U.S. patent application number 09/871734 was filed with the patent office on 2002-04-11 for fungicidal mixtures.
Invention is credited to Ammermann, Eberhard, Birner, Erich, Leyendecker, Joachim, Lorenz, Gisela, Muller, Bernd, Saur, Reinhold, Sauter, Hubert, Schelberger, Klaus, Scherer, Maria, Strathmann, Siegfried.
Application Number | 20020042437 09/871734 |
Document ID | / |
Family ID | 26036816 |
Filed Date | 2002-04-11 |
United States Patent
Application |
20020042437 |
Kind Code |
A1 |
Schelberger, Klaus ; et
al. |
April 11, 2002 |
Fungicidal mixtures
Abstract
A fungicidal mixture comprises a) a phenyl benzyl ether
derivative of the formula I.a, I.b or I.c, 1 where X is CH or N, n
is 0, 1 or 2 and R is halogen, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-haloalkyl, it being possible for the radicals R to
be different if n is 2, or a salt or adduct thereof, and b) a
N-acetonylbenzamide of the formula II 2 where: R.sup.1 and R.sup.3
independently of one another are each halogen or
C.sub.1-C.sub.4-alkyl; R.sup.2 is cyano, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl or
C.sub.1-C.sub.4-alkoxy; R.sup.4 is hydrogen or
C.sub.1-C.sub.4-alkyl; R.sup.5 is C.sub.2-C.sub.4-alkyl; R.sup.6 is
thiocyano, isothiocyano or halogen, or a salt or adduct thereof, in
a synergistically effective amount.
Inventors: |
Schelberger, Klaus;
(Gonnheim, DE) ; Scherer, Maria; (Landau, DE)
; Sauter, Hubert; (Mannheim, DE) ; Muller,
Bernd; (Frankenthal, DE) ; Birner, Erich;
(Altleiningen, DE) ; Leyendecker, Joachim;
(Ladenburg, DE) ; Ammermann, Eberhard;
(Heppenheim, DE) ; Lorenz, Gisela; (Neustadt,
DE) ; Strathmann, Siegfried; (Limburgerhof, DE)
; Saur, Reinhold; (Bohl-Iggelheim, DE) |
Correspondence
Address: |
Herbert B. Keil
KEIL & WEINKAUF
1101 Connecticut Ave., N.W.
Washington
DC
20036
US
|
Family ID: |
26036816 |
Appl. No.: |
09/871734 |
Filed: |
June 4, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09871734 |
Jun 4, 2001 |
|
|
|
09423859 |
Nov 17, 1999 |
|
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Current U.S.
Class: |
514/384 ;
514/407; 514/617 |
Current CPC
Class: |
A01N 47/24 20130101;
A01N 37/50 20130101; A01N 47/24 20130101; A01N 37/50 20130101; A01N
47/24 20130101; A01N 37/34 20130101; A01N 2300/00 20130101; A01N
37/20 20130101; A01N 2300/00 20130101; A01N 37/34 20130101; A01N
37/20 20130101; A01N 37/50 20130101 |
Class at
Publication: |
514/384 ;
514/407; 514/617 |
International
Class: |
A01N 043/64; A01N
043/56; A01N 037/18 |
Foreign Application Data
Date |
Code |
Application Number |
May 26, 1997 |
DE |
19721849.0 |
May 26, 1997 |
DE |
19721848.2 |
Claims
We claim:
1. A fungicidal mixture comprising a) a phenyl benzyl ether
derivative of the formula I.a, I.b or I.c, 7 where X is CH or N, n
is 0, 1 or 2 and R is halogen, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-haloalkyl, it being possible for the radicals R to
be different if n is 2, or a salt or adduct thereof, and b) a
N-acetonylbenzamide of the formula II 8 where: R.sup.1 and R.sup.3
independently of one another are each halogen or
C.sub.1-C.sub.4-alkyl; R.sup.2 is cyano, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl or
C.sub.1-C.sub.4-alkoxy; R.sup.4 is hydrogen or
C.sub.1-C.sub.4-alkyl; R.sup.5 is C.sub.2-C.sub.4-alkyl; R.sup.6 is
thiocyano, isothiocyano or halogen, or a salt or adduct thereof, in
a synergistically effective amount.
2. A fungicidal mixture as claimed in claim 1, wherein the weight
ratio of the compound I to the compound II, or a salt or adduct
thereof, is from 10:1 to 0.01:1.
