IE45637B1

IE45637B1 - Novel halogenated 1-azolyl-butane derivatives and their use as fungicides

Info

Publication number: IE45637B1
Application number: IE1506/77A
Authority: IE
Original assignee: Bayer Ag
Priority date: 1976-07-20
Filing date: 1977-07-19
Publication date: 1982-10-20
Also published as: DE2632602A1; RO71574A; IE45637L; ZA774331B

Abstract

New triazole and imidazole derivs. of formula (I) and their salts (where R is opt. substd. phenyl or alkyl; X is H, alkyl or halogen; Y is halogen, Z is halogen, alkyl, cycloalkyl, alkoxy, haloalkyl, alkylthio, alkoxycarbonyl, opt. substd. phenyl, phenoxy or phenylalky, NH2, CN or NO2; n is 0-5; A is CO or CHOH; B is N or CH). Cpds. (I) are useful as agricultural fungicides and bactericides, e.g. for control of Podosphaera, Erysiphe, Fusicladium and Uromyces. A typical cpd. is 4-chloro-1-(4-chlorophenoxy)-3,3-dimethyl-1(1,2,4-triazol-1-yl)-2- -butanone. In an example, this is prepd. from 1-bromo-4-chloro-1-(4-chlorophenoxy)-3,3-dimethyl-2-butanone and 1,2,4-triazole.

Description

PATENT APPLICATION BY (71) BAYER AKTIENGESELLSCHAFT, A BODY CORPORATE ORGANISED UNDER THE LAWS OF THE FEDERAL REPUBLIC OF GERMANY, OF LEVERKUSEN, FEDERAL REPUBLIC OF GERMANY.

Price. 9 Op s 56 3? ' γ The present invention relates to certain newhalo- ; genated 1-azolyl-butane derivatives, to a process for their r .? preparation and to their use as fungicides.

It has already been disclosed that certain 1,2,4— ' triazole derivatives, especially 3,3-dimethyl-1-phenoxy-1- . (1,2,4-triazol-1-yl)-butan-2-ones and -ols which are substituted in the phenyl part, exhibit good fungicidal properties (see German Offenlegungsschriften (German Published Specifications) 2,201,063 [Le A 14 118] and 2,324,G10 [Le A 14 971]. Furthermore, it has been disclosed that imidazole derivatives, especially 3,3-dimethyl-1(imidasol-1-yl)-1-phenoxy-butan-2-ones and -ols which are substituted in the phenyl part, and m-(imidazol-l-yl)ω-phenoxy-acetophenones which are substituted in the phenoxy part, exhibit good fungicidal properties (see German Offenlegungsschriften (German Published Specifications) 2,325,156 [Le A 14 999] and 2,333,354 [Le A 15 148]). However, the activity of the previously known compounds is not always entirely satisfactory, especially when low amounts and low concentrations are used.

The. present invention now provides, as new compounds, the halogenated 1-azolyl-butane derivatives of the general formula ' CH2X . <0-0 - cn - A - = . cm (I)jZn X-'O 11 w II in which R represents alkyl or optionally substituted phenyl, X represents hydrogen, alkyl or halogen, - 2 43637 Y represents halogen, Z represents halogen, alkyl, cyeloalkyl, alkoxy, halogenoalkyl, alkylthio, alkoxycarbonyl, optionally substituted phenyl or phenoxy, optionally substituted phenylalkyl, amino, cyano or nitro, n represents 0, 1, 2, 3, 4 or 5, A represents a keto group or a CH(OH) grouping and B represents a nitrogen atom or a CH group, and their salts.

When n is 2,3,4 or 5, the various radicals Z may of course be different from each other as well as each case within the above definition.

The compounds of the present invention exhibit powerful fungicidal properties.

Preferably, R represents alkyl with ί to 4 carbon atoms (especially methyl or ethyl) or phenyl which is optionally substituted by halogen (especially fluorine, chlorine or bromine) and/or alkyl with 1 or 2 carbon atoms; X represents hydrogen, alkyl with 1 to 4 carbon atoms (especially methyl) or halogen (especially chlorine or bromine); Y represents halogen (especially chlorine or bromine); Z represents halogen (namely fluorine, chlorine, bromine or iodine), straight-chain or branched alkyl with 1 to 4 carbon atoms, cyeloalkyl with 5 to 7 oarbon atoms (preferably cyclohexyl), halogenoalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms (especially fluorine and chlorine atoms, the trifluoromethyl group being an example), alkoxy with 1 or 2 carbon atoms, alkylthio with 1 or 2 carbon atoms, alkoxycarbonyl with 1 to 5 carbon atoms in the alkoxy part, amino, cyano, nitro, or optionally substituted phenyl or phenoxy, the substituents being selected from halogen (namely fluorine, chlorine, bromine or iodine), - 0 43637 amino, cyano, nitro and alkyl with 1 to 2 carbon atoms or Z represents phenylalkyl with 1 or 2 oarbon atoms in the alkyl part and which may be substituted in the alkyl part by alkylcarbonyl with a total of up to 3 carbon atoms and which may be substituted in the phenyl part by halogen, nitro or cyano; and n represents 0, 1, 2 or 3.

Those compounds of the formula (I) in which A represents a CH(QH) group, possess two asymmetrical oarbon atoms; they can therefore exist in the two geometric isomers (erythro form and threo firm), which may be produced in different ratios. In both cases they exist as optical isomers. The formula (I) should be construed as covering all such isomers.

The present invention also provides a process for the preparation of a halogenated 1-azolylbutane derivative of the formula (I), in whioh (a) a bromoether-ketone of the general formula CH2X . - 0 - CH - CO - C - CH2Y I I fer R in which R, X, Y, Z and n have the above-mentioned meanings, is reacted with an azole of thu general formula (V) ,H in which B has the above-mentioned meaning, if appropriate in the presence of an acid-binding agent and, if appropriate, in the presence of a diluent, and optionally thereafter - 4 (b) the keto-derivative obtained according to process variant (a) is (1) reduced with hydrogen in the presence of a catalyst and optionally in the presence of a polar solvent, or (2) reduced with aluminium isopropylate in the presence of a solvent, or (3) reduced with a complex hydride, optionally in the presence of a polar solvent, or (4) reduced with formamidinesulphinic acid and an alkali metal, hydroxide, optionally in the presence of a polar Solvent.

Furthermore, the halogenated 1-azolyl-butane derivatives obtainable according to the invention can be converted to the salts by reaction with acids.

Surprisingly, the active compounds according to the invention exhibit a substantially higher fungicidal activity, especially against species of rust and species of mildew, as well as against rice diseases, than the 3,3dimethyl-1-phenoxy-1-(1,2,4-triazol-1-yl)-butan-2-ones and -ols, the corresponding imidazolyl derivatives and theω-(imidazol-l-yl)-w-phenoxy-acetophenones known from the prior art, which are the closest active compounds of the same type of action. The active compounds according to the invention thus represent an enrichment of the art.

