U.S. patent application number 13/247191 was filed with the patent office on 2012-01-19 for mixtures of strobilurins with triexapac-ethyl.
This patent application is currently assigned to BASF SE. Invention is credited to Ted R. BARDINELLI, Edson BEGLIOMINI, Albert C. EVERSON, John S. HARDEN, Thomas J. HOLT, Wilhelm RADEMACHER, Dan E. WESTBERG, Hendrik YPEMA, Joseph E. ZAWIERUCHA.
Application Number | 20120015812 13/247191 |
Document ID | / |
Family ID | 34572970 |
Filed Date | 2012-01-19 |
United States Patent
Application |
20120015812 |
Kind Code |
A1 |
RADEMACHER; Wilhelm ; et
al. |
January 19, 2012 |
Mixtures of strobilurins with triexapac-ethyl
Abstract
The present invention relates to mixtures comprising a) a
compound of the formula I ##STR00001## in which X, m, Q and a are
as defined in the description and b) one or more ethylene
modulators (II) selected from the group consisting of: inhibitors
of ethylene biosynthesis which inhibit the conversion of
S-adenosyl-L-methionine into 1-aminocyclopropane-1-carboxylic acid
(ACC), inhibitors of ethylene biosynthesis which block the
conversion of ACC into ethylene, or inhibitors of ethylene action,
and also compositions comprising them and to their use for
controlling harmful fungi.
Inventors: |
RADEMACHER; Wilhelm;
(Limburgerhof, DE) ; HARDEN; John S.; (Raleigh,
NC) ; WESTBERG; Dan E.; (Cary, NC) ;
ZAWIERUCHA; Joseph E.; (Cary, NC) ; HOLT; Thomas
J.; (Holly Springs, NC) ; YPEMA; Hendrik;
(Cary, NC) ; BARDINELLI; Ted R.; (Durham, NC)
; EVERSON; Albert C.; (Cary, NC) ; BEGLIOMINI;
Edson; (Sao Paulo, BR) |
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
34572970 |
Appl. No.: |
13/247191 |
Filed: |
September 28, 2011 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10578333 |
May 4, 2006 |
8044084 |
|
|
PCT/EP2004/012514 |
Nov 5, 2004 |
|
|
|
13247191 |
|
|
|
|
60517883 |
Nov 7, 2003 |
|
|
|
Current U.S.
Class: |
504/282 ;
514/407 |
Current CPC
Class: |
A01N 47/24 20130101;
A01N 47/24 20130101; A01N 47/24 20130101; A01N 37/50 20130101; A01N
47/24 20130101; A01N 37/50 20130101; A01N 47/24 20130101; A01N
37/50 20130101; A01N 47/24 20130101; A01N 37/50 20130101; A01N
37/50 20130101; A01N 37/40 20130101; A01N 37/50 20130101; A01N
61/00 20130101; A01N 2300/00 20130101; A01N 61/00 20130101; A01N
37/40 20130101; A01N 61/00 20130101; A01N 59/16 20130101; A01N
37/40 20130101; A01N 59/16 20130101; A01N 61/00 20130101; A01N
59/16 20130101; A01N 2300/00 20130101; A01N 37/40 20130101; A01N
59/16 20130101; A01N 59/16 20130101; A01N 61/00 20130101; A01N
61/00 20130101; A01N 37/40 20130101; A01N 59/16 20130101; A01N
37/40 20130101; A01N 59/16 20130101; A01N 59/16 20130101; A01N
61/00 20130101; A01N 61/00 20130101; A01N 37/40 20130101; A01N
37/40 20130101 |
Class at
Publication: |
504/282 ;
514/407 |
International
Class: |
A01N 43/56 20060101
A01N043/56; A01P 21/00 20060101 A01P021/00; A01P 3/00 20060101
A01P003/00 |
Claims
1-18. (canceled)
19. A mixture, comprising a) a compound of the formula I
##STR00003## in which X is halogen, C.sub.1-C.sub.4-alkyl or
trifluoromethyl; m is 0 or 1; Q is
C(.dbd.CH--CH.sub.3)--COOCH.sub.3,
C(.dbd.CH--OCH.sub.3)--COOCH.sub.3,
C(.dbd.N--OCH.sub.3)--CONHCH.sub.3,
C(.dbd.N--OCH.sub.3)--COOCH.sub.3or N(OCH.sub.3)--COOCH.sub.3; A is
--O--B, --CH.sub.2O--B, --OCH.sub.2--B, --CH.dbd.CH--B,
--CH.sub.2O--N.dbd.C(R.sup.1)--B or
--CH.sub.2O--N.dbd.C(R.sup.1)--C(R.sup.2).dbd.N--OR.sup.3, where B
is phenyl, naphthyl, 5-membered or 6-membered hetaryl or 5-membered
or 6-membered heterocyclyl which contains one to three nitrogen
atoms and/or one oxygen or sulfur atom or one or two oxygen and/or
sulfur atoms, where the ring systems are unsubstituted or
substituted by one to three radicals R.sup.a: R.sup.a is cyano,
nitro, amino, aminocarbonyl, aminothiocarbonyl, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkylcarbonyl, C.sub.1-C.sub.6-alkylsulfonyl,
C.sub.1-C.sub.6-alkylsulfoxyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy,
C.sub.1-C.sub.6-alkyloxycarbonyl, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.6-alkylamino, di-C.sub.1-C.sub.6-alkylamino,
C.sub.1-C.sub.6-alkylaminocarbonyl,
di-C.sub.1-C.sub.6-alkylaminocarbonyl,
C.sub.1-C.sub.6-alkylaminothiocarbonyl,
di-C.sub.1-C.sub.6-alkylaminothiocarbonyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkenyloxy, phenyl, phenoxy, benzyl, benzyloxy, 5-
or 6-membered heterocyclyl, 5- or 6-membered hetaryl, 5- or
6-membered hetaryloxy, C(.dbd.NOR')--OR'' or
OC(R').sub.2-C(R'').dbd.NOR'', where the cyclic radicals for their
part are unsubstituted or substituted by one to three radicals
R.sup.b: R.sup.b is cyano, nitro, halogen, amino, aminocarbonyl,
aminothiocarbonyl, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkylsulfonyl,
C.sub.1-C.sub.6-alkylsulfoxyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy,
C.sub.1-C.sub.6-alkoxycarbonyl, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.6-alkylamino, di-C.sub.1-C.sub.6-alkylamino,
C.sub.1-C.sub.6-alkylaminocarbonyl,
di-C.sub.1-C.sub.6-alkylaminocarbonyl,
C.sub.1-C.sub.6-alkylaminothiocarbonyl,
di-C.sub.1-C.sub.6-alkylaminothiocarbonyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkenyloxy, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkenyl, phenyl, phenoxy, phenylthio, benzyl,
benzyloxy, 5- or 6-membered heterocyclyl, 5- or 6-membered hetaryl,
5- or 6-membered hetaryloxy or C(.dbd.NOR')--OR''; R' is hydrogen,
cyano, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or
C.sub.1-C.sub.4-haloalkyl; R'' is hydrogen, C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkinyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.3-C.sub.6-haloalkenyl or
