U.S. patent application number 12/908634 was filed with the patent office on 2011-02-10 for method for yield improvement in glyphosate-resistent legumes.
Invention is credited to Annette FREUND, Peter OAKLEY, Klaus SCHELBERGER.
Application Number | 20110034333 12/908634 |
Document ID | / |
Family ID | 32308532 |
Filed Date | 2011-02-10 |
United States Patent
Application |
20110034333 |
Kind Code |
A1 |
OAKLEY; Peter ; et
al. |
February 10, 2011 |
Method for yield improvement in glyphosate-resistent legumes
Abstract
Method for increasing the yield in glyphosate-resistant legumes,
which comprises treating the plants or the seed with a mixture
comprising a) azoxystrobin where X, m, Q, A have the meaning given
in the description and b) a glyphosate derivative II in a
synergistically active amount.
Inventors: |
OAKLEY; Peter; (Neustadt,
DE) ; FREUND; Annette; (Limburgerhof, DE) ;
SCHELBERGER; Klaus; (Gonnheim, DE) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Family ID: |
32308532 |
Appl. No.: |
12/908634 |
Filed: |
October 20, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10534637 |
May 12, 2005 |
7838464 |
|
|
12908634 |
|
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Current U.S.
Class: |
504/128 |
Current CPC
Class: |
A01N 57/20 20130101;
A01N 57/20 20130101; A01N 2300/00 20130101; A01N 57/20 20130101;
A01N 61/00 20130101; A01N 47/24 20130101 |
Class at
Publication: |
504/128 |
International
Class: |
A01N 57/20 20060101
A01N057/20; A01P 13/00 20060101 A01P013/00; A01P 3/00 20060101
A01P003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 12, 2002 |
DE |
10252881.0 |
Claims
1. A method for synergistically increasing the yield in
glyphosate-resistant legumes, which comprises treating the plants
with a mixture comprising (a) azoxystrobin and (b) a glyphosate
derivative II selected from the group consisting of
N-(phosphonomethyl)glycine as a free acid or a salt thereof in a
synergistically active amount, wherein the weight ratio of the
compound of the formula Ia to the glyphosate derivative II is from
1:1 to 0.01:1.
2. The method as claimed in claim 1, wherein the salt of
N-(phosphonomethyl)glycine is selected from the group consisting of
the isopropylammonium salt, sodium salt, ammonium salt and
trimethylsulfenium salt.
3. The method as claimed in claim 1, wherein the mixture comprises:
(a) azoxystrobin and (b) a glyphosate derivative II.
4. The method as claimed in claim 1, wherein component (b) is
N-(phosphonomethyl)glycine as a free acid.
5. A method as claimed in claim 1, wherein a fungicidal azole
selected from the group consisting of: fluquinconazole,
metconazole, prochloraz, propiconazole, prothioconazole,
tebuconazole, epoxiconazole or myclobutanil is employed as
component a) in addition to the active compound of the formula
Ia.
6. A synergistic mixture comprising (a) azoxystrobin and (b) a
glyphosate derivative II selected from the group consisting of
N-(phosphonomethyl)glycine as a free acid or a salt thereof wherein
the weight ratio of the compound of the formula Ia to the
glyphosate derivative II is from 1:1 to 0.01:1.
7. A mixture as claimed in claim 6, wherein the mixture comprises:
(a) azoxystrobin and (b) a glyphosate derivative II.
8. A mixture as claimed in claim 7, wherein component a) comprises
an azole selected from the group consisting of: metconazole,
myclobutanil, epoxiconazole, propiconazole, prothioconazole and
tebuconazole in addition to the active compound pyraclostrobin.
9. A mixture as claimed in claim 7, wherein component (b) is a salt
of N-(phosphonomethyl)glycine selected from the group consisting of
the isopropylammonium salt, sodium salt, ammonium salt and
trimethylsulfenium salt.
10. The method as claimed in claim 3, wherein the weight ratio of
the compound pyraclostrobin to the glyphosate derivative II is 1:1
to 0.1:1.
11. A mixture as claimed in claim 7, wherein the weight ratio of
the compound pyraclostrobin to the glyphosate derivative II is 1:1
to 0.1:1.
Description
[0001] The present application is a 37 C.F.R. .sctn.1.53(b)
divisional of Ser. No. 10/534,637, and claims priority to, U.S.
application Ser. No. 10/534,637 filed May 12, 2005. application
Ser. No. 10/534,634 is the national phase under 35 U.S.C. .sctn.371
of International Application No. PCT/EP2003/012483, filed on Nov.
8, 2003. Priority is also claimed to German application 10252881.0
filed on Nov. 12, 2002. The entire contents of each of these
applications is hereby incorporated by reference.
[0002] The present invention relates to a method for increasing the
yield in glyphosate-resistant legumes, which comprises treating the
plants or the seed with a mixture comprising
a) compound of formula I
##STR00001##
in which [0003] X is halogen, C.sub.1-C.sub.4-alkyl or
trifluoromethyl, [0004] m is 0 or 1, [0005] 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,
[0006] A is --O--B, --CH.sub.2O--B, --OCH.sub.2--B, --CH.dbd.CH--B,
--C.ident.C--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
[0007] B is phenyl, naphthyl, 5-membered or 6-membered hetaryl or
5-membered or 6-membered heterocyclyl, comprising one to three N
atoms and/or one O or S atom or one or two O and/or S atoms, the
ring systems being unsubstituted or substituted by one to three
radicals R.sup.a: [0008] R.sup.a being 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'' the cyclic radicals, in turn, being
unsubstituted or substituted by one to three radicals R.sup.b:
[0009] R.sup.b being 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,
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'', [0010] 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, [0011] R'' is hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.3-C.sub.6-alkynyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.3-C.sub.6-haloalkenyl or haloalkynyl, [0012] 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-alkoxy, [0013]
R.sup.2 is phenyl, phenylcarbonyl, phenylsulfonyl, 5- or 6-membered
hetaryl, 5- or 6-membered hetarylcarbonyl or 5- or 6-membered
hetarylsulfonyl, the ring systems being unsubstituted or
substituted by one to three radicals R.sup.a, [0014]
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-alkynyl,
C.sub.1-C.sub.10-alkylcarbonyl, C.sub.2-C.sub.10-alkenylcarbonyl,
C.sub.3-C.sub.10-alkynylcarbonyl, C.sub.1-C.sub.10-alkylsulfonyl or
C(R').dbd.NOR'', the hydrocarbon radicals of these groups being
unsubstituted or substituted by one to three radicals R.sup.c:
[0015] R.sup.c being 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
and hetarylthio, it being possible for the cyclic groups, in turn,
to be partially or fully halogenated or to have attached to them
one to three radicals R.sup.a, and [0016] 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-alkynyl, the hydrocarbon radicals of these groups
being unsubstituted or substituted by one to three radicals
R.sup.c, and b) a glyphosate derivative in a synergistically active
amount.
[0017] It is already known from the literature that active
ingredients of the formula I, which are generally referred to as
strobilurins, are capable of bringing about increased yields in
crop plants in addition to their fungicidal action (Koehle H. et
al. in Gesunde Pflanzen 49 (1997), pages 267-271; Glaab J. et al.
Planta 207 (1999), 442-448).
[0018] Furthermore, it is known from WO-A 97/36488 that the
application of glyphosate derivatives in glyphosate-tolerant plants
selected from the group consisting of sugar beet, fodder beet,
maize, oilseed rape and cotton may bring about increased yields.
Furthermore, it is known from U.S. Pat. No. 3,988,142 that the
sublethal application of glyphosate in plants such as sugar cane
increases starch and sugar production and thus the overall yield of
the plant.
[0019] Surprisingly, it has now been found that the application of
glyphosate and strobilurins such as, in particular, pyraclostrobin
results in a synergistic effect in legumes. This means that the
purely additive (in mathematical terms) yield-increasing effect of
strobilurin and of the glyphosate derivative is surpassed by
application of the mixture according to the invention. This
synergistic effect is more than surprising, since normally it can
be assumed that a fungicide and herbicide have completely different
mechanisms of action.
[0020] Accordingly, the method defined at the outset has been
found. The active ingredients of the formula I which are used are
known as fungicides and in some cases also as insecticides (EP-A
253 213; WO-A 95/18789; WO-A 95/24396; WO-A 96/01256; WO-A
97/15552). However, there has been no suggestion to date that these
active ingredients in combination with glyphosate derivatives might
possibly bring about an increased yield in legumes.
[0021] The good tolerance of the active ingredients of the formula
I by plants, at the concentrations required for controlling plant
diseases, permits the treatment of aerial plant parts.
[0022] In the method according to the invention, the active
ingredient I is preferably taken up by the leaves and distributed
throughout the entire plant in the plant sap.
[0023] In a preferred embodiment of the method, the above-ground
plant parts of genetically modified legumes are treated with a
mixture according to the invention comprising a) a strobilurin
derivative I and b) a glyphosate derivative. The application of
glyphosate reduces the competition of the crop plant and the weed
plants for nutrients and light and thus increases the yield of the
crop plant. The mixture according to the invention is especially
preferably applied to the above-ground part of the plant.
[0024] Methods for generating plants which are resistant to the
effect of glyphosate are described in the more recent literature
(EP-A 218 571, EP-A 293 358, WO-A 92/00377 and WO-A 92/04449).
Chemical Abstracts, 123, No. 21 (1995) A.N. 281158c describes the
generation of glyphosate-resistant soybean plants. Other
glyphosate-resistant legumes can be generated in a similar manner.
Methods for the transformation of legumes are known in the
literature and can be used--as outlined further above--for
generating, 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.
[0025] For example soya varieties such as NIDERA AX 4919.RTM. which
are resistant to numerous fungal diseases and the herbicide
glyphosate can be used.
[0026] The preparation of the active ingredients used in the method
according to the invention is known from the literature cited at
the outset.
[0027] Active ingredients with the following meanings of the
substituents, in each case on their own or in combination, are
especially preferred for the method according to the invention:
[0028] Especially preferred active ingredients for the method
according to the invention are, in particular, those of the
formulae Ia to Ig in which
V is OCH.sub.3 or NHCH.sub.3 and Y is CH or N.
[0029] Preferred active ingredients of the formula I in which Q is
C(.dbd.N--OCH.sub.3)--COOCH.sub.3 are the compounds described in
the publications EP-A 253 213 and EP-A 254 426.
[0030] Preferred active ingredients of the formula I in which Q is
C(.dbd.N--OCH.sub.3)--CONHCH.sub.3 are the compounds described in
the publications EP-A 398 692, EP-A 477 631 and EP-A 628 540.
[0031] Preferred active ingredients of the formula I in which Q is
N(--OCH.sub.3)--COOCH.sub.3 are the compounds described in the
publications WO-A 93/15046 and WO-A 96/01256.
[0032] Preferred active ingredients of the formula I in which Q is
C(.dbd.CH--OCH.sub.3)--COOCH.sub.3 are the compounds described in
the publications EP-A 178 826 and EP-A 278 595.
[0033] Preferred active ingredients of the formula I in which Q is
C(.dbd.CH--CH.sub.3)--COOCH.sub.3 are the compounds described in
the publications EP-A 280 185 and EP-A 350 691.
[0034] Preferred active ingredients of the formula I in which A is
--CH.sub.2O--N.dbd.C(R.sup.1)--B are the compounds described in the
publications EP-A 460 575 and EP-A 463 488.
[0035] Preferred active ingredients of the formula I in which A is
--O--B are the compounds described in the publications EP-A 382 375
and EP-A 398 692.
[0036] EP-A 382 375 describes pyrimidines having the formula
(I):
##STR00002##
in which any two of K, L and M are nitrogen and the other is CE; X
and Y are independently hydrogen, halogen, C.sub.1-4 alkyl,
C.sub.3-6 cycloalkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl,
C.sub.2-4 alkynyloxy, phenyl, benzyloxy, cyano, isocyano,
isothiocyanato, nitro, NR.sup.1R.sup.2, NR.sup.1OR.sup.2, N.sub.3,
NHCOR.sup.1, NR.sup.1CO.sub.2R.sup.2, NHCONR.sup.1R.sup.2,
N.dbd.CHNR.sup.1R.sup.2, NHSO.sub.2R.sup.1, OR.sup.1, OCOR.sup.1,
OSO.sub.2R.sub.1, SR.sup.1, SOR.sup.1, SO.sub.2R.sup.1,
SO.sub.2OR.sup.1, SO.sub.2NR.sup.1R.sup.2, COR.sup.1,
CR.sup.1.dbd.NOR.sup.2, CHR.sup.1CO.sub.2R.sup.2, CO.sub.2R.sup.1,
CONR.sup.1R.sub.2, CSNR.sup.1R.sup.2,
CH.sub.3O.sub.2C.C:CH.OCH.sub.3, 1-(imidazol-1-yl) vinyl, a
5-membered heterocyclic ring containing one, two or three nitrogen
heteroatoms, or a 5- or 6-membered heterocyclic ring containing one
or two oxygen or sulphur heteroatoms, optionally a nitrogen
heteroatom and optionally one or two oxo or thioxo substituents; or
X and Y, when ortho to one another, join to form a 5- or 6-membered
aliphatic or aromatic ring optionally containing one or two oxygen,
sulphur or nitrogen atoms or one, two or three nitrogen atoms; A,
B, D, E, G, U and V are independently hydrogen, halogen (especially
fluorine and chlorine), C.sub.1-4 alkyl (especially methyl),
C.sub.1-4 alkoxy (especially methoxy), cyano, nitro or
trifluoromethyl; and R.sup.1 and R.sup.2 are independently
hydrogen, C.sub.1-4 alkyl, C.sub.2-4 alkenyl or phenyl; the
aliphatic moieties of any of the foregoing being optionally
substituted with one or more of halogen, cyano, OR.sup.1, SR.sup.1,
NR.sup.1R.sup.2, SiR.sup.1.sub.3 or OCOR.sup.1 and the phenyl
moieties of any of the foregoing being optionally substituted with
one or more of halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, nitro or
cyano.
[0037] Because of the unsymmetrically substituted double bond of
the propenoate group, the compounds of the invention may be
obtained in the form of mixtures of (E) and (Z) geometric isomers.
However, these mixtures can be separated into individual isomers,
and this invention embraces such isomers and mixtures thereof in
all proportions including those which consist substantially of the
(Z)-isomer and those which consist substantially of the
(E)-isomer.
[0038] The (E)-isomer, in which the groups --CO2CH3 and --OCH3 are
on opposite sides of the olefinic bond of the propenoate group, are
the more fungicidally active and form a preferred embodiment of the
invention.
[0039] Alkyl groups contain from 1 to 4 carbon atoms and may be in
the form of straight or branched chains. Examples are methyl,
ethyl, iso-propyl, n-butyl and t-butyl. Cycloalkyl groups contain
from 3 to 6 carbon atoms and include cyclopropyl and
cyclohexyl.
[0040] Alkenyl and alkynyl groups contain from 2 to 4 carbon atoms
and may be in the form of straight or branched chains. Examples are
ethenyl, allyl, methylallyl and propargyl.
[0041] Halogen is typically fluorine, chlorine or bromine.
[0042] Substituted aliphatic moieties include, in particular,
halo(C.sub.1-4) alkyl, halo(C.sub.1-4alkoxy,
halo(C.sub.1-4)alkylthio, CH.sub.2OR.sup.1, CH.sub.2SR.sup.1 and
CH.sub.2NR.sup.1R.sup.2, wherein R.sup.1 and R.sub.2 are H,
C.sub.1-4 alkyl or phenyl.
[0043] Typical optional substituents of phenyl moieties are
fluorine, chlorine, methyl, methoxy, nitro and cyano.
[0044] The ring
##STR00003##
in formula (I) is a pyrimidine ring which may be joined to the
phenoxy groups by any two of its ring carbon atoms adjacent to a
ring nitrogen atom. Of particular interest are those compounds of
formula (I) in which K and L are both nitrogen and M is CH.
Typically, one or both of X and Y are hydrogen. When one of X and Y
is not hydrogen it is preferably attached to the 2-position of the
phenyl ring.
[0045] Thus, in one aspect, EP-A 382 375 describes compounds of
formula (I) in which K, L and M have the meanings previously given;
X, which is preferably attached to the 2-position of the phenyl
ring, is hydrogen, halogen (e.g. fluorine, chlorine or bromine),
C.sub.1-4 alkyl (e.g. methyl or ethyl), C.sub.1-4 alkyl (especially
methyl) substituted with halogen (e.g. fluorine, chlorine or
bromine), hydroxy, cyano, C.sub.1-4 alkoxy (e.g. methoxy) or
C.sub.1-4 alkanoyloxy (e.g. acetoxy), C.sub.2-4 alkenyl (e.g.
ethenyl, allyl or methylallyl), C.sub.2-4 alkynyl (e.g. ethynyl or
propargyl), C.sub.2-4 alkenyloxy (e.g. allyloxy), C.sub.2-4
alkynyloxy (e.g. propargyloxy), phenyl, benzyl, cyano, isocyano,
isothiocyanato, nitro, amino, mono- or di(C.sub.1-4)alkylamino
(e.g. methylamino or dimethylamino), formylamino, C.sub.1-4
alkanoylamino (e.g. acetamido), benzylamino, ureido, phenylureido,
C.sub.1-4 alkylsulphonylamino (e.g. mesylamino),
phenylsulphonylamino, hydroxy, C.sub.1-4 alkoxy (e.g. methoxy or
ethoxy), phenoxy, C.sub.1-4 alkanoyloxy (e.g. acetoxy), C.sub.1-4
alkylsulphonyloxy (e.g. mesyloxy), phenylsulphonyloxy, C.sub.1-4
alkylthio (e.g. methylthio), C.sub.1-4 alkylsulphinyl (e.g.
methylsulphinyl), C.sub.1-4 alkylsulphonyl (e.g. mesyl and
n-butylsulphonyl), formyl, C.sub.1-4 alkanoyl (e.g. acetyl),
benzoyl, hydroxyimino(C.sub.1-4)alkyl (e.g. hydroxyiminomethyl),
C.sub.1-4 alkoxyimino(C.sub.1-4)alkyl (e.g. methoxyiminomethyl),
carbamoyl, C.sub.1-4 alkylcarbamoyl (e.g. methylcarbamoyl),
thiocarbamoyl or C.sub.1-4 alkylthiocarbamoyl (e.g.
methylthiocarbamoyl), the phenyl ring of any of the foregoing being
optionally substituted with halogen (e.g. fluorine or chlorine),
C.sub.1-4 alkyl (e.g. methyl), C.sub.1-4 alkoxy (e.g. methoxy),
nitro or cyano; and Y is halogen (e.g. fluorine or chlorine),
C.sub.1-4 alkyl (e.g. methyl), C.sub.1-4 alkoxy (e.g. methoxy),
nitro, cyano or preferably, hydrogen, or X and Y, when ortho to one
another, together form methylenedioxy, or together with the phenyl
ring to which they are attached form a naphthalene, quinoline,
benzimidazole or benzothienyl ring.
[0046] In another aspect EP-A 382 375 describes compounds of the
formula (I.1):
##STR00004##
in which X is hydrogen, halogen (especially chlorine), C.sub.1-4
alkyl (especially methyl), C.sub.1-4 alkoxy (especially methoxy),
trifluoromethyl, cyano, thiocarbamoyl or nitro, and Y is hydrogen
or fluoro.
[0047] EP-A 382 375 also discloses compounds listed in Tables I to
III which follow. Throughout these Tables the methyl
3-methoxypropenoate group has the (E)-configuration and the
substituents E, G, U and in are all hydrogen.
TABLE-US-00001 TABLE I ##STR00005## Compound Melting No. X Y point
(.degree. C.) Olefinic* 1 H H glass 7.46 2 2-F H gum 7.47 3 3-F H
gum 7.47 4 4-F H 87-9 7.46 5 2-Cl H glass 7.38 6 3-Cl H 7 4-Cl H 8
2-Br H glass 7.42 9 2-Cyano H 118-119 7.50 10 3-Cyano H gum 7.49 11
4-Cyano H gum 7.49 12 2-Isocyano H 13 2-NO.sub.2 H 120-121 7.52 14
3-NO.sub.2 H gum 7.49 15 4-NO.sub.2 H gum 7.48 16 2-NH.sub.2 H gum
7.46 17 3-NH(CH.sub.3) H 18 2-N(CH.sub.3).sub.2 H 19 2-NH.cndot.CHO
H 20 2-NH.cndot.COCH.sub.3 H 21 3-NH.cndot.COC.sub.6H.sub.5 H 22
2-NH.cndot.CONH.sub.2 H 23 3-NH.cndot.CONH(C.sub.2H.sub.5) H 24
2-NH.cndot.SO.sub.2CH.sub.3 H 25 3-NH.cndot.SO.sub.2C.sub.6H.sub.5
H 26 2-OH H 159-161 7.45 27 3-OH H 28 4-OH H 29 2-OCH.sub.3 H gum
7.49 30 3-OCH.sub.3 H gum 7.47 31 4-OCH.sub.3 H 88-90 7.45 32
2-OC.sub.2H.sub.5 H glass 7.46 33 3-(2-F--C.sub.6H.sub.4O) H 34
2-OCOCH.sub.3 H gum 7.47 35 2-OSO.sub.2CH.sub.3 H foam 7.47 36
3-(4-CH.sub.3--C.sub.6H.sub.4SO.sub.2O) H 37 2-SCN H 38 3-SCN H 39
4-SCN H 40 2-SCH.sub.3 H gum 7.48 41 3-SCH.sub.3 H 42 4-SCH.sub.3 H
43 2-S(O)CH.sub.3 H 135-6 7.48 44 2-SO.sub.2CH.sub.3 H 61-4 7.49 45
4-SO.sub.2(CH.sub.2).sub.3CH.sub.3 H 46 2-CHO H foam 7.50 47 3-CHO
H 48 4-CHO H 49 2-COCH.sub.3 H 99-101 7.42 50 3-COC.sub.6H.sub.5 H
51 2-(E)--CH.dbd.NOH H 146-7 7.45 52 3-(E)--CH.dbd.NOH H 53
4-(E)--CH.dbd.NOH H 54 2-(E)--CH.dbd.NOCH.sub.3 H 55
2-(E)--C(CH.sub.3).dbd.NOH H 56 2-CONH.sub.2 H 57 3-CONH(CH.sub.3)
H 58 4-CON(CH.sub.3).sub.2 H 59 2-CSNH.sub.2 H 131-3 7.49 60
2-CSNH(CH.sub.3) H 61 2-CH.sub.3 H gum 7.48 62 3-CH.sub.3 H 92-5
7.45 63 4-CH.sub.3 H gum 7.46 64 2-C.sub.2H.sub.5 H 60-2 7.47 65
2-CH.sub.2F H 66 2-CH.sub.2Br H 67 2-CH.sub.2Cl H 68 2-CH.sub.2CN H
69 2-CH.sub.2OH H 70 2-CH.sub.2OCH.sub.3 H 71 2-CH.sub.2OCOCH.sub.3
H 72 3-CH.sub.2CN H 73 4-CH.sub.2OH H 74 3-CH.sub.2OCH.sub.3 H 75
2-CH.dbd.CH.sub.2 H 76 2-CH.sub.2CH.dbd.CH.sub.2 H gum 7.47 77
2-C.ident.CH H 66-8 7.46 78 2-CH.sub.2C.ident.CH H 79
3-CH.sub.2C(CH.sub.3).dbd.CH.sub.2 H 80 2-OCH.sub.2CH.dbd.CH.sub.2
H glass 7.47 81 2-OCH.sub.2C.ident.CH H gum 7.47 82
2-C.sub.6H.sub.5 H 55 7.40 83 3-C.sub.6H.sub.5 H 84
4-C.sub.6H.sub.5 H 85 2-C.sub.6H.sub.5O H 86 3-C.sub.6H.sub.5O H 87
4-C.sub.6H.sub.5O H 88 2-(4-Cl--C.sub.6H.sub.4O) H 89
2-C.sub.6H.sub.5CH.sub.2O H 90 2-Cyano 4-Cl 91 2-NO.sub.2 4-F 92
2-Cl 4-Cl 93 2-OCH.sub.3 3-OCH.sub.3 94 2-Cyano 5-Cl 95 2-Cyano
6-Cyano 96 2-F 5-Cl 97 3-OCH.sub.3 5-OCH.sub.3 98 3-Cyano 4-F 99
2-NO.sub.2 3-OCH.sub.3 100 3-OCH.sub.3 5-Cyano 101
2-CO.sub.2CH.sub.3 H glass 7.50 102 2-I H glass 7.48 103 2-CF.sub.3
H 99-101 7.48 104 2-i-C.sub.3H.sub.7 H 63-5 7.47 105
2-i-C.sub.3H.sub.7O H glass 7.47 106 2-F 6-F 87-8 7.49 107 2-F 4-F
92-4 7.48 108 2-F 3-F gum 7.48 109 2-n-C.sub.3H.sub.7O H gum 7.46
110 2-n-C.sub.4H.sub.9O H gum 7.47 111 2-CH(OH)CH.sub.3 H 50-3 7.46
112 2-t-C.sub.4H.sub.9 H gum 7.47 113 2-s-C.sub.4H.sub.9 H gum 7.47
114 2-n-C.sub.3H.sub.7 H gum 7.47 115 2-(E/Z)--CH.dbd.CH(CH.sub.3)
H glass 7.46.sup.1 116 2-Cyano 4-OCH.sub.3 gum 7.50 117 2-Cyano
5-OCH.sub.3 oil 7.50 118 2-Cyano 4-Cl 78-82 7.50 119 2-Cyano
5-N(C.sub.2H.sub.5).sub.2 oil 7.50 120 2-CONH.sub.2 H 138-141 7.46
121 2-C.ident.CSi(CH.sub.3).sub.3 H gum 7.46 122 2-F 5-F 100-101
7.48 123 2-(E)--CH.sub.3O.sub.2C.cndot.C.dbd.CH.cndot.OCH.sub.3 H
130-131 7.45 124 3-F 5-F 68-70 7.47 125 2-NHOH H 126
2-CH.sub.2OCH.sub.3 H 127 2-CH.sub.2CN H 128 2-N.sub.3 H 129
2-Cyano 6-F 130 2-NO.sub.2 6-F 131 2-CSNH.sub.2 6-F 132 2-Cyano 3-F
133 2-Cyano 5-F 134 2-Cyano 3-OCH.sub.3 135 2-Cyano 6-OCH.sub.3 136
2-NO.sub.2 4-OCH.sub.3 137 2-NO.sub.2 5-OCH.sub.3 138 2-NO.sub.2
6-OCH.sub.3 139 2-CSNH.sub.2 3-OCH.sub.3 140 2-CSNH.sub.2
4-OCH.sub.3 141 2-CSNH.sub.2 5-OCH.sub.3 142 2-CSNH.sub.2
6-OCH.sub.3 143 2-Cyano 3-Cyano 144 2-F 3-Cyano 144 2-OCH.sub.3
3-Cyano 145 3-Cyano 6-F 146 ##STR00006## H 147 ##STR00007## H 148
##STR00008## H 149 ##STR00009## H 150 2-Cyano 4-Br 151 2-Cyano 6-Br
152 2-Cyano 4-NO.sub.2 153 2-Cyano 6-NO.sub.2 154 2-Cyano
6-OC.sub.2H.sub.5 155 2-Cyano 4-CO.sub.2CH.sub.3 156 2-Cyano
6-CO.sub.2C.sub.2H.sub.5 157 2-Cyano 6-CH.sub.3 158 2-Cyano
5-CH.sub.2C.sub.6H.sub.5 159 2-Cyano 4-OCF.sub.3 160 2-Cyano
4-Cyano ##STR00010## Compound Melting No. Ar point (.degree. C.)
Olefinic* 161 ##STR00011## 133-5 7.52 162 ##STR00012## 163
##STR00013## 164 ##STR00014## 165 ##STR00015## 166 ##STR00016## 167
Pentafluorophenyl 168 2,4,6-Tri-F--C.sub.6H.sub.2 169
2,3,5,6-Tetra-F--C.sub.6H 170 2,3,6-Tri-F--C.sub.6H.sub.2 171
2,3-Di-cyano-6-F--C.sub.6H.sub.2 172
2,6-Di-F-3-CH.sub.3O--C.sub.6H.sub.2 173
2,6-Di-F-4-CH.sub.3O--C.sub.6H.sub.2 174
2,6-Di-F-3-NO.sub.2--C.sub.6H.sub.2 175
2,6-Di-F-4-NO.sub.2--C.sub.6H.sub.2 176
2,6-Di-F-3,5-di-CH.sub.3O--C.sub.6H 177
4,6-Di-Br-2-cyano-C.sub.6H.sub.2 178
3-Cyano-2,6-di-F--C.sub.6H.sub.2 179
6-Br-2-cyano-4-CH.sub.3O--C.sub.6H.sub.2 180
6-Br-4-Cl-2-cyano-C.sub.6H.sub.2 181
6-Br-2-cyano-4-NO.sub.2--C.sub.6H.sub.2 182
3-Br-2-cyano-6-CH.sub.3O--C.sub.6H.sub.2 183
3,5-Di-Cl-2-cyano-C.sub.6H.sub.2 184
4,6-Di-Cl-2-cyano-C.sub.6H.sub.2 185
3-Br-2-cyano-4-CH.sub.3O--C.sub.6H.sub.2 186
4-Br-2-cyano-6-NO.sub.2--C.sub.6H.sub.2 187
4-Br-2-cyano-6-CH.sub.3O--C.sub.6H.sub.2 188
2-Cyano-4-I-6-CH.sub.3O--C.sub.6H.sub.2 189
2-Cyano-6-CH.sub.3O-4-NO.sub.2--C.sub.6H.sub.2 190
2-Cyano-4,6-di-NO.sub.2--C.sub.6H.sub.2 191
2-Cyano-4-CH.sub.3-6-NO.sub.2--C.sub.6H.sub.2 192
2-Cyano-4-CH.sub.3O-6-NO.sub.2--C.sub.6H.sub.2 193
2-Cyano-5,6-di-CH.sub.3O--C.sub.6H.sub.2 194
2-Cyano-5,6-di-CH.sub.3O-3-CH.sub.3--C.sub.6H 195
3,4-Di-Br-2-cyano-6-CH.sub.3O--C.sub.6H 196
3-Br-2-cyano-6-CH.sub.3O-4-NO.sub.2--C.sub.6H 197
2-Cyano-6-CH.sub.3CH.sub.2O-4-NO.sub.2--C.sub.6H.sub.2 198
##STR00017## 199 ##STR00018## *Chemical shift of singlet from
olefinic proton on beta-methoxypropenoate group (ppm from
tetramethyl-silane). Solvent: CDCl.sub.3 unless otherwise stated.
.sup.1The ratio of the (E)- and (Z)-isomers of the prop-1-enyl
group of compound No. 115 is either 2:1 or 1:2.
TABLE-US-00002 TABLE II ##STR00019## Compound Melting No X Y Point
(.degree. C.) Olefinic* 1 H H 114-115 7.46 123
2-(E)--CH.sub.3O.sub.2C.cndot.C.dbd.CH.cndot.OCH.sub.3 H 60-70 7.44
and 7.47 *Chemical shift of singlet from olefinic proton on
beta-methoxypropenoate group (ppm from tetramethylsilane). Solvent:
CDCl.sub.3 unless otherwise stated.
[0048] Table II comprises 199 compounds of the general structure
above with all the values of X and Y listed in Table I. That is,
compounds numbers 1 to 199 of Table II are the same as those of
Table I except that the pyrimidine ring is 4,6-disubstituted in
Table 1 and 2,4-disubstituted as shown in Table II.
TABLE-US-00003 TABLE III ##STR00020## Compound Melting No X Y Point
(.degree. C.) Olefinic* 1 H H 96-97 7.42 9 2-Cyano H foam 7.43
*Chemical shift of singlet from olefinic proton on
beta-methoxypropenoate group (ppm from tetramethylsilane). Solvent:
CDCl.sub.3 unless otherwise stated.
[0049] Table III comprises 199 compounds of the general structure
above with all the values of X and Y listed in Table I. That is,
compounds numbers 1 to 199 of Table III are the same as those of
Table I except that the pyrimidine ring is 4,6-disubstituted in
Table I and 2,4-disubstituted as shown in Table III.
EXAMPLE
[0050] This example illustrates the preparation of (E)-methyl
2-[2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenyl]-3-methoxypropenoate
(compound No. 9 of Table I or "azoxystrobin").
[0051] To a solution of 4,6-dichloropyrimidine (0.76 g, 5.10 mmol)
in dry DMF (4 ml) at 0.degree. C. was added anhydrous potassium
carbonate (0.70 g, 5.10 mmol). A solution of (E)-methyl
2-(2-hydroxyphenyl)-3-methoxypropenoate (0.53 g, 2.55 mmol,
prepared as described in Example 3 of EP-A-0242081) in dry DMF (2
ml) was then added dropwise with stirring. After the addition was
complete, the reaction mixture was allowed to warm to room
temperature and stirring continued over the weekend. The reaction
mixture was then diluted with water (15 ml) and extracted with
ether (3.times.20 ml). The combined ether extracts were washed with
brine and dried. Evaporation afforded a brown liquid (1.10 g) which
was chromatographed (eluent ether:n-hexane, 3:2) to give (E)-methyl
2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxypropenoate as a
thick, pale yellow oil (0.58, 71 percent yield) which crystallised
on standing. Recrystallisation from ether/dichloromethane
(trace)/n-hexane at -78.degree. C. gave the product as a white
powder (0.25 g), mp 94-5.degree. C. In a separate preparation, 15 g
of product was obtained from 4,6-dichloropyrimidine (15.90 g),
(E)-methyl 2-(2-hydroxyphenyl)-3-methoxypropenoate (14.80 g) and
anhydrous potassium carbonate (19.64 g).
[0052] (E)-Methyl
2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxypropenoate (1.50
g, 4.68 mmol) was heated overnight at 95-100.degree. C. with
2-cyanophenol (0.61 g, 5.15 mmol) and potassium carbonate (0.71 g,
5.15 mmol) in DMF (35 ml) in the presence of a catalytic amount of
copper(I) chloride. The reaction mixture was cooled, diluted with
water and then extracted with ether. The combined ether layers were
washed with 2M sodium hydroxide solution and brine and then dried.
Evaporation of the solvent gave a pale yellow oil (1.52 g).
Recrystallisation from ether/dichloromethane/n-hexane gave the
title compound as a pale yellow powder (1.20 g, 64% yield), mp
110-111.degree. C.; .sup.1H NMR .delta.: 3.63 (3H, s); 3.74 (3H,
s); 6.42 (1H, s); 7.19-7.47 (6H, m); 7.50 (1H, s); 7.62-7.75 (2H,
m); 8.40 (1H, s) ppm. In a subsequent preparation of the title
compound, recrystallisation gave a white crystalline solid, mp
118-119.degree. C.
[0053] Preferred active ingredients of the formula I in which A is
--CH.sub.2O--N.dbd.C(R.sup.1)--C(R.sup.2).dbd.N--OR.sup.3 are the
compounds described in the publications WO-A 95/18789, WO-A
95/21153, WO-A 95/21154, WO-A 97/05103, WO-A 97/06133 and WO-A
97/15552.
[0054] Especially preferred are active ingredients of the formula I
in which [0055] Q is C(.dbd.N--OCH.sub.2)--COOCH.sub.3 or
C(.dbd.N--OCH.sub.2)--CONHCH.sub.2, [0056] A is CH.sub.2--O-- and
[0057] B is --N.dbd.C(R.sup.1)--C(R.sup.2).dbd.N--OR.sup.2, where
[0058] R.sup.1 is hydrogen, cyano, cyclopropyl,
C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.2-haloalkyl, in particular
methyl, ethyl, 1-methylethyl or trifluoromethyl, and [0059] R.sup.2
is C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.5-alkenyl, phenyl which is
substituted by one or two halogen atoms, or is C(R').dbd.NOR'',
where [0060] R' is one of the groups mentioned above under R.sup.1
and [0061] R'' is hydrogen, cyclopropyl or C.sub.1-C.sub.4-alkyl,
in particular methyl, ethyl or isopropyl, and [0062] R.sup.3 is one
of the groups mentioned under R''; these active ingredients are
described by the formula Ib
##STR00021##
[0062] in which the variables have the abovementioned meanings.
[0063] Active ingredients of the formula Ib'
##STR00022##
in which the variables have the abovementioned meanings are
particularly preferred.
[0064] In addition, other compounds which are especially preferred
are those of the formula Ia where T is CH or N and R' and R.sup.b
are halogen or C.sub.1-C.sub.4-alkyl and x is 0, 1 or 2 and y is 0
or 1.
##STR00023##
[0065] The active ingredients compiled in the tables which follow
are especially preferred with regard to their use in increasing
yield.
TABLE-US-00004 TABLE I Ia ##STR00024## Position of the No. T
(R.sup.a').sub.y group phenyl-(R.sup.b).sub.x (R.sup.b).sub.x
Reference Ia-1 N -- 1 2,4-Cl.sub.2 WO-A 96/01256 Ia-2 N -- 1 4-Cl
WO-A 96/01256 Ia-3 CH -- 1 2-Cl WO-A 96/01256 Ia-4 CH -- 1 3-Cl
WO-A 96/01256 Ia-5 CH -- 1 4-Cl WO-A 96/01256 Ia-6 CH -- 1
4-CH.sub.3 WO-A 96/01256 Ia-7 CH -- 1 H WO-A 96/01256 Ia-8 CH -- 1
3-CH.sub.3 WO-A 96/01256 Ia-9 CH 5-CH.sub.3 1 3-CF.sub.3 WO-A
96/01256 Ia-10 CH 1-CH.sub.3 5 3-CF.sub.3 WO-A 99/33812 Ia-11 CH
1-CH.sub.3 5 4-Cl WO-A 99/33812 Ia-12 CH 1-CH.sub.3 5 -- WO-A
99/33812
[0066] The active ingredient Ia-5 (common name: pyraclostroblin) is
especially preferred.
TABLE-US-00005 TABLE II II ##STR00025## No. V R.sup.1 R.sup.2
R.sup.3 Reference Ib-1 OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 WO-A
95/18789 Ib-2 OCH.sub.3 CH.sub.3 CH(CH.sub.3).sub.2 CH.sub.3 WO-A
95/18789 Ib-3 OCH.sub.3 CH.sub.3 CH.sub.2CH.sub.3 CH.sub.3 WO-A
95/18789 Ib-4 NHCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 WO-A 95/18789
Ib-5 NHCH.sub.3 CH.sub.3 4-F--C.sub.6H.sub.4 CH.sub.3 WO-A 95/18789
Ib-6 NHCH.sub.3 CH.sub.3 4-Cl--C.sub.6H.sub.4 CH.sub.3 WO-A
95/18789 Ib-7 NHCH.sub.3 CH.sub.3 2,4-C.sub.6H.sub.3 CH.sub.3 WO-A
95/18789 Ib-8 NHCH.sub.3 Cl 4-F--C.sub.6H.sub.4 CH.sub.3 WO-A
98/38857 Ib-9 NHCH.sub.3 Cl 4-Cl--C.sub.6H.sub.4 CH.sub.2CH.sub.3
WO-A 98/38857 Ib-10 NHCH.sub.3 CH.sub.3
CH.sub.2C(.dbd.CH.sub.2)CH.sub.3 CH.sub.3 WO-A 97/05103 Ib-11
NHCH.sub.3 CH.sub.3 CH.dbd.C(CH.sub.3).sub.2 CH.sub.3 WO-A 97/05103
Ib-12 NHCH.sub.3 CH.sub.3 CH.dbd.C(CH.sub.3).sub.2 CH.sub.2CH.sub.3
WO-A 97/05103 Ib-13 NHCH.sub.3 CH.sub.3 CH.dbd.C(CH.sub.3)
CH.sub.2CH.sub.3 CH.sub.3 WO-A 97/05103 Ib-14 NHCH.sub.3 CH.sub.3
O--CH(CH.sub.3).sub.2 CH.sub.3 WO-A 97/06133 Ib-15 NHCH.sub.3
CH.sub.3 O--CH.sub.2CH(CH.sub.3).sub.2 CH.sub.3 WO-A 97/06133 Ib-16
NHCH.sub.3 CH.sub.3 C(CH.sub.3).dbd.NOCH.sub.3 CH.sub.3 WO-A
97/15552 Ib-17 NHCH.sub.3 CH.sub.3
C(CH.sub.3).dbd.NOCH.sub.2CH.sub.3 CH.sub.2CH.sub.3 WO-A 97/15552
Ib-18 NHCH.sub.3 CH.sub.3 C(CH.sub.3).dbd.NOCH(CH.sub.3).sub.2
CH(CH.sub.3).sub.2 WO-A 97/15552 Ib-19 NHCH.sub.3 CH.sub.3
C(CH.sub.3).dbd.NO(c-C.sub.3H.sub.5) c-C.sub.3H.sub.5 WO-A 97/15552
Ib-20 NHCH.sub.3 CH.sub.3 C(CH.sub.3).dbd.NOCH.sub.2CH.dbd.CH.sub.2
CH.sub.2CH.dbd.CH.sub.2 WO-A 97/15552 Ib-21 NHCH.sub.3 CF.sub.3
C(CF.sub.3).dbd.NOCH.sub.3 CH.sub.3 WO-A 97/15552 Ib-22 NHCH.sub.3
CF.sub.3 C(CF.sub.3).dbd.NOCH.sub.2CH.sub.3 CH.sub.2CH.sub.3 WO-A
97/15552 Ib-23 NHCH.sub.3 CF.sub.3
C(CF.sub.3).dbd.NOCH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 WO-A
97/15552 Ib-24 NHCH.sub.3 CF.sub.3
C(CF.sub.3).dbd.NO(c-C.sub.3H.sub.5) c-C.sub.3H.sub.5 WO-A 97/15552
Ib-25 NHCH.sub.3 CF.sub.3 C(CF.sub.3).dbd.NOCH.sub.2CH.dbd.CH.sub.2
CH.sub.2CH.dbd.CH.sub.2 WO-A 97/15552 Ib-26 OCH.sub.3 CH.sub.3
C(CH.sub.3).dbd.NOCH.sub.3 CH.sub.3 WO-A 97/15552 Ib-27 OCH.sub.3
CH.sub.3 C(CH.sub.3).dbd.NOCH.sub.2CH.sub.3 CH.sub.2CH.sub.3 WO-A
97/15552 Ib-28 OCH.sub.3 CH.sub.3
C(CH.sub.3).dbd.NOCH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 WO-A
97/15552 Ib-29 OCH.sub.3 CH.sub.3
C(CH.sub.3).dbd.NO(c-C.sub.3H.sub.5) c-C.sub.3H.sub.5 WO-A 97/15552
Ib-30 OCH.sub.3 CH.sub.3 C(CH.sub.3).dbd.NOCH.sub.2CH.dbd.CH.sub.2
CH.sub.2CH.dbd.CH.sub.2 WO-A 97/15552 Ib-31 OCH.sub.3 CF.sub.3
C(CF.sub.3).dbd.NOCH.sub.3 CH.sub.3 WO-A 97/15552 Ib-32 OCH.sub.3
CF.sub.3 C(CF.sub.3).dbd.NOCH.sub.2CH.sub.3 CH.sub.2CH.sub.3 WO-A
97/15552 Ib-33 OCH.sub.3 CF.sub.3
C(CF.sub.3).dbd.NOCH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 WO-A
97/15552 Ib-34 OCH.sub.3 CF.sub.3
C(CF.sub.3).dbd.NO(c-C.sub.3H.sub.5) c-C.sub.3H.sub.5 WO-A 97/15552
Ib-35 OCH.sub.3 CF.sub.3 C(CF.sub.3).dbd.NOCH.sub.2CH.dbd.CH.sub.3
CH.sub.2CH.dbd.CH.sub.2 WO-A 97/15552
TABLE-US-00006 TABLE III Ic ##STR00026## No. V Y T R.sup.a
Reference Ic-1 OCH.sub.3 CH N 2-OCH.sub.3, 6-CF.sub.3 WO-A 96/16047
Ic-2 OCH.sub.3 CH N 2-OCH(CH.sub.3).sub.2, 6-CF.sub.3 WO-A 96/16047
Ic-3 OCH.sub.3 CH CH 5-CF.sub.3 EP-A 278 595 Ic-4 OCH.sub.3 CH CH
6-CF.sub.3 EP-A 278 595 Ic-5 NHCH.sub.3 N CH 3-Cl EP-A 398 692 Ic-6
NHCH.sub.3 N CH 3-CF.sub.3 EP-A 398 692 Ic-7 NHCH.sub.3 N CH
3-CF.sub.3, 5-Cl EP-A 398 692 Ic-8 NHCH.sub.3 N CH 3-Cl, 5-CF.sub.3
EP-A 398 692
TABLE-US-00007 TABLE IV Id ##STR00027## No. V Y R.sup.1 B Reference
Id-1 OCH.sub.3 CH CH.sub.3 (3-CF.sub.3)C.sub.6H.sub.4 EP-A 370 629
Id-2 OCH.sub.3 CH CH.sub.3 (3,5-Cl.sub.2)C.sub.6H.sub.3 EP-A 370
629 Id-3 NHCH.sub.3 N CH.sub.3 (3-CF.sub.3)C.sub.6H.sub.4 WO-A
92/13830 Id-4 NHCH.sub.3 N CH.sub.3 (3-OCF.sub.3)C.sub.6H.sub.4
WO-A 92/13830 Id-5 OCH.sub.3 N CH.sub.3 (3-OCF.sub.3)C.sub.6H.sub.4
EP-A 460 575 Id-6 OCH.sub.3 N CH.sub.3 (3-CF.sub.3)C.sub.6H.sub.4
EP-A 460 575 Id-7 OCH.sub.3 N CH.sub.3 (3,4-Cl.sub.2)C.sub.6H.sub.3
EP-A 460 575 Id-8 OCH.sub.3 N CH.sub.3 (3,5-Cl.sub.2)C.sub.6H.sub.3
EP-A 463 488
TABLE-US-00008 TABLE V Ie ##STR00028## No. V Y R.sup.a Reference
Ie-1 OCH.sub.3 N 2-CH.sub.3 EP-A 253 213 Ie-2 OCH.sub.3 N
2,5-(CH.sub.3).sub.2 EP-A 253 213 Ie-3 NHCH.sub.3 N
2,5-(CH.sub.3).sub.2 EP-A 477 631 Ie-4 NHCH.sub.3 N 2-Cl EP-A 477
631 Ie-5 NHCH.sub.3 N 2-CH.sub.3 EP-A 477 631 Ie-6 NHCH.sub.3 N
2-CH.sub.3, 4-OCF.sub.3 EP-A 628 540 Ie-7 NHCH.sub.3 N 2-Cl,
4-OCF.sub.3 EP-A 628 540 Ie-8 NHCH.sub.3 N 2-CH.sub.3,
4-OCH(CH.sub.3)--C(CH.sub.3).dbd.NOCH.sub.3 EP-A 11 18 609 Ie-9
NHCH.sub.3 N 2-Cl, 4-OCH(CH.sub.3)--C(CH.sub.3).dbd.NOCH.sub.3 EP-A
11 18 609 Ie-10 NHCH.sub.3 N 2-CH.sub.3,
4-OCH(CH.sub.3)--C(CH.sub.2CH.sub.3).dbd.NOCH.sub.3 EP-A 11 18 609
Ie-11 NHCH.sub.3 N 2-Cl,
4-OCH(CH.sub.3)--C(CH.sub.3).dbd.NOCH.sub.2CH.sub.3 EP-A 11 18
609
TABLE-US-00009 TABLE VI If ##STR00029## No. V Y R.sup.a Reference
If-1 NHCH.sub.3 N H EP-A 398 692 If-2 NHCH.sub.3 N 3-CH.sub.3 EP-A
398 692 If-3 NHCH.sub.3 N 2-NO.sub.2 EP-A 398 692 If-4 NHCH.sub.3 N
4-NO.sub.2 EP-A 398 692 If-5 NHCH.sub.3 N 4-Cl EP-A 398 692 If-6
NHCH.sub.3 N 4-Br EP-A 398 692
TABLE-US-00010 TABLE VII Ig ##STR00030## No. .sup.V .sup.Y T
R.sup.a Reference Ig-1 OCH.sub.3 CH N 6-O--(2-CN--C.sub.6H.sub.4)
EP-A 382 375 Ig-2 OCH.sub.3 CH N 6-O--(2-Cl--C.sub.6H.sub.4) EP-A
382 375 Ig-3 OCH.sub.3 CH N 6-O--(2-CH.sub.3--C.sub.6H.sub.4) EP-A
382 375 Ig-4 NHCH.sub.3 N N 6-O--(2-Cl--C.sub.6H.sub.4) GB-A 22 53
624 Ig-5 NHCH.sub.3 N N 6-O--(2, 4-Cl.sub.2--C.sub.6H.sub.3) GB-A
22 53 624 Ig-6 NHCH.sub.3 N N 6-O--(2-CH.sub.3--C.sub.6H.sub.3)
GB-A 22 53 624 Ig-7 NHCH.sub.3 N N 6-O--(2-CH.sub.3,
3-Cl--C.sub.6H.sub.3) GB-A 22 53 624 Ig-8 NHCH.sub.3 N N 2-F,
6-O--(2-CH.sub.3--C.sub.6H.sub.4) WO-A 98/21189 Ig-9 NHCH.sub.3 N N
2-F, 6-O--(2-Cl--C.sub.6H.sub.4) WO-A 98/21189 Ig-10 NHCH.sub.3 N N
2-F, 6-O--(2-CH.sub.3, WO-A 98/21189 3-Cl--C.sub.6H.sub.3)
[0067] Fungicidal active ingredients which can be employed are the
strobilurins I alone or in mixture with other fungicidal active
ingredients, in particular those from the class of the azoles
I.sub.x.
[0068] Azole active ingredients which are suitable for this purpose
are: [0069] fluquinconazole, Proc. Br. Crop Prot. Conf.--Pests
Dis., 5-3, 411 (1992); [0070] metconazole, Proc. Br. Crop Prot.
Conf.--Pests Dis., 5-4, 419 (1992); [0071] prochloraz, U.S. Pat.
No. 3,991,071; [0072] propiconazole, GB-A 1,522,657; [0073]
prothioconazole, WO-A 96/016048; [0074] tebuconazole, U.S. Pat. No.
4,723,984; [0075] epoxiconazole, EP-A 196038; [0076] myclobutanil,
CAS RN [88671-89-0];
[0077] Azoles which are especially suitable are: metconazole,
myclobutanil, epoxiconazole, propiconazole, prothioconazole or
tebuconazole.
[0078] If fungicide mixtures of, for example, strobilurins I and
azoles I.sub.x are employed, they are generally employed in a
weight ratio I to I.sub.x of 20:1 to 0.05:1, preferably 10:1 to
0.1:1.
[0079] Glyphosate derivatives II are essentially understood as
meaning the following compounds, which are mentioned in The
Pesticide Manual: for example, glyphosate may be employed as the
free acid or in the form of salts such as the isopropylammonium
salt, the sodium salt, the ammonium salt or the trimesium
(trimethylsulfenium) salt. Mixtures of the salts may also be
employed. Moreover, the glyphosate derivatives II include the
compound N-(phosphonomethyl)glycine. The preparation of the
glyphosate derivatives II can be found in the literature cited in
The Pesticide Manual (12th edition).
[0080] The compounds I in combination with glyphosate derivatives
raise the yield potential in legumes. They are especially important
for the treatment of various glyphosate-resistant crop plants such
as peas, beans, lentils, peanuts, lupins and in particular
soybeans. The synergistic effect is demonstrated independently of
the generation of the glyphosate-resistant legumes.
[0081] Specifically, they are suitable for controlling the
following symptoms: [0082] signs of wilting despite the
availability of sufficient nutrients, [0083] discolorations of the
green leaf tissue such as, for example bleaching of soybeans.
[0084] The compounds I are applied by treating the plants to be
protected with an effective amount of the active ingredients.
Application can be effected both before and after application of
the glyphosate derivatives II to the plants.
[0085] In a preferred embodiment of the method, the treatment of
the plant is effected jointly with the application of the fungicide
I and the herbicide II. The synergistic effect is particularly
pronounced in this case.
[0086] When using an active ingredient I, the application rates are
in the range of from 0.01 to 2.0 kg of active ingredient per
hectare, depending on the weather conditions and the plant
species.
[0087] When using a glyphosate derivative II, the application rates
are in the range of from 0.1 to 6.0 kg of active ingredient (acid
equivalent) per hectare, depending on the weather conditions and
the plant species.
[0088] As a rule, the fungicide I, or the fungicidal mixture I and
I.sub.x, is employed in a weight ratio to the herbicide II of 5:1
to 0.01:1, preferably 1:1 to 0.1:1.
[0089] The compounds I and the glyphosate derivatives II may be
converted into the formulations conventionally used for crop
protection products, for example solutions, emulsions, suspensions,
dusts, powders, pastes and granules. The use form depends on the
application in question; in any case, it should ensure uniform and
even distribution of the mixture according to the invention.
[0090] The formulations are prepared in the known manner, for
example by extending the active ingredient with solvents and/or
carriers, if desired using emulsifiers and dispersants, it also
being possible to use other organic solvents as cosolvents if water
is used as the diluent. Auxiliaries are essentially those also
conventionally used for fungicides.
[0091] In general, the formulations comprise between 0.01 and 95%
by weight, preferably between 0.1 and 90% by weight, of the active
ingredient. The active ingredients are employed in a purity of from
90% to 100%, preferably 95% to 100% (according to NMR
spectrum).
[0092] Examples of formulations are known from the publications
cited at the outset.
[0093] Aqueous use forms can usually be prepared from emulsion
concentrates, pastes or wettable powders (sprayable powders, oil
dispersions) by addition of water. To prepare emulsions, pastes or
oil dispersions, the substances, as such or dissolved in an oil or
solvent, may be homogenized in water by means of wetter, sticker,
dispersant or emulsifier. Alternatively, it is possible to prepare
concentrates consisting of active substance, wetter, sticker,
dispersant or emulsifier and, if appropriate, solvent or oil, and
such concentrates are suitable for dilution with water.
[0094] The active ingredient concentrations in the ready-to-use
products may be varied within substantial ranges. In general, they
are between 0.0001 and 10%, preferably between 0.01 and 1%.
[0095] The active ingredients may also be used successfully by the
ultra-low-volume (ULV) method, it being possible to apply
formulations comprising more than 95% by weight of active
ingredient, or indeed the active ingredient without additions.
[0096] Various types of oils or herbicides, other fungicides, other
pesticides or bactericides may be added to the active ingredients,
if appropriate just prior to use (tank mix). These agents can be
admixed with the compositions according to the invention in a
weight ratio of from 1:10 to 10:1.
[0097] The active ingredients I are preferably applied to the plant
jointly or separately with the glyphosate II.
[0098] In general, the compounds I and II are applied within a
period of weeks to 3 months, preferably within 1 to 2 months, after
planting the legume seeds. It may be advantageous to carry out the
fungicide or herbicide treatment repeatedly, preferably twice.
[0099] In the case of separate use, it may be advantageous to apply
the herbicide II for example 3-6 weeks after planting the legume
seeds and then to apply either the fungicide I alone or a mixture
of fungicide I and herbicide II in a second application 4-8 weeks
after planting.
[0100] In the case of joint application, a mixture of the compounds
I and II is generally applied once to twice within a period of 1 to
3 months after planting the legume seeds.
[0101] The abovementioned application methods are understood as
meaning foliar treatment of the legumes. In comparison to, for
example, a seed treatment, these methods have pronounced
advantages.
[0102] The use examples demonstrate the increased yield achieved by
the use of pyraclostrobin and glyphosate in soya plantations.
[0103] It must be added that the increased yield is not connected
to a successful control of harmful fungi. In the experiments, the
experimental fields were free from disease. Naturally, in such a
case the yield would be increased even more since the fungicidal
active ingredients I (strobilurins) and I.sub.x (azoles) or their
mixtures constitute extremely efficient fungicides. Yield losses
caused by harmful fungi can be counteracted effectively by the
methods according to the invention.
[0104] Mention of the use according to the invention of the active
ingredients I may be made in the form of an imprint on the
packaging or else in product data sheets. Such mention may also be
made in the case of products which can be used in combination with
the active ingredients I.
[0105] Use examples for the increased yield in legumes
Use Example
[0106] The results shown hereinbelow were obtained in experiments
in the open which were carried out during the winter season in the
Argentinian northern pampas. The plots used were arranged randomly
relative to one another. Each treatment variant was replicated four
times. The crop plant used was the soya variety NIDERA AX 4910,
which is resistant to numerous fungal diseases and to the herbicide
glyphosate.
[0107] In all 5 experiments, two foliar treatments with glyphosate
were carried out 30 or 60 days after planting the soya seeds, using
equipment conventionally used under practice conditions. In the
experiments 2 and 3, pyraclostrobin was added at "30 days after
planting", while pyraclostrobin was added at "60 days after
planting" in the experiments 4 and 5. As demonstrated by the
results, the addition of pyraclostrobin in amounts of 50 or 100 g
of a.s./ha at both the early and the late treatment times markedly
increased the yield in comparison with the conventional use of
glyphosate alone.
TABLE-US-00011 Treatment 30 Treatment 60 Experiment days after a.s.
days after a.s. number planting g/ha planting g/ha Yield 1
glyphosate 360 glyphosate 360 100% 2 glyphosate 360 glyphosate 360
116% pyra- 50 clostrobin 3 glyphosate 360 glyphosate 360 129% pyra-
100 clostrobin 4 glyphosate 360 glyphosate 360 122% pyra- 50
clostrobin 5 glyphosate 360 glyphosate 360 135% pyra- 100
clostrobin a.s. = active substance
* * * * *