DK150591B - FUNGICID AGENT AND USE OF HYDROXYALKYL TRIAZOLES - Google Patents
FUNGICID AGENT AND USE OF HYDROXYALKYL TRIAZOLES Download PDFInfo
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- DK150591B DK150591B DK216380AA DK216380A DK150591B DK 150591 B DK150591 B DK 150591B DK 216380A A DK216380A A DK 216380AA DK 216380 A DK216380 A DK 216380A DK 150591 B DK150591 B DK 150591B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or 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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- 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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
- C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Description
150591 i o150591 i o
Den foreliggende opfindelse angår et fungicidt middel indeholdende mindst én hydroxyalkyl-triazol.The present invention relates to a fungicidal agent containing at least one hydroxyalkyl triazole.
Det er allerede kendt, at i phenyIdelen substituerede l-phenyl-2-triazolyl-l-ethanoler besidder gode fun-5 gicide egenskaber, jfr. DE-offentliggørelsesskrift nr.It is already known that in the phenyl moiety substituted l-phenyl-2-triazolyl-1-ethanols possess good fungicidal properties, cf. DE publication no.
2.431.407, der svarer til DK-fremlæggelsesskrift nr.2,431.407, which corresponds to DK publication no.
138.601. Deres virkning er imidlertid ikke altid ganske tilfredsstillende, især ved lavere anvendelsesmængder og -koncentrationer.138,601. However, their effect is not always quite satisfactory, especially at lower application rates and concentrations.
10 Det har nu vist sig, at hydroxyalkyl-triazolerne med den almene formel R1 JL ?h 15 <0)-‘r-(CH2>m-R (I> ^-* CH~ I ^It has now been found that the hydroxyalkyl triazoles of the general formula R1 JL? H 15 <0) - 'r- (CH2> m-R (I> ^ - * CH ~ I ^
Az hvilken Az betyder triazolyl, R betyder eventuelt halo-20 gensubstitueret phenyl, betyder eventuelt halogensubstitueret phenyl, og m betyder O eller 1, og deres fysiologisk tålelige syreadditionssalte udviser gode fungicide egenskaber.Az which Az represents triazolyl, R optionally represents halogen-substituted phenyl, optionally represents halogen-substituted phenyl, and m means O or 1, and their physiologically tolerable acid addition salts exhibit good fungicidal properties.
Det fungicide middel ifølge opfindelsen er således 25 ejendommeligt ved, at hydroxyalkyl-triazolen har den ovenfor viste formel (I) eller er et fysiologisk tåleligt syreadditionssalt deraf.Thus, the fungicidal agent of the invention is characterized in that the hydroxyalkyl triazole has the above formula (I) or is a physiologically tolerable acid addition salt thereof.
Overraskende nok udviser de ifølge opfindelsen anvendelige hydroxyalkyl-triazoler med formlen (I) en bed-30 re fungicid virkning end de ovennævnte, fra teknikkens stade kendte, substituerede l-phenyl-2-triazol-l-ethanoler, der er i kemisk og virkningsmæssig henseende nærtstående forbindelser. De ifølge opfindelsen anvendelige forbindelser udgør således en berigelse af teknikken.Surprisingly, the hydroxyalkyl triazoles of formula (I) useful according to the invention exhibit a better fungicidal effect than the above-mentioned substituted, prior art substituted l-phenyl-2-triazole-1-ethanols which are in chemical and effective form. in respect of related relations. Thus, the compounds of this invention enrich the technique.
35 Opfindelsen angår også anvendelsen af forbindelserneThe invention also relates to the use of the compounds
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150591 2 (I) eller fysiologisk syreadditionssalte deraf til bekæmpelse af svampe.(I) or physiological acid addition salts thereof to control fungi.
Blandt de ifølge opfindelsen anvendelige hydroxy-alkyl-triazoler med formlen (I) foretrækkes de forbindel-5 ser, i hvilke Az betyder 1,2,4-triazol-l-yl eller 1,2,4--triazol-4-yl, R betyder eventuelt med fluor, chlor eller brom substitueret phenyl, R^ betyder eventuelt med fluor, chlor eller brom substitueret phenyl, og m betyder 0 eller 1.Among the hydroxyalkyl triazoles of the invention useful in the formula (I), the compounds in which Az means 1,2,4-triazol-1-yl or 1,2,4-triazol-4-yl are preferred. R is optionally substituted by fluorine, chlorine or bromine, phenyl, R4 is optionally substituted by fluorine, chlorine or bromine, and m is 0 or 1.
10 De ifølge opfindelsen anvendte virksomme forbin delser og deres syreadditionssalte kan fremstilles ved, at man a) omsætter triazolylmethyl-phenyl-ketoner med formlen 1.The active compounds used according to the invention and their acid addition salts can be prepared by a) reacting triazolylmethyl-phenyl-ketones of formula 1.
/"'tX-c-CH-.-Az (II) vxv 2 20 i hvilken Az og R^ har den ovenfor angivne betydning, med en Grignard-forbindelse med formlen R " (CH2)m - Mg - X (III) 25 i hvilken R og m har den ovenfor angivne betydning, og X betyder halogen, især chlor eller brom, i nærværelse af et for en Grignard-reaktion sædvanligt opløsningsmiddel, f.eks. fortrinsvis ether, ved temperaturer mellem ca. 30 og ca. 80°C, eller at man 30 b) omsætter 1-halogen-alkylalkoholer med formlen R1in which Az and R 2 have the meaning given above, with a Grignard compound of formula R "(CH 2) m - Mg - X (III) Wherein R and m are as defined above and X is halogen, especially chlorine or bromine, in the presence of a usual solvent for a Grignard reaction, e.g. preferably ether, at temperatures between ca. 30 and approx. Or b) reacting 1-halo-alkyl alcohols of formula R 1
\ ?H\? H
νδ)-?"<εΗ2^-κ (iv) 35 CH2νδ) -? "<εΗ2 ^ -κ (iv) 35 CH2
YY
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150591 3 i hvilken R, og m har den ovenfor angivne betydning, og Y betyder halogen, især chlor eller brom, med tria-zol, eventuelt i nærværelse af et syrebindende middel, f.eks. et overskud af triazol, og eventuelt i nærværel-5 se af et indifferent organisk opløsningsmiddel, f.eks. acetonitril, ved temperaturer mellem 30 og 200°C, fortrinsvis ved opløsningsmidlets kogetemperatur. I mange tilfælde viser det sig at være fordelagtigt at anvende triazolerne i form af deres alkalimetalsalte, f.eks. na-10 trium- eller kaliumsaltet.Wherein R and m are as defined above and Y is halogen, especially chlorine or bromine, with triazole, optionally in the presence of an acid-binding agent, e.g. an excess of triazole, and optionally in the presence of an inert organic solvent, e.g. acetonitrile, at temperatures between 30 and 200 ° C, preferably at the boiling temperature of the solvent. In many cases it is found to be advantageous to use the triazoles in the form of their alkali metal salts, e.g. the sodium or potassium salt.
De ifølge opfindelsen anvendte virksomme stoffer, i hvilke m har værdien 0, kan også fås ved hjælp af en yderligere fremgangsmåde, ved hvilken man c) omsætter oxiraner med formlen 15 R1 \ (v) 20 CH2—-b hvilken R og R1 har den ovenfor angivne betydning, med triazol i nærværelse af et alkalimetalalkoholat, f.eks. natriummethylat, og i nærværelse af et indifferent orga-25 nisk opløsningsmiddel, f.eks. dimethylformamid, ved temperaturer mellem 30 og 100°C.The active substances used according to the invention, in which m has the value 0, can also be obtained by a further process by which c) reacting oxiranes of the formula 15 R1 \ (v) 20 CH2 - b which R and R1 have the above, with triazole in the presence of an alkali metal alcoholate, e.g. sodium methylate, and in the presence of an inert organic solvent, e.g. dimethylformamide, at temperatures between 30 and 100 ° C.
Triazolylmethyl-phenyl-ketonerne med formlen (II) er hidtil ukendte. De kan imidlertid fremstilles på almindelig gængs og kendt måde, idet man omsætter tilsva-30 rende phenacylhalogenider (dvs. a-halogen-acetophenon--derivater) med triazol i nærværelse af et fortyndingsmiddel, f.eks. dimethylformamid, og i nærværelse af et syrebindende middel, især et overskud af triazol, ved temperaturer mellem 20 og 80°C.The triazolylmethyl phenyl ketones of formula (II) are novel. However, they can be prepared in the usual and known manner by reacting the corresponding phenacyl halides (i.e., α-halo-acetophenone derivatives) with triazole in the presence of a diluent, e.g. dimethylformamide, and in the presence of an acid-binding agent, especially an excess of triazole, at temperatures between 20 and 80 ° C.