3. A method for controlling harmful fungi, which comprises treating
the harmful fungi, their habitat, or the plants, seeds, soils,
areas, materials or spaces to be kept free from them with a
compound of the formula I, as set forth in claim 1 and a compound
of the formula II, or a salt or adduct thereof, as set forth in
claim 1.
4. A method as claimed in claim 3, wherein a compound I, as set
forth in claim 1 and a compound II, or a salt or adduct thereof, as
set forth in claim 1 are applied simultaneously, separately as well
as together, or in succession.
5. A method as claimed in claim 3 or 4, wherein the compound I, as
set forth in claim 1 is applied in an amount of from 0.01 to 2.5
kg/ha.
6. A method as claimed in any of claims 3 to 5, wherein the
compound II, or a salt or adduct thereof, as set forth in claim 1
is applied in an amount of from 0.01 to 10 kg/ha.
7. The use of a compound I, as set forth in claim 1 for preparing a
fungicidally effective synergistic mixture as claimed in claim
1.
8. The use of a compound II, or a salt of adduct thereof, as set
forth in claim 1 for preparing a fungicidally effective synergistic
mixture as claimed in claim 1.
9. A composition as claimed in claim 1 which is conditioned in two
parts, one part comprising a compound of the formula I, as set
forth in claim 1 in a solid or liquid carrier and the other part
comprising a compound of the formula II, or a salt or adduct
thereof, as set forth in claim 1 in a solid or liquid carrier.
Description
[0001] The present invention relates to a fungicidal mixture which
comprises
[0002] a) a phenyl benzyl ether derivative of the formula I.a, I.b
or I.c, 3
[0003] where X is CH or N, n is 0, 1 or 2 and R is halogen,
C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-haloalkyl, it being
possible for the radicals R to be different if n is 2, or a salt or
adduct thereof, and
[0004] b) a N-acetonylbenzamide of the formula II 4
[0005] where:
[0006] R.sup.1 and R.sup.3 independently of one another are each
halogen or C.sub.1-C.sub.4-alkyl;
[0007] R.sup.2 is cyano, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl or
C.sub.1-C.sub.4-alkoxy;
[0008] R.sup.4 is hydrogen or C.sub.1-C.sub.4-alkyl;
[0009] R.sup.5 is C.sub.2-C.sub.4-alkyl;
[0010] R.sup.6 is thiocyano, isothiocyano or halogen,
[0011] or a salt or adduct thereof,
[0012] in a synergistically effective amount.
[0013] The invention further relates to methods for controlling
harmful fungi using mixtures of the compounds I (I.a, I.b and I.c)
and II and to the use of the compound I and the compound II for
preparing such mixtures.
[0014] The compounds of the formula Ia-c, their preparation and
their activity against harmful fungi are known from the literature
(EP-A 253 213; EP-A 254 426; EP-A 398 692).
[0015] The compounds of the formula Id, their preparation and their
activity against harmful fungi are known from the literature (WO-A
93/15,046; WO-A 96/01,256 and WO-A 96/01,258).
[0016] Also known are synergistic mixtures of the compounds II with
dithiocarbamates, their preparation and their activity against
harmful fungi (EP-A 753 258; US-A 5,304,572).
[0017] It is an object of the present invention to provide mixtures
which have an improved activity against harmful fungi combined with
a reduced total amount of active ingredients applied (synergistic
mixtures), with a view to reducing the application rates and to
improving the activity spectrum of the known compounds I and
II.
[0018] We have found that this object is achieved by the mixture
defined at the outset. In addition, we have found that better
control of harmful fungi is possible by applying the compound I and
the compound II simultaneously, separately as well as together, or
by applying the compound I and the compounds II in succession, than
when the individual compounds are used.
