EP0000539A1 - N-Pyrazol, N-Imidazol und N-Triazolacetanilid-Kupferkomplexe, ihre Herstellung und ihre Verwendung als Fungizide - Google Patents

N-Pyrazol, N-Imidazol und N-Triazolacetanilid-Kupferkomplexe, ihre Herstellung und ihre Verwendung als Fungizide Download PDF

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Publication number
EP0000539A1
EP0000539A1 EP78100432A EP78100432A EP0000539A1 EP 0000539 A1 EP0000539 A1 EP 0000539A1 EP 78100432 A EP78100432 A EP 78100432A EP 78100432 A EP78100432 A EP 78100432A EP 0000539 A1 EP0000539 A1 EP 0000539A1
Authority
EP
European Patent Office
Prior art keywords
copper complex
formula
triazole
methyl
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP78100432A
Other languages
English (en)
French (fr)
Inventor
Jürg Eberle
Jean Jacques De Wijs
Walter Dr. Kunz
Adolf Dr. Hubele
Wolfgang Dr. Eckhardt
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
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0000539A1 publication Critical patent/EP0000539A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages

Definitions

  • the present invention relates to copper complexes of N-pyrazole, N-imidazole-and N-triazole-aniline derivatives, a process for their preparation, compositions containing them and their use in combatting phytopathogenic fungi.
  • aniline derivatives which form the basis of the copper complexes of the invention are in part known from German Offenlegungsschrift No. 2,643,477 which also describes their fungicidal activity.
  • the complexes of the present invention have been found to possess a high fungicidal activity over a prolonged period.
  • alkyl or alkyl moiety of an alkoxy group methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec- butyl or tert-butyl.
  • Halogen stands for fluorine, chlorine, bromine or iodine.
  • anion A may be derived e.g. hydrochloric acid, hydrobromic acid, hydriodic acid, nitric acid, phosphoric acid, sulphuric acid, methanesulphonic acid, acetic acid, haloacetic acids, propionic acid, halopropionic acids, butyric acid, lactic acid, oxalic acid, maleic acid or benzoic acid.
  • the number p indicates the degree of hydration and will not necessarily be a whole number.
  • the complexes of the invention are stoichiometrically precisely defined compounds.
  • the complexes of the formula I may be prepared analogously to known methods for example as follows suitable solvents are for example alcohols such as methanol and ethanol; ketones such as acetone and methylethylketone; acetonitrile, dimethylformamide, dimethylsulphoxide, methylcellosolve and water as well. as mixtures thereof.
  • suitable solvents are for example alcohols such as methanol and ethanol; ketones such as acetone and methylethylketone; acetonitrile, dimethylformamide, dimethylsulphoxide, methylcellosolve and water as well. as mixtures thereof.
  • the process is advantageously carried out in the presence of ammonium chloride.
  • the reaction temperature lies between 0° and 100° C preferably 20°-50° C.
  • the process is carried out under normal pressure.
  • the complexes of the formula I contain in the group R 5 an asymetrical carbon atom adjacent to the aniline nitrogen and may be obtained as optical antipodes in conventional manner (e.g. employing already separated starting materials).
  • the two configurations of such a compound of the formula I exhibit different degrees of microbicidal activity.
  • the effect of further possible centres of asymetry and the atropisomerism about the phenyl - N axis on the microbicidal action of the entire molecule is apparently negligible. Carrying out the process of the invention without attempting to separate the pure isomers of the complex produces a racemic mixture thereof.
  • the complexes of the formula I are mixed with suitable carriers and/or other additives to give fungicidal compositions.
  • Suitable carriers and additives can be solid or liquid and are those normally used in the art of formulation, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.
  • the preparation of the compositions is effected in known manner by intimately mixing the constituents.
  • compositions according to the invention are examples of compositions according to the invention (percentages refer to advantageous amounts by weight of active substance):
  • the content of active substance in the above described compositions is between 0.1 % and 90 % by weight.
  • the compounds of the formula I can be used together with other suitable pesticides, for example fungicides, insecticides, acaricides or active substances which influence plant growth, in order to broaden the activity spectrum of the formulations and to adapt them to prevailing circumstances.