If 1-bromo-4-chloro-1-(4-chlorophenoxy)-3,3-dimethylbutan-2-one and 1,2,4-triazole are used as starting materials in process variant (a), the course of the reaction can be represented by the following equation: 43637 Cl CH3 O-CH-CO-C-CH,Cl ι Br CH, |Π 'Nz H Base CHj - HBr Cl-«^»-O-CH-CO-C-CIk Cl CH, If, on the other hand, 1-bromo-4-chloro-1-(4-chlorophenoxy)-3,3-dimethyl-butan-2-one and imidazole are used as starting materials, the course of the reaction can be represented by the following equations Cl CH, I * O-CH-CO-C-CH*Cl I 4 Br CH, Base -HBr CH, F\o-cr-co-c-ckz Cl - CHS If 4-chloro-1-(4-chlorophenoxy)-3,3-dimethyl-1-(l,2,4triazol-1-yl)-butan-2-one and sodium borohydride are used as starting materials in process variant (b)(3), the course of . the reaction can be represented by the following equation: Cl 4 5 6 3 7 If, on the other hand, 4-chloro-1-(4-chlorophenoxy)3,3-dimethyl-1-(imidazol-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: UaBH4 OH CH, ι I 3 O-CH-CH-C-CH,Cl ι ι 2 The reduction reactions according to process variants (b)(1), (b)(2) and (b)(4) are of a similar type and can be formulated analogously.

The following may be mentioned as examples of starting materials of the formula (II): 1-bromo-4-chloro-1-(3-chlorophenoxy)-3,3-dimethyl-butan-2-one, 1-bromo-4-ohloro-3,3dimethyl-1-(4-fluorophenoxy)-butan-2-one, 1-bromo-4-chloro3,3-di methyl-1-(4-iod ophenoxy)-butan-2-one, 1-bromo-1-(4bromophenoxy)-4-chloro-3,3-dim ethyl-butan-2-one, 1 -bromo-4chloro-3,3-dimethyl-1-(2,4,5-trichlorophenoxy)-butan-2-one, 1-bromo-4-ohloro-3,3-dimethyl-1-(2-methylphenoxy)-butan-2one, 1-bromo-4~ehloro-3,3-dimethyl-1-(4-methylphenoxy)butan-2-one, 1-bromo-4-chloro-3,3-dimethyl-1 -(3,4-dimethylphenoxy)-butan-2-one, 1-bromo-4-chloro-1-(4-chloro-2methylphenoxy)-3,3-dimethyl-butan-2-one, 1-bromo-4-chloro1-(4-chloro-3,5-dimethylphenoxy)-3,3-dimethyl-butan-2-one, 1-bromo-4-chloro-3,3-dimethyl-1-(2-methyl-5-nitrophenoxy)butan-2-on e, 1 -bromo-4-ehloro-1-(2-oycloh exylphenoxy)-3,3dimethyl-butan-2-one, 1-bromo-4-chloro-1-(4-cyclohexyl4 3 6 3 7 phenoxy )-3,5-dimethyl-butan-2-one, 1-brom!o-4-chloro-3,5dimethyl-1-(4-methoxyphenoxy)-butan-2-one, 1-bromo-4-chloro 3,3-dimethy1-1-(3-trifluoromethylphenoxy)-butan-2-one, 1 bromo-4-chloro-3,3-dimethyl-1-(4-methylthiophenoxy)-butan2-one, 1-bromo-4-chloro-3,3-dimethyl-1-(4-methoxycarbonylphenoxy)-butan-2-one, 1-bromo-4-chloro-3,3-dimethyl-1-(2phenylphenoxy)-butan-2-one, 1-bromo-4-chloro-1-(2-chloro4-phenylphenoxy)-3,3-dimethyl-butan-2-one, 1-bromo-4-chloro /4-(4'-ehlorophenoxy)-phenoxy7-3,3-dimethyl-butan-2-one, 1bromo-1-/4-(4'-chlorobenzyl)-phenoxy/-?,3-dimethyl-butan-2one, 1-bromo-4-chloro-1-/4-(phenyl-acetyloxy-methyl)phenoxy7-3,3-dimethyl-butan-2-one, 1 -bromo-4-chloro-1-(4cyanophenoxy)-3,3-dimethyl-hutan-2-one, 1-(4-aminophenoxy )1- hromo-4-chloro-3,3-dimethyl-butan-2-one, 1-(4-chlorophenoxy )-1,4-dihromo-3,3-dimethyl-butan-2-one, 1-bromo-4chloro-1-(4-chlorophenoxy)-3,3-diethyl-butan-2-one, 1-bromo· 4-chloro-3-chloromethyl-1-(4-ohlorophenoxy)-3-methyl-hutan2- one and 1-hromo-4-chloro-3-chloromethyl-1-(4-chlorophsnxy )-3-( 4-chlorophenyl) -hut an-2-one.

The bromoether-ketones of the formula (II) to he used as starting materials according to the invention have not previously been described in the literature, but can be prepared in accordance with known processes, for example by f reacting phenols of the general formula in which • Z and n have the above-mentioned meanings, with a bromoketone of the formula - 8 43637 OfcX Br - CHa - CO - C - CH2Y VlV), ι R in which R, X aid Y have the above-mentioned meanings.

The active hydrogen atom which still remains is then replaced by bromine in the usual manner (see also the preparative Examples given later in this text).

The phenols of the formula (III) are compounds generally known in organic chemistry.

The bromoketones of the formula (IV) are also compounds which are generally known in organic chemistry or can be prepared in the generally customary and known manner (see also the preparative Examples).

The azoles (V) to be used a3 starting materials for process (a) are 1,2,4-triazole and imidazole.

Preferred salts of the compounds of the formula (I) are (from the point of view of phytotoxicity) the physiologically tolerated salts, these being generally salts with physiologically tolerated acids. The preferred acids include the hydrogen halide acids (such as, for example, hydrobromic acid and especially hydrochloric acid), phosphoric acid, nitric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (such as, for example, acetic acid, maleic acid, succinic acid, fumarie acid, tartaric acid, salicylic acid, citric acid, sorbic acid and lactic acid) and 1,5-naphthalenedisulphonic acid.

Conversely, the acid-addition salts can be treated with a base to liberate, if desired, the free base of the formula (I). - 9 Possible diluents for the reaction according to process variant (a) are inert organic solvents, especially ketones, such as diethyl ketone and especially acetone and methyl ethyl ketone { .nitriles, such as propionitrile and especially acetonitrile; alcohols, such as ethanol or isopropanol; ethers, such as tetrahydrofuran or dioxan; benzene; formamides, such as, in particular, dimethylformamide; and halogenated hydrocarbons.

If the reaction according to process variant (a) is carried, out in the presence of an aoid-binding agent, all inorganic and/or organic acid-binding agents which can usually be employed may be added, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, or such as lower tertiary alkylamines, cycloalkylamines or aralkylamines, far example triethylamine, Ν,Ν-dimethylcyclohexylamine, dicyclohexylmethylamine and N,N~dimethyIbenzylamlne, and also pyridine ani diazabicyclooctane.

Preferably, however, an appropriate excess of the azole is used aa. the acid acceptor.