[0019] The formula Id in particular represents carbamates in which
the combination of the substituents corresponds to a line of the
Table below:
1 (Id) 5 No. X R.sub.n I.1 N 2-F I.2 N 3-F I.3 N 4-F I.4 N 2-Cl I.5
N 3-Cl I.6 N 4-Cl I.7 N 2-Br I.8 N 3-Br I.9 N 4-Br I.10 N
2-CH.sub.3 I.11 N 3-CH.sub.3 I.12 N 4-CH.sub.3 I.13 N
2-CH.sub.2CH.sub.3 I.14 N 3-CH.sub.2CH.sub.3 I.15 N
4-CH.sub.2CH.sub.3 I.16 N 2-CH(CH.sub.3).sub.2 I.17 N
3-CH(CH.sub.3).sub.2 I.18 N 4-CH(CH.sub.3).sub.2 I.19 N 2-CF.sub.3
I.20 N 3-CF.sub.3 I.21 N 4-CF.sub.3 I.22 N 2,4-F.sub.2 I.23 N
2,4-Cl.sub.2 I.24 N 3,4-Cl.sub.2 I.25 N 2-Cl, 4-CH.sub.3 I.26 N
3-Cl, 4-CH.sub.3 I.27 CH 2-F I.28 CH 3-F I.29 CH 4-F I.30 CH 2-Cl
I.31 CII 3-Cl I.32 CH 4-Cl I.33 CH 2-Br I.34 CH 3-Br I.35 CH 4-Br
I.36 CH 2-CH.sub.3 I.37 CH 3-CH.sub.3 I.38 CH 4-CH.sub.3 I.39 CH
2-CH.sub.2CH.sub.3 I.40 CH 3-CH.sub.2CH.sub.3 I.41 CH
4-CH.sub.2CH.sub.3 I.42 CH 2-CH(CH.sub.3).sub.2 I.43 CH
3-CH(CH.sub.3).sub.2 I.44 CH 4-CH(CH.sub.3).sub.2 I.45 CH
2-CF.sub.3 I.46 CH 3-CF.sub.3 I.47 CH 4-CF.sub.3 I.48 CH
2,4-F.sub.2 I.49 CH 2,4-Cl.sub.2 I.50 CH 3,4-Cl.sub.2 I.51 CH 2-Cl,
4-CH.sub.3 I.52 CH 3-Cl, 4-CH.sub.3
[0020] Particular preference is given to the compounds I.12, I.23,
I.32 and I.38.
[0021] The formula II in particular represents N-acetonylbenzamides
in which the combination of the substituents corresponds to a line
of the Table below:
2 (II) 6 No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 II.1
Cl CH.sub.3 Cl CH.sub.2CH.sub.3 CH.sub.3 Cl II.2 Cl
CH.sub.2CH.sub.3 Cl CH.sub.2CH.sub.3 CH.sub.3 Cl II.3 Cl OCH.sub.3
Cl CH.sub.2CH.sub.3 CH.sub.3 Cl II.4 Cl OCH.sub.2CH.sub.3 Cl
CH.sub.2CH.sub.3 CH.sub.3 Cl II.5 Cl CN Cl CH.sub.2CH.sub.3
CH.sub.3 Cl II.6 Br CH.sub.3 Br CH.sub.2CH.sub.3 CH.sub.3 Cl II.7
Br CN Br CH.sub.2CH.sub.3 CH.sub.3 Cl
[0022] Particular preference is given to those N-acetonylbenzamides
which are generally and particularly preferred in EP-A 753 258.
[0023] Owing to the basic character of their nitrogen atoms, the
compounds Id and II are capable of forming adducts or salts with
inorganic or organic acids or with metal ions.
[0024] Examples of inorganic acids are hydrohalic acids such as
hydrofluoric acid, hydrochloric acid, hydrobromic acid and
hydriodic acid, sulfuric acid, phosphoric acid and nitric acid.
[0025] Suitable organic acids are, for example, formic acid,
carbonic 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 of 1 to 20 carbon atoms), arylsulfonic
acids or aryldisulfonic acids (aromatic radicals, such as phenyl
and naphthyl, which carry one or two sulfo groups), alkylphosphonic
acids (phosphonic acids having straight-chain or branched alkyl
radicals of 1 to 20 carbon atoms), arylphosphonic acids or
aryldiphosphonic acids (aromatic radicals, such as phenyl and
naphthyl, which carry one or two phosphoric acid radicals), it
being possible for the alkyl or aryl radicals to carry further
substituents, eg. p-toluenesulfonic acid, dodecylbenzenesulfonic
acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid
and 2-acetoxybenzoic acid, etc.
[0026] Suitable metal ions are, in particular, the ions of the
elements of the first to eighth sub-group, in particular chromium,
manganese, iron, cobalt, nickel, copper, zinc and of the second
main group, in particular calcium and magnesium, and of the third
and fourth main group, in particular aluminum, tin and lead. The
metals can exist in the various valencies which they can
assume.
[0027] When preparing the mixtures, it is preferred to employ the
pure active ingredients I and II, to which further active
ingredients against harmful fungi or other pests, such as insects,
arachnids or nematodes, or else herbicidal or glineth-regulating
active ingredients or fertilizers can be admixed.
