EP0000203B1 - 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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- EP0000203B1 EP0000203B1 EP78100280A EP78100280A EP0000203B1 EP 0000203 B1 EP0000203 B1 EP 0000203B1 EP 78100280 A EP78100280 A EP 78100280A EP 78100280 A EP78100280 A EP 78100280A EP 0000203 B1 EP0000203 B1 EP 0000203B1
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- carbonsäure
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- chinolon
- chlor
- fluor
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- 0 C=*(C=*)C(C(c1c2)=O)=CNc1cc(Cl)c2F Chemical compound C=*(C=*)C(C(c1c2)=O)=CNc1cc(Cl)c2F 0.000 description 1
Classifications
-
- 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 1-ethyl-7-chloro-6-fluoro-4-quinolone-3-carboxylic acid, bactericidal compositions containing this compound as an active ingredient and a method for controlling Erwinia species by applying this compound of the formula or one of its salts Salts are to be understood as meaning such strong organic bases as methylamine, triethylamine, but above all those of inorganic alkali and alkaline earth metals and ammonia.
- E. carotovora the causative agent of wet rot on plants
- E. atroseptica the causative agent of the fire blight
- E. amylovora the causative agent of the fire blight
- 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 NaOCI
- spray applications with streptomycin carried out with insufficient success.
- Quinolonecarboxylic acids are in general form as therapeutic agents in the GB-PS. 830,832 has been proposed. A plant bactericidal effect is not mentioned. The majority of the compounds mentioned there are completely ineffective against E. amylovoro.
- the compound of the formula I is prepared by reacting an aniline derivative of the formula 11 with an alkoxymethylene malonic ester with elimination of alkanol at 20 ° -160 ° C and ring closure of the anilinomethylene malonic ester of the formula 111 obtained at an elevated temperature of 200 ° to 280 ° C and cleaving off the alcoholic part of one of the ester groups to the 4-hydroxyquinoline-3-carboxylic acid ester of the formula IV and subsequent introduction of the ethyl group in 1- Position by usual alkylation with, for example, an ethyl halide (such as ethyl bromide or ethyl iodide).
- an ethyl halide such as ethyl bromide or ethyl 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 radicals).
- the quinolonecarboxylic acid of formula 1 is a stable compound which is insoluble in most organic solvents at normal temperature, partially soluble in water, but readily soluble when alkalis or strong amines are added.
- acidifying with e.g. Mineral acids can be precipitated or stabilized in the form of a colloidal solution.
- the invention also relates to the new compound of formula I and its preparation from compounds of formula IV.
- the compound of the formula 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.
- the active substance content in commercially available agents is between 0.1 and 90%.
- the active ingredient of the formula I of the present invention can be formulated, for example, as follows:
- Spray powder The following ingredients are used to produce (a) 40% and (b) 10% spray powder:
- the active ingredient is intimately mixed with the additives in suitable mixers and ground on appropriate mills and rollers. This gives wettable powders of excellent wettability and suspension which can be diluted with water to form suspensions of the desired concentration and can be used in particular for leaf application.
- Emulsifiable concentrates For the production of a 25% emulsifiable. The following substances are used in concentrate:
- emulsions of the desired concentration which are particularly suitable for foliar application, can be produced by dilution with water.
- test substance formulated as a wettable powder
- various concentrations 1000 to 100 ppm AS
- the trees are infected 24 hours later by spraying them with an aqueous suspension of a virulent strain of Erwinia amylovora.
- 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 compound of formula 1 shows full protective action at 40 ppm and 10 ppm throughout.
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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)
- Plural Heterocyclic Compounds (AREA)
- Quinoline Compounds (AREA)
Description
Die vorliegende Erfindung betrifft 1 - Aethyl - 7 - chlor - 6 - fluor - 4 - chinolon - 3 - carbonsäure, bakterizide Mittel enthaltend diese Verbindung als Wirkstoff und ein Verfahren zur Bekämpfung von Erwinia-Arten durch Applikation dieser Verbindung der Formel oder eines ihrer Salze
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,. Group named after its main pathogen E. carotovora 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 (NaOCI) oder Spritzapplikationen mit Streptomycin mit ganz ungenügendem Erfolg durchgeführt.To combat these bacteria, Diving treatments with Na hypochlorite (NaOCI) or spray applications with streptomycin carried out with insufficient success.
Demgegenüber erweist sich die halogenierte Chinoloncarbonsäure der Formel I als ausserordentlich wirksam.In contrast, the halogenated quinolonecarboxylic acid of the formula I has proven to be extremely effective.
