1-phenoxy-1-(1,2,4-triazolyl)-alkanols their preparation and fungicidal compositions containing them

preparation and ’togiciflai. compositions containing W®

BAIER ASIWESB1S0HO'

C. 42709

The present invention relates to certain new triazolyl-׳ Ο,Ν-acetals, to a process for their preparation and to their use as fungicides.

It has already been disclosed that trityl-imidazoles and —1,2,4-triazoles, such as tripheny!imidazole and triphenyl-

1,2,4-triazole, possess good fungicidal activity (see U.S. Patent Specification 3,321,366 and Belgian Patent Specification 738,095), However, their action is not always entirely satisfactory, especially if low amounts and concentrations are used. It is also known that zinc ethylene-1,2-bis-dithiocarbamate displays a good fungicidal activity against Phycomvcetes. for example against Phytonhthora infestans. the pathogen of potato blight and tomato blight, and against various soil-borne fungi. However, its activity if used as a seed dressing is not always entirely satisfactory.

The present invention provides, as new compounds, the triazolyl-0,N-acetals of the general formula ,

H² OH

I. I _A ־ a¹- 0- 0-r⁴ (!) ¹ 13

A2 in which

1Λ is phenyl optionally substituted by one, two or more substituents selected from halogen, alkyl, nitro, phenyl, cycloalkyl or alkoxycarbonyl;

.

R is hydrogen;

R .is hydrogen, alkyl or'phenyl lower alkyl;

R⁴ is alkyl or phenyl; and

Az is a 1,2,4-triazol-l-yl, l,2,4-triazol-4-yl, or

1,2,3-triazol-l-yl radical, and their salts.

44793/2

The compounds of the present invention have been found י; to. display strong fungicidal properties.

Preferably R^ is cycloalkyl with 5 to 7, especially 5 or 6 carbon atoms, optionally substituted phenyl, the preferred sub-^! stituents being selected from halogen, especially fluorine, | i

chlorine or bromine, straight-chain or branched alkyl with ¹ to 6, especially 1 to 4, carbon atoms, carbalkoxy with to 4 carbon atoms in the alkoxy part, phenyl in the 0- or jn-position, and nitro;

R is hydrogen;

R5׳ is hydrogen, alkyl with up to 8 carbon atoms or phenyl lower alkyl;

R^ is straight-chain or branched alkyl with 1 to 8 carbon atoms or phenyl; and

Az is one of the following radicals:

<img file="IL44793A_D0001.tif" />

¹ I ¹

The compounds of the formula (I) possess two'asymmetrical carbon atoms and can therefore be in the erythro form and in the threo form; in both cases they are predominantly in the form of racemates.

The present invention also provides a process for the preparation of a compound of the general formula (I), in which a triazole derivative of the general formula ' R² 0 . I H .

r'-O-C-C-R⁴ (II),

I Az , 44793/2 in which r\ , R⁴ and Az have the above-mentioned meanings, is (a) reduced with hydrogen in the presence of a catalyst and^ optionally of a polar solvent, or (b) reduced with aluminium ieopropylate in the presence of a solvent, or (c) reduced with complex hydrides, optionally in the presence of a polar solvent, or (d) reduced with formamidine-sulphinic acid and alkali metal hydroxide, optionally in the presence of a polar solvent, or (e) reacted with an organo-metallic compound of the general formula '

M - R⁵ (Hl), in which 3

R has the above-mentioned meaning, and

M is an alkali metal or the radical X-Mg, wherein

X is chlorine, bromine or iodine, in the presence of an inert solvent.

Surprisingly, the active compounds according to the invention display a substantially greater fungicidal action than the compounds triphenylimidazole, triphenyl-1,2,4triazole and zinc ethylene-1,2-bis-dithiocarbamate known from the state of the art. The active compounds according to the invention thus represent an enrichment of the art. _t

If 1-phenoxy-1-[1,2,4-triazolyl-(1¹)]-3,3-dimethylbutan2-one and hydrogen are used as starting materials, the course of the reaction in process variant (a) can be represented by the following equation! ‘ 1

<img file="IL44793A_D0002.tif" />

<img file="IL44793A_D0003.tif" />

If 1-phenoxy-1-[1,2,4-triazolyl-(1')]-3,3-dimethylbutan2-one and aluminium isopropylate are used as starting materials, the course of the reaction in process variant (b) can be represented by the following equation:

CH} J/C-O-Al/3 ⁰ + CH, .

