EP0000112A1 - Triazol-substituted sulphur derivatives, their preparation and their utilisation as fungicides - Google Patents
Triazol-substituted sulphur derivatives, their preparation and their utilisation as fungicides Download PDFInfo
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- EP0000112A1 EP0000112A1 EP78100044A EP78100044A EP0000112A1 EP 0000112 A1 EP0000112 A1 EP 0000112A1 EP 78100044 A EP78100044 A EP 78100044A EP 78100044 A EP78100044 A EP 78100044A EP 0000112 A1 EP0000112 A1 EP 0000112A1
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- carbon atoms
- phenyl
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- triazole
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- DXGUEJDALLFSBS-ONEGZZNKSA-N CC(CCCCC1CCCCC1)C/C=C/C Chemical compound CC(CCCCC1CCCCC1)C/C=C/C DXGUEJDALLFSBS-ONEGZZNKSA-N 0.000 description 1
- KMJOIHAXYSQIFK-UHFFFAOYSA-N CN1CN(C)NC1 Chemical compound CN1CN(C)NC1 KMJOIHAXYSQIFK-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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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
- A01N43/64—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 present invention relates to new valuable triazole-substituted sulfur compounds and their salts and metal complex salts with good fungicidal activity, to processes for their preparation and to fungicides which contain these compounds as active compounds.
- imidazole-substituted sulfur compounds as fungicides for controlling phytopathogenic fungi (DE-OS 25 41 833).
- they often only act against a certain fungus or against a certain class of fungus, or cause damage to the crop plants or, when used as a mordant, cause germination delays and damage to the emergence, so that their general and broad application are subject to strict limits.
- the salts have the general formula II in which R 1 , R 2 , n and k have the meanings given above and HS denotes any organic or inorganic acid which, however, must not be phytotoxic at the application rates used and must be able to form salts with the compounds of the formula I. to build.
- Particularly suitable acids are sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, trichloroacetic acid, dichloropropionic acid, oxalic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid.
- the compounds of the formula II can be prepared by simply adding the acids HS to the compounds of the formula I, if appropriate in a solvent.
- the metal complex salts have the general formula in which R 1 , R 2 , n and k have the meanings given above, p and q are the numbers 1 to 4, Y ° is an equivalent of an anion of an inorganic or organic acid and Me is a metal from I., II. and IV. to VIII. Subgroup and from the II. and IV. Main group of the periodic system.
- Such metals are for example: copper, iron, zinc, tin.
- the metal complex salts can be prepared by reacting a metal salt with a compound of the formula I in a solvent.
- the compounds of the formula I can be reacted with 2-haloethyl-2,2,4-triazoles of the formula III in which R 1 and n have the meaning given above and X is chlorine, bromine or iodine, with a mercaptide of the general formula IV in which R 2 has the meaning given above, in a solvent.
- the mercaptide is prepared from the associated mercaptan by reaction with a base before or during the reaction.
- the compounds of the formula I in which k represents the numbers 1 or 2 are obtained from compounds of the formula I in which k represents the number 0 by oxidation with an oxygen-donating reagent according to the customary, generally known methods of oxidizing sulfides. Sulfoxides and sulfones manufactured.
- the new fungicidal compounds are obtained either in the form of the free bases or their salts.
- the salts can be converted to the free bases in the usual manner, e.g. by reaction with alkali such as sodium or potassium hydroxide, sodium or potassium carbonate, ammonia or similar alkalis.
- alkali such as sodium or potassium hydroxide, sodium or potassium carbonate, ammonia or similar alkalis.
- the compounds in base form can be reacted with suitable acids, e.g.
- inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, organic acids such as trichloroacetic acid, dichloropropionic acid, oxalic acid, toluenesulfonic acid or higher alkylbenzenesulfonic acids such as dodecylbenzenesulfonic acid can be converted into the salts which are valuable in terms of application technology.
- the triazole-substituted sulfur compounds according to the invention and their salts and metal complex salts are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi. Some of them are systemically effective and can be used as foliar and soil fungicides, but also as mordants and as technical fungicides.
- the fungicidal compounds are particularly interesting for controlling a large number of fungi on different crop plants.
- crops in In this context in particular wheat, rye, barley, oats, rice, corn, cotton, soybeans, coffee, sugar cane, fruit and ornamental plants in horticulture, and also vegetables such as cucumbers, beans and pumpkin plants.
- the substances according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
- the application forms * depend entirely on the purposes; in any case, they should ensure a fine and uniform distribution of the active substance.
- the formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if appropriate using emulsifiers and dispersants, where - if used - water as a diluent, other organic solvents can also be used as auxiliary solvents.
- auxiliaries whose compounds according to the invention.
- Solvents such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g.
- Ethanolamine, dimethylformamide) and water such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, S. silicates.); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene - fatty alcohol - ether, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin, sulfite liquors and methyl cellulose.
- Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, S. silicates.); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene - fatty alcohol - ether, alkyl sulfonates and aryl sulfonates) and dispers
- the formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
- formulations or the ready-to-use preparations produced therefrom, such as solutions, emulsions, suspensions, powders, dusts, pickles, pastes or granules, are used in a known manner.
- the application rates are between 0.01 and 3, but preferably between 0.01 and 1 kg of active ingredient per hectare.
- the agents according to the invention can also be present together with other active ingredients, such as Herbicides, insecticides, growth regulators and fungicides. Or mixed with fertilizers and applied. When mixed with fungicides you get in many. Cases an increase in the fungicidal spectrum of activity; a number of these fungicide mixtures also have synergistic effects, i.e. the fungicidal activity of the combination product is greater than that of the added activity of the individual components.
- active ingredients such as Herbicides, insecticides, growth regulators and fungicides.
- fertilizers When mixed with fungicides you get in many. Cases an increase in the fungicidal spectrum of activity; a number of these fungicide mixtures also have synergistic effects, i.e. the fungicidal activity of the combination product is greater than that of the added activity of the individual components.
- Eluciter_von barley seedlings grown in pots are sprayed with aqueous emulsions of 80% (wt.%) Active ingredient and 20% emulsifier and, after the spray coating has dried on, are dusted with (spores) of the barley powdery mildew (Erysiphe graminis var. Hordei).
- the test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. After 10 days, the extent of the development of mildew is determined.
- Leaves of potted wheat seedlings of the "Jubilar” variety are sprayed with aqueous emulsions of 80% (weight percent) active ingredient and 20% emulsifier and, after the spray coating has dried on, are dusted with oidia (spores) of the powdery mildew (Erysiphe graminis var. Tritici) .
- the test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. The extent of mildew development is determined after 10 days. 0 no infection, graded to 5 total infection.
- Leaves of potted wheat seedlins of the "Caribo" variety are dusted with spores of the brown rust (Puccinia recondita).
- the pots are then placed in a chamber with high humidity (90 to 95%) at 20 to 22 ° C for 24 hours. During this time, the spores germinate and the germ tubes penetrate the leaf tissue.
- the infected plants are then sprayed to runoff point with 0.05%, 0.025 and 0.012% (wt.%) Aqueous spray liquors which contain 80% active ingredient and 20% lignin sulfonate in the dry substance. After the spray coating has dried on, the test plants are placed in the greenhouse at temperatures between 20 and 22 ° C. and 65 to 70% relative atmospheric humidity. After 8 days, the extent of the rust fungus development on the leaves is determined.