In process variant (a), the reaction temperatures can be varied within a substantial range. In general, the reaction is carried out at from 20° to 150°C, preferably at from 60° to 120°C. In the prese ice of a solvent, the re25 action is advantageously carried out at the boiling point of the particular solvent.

In carrying out process variant (a), preferably 2 moles of the azole and 1 to 2 moles of acid-binding agent are employed per mole of the cimpound of the foimula (II). To isolate the compound of the foimula (I), the solvent is distilled off and the residue iB taken up in an organic solvent - 10 and. waehed with water. The organic phase is dried over sodium sulphate and freed from the solvent in vacuo. The residue is purified by distillation-or recrystallisation.

Possible diluents for the reaction according to process variant (b)(1) are polar organic solvents, preferably alcohols; such as methanol and ethanol, and nitriles, such as acetonitrile. The reaotion is carried out in the presence of a catalyst. Preferably, noble metal catalysts, noble metal oxide (or noble metal hydroxide) catalysts or so-called Raney catalysts are used, especially platinum, platinum oxide and nickel. The reaction temperatures can be varied within a substantial range. In general, the reaotion is carried out at from 20° to 50°C, preferably at from 20° to 40°C. The reaotion can be carried out not. only under normal pressure, but also under elevated pressure (for example 1 or 2 atmospheres gauge). In the reaction according to process variant (b)(1), 1 mole of hydrogen and 0.1 mole of catalyst are preferably employed per mole of the compound of the formula (II); to isolate the product, the catalyst is filtered off, the filtrate is freed from the solvent in vacuo and the resulting compound of the formula (I) is purified by distillation or recrystallisation.

If process variant (b)(2) is followed, preferred diluents for the reaction are alcohols, such as isopropanol, or inert hydrocarbons, such as benaene. The reaction temperatures can again be varied within a substantial range; in general, the reaction is carried out at frcm 20° to 120°C, preferably at 50° to 100°C, To carry out the reaction, 1 to 2 moles of aluminium isopropylate are preferably employed per mole of the compound of the formula (II). - 11 4 3 6 3 7 To isolate the compounds of. the formula (I), the excess solvent is removed by distillation in vaouo and the resulting aluminium compound is decomposed with dilute sulphuric acid or sodium hydroxide solution» The further working up is carried out in the usual manner.

If process variant (b)(3) is followed, possible diluents for the reaction are polar organic solvents, especially alcohols, such as methanol, ethanol, butanol or isopropanol, and ethers, such as diethyl ether or tetrahydrofuran. The reaction is in general carried out at from 0° to 3θ°θ, preferably at 0° to 20°C. For this reaction, preferably 1 mole of a complex hydride, such as sodium borohydride or lithium aluminium hydride, is employed per mole of the compound of the formula (II). To isolate the compounds of the formula (I), the residue is taken up in dilute hydrochloric acid, then rendered alkaline and extracted with an organic solvent. The further working up Is carried out in the usual manner.

Possible diluents for the reaction according to variant (b)(4), are polar organic solvents, preferably alcohols, such as methanol and ethanol, and also water. Here again the reaction temperatures can be varied within a substantial range; the. reaction is in general carried out at temperatures from 20° to 100°C, preferably at 50° to 100°G. To carry out the reaction, 1 to 3 moles of formamidinesulphinic aoid and 2 to 3 moles of alkali metal hydroxide are generally employed per mole of the compound of the foimula (II). To isolate the end product, the reaction mixture is freed from the solvent and the- residue is extracted with water and organic solvents, worked up in the usual manner and purified» - 12 4 5 6 3 7 The active compounds according to the invention exhibit a powerful fungitoxic action and a bacteriotoxic action.

They do not damage crop plants in the concentrations required for combating fungi and bacteria. For these reasons, they are suitable for use as plant protection agents for combating fungi and bacteria. Fungitoxic agents are employed in plant protection for combating Plasmodiophoromycetes. Oomycetes. Chytridlomvcetes. Zygomycetes. Ascomycetes, Basidlomycetes and Deuteromycetes.

The active compounds according to the invention have a broad spectrum of action and can be us fed against parasitic fungi which attack above-ground parts of plants or which attack the plants through tiie soil, as well as against seedhome pathogens.

They display a particularly good activity against parasitic fungi on above-ground parts of plants, such as species of Erysiphe. species of Podosphaera and species of Venturia, and also against species of Pyricularia and species of Pellicularia. Good actions are achieved against the pathogens of apple mildew (PodoBpharea'leucotricha). apple scab (Fuaicladium dendrlticum). powdery mildew of cucumbers (ErvslPfae cichoraoearam) and bean rust (Uromyces phaseoli). as well against the fungi Pyricularia oryzae and Pellioularia sasakli. They furthermore exhibit a high activity against.cereal diseases, such as against cereal mildew and cereal rust. An aspect to be singled out particularly is that the active compounds according to the invention not only display a protective action but are also curatively active, that is to say are active when used after infection has taken place. Furthermore, the fact that in part a - 13 4 3 6 3 7 systemic action is found should be pointed out. Thus it proves possible to protect plants against fungal attack by supplying the active compound to the above-ground parts of the plant through the soil and the root, or through the seed Ab plant protection agents, -the compounds according to the invention can be used for the treatment of soil, for the treatment of seed and for the treatment of above-ground parts of plants.

The compounds according to the invention are well tolerated by plants. They have only a low toxicity to warmblooded animals and, because of their low odour and their good toleration by human skin, they are not unpleasant to handle.

The aocive compounds according to the invention can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granules; These may be produced in known manner, for example by mixing the active compounds with extenders, that is to say, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is to say, emulsifying agents and/or dispersing agents and/or foaming agents. In the case of the use of water as an extender, organic solvents can, for exampla, 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, benzene or alkyl-naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or - 14 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, stch as dimethylformamide and dimethylsulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature ahd under normal pressure, for example aerosol propellants, such as dichlorodifluoromethane or trichlorofluoromethane.

As solid carriers there are preferably used ground natural minerals, such as kaolins, clays, talc, chalk, quarts, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly dispersed silicic acid, alumina and silicates.

Preferred examples of emulsifying and foam-forming agents include nonionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as well as albumin hydrolysis products; and preferred examples of dispersing agents include lignin sulphite waste liquors and methylcellulose.

The active compounds according to the invention can be present in the formulations as a mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure.

The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably frcm 0.5 to 90 - 15 4 3 ϋ 3 7 per cent.

The active compounds can he used as such, as their formulations or as the use forms prepared therefrom by further dilution, such as ready-to-u.se solutions, emulsions, suspensions, powders, pastes and granules. They are used in the customaiy manner, for example by watering, spraying, atomising, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.

Especially when used as leaf fungicides, the active compound concentrations in the use foims can be varied within a substantial range. They are, in general, from 0.1 to 0,00001 per cent by weight, preferably from 0,05 to 0.0001 per cent.

For the treatment of seed, amounts of active compound of 0,001 to 50 g per kilogram of seed, preferably 0.01 to g, are generally employed.