’ \ It 2 π (/ A-O-CH-C-C(CH-), ------—--->

W ^{ג כ} י CH, β '¹ί - ³0=ס^א k־~CH^

Ζ־־λ ?¹γ⁵ + (η ®)Η₂0 (/ xyo-CH-CH-C(CH-),--±—>

גן - ³י (OH)

1^ן_____J ®y-O-CH-CH-C (CHj)_ל ־ ά

If ί-phenoxy-1-[1,2,4-triazolyl-(1')-3,3-dimethylbutan2-one and sodium borohydride are used as starting materials, the course of the reaction in process variant (c) can be represented by the following equation:

<img file="IL44793A_D0004.tif" />

Le A 14 971

<img file="IL44793A_D0005.tif" />

+ 2. H₂0 —--->

- NaBO₂

If 1-phenoxy-1-[1,2,4-triazolyl-(1 ')]-3,3-dimethylbutan-2-one and formamidinesulphlnic acid are used as starting materials, the course of the reaction in process variant (d) can be represented by the following equation:

<img file="IL44793A_D0006.tif" />

If 1-phenoxy-1.-[1 2,4_׳-triazolyl-(1')]-3,3-dimethylbutan-2-one and methyl-magnesium iodide are used as starting

Le A 14 971 materials, the course of the reaction in process variant (e) can be represented by the following equation:

+ CH^MgBr .

//^Υθ-ΟΗ-Ο-ΟίΟΙί^)^ Δ ,N, _ז π It

OMgBr -+ H ׳Jy-o-GH-cH-c(CH^ )^ ! -x | CH^ - MgBr(.OH)

The following may be mentioned as examples of starting compounds of. the formula (II); [ω-(1,2,4-triazolyl-1 *)[ω— phenoxy]-acetophenone; [ω-( 1,2,4-triazblyl-!¹)]-[ω-4'-chlorophenoxy]-acetophenone; [ω-(1,2,4-triazolyl-l')]-[ω-J'-chlorophenoxy]-acetophenone; [ω-(1,2,4-triazolyl-1’)]-[ω-2¹,4'dichlorophenoxy]-acetophenone; [ω-(1,2,4-triazolyl-1')]-[ω2-',4'-dichlorophenoxy]-4-chloro-acetophenone; [ω-(1,2,4triazolyl-1*)]-[ω-2’,6’-dichlorophenoxy]-acetophenone; [ω- (1,2,4-triazolyl-1’)]-[ω-4*-methylphenoxy]-acetophenone; [ω(1,2,4-triazolyl-1’)]-[ω-2'-methylphenoxy]-acetophenone; [ωmethyl]-[!*»-(! ,2,4-triazolyl-l *)]-[ω-4’-chlorophenoxy]-acetophenone; [ω-phenyl]-[(!)-(! ,2,4-triazolyl-l' )]-[ω-2' ,4'-dichloro- 7 44793/2 triazolyl-1')]-[1-(£-diphenoxy)]-3>3-dimethyl-butan-2-one;

[1-(1,2,4-triazolyl-1') ]-[1-(o-diphenoxy)]-3,,3-dimethyl-butan2-one; [2-(1,2,4-triazolyl-1')]-[2-phenoxy]-4,4-dimethylpentan-3-one; [2-(1,2,4-triazolyl-1')]-[2-(4-fluorophenoxy)]-

4,4-dimethyl-pentan-3-one; [2-(12,4_׳-triazolyl-1')]-[2-(2',4’-j dichlorophenoxy)]-4,4-dimethyl-pentan-3-one; [1 -phenyl]-[!

(1,2,4-triazolyl-l')]-[1-phenoxy]-3»3-dimethyl-butan-2-one;

[1-phenyl]-[1-(1,2,4-triazolyl-1')]-[1-(4'-fluorophenoxy)]-

3,3-dimethyl-butan-2־one; [1-phenyl]-[1-(1,2,4-triazolyl-1')]

[.1-(2¹,4'-dichlorophenoxy)]-3>3-dioethyl-butan-2-one; [2(12,4_׳-triazolyl-14,'2)-2]-[(י'-dichlorophenoxy)]-1-cyclohexyl ethan-1-one; [2-(1,2,4-triazolyl-1')]-(2-(2',4'-dichlorophenoxy)]-1-cyclopentyl-ethan-1-one and [2-(1,2,4-triazolyl1')]-(2-(2¹,4'-dichlorophenoxy)]-3-cyclohexyl-propan-3-one.