- compound 2 20 parts by weight of compound 2 are mixed. dissolved, which consists of 80 parts by weight of xylene, 10 parts by weight of the adduct, from 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dädecylbenzenesulfonic acid and 5 parts by weight of the additive of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
- 20 parts by weight of active ingredient 2 are mixed well with 3 parts by weight of the sodium salt of diiaebutylnaphthalene- ⁇ -sulfonic acid, 17 parts by weight of the sodium salt of lignin sulfonic acid from a Su.lfit waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill.
- a spray mixture is obtained which contains 0.1% by weight of the active ingredient.
- active ingredient 1 40 parts by weight of active ingredient 1 are intimately mixed with 10 parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion which contains 0.04% by weight of active ingredient.
- 20 parts of the compound 2 is lfonTalkre with 2 parts of calcium salt 'of the Dodecylbenzolsu', 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a Phen'olsulfonklare- urea-formaldehyde condensate and 68 parts of a paraffinic mineral intimately mixed.
- a stable oily dispersion is obtained.
Abstract
Description
Die vorliegende Erfindung betrifft neue wertvolle triazolsubstituierte Schwefelverbindungen und ihre Salze und Metallkomplexsalze mit guter fungizider Wirkung sowie Verfahren zu ihrer Herstellung und Fungizide, die diese Verbindungen als Wirkstoffe enthalten.The present invention relates to new valuable triazole-substituted sulfur compounds and their salts and metal complex salts with good fungicidal activity, to processes for their preparation and to fungicides which contain these compounds as active compounds.
Es ist bekannt, imidazolsubstituierte Schwefelverbindungen als Fungizide zur Bekämpfung pflanzenpathogener Pilze zu verwenden (DE-OS 25 41 833). Sie wirken jedoch häufig nur gegen einen bestimmten Pilz oder nur gegen eine bestimmte Pilzklasse, oder verursachen Schäden an den Kulturpflanzen oder bewirken bei der Verwendung als Beizittel Keimverzögerungen und Auflaufschäden, so daß ihrer allgemeinen und breiten Anwendung enge Grenzen gesetzt sind.It is known to use imidazole-substituted sulfur compounds as fungicides for controlling phytopathogenic fungi (DE-OS 25 41 833). However, they often only act against a certain fungus or against a certain class of fungus, or cause damage to the crop plants or, when used as a mordant, cause germination delays and damage to the emergence, so that their general and broad application are subject to strict limits.
Es. wurde gefunden,daß triazolsubstituierte Schwefelverbindungen der allgemeinen Formel I
- R1 Wasserstoff, Fluor, Chlor, Brom, einen gegebenenfalls substituierten Alkylrest mit 1 bis 5 Kohlenstoffatomen, eine Trifluormethyl-, Phenyl- oder Alkoxygruppe mit 1 bis 3 Kohlenstoffatomen,
- n die Zahlen 1 bis 3 bedeutet, wobei für n gleich 2 oder 3 die Reste R1 gleich oder verschieden sein können,
- R2 einen geradkettigen.oder verzweigten Alkyl-,'Alkenyl-oder Alkinylrest mit 1 bis 14 Kohlenstoffatomen, einen Phenylrest der Formel
- R4 Wasserstoff, Fluor, Chlor, Brom, einen gegebenenfalls substituierten Alkylrest mit 1 bis 5 Kohlenstoffatomen, eine Trifluormethyl-, Phenyl- oder Alkoxygruppe mit 1 bis 3 Kohlenstoffatomen,
- R5 Wasserstoff, Fluor, Chlor, Brom, einen gegebenenfalls substituierten Alkylrest.mit 1 bis 5 Kohlenstoffatomen, eine Trifluormethyl-, Phenyl- oder Alkoxygruppe mit 1 bis .3 Kohlenstoffatomen, .
- m die Zahlen 1 bis 3 bedeutet, wobei für n gleich 2 oder 3 die Reste R4 gleich oder verschieden sein können,
- 1 die Zahlen 1 bis 3 bedeutet, wobei für n gleich 2 oder 3 die Reste R5 gleich oder verschieden sein können und
- k die Zahlen 0, 1 oder 2 bedeutet,
und ihre Salze und Metallkomplexsalze eine sehr gute fungizide Wirkung besitzen, - keine mit den bekannten Wirkstoffen vergleichbaren Schädigungen an Kulturpflanzen hervorrufen und in ihrer ausgezeichneten Wirksamkeit gegen ein breites Spektrum von Pilzen den bekannten Wirkstoffen überlegen sind, wobei ihregleichzeitige Wirksamkeit sowohl gegen Pilze aus der Klasse der Ascomyceten als auch gegen solc.he aus der Klasse der Basidiomyceten hervorzuheben ist.
- R 1 is hydrogen, fluorine, chlorine, bromine, an optionally substituted alkyl radical with 1 to 5 carbon atoms, a trifluoromethyl, phenyl or alkoxy group with 1 to 3 carbon atoms,
- n denotes the numbers 1 to 3, where for n equal to 2 or 3 the radicals R 1 can be identical or different,
- R 2 is a straight-chain or branched alkyl, alkenyl or alkynyl radical having 1 to 14 carbon atoms, a phenyl radical of the formula
- R 4 is hydrogen, fluorine, chlorine, bromine, an optionally substituted alkyl radical with 1 to 5 carbon atoms, a trifluoromethyl, phenyl or alkoxy group with 1 to 3 carbon atoms,
- R 5 is hydrogen, fluorine, chlorine, bromine, an optionally substituted alkyl radical with 1 to 5 carbon atoms, a trifluoromethyl, phenyl or alkoxy group with 1 to .3 carbon atoms,.
- m denotes the numbers 1 to 3, where the radicals R 4 can be identical or different for n equal to 2 or 3,
- 1 means the numbers 1 to 3, where for n is 2 or 3 the radicals R 5 may be the same or different and
- k denotes the numbers 0, 1 or 2,
and their salts and metal complex salts have a very good fungicidal action, - cause no damage to crop plants comparable to the known active substances and are superior in their excellent activity against a broad spectrum of fungi to the known active substances, with their simultaneous effectiveness being emphasized both against fungi from the class of the Ascomycetes and against solc.he from the class of the Basidiomycetes is.
Die Salze haben die allgemeine Formel II
Die Verbindungen der Formel II können durch einfache Addition der Säuren HS an die Verbindungen der Formel I, gegebenenfalls in einem Lösungsmittel, hergestellt werden.The compounds of the formula II can be prepared by simply adding the acids HS to the compounds of the formula I, if appropriate in a solvent.
Die Metallkomplexsalze haben die allgemeine Formel
Solche Metalle sind beispielsweise: Kupfer, Eisen, Zink, Zinn.Such metals are for example: copper, iron, zinc, tin.
Die Metallkomplexsalze können durch Umsetzung eines Metallsalzes mit einer Verbindung der Formel I in einem Lösungsmittel hergestellt werden. ,The metal complex salts can be prepared by reacting a metal salt with a compound of the formula I in a solvent. ,
Die Verbindungen der Formel I lassen sich für den Fall k = 0 durch Umsetzung von 2-Halogenäthyl-2,2,4-triazolen der Formel III
Dle Verbindungen der Formel III sind bekannt aus der DE-OS 25 47 954.The compounds of formula III are known from DE-OS 25 47 954.
