CA1132579A - Halogenated 1-azolyl-1-fluorophenoxy- butane derivatives, a process for their preparation and their use as fungicides - Google Patents
Halogenated 1-azolyl-1-fluorophenoxy- butane derivatives, a process for their preparation and their use as fungicidesInfo
- Publication number
- CA1132579A CA1132579A CA336,500A CA336500A CA1132579A CA 1132579 A CA1132579 A CA 1132579A CA 336500 A CA336500 A CA 336500A CA 1132579 A CA1132579 A CA 1132579A
- Authority
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- Canada
- Prior art keywords
- compound
- fluorophenoxy
- dimethyl
- butan
- triazol
- 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.)
- Expired
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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
- A01N43/64—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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/16—Saturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
1-Azolyl-4-halo-3,3-dimethyl-1-fluorophenoxy butanes of the formula
1-Azolyl-4-halo-3,3-dimethyl-1-fluorophenoxy butanes of the formula
Description
Type Ia The present invention relates to certain new l-azolyl-l-fluorophenoxy-butane derivatives,to a process for their preparation and to their use as fungicides.
It has already been disclosed that l-a~olyl-l-chloro-phenoxy-butane derivatives, for example 4-chloro-1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)- or -(imidazol-l-yl)-butan-2-one and 4-bromo-1-(4-chloro-phenoxy)-3,3-dimethyl-1-(imidazol-1-yl)-butan-2-ol have good fungicidal properties (see DT-ûS (German Published lû Specification) 2,632,602 (Le A 17 274) and DT-OS (German Published Specification) 2,632,603 (Le A 17 273)).
However, their good action is not always completely satisfactory, especially when low amounts and concentrations are used.
The present invention now provides, as new compounds, the halogenated l-azolyl-l-fluorophenoxy-butane derivatives of the general formula ~ -O - CH - A - 7 CH2Y (I) ~N~B CH3 N-in which 2û A represents a keto group or a CH(OH) group, B represents a nitrogen atom or a CH group and Y represents halogen, and their physiologically acceptable salts. They have powerful fungicidal properties.
Preferably, in formula (I), Y represents chlorine or bromine.
These compounds of the formula (I) in which A
represents the CH(OH) group have two asymmetric carbon Le A 19 168 1~32579 atoms; they can therefore exist in the form of the two geometic isomers (erythro form and threo form), which can be obtained in various proportions. In both cases, they exist in the form of optical isomers. All the isomers are incl~ded within the`formula (I).
The invention also provides a process for the preparation of a halogenated l-azolyl-l-fluorophenoxy-butane derivative of the formula (I) in which a bromo-ether-ketone of the general formula --O - ~ - CO - C - CH2 Y ( I I ), ~ CH~
.
in which Y has the meaning stated above, is reacted with an azole of the general formula ~1 ~~ ~ (III) , in which B has the meaning stated above, in the presence of an acid-binding agent and in the presence of a diluent, and the ketone derivative thereby obtained is optionally reduced with a Complex borohydride in a manner which i9 in itself known, if appropriate in t~ presence of a diluent.
~urthermore, the halogenated l-azolyl-l-fluoro-phenoxy-butane derivatives obtainable according to the invention can be converted into the salts by reaction with acids.
Surprisingly, the active compounds according to the invention exhibit a considerably higher fungicidal activity, in particular against species of powdery Le A l9 16~
_ ~
'257~
~ 3 --mildew, than the l-azolyl-1-chlolophenoxy-butane derivatives known from the state of the art, such as 4-chloro-1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)- or -(imidazol-l-yl)-butan-2-one and 4-bromo-1-(4-chloro-phenoxy)-3,3-dimethyl-1-(imidazol-1-yl)-butan-2-ol, which are very closely related compounds chemically and from the point of view of their action. The active compounds according to the invention thus represent an enrichment of the art If l-bromo-4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-butan-2-one and 1,2,4-triazole are used as starting materials, the course of the reaction can be represented by the following equation:
F ~ O-CH-CO-~-CH2Cl + ~ ~ Ib~ase F ~ O-CH-CO-C-CH2Cl .~ - .
If 4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-one and sodium borohydride are used as starting materials, the course of the reaction can be represented by the following equation:
F ~ O-C~H-CO-~-CH2Cl ~ -~
`N CH~
N_U
F~O-CH-C~I-C-CH2 Cl N~N - CH3 N
Le A 19 168 ~325'79 The formula (II ! provides a general definition of the bromoether-ketones to ~e used as starting substances.
In this formula, Y preferably represents chlorine or bromine.
The bromoether-keton`es of the formula (II) have not hitherto been disclosed in the literature, but can be obtained by known processes, for example by reacting fluorophenol with a bromoketone of the formula CH3 (IV) Br - C~2 - C0 - I - CH2 Y
CH~
10 in which Y has the meaning stated above.
The active hydrogen atom which still remains is then re-placed by bromine in the customary manner (see also the preparative examples later in this text).
Examples which may be mentioned of the starting com-pounds of the formula (II) are: l-bromo-4-chloro-(4-fluorophenoxy)-3,3-dimethyl-butan-2-one and 1,4-dibromo-(4-fluorophenoxy)-3,3-dimethyl-butan-2-one~
The azoles (III) are well known compounds in organic chemistrY-Possible salts of the compounds of ~he formula (I)are salts with physiologically acceptable acids. These include, as preferences, the hydrogen halide acids(for example hydrobromic acid and in particular hydrochloric acid), phosphoric acid, nitric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (for example acetic acid, citric acid, sorbic acid and lactic acid), and sulphonic acids (for example 1,5-naphthalenedisulphonic acid).