35 Grignard-forbindelserne med formlen (III) er al- 150591 4 o mindelicjt kendte forbindelser fra den organiske kemi.The Grignard compounds of formula (III) are generally known compounds of organic chemistry.
1-Halogen-alkylalkoholerne med formlen (IV) er hidtil ukendte. De kan imidlertid fremstilles på almindelig gængs og kendt måde, idet man omsætter tilsvarende 5 phenacylhalogenider med Grignard-forbindelser med formlen (III) i overensstemmelse med den ovenfor beskrevne fremgangsmådevariant a) .The 1-haloalkyl alcohols of formula (IV) are novel. However, they can be prepared in the usual and known manner by reacting similarly 5 phenacyl halides with Grignard compounds of formula (III) according to the process variant described above a).
Oxiranerne med formlen (V) er hidtil ukendte forbindelser og kan fås på den måde, at man omsætter til-10 svarende ketoner enten med dimethyloxosulfonium-methylid på i og for sig kendt måde i nærværelse af et fortyndingsmiddel, f.eks. dimethylsulfoxid, ved temperaturer mellem 20 og 80°C, eller med trimethylsulfonium-methylsulfat på i og for sig kendt måde i nærværelse af et tofasesystem 15 og eventuelt i nærværelse af en faseoverføringskatalysator, ved temperaturer mellem 0 og 100°C.The oxiranes of formula (V) are novel compounds and can be obtained by reacting corresponding ketones either with dimethyloxosulfonium methylide in a manner known per se in the presence of a diluent, e.g. dimethylsulfoxide, at temperatures between 20 and 80 ° C, or with trimethylsulfonium methylsulfate in a manner known per se in the presence of a two-phase system 15 and optionally in the presence of a phase transfer catalyst, at temperatures between 0 and 100 ° C.
Til fremstilling af syreadditionssalte af forbindelser med formlen (I) kommer alle fysiologisk tålelige syrer på tale. Hertil hører fortrinsvis hydrogenhalogenid-20 syrerne, f.eks. hydrogenchloridsyre og hydrogenbromidsyre, især hydrogenchloridsyre, og endvidere phosphorsyre, salpetersyre, svovlsyre, mono- og bifunktionelle carboxylsyrer og hydroxycarboxylsyrer, f.eks. eddikesyre, maleinsy-re, ravsyre, fumarsyre, vinsyre, citronsyre, salicylsyre, 25 sorbinsyre, mælkesyre samt sulfonsyrer, f.eks. p-toluen-sulfonsyre og 1,5-naphthalendisulfonsyre.For the preparation of acid addition salts of compounds of formula (I), all physiologically tolerable acids are discussed. Preferably, the hydrogen halide acids, e.g. hydrochloric acid and hydrobromic acid, especially hydrochloric acid, and furthermore phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, e.g. acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid and sulfonic acids, e.g. p-toluene sulfonic acid and 1,5-naphthalene disulfonic acid.
Saltene af forbindelserne med formlen (I) kan fås på en enkel måde ved hjælp af gængse saltdannelsesmetoder, f.eks. ved opløsning af en forbindelse med formlen (I) i 30 et egnet indifferent opløsningsmiddel og tilsætning af en syre, f.eks. saltsyre, og saltene kan isoleres på kendt måde, f.eks. ved filtrering, og eventuelt renses ved vask med et indifferent organisk opløsningsmiddel.The salts of the compounds of formula (I) can be obtained in a simple manner by conventional salt formation methods, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding an acid, e.g. hydrochloric acid, and the salts can be isolated in known manner, e.g. by filtration, and optionally purified by washing with an inert organic solvent.
De virksomme forbindelser, der anvendes ifølge op-35 findelsen, udviser en kraftig mikrobiocid virkning og kanThe active compounds used according to the invention exhibit a strong microbiocidal effect and can
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150591 5 i praksis anvendes til bekæmpelse af uønskede mikroorganismer. De virksomme forbindelser er egnede til anvendelse som plantebeskyttelsesmidler.In practice, it is used to control undesirable microorganisms. The active compounds are suitable for use as plant protection agents.
Fungicide midler anvendes ved plantebeskyttelse 5 til bekæmpelse af Plasmodiophoromycetes, Oomycetes, Chy-tridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes . og Deuteromycetes.Fungicidal agents are used in plant protection 5 to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes. and Deuteromycetes.
Planternes gode tålelighed over for de virksomme forbindelser i de til bekæmpelse af plantesygdomme nødven-10 dige koncentrationer tillader en behandling af over jorden værende plantedele, af plante- og såsæd og af jorden.The good tolerability of the plants to the active compounds in the necessary concentrations to control plant diseases permits the treatment of plant parts, of plant and seed and of the soil.
Som plantebeskyttelsesmidler kan de virksomme forbindelser, der anvendes ifølge opfindelsen, med særligt godt resultat anvendes til bekæmpelse af Podosphaera-, 15 Uromyces- og Erysiphe-arter, samt mod fremkalderen af den ægte æblemeldug (Podosphaera leucotricha), fremkalderen af bønnerust (Uromyces phaseoli) og mod fremkalderen af ægte agurkemeldug (Erysiphe cichoacearum). Gode resultater opnås også ved bekæmpelse af kornsygdomme, f.eks.As plant protection agents, the active compounds used according to the invention can be used with particular good results in the control of Podosphaera, 15 Uromyces and Erysiphe species, and against the inducer of the true apple dew (Podosphaera leucotricha), the developer of bean rust (Uromyces phaseoli) and against the inducer of true cucumber mildew (Erysiphe cichoacearum). Good results are also obtained by combating grain diseases, e.g.
20 kornmeldug og kornrust.20 grain mildew and grain rust.
I bestemte anvendelsesmængder udviser de her omhandlede virksomme stoffer også en vækstregulerende virkning.In certain applications, the active substances in question also exhibit a growth-regulating effect.
De virksomme forbindelser kan overføres i de gæng-25 se præparater, såsom opløsninger, emulsioner, suspensio ner, pulvere, skum, pastaer, granulater, aerosoler, med virksomme forbindelser imprægnerede, naturlige og syntetiske forbindelser, indkapslinger i fineste form i polymere forbindelser og i indhylningsmasser til såsæd, og 30 endvidere i præparater med tændsatser, såsom rygningspatroner, -dåser og -spiraler, samt ULV-kold- og varmtåge-dannelsespræparater.The active compounds can be transferred into the usual compositions such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, with active compounds impregnated, natural and synthetic compounds, encapsulations in finest form in polymeric compounds and in seed compositions, and furthermore in primer compositions such as smoking cartridges, cans and coils, as well as ULV cold and hot mist formation compositions.
Disse præparater fremstilles på kendt måde, f.eks. ved blanding af de aktive forbindelser med strækkemidler, 35 dvs. flydende opløsningsmidler, under tryk stående, for- 0 150591 6 tættede gasser og/eller faste bærestoffer, eventuelt under anvendelse af overfladeaktive midler, dvs. emulgeringsmidler og/eller dispergeringsmidler og/eller skumfrembrin-gende midler. Hvis der anvendes vand som strækkemiddel, kan 5 der f.eks. også anvendes organiske opløsningsmidler som hjælpeopløsningsmiddel. På tale som flydende opløsningsmidler kommer først og fremmest aromater, såsom xylen, toluen eller alkylnaphthalener, chlorerede aromatiske eller aliphatiske carbonhydrider, såsom chlorbenzener, chlor-10 ethylener eller methylenchlorid, aliphatiske carbonhydri der, såsom cyclohexan, eller paraffiner, f.eks. jordolie-fraktioner, alkoholer, f.eks. butanol eller glycol samt deres ethere og estere, ketoner såsom acetone, methylethyl-keton, methylisobutylketon eller cyclohexanon, stærkt po-15 lære opløsningsmidler, såsom dimethylformamid og dimethyl-sulfoxid, samt vand. Med fortættede, gasformige strækkemidler eller bærestoffer menes sådanne væsker, der er gasformige ved normal temperatur og under normalt tryk, f.eks. aerosol-drivgasser, såsom halogencarbonhydrider, samt bu-20 tan, propan, nitrogen og carbondioxid. På tale som faste bærestoffer kommer naturlige stenmelarter, såsom kaoliner, lerjordarter, talkum, kridt, kvarts, attapulgit, montmo-rillonit eller diatoméjord, og syntetiske stenmelarter, såsom højdispers kiselsyre, aluminiumoxid og silicater. På 25 tale som faste bærestoffer for granulater kommer brudte og fraktionerede stenarter, såsom calcit, marmor, pimpsten, sepiolith og dolomit, samt syntetiske granulater ud fra uorganiske og organiske melarter samt granulater ud fra organisk materiale, såsom savsmuld, kokosnøddeskaller, majs-30 kolber og tobaksstængler. På tale som emulgeringsmidler og/eller skumfrembringende midler kommer ikke-ioniske og anioniske emulgatorer, såsom polyoxyethylen-fedtsyreeste-re, polyoxyethylen-fedtalkoholethere, f.eks. alkylaryl-polyglycolethere, alkylsulfonater, alkylsulfater, aryl-35 sulfonater samt proteinhydrolysater, og som dispergerings-These compositions are prepared in a known manner, e.g. by mixing the active compounds with excipients, i.e. liquid solvents, pressurized, saturated gases and / or solid carriers, optionally using surfactants, ie. emulsifiers and / or dispersants and / or foaming agents. If water is used as an extender, e.g. also organic solvents are used as auxiliary solvent. Speaking as liquid solvents come primarily aromatics such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane, or paraffins, e.g. petroleum fractions, alcohols, e.g. butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polymeric solvents such as dimethylformamide and dimethyl sulfoxide, and water. By liquefied, gaseous extenders or carriers is meant such liquids which are gaseous at normal temperature and under normal pressure, e.g. aerosol propellants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Speaking as solid carriers come natural stone melts, such as kaolines, clay soils, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone melts such as high-dispersion silica, alumina and silicates. Speaking as solid carriers for granules, broken and fractional rocks such as calcite, marble, pumice, sepiolith and dolomite, as well as synthetic granules come from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn flasks and tobacco stalks. Speaking as emulsifiers and / or foaming agents, nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolysates, and as dispersants.
