EP0000203B1 - 1-Ethyl-7-chloro-6-fluoro-4-quinolone-3-acide carboxylique, sa préparation et son application comme bactéricide pour plantes - Google Patents

1-Ethyl-7-chloro-6-fluoro-4-quinolone-3-acide carboxylique, sa préparation et son application comme bactéricide pour plantes Download PDF

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Publication number
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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EP
European Patent Office
Prior art keywords
carbonsäure
oder
chinolon
chlor
fluor
Prior art date
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Expired
Application number
EP78100280A
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German (de)
English (en)
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EP0000203A1 (fr
Inventor
Elmar Dr. Sturm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
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Ciba Geigy AG
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Publication of EP0000203A1 publication Critical patent/EP0000203A1/fr
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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
    • 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.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Quinoline Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Claims (4)

1. L'acide 1 - éthyl - 6 - fluoro - 7 - chloro - 4 - quinolone - 3 - carboxylique et ses sels de bases organiques ou minérales.
2. Produit bactéricide pour les végétaux, contenant au moins un composant actif consistant en le composé selon la revendication 1 ou ses sels.
3. Procédé pour traiter ou prévenir les maladies bactériennes causées par Erwinia-spp, par application du composé selon la revendication 1 ou d'un de ses sels.
4. Procédé de préparation de l'acide 1 - éthyl - 6 - fluoro - 7 - chloro - 4 - quinolone - 4 - carboxylique et de ses sels bases organiques ou minérales, caractérisé en ce que l'on alkyle un composé de formule IV
Figure imgb0007
dans laquelle alk' représente un groupe alkyle éliminable quelconque, à l'aide d'un halogénure d'éthyle, on saponifie ensuite le groupe ester par une base et, si on le désire, on convertit le sel formé en l'acide carboxylique libre par traitement à l'aide d'un acide.
EP78100280A 1977-07-01 1978-06-29 1-Ethyl-7-chloro-6-fluoro-4-quinolone-3-acide carboxylique, sa préparation et son application comme bactéricide pour plantes Expired EP0000203B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH813077 1977-07-01
CH8130/77 1977-07-01
CH628578 1978-06-08
CH6285/78 1978-06-08

Publications (2)

Publication Number Publication Date
EP0000203A1 EP0000203A1 (fr) 1979-01-10
EP0000203B1 true EP0000203B1 (fr) 1981-07-01

Family

ID=25699309

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100280A Expired EP0000203B1 (fr) 1977-07-01 1978-06-29 1-Ethyl-7-chloro-6-fluoro-4-quinolone-3-acide carboxylique, sa préparation et son application comme bactéricide pour plantes

Country Status (9)

Country Link
US (1) US4264604A (fr)
EP (1) EP0000203B1 (fr)
JP (1) JPS5414978A (fr)
AT (1) AT361739B (fr)
AU (1) AU523882B2 (fr)
DE (1) DE2860810D1 (fr)
IL (1) IL55043A (fr)
IT (1) IT7825237A0 (fr)
SU (1) SU931089A3 (fr)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5845426B2 (ja) * 1978-09-29 1983-10-08 杏林製薬株式会社 置換キノリンカルボン酸誘導体
JPS604820B2 (ja) * 1979-02-26 1985-02-06 大塚製薬株式会社 キノリンカルボン酸誘導体
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 (ja) * 1981-12-15 1983-06-24 Nippon Shinyaku Co Ltd 置換キノリンカルボン酸誘導体
DD207098A3 (de) * 1981-12-22 1984-02-15 Schmidt Hans Joerg Verfahren zur herstellung von 1-alkyl-6,7-methylendioxy-4(1h)-oxo-cinnolin-3-carbonsaeuren
DE3248507A1 (de) * 1982-12-29 1984-07-05 Bayer Ag, 5090 Leverkusen Mikrobizide mittel auf chinoloncarbonsaeure basis
DE3308908A1 (de) * 1983-03-12 1984-09-13 Bayer Ag, 5090 Leverkusen Bakterizide mittel
GB8412094D0 (en) * 1984-05-11 1984-06-20 Scras Quinoline derivatives
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
DE19738616A1 (de) * 1997-09-04 1999-03-11 Clariant Gmbh 4-Hydroxychinolin-3-carbonsäure-Derivate als Lichtschutzmittel
DE10149557A1 (de) * 2001-10-08 2003-04-10 Jobeck Gmbh Zubereitung und Verwendung dieser Zubereitung zur Bekämpfung und/oder Vorbeugung gegen den Erreger des Feuerbrandes 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
EP2579830B2 (fr) 2010-06-08 2018-10-31 CSP Technologies, Inc. Distributeur de comprimés
CN108617661A (zh) * 2017-03-24 2018-10-09 中国海洋大学 一种生物碱类化合物在农用药物中的应用
CN109912504B (zh) * 2019-04-04 2020-11-10 山东省联合农药工业有限公司 一种喹啉羧酸类化合物及其制备方法与用途
CN110122493B (zh) * 2019-06-14 2022-04-12 山东省联合农药工业有限公司 喹诺酮类化合物用于防治有用植物中细菌性有害生物的用途
KR102668356B1 (ko) * 2022-01-07 2024-05-21 한국화학연구원 날리딕스산 유도체의 화상병 방제제

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7101049A (fr) * 1970-01-28 1971-07-30
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

Also Published As

Publication number Publication date
ATA478578A (de) 1980-08-15
IL55043A (en) 1981-09-13
AU523882B2 (en) 1982-08-19
IL55043A0 (en) 1978-08-31
SU931089A3 (ru) 1982-05-23
EP0000203A1 (fr) 1979-01-10
US4264604A (en) 1981-04-28
DE2860810D1 (en) 1981-10-08
IT7825237A0 (it) 1978-06-30
AT361739B (de) 1981-03-25
AU3767578A (en) 1980-01-03
JPS5414978A (en) 1979-02-03

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