Preferred diluents for the reaction according to the invention are inert organic solvents. These include Le A 19 168 ~32~7~
-- 5 ~
as preferences, ketones, such as diethyl ketone, and in particular acetone and methyl ethyl ketone; nitriles, such as propionitrile, and in particular acetonitrile;
alcohols, such as ethanol or isopropanol, ethers, such as tetrahydrofuran or dioxan; aromatic, optionally halogenated hydrocarbons, such as toluene, 1,3-dichlorobenzene or benzene; formamides, such as, in particular, dimethyl-formamide; and halogenated aliphatic hydrocarbons, such as methylene chloride, carbon tetrachloride or chloroform.
The reaction is carried out in the presence of an acid-binding agent. Any of the inorganic or organic acid-binding agents which can customarily be used, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, or such as lower tertiary alkylamines, cycloalkylamines or aralkylamines, for example triethylamine, N,N-dimethylcyclohexylamine, dicyclohexylmethylamine or N,N-dimethylbenzylamine, and furthermore pyridine and diazabicyclooctane, can be added.
An appropriate excess of the azole of the formula (III) is preferably used.
The reaction temperatures can be varied within a substantial range. In general, the reaction is carried out at from 0 to 150C, preferably at from 60 to 120C.
In carrying out the process according to the invention, 1 to 2 moles of azole and 1 to 2 moles of acid-binding agent are preferably employed per mole of the compound of the formula (II). In order to isolate the compound of the formula (I), the solyent is distilled off, the residue is taken up in an organic solvent and the mixture is washed with water. The organic phase is dried over sodium sul-phate and freed from solvent in vacuo. The residue is purified by distillation or recrystallisation.
For the optional reduction of the keto compounds, poss-ible diluents for the reaction according to the invention are Le A 19 168 1~3Z57~
polar organic solvents.` These 'lnclude, as preferences, alcohols, such as methanol', ethanol, butanol or isopropanol, and ethers, such as diethyl ether or tetrahydrofuran. In general, the reaction is carried out at from 0 to 30C, preferably at from 0 to 20C. For this reaction, about 1 mole of a borohydride, such as sodium borohydride or ' lithium borohydride, is employed per mole of the corres-- ponding keto compound. In order to isolate the compound of the formula (I), the residue is taken up in, for example, dilute hydrochloric acid and the mixture is then rendered alkaline and extracted with an organic solvent, or only water is added to the mixture and the mixture is extracted by shaking with an organic solvent. Further working up is carried out in the customary manner.
The active compounds according to the invention ex-hibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organisms. The active compounds are suitable for use as plant protection agents.
Fungicidal agents in plant protection are employed for combating Plasmod'iop'ho'romy'cetes, Oomycetes, Chytridio-mycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
The good toleration, by plants, of the active com-pounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating Erysiphe speci~s. It should be emphasised that the active compounds according to the invention not only develop a protective action, but also have a systemic action. Thus, it is possible to protect plants against fungal attack when the active compound is fed to the above-ground parts of the plant via the soil and the root or via the seed.
Le A 19 168 :1~325~79 The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ~LV
cold mist and warm mist formulations.
These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl-sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, Le A 19 168 propane, nitrogen and carbon dloxide:
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and -~ 5 ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers ~or granules there may be used crushed and fractionated natural rocks - such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxy-ethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methyl-cellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other active compounds, such as fungi-cides, bactericides, insecticides, acaricides, nematicides, Le A 19 168 1.~3Z5~79 herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure.
The active compounds can be used-as such or in the form of their formulations or the use forms prepared there-from by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in t~e customary manner, for example by watering, immersion, spraying, atomising, misting, vaporising, inject-ing, forming a slurry, brushing on, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.
Especially in the treatment of parts of plants, the act-ive compound concentrations in the use forms can be varied within a substantial range. They are, in general, from 1 to 0.0001% by weight, preferably from 0.5 to 0.001%.
In the treatment of seed, amounts of active compound of 0.001 to 50 g, especially 0.01 to 10 g, are generally employed per kilogram of seed.
For the treatment of soil, active compound concen-trations of 0.00001 to 0.1% by weight, especially of 0.0001 to 0.02%, are generally employed at the place of action.
The present invention also provides a fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a compound of the present in-vention alone or in the form of a composition containing as active lngredient a compound of tne present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound Le A 19 168 1:1L3:257~
of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The fungicidal activity of the compounds of this invention is illustrated by the following biotest Examples.
Example A
Shoot treatment test/powdery mildew of cereals (leaf-destructive mycosis)/protective To produce a suitable preparation of active compound, 0.25 part by weight of active compound was taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether; 975 parts by weight of water were then added. The concentrate was diluted with water to the desired final concentration of the spray liquor.
To test for protective activity, single-leaved young barley plants of the Amsel variety were sprayed with the preparation of active compound until dew-moist.
After drying, the barley plants were dusted with spores of Erysiphe graminis var. hordei.
-- After 6 days' dwell time of the plants at a tempera-ture of 21-22 deg.C and 80-90% atmospheric humidity the occurrence of mildew pustules on the plants was evaluated.
The degree of infection was expressed as a percentage of the infection of the untreated control plants. 0%
denoted no infection and 100% denoted the same degree of infection as in the case of the untreated control.