Die Verbindungen der Formel I, in denen k die Zahlen 1 oder 2 darstellt, werden aus Verbindungen der Formel I, in denen k die Zahl 0 bedeutet, durch Oxidation mit einem - sauerstoffabgebenden Reagens nach den üblichen allgemein bekannten Verfahren der Oxidation von Sulfiden zu-Sulfoxiden und Sulfonen hergestellt. Die Verbindungen der Formel I, bei denen k = 2 bedeutet, lassen sich auch durch Oxidation der Verbindungen der Formel I, bei denen k = 1 bedeutet, nach den üblichen Methoden herstellen.The compounds of the formula I in which k represents the numbers 1 or 2 are obtained from compounds of the formula I in which k represents the number 0 by oxidation with an oxygen-donating reagent according to the customary, generally known methods of oxidizing sulfides. Sulfoxides and sulfones manufactured. The compounds of the formula I in which k = 2 can also be prepared by oxidation of the compounds of the formula I in which k = 1 by the customary methods.
In Abhängigkeit von den Bedingungen, unter denen die Reaktionen durchgeführt werden, fallen die neuen fungiziden Verbindungen entweder in Form der freien Basen oder ihrer Salze an. Die Salze können in der üblichen Weise in die freien Basen umgewandelt werden, z.B. durch Umsetzung mit Alkali wie Natrium- oder Kaliumhydroxid, Natrium- oder Kaliumcarbonat, Ammoniak oder ähnlichen Alkalien. Die Verbindungen in Basenform können durch Umsetzung mit geeigneten Säuren, z.B. anorganischen Säuren, wie Salzsäure, Bromwasserstoffsäure, Jodwasserstoffsäure, Schwefelsäure, Salpetersäure, Phosphorsäure, organischen Säuren, wie Trichloressigsäure, Dichlorpropionsäure, Oxalsäure, Toluolsulfonsäure oder höhere Alkylbenzolsulfonsäuren wie Dodecylbenzolsulfonsäure in die anwendungstechnisch wertvollen Salze umgewandelt werden.Depending on the conditions under which the reactions are carried out, the new fungicidal compounds are obtained either in the form of the free bases or their salts. The salts can be converted to the free bases in the usual manner, e.g. by reaction with alkali such as sodium or potassium hydroxide, sodium or potassium carbonate, ammonia or similar alkalis. The compounds in base form can be reacted with suitable acids, e.g. inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, organic acids such as trichloroacetic acid, dichloropropionic acid, oxalic acid, toluenesulfonic acid or higher alkylbenzenesulfonic acids such as dodecylbenzenesulfonic acid can be converted into the salts which are valuable in terms of application technology.
Einige charakteristische Beispiele sollew das Herstellungsverfahren erläutern.Some characteristic examples should explain the manufacturing process.
Im folgenden verstehen sich alle Teile als Gewichtsteile und alle Prozente als Gewichtsprozente.In the following, all parts are parts by weight and all percentages are percentages by weight.
21 Teile 4-Chlorthiophenol, 400 Teile Aceton, 20,2 Teile 1-[2-(3-Bromphenyl)-2-chloräthyl-(1)]-1,2,4-triazol und 22 Teile Kaliumcarbonat werden unter gutem Rühren 8 Stunden zum Sieden erhitzt. Man engt ein und verrührt den Rückstand mit 200 Teilen Wasser, extrahiert 2 mal mit 150 Teilen Methylenchlorid, wäscht den Extrakt 2 mal mit 50 Teilen Wasser, trocknet mit Magnesiumsulfat, filtriert und dampft ein. Das zurückbleibende Öl wird in Äthylacetat gelöst und in die Lösung Chlorwasserstoff bis zur Sättigung eingeleitet.- Beim Absaugen erhält man 30 Teile 1-[2-(3-Bromphenyl)-2-(4-chlorphenylmercaptoj-äthyl-(1)}-,. 1,2,4-triazolhydrochldrid, das nach dem Umkristallisieren aus Isopropanol bei 172 bis 173°C schmilzt.21 parts of 4-chlorothiophenol, 400 parts of acetone, 20.2 parts of 1- [2- (3-bromophenyl) -2-chloroethyl- (1)] - 1,2,4-triazole and 22 parts of potassium carbonate are 8 with good stirring Heated to boiling for hours. The mixture is concentrated and the residue is stirred with 200 parts of water, extracted twice with 150 parts of methylene chloride, the extract is washed twice with 50 parts of water, dried with magnesium sulfate, filtered and evaporated. The remaining oil is dissolved in ethyl acetate and introduced into the solution to hydrogen saturation. 30% of 1- [2- (3-bromophenyl) -2- (4-chlorophenylmercaptoj-ethyl- (1)} -, 1,2,4-triazole hydrochloride, which melts after recrystallization from isopropanol at 172 to 173 ° C.
Eine Mischung von 24 Teilen 4-Chlorthiopher.ol, 22 Teilen l-r2-Chlor-2- (2 ,.4-diehlorphenyl)-äthyl- (l )j-l,2,4-triazpl,. 25 Teilen Kaliumcarbonat und 400 Teilen Aceton wird 12 Stunden unter Luftausschluß zum Sieden erhitzt. Anschließend wird filtriert und das Filtrat eingeengt.- Nach dem Umkristallisieren aus Cyclohexan verbleiben 22 Teile 1-C2-(4-Chlorphenylmercapto)-2- --(2.,4-dichlorph*e'nyl)-äthyl-(l)J-l,2,4-triazol vom Schmelzpunkt 72°C.A mixture of 24 parts of 4-chlorothiopherol, 22 parts of l-r2-chloro-2- (2, .4-diehlorphenyl) -ethyl- (l) jl, 2,4-triazole ,. 25 parts of potassium carbonate and 400 parts of acetone are heated to boiling in the absence of air for 12 hours. It is then filtered and the filtrate eingeengt.- After recrystallization from cyclohexane remaining 22 parts of 1-C2- (4-Chlorphenylmercapto) -2 - (. 2, 4-dichlorph * e'nyl) -äthyl- (l) Jl , 2,4-triazole, melting point 72 ° C.
Zu einer gut gerührten Suspension von 3,33. Teilen Natriumhydrid in 150 Teilen Tetrahydrofuran gibt man 22,4 Teile 4-Chlorbenzylmercaptan und rührt 1/2 Stunde. Anschließend tropft man 27,5 Teile l-i!2-Chlor―2-(2,4-dichlorphenyl)- --äthyl-(l)]-l,2,4-triazol, gelöst in 40 Teilen Tetrahydrofuran, zu und'läßt 2 Tage rühren. Danach werden 10 Teile.To a well-stirred suspension of 3.33. Parts of sodium hydride in 150 parts of tetrahydrofuran are added to 22.4 parts of 4-chlorobenzyl mercaptan and stirred for 1/2 hour. Then 27.5 parts of li! 2-chloro Chlor 2- (2,4-dichlorophenyl) - ethyl- (l)] - l, 2,4-triazole, dissolved in 40 parts of tetrahydrofuran, are added dropwise Stir for 2 days. After that, 10 parts.
*Wasser zugetropft und die Reaktionsmischung wird eingedampft. Man verrührt den Rückstand mit 200 Teilen Wasser und ebensoviel Essigester, trennt .den letzteren ab, wäscht ihn mit Wasser, trocknet mit Natriumsulfat, filtriert und leitet Chlorwasserstoff bis zur Sättigung ein. Es fallen 30,6 Teile l-[2-(4-Chlorbenzylmercapto)-2-(2,4-dichlor-* . phenyl)-äthyl- (1 1.2.4-triazolhydrochlorid aus, die nach dem Umkristallisieren bei 178°C schmelzen. * Water is added dropwise and the reaction mixture is evaporated. The residue is stirred with 200 parts of water and just as much ethyl acetate, the latter is separated off, washed with water, dried with sodium sulfate, filtered and hydrogen chloride is passed in until saturated. There are 30.6 parts of l- [2- (4-chlorobenzylmercapto) -2- (2,4-dichloro- *. Phenyl) -ethyl- (1 1.2.4-triazole hydrochloride, which after recrystallization at 178 ° C. melt.
