Note: Descriptions are shown in the official language in which they were submitted.
PF 54675 CA 02531540 2006-O1-04
Fungicidal mixtures
T he present invention relates to fungicidai mixtures for controiiing rice
pathogens,
comprising, as active comnponents,
1) the triazolopyrimidine derivative of the formula I,
CH3
JF F
N
N,N
~i \F
N
N CI
and
2) kresoxim-methyl of the formula II,
CH3
O
w I I
H3CO,N O
OCH3
in a synergistically effective amount.
Moreover, the invention relates to a method for controlling rice pathogens
using mix-
tures of the compound I with the compound II and to the use of.the compound I
with the
compound II for preparing such mixtures and compositions comprising these
mixtures.
The compound I, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-
[1,2,4]tri-
azolo[1,5-a]pyrimidine, its preparation and its action against harmful fungi
are known
from the literature (WO 98/46607).
The compound II, methyl methoxyimino-(2-o-tolyloxymethylphenyl)acetate, its
prepara-
+ir.n r1 '+.. +i~ ' + L,.~rmfn n1 fn mni rn IiLwuin Lnwern frnm fhn lifnrn+n
irn /CD~!\
uVl~ OIiV i~J ai.uvn againJ~ iiai~iW n iuiitJ.i cW c W vovvw~ mivrr~~ mmi~ um.
mnW nt. ~~.n n
253 213; common name: kresoxim-methyl). Kresoxim-methyl is commercially estab-
lished, mainly as fungicide for cereals, acting against mildew and rust
diseases caused
by Ascomycetes or Basidiomycetes.
Mixtures of triazolopyrimidine derivatives with kresoxim-methyl are known in a
general
manner from EP-A 988 790. The compound I is embraced by the general disclosure
of
PF 54675 CA 02531540 2006-O1-04
2
this publication, but not explicitly mentioned. Accordingly, the combination
of compound
I with kresoxim-methyl is novel.
The synergistic mixtures known from EP-A 988 790 are described as being
fungicidally
active against various diseases of cereals, fruit and vegetables, such as
mildew on
wheat and barley or gray mold on apples.
Owing to the special cultivation conditions of rice plants, the requirements
that a rice
fungicide has to meet are clearly different from those that fungicides used in
cereal or
fruit growing have to meet. There are differences in the application method:
In addition
to the foliar application used in many places, in modern rice cultivation the
fungicide is
applied directly onto the soil during or shortly after sowing. The fungicide
is taken up
into the plant via the roots and transported in the sap of the plant to the
plant parts to
be protected. For rice fungicides, high systemic action is therefore
essential. In con-
trast, in cereal or fruit growing, the fungicide is usually applied onto the
leaves or the
fruits; accordingly, in these crops the systemic action of the active
compounds is con-
siderably less important.
Moreover, typical rice pathogens are different from those in cereals or fruit.
Pyricularia
oryzae and Corticium sasakii (syn. Rhizoctonia solani~ are the pathogens of
the dis-
eases most prevalent in rice plants. Rhizoctonia solani is the only pathogen
of agricul-
tural significance from the sub-class Agaricomycetidae. In contrast to most
other fungi,
this fungus attacks the plant not via spores but via a mycelium infection.
For these reasons, findings concerning the fungicidal activity in the
cultivation of cere-
als or fruit cannot be transferred to rice crops.
Practical agricultural experience has shown that the repeated and exclusive
application
of an individual active compound in the control of harmful fungi may lead in
many
cases to a rapid selection of fungus strains which have developed natural or
adapted
resistance against the active compound in question. Effective control of these
fungi
with the active compound in question is then no longer possible.
To reduce the risk of selection of resistant fungus strains, mixtures of
different active
compounds are nowadays usually employed for controlling harmful fungi. By
combining
active compounds having different mechanisms of action, it is possible to
ensure a
successful control over a relatively long period of time.
It is an object of the present invention to provide, with a view to effective
resistance
management and an effective control of rice pathogens at application rates
which are
PF 54675 CA 02531540 2006-O1-04
3
as low as possible, mixtures which, at a reduced total amount of active
compounds
applied, have an improved effect against the harmful fungi.
We have found that this object is achieved by the mixtures defined at the
outset. More
over, we have found that simultaneous, that is joint or separate, application
of the com
pound I and the compound II or successive application of the compound I and
the
compound II allows better control of rice pathogens than is possible with the
individual
compounds.