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150591 7 midler f.eks. lignin-sulfitaffaldslud og methylcellulose.7 agents e.g. lignin sulfite waste liquor and methyl cellulose.
I præparaterne kan der anvendes klæbemidler, såsom carboxymethylcellulose og naturlige og syntetiske pulver-formige, kornformige eller latexformige polymere, såsom 5 gummi arabicum, polyvinylalkohol og polyvinylacetat.Adhesives such as carboxymethyl cellulose and natural and synthetic powdered, granular or latex polymers such as 5 gum arabic, polyvinyl alcohol and polyvinyl acetate can be used in the compositions.
Der kan også anvendes farvestoffer, såsom uorganiske pigmenter, f.eks. jernoxid, titanoxid og ferrocyanblåt, og organiske farvestoffer, såsom alizarin- og azometalphtha-locyaninfarvestoffer, samt spornæringsstoffer, såsom salte 10 af jern, mangan, bor, kobber, cobalt, molybden og zink.Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide and ferrocyan blue, and organic dyes such as alizarin and azometalphtha-locyanin dyes, as well as trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Præparaterne indeholder almindeligvis mellem 0,1 og 95 vægt% aktiv forbindelse, fortrinsvis mellem 0,5 og 90%.The compositions generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
I præparaterne eller i de forskellige anvendelses-15 former kan de her omhandlede, aktive forbindelser foreligge i blanding med andre, kendte, aktive forbindelser, såsom fungicider, insekticider, acaricider, nematodicider, herbicider, beskyttelsesstoffer mod fugleangreb, vækststoffer, plantenæringsstoffer og jordstrukturforbedringsmidler.In the compositions or in the various forms of use, the present active compounds may be in admixture with other known active compounds such as fungicides, insecticides, acaricides, nematodicides, herbicides, bird protection agents, growth substances, plant nutrients and soil structure enhancers.
20 De aktive forbindelser kan anvendes som sådanne, i form af deres præparater eller de derudfra ved yderligere fortynding tilberedte anvendelsesformer, såsom brugsfærdige opløsninger, emulsioner, suspensioner, pulvere, pastaer og granulater. Anvendelsen sker på gængs måde, f.eks.The active compounds can be used as such, in the form of their preparations or the forms of use prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. The application is carried out in a conventional manner, e.g.
25 ved udhældning, dypning, sprøjtning, forstøvning, tågedan-nelse, fordampning, injektion, opslæmning, udstrygning, pudring, udstrøning, tørbejdsning, fugtighedsbejdsning, vådbejdsning, opslæmningsbejdsning eller inkrustering.25 by pouring, dipping, spraying, atomizing, misting, evaporation, injection, slurry, smearing, powdering, scrubbing, drying, moisturizing, wetworking, slurrying or encrusting.
Ved behandlingen af plantedelene kan koncentratio-30 nerne af aktiv forbindelse i anvendelsesformerne varieres inden for et større område. De ligger almindeligvis på mellem 1 og 0,0001 vægt%, fortrinsvis mellem 0,5 og 0,001%.In treating the plant parts, the concentrations of active compound in the forms of use can be varied within a larger range. They are usually between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.
Ved såsædbehandling kræves almindeligvis mængder af aktiv forbindelse på fra 0,001 til 50 g pr. kg såsæd, 35 fortrinsvis fra 0,01 til 10 g.In the case of seed treatment, amounts of active compound of 0.001 to 50 g per gram are usually required. preferably from 0.01 to 10 g.
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150591 8150591 8
Til jordbehandling kræves der koncentrationer af aktiv forbindelse på fra 0,00001 til 0,1 vægt% på virkningsstedet, fortrinsvis fra 0,0001 til 0,02 vægt%.For soil treatment, active compound concentrations of from 0.00001 to 0.1% by weight at the site of action are required, preferably from 0.0001 to 0.02% by weight.
I de følgende eksempler anvendes de følgende for-5 bindeiser (A)-(F) som sammenligningsforbindelser:In the following examples, the following linkage terminals (A) - (F) are used as comparison compounds:
°H _N° H _N
(A) 10(A) 10
0H N0H N
(B> cl-{o}-(o)-iH-CH2-^Z(B> cl- {o} - (o) -iH-CH 2 - ^ Z
_ OH _N_ OH _N
15 (C) Br- ^ Q^) -CH-CH2-l/~(C) Br- (Q 1) -CH-CH 2 -l / ~
?H? H
(D) Cl- ζQy -CH-CH2-l·^ _ 20(D) Cl- ζQy -CH-CH2-l · 20
OHOH
(E) h3 c- {q) -ch-ch2-/^(E) h3 c- {q) -ch-ch2 - / ^
SO.HSO.H
25 ?H ^25? H ^
(F) C1-/Q)-ch“ch2-N x 1/2 lOjOJ(F) C1- / Q) -ch «ch2-N x 1/2 lOjOJ
Nci so3hNci so3h
OISLAND
150591 9150591 9
Eksempel AExample A
Podospaera-forsøg (æble)/protektivt.Podospaera trial (apple) / protective.
Opløsningsmiddel: 4,7 vægtdele acetoneSolvent: 4.7 parts by weight of acetone
Emulgator: 0,3 vægtdele alkylarylpolyglycolether 5 Vand: 95,0 vægtdeleEmulsifier: 0.3 parts by weight of alkylaryl polyglycol ether 5 Water: 95.0 parts by weight
Man blander den til opnåelse af den ønskede koncentration af virksomt stof i sprøjtevæsken nødvendige mængde virksomt stof med den angivne mængde af opløsningsmidlet og fortynder koncentratet med den angivne mængde vand, der in-10 deholder de nævnte tilsætninger.Mix the required amount of active substance necessary to obtain the desired concentration of active substance in the spray liquid with the indicated amount of the solvent and dilute the concentrate with the specified amount of water containing the said additives.
Med sprøjtevæsken sprøjtes unge æblefrøplanter, der befinder sig på det 4- til 6-bladede stadium, indtil de er drypvåde. Planterne forbliver i 24 timer ved 20°C og en relativ luftfugtighed på 70% i væksthus. Derefter inokuleres 15 de ved bestøvning med konidier af æblemeldugfremkalderen (Podosphaera leucotricha) og anbringes i et væksthus med en temperatur på 21-23°C og en relativ luftfugtighed på 70%.With the spray liquid, young apple seedlings that are on the 4- to 6-leaf stage are sprayed until they are dripping wet. The plants remain for 24 hours at 20 ° C and a relative humidity of 70% in the greenhouse. Then, they are inoculated with conidia by the conjugates of the apple cloth developer (Podosphaera leucotricha) and placed in a greenhouse with a temperature of 21-23 ° C and a relative humidity of 70%.
10 dage efter inokuleringen bestemmes angrebet på frøplanterne. De opnåede bonitetsværdier omregnes til pro-20 cent angreb. 0% betyder intet angreb, og 100% betyder, at planterne er angrebet totalt.Ten days after inoculation, the attack on the seedlings is determined. The obtained goodness values are converted into per cent attack. 0% means no attack and 100% means the plants are totally attacked.