The triazole derivatives of the formula (II) which can be used according to the invention have not previously been described in the literature but they form, in part, the , subject-matter of Israel Patent Specification 41252. They can be prepared, for example, by reacting a halogenqether-ketone

ץ with a 1,2,4-triazole in a stoichiometric ratio, optionally in the presence ofa solvent or diluent and of an acid-binding agent, at temperatures of, preferably, Θ0 to 120°C. Amongst other processes of preparation, the reaction of hydroxyetherketones with 1,2,4-triazoles in the presence of a dehydrating agent 8nd optionally in the presence of a diluent, at temperatures between, preferably, 140 and 200°C, should also be mentioned.

44793/2 i יי . Depending on the process of preparation and on the con- w ditions of working up, the triazole derivatives of the formula (II) may be obtained as 1,2,4-triazolyl-(4) derivatives or as 1,2,4-triazolyl-(1) derivatives in accordance with the tautomeric character of 1,2,4-triazole ל - υ a mixture of both forms frequently results.

Salts of compounds of the formula (I) which can be used are salts with physiologically tolerated acids. Preferred acids include the hydrogen halide acids, such as hydrobromic acid and, in particular, hydrochloric acid, as well as phosphoric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and 1,5naphthalene-disulphonic acid.

Polar organic solvents can be used as diluents for the reaction in accordance with process variant (a). Preferred solvents include alcohols, such as methanol and ethanol, and nitriles, such as acetonitrile. The reaction is carried out in the presence of a catalyst. Preferably, noble metal catalysts, noble metal oxide (or noble metal hydroxide) catalysts or Raney .catalysts are used, especially platinum, platinum oxide or nickel. The reaction temperatures can be varied within a fairly wide range: in general, the reaction is carried out at from 20° to 50°C, preferably' at from 20° to 40°C. The ‘reaction can be carried out under normal pressure and under elevated an?.*¹ י^, ' pressure (1 to 2 atmospheres gauge). In the reaction according to variant (a), about 1 mole of hydrogen and 0.1 mole of catalyst are generally employed per 1 mole of the compound of the formula (II); to isolate the compound, the catalyst is filtered off, the filtrate is freed from the.solvent in vacuo and the resulting product of the formula (I) is purified by recrystallisation. If desired, the salts of the compounds according to the invention are obtained according to customary methods.

IQ If process variant (b) is followed, preferred diluents for the reaction are alcohols, such as isopropanol, or inert hydrocarbons, such as benzene. The reaction temperatures can again be varied within a fairly wide range; in general, the reaction is carried out at from 20° to 120°C, preferably at 15 50°to 100°C. About,1 to 2 moles of aluminium isopropylate are generally employed per mole of the compound of the formula (II) in carrying out the reaction. To isolate the compound of the formula (I), the excess solvent is removed by distillation in vacuo and the resulting aluminium compound 20 is decomposed with dilute sulphuric acid or sodium hydroxide solution. The further working-up is carried out in the customary manner.

If process variant (c) is followed, possible diluents for the reaction are polar organic solvents, preferably alcohols, 25 such as methanol, ethanol, butanol and isopropanol, and ethers, such as diethyl ether or tetrahydrofurane. In general, the reaction is carried outatfrom 0° to JO°C, preferably at from 0° to 20°C. For this reaction, about 1 mole of a complex hydride, such as sodium borohydride .or lithium

JO alanate, is generally employed per mole of the compound of the

Le A '14 971 i| formula (II). To isolate the compound of the formula (I), the residue is taken up in dilute hydrochloric acid and the solution, is then rendered alkaline and extracted with an organic solvent. The further working-up is carried out in 5 the usual manner.

_;Possible diluents for the .reaction according to process, variant (d) are polar organic solvents, preferably alcohols, such as methanol and ethanol, as well as water. Here again the reaction temperatures can be varied within a fairly wide 10 range; in general, the reaction is carried out at a .

temperature of from 20° to 100°C, preferably at from 50° to 100°C. To carry out the reaction, about 1 to 3 moles of formamidinesulphinic acid and 2 to 3 moles of alkali metal hydroxide are generally employed per mole of the compound of 15 the formula (II). To isolate the end product, the reaction mixture is freed from the solvent and the residue is extracted with water and organic solvents, and worked up and purified . in the customary manner; if desired, the salt is prepared.

In the reaction according to process variant (e), 20 compounds of the general formula, (I) in which is not hydrogen are obtained. In contrast thereto, the reactions according to process variants (a) to (d) are reduction reactions; the compounds of the formula (I) thereby obtained 3 are secondary alcohols in which R is, in every case, 25 hydrogen only.

