IE42758B1 - Fungicidal agents - Google Patents

Abstract

Described is the novel use of diaryloxyimidazolyl O,N-acetals and of the salts thereof for controlling fungi. These compounds have the formula (I) in which X and Y represent halogen, alkyl, alkoxy, haloalkylthio, nitro, amino, alkylamino or dialkylamino, Z represents a direct bond and furthermore represents oxygen or sulphur, and furthermore a methylene, sulphonyl, alkoxymethylene or keto group, A represents a keto or group in which R represents hydrogen or alkyl and a and b represent 0 or an integer from 1 to 3.

Description

The present invention relates to the use as fungicidal agents certain diaryloxy-imidazolyl-O.N-acetal compounds It has already been disclosed that triazolyl-0,Nacetals, such as, for example, l-(p-chlorophenoxy)-l-[l,2,4triazolyl-(l)]-3,3-dimethylbutan-2-one, possess a very good fungicidal activity (compare German Offenlegungsschrift (German Published Specification) 2,201,063)· Furthermore, it is already known that tris-phenyl-l,2,4-imidazolyl-(l)- and -triazolyl-(l)-methane exhibit a fungicidal action against phytopathogenic fungi (compare U.S. Patent Specification 3»321,366 and German Offenlegungsschrift (German Published Specification) 1,795,249). However, the effect of these compounds is not always entirely satisfactory in sane fields of use, especially if low amounts and low concentrations are used.

It has been found that compounds which are diaryloxy imidazolyl-O.H-acetals or salts thereof, the diaryloxyimidazolyl-0,H-acetals being of the general formula X. in which X and Y, whioh may be the same or different, are halogen, alkyl, alkoxy, haloalkylthio, nitro, amino, alkylamino or dialkylamino, Z is a direct bond or oxygen, sulphur, methylene, sulphonyl, alkoxymethylene or keto, A represents keto or a —Q(OH)— group (wherein R R is hydrogen or alkyl), and - 2 42758 a and b are integers from 0 to 3, exhibit powerful fungicidal properties.

The invention provides a fungicidal composition containing as active ingredient a compound as defined in the last paragraph above, in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier, such liquid diluent or carrier preferably containing a surface-active agent. The invention also provides a method of combating fungus pests which comprises applying to the pests or a habitat thereof a compound as defined in the last paragraph above alone or in admixture with a diluent or carrier.

Surprisingly, the diaryloxy-imidazolyl-0,N-acetals to be used according to the invention exhibit a substantially greater fungicidal action than the azole derivatives known in the art, for example tris-phenyl-1,2,4-triazoly1-(1)methane, tris-phenyl-imidazolyl-(1)-methane and l-(p-chlorophenoxy)-l-[l,2,4-triazolyl-(l)J -3,3-dimethylbutan-2-one. The very good action against species of Erysiphe, Fuslcladlum and Uromyces should be singled out for particular mention. The compounds usable according to the invention thus represent an enrichment of the art.

The formula I provides a general definition of the active compounds according to the invention.

X and Y are preferably fluorine, chlorine or bromine, alkyl with up to 4 carbon atoms, (for example methyl, ethyl, isopropyl and tertiary butyl), alkoxy with up to 4, especially with 1 or 2, carbon atoms, (for example methoxy), haloalkylthio with up to 4 carbon atoms and up to 5 halogen atoms, especially with 1 or 2 carbon atoms and up to 3 identical or different halogen atoms, preferred halogens being fluorine, and chlorine, (for example trifluoromethylthio), - 3 42758 nitro, amino or alkylamino or dialkylamino with up to 4, especially with 1 or 2, oarbon atoms in each alkyl moiety, (for example ethylamino and dimethylamino). The indices a and b are preferably 0, 1 or 2. · When Z is alkoxymethylene it is preferably methoxymethylene or. ethoxymethylene. When A is a -C(OH)- group, R is preferably hydrogen, methyl or I R ethyl.

If the active compound is used in the form of a salt, it is usually preferable that the acid forming the salt should be a physiologically tolerated acid. Preferred acids include the hydrogen halide acids, for example hydrochloric acid and hydrobromic acid, phosphoric acid, nitric acid, the monofunctional and bifunctional carboxylic acids and the hydroxycarboxylic acids, for example acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and 1,5-naphthalenedisulphonic acid.

The following may be mentioned as examples of the active compounds to be used according to the invention: ΙΣΟ (imidazolyl-(l))-1-(4'-(3-methylphenyl)-phenoxy)-3,3-dimethylbutan-2-one, l-(imidazolyl-(l)]-l-[4'-(2-chlorophenyl)3'-chlorophenoxy))-3,3-dimethylbutan-2-ones, l-(imidazolyl(l))-1(4'-(2-hromo-4-chlorophenyl)-(2'-bromophenoxy))-3,3dimethylbutan-2-one, l-[imidazolyl-(l)]-l .-[4'-(4-nitrophenyl) (2',6'-dichlorophenoxy)]-3,3-dimethylbutan-2-one, l-[imidazolyl-(l))-1-(4'-(4-ethoxyphenyl)-(2'-bromo-6'-chlorophenoxy))3,3-dimethylbutan-2-one, l-[imidazolyl-(l))-1-(4'-(3-aminophenyl)-(2'-methyiphenoxy))-3,3-dimethylbutan-2-one, 1(imidazolyl-(l))-1-(4'-(2-methylphenoxy)-(2’-chlorophenoxy))3° 3,3-dimethylbutan-2-one, l-[imidazolyl-(l))-1-(4'-(3-ohloro- 4 42758 phenoxy)-phenoxy]-3,3-dimethylbutan-2-one, l-[Imidazoly1-(1)]l-[ 4' -phenoxy-2', 6' -dibromophenoxy ]-3,3-dimethy lbu.tan-2-one, 1- [imidazolyl-(l)]-l-[4'-(3-nitrophenylthio)-(2'-bromophenoxy) ]-3ι3-dimethylbutan-2-one, l-[imidazolyl-(l)]-l-[4'(2-methoxyphenyIthio)-(2’-chlorophenoxy)]-3,3-dimethylbutan2- one, 1—[ imidazolyl-(l) )J.-[4’44-bromopheny Ithio)-(3' -chlorophenoxy )]-3,3-dimethylbutan-2-one, l-[imidazoly 1-(1)]-l-[4’(2-chlorophenylsulphonyl)-phenoxy]-3,3-dimethylbutan-2-one, l-[imidazolyl-(l)]-l-[4'-(4-ethylphenylsulphonyl)-(2',6'dichlorophenoxy)]-3,3-dimethylbutan-2-one, l-[imidazolyl(l)]-l-[4'-(2-chlorophenylcarbonyl)-(2'-bromophenoxy)]3,3-dimethylbutan-2-one, l-[imidazolyl-(l)]-l-[4’-(2,6dichlorophenylcarbonyl)-(2'-chlorophenoxy)]-3,3-dimetbylbutan-2-one, l-[imidazolyl-(l)]-l-[4'-(2-nitrophenylcarbonyl)phenoxy]-3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-l-[4'(4-bromobenzyl)-(3'-bromophenoxy)]-3,3-dimethylbutan-2-one, l-[imidazolyl-(l)]-l-[4'-(4-trifluoromethylthiobenzyl)-(2',3'dichlorophenoxy) ]-3,3-dimethylbutan-2-one, l-[imidazolyl(1)]—1—[4'-(3,5-dichlorobenzy1)-(2'-methylphenoxy)]-3,3dimethylbutan-2-one, l-[imidazoly 1-(1)]-l-(4'-(4-tert.butylbenzyl)-phenoxy]-3,3-dimethylbutan-2-one and l-[imidazolyl-(1)]-l-[4'-(2-ethylaminobenzyl)-(2'-nitrophenoxy ·) ]-3,3dimethylbutan-2-one, and their salts with the acids specified above.

The active compounds to be used according to the invention have not yet been disclosed. Some of them are the subject of an earlie- patent application by the present applicants, Patent Specification No. 4116^ Those compounds to be used according to the present invention in which, in formula I, A is a carbonyl group, can be prepared according to a method described in Patent Specification No.42187.

The method is given below as (a), as are methods (b) and (c) applicable respectively to compounds in which A is a -CH(OH)- group and to conpounds in which A is a —C (OH)-group (R being alkyl).