C.sub.3-C.sub.6-haloalkinyl; R.sup.1 is hydrogen, cyano,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.3-C.sub.6-cycloalkyl, or C.sub.1-C.sub.4-alkoxyl; R.sup.2 is
phenyl, phenylcarbonyl, phenylsulfonyl, 5- or 6-membered hetaryl,
5- or 6-membered hetarylcarbonyl or 5- or 6-membered
hetarylsulfonyl, where the ring systems are unsubstituted or
substituted by one to three radicals R.sup.a, is
C.sub.1-C.sub.10-alkyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.2-C.sub.10-alkenyl, C.sub.2-C.sub.10-alkinyl,
C.sub.1-C.sub.10-alkylcarbonyl, C.sub.2-C.sub.10-alkenylcarbonyl,
C.sub.3-C.sub.10-alkinylcarbonyl, C.sub.1-C.sub.10-alkylsulfonyl or
C(R').dbd.NOR'', where the hydrocarbon radicals of these groups are
unsubstituted or substituted by one to three radicals R.sup.c:
R.sup.c is cyano, nitro, amino, aminocarbonyl, aminothiocarbonyl,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkylsulfonyl, C.sub.1-C.sub.6-alkylsulfoxyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy,
C.sub.1-C.sub.6-alkoxycarbonyl, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.6-alkylamino, di-C.sub.1-C.sub.6-alkylamino,
C.sub.1-C.sub.6-alkylaminocarbonyl,
di-C.sub.1-C.sub.6-alkylaminocarbonyl,
C.sub.1-C.sub.6-alkylaminothiocarbonyl,
di-C.sub.1-C.sub.6-alkylaminothiocarbonyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkenyloxy, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkyloxy, 5- or 6-membered heterocyclyl, 5- or
6-membered heterocyclyloxy, benzyl, benzyloxy, phenyl, phenoxy,
phenylthio, 5- or 6-membered hetaryl, 5- or 6-membered hetaryloxy
or hetarylthio, where the cyclic groups for their part may be
partially of fully halogenated or may carry one to three radicals
R.sup.a; and R.sup.3 is hydrogen, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl or C.sub.2-C.sub.6-alkinyl, where the
hydrocarbon radicals of these groups may be unsubstituted or
substituted by one to three radicals R.sup.c; b) trinexapac-ethyl;
in a weight ratio of I to trinexapac-ethyl of from 20:1 to
0.05:1
20. The mixture of claim 19, wherein the compound of the formula I
is a strobilurin derivative selected from the group consisting of
azoxystrobin, dimoxy-strobin, fluoxastrobin, kresoxim-methyl,
metominostrobin, orysastrobin, trifloxy-strobin, picoxystrobin or
pyraclostrobin.
21. The mixture of claim 19, wherein the compound of the formula I
is pyraclostrobin.
22. The mixture of claim 19, wherein 1-methylcyclopropene is
selected as ethylene modulator (II).
23. The mixture of claim 19, which additionally comprises an azole
III selected from the group consisting of bromoconazole,
cyproconazole, epoxiconazole, fenbuconazole, fluquiconazole,
flusilazole, metconazole, myclobutanil, propiconazole, prochloraz,
prothioconazole, tebuconazole and triticonazole.
24. The mixture of claim 19, which additionally comprises a
surfactant selected from the group consisting of: polyoxyethylene
sorbitan monolaurate, alkylphenoxy polyethoxy ethanol, fatty
alcohol, fatty alcohol alkoxylate and sodium dodecylsulfate.
25. A method for controlling rust infections in legumes, which
comprises treating the above-ground plant parts of the legumes with
an aqueous formulation of a mixture as claimed in claim 19.
26. The method of claim 25, wherein rust infection on leaves and
fruits of soya plants is controlled.
27. The method of claim 26, wherein the rust infection is caused by
Phakopsora pachyrhizi and/or Phakopsora meibomiae.
28. The method of claim 25, wherein the compound of the formula I
is a strobilurin derivative selected from the group consisting of
azoxystrobin, dimoxy-strobin, fluoxastrobin, kresoxim-methyl,
metominostrobin, orysastrobin, trifloxy-strobin, picoxystrobin or
pyraclostrobin.
29. The method of claim 28, where the compound of the formula I is
pyraclostrobin.
30. The method of claim 28, wherein 1-methylcyclopropene is
selected as ethylene modulator (II).
31. The method of claim 30, wherein the mixture additionally
comprises an azole III selected from the group consisting of
bromoconazole, cyproconazole, epoxiconazole, fenbuconazole,
fluquiconazole, flusilazole, metconazole, myclobutanil,
propiconazole, prochloraz, prothioconazole, tebuconazole or
triticonazole.
32. The method of claim 30, wherein the mixture additionally
comprises a surfactant selected from the group consisting of:
polyoxyethylene sorbitan monolaurate, alkylphenoxy polyethoxy
ethanol, fatty alcohol, fatty alcohol alkoxylate and sodium
dodecylsulfate.
33. A method for reducing the ethylene evolution of plants by
applying an effective amount of a mixture as claimed in claim
19.
34. The method of claim 33, wherein the compound of the formula I
is a strobilurin derivative selected from the group consisting of
azoxystrobin, dimoxy-strobin, fluoxastrobin, kresoxim-methyl,
metominostrobin, orysastrobin, trifloxy-strobin, picoxystrobin or
pyraclostrobin.
35. The method of claim 34, where the compound of the formula I is
pyraclostrobin.
36. The method of claim 34, wherein 1-methylcyclopropene is
selected as ethylene modulator (II).
37. The method of claim 36, wherein the mixture additionally
comprises an azole III selected from the group consisting of
bromoconazole, cyproconazole, epoxiconazole, fenbuconazole,
fluquiconazole, flusilazole, metconazole, myclobutanil,
propiconazole, prochloraz, prothioconazole, tebuconazole or
triticonazole.
38. A method for reducing undesired defoliation of crop plants by
applying an effective amount of a mixture as claimed in claim 19.