Ved dette forsøg viser f.eks. de følgende forbindelser en særdeles god virkning, der er tydeligt overlegen i forhold til virkningen af de fra teknikkens stade 25 kendte forbindelser (A) og (B): forbindelserne ifølge fremstillingseksemplerne nr. 1 og 3, jfr. den følgende tabel A.In this experiment, e.g. the following compounds have a very good effect which is clearly superior to the effect of the compounds (A) and (B) known in the prior art: the compounds of Preparative Examples Nos. 1 and 3, cf. the following Table A.
10 150591 o10 150591 o
Tabel ATable A
Podosphaera-forsøg/protekvivtPodosphaera test / protekvivt
Angreb i % ved en koncentration af virksomt stofAttack in% at a concentration of active substance
Virksomt stof_på 0,001%_ 5Active substance_ at 0.001% _ 5
0H N0H N
{0)-(0)-^2-^ 100 (A) (kendt) 10{0) - (0) - ^ 2- ^ 100 (A) (known) 10
__ OH __N__ OH __N
cl-{o)-{o)-iH-CH2-Q 100 (B) (kendt) 15 _ _ OH _ {o)-(o)-Hh2-(o)-c1 51 CH„ / ' i Cl Λ 20 (1) N_!c1- (o) - {o) -iH-CH2-Q 100 (B) (known) 15 _ _ OH _ {o) - (o) -Hh2- (o) -c1 51 CH2 20 (1) N_!
OHOH
{§>-<§>-fCH2-{0) 0 CH« 25 Λ (3, Jul{§> - <§> -fCH2- {0) 0 CH «25 Λ (3, Jul
Eksempel BExample B
Erysiphe-forsøg (agurker)/protektivt.Erysiphe trial (cucumbers) / protective.
30 Opløsningsmiddel: 4,7 vægtdele acetoneSolvent: 4.7 parts by weight of acetone
Emulgator: 0,3 vægtdele alkylarylpolyglycoletherEmulsifier: 0.3 parts by weight of alkylaryl polyglycol ether
Vand: 95,0 vægtdele.Water: 95.0 parts by weight.
Man blander den til opnåelse af den ønskede koncentration af virksomt stof i sprøjtevæsken nødvendige 35 mængde virksomt stof med den angivne mængde af opløsnings- 11 150591 o midlet og fortynder koncentratet med den angivne mængde vand, der indeholder de nævnte tilsætninger.To obtain the desired concentration of active substance in the spray liquid, mix the required amount of active substance with the specified amount of the solvent and dilute the concentrate with the indicated amount of water containing said additives.
Med sprøjtevæsken sprøjtes unge agurkeplanter med c'a. 3 løvblade, indtil disse er drypvåde. Agurkeplanter-5 ne forbliver til tørring i 24 timer i væksthus. Derpå bestøves de til inokulering med konidier af svampen Erysi-phe cichoracearum. Planterne anbringes derefter ved 23--24°C og ved en relativ luftfugtighed på ca. 75% i et væksthus.With the spray liquid, young cucumber plants are sprayed with c'a. 3 leaves until these are dripping wet. The cucumber plants remain for drying for 24 hours in a greenhouse. They are then sprayed for inoculation with conidia of the fungus Erysi-phe cichoracearum. The plants are then placed at 23--24 ° C and at a relative humidity of approx. 75% in a greenhouse.
10 Efter 12 dage bestemmes angrebet på agurkeplanter- ne. De opnåede bonitetsværdier omregnes til % angreb. 0% betyder intet angreb, og 100% betyder, at planterne er totalt angrebet.10 After 12 days, the attack on the cucumber plants is determined. The obtained goodness values are converted to% attack. 0% means no attack and 100% means the plants are totally attacked.
Ved dette forsøg viser f.eks. de følgende forbin-15 delser en særdeles god virkning, der er overlegen i forhold til virkningen af de fra teknikkens stade kendte forbindelser (C) og (D): forbindelserne ifølge fremstillingseksemplerne nr. 1, 7, 10, 12, 14 og 5, jfr. de følgende tabeller B^ og B2· o 12 150591In this experiment, e.g. the following compounds have a very good effect superior to the effect of the prior art compounds (C) and (D): the compounds of Preparation Examples Nos. 1, 7, 10, 12, 14 and 5, cf. the following Tables B ^ and B2 · o 12 150591
Tabel B-^Table B-
Erysiphe-forsøg (agurker). / protektivtErysiphe trial (cucumbers). / protective
Angreb i % ved en koncentration af virksomt stof påAttack in% at a concentration of active substance on
Virksomt stof _0/005%_Active substance _0 / 005% _
__ 0H N__ 0H N
10 Br-^o)-CH-CH2-Q 75 (C)(Kendt)(Br) (CH) -CH-CH 2 -Q 75 (C) (Known)
_ OH_ OH
15 <o><g>tv©-01 ?H2 Cl·^ Λ (1) Jf_jl 2015 <o> <g> tv © -01? H2 Cl · ^ Λ (1) Jf_jl 20
OHOH
<ο)-(ο)±^-(9}-01 ?H2 “ fi<ο) - (ο) ± ^ - (9} -01? H2 “fi
OHOH
30 (0)-(0)-^2-(0)-=1 2530 (0) - (0) - ^ 2- (0) - = 1 25
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(10) N_11 13 150591 o . ..(10) N_11 13 150591 o. ..
Tabel B2Table B2
Erysiphe-forsøg (agurker) / protektivtErysiphe trial (cucumbers) / protective
Angreb i % ved en koncentra- 5 tion af virksomt stof påAttack in% at an active substance concentration of
Virksomt stof 0,0005%Active substance 0.0005%
0H N0H N
ci-(^-iH-cH2-NQ 100 (D) (Kendt)ci - (1H-cH2-NQ 100 (D) (Known)
OHOH
15 cl-<o}-<o}ir<o}-cl CEL· r ^ (12) N_[i 2015 cl- <o} - <o} ir <o} -cl CEL · r ^ (12) N_ [i 20
OHOH
25 i" IlC1 (14) “--'25 in "IlC1 (14)" -
OHOH
30 <oV{o}030 <oV {o} 0
Cl ?H2 Λ (5) N_!l o 14 150591Cl? H2 Λ (5) N_! L o 14 150591
Eksempel CExample C
Uromyces-forsøg (bønnerust) / protektivt.Uromyces trial (bean rust) / protective.
Opløsningsmiddel: 4,7 vægtdele acetoneSolvent: 4.7 parts by weight of acetone
Emulgator: 0,3 vægtdele alkylarylpoly- 5 glycoletiierEmulsifier: 0.3 parts by weight of alkylaryl polyglycolethyls
Vand: 95,0 vægtdele.Water: 95.0 parts by weight.
Man blander den til opnåelse af den Ønskede koncen tration af virksomt stof i sprøjtevæsken nødvendige mæng-10 de virksomt stof med den angivne mængde af opløsningsmid let og fortynder koncentratet med den angivne mængde vand, der indeholder de nævnte tilsætninger.To obtain the desired concentration of active substance in the spray liquid, mix the active substance with the specified amount of solvent lightly and dilute the concentrate with the specified amount of water containing the said additives.
Med sprøjtevæsken sprøjter man unge bønneplanter, der befinder sig på det 2-bladede stadium, indtil dryp-15 vådhed. Planterne forbliver til tørring i 24 timer ved 20-22°C og en relativ luftfugtighed på 70% i væksthus.With the spray liquid, young bean plants that are on the 2-leaf stage are sprayed until dripping-15 wetness. The plants remain dry for 24 hours at 20-22 ° C and a relative humidity of 70% in greenhouse.
Derefter inokuleres de med en vandig uredosporesuspension af bønnerustfremkalderen (Uromyces phaseoli) og inkuberes i 24 timer i et mørkt fugtigt kammer ved 20-22°C og 100%'s 20 relativ luftfugtighed.Then they are inoculated with an aqueous uredospore suspension of the bean rust developer (Uromyces phaseoli) and incubated for 24 hours in a dark humid chamber at 20-22 ° C and 100% relative humidity.
Planterne anbringes derpå under intensiv belysning i 9 dage ved 20-22°C og en relativ luftfugtighed på 70-80% i et væksthus.The plants are then placed under intense lighting for 9 days at 20-22 ° C and a relative humidity of 70-80% in a greenhouse.
10 dage efter inokuleringen bestemmes angrebet på 25 planterne. De opnåede bonitetsværdier omregnes til procent angreb. 0% betyder intet angreb, og 100% betyder, at planterne er angrebet totalt.Ten days after inoculation, the attack on the 25 plants is determined. The obtained quality values are converted to percent attack. 0% means no attack and 100% means the plants are totally attacked.
