CA1106757A

CA1106757A - Fungicidal agents

Info

Publication number: CA1106757A
Application number: CA296,583A
Authority: CA
Inventors: Wolfgang Kramer; Karl H. Buchel; Wilhelm Brandes; Paul-Ernst Frohberger
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1977-02-11
Filing date: 1978-02-09
Publication date: 1981-08-11
Also published as: DE2705676A1; JPS53101532A; ZA78822B; DK61478A; CS194197B2; BR7800791A; TR19543A; SE7801525L; PL109892B1; IL54003A0; GB1590932A; AU3324278A; FR2379983A1; NL7801578A; GB1590933A; PL204556A1; DD134719A5; BE863850A; PT67627B; ATA94278A

Abstract

Fungicidal Agents Abstract of the Disclosure 1-Phenoxy-2-(2,4-dichlorophenyl)-1-imidazol-1-yl-ethan-2-ones and -ols of the formula (I) in which A is -C(O)- or -CH(OH)- , X independently is halogen, alkyl or optionally substituted phenyl 9 and n is 0, 1, 2 or 3.
or salts thereof, which possess fungicidal properties.

Le A 17 829-CA

Description

The present invention relates to the use as fungi-cides of certain 2,4-dichlorophenyl-imidazolyl-ethan-ones and -ols.
It has already been disclosed that, in particular, 3,3-dimethyl-1-phenoxy-1-imiclazolyl-butan-2-ols possess a good fungicidal activity (see German Offenle~ungsschrift (German Published Specification) 2,333,354). However, their action is not always completely satisfactory, in particular when lo~ application amounts and concentrations are used.
It has now been found that the 2,4-dichlorophenyl-imidazolyl-ethan-ones and -ols of the general formula Cl~
~ - O - CH - A - ~ (I), Xn C~l N
in which A represents a keto group or a CH(OH) grouping, X represents halogen, alkyl or optionally substituted phenyl and n represents 0, 1, 2 or 3, the X's being selected independently of one another when n is 2 or 3, and their salts have powerful fungicidal properties.
The present invention therefore provides a fungicidal composition containing as active ingredient a compound of the for-mula (I),or a salt thereof, in admixture with a solid or liquefied gaseous diluent or carrier or in ad-mixture with a liquid diluent or carrier containing a surface-act:ive agent.
` The present invention also provides a method of Le A 17 829 - 2 -~ 167~i'7 .

; combating fun~i which comprises applyin~ to the fun~i,or to a habitat thereof, a compound of the formula (I), or a salt thereof, alone or in admixture with a diluent or carrier.
Preferably, in formula (I), X represents ~luorine~
chlorine, bromine, iodine, straight~chain or branched alkyl with 1 to 4 carbon atoms9 or phenyl which is optionally substituted by halo~en (especially chlorine) and n re-presents O, 1 or 2.
1 Those compounds of the formula (I) in which A repres-ents the CH(OH) group possess two asymmetric carbon atoms;
they can therefore be present in the Porm of two geometric isomers (erythro form and threo form), which can be obtained in various proportions. They are pre~ent in both cases as optical isomers. It is intended that formula (I) should cover all of the isomers.
Examples which may be mentioned of particularly active compounds to be u3ed according to the invention are: 1~(2~
chlorophenoxy)~2-(2,4-dichlorophenyl)~l~imidazol~l~yl~ethane-

2~one and ~ol, 1-(2-isopropylphenoxy)-2~2,4-dichlorophenyl)-1~
imidazol-l~yl~ethan~2-one and ~ol, 1~(2-methylphenoxy)-2~
(2,4-dichlorophenyl)-l~imidazol-1-yl-ethan-2-one and -ol, 1-(2-chloro-4~methylphenoxy)-2-(2,4-dichlorophenyl)-1-imidazol l-yl-ethan-2-one and -ol, 1-(4-bromphenoxY)-2-(2,4-dichlorophenyl)-1-imidazol-1-yl-ethan-2-one and ~ol, 1~(4-iodc~phenoxy)-2-(2,4-dichlorophenyl)-1-imidazol-1-yl-ethan-2-one and -ol, 1-(2,6-dichlorophenoxy)-2-(2,4-dichloro-phenyl)-'L-imidazol-l-yl-ethan-2-one and -ol, 1-(2,5-dichloro~
phenoxy)--2-(2,4-dichlorophenyl)-1-imidazol-1-yl-ethan-2-one and -ol, 1-(3-Pluorophenoxy)-2-(2 9 4-dichlorophenyl)-Le A 17 829 - 3 -6~5~

