Note: Descriptions are shown in the official language in which they were submitted.
757
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
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.
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 -
.
~ 36757
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Le A 17 829 - 15 -
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Le A 17 82~ - 16 -