Ved dette forsøg viser f,eks. de følgende forbindelser en særdeles god virkning, der er tydeligt overlegen 30 i forhold til virkningen af den fra teknikkens stade kendte forbindelse (E): forbindelserne ifølge fremstillingseksemplerne nr. 12, 14 og 5, jfr. den følgende tabel C.In this experiment, e.g. the following compounds have a very good effect which is clearly superior to the effect of the prior art compound (E): the compounds of Preparation Examples Nos. 12, 14 and 5, cf. the following table C.
o 15 150591o 15 150591
Tabel CTable C
Uromyces-forsøg / protektivtUromyces trial / protective
Angreb i % ved en koncentration af virksomt stof på 5 Virksomt stof 0,001%Attack in% at a concentration of active substance of 5 Active substance 0.001%
0H0H
H3C-{0)-iH-CH2-^J 100 10 (E) (Kendt)H3C- (O) -iH-CH2- ^ J 100 10 (E) (Known)
OHOH
=.-/0)-(0)-^(0)-=1 15 Urt« 1 ^ Λ (12) I_li= .- / 0) - (0) - ^ (0) - = 1 15 Hours «1 ^ Λ (12) I_li
20 OH20 OH
• 2 Cl oil 25 (14)• 2 Cl oil 25 (14)
OHOH
30 XC1 ,2 /N>30 XC1, 2 / N>
0 I0 I
N_UNOW
(5) o 16 150591(5) o 16 150591
Eksempel DExample D
Spirebehandlingsforsøg / kornmeldug / protektivt v (bladødelæggende mykose).Sprouting experiments / cereal mildew / protective v (leaf-destroying mycosis).
Til fremstilling af et hensigtsmæssigt præparat af 5 virksomt stof optager man 0,25 vægtdele virksomt stof i 25 vægtdele dimethylformamid og 0,06 vægtdele emulgator (alkylarylpolyglycolether), og der tilsættes 975 vægtdele vand. Koncentratet fortyndes med vand til den ønskede slutkoncentration i sprøjtepræparatet.To prepare a suitable composition of 5 active substance, 0.25 parts by weight of active substance is taken up in 25 parts by weight of dimethylformamide and 0.06 parts by weight of emulsifier (alkylaryl polyglycol ether) and 975 parts by weight of water are added. Dilute the concentrate with water to the desired final concentration in the syringe preparation.
10 Til afprøvning af den protektive virkning sprøjter man énbladede unge bygplanter af sorten Amsel dugvåde med præparatet af det virksomme stof. Efter tørring bestøves bygplanterne med sporer af Erysiphe graminis var.hordei.10 To test the protective effect, one-leaf young barley plants of the Amsel dewy variety are sprayed with the preparation of the active substance. After drying, the barley plants are sprayed with spores of Erysiphe graminis var.hordei.
Efter 6 dages opholdstid for planterne ved en tem-15 peratur på 21-22°C og en luftfugtighed på 80-90% bedømmes angrebet på planterne med meldugblegner. Angrebsgraden udtrykkes i procent af angrebet på de ubehandlede kontrolplanter. Herved betyder 0% intet angreb og 100% samme angrebsgrad som ved de ubehandlede kontrolplanter. Jo mindre 20 meldugangrebet er, desto mere aktivt er det virksomme stof.After 6 days of residence of the plants at a temperature of 21-22 ° C and a humidity of 80-90%, the attack on the plants is assessed by mildew bleaching. The degree of attack is expressed as a percentage of the attack on the untreated control plants. By this, 0% means no attack and 100% the same degree of attack as with the untreated control plants. The smaller the mildew attack, the more active the active substance.
Ved dette forsøg viser f.eks. de følgende forbindelser en særdeles god virkning, der er tydeligt overlegen i forhold til virkningen af de fra teknikkens stade kendte forbindelser (Dj og (F): forbindelserne ifølge fremstil-25 lingseksemplerne nr. 1, 3, 7, 10, 12, 14 og 5, jfr. den følgende tabel D.In this experiment, e.g. the following compounds have a very good effect which is clearly superior to the effect of the prior art compounds (Dj and (F)): the compounds of Preparation Examples Nos. 1, 3, 7, 10, 12, 14 and 5, cf. the following table D.
o 17 150591o 17 150591
Tabel DTable D
Spirebehandlingsforsøg / kornmeldug / protektivtSprouting trials / grain mildew / protective
Koncentration af virksomt stof i Angreb i % sprøjtevæsken af de ubehand-Concentration of active substance in Attack in% spray liquid of the untreated
Virksomt stof i vægtprocent lede kontrollerActive substance in weight percent lead controls
OH NOH N
Cl-/n\-CH-CH i 0,025 100Cl- / n \ -CH-CH in 0.025 100
10 Siv 2 HiJ10 Siv 2 HiJ
(D) (Kendt) 15 C1-/q\_CH-CH2-N _j 0,025 100 ^Cl SO^H t 3 (F) x 1/2 foTol 20 (Kendt) so3h(D) (Known) 15 C1- / q \ _CH-CH2-N _j 0.025 100 ^ Cl SO ^ H t 3 (F) x 1/2 foTol 20 (Known) so3h
OHOH
“ <o>-<o)-«-.-<oV* -/ v-/ CH - 0,025 0,0 ' C1 li ^ 11 ri"<o> - <o) -" -.- <oV * - / v- / CH - 0.025 0.0 'C1 li ^ 11 ri
(1) N U(1) N U
3030
_ OH_ OH
°'025 3'8 1 2° '025 3'8 1 2
(3) N U(3) N U
35 o 18 15059135 o 18 150591
Tabel D (fortsat)Table D (continued)
Spirebehandlingsforsøg / kornmeldug / protektivtSprouting trials / grain mildew / protective
Koncentration af virksomt stof i Angreb i % 5 sprøjtevæsken af de ubehand-Concentration of active substance in Attack in% 5 spray liquid of the untreated
Virksomt stof i vægtprocent lede kontroller OH _ 10 ,2 0,025 12,5 Λ (7) N ilActive substance in weight percent lead controls OH _ 10, 2 0.025 12.5 Λ (7) N il
OHOH
15 <®-(o)-rCH2-(o)-cl N-<C1 '-/ CH2 v/ 0,025 16,3<O- (o) -rCH2- (o) -cl N- <C1 '- / CH2 v / 0.025 16.3
An (10) N il 20In (10) N il 20
OHOH
C1-(0>-(0>-?"(0>-C1 0,025 12,5 -1 ' ch '- I ^C1- (0> - (0> -? "(0> -C1 0.025 12.5 -1 'ch' - I
/ N/ N
25 (12) N_il OH _ (β) 0/025 16/3 30 Cl (\ |f (14) N_Li25 (12) N_il OH _ (β) 0/025 16/3 30 Cl (\ | f (14) N_Li
_ OH_ OH
35 y~^Q^~?~^Q^~cl 0,025 11,3 35 Ncl ^ .Nn35 y ~ ^ Q ^ ~? ~ ^ Q ^ ~ cl 0.025 11.3 35 Ncl ^ .Nn
/ N/ N
(5) N_il o 19 150591(5) N_il o 19 150591
Eksempel EExample E
Spirebehandlingsforsøg / kornrust / protektivt (bladødelæggende mykose).Sprouting trial / cereal rust / protective (leaf-destroying mycosis).
5 Til fremstilling af et hensigtsmæssigt præparat af virksomt stof optager man 0,25 vægtdele virksomt stof i 25 vægtdele dimethylformamid og 0,06 vægtdele emulgator (alkylarylpolyglycolether), og der tilsættes 975 vægtdele ,vand. Koncentratet fortyndes med vand til den ønskede 1Q slutkoncentration i sprøjtepræparatet,To prepare a suitable composition of active ingredient, 0.25 parts by weight of active substance is taken up in 25 parts by weight of dimethylformamide and 0.06 parts by weight of emulsifier (alkylaryl polyglycol ether) and 975 parts by weight of water are added. Dilute the concentrate with water to the desired 1Q final concentration in the syringe preparation,
Til afprøvning af den protektive virkning inoku-lerer man énbladede unge hvedeplanter af sorten Michigan Amber med en uredosporesuspension af Puccinia recondita i 0,1%’s vandagar. Efter tørring af sporesuspensionen 15 sprøjtes hvedeplanterne dugfugtige med præparatet af det aktive stof og anbringes til inkubering i 24 timer ved ca.To test the protective effect, one-leaf young wheat seed of the Michigan Amber variety is inoculated with an uredospores suspension of Puccinia recondita in 0.1% of the day. After drying the spore suspension 15, the wheat plants are sprayed dew-moist with the active ingredient composition and placed for incubation for 24 hours at ca.
20°C og 100%’s luftfugtighed i et væksthus.20 ° C and 100% humidity in a greenhouse.