Description
[0001] The invention relates to mixtures comprising
[0002] a) a compound of the formula I
##STR00002## [0003] in which [0004] X is halogen,
C.sub.1-C.sub.4-alkyl or trifluormethyl; [0005] m is 0 or 1; [0006]
Q is C(.dbd.CH--CH.sub.3)--COOCH.sub.3,
C(.dbd.CH--OCH.sub.3)--COOCH.sub.3,
C(.dbd.N--OCH.sub.3)--CONHCH.sub.3,
C(.dbd.N--OCH.sub.3)--COOCH.sub.3 or N(--OCH.sub.3)--COOCH.sub.3;
[0007] A is --O--B, --CH.sub.2O--B, --OCH.sub.2--B, --CH.dbd.CH--B,
--CH.sub.2O--N.dbd.C(R.sup.1)--B or
--CH.sub.2O--N.dbd.C(R.sup.1)--C(R.sup.2).dbd.N--OR.sup.3, where
[0008] B is phenyl, naphthyl, 5-membered or 6-membered hetaryl or
5-membered or 6-membered heterocyclyl which contains one to three
nitrogen atoms and/or one oxygen or sulfur atom or one or two
oxygen and/or sulfur atoms, where the ring systems are
unsubstituted or substituted by one to three radicals R.sup.a:
[0009] R.sup.a is cyano, nitro, amino, aminocarbonyl,
aminothiocarbonyl, halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkylcarbonyl,
C.sub.1-C.sub.6-alkylsulfonyl, C.sub.1-C.sub.6-alkylsulfoxyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkyloxycarbonyl,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkylamino;
di-C.sub.1-C.sub.6-alkylamino, C.sub.1-C.sub.6-alkylaminocarbonyl,
di-C.sub.1-C.sub.6-alkylaminocarbonyl,
C.sub.1-C.sub.6alkylaminothiocarbonyl,
di-C.sub.1-C.sub.6-alkylaminothiocarbonyl, [0010]
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkenyloxy, phenyl,
phenoxy, benzyl, benzyloxy, 5- or 6-membered heterocyclyl, 5- or
6-membered hetaryl, 5- or 6-membered hetaryloxy, C(.dbd.NOR')--OR''
or OC(R').sub.2--C(R'').dbd.NOR'', [0011] where the cyclic radicals
for their part are unsubstituted or substituted by one to three
radicals R.sup.b: [0012] R.sup.b is cyano, nitro, halogen, amino,
aminocarbonyl, aminothiocarbonyl, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alklsulfonyl,
C.sub.1-C.sub.6-alkylsulfoxyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy,
C.sub.1-C.sub.6-alkoxycarbonyl, C.sub.1-C.sub.6-alkyithio,
C.sub.1-C.sub.6-alkylamino, di-C.sub.1-C.sub.6-alkylamino,
C.sub.1-C.sub.6-alkylaminocarbonyl,
di-C.sub.1-C.sub.6-alkylaminocarbonyl,
C.sub.1-C.sub.6-alkylaminothiocarbonyl,
di-C.sub.1-C.sub.6-alkylaminothiocarbonyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkenyloxy, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkenyl, phenyl, phenoxy, phenylthio, benzyl,
benzyloxy, 5- or 6-membered heterocyclyl, 5- or 6-membered hetaryl,
5- or 6-membered hetaryloxy or C(.dbd.NOR')--OR''; [0013] R' is
hydrogen, cyano, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl
or C.sub.1-C.sub.4-haloalkyl; [0014] R'' is hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.3-C.sub.6-alkinyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.3-C.sub.6-haloalkenyl or C.sub.3-C.sub.6-haloalkinyl; [0015]
R.sup.1 is hydrogen, cyano, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.4-alkoxy; [0016] R.sup.2 is phenyl, phenylcarbonyl,
phenylsulfonyl, 5- or 6-membered hetaryl, 5- or 6-membered
hetarylcarbonyl or 5- or 6-membered hetarylsulfonyl, where the ring
systems are unsubstituted or substituted by one to three radicals
R.sup.a, [0017] is C.sub.1-C.sub.10-alkyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.10-alkenyl,
C.sub.2-C.sub.10-alkinyl, C.sub.1-C.sub.10-alkylcarbonyl,
C.sub.2-C.sub.10-alkenylcarbonyl, C.sub.3-C.sub.10-alkinylcarbonyl,
C.sub.1-C.sub.10-alkylsulfonyl or C(R').dbd.NOR'', where the
hydrocarbon radicals of these groups are unsubstituted or
substituted by one to three radicals R.sup.c: [0018] R.sup.c is
cyano, nitro, amino, aminocarbonyl, aminothiocarbonyl, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkylsulfonyl, C.sub.1-C.sub.6-alkylsulfoxyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy,
C.sub.1-C.sub.6-alkoxy-carbonyl, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.6-alkylamino, di-C.sub.1-C.sub.6-alkyl-amino,
C.sub.1-C.sub.6-alkylaminocarbonyl,
di-C.sub.1-C.sub.6-alkylaminocarbonyl,
C.sub.1-C.sub.6-alkylaminothiocarbonyl,
di-C.sub.1-C.sub.6-alkylaminothiocarbonyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkenyloxy, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkyloxy, 5- or 6-membered heterocyclyl, 5- or
6-membered heterocyclyloxy, benzyl, benzyloxy, phenyl, phenoxy,
phenylthio, 5- or 6-membered hetaryl, 5- or 6-membered hetaryloxy
or hetarylthio, where the cyclic groups for their part may be
partially of fully halogenated or may carry one to three radicals
R.sup.a; and [0019] R.sup.3 is hydrogen, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl or C.sub.2-C.sub.6-alkinyl where the
hydrocarbon radicals of these groups may be unsubstituted or
substituted by one to three radicals R.sup.c; [0020] and
[0021] b) one or more ethylene modulators (II) selected from the
group consisting of: [0022] ethylene biosynthesis inhibitors which
inhibit the conversion of S-adenosyl-L-methionine into
1-aminocyclopropane-1-carboxylic acid (ACC), such as derivatives of
vinyiglycine, hydroxylamines, oxime ether derivatives; [0023]
ethylene biosynthesis inhibitors which block the conversion of ACC
into ethylene, selected from the group consisting of: Co.sup.++ or
Ni.sup.++ ions in plant-available forms; phenolic radical
scavengers such as n-propyl gallate; polyamines, such as
putrescine, spermine or spermidine; structural analogs of ACC, such
as .alpha.-aminoisobutyric acid or L-aminocyclopropene-1-carboxylic
acid; salicylic acid or acibenzolar-S-methyl; structural analogs of
ascorbic acid which act as inhibitors of ACC oxidase, such as
prohexadione-Ca or trinexapac-ethyl; and triazolyl compounds such
as paclobutrazol or uniconazole as inhibitors of cytochrome
P-450-dependent monooxygenases, whose main action is to block the
biosynthesisof gibberellins; [0024] inhibitors of the action of
ethylene selected from the group consisting of: structural analogs
of ethylene such as 1-methylcyclopropene or 2,5-norbornadiene and
3-amino-1,2,4-triazole or Ag.sup.++ ions in a weight ratio of I to
II of from 20:1 to 0.05:1.