I R (a) A haloether-ketone is reacted with an imidazole, for example in equimolar amounts, if appropriate in the presence of aninorganic acid-binding agent, for example potassium carbonate, or in the presence of an organic acidbinding agent, for example triethylamine or excess imidazole, and in the presence of a polar solvent, for example aceto15 nitrile, at temperatures of 20 to 150°C; the resulting reaction mixture is evaporated in vacuo; the residue is taken up with an organic solvent, for example methylene chloride; the solution is extracted by shaking with water; and the organic phase is distilled in vacuo. The oil which remains after the solvent has passed over is purified according to customary methods (compare the preparation Examples hereinbelow) . (b) A compound obtained according to method (a), is reduced, for example by a generally customary method. The reduction can be effected for example (l) with hydrogen in the presence of a catalyst, for example Raney nickel (Raney is a Registered Trade Mark) , and a polar solvent, for example methanol, at 2O-5O°C; or (2) with aluminium isopropylate in the preeence of an inert solvent at 20-120°C, with subsequent hydrolysis; or (3) with a complex hydride (for example sodium borohydride or lithium alanate) in the presence of a polar solvent, for example, methanol, at 0-20°C, followed by hydrolysis, for example with hydrochloric aoid; or (4) with formamidinesulphinic acid and alkali metal hydroxide, for example sodium hydroxide, in aqueous solution at 20-100°C in the presence of a polar solvent, for example ethanol. (o) A compound obtained according to method (a) is subjected to reductive alkylation, especially by means of a Grignard reagent, such as an alkyl-magnesium halide (preferably an iodide or bromide), for example with methylmagnesium iodide in anhydrous diethyl ether at 20-80°C, and the product is hydrolysed, for example with aqueous ammonium chloride solution. The compounds of the formula I, thus obtained, may be isolated according to customary methods and purified if appropriate (compare also the preparation Examples hereinbelow).

The salts of the compounds of the formula I can be obtained in a simple manner in accordance with customary methods of forming salts, for example by dissolving the base in ether; for example diethyl ether, and adding the aoid, for example hydrogen chloride, and they can be isolated in a known manner, for example by filtering off, and can be purified if desired (compare also the preparation Examples hereinbelow).

The haloether-ketones to be used as starting materials have not previously been disclosed but can be prepared according to processes which have been known for a long time, for example by reacting the corresponding phenol derivative with a haloketone (the so-called Williamson ether - 7 42758 synthesis)» The active hydrogen atom which still remains is then replaced hy halogen in the usual manner (compare also the preparation Examples hereinbelow).

The fungicidal active compounds according to the in5 vention have a very broad spectrum of action and can he used against parasitic fungi which infect above-ground parts of piantfl or attack the plants through the soil, and also against seed-borne pathogens.

Fungitoxic agents are employed in plant protection for combating fungi from very diverse classes of fungi, such as Archimycetes. Fhycomvcetes. Ascomycetes. Basidiomyoetes and Fungi Imperfect!.

As has in part already been mentioned, the active compounds to he used according to the invention display a particularly good activity against parasitic fungi on aboveground parts of plants, such as species of Erysiphe and speciei of Venturia, as well as against species of Firicularia and species of Fellioularia. Good effects are achieved against the pathogens of apple scab (Fusicladium dendritioum), of powdery mildew of cereals (Erysiphe araminis) and of bean rust (Promyces phaseoli). A point to he singled out particularly is that these active compounds not only display a protective action hut are also curatively active, that is to say active on application after contamination with the spores of the fungus. Furthermore, the systemic action of the compounds should be pointed out. Thus it proves possible to protect plants against fungal infection if the active compound is supplied to the above-ground parts of the plant via the soil and the root. As plant protection agents, these compounds can be used for the treatment of soil, for the treatment of seed and for the treatment of above-ground parts of plants. - 8 42758 The active compounds to be used according to the invention are well tolerated by plants. They have only a low toxicity to warm-blooded animals and because of their low odour and tiieir good toleration by human skin they are not unpleasant to handle.

The active compounds to be used according to the present invention can be converted into ihe usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foamforming 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, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydro20 carbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic 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 iso25 butyl ketone or cyclohexanone, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or acetonitrile, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatures and ° pressures, e.g. aerosol propellants, such as halogenated hydrocarbons, e.g. Freon. Freon is a Registered Trade Mark. - 9 42758 As solid diluents or carriers, there are preferably used ground natural minerals, axch as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates.

Preferred examples of emulsifying and foam-forming agents include non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as well as albumin hydrolyzation products; and preferred examples of dispersing agents include lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be ueed as a mixture with other active compounds, such as other fungicides, insectioides, acaricides, nematocides, herbicides, bird repellents, growth regulating agents, plant ' nutrients end agents for improving soil structure.

The compositions generally contain 0,1 to 95 per cent by weight of active compound, preferably 0.5 to 90%.

The active compounds can be used as suoh or in the form of their foniiulations or the application forms prepared therefrom, suoh as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They may be used in the customazy manner, for example by watering, spraying, atomising, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.

The eompositicnsmay be diluted for actual application.

When used as leaf fungicides, the concentrations of active oompound in compositions used for application oan be varied within a substantial range. They are in general from - 10 42758 0.1 to 0.00001 per cent by weight, preferably 0.05 to 0.0001$.

In the treatment of seed, amounts of active ccopound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are in general applied to the seed.

