Note: Descriptions are shown in the official language in which they were submitted.
BASF Aktiengesellschaft 931555 O.Z. 0050/44323
21320~
Fungicidal mixtures
The present invention relates to a fungicidal mixture which con-
5 tains
a) the oxime ether carboxamide of the formula I
C=NOCH3
CH3 CONHCH3
and
b) a dithiocarbamate (II) selected from the group
- manganese ethylenebis(dithiocarbamate) (zinc
complex) (IIa),
- manganese ethylenebis(dithiocarbamate) (IIb),
- zinc ammoniate ethylenebis(dithiocarbamate) (IIc) and
- zinc ethylenebis(dithiocarbamate) (IId)
25 in a synergistically active amount.
The invention additionally relates to processes for controlling
harmful fungi using mixtures of the compounds I and II and the
use of the compound I and the compounds II for the production of
30 mixtures of this type.
The compound of the formula I, its preparation and its action
against harmful fungi are disclosed in the literature
(EP-A 477 631).
The dithiocarbamates II (IIa: common name: mancozeb,
US-A 3,379,610; IIb: common name: maneb, US-A 2,504,404; IIc:
former common name: metiram, US-A 3,248,400; IId: common name:
zineb, US-A 2,457,674), their preparation and their action
40 against harmful fungi are likewise known.
With respect to a decrease in the application rates and an im-
provement of the spectrum of action of known compound3, the pres-
ent invention is based on mixtures which, with a reduced total
45 amount of applied active compo~nds, have an improved action -
against harmful fungi (synergistic mixtures).
- . , . , - : . ~ ,, , . , :
BASF Aktiengesellschaft 931555 0.Z. 0050/44323
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Accordingly, the mixtures defined at the beginning have been
found. It has-additionally been found that on simultaneous joint
or separate application of the compound I and the compounds II or
on application of the compound I and the compounds II in succes-
5 sion, harmful fungi can be controlled better than with the indi-
vidual compounds.
The compound of the formula I can be present in the E or the Z
configuration with respect to the C=X double bond (with respect
10 to the carboxylic acid function group). Accordingly, it can be
used in the mixture according to the invention in each case ei-
ther as the pure ~ or Z isomer or as an ~/Z isomer mixture. The
E/Z isomer mixture or the E isomer is preferably used, the E iso-
mer being particularly preferred.
~ecause of the basic character of the NH group, the compound I is
ab~e to form salts or adducts with inorganic or organic acids or
with metal ions.
20 ~xamples of inorganic acids are hydrohalic acids such as hydro-
fluoric acid, hydrochloric acid, hydrobromic acid and hydriodic
acid, sulfuric acid, phosphoric acid and nitric acid.
Suitable organic acids are, for example, formic acid, carbonic
25 acid and alkanoic acids such as acetic acid, trifluoroacetic
acid, trichloroacetic acid and propionic acid and also glycolic
acid, thiocyanic acid, lactic acid, succinic acid, citric acid,
benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids
(sulfonic acids having straight-chain or branched alkyl radicals
30 having 1 to 20 carbon atoms), arylsulfonic acids or -disulfonic
acids (aromatic radicals such a~ phenyl and naphthyl which carry
one or two sulfonic acid groups), alkylphosphonic acids (phos-
phonic acids having straight-chain or branched alkyl radicals
having 1 to 20 carbon atoms), arylphosphonic acids or -diphos-
~5 phonic acids (aromatic radicals ~uch as phenyl and naphthyl whichcarry one or two phosphoric acid radicals), the alkyl and aryl
radicals being able to carry further substituents, eg. p-toluene-
sulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxy-
benzoic acid, 2-acetoxybenzoic acid etc.
- 40
Suitable metal ions are in particular the ions of the elements of
the second main group, in particular calcium and magnesium, of
the third and fourth main group, in particular aluminum, tin and
lead, as well as of the first to eighth subgroup, in particular
45 chromium, manganese, iron, cobalt, nickel, copper, zinc and oth-
ers. The metal ions of the elements of the subgroups of the
fourth period are particularly preferred. The metals can in this
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BASF Aktiengesellschaft 931555 O.Z. 0050/44323
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case be present in the different valencies applicable to them.
Preferably, the pure active compounds I and II are employed in
the preparation of the mixtures, to which, if required, further
5 active compounds against harmful fungi or other pests such as in-
sects, arachnids or nematodes, or alternatively herbicidal or
growth-regulating active compounds or fertilizers, can be ad-
mixed.
10 The mixtures of the compounds I and II and the simultaneous joint
or separate use of the compounds I and II are distinguished by an
outstanding action against a wide spectrum of phytopathogenic
fungi, in particular from the Ascomycetes and Basidiomycetes
class. In some cases they are systemically active and can there-
15 fore also be employed as foliar and soil fungicides.