[0025] Furthermore, the invention relates to a method for
controlling harmful fungi such as Phakopsora pachyrhizi or
Phakopsora meibomiae on legumes and to a method for increasing the
yield of legumes by using the mixtures according to the
invention.
[0026] Also the present invention relates to a method for reducing
the ethylene evolution of plants and to a method for reducing
undesired defoliation of crop plants.
[0027] Until recently, in the most important regions of cultivation
of legumes (in particular soybeans) there were no infections by
harmful fungi such as rust which were of major economical
importance. In 2001 and 2002, however, there were increasing
incidents of strong rust infections in South America by the harmful
fungi Phakopsora pachyrhizi and Phakopsora meibomiae in crops of
soybeans. There were considerable harvest and yield losses. In
addition to soybeans, these harmful fungi also attack other legume
genera and species.
[0028] In the literature, compounds of the formula I are known
under the name strobilurins. Like the azoles (III), they belong to
the modern and highly effective fungicidally active compounds (see,
for example, Angew. Chem. Int. Ed. 1999, 38, 1328-1349; Pesticide
Manual, editor C. Tomlin, 12.sup.th edition). Hitherto, little has
been known concerning the action of the abovementioned compounds
specifically against harmful fungi such as Phakopsora pachyrhizi
and Phakopsora meibomiae.
[0029] In the specialist literature few results were found, for
example: [0030]
http://www.saspp.org/archived_articles/tablesoybeanrust.sub.--2002-
.html Cyproconazole, tridimend, flusilazole, tebuconazole,
flusilazole+carbentazim, difenoconazole tridimend and triforine
have been used as emergency fungicides for soybean rust control in
South Africa for the growing season 2001/2002. [0031]
http://www.aphis.usda.gov/ppq/ep/soybean_rust/UreMelPp502.pdf In
Zimbabwe following fungicides have been approved for the control of
soybean rust: cyproconazole, tebuconazole, triforine, flutriafol,
flusilazole+carbentazim, difenoconazole, triadimenol and
propiconazole.
[0032] However, recent documents teach the use of stobilurin
fungicides to control soybean rust, like: [0033]
http://www.ipmcenters.org/NewsAlerts/soybeanrust/Brazil2002.pdf In
Brazil tests have been conducted with Topsin 500 SC (thiophanate),
Stratego 250 EC (trifloxystrobin+propiconazole), tebuconazole and
tebuconazole triadimenol for the control of soybean rust in 2002.
[0034] http://www.ipmcenters.org/NewsAlerts/soybeanrust/USDA.pdf
Also in Paraguay trials have been conducted with various fungicides
like azoxystrobin, propiconazole, fenbuconazole, mancozep etc. to
evaluate soybean rust control there.
[0035] All fungicide recommendations given here appear to have a
rather preliminary character. Effects on leaf drop are not
described.
[0036] A further problem consists in the fact that even by using
extremely effective fungicides, it is not possible completely to
avoid damage to the plants. Following infection, the assimilation
performance of the plants is reduced by leaf necroses occurring.
Furthermore, in the soybean plant, the pathogens cause premature
aging of the leaves and defoliation of the plants. This results in
harvest and yield losses. It was an object of the present invention
to provide a method which allows both control of the harmful fungi
and the premature leaf drop caused by the harmful fungi in the host
plants to be prevented.
[0037] We have found that this object is achieved, surprisingly, by
applying the combination according to the invention of a
strobilurin fungicide and an ethylene modulator. Following the
control of harmful fungi with the mixture according to the
invention, the host plants are damaged to a considerably lesser
degree than after treatment with a customary fungicide.
[0038] Ethylene modulators are to be understood as meaning
substances which block the natural formation of the plant hormone
ethylene or else its action. [Reviews for example in M. Lieberman
(1979), Biosynthesis and action of ethylene, Annual Review of Plant
Physiology 30: 533-591//S. F. Yang and N. E. Hoffman (1984),
Ethylene biosynthesis and its regulation in higher plants, Annual
Review of Plant Physiology 35: 155-189//E. S. Sisler et. al.
(2003), 1-substituted cyclopropenes: Effective blocking agents for
ethylene action in plants, Plant Growth Regulation 40: 223-228].
Essentially, three groups have to be distinguished here: [0039]
Inhibitors of ethylene biosynthesis which inhibit the conversion of
S-adenosyl-L-methionine into 1-aminocyclopropane-1-carboxylic acid
(ACC) [0040] for example vinylglycine derivatives (rhizobitoxin,
aminoethoxyvinylglycine, methoxyvinylglycine), hydroxylamines
(L-canaline, aminooxyacetic acid) or oxime ether derivatives
[according to EP-A-0 243 834 and EP-A 0 501 326 or J. Kirchner et
al. (1993), Effects of novel oxime ether derivatives of
aminooxyacetic acid on ethylene formation in leaves of oilseed rape
and barley and on carnation flower senescence, Plant Growth
Regulation 13: 41-46]. [0041] Inhibitors of ethylene biosynthesis
which block the conversion of ACC into ethylene [0042] for example
Co.sup.++ or Ni.sup.++ ions, radical-scavenging phenolic substances
(for example n-propyl gallate), polyamines (for example putrescine,
spermine, spermidine), structural ACC analogs (for example
.alpha.-aminoisobutyric acid, L-aminocyclopropene-1-carboxylic
acid), salicylic acid [C. A. Leslie and R. J. Romani (1988),
Inhibition of ethylene bio-synthesis by salicylic acid, Plant
Physiology 88: 833-837] including its synthetic analogon
acibenzolar-S-methyl, structural analogs of ascorbic acid which act
as inhibitors of ACC oxidase [for example prohexadione-Ca,
trinexapac-ethyl--W. Rademacher (2000), Growth retardants: Effects
on gibberellin biosynthesis and other metabolic pathways, Annual
Review of Plant Physiology and Plant Molecular Biology 51: 501-531]
and also triazolyl compounds as inhibitors of cytochrome
P-450-dependent monooxygenases whose main action is to block the
biosynthesisof gibberellins [for example paclobutrazol,
uniconanzole--W. Rademacher (2000), Growth retardants: Effects on
gibberellin biosynthesis and other metabolic pathways, Annual
Review of Plant Physiology and Plant Molecular Biology 51:
501-531]. [0043] Inhibitors of the action of ethylene [0044] These
substances bind, for example, with high affinity to the ethylene
receptor in the target tissue, thus blocking the action of ethylene
[structural analogs of ethylene (for example 1-methylcyclopropene,
2,5-norbornadiene), 3-amino-1,2,4-triazole or Ag.sup.++ ions (for
example from silver thiosulfate)].