3,33 Teile Natriumhydrid werden in 150 Teilen Tetrahydrofuran suspendiert und mit 12,6 Teilen Butylmercaptan zur Reaktion gebracht. Dann gibt man bei Raumtemperatur 27,5 Teile IT- 2-Chlor-2-(2,4-dichlorphenyl)-äthyl-(i 1,2,4-triazol, die man zuvor in 50 Teilen Tetrahydrofuran gelöst hat, zu und läßt 3 Tage rühren. Anschließend tropft man 10 Teile Wasser zu, dampft ein, schlämmt mit Wasser auf und extrahiert mit Äthylacetat. In den Extrakt gast man Chlorwasserstoff ein, wobei 25,9 Teile 1 Butylmercauto-2-(2,4-dichlorphenyl)-äthyl-(1 1.,2,4-(-.riaz olhydrochlorid ausfallen, die nach dem.Umkristallisieren aus Äthylacetat bei 143 OC schmelzen.3.33 parts of sodium hydride are suspended in 150 parts of tetrahydrofuran and reacted with 12.6 parts of butyl mercaptan. Then 27.5 parts of IT-2-chloro-2- (2,4-dichlorophenyl) ethyl (1,2,4-triazole, which had previously been dissolved in 50 parts of tetrahydrofuran) are added at room temperature and are allowed to Stir for 3 days, then add 10 parts of water, evaporate, slurry with water and extract with ethyl acetate, and hydrogen chloride is gassed into the extract, 25.9 parts of 1 butyl mercauto-2- (2,4-dichlorophenyl) - ethyl- (1 1., 2,4 - (-. riaz olhydrochloride fail, which after recrystallization from ethyl acetate at 143 OC melt.
1.0 Teile l-[2-(4-Chlorphenylmercapto)-2-(2,4-dichlorphenyl)-.äthyl-(i)1-l,2,4-triazol werden in 100 Teilen Diäthyläther gelöst und mit einer gesättigten Lösung von Oxalsäure in Diäthyläther versetzt.'Es fallen 9,5 Teile l-T2-(4-Chlorphenylmercapto)-2-(2,4-dichlorphenyl)-äthyl-(lf]-l,2,4- triäzoloxalät mit dem Schmelzpunkt 155°C aus..1.0 part of l- [2- (4-chlorophenylmercapto) -2- (2,4-dichlorophenyl) - . Ethyl- (i) 1-l, 2,4-triazole are dissolved in 100 parts of diethyl ether and mixed with a saturated solution of oxalic acid in diethyl ether. 9.5 parts of l-T2- (4-chlorophenylmercapto) -2- (2,4-dichlorophenyl) -ethyl- (lf] -l, 2,4-triazoloxalate with a melting point of 155 ° C from ..
10 Teile 1-2-(4-Chlorphenylmercapto)-2--(2.,4-dich .lorphenyl)-äthyl-(l)J-l,2,4,-triazol werden in 50 Teilen Eisessig gelöst und bei 10°C mit 2,95 Teilen 30 prozentigem Wasserstoffperoxid versetzt. Nach mehrtägigem Stehen bei Raumtemperatur gießt man auf 500 Teile Wasser, extrahiert die Mischung mit'Methylenehlorid, wäscht letzteres mit-'Wasser, trocknet es mit Magnesiumsulfat und dampft ein. Man erhält 8 Teile l-[_2-(2-Chlprphenylmercapto)-2-(2,4-dichlorphenyl)-äthyl-(l)J-l,2,4-triazoloxid, die nach dem Um- kristallisieren aus Tetrachlormethan bei 1270C schmelzen.10 parts of 1-2- (4-chlorophenylmercapto) -2 - (2nd, 4-dichlorophenyl) ethyl (l) III, 2,4, -triazole are dissolved in 50 parts of glacial acetic acid and at 10 ° C. mixed with 2.95 parts of 30 percent hydrogen peroxide. After standing at room temperature for several days, the mixture is poured onto 500 parts of water, the mixture is extracted with methylene chloride, the latter is washed with water, dried with magnesium sulfate and evaporated. One obtains 8 parts of l - [_ 2- (2-Chlprphenylmercapto) -2- (2,4-dichlorophenyl) -äthyl- (l) Jl, 2,4-triazoloxid after the environmental crystallized from tetrachloromethane at 127 0 C melt.
10 Teile l-j2-(4-Chlorphenylmercapto)-2-(2,4-dichlorphenyl)-äthyl-(1)j-1,2,'41triazol werden in einer Mischung aus 50 Teilen Eisessig und 50 Teilen Acetanhydrid gelöst und mit 9 Teilen 30 %igem Wasserst.offperoxid versetzt. Man erwärmt 1 Tag auf 80°C, gießt dann auf 300 Teile Wasser und saugt die ausfallenden Kristalle ab. Man erhält 8,4 Teile l-f2-(4-Chlorphenylmercapto)-2-(2,4-dichlorphenyl)-äthyl-(l)1-l,2,4-triazoldioxid, die nach dem Reinigen bei. 1450C schmelzen.10 parts of l-j2- (4-chlorophenylmercapto) -2- (2,4-dichlorophenyl) ethyl- (1) j-1,2, '41triazole are dissolved in a mixture of 50 parts of glacial acetic acid and 50 parts of acetic anhydride and with 9 parts of 30% hydrogen peroxide added. The mixture is heated to 80 ° C. for 1 day, then poured onto 300 parts of water and the crystals which precipitate are filtered off with suction. 8.4 parts of l-f2- (4-chlorophenylmercapto) -2- (2,4-dichlorophenyl) -ethyl- (l) 1-l, 2,4-triazole dioxide are obtained, which after cleaning. Melt 145 0 C.
Die folgende Tabelle zeigt eine Auswahl der neuen biologisch aktiven Schwefelverbindungen der allgemeinen Formel I bzw. II, welche auf die in den Beispielen angegebene Art hergestellt wurden:The following table shows a selection of the new biologically active sulfur compounds of the general formula I or II, which were prepared in the manner given in the examples:
Die erfindungsgemäßen triazolsubstituierten Schwefelverbindungen und ihre Salze und Metallkomplexsalze zeichnen sich durch eine hervorragende Wirksamkeit gegen ein breites Spektrum von pflanzenpathogenen Pilzen aus. Sie sind zum Teil systemisch wirksam und können als Blatt- und Bodenfungizide, aber auch als Beizmittel sowie als technische Fungizide eingesetzt werden.The triazole-substituted sulfur compounds according to the invention and their salts and metal complex salts are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi. Some of them are systemically effective and can be used as foliar and soil fungicides, but also as mordants and as technical fungicides.
Besonders interessant sind die fungiziden Verbindungen für die Bekämpfung einer Vielzahl von Pilzen an verschiedenen Kulturpflanzen. Unter Kulturpflanzen verstehen wir in rdiesem Zusammenhang insbesondere Weizen, Roggen, Gerste, Hafer, Reis, Mais, Baumwolle, Soja, Kaffee, Zuckerrohr, Obst und Zierpflanzen im Gartenbau, sowie Gemüse wie Gurken, Bohnen und Kürbisgewächse.The fungicidal compounds are particularly interesting for controlling a large number of fungi on different crop plants. We understand crops in In this context, in particular wheat, rye, barley, oats, rice, corn, cotton, soybeans, coffee, sugar cane, fruit and ornamental plants in horticulture, and also vegetables such as cucumbers, beans and pumpkin plants.