When preparing the mixtures, it is preferred to employ the pure active
compounds I and
i1, to which further active compounds III and IV against harmful fungi or
other pests,
such as insects, arachnids or nematodes, or else herbicidal or growth-
regulating active
compounds or fertilizers can be added as required.
Further suitable active compounds in the above sense are, in particular,
fungicides
selected from the following group:
~ acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl,
~ amine derivatives, such as aldimorph, dodemorph, fenpropimorph, fenpropidin,
guazatine, iminoctadine or tridemorph,
~ antibiotics, such as cycloheximide, griseofulvin, kasugamycin, natamycin,
polyoxin
or streptomycin,
~ azoles, such as bitertanol, bromoconazole, cyproconazole, difenoconazole,
dinitro-
conazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole,
flutriafol, hex-
aconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, propi-
conazole, prochloraz, prothioconazole, simeconazole, tebuconazole,
tetraconazole,
triadimefon, triadimenol, triflumizole or triticonazole,
~ dicarboximides, such as myclozofin or procymidone,
~ dithiocarbamates, such as ferbam, nabam, metam, propineb, polycarbamate,
ziram
or zineb,
~ heterocyclic compounds, such as anilazine, boscalid, carbendazim, carboxin,
oxy-
carboxin, cyazofamid, dazomet, famoxadone, fenamidone, fuberidazole,
flutolanil,
t.._....,...a.... - ~~;...~..~,. n . 4"..,.,-.,,~.. -.,..,
i m ai i icyyr, iwpr vu uma~ ic, i i iepr vnii, i iuar iii i ivi, pr vuci
ia~mc, pyr vquiivi i, i,ii.iii vxy-
fen, silthiofam, thiabendazole, thifluzamide, tiadinil, tricyclazole or
triforine,
~ nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton or
nitrophthal-
isopropyl,
~ phenylpyrroles, such as fenpiclonil or fludioxonil,
~ sulfur,
~ other fungicides, such as acibenzolar-S-methyl, carpropamid, chlorothalonil,
cy-
flufenamid, cymoxanil, diclomezine, diclocymet, diethofencarb, edifenphos, eth-
PF 54675 CA 02531540 2006-O1-04
4
aboxam, fenhexamid, fentin acetate, fenoxanil, ferimzone, fluazinam, fosetyl,
fo-
setyl-aluminum, phosphorous acid, hexachlorobenzene, metrafenone, pencycuron,
propa~~~ocarb, p hthalide, tolclofos-niethyl, c~uiritozerie or zoxamide,
~ strobilurins, such as fluoxastrobin, metominostrobin, orysastrobin,
pyraclostrobin or
trifloxystrobin,
~ sulfenic acid derivatives, such as captafol,
~ cinnamides and analogous compounds, such as flumetover.
In one embodiment of the mixtures according to the invention, the compounds I
and II
are admixed with a further fungicide Ill or two fungicides III and IV.
Suitable components III and IV are in particular the following fungicides.
Amine derivatives, such as dodemorph, fenpropimorph, fenpropidin, iminoctadine
or
tridemorph;
azoles, such as bromoconazole, cyproconazole, difenoconazole, dinitroconazole,
ep-
oxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol,
hexaconazole, ip-
conazole, metconazole, myclobutanil, penconazole, propiconazole, prochloraz,
prothioconazole, simeconazole, tebuconazole, tetraconazole, triflumizole or
triticona-
zole;
heterocyclic compounds, such as boscalid, carbendazim, carboxin, cyazofamid,
fluto-
lanil, quinoxyfen;
dithiocarbamates and
other fungicides, such as benthiavalicarb, chlorothalonil, cyflufenamid,
diclofluanid,
fenhexamid, fluazinam, fosetyl, fosetyl-aluminum, phosphorous acid,
metrafenone and
pencycuron.
Preference is given to mixtures of the compounds I and II with one component
III.
Particular preference is given to mixtures of the compounds I and II.
The mixtures of compounds I and II, or the compounds I and II used
simultaneously,
that is jointly or separately, exhibit outstanding action against rice
pathogens from the
classes of the Ascomycetes, Deuteromycetes and Basidiomycetes. They can be
used
for the treatment of seed and as foliar- and soil-acting fungicides.
