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
  • A01N43/64—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

Definitions

• the invention relates to new metal salt complexes of 1-phenyl-2-triazolyl-ethyl derivatives, a process for their preparation and their use as fungicides.
• the metal complexes of 1-phenyl-2-triazolyl-ethyl derivatives according to the invention show a considerably higher fungicidal activity, in particular against rust and mildew types, than the 1- [ß-aryl-ß (R-oxy ) -ethyl] -imidazoles and -triazoles, for example 1- [ß-butoxy-ß- (4'-chlorophenyl) -ethyl] -imidazole, which are chemically and effectively obvious substances, and as the zinc-ethylene-1,2 -bis-dithio- carbamidate, which is a known substance with the same direction of action.
• the active ingredients according to the invention thus represent an enrichment of technology.
• reaction sequence can be represented by the following formula:
• Formula 1 generally defines the 1-phenyl-2-triazolyl-ethyl derivatives to be used as starting materials.
• the procedure is expediently started from a 1-hydroxy-1-phenyl-2-triazolylethane derivative, the latter in a suitable inert solvent using alkali metal hydride or alkali metal amide in the alkali metal alcoholate of the formula IV transferred, and the latter is reacted immediately without isolation with a halide of the formula V, the compounds of the formula 11 being obtained in one operation with the emergence of alkali halide.
• the preparation of the alkanolates of the formula IV and the reaction with the halide of the formula V are expediently carried out in a two-phase system, for example aqueous sodium hydroxide solution or potassium hydroxide solution / toluene or methylene chloride, with the addition of a phase transfer catalyst, for example Ammonium or phosphonium compounds performed.
• a phase transfer catalyst for example Ammonium or phosphonium compounds performed.
• the 1-hydroxy-1-phenyl-2-triazolyl-ethane derivatives on which the alkanolates of the formula IV are based are known (cf. DT-OS 2431407 and DT-OS 2547953).
• the 1-halogen-1-phenyl-2-triazolyl-ethane derivatives of the formula VI are also known (cf. DT-OS 2547954).
• Examples of the 1-phenyl-2-triazolyl-ethyl derivatives of the formula 11 to be used as starting materials according to the invention are the following compounds in Tables 1, 2 and 3:
• the required metal salts of formula 111 are well known, easily accessible compounds.
• Suitable diluents for the reaction according to the invention are water and all inert organic solvents. These preferably include alcohols such as methanol and ethanol, ketones such as acetone or ethyl methyl ketone, and ethers such as e.g. Diethyl ether and dioxane.
• reaction temperatures can be varied over a wide range. Generally one works between 0 and 40 ° C, preferably between 15 and 30 ° C.
• the stoichiometric amount (depending on the oxidation state of the metal) of the compound of the formula 11 is employed per mol of the metal salt 111. These ratios can be exceeded by up to 20 mol% without significant reduction in yield.
• Working up is carried out in a manner which is customary and generally known for organic compounds, e.g. by suctioning off the precipitated complex and cleaning by recrystallization, e.g. from alcohol.
• the active substances according to the invention have a strong fungitoxic effect. They do not damage crops in the concentrations necessary to control fungi. For these reasons, they are suitable for use as crop protection agents for combating fungi. Fungitoxic agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
• the active compounds according to the invention have a broad spectrum of activity and can be used against parasitic fungi which attack parts of the plants above ground or attack the plants from the ground, and against seed-borne pathogens. They are particularly effective against parasitic fungi on above-ground parts of plants.
• the active compounds according to the invention can be used with particularly good success for combating Venturia species, such as against the apple scab pathogen (Fusicladium dendriticum), for powdery mildew fungi, for example for combating powdery mildew (Podosphaera leucotricha) and powdery mildew, and for other cereal diseases.
• Venturia species such as against the apple scab pathogen (Fusicladium dendriticum)
• powdery mildew fungi for example for combating powdery mildew (Podosphaera leucotricha) and powdery mildew, and for other cereal diseases.
• the active compounds according to the invention can be used as crop protection agents for treating seeds or soil and for treating above-ground parts of plants.
• the active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents.
• aromatics such as xylene, toluene, benzene or alkylnaphthalenes
• chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
• aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
• Petroleum fractions alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water; liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and pressure, e.g.
• Aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural rock flour, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; as an emulsifier; nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g.
• the active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth agents, plant nutrients and agents which improve soil structure.
• active compounds such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth agents, plant nutrients and agents which improve soil structure.
• the formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
• the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, dusting, scattering, dry pickling, wet pickling, wet pickling, slurry pickling or incrusting.
• the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 0.1 and 0.00001% by weight. Preferably between 0.05 and 0.0001%.
• active compound 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
• active ingredient For soil treatment, amounts of active ingredient from 1 to 1000 g per cbm of soil, in particular 10 to 200 g, are required.
• the amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.
• the spray liquid is used to spray young apple seedlings, which are in the 4- to 6-leaf stage, until they drip wet.
• the plants remain in the greenhouse for 24 hours at 20 ° C. and a relative humidity of 70%. They are then inoculated with an aqueous conidia suspension of the apple scab pathogen (Fusicladium dendriticum) and incubated for 18 hours in a humid chamber at 18 to 20 ° C and 100% relative humidity.
• the infestation of the seedlings is determined 15 days after the inoculation.
• the rating values received are converted into percent infestation. 0% means no infection, 100% means that the plants are completely infected.
• the amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.
• the spray liquid is used to spray young apple seedlings, which are in the 4- to 6-leaf stage, until they drip wet.
• the plants remain in the greenhouse for 24 hours at 20 ° C. and a relative humidity of 70%. They are then inoculated by dusting them with conidia of the powdery mildew pathogen (Podosphaera leucotricha) and placed in a greenhouse with a temperature of 21 to 23 ° C and a relative humidity of approx. 70%.
• the infestation of the seedlings is determined 10 days after the inoculation.
• the rating values obtained are converted into% infestation. 0% means no infection, 100% means that the plants are completely infected.
• active compound 0.25 part by weight of active compound is taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether, and 975 parts by weight of water are added.
• the concentrate is diluted with water to the desired final concentration of the spray mixture.
• the single-leafed barley young plants of the Amsel variety are sprayed with the preparation of active compound as dewy. After drying, the barley plants are dusted with spores from Erysiphe graminis var.hordei.
• the stocking of the plants with mildew pustules is evaluated.
• the degree of infestation is expressed as a percentage of the infestation of the untreated control plants. 0% means no infection and 100% the same degree of infection as in the untreated control. The lower the mildew infestation, the more effective the active ingredient.
• Active substances Active substances, active substance concentrations in the spray mixture and degrees of infestation are shown in the table below.
• Barley powdery mildew test (Erysiphe graminis var. Hordei) / ystemic (fungal cereal sprout disease)
• the active ingredients are used as powdered seed treatment agents. They are produced by stripping the respective active ingredient with a mixture of equal parts by weight of talc and kieselguhr to a fine powdery mixture with the desired active ingredient concentration.
• the degree of infestation is expressed as a percentage of the infestation of the untreated control plants. 0% means no infection and 100% means the same degree of infection as in the untreated control. The lower the mildew infestation, the more effective the active ingredient.
• Active substances, active substance concentrations in the seed treatment agent as well as its application rate and the percentage of mildew infestation are shown in the table below.
• Mycelial growth test Medium used:
• composition of solvent mixture :
• the amount of active ingredient required for the desired active ingredient concentration in the culture medium is mixed with the stated amount of the solvent mixture.
• the concentrate is thoroughly mixed with the liquid nutrient medium cooled to 42 ° C in the stated ratio and poured into Petri dishes with a diameter of 9 cm. Control plates are also set up without admixture. When the culture medium has cooled down and is solid, the plates are inoculated with the fungus species listed in the table and incubated at about 21 ° C.
• the evaluation takes place after 4 to 10 days, depending on the growth rate of the fungi.
• the radial mycelial growth on the treated culture media is compared with the growth on the control culture media. Mushroom growth is rated using the following indicators:

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)

Applications Claiming Priority (2)

Publications (2)

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• 1977
  • 1977-06-03 DE DE19772725214 patent/DE2725214A1/de not_active Withdrawn
• 1978
  • 1978-05-22 DD DD78205506A patent/DD137659A5/xx unknown
  • 1978-05-25 US US05/909,602 patent/US4366152A/en not_active Expired - Lifetime
  • 1978-05-29 PT PT68099A patent/PT68099A/pt unknown
  • 1978-05-30 CS CS783505A patent/CS199530B2/cs unknown
  • 1978-05-30 TR TR19767A patent/TR19767A/xx unknown
  • 1978-05-31 AR AR272409A patent/AR226278A1/es active
  • 1978-06-01 NZ NZ187449A patent/NZ187449A/xx unknown
  • 1978-06-01 DE DE7878100030T patent/DE2860395D1/de not_active Expired
  • 1978-06-01 IL IL7854841A patent/IL54841A0/xx not_active IP Right Cessation
  • 1978-06-01 JP JP6499778A patent/JPS543069A/ja active Granted
  • 1978-06-01 SU SU782619251A patent/SU1001848A3/ru active
  • 1978-06-01 EP EP78100030A patent/EP0000018B1/de not_active Expired
  • 1978-06-02 ES ES470459A patent/ES470459A1/es not_active Expired
  • 1978-06-02 HU HU78BA3661A patent/HU179670B/hu unknown
  • 1978-06-02 BR BR787803550A patent/BR7803550A/pt not_active IP Right Cessation
  • 1978-06-02 AT AT401778A patent/AT357374B/de not_active IP Right Cessation
  • 1978-06-02 IT IT24172/78A patent/IT1098307B/it active
  • 1978-06-02 ZA ZA00783177A patent/ZA783177B/xx unknown
  • 1978-06-02 DK DK248778A patent/DK248778A/da not_active Application Discontinuation
  • 1978-06-02 PL PL1978207335A patent/PL109268B1/pl unknown
  • 1978-06-02 CA CA304,643A patent/CA1106386A/en not_active Expired
  • 1978-06-03 EG EG351/78A patent/EG13358A/xx active
  • 1978-06-06 AU AU36850/78A patent/AU516653B2/en not_active Expired

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