Note: Descriptions are shown in the official language in which they were submitted.
~o66~s8
The present invention relates to and has for its
objects the provision of particular new fungicidal compos-
itions containing, and methods of combating fungi using,
l-(diaryloxy)-l-imidazoL~ -dimethyl-butan-2-ones
and derivatives, which compositions are in the form of mix-
tures of such compounds with solid and liquid dispersible
carrier vehicles. Oth~r and further objects will become
apparent from a study of the within specification and ac-
companying examples.
lQ It has been disclosed in German Published Spec-
ification DOS 2,201,063 that triazolyl-O,N-acetals such as,
for example, l-(p-chlorophenoxy)-1-[1,2,4-triazolyl-(1)~-
3,3-dimethylbutan-2-one (Compound A), possess a very good
fungicidal activity. Furthermore, it is known from Patent
Specification 3,321,366 and German Published Specification
DOS 1,795,24~ that tris-phenyl-imidazolyl-(l)-(Compound B)
and -1,2,4-triazolyl-(1)-methane (Compound C) exhibit a
fungicidal action against phytophathogenic fungi. However,
the effect of these compounds is not always entirely satis-
factory in some fields of use9 especially if low amounts and
low concentrations are used.
It has been iound that compounds which are diaryloxy-
imidazolyl-O,N-acetals or ~alts thereof, the diaryloxy-
imidazolyl-O,N-acetal~ being oi the generPl formula
Le A 16 091 -2- ~
g~
10661~8
~ z ~3 O-CH-A-C(CH3)3
X Y (I)
a b ~ ~
N
in which X and Y each independently is halogen, alkyl, alkoxy, haloalkyl-
thio, nitro, amino, alkylamino, or dialkylamino, Z is a direct bond, oxygen,
sulfur, methylene, sulfonyl, alkoxymethylene or keto, A is -CO-, -CHOH- or
-C(OH)-, R is alkyl, A is an integer from 1 to 3 and may also be O if Z is
not a direct bond, and b is an integer from O to 3, exhibit powerful fungi-
cidal properties against phytopathogenic fungi, and are thus useful as the
active ingredient in fungicidal compositions for plant protection use.
Surprisingly, the diaryloxy-imidazolyl-O,N-acetals to be used
according to the invention exhibit a substantially greater fungicidal action
than the azole derivatives known in the art, for example tris-phenyl-1,2,4-
triazolyl-(l)-methane, tris-phenyl-imidazolyl-(l)-methane and l-(p-chloro-
phenoxy)-1-[1,2,4-triazolyl-(1)]-3,3-dimethylbutan-2-one. The very good
action against species of Erysiphe, Fusicladium and Uromyces should be
singled out for particular mention. The compounds usable according to the
invention thus represent an enrichment of the art.
X and Y are preferably fluorine, chlorine or bromine, alkyl
with up to 4 carbon atoms, (for example methyl, ethyl, isopropyl and ter-
tiary butyl), alkoxy with up to 4, especially with 1 or 2, carbon atoms,
(for example methoxy),
,~
;
~066~8B
haloalkylthio with up to 4 carbon atom~ and up to 5 halogen
atom~, especially with 1 or 2 carbon atoma and up to 3 identi-
cal or di~ierent halogen atoms, preierred halogene being
fluorine, and chlorine, (for example triiluoromethylthio),
nitro, amlno or alkylamino or dialkylamino with up to 4,
especially with 1 or 2, carbon atoms in each alkyl moiety,
(~or example ethylamino and dimethylamino). The indices a
and b are preierably 0, 1 or 2. When Z i~ alkoxymethylene
it is preierably methoxymethylene or etho~ymethylene. When
A is a -C(OH)- group, R is preferably methyl or ethyl.
R
If the active compound i~ used in the iorm of a
salt, it is usually preferable that the acid forming the
salt should be a physiologically tolerated acid. Preierred
acids include the hydrogen halide acids, ior example hydro-
chloric acid and hydrobromic acid, phosphoric acid, nitricacid, the monofunctional and biiunctional carboxylic acids
and the hydroxycarboxylic acids, ior example acetic acid,
maleic acid, succinic acid, iumaric acid, tartaric acid,
citric acid, salicylic acid, sorbic acid and lactic acid,
and 1,5-naphthaleneaisu~fonic acid.