For the treatment of soil, amounts of 1 to 1,000 g per cubic metre of soil, preferably of 10 to 200 g, are generally employed. Ιί appropriate amounts are used, the compounds according to tile invention also exhibit a growth-regulating activity.

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 invention alone or in the form of a composition containing as active ingredient - 16 4 3 6 3 7 a compound of the 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 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.

In these Examples, the active compounds of the present invention are each identified by the number, given in brackets, of the corresponding preparative Example, which will be found later in the text. The known comparison compounds are identified as follows.

?H (B) = (CHj )?C-/Q \-O-CH-C®-C(C®3)3 ο/ ά OH (0) = CI-ZQVo-CH-CH-OCOHj)^ Lj (D) OH »-O-CH-CH-C(CH3)5 - 17 4 3 6 3 7 (E) = ? V ό (Τ) = (G) ύ · = <5>ο-οη-οο^> .HC1 (Η) = ΟΗ o-ch-ch-c(ch3)3 _J31 ΟΗ /Q VO-OH-CH-C (GHj) 3 ^-7 Η „ it (κ) = J31 (Ο )-0-011-00-0(0^ )5 ΟΗ (L) = C1-/q\—O-CH-CH-C CH3)5 Λ (Μ) = /qVo-GH-CO-G(CH3)5 - 1,3 4 36 3 7 (Μ) = Cl-^\-0-CH-0H-C(CH3), ά (Ρ) = C1-/Q\-O-CH-GO-C(CH5)5 Cl (Q) = Cl -CH-CO-CHi 2 Example A Podosphaera test (apple)/protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: S5 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 sprayed with the spray liquid until dripping wet. Ihe plants remained in a greenhouse for 24 hours at 20°C and at a relative atmospheric humidity of 70/=. They were then inoculated by dusting the oonidia of the apple powdery mildew causative organism (Podosphaera leucotricha) and placed in a greenhouse at a temperature of 21 - 23°C and at a relative atmospheric humidity of about 70?=. - 19 4 5 6 3 7 days after the inoculation, the infection of the seedlings was determined. The assessment data were converted to % infection. 0% meant no infection; 100% meant that the plants were completely infected.

The active compounds, the concentrations of the active . compounds and the results can be seen from the following table; T a b 1 e A Podosphaera test (apple)/protective Active Infection in % at an compound active compound concentration of 0.01% 0.0025% U) 100 - (4) - - 79 (16) - 55 (6). - 75 15 (18) - 2 Example B Erysiphe test (cucumbers)/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 the active compound required for the desired concentration of active compound in the spray liquid was mixed witii the stated amount of the solvent, and the concentrate was diluted with the staged amount of water con25 taining the stated additions.

Young cucumber plants with about three foliage leaves were sprayed with the spray liquid until dripping wet. The cucumber plants remained in a greenhouse for 24 hours.to dry. They were then, for the purpose of inoculation, dusted with - 20 4863? conidia of the fungus Erysiphe cichoriacearum. The plants were subsequently placed in a greenhouse at 23-24°C and at a relative atmospheric humidity of about 75%.

After 12 days, the infection of the cucumber plants 5 was determined. The assessment data were converted to per cent infection. 0% meant no infection; 100% meant that the plants were completely infected.

The active compounds, the concentrations of the active compounds and the results can be 3een from the following table.

Table B Erysiphe test (cucumbers)/protective Active Infection in % at an active corncompound pound concentration of '_0,00062% ,0.0005%___ (A) 100 (4) - 62 (15) - 46 (16) - 62 1.17) - 66 (6) - 22 (18) - 0 Example C Erysiphe test (cucumbers)/systemic Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alxyiaryl polygxyc'.·^ ether - 21 4 3 6 3 7 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 which contained the stated additives.

Cueumb'er 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 ml of soil.

The plants treated in this way were inooulated, after treatment, with conidia of the fungus Erysiphe cichoracearum. The plants were then set up in a greenhouse at 23-24°C and 70% relative atmospheric humidity. After 12 days, the infection of the cucumber plants was determined. The assessment data were converted to per cent infection. 0% denoted no infection and 100% denoted that the plants were completely infected.

The active compounds, active compound concentrations and results can be seen from the table which follows: Table C Ezyalphe test/systemic (cucumbers) Active Infection in % of the infection of compound the untreated control at an active compound. ΟΟηοΒηΐΓΗΐΙοη of 1 ppm/ (D) 100 (0) 100 (1) 27 (10) 75 (11) 6 - 2? Example D Euaicladium test (apple/(protective) 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 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 (Fusicladium dendriticum) and incubated for 18 hours in a humidity chamber at 18-20°C and at a relative atmospheric humidity of 100%.

The plants were then brought into a greenhouse again for 14 days. days after inoculation, the infection of the seedlings was determined. The assessment data were converted to per cent infection. 0% meant no infection; 100% meant that the plants were totally infected.

The active compounds, the concentrations of the active compounds and the results can be seen from the following table: 43637 Table Β Puslcladium test (apple)/protective Active Infection in % at an active compound compound concentration of 0.025% 0.01% (E) 43 (C) - 62 (1) - 11 (7) - 16 (8)-0 Example E Uromvces test (bean rust)/protective 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 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°C 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 (Uromyces phaseoli) and incubated for 24 hours in 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%. - 24 43637 days after the inoculation, the infection of the plants was determined. The assessment data were converted to % infection. 0% denoted no infection and 100% denoted that the plants were completely infected.

The active compounds, active compound concentrations and results can be seen from the following table: Table E Uromyces test/protective Active Infection in % of the infection compound of the untreated control at an active compound concentration (in %) of 0.005_0.00025 (A) 71 - (6) - 84 (16) - 10 (4) - 29 Example F Shoot treatment test/cereal mildew/protective/curative (leaf-destructive mycosis) 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 and then 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 graminia var. hordei.

To test for curative activity the corresponding procedure was followed in converse sequence. The treatment of - 25 45637 the single-leaved, young barley plants with the preparation of active compound was carried out 48 hours after inoculation, when the infection was already manifest.

After 6 days' dwell time of the plants at a temperature 5 of 21-22°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 the degree cf mildew infection.

