EP0000203A1 - 1-Ethyl-7-chloro-6-fluoro-4-quinolone-3-carboxylic acid, its preparation and application as plant bactericide - Google Patents
1-Ethyl-7-chloro-6-fluoro-4-quinolone-3-carboxylic acid, its preparation and application as plant bactericide Download PDFInfo
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- EP0000203A1 EP0000203A1 EP78100280A EP78100280A EP0000203A1 EP 0000203 A1 EP0000203 A1 EP 0000203A1 EP 78100280 A EP78100280 A EP 78100280A EP 78100280 A EP78100280 A EP 78100280A EP 0000203 A1 EP0000203 A1 EP 0000203A1
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- 0 CCC(CC(C(*(C=C)N)=CC1*)=CC1=N)=C Chemical compound CCC(CC(C(*(C=C)N)=CC1*)=CC1=N)=C 0.000 description 5
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
- C07D215/54—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3
- C07D215/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3 with oxygen atoms in position 4
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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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
Definitions
- the present invention relates to bactericidal agents and to a method for controlling Erwinia species by applying a compound of the formula I or its salts where X is hydrogen, fluorine or chlorine and R is a lower alkyl radical.
- the lower alkyl radical are methyl, ethyl, propyl, isopropyl, butyl, isobutyl and sec. Understand butyl.
- the salts are those of strong organic bases such as methylamine. Triethylamine, but especially to understand such inorganic alkali and alkaline earth metals and ammonia.
- E. carotovora E. atroseptica
- E. chrysanthemi E. amylovora
- pathogens of the E. carotovora group can also seed the field, e.g. Potato tubers to be destroyed before germination ("Seed Piece decay"). Potato plants can show the symptoms of black leg, beets, cabbage and Konnyaku can be damaged in a similar way.
- Na hypochlorite Na0C1
- spray applications with streptomycin carried out with insufficient success.
- X is hydrogen or chlorine and R is a lower alkyl radical, preferably ethyl, propyl and isopropyl.
- Chino.loncarboxylic acids are in general form as therapeutic agents in the GB-PS. 830,832 A plant bactericidal effect is not mentioned. The majority of the compounds mentioned there are completely ineffective against E. amylovora,
- the compounds of the formula I are prepared by reacting an aniline derivative of the formula II with an alkoxymethylene malonic acid ester with elimination of alkanol at 20 ° to 160 ° C. and ring closure of the anilinomethylene malonic acid ester of the formula III obtained at elevated temperature from 200 ° to 280 ° C. and splitting off the alcoholic part of one of the ester groups for the 4-hydroxyquinoline-3-carboxylic acid ester of the formula IV and subsequent introduction of a substituent R by conventional alkylation with, for example, an alkyl halide (such as alkyl bromide or alkyl iodide).
- an alkyl halide such as alkyl bromide or alkyl iodide
- the quinolonecarboxylic acid ester of the formula V obtained can be saponified with bases to give compounds of the formula I and is in the salt form from which it can, if desired, be converted into the free carboxylic acid by acidification: (alk and alk 'are any releasable alkyl residues)
- quinolonecarboxylic acids of the formula I are stable compounds which are insoluble in most organic solvents at normal temperature, partially soluble in water, but readily soluble when alkali or strong amines are added.
- acidifying with e.g. Mineral acids can be precipitated or stabilized as a colloidal solution.
- the invention also relates to the new compounds of the formula I in which X is fluorine or chlorine and R is a lower alkyl radical, or in which X is hydrogen and R is methyl, propyl, isopropyl, butyl, isobutyl and sec. Butyl means.
- Suitable carriers and additives can be solid or liquid and correspond to the substances commonly used in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.
- the active substance content in commercially available agents is between 0.1 and 90%.
- the active compounds of the formula I of the present invention can be formulated, for example, as follows:
- Spray powder The following components are used to produce a) 40% and b) 10% spray powder:
- the active ingredients are intimately mixed with the additives in suitable mixers and ground on appropriate heaters and rollers.
- suitable mixers and ground on appropriate heaters and rollers.
- Emulsifiable concentrates The following substances are used to produce a 25% emulsifiable concentrate: Such concentrates can be used to produce emulsions of the desired concentration by dilution with water, which are particularly suitable for leaf application.