Moreover, the inventive combination of compounds I and II is also suitable for
control-
ling other pathogens, such as, for example, Septoria and Puccinia species in
cereals
such as wheat and barley and Alternaria and Botrytis species in vegetables,
fruit and
grapevines.
PF 54675 CA 02531540 2006-O1-04
They are especially important for controlling harmful fungi on rice plants and
their
seeds, such as Bipolaris and Drechslera species, and Pyricularia oryzae. They
can be
used particularly advantageously for controfiing sheath blight on rice, caused
by Corfi-
cium sasakii (syn. Rhizoctonia solan~).
5
The compound I and the compound II can be applied simultaneously, that is
jointly or
separately, or in succession, the sequence, in the case of separate
application, gener-
ally not having any effect on the result of the control measures.
The compound I and the compound II are usually applied in a weight ratio of
from
100:1 to 1:100, preferably from 20:1 to 1:50, in particular from 2:1 to 1:10.
The components III and IV are added if required in a ratio of from 20:1 to
1:20 with re-
spect to the compound I.
Depending on the type of compound and desired effect, the application rates of
the
mixtures according to the invention are from 5 g/ha to 2000 glha, preferably
from 50 to
1500 g/ha, in particular from 50 to 750 g/ha.
Correspondingly, the application rates of the compound I are generally from 1
to
1000 g/ha, preferably from 10 to 750 g/ha, in particular from 20 to 500 g/ha.
Correspondingly, the application rates of the compound II are generally from 1
to
1000 g/ha, preferably from 10 to 750 g/ha, in particular from 20 to 500 g/ha.
In the treatment of seed, the application rates of the mixture are generally
from 0.001 to
1 g/kg of seed, preferably from 0.01 to 0.5 g/kg, in particular from 0.01 to
0.1 g/kg.
In the control of harmful fungi which are rice pathogens, the separate or
joint applica-
tion of the compounds I and II or of the mixtures of the compounds I and II is
carried
out by spraying or dusting the seeds, the seedlings, the plants or the soils
before or
after sowing of the plants or before or after emergence of the plants. The
compounds
are preferably applied jointly or separately, by applying granules or by
dusting the soils.
The mixtures according to the invention or the compounds I and II can be
converted
into the customary formulations, for example solutions, emulsions,
suspensions, dusts,
powders, pastes and granules. The application form depends on the particular
pur-
pose; in each case, it should ensure a fine and uniform distribution of the
compound
according to the invention.
PF 54675 CA 02531540 2006-O1-04
s
The formulations are prepared in a known manner, for example by extending the
active
compound with solvents and/or carriers, if desired using emulsifiers and
dispersants.
Soivei tsiauxiiiaries which are suitable are essentiaify:
- Water, aromatic solvents (for example Solvesso products, xylene), paraffins
(for
example mineral fractions), alcohols (for example methanol, butanol, pentanol,
benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone),
pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid
dimethylamides, fatty acids and fatty acid esters. In principle, solvent
mixtures
may also be used.
- Carriers such as ground natural minerals (for example kaolins, clays, talc,
chalk) and ground synthetic minerals (for example highly disperse silica,
silicates); emulsifiers such as nonionic and anionic emulsifiers (for example
polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and
dispersants such as lignin-sulfite waste liquors and methylcellulose.
Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts
of
lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid,
dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates,
alkylsulfonates, fatty
alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers,
furthermore
condensates of sulfonated naphthalene and naphthalene derivatives with
formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with
phenol
and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated
isooctylphenol,
octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl
polyglycol ether,
tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and
fatty
alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene
alkyl
ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal,
sorbitol
esters, lignin-sulfite waste liquors and methylcellulose.
Substances which are suitable for the preparation of directly sprayable
solutions
emulsions, pastes or oil dispersions are mineral oil fractions of medium to
high boiling
point, such as kerosene or diesel oil, furthermore coal tar oils and oils of
vegetable or
animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example
toluene, xylene,
paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives;
methanol;
ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly
polar
solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dustable products can be prepared by
mixing or
concomitantly grinding the active substances with a solid carrier.
PF 54675 CA 02531540 2006-O1-04
7
Granules, for example coated granules, impregnated granules and homogeneous
granules, can be prepared by binding the active compounds to solid carriers.