The active compounds, active compound concentrations in the spray liquor and degrees of infection can be seen from the table which follows; Table P Shoot treatment test/cereal mildew/protective/ curative Active Active compound con- Infection in % compounds centration in the of the untreated spray liquor in % control by weight_Protective Curative Untreated - 100.0 100.0 (?) 0.01 66.3 - (s) 0.01 - 50.0 (H) 0.01 - 17.4 (E) 0.001 91.3 - (J) 0.001 82.5 - (4) 0.01 0.0 0.0 (15) 0.01 0.0 0.0 (16) 0.01 0.0 7.5 (18) 0.01 21.3 (6) 0.01 0.0 0.0 (2) 0.001 0.0 ο 6 3 '7 Table Ε (continued) Shoot treatment test/cereal mildew/protective/ curative Active Active compound con- Infection in % compounds centration in the of the untreated spray liquor in % control by weight_Protective Curative (12) 0.001 0.0 - (5) 0.001 0.0 - (7) 0.001 0.0 - (8) 0.001 0.0 - (13) 0.00025 21.3 - (14) 0.00025 0.0 - Example 5 Powdery mildw of barley test (Erysiphe graminis var.hordei)/ systemic (fungal disease of cereal shoots) The active compounds were used as pulverulent seed treatment agents. They were 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 mixture of active compound and extender 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 Pruhstorfer 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 bed developed their first leaf, they were dusted with fresh spores of Erysiphe graminis var. hordei and grown further at 21-22°C and 80-90% relative atmospheric humidity and 16 hours’ exposure to light. The - ?7 ; 43637 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 amount used of the latter, and the percentage infection with mildew can be seen from the table which follows: Table G Powdery mildew of barley test (Erysiphe graminis var. horde!)/systemic Active compounds Active compound concentration in the dressing in % by weight Amount of Infection dressing in % of used in g/kg of seed the untreated control Without dressing -. 100.0 (E) 10 2 100.0 (B) 25 10 100.0 (K) 25 10 100.0 (I) 25 10 48.8 (9) 10 2 0.0 (10) . 10 2 0.0 (11) 10 .2 0.0 (15) 25 10 0.0 (17) 25 10 0.0 (6) 25 10 0.0 - 28 45637 Example Η Shoot treatment test/cereal rust/protective (leaf-destructive mycosis) 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 and then 975 parts by weight of water were added. The concentrate was diluted with water to the desired final concentration of the spray liquor.

Tc test the protective activity, one-leaved young wheat plants of the Michigan Amber variety were inoculated With a uredospore suspension of Puccinia recondita in 0.1% strength aqueous agar. After the spore suspension had dried on, the wheat plants were sprayed with the preparation of active compound until dew-moist and were placed, for incubation, in a greenhouse for 24 hours at about 20°C and 100% relative atmospheric humidity.

After 10 days3 dwell time of the plants at a temperature ef 20°C and 80-90% atmospheric humidity, the occurrence of rust pustules on the plant 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 the degree of rust infection.

The active compounds, active compound concentrations in the spray liquor and degrees of infection can be seen from the table which follows: - 29 637 Table Η Shoot treatment test/cereal rust/protective Active compounds Active compound concentration in the spray liquor in % by weight Infection in % of the untreated control Untreated - . 100.0 (B) 0.025 75.0 (M) 0.025 90.0 (1) 0.025 8.8 (7) 0.025 0.0 (9) ,0.025 33*8 (10) 0,025 41.3 (11) 0.025 50.0 (2) 0.025 0.0 (12) 0.025 0.0 (3) 0.025 0.0 (13) 0.025 8.8 (14) 0.025 0,0 (4) 0.025 0.0 (15) 0.025 40.0 (18) 0.025 0.0 Example I Pyricularia and Pellicularia test Solvent: 11.75 parts by weight of acetone Dispersing agent: 6.75 parts by weight of alkylaryl polyglycol ether Water: 987.50 parts by weight The amount of active compound required for the desired concentration of active compound in the spray liquid was mixed with the stated amount of the solvent and of the dis- 30 43637 persing agent and the concentrate was diluted with the j stated amount of water. x 30 rice plants about 2-4 weeks old were sprayed with the spray liquid until dripping wet. The plants re5 mained in a greenhouse at temperatures of 22 to 24°G and a relative atmospheric humidity of about 70% until they were dry. Thereafter, some of the plants were inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml of Pyricularia oryzae and placed in a chamber at 24 to 26°C and 100% relative atmospheric humidity. The other plants were infected with a culture of Pellicularia sasakii grown on malt agar and were set up at 28 to 30°0 and 100% relative atmospheric humidity. to 8 days after the inoculation, the infection of all the leaves present at the time of inoculation with Pyrioularia oryzae was determined as a percentage of the untreated but also inoculated control plants. In the case of the plants infected with Pellicularia sasakii. the infection at the leaf sheaths after the same time was determined, again in relation to the untreated but infected control. The evaluation was made on a scale of from 1 to 9· 1 denoted 100% action,3 denoted good action, 5 denoted moderate action and 9 denoted no action.

The active compounds, the concentrations of the active compounds and the results can be seen from the table which follows. - 31 Table I Pyricularia (a) and Pellicularia (b) test Active Infection in % of the compound infection of the untreated control at an active compound concentration of 0.025% (a) (il (N) 9 9 (1) 3 (8) 3 (2) 5 1 Example K Mycelium growth test 10 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 Eatio of solvent mixture to nutrient medium: parts by weight of solvent mixture 100 parts by weight of agar nutrient medium Composition of the solvent mixture: 0.19 part by weight of DMP or acetone 0.01 part by weight of emuloifier (alkylaryl polyglycol ether) 1 80 parts by weight of water The amount of active compound required for the desired active compound concentration in the nutrient medium was mixed with the stated amount of solvent mixture. The con- 32 4 3 6 3 oentrate wa3 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 the table and incubated at about 21 °C.

Evaluation was carried out after 4-10 days, dependent upon the speed of growth of the fungi. When evaluation wtas carried out the radial growth of the mycelium on the treated nutrient media was compared with the growth on the control nutrient medium. In the evaluation of the fungus growth, the following characteristic values were used: 1 no fungus growth up to 3 very strong inhibition of growth up to 5 medium inhibition of growth up to 7 slight inhibition of growth growth equal to that of untreated control.

The active compounds, the active compound concentrations and the results can be seen from the following table: „ 43637 ΤτχΒΒΒΒ Bpoofsniir •Bxxeje'B'qd.soo^M nmsirrnnSft? ϊπητΰδα -soqq.UTnrc8H ft SUBOSBUBUTO •BUOqQOTBflfJ ΘΒΖΛ'αΟ ΒτΰΒχηδτϊΔϊ mnjq.BoqxB ®nTXXxoxq.J9A •ρ a ο ρ Λ I h Μ BBUBUTO ΒΤΪΰΒθξΒΪτΠ snxoq -οττίίοοο nronrcq-xn •piBXOS Β-μιοψοοζτιηι umuosjjoo mnqojjiq -oq-enoD ΘΤΒΔΧΙΧ nmyuBSTig πιηαοτψοαθΤΟΒ BTUxqoaBXos umuourpno tn cn cn 1 in 1 in ·«· tn - cn cn ‘ - - - - - in tn cn tn tn tn tn in σι cn in tn 1 in - - 1 I cn cn 1 I 1 1 1 tn tn σ» cn in I t tn tn in cn in σ» in I in m tn tn cn cn cn 1 tn 1 in T" CM in cn cn CM in - CM - tn in cn cn tn in in tn T" . 1 cn cn 1 1 1 1 1 in 1 cn cn 1 1 1 ί 1 tn cn cn cn in in tn in tn tn ο cn cn , . in I 1 in tn m K\ r~ ΙΛ CM I Vin m tn T- v- cm . t- τ- ί— tn ωηταΒΒη^ mid uoi:q.Bj:q.U30iioo ponodmoo BArqoy ra τί o i* o o Q) -P o < CM I ΙΛ CM *I tn (15) (16) (17) (18) - 34 43637 The process of the present invention is illustrated by the following preparative Examples.