Efter 10 dages opholdstid for planterne ved en temperatur på 20°C og en luftfugtighed på 80-90% bedømmes an-20 grebet på planterne med rustblegn. Angrebsgraden udtrykkes i procent af angrebet på de ubehandlede kontrolplanter. Herved betyder 0% intet angreb og 100% samme angrebsgrad som ved de ubehandlede kontrolplanter. Jo mindre rustangrebet er, desto mere aktivt er det virksomme stof.After 10 days of residence of the plants at a temperature of 20 ° C and a humidity of 80-90%, the attack on the plants is judged by rust pale. The degree of attack is expressed as a percentage of the attack on the untreated control plants. By this, 0% means no attack and 100% the same degree of attack as with the untreated control plants. The less rust attack, the more active the active substance.
25 Ved dette forsøg viser f.eks. de følgende forbindel ser en særdeles god virkning, der er tydeligt overlegen i forhold til virkningen af den fra teknikkens stade kendte forbindelse (D): forbindelserne ifølge fremstillingseksemplerne nr. 8, 12, 14 og 5, jfr. den følgende tabel E.In this experiment, e.g. The following compounds show a very good effect which is clearly superior to the effect of the prior art compound (D): the compounds of Preparation Examples Nos. 8, 12, 14 and 5, cf. the following Table E.
o 20 150591o 20 150591
Tabel ETable E
Spirebehandlingsforsøg / kornrust / protektivtSprouting trial / grain rust / protective
Koncentration af virksomt stof i Angreb i % 5 sprøjtevæsken af de ubehand-Concentration of active substance in Attack in% 5 spray liquid of the untreated
Virksomt stof i vægtprocent lede kontrollerActive substance in weight percent lead controls
0H >T0H> T
r~~\ 'r ~~ \ '
Cl-/ Q ^-CH-CH2~N _| 0,025 83,3 (D) (Kendt)Cl- / Q ^ -CH-CH2 ~ N _ | 0.025 83.3 (D) (Known)
OHOH
cl-(oY- (o)·-=-cv <oY-ci 15 '-/ '-( CH„ ^-1 0,025 3,8 I ^ - Λ (8) I_y 20 C1-<^-(o)-?-(0}-C1 0,025 0,0 * · >«4 · i '—* CH *"""*"* i 2 Λ II ii (12) N__il 25 OH _ —{o) 0,025 0,0 CH9 / ' C1cl- (oY- (o) · - = - cv <oY-ci 15 '- /' - (CH + -1 0.025 3.8 I ^ - Λ (8) I_y 20 C1 - <^ - (o) -? - (0} -C1 0.025 0.0 * ·> «4 · i '- * CH *" "" * "* i 2 Λ II ii (12) N__il 25 OH _ - {o) 0.025 0.0 CH9 / C1
(\ N(\ N
30 (14) N___!l OH _ (ο^(δ)-* -(o)-ci °^°25 i6'3(14) N ___! OH OH _ (ο ^ (δ) - * - (o) -ci ° ° ° i6'3
Cl ' 2 35 Λ (5) N_!i o 21 150591Cl '2 35 Λ (5) N_! I o 21 150591
Fremstillingseksempler Eksempel 1 og 2Preparation Examples Examples 1 and 2
5 __ OH5 __ OH
(0>-<0>tCH2-i°>-cl J 2 Cl Az(0> - <0> tCH2-i °> -cl J 2 Cl Az
NN
10 Az = -N I = Eksempel 1Az = -N I = Example 1
\n;=J\ N; J =
^ N^ N
Az = -N I = Eksempel 2 "V.—_NAz = -N I = Example 2 "V. - _ N
15 (Fremgangsmåde b)(Method b)
Til en opløsning af 3,5 g (0,065 mol) natriummethy-lat i 18 ml methylalkohol sættes der 7,6 g (0,11 mol) 1,2,4-triazol. Derpå tildryppes der en opløsning af 19,5 g 20 (0,05 mol) 2-(4-biphenylyl)-3-chlor-l-(2,4-dichlorphenyl)- propan-2-ol i 38 ml dimethylformamid, og der opvarmes til 70°C i 90 minutter. Opløsningsmidlerne fjernes i vakuum på en rotationsfordamper, og remanensen sammenrøres med vand.To a solution of 3.5 g (0.065 mole) of sodium methylate in 18 ml of methyl alcohol is added 7.6 g (0.11 mole) of 1,2,4-triazole. Then a solution of 19.5 g of 20 (0.05 mol) of 2- (4-biphenylyl) -3-chloro-1- (2,4-dichlorophenyl) propan-2-ol in 38 ml of dimethylformamide is added dropwise and heated to 70 ° C for 90 minutes. The solvents are removed in vacuo on a rotary evaporator and the residue is stirred with water.
De fremkomne krystaller vaskes med diethylether og omkry-25 stalliseres fra acetonitril. Der fas 2,2 gram 2-(4-biphenylyl) -1-(2,4-dichlor-phenyl)-3-(1,2,4-triazol-4-yl)--propan-2-ol med smp. 260°C.The crystals obtained are washed with diethyl ether and recrystallized from acetonitrile. 2.2 grams of 2- (4-biphenylyl) -1- (2,4-dichloro-phenyl) -3- (1,2,4-triazol-4-yl) propan-2-ol are m.p. . 260 ° C.
Acetonitril-opløsningen (moderluden) inddampes, og de fremkomne krystaller vaskes med diethylether og eddike-30 ester. Der fås 6,5 g 2-(4-biphenylyl)-1-(2,4-dichlor-phenyl )-3-(1,2,4-triazol-l-yl)-propan-2-ol med smp. 124°C.The acetonitrile (mother liquor) solution is evaporated and the resulting crystals are washed with diethyl ether and vinegar ester. 6.5 g of 2- (4-biphenylyl) -1- (2,4-dichloro-phenyl) -3- (1,2,4-triazol-1-yl) -propan-2-ol are obtained. 124 ° C.
22 1505922 15059
OISLAND
Fremstilling af udgangsproduktetPreparation of the starting product
Cl _ OH \ (o>-<o>-=—2-<o)-ci 5 uri« i ^Cl _ OH \ (o> - <o> - = - 2- <o) -ci 5 uri «i ^
ClCl
Til opløsning af 0,6 mol 2,4-dichlorbenzylmagne-siumchlorid, fremstillet ud fra 15,9 g (0,65 mol) magnesium og 117,3 g (0,6 mol) 2,4-dichlorbenzylchlorid i 300 ml ether, sættes der portionsvis 69,3 g (0,3 mol) 4-phenylphenacylchlorid. Derefter hældes reaktionsblandingen ud i en vandig ammoniumchloridopløsning, og ether-fasen skilles fra, vaskes med vand, tørres med natriumsulfat og inddampes. Den tilbageblivende olie ekstraheres med petroleumsether, og petroleumsetheropløsningen inddampes. Krystallerne skilles fra ved filtrering og tørres.To dissolve 0.6 mole of 2,4-dichlorobenzyl magnesium chloride, prepared from 15.9 g (0.65 mole) of magnesium and 117.3 g (0.6 mole) of 2,4-dichlorobenzyl chloride in 300 ml of ether, 69.3 g (0.3 mole) of 4-phenylphenacyl chloride are added portionwise. Then, the reaction mixture is poured into an aqueous ammonium chloride solution and the ether phase is separated, washed with water, dried with sodium sulfate and evaporated. The residual oil is extracted with petroleum ether and the petroleum ether solution is evaporated. The crystals are separated by filtration and dried.
Der fås 62 g (53% af det teoretiske) 2-(4-biphenylyl)-20 -3-chlor-l-(2,4-dichlorphenyl)-propan-2-ol med smp. 84°C.62 g (53% of theory) of 2- (4-biphenylyl) -20 -3-chloro-1- (2,4-dichlorophenyl) propan-2-ol are obtained. 84 ° C.