For the reaction according to process variant (e), an organo-metallic compound of the formula (III) is required . in addition to the triaz.ole derivative of . the formula (II) . M in the formula (III) is preferably lithium, sodium or a 5° so-called Grignard grouping Mg-X, wherein X is chlorine, bromine or iodine. The organo-metallic compounds of the

Le A 14 971 - J#־lx.

ץ ( יי formula (III) are generally known: a summary and survey of . numerous publications is to be found,, for example, in G.E.

Coates, Organo-Mctallic Compounds, 2nd edition, Methuen and Co., London (I960).

' Anhydrous ethers, such as. diethyl ether or dibutyl ether, are preferably used for the reaction in accordance with process variant (e). The reaction temperature can, in general, be from 0° to 80°C, preferably from 3Q°to 60°C. In carrying out the process variant (e), about 1 mole of this . organo-metallic compound of the formula (III) is generally employed per mole of the compound of the formula (II). The mixtures obtained by organo-metallic reactions are worked up in the customary and generally known manner.

The active compounds according to the invention dis15 play a strong fungitoxic action. They do not harm crop plants in the concentrations required to combat fungi. For these reasons, they are suitable for use as plant-protection agents for. combating fungi. Fungitoxic agents are employed in plant protection for Combating Archimycetes, Phycomycetes. Asco20 mycetes. Basidiomycetes and Fungi Imperfecti.

The active compounds according to the invention have a very broad spectrum of action and can be employed against parasitory fungi which attack above-ground parts of plants or attack the plants through the soil, and against seed-trans25 farable pathogens.

They display particularly good action against parasitory fungi on above-ground parts of plants, such as species of Erysiphe. species of Podosphaera. species of Sphaerotheca. species of Venturia and also species of Piricularia and

JO. species of Pellicularia. They are also highly active against

Le A 14 971 - Λ5׳־־13 rust fungi and smut fungi, for example against the pathogen of bunt of wheat. It is to be emphasized that the active compounds according to the invention display not only a protective action but also a curative action; that is to say, they can also be employedafter infection has occurred. The systemic action of the compounds should also be pointed out. Thus it proves possible to protect plants against fungal attack by.supplying the active compound to the above-ground . part of plants through the soil, through the plant or through . the seed. As 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 only have a low toxicity to warmblooded animals and because of their low odour and good tolerance are not unpleasant to the human skin when handled.

The active compounds according to the present. invention can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced, in known manner, for οτηιηρίι* 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 foam-forming agents.

In the case of the use of water as an extender, organ1c 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 hydro

Le A 14 971 ->frcarbone, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such ae butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, ’ such as dimethyl formamide, dimethyl sulphoxide or acetonitrile, as well as water»

By liquefied gaseous diluents or carriers are meant 10 liquids which would be gaseous at normal temperatures and pressures, for example aerosol propellants, such as halogenated hydrocarbons, for example freon.

As solid diluents or carriers, there are preferably used , ground natural minerals, such as kaolins, clays, talc, chalk, 15 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 polyoxy20 ethylehe-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 25 methyl cellulose.

The active compounds according to the invention can be present in the formulations as a mixture with other active compounds such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth-regulating JO substances, plant nutrients and agents for improving the soil

Le A 14 971 structure.

In general, the formulations contain from 1 to 95 per cent by weight of active compound, preferably, from 5 to 90 per cent.

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

When used as leaf fungicides, the concentrations of active compound in the. application forms can be varied within . a fairly wide range. In general, the concentrations are between 0.1 and 0.00001 per cent by weight, preferably between 0.05 and 0.0001 per cent.

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

The amounts Of active compound required for soil treatment are generally from 1 to 1,000 g per cubic metre of soil, preferably 10 to 200 g.

The active compounds according to the invention also display a good microbistatic 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

JO carrier containing a surface-active agent.

Le A 14 971 lb

The present invention also provides a method of combating fungi which comprises applying to the fungi or a fungus habitat a compound of the present invention alone or in the form of a composition containing as active ingredient 5 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 10. 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 present compounds is 15 illustrated by the following test Examples. The compounds of the present invention are each identified by the number of the corresponding preparative Example hereinafter.

Example A

Ervs'i-phe test / 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 the active compound required for the desired concentration of active compound in the spray liquid 25 was mixed with the stated amount of the solvent, and the concentrate was diluted with the stated amount of water contain— ing the stated additions.

