmåde til bekæmpelse af svampe, kendetegnet ved, at der på en plante, frø af en plante eller vokse- jq stedet for en plante påføres en fungicidt effektiv mængde af en forbindelse ifølge krav 1.
8. Fremgangsmåde til dræbning eller bekæmpelse af insekter eller mider, kendetegnet ved, ved administrering 1 til insektet eller miden eller dets levested af en insekticidt eller miticidt effektiv mængde af en forbindelse ifølge krav « 1. 15
DK198905847A 1988-11-21 1989-11-21 Fungicide, insekticide og miticide forbindelser, fremgangsmåde til fremstilling deraf, midler indeholdende dem og fremgangsmåde til anvendelse heraf DK174963B1 (da)

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