Example 1 7il NO-CH - CO O.H (1) SO.H Process variant (a) 268.3 g (0.79 mol) of crude 1-bromo-4-ehloro-1-(4chlorophenoxy)-3,3-dimethyl-butan-2-one were dissolved in 2 1 of absolute acetonitrile. 190 g (2.7 mol) of 1,2,4triazols were added thereto and the mixture was heated for. hours under reflux. It was then concentrated by distilling off the solvent in vacuo and the residue was taken up in 1,000 ml of methylene chloride. The mixture was washed three times with 250 ml of water at a time, dried over sodium sulphate and again concentrated in vacuo. The oil which remained was dissolved in 1,000 ml of acetone and a solution of 140 g (0.48 mol) of naphthalenedisulphonic acid in 500 ml of.acetone was added. After 30 minutes, the resulting precipitate was filtered off. 285 g (76.6% of theory) of 4-chloro~1-(4-chlorophenoxy)-3,3-dimethyl-120 (1,2,4"triazol-1-yl)-butan-2-one naphthalene-1,5-disulphonate of melting point 245°C (with decomposition) were obtained» Preparation of ths starting material ClCH t Sr co CH, .

I 3 C - CH2C1 e% - 35 43637 213 g (1 mol) Of 1-bromo-4-chloro-3,3-dimethyl-butan2-one were added dropwise to a boiling suspension of 128.5 g (1 mol) of 4-chlorophenol and 140 g (1 mol) of potassium carbonate in 1,000 ml of absolute acetone. The mixture was stirred for 15 hours under reflux and was then allowed to cool, and the inorganic residue was filtered off and rinsed with acetone. The filtrate was concentrated by distilling off the solvent in vaouo and the residue was taken up in 1,000 ml Of methylene chloride, washed three times with 250 ml of water at a time, dried over sodium sulphate and distilled. 210 g (80.7% of theory) of 4-chloro-1-(4-chloro-. phenoxy)-3,3-dimethyl-butan-2-one of boiling point 125-127°C/ 0.1 ram Hg were obtained. 21Q g (0.81 mol) of 4-chloro-1-(4-chlorophenoxy)-3,315 dimethyl-butan-2-one were dissolved in 1,000 ml of carbon tetrachloride. 41 ml (0.81 mol) of bromine were added dropwise at room temperature at a rate such that the bromine was steadily consumed. The mixture was then stirred for 30 minutes at room temperature. After distilling off the solvent in vacuo. 268.3 g (98% of theory) of crude 1-bromo4-chloro-1-(4-chlorophenoxy)-3,3-dimethyl-butan-2-one were obtained and were directly reacted further.

Preparation of the precursors CH3 BrCH2 - CO - C - CHaCl I CHj 134.5 g (1 mol) of l-chloro-2,2-dimethyl-butan.-3-one were dissolved in 500 ml of ether. 51 ml (1 mol) of hrnm-i ne were added dropwise at room temperature, with slight cooling, - 36 43637 at a rate such that the bromine was steadily consumed. The solution was then stirred into 1,000 ml of ice-water and the organic phase was separated off, rinsed with 250 ml of water, dried over sodium sulphate and distilled. 169 g (80% of theory) of 1-bromo-4-chloro-3,3-dimethyl-butan-2one of boiling point 95-1O6°C/13 mm Hg were obtained.

CHS I CH, - CO - C - CH2C1 CH3 11.6 g (0.1 mol) of 2,2-dimethyl-1-hydroxy-butan-3-one Were added dropwise at 50° to 60°C (whilst cooling with ice) to 20.5 g (0.1 mol) of N,N-diethyl-1,2,2-trichlorovinylamine. After stirring for two hours at 60°C, the mixture was distilled in a waterpump vacuum. 8.1 g (60% of theory) of 1chloro-2,2-dimeth.yl-butan-3-one of melting point 60 - 62°C/ mm Hg were obtained. (1-Chloro-2,2-dimethyl-butan-3-one was obtained in a yield of 90% when equimolar amounts of 2,2-dimethy1-1hydroxy-butan-3-one and triphenylphosphine, in a ten-fold amount of carbon tetrachloride, were heated for 12 hours under reflux. The solvent was distilled off, the residue was taken up in ether and the solution was filtered and dis- CKj - CO « C - CEgOH 1 CHS g (2.2 mol) of paraformaldehyde and 1 g of potassium hydroxide in 10 ml of methanol were added dropwise to 172 g (2 mol) of methyl isopropyl ketone in 1,000 ml of methanol. - '-'7 43637 The mixture was heated for 15 hours under reflux and the . methanol was then distilled off through a column, at 82°C internal temperature. The residue was distilled in a waterpump vacuum. 152.7 g (68% of theory) of 2,2-dimethyl-l5 hydroxy-butan-3-one of boiling point 80 - 82°C/12 mm Hg were obtained.

Example 2 285 g (0.6 mol) of 4-chloro-1-(4-chlorophenoxy)-3,3dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one naphthalene1, 5-disulphonate, obtained according to Example 1, were neutralised with aqueous sodium hydroxide solution. 221.7 g (67.5% of theory, relative to the 1-bromo-4-chloro-1-(4chlorophenoxy)-3,3-dimethyl-butan-2-one employed) of 4chloro-1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1yl)-butan-2-one were obtained as a colourless oil having a 20 refractive index η-θ of 1.546.

Example 3 ClOH CH3 -O-CH-CH-C-CHj, Cl 1 CH3 . HC1 The reaction mixture was then stirred into 500 ml of saturated sodium bicarbonate solution and was extracted three times with 150 ml of methylene chloride at a time, and the combined organic phases were washed twice with 100 ml of water at a time, dried over sodium sulphate and concentrated in a waterpump vacuum by distilling off the solvent. The residue was dissolved in acetone, 100 ml of a solution of hydrogen chloride in ether were added and the mixture was concentrated in a waterpump vacuum. The residue was taken up in 100 ml of ethyl acetate and was allowed to crystallise out at 0°C. 41.4 g (38% of theory) of 4-chloro1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-ol hydrochloride (erythro form and threo form) of melting point 157°C were obtained.

Example 4 Cl (4) Process variant (a) .8 g (0.05 mol) of crude 1-bromo-4-chloro-1-[4-(4'chlorophenyl)-phenoxy]-3,3-dimethyl-butan-2-one were dissolved in 120 ml of absolute acetonitrile. 12 g (0.175 mol) of imidazole were added and the mixture was heated for 40 hours under reflux. It was then concentrated by distilling off the solvent in vacuo and the residue was taken up in 300 - Q ml of methylene chloride. The solution was washed three times with 100 ml of water at a time and was dried over sodium sulphate and again concentrated in vacuo. The residue was taken up in 100 ml of acetone and a solution of 9 g (0.038 mol) of 1,5-naphthalenedisulphonic acid in 50 ml of acetone was added. After 2 hours, the precipitate formed, was filtered off and dried. 19.6 g (72% of theory) of 4chloro-1-[4-(4’-chlorophenyl)-phenoxy]-3,3-dimethyl-1(imidazol-1-yl)-butan-2-one naphthalene-1,5-disulphonate of melting point 246°0 were obtained.