The active compound was the more active, the lower was 3 the degree of mildew infection.
The active compounds, active compound concentrations in the spray liquor and degrees of infection can be seen from the table which follows:
Le A 19 168 1~32~
'' a b'`l''e'''A
Shoot treatment test/powdery mildew of cereal/protective Active com- Infection pound concen- in % of Active compounds tration in the un-the spray treated liquor in % control by weight .
~H~
Cl- ~ -0-CIH-CO-C-CHzCl 0,00025 100 CH~
N ~ SO~H
- -- x l/2 ~
CHI
_ F-~ ~ ~0-C~H-C0-CI-CHzCl 0.00025 37,5 ~N~N CH~
x l/2 ~
SO~H
Cl- ~ -0-C -C0-C-CHzCl 0,00025 5 t ~ N ~03H
(known) ~ l/2 ~
SO~H
~H3 F- ~ -0-CH C0-~-CH2Cl 0~00025 10~0 (6) ~ N x l/2 ~
SO~H
Le A 19 168 ` 1~3Z57~
ExampIe B
Powdery mildew of barley ('Erys'i'~'he''g~a'mi'~is var.''h'o'rd'ei) . _ , , (fungal disease of cereal shoots)/systemic The active compound w'as used as a pulverulent seed treatment agent. mis was prepared by extending the particular active compound with a mixture of equal parts by weight of talc and kieselguhr to give a finely pulverulent mixture of the desired concentration of active compound.
For the treatment of seed, barley seed was shaken with the extended active compound in a closed glass bottle. The seed was sown at the rate of 3 x 12 grains in flowerpots, 2 cm deep in a mixture of one part by volume of Fruhstorfer standard soil and one part by volume of quartz sand. The germination and emergence took place under favourable conditions in a greenhouse. 7 days after sowing, when the barley plants had developed their first leaf, they were dusted with fresh spores of Erysiphe gra~inis var. hordei and grown on at 21-22 deg.C and 80-90% relative atmospheric humidity and 16 hours' exposure to light. The typical mildew pustules formed on the leaves over the course of 6 days.
The degree of infection was expressed as a percentage of the infection of the untreated control plants. Thus, 0% denoted no infection and 100% denoted the same degree of infection as in the case of the untreated control.
The active compound was the more active, the lower was the degree of mildew infection.
The active compounds and concentrations of active compound in the seed treatment agent, as well as the 3 amount used of the latter, and the percentage infection with mildew can be seen from the table which follows:
Le A 19 168 1~3Z~
.
a~
~ a~ -o O U~
o o ~
H ~ C~ . Lr~ r~l .
~ .
U~
~rl 0 ~ .
O bO . ' aD
rn ~ u~ O O
~13~ ~ -m ~1 ~ rl ~
~ .~ 0~ 0~
. t~q 0~ S~O, 3 .IS~
. ~ ~S5 ?~
' S~ .
. ~ P~
V~
~ ~-~
E . g_ ~z ~3 ~ (~
Le A 19 16 8 1~325~79 Preparative''e'x'a'mp'les Example 1 CH~
F - ~ - 0 - CH - C0 - C - CH2Cl CH~ (1) S~ H
x 1/2 ~
~ . .. . .. . .. ..
SO~H
57 g (0.177 mol) of 1-bromo-4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-butan-2-one were dissolved in 600 ml of absolute acetonitrile, 24.2 g (0.35 mol) of 1,2,4-triazole were added and the mixture was heated under reflux for 6 hours. m e solvent was distilled off under a waterpump vacuum, the residue was taken up in 700 ml of methylene chloride and the organic phase was extracted twice with 1.5 litresof water and dried over sodium sulphate. The solvent was distilled off under a waterpump vacuum and the oil which remained was taken up in 200 ml of acetone. 18 g (0.1 mol) of 1,5-naphthalenedisulphonic acid, dissolved in 100 ml of acetone, were added and the precipitate which had formed was filtered off. 47 g ~55.7% of theory) of 4-chloro-3,3-dimethyl-l-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-
It has already been disclosed that l-a~olyl-l-chloro-phenoxy-butane derivatives, for example 4-chloro-1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)- or -(imidazol-l-yl)-butan-2-one and 4-bromo-1-(4-chloro-phenoxy)-3,3-dimethyl-1-(imidazol-1-yl)-butan-2-ol have good fungicidal properties (see DT-ûS (German Published lû Specification) 2,632,602 (Le A 17 274) and DT-OS (German Published Specification) 2,632,603 (Le A 17 273)).
However, their good action is not always completely satisfactory, especially when low amounts and concentrations are used.
The present invention now provides, as new compounds, the halogenated l-azolyl-l-fluorophenoxy-butane derivatives of the general formula ~ -O - CH - A - 7 CH2Y (I) ~N~B CH3 N-in which 2û A represents a keto group or a CH(OH) group, B represents a nitrogen atom or a CH group and Y represents halogen, and their physiologically acceptable salts. They have powerful fungicidal properties.
Preferably, in formula (I), Y represents chlorine or bromine.
These compounds of the formula (I) in which A
represents the CH(OH) group have two asymmetric carbon Le A 19 168 1~32579 atoms; they can therefore exist in the form of the two geometic isomers (erythro form and threo form), which can be obtained in various proportions. In both cases, they exist in the form of optical isomers. All the isomers are incl~ded within the`formula (I).