Young cucumber plants with about three foliage leaves were sprayed with the spray liquid until dripping wet. The 30 cucumber plants remained in a greenhouse for 24 hours to dry. They were then, for the purpose of inoculation, dusted with

Le A 14 971 -ΛΤ-

7־1 f

conidia of the fungus Erysiphe clohoreacearum. 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 was determined as a percentage of the untreated but also inoculated control plants, 0% means no infection; 100% 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:

T a b 1 e A

Erysiphe test

Active compound Infection in % of the , infection of the untreated control at an active compound concentration of 0.00025% __________________________ by weight_____________

<img file="IL44793A_D0007.tif" />

<img file="IL44793A_D0008.tif" />

(known) (2) (B) (9) (15) (13)

<img file="IL44793A_D0009.tif" />

I»e A 14 971

Example Β

Eryeiphe test / systemic

Solvent: 4.7 parts by 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 for the desired conceritration of the active compound in the watering liquid was mixed with the stated amount of the solvent and the con10 centrate was diluted with the stated amount of water which contained the stated additions.

Cucumber plants grown in standard soil, in the 1-2 leaf stage, were watered three times within a week with 20 ml of the watering liquid having the stated concentration of active 15 compound, per 100 ml of soil.

After the treatment, the plants treated in this way were inoculated with conidia of the fungus Erysjphe cichoraceartiin The plants were then placed in a greenhouse at 23 to 24°C and a relative atmospheric humidity of 70%. After 12 days, the 20 infection of the cucumber plants was determined as a percentage of the untreated but also inoculated control plants. .

0% means no Infection and 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 25 compounds and the results can be seen from the table which follows:

I׳e A 14 971

ף׳ י

Table B

Erysiphe teat / systemic

Active compound Infection in % of the infection of the untreated control at an active compound concentration of .

•_______ 100 ppm________ .1 ppm

<img file="IL44793A_D0010.tif" />

(known) (14-threo form)0 (14-erythro form)0 (4)0 • (2) '0

Example C

Podosphaera. test (powdery mildew of apples) / 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 in . le A 14 971 zo oculated by dusting with conidia of the apple powdery mildew causative organism (Podosphaera leucotricha Salm.) and placed in a greenhouse at a temperature of 21 - 23°0 and at a relative atmospheric humidity of about 70¢.

Ten days after the 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 C

Podosphaera test I protective

Active compound Infection in ¢ of the infection of the untreated control at an active compound concentration (in % by weight) of ________________ .________0,00062 0,00031_________

<img file="IL44793A_D0011.tif" />

(known)

<td> (2)</td><td> 5 . 16</td>

<td> (14-threo form)</td><td> 0</td>

<td> (14-erythro form) (4)</td><td> 0 0</td>

<td> (15)</td><td> 4</td>

Le A 14 971

Example D

Shoot treatment teat / powdery mildew of cereals / protective , (leaf-destructive mycosis)

To prepare a suitable preparation of active compound, 5 0.25 part by weight of active compound was taken up in 25 parts by weight of dimethy!formamide and 0.06 part by weight of emulsifier W; and 975 parts by weight of water were added. The concentrate was diluted with water to the desired f 1 n»i concentration of the spray, liquor.

test the protective activity, young barley plants of the Amsel variety, having one leaf, were sprayed with the preparation of the active compound until dew-moist. After drying, the barley plants were dusted with spores of Eryeiphe graminis var. horde!.

After 6 days residence time of the plants at a temperature of 21 to 22°C and an atmospheric humid tty of SO to 90% 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 untreated control. The active compound is regarded as the more active, the lower the infection withpowdery mildew.

The active compounds, active-compound, concentrations in ths spray liquor and degrees of infection can be seen from 25 the table which followsi

Le A 14 971 b . . .

״ ..'. Table D .

. Shoot treatment test / powdery mildew of cereals / protective

Active compounds Active compound ' Infection in $ concentration in of the untreated the spray liquor, in. . control • . My weight untreated - . 100 .

<td></td><td> 3L-WS-S.</td><td rowspan="2"> 0.3</td><td rowspan="2"> 64.0</td>

<td></td><td> \n</td>

<td> 1 1</td><td> 3H₂-NH-CS-S ,</td><td> 0.1.</td><td> 80,5</td>

<td> 5 V 1 1</td><td> [known)</td><td></td><td></td>

<td colspan="2"> . (2) '</td><td> 0.01 </td><td> . 0.0</td>

<td colspan="2"></td><td> 0,001</td><td> 0.0</td>

<td colspan="2"> (6)...</td><td> 0.01</td><td> ' 6.5</td>

<td colspan="2"></td><td> 0.001</td><td> 10.8</td>

<td colspan="2"> (14-erythro font)</td><td> 0.01</td><td> 0.0</td>

<td colspan="2"></td><td> . 0.001</td><td> 0.0</td>

<td colspan="2"> (14-threo form)</td><td> . 0.01</td><td> 0.0</td>

<td colspan="2"></td><td> 0.001</td><td> ., 0,0</td>

<img file="IL44793A_D0012.tif" />

<td></td><td> Table D (continued) Shoot treatment test / powdery mildew of cereals / protective</td>