Preparation of the intermediate CHj C1 ΌΌ o - CH - CO - C - CHj Cl Br CHj 42.7 g (0.2 mol) of 1-bromo-4-chloro-3,3-dimethylbutan-2-one were added dropwise to a boiling suspension of 41 g (0.2 mol) of 4-(4'-chlorophenyl)-phenol and 28 g (0.2 mol) of potassium carbonate in 300 ml of absolute acetone. The mixture was stirred for 15 hours under reflux and was then allowed to cool and the inorganic residue was filtered off and rinsed with acetone. The filtrate was concentrated by distilling off the solvent in vacuo. The residue crystallised after the addition of 50 ml of diisopropyl ether. 37.5 g (55% of theory) of 4-chloro-1-4-(4’-chlorophenyl )-phenoxy-3,3-dimethyl-butan-2-one of melting point 67-68°C were obtained. 33.7 g (0.1 mol) of 4-ehloro-1-[4-(4’-chlorophenyl)phenoxy]-3»3-dimethyl-butan-2-one were dissolved in 250 ml of carbon tetrachloride. 5.1 ml (0,1. mol) of bromine were - 4C 43637 added dropwise at room temperature at a rate such that the bromine was steadily consumed. The mixture was then stirred for 30 minutes at room temperature. After distilling off the solvent in vacuo, crude 1-bromo-4-chloro-1[4-(41-chlorophenyl)-phenoxy]-3,3-dimethyl-butan-2-one was obtained in quantitative yield and was directly reacted further.

Example 5 Cl O-CH CH, I CO - C - CH2C1 CHS (5) She 4-chloro-1-[4-(4’-chlorophenyl)-phenoxy]-3,3dimethyl-1-(imidazol-1-yl)-butan-2-one naphthalene-1,5disulphonate obtained according to Example 4 was neutralised with sodium bicarbonate solution. 4-Chloro-1-[4-(4'cblorophenyl)-phenoxy]-3,3-dimethyl-1-(imidazol-1yl)-butan15 2-one of melting point 97-99°C was obtained quantitatively.

Example 6 OH Cl vQ-o-cs - k Λ1' ch3 I C - CHoCl I CH, (6) Process variant (b) 18.8 g (0.04 mol) of 4-chloro-1-(4-chlorophenoxy)-3,320 dimethyl-1-(imidasol-1-yl)-butan-2-one naphthalene-1,5disulphonate [= Example 15? prepared in accordance with Example 1, in 81% yield] were suspended in 100 ml of methylene chloride and 100 ml of sodium bicarbonate solution were added. The organic phase was separated off, dried over sodium sulphate and concentrated by distilling off the solvent in vacuo. The base thus obtained was taken up in 100 ml of isopropanol and 2 g (0.05 mol) of sodium borohydride were introduced in portions at 5 to 10°C. The mixture was stirred for 15 hours, at room temperature and the isopropanol was then distilled off. The residue was taken up in 100 ml of methylene chloride and, after adding 100 ml of water, was stirred for a further 15 hours at room temperature. The organic phase was then separated off, washed twice with 50 ml of water at a time, dried over sodium sulphate and concentrated. The oil which remained was boiled up in 100 ml of petroleum ether, which caused it to crystallise. 9.8 g (75% of theory) of 4-chloro-1-(4-chlorophenoxy)-3,3dimethyl-1-(imidazol-1-yl)-butan-2-ol were obtained as an isomer mixture (erythro form and threo form) of melting point 120-125°C.

The following examples of the general formula X -0-CH-A-f-CH2Y j were obtained analogously to the examples mentioned: if* - 42 43637 in Ο ι co co 50, H as u co m n m S as as as u u u Μ Μ Μ ΡΊ as a as as u u o u ω as u as as as as o ooo o u u υ fi, 'M* CM as bs as as as o as o as o as o u u I—) f—ί o o I ’M’ CM <Ό LH - 43 43637 4-Cl CH(OH) Cl Cl CH, CH 113-119 43637 Preparation of further precursors CHS (β) BrCH2 - CO - C -. CHgBr I CHS 34.8 g (0.3 mol) of 2,2-dimethyl-1-hydroxy-butan-3-one and, at 0 to 5°C, 40 ml (0.5 mol) of pyridine were added dropwise to 47.6 g (0.25 mol) of £-toluenesulphochloride in 100 ml of chloroform. The mixture was stirred for 15 hours at room temperature and was then poured onto 200 g of ice and 70 ml of concentrated hydrochloric acid. The organic phase was separated off, washed three times with 100 ml of water at a time, dried over sodium sulphate and concentrated by distilling off the solvent in a waterpump vacuum. 200 ml of petroleum ether were added to the residue, whereupon 48 g (71% of theory) of 2,2-dimethyl-3-keto-butoxy-£-toluene~ sulphonic aeid ester of melting point 49-52°C precipitated. g (0.1 mol) of this £-toluenesulphonic acid ester were dissolved in 100 ml of methyl ethyl ketone and heated with 52 g (0.6 mol) of lithium bromide for 48 hours under reflux. The mixture was filtered, the solvent was distilled off under normal pressure, the residue was dissolved in methylene chloride and the solution was washed four times with 100 ml of water at a time. The organic phase was dried over sodium sulphate and concentrated in a waterpump vacuum. g (84% of theory) of 1-bromo-2,2-dimethyl-butan-3-one were obtained and this was reacted, analogously to 1-chloro-2,2dimethyl-butan-3-one (compare Example 1), with bromine to give 1,4-dibromo-3,3-dimethyl-butan-2-one. - 45 4363 CHj Cl ' ι (γ) BrCH2 - CO - C - CH,C1 ι CH3 Analogously to Example 1(a), 2,2-bis-hydroxy-methylbutan-3-one was first prepared by formylation of methyl ethyl ketone; thereafter, the reaction of the 2,2-bis-hydroxy- . methyl-butan-3-one with two equivalents of N,N-diethyl-1,2,2trichlorovinylamine to give 2,2-bis-chloromethyl-butan-3-one was carried out.

Finally, the 2,2-bis-chloromethyl-butan-3-one was then reacted with bromine to give 1-bromo-3,3-bis-chloromethyl10 butan-2-one.

Claims

1. CLAIMS:1. Halogenated 1-azolyl-butane derivatives of the general formula CHjX z, A - C - CHjY I (I) in which R represents alkyl or optionally substituted phenyl, X represents hydrogen, alkyl or halogen, Y represents halogen, Z represents halogen, alkyl, cycloalkyl, alkoxy, halogenoalkyl, alkylthio, alkoxycarbonyl, optionally substituted phenyl or phenoxy, optionally substituted phenylalkyl, amino, cyano or nitro, n represents 0, 1, 2, 3, 4 or 5, A represents a keto group or a CH(OH) grouping and B represents a nitrogen atom or a CH group, and their salts.