Eksempel 3 og 4Examples 3 and 4
OHOH
25 <cT}-<oyfcH2-(o) -' ----v ch9 ^-/<CT} - <oyfcH2- (o) - '---- v ch9 ^ - /
Azaz
Az = -N i = eksempel 3Az = -N i = Example 3
30 -N30 -N
Az = -N I - eksempel 4 Y^NAz = -N I - Example 4 Y ^ N
(Fremgangsmåde b) o 23 150591(Method b) o 23 150591
Til en opløsning af 17,9 g (0,33 mol) natriummethylat i 90 ml methylalkohol sættes der 38,3 g (0,56 mol) 1,2,4-triazol. Der tildryppes derpå en opløsning af 82 g (0,254 mol) 2-(4-biphenylyl)-3-chlor-l-phenyl-propan-2-ol 5 i 191 ml dimethylformamid og opvarmes til 60°C i 90 minutter. Opløsningsmidlerne fjernes i vakuum på en rotationsfordamper, og remanensen opløses i methylenchlorid og vaskes med vand. Methylenchloridopløsningen tørres med natriumsulfat, filtreres og koncentreres i vakuum. Den frem-10 komne olie fraskilles chromatografisk. Der fås 13,8 g 2-(4-biphenylyl)-l-phenyl-3-(1,2,4-triazol-l-yl)-propan--2-ol med smp. 124°C og 2,7 g 2-(4-biphenylyl)-1-phenyl--3-(1,2,4-triazol-4-yl)-propan-2-ol med smp. 246°C.To a solution of 17.9 g (0.33 mole) of sodium methylate in 90 ml of methyl alcohol is added 38.3 g (0.56 mole) of 1,2,4-triazole. Then, a solution of 82 g (0.254 mol) of 2- (4-biphenylyl) -3-chloro-1-phenyl-propan-2-ol 5 in 191 ml of dimethylformamide is added dropwise and heated to 60 ° C for 90 minutes. The solvents are removed in vacuo on a rotary evaporator and the residue is dissolved in methylene chloride and washed with water. The methylene chloride solution is dried over sodium sulfate, filtered and concentrated in vacuo. The resulting oil is chromatographically separated. 13.8 g of 2- (4-biphenylyl) -1-phenyl-3- (1,2,4-triazol-1-yl) propan-2-ol are obtained, m.p. 124 ° C and 2.7 g of 2- (4-biphenylyl) -1-phenyl-3- (1,2,4-triazol-4-yl) -propan-2-ol, m.p. 246 ° C.
15 Fremstilling af udgangsproduktet15 Preparation of the starting product
OHOH
®-<o>-rv© CH0 20 · Δ®- <o> -rv © CH0 20 · Δ
ClCl
Til en opløsning af benzylmagnesiumchlorid, der er fremstillet ud fra 24,3 g (1 mol) magnesium og 115 ml (1 mol) benzylchlorid i 150 ml diethylether, sættes der 25 portionsvis 115,3 g (0,5 mol) 4-phenylphenacylchlorid. Reaktionsblandingen opvarmes i 90 minutter under tilbagesvaling og hældes derpå ud i en vandig opløsning af am-moniumchlorid. Den fraskilte etherfase vaskes med vand, tørres med natriumsulfat og inddampes. Den tilbagebliven-30 de olie bringes til krystallisation ved sammenrøring med petroleumsether. Der fås 50 g (31% af det teoretiske) 2-(4-biphenylyl)-3-chlor-l-phenyl-propan-2-ol med smp. 9 6°C.To a solution of benzyl magnesium chloride prepared from 24.3 g (1 mole) of magnesium and 115 ml (1 mole) of benzyl chloride in 150 ml of diethyl ether is added portionwise 115.3 g (0.5 mole) of 4-phenylphenacyl chloride. . The reaction mixture is heated at reflux for 90 minutes and then poured into an aqueous solution of ammonium chloride. The separated ether phase is washed with water, dried over sodium sulfate and evaporated. The residual oil is crystallized by stirring with petroleum ether. 50 g (31% of theory) of 2- (4-biphenylyl) -3-chloro-1-phenyl-propan-2-ol are obtained. 9 6 ° C.
o 24 15059o 24 15059
Eksempel 5 OH _ 5 <5}-<pH<o>-cl ^Cl “2 IL_£ 10 (Fremgangsmåde b)Example 5 OH-5 <5} - <pH <0> -cl 2 Cl 2 2 IL_ £ 10 (Method b)
Til en opløsning af 7,02 g (0,13 mol) natriummethyl- at i 36 ml methylalkohol sættes der 14,96 g (0,22 mol) triazol. Derpå tildryppes der en opløsning af 40 g 15 (0,1 mol) l-(2'-chlor-4-biphenylyl)-2-chlor-l-(4-chlor-phenyl)-ethanol i 75 ml dimethylformamid, og der opvarmes i 3 timer til 70°C. Reaktionsblandingen koncentreres i vakuum ved afdestillation af opløsningsmidlerne, og remanensen sanmenrøres med vand. De tilbageblivende krystaller 20 vaskes med acetonitril og omkrystalliseres. Der fås 16,2 g (40% af det teoretiske) 1-(2'-chlor-4-biphenylyl)-1--(4-chlorphenyl)-2-(1,2,4-triazol-l-yl)-ethanol med smp.To a solution of 7.02 g (0.13 mole) of sodium methylate in 36 ml of methyl alcohol is added 14.96 g (0.22 mole) of triazole. Then, a solution of 40 g (0.1 mole) of 1- (2'-chloro-4-biphenylyl) -2-chloro-1- (4-chloro-phenyl) -ethanol is added dropwise in 75 ml of dimethylformamide and heated for 3 hours to 70 ° C. The reaction mixture is concentrated in vacuo by distilling off the solvents and the residue is gently stirred with water. The remaining crystals 20 are washed with acetonitrile and recrystallized. 16.2 g (40% of theory) of 1- (2'-chloro-4-biphenylyl) -1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) are obtained. ethanol with m.p.
190°C.190 ° C.
2525
Fremstilling af udgangsproduktetPreparation of the starting product
OHOH
^C1 30 Cl30 C1 Cl
Ud fra 10,69 g (0,44 mol) magnesium, 76,6 g (0,4 mol) 4-bromchlorbenzen og 53 g (0,2 mol) 4-(2-chlor- phenyl)-phenacylchlorid fås der analogt med eksempel 1 75 g 1-(21 —chlor—4-biphenylyl)—2—chlor—1—(4—chlorphenyl) — ethanol.From 10.69 g (0.44 mole) of magnesium, 76.6 g (0.4 mole) of 4-bromochlorobenzene and 53 g (0.2 mole) of 4- (2-chlorophenyl) phenacyl chloride are obtained by analogy Example 1 75 g of 1- (21-chloro-4-biphenylyl) -2-chloro-1- (4-chlorophenyl) ethanol.
35 o 25 150591 (0^-(0) - C0CH2C1 5 C1 I en opløsning af 377 g (2 mol) 2-chlor-biphenyl i 160 ml (2 mol) chloracetylchlorid og 1000 ml methy-lenchlorid indføres der portionsvis 293,7 g (2,2 mol) 10 aluminiumchlorid. Efter 18 timer hældes reaktionsblandingen ud på is og saltsyre. Den organiske fase skilles fra, vaskes, tørres med natriumsulfat og koncentreres i vakuum ved afdestillation af opløsningsmidlet. Den tilbageblivende olie renses ved destillation. Der fås 15 478,7 g (90% af det teoretiske) 4-(2-chlorphenyl)-phen- acylchlorid med smp. 47°C.In a solution of 377 g (2 moles) of 2-chloro-biphenyl in 160 ml (2 moles) of chloroacetyl chloride and 1000 ml of methylene chloride, portionwise 293.7 is introduced. After 18 hours, the reaction mixture is poured onto ice and hydrochloric acid, the organic phase is separated, washed, dried with sodium sulfate and concentrated in vacuo by distillation of the solvent. 478.7 g (90% of theory) of 4- (2-chlorophenyl) phenacyl chloride, mp 47 ° C.