<td> Active compounds</td><td> Active compound Infection in $ concentration in . of the untreated the spray liquor, in control ' . $ by weight</td>

<td> (12)</td><td> 0,01 0.0 0.001 0.0</td>

<td> (7)</td><td> 0.01 ’ 0.0 0.001 25.8</td>

<td> (4)</td><td> 0.01 0,0 '</td>

<td> (17)</td><td> 0.001 0.0 0.01 0.0 0.001 6.5</td>

Example

Powdery mildew of barley test (Ervsiphe graminis var. hordel)/ systemic . (fungal cereal shoot disease)

5. The active compounds were applied as pulverulent seed dressings. 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 extended active, compound in a closed glass bottle. The seed was sown at the rate of 5 x 12 grains in flower pots, 2 cm deep in a mixture of one part by volume of Fruhstorfer standard soil and one part by volume of quartz sand. Germination and emergence took place under favourable conditions in a greenhouse. 7 days after sowing,, when the barley plants had developed their first leaf, they were dusted with fresh spores of Erysiphe graminis var. horde! and grown further at 21 to 22 °C and 80 to 90¢ relative atmospheric humidity and 16 hours’ light exposure. The typical powdery mildew pustules formed on the leaves within 6 days.

The degree of infection is expressed as a percentage of the infection of the untreated control plants. Thus, 0% denotes no infection and 100¢ denotes the same degree of in25 fection as in the case of the untreated control. The active compound is regarded as the more active, the lower the infection with powdery mildew.

The active compounds, active-compound concentrations in the seed dressing and the amount used of the latter, and the 30 percentage infection with powdery mildew can be seen from the table which follows!

' ' . i

Le A 14 971 - 27 - .

ג S'

Table E .

Powdery mildew of barley test (־Eryeiphe mmlnis van horde!) 7 systemic

Active׳ compounds Active compound Amount of dressing Infection in ji of concentration in used in g/kg of the untreated the dressing seed control ־ in $ by weight ־

<td> without dressing</td><td> 100 , ־ ' .'.</td>

<td rowspan="2"> ' ה N 4 ¾¼⁰5 . ד (known) CH₂-NH־CS-8 Zn</td><td> 30 10 100</td>

<td> 50. 10 . 100</td>

<td> CH^ffi-CS-S⁷ . (known) ׳ (2)</td><td> 25 . 10 0.0</td>

Example F

Fusioladium test (apple ecab)/Protective v

Solvent; 4.7 parte by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether 5 Water: 95 parts by weight

Ths amount of active compound required for the desired concentration of the active compound in the epray liquid was mixed with,the stated amount of solvent, and the concentrate wae diluted with the stated amount of water which contained ,10 the stated additions. , *

Young appd e 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$. They were then . 15 inoculated with an aqueous conidium suspension of the apple scab causative organism (Fusicladium dendriticum Fuckel) and incubated for 18 hours in a humidity chamber at 18 - 20°C and at a relative atmospheric humidity of 100$.

The plants were then brought into a greenhouse for 14 20 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 25 wae 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:

Le A 14 971

<td></td><td> Table F Fusicladium test / protective Active compound Infection in % of the infection of the untreated control at an active compound concentration (in % by weight) of 0.025 . 0.00125 &amp; ⁹⁷ -</td>

<td> 5</td><td> 0 (known) (2) - 16 (14-threo form) - 7 (14-erythro form) - 5 (12) - 0 . (4) . - 12 The process of this invention is illustrated by the following preparative Examples. Example 1 OH cU^O-CH-feZA (1) \— / . \ — / a</td>

<td> 10</td><td> 51•4 g of (0.1 mole) of ω-[4’-chlorophenoxy]—ω—[1,2,4-</td>

<td></td><td> triazoly1-(1')]-acetophenone were dissolved in 500 ml of methanol and 5 g (0.08 mole) df sodium borohydride were Le A 14 971 -J©־- *8</td>