Examples
of sUlld carriers are mineral earths such as silica gels, silicates, talc,
kaolin, attaclay,
limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth,
calcium sulfate,
magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers,
such as,
for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, areas,
and
products of vegetable origin, such as cereal meal, tree bark meal, wood meal
and
nutshell meal, cellulose powders and other solid carriers.
In general, the formulations comprise from 0.01 to 95% by weight, preferably
from 0.1
to 90% by weight, of the active compounds. The active compounds are employed
in a
purity of from 90% to 100%, preferably 95% to 100% (according to NMR
spectrum).
The following are examples of formulations: 1. Products for dilution with
water
A) Soluble concentrates (SL)
10 parts by weight of the active compounds are dissolved in water or in a
water-soluble
solvent, As an alternative, wetters or other auxiliaries are added. The active
compound
dissolves upon dilution with water.
B) Dispersible concentrates (DC)
20 parts by weight of the active compounds are dissolved in cyclohexanone with
addition of a dispersant, for example polyvinylpyrrolidone. Dilution with
water gives a
dispersion.
C) Emulsifiable concentrates (EC)
15 parts by weight of the active compounds are dissolved in xylene with
addition of
calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%
strength).
Dilution with water gives an emulsion.
D) Emulsions (EW, EO)
parts by weight of the active compounds are dissolved in xylene with addition
of
calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%
strength).
This mixture is introduced into water by means of an emulsifier (Ultraturax)
and made
35 into a homogeneous emulsion. Dilution with water gives an emulsion.
E) Suspensions (SC, OD)
In an agitated ball mill, 20 parts by weight of the active compounds are
comminuted
with addition of dispersants, wetters and water or an organic solvent to give
a fine
PF 54675 CA 02531540 2006-O1-04
active compound suspension. Dilution with water gives a stable suspension of
the
active compound.
F) Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of the active compounds are ground finely with addition of
dispersants and wetters and made into water-dispersible or water-soluble
granules by
means of technical appliances (for example extrusion, spray tower, fluidized
bed).
Dilution with water gives a stable dispersion or solution of the active
compound.
G) Water-dispersible powders and water-soluble powders (WP, SP)
75 parts by weight of the active compounds are ground in a rotor-stator mill
with
addition of dispersants, wetters and silica gel. Dilution with water gives a
stable
dispersion or solution of the active compound.
2. Products to be applied undiluted
H) Dustable powders (DP)
5 parts by weight of the active compounds are ground finely and mixed
intimately with
95% of finely divided kaolin. This gives a dustable product.
I) Granules (GR, FG, GG, MG)
0.5 part by weight of the active compounds is ground finely and associated
with 95.5°I°
carriers. Current methods are extrusion, spray-drying or the fluidized bed.
This gives
granules to be applied undiluted.
J) ULV solutions (UL)
10 parts by weight of the active compounds are dissolved in an organic
solvent, for
example xylene. This gives a product to be applied undiluted.
The active compounds can be used as such, in the form of their formulations or
the use
forms prepared therefrom, for example in the form of directly sprayable
solutions,
powders, suspensions or dispersions, emulsions, oil dispersions, pastes,
dustable
products, materials for spreading, or granules, by means of spraying.
atomizing;
dusting, spreading or pouring. The use forms depend entirely on the intended
purposes; it is intended to ensure in each case the finest possible
distribution of the
active compounds according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or
wettable
powders (sprayable powders, oil dispersions) by adding water. To prepare
emulsions,
pastes or oil dispersions, the substances, as such or dissolved in an oil or
solvent, can
PF 54675 CA 02531540 2006-O1-04
9
be homogenized in water by means of a wetter, tackifier, dispersant or
emulsifier.
Alternatively, it is possible to prepare concentrates composed of active
substance,
wetter, tackifier, dispersarit or er-nuisifier and, if appropriate, solvent or
oil, and such
concentrates are suitable for dilution with water.
The active compound concentrations in the ready-to-use preparations can be
varied
within relatively wide ranges. In general, they are from 0.0001 to 10%,
preferably from
0.01 to 1 %.
The active compounds may also be used successfully in the ultra-low-volume
process
(ULV), it being possible to apply formulations comprising over
95°I° by weight of active
compound, or even to apply the active compound without additives.
Various types of oils, wetters, adjuvants, herbicides, fungicides, other
pesticides, or
bactericides may be added to the active compounds, if appropriate just
immediately
prior to use (tank mix). These agents can be admixed with the compositions
according
to the invention in a weight ratio of 1:10 to 10:1.
The compounds f and II or the mixtures or the corresponding formulations are
applied
by treating the harmful fungi or the plants, seeds, soils, areas, materials or
spaces to
be kept free from them with a fungicidally effective amount of the mixture or,
in the
case of separate application, of the compounds I and II. Application can be
carried out
before or after infection by the harmful fungi.
The fungicidal action of the compound and the mixtures can be demonstrated by
the
experiments below:
The active compounds, separately or jointly, were prepared as a stock solution
with
0.25% by weight of active compound in acetone or DMSO. 1 % by weight of the
emulsi-
fier Uniperol~ EL (wetting agent having emulsifying and dispersing action
based on
ethoxylated alkylphenols) was added to this solution, and the solution was
diluted with
water to the desired concentration.
Use example - Activity against sheath blight on rice caused by Corticium
sasakii (syn.
Rhizoctonia solany
Pots of rice plants of the cultivar "Tai-Nong 67" were sprayed to runoff point
with an
aqeuous suspension having the concentration of active compound stated below.
The
next day, oat grains infected with Corticium sasakii were placed into the pots
(in each
case 5 grains per pot). The plants were then placed in a chamber at
26°C and
PF 54675 CA 02531540 2006-O1-04
maximum atmospheric humidity. After 11 days, the sheath blight on the
untreated but
infected control plants had developed to such an extent that the infection
could be
deters i sir ied ViSUaliy in ~o.
5 Evaluation is carried out by determining the infected leaf areas in percent.
These
percentages were converted into efficacies.
The efficacy (E) is calculated as follows using Abbot's formula:
10 E=(1-a/(3)~100
a. corresponds to the fungicidal infection of the treated plants in
°!° and
[3 corresponds to the fungicidal infection of the untreated (control) plants
in
An efficacy of 0 means that the infection level of the treated plants
corresponds to that
of the untreated control plants; an efficacy of 100 means that the treated
plants are not
infected.
The expected efficacies of the mixtures of active compounds are determined
using
Colby's formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the
observed
efficacies.
Colby's formula:
E=x+y-x~y/100
E expected efficacy, expressed in % of the untreated control, when using the
mix-
ture of the active compounds A and B at the concentrations a and b
x efficacy, expressed in % of the untreated control, when using active
compound A
at the concentration a
y efficacy, expressed in % of the untreated control, when using active
compound B
at the concentration b
The comparative compoonc_ls used were ~nmpnyndc A and R known from the
kresoxim-methyl mixtures described in EP-A 988 790:
PF 54675 CA 02531540 2006-O1-04
11
CH3
CF3
F
~F H3C~,NH F
N I / A /N\N \ , B
N,N ~ \ v
F
N~ , CI N N CI
N CI
Table A - Individual active compounds
Concentration of
active
Efficacy in % of
the
ExampleActive compoundcompound in the spray
untreated control
liquor [ppm]
1 control (untreated)- (90% infection)
2 I 1 33
4 0
3 II (kresoxim-methyl)
1 0
4 comparative 1 0
com-
pound A
comparative
com-
1 0
pound B
Table B - Mixtures according to the invention
Mixture of active compounds
ExampleConcentration Observed efficacyCalculated efficacy*)
Mixing ratio
I+II
6 1 + 1 ppm 89 33
1:1
-.
I+II
7 1 + 4 pm 100 33
1:4
5 *) efficacy calculated using Colby's formula
PF 54675 CA 02531540 2006-O1-04
12
Table C - Comparative experiments - mixtures known from EP-A 988 780
Mixture of active compounds
ExampleConcentration Observed efficacyCalculated efficacy*)
Mixing ratio
A+II
8 1 + 1 ppm 0 0
1:1
A+II
9 1 + 4 pm 0 0
1:4
B+II
1 + 1 ppm 22 0
1:1
B+II
11 1 + 4 pm 33 0
1:4
*) efficacy calculated using Colby's formula
The test results show that the mixtures according to the invention are, owing
to strong
5 synergism, considerably more effective against sheath blight than the
kresoxim-methyl
mixtures known from EP-A 988 780.