- test substances formulated as wettable powder
- the test substances are suspended in water and sprayed in various concentrations (1000 to 100 ppm AS) on annual Bartlett pear seedlings to the point of dripping wet.
- the trees are infected 24 hours later by spraying them with an aqueous suspension of a virulent strain of Erwinia amylovora.
- the plants are kept in a climate room at 25 ° C. and 100% rel. For 24 hours. Humidity set up. The further incubation then takes place in a conventional greenhouse. Seven days after infection, the trial is evaluated by determining the percentage of infected plants per treatment. 20 trees are used for each treatment. Streptomycin serves as the standard and only infected trees treated with water are used as controls.
- Potato tubers are cut in half. The halves are kept for 5 min. immersed in an aqueous suspension with 40 ppm or 10 ppm of active ingredient and allowed to dry on the surface of glass dishes. After 2 hours they are sprayed with a bacterial suspension from Erwinia carotovora. Unmerged tuber halves are also infected and serve as a control. All infected tubers are then incubated at approx. 26 ° C and 90 - 100% relative humidity. Four days after infection, the untreated tubers decomposed to a pulp, so the effect on treated tubers can be assessed visually.
- the compounds of formula I consistently showed protective effects at 40 ppm. Among others, compound No. 2 in particular showed this effect even at a concentration of 10 ppm.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Quinoline Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Pflanzenbakterizide Mittel, die als Wirkstoff eine Verbindung der Formel I oder eines ihrer Salze enthalten <IMAGE> worin X Wasserstoff, Fluor oder Chlor und R einen niederen Alkylrest bedeuten, eignen sich zur Bekämpfung von Erwinia spp., vor allem E. amylovora (Feuerbrand an Obstbäumen) und E. carotovora (Nassfäule an Kartoffeln und Gemüse).Plant bactericidal compositions which contain a compound of the formula I or one of their salts as active ingredient <IMAGE> in which X is hydrogen, fluorine or chlorine and R is a lower alkyl radical are suitable for combating Erwinia spp., Especially E. amylovora (fire blight Fruit trees) and E. carotovora (wet rot on potatoes and vegetables).
Description
Die vorliegende Erfindung betrifft bakterizide Mittel und ein Verfahren zur Bekämpfung von Erwinia-Arten durch Applikation einer Verbindung der Formel I oder ihrer Salze
Als niederer Alkylrest sind im Rahmen dieser Erfindung Methyl, Aethyl, Propyl, Isopropyl, Butyl, Isobutyl und sek. Butyl zu verstehen.In the context of this invention, the lower alkyl radical are methyl, ethyl, propyl, isopropyl, butyl, isobutyl and sec. Understand butyl.
Als Salze sind solche starker organischer Basen wie Methylamin. Triäthylamin, vor allem aber solche anorganischer Alkali- und Erdalkali-Metalle sowie Ammoniak zu verstehen.The salts are those of strong organic bases such as methylamine. Triethylamine, but especially to understand such inorganic alkali and alkaline earth metals and ammonia.
Unter den Erwinia-Arten befinden sich einige, die bedeutende, wirtschaftlich sehr nachteilige Bakteriosen hervorrufen. Es sind dies einmal die Erreger der Nassfäule an Pflanzen, z.B. E. carotovora, E. atroseptica, E. chrysanthemi, zum anderen der Erreger des Feuerbrands, E. amylovora. In der ersten, nach ihrem Haupterreger .E. carotovora benannten Gruppe fasst man alle Arten der gefürchteten Nassfäulen zusammen, die nach der Ernte bei vielen Gemüse-Arten, bei Rüben und bei Kartoffeln unter ungünstigen Lagerbedingungen (hohe Luftfeuchtigkeit und Sauerstoffmangel infolge schlechter Belüftung) verheerende Schäden ausrichten können. Doch auch im Feld vermögen Erreger der E. carotovora-Gruppe das Saatgut, z.B. Kartoffelknollen, noch vor der Keimung zu zerstören ("Seed Piece decay"). Kartoffelstauden können die Symptome der Schwarzbeinigkeit ("Black leg") zeigen, Rüben, Kohl und Konnyaku können ähnlich geschädigt werden.There are some of the Erwinia species that cause significant, economically very disadvantageous bacteriosis. These are the causative agents of wet rot on plants, e.g. E. carotovora, E. atroseptica, E. chrysanthemi, and secondly the causative agent of the fire blight, E. amylovora. In the first, after its main pathogen .E. carotovora named group summarizes all types of dreaded wet rot that can cause devastating damage after harvesting many vegetables, beets and potatoes under unfavorable storage conditions (high humidity and lack of oxygen due to poor ventilation). However, pathogens of the E. carotovora group can also seed the field, e.g. Potato tubers to be destroyed before germination ("Seed Piece decay"). Potato plants can show the symptoms of black leg, beets, cabbage and Konnyaku can be damaged in a similar way.