Analogt med eksemplerne 1-5 kan der fremstilles følgende forbindelser med den almene formel:Analogously to Examples 1-5, the following compounds of the general formula can be prepared:
20 R* .__ OH20 R * .__ OH
Ύθ> -? - ^Vm"* (I) CH„ i ^Ύθ> -? - ^ Vm "* (I) CH" i ^
Az 26 15059Az 26 15059
OISLAND
Smp. (°C)Mp. (° C)
Eks. eller nr. R R1 Az m brydningsindeks 6 -<S>-C1 4'(o) '\ϊΙ 1 250 7 -<o)-cl <-<o) 1 104Ex. or No. R R1 Az m refractive index 6 - <S> -C1 4 '(o)' \ ϊΙ 1 250 7 - <o) -cl <- <o) 1 104
_N_N
8 -(o)-cl 4-{o)-cl 1 144 10 Λ-Λ C1>-A ^ 9 -/T) \-Cl 4-/o\ -N I 1 1758 - (o) -cl 4- (o) -cl 1 144 10 Λ-Λ C1> -A ^ 9 - / T) \ -Cl 4- / o \ -N I 1 175
VJ / \./ \-NVJ / \ ./ \ -N
10 -<o)-cl ΛΐΙ 1 n°°: 1,599210 - <o) -cl ΛΐΙ 1 n °°: 1.5992
15 __ C1-'y y__-N15 __ C1-y y __- N
11 ~\o)~C1 4-(o>-cl "s — 1 160 12 -/7T\-C1 4-/7A-C1 -N " 0 189 \lr_/ VrL/ 20 t \ ---\ 13 \-F 4- { -N O 21711 ~ \ o) ~ C1 4- (o> -cl "s - 1 160 12 - / 7T \ -C1 4- / 7A-C1 -N" 0 189 \ lr_ / VrL / 20 t \ --- \ 13 \ -F 4- {-NO 217
Viv \v/ xn=JViv \ v / xn = J
__ ^_N__ ^ _N
14 ~/r\ / \ -Cl -N 0 14414 ~ / r \ / \ -Cl -N 0 144
Viv vrv \n.~IViv vrv \ n. ~ I
f-'7—' /—\ 25 15 \ 4-/,'-. \ -Η I O 164 / Viv 'ni i6 -7cT) 4-^q\, -iTv 0 170 C1 ivr >7Γλ . 7T7\ o 160f-'7— '/ - \ 25 15 \ 4 - /,' -. \ -Η I O 164 / Viv 'ni i6 -7cT) 4- ^ q \, -iTv 0 170 C1 ivr> 7Γλ. 7T7 \ o 160
30 17 -<q} 4-<o) -?NJ30 17 - <q} 4- <o) -? NJ
C1 KlC1 Kl
"s.-- ---- —N"p .-- ---- —N
18 -J C) \ 4-/f)\ -N I O 25018 -J C) \ 4- / f) \ -N I O 250
\±J \±J \r:N\ ± J \ ± J \ r: N
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19792920374 DE2920374A1 (en) | 1979-05-19 | 1979-05-19 | FUNGICIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| DE2920374 | 1979-05-19 |
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| Publication Number | Publication Date |
|---|---|
| DK216380A DK216380A (en) | 1980-11-20 |
| DK150591B true DK150591B (en) | 1987-04-06 |
| DK150591C DK150591C (en) | 1987-12-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| Country | Link |
|---|---|
| EP (1) | EP0019189B1 (en) |
| JP (1) | JPS55154907A (en) |
| AR (1) | AR226063A1 (en) |
| AT (1) | ATE1360T1 (en) |
| AU (1) | AU536644B2 (en) |
| BG (1) | BG31792A3 (en) |
| BR (1) | BR8003064A (en) |
| CA (1) | CA1145253A (en) |
| CS (1) | CS214711B2 (en) |
| DD (1) | DD151039A5 (en) |
| DE (2) | DE2920374A1 (en) |
| DK (1) | DK150591C (en) |
| EG (1) | EG14294A (en) |
| GR (1) | GR68454B (en) |
| IL (1) | IL60098A (en) |
| NZ (1) | NZ193745A (en) |
| PH (1) | PH16068A (en) |
| PL (1) | PL121128B1 (en) |
| PT (1) | PT71210A (en) |
| TR (1) | TR20400A (en) |
| ZA (1) | ZA802936B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4927839A (en) * | 1979-03-07 | 1990-05-22 | Imperial Chemical Industries Plc | Method of preventing fungal attack on wood, hides, leather or paint films using a triazole |
| US4654332A (en) * | 1979-03-07 | 1987-03-31 | Imperial Chemical Industries Plc | Heterocyclic compounds |
| AU542623B2 (en) * | 1980-05-16 | 1985-02-28 | Bayer Aktiengesellschaft | 1-hydroxyethyl-azole derivatives |
| ATE73293T1 (en) * | 1980-08-18 | 1992-03-15 | Ici Plc | USE OF TRIAZOLYLAETHANOL DERIVATIVES AND THEIR COMPOSITIONS AS NON-AGRICULTURAL FUNGICIDES. |
| EP0052425A3 (en) * | 1980-11-13 | 1982-08-11 | Imperial Chemical Industries Plc | Triazole and imidazole compounds, a process for preparing them, their use as plant fungicides and fungicidal compositions containing them |
| DE3175673D1 (en) * | 1980-11-19 | 1987-01-15 | Ici Plc | Triazole compounds, a process for preparing them, their use as plant fungicides and fungicidal compositions containing them |
| DE3235935A1 (en) * | 1982-09-29 | 1984-03-29 | Bayer Ag, 5090 Leverkusen | AZOLYLBUTANOLE |
| DE3245504A1 (en) * | 1982-12-09 | 1984-06-14 | Bayer Ag, 5090 Leverkusen | FUNGICIDES, THEIR PRODUCTION AND USE |
| DE3342693A1 (en) * | 1983-11-25 | 1985-06-05 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING SS-HYDROXY-ETHYL- (1,2,4-TRIAZOLE) DERIVATIVES |
| DE3342692A1 (en) * | 1983-11-25 | 1985-06-05 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING SS HYDROXYETHYL (1,2,4-TRIAZOLE) DERIVATIVES |
| DE3413173A1 (en) * | 1984-04-07 | 1985-10-17 | Bayer Ag, 5090 Leverkusen | (1,2,4-TRIAZOL-1-YL) METHYL CARBINOLE |
| US5049570A (en) * | 1990-01-23 | 1991-09-17 | Du Pont Merck Pharmaceutical Company | Pyridylphenyl nitrogen heterocycle-substituted carbinols and derivatives thereof with anti-inflammatory activity |
| JP4938555B2 (en) * | 2007-06-06 | 2012-05-23 | アール・ビー・コントロールズ株式会社 | Grill equipment |
| EP2984082B1 (en) | 2013-04-12 | 2017-08-02 | Bayer CropScience Aktiengesellschaft | Novel triazole derivatives |
| CN107602547A (en) * | 2017-09-28 | 2018-01-19 | 南开大学 | Heterocycle triazole derivative and its production and use |
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| IE44186B1 (en) * | 1975-12-03 | 1981-09-09 | Ici Ltd | 1,2,4-triazolyl alkanols and their use as pesticides |
| US4654332A (en) * | 1979-03-07 | 1987-03-31 | Imperial Chemical Industries Plc | Heterocyclic compounds |
-
1979
- 1979-05-19 DE DE19792920374 patent/DE2920374A1/en not_active Withdrawn
-
1980
- 1980-05-06 DE DE8080102450T patent/DE3060698D1/en not_active Expired
- 1980-05-06 AT AT80102450T patent/ATE1360T1/en not_active IP Right Cessation
- 1980-05-06 EP EP80102450A patent/EP0019189B1/en not_active Expired
- 1980-05-09 PT PT71210A patent/PT71210A/en unknown
- 1980-05-09 PH PH23991A patent/PH16068A/en unknown
- 1980-05-14 BG BG8047764A patent/BG31792A3/en unknown
- 1980-05-15 AU AU58416/80A patent/AU536644B2/en not_active Expired - Fee Related
- 1980-05-15 DD DD80221140A patent/DD151039A5/en unknown
- 1980-05-15 CS CS803399A patent/CS214711B2/en unknown
- 1980-05-16 GR GR61964A patent/GR68454B/el unknown
- 1980-05-16 CA CA000352114A patent/CA1145253A/en not_active Expired
- 1980-05-16 TR TR20400A patent/TR20400A/en unknown
- 1980-05-16 ZA ZA00802936A patent/ZA802936B/en unknown
- 1980-05-16 BR BR8003064A patent/BR8003064A/en unknown
- 1980-05-16 DK DK216380A patent/DK150591C/en active
- 1980-05-16 JP JP6417680A patent/JPS55154907A/en active Granted
- 1980-05-16 NZ NZ193745A patent/NZ193745A/en unknown
- 1980-05-16 IL IL60098A patent/IL60098A/en unknown
- 1980-05-17 PL PL1980224311A patent/PL121128B1/en unknown
- 1980-05-19 AR AR281111A patent/AR226063A1/en active
- 1980-05-19 EG EG313/80A patent/EG14294A/en active
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55154907A (en) | 1980-12-02 |
| PL121128B1 (en) | 1982-04-30 |
| DK216380A (en) | 1980-11-20 |
| DD151039A5 (en) | 1981-09-30 |
| EG14294A (en) | 1984-03-31 |
| IL60098A (en) | 1984-02-29 |
| DE3060698D1 (en) | 1982-09-16 |
| DE2920374A1 (en) | 1980-11-20 |
| ATE1360T1 (en) | 1982-08-15 |
| ZA802936B (en) | 1981-06-24 |
| JPS6337764B2 (en) | 1988-07-27 |
| TR20400A (en) | 1981-06-03 |
| PT71210A (en) | 1980-06-01 |
| PH16068A (en) | 1983-06-16 |
| BG31792A3 (en) | 1982-03-15 |
| IL60098A0 (en) | 1980-07-31 |
| EP0019189A1 (en) | 1980-11-26 |
| NZ193745A (en) | 1982-02-23 |
| PL224311A1 (en) | 1981-02-13 |
| EP0019189B1 (en) | 1982-07-28 |
| BR8003064A (en) | 1980-12-23 |
| AU536644B2 (en) | 1984-05-17 |
| AU5841680A (en) | 1980-11-27 |
| CA1145253A (en) | 1983-04-26 |
| AR226063A1 (en) | 1982-05-31 |
| GR68454B (en) | 1981-12-30 |
| DK150591C (en) | 1987-12-21 |
| CS214711B2 (en) | 1982-05-28 |
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