They have particular importance for the control of a multiplicityof fungi on various crop plants such as cotton, vegetable plants
(eg. cucumbers, beans and cucurbit~), barley, grass, oats, cof-
20 fee, maize, fruit plants, rice, rye, soybean, grape, wheat, deco-
rative plants, sugar cane and a multiplicity of seeds.
In particular, they are suitable for the control of the following
phytopathogenic fungi: Erysiphe graminis (powdery mildew) on ce-
25 reals, Erysiphe cichoracearum and Sphaerotheca fuliginea on cu-
curbits, Podosphaera leucotricha on apples, Puccinia species on
cereals, Rhizoctonia species on cotton and lawns, Ustilago spe-
cies on cereals and sugar cane, Venturia inaequalis (scab) on ap-
ples, Helminthosporium species on cereals, Septoria nodorum on
30 wheat, Botrytis cinerea (gray mold) on strawberries and vines,
Cercospora arachidicola on groundnuts, Pseudocercosporella herpo-
trichoides on wheat and barley, Pyricularia oryzae on rice, Phy-
tophthora infestans on potatoes and tomatoes, Plasmopara viticola
on vines, Alternaria species on vegetables and fruit and also Fu-
35 sarium and Verticillium species.
They are additionally applicable in the protection of materials ;~
(eg. wood preservation), for example against Paecilomyces
variotii.
- 40
The compounds I and II can be applied ~imultaneously ~ointly or
separately, or in succession, the sequence in the case of sepa-
rate application in general having no effect on the control suc-
cess.
The compounds I and II are customarily applied in a weight ratio
of from 2000:1 to 5:1, preferably from 1000:1 to 5:1, in
BASF Aktienges~llschaft 931555 O.Z. 0050/4g3~3
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particular from 500:1 to 5:1 (II:I).
Depending on the type of effect desired, the application rates of
the mixtures according to the invention are from 0.005 to
5 0.5 kg/ha~, preferably from 0.01 to 0.5 kg/ha, in particular from
0.01 to 0.3 kg/ha, for the compound I. The application rates for
the compound~ II are correspondingly from 0.1 to 10 kg/ha, pre-
rerably from 0.5 to 5 kg/ha, in particular from 1 to 4 kg/ha.
10 In the treatment of seed, application rateQ of mixture of from
0.001 to 100 g/kg of seed, preferably from 0.01 to 50 g/kg, in
particular from 0.01 to 10 g/kg, are generally used.
If harmful fungi which are pathogenic for plants are to be con-
15 trolled, the separate or joint application 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 plants or the soil before or -
after sowing of the plants or before or after emergence of the -~
plants.
The fungicidal synergistic mixtures according to the invention
and the compounds I and II can be prepared, for example, in the
form of directly sprayable solutions, powder~ and ~uspensions or
in the form of high-percentage aqueous, oily or other suspen-
25 sions, dispersions, emulsions, oil dispersions, pastes, dustingcompositions, brcadcasting compositions or granules and applied
by spraying, atomizing, dusting, broadcasting or watering. The
application form is dependent on the intended use; it should in
each case guarantee a dispersion of the mixture according to the
30 invention which i8 as fine and uniform as possible.
The formulations are prepared in a manner known per se, eg. by
addition of solvents and/or carriers. Inert additives such as
emulsifiers or dispersants are customarily admixed to the
35 formulations.
Suitable surface-active substances are the alkali metal, alkaline
earth metal or ammonium salts of aromatic sulfonic acids, eg.
lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid
40 and dibutylnaphthalene~ulfonic acid, as well as of fatty acids,
alkyl- and alkylarylsulfonates, alkyl-, lauryl ether and fatty
alcohol sulfates, and also salts of sulfated hexa-, hepta- and
octadecanols or fatty alcohol glycol ethers, condensation prod-
ucts of sulfonated naphthalene and its derivatives with formalde-
45 hyde, condensation products of naphthalene or of naphthalenesul-
fonic acids with phenol and formaldehyde, polyoxyethylene octyl-
- phenol ethers, ethoxylated isooctyl-, octyl- or nonylphenol,
- ..
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~ ' ' '
BASF Aktienge~ellschaft 931555 0.Z. 0050/44323
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alkylphenol or tributylphenyl polyglycol ethers, alkylaryl poly-
ether alcohols, i otridecyl alcohol, fatty alcohol-ethylene oxide
condensates, ethoxylated castor oil, polyoxyethylene or polyoxy-
propylene alkyl ethers, lauryl alcohol polyglycol ether acetate,
5 sorbitol-esters, lignin-sulfite waste liquors or methylcellulose.