2. Compounds according to claim 1, in which R represents alkyl with 1 to 4 carbon atoms or phenyl which is optionally substituted by halogen and/or alkyl with 1 or 2 carbon atoms; X represents hydrogen, alkyl with 1 to 4 carbon atoms or halogen; Y represents halogen; Z represents halogen, straight-chain or branched alkyl with 1 to 4 carbon atoms, oyoloalkyl with 5 to 7 carbon atoms, halogenoalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms, alkoxy with 1 or 2 carbon atoms, alkylthio with 1 or 2 carbon atoms, alkoxycarbonyl with 1 to 5 carbon atoms in the alkoxy part, amino,' cyano, nitro, or optionally substituted phenyl or phenoxy-’, the substituents being selected from halogen, amino, cyano, nitro and alkyl with 1 to 2 carbon atoms or Z represents phenylalkyl with 1 or 2 carbon atoms in the alkyl part and which may be substituted in the alkyl part by alkylcarbonyl with a total of up to 3 carbon atoms and which may be substituted in the phenyl part by halogen, nitro or cyano; and n represents 0, 1, 2 or 3.

3. The compound disclosed in any one of Bxamples 1-3 and 7-12.

4. The compound disclosed in any one of Bxamples 4-6 and 15-18.

5. The compound disclosed in any one of Examples 13, 14 and 19-21.

6. Compounds according to olaim 1 or 2, being compounds of the formula (I) in which B represents a nitrogen atom, and their physiologically tolerated salts.

7. Compounds according to claim 1 or 2, being compounds of the formula (I) in which B represents a CH group, and their physiologically tolerated salts.

8. A process for the preparation of a halogenated 1-azolylbutane derivative according to claim 1 in which (a) a bromoether-ketone of the general formula R in which - 48 4 3 6 3 7 R , Χ·, Υ, Ζ and η have the meanings stated in claim 1, is reacted with an azole of the general formula Vj (V), N I H in which 5 3B has the meaning stated in claim 1, if appropriate, in the presence of a diluent and optionally thereafter (b) the keto-derivative obtained according to (a) is (1) reduced with hydrogen in the presence of a cata10 lyst and optionally in the presence of a polar solvent, or (2) reduced with aluminium isopropylate in the presence of a solvent, or (3) reduced with a complex hydride, optionally in the presence of a polar solvent, or 15 (4) reduced with formamidinesulphinic acid and an alkali metal hydroxide, optionally in the presence of a polar solvent

9. A process according to claim 8(a) in whioh the starting material (II) is one that is hereinbefore specifically mentioned. 20 10. A process according to claims 8(a) or 9, in which the reaction is effected at from 20° to 150°C· 11. A process according to claim 10, in which the reaction is effected at 60° to 120°C. 12. A process according to claim 8(a), 9, 10 or 11, in 25 which the reaction is effected in the presence of an acidbinding agent. 13. A process according to claim 12, in which the acidbinding agent is an alkali metal carbonate, a lower tertiary alkylamine, cycloalkylamine or aralkylamine, pyridino, - 49 - 4 3 6 3 '7 r jtt ♦ · V diazabicyclooctane or an excess of the azole (V). 14. A process according to claim 12 or 13, in whioh 2 moles of the azole and 1-2 moles of the acid-binding agent are employed per mole of the starting material (IX). 5 15. A process according to any of claims 8(a) and 9 to 14, in which the reaction is effected in the presence of an inert organic solvent. 16. A process according to claim 8(b)(1), in which the catalyst is platinum, platinum oxide or Raney nickel.

10. 17. A process according to claim 8(b)(1) or 16, in which the hydrogenation is effected at from 20° to 50°C. 18. A process according to claim 8(b)(1), 16 or 17, in which 1 mole of hydrogen and 0.1 mole of catalyst are employed per mole of the compound (II).

11. 15 19· A process according to claim 8(b)(2), in whioh the solvent is an alcohol or an inert hydrocarbon.

12. 20. A process according to claim 8(b)(2) or 19, in which the reaction is effected at from 20° to 120°C.

13. 21. A process according to claim 8(b)(2), 19 or 20, 20 in which 1-2 moles of aluminium isopropylate are employed per mole of the compound (II).

14. 22. A process according to claim 8(b)(3), in which the hydride is sodium borohydride or lithium aluminium hydride.

15. 23. A process according to claim 8(b)(3) or 22, in which 25 the solvent is an alcohol or an ether.

16. 24. A process according to claim 8(b)(3), 22 or 23 in which the reaction is effected at from 0° to 30°0.

17. 25. A process according to any of claims 8(b)(3) and 22 to 24, in which 1 mole of hydride is employed per mole of the 30 compound (II). - 50 43637

18. 26. A process according to claim 8(b)(4), in which the solvent is an alcohol or water.

19. 27. A process according to claim 8(b)(4) or 26, in which the reaction is effected at from 20° to 100°C.

20. 28. A process according· to claim 8(b)(4), 26 or 27, in which 1-3 moles of formamidinesulphinic acid and 2-3 moles of alkali metal hydroxide are employed per mole of the compound (II),

21. 29. A process according to any of claims 8 to 28 in whioh the 1-azolyl-butane derivative (I) is dissolved in an ether and converted to a salt by addition of an acid.

22. 30. A process according to any of claims 8 to 29 wherein a compound according to claim 6 is prepared.

23. 31. A process according to any of claims 8 to 29 wherein a compound according to claim 7 is prepared.

24. 32. A process for the preparation of a compound according to claim 1, substantially as described in any of Examples 1 to 3.

25. 33. A process for the preparation of a compound according to claim 1, substantially as described in any of Examples 4-6.

26. 34. Compounds according to claim 1 whenever prepared by a process according to any of claims 8 to 33.

27. 35· A fungicidal composition containing as active ingredient a compound according to any of claims 1 to 7 and 34 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.

28. 36. A composition according to claim 35, in which the active compound is according to claim 6.

29. 37. A composition according to claim 35, in which the active /43637 A / compound is according to claim 7.

30. 38. A method according to claim 37 in which a composition is used containing from 0.00001 to 0.1% of the active compound, by weight, 5

31. 39, A method according to claim 38 in which a composition is sued non·!:aining from 0.0001 to 0.05% of the active compound, by weight.

32. 40. A method according to claim 37, 38 or 39, in which the active compound is applied to soil in an amount of 1 g to 1 10 kg per cubic metre of soil.

33. 41. A method according to claim 40, in which the active compound is applied to soil in an amount of 10 g to 200 g per cubic metre of soil.

34. 42. A method according to claim 37, 38 or 39» in which the ' · 15 active compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.

35. 43» A method according, to claim 42, in which the active compound is applied to seed in an amount of 0.01 to 10 g per jr kg of seed. 20

36. 44. A method according to any of claims 37 to 43 in which the active compound is according to claim 6.

37. 45» A method according to any of claims 37 to 43 in which the active oompound is according to claim 7» r Harvested

38. 46./ Crops protected from damage by fungi by being grown in 25 areas in which immediately prior to and/or during the time of the growing a oompound according to any of claims 1 to 7 and 34 was applied alone or in admixture with a diluent or carrier.