Die neuen Verbindungen sind insbesondere geeignet zur Bekämpfung folgender Pflanzenkrankheiten:
- Erysiphe graminis (echter Mehltau) in Getreide,
- Erysiphe cichoriacearum (echter Mehltau) an Kürbisgewächsen, Podosphaera leucotricha an Äpfeln, \
- Uncinula necator an Reben,
- Erysiphe polygoni an Bohnen,
- Sphaerotheca pannosa an Rosen,
- Puccinia-Arten an Getreide,
- Uromyces-Arten an Bohnen.
- Erysiphe graminis (powdery mildew) in cereals,
- Erysiphe cichoriacearum (powdery mildew) on pumpkin plants, Podosphaera leucotricha on apples, \
- Uncinula necator on vines,
- Erysiphe polygoni on beans,
- Sphaerotheca pannosa on roses,
- Puccinia species on cereals,
- Uromyces species on beans.
Die erfindungsgemäßen Substanzen können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Stäube, Pulver, Pasten und Granulate. Die Anwendungsformen richten*sich ganz nach den Verwendungszwecken; sie sollen in jedem Fall eine feine und gleichmäßige Verteilung der wirksamen Substanz gewährleisten. Die Formulierungen werden in'bekannter Weise hergestellt, z'.B. durch Verstrecken des Wirkstoffs mit Lösungsmitteln und/oder Trägerstoffen, gegebenenfalls unter Verwendung von Emulgiermitteln und Dispergiermitteln, wobei-im Falle der Benutzung-von Wasser als Verdünnungsmittel auch andere orga- 'nische Lösungsmittel als Hilfslosunssmittel verwendet wer-' den können. Als Hilfsstoffe kommen dafür im wesentlichen in Frage: ' The substances according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms * depend entirely on the purposes; in any case, they should ensure a fine and uniform distribution of the active substance. The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if appropriate using emulsifiers and dispersants, where - if used - water as a diluent, other organic solvents can also be used as auxiliary solvents. The following are essentially suitable as auxiliaries: '
Lösungsmittel wie Aromaten (z.B. Xylol, Benzol), chlorierte Aromaten (z.B. Chlorbenzole), Paraffine (z.B. Erdölfraktionen), Alkohole.(z.B. Methanol, Butanol), Amine (z.B.Solvents such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g.
Athanolamin, Dimethylformamid) und Wasser; Trägerstoffe wie natürliche Gesteinsmehle (z.B. Kaoline, Tonerden, Talkum, Kreide) und synthetische Gesteinsmehle (z.B. hochdisperse Kieselsäure, S.ilikate.); Emulgiermittel wie nichtionogene und anionische Emulgatoren (z.B. Polyoxyäthylen - Fettalkohol - Äther, Alkylsulfonate und Arylsulfonate) und Dispergiermittel, wie Lignin, Sulfitablaugen und Methyl cellulose.Ethanolamine, dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, S. silicates.); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene - fatty alcohol - ether, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin, sulfite liquors and methyl cellulose.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gew.% Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
Die Formulierungen, bzw. die daraus hergestellten gebrauchsfertigen Zubereitungen, wie Lösungen, Emulsionen, Suspensionen, Pulver, Stäube, Beizen, Pasten oder Granulate werden in bekannter Weise angewendet.The formulations, or the ready-to-use preparations produced therefrom, such as solutions, emulsions, suspensions, powders, dusts, pickles, pastes or granules, are used in a known manner.
Die Aufwandmengen liegen nach Art des gewünschten Effektes zwischen 0,01 und 3, vorzugsweise jedoch zwischen 0,01 und 1 kg Wirkstoff pro Hektar.Depending on the type of effect desired, the application rates are between 0.01 and 3, but preferably between 0.01 and 1 kg of active ingredient per hectare.
Die erfindungsgemäßen Mittel können in diesen Anwendungsformen auch zusammen-mit anderen Wirkstoffen vorliegen, wie z.B. Herbiziden, Insektiziden, Wachstumsregulatoren und Fungiziden.oder auch mit Düngemitteln vermischt und ausgebracht werden. Beim Vermischen mit Fungiziden erhält man dabei in vielen. Fällen eine Vergrößerung des fungiziden Wirkungsspektrums; bei einer Anzahl dieser Fungizidmischungen treten auch synergistische Effekte auf, d.h. die fungizide Wirksamkeit des Kombinationsproduktes ist größer als die der addierten Wirksamkeiten der Einzelkomponenten.In these use forms, the agents according to the invention can also be present together with other active ingredients, such as Herbicides, insecticides, growth regulators and fungicides. Or mixed with fertilizers and applied. When mixed with fungicides you get in many. Cases an increase in the fungicidal spectrum of activity; a number of these fungicide mixtures also have synergistic effects, i.e. the fungicidal activity of the combination product is greater than that of the added activity of the individual components.
Die folgende Liste von Fungiziden, mit denen die erfindungsgemäßen Verbindungen kombiniert werden können, soll die Kombinationsmöglichkeiten erläutern, nicht aber einschränken Fungizide, die mit den erfindungsgemßen. Verbindungen kombiniert werden können, sind beispielsweise:
- Dithiocarbamate und deren Derivate, wie
- Ferridimethyldithiocarbamat,
- Zinkdimethyldi,t hio carbamat ,
- Manganäthylenbisdithiocarbamat,
- Mangan-Zink-äthylendiamin-bis-dithiocarbamat,
- Zinkäthylenbisdithiocarbamat,
- Tetramethylthiuramdisulfide,
- Ammoniak-Komplex von Zink-(N,N-äthylen-bis-dithiocarbamat)
- und M,N'-Polyäthylen-bis-(thiocarbamoyl)-disulfid,
- Zink-(N,N'-propylen-bis-dithiocarbamat),
- Ammoniak-Komplex von Zink-(M,N'-propylen-bis-dithiocarbamat)
- und N,N'-Polypropylen-bis-(thiocarbamoyl)-disulfid
- Nitroderivate, wie
- Dinitro-d-methylheptyD-phenylcrotonat,
- 2-sec-Butyl-4,6-dinitrophenyl-3,3-dimethylacrylat,
- 2-sec-Butyl-4,6-dinitrophenyl-isopropylcarbonat;
- heterocyclische Strukturen, wie
- N-Trichlormethylthio-tetrahydrophthalimid,
- N-Trichlormethylthio-phthalimid,
- 2-Heptadecyl-2-imidazolin-acetat,
- 2,4-Dichlor-6-(o-chloranilino)-s-triazin,.
- 0«,0-Diäthyl-phthalimidophosphonothioat,'
- 5-Amino.-l-(bis'-(dimethylamino)-phosphinyl)-3-phenyl-l,2,4-triazol,
- 5-Xthoxy-3-trichiormethyl-l,2,4-tiadiazol,
- 2,3-Dicyano-1,4-dithiaanthrachinon,
- 2-Thio-l,3-dithio-(4,5-b)-chinoxylin,
- l-(Butylcarbamoyl)-2-benzimidazol-carbaminsäuremethylester,
- 2-Methoxycarbonylamino-benzimidazol
- 2-Rhodanmethylthio-benzthiazol,
- 4-(2-Chlbrphenylhydrazono)-3-niethyl-5-'isoxazplon, '
- Pyridin-2-thio-1-oxid,
- 8-Hydroxychinoli bzw. dessen Kupfersalz,
- 2,3-Dihydro-5-carboxanilido-6-methyl-1;4-oxathün-4,4- . dioxid,
- 2,3-Dihydro-5-carboxanilido-6-methyl-1,c-oxathün,
- 2-(Furyl-(2))-benzimidazol,
- 5-Methyl-5-vinyl-3-(3,5-dichlorphenyl)-2,4-dioxö-1,3-oxazolidin,
- N-Cy"clohexyl-2,5-dimethylfuran-3-hydroxamsäuremethylester.,
- Piperazin-1,4-diyl-bis-(1-(2.2.,2-trichlor-Kthyl)-formamid)_,.