~ he following may be mentioned as example~ of the
active compounds to be used according to the invention: 1-
[imidazolyl-(1)]-1-[4'-(3"-methylphenyl)-phenoxy]-3,3-di-
methylbutan-2-one, l-[imidazolyl-(1)]-1-[4'-(2"-chlorophenyl)-
3'-chlorophenoxy)]-3,3-dimethylbutan-2-ones, l-[imidazolyl-
(1)]-~ 4'-(2"-bromo-4"-chlorophenyl)-(2'-bromophenoxy)]-3,3-
dimethylbutan-2-one, l-[imidazolyl-(1)]-1 -[4'-(4"-nitrophenyl)-
(2',6'-dichloropheno~y)]-3,3-dimethylbutan-2-one, l-[imidazo-
Le A 16 091 _4_
~066188
lyl-(l)]-1-[4'-(4"-ethoxyphenyl)-(2'-bro~no-6'-chloropheno~cy)]-
3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-(3"-a~ino-
phenyl)-(2'-metbylphenoxy)]-3,3-dimethylbutan-2-one, 1-
[imidazolyl-(1)]-1-[4'-(2"-methylphenoxy)-(2'-chlorophenoxy)]-
c 3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-~4'-(3"-chloro-
phenoxy)-phenoxy]-3,3_dimethylbutan_2_one, l-[lmldazolyl-(l)]-
1-[4'-phenoxy-2',6'-dibromophenoxy]-3,3-dimethylbutan-2-one,
l-[imidazolyl-(1)]-1-~4'-(3"-nitrophenylthio)-(2'-bromophen-
o~y)]-3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-
(2"-methoxyphenylthio)-(2'-chlorophenoxy)]-3,3-dimethylbutan-
2-one, 1-[imidazolyl-(1)}-1-[4~4"bromophenylthio)-(3'-chloro-
pheno~y)]-3,3-dimethylbutan-2-one, l-[imidazolyl-(1)]-1-[4'-
(2"-chlorophenylsul fonyl )-phenoxy]-3,3-diEnethylbutan-2-one,
l-[imidazolyl-(1)]-1-[4'-(4"-ethylphenylsulfonyl )-(2',6'-
dichlorophenoxy)]-3,3-dimethylbutan-2-one, l-[imidazolyl-
(1)~-1-[4'-(2"-ch~orophenylcarbonyl)_(2'-bromophenoxy)]_
3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-(2",6"-
dichlorophenylcarbonyl)-(2'-chlorophenoxy)]-3,3-dimethyl-
butan-2-one, 1-[imidazolyl-(1)]-1-[4'-(2"-nitrophenylcarbonyl)-
phenoxy]-3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-
(4"-bromobenzyl)-(3'-bromophenoxy)]-3,3-dimethylbutan-2-one,
l-[imidazolyl-(l)J~ 4'-(4"-trifluoromethylthiobenzyl)-(2',3'-
dichlorophenoxy)]-3,3-dimethylbutan-2-one, l-[imidazolyl-
(1)]-1-[4'-(3",5"-dichlorobenzyl)-(2'-methylphenoxy)]-3,3-
dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-(4"-tert.-
butylbenzyl)-phenoxy]-3,3-dimethylbutan-2-one and l-[imidaz-
olyl-(l)]-l-[4'-(2"-ethylaminobenzyl)-(2'-nitrophenoxy~]-3,3-
dimethylbutan-2-one, and their salts with the acids specified
above.
Le A 16 091
~066188
Active compounds to be used according to the invention are
prepared in German Application P 24 29 514.5, filed 3une 20, 1974 and laid
open for inspection in December 1975.
Those compounds to be used according to the present invention
in which, in formula I, A is a carbonyl group, can be prepared according
to a method described in our Canadian Patent Application Serial No. 240,533,
filed November 26, 1975; the method is given below as (a). Methods (b) and
(c) below are applicable respectively to compounds in which A is a -CH(OH)-
group and to compounds in which A is a -~(OH)-group.
(a) A haloether-ketone is reacted with an imidazole, for example
in equimolar amounts, if appropriate in the presence of an inorganic acid-
binding agent, for example potassium carbonate, or in the presence of an
organic acid-binding agent, for example triethylamine or excess imidazole,
and in the presence of a polar solvent, for example acetonitrile, at tem-
peratures of 20 to 150C; the resulting reaction mixture is evaporated in
vacuo; the residue is taken up with an organic solvent, for example methy-
lene chloride; the solution is extracted by shaking with water; and the
organic phase is distilled in vacuo. The oil which remains after the sol-
vent has passed over is purified according to customary methods (see Example
7C hereinbelow).
106618t3
(b) A compound obtained according to method (a), i~
reduced, for example by a generally c~,tomary method. The
reduction ca.n be e~fected for example (1) with hydrogen in the
presence of a catalyst, for example Raney nickel, and a polar
solvent, ~or example methanol, at 20-~0C; or (2) with
aluminum isopropylate in the presence o~ an inert solvent at
20-120C, with subsequent hydroly~i~; or (3) with a complex
hydride (for example sodium borohydride or lithium alanate)
in thepresence of a polar solvent, ~or example methanol, at
l.0 0-30C, followed by hydrolysis, ~or example with hydrochloric
acid; or (4) with formamidinesulfinic acid and alkali metal
hydroxide, ~or example sodium hydroxide, in aqueous solution
at 20-100C in the presence of a polar solvent, for example
ethanol.
(c) A compound obtained according to method (a) is
subjected to reductive alkylation, especially by means of
a Grignard reagent, such as an alkyl-magne~ium halide (pre-
ferably an iodide or bromide), for example with methyl-
magnesium iodide in anhydrous diethyl ether at 20-80C, and
the product is hydrolyzed, ~or example with aqueous ammonium
chloride solution. The compounds of the ~ormula I, thus
obtained, may be isolated according to customary methods and
purified if appropriate (see Example 9A hereinbelow).
The salts o~ the compounds oi the formula I can be
2~ obtained in a simple ma~ner in accordance with customary methods
of forming salts, ~or example by dissolving the ba~e in ether;
for example diethyl ether, and adding the acid, ~or example
hydrogen chloride, and they can be isolated in a known manner,
~or example by filtering o~P, and can be purified if desired
(see Example 9B hereinbelow).
Le A 16 091 -7-
1066181B
The haloether-ketones to be used as 8tarting
materials have not previously been disclosed but can be pre-
pared according to processes whlch have been known for a
long time, for example by reacting the corresponding phenol
derivative with a haloketone (the so-called "Williamson ether
synthesi~"). The active hydrogen atom which still remains
i~ then replaced by halogen in the usual manner (see Example
7A an~ ~ he~einbelow).