l-imidazol-l-yl-ethan-2-one and -ol, 1-(3-bromophenoxy)-2-(2 3 4-dichlorophenyl)-1-imidazol-l~yl-ethan-2 one and -ol, 1-(4-methylphenoxy)-2-(2,4-dichlorophenyl)-1-imidazol-1-yl-ethan-2-one and -ol, 1-t4-ethylphenoxy)-2-(2,4 dichloro-phenyl)-1-imidazol-1-yl-ethan-2-one and -ol, 1-(3~methyl-phenoxy)-2-(2,4-dichloro~henyl)-1-imidazol-1-yl-ethan-2-one and -ol, 1-(2-methyl-phenoxy~-2-(2,4-dichlorophenyl)-1-imidazol-l-yl-ethan-2-one and -ol, 1-(4-chloro-2-methyl-phenoxy)-2-(2,4-dichlorophenyl)-l-imidazol-1-yl-ethan-2-one and -ol, 1-(4-bromo-2-methylphenoxy~-2-(2,4-dichloro-phenyl)-l-imidazol-l-yl-ethan-2-one and -ol, 1-(4-fluoro-2-methylphenoxy)-2 (2,4-dichlorophenyl)-1-imidazol-1-yl-ethan-2-one and -ol, 1-(4-iodo-2-methylphenoxy)-2-(2~4-dichlorophenyl)-l-imidazol-l-yl-ethan-2-one and -ol, 1-(2,3-dimethylphenoxy)-2-(2,4-dichlorophenyl)-1-imidazol-l-yl-ethan-2-one and -ol, 1-(4-2'~4'-dichlorobiphenylyloxy)-2-~2,4-dichlorophenyl)-1-imidazol-1-yl-ethan-2-one and -ol, 1-(4-2,4'-dichlorobiphenylyloxy).2-(2,4-dichlorophenyl)-l-imidazol-l-yl-ethan-2-one and -ol, 1-(4-4'-bromobiphenylyl-oxy)-2-(2,4-dichlorophenyl)-1-imidazol-1-yl-ethan-2-one and -ol and 1-(4-2-chlorobiphenylyloxy)-2-(2,4-dichlorophenyl)-l-imidazol-l-yl-ethan-2-one and -ol. Further compounds are given in the preparative Examples to be found later ; in this text.
The active compounds to be used according to the invention,, and their salts, have not yet been de~cribed in the literature. However, they can be prepared by reacting l-bromo-2~(2,4-dichlorophenyl)-1-phenoxy-ethan-2-ones o~
the formu:La Le A 17 829 - 4 -.

6~75~' :.
Xn ~ - 0 - CH - C0 - ~ - C1 (Il), in which X and n have the meanings stated above, with imidazole in the presence of an inert organic solvent, ; 5 for example acetonitrile, and in the presence o~ an acid-binding agent, ~or example potassium carbonate or an excess : of imidazole, at temperatures between 0 and 150C, prefer-: ably at 60 to 120C, and optionally reducing the imidazolyl-ethanones, thereby obtained, with complex borohydrides, for example sodium borohydride, in a manner which is in itself known in the presence of a polar organic solvent, ~or example methanol, at temperatures between 0 and 30 C. The ~ .
: compounds of the formula (I) are isolated in a manner which is generally customary.
The l-bromo-2-(2,4-dichlorophenyl)-1-phenoxy-ethan-2-ones of the ~ormula (II) to be used as starting materials have not yet been described in the literature. ~owever, they can be prepared by known processes by reacting corres-ponding phenols with ~-bromo-2,4-dichloroacetophenone and subsequently replacing the active hydrogen atom, which still remains, by bromine in the customary manner.
Pre~erred salts of the compounds o~ the formula (I) are - from the standpoint o~ phytotoxicity - physiolcgically acceptable salts, these being generally salts with physio-logically acceptable acids. The pre~erred acids include hydrogen halide acids (~or example hydrobromic acid and, in Le A 17 829 - 5 -~ 6~ ~ 7 particular, hydrochloric acid)~ phosphoric acid, nitric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (for example acet;c aoid, citric acid, sorbic acid and lactic acid), and 1,5-naphthalene-disulphonic acid.
The active compounds according to the invention exhibit a powerful fungitoxic action. They do not damage crop plants in the concentrations required for combating 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 Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, ~y~omycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
The active compounds according to the invention have a broad spectrum of action and can be used against parasitic fungi which attack above-ground parts of plants or which attack the plants through the soil, as well as against seed-borne pathogens.
They display a particularly good activity against parasitic fungi on above-ground parts of plants.
As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating powdery mildew fungi, for example for combating powdery mildew of cucumbers (Erysiphe cichoriacearum), as well as against cereal diseases, for example cereal rust.
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-3o ground part;s of plants.

Le A 17 829 - 6 -~96757 The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, sus-pension-emulsion concentrates, seed-tre~tment powders, natural and synthetic materials impregnated with active compound9 very fine capsules in polymeric substances, coating compositions for use on seed, and ~ormulations used with burning equipment, such as fumigatin~ cartridges, fumigating cans and fumigating coils, as well as ULV
cold mist and warm mist formulations.
These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or lique~ied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents andJor dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid solvents diluents or carriers, especially solvents, there are suitable in the main, aromatic hydro-carbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl-Le A 17 829 - 7 -~ L0~7 sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are l~eant liquids which would be ~aseous at normal temperature and under normal pressure, for example aerosol propellantsg such as halogenated hydrocarbons as well aæ butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmor;llonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules Or inorganic and organic meals, and granules o~ organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-~orming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-~atty alcohol ethers, for example alkylaryl polyglycol ethers~
alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.
The active compounds according to the invention can be present in the ~ormulations as a mixture with other active compounds 3 such as ~ungicides, insecticides, acaricides, nematicides~ herbicides, bird repellants, growth factors, plant nutrients and agents for improving 3o soil structure.

Le A 17 829 - 8 -67~i7 The formulations in general conta n from 0.1 to 95 per cent by weight of active compound, preferably from ~.5 to 9~ per cent.
The active compounds can be used as such, as their formulations or as the use forms prepared there~rom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They may be used in the customary manner, for example by watering, spraying, atomising, dusting, scattering9 dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.
Especially when used as leaf fungicides, the active compound concentrations in the use forms can be varied within a fairly wide range. They are, in general, from O.OOOOlto 0.1 per cent by weight, preferably from 0.00~1 to 0.05 per cent.
For treatment of seed, amounts of active compound of from 0.001 to 50 g per kilogram of seed, preferably from 0.01 to 10 g, are generally employed.
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 formula (I), or a salt thereof,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 compounds according to the present invention are each identified by the number (given 3o in brackets) of the corresponding preparative Example, Le A 17 829 - 9 -which will be found later in this specification.
The known comparison compounds are identified as ~ollows:

- OH
(A) ~ O-CH-CH-C(CH~ )3 ~ N

(B) =Cl- ~ -O-CH-~I-C(CH3 )3 ~ ~ OH

Example A
Erysiphe test (cucumber)/protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight o~ 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 with the stated amount of solvent and the concentrate was diluted with the stated amount of water containing the stated amount of emulsifier.
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 conidia of the fungus Erysiphe cichoriacearum. The plants were subsequently placed in a greenhouse at 23-24 degrees C and at a relative atmospheric humidity of about 75%.

Le A 17 829 - 10 -6'~

Arter 12 daysJ the infection of the cucumber plants was determined. The ass?ssment data were converted to percent infection. 0% meant no infection; 100% meant that the plants were totally infected.
The active compounds, t~e concentrations of the active compounds and the results can be seen from the following table:
T a b 1 e A
Erysiphe test (cucumbers)/protective Active compound Infection in % at an active compound con-centration of 0.00025%
(A) 91 (2) 34 (13) 71 Example B
Shoot treatment test/cereal rust (leaf-destructive mycosis)/protective To produce a suitable preparation of active compound, 0,25 part by ~eight 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 the protective activityJ one-leaved young wheat plants of the Michigan Amber variety were inoculated with a ureclospore suspension of Puccinia recondita in 0.1% stren~:th aqueous agar. A~ter the spore suspension had dried on, the wheat plants were sprayed with the preparation of active compound until dew-moist and were Le A 17 829 placed~ for incubation, in a greenhouse for 24 hours at about 20 deg.C and 100% relative atmospheric humidity.
After lQ days' dwell tirne of the plants at a tempera-ture of 20 deg.C and 80-go~ 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.
0 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:
T a b 1 e B
Shoot treatment test/cereal rust/protective Active Active compound con- Infection in %
compounds centration in the of the untreated spray liquor in % by control wei~ht untreated - 100 (B) 0.025 50.0 (A) 0.025 58.8 (4) 0.025 23.8 (5) 0.025 23.8 (12) 0.025 33.8 (13) 0.025 25.0 25 Preparative Examples Example 1 Cl Cl- ~ - 0 - CH - C0 - ~ - C1 / N \
~ IN . HCl Le A 17 829 - 12 -- . - - . . -.
.
.

6'~

103 g (0.26 mol) of 1-bromo-1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one were added dropwise at the boil to 65 g (1 mol) of irnidazole ln 650 ml of acetonitrile.
The mixture was heated under reflux for 40 hours. There-after, the solvent was listilled off in vacuo, the residue was taken up in 500 ml of methylene chloride and the methylene chloride solution was extracted by shaking four times with 250 ml Or water each time. The organic phase was dried over sodium sulPhate and concentrated by dis-tilling off the solvent _ vacuo. The residue was taken up in 1,000 ml of acetone and 47 g (0.26 mol) Or 1,5-naphthalene-d-sulphonic acid in 100 ml of acetone were added. The precipitate which formed was filtered off and boiled up with 100 ml of acetone. 200 ml of sodium bi-carbonate solution and 500 ml of methylene chloride were added to the residue. The organic phase was separated off, washed with 200 ml of water and concentrated by distilling off the solvent in vacuo. The residue was taken up in 200 ml of ether and dry hydrogen chloride was added in excess.
After distilling off the ether in vacuo, the oily residue was recrystallised from acetone. 31.6 g (29% of theory) of 1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-1-imidazol-l-yl-ethan-2-one hydrochloride of melting point 146-148C
were obtained.
Example 2 Cl Cl- ~ - O - CH - CH - ~ - Cl ~N~ OH (2) ~ N

Le A 17 82~ - 13 -'75~

45.5 g (0.108 mol) of 1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-l-imidazol-l-yl-ethan-2-one hydrochloride (Example 1) were dissolved in 100 ml of methanol and 4.32 g (0.108 mol) of sodium hydroxide were added. 4.5 g (0.12 mol) of sodium borohydride were added in portions of 0 to 5C and the mixture was stirred for 15 hours at room temperature. 60 ml of concentrated hydrochloric acid were then added dropwise at 0C and the mixture was stirred again for 15 hours at room temperature. The reaction mixture was then stirred into 800 ml of saturated sodium bicarbonate solution and extracted by shaking with 500 ml of methylene chloride. The organic phase was dried over sodium sulphate and concentrated by distilling off the solvent _ vacuo. The residue was recrystallised from ether. 30 g (72.5~ of theory) of 1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-1-imidazol-1-yl-ethan-2-ol were obtained as an isomer mixture of melting point 108 - 110C.
The compounds which follow in Table 1 were obtained analogously to the Examples given above.

Le A 17 829 - 14 -.

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Le A 17 829 - 15 -.
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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A fungicidal plant-protection composition containing as active ingredient a 2,4-dichlorophenyl-imidazolyl-ethan-one or -ol of the general formula (I) in which A represents a keto group or a CH(OH) grouping, X represents halogen, alkyl or optionally subsituted phenyl and n represents 0, 1, 2 or 3, the X's being selected independently of one another when n is 2 or 3, or a salt thereof, in admixture with a solid diluent or carried or a liquefied normally gaseous diluent or carrier, or in admixture with a liquid diluent or carrier containing a surface-active agent.

2. A composition according to claim 1, which contains a compound of the formula (I), or a salt thereof, in which X represents fluorine, chlorine, bromine, iodine, straight-chain or branched alkyl with 1 to 4 carbon atoms, or phenyl which is optionally substituted by halogen and n represents O, 1 or 2.

3. A composition according to claim 1 or 2, which contains a compound of the formula (I) or a salt thereof with a physiologically tolerated acid.

4. A composition according to any of claims 1 or 2 containing from 0.1 to 95% of the active compound, by weight.

5. A composition according to any of claims 1 or 2 containing from 0.5 to 90% of the active compound, by weight.

6. A composition according to claim 1 wherein the compound has the formula

7. A composition according to claim 1 wherein the compound has the formula .HCl

8. A composition according to claim 1 wherein the compound has the formula .HCl

9. A composition according to claim 1 wherein the compound has the formula ,HCl

10. A composition according to claim 1 wherein the compound has the formula .HCl

11. A composition according to claim 1 or 2 wherein the compound is in the free base form.

12. A composition according to claim 1 or 2 wherein the compound is in the form of its hydrochloride.

13. A method of combating plant fungi which comprises applying to the fungi, or to a habitat thereof, a compound of the formula (I) as defined in claim 1, or a salt thereof.

14. A method according to claim 13, wherein the compound is applied in the form of a composition comprising said compound as active ingredient in admixture with a diluent or carrier.

15. A method according to claim 14 in which the composition comprises from 0.00001 to 0.1% of the active ingredient, by weight.

16. A method according to claim 14 in which the composition comprises from 0.0001 to 0.05% of the active ingredient by weight.

17. A method according to claim 13, 14 or 16 in which the compound is applied to seed in an amount of 0.001 to 50g per kg of seed.

18. A method according to claim 13, 14 or 16 in which the compound is applied to seed in an amount of 0.01 to 10g per kg of seed.

19. A method for combatting plant fungi which comprises applying to the fungi or to a habitat thereof, a fungicidally effective amount of a compound as defined in claim 6, 7 or 8.

20. A method for combatting plant fungi which comprises applying to the fungi or to a habitat thereof, a fungicidally effective amount of a compound as defined in claim 9 or 10.