  • suitable pesticides for example fungicides, insecticides, acaricides or active substances which influence plant growth, in order to broaden the activity spectrum of the formulations and to adapt them to prevailing circumstances.
  • the complexes of the formula I are suitable for the protection of horticultural and agricultural crops and cultures from attack by phytopathogenic fungi.
  • crops and cultures are maize, vegetables, sugarbeet, soya, ground nuts, fruit trees, ornamentals, vines, hbps, cucumber plants (cucumber, marrows, melons t squash), solanaceae such as potatoes, tobacco plants and tomatoes and also banana, cocoa and rubber plants.
  • the active compounds of the formula I it is possible to inhibit or destroy the fungi which occur in plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in these and related cultures and also to protect from attack by such fungi parts of the plants which grow later.
  • Typical of such fungi are those which belong to the following classestAscomycetes (e.g. Erysiphaceae); Basidiomycetes, in particular rust fungi; fungi imperfecti (e.g. Cercospora); and especially Oomycetes belonging to the class of the Phycomycetes, such as Phytophthora, Pythium or Plasmopara.
  • the compounds of the formula I possess a systemic action. They can also be used as seed dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings from fungal infections and from phytopathogenic fungi which occur in the soil.
  • a further aspect of the invention therefore concerns the use of the complexes of the Formula I in combatting phytopathogenic fungi.
  • Preferred complexes are those of the formula I wherein
  • Preferred as substituent R 6 is the 1,2,4-triazole group.
  • the anions of inorganic acids are preferred as the group A.
  • X is preferably the group or group and especially the group.
  • the ice-cooled reaction mixture was then treated with 20 ml water, filtered, washed through with water and the obtained crystals dried under vacuum, m.p. 190-195°.
  • the active substances are mixed with the carriers and ground and in this form can be processed to dusts for application.
  • Granulate The following substances are used to prepare a 5 % granulator
  • the active resistance is mixed with epichlorohydrin and the mixture is dissolved in 6 parts of acetone. Then polyethylene glycol and cetyl polyglycol ether are added. The resultant solution is sprayed on kaolin and the acetone is evaporated in vacuo. Such a microgranulate may be used for example in combating soil fungi.
  • Wettable powders The following constituents are used to prepare a) a 70 %, b) a 40 %, c) and d) a 25 % and e) a 10 % wettable powder.
  • the active substances are intimately mixed in suitable mixers with the additives and ground in appropriate mills and rollers. Wettable powders of excellent wettability and suspension power are obtained. These wettable powders can be diluted with water to give suspensions of the desired concentration and can be used in particular for leaf application.
  • Emulsifiable copcentrates The following substances are used 2 prepare a 25 % emulsifiable concentrate:
  • “Roter Gnom” tomato plants were sprayed when 3 weeks old with a zoospore suspension of the fungus and incubated for 24 hours at 18° to 20° C and 100 % humidity. After drying, the plants were sprayed with a broth (active substance concentration 0,06 %) prepared from a wettable powder containing the active substance. After the spray coating had dried, the plants were returned to the humid chamber for a further 4 days. The effectiveness of the tested substances was assessed by determining the size and number of the typical leaf specks which had appeared on the treated plants in comparison with the untreated but infected control plants.
  • the acrive substance formulated as a wettable powder was applied in a conceutration of 0.006 % (referred to the volume of the soil) to the surface of the soil in pots containing 3-week-old "Roter Gnom" tomato plants. Three days later the underside of the leaves of the plants was sprayed with a suspension of the fungus. The plants were then kept in a spray chamber at 18° to 20° C and for 5 days whereupon typical leaf specks appeared.
  • the fungus was cultivated on sterile oat grains and added to a mixture of earth and sand. Sugar beet and maize seeds were then sown into flower pots filled with the infected soil. Immediately after sowing, the active substance was poured in the form of aqueous suspension over the soil (20 ppm of active substance referred to the volume of the soil). The pots were then placed for 2-3 weeks in a greenbouse at 20°-24° C. The soil was kept uniformly moist by gently spraying it with water. The emergence of the plants as well as the relative number of healthy and sick plants were determined.
  • Phytophthora infestans Cmpds. nos, 2, 3, 10, 11, 13 and 16
  • Pythium debaryanum Cmpds. nos. 2, 3, 10, 11 and 16.