׳ introduced into this solution whilst stirring and cooling with ice. The reaction mixture was stirred for 1 hour at >room temperature and the solvent was then distilled off in vacuo. The residue was taken up in dilute hydrochloric acid and the solution was briefly heated and filtered. The filtrate was then rendered alkaline with sodium hydroxide solution. The precipitate thereby produced was filtered off and taken up in ethyl acetate. After distilling off the ethyl acetate, an oil remained, which crystallised on trituration with ligroin. After recrystallisation from ligroin/isopropanol, . 25 g (98% of theory) of 1-(4'-chlorophenoxy)-1-(1,2,4-triazolyl(1')]-2-phenyl-ethanol of melting point 117°C were obtained. Preparation of the intermediate:

32.5 g (0.1 mole) of to-bromo-u)-(4'-chlorophenoxy)- acetophenone and 30 g (0.44 mole) of 1,2,4-triazole were dissolved in 240 ml of acetonitrile and the solution was heated for 48 hours under reflux. After distilling off the solvent, the residue was taken up in 800 ml of water. This ־ aqueous solution was repeatedly extracted with methylene chloride and the methylene chloride solution was twice washed with 200 ml of water at a time and then dried over sodium sulphate, and the solvent'was distilled off in vacuo. The residue crystallised out; it could be recrystallised: from ligroin/isopropanol (2 : 1); the melting point was'about 98 to 100°C.

(1>-Bromo-u)-(4^,-chlorophenoxy)-acetophenone, required as , the starting material for the preparation of the intermediate, was prepared by condensation of 4-chlorophenol with ω-chloroacetophenone and bromination of the resulting ω-(4'-chloro30 pheno^-acetophenone in the usual, manner and had a melting

Le A 14 971 point of 71 °C.

Example 2

OH

C1^27-O-CH-OT-C(CH₅)₅ (2)

A L.!

5θ7 g (2 moles) of 1-( 4'-chlorophenoxy )-1-[1,2,4-tri5 azolyl-(1')]-3,3-dimethyl-butan-2-one were dissolved in 5 1 of methanol. A total of 80 g (2 moles) of sodium borohydride was added thereto in portions of 5 g at 0 to 10°C, whilst stirring and cooling with ice, and the mixture was stirred for 2 hours at 5 to 10°C and then for 1.2 hours at room temperature. It was then cooled to 10°C and 300 g (3 moles) of concentrated aqueous hydrochloric acid were added at 10 to 20°0. After stirring for six hours at room temperature, the resulting . suspension was diluted with 3«θ 1 of water which contained 400 g (4.8 moles) of sodium bicarbonate. The precipitate thereby produced was filtered off. 502 g (85$ of theory) of

1-(4'-chlorophenoxy)-1-[1^,A-triazolyl.(!’)]-3,3-dimethylbutan-2-01 of melting point 112 to 117°C were obtained. Example 3

<img file="IL44793A_D0013.tif" />

(5)

A solution of 31 •2 g (0.22 mole) of methyl iodide in

100 ml of anhydrous ether was added dropwise to a suspension of 4.8 g (0.22 mole) of magnesium filings in 50 ml of anhydrous ether, with stirring and reflux cooling; during the addition,

Le A 14 971

3*

I ־ .

.U ' . .. .

the solvent started to boil. After completion of the addition, a solution of 29.4 g,(0.1 mole) of 1-(4'-chlorophenoxy)-

1-[1,2,4-triazolyl-(1')]-3,3-dimethyl-butan-2-ohe in 100 ml of anhydrous ether was added dropwise to this Grignard solution and the mixture was heated to the boil for 18 hours with reflux cooling. After cooling, the reaction mixture was introduced into a solution of 80 g of ammonium chloride in 600 ml of water, 250 ml of ethyl acetate were added and the mixture was stirred for 15 minutes. The organic phase was separated off and the aqueous phase was extracted with ethyl acetate. Both ethyl acetate extracts were washed twice with 100 ml of water at a time,, dried over sodium sulphate and freed of the solvent in vacuo. The crystalline precipitate was taken up in hot petroleum ether, in which it remained uhdissolved, and is filtered off hot. 11 g (36% of theory) of 1-(4 *-chlorophenoxy )-11,2,4-triazolyl-(1 ¹) ]-2,3,3-

־4 trimethy1-butan^ol of melting point 158 to 160°C were bbtained.

Example 4 _ ^0H

BrZ_n-O-CH-CH-C(CH₅)₃ . (4)

33.6 g (0.1 mole) of 1-(4'-bromophenoxy)4-[1,2,4-triazolyl-(1¹)-]-3,3-dimethyl-butan-2-one were dissolved in 300 ml of ethanol and a sodium hydroxide solution, containing 8 g (0.2 mole) of sodium hydroxide in 40 ml of water, was added thereto, followed by 32.4 g (0.3 mole) of formamidinesulphinic acid. The reaction mixture was heated to the boil under reflux for 3 hours and filtered, and the solvent was distilled

Le A 14 971 -

׳3 ־ ׳ u in vacuo. The oily residue was taken up in 100 ml of water and extracted with twice 100 ml :of methylene chloride. The combined organic phases were washed with twice 100 ml of water, dried over sodium sulphate and freed of the solvent in vacuo.