- 2-(Thiazolyl-(4))-benzimidazol,
- 5-Butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidin,
- Bis-(p-Chlorphenyl)-3-pyridinmethanol,
- 1,2-Bis-(3-äthoxycarbonyl-2-thioureido)-benzol,
- l,2-Bis-(3-methoxycarbonyl-2-thioureido)-benzol und verschiedene Fungizide, wie
- Dodecylguanidinacetat,
- 3-(2-(3t5-Dimethyl-2-oxycyclohexyl)-2-hydroxyäthyl)-glutarimid, '
- Hexachlorbenzol,
- N-Dichlorfluonnethylthio-N',N'-dimethyl-N-pheny-l-schwefel- säurediamid,
- 2,5-Dimethyl-furan-3-carbonsäureanilid,
- 2,5-Dimethyl-furan-3-carbonsäure-cyclohexylamid, 2-Methyl-benzoesäure-anilid,
- 2-Jod-benzoesäure-anilid,
- 1-(3t4-Dichloranilino)-l-formylamino-2,2,2-trichloräthan
- 2,6-Dimethyl-N-tridecyl-morpholin bzw. dessen Salze,
- 2,6-Dimethyl-N-cyclododecyl-morpholin bzw. dessen Salze.
- Dithiocarbamates and their derivatives, such as
- Ferridimethyldithiocarbamate,
- Zinc dimethyldi, thio carbamate,
- Manganese ethylene bisdithiocarbamate,
- Manganese-zinc-ethylenediamine-bis-dithiocarbamate,
- Zinc ethylene bisdithiocarbamate,
- Tetramethylthiuram disulfide,
- Ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate)
- and M, N'-polyethylene-bis- (thiocarbamoyl) disulfide,
- Zinc (N, N'-propylene-bis-dithiocarbamate),
- Ammonia complex of zinc (M, N'-propylene-bis-dithiocarbamate)
- and N, N'-polypropylene bis (thiocarbamoyl) disulfide
- Nitroderivatives, such as
- Dinitro-d-methylheptyD-phenylcrotonate,
- 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate,
- 2-sec-butyl-4,6-dinitrophenyl-isopropyl carbonate;
- heterocyclic structures, such as
- N-trichloromethylthio-tetrahydrophthalimide,
- N-trichloromethylthio-phthalimide,
- 2-heptadecyl-2-imidazoline acetate,
- 2,4-dichloro-6- (o-chloroanilino) -s-triazine ,.
- 0 « , 0-diethyl phthalimidophosphonothioate, '
- 5-amino.-1- (bis' - (dimethylamino) phosphinyl) -3-phenyl-l, 2,4-triazole,
- 5-xthoxy-3-trichiormethyl-l, 2,4-tiadiazole,
- 2,3-dicyano-1,4-dithiaanthraquinone,
- 2-thio-1,3-dithio- (4,5-b) -quinoxylin,
- methyl l- (butylcarbamoyl) -2-benzimidazole carbamate,
- 2-methoxycarbonylamino-benzimidazole
- 2-rhodanmethylthio-benzothiazole,
- 4- (2-chlorophenylhydrazono) -3-niethyl-5-'isoxazplon, '
- Pyridine-2-thio-1-oxide,
- 8-hydroxyquinoli or its copper salt,
- 2,3-dihydro-5-carboxanilido-6-methyl-1; 4-oxathün-4,4-. dioxide,
- 2,3-dihydro-5-carboxanilido-6-methyl-1, c-oxate green,
- 2- (furyl- (2)) - benzimidazole,
- 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine,
- N-Cy "clohexyl-2,5-dimethylfuran-3-hydroxamic acid methyl ester . ,
- Piperazin-1,4-diyl-bis- (1- (2.2., 2-trichloro-kthyl) -formamide) _ ,.
- 2- (thiazolyl- (4)) - benzimidazole,
- 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine,
- Bis- (p-chlorophenyl) -3-pyridinemethanol,
- 1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene,
- 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene and various fungicides, such as
- Dodecylguanidine acetate,
- 3- (2- (3 t5 -dimethyl-2-oxycyclohexyl) -2-hydroxyethyl) glutarimide, '
- Hexachlorobenzene,
- N-dichlorofluoromethylthio-N ', N'-dimethyl-N-pheny-1-sulfuric acid diamide,
- 2,5-dimethyl-furan-3-carboxylic acid anilide,
- 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide, 2-methyl-benzoic acid anilide,
- 2-iodo-benzoic acid anilide,
- 1- (3t4-dichloroanilino) -l-formylamino-2,2,2-trichloroethane
- 2,6-dimethyl-N-tridecyl-morpholine or its salts,
- 2,6-dimethyl-N-cyclododecyl-morpholine or its salts.
Für die folgenden Versuche wurden.zu Vergleichszwecken die beiden folgenden bekannten Wirkstoffe verwendet
Elätter_von in Töpfen gewachsenen Gerstenkeimlingen werden mit wäßrigen Emulsionen aus 80 % (Gew.%) Wirkstoff und 20% Emulgiermittel besprüht und nach dem Antrocknen des Spritzbelages mit (Sporen) des Gerstenmehltaus (Erysiphe graminis var. hordei) bestäubt. Die Versuchspflanzen werden anschließend im Gewächshaus bei Temperaturen zwischen 20 und 22°C und 75 bis 80 % relativer Luftfeuchtigkeit aufgestellt. Nach 10 Tagen wird das Ausmaß der Mehltaupilzentwicklung ermittelt.
0 .kein Befall, abgestuft bis 5 Totalbefall0. No infestation, graded up to 5 total infestation
Blätter von in Töpfen gewachsenen Weizenkeimlingen der Sorte "Jubilar" werden mit wäßrigen Emulsionen aus 80% (Gewichtsprozent) Wirkstoff und 20 % Emulgiermittel besprüht und nach d.em Antrocknen des Spritzbelages mit Oidien (Sporen) des Weizenmehltaus (Erysiphe graminis var. tritici) bestäubt. Die Versuchspflanzen werden anschließend im Gewächshaus bei Temperaturen zwischen 20 und 22°C und 75 bis 80 % relativer Luftfeuchtigkeit aufgestellt. Nach 10 Tagen wird das Ausmaß der Mehltauentwicklung ermittelt.
Blätter von in Töpfen gewachsenen Weizensämlinen der Sorte "Caribo" werden mit Sporen des Braunrostes (Puccinia recondita) bestäubt. Danach werden die Töpfe für 24 Stunden bei 20 bis 22°C in eine Kammer mit hoher Luftfeuchtigkeit (90 bis 95 %) gestellt. Während-dieser Zeit keimen die Sporen aus und.die Keimschläuche dringen in das Blattgewebe ein. Die infizierten Pflanzen werden anschließend.mit 0,05 %, 0,025 und 0,012 %igen (Gew.'%) wäßrigen Spritzbrühen, die 80 % Wirkstoff und 20 % Ligninsulfonat in der Trockensubstanz enthalten, tropfnass gespritzt. Nach dem Antrocknen des Spritzbelages werden die Versuchspflanzen im Gewächshaus bei Temperaturen zwischen 20 und 22°C und 65 bis 70 % relativer Luftfeuchte aufgestellt. Nach 8 Tagen wird das Ausmaß der Rostpilzentwicklung auf den Blättern ermittelt.Leaves of potted wheat seedlins of the "Caribo" variety are dusted with spores of the brown rust (Puccinia recondita). The pots are then placed in a chamber with high humidity (90 to 95%) at 20 to 22 ° C for 24 hours. During this time, the spores germinate and the germ tubes penetrate the leaf tissue. The infected plants are then sprayed to runoff point with 0.05%, 0.025 and 0.012% (wt.%) Aqueous spray liquors which contain 80% active ingredient and 20% lignin sulfonate in the dry substance. After the spray coating has dried on, the test plants are placed in the greenhouse at temperatures between 20 and 22 ° C. and 65 to 70% relative atmospheric humidity. After 8 days, the extent of the rust fungus development on the leaves is determined.