Zur Bekämpfung dieser Bakterien werden z.T. Tauchbehandlungen mit Na-Hypochlorit (Na0C1) oder Spritzapplikationen mit Streptomycin mit ganz ungenügendem Erfolg durchgeführt.To combat these bacteria, Diving treatments with Na hypochlorite (Na0C1) or spray applications with streptomycin carried out with insufficient success.
Demgegenüber erweist sich die kleine Gruppe von halogenierten Chinoloncarbonsäuren der Formel I als ausserordentlich wirksam.In contrast, the small group of halogenated quinolonecarboxylic acids of the formula I has proven to be extremely effective.
Bevorzugt sind unter diesen vor allem solche der Formel I und ihre Salze, bei denen X für Wasserstoff oder Chlor und R für einen niederen Alkylrest, bevorzugt Aethyl, Propyl und Isopropyl steht.Preferred among these are especially those of the formula I and their salts in which X is hydrogen or chlorine and R is a lower alkyl radical, preferably ethyl, propyl and isopropyl.
Der Feuerbrand, verursacht durch das Bakterium Erwinia amylovora, ist eine der gefürchtetsten und wirtschaftlich bedeutendsten Krankheiten des Kernobstes. Diese Bakteriose wurde erstmals an der Ostküste der USA beobachtet, durchschritt dann in einem einmaligen Seuchenzug den nordamerikanischen Kontinent und löste anfangs des zwanzigsten Jahrhunderts in Kalifornien, Oregon und Washington eine verheerende Epidemie in den dortigen Apfel- und Birnen-Pflanzungen aus. Als Folge des Feuerbrandes ist heute der kommerzielle Birnenanbau in den USA hauptsächlich-auf die ariden Gebiete von Kalifornien beschränkt. Im Jahr 1957 wurde der Feuerbrand in England festgestellt und etwa 10 Jahre später wurden auch'auf dem europäischen Kontinent einzelne Herde dieser Krankheit beobachtet. Trotz gewaltiger Rodungsaktionen, mit denen man versuchte, diese Befallsherde auszulöschen, konnte sich der Feuerbrand ausbreiten und in Nord-Europa fest etablieren (Dänemark, Schleswig-Holstein, Holland, Regionen von Frankreich und Belgien). Vorläufig sind in den betroffenen europäischen Gebieten vor allem Büsche aus der Familie der Rosaceen (Crataegus, Cotoneaster etc.) befallen, doch am weiteren Vordringen der Krankheit auch in die grossen Obstbau-Regionen ist nicht zu zweifeln.The blight, caused by the Erwinia amylovora bacterium, is one of the most feared and economically significant diseases in pome fruit. This bacteriosis was first observed on the east coast of the USA, then crossed the North American continent in a single epidemic and, at the beginning of the twentieth century, triggered a devastating epidemic in the apple and pear plantations in California, Oregon and Washington. As a result of the fire blight, commercial pear cultivation in the United States is now mainly limited to the arid areas of California. In 1957 the fire blight was discovered in England and about 10 years later, individual foci of this disease were also observed on the European continent. In spite of the enormous clearing operations with which attempts were made to extinguish these foci, the fire blight spread and became firmly established in Northern Europe (Denmark, Schleswig-Holstein, Holland, regions of France and Belgium). For the time being, mainly bushes from the Rosaceae family (Crataegus, Cotoneaster etc.) are affected in the affected European areas, but there is no doubt about the further spread of the disease into the large fruit-growing regions.
Das stetige Vordringen dieser Krankheit beweist die Unzulänglichkeit der bisherigen Massnahmen (Streptomycin-Einsätze, Kupferpräparate u.a.)The constant advancement of this disease proves the inadequacy of the previous measures (streptomycin inserts, copper preparations, etc.)