For tiie treatment of soil, amounts of active compound of 1 to 1,000 g per cubic metre of soil, preferably of 10 to 200 g, are generally applied to the soil.

At somewhat higher concentrations, the active compounds also possess plant growth-regulating properties.

The active compounds to be used according to the invention, and their use and their preparation, are illustrated by the following Examples.

A.;„ Mycelium growth test Nutrient medium used: parts by weight of agar-agar 200 parts by weight of potato decoction parts by weight of malt parts by weight of dextrose parts by weight of peptone parts by weight of disodium hydrogen phosphate 0.3 part by weight of calcium nitrate Proportion of solvent mixture to nutrient medium: parts by weight of solvent mixture 100 parts by weight of agar nutrient medium Composition of solvent mixture 0.19 part by weight of dimethy If oraamide or acetone 0.01 part by weight of emulsifier (alkylaryl polyglycol ether) 1.80 parts by weight of water thus giving 2 parts by weight of solvent mixture The amount of active compound required for the desired concentration of active compound in the nutrient medium was mixed with the stated amount of solvent mixture. The concentrate was thoroughly mixed, in the stated proportion, with the liquid nutrient medium (which had been cooled to 42°C) and was then poured into Petri dishes of 9 cm diameter. Control plates to which the preparation had not been added were also set up.

When the nutrient medium had cooled and solidified, the plates were inoculated with the species of fungi stated in Table A and incubated at about 21°C. j Evaluation was carried out after 4 - 10 days, dependent - i upon the speed of growth of the fungi. When evaluation was carried out the radial growth of the mycelium on the 1$ treated nutrient media was compared with the growth on the control nutrient media. In the evaluation of the fungus growth, the following characteristic values are used: no fdngus growth up to 2 very Strong inhibition of growth up to 5 medium inhibition of growth up to 7 slight inhibition of growth growth equal to that of the untreated control.

The active compounds, the active compound concentrations and results can be seen from the table wh-i oh follows: In the tables the compounds (which were used in a concentration of active compound of 10 ppm) are identifed by the letters A, B, C, D, E, F and G, which have the followir . significance: sezAjo SBUOUIOtlftUEX TJXESES E-paETnoftiea STTEnbEEirr E-pxnquEA amjoqoEO BjoxnqaoqXqa _BTOOfsniii ETteasEqdsooAw _ umaufuiEjB um-pjodsoERujuiTeH SUS0S8JSUT0 ExoqdoxBpqa LH Α Η A Η A H O' A If) A in in A A A A A A O' A A A A A CM O' AAA Mycelium growth test 0» aezZjo efjeinofoXi umjq.BoqTE ωηττττοη-ΐθΛ Esjeu-po s-pq.£:cq.0g snuBegEX-pui snjoqofpqooo umuiThTn umyipAa •pUEJOS BTUoqooz-pqH umuEajjoo ιιιηηο·ρΛ3.οη.θ·[γοο a^EA~pu umiaEsna umaoTqoj3Tos B-pu-pqoiSTog umaouritio umpaEsna to Ct +> 0 S & o O' cn a m tn a A tn cn in cn cn in tn σ» cm cn cm cn ι cn σ» cm a cn a in A o\ a a A A cm cn tn A A A A tn CM O' in ι A A cn cn O' cn cn a a in in O' in cn cn cn ι m O' cm cn cm cm in m - 13 43758 Example Β Shoot treatment test/powdery mildew of cereal/protective (leaf-destructive mycosis) To produce a suitable preparation of active compound, 0.25 g 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 emulsifier and 975 parts by weight of water were 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 greminis var, horde!.

After 6 days' dwell time of the plants at a temperature of 21-22°C and 80-90% atmospheric humidity the occurrence of mildew pustules on the plants was evaluated. The degree of infection is expressed as a percentage of the infection of the untreated control plants. 0% denotes no infection and 100% denotes the same degree of infection as in the case of the untreated control. The active compound is the more active, the lower is 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. - 14 42758 Table Β Shoot treatment test/powdery mildew of cereal/ protective Active compounds Active compound concentration in the spray liquor in $ by weight Infection in $ of the totreated control untreated 100 0-C-0 (known) 0.01 50.0 0.001 68.8 C!-^Q>-0-CH-C0-C(CH3 )3 0.0^ 12.5 37.5 O0_O0?H“C0’C(CHs )s °·01 Q -HC1 16.3 Q-^^-o-ch-co-c(ch3 )3 0.01 6.3 4375® Table B (continued) Shoot treatment test/powdery mildew of cereal/ protective Active compounds Active compound concentration in the spray liquor in % by weight Infection in % of the untreated control ^h-Q-o-ch-ch-cCch, )3 OCH, IK OH 0.01 0.001 0.0 32.5 Cl· Cl ^-O-CH-CO-C(CHS)s 'ά 0.01 0.001 0.0 33.8 Example C Erysiphe test/systemic Solvent: 4.7 parts hy weight of acetone Dispersing agent: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required to give the desired concentration of active compound in the watering liquid was mixed with the stated amount of solvent and the concentrate was diluted with the stated amount of water whioh contained the stated additives.