0 kein Befall, abgestuft bis 5 Totalbefall0 no infection, graded to 5 total infection
In gleicher Weise wie in Beispiel 10 angeführt, werden Blätter von in Töpfen gewachsenen Hafersämlingen der Sorte "Flämings Krone" mit Sporen des Haferkronenrostes (Puecinia coronata) bestäubt und in eine Kammer mit hoher Luftfeuchtigkeit gestellt. Die infizierten Pflanzen werden anschliessend mit 0,05 %igen (Gew.%). wäßrigen Spritzbrühen, die 80 % Wirkstoff und 20 % Ligninsulfonat in der Trockensubstanz enthalten, tropfnaß gespritzt. Nach dem Antrocknen des Spritzbelages werden die Versuchspflanzen im Gewächshaus bei Temperaturen zwischen 20 und 22°c und 65 bis 70 % rel. Luftfeuchte aufgestellt. Nach 8 Tagen wird das Ausmaß' der Rostpilzentwicklung auf den Blättern.ermittelt.
100 g-Proben Gerstensaatgut der Sorte "Asse" werden in Glasflaschen etwa 5 Minuten lang mit jeweils 300 mg (= 0,3 Gew.%) der in der Tabelle angeführten Beizmittel sorgfältig gebeizt. Danach werden jeweils 8 Körner in Töpfe eingelegt und mit Erde bedeckt. Zehn Tage nach dem Auflauf des Getreides werden die Blätter mit Oidium (Konidien) des Gerstenmehltaus (Erysiphe graminis var. hordei) bestäubt. Die Versuchspflanzen werden anschließend im Gewächshaus bei'Temperaturen zwischen 20 und 22°C rel. Luftfeuchte aufgestellt. Nach weiteren 10 Tagen wird das 'Ausmaß der Mehltaupilzentwicklung auf den Blättern ermittelt.100 g samples of barley seeds of the "Asse" variety are carefully dressed in glass bottles for about 5 minutes each with 300 mg (= 0.3% by weight) of the dressing agents listed in the table. Then 8 grains are placed in pots and covered with earth. Ten days after the emergence of the grain, the leaves are dusted with oidium (conidia) of barley powdery mildew (Erysiphe graminis var. Hordei). The test plants are then in the greenhouse at ' temperatures between 20 and 22 ° C rel. Humidity set up. After a further 10 days, the extent of the development of mildew on the leaves is determined.
Man vermischt 90 Gewichtsteile der Verbindung 1 mit 10 Gewichtsteilen N-Methyl-cα-pyrrolidon und erhält eine Lösung, die zur Anwendung in Form kleinster Tropfen geeignet ist.90 parts by weight of compound 1 are mixed with 10 parts by weight of N-methyl-cα-pyrrolidone, and a solution is obtained which is suitable for use in the form of tiny drops.
20 Gewichtsteile der Verbindung 2 werden in einer Mischung . gelöst, die aus 80 Gewichtsteilen Xylol, 10 Gewichtsteilen des Anlagerungsproduktes, von 8 bis 10 Mol Äthylenoxid an 1 Mol ölsäure-N-monoäthanolamid, 5 Gewichtsteilen Calciumsalz der Dädecylbenzolsulfonsäure und 5 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Äthylenoxid an 1 Mol Ricinusöl besteht. Durch Ausgießen und feines Verteilen der Lösung in 100 000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gewichtsprozent des Wirkstoffs enthält.20 parts by weight of compound 2 are mixed. dissolved, which consists of 80 parts by weight of xylene, 10 parts by weight of the adduct, from 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dädecylbenzenesulfonic acid and 5 parts by weight of the additive of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
20 Gewichtsteile der Verbindung 3 werden in einer Mischung gelöst, die aus 40 Gewichtsteilen Cyclohexanon, 30 Gewichtsteilen Isobutanol, 20 Gewichtsteilen des Anlagerungsproduktes von 7 Mol Äthylenoxid an 1 Mol Isooctylphenol und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Äthylenoxid an 1 Mol Ricinusol'besteht. Durch Eingießen und feines Verteilen der Lösung in 100 000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gewichtsprozent des Wirkstoffs enthält.20 parts by weight of compound 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor sol. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
20 Gewichtsteile der Verbindung 1 werden in einer Mischung gelöst, die aus 25 Gewichtsteilen Cyclohexanol, 65 Gewichtsteilen einer Mineralölfraktion vom Siedepunkt 210 bis 2800C und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Äthylenoxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100 000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gewichtsprozent des Wirkstoffs enthält.20 parts by weight of compound 1 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
20'Gewichtsteile des Wirkstoffs 2 werden mit 3 Gewichtsteilen des Natriumsalzes der Diieäbutylnaphthalin-α-sulfonsäure, 17 Gewichtsteilen des Natriumsalzes einer Ligninsulfonsäure.aus einer Su.lfit-Ablauge.und 60 Gewichtsteilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle'vermahlen. Durch feines*Verteilen.der Mischunr in 20 OOO.Gewiehtsteilen Wasser erhält man eine Spritzbrühe, die 0,1 Gewichtsprozent des Wirkstoffs enthält.20 parts by weight of active ingredient 2 are mixed well with 3 parts by weight of the sodium salt of diiaebutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of lignin sulfonic acid from a Su.lfit waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely * distributing the mixture in 20 parts by weight of water, a spray mixture is obtained which contains 0.1% by weight of the active ingredient.
3 Gewichtsteile der Verbindung 3 werden mit 97 Gewichtsteilen feinteiligem Kaolin innig vermischt. Man erhält auf diese Weise ein Stäubemittel, das 3 Gewichtsprozent des Wirkstoffs enthält.3 parts by weight of compound 3 are intimately mixed with 97 parts by weight of finely divided kaolin. In this way a dust is obtained which contains 3 percent by weight of the active ingredient.
30 Gewichtsteile der Verbindung 4 werden mit einer Mischung aus 92 Gewichtsteilen pulverförmigem Kieselsäuregel und 8 Gewichtsteilen Paraffinöl, das auf die Oberfläche dieses Kieselsäuregels gesprüht wurde, innig vermischt. Man erhält ' ' auf diese Weise eine Aufbereitung des Wirkstoffs mit-guter Haftfähigkeit.30 parts by weight of compound 4 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. This gives '' in this way the active ingredient having-good adherence.
40 Gewichtsteile des Wirkstoffs 1 werden mit 10 Teilen Natriumsalz eines Phenolsulfonsäure-harnstoff-formaldehyd- , Kondensats, 2 Teilen Kieselgel und 48 Teilen Wasser innig vermischt. Man erhält eine.stabile wäßrige Dispersion. Durch Verdünnen mit 100 000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,04 Gewichtsprozent-Wirkstoff enthält.40 parts by weight of active ingredient 1 are intimately mixed with 10 parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion which contains 0.04% by weight of active ingredient.