Es wurde nun überraschend gefunden, dass die kleine Gruppe von Chinoloncarbonsäuren der Formel I insbesondere diese Krankheit protektiv verhüten kann.It has now surprisingly been found that the small group of quinolonecarboxylic acids of the formula I can protectively prevent this disease in particular.
Chino.loncarbonsäuren sind in allgemeiner Form als Therapeutika in der GB-PS. 830,832 
Die Herstellung der Verbindungen der Formel I erfolgt durch Reaktion eines Anilinderivats der Formel II mit einem Alkoxymethylenmalonsäureester unter Alkanol-Abspaltung bei 20°- 160° C und Ringschluss des erhaltenen Anilinomethylenmalonsäureesters der Formel III bei erhöhter Temperatur von 200°bis 280° C und Abspaltung des alkoholischen Teils einer der Estergruppen zum 4-Hydroxychinolin-3-carbonsäureester der Formel IV und nachfolgende Einführung eines Substituenten R durch übliche Alkylierung mit z.B. einem Alkylhalogenid (wie Alkylbromid oder Alkyljodid). Der erhaltene Chinoloncarbonsäureester der Formel V kann mit Basen zu Verbindungen der Formel I verseift werden und liegt dabei in der Salzform vor, aus der er, falls gewünscht, durch Ansäuern in die freie Carbonsäure überführt werden kann:
Die Chinoloncarbonsäuren der Formel I sind stabile, in den meisten organischen Lösungsmitteln bei Normaltemperatur unlösliche Verbindungen, teillöslich in Wasser, jedoch bei Zusatz von Alkalien oder starken Aminen leicht löslich. Durch Ansäuern mit z.B. Mineralsäuren lassen sie sich ausfällen bzw. als kolloidale Lösung stabilisieren.The quinolonecarboxylic acids of the formula I are stable compounds which are insoluble in most organic solvents at normal temperature, partially soluble in water, but readily soluble when alkali or strong amines are added. By acidifying with e.g. Mineral acids can be precipitated or stabilized as a colloidal solution.
Eine der in ihrer Wirkung besonders hervorzuhebende Verbindung ist die im folgenden Beispiel beschriebene Verbindung Nr. 2, andere sind die nachfolgenden Verbindungen Nr. 1 und 14.One of the compounds to be particularly emphasized in its action is compound No. 2 described in the following example, others are the following compounds No. 1 and 14.
Die Erfindung bezieht sich auch auf die neuen Verbindungen der Formel I, worin X für Fluor oder Chlor steht und R einen niederen Alkylrest bedeutet, oder worin X für Wasserstoff steht und R Methyl, Propyl, Isopropyl, Butyl, Isobutyl und sek. Butyl bedeutet.The invention also relates to the new compounds of the formula I in which X is fluorine or chlorine and R is a lower alkyl radical, or in which X is hydrogen and R is methyl, propyl, isopropyl, butyl, isobutyl and sec. Butyl means.
Herstellung von 1-Aethyl-7-chlor-6-fluor-4-chinolon-3-carbonsäure
- 1. Stufe: 21,8 g 3-Chlor-4-fluoranilin werden mit 32,4 g Aethoxymethylenmalonsäurediäthylester gemischt und 30 Min. auf 150° erhitzt, wobei Alkohol abdestilliert. Die Schmelze erstarrt nach dem Erkalten zu einer Kristallmasse. Man erhält so 47 g rohen 3-Chlor-4-fluoranilino- methylenmalonsäurediäthylester vom Smp. 67-70° C.
- 2. Stufe: 35,5 g der voranstehenden Verbindung werden in 300 ml DOWTHERM A 1 Std.. lang auf 240-250° erhitzt, wobei Alkohol abdestilliert. Nach dem Erkalten verrührt man das Gemisch mit dem doppelten Volumen Petroläther, saugt den Kristallbrei ab und erhält 20 g 7-Chlor-6-fluor-4-hydroxychinolin-3-carbonsäureäthylester vom Smp. 283-290° C.
- 3. Stufe: 20 g der vorstehend beschriebenen Verbindung werden in 200 ml Dimethylformamid aufgeschlämmt und 3,9 g einer 50 %igen Natriumhydrid-Dispersion zugefügt. Nach Abklingen der Wasserstoff-Entwicklung erwärmt man 1 Std. auf 80° und fügt 17 g 'A'thyljodid zu. Man rührt bei 80-90° Innen-Temperatur unter Rückfluss 5 Std. lang, bis eine klare Lösung entstanden ist. Das Dimethylformamid wird weitgehend im Vakuum entfernt, 200 ml Wasser und 10 g Natriumhydroxid zugesetzt und die Mischung 2 Std. unter Rückfluss gerührt. Die alkalische Lösung wird mit etwas Tierkohle versetzt, filtriert und mit konz.-Chlorwasserstoffsäure sauer gestellt. Der ausgefallene Niederschlag wird abgesaugt und noch feucht aus Dimethylformamid umkristallisiert. Man erhält 15 g der Titelverbindung als farblose Kristalle, Smp. 279-281°C.
- 1st stage: 21.8 g of 3-chloro-4-fluoroaniline are mixed with 32.4 g of ethyl ethoxymethylene malonate and heated at 150 ° for 30 minutes, alcohol being distilled off. After cooling, the melt solidifies to a crystal mass. This gives 47 g of crude 3-chloro-4-fluoroanilino-methylenmalonsäurediäthylester of mp 67-70 ° C.
- 2nd stage: 35.5 g of the above compound are heated in 300 ml of DOWTHERM A for 1 hour at 240-250 °, alcohol being distilled off. After cooling, the mixture is stirred with twice the volume of petroleum ether, the crystal slurry is filtered off and 20 g of 7-chloro-6-fluoro-4-hydroxyquinoline-3-carboxylic acid ethyl ester of mp 283-290 ° C. are obtained.
- 3rd stage: 20 g of the compound described above are slurried in 200 ml of dimethylformamide and 3.9 g of a 50% strength sodium hydride dispersion are added. After the evolution of hydrogen has subsided, the mixture is heated at 80 ° for 1 hour and 17 g of 'ethyl iodide are added. The mixture is stirred at 80-90 ° internal temperature under reflux for 5 hours until a clear solution is obtained. The dimethylformamide is largely removed in vacuo, 200 ml of water and 10 g of sodium hydroxide are added and the mixture is stirred under reflux for 2 hours. A little animal charcoal is added to the alkaline solution, filtered and acidified with concentrated hydrochloric acid. The precipitate is filtered off and recrystallized while still moist from dimethylformamide. 15 g of the title compound are obtained as colorless crystals, mp. 279-281 ° C.
Auf diese oder gleiche Art werden folgende Verbindungen hergestellt:
Die Verbindungen der Formel I können für sich allein oder zusammen mit geeigneten Trägern und/oder anderen Zuschlagstoffen verwendet werden. Geeignete Träger und Zuschlagstoffe können fest oder flüssig sein und entsprechen den in der Formulierungstechnik üblichen Stoffen wie z.B. natürlichen oder regenerierten mineralischen Stoffen, Lösungs-, Dispergier-, Netz-, Haft-, Verdickungs-, Binde-oder Düngemitteln.The compounds of formula I can be used alone or together with suitable carriers and / or other additives. Suitable carriers and additives can be solid or liquid and correspond to the substances commonly used in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.
Der Gehalt an Wirkstoff in handelsfähigen Mitteln liegt zwischen 0,1 bis 90 %.The active substance content in commercially available agents is between 0.1 and 90%.