Cucumber plants grown In standard soil, in the 1-2 leaf stage, were watered three times within one week with 10 ml of the watering liquid, of the stated concentration of active compound, per 100 cc of soil.

The plants treated in this way were inoculated, after treatment, with conidia of the fungus Erysiphe oiohoracearum. - 16 43758 The plants were then set up in a greenhouse at 25-24°C and 70% relative atmospheric humidity. After 12 days, the infection of the cucumber plants was determined as a percentage of the untreated, but also inoculated, control plants. 0% denotes no infection and 100% denotes that the infection was exactly as great as in the case of the control plants.

The active compounds, active compound concentrations and results can be seen from the table which follows.

Table 0 Erysiphe test/systemic Active Infection in % of the compound infection of the untreated control at an active compound concentration of 100 ppm 25 ppm 100 O, 01-^)-0-0-^-00-0(0¾ )j ~ 25 ’ ft Example D Fusicladium test (apple scab) (Protective) Solvent: 4.7 parts by weight of acetone Emulsifier:0.5 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the - 17 58 desired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent, and the concentrate was diluted with the stated amount of water which contained the stated additions.

Young apple seedlings in -Hie 4-6 leaf stage were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20°C and at a relative atmospheric humidity of 70%. They were then inoculated with an aqueous conidium suspension of the apple scab causative organism (Pusicladium dendriticum ) and incubated for 18 hours in a humidity chamber at 18-20°C and at a relative atmospheric humidiiy of 100%.

The plants then again came into a greenhouse far 14 days. days after inoculation, the infection of the seedlings was determined as a percentage of the untreated but also inoculated control plants. 0% means no infection? 100% means that the infection was exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following table: Table D Pusicladium test/protective Active compound Infection in % of the infection of the untreated control at an active compound concentration (in %) of . -. _0.0025 Q Q-C-Q (known) 66 Q - 18 42758 Table D (continued) Fusicladium test/protective Active compound Infection in % of the infection of the untreated control at an active compound concentration (in %) of 0.0025 Ν02-£^·ζ)-0-?Η-00-0(ΟΗ3 )3 Example J Pusicladium test (apple scab) [Curative] Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent, and the concentrate was diluted with the stated amount of water which contained the stated additions.

Young apple seedlings in the 4-6 leaf stage were inoculated with an aqueous conidium suspension of the apple scab causative organism (Pusicladium dendriticum ) and incubated for 18 hours in a humidity chamber at 18-20°C and at a relative atmospherio humidity of 100%. The plants then came into a greenhouse. They were allowed to dry.

After standing for a suitable period of time, the plants were sprayed dripping wet with the spray liquid prepared in the manner described above. The plants then again came into a greenhouse. days after inoculation, the infection of the apjle seedlings was determined as a percentage of the untreated but also inoculated control plants. 0$ means no infection; 100$ means that the infection was exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds, the period of time between inoculation and spraying and the results obtained can be seen from the following table: Table B Fusicladium test/curative Active compound Dwell Infection in $ of the time in infection of the unhours treated control at an active compound 42 concentration (in $) of (known) 0.025 0.0062 100 Example F Uromyces test (bean rus-0/ protective 25 Solvent: 4.7 parts by weight of acetone Emulsifiers 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight - 20 42758 The amount of active compound required for the desired concentration of active compound in the spray liquor was mixed with the stated amount of the solvent and the concentrate was diluted with the stated amount of water which contained the stated additives.

The young bean plants, which were in the 2-leaf stage, were sprayed with the spray liquor until dripping wet. The plants remained in a greenhouse for 24 hours at 20-22°0 and a relative atmospheric humidity of 70% in order to dry. They were then inoculated with an aqueous uredospore suspension of the causative organism of bean rust (Uromvces phaseoli ) and incubated for 24 hours ln a dark humidity chamber at 20-22°C and 100% relative atmospheric humidity.