[0045] For some of these ethylene modulators, various additional
actions are described in the literature. It is mentioned, for
example, that acylcyclohexanediones such as pro-hexadione-Ca or
trinexapac-ethyl can provide protection of crop plants against
biotic and abiotic stressors [for example EP 0 123 001 A1, page 27,
lines 20 and 21 (for pro-hexadione and related substances) or for
trinexapac-ethyl and related compounds in EP 0 126 713]. Bazzi et
al. (European Journal of Horticultural Science 68: 108-114 and
115-122) mention a number of examples in which the compounds
mentioned induce resistance against specific pathogens in certain
host plants. However, in some host/pathogen combinations, no such
effect is achieved. There are no examples for legumes.
[0046] Cobalt is important as a trace element for plant nutrition.
Inhibitors of ethylene biosynthesis which inhibit the conversion of
S-adenosyl-L-methionine into ACC are described as also being able
to reduce the formation of ethylene in soils used for agriculture.
This facilitates improved plant growth and, in the case of legumes,
a more intensive root nodulation (EP-A 0 767 607).
[0047] Other types of the ethylene modulators mentioned have been
examined by different groups for their ability to exert an effect
against biotic or abiotic stressors on crop plants. It is known
that triazolyl compounds such as paclobutrazol and uniconazole have
a certain fungicidal action owing to their structural similarity to
certain fungicides [cf. W. Rademacher (2000), Growth retardants:
Effects on gibberellin biosynthesis and other metabolic pathways,
Annual Review of Plant Physiology and Plant Molecular Biology 51:
501-531]. Salicylic acid and acibenzolar-S-methyl, which is derived
therefrom, trigger resistance reactions against infection by
pathogens [M. Oostendorp et al. (2001), Induced disease resistance
in plants by chemicals, European Journal of Plant Pathology
107:19-28]. However, there are no indications in the relevant
literature that the ethylene modulators mentioned act against plant
damage caused by fungi specifitally in soybeans.
[0048] Surprisingly, it has now been found that the simultaneous
use of fungicidal compounds of the formula I and, if appropriate,
azoles Ill, and of ethylene modulators II allows better prevention
of plant damage caused by pathogens (in particular premature leaf
drop) in legumes than treatment with fungicide alone. The direct
results are increased yields, combined with a better quality of the
harvested material.
[0049] Also it has been found that the simultaneous use of
fungicidal compounds of formula I and, if appropriate, azoles III,
and of ethylene modulators III reduce the ethylene evolution of
non-pathogen effected plants.
[0050] Fungicides suitable for controlling harmful fungi, in
particular Phakopsora pachyrhizi and Phakopsora meibomiae, are the
compounds of the formula I mentioned at the outset
(strobilurins).
[0051] Azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl,
metominostrobin, orysastrobin, picoxystrobin and trifloxystrobin
and particularly preferably pyraclostrobin have been found to be
particularly suitable for controlling the fungal diseases mentioned
above.
[0052] The strobilurins mentioned above are known from the
literature [0053] dimoxystrobin,
(E)-2-(methoxyimino)-N-methyl-2-[.alpha.-(2,5-xylyloxy)-o-tolyl]acetamide-
, known from EP-A 477 631 and EP-A 398 692; [0054] azoxystrobin,
methyl
(E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate,
known from EP 382375; [0055] fluoxastrobin,
(E)-{2-[6-(2-chlorophenoxy)-5-fluoropyrimidin-4-yloxy]phenyl}(5,6-dihydro-
-1,4,2-dioxazin-3-yl)methanone O-methyloxime, known from WO
95/04728; [0056] kresoxim-methyl, methyl
(E)-methoxyimino[.alpha.-(o-tolyloxy)-o-tolyl]acetate, known from
EP 253 213; [0057] metominostrobin,
(E)-2-(methoxyimino)-N-methyl-2-(2-phenoxyphenyl)-acet-amide, known
from EP-A 398 692; [0058] orysastrobin,
(2E)-2-(methoxyimino)-2-{2-[(3E,5E,6E)-5-(methoxyimino)-4,6-dimethyl-2,8--
dioxa-3,7-diazanona-3,6-dien-1-yl]phenyl}-N-methylacetamide, known
from WO-A 97/15552; [0059] picoxystrobin, methyl
(E)-3-methoxy-2-{2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenyl}acrylat-
e, known, for example, from EP 278595; [0060] pyraclostrobin,
methyl
N-{2-[1-(4-chlorophenyl)-1H-pyrazol-3-yloxymethyl]phenyl}(N-methoxy)carba-
mate, known, for example, from EP 804 421; [0061] trifloxystrobin,
methyl
(E)-methoxyimino-{(E)-.alpha.-[1-(.alpha.,.alpha.,.alpha.-trifluoro-m-tol-
yl)ethylideneaminooxy]-o-tolyl}acetate, known from EP-A 460575.
[0062] In addition to their excellent action against rust fungi,
the strobilurins also increase the yield capacity of legumes.
Legumes include, in particular, the following crop plants: lupins,
clover, lucerne, peas, beans (Phaseolus and Vicia species),
lentils, chick-peas, peanuts and in particular soybeans. Yield
increases not due to the fungicidal action of the strobilurins have
already been reported for the use of strobilurins in cereals
(Koehle H. et al, in Gesunde Pflanzen 49 (1997), pages 267-271;
Glaab J. et al. Planta 207 (1999), 442-448).
[0063] When using strobilurins, in particular pyraclostrobin, in
soybeans, the yield increase is surprisingly high. The increase in
yield capacity in combination with the excellent action of the
strobilurins against rust in legumes makes the method according to
the invention particularly interesting for the farmer. Excellent
results can be obtained when using pyraclostrobin.
[0064] Furthermore, the method according to the invention also
allows effective control of other harmful fungi frequently
encountered in legumes. The most important fungal diseases in
soybeans are listed below: [0065] Microsphaera diffusa [0066]
Cercospora kikuchii [0067] Cercospora sojina [0068] Septoria
glycines [0069] Colletotrichum truncatum [0070] Corynespora
cassiicola
[0071] As mentioned at the outset, ethylene modulators are
preferably to be understood as meaning the following compounds:
rhizobitoxin, aminoethoxyvinylglycine, methoxyvinylglycine,
L-canaline, aminooxyacetic acid, oxime ether derivatives (according
to EP-A-0 243 834 and EP-A 0 501 326), Co.sup.++ or Ni.sup.++ ions,
n-propyl gallate, putrescine, spermine, spermidine,
.alpha.-aminoisobutyric acid, L-aminocyclopropene-1-carboxylic
acid, salicylic acid, acibenzolar-S-methyl, prohexadione-Ca,
trinexapac-ethyl, paclobutrazol, uniconanzole,
1-methylcyclopropene, 2,5-norbomadiene, 3-amino-1,2,4-triazole or
Ag.sup.++ ions.