Zur Applikation können die Verbindungen der Formel I in den folgenden Aufarbeitungsformen vorliegen (wobei die Gewichts-Prozentangaben in Klammern vorteilhafte Mengen an Wirkstoff darstellen):
- Feste Aufarbeitungsformen: Stäubemittel und Streumittel (bis zu 10 %) Granulate, Umhüllungsgranulate, Imprägnierungsgranulate und Homogengranulate, Pellets (Körner) 1 bis 80 %) ;
- Solid processing forms: dusts and scattering agents (up to 10%) granules, coating granules, impregnation granules and homogeneous granules, pellets (grains) 1 to 80%);
Flüssige Aufarbeitungsformen:
- a) in Wasser dispergierbare Wirkstoffkonzentrate: Spritzpulver (wettable powders) und Pasten (25-90 % in der Handelspackung, 0,01 bis 15 % in gebrauchsfertiger Lösung) ; Emulsions- und Lösungskonzentrate (10 bis 50 %; 0,01 bis 15 % in gebrauchsfertiger Lösung);
- b) Lösungen (0,1 bis 20 %); Aerosole
- a) Water-dispersible active ingredient concentrates: wettable powders and pastes (25-90% in the retail pack, 0.01 to 15% in a ready-to-use solution); Emulsion and solution concentrates (10 to 50%; 0.01 to 15% in ready-to-use solution);
- b) solutions (0.1 to 20%); Aerosols
Die Wirkstoffe der Formel I vorliegender Erfindung können beispielsweise wie folgt formuliert werden:The active compounds of the formula I of the present invention can be formulated, for example, as follows:
Spritzpulver: Zur Herstellung eines a) 40 %igen und b) 10 %igen Spritzpulvers werden folgende Bestandteile verwendet:
Die Wirkstoffe werden in geeigneten Mischern mit den Zuschlagstoffen innig vermischt und auf entsprechenden Hühlen und Walzen vermahlen. Man erhält Spritzpulver von vorzüglicher Benetzbarkeit und Schwebefähigkeit, die sich. mit Wasser zu Suspensionen der gewünschten Konzentration verdünnen und insbesondere zur Blattapplikation verwenden lassen.The active ingredients are intimately mixed with the additives in suitable mixers and ground on appropriate heaters and rollers. One obtains wettable powder of excellent wettability and suspension, which. Dilute with water to form suspensions of the desired concentration and have them used especially for leaf application.
Emulgierbare Konzentrate: Zur Herstellung eines 25 %igen emulgierbaren Konzentrates werden folgende Stoffe verwendet:
Die Prüfsubstanzen, formuliert als Spritzpulver, werden in Wasser suspendiert und in verschiedenen Konzentrationen (1000 bis 100 ppm AS) auf einjährige Birnensämlinge der Sorte Bartlett bis zur Tropfnässe gesprüht. 24 Std. später erfolgt die Infektion der Bäumchen, in dem diese mit einer wässrigen Suspension eines virulenten Stammes von Erwinia amylovora besprüht werden. Unmittelbar nach der Infektion werden die Pflanzen während 24 Std. in einem Klimaraum bei 25° C und 100 % rel. Luftfeuchtigkeit aufgestellt. Anschliessend erfolgt die weitere Inkubation in einem konventionellen Gewächshaus. Sieben Tage nach der Infektion wird der Versuch ausgewertet, indem der Prozentsatz befallener Pflanzen pro Behandlung bestimmt wird. Für jede Behandlung werden 20 Bäumchen verwendet. Als Standard dient Streptomycin und als Kontrollen werden nur mit Wasser behandelte, infizierte Bäumchen herangezogen.The test substances, formulated as wettable powder, are suspended in water and sprayed in various concentrations (1000 to 100 ppm AS) on annual Bartlett pear seedlings to the point of dripping wet. The trees are infected 24 hours later by spraying them with an aqueous suspension of a virulent strain of Erwinia amylovora. Immediately after infection, the plants are kept in a climate room at 25 ° C. and 100% rel. For 24 hours. Humidity set up. The further incubation then takes place in a conventional greenhouse. Seven days after infection, the trial is evaluated by determining the percentage of infected plants per treatment. 20 trees are used for each treatment. Streptomycin serves as the standard and only infected trees treated with water are used as controls.
Im Gegensatz zu den unbehandelten Bäumchen und den mit Streptomycin behandelten wurde der Befall bei den mit den Verbindungen Nr. 1, 3 und,17 behandelten Bäumen fast vollständig verhindert. Bäume, die mit Suspensionen der Verbindung Nr. 2 oder der Verbindung Nr. 14 behandelt worden waren, zeigten gar keinen Befall durch E. amylovora.In contrast to the untreated trees and those treated with streptomycin, the infection was almost completely prevented in the trees treated with the compounds No. 1, 3 and, 17. Trees treated with suspensions of Compound No. 2 or Compound No. 14 showed no infection by E. amylovora.