The plants were then set up in a greenhouse under intensive illumination for 9 days at 20-22°C and a relative atmospheric humidity of 70-80%. days after the inoculation, the infection of the plants was determined in % of the untreated but also inoculated control plants. 0% denotes no infection and 100% denotes that the Infection was just as high as in the case of the control plants.

The active compounds, active compound concentrations and results can be seen from the table which follows: Table F Urorayces test/protective Active compound Infection in % of the infection of the untreated control at an active compound concentration (in%) of 0.00156 Cl -fVo -CH-CO-C(CH,)s (known) Table F (continued) Uromyces test/protective Active compound Infection in % of the infection of the untreated control at an active compound concentration (in $) of 0.00156 Cl-@-£>0-CH-C0-C(CH3 ), '0 Cl-Q-^*0-CH-(jK-C(CH3 )3 OH Q ^-C^-^O-CH-CO-CCCH, )3 Cl Br-^-(^O-CH-CO-C(CHs )3 Br ^-SOj-^-O-CH-CH-CiCHj ) Q a 75 @-CHs -^-O-CH-Oi-C(CHj) .L OH Q s 70 Cl Cl Br 0-CH-C0-C(CH3)3 - 22 42758 Table F (continued) Uromyces test/protective Active compound Infection in % of the infection of the un5 treated control at an active compound concentration (in %) of 0.00156 (preparation according to method (a)) g (0.107 mol) of l-bromo-l-(4'-phenylsulphonyl15 phenoxy)- 3,3-dimethylbutan-2-one in 500 ml of absolute acetonitrile were heated with 34 g (0.5 mol) of imidazole for 26 hours under reflux. The solvent was then distilled off in a water pump vacuum and the residue was taken up in 100 ml of water. The resulting precipitate was washed with twice 100 ml of water and recrystallised from benzene. 26 g (66% of theory) of l-[imidazolyl-(l)]-l-[4'-(pherylsulphonyl)phenoxy]-3,3-dimethylbutan-2-one of melting point 146°O were obtained.

Intermediate product: 0- Br 3>3 g of bromine were added dropwise at room temperature to 99.6g(0.3 mol) of l-(4’-phenylsulphonyl-phen5 oxy)-5»3-dimethylbutan-2-one suspended in 600 ml of carbon tetrachloride. After the mixture had lost its colour, the resulting precipitate was filtered off, washed with petroleum ether and recrystallised from benzene. 89 g (72% of theory) of l-bromo-l-(4'-phenylsulphonyl-phenoxy)-3,510 dimethylbutan-2-one of melting point 157-162°C were obtained.

Starting material: 0-CH2-C0-C(CH3)3 280 g. (2 mols) of powdered potassium hydroxide were suspaided, in 2 litres of methyl ethyl ketone. 467 g (2 mols) of 4-phenylsulphonyl-phenol were added and the mixture was heated to the boil. Thereafter 269 g (2 mols) of achlorepinacolone were added dropwise over the course of 1 hour and the mixture was heated for 15 hours under reflux. After cooling, the solid residue was filtered eff, washed and recrystallised from ligroin. 68? g (85% of theory) of 1-(4'-phenylsulphonyl-phenoxy)-3,3-dimethylbutan-2-one of melting point 105-108°C were obtained. 43758 Example 2 (preparation according to method (b)(3)) 1.6 g (0.042 mol) of sodium borohydride were added in portions to 11 g (0.028 mol) of l-[imIdazolyl-(l)]-l-[4'(phenylsulphonyl)-phenoxy]-3,3-dimethylbutan-2-one suspended in 100 ml of methanol, at a temperature of -5°C. The reaction mixture was stirred for 17 hours at room temperature, 6.5 ml of concentrated hydrochloric acid were then added and the mixture was again stirred for 17 hours at room temperature.

It was then extracted by shaking with three times 200 ml of methylene chloride. The combined organic phases were dried over sodium sulphate. The solvent was distilled off in a water pump vacuum. 50 ml of n-pentane was added to the residue and the crystals were filtered off. 10 g (90% Of theory) of l-[imidazoly1-(1)3—1—[4'-(phenylsulphonyl)-phenoxy]-3»3dimethylbutan-2-ol of melting point 198°C were obtained. Example·3 h3 01-/Λ—ΛΛ- 0-ch-c-c(ch3 )3 I OH Ol (preparation according to method (c)) 2.4 g (0.1 mol) of magnesium filings were suspended in ml of ether. A solution of 14.2 g (0.1 mol) of methyl 43758 iodide in 50 ml of absolute ether was added dropwise thereto. After 2 hours, a solution of 18.4 g (0.05 mol) of 1-[4'-(4chlorophenyl)-phenoxy]-l-[imidazo3yl-(l)]-3,3-dimethylbutan2-one in 100 ml of absolute tetrahydrofurane was added dropwise at 10°C and the mixture was stirred for a further 15 hours at room temperature. Thereafter, the reaction mixture was stirred, at 0°C, into a solution of 10 g of ammonium chloride in 500 ml of water and the mixture was left to stand overnight. The ether phase was separated off, washed with twice 100 ml of water and dried over sodium sulphate, and the solvent was distilled off in a water pump vacuum. An oil remained, which crystallised on trituration with hot petroleum ether. It was recrystallieed from 40 ml of ethyl acetate. 16.6 g (86% of theory) of l-[4'-(4-chlorophenyl)phenoxy]-l-[imidazolyl-(l)]-2-methyl-3,3-dimethylbUtan-2-ol of melting point 177°0 were obtained.