Der Feuerbrand, verursacht durch das Bakterium Erwinia amylovora, ist eine der gefürchtetsten und wirtschaftlich bedeutendsten Krankheiten des Kernobstes. Dieses Bakteriose wurde erstmals an der Ostküste der USA beobachtet, durchschritt dann in einem einmaligen Seuchenzug den nordamerikanischen Kontinent und löste anfangs des zwanzigsten Jahrunderts 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 Krankeit 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 is 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 triggered a devastating epidemic in the apple and pear plantations there in California, Oregon and Washington at the beginning of the twentieth century. 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 flocks 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 that the disease will advance further 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 Chinoloncarbonsäure der Formel I insbesondere diese Krankheit protektiv verhüten kann.It has now surprisingly been found that the quinolonecarboxylic acid of the formula I can protectively prevent this disease in particular.
Chinoloncarbonsäuren sind in allgemeiner Form als Therapeutika in der GB-PS. 830,832 vorgeschlagen worden. Eine pflanzenbakterizide Wirkung wird nicht erwähnt. Der überwiegende Teil der dort genannten Verbindungen ist gegen E. amylovoro völlig wirkungslos.Quinolonecarboxylic acids are in general form as therapeutic agents in the GB-PS. 830,832 has been proposed. A plant bactericidal effect is not mentioned. The majority of the compounds mentioned there are completely ineffective against E. amylovoro.
Weiterhin ist in Chem. Substance Index, Seite 3753, Spalte 3, Zeilen 93 bis 96 1 - Äthyl - 7 - fluor - 4 - chinolon - 3 - carbonsäure genannt.Furthermore, in Chem. Substance Index, page 3753, column 3, lines 93 to 96 1-ethyl-7-fluoro-4-quinolone-3-carboxylic acid is mentioned.
Die anmeldungsgemäße Verbindung der Formel I besitzt, wie Vergleichsversuche zeigen, gegenüber diesen bekannten Halogen-Analogen hinsichtlich der bakteriziden Wirkung eine sprunghafte Uberlegenheit.Comparative experiments show that the compound of the formula I according to the application has an abrupt superiority over these known halogen analogs with regard to the bactericidal action.
Der Anmelder hat sich unter Bezugnahme auf die älteren Anmeldungen Nr. 863 429 in Belgien, P 28 04 097.3 in der Bundesrepublik Deutschland, 78 02706 in Frankreich und 3763/78 im Vereinigten Königreich freiwillig eingeschränkt und gesonderte Patentansprüche für die genannten Staaten vorgelegt.The applicant has voluntarily restricted himself with reference to earlier applications No. 863,429 in Belgium, P 28 04 097.3 in the Federal Republic of Germany, 78 02706 in France and 3763/78 in the United Kingdom and submitted separate patent claims for the states mentioned.
Die Herstellung der Verbindung der Formel I erfolgt durch Reaktion eines Anilinderivats der Formel 11 mit einem Alkoxymethylenmalonsäureester unter Alkanol-Abspaltung bei 20°-160°C und Ringschluss des erhaltenen Anilinomethylenmalonsäureesters der Formel 111 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 der Aethylgruppe in 1-Position durch üliche Alkylierung mit z.B. einem Aethylhalogenid (wie Aethylbromid oder Aethyljodid). 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 Ansäuren in die freie Carbonsäure überführt werden kann:
Die Chinoloncarbonsäure der Formel 1 ist eine stabile, in den meisten organischen Lösungsmitteln bei Normaltemperatur unlösliche Verbindung, teillöslich in Wasser, jedoch bei Zusatz von Alkalien oder starken Aminen leicht löslich. Durch Ansäuern mit z.B. Mineralsäuren lässt sie sich ausfällen bzw. in Form einer kolloidalen Lösung stabilisieren.The quinolonecarboxylic acid of formula 1 is a stable compound which is insoluble in most organic solvents at normal temperature, partially soluble in water, but readily soluble when alkalis or strong amines are added. By acidifying with e.g. Mineral acids can be precipitated or stabilized in the form of a colloidal solution.
Die Erfindung bezieht sich auch auf die neue Verbindung der Formel I und ihre Herstellung aus Verbindungen der Formel IV.The invention also relates to the new compound of formula I and its preparation from compounds of formula IV.
Das folgende Herstellungsbeispiel dient der Illustration.The following manufacturing example is for illustration.
- 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 - fluoranilinomethylenmalonsäurediäthylester vom Smp. 67-70°C.1st stage: 21.8 g of 3-chloro-4-fluoroaniline are mixed with 32.4 g of ethyl ethoxymethylene malonate and heated to 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-fluoroanilinomethylene malonate with a melting point of 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. 283-2900C.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 drawn off to give 20 g of 7 - chloro - 6 - fluoro - 4 - hydroxyquinoline - 3 - carboxylic acid ethyl ester, mp 283-290 0 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 Äthyljodid 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.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. The alkaline solution is mixed with some animal charcoal, filtered and with conc. Hydrochloric acid acidified. 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.