[0072] Ethylene modulators which are particularly suitable for the
mixtures according to the invention are aminoethoxyvinylglycine,
aminooxyacetic acid, Co.sup.++ ions in plant-available form
(inorganic salts, complexes or chelates with organic compounds,
examples hereof are inter alia CoCl.sub.2.times.6 H.sub.2O,
PhytoPlus Cobalt [Baicor LC, Logan Utah 84321, USA], Keylate Cobalt
[Stoller Enterprises, Houston, Tex. 77043]),
.alpha.-aminoisobutyric acid, salicylic acid, acibenzolar-S-methyl,
prohexadione-Ca and trinexapac-ethyl.
[0073] Particular preference is given to Co.sup.++ ions in
plant-available form (inorganic salts, complexes or chelates with
organic compounds, like CoCl.sub.2.times.6 H.sub.2O, PhytoPlus
Cobalt [Baicor LC, Logan Utah 84321, USA], Keylate Cobalt [Stoller
Enterprises, Houston, Tex. 77043]), salicylic acid and
prohexadione-Ca (EP- A 123001). Here, it is possible to use,
according to the invention, one or more of these ethylene
modulators in a mixture with strobilurins (if appropriate together
with an additional azole).
[0074] In general, the strobilurins (I) and the ethylene modulators
(II) are employed in a weight ratio of from 20:1 to 0.05:1,
preferably in a weight ratio of from 10:1 to 0.05:1 and with
particular preference in a weight ratio of from 5:1 to 0.1:1. The
weight proportion of the ethylene modulators may be made up of a
number of active compounds.
[0075] The mixtures of strobilurin with ethylene modulators are
suitable for controlling the abovementioned diseases. However, it
is possible to add further active compounds to the mixtures, such
as, for example, herbicides, insecticides, growth regulators,
fungicides or else fertilizers. When the strobilurins or the
compositions comprising them in the use form as fungicide are mixed
with other fungicides, frequently a broader fungicidal activity
spectrum is obtained.
[0076] The following list of fungicides, together with which the
compounds according to the invention can be used, is intended to
illustrate the possible combinations, but not to impose any
limitation: [0077] acylalanines such as benalaxyl, metalaxyl,
ofurace, oxadixyl, [0078] amine derivatives such as aldimorph,
dodine, dodemorph, fenpropimorph, fenpropidin, guazatine,
iminoctadine, spiroxamin, tridemorph [0079] anilinopyrimidines such
as pyrimethanil, mepanipyrim or cyprodinyl, [0080] antibiotics such
as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or
streptomycin, [0081] dicarboximides such as iprodion, myclozolin,
procymidon, vinclozolin, [0082] dithiocarbamates such as ferbam,
nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate,
thiram, ziram, zineb, [0083] heterocylic compounds such as
anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin,
cyazofamid, dazomet, dithianon, famoxadon, fenamidon, fenarimol,
fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil,
nuarimol, probenazole, proquinazid, pyrifenox, pyroquilon,
quinoxyfen, silthiofam, thiabendazole, thifluzamide,
thiophanate-methyl, tiadinil, tricyclazole, triforine, [0084]
copper fungicides such as Bordeaux mixture, copper acetate, copper
oxychloride, basic copper sulfate, [0085] nitrophenyl derivatives
such as binapacryl, dinocap, dinobuton, nitrophthalisopropyl [0086]
phenylpyrroles such as fenpiclonil or fludioxonil, [0087] sulfur
[0088] other fungicides such as benthiavalicarb, carpropamid,
chlorothalonil, cyflufenamid, cymoxanil, dazomet, diclomezin,
diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamid,
fentin-acetate, fenoxanil, ferimzone, fluazinam, fosetyl,
fosetyl-aluminum, iprovalicarb, hexachlorobenzene, metrafenon,
pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene,
zoxamide [0089] sulfenic acid derivatives such as captafol, captan,
dichlofluanid, folpet, tolylfluanid [0090] cinnamides and analogs
such as dimethomorph, flumetover or flumorph.
[0091] Mixtures which, in addition to strobilurins I and ethylene
modulators II, contain an azole III, such as, for example,
bromoconazole, cyproconazole, epoxiconazole, fenbuconazole,
fluquiconazole, flusilazole, metconazole, myclobutanil,
propiconazole, prochloraz, prothioconazole, tebuconazole or
triticonazole, have been found to be suitable for the process
according to the invention. Particular preference is given to the
mixture of pyraclostrobin, ethylene modulators II and
epoxiconazole.
[0092] The mixtures according to the invention are used by treating
the fungi or the plants, materials or the soil to be protected
against fungal attack with an effective amount of the combinations
of active compounds. Especially the above-ground plant parts of the
legumes, in particular the leaves, are treated with an aqueous
preparation of the active compounds. Application can be carried out
either before or after the infection of the materials or plants by
the fungi.
[0093] The mixtures increase the yield capacity in particular of
legumes. They are of particular importance for the treatment of
lupins, clover, lucerne, peas, beans (Phaseolus and Vicia species),
lentils, chick-peas, peanuts and especially soybeans.
[0094] As mentioned further above, certain ethylene modulators
reduce the formation of ethylene in the soil, i.e. in the root
region of the useful plants (EP-A 767 607). It has to be assumed
that even after foliar application a certain proportion of such
substances will end up in the soil (for example when being washed
off by falling rain). Accordingly, part of the active compound
combination according to the invention has an additional useful
effect in improving the soil: a reduced ethylene content in the
rhizosphere generally allows better plant growth; in the case of
legumes, more root nodules are formed, resulting in increased
assimilation of N.sub.2. These effects may additionally enhance the
yield.
[0095] A particular embodiment of the process according to the
invention relates to the use of the mixtures in genetically
modified legumes, in particular soybeans. Soybeans which, for
example, are resistant against herbicides such as glyphosate or
plants which form insecticidally active compounds are now
commercially available. Some of the genetically modified plants are
more sensitive than customary breeds. Moreover, the corresponding
seed is generally more expensive, so that the protection of these
crop plants is particularly important.
[0096] Methods for producing plants which are resistant to
glyphosate action have been described in the recent literature
(EP-A 218 571, EP-A 293 358, WO-A 92/00377 and WO-A 92104449).
Chemical Abstracts, 123, No. 21 (1995) A.N. 281158c describes the
production of glyphosate-resistant soybeans. Other
glyphosate-resistant legumes can be produced in a similar manner.
Methods for transforming legumes are known in the literature and
can be used as outlined above to produce, for example,
glyphosate-resistant beans, peas, lentils, peanuts and lupins:
Plant Science (Shannon) 150(1) Jan. 14, 2000, 41-49; J. of Plant
Biochemistry & Biotechnology 9(2) July, 2000, 107-110; Acta
Physiologiae Plantarum 22(2), 2000, 111-119; Molecular Breeding
5(1) 1999, 43-51; In Vitro Cellular & Developmental Biology,
Animal 34 (3 Part 2) March, 1998, 53A; Plant Cell Reports 16(8),
1997, 513-519 and 541-544; Theoretical & Applied Genetics
94(2), 1997, 151-158; Plant Science, 117 (1-2), 1996, 131-138;
Plant Cell Reports 16(1-2), 1996, 32-37.
[0097] It is possible to use, for example, soybean cultivars such
as NIDERA AX 4919 which are resistant against numerous fungal
diseases and the herbicide glyphosate.
[0098] When using the active compound mixtures according to the
invention in crop protection, the application rates are from 0.05
to 2.0 kg of active compound per ha, depending on the nature of the
desired effect.
[0099] If mixtures of strobilurins (I) and azoles (III) are used in
mixing component a), the weight ratio of the compounds I to III is
usually from 20:1 to 0.05:1 and preferably from 10:1 to 0.1:1.
[0100] In the case of mixtures according to the invention of
fungicides (I+III) and ethylene modulators (II), the weight ratio
is from 20:1 to 0.05: 1, preferably from 10:1 to 0.1:1. Here, a
plurality of ethylene modulators (II) may be present together.
[0101] The mixtures can be converted into the customary
formulations, for example solutions, emulsions, suspensions, dusts,
powders, pastes and granules. The use form depends on the
particular purpose; in any case, it should ensure a fine and
uniform distribution of the compound according to the
invention.
[0102] 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. Solvents/auxiliaries
which are suitable are essentially: [0103] water, aromatic solvents
(for example Solvesso products, xylene), paraffins (for example
mineral oil 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,
[0104] 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 lignosulfite waste liquors and methylcellulose.
[0105] Suitable surfactants are alkali metal, alkaline earth metal
and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid,
phenolsulfonic acid, dibutylnaphthalenesulfonic acid,
alkylarylsulfonates, alkyl sulfates (for example sodium dodecyl
sulfate), alkylsulfonates, fatty alcohols (for example
Lutensol.RTM. AO 10), 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 octyl phenyl
ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,
alkyiphenyl polyglycol ether (for example Triton.RTM. X-100),
tributylphenyl polyglycol ether, tristerylphenyl polyglycol ether,
alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene
oxide condensates, fatty alcohol alkoxylates (for example
Wettol.RTM. LF700), ethoxylated castor oil, polyoxyethylene alkyl
ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol
ether acetal, sorbitol esters, polyoxyethylene sorbitan monolaurate
(for example Tween.RTM. 20), lignosulfite waste liquors and
methylcellulose.
[0106] In a preferred embodiment, mixtures according to the
invention comprising strobilurins I, ethylene modulators II, if
appropriate azoles III and surfactants selected from the group
consisting of alkyl sulfates (for example sodium dodecyl sulfate),
fatty alcohols (for example Lutensol.RTM. AO 10), polyoxyethylene
sorbitan monolaurate (for example Tween.RTM. 20), alkylphenyl
polyglycol ethers (for example Triton.RTM. X-100), fatty alcohol
alkoxylates (for example Wettol.RTM. LF700) are used.
[0107] 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 or water.
[0108] Powders, materials for spreading and dusts can be prepared
by mixing or concomitantly grinding the active substances with a
solid carrier.
[0109] Granules, for example coated granules, impregnated granules
and homogeneous granules, can be prepared by binding the active
compounds to solid carriers. Examples of solid 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, for example 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 and other solid carriers.
[0110] In general, the formulations comprise from 0.01 to 95% by
weight, preferably from 0.1 to 90% by weight, of "the active
ingredient". ("The active ingredients" means in this context a
compound of the formula I, one or more ethylene modulators (II)
and, if desired, one or more further active compound, like a
herbicide, insecticide, another fungicide etc.) The compounds of
formula I, the ethylene modulators and, if desired, the further
active compounds are in this case employed in a purity of from 90%
to 100%, preferably 95% to 100% (according to NMR spectrum).
[0111] The following are exemplary formulations:
1. Products for Dilution with Water
A) Water-Soluble Concentrates (SL)
[0112] 10 parts by weight of "the active ingredients" according to
the invention 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)
[0113] 20 parts by weight of "the active ingredients" according to
the invention are dissolved in cyclohexanone with addition of a
dispersant, for example polyvinylpyrrolidone. Dilution with water
gives a dispersion.
C) Emulsifiable Concentrates (EC)
[0114] 15 parts by weight of "the active ingredients" according to
the invention 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)
[0115] 40 parts by weight of "the active ingredients" according to
the invention 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 (Ultraturrax) and made into a homogeneous emulsion.
Dilution with water gives an emulsion.
E) Suspensions (SC, OD)
[0116] In an agitated ball mill, 20 parts by weight of "the active
ingredients" according to the invention are comminuted with
addition of dispersants, wetters and water or an organic solvent to
give a fine active compound suspension. Dilution with water gives a
stable suspension of the active compound.
F) Water-Dispersible Granules and Water-Soluble Granules (WG,
SG)
[0117] 50 parts by weight of "the active ingredients" according to
the invention 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)
[0118] 75 parts by weight of "the active ingredients" according to
the invention are ground in a rotor-stator mill with addition of
dispersants, welters 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)
[0119] 5 parts by weight of "the active ingredients" according to
the invention are ground finely and mixed intimately with 95% of
finely divided kaolin. This gives a dustable product.
I) Granules (GR, FG, GG, MG)
[0120] 0.5 part by weight of "the active ingredients" according to
the invention is ground finely and associated with 95.5% carriers.
Customary methods are extrusion, spray-drying or the fluidized bed.
This gives granules to be applied undiluted.
J) ULV Solutions (UL)
[0121] 10 parts by weight of "the active ingredients" according to
the invention are dissolved in an organic solvent, for example
xylene. This gives a product to be applied undiluted.
[0122] "The active ingredients" 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, dusts,
materials for spreading, or granules, by means of spraying,
atomizing, dusting, spreading or pouring. The use forms depend
entirely on the intended purposes; in any case, they are intended
to ensure the finest possible distribution of the active compounds
according to the invention.
[0123] Aqueous use forms can be prepared from emulsion
concentrates, pastes or wettable powders (wettable 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 be homogenized in water by means of wetter, tackifier,
dispersant or emulsifier. Alternatively, it is possible to prepare
concentrates composed of active substance, wetter, tackifier,
dispersant or emulsifier and, if appropriate, solvent or oil, and
such concentrates are suitable for dilution with water.
[0124] "The active ingredients" concentrations in the ready-to-use
preparations can be varied within substantial ranges. In general,
they are from 0.0001 to 10%, preferably from 0.01 to 1%.
[0125] "The active ingredients" may also be used successfully in
the ultra-low-volume process (ULV), it being possible to apply
formulations comprising over 95% by weight of "active ingredients",
or even "the active ingredients" without additives.