The invention also provides a process for the preparation of a halogenated l-azolyl-l-fluorophenoxy-butane derivative of the formula (I) in which a bromo-ether-ketone of the general formula --O - ~ - CO - C - CH2 Y ( I I ), ~ CH~
.
in which Y has the meaning stated above, is reacted with an azole of the general formula ~1 ~~ ~ (III) , in which B has the meaning stated above, in the presence of an acid-binding agent and in the presence of a diluent, and the ketone derivative thereby obtained is optionally reduced with a Complex borohydride in a manner which i9 in itself known, if appropriate in t~ presence of a diluent.
~urthermore, the halogenated l-azolyl-l-fluoro-phenoxy-butane derivatives obtainable according to the invention can be converted into the salts by reaction with acids.
Surprisingly, the active compounds according to the invention exhibit a considerably higher fungicidal activity, in particular against species of powdery Le A l9 16~
_ ~
'257~
~ 3 --mildew, than the l-azolyl-1-chlolophenoxy-butane derivatives known from the state of the art, such as 4-chloro-1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)- or -(imidazol-l-yl)-butan-2-one and 4-bromo-1-(4-chloro-phenoxy)-3,3-dimethyl-1-(imidazol-1-yl)-butan-2-ol, which are very closely related compounds chemically and from the point of view of their action. The active compounds according to the invention thus represent an enrichment of the art If l-bromo-4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-butan-2-one and 1,2,4-triazole are used as starting materials, the course of the reaction can be represented by the following equation:
F ~ O-CH-CO-~-CH2Cl + ~ ~ Ib~ase F ~ O-CH-CO-C-CH2Cl .~ - .
If 4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-one and sodium borohydride are used as starting materials, the course of the reaction can be represented by the following equation:
F ~ O-C~H-CO-~-CH2Cl ~ -~
`N CH~
N_U
F~O-CH-C~I-C-CH2 Cl N~N - CH3 N
Le A 19 168 ~325'79 The formula (II ! provides a general definition of the bromoether-ketones to ~e used as starting substances.
In this formula, Y preferably represents chlorine or bromine.
The bromoether-keton`es of the formula (II) have not hitherto been disclosed in the literature, but can be obtained by known processes, for example by reacting fluorophenol with a bromoketone of the formula CH3 (IV) Br - C~2 - C0 - I - CH2 Y
CH~
10 in which Y has the meaning stated above.
The active hydrogen atom which still remains is then re-placed by bromine in the customary manner (see also the preparative examples later in this text).
Examples which may be mentioned of the starting com-pounds of the formula (II) are: l-bromo-4-chloro-(4-fluorophenoxy)-3,3-dimethyl-butan-2-one and 1,4-dibromo-(4-fluorophenoxy)-3,3-dimethyl-butan-2-one~
The azoles (III) are well known compounds in organic chemistrY-Possible salts of the compounds of ~he formula (I)are salts with physiologically acceptable acids. These include, as preferences, the hydrogen halide acids(for example hydrobromic acid and in particular hydrochloric acid), phosphoric acid, nitric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (for example acetic acid, citric acid, sorbic acid and lactic acid), and sulphonic acids (for example 1,5-naphthalenedisulphonic acid).
Preferred diluents for the reaction according to the invention are inert organic solvents. These include Le A 19 168 ~32~7~
-- 5 ~
as preferences, ketones, such as diethyl ketone, and in particular acetone and methyl ethyl ketone; nitriles, such as propionitrile, and in particular acetonitrile;
alcohols, such as ethanol or isopropanol, ethers, such as tetrahydrofuran or dioxan; aromatic, optionally halogenated hydrocarbons, such as toluene, 1,3-dichlorobenzene or benzene; formamides, such as, in particular, dimethyl-formamide; and halogenated aliphatic hydrocarbons, such as methylene chloride, carbon tetrachloride or chloroform.
The reaction is carried out in the presence of an acid-binding agent. Any of the inorganic or organic acid-binding agents which can customarily be used, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, or such as lower tertiary alkylamines, cycloalkylamines or aralkylamines, for example triethylamine, N,N-dimethylcyclohexylamine, dicyclohexylmethylamine or N,N-dimethylbenzylamine, and furthermore pyridine and diazabicyclooctane, can be added.
An appropriate excess of the azole of the formula (III) is preferably used.
The reaction temperatures can be varied within a substantial range. In general, the reaction is carried out at from 0 to 150C, preferably at from 60 to 120C.
In carrying out the process according to the invention, 1 to 2 moles of azole and 1 to 2 moles of acid-binding agent are preferably employed per mole of the compound of the formula (II). In order to isolate the compound of the formula (I), the solyent is distilled off, the residue is taken up in an organic solvent and the mixture is washed with water. The organic phase is dried over sodium sul-phate and freed from solvent in vacuo. The residue is purified by distillation or recrystallisation.
For the optional reduction of the keto compounds, poss-ible diluents for the reaction according to the invention are Le A 19 168 1~3Z57~
polar organic solvents.` These 'lnclude, as preferences, alcohols, such as methanol', ethanol, butanol or isopropanol, and ethers, such as diethyl ether or tetrahydrofuran. In general, the reaction is carried out at from 0 to 30C, preferably at from 0 to 20C. For this reaction, about 1 mole of a borohydride, such as sodium borohydride or ' lithium borohydride, is employed per mole of the corres-- ponding keto compound. In order to isolate the compound of the formula (I), the residue is taken up in, for example, dilute hydrochloric acid and the mixture is then rendered alkaline and extracted with an organic solvent, or only water is added to the mixture and the mixture is extracted by shaking with an organic solvent. Further working up is carried out in the customary manner.
The active compounds according to the invention ex-hibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organisms. The active compounds are suitable for use as plant protection agents.
Fungicidal agents in plant protection are employed for combating Plasmod'iop'ho'romy'cetes, Oomycetes, Chytridio-mycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
The good toleration, by plants, of the active com-pounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating Erysiphe speci~s. It should be emphasised that the active compounds according to the invention not only develop a protective action, but also have a systemic action. Thus, it is possible to protect plants against fungal attack when the active compound is fed to the above-ground parts of the plant via the soil and the root or via the seed.
Le A 19 168 :1~325~79 The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ~LV
cold mist and warm mist formulations.
These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl-sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, Le A 19 168 propane, nitrogen and carbon dloxide:
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and -~ 5 ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers ~or granules there may be used crushed and fractionated natural rocks - such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxy-ethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methyl-cellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other active compounds, such as fungi-cides, bactericides, insecticides, acaricides, nematicides, Le A 19 168 1.~3Z5~79 herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure.
The active compounds can be used-as such or in the form of their formulations or the use forms prepared there-from by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in t~e customary manner, for example by watering, immersion, spraying, atomising, misting, vaporising, inject-ing, forming a slurry, brushing on, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.
Especially in the treatment of parts of plants, the act-ive compound concentrations in the use forms can be varied within a substantial range. They are, in general, from 1 to 0.0001% by weight, preferably from 0.5 to 0.001%.
In the treatment of seed, amounts of active compound of 0.001 to 50 g, especially 0.01 to 10 g, are generally employed per kilogram of seed.
For the treatment of soil, active compound concen-trations of 0.00001 to 0.1% by weight, especially of 0.0001 to 0.02%, are generally employed at the place of action.
The present invention also provides a fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a compound of the present in-vention alone or in the form of a composition containing as active lngredient a compound of tne present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound Le A 19 168 1:1L3:257~
of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The fungicidal activity of the compounds of this invention is illustrated by the following biotest Examples.
Example A
Shoot treatment test/powdery mildew of cereals (leaf-destructive mycosis)/protective To produce a suitable preparation of active compound, 0.25 part by weight of active compound was taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether; 975 parts by weight of water were then added. The concentrate was diluted with water to the desired final concentration of the spray liquor.
To test for protective activity, single-leaved young barley plants of the Amsel variety were sprayed with the preparation of active compound until dew-moist.
After drying, the barley plants were dusted with spores of Erysiphe graminis var. hordei.
-- After 6 days' dwell time of the plants at a tempera-ture of 21-22 deg.C and 80-90% atmospheric humidity the occurrence of mildew pustules on the plants was evaluated.
The degree of infection was expressed as a percentage of the infection of the untreated control plants. 0%
denoted no infection and 100% denoted the same degree of infection as in the case of the untreated control.
The active compound was the more active, the lower was 3 the degree of mildew infection.
The active compounds, active compound concentrations in the spray liquor and degrees of infection can be seen from the table which follows:
Le A 19 168 1~32~
'' a b'`l''e'''A
Shoot treatment test/powdery mildew of cereal/protective Active com- Infection pound concen- in % of Active compounds tration in the un-the spray treated liquor in % control by weight .
~H~
Cl- ~ -0-CIH-CO-C-CHzCl 0,00025 100 CH~
N ~ SO~H
- -- x l/2 ~
CHI
_ F-~ ~ ~0-C~H-C0-CI-CHzCl 0.00025 37,5 ~N~N CH~
x l/2 ~
SO~H
Cl- ~ -0-C -C0-C-CHzCl 0,00025 5 t ~ N ~03H
(known) ~ l/2 ~
SO~H
~H3 F- ~ -0-CH C0-~-CH2Cl 0~00025 10~0 (6) ~ N x l/2 ~
SO~H
Le A 19 168 ` 1~3Z57~
ExampIe B
Powdery mildew of barley ('Erys'i'~'he''g~a'mi'~is var.''h'o'rd'ei) . _ , , (fungal disease of cereal shoots)/systemic The active compound w'as used as a pulverulent seed treatment agent. mis was prepared by extending the particular active compound with a mixture of equal parts by weight of talc and kieselguhr to give a finely pulverulent mixture of the desired concentration of active compound.
For the treatment of seed, barley seed was shaken with the extended active compound in a closed glass bottle. The seed was sown at the rate of 3 x 12 grains in flowerpots, 2 cm deep in a mixture of one part by volume of Fruhstorfer standard soil and one part by volume of quartz sand. The germination and emergence took place under favourable conditions in a greenhouse. 7 days after sowing, when the barley plants had developed their first leaf, they were dusted with fresh spores of Erysiphe gra~inis var. hordei and grown on at 21-22 deg.C and 80-90% relative atmospheric humidity and 16 hours' exposure to light. The typical mildew pustules formed on the leaves over the course of 6 days.
The degree of infection was expressed as a percentage of the infection of the untreated control plants. Thus, 0% denoted no infection and 100% denoted the same degree of infection as in the case of the untreated control.
The active compound was the more active, the lower was the degree of mildew infection.
The active compounds and concentrations of active compound in the seed treatment agent, as well as the 3 amount used of the latter, and the percentage infection with mildew can be seen from the table which follows:
Le A 19 168 1~3Z~
.
a~
~ a~ -o O U~
o o ~
H ~ C~ . Lr~ r~l .