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
EP78100432A 1977-07-27 1978-07-19 N-Pyrazol, N-Imidazol und N-Triazolacetanilid-Kupferkomplexe, ihre Herstellung und ihre Verwendung als Fungizide Withdrawn EP0000539A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH928377 1977-07-27
CH9283/77 1977-07-27

Publications (1)

Publication Number Publication Date
EP0000539A1 true EP0000539A1 (de) 1979-02-07

Family

ID=4350303

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100432A Withdrawn EP0000539A1 (de) 1977-07-27 1978-07-19 N-Pyrazol, N-Imidazol und N-Triazolacetanilid-Kupferkomplexe, ihre Herstellung und ihre Verwendung als Fungizide

Country Status (6)

Country Link
EP (1) EP0000539A1 (de)
JP (1) JPS5424871A (de)
ES (1) ES472009A1 (de)
IL (1) IL55217A0 (de)
PT (1) PT68344A (de)
ZA (1) ZA784258B (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0013873A1 (de) * 1979-01-17 1980-08-06 BASF Aktiengesellschaft N-Azolylessigsäureanilide, Verfahren zu ihrer Herstellung und ihre Anwendung als Herbizide
FR2499077A1 (fr) * 1981-02-05 1982-08-06 Ciba Geigy Ag Derives de l'aniline, leur preparation et produits microbicides en contenant
FR2499078A1 (fr) * 1981-02-05 1982-08-06 Ciba Geigy Ag Derives de l'aniline, procedes pour leur preparation et produits microbicides en contenant

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2915026A1 (de) * 1979-04-12 1980-10-30 Bayer Ag N,n-disubstituierte ethylglycin (thiol)ester, verfahren zu ihrer herstellung sowie ihre verwendung als fungizide
JPS58169065A (ja) * 1982-04-27 1983-10-05 テクトロニクス・インコ−ポレイテツド ピ−ク・ピ−ク検出装置
DE10029077A1 (de) * 2000-06-13 2001-12-20 Bayer Ag Thiazolylsubstituierte Heterocyclen
CN106243053B (zh) * 2016-09-12 2018-09-28 三峡大学 一种三唑酰胺酮类杀菌剂，合成方法及其应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7610793A (nl) * 1975-09-30 1977-04-01 Ciba Geigy Microbicide-middelen.
NL7801231A (nl) * 1977-02-04 1978-08-08 Ciba Geigy Fungicide preparaten.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7610793A (nl) * 1975-09-30 1977-04-01 Ciba Geigy Microbicide-middelen.
NL7801231A (nl) * 1977-02-04 1978-08-08 Ciba Geigy Fungicide preparaten.

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0013873A1 (de) * 1979-01-17 1980-08-06 BASF Aktiengesellschaft N-Azolylessigsäureanilide, Verfahren zu ihrer Herstellung und ihre Anwendung als Herbizide
FR2499077A1 (fr) * 1981-02-05 1982-08-06 Ciba Geigy Ag Derives de l'aniline, leur preparation et produits microbicides en contenant
FR2499078A1 (fr) * 1981-02-05 1982-08-06 Ciba Geigy Ag Derives de l'aniline, procedes pour leur preparation et produits microbicides en contenant

Also Published As

Publication number Publication date
ES472009A1 (es) 1979-02-01
ZA784258B (en) 1979-07-25
IL55217A0 (en) 1978-09-29
PT68344A (en) 1978-08-01
JPS5424871A (en) 1979-02-24

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PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

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RIN1 Information on inventor provided before grant (corrected)

Inventor name: HUBELE, ADOLF, DR.

Inventor name: DE WIJS, JEAN JACQUES

Inventor name: EBERLE, JUERG

Inventor name: ECKHARDT, WOLFGANG, DR.

Inventor name: KUNZ, WALTER, DR.