Example 4 : • CH, I * ci-00-o-ch-c-c(ch3 )3 ,ΪΚΟΗ . HCl (preparation of a salt) g (0.013 mol) of l-[4'-(4-chlorophenyl)-phenoxy]l-[imidazolyl-(l)]-2-methyl-3,3-dimethylbutan-2-ol were dissolved in 25 ml of acetone and 25 ml of methylene chloride 20 ml of ethereal hydrochloric aoid were added thereto, the solvent was distilled off in a water pump vacuum and the residue was boiled up with acetone. 4.7 g (86% of theory) of l=[4’-(4-chlorophenyl)-phenoxy]-l-[imidazolyl-(l)]-2-methyl3,3-dimethylbutan-2-ol hydrochloride of melting point 220224°C (decomposition) were obtained. - 26 43758 Examples 5-28 The following compounds of the general formula 0-3)3 were obtained analogously to Examples 1 to 4: - 27 4-27 58 g ‘Η •P'd ra φ •SS g s ri β O 'd o § ω •H O-P Q H ra ra β ra Ο ΪΗ ΛΦ S o rt M rt a 0* H 8 /1 cm S of I K cm K • X*·» • x/ * x^ S-/ • • »x-* O -4- o\ rt IA Ex CM o o o N> CM c- CO m |x ch VO in rd H rd rd cn r-i rt CO rd rt rd rd rd CM I CM 1 l in 1 CM | 1 1 1 CM s CM CO IS -4- rd o . rt CM m IS co in rt O vo m CM σ> co IA Ex co in H rd H rt rd rt rd rd rd a ft CG ft a O o o o σ O O o O O O o O O O ί£ a w CC a; ?! O o O O O u ϋ O O O o s δ δ ¢3 I CHOH 120-124 fi ra I o o I S-S I I M Φ rd ft rd rd CM O CM o o O o o o o o O o o flj rd H rd rd O v O f O 1 VO * CM CM VO I 1 1 1 1 1 1 1 1 I 1 , ·» CM CM rt rd rd o rt o o rt o rt rd rt η rd o o rd rd k ft C? rt rd rt rd rd O O ft ¢1 a ϋ O O O O 1 <3- -4- J- 1 -4 1 1 xf 1 •4* 1 4* 1 1 -4- in vo Εχ co cn o rt CM m -4- in <0 s- ¢0 σι o rd rt rt rd rt rd rt rd rd rt CM 43758 c ο •Η +) Ό ιβ ω ο β •Η Η Ό 0) β Ο Η β Ό Ο § 0) Ή υ-υ Ρ fi fi 3 Ο Μ 04 0 ft tnft 3 Ε Ο £ϊ υ fi ο fi κ ο ^3 fi 3 0 2 3 fi Ρ ϋ 3 8.8 βΡ Ο Μ Ο fi 0 Ρ 3 tf Ο to Οί « tf Ο ί*) « OJ 0 3 Ο VO ιη Ο ο οι Ο 3 co η ιη ο Η 3 CO ο- 3 3 Η ο 1 1 1 Ι 1 1 | Μ 0* σι tf Ο η co CO 3 3 co to (0 ω tf Ο 3 3 3 οοο 3 3 3 3 3 3 3 3 Ο □ U Ο I O I O I υ I O 1 tf 1 tf tf 1 tf 1 tf 1 tf tf tf OJ tf OJ in OJ r* Οί co οι I r-l >1 Ο Μ fi 03 β 0 fi M 3 M O 0 O fi fi O 3 0 3 fi P OJ P 03 3 κ 3 0 fi 3 3 3 fi 03 ft υ fi i fi 0 P 3 03 3 ft 04 P 0 3 fi P β Ο •ri Ρ •rl ο £ ο ϋ Χί Ρ β fi I υ fi 0 tn 3 © 3 >1 3 fi «. 0 0 £ 3 O β 0 0 M 3 © 0 fi © G ft P O 3 3 0 3 fi P 0 P 3 >1 3 3 x: X P ft M P 04 IM fi tn >1 fi fi >1 0 n 0 3 ft 3 0 ft fi P fi 0 0 3 o 0 3 fi 3 & M fi M © fi 0 3 0 03 β 0 β fi © 3 M ft g B Χί 3 Q 0 fi 3 fi fi ft M © 3 J) fi ft 0 3 ε 04 fi fi £ 3 04 £ O 0 0 O u 0 0 H 0 Φ 3 3 © 3 • 3 fi • fi fi < fi Q P fi fi P fi tn β fi fi fi P 0 0 © fi 3 3 fi 21 03 H 3 0 0 fi 0 fi 0 3 © 3 O 3 3 © 0 0 3 ft 3 O 0 0 fi M 3 0 0 3 3 tn O M P fi ft •H 0 fi fi © tn ϋ fi P U) 3 3 fi 0 3 0 O 3 3 3 n 3 > fi 3 .0 0 3 3 1 ΛΙ Ό e 3 fi ϋ 3 P 3 2 3 OJ M fi 3 0 tt 3 ra M tf 0 tf fi 3 3 ft fit fi © I O P © 0 0 fi O 2 N © K tn « E fi n fi © © k. fi 2 fi 0 3 fi fi © 0 ft 3 0 ft fi 0 0 fi fi ft p O 3 ft 3 3 3 3 P 0 P o P P tn n 3 0 fi 3 & 3 fi fi 0 P 0 o 0 & © 0 3 3 fi fi 3 0 0 3 fi ft 0 0 0 3 0| 0 04 3 3 0 fi © 3 ©1 β 3 fi 3 3 0 ϋ 0 8 0 P © ft 3 n 0 m| © 0 0 fi 3 X 3 04 04 0 0 04 0 3 to al ft 3 to 0 X 1 3 •H £ P © P § P fi fi fi fi P fi 3 tn fi 0 3 σ* 0 fi fi © 0 3 0 fi 3 fi P P 3 3 P P M 3 3 3 fi 0 « fi fi 3 0 04 O 3 3 04 © ft O fi P fi fi 0 0 & 04 I P 04 Qi © ft 0 E fi a fi 3 P 0 0 0 0 W 3 X O 0 0 0 ft 0