Kartoffelknollen werden halbiert. Die Hälften werden während 5 min. in eine wässrige Suspension mit 40 ppm bzw. 10 ppm Wirkstoff getaucht und auf Glasschalen oberflächlich betrocknen gelassen. Nach 2 Std. werden sie mit einer Bakteriensuspension von Erwinia carotovora besprüht. Ungetauchte Knollenhälften werden gleichfalls infiziert und dienen als Kontrolle. Anschliessend erfolgt eine Inkubation aller infizierten Knollen bei ca. 26° C und 90 - 100 % relativer Luftfeuchtigkeit. Vier Tage nach der Infektion sind die unbehandelten Knollen breiartig zersetzt, die Wirkung an behandelten Knollen kann daher visuell bonitiert werden.Potato tubers are cut in half. The halves are kept for 5 min. immersed in an aqueous suspension with 40 ppm or 10 ppm of active ingredient and allowed to dry on the surface of glass dishes. After 2 hours they are sprayed with a bacterial suspension from Erwinia carotovora. Unmerged tuber halves are also infected and serve as a control. All infected tubers are then incubated at approx. 26 ° C and 90 - 100% relative humidity. Four days after infection, the untreated tubers decomposed to a pulp, so the effect on treated tubers can be assessed visually.
Die Verbindungen der Formel I zeigten durchweg bei 40 ppm voile protektive Wirkung. Neben anderen zeigte insbesondere die Verbindung Nr. 2 diese Wirkung auch noch bei einer Konzentration von 10 ppm.The compounds of formula I consistently showed protective effects at 40 ppm. Among others, compound No. 2 in particular showed this effect even at a concentration of 10 ppm.
Claims (7)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH8130/77 | 1977-07-01 | ||
| CH813077 | 1977-07-01 | ||
| CH6285/78 | 1978-06-08 | ||
| CH628578 | 1978-06-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000203A1 true EP0000203A1 (en) | 1979-01-10 |
| EP0000203B1 EP0000203B1 (en) | 1981-07-01 |
Family
ID=25699309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100280A Expired EP0000203B1 (en) | 1977-07-01 | 1978-06-29 | 1-ethyl-7-chloro-6-fluoro-4-quinolone-3-carboxylic acid, its preparation and application as plant bactericide |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4264604A (en) |
| EP (1) | EP0000203B1 (en) |
| JP (1) | JPS5414978A (en) |
| AT (1) | AT361739B (en) |
| AU (1) | AU523882B2 (en) |
| DE (1) | DE2860810D1 (en) |
| IL (1) | IL55043A (en) |
| IT (1) | IT7825237A0 (en) |
| SU (1) | SU931089A3 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0028698A1 (en) * | 1979-10-05 | 1981-05-20 | Tanabe Seiyaku Co., Ltd. | Quinoline compounds, process for their preparation, and pharmaceutical compositions |
| EP0113091A1 (en) * | 1982-12-29 | 1984-07-11 | Bayer Ag | Microbiocidal agents based on quinolone-carboxylic acids |
| US4563448A (en) * | 1983-03-12 | 1986-01-07 | Bayer Aktiengesellschaft | Bactericidal agents |
| EP2579830B1 (en) | 2010-06-08 | 2015-08-12 | CSP Technologies, Inc. | Tablet dispenser |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5845426B2 (en) * | 1978-09-29 | 1983-10-08 | 杏林製薬株式会社 | Substituted quinoline carboxylic acid derivatives |
| JPS604820B2 (en) * | 1979-02-26 | 1985-02-06 | 大塚製薬株式会社 | Quinoline carboxylic acid derivative |
| JPS56128703A (en) * | 1980-03-14 | 1981-10-08 | Otsuka Pharmaceut Co Ltd | Antimicrobial agent |
| JPS58105965A (en) * | 1981-12-15 | 1983-06-24 | Nippon Shinyaku Co Ltd | Substituted quinolinecarboxylic acid derivative |
| DD207098A3 (en) * | 1981-12-22 | 1984-02-15 | Schmidt Hans Joerg | PROCESS FOR THE PREPARATION OF 1-ALKYL-6,7-METHYLENDIOXY-4 (1H) -OXO-CINNOLINE-3-CARBONSAEURES |
| US4914110A (en) * | 1984-05-11 | 1990-04-03 | Societe De Conseils De Recherches Et D'applications Scientifiques | Quinoline derivatives, their preparation and therapeutic compositions containing the same |