~ .
U~
~rl 0 ~ .
O bO . ' aD
rn ~ u~ O O
~13~ ~ -m ~1 ~ rl ~
~ .~ 0~ 0~
. t~q 0~ S~O, 3 .IS~
. ~ ~S5 ?~
' S~ .
. ~ P~
V~
~ ~-~
E . g_ ~z ~3 ~ (~
Le A 19 16 8 1~325~79 Preparative''e'x'a'mp'les Example 1 CH~
F - ~ - 0 - CH - C0 - C - CH2Cl CH~ (1) S~ H
x 1/2 ~
~ . .. . .. . .. ..
SO~H
57 g (0.177 mol) of 1-bromo-4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-butan-2-one were dissolved in 600 ml of absolute acetonitrile, 24.2 g (0.35 mol) of 1,2,4-triazole were added and the mixture was heated under reflux for 6 hours. m e solvent was distilled off under a waterpump vacuum, the residue was taken up in 700 ml of methylene chloride and the organic phase was extracted twice with 1.5 litresof water and dried over sodium sulphate. The solvent was distilled off under a waterpump vacuum and the oil which remained was taken up in 200 ml of acetone. 18 g (0.1 mol) of 1,5-naphthalenedisulphonic acid, dissolved in 100 ml of acetone, were added and the precipitate which had formed was filtered off. 47 g ~55.7% of theory) of 4-chloro-3,3-dimethyl-l-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-
2-one 1,5-naphthalenedisulphonate of melting point 200C
were obtained.
Preparation 'of the starting material CH~
F - ~ - 0 - ICH - C0 - C - CH2Cl Br CH~
100.2 g (0.617 mol) of 1,4-dichloro-3,3-dimethyl-butan-2-one were added dropwise to a solution of 56 g (0.5 mol) of p-fluorophenol and 85 g of potassium carbonate in Le A I9 168 113Z5'79 700 ml of acetone at the boiling point. The mixture was - stirred under reflux for 6 hours and filtered off and the solvent was distilled under the filtrate. 101.5 g (83% of theory) of 4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-butan-2-one were obtained and were dissolved in the crude state in 600 ml of methylene chloride. 66.3 g (0.415 mol) of bromine were then added dropwise at room temperature in a manner such that decoloration occurred. The mixture was subsequently stirred for 30 minutes, the solvent was dis-tilled off under a waterpump vacuum and 100 ml of pentanewere added to the residue, whereupon the residue crystallised. 114 g (85% of theory) of 1-bromo-4-chloro-
were obtained.
Preparation 'of the starting material CH~
F - ~ - 0 - ICH - C0 - C - CH2Cl Br CH~
100.2 g (0.617 mol) of 1,4-dichloro-3,3-dimethyl-butan-2-one were added dropwise to a solution of 56 g (0.5 mol) of p-fluorophenol and 85 g of potassium carbonate in Le A I9 168 113Z5'79 700 ml of acetone at the boiling point. The mixture was - stirred under reflux for 6 hours and filtered off and the solvent was distilled under the filtrate. 101.5 g (83% of theory) of 4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-butan-2-one were obtained and were dissolved in the crude state in 600 ml of methylene chloride. 66.3 g (0.415 mol) of bromine were then added dropwise at room temperature in a manner such that decoloration occurred. The mixture was subsequently stirred for 30 minutes, the solvent was dis-tilled off under a waterpump vacuum and 100 ml of pentanewere added to the residue, whereupon the residue crystallised. 114 g (85% of theory) of 1-bromo-4-chloro-
3 3 3-dimethyl-1-(4-fluorophenoxy)-butan-2-one of melting point 74C were obtained.
CH, ClCH2 - CO - C - CH2Cl 1,050 g (7.8 mol) of 78% pure 4-chloro-3,3-dimethyl-butan-2-one were dissolv~d in 6 litres of methylene chloride, and 450 g of chlorine were passed in at 10 to 11C in the course of 6 hours. Thereafter, the mixture was subsequently stirred for 30 minutes, excess hydrogen chloride was driven off with nitrogen and the reaction mixture was distilled over a 60 cm packed column. 832 g (63% of theory) of 1,4-dichloro-3,3-dimethyl-butan-2-one of boiling point 52-54~C/
0.1 mm Hg were obtained in a purity of 75%.
E ample 2 .
OH CH~
F - ~ - O - CH - CH - C - CH2Cl (2) N ~ CH3 N ~
CH, ClCH2 - CO - C - CH2Cl 1,050 g (7.8 mol) of 78% pure 4-chloro-3,3-dimethyl-butan-2-one were dissolv~d in 6 litres of methylene chloride, and 450 g of chlorine were passed in at 10 to 11C in the course of 6 hours. Thereafter, the mixture was subsequently stirred for 30 minutes, excess hydrogen chloride was driven off with nitrogen and the reaction mixture was distilled over a 60 cm packed column. 832 g (63% of theory) of 1,4-dichloro-3,3-dimethyl-butan-2-one of boiling point 52-54~C/
0.1 mm Hg were obtained in a purity of 75%.
E ample 2 .