Die Verbindung der Formel kann 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 compound of the formula 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 kann die Verbindung der Formel 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%);
- (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);(a) active ingredient concentrates dispersible in water: wettable powders and pastes (25-90% in the commercial pack, 0.01 to 15% in ready-to-use solution); Emulsion and solution concentrates (10 to 50%; 0.01 to 15% in ready-to-use solution);
- (b) Lösungen (0,1 bis 20%); Aerosole(b) solutions (0.1 to 20%); Aerosols
Der Wirkstoff der Formel I vorliegender Erfindung kann beispielsweise wie folgt formuliert werden:The active ingredient of the formula I of the present invention can be formulated, for example, as follows:
Der Wirkstoff wird in geeigneten Mischern mit den Zuschlagstoffen innig vermischt und auf entsprechenden Mühlen 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 ingredient is intimately mixed with the additives in suitable mixers and ground on appropriate mills and rollers. This gives wettable powders of excellent wettability and suspension which can be diluted with water to form suspensions of the desired concentration and can be used in particular for leaf application.
Aus solchen Konzentration können durch Verdünnen mit Wasser Emulsionen der gewünschten Konzentration hergestellt werden, die besonders zur Blattapplikation geeignet sind.From such a concentration, emulsions of the desired concentration, which are particularly suitable for foliar application, can be produced by dilution with water.
Die Prüfsubstanz, formuliert als Spritzpulver, wird 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 wahrend 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 substance, formulated as a wettable powder, is 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 the 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 tritt bei den mit der Verbindung der Formel behandelten Bäumen kein Befall durch E. amylovora auf.In contrast to the untreated trees and those treated with streptomycin occurs the trees treated with the compound of the formula 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 Verbindung der Formel 1 zeigt durchweg bei 40 ppm un 10 ppm volle protektive Wirkung.The compound of formula 1 shows full protective action at 40 ppm and 10 ppm throughout.
Claims (4)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH8130/77 | 1977-07-01 | ||
| CH813077 | 1977-07-01 | ||
| CH628578 | 1978-06-08 | ||
| CH6285/78 | 1978-06-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000203A1 EP0000203A1 (en) | 1979-01-10 |
| EP0000203B1 true 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) |
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| 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 |
| JPS5653656A (en) * | 1979-10-05 | 1981-05-13 | Tanabe Seiyaku Co Ltd | Quinoline derivative and its preparation |
| 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 |
| DE3248507A1 (en) * | 1982-12-29 | 1984-07-05 | Bayer Ag, 5090 Leverkusen | MICROBICIDE AGENTS BASED ON CHINOLONIC CARBONIC ACID |
| DE3308908A1 (en) * | 1983-03-12 | 1984-09-13 | Bayer Ag, 5090 Leverkusen | BACTERICIDAL AGENTS |
| 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 |
| WO2011154018A1 (en) | 2010-06-08 | 2011-12-15 | Csp Technologies, Inc. | Tablet dispenser |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2103805C3 (en) * | 1970-01-28 | 1980-03-20 | Sumitomo Chemical Co., Ltd., Osaka (Japan) | Process for the preparation of N-substituted 6,7-methylenedioxy-4-quinolones |
| US3924042A (en) * | 1973-03-26 | 1975-12-02 | Minnesota Mining & Mfg | Method for treatment of bacterial plant disease |
| 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 |
| JPS53141286A (en) * | 1977-05-16 | 1978-12-08 | Kyorin Seiyaku Kk | Novel substituted quinolinecarboxylic acid |
-
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 IL IL55043A patent/IL55043A/en unknown
- 1978-06-29 DE DE7878100280T patent/DE2860810D1/en not_active Expired
- 1978-06-30 AU AU37675/78A patent/AU523882B2/en not_active Expired
- 1978-06-30 SU SU782633445A patent/SU931089A3/en active
- 1978-06-30 AT AT478578A patent/AT361739B/en not_active IP Right Cessation
- 1978-06-30 IT IT7825237A patent/IT7825237A0/en unknown
- 1978-07-01 JP JP8046678A patent/JPS5414978A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| IT7825237A0 (en) | 1978-06-30 |
| AT361739B (en) | 1981-03-25 |
| DE2860810D1 (en) | 1981-10-08 |
| SU931089A3 (en) | 1982-05-23 |
| AU523882B2 (en) | 1982-08-19 |
| ATA478578A (en) | 1980-08-15 |
| AU3767578A (en) | 1980-01-03 |
| US4264604A (en) | 1981-04-28 |
| IL55043A (en) | 1981-09-13 |
| EP0000203A1 (en) | 1979-01-10 |
| JPS5414978A (en) | 1979-02-03 |
| IL55043A0 (en) | 1978-08-31 |
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