The resulting oil was boiled up with petroleum ether, whereupon it crystallised. Filtration gave 26.5 g (79% of theory) of 1-(4*-bromophenoxy)-1-(1,2,4-triazolyl-(1 ' )]-3,3-dimethylbutan-2-01 of melting point 115 to 118°C.

Example 5 z־־\ ?^H

4 \\_0-CH-CH-C(CH₅)₅ (5) ־ ώ , (erythro form and threo form) . 29.5 g (0.114 mole) of 1-phenoxy-1-(1,2,4-triazolyl(1¹)]-3,3-dimethyl-butan-2-one were dissolved in 250 ml of methanol and 5.8 g (0.15 mole) of sodium borohydride were added in portions at 0 to 5°C, with stirring and reflux cooling. After stirring for twelve hours at room temperature the mixture was next worked up, as described in Example 2, with 20 ml of concentrated hydrochloric acid and 250 ml of saturated sodium bicarbonate solution. The suspension containing sodium bi20 carbonate was extracted twice with 150 ml of methylene chloride at a time. The combined organic extracts were washed with twice 100 ml of water until neutral, dried and freed of the solvent in vacuo. The resulting oil was boiled up with hot petroleum ether. This left a crystalline residue (A) which was filtered off hot, and dried. The filtrate was freed of the solvent in vacuo and this residue (B) was triturated with

Le A 14 971 _

3V petroleum ether and a little ether. A total of 23.4 g (79$ of theory) of 1-phenoxy-1-[1,2,4-triazolyl-(1')]-3,3dimethyl-butan-2-0^/ is obtained, comprising 4.1 g (residue A) of the erythro-form of melting point 132°C and 19.3 g (residue B) of the threo-form of melting point 88 to 94°C, The following compounds of the formula

R² OH R¹O-C— C-R⁴ (!)

Az: 1P were obtained analogously:

le A 14 971 ® $ £ r\ JU . Melting point (°C) or

..־ refractive index (nJ⁰)' /

196 ־ 194

115-117

125 - 127

107-112

<img file="IL44793A_D0014.tif" />

c(ca₅)₅

<img file="IL44793A_D0015.tif" />

<img file="IL44793A_D0016.tif" />

114-115

UJL6 ־fr L

<img file="IL44793A_D0017.tif" />

R^ Az Melting point (°C) or • refractive index

<img file="IL44793A_D0018.tif" />

100 ־ 98 threo: 115 - 117 erythro: 186-190

V2.6 *r L ® Example > No. R’ r² fi’ . I_Z .Melting point (°C) or refractive index

<img file="IL44793A_D0019.tif" />

<img file="IL44793A_D0020.tif" />

<img file="IL44793A_D0021.tif" />

<img file="IL44793A_D0022.tif" />

<img file="IL44793A_D0023.tif" />

threo: 114-116 erythro; 161-164

107-110

133-135

<img file="IL44793A_D0024.tif" />

Example 1 ₄ ו ק Melting point (°C) or

Ho. ί R r . R’ Az refractive index («?)

<img file="IL44793A_D0025.tif" />

185 - 187

84-90

101 - 10]

<img file="IL44793A_D0026.tif" />

Melting Point (°C) or.

refractive index

Example . , .

No. R R²_r4

<img file="IL44793A_D0027.tif" />

I 'J

נס

<td> 22 CH^O-CO-0-</td><td> 3\ Η H C(CH₃)₃ .ן ן</td><td> 136-138</td>

<td> 23 Cl-β- Cl</td><td>^{H CH}3</td><td> 171-173</td>

<td> Cl</td><td> Η H C(CH₃)₃ Δ</td><td> 95-98</td>

<td> ל2 Cl</td><td>^{7 H} °^3 0</td><td> 142-144</td>

<td> ־00“ י m</td><td> ’ * ^e5־rt ή 1</td><td> 115-120</td>

<td> 27 0⁷ Π-</td><td>^J *A 0 I</td><td> 92-5</td>

<td></td><td>_yN Η ׳B C(CH₃)₃ £{</td><td> 97-10¢</td>

&amp; /36 L. &amp; tr