OH CH~
F - ~ - O - CH - CH - C - CH2Cl (2) N ~ CH3 N ~
4.75 g (0.12 mol) of sodium borohydride were added Le A 19 168 ~3Z5 in portions to 25 g ~0.053 mol) of 4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-one naphthalenedisulphonate (Example l),-dissolved in 400 ml of methanol~ and the mixture was subsequently stirred at room temperature for 15 hours. 15 ml of concentrated hydro-chloric acid were carefully added dropwise, whilst cooling, the mixture was stirred at room temperature for 2 hours and half of the solvent was distilled off under a waterpump vacuum. The reaction mixture was added to 400 ml of saturated sodium bicarbonate solution and extracted with 300 ml of methylene chloride and the organic phase was separated off, washed twice with 100 ml of water each time, dried over sodium sulphate and concentrated by distilling off the solvent. After adding 100 ml of diisopropyl ether, the residue crystallised. 9.1 g (36.4% of theory) of 4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-ol of melting point 87-goc were obtained.
The following compounds of the general formula CH., F - ~ - O - CH - A ~ d - CH2 Y
~ N b H~ (I) N
were obtained analogously:
Ex-amplè A B Y Melting point (C) .. , , 3 CO N Br 180 (x ~ NDS) 4 CHOH N Br 100 CO CH Br 241 (x ~ NDS) 6 CO CH Cl 254 (x ~ NDS) 7 CHOH CH Br 116 8 CHOH CH Cl 115 NDS = 1,5-naphthalenedisulphonic acid Le A 19 168
The following compounds of the general formula CH., F - ~ - O - CH - A ~ d - CH2 Y
~ N b H~ (I) N
were obtained analogously:
Ex-amplè A B Y Melting point (C) .. , , 3 CO N Br 180 (x ~ NDS) 4 CHOH N Br 100 CO CH Br 241 (x ~ NDS) 6 CO CH Cl 254 (x ~ NDS) 7 CHOH CH Br 116 8 CHOH CH Cl 115 NDS = 1,5-naphthalenedisulphonic acid Le A 19 168
Claims (18)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A 1-azolyl-4-halo-3,3-dimethyl-1-fluorophenoxy-butane of the formula in which A is a keto group or a CH(OH) group, B is a nitrogen atom or a CH group, and Y is halogen, or a non-phytotoxic salt thereof.
2. A compound according to claim 1, in which Y is chlorine or bromine, and F is in the 4-position, or a salt thereof with an acid selected from the group consisting of hydrogen halide acids, phosphoric acid, nitric acid, acetic acid, citric acid, sorbic acid, lactic acid and sulphonic acids.
3. 4-Chloro-3,3-dimethyl-1-14-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-one of the formula .
4. 4-Chloro-3,3-dimethyl-1-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-ol of the formula
5. 4-Bromo-3,3-dimethyl-1-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-one of the formula
6. 4-Bromo-3,3-dimethyl-1-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl) butan-2-ol of the formula
7. A method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a fungicidally effective amount of a compound according to claim 1.
8. A method according to claim 7 wherein said compound is applied in the form of a composition containing said compound in admixture with a suitable carrier or diluent.
9. A method according to claim 8 in which a composition is used con-taining from 0.0001 to 1% of said compound, by weight.
10. A method according to claim 8 in which a composition is used con-taining from 0.001 to 0.5% of said compound, by weight.
11. A method according to claim 7 or 8, in which said compound is applied to soil in an amount of 0.00001 to 0.1% by weight.
12. A method according to claim 7 or 8, in which said compound is applied to soil in an amount of 0.0001 to 0.0% by weight.
13. A method according to claim 7 or 8, in which said compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.
14. A method according to claim 7 or 8, in which said compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.
15. A method according to claim 7 or 8, in which said compound is 4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-one.
16. A method according to claim 7 or 8, in which said compound is 4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-ol.
17. A method according to claim 7 or 8, in which said compound is 4-bromo-3,3-dimethyl-1-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-1-one.
18. A method according to claim 7 or 8, in which said compound is 4-bromo-3,3-dimethyl-1-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-ol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2842137.6 | 1978-09-28 | ||
| DE19782842137 DE2842137A1 (en) | 1978-09-28 | 1978-09-28 | HALOGENED 1-AZOLYL-1-FLUORPHENOXYBUTANE DERIVATIVES, METHODS FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1132579A true CA1132579A (en) | 1982-09-28 |
Family
ID=6050641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA336,500A Expired CA1132579A (en) | 1978-09-28 | 1979-09-27 | Halogenated 1-azolyl-1-fluorophenoxy- butane derivatives, a process for their preparation and their use as fungicides |