Powder, broadcasting and dusting compositions can be prepared by
mixing or joint grinding of the compounds I or II or the mixture
of the compounds I and II with a solid carrier.
Granules (eg. coated, impregnated or homogeneous granules) are
customarily prepared by binding the active compound or the active
compounds to a solid carrier.
lS Fillers or solid carriers used are, for example, mineral earths
such as silica gel, silicic acids, silicates, talc, kaolin, lime-
stone, lime, chalk, bole, loess, clay, dolomite, diatomaceous
earth, calcium and magnesium sulfate, magnesium oxide, ground
plastic~, and fertilizers such as ammonium sulfate, ammonium
20 phosphate, ammonium nitrate, ureas and vegetable products such a
cereal flour, tree bark meal, wood meal and nutshell meal, cellu-
lose powder or other solid carriers.
The formulations in general contain from 0.1 to 95 % by weight,
25 preferably from 0.5 to 90 % by weight, of one of the compounds I
or II or the mixture of the compounds I and II. The active com-
pounds are in this case employed in a purity of from 90 % to
100 %, preferably from 95 ~ to 100 % (according to NMR spectrum
or HPLC).
The compounds I or II and the mixtures or the corresponding for-
mulations are applied by treating the harmful fungi or the
plants, seeds, 80ils, surfaces, materials or space~ to be kept
free from them with a fungicidally active amount of the mixture, -~
35 or of the compounds I and II in the case of separate application.
Application can be carried out before or after attack by the
harmful fungi.
Examples of the synergistic action of the mixtures according to
~ 40 the invention against harmful fungi.
It was possible to show the fungicidal action of the compounds
and of the mixtures by the following tests:
45 The active compounds were prepared separately or jointly as a 20%
strength emulsion in a mixture of 70% by weight of cyclohex-
anone, 20% by weight of Nekanil~ L~ (Lutensol~ AP6, wetting agent
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.,:
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BASF Aktiengesellschaft 931555 O.Z. 0050/44323
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having emulsifier and dispersant action based on ethoxylated al-
kylphenols) and 10% by weight of Emulphor~ EL (Emulan~ EL, emul-
sifier based on ethoxylated fatty alcohols) and accordingly
diluted to the desired concentration with water.
Assessment fo~lowed determination of the attacked leaf areas in
percent. These percentage values were converted into degrees of
action. The degrees of action of the active compound mixtures to
be expected were determined according to the Colby formula
lO [R.S. Colby, Weeds 15, (1967) 20-22] and compared with the de-
grees of action observed.
Colby formula:
E = x + y - x X y/100
E is the degree of action to be expected, expressed in ~ of the
untreated control, when using the mi~ture of the active
compounds A and B in the concentrations a and b
x is the degree of action, expressed in ~ of the untreated
control, when using the active compound A in the
concentration a
25 y is the degree of action, expressed in % of the untreated
control, when using the active compound ~ in the
concentration b
At a degree of action of 0, the attack of the treated plants cor-
30 responds to that of the untreated control plants; at a degree of
action of 100 the treated plants showed no attack.
Activity against Fusarium culmorum on wheat
35 Primary leaves of wheat of the variety Kanzler which has been
grown in pots were sprayed until dripping wet with aqueous spray
liquor which contained 80% of active compound and 20% of emulsi-
fier in the dry matter. On the following day, they were inocu-
lated with a spore suspension of Fuisarium culmorum and then
~ 40 placed in a climatic chamber having high atmospheric humidity
(> 90~) at 22-24-C. After 6 days, the extent of symptom develop-
ment was asses~ed visually.
, . .
.~
BASF Aktiengesellschaft 931555 O.Z. 0050/44323
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Active compound Active compound con- Degree of action in
centration in the ~ of the untreated
spray liquor in ppm control
Control (untreated) _ 0
5 I. - 750 41
.
S00 21
_
II. 750 0
_ _
500 0
_
10 Mixture according to degree of action degree of action
the invention observed calculated*)
I + II 750 + 750 61 41
1:1 mixture
I + II 500 + 500 41 21
15 1:1 mixture
I + II 750 + 75 41 21
10:1 mixture _ .
I + II 75 + 750 41 21
1:10 mixture .
Active compound Active compound con- Degree of action in
centration in the % of the untreated : :
spray liquor in ppm control :-~
_ _
Control (untreated) _ 0 ::~
_
I. 500 21
25 III. 500 0
Mixture according to degree of action degree of action
the invention observed calculated*) ~:
_
I + III 500 + 500 41 21 ~:~
1:1 mixture
I + III 500 + 50 41 21
10:1 mixture
I + III 50 + 500 68
1:10 mixture _
35 *) calculated by the Colby formula
From the results of the test it emerges that the degree of action
observed in all mixture ratios is higher than the degree of
action forecast by the Colby formula.
- 40
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