~he fungicidal active compounds according to the in-
vention have a very broad spectrum of action and can be used
against parasitic fungi which infect above-ground part~ of
plants or attack the plants through the soil, and also Qgainst
seed-borne pathogens.
Fungitoxic agEnts are employed in plant protection for
1~ combating fungi from very diverse classes of fungi, such as
Archim.ycetes, PhYcom.vcetes, Ascomvcetes, LasidiomYcetes and
un~i ImPerfecti
.
As has in part already been mentioned, the active com-
pounds to be used according to the invention display a
20 particularly good activ$ty against parasitic fungi on above-
ground parts of plants, such as species o~ Er~siphe and species
of Venturia, as well as against epecie~ o~ ricularia and
species of Pellicularia. Good eiiecte are achieved ag~inst
the pathogens o~ apple scab (Fusiclad$um dendriticum), of
25 powdsry mildew oi cereals (~E_siPhe ~raminis) and of bean rust
(Uromyces Phaseoli). A point to be singled out particularly
is that these active compounds not only display a protective
action but are also curatively active, that iB to say active
on application after con.tamination with the ~pores of the
30 fungus. Furthermore, the systemic action of the compounds
Le A 16 091
106618E3
should be pointed out. Thus it proves possible to protect
plants against fungal iniection if the active compound is
~upplied to the above-ground parts of the plant ~ia the ~oil
and the root. As plant protection agents, these compounds
can be used for the treatment of soil, ior the treatment o*
seed and ior the treatment oi above-ground parts oi plants.
The active compounds to be used according to the
invention are well tolerated by plants. ~hey have only a low
toxicity to warm-blooded animals and because of their low
oaor and their good toleration by human skin they are not
unpleasant to handle.
The active compound~ to be u~ed according to the present
invention can be converted into the usual iormulations, such
as solutions, emulsions, ~uspensions, powders, pastes and
granulates. These may be produced in known manner, ior
example by mixing the active compounds with extenders, that
is, liquid or solid or liquefied gaseous diluents or carriers,
optionally with the use of suriace-active agents, that is,
emulsifying agents and/or dispersing agents, and/or foam-
iorming agents. In the case oi the use of water as an
extender, organic solvents can, for example, also be used as
auxiliary solvents.
AB liquid diluents or carriers, there are preferably
used aromatic hydrocarbons, such as xylenes, toluene, benzene
or alkyl naphthalenes, chlorinated aromatic or aliphatic hydro-
carbons, such as chlorobenzenes, chloroethylenes or methylene
chloride, aliphatic hydrocarbons, such as cyclohexane or
parafiins, for example mineral oil iraction~, alcohols, such
as butanol or glycol as well as their ethers and esters,
ketones, such a9 acetone, methyl ethyl ketone, methyl i80-
Le A 16 091 -9-
~3i66~88
butyl ketone or cyclohexanone, or ~trongly polar solYent8,
such as dimethyl formamide, dimethyl ~ulphoxide or aceto-
nitrile, as well as water.
Ly liquefied gaseou~ diluent~ or carriers are meant
liquid~ which wolld be ga~eous at normal temperature~ and
pressure~, e.g. aero~ol propell~nt~, 9uch as halogenated
hydrocarbons, e.g. ~reon.
The active compounds according to the instant
invention can be utilized, if desired, in the form of
the usual formulations or compositions with conventional
inert (i.e. plant compatible or herbicidally inert)
pesticide diluents or extenders, i.e. diluents, carriers
or extenders of the type usable in conventional pesti-
cide formulations or compositions, e.g. conventional
pesticide dispersible carrier vehicles such as gases,
solutions, emulsions, suspensions, emulsifiable concentrates,
spray powders, pastes, soluble powders, dusting agents,
granules, etc. These are prepared in known manner, for
instance by extending the active compounds with conventional
pesticide dispersible liquid diluent carriers and/or
dispersible solid carriers optionally with the use of
carrier vehicle assistants, e.g. conventional pesticide
surface-active agents, including emulsifying agents and/or
dispersing agents, whereby, for example, in the case where
water is used as diluent, organic solvents may be added
as auxiliary solvents. The following ~ay be chiefly
conside~ed for use as conventional carrier vehicles for
Le A 16 091 -10-
1066188
this purpose: aerosol propellants which are gas ous at
normal temperatures and pressures, such as Freon; inert
dispersible liquid diluent carriers, including inert
organic solvents, such as aromatic hydrocarbons (e.g. benzene,
toluene, xylene, alkyl naphthalenes, etc.), halogenated,
especially chlorinated, aromatic hydrocarbons (e.g. chloro-
benzenes, etc.), cycloalkanes, (e.g. cyclohexane, etc.),
paraffins (e.g. petroleum or mineral oil fractions),
chlorinated aliphatic hydrocarbons (e.g. methylene
chloride, chloroethylenes, etc.), alcohols (e.g. methanol,
ethanol, propanol, butanol, glycol, etc.) as well as ethers
and esters thereof (e.g. glycol monomethyl ether, etc.),
amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl
formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.),
acetonitrile, ketones (e.g. acetone, methyl ethyl ketone,
methyl isobutyl ketone, cyclohexanone, etc.), and/or
water; as well as inert dispersible finely divided solid
carriers, such as ground natural minerals (e.g. kaolins,
clays, alumina, silica, chalk, i.e. calcium carbonate, talc,
attapulgite, montmorillonite, kieselguhr, etc.) and ground
synthetic minerals (e.g. highly dispersed silicic acid,
silicates, e.g. alkali silicates, etc.); whereas the following
may be chiefly considered for use as conventional carrier
vehicle assistants, e.g. surface-active agents, for this
purpose: emulsifying agents, such as non-ionic and/or
anionic emulsifying agents (e.g. polyethylene oxide esters
~ad~ ~har~l~
Le A 16 091 -11-
10661~8
of fatty acids, polyethylene oxide ethers of fatty alcohols,
alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin
hydrolyzates, etc., and especially alkyl arylpolyglycol
ethers, magnesium stearate, sodium oleate, etc.); and/or
dispersing agents, such as lignin, sulfite waste liquors,
methyl cellulose, etc.
Such active compounds may be employed alone or
in the form of mixtures with one another and/or with such
solid and/or li~uid dispersible carrier vehicles and/or
with other known compatible active agents, especially
plant protection agents, such as ot'ner fungicides, or
insecticides, acaricides, nematocides, bactericides, ro-
denticides, herbicides, fertilizers, growth-regulating
agents, bird repellents, plant nutrients, agents for improving
soil stnlcture, etc., if desired or in the form of particular
dosage preparations for specific application made therefrom,
such as solutions, emulsions, suspensions, powders, pastes,
and granules which are thus ready for use.
As concerns commercially marketed preparations,
these generally contemplate carrier composition mixtures
in which the active compound is present in an amount
substantially between about 0.1-95% by weight, and
preferablyO.5-90% by weight, of the mixture, whereas carrier
composition mixtures suitable for direct application or
field application generally contemplate those in which the
active compound is present in an amount substantially
between about 0.0001-10%, preferably 0.01-1%, by we~ght of
Le A 16 091 -12-
~066188
the mixture. Thus, the present invention contemplates over-
all compositions which comprise mixtures of a conventional
dispersible carrier vehicle such as (1) a dispersible
inert finely divided carrier solid, and/or (2) a dispersible
carrier liquid such as an inert organic solvent and/or
water, preferably including a surface-active effective
amount of a carrier vehicle assistant, e.g. a surface-
active agent, such as an emulsifying agent and/or a
dispersing agent, and an amount of the active compound
which is effective for the purpose in question and which
is generally between about 0.0001-95%, and preferably
0.01-95%, by weight of the mixture.
The active compounds can also be used in accordance
with the well known ultra-low-volume process with good
success, i.e. by applying such compound if normally a
liquid, or by applying a liquid composition containing
the same, via very effective atomizing equipment, in
finely divided form, e.g. average particle diameter of
from 50-100 microns, or even less, i.e. mist form, for
example by airplane crop spraying techniques. Only up to
at most about a few liters/hectare are needed, and often
amounts only up to about 15 to 1000 g/hectare, preferably
40 to 600 g/hectare, are sufficient. In this process
it is possible to use highly concentrated liquid compos-
itions with said liquid carrier vehicles containing from
about 20 to about 95% by weight of the active compound
or even the 100% active substance alone, e.g. about
20-100% by weight of the active compound.
Le A 16 091 -13-
~066~
When u~ed Be lea~ ~ungicides, the concentratione o~
active compound in compositione used ~or application can be
varied within a ~ubstantial range. They are in general from
0.1 to 0.00001 per cent by weight, pre~erably 0.05 to
0.0001~.
In the treatment o~ ~eed, amount~ oi active compound
of 0.001 to 50 g per kilogram o~ ~eed, preferably 0.01 to
10 g, are in general applied to the ~eed.
For the treatment of 90il, amounts o~ active compound
of 1 to 1,000 g per cubic meter of 80il, preferably of 10
to 200 g, are generally applied to the ~oil.
At somewhat higher concentrations, the active compounds
alao po~sess plant growth-regulating properties.
Furthermore, the present invention contemplates
methods of selectively killing, combating or controlling
pests, e.g. fungi, which comprises applying to at least one
of correspondingly (a) such fungi, and (b) the corresponding
habitat thereof, i.e. the locus to be protected, e.g. to à
growing crop, to an area where a crop is to be grown or to
a domestic animal, a correspondingly combative or toxic
amount, i.e. a fungicidally effective amount, of the part-
icular active compound of the invention alone or together
with a carrier vehicle as noted above. The instant form-
ulations or compositions are applied in the usual manner,
for instance by spraying, atomizing, vaporizing, scattering,
dusting, watering, squirting, sprinkling, pouring, fumigating,
dry dressing, moist dressing, wet dressing, slurry dressing
encrusting and the like.
Le A 16 091 -14-
1066188
It will be realized, of course, that the concen-
tration of the particular active compound utilized in
admixture with the carrier vehicle will depend upon the
intended application. Therefore, in special cases it is
possible to go above or below the aforementioned concen-
tration ranges.
The unexpected superiority and outstanding activity
of the particular new compounds of the present invention
are illustrated, without limitation, by the following
examples:
Example 1.
Mycelium growth test
Nutrient medium used:
20 parts by weight of agar-agar
200 part~ by weight oi potato decoction
5 parts by weight of malt
15 part~ by weight of dextrose
5 parts by weight of peptone
2 parts by weight of disodium hydrogen phosphate
0-3 part by weight of calcium nitrate
Proportion of solvent mixture to nutrient medium:
2 parts by weight of solvent mi~ture
100 parts by weight o~ agar nutrient medium
Composition o~ solvent mixture
0.19 part by weight o~ dimethyl~ormamide or acetone
0.01 part by weight of emulsi~ier (alkylaryl polyglycol
ether)
1.80 parts bY weiRht oi water
2 parts by weight oi solvent mixture
Le A 16 091 -15-
106611~8
The amount o~ active compound required ~or the desired
concentration of active compound in the nutrient medium was
mixed with the stated amount of solvent mixture. The
concentrate was thoroughly mixed, in the ~tated proportion,
with the liquid nutrient medium which had been cooled to
42C and was then poured into Petri dishes of 9 cm di-
ameter. Control plates to which the preparation had not
been added were also set up.
When the nutrient medium had cooled and solidified,
the plateæ were inoculated with the species of ~ungi stated
in Table 1 and incubated at about 21C.
Evaluation wa~ carried out after 4 - 10 days, dependent
upon the speed of growth of the fungi. When evaluation
was carried out the radial growth of the mycelium on the
treated nutrient media was compared with the growth on the
control nutrient media. In the evaluation of the iungu8
growth, the iollowing characteristic values are used:
1 no fungus growth
up to 3 very strong inhibition oi growth
up to 5 medium inhibition of growth
up to 7 slight inhibition o~ growth
9 growth equal to that of the untreated
control.
The active compounds, the active compound concen-
trations and results can be ~een from the table which
follows:
Le A 16 091 -16-
1066~88
aBzLIo SBUO-mOl~UB
BFlB¦noF~ 1~ ,1 ,~
SF~Bn ~aBUi
s~'m~ua~
~-IO~
Blo~lsnT~
a~a~d so OA~ 1
mnau
~nF.IOdSOII~U~ H o~
sue~selaul~
o~dol~li~ ~ ~1 ~1
a~z~o
~FI~ln~FlFa c~
lIln I~BOqlB
umFIIF~F~a~ ~ ~ u~
salaulo
sl.-~A'I~og ~ N
~i~qBAlW
snloqFI~~ o~ N ~-J
IU~IOS
~oZF~
mnu~
~n~7;:)FI~o~allo~ o~
el'eJLFU~ IBS~ 0
OF~oï-al~s
BFUF~O'Iel~s ~ L~
mn.Iom [no
~nF-Issn,~
~dd ' punod
-~o~ a~F~s ~o
UoF~Bl~uaouo~ ~11
;o~ uf ~ u ~~~
Le A 16 091 -17-
1066~
aBzAlo s~uo~ol~usX
1~
Bl:l~ ~1 ,~ .
a~u
~Fm ~U3
~tllO
~a
ool~nm
a~dso~ ,,
umaulm~
u~nl~odSol~uFwl~H ,~
suaosalaulo
elo~dol~F~a ,1 ,,
a~zA:~Io
~, ~FI'eln~FIFa U~
~TT~
~alaul~ ~F~ ~
snu~aq~
snloqoFl~ob
mnm~.-~ln ~nF~l'a . '
~u~los
- ~FUo~oozl~N ~ ~1
mnu~a,~,~oa
mn~oFI~o~allo;
a~ Fu ~n}~I~sn,~
mn.IoF~o~alos
~FuF~
nlo~no
m~ ~sn,a 31 ~ N 11
~ ~ 'punodmoo al~F~ ,~
+~ o uoF~ uaouo"
o~ z;~ Z51
.IP~ ~ =o l
Le A 16 091 -18-
1066~88
OBZA~O SBUOmO~T~UBX
~ F~BB~B
BFI~In~llaa
8 'FIBn ~ aBU~ sFIn ~uë,ll.
lI~n.IO~OBO
BlO~ dO~ a
B~OO~Bn~l
alas~dsoo~
mnau~ms
Od~o~uF~l aH N
6ua~sa~Iaulo
BlOl~olsF~a
aBZLIO
sF~ n~F~F
lIml~BOqlB
~nn~ F~al~
~alauFo
Eil~ SF~o~
SnU-BaqB~I~
snl-oqoFI~oo~ ~1
~n~F~In
mnF~A;a
I~BIOS
BFUo~oOZF~
mnusa,~,~E
mn~o~l~o~allo~
els~Fu mnFIssn,~
mnlo-~o,Ialos
BFUF~OIalo$ u~
mn.IoT~no mnFIssn,~ u~
d~ n
' punotI~oo a~F~os l
,~o UoF~B~uaouo~
o
~lo ~
Le A 16 091
1~)66~88
Exam~le 2
Shoot treatment test/powdery mildew of cereal/protective
(leaf-destru~tive mycosi~)
To produce a suitable preparation of active compound,
0.25 g part by weight o~ active compound was taken up in ?5
parts by weight of dimethylformamide and 0.06 part by weight
of alkylaryl polyglycol ether emulsifier and 975 parts by
weight of water were added. The concentrate was diluted
with water to the desired final concentration of the spray
liquor.
To test for protective activity, ~ingle-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
Ervsi~he r~minis var. hordei.
After 6 days' dwell time of the plants at a temperature
of 21-22C and 80-90~o atmospheric humidity the occurrence of
mildew pustules on the plants was evaluated. ~he degree
of ~fection is expressed as a percentage of the infection
of the untreated control plants. 0% denotes no infection
and lOO~o denotes the same degree of infection as in the case
of the untreated control. The more active the compound,
the lower is the degree of mildew infection.
~he active compounds, active compound concentrations
in the spray liquor and degrees of infection can be seen from
thetable which follows.
Le A 16 091 20
1066181E~
Table 2
Shoot treatment test/powdery mildew o~ cereal/
protective
Active Active com- In~ection
compounds pound concen- .n % f
in % bg weight treated
.
untreated - 100
0.01 50.0
.N~ ((kcn)wn) 0.001 68.8
N ~
Cl ~ 0-ICH-C0-C(CH3)~ 0 001 317 5
L~ (14)
Cl
Br ~ 0-CIH-CO-C(CH~)~ 0.01 16.
~N (7)
0 ~ 0-ICH-C0-C(CH3)~ 0.01 16.3
. (8a)
0-CH-C0-C(CH~)~ 6.3
~`11 (10)
Le A 16 091 -21-
106618~3
Table 2 (continued)
Shoot treatment te~t/powdery mildew of cereal/
protective
Active Acti~e com- Infection
compound~ pound con- in % of the
centration in untreated
the spray liquor control
in ~ by weight
H ~ 3 0-CH-CH-CtCH~),
OCH~ N OH 0.01 0.0
0.00132.5
~ 13)
Cl
Cl ~ O-CH-CO-C(CH~)~
N 0,01 0.0
~ ~ (4) 0-00133.8
am~le 3
Erysiphe test/~ystemic
Solvent: 4,7 part~ by weight of acetone
Dispersing agent: 0.3 part by weight of alkylaryl polyglycol
15ether
Water: 95 parts by weight
The amount of active compound required to give the
desired concentration Or active compound in the watering
liquid wa~ mixed with the stated amount of solvent and the
concentrate wa~ diluted with the stated amount of water which
contained the stated additi~es.
Cucumber plants grown in standard 80il, in the 1-2
leaf ~tage, were watered three times within one week with
10 ml of the watering liquid, o~ the stated concentration of
actiYe compound, per 100 cc Or ~oil.
The plants treated in this way were inoculated, after
treatment, with conidia of the rungus Erlvci~he cichoracearum.
Le A 16 091 -22-
1066188
The plants were then get up in a greenhouga at 2~-24C and
70% relative atmospheric humidity After 12 days, the
infection of the cucumber plants was determined as a per-
centage of the untreated, but also inoculated, control
plants.
0~0 denotes no infection and 100% denotes that the
infection was exactly as great as in the case of the
control plants.
The active compounds, active compound concentrations
and re~ult~ can be seen from the table which follows.
Table 3
Erysiphe test/systemic
Active Infection in ~ of the
compound infection of the un-
treated control at an
active compound con-
centration of
100 ppm 25 ppm
1~1 100
~3c,~
.N~
L~ (known) (B)
Cl ~ 0-1CH-C0-C(CH~)~ 25
~ ~ (14)
_xamPle 4
Fusicladium test (apple scab) (Protective)
Solvent: 4.7 parts by weight of acetone
Emulsiiier:0.~ part by weight of alkylaryl polyglycol
ether
Water: 95 parts by weight
The amount oi active compound required ior the
Le A 16 091 -23-
~06618~
desired concentration oi the active compound in the spray
liquid wa~ mixed with the gtated amount of solvent, and the
concentrate wa~ diluted with the 8tated amount oi water which
contained the stated additions.
Young apple seedling~ 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 20C and àt
a relative atmospheric humidity of 70~0. They were then
inoculated with an aqueous conidium suspension of the apple
scab causative organism (Fusicladium dendriticum)
and incubated for 18 hour~ in a humidity chamber at 18-20C
and at a relative atmospheric humidity of 100%.
The plants then again were put in the greenhouse for
14 days,
15 day3 after inoculation, the infection of the seed-
lings was determined as a percentage oi the untreated but
also inoculated control plants.
O~o means no infection; 100% means that the infection
was exactly as great as in the case of the control plants.
The active compound~, the concentrations of the active
compounds and the results can be seen from the ~ollowing table:
Table4
~usicladium test/protective
Active compound Infection in % of the
iniection oi the un-
treated control at an
active compound con-
centration (in ~o) of
0.002~
. ~
C ~ (known) 66
~ (B)
Le A 16 091 -24-
1066~88
~able 4(continued)
Fu~icladium test/protective
Active compound Infection in % of the
infection of the un-
treated control at an
: active compound con-
centration (in Yo) of
0.0025
Cl ~ 0-CH-C0-C(CH~)~ 35
~ (14)
NO2 ~ 0-~H-C0-C(CH~)~
~ ~ . HCl 29
~xample 5
Fusicladium test (apple scab) [Curative]
Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.~ 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 ~tated additions.
Young apple seedling~ in the 4-6 leaf stage were in-
oculated with an aqueous conidium suspen~ion of the apple
~cab cau~ati~e organi~m (Fusicladium dendriticum )
and incubated for 18 hour3 in a humidity chamber at 18-20C
and at a relative atmospheric humidity o~ lOO~o. The plants
then were wt in a greenhouse and were allowed to dry.
After standing for-a suitable period of time, the plants
were sprayed dripping wet with the spray liquid prepared in
Le A 16 091 -25-
~06618~3
the manner described above. The plants then again were put
;n the ~reenhouse.
15 days after inoculation, the infection of the
ap~e ~eedlings wa~ determined a~ a percentage o~ the un-
treated but also inoculated control plant~.
O~o means no infection; 100% means that the infection
was exactly as great as in the case of the control plantæ.
The active compounds, the concentrations of the active
compounds, the period of time between inoculation and
~praying ~lnd the results obtained can be seen from the
following table:
Table S
Fu~icladium test/curative
Active Dwell Infection in % of the
compound time in infection of the un-
hours treated control at
an active compound
42 concentration (in ~)
of
-?~ 0.0062 _
~'
~C~3 100
~=) N (known)
- ~ ~ (B)
C1 ~ 0-CH-C0-C(CH~)~ _ 21
- L~ (14)
Example _6
Uromyces test (bean rus~/ protective
Solvent: 4.7 part~ by weight of acetone
Emulsifier: 0.3 part by weight of alkylaryl polyglycol
ether
Water: 95 parts by weight
Le A 16 091 -26-
~066188
The amount oi active compound required ior the deelred
concentratlon of active compound in the spray liquor was
mixed with the stated ~mount oi the solvent and the con-
centrate was diluted with the stated amount of water which
contained the stated additives.
The y~ung bean plant~, 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 20-22C and
a relative atmospheric humidity of 70% in order to dry. They
were then inoculated with an aqueous uredospore suspension
of the causative organi~m of bean rust (Uro~vces R aseoli )
and lncubated rOr 24 hour~ in a dark humidlty
chamber at 20-22C and 100% relative atmospheric humidity.
The plants were then set up in a greenhouse under
intensive illumination for 9 days at 20-22C and a relative
atmospheric humidity of 70-80%.
10 days after the inoculation, the infection of the
plants was determined in ~ of the untreated but also in-
oculated control plants.
0~O denote~ no infection and 100% denotes that the
infection was just as high as in the case of the c~ntrol
plants.
The active compounds, active compound concentrations
and results can be seen from the table which follows:
~able 6
Uromyces test/protective
Active compound Infection in % of the in-
fection of the untreated
control at an active compound
concentration (in%) of
0.00156
Cl ~ 0-CH-C0-C(CH~)~ 91
~ ~ (known) (A)
Le A 16 091 -27-
1066188
Table 6 (continued)
Uromyce~ te~t/protective
Active compound Infection in % of the
in~ection of the untreated
control at an active com-
pound concentration (in ~o)
_ _ _ 0.001~6
Cl ~ O-CH-CO-C(CH3 )3 10
~ ~ (14)
Cl ~ O-cH-lcH-c(cH~ )3 34
,N~ OH
~ I (11)
CH~ ~ O-ICH-CO-C(CH~)~ 70
~ ~ (6)
Br ~ O-CH-CO-C(CH~)~
L~
SO~ ~ O-CH-CH-C(CH~)I 75
~N~ OH
(2)
CH2 ~ 0-CH-ICH-C(CH~)~ 70
N~ OH
~ 1 (12)
Cl
Br ~ O-CH-CO-C(CH~ )3 70
Cl ~ (5) .
Le A 16 091 -28-
: 1066188
~able 6 (continued)
Uromyces test/protective
Active compound Iniection in ~ o~ the
inrection of the un-
tre~ted control at an
active compound concen-
tration ~in %) Or
0.00156
o~ o-cH-co-C(CH~),
~ ~ (8)
Cl
Cl ~ 0-CH-C0-C(CH~)~ 0
~ ~ (4)
Exam~le 7
~ S2 ~ 0-CH2-C0-C(C~ )
S2 ~ 0-fH-C0-C(CH3)3
Br
~ S2 ~ f-cH-co-c(cH3)3
~1 (1)
N
(preparation according to method (a))
44 g (0.107 mole)of 1-bromo-1-(4'-phenylsulfn~1~
phenoxy)- 3,3-dimethylbutan-2-one in 500 ml o~ absolute
acetonitrile were heated with 34 g (0.5 mole)of imidazole
ior 26 hour~ under re~lux. The solvent wa~ then distilled
Oir in a water pump vacuum and the residue wa~ taken up in
Le A 16 091 -29-
1066188
100 ml of water, The re~ulting precipitate was wa~hed with
twice 100 ml of water and recrystallized irom benzene. 26 g
(66~ of theory) of 1-[lmidazolyl-(1)]-1-[4'-(phenylsul fonyl)-
phenoxy]-3,~-dimethylbutan-2-one of melting point 146C were
obtained,
Intermediate product:
S2 ~ 0-fH-C0-C(CH3)3
Br
49 g of bromine were added dropwise at room
temperature to 99.6g(0.3 mol~ ~f 1-(4~-phenyl~ulfonyl-phen-
oxy)-3,~-dimethylbutan-2-one suspended in 600 ml of c~rbon
tetrachloride. After the mixture had lo~t its cOlcr, the
resulting precipitate wa~ filtered off, washed with
petroleum ether and recrystallized ~rom benzene, 89 g (72~o
of theory) of l-bromo-1-(4'-phenyl~ulfonyl--phenoxy)-3,3-
dimethylbutan-2-one of melting point 157-162C were obtained.
Starting material:
~ S2 ~ 0-CH2-C0-C(CH3)3
280 g (2 moles) of powdered pota~ium hydroxide were
~uspended in 2 liters of methyl ethyl ketone. 467 g (2
moles)of 4-phenylsulfonyl -phenol were added and the mixture
wa~ heated to the boil, Thereafter 269 g (2 moles) of ~-
chloropinacolone were added dropwi~e over the course of
1 hour and the mixture was heated for 15 hour~ under reflux,
After cooling, the ~olid re~idue was filtered ~f, washed
and recry~ta~iæed from ligroin. 687 g (85% of theory) of
1-(4'-phenyl~ulfonyl -phenoxy)-3,3-dimethylbutan-2-one o~
melting point 105-108C were obtained,
Le A 16 091 -30-
. _ ~
~066~8
~xamPle 8
2~ 0-TH-~H-C(CH3)3
~ (2)
(preparation according to method (b)(3))
1.6 g to.o42 mol~ of sodium borohydride were added in
portions to 11 g (0.028 mol~ of 1-[imidazolyl-(1)]-1-[4'-
(phenylsulfonyl) -phenoxy~-3,3-dimethylbutan-2-one suspended
in 100 ml of methanol, at a temperature of -5C. The re-
~ction mixture was stirred for 17 hours at room temperature,
6.5 m] of concentrated hydrochloric acid were then added and
the mixture was again stirred ior 17 hour~ at room temperature.
It was then extracted by shaking with three times 200 ml oi
methylene chloride. The combined organic phases were drl~d
over sodium sulfate. The solvent was di~tilled ofi in a
water pump vacuum. 50 ml oi n-pentane was added to the residue
and the crystals were iiltered off. 10 g (90~o bi theory) oi
l-[imidazolyl-(1)]-1-[4'-(phenylsul-fonyl) -phenoxy]-3,3-
dimethylbutan-2-ol of melting point 198C were obtained.
ExamPle 9
fH3
(A) Cl ~ ~ o-fH- ,C_c ( CH3)3
~' l
20(preparation according to method (c))
2.4 g (0.1 mol~ of magnesium filings were suspended in
30 ml oi ether. A solution oi 14.2 g (0.1 mol~ o~ methyl
Le A 16 091 -31-
10661~8
iodide in 50 ml o~ absolute ether was added drapwise thereto.
After 2 hours, a solution o~ 18.4 g (0.05 mol) of 1-[4'-(4"-
chlorophenyl)-phenoxy]~ midazolyl~ -3~3-dimethylbutan-
2-one in 100 ml of absolute tetrahydrofurane was added drop-
wise at 10C and the mixture was stirred for a further 15
hours at room temperature. Thereafter, the reaction mixture
was stirred, at oC, into a solution of 10 g of ammonium
chloride in 500 ml of water and the mixture was left to
stand overnight. The ether phase was separated off, washed
with twice 100 ml of water and dried over sodium sulfate,
and the solvent was distilled off in a water pump vacuum. An
oil remained, which crystallized on trituration with hot
petroleum ether. It was recrystall~ ed ~rom 40 ml of ethyl
acetate. 16.6 g (86% o~ theory) of 1-[4'-(4"-chlorophenyl)-
phenoxy]-1-[imidazolyl-(1)]-2-methyl-3,3-dimethylbutan-2-ol
of melting point 177C were obtained.
(B) ~ 0-CH-C-C(CH~)~
L ~ OH . HCl (3a)
(preparation oi a salt1
5 g (0.013 mol~ of 1-[4'-(4"-chlorophenyl)-phenoxy]-
l-[imidazolyl-(1)]-2-methyl-3,3-dimethylbutan-2-ol were
dissolved in 25 ml of acetone and 25 ml of methylene chloride.
20 ml of ethereal hydrochloric acid were added thereto, the
solvent was distilled off in a water pump vacuum and the
residue was boiled up with acetone. 4.7 g (86~ of theory) oi
1=~4'-(4"-chlorophenyl)-phenoxy]-1-[imidazolyl-(1)]-2-methyl-
3,3-dimethylbutan-2-ol hydrochloride of melting point 220-
224C (decomposition) were obtained.
Le A 16 091 -32-
~066188
The following compounds of the general formula
Z - ~ 0-~H-A-C(CH3)3
X~ Yb ~ N
were obtained analogously to ~xample~ 7 to 9:
Le A 16 091
~066~88
-o`
h~
O O
~:
L~
L O ~ ~ ~a L~ ~ ~L~ L~) L~ ~ ~ D ,D ~ ~ p 5
Ll) L~
h ~1 O
h
U
C)
L~ _
_ -- ~ O ~ ~ ~
O h _ _ _ ~_ _ _ _
P~ a)
O g ~ N ~ 0 Ir~ O Lr~ N
t--~I 0 1~ J ~_1 o ~ I ~ t-- 0 U~ ~1 0
0 ~1 ~ 0 1~ t-- 0 U~
r-- ~ o
¢ 8 ~ c~ ~) ~~ ~O~ ~o) ~c r~
~ ~ I v,,,,,
,o ~ JO ~U O O O O O O O O O O O
rl ~
c~
P~ I I I ~
~J N~D I h ~ I I I I I I I I I I I
N m
.~ ~ 1 o ~1 o o ~1 o ~ ,~ o o
v v m~ ~ m~
Le A 16 091 -34-
1066~88
bD I
h
O
~
h O O
~ Y
h O
P~ h
~d
O
.
~ V
~ ~ m ~ . _
~ ' ~
_ C~ ~
C) cd O O ''
_ ~
-~ ~ ~ o~ P~
a~ ~ 0~ ~ o o ~ P:
.~ O ~ O ~ ~
0~ ~ C)
o------a~
c~ o ~d
a) o ~ o
~ ~ o ~ ~ ~ ~ U~
.,, o--_I o,1 a) ,~ ~1
O h~I t ~ 0 r- I I
IO ~ I I I ~ 0
co~,1a~ ~ o
o
¢ 8 8 8 8 u 8
~ o o o o o o o o
~ l l l l l l l l
~,~ ~
o
Le A 16 091 35
1(~661~8
Other compounds which can be similarly prepared
from appropriate starting materials and thereafter converted
to salts, if desired, include:
Table 8
Compound X a Y b ` Z A
No.
2~4-di-cH3 2 2-F 1 _ -C(C2H5)(0H)
16 3-C3H7-i 1 2-oCH3 1 -S- -CO-
17 4-NH(C2H5) 1 3-SCF3 1 -O- -CO-
18 4-SCC12F ( 3)2 -CO-
It will be appreciated that the instant specification
and examples are set forth by way of illustrat~ n and not
limitation, and that various difications and changes may
be made without departing from the spirit and scope of the
present inventionO
Le A 16 091
-36-