[0126] Various types of oils, wetting agents, adjuvants,
herbicides, fungicides, other pesticides, or bactericides may be
added to the active compounds, if appropriate also just prior to
use (tank mix). These agents can be admixed with the agents
according to the invention in a weight ratio of 1:10 to 10:1.
[0127] It has also been found that Co.sup.++ ions in
plant-available form (inorganic salts, complexes or chelates with
organic compounds, examples hereof are inter alia
CoCl.sub.2.times.6 H.sub.2O, PhytoPlus Cobalt [Baicor LC, Logan
Utah 84321, USA], Keylate Cobalt [Stoller Enterprises, Houston,
Tex. 77043]) are useful to control harmful fungi.
[0128] Usually these Co.sup.++ ions in plant-available form are
applied at an application rate of 10 to 100 g/ha (based on
Co.sup.++).
[0129] The Co.sup.++ ions in plant-available form may also be mixed
together or applied together with further active compounds, such
as, for example, herbicides, insecticides, growth regulators, other
fungicides or fertilizers. When the Co.sup.++ ions in
plant-available form or the compositions comprising them in the use
form as fungicide are mixed with other fungicides, frequently a
broader fungicidal activity spectrum is obtained. The additional
fungicides are, such as, for example, strobilurins as mentioned
before and/or acylalanines, amine derivatives, anilinopyrimidines,
antibiotics, dicarboximides, dithiocarbamates, heterocyclic
compounds, copper fungicides, nitrophenyl derivatives,
phenylpyrroles, sulphur, other fungicides, sulfenic acid
derivatives cinnamides and analogs as mentioned before.
[0130] The Co.sup.++ ions in plant-available form can be converted
into the customary formulations similar to those of the mixtures as
mentioned before. These are prepared in a known manner also similar
to the preparation of the mixtures as mentioned before.
[0131] The Co.sup.++ ions in plant-available form according to the
invention are used by treating the fungi or the plants, materials
or the soil to be protected against fungal attack with an effective
amount of the combinations of active compounds. Especially the
above-ground plant parts of the legumes, in particular the leaves,
are treated with an aqueous preparation of the active compounds.
Application can be carried out either before or after the infection
of the materials or plants by the fungi.
USE EXAMPLE
Example 1
[0132] During fruit formation, soybeans of the cultivar RS10 with
8-12% preinfection by Phakopsora pachyrhizi were treated by spray
application using customary sprayers with a mixture of 133 g/ha of
pyraclostrobin, 80 g/ha of CoCl.sub.2.times.6 H.sub.2O(=20 g/ha of
cobalt) and 100 g/ha of prohexadione-Ca. Entirely untreated plants
and plants treated with 133 g/ha of pyraclostrobin were used for
comparison. 8 days after the treatment, the plants which had been
treated with the pure fungicide variant showed less infection by
pathogen than the entirely untreated plants. However, here, too,
there was considerable leaf drop. This leaf drop was considerably
less pronounced when the treatment was carried out using the
mixtures according to the invention. Furthermore, compared with the
pure fungicide mixture and even more so compared with the entirely
untreated plants the mixture according to the invention gave a
significant additional yield of soybeans.
Example 2
[0133] Soybean plants were raised under greenhouse conditions with
two plants each per 12-cm pot. Spray treatments of the leaves were
carried out with a volume of liquid of 750 l/ha when the plants had
developed one to two trifoliate leaves. 24 hours after treatment,
the shoots of the soybean plants were dissected above the
cotyledons and wilted for 10 minutes under laboratory conditions.
Shoots representing a distinct treatment were incubated for 60
minutes under laboratory conditions in a 100-ml Erlenmeyer flask
sealed with a rubber cap. Thereafter, gas samples were taken and
analyzed for their ethylene content by gas chromatography.
[0134] Reduction of ethylene formation in leaves of soybean plants
(cv. "Delta Pine")
TABLE-US-00001 Ethylene Evolution Dosage per Unit Active [g/ha Leaf
Weight No. Product Name Ingredient (ai) of ai] [% of Control] 1
Control -- 0 100 2 CoCl.sub.2 .times. 6 H.sub.2O Co.sup.++ 40 41 3
Cabrio.sup.(a) Pyraclostrobin 100 87 4 Salicylic Acid Salicylic
Acid 500 97 5 Cabrio.sup.(a) + Pyraclostrobin + 100 + 34 CoCl.sub.2
.times. 6 H.sub.2O Co.sup.++ 40 6 Cabrio.sup.(a) + Pyraclostrobin +
100 + 74 Salicylic Acid Salicylic Acid 500 .sup.(a)Producer, Holder
of Trade Name: BASF AG, Germany
[0135] The results obtained indicate that the fungicide
pyraclostrobin inhibits ethylene formation in drought-stressed
soybean leaves. Similar effects are obtained with several ethylene
modulators. Combinations of pyraclostrobin with ethylene modulators
give additive effects.
Example 3
[0136] Seeds of soybean cv. "Embrapa 48" were planted and grown
under standard conditions with adequate supply of water and
nutrients. Infection with Phakopsora pachyrhizi occurred naturally.
The active ingredients have been applied twice, 62 and 68 days
after seeding. The dosages used and the obtained results are shown
below.
[0137] Yield improvement of soybeans (cv. "Embrapa 48)
TABLE-US-00002 Dosage Seed Active Ingredient [g/ha of active Yield
No. Product Name (ai) ingredient] [kg/ha] 1 Control -- -- 1439 2
Headline.sup.(a) Pyraclostrobin 112.5 1782 3 Keylate Cobalt.sup.(b)
Co.sup.++ 29 1760 4 Headline.sup.(a) + Pyraclostrobin + 112.5 +
2490 Keylate Cobalt.sup.(b) Co.sup.++ 29 .sup.(a)Producer, Holder
of Trade Name: BASF AG, Germany .sup.(b)Producer, Holder of Trade
Name: Stoller Enterprise, Houston TX 77043, USA
[0138] The results obtained demonstrate that the fungicide
pyraclostrobin as well as the ethylene modulator Co.sup.++ increase
the seed yield. This yield is increased significantly when
combinations of the fungicide with the ethylene modulator is used.
The seed yield amounts 73% above the control compared to a seed
yield improvement of 24% and 22%, respectively, in case
pyraclostrobin and Co.sup.++ are applied alone.
Example 4
[0139] Soybeans cv. "Embrapa 48" have been planted and grown under
standard conditions and have been infected with Phakopsora
pachyrhizi. 62 and 68 days after seeding the soybeans have been
treated with 29 g/ha Co.sup.++ (Keylate Cobalt with 5% Cobalt
[Producer, Holder of Trade Name: Stoller Enterprise, Houston Tex.
77043, USA]). 8 days later the treated soybeans showed a damage of
7.9% whereas the damage of the control plants has been 13%.
* * * * *
References