20 Teile des Wirkstoffs 2 werden mit 2 Teilen Caiciumsalz ' der Dodecylbenzolsu'lfonsäure, 8 Teilen Fettalkohol-polyglykoläther, 2 Teilen Natriumsalz eines Phen'olsulfonsäure- harnstoff-formaldehyd-Kondensats und 68 Teilen eines paraffinischen Mineralöls innig vermischt. Man erhält eine stabile ölige Dispersion.20 parts of the compound 2 is lfonsäure with 2 parts of calcium salt 'of the Dodecylbenzolsu', 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a Phen'olsulfonsäure- urea-formaldehyde condensate and 68 parts of a paraffinic mineral intimately mixed. A stable oily dispersion is obtained.
9,58 Teile l-r2-(4-Chlorphenyimerca.pte)-2-(2,4-diehlor- phenyl)-äthyl-(l)J-l.,2,4-triazol werden in 300 Teilen Äthanol gelöst- und tropfenweise mit einer Lösung von 2,2 Teilen hydratwasserhaltigem Kupfer-(II')-chlorid in 3 Teilen Wasser versetzt. Nach 20-minutigem Rühren wird abgesaugt. Man erhält 10 Teile Bis-1-(2-(4-chlorphenyl-' mercapto)-2-(2,4-dichlorphenyi)-&thyl-(l))-l,2/4-triazol]-Kupfer-(II)-chlorid vom Schmelzpunkt 196°C.9.58 parts of l-r2- (4-chlorophenyimerca.pte) -2- (2,4-diehlorophenyl) ethyl (l) Il., 2,4-triazole are dissolved in 300 parts of ethanol and added dropwise with a solution of 2.2 parts of hydrated copper (II ') chloride in 3 parts of water. After stirring for 20 minutes, the product is filtered off with suction. 10 parts of bis-1- (2- (4-chlorophenyl- 'mercapto) -2- (2,4-dichlorophenyi) - ethyl- (l)) - 1,2,4-triazole] copper (II ) chloride with a melting point of 196 ° C.
Claims (19)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19772724684 DE2724684A1 (en) | 1977-06-01 | 1977-06-01 | TRIAZOLE-SUBSTITUTED SULFUR COMPOUNDS |
DE2724684 | 1977-06-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000112A1 true EP0000112A1 (en) | 1978-12-20 |
EP0000112B1 EP0000112B1 (en) | 1981-09-09 |
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ID=6010391
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100044A Expired EP0000112B1 (en) | 1977-06-01 | 1978-06-01 | Triazol-substituted sulphur derivatives, their preparation and their utilisation as fungicides |
Country Status (2)
Country | Link |
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EP (1) | EP0000112B1 (en) |
DE (2) | DE2724684A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0022531A1 (en) * | 1979-07-17 | 1981-01-21 | Bayer Ag | 1-(2,4-Dichlorophenyl)-1-(2,6-dihalogenobenzylmercapto)-2-(1,2,4-triazol-1-yl)-ethanes, process for their preparation and their use as fungicides |
EP0059894A1 (en) * | 1981-03-07 | 1982-09-15 | Bayer Ag | Triazolyl-alkyl-thioethers, process for their preparation and their application as plant growth regulators and as fungicides |
EP0146755A1 (en) * | 1983-11-23 | 1985-07-03 | Bayer Ag | Use of 1-(2,4-dichlorophenyl)-1-(4-chlorobenzyl(thio)-2-(1,2,4-triazol-1-yl) ethane for regulating the growth of plants |
EP0061789B1 (en) * | 1981-03-27 | 1985-10-23 | Janssen Pharmaceutica N.V. | Novel antimicrobial triazole derivatives |
WO1993011118A1 (en) * | 1991-12-04 | 1993-06-10 | Agrevo Uk Limited | Azole derivative herbicides and fungicides |
WO1994008978A1 (en) * | 1992-10-09 | 1994-04-28 | Uniroyal Chemical Company, Inc. | Fungicidal substituted azole derivatives |
WO2003055850A1 (en) * | 2001-12-27 | 2003-07-10 | Daiichi Pharmaceutical Co., Ltd. | β-AMYLOID PROTEIN PRODUCTION/SECRETION INHIBITORS |
US7932271B2 (en) | 2003-06-30 | 2011-04-26 | Daiichi Pharmaceutical Co., Ltd. | Heterocyclic methyl sulfone derivative |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL7710992A (en) * | 1976-10-08 | 1978-04-11 | Bayer Ag | METHOD FOR PREPARING (1-PHENYL-2-TRIAZOLYL-ETHYL) THIOETHER DERIVATIVES AND USE THEREOF AS FUNGICIDES AND GROWTH CONTROLS. |
-
1977
- 1977-06-01 DE DE19772724684 patent/DE2724684A1/en not_active Withdrawn
-
1978
- 1978-06-01 EP EP78100044A patent/EP0000112B1/en not_active Expired
- 1978-06-01 DE DE7878100044T patent/DE2861048D1/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL7710992A (en) * | 1976-10-08 | 1978-04-11 | Bayer Ag | METHOD FOR PREPARING (1-PHENYL-2-TRIAZOLYL-ETHYL) THIOETHER DERIVATIVES AND USE THEREOF AS FUNGICIDES AND GROWTH CONTROLS. |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0022531A1 (en) * | 1979-07-17 | 1981-01-21 | Bayer Ag | 1-(2,4-Dichlorophenyl)-1-(2,6-dihalogenobenzylmercapto)-2-(1,2,4-triazol-1-yl)-ethanes, process for their preparation and their use as fungicides |
EP0059894A1 (en) * | 1981-03-07 | 1982-09-15 | Bayer Ag | Triazolyl-alkyl-thioethers, process for their preparation and their application as plant growth regulators and as fungicides |
US4507141A (en) * | 1981-03-07 | 1985-03-26 | Bayer Aktiengesellschaft | Triazolylalkyl-thioether plant growth regulators and fungicides |
EP0061789B1 (en) * | 1981-03-27 | 1985-10-23 | Janssen Pharmaceutica N.V. | Novel antimicrobial triazole derivatives |
EP0146755A1 (en) * | 1983-11-23 | 1985-07-03 | Bayer Ag | Use of 1-(2,4-dichlorophenyl)-1-(4-chlorobenzyl(thio)-2-(1,2,4-triazol-1-yl) ethane for regulating the growth of plants |
WO1993011118A1 (en) * | 1991-12-04 | 1993-06-10 | Agrevo Uk Limited | Azole derivative herbicides and fungicides |
WO1994008978A1 (en) * | 1992-10-09 | 1994-04-28 | Uniroyal Chemical Company, Inc. | Fungicidal substituted azole derivatives |
WO2003055850A1 (en) * | 2001-12-27 | 2003-07-10 | Daiichi Pharmaceutical Co., Ltd. | β-AMYLOID PROTEIN PRODUCTION/SECRETION INHIBITORS |
US7399775B2 (en) | 2001-12-27 | 2008-07-15 | Daiichi Pharmaceutical Co., Ltd. | β-amyloid protein production/secretion inhibitor |
US7932271B2 (en) | 2003-06-30 | 2011-04-26 | Daiichi Pharmaceutical Co., Ltd. | Heterocyclic methyl sulfone derivative |
Also Published As
Publication number | Publication date |
---|---|
EP0000112B1 (en) | 1981-09-09 |
DE2724684A1 (en) | 1978-12-14 |
DE2861048D1 (en) | 1981-11-26 |
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