| GB8412094D0 (en) * | 1984-05-11 | 1984-06-20 | Scras | Quinoline derivatives |
| DE19738616A1 (en) * | 1997-09-04 | 1999-03-11 | Clariant Gmbh | 4-hydroxyquinoline-3-carboxylic acid derivatives as light stabilizers |
| DE10149557A1 (en) * | 2001-10-08 | 2003-04-10 | Jobeck Gmbh | Preparation and use of this preparation for combating and / or preventing the causative agent of the fire blight Erwinia amylovora |
| AU2003209861A1 (en) * | 2002-03-01 | 2003-09-16 | Realco 2001 S.A. | Method for fighting against plant diseases by inhibiting extracellular enzymes of contaminating micro-organisms |
| CN108617661A (en) * | 2017-03-24 | 2018-10-09 | 中国海洋大学 | A kind of application of alkaloid compound in agricultural drugs |
| CN109912504B (en) * | 2019-04-04 | 2020-11-10 | 山东省联合农药工业有限公司 | Quinoline carboxylic acid compound and preparation method and application thereof |
| CN110122493B (en) * | 2019-06-14 | 2022-04-12 | 山东省联合农药工业有限公司 | Use of quinolone compounds for controlling bacterial harmful organisms in useful plants |
| KR102668356B1 (en) * | 2022-01-07 | 2024-05-21 | 한국화학연구원 | Fire blight control agent of nalidixic acid derivatives |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USB344479I5 (en) * | 1973-03-26 | 1975-01-28 | ||
| BE863429A (en) * | 1977-05-16 | 1978-05-16 | Kyorin Seiyaku Kk | QUINOLEIN-CARBOXYLIC ACID DERIVATIVES |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7101049A (en) * | 1970-01-28 | 1971-07-30 | ||
| US4146625A (en) * | 1976-07-16 | 1979-03-27 | E. I. Du Pont De Nemours And Company | Quinolonecarboxylic acids for control of bacterial diseases in plants |
-
1978
- 1978-06-26 US US05/918,999 patent/US4264604A/en not_active Expired - Lifetime
- 1978-06-29 EP EP78100280A patent/EP0000203B1/en not_active Expired
- 1978-06-29 DE DE7878100280T patent/DE2860810D1/en not_active Expired
- 1978-06-29 IL IL55043A patent/IL55043A/en unknown
- 1978-06-30 AT AT478578A patent/AT361739B/en not_active IP Right Cessation
- 1978-06-30 AU AU37675/78A patent/AU523882B2/en not_active Expired
- 1978-06-30 IT IT7825237A patent/IT7825237A0/en unknown
- 1978-06-30 SU SU782633445A patent/SU931089A3/en active
- 1978-07-01 JP JP8046678A patent/JPS5414978A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USB344479I5 (en) * | 1973-03-26 | 1975-01-28 | ||
| BE863429A (en) * | 1977-05-16 | 1978-05-16 | Kyorin Seiyaku Kk | QUINOLEIN-CARBOXYLIC ACID DERIVATIVES |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, 81, 57742V (1974) "Chemical substance index"; Seite 3753, Spalte 3, Zeile 93.4 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0028698A1 (en) * | 1979-10-05 | 1981-05-20 | Tanabe Seiyaku Co., Ltd. | Quinoline compounds, process for their preparation, and pharmaceutical compositions |
| EP0113091A1 (en) * | 1982-12-29 | 1984-07-11 | Bayer Ag | Microbiocidal agents based on quinolone-carboxylic acids |
| US4563459A (en) * | 1982-12-29 | 1986-01-07 | Bayer Aktiengesellschaft | Microbicidal agents based on quinolonecarboxylic acid |
| US4563448A (en) * | 1983-03-12 | 1986-01-07 | Bayer Aktiengesellschaft | Bactericidal agents |
| EP2579830B1 (en) | 2010-06-08 | 2015-08-12 | CSP Technologies, Inc. | Tablet dispenser |
Also Published As
| Publication number | Publication date |
|---|---|
| AT361739B (en) | 1981-03-25 |
| ATA478578A (en) | 1980-08-15 |
| IL55043A (en) | 1981-09-13 |
| SU931089A3 (en) | 1982-05-23 |
| EP0000203B1 (en) | 1981-07-01 |
| AU3767578A (en) | 1980-01-03 |
| US4264604A (en) | 1981-04-28 |
| IT7825237A0 (en) | 1978-06-30 |
| IL55043A0 (en) | 1978-08-31 |
| DE2860810D1 (en) | 1981-10-08 |
| AU523882B2 (en) | 1982-08-19 |
| JPS5414978A (en) | 1979-02-03 |
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