Claims (10)

1. CLAIMS:1. A fungicidal composition containing as active ingredient a compound which is a diarylory—imidazolyl—0,N— acetal or salt thereof, the diaryloxy-imidazolyl-0,lf-acetal being of the general formula \y z 0-JH-a-c (CI^ ) 3 in which X and Y, which may be the same or different, are halogen, alkyl, alkoxy, haloalkylthio, nitro, amino, alkylamino Dr dialkylamino, Z is a direct bond, or oxygen, sulphur, methylene, sulphonyl, alkoxymethylene or keto, A represents keto or a -C(OH)- group (wherein R is R hydrogen or alkyl), and a and b are integers from 0 to 3, in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or earlier.

2. A composition according to claim 1 in which the active compound is of the formula given in claim 1 in which X and Y are fluorine, chlorine, bromine, alkyl with up to 4 carbon atoms, alkoxy with up to 4 carbon atoms, haloalkylthio with up to 4 carbon atoms and up to 5 fluorine or chlorine atoms, nitro, amino, alkylamino with up to 4 carbon atoms or dialkyl· amino with up to 4 carbon atoms in each alkyl moiety.

3. A composition according to claim 1 in which the active - 30 42758 compound is any of those hereinbefore specifically identified.

4. A composition according to any of claims 1-3 containing from 0.1 to 95% by weight of the active compound.

5. A composition according to any of claims 1-4 in which 5 the diluent or carrier is a liquid diluent or carrier containing a surface active agent.

6. A method of combating fungus pests which comprises applying to the pests or a habitat thereof an active compound as defined in any of claims 1-3, alone or in admixture with a 10 diluent or carrier.

7. A method according to claim 6 in which the active compound is applied as a leaf fungicide in the form of a composition containing from 0.00001 to 0.1% by weight of the active compound.

8. A method according to claim 6 in which the active compound 15 is applied to the treatment of seed in an amount of 0.001 to 50 g per kg of seed.

9. A method according to claim 6 in which the active compound is applied to soil in an amount of 1 to 1000 g per cubic metre of soil. 20

10. A method according to any of claims 6 to 9 in which the fungus pests are species of Erysiphe, Fusicladium or Uromyces.