Country Status (20)
| Country | Link |
|---|---|
| EP (1) | EP0009707B1 (en) |
| JP (1) | JPS5545696A (en) |
| AT (1) | ATE488T1 (en) |
| BR (1) | BR7906217A (en) |
| CA (1) | CA1132579A (en) |
| CS (1) | CS208456B2 (en) |
| DD (1) | DD146292A5 (en) |
| DE (2) | DE2842137A1 (en) |
| DK (1) | DK405679A (en) |
| EG (1) | EG13799A (en) |
| ES (1) | ES484524A1 (en) |
| FI (1) | FI62295C (en) |
| IL (1) | IL58320A0 (en) |
| MA (1) | MA18596A1 (en) |
| NO (1) | NO792970L (en) |
| NZ (1) | NZ191662A (en) |
| PL (1) | PL120444B1 (en) |
| PT (1) | PT70217A (en) |
| TR (1) | TR20421A (en) |
| ZA (1) | ZA795145B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2918894A1 (en) * | 1979-05-10 | 1980-11-20 | Bayer Ag | FLUORINATED 1-TRIAZOLYL-BUTANE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| DE2918893A1 (en) * | 1979-05-10 | 1980-11-20 | Bayer Ag | FLUORINATED 1-IMIDAZOLYL BUTANE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| DE2918897A1 (en) * | 1979-05-10 | 1980-11-20 | Bayer Ag | ANTIMICROBIAL AGENTS |
| DE2918896A1 (en) * | 1979-05-10 | 1980-11-20 | Bayer Ag | ANTIMICROBIAL AGENTS |
| DE3019049A1 (en) * | 1980-05-19 | 1981-12-03 | Basf Ag, 6700 Ludwigshafen | NEW AZOLES |
| DE3048266A1 (en) * | 1980-12-20 | 1982-07-29 | Bayer Ag, 5090 Leverkusen | SUBSTITUTED 1-AZOLYL-BUTANE-2ONE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES AND AS INTERMEDIATE PRODUCTS |
| AR228764A1 (en) * | 1980-12-20 | 1983-04-15 | Bayer Ag | 1-AZOLIL-3,3-DIMETILALCAN (C3-4) -2-ONAS Y-2-OLES, SUBSTITUTED, PROCEDURE FOR THEIR PRODUCTION AND PROTECTIVE COMPOSITIONS OF PLANTS FUNGICIDES AND REGULATORS OF THE GROWTH OF PLANTS BASED ON SUCH COMPOUNDS |
| DE3279417D1 (en) * | 1981-03-18 | 1989-03-09 | Ici Plc | Triazole compounds, a process for preparing them, their use as plant fungicides and fungicidal compositions containing them |
| DE3540523A1 (en) * | 1985-11-15 | 1987-05-27 | Bayer Ag | AZOLYLETHERKETONES AND ALCOHOLS |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2455955A1 (en) * | 1974-11-27 | 1976-08-12 | Bayer Ag | FUNGICIDALS |
| DE2632602A1 (en) * | 1976-07-20 | 1978-01-26 | Bayer Ag | Halogenated triazolyl and imidazolyl-(2)-butanone and butanol cpds. - for use as fungicides and bactericides |
| DE2632601A1 (en) * | 1976-07-20 | 1978-01-26 | Bayer Ag | ANTIMICROBIAL AGENTS |
| DE2632603A1 (en) * | 1976-07-20 | 1978-01-26 | Bayer Ag | Halogenated triazolyl and imidazolyl-(2)-butanone and butanol cpds. - for use as fungicides and bactericides |
-
1978
- 1978-09-28 DE DE19782842137 patent/DE2842137A1/en not_active Withdrawn
-
1979
- 1979-09-13 NO NO792970A patent/NO792970L/en unknown
- 1979-09-17 EP EP79103486A patent/EP0009707B1/en not_active Expired
- 1979-09-17 DE DE7979103486T patent/DE2961613D1/en not_active Expired
- 1979-09-17 MA MA18796A patent/MA18596A1/en unknown
- 1979-09-17 AT AT79103486T patent/ATE488T1/en active
- 1979-09-21 CS CS796373A patent/CS208456B2/en unknown
- 1979-09-24 PT PT70217A patent/PT70217A/en unknown
- 1979-09-25 IL IL58320A patent/IL58320A0/en unknown
- 1979-09-25 NZ NZ191662A patent/NZ191662A/en unknown
- 1979-09-26 EG EG571/79A patent/EG13799A/en active
- 1979-09-26 DD DD79215826A patent/DD146292A5/en unknown
- 1979-09-26 FI FI792996A patent/FI62295C/en not_active IP Right Cessation
- 1979-09-26 JP JP12274079A patent/JPS5545696A/en active Pending
- 1979-09-26 PL PL1979218528A patent/PL120444B1/en unknown
- 1979-09-27 TR TR20421A patent/TR20421A/en unknown
- 1979-09-27 ES ES484524A patent/ES484524A1/en not_active Expired
- 1979-09-27 ZA ZA00795145A patent/ZA795145B/en unknown
- 1979-09-27 BR BR7906217A patent/BR7906217A/en unknown
- 1979-09-27 DK DK405679A patent/DK405679A/en unknown
- 1979-09-27 CA CA336,500A patent/CA1132579A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NO792970L (en) | 1980-03-31 |
| BR7906217A (en) | 1980-05-27 |
| ES484524A1 (en) | 1980-06-16 |
| ATE488T1 (en) | 1982-01-15 |
| ZA795145B (en) | 1980-10-29 |
| EG13799A (en) | 1982-06-30 |
| TR20421A (en) | 1981-06-26 |
| DD146292A5 (en) | 1981-02-04 |
| CS208456B2 (en) | 1981-09-15 |
| NZ191662A (en) | 1982-12-21 |
| PL218528A1 (en) | 1980-06-16 |
| FI62295C (en) | 1982-12-10 |
| EP0009707A1 (en) | 1980-04-16 |
| IL58320A0 (en) | 1979-12-30 |
| PL120444B1 (en) | 1982-02-27 |
| DK405679A (en) | 1980-03-29 |
| DE2961613D1 (en) | 1982-02-11 |
| FI792996A (en) | 1980-03-29 |
| PT70217A (en) | 1979-10-01 |
| EP0009707B1 (en) | 1981-12-23 |
| FI62295B (en) | 1982-08-31 |
| DE2842137A1 (en) | 1980-04-17 |
| MA18596A1 (en) | 1980-04-01 |
| JPS5545696A (en) | 1980-03-31 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |