U.S. patent application number 11/323085 was filed with the patent office on 2006-05-25 for herbicidal compositions for tolerant or resistant maize crops.
Invention is credited to Hermann Bieringer, Erwin Hacker, Lothar Willms.
Application Number | 20060111240 11/323085 |
Document ID | / |
Family ID | 26048135 |
Filed Date | 2006-05-25 |
United States Patent
Application |
20060111240 |
Kind Code |
A1 |
Hacker; Erwin ; et
al. |
May 25, 2006 |
Herbicidal compositions for tolerant or resistant maize crops
Abstract
Herbicide combinations (A)+(B), if appropriate in the presence
of safeners, with an effective content of (A) broad-spectrum
herbicides from the group (A1) glufosinate (salts) and related
compounds (A2) glyphosate (salts) and related compounds such as
sulfosate, (A3) imidazolinones, (A4) herbicidal azoles from the
group of the protoporphyrinogen oxidase inhibitors (PPO inhibitors)
(A5) cyclohexanedione herbicides and (A6)
heteroaryloxyphenoxypropionic acid herbicides and (B) one or more
herbicides from the group of the compounds consisting of (B0) one
or more structurally different herbicides from the abovementioned
group (A) or (B1) foliar- and soil-acting herbicides against
monocotyledonous and dicotyledonous harmful plants or (B2)
herbicides which can be employed selectively in maize against
dicots, or (B3) foliar- and soil-acting herbicides which can be
employed selectively in maize, predominantly against dicotyledonous
harmful plants, or herbicides from several of groups (B0) to (B3)
are suitable for controlling harmful plants in maize which consists
of tolerant or resistant mutants or transgenic maize plants and the
maize crops are tolerant to the herbicides (A) and (B), if
appropriate in the presence of safeners, which are contained in the
combination.
Inventors: |
Hacker; Erwin; (Hochheim,
DE) ; Bieringer; Hermann; (Eppstein, DE) ;
Willms; Lothar; (Hofheim, DE) |
Correspondence
Address: |
FROMMER LAWRENCE & HAUG
745 FIFTH AVENUE- 10TH FL.
NEW YORK
NY
10151
US
|
Family ID: |
26048135 |
Appl. No.: |
11/323085 |
Filed: |
December 30, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09370373 |
Aug 10, 1999 |
7012040 |
|
|
11323085 |
Dec 30, 2005 |
|
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Current U.S.
Class: |
504/128 |
Current CPC
Class: |
A01N 57/20 20130101;
A01N 2300/00 20130101; A01N 57/20 20130101 |
Class at
Publication: |
504/128 |
International
Class: |
A01N 57/00 20060101
A01N057/00 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 13, 1998 |
DE |
198 36 737.6 |
Apr 30, 1999 |
DE |
199 19 993.0 |
Claims
1-12. (canceled)
13. A method for controlling harmful plants in maize crops in an
area under cultivation which comprises applying an effective amount
of a herbicidal combination to the harmful plants, seeds of the
maize crops or the area or the area under cultivation, wherein said
herbicidal combination comprises a synergistically effective amount
of (IA) one or more herbicides from the group consisting of
compounds of the formula (A1), ##STR4## in which Z is a radical of
the formula --OH or a peptide radical of the formula
--NHCH(CH.sub.3)CONHCH(CH.sub.3)COOH or
--NHCH(CH.sub.3)CONHCH[CH.sub.2CH(CH.sub.3).sub.2]COOH, and their
esters and salts and other phosphinothricin derivatives, and (IB)
one or more herbicides selected from the group consisting of (B1)
atrazine, terbuthylazine, acetochlor, metolachlor, terbutryn,
nicosulfuron, primisulfuron, dimethenamid, and simazine; (B2)
pendimethalin, pyridate, iodosulfuron, isoxaflutole and
flumetsulam; and (B3) bromoxynil, dicamba, clopyralid and
prosulfuron; or, where applicable, ester or salts of these
herbicides; or (IIA) one or more herbicides from the group
consisting of compounds of the formula (A2) and their salts,
##STR5## and (IIB) one or more herbicides selected from the group
consisting of (B1) atrazine, terbuthylazine, acetochlor,
metolachlor, terbutryn, primisulfuron, dimethenamid and simazine,
(B2) pyridate and iodosulfuron, and (B3) dicamba and prosulfuron,
or, where applicable, ester or salts of these herbicides; or (IIIA)
one or more compounds from the group consisting of herbicides of
imidazolinones (A3) and salts thereof, and (IIIB) one or more
herbicides selected from the group consisting of (B1) acetochlor,
metolachlor, nicosulfuron, rimsulfuron, primisulfuron and
sulcotrione; (B2) pendimethalin, pyridate and flumetsulam and (B3)
bromoxynil, dicamba, 2,4-D, prosulfuron and thifensulfuron, and
additionally in case that (A3) is imazamethabenz, (B2)
iodosulfuron, or, where applicable, ester or salts of these
herbicides; and, optionally one or more safeners, wherein the maize
crops are tolerant to the herbicides (A) and (B) which form a
constituent of the combination.
14. The method as claimed in claim 13, wherein the (IA) herbicides
are selected from the group consisting of (A1.1) glufosinate acid
(A1.2) glufosinate-monoammonium salt, (A1.3) L-glufosinate (A1.4)
L-glufosinate monoammonium salt, (A1.5) bialaphos (or bilanafos) or
its sodium salt; and the (IIA) herbicides are selected from the
group consisting of (A2.1) glyphosate acid, (A2.2)
glyphosate-monoisopropylammonium salt, (A2.3) glyphosate-sodium
salt, (A2.4) sulfosate; and the (IIIA) herbicides are selected from
the group consisting of (A3.1) imazapyr and its salts and esters,
(A3.2) imazethapyr and its salts and esters, (A3.3) imazamethabenz
and its salts and esters, (A3.4) imazamethabenz-methyl, (A3.5)
imazamox and its salts and esters, (A3.6) imazaquin and its salts
and esters, (A3.7) imazapic (AC 263,222) and its salts and
esters.
15. The method as claimed in claim 13, wherein the herbicide (IA)
is glufosinate-ammonium.
16. The method as claimed in claim 13, wherein the herbicide (IIA)
is glyphosate-isopropylammonium.
17. The method as claimed in claim 13, wherein the herbicidal
combination is used together with other crop protection active
ingredients additionally.
18. The method as claimed in claim 13, wherein the herbicidal
combination is used together with adjuvants and formulation
auxiliaries conventionally used in crop protection.
19. A method for controlling harmful plants in maize crops in an
area under cultivation which comprises applying an effective amount
of a herbicidal combination to the harmful plants, seeds of the
maize crops or the area or the area under cultivation, wherein said
herbicidal combination comprises a synergistically effective amount
of (IA) one or more herbicides from the group consisting of
compounds of the formula (A1), ##STR6## in which Z is a radical of
the formula --OH or a peptide radical of the formula
--NHCH(CH.sub.3)CONHCH(CH.sub.3)COOH or
--NHCH(CH.sub.3)CONHCH[CH.sub.2CH(CH.sub.3).sub.2]COOH, and their
esters and salts and other phosphinothricin derivatives, and (IB)
one or more herbicides selected from the group consisting of (B1)
atrazine, terbuthylazine, acetochlor, metolachlor, terbutryn,
nicosulfuron, primisulfuron, dimethenamid, and simazine; (B2)
pendimethalin, pyridate, iodosulfuron, isoxaflutole and
flumetsulam; and (B3) bromoxynil, dicamba, clopyralid and
prosulfuron; or, where applicable, ester or salts of these
herbicides; and, optionally one or more safeners, wherein the maize
crops are tolerant to the herbicides (A) and (B) which form a
constituent of the combination.
20. The method as claimed in claim 19, wherein the (IA) herbicides
are selected from the group consisting of (A1.1) glufosinate acid
(A1.2) glufosinate-monoammonium salt, (A1.3) L-glufosinate (A1.4)
L-glufosinate monoammonium salt, (A1.5) bialaphos (or bilanafos) or
its sodium salt.
21. The method as claimed in claim 19, wherein the herbicide (IA)
is glufosinate-ammonium.
22. The method as claimed in claim 19, wherein the herbicidal
combination is used together with other crop protection active
ingredients additionally.
23. The method as claimed in claim 19, wherein the herbicidal
combination is used together with adjuvants and formulation
auxiliaries conventionally used in crop protection.
24. A method for controlling harmful plants in maize crops in an
area under cultivation which comprises applying an effective amount
of a herbicidal combination to the harmful plants, seeds of the
maize crops or the area or the area under cultivation, wherein said
herbicidal combination comprises a synergistically effective amount
of (IIA) one or more herbicides from the group consisting of
compounds of the formula (A2) and their salts, ##STR7## and (IIB)
one or more herbicides selected from the group consisting of (B1)
atrazine, terbuthylazine, acetochlor, metolachlor, terbutryn,
primisulfuron, dimethenamid and simazine, (B2) pyridate and
iodosulfuron, and (B3) dicamba and prosulfuron, or, where
applicable, ester or salts of these herbicides; and, optionally one
or more safeners, wherein the maize crops are tolerant to the
herbicides (A) and (B) which form a constituent of the
combination.
25. The method as claimed in claim 24, wherein the (IIA) herbicides
are selected from the group consisting of (A2.1) glyphosate acid,
(A2.2) glyphosate-monoisopropylammonium salt, (A2.3)
glyphosate-sodium salt, (A2.4) sulfosate.
26. The method as claimed in claim 24, wherein the herbicide (IIA)
is glyphosate-isopropylammonium.
27. The method as claimed in claim 24, wherein the herbicidal
combination is used together with other crop protection active
ingredients additionally.
28. The method as claimed in claim 24, wherein the herbicidal
combination is used together with adjuvants and formulation
auxiliaries conventionally used in crop protection.
29. A method for controlling harmful plants in maize crops in an
area under cultivation which comprises applying an effective amount
of a herbicidal combination to the harmful plants, seeds of the
maize crops or the area or the area under cultivation, wherein said
herbicidal combination comprises a synergistically effective amount
of (IIIA) one or more compounds from the group consisting of
herbicides of imidazolinones (A3) and salts thereof, and (IIIB) one
or more herbicides selected from the group consisting of (B1)
acetochlor, metolachlor, nicosulfuron, rimsulfuron, primisulfuron
and sulcotrione; (B2) pendimethalin, pyridate and flumetsulam and
(B3) bromoxynil, dicamba, 2,4-D, prosulfuron and thifensulfuron,
and additionally in case that (A3) is imazamethabenz, (B2)
iodosulfuron, or, where applicable, ester or salts of these
herbicides; and, optionally one or more safeners, wherein the maize
crops are tolerant to the herbicides (A) and (B) which form a
constituent of the combination.
30. The method as claimed in claim 29, wherein the (IIIA)
herbicides are selected from the group consisting of (A3.1)
imazapyr and its salts and esters, (A3.2) imazethapyr and its salts
and esters, (A3.3) imazamethabenz and its salts and esters, (A3.4)
imazamethabenz-methyl, (A3.5) imazamox and its salts and esters,
(A3.6) imazaquin and its salts and esters, (A3.7) imazapic (AC
263,222) and its salts and esters.
31. The method as claimed in claim 29, wherein the herbicidal
combination is used together with other crop protection active
ingredients additionally.
32. The method as claimed in claim 29, wherein the herbicidal
combination is used together with adjuvants and formulation
auxiliaries conventionally used in crop protection.
Description
[0001] The invention is in the field of the crop protection
products which can be employed against harmful plants in tolerant
or resistant crops of maize and which comprise, as herbicidally
active substances, a combination of two or more herbicides.
[0002] The introduction of tolerant or resistant maize varieties
and maize lines, in particular transgenic maize varieties and maize
lines, adds novel active substances which per se are not selective
in conventional maize varieties, to the conventional weed control
system. The active substances are, for example, the known
broad-spectrum herbicides such as glyphosate, sulfosate,
glufosinate, bialaphos and imidazolinone herbicides [herbicides
(A)], which can now be employed in the tolerant crops developed
specifically for them. The efficacy of these herbicides against
harmful plants in the tolerant crops is high, but
depends--similarly to other herbicide treatments--on the nature of
the herbicide employed, its application rate, the preparation in
question, the harmful plants to be controlled, the climatic
conditions, the soil conditions etc. Furthermore, the herbicides
exhibit weak points (zero effect) against specific species of
harmful plants. Another criterion is the duration of action, or the
degradation rate of the herbicide. If appropriate, changes in the
sensitivity of harmful plants, which may occur upon prolonged use
of the herbicides or within a geographical limited area, must also
be taken into consideration. The loss of action against individual
plants can only be compensated for to some extent by higher
application rates of the herbicides, if at all. Moreover, there is
always a demand for methods to achieve the herbicidal effect with
lower application rates of active substances. A lower application
rate not only reduces the amount of an active substance required
for application, but as a rule, also reduces the amount of
formulation auxiliaries required. Both reduce the economic outlay
and improve the eco-friendliness of the herbicide treatment.
[0003] One possibility for improving the use profile of a herbicide
may consist in combining the active substance with one or more
other active substances which contribute the desired additional
properties. However, the combined use of a plurality of active
substances does not infrequently lead to phenomena of a physical
and biological incompatibility, for example lacking stability of a
coformulation, decomposition of an active substance or antagonism
of the active substances. In contrast, what is desired are
combinations of active substances with a favorable profile of
action, high stability and as synergistic an increased action as
possible, which allows the application rate to be reduced in
comparison with the individual application of the active substances
to be combined.
[0004] Surprisingly, it has now been found that active substances
from the group of the abovementioned broad-spectrum herbicides (A)
in combination with other herbicides from group (A) and, if
appropriate, specific herbicides (B) interact especially favorably
when they are employed in the maize crops which are suitable for
the selective use of the first-mentioned herbicides.
[0005] The invention therefore relates to the use of herbicide
combinations for controlling harmful plants in maize crops, wherein
the herbicide combination in question has a synergistically active
content of [0006] (A) a broad-spectrum herbicide from the group of
the compounds consisting of [0007] (A1) compounds of the formula
(A1), ##STR1## [0008] in which Z is a radical of the formula --OH
or a peptide radical of the formula
--NHCH(CH.sub.3)CONHCH(CH.sub.3)COOH or [0009]
--NHCH(CH.sub.3)CONHCH[CH.sub.2CH(CH.sub.3).sub.2]COOH, and their
esters and salts, preferably glufosinate and its salts with acids
and bases, in particular glufosinate-ammonium, L-glufosinate or its
salts, bialaphos and its salts with acids and bases, and other
phosphinothricin derivatives, [0010] (A2) compounds of the formula
(A2) and their esters and salts, ##STR2## [0011] preferably
glyphosate and its alkali metal salts or salts with amines, in
particular glyphosate-isopropylammonium, and sulfosates, [0012]
(A3) imidazolinones, preferably imazethapyr, imazapyr,
imazamethabenz, imazamethabenz-methyl, imazaquin, imazamox,
imazapic (AC 263,222) and their salts and [0013] (A4) herbicidal
azoles from the protoporphyrinogen-oxidase inhibitors (PPO
inhibitors), such as WC9717 (=CGA276854), [0014] (A5)
cyclohexanedione herbicides and, if appropriate, also [0015] (A6)
heteroaryloxyphenoxypropionic acid herbicides, and [0016] (B) one
or more herbicides from the group of the compounds which consists
of [0017] (B0) one or more structurally different herbicides from
the abovementioned group (A) and/or [0018] (B1) foliar- and
soil-acting herbicides which are effective against monocotyledonous
and dicotyledonous harmful plants, and/or [0019] (B2) herbicides
which can be employed selectively in maize against dicots, and/or
[0020] (B3) foliar- and soil-active herbicides which can be
employed selectively in maize, predominantly against dicotyledonous
harmful plants, and the maize crops are tolerant to the herbicides
(A) and (B) which form a constituent of the combination, if
appropriate in the presence of safeners.
[0021] "Structurally different herbicides from the abovementioned
group (A)" in group (B0) only include herbicides which are covered
by the definition of group (A), but which are not component (A) in
the combination in question.
[0022] In addition to the herbicide combinations according to the
invention, other crop protection active substances and adjuvants
and formulation auxiliaries conventionally used in crop protection
may be used.
[0023] The synergistic effects are observed when the active
substances (A) and (B) are applied together, but can also be
observed upon split application (splitting). Another possibility is
to apply the herbicides or herbicide combinations in several
portions (sequential application), for example after pre-emergence
applications, followed by post-emergence applications or after
early postemergence applications, followed by applications at
medium or late post-emergence. Preferred is the simultaneous
application of the active substances of the combination in
question, if appropriate in several portions. However, a staggered
application of the individual active substances of a combination is
also possible and may be advantageous in individual cases. Other
crop protection agents such as fungicides, insecticides, acaricides
and the like, and/or different auxiliaries, adjuvants and/or
fertilizer applications may also be integrated into this system
application.
[0024] The synergistic effects allow the application rates of the
individual active substances to be reduced, a more potent action
against the same species of harmful plant combined with the same
application rate, the control of species to which the action has
hitherto not extended (zero effect), an extended application period
and/or a reduced number of required individual applications and--as
a result for the user--economical and ecologically more
advantageous weed control systems.
[0025] For example, the combinations of (A)+(B) according to the
invention allow synergistically increased effects which far and
unexpectedly exceed the effects which can be achieved with the
individual active substances (A) and (B).
[0026] WO-A-98/09525 has already described a method of controlling
weeds in transgenic crops which are resistant to
phosphorus-containing herbicides such as glufosinate or glyphosate,
herbicide combinations being employed which comprise glufosinate or
glyphosate and at least one herbicide from the group consisting of
prosulfuron, primisulfuron, dicamba, pyridate, dimethenamid,
metolachlor, flumeturon, propaquizafop, atrazine, clodinafop,
norflurazone, ametryn, terbuthylazine, simazine, prometryn,
NOA-402989 (3-phenