|Title of Invention||
|Abstract||Fungicidal mixtures comprising 1) enestroburin of formula I: and 2) dimethomorph of formula II: as active components in a synergistically effective amount, method of controlling harmful fungi using mixtures of compound I with compound II, use of compound I with compound II for the preparation of such mixtures, and compositions comprising these mixtures.|
|Full Text||Fungicidal mixtures
The present invention relates to fungicidal mixtures comprising
1) enestroburin of formula I:
2) dimethomorph of formula II:
as active components in a synergistically effective amount.
The invention further relates to a method of controlling harmful fungi using mixtures of
compound I with compound II, to the use of compound I with compound II for the
preparation of such mixtures, and to compositions comprising these mixtures.
The strobilurin derivative of formula I described above as component 1, i.e. methyl
its preparation and its action against harmful fungi are known from the literature (EP-A
936,213 common name enestroburin).
The compound of formula II, i.e. 3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)-1-
morpholin-4-ylpropenone, its preparation and its action against harmful fungi are like-
wise known from the literature (EP-A 120 321', common name:dimethomorph). The
compound is in the form of a mixture of E,Z isomers.
In order to reduce the applied amounts and broaden the spectrum of action of the
known compounds, the object of the present inventions was to provide mixtures that
exhibit an improved action against harmful fungi, especially those of the class oomy-
cetes, coupled with a reduced total amount of applied active substances.
Accordingly, the mixtures defined at the outset were found. It was also found that by
using compound I and compound II simultaneously, either together or separately, or by
using compound I and compound II successively, harmful fungi can be controlled better
than with the individual compounds (synergistic mixtures). The simultaneous use of
compound I with compound II, either together or separately, increases the fungicidal
efficacy to a superadditive extent.
The mixtures of compound I and compound II, or the simultaneous use of compound l
sand compound II, either together or separately, are distinguished by an outstanding
efficacy against a broad spectrum of phytopathogenic fungi, especially of the classes
ascomycetes, deuteromycetes, oomycetes and basidiomycetes. They have a systemic
effect in some cases and can be used in plant protection as leaf and soil fungicides.
They are particularly important for controlling a large number of fungi on various crop
plants such as bananas, cotton, vegetable plants, (e.g. cucumbers, beans and Cucurbi-
taceae), barley, grass, oats, coffee, potatoes, maize, fruit plants, rice, rye, soybean,
tomatoes, vine, wheat, ornamental plants, sugar cane and a large number of seeds.
Advantageously, they are suitable for controlling the following phytopathogenic fungi:
Blurneria graminis (true mildew) on cereals, Erysiphe cichoracearum and Sphaero-
theca fuliginea on Cucurbitaceae, Podosphaera leucotricha on apples, Uncinula neca-
for on vines, Puccinia species on cereals, Rhizoctonia species on cotton, rice and turf,
Ustilago species on cereals and sugar cane, Venturis inaequalis on apples, Bipolaris
and Drechslera species on cereals, rice and turf, Septoria species on wheat, Botrytis
cinerea on strawberries, vegetables, ornamental plants and vines, Mycosphaerella
species on bananas, groundnuts and cereals, Pseudocercosporella herpqtrichoides on
wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and
tomatoes, Pseudoperonospora species on Cucurbitaceae and hops, Plasmopara viti-
cola on vines, Alternaria species on vegetables and fruit, and Fusarium and Verticillium
Mixtures of compound I and compound II are particularly suitable for controlling true
and false mildew fungi (Erysiphales and oomycetes).
They can also be used to protect materials (e.g. wood), for example.against Paecilo-
Compound I and compound II can be applied simultaneously, either together or sepa-
rately, or successively, the success of the control generally being unaffected by the
order when they are applied separately.
lt is conventional to use mixtures of compound I with compound II, but mixtures of
compound I with two or, if appropriate, several active components may be advanta-
geous under certain circumstances.
Fungicidal active substances from the following group are particularly suitable as other
active components in the above sense:
• acylalanines such as benalaxyl, metalaxyl, ofurace or oxadixyl,
• amine derivatives such as aldimorph, dodine, dodemorph. fenpropimorph, fen-
propidin, guazatine, iminoctadine, spiroxamin or tridemorph,
• anilinopyrimidines such as pyrimethanil, mepanipyrim or cyprodinil,
• antibiotics such as cycloheximide, griseofuivin, kasugamycin, natamycin, polyoxin
• azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitro-
conazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole,
flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, pencona-
zole, propiconazole, prachloraz, prothioconazole, simeconazole, tebuconazole, tet-
raconazole, triadimefon, triadimenol, triflumizole ortriticonazole,
• dicarboximides such as iprodione, myclozolin, procymidone or vinclozolin,
• dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metam, metiram,
propineb, polycarbamate, thiram, ziram or zineb,
• heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, car-
boxin, oxycarboxin, cyazofamid, dazomet, dithianone, famoxadone, fenamidone,
fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronil, nuarimol, pi-
cobenzamid, probenazole, proquinazid, pyrifenox, pyroquilone, quinoxyfen, silthio-
fam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole, triforine,
3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine or 5-chloro-7-(4-
• copper fungicides such as Bordeaux mixture, copper acetate, copper oxychloride or
basic copper sulfate,
• nitrophenyl derivatives such as binapacryl, dinocap, dinobuton or nitrophthal-
• phenylpyrroles such as fenpiclonil or fludioxonil,
other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamid,
chlorothalonil, cyflufenamid, cymoxanil, diclomezin, diclocymet, diethofencarb,
edifenphos, ethaboxam, fenhexamid, fentin acetate, fenoxanil, ferimzone,-fluazi-
nam, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, iprovalicarb, hexa-
chlorobenzene, metrafenone, pencycurone, propamocarb, phthalid, toloclofos-
methyl, quintozene or zoxamid,
strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl,
metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin,
sulfenic acid derivatives such as captafol, captan, dichlofluanid. folpet or tolylflua-
Compbund I and compound II are conventionally used in a weight ratio of 100:1 to
1.100, preferably of 20:1 to 1:20 and particularly preferably of 20:1 to 1:10.
If desired, the other active components are admixed to compound I in a ratio of 20:1 to
The applied amounts of the mixtures according to the invention are 5 g/ha to 2000
g/ha preferably 50 to 900 g/ha and particularly preferably 50 to 750 g/ha, depending
on the type of compound and desired effect.
Correspondingly, the applied amounts of compound I are normally i to 1000 g/ha,
preferably 10 to 900 g/ha and particularly preferably 20 to 750 g/ha.
Correspondingly, the applied amounts of compound II are normally 1 to 2000 g/ha,
preferably 10 to 900 g/ha and particularly preferably 40 to 500 g/ha.
In the case of seed treatment, the applied amounts of mixture are generally 1 to 1000
g/100 kg of seed, preferably 1 to 750 g/100 kg and particularly preferably 5 to 500
The method of controlling harmful fungi comprises the application of compound I and
compound II, either separately or together, or of mixtures of compound I and com-
pound II, by spraying or dusting the seeds, the plants or the soil before or after the
plants have been sown or before or after they have emerged.
The mixtures according to the invention, or compound I and compound II, can be con-
verted to the conventional formulations, e.g. solutions, emulsions, suspensions, dusts,
powders, pastes and granules. The application form is governed by the particular pur-
pose in every case it shall ensure a fine and uniform distribution of the compound ac-
cording to the invention.
The formulations are prepared in known manner, e.g. by extending the active sub-
stance with solvents and/or carriers, if desired using emulsifiers and dispersants. The
following are substantially suitable as solvents/auxiliary substances for this purpose:
- water, aromatic solvents (e.g. Solvesso products, xylene), paraffins (e.g. petroleum
fractions), alcohols (e.g. methanol, butanol, pentanol, benzyl alcohol), ketones (e.g.
cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol
diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. Sol-
vent mixtures can also be used in principle.
- carriers such as natural crushed rocks (e.g. kaolins, aluminas, talcum, chalk) and
synthetic crushed rocks (e.g. highly disperse silicic acid, silicates), emulsifiers such
as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, al-
kylsulfonates and arylsulfonates) and dispersants such as lignosulfite spent liquors
and methyl cellulose.
Surface-active substances used are alkali metal, alkaline earth metal and ammonium
salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid and dibutyl-
naphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alco-
hol sulfates fatty acids and sulfated fatty alcohol glycol ethers, other suitable surface-
active substances being condensation products of sulfonated naphthalene and naph-
thalene derivatives with formaldehyde, condensation products of naphthalene or naph-
thalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol'
ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol
ethers, tributylphenyl polyglycol ethers, tristearylphenyl polyglycol ethers, alkylaryl
polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated.
castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryr alcohol
polyglycol ether acetal, sorbitol esters, lignosulfite spent liquors and methyl cellulose.
The following are suitable for the preparation of directly sprayable solutions, emulsions'i
pastes or oily dispersions: medium-boiling to high-boiling mineral oil fractions such as
kerosene or diesel oil, as well as coal tar oils and oils of vegetable or animal origin,
aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydro-
naphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propa-
nol, butanol, cyclohexanol, cyclohexanone, isophorone, and strongly polar solvents,
e.g. climethyl sulfoxide, N-methylpyrrolidone or water.
Powders, tracking powders and dusts can be prepared by mixing the active sub-
stances, or grinding them together, with a solid carrier.
Granules, e.g. coated, impregnated and homogeneous granules, can be prepared by
binding the active substances to solid carriers. Examples of solid carriers are mineral
earths such as silica gels, silicates, talcum, kaolin, attaclay, limestone; lime, chalk,
bole, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfates and
magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium
phosphate, ammonium nitrate and ureas, and vegetable products such as cereal flour,
ground bark, wood flour and ground nutshells, cellulose powders and other solid carri-
The formulations generally comprise between 0.01 and 95% by weight, preferably be-
tween 0.1 and 90% by weight, of active substances, the latter being used in a purity of
90% to 100% preferably of 95% to 100% (according to NMR spectrum).
Examples of formulations are: 1. Products for dilution in water
A Water-soluble concentrates (SL, LS)
10 parts by weight of active substances are dissolved in 90 parts by weight of water or
water-solubIe sqlvent. Alternatively, wetting agents or other auxiliary substances are
added. Theactiye substance dissolves on solution in water to give a formulation with
an active substance content of 10% by weight.
B Dispersible concentrates (DC)
20 pais by weight of active substances are dissolved in 70 parts by weight of cyclo-
hexanone with the addition of 10 parts by weight of a dispersant, e.g. polyvinyl-
pyrrolidone. A dispersion is obtained on dilution in water. The active substance content
is 20% by weight.
C Emulsifiable concentrates (EC)
15 pats by weight of active substances are dissolved in 75 parts by weight of xylene
with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5 parts
by weight in each case). An emulsion is obtained on dilution in water. The formulation
has an active substance content of 15% by weight.
D Emulsions (EW, EO, ES)
25 parts by weight of active substances are dissolved in 35 parts by weight of xylene
with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5 parts
by weight in each case). Using an emulsifying machine (e.g. Ultraturax), this mixture is
added to 30 parts by weight of water and processed to a homogeneous emulsion. An
emulsion is obtained on dilution in water. The formulation has an active substance con-
tent of.25% by weight.
E Suspensions (SC, OD, FS)
Using a stirred ball mill, 20 parts by weight of active substances are comminuted to a
fine active substance suspension with the addition of 10 parts by weight of dispersants
and wetting agents and 70 parts by weight of water or organic solvent. A stable sus-
pension of active substance is obtained on dilution in water. The active substance con-
tent of the formulation is 20% by weight.
F Water-dispersible and water-soluble granules (WG, SG)
50 parts by weight of active substances are finely ground with the addition of 50 parts
by weight of-dispersants and wetting agents, and processed to water-dispersible or
water-soluble granules by technical means (e.g. extrusion, spraying tower, fluidized
bed); A stable dispersion or solution of the active substance is obtained on dilution in
Water. The formulation has an active substance content of 50% by weight.
G Water-dispersible and water-soluble powders (WP, SP:, SS, WS)
75 Parts by weight of active substances are ground in a roton-stator mill with the addi-
tion of 25 parts by. weight of dispersants and wetting agents and also silica gel. A stable
dispersion or solution of the active substance is obtained on dilution in water. The ac-
tive substance-content of the formulation is 75% by weight.
H Gel formulations
20 parts by weight of active substances, 10 parts by weight of dispersant, 1 part by
weight of gelling agent and 70 parts by weight of water or organic solvent are ground to
a fine suspension in a ball mill. A stable suspension with an active substance content of
20% by weight-is obtained on dilution in water.
2 Products for direct application
J Dusts. (DP, DS)
5 parts by weight of active substances are finely ground and intimately mixed with 95
parts by weight of finely divided kaolin to give a dust with an active substance content
of 5% by weight.
J Granules (GR, FG, GG, MG)
0.5 part by weight of active substances is finely ground and combined with 99.5 parts
by weight of carriers. Extrusion, spray drying and fluidized bed are common processes
usedito obtain granules for direct application which have an active substance content
of 0.5% by weight.
K ULV solutions (UL)
10 parts by weight of active substances are dissolved in 90 parts by weight of organic
solvent, e.g. xylene, to give a product for direct application which has an active sub-
stance content of 10% by weight.
Seed treatment is conventionally effected using water-soluble concentrates (LS), sus-
pensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS),
emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF). These for-
mulations-can be applied to the seed undiluted or, preferably, diluted, and they can be
apblied before sowing.
It is preferable to use FS formulations for seed treatment. Conventionally, such formu-
lations comprise 1 to 800 g/l of active substance, 1 to 200 g/l of surfactants, 0 to 200 g/l
of antifreeze agents, 0 to 400 g/l of binders, 0 to 200 g/l of colorants, and solvents,
The active substances can be used as such, in the form of their formulations or the
application forms prepared therefrom, e.g. in the form of directly sprayable solutions,
powders, suspensions or dispersions, emulsions, oily dispersions, pastes, dusts, track-
ing powders or granules, by spraying, nebulization, dusting, sprinkling or watering. The
application forms are wholly governed by the purpose; in every case they should en-
sure the finest possible distribution of the active substances according to the invention.
Aqueous application forms can be prepared from emulsifiable concentrates, pastes or
wettable powders (wettable powders, oily dispersions) by the addition of water. To pre-
pare emulsions, pastes or oily dispersions, the substances, as such or dissolved in an
oil or solvent, can be homogenized in water by means of wetting agents, tackifiers,
dispersants or emulsifiers. However, it is also possible to prepare concentrates consist-
ing of active substance, wetting agent, tackifier, dispersanf or emulsifier and optionally
solvent or oil, said concentrates being suitable for dilution with water.
The active substance concentrations of the ready-to-use formulations can be varied
within wide limits. They are generally between 0.0001 and 10%, preferably between
0.01 and 1%.
The active substances can also be used successfully by the ultra-low-volume (ULV)
method, it being possible to apply formulations with an active substance content of
more than 95% by weight, or even the active substance without additives.
Oils of different types, wetting agents, adjuvants, herbicides, fungicides, other pest con-
trol agents and bactericides can be added to the active substances, if appropriate just
before application (tank-mix method). These agents can be admixed to the composi- .
tions according to the invention in a weight ratio of 1:100 to 100:1, preferably of 1:10 to
The following are particularly suitable as adjuvants in this sense: organically modified
polysiloxanes, e.g. Break Thru S 240®; alcohol alkoxylates, e.g. Atplus 245®, Atplus
MBA 1303® Plurafac LF 300® and Lutensol ON 30®; EO-PO block polymers, e.g. Plu-
ronic RPE2035® and Genapol B®; alcohol ethoxylates, e.g. Lutensol XP 80®; and so-
dium dioctylsulfosuccinate, e.g. Leophen RA®.
The compounds I and II, or the mixtures or corresponding formulations, are applied by
treating the harmful fungi, or the plants, seeds, soil, surfaces; materials or spaces to be
kept free of said fungi, with a fungicidally effective amount of the mixture or of com-
pounds I and II applied separately. They can be applied before or after infestation by
the harmful fungi.
The fungicidal action of the compound and mixtures can be demonstrated by the fol-
The active substances were prepared, either separately or.together, as a stock solution
containig 25 mg of active substance, which was made up to 10 ml with a mixture of
acetone and/or DMSO and the emulsifier Uniperol® EL (wetting agent with an
emulsifying and dispersing effect based on ethoxylated alkylphenols) in a solvent/
ernulsifier volume ratio of 99 to 1. The volume was then made up to 100 ml with water.
The solvent/emulsifier/water mixture described was used to dilute this stock solution to
the active substance concentration indicated below.
Application Example 1 -Activity against tomato leaf mold caused by Phytophthora
infestans (protective treatment)
Leaves of potted tomato plants were sprayed until dripping wet with an aqueous suspen-
sion having the active substance concentration indicated below. The leaves were infested
the next day with an aqueous slurry of Phytophthora infestans sporangia. The plants were
then-placed in a water vapor-saturated chamber at temperatures of between 18 and 20°C.
After 6 days the leaf mold had developed so extensively on the untreated but infested
control plants that the infestation could be determined visually in %.
The visually determined values for the percentage of infested leaf surfaces were con-
verted to efficiencies as % of the untreated control:
The efficiency (E) is calculated as follows according to Abbot's formula:
α corresponds to the fungal infestation of the treated plants in % and
β corresponds to the fungal infestation of the untreated (control) plants in %
When the efficiency is 0, the infestation of the treated plants corresponds to that of the
untreated control plants; when the efficiency is 100, the treated plants exhibit no infes-
The expected efficiencies for active substance combinations were determined according
to Colby's formula (Colby, S.R. "Calculating synergistic and antagonistic responses of
herbicide combinations", Weeds, 15, pp 20 - 22,1967). and compared with the observed
E expected efficiency, expressed in % of the untreated control, when using the mix-
ture of active substances A and B in the concentrations a and b
x efficiency, expressed in % of the untreated control, when using active substance
A in the concentration a
y efficiency, expressed in % of the untreated control, when using active substance
B in the concentration b
Application Example 2 - Efficacy against wheat mildew caused by Erysiphe [syn.
Blumeria] graminis forma specialis. tritici
The comparative active substance used was the compound 4-[3-(3,4-dimethoxyphenyl)-
3-(4-fluorophenyl)-1-oxo-2-propenyl]morpholine [common name: flumorph), known
from EP-A 860 438.
Leaves of pot-grown wheat seedlings were sprayed until dripping wet with an aqueous
suspension having the active substance concentration indicated below. The suspension
or emulsion was prepared as described above. 24 hours after the spray coating had dried,
...dusted with spores of wheat mildew (Erysiphe [syn, Blumeria] graminis forma specialis-
tritici). The experimental plants were then placed in a greenhouse at temperatures of be-
tween 20 and 24°C and 60 to 90% relative humidity. After 7 days the extent of mildew
development was determined visually in % infestation of the total leaf surface.
The experimental results show that, due to synergism, the mixtures according to the
invention are appreciably more effective than previously calculated according to
WE CLAIM :
1. A fungicidal mixture for controlling phytopathogenic harmful fungi, comprising
two active components:
1) cnestroburin of formula I:
2) dimethomorph of formula II:
in a weight ratio of 100:1 to 1:100.
2. The fungicidal mixture as claimed in claim 1 comprising enestroburin of formula 1
and dimethomorph of formula II in a weight ratio of 20:1 to 1:20.
3. A composition comprising a liquid or solid carrier and a mixture as claimed in
claim 1 or 2.
Fungicidal mixtures comprising
1) enestroburin of formula I:
2) dimethomorph of formula II:
as active components in a synergistically effective amount, method of controlling harmful
fungi using mixtures of compound I with compound II, use of compound I with compound
II for the preparation of such mixtures, and compositions comprising these mixtures.
|Indian Patent Application Number||2037/KOLNP/2007|
|PG Journal Number||12/2013|
|Date of Filing||05-Jun-2007|
|Name of Patentee||BASF AKTIENGESELLSCHAFT|
|Applicant Address||67056 LUDWIGSHAFEN|
|PCT International Classification Number||N/A|
|PCT International Application Number||PCT/EP2005/013779|
|PCT International Filing date||2005-12-21|