[0028] The mixtures of the compounds I and II, or the simultaneous
joint or separate use of the compounds I and II, have outstanding
action against a wide range of phytopathogenic fungi, in particular
from the classes of the Ascomycetes, Basidiomycetes, Phycomycetes
and Deuteromycetes. Some of them act systemically and can therefore
also be employed as foliar and soil-acting fungicides.
[0029] They are specially important for controlling a large number
of fungi in a variety of crop plants, such as cotton, vegetable
species (eg. cucumbers, beans, tomatoes, potatoes and cucurbits),
barley, grass, oats, bananas, coffee, maize, fruit species, rice,
rye, soya, grapevine, wheat, ornamentals, sugar cane, and a variety
of seeds.
[0030] They are particularly suitable for controlling the following
phytopathogenic fungi: Erysiphe graminis (powdery mildew) in
cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in
cucurbits, Podosphaera leucotricha in apples, Uncinula necator in
grapevines, Puccinia species in cereals, Rhizoctonia species in
cotton, rice and lawns, Ustilago species in cereals and sugar cane,
Venturia inaequalis (scab) in apples, Helminthosporium species in
cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in
strawberries, vegetables, ornamentals and grapevines, Cercospora
arachidicola in groundnuts, Pseudocercosporella herpotrichoides in
wheat and barley, Pyricularia oryzae in rice, Phytophthora
infestans in potatoes and tomatoes, Plasmopara viticola in
grapevines, Pseudoperonospora species in hops and cucumbers,
Alternaria species in vegetables and fruit, Mycosphaerella species
in bananas and Fusarium and Verticillium species.
[0031] Furthermore, they can be used in the protection of materials
(eg. in the protection of wood), for example against Paecilomyces
variotii.
[0032] The compounds I and II can be applied simultaneously, that
is either together or separately, or in succession, the sequence,
in the case of separate application, generally not having any
effect on the result of the control measures.
[0033] The compounds I and II are usually applied in a weight ratio
of 10:1 to 0.01:1, preferably 5:1 to 0.05:1, in particular 1:1 to
0.05:1.
[0034] Depending on the nature of the desired effect, the
application rates of the mixtures according to the invention are,
in particular in agricultural crops, from 0.01 to 8 kg/ha,
preferably 0.1 to 5 kg/ha, in particular 0.5 to 3.0 kg/ha.
[0035] The application rates of the compounds I are from 0.01 to
2.5 kg/ha, preferably 0.05 to 2.5 kg/ha, in particular 0.05 to 1.0
kg/ha.
[0036] Correspondingly, in the case of the compounds II, the
application rates are from 0.01 to 10 kg/ha, preferably 0.05 to 5
kg/ha, in particular 0.1 to 2.0 kg/ha.
[0037] For seed treatment, the application rates of the mixture are
generally from 0.001 to 250 g/kg of seed, preferably 0.01 to 100
g/kg, in particular 0.01 to 50 g/kg.
[0038] If phytopathogenic harmful fungi are to be controlled, the
separate or joint application of the compounds I and II or of the
mixtures of the compounds I and II is effected by spraying or
dusting the seeds, the plants or the soils before or after sowing
of the plants, or before or after plant emergence.
[0039] The fungicidal synergistic mixtures according to the
invention, or the compounds I and II, can be formulated for example
in the form of ready-to-spray solutions, powders and suspensions or
in the form of highly concentrated aqueous, oily or other
suspensions, dispersions, emulsions, oil dispersions, pastes,
dusts, materials for broadcasting or granules, and applied by
spraying, atomizing, dusting, broadcasting or watering. The use
form depends on the intended purpose; in any case, it should
guarantee as fine and uniform as possible a distribution of the
mixture according to the invention.
[0040] The formulations are prepared in a manner known per se, eg.
by adding solvents and/or carriers. It is usual to admix inert
additives, such as emulsifiers or dispersants, to the
formulations.
[0041] Suitable surfactants are the alkali metal salts, alkaline
earth metal salts and ammonium salts of aromatic sulfonic acids,
eg. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic
acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl,
lauryl ether and fatty alcohol sulfates, and salts of sulfated
hexa-, hepta- and octadecanols, or of fatty alcohol glycol ethers,
condensates of sulfonated naphthalene and its derivatives with
formaldehyde, condensates of naphthalene or of the
naphthalenesulfonic acids with phenol and formaldehyde,
polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or
nonylphenol, alkylphenol polyglycol ethers, tributylphenyl
polyglycol ethers, alkylaryl polyether alcohols, isotridecyl
alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated
castor oil, polyoxyethylene alkyl ethers or polyoxypropylene
[lacuna], lauryl alcohol polyglycol ether acetate, sorbitol esters,
lignosulfite waste liquors or methylcellulose.
[0042] Powders, materials for broadcasting and dusts can be
prepared by mixing or jointly grinding the compounds I or II or the
mixture of the compounds I and II with a solid carrier.
[0043] Granules (eg. coated granules, impregnated granules or
homogeneous granules) are usually prepared by binding the active
ingredient, or active ingredients, to a solid carrier.
[0044] Fillers or solid carriers are, for example, mineral earths,
such as silica gel, silicas, silica gels, silicates, talc, kaolin,
limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous
earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground
synthetic materials, and fertilizers, such as ammonium sulfate,
ammonium phosphate, ammonium nitrate, ureas, and products of
vegetable origin, such as cereal meal, tree bark meal, wood meal
and nutshell meal, cellulose powders or other solid carriers.
[0045] The formulations generally comprise 0.1 to 95% by weight,
preferably 0.5 to 90% by weight, of one of the compounds I or II or
of the mixture of the compounds I and II. The active ingredients
are employed in a purity of from 90% to 100%, preferably 95% to
100% (according to NMR spectrum or HPLC).
[0046] The compounds I or 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
of the compounds I and II in the case of separate application.
[0047] Application can be effected before or after infection by the
harmful fungi.
[0048] The synergistic action of the mixtures according to the
invention was demonstrated by the following experiments:
USE EXAMPLE 1
Activity Against Phytophthora infestans on Tomatoes
[0049] Leaves of plants of the cultivar "Gro.beta.e Fleischtomate"
in pots were sprayed to run-off with an aqueous suspension made
with a stock solution of 10% of active ingredient, 63% of
cyclohexanone and 27% of emulsifier. The next day, the leaves were
infected with an aqueous zoospore suspension of Phytophthora
infestans. The plants were subsequently placed in a
water-vapor-saturated chamber at from 16 to 18.degree. C. After 6
days, the tomato blight had developed on the untreated, but
infected, control plants to such an extent that it was possible to
evaluate the disease level visually in %.
[0050] Evaluation was carried out by determining the infected leaf
areas in percent. These percentages were converted into degrees of
action. The efficacy (E) was calculated as follows using Abbot's
formula:
E=(1-.alpha.).multidot.100/.beta.
[0051] .alpha. corresponds to the fungal infection of the treated
plants in % and
[0052] .beta. corresponds to the fungal infection of the untreated
(control) plants in %
[0053] A degree of action of 0 means that the infection level of
the treated plants corresponds to that of the untreated control
plants; a degree of action of 100 means that the treated plants
were not infected.
[0054] The expected degrees of action of the mixtures of the active
ingredients were determined using Colby's formula [R. S. Colby,
Weeds 15, (1967) 20-22] and compared with the observed degrees of
action.
Colby's formula: E=x+y-x.multidot.y/100
[0055] E expected degree of action, expressed in % of the untreated
control, when using the mixture of the active ingredients A and B
at the concentrations of a and b
[0056] x degree of action, expressed in % of the untreated control,
when using active ingredient A at a concentration of a
[0057] y degree of action, expressed in % of the untreated control,
when using active ingredient B at a concentration of b
[0058] The results are shown in Tables 2 and 3 below.
3TABLE 2 Concentration of active Efficacy in % of ingredient in the
spray the untreated Active ingredient liquor in ppm control Control
(untreated) (100% infection) 0 Ia 1 0 0.5 0 0.25 0 Ib 0.25 0
Compound I.32 0.25 70 Compound II.1 0.5 20 0.25 0
[0059]
4TABLE 3 Mixtures according to the invention Observed efficacy
Expected efficacy *) 1 ppm Ia 30 0 + 0.25 ppm II.1 0.5 ppm Ia 50 20
+ 0.5 ppm II.1 0.25 ppm Ia 40 20 + 0.5 ppm II.1 0.25 Ib 60 20 + 0.5
ppm II.1 0.25 ppm 1.32 97 76 + 0.5 ppm II.1 *) calculated using
Colby's formula
[0060] The experimental results reveal that the observed efficacy
in all mixing ratios is higher than the efficacy calculated
before-hand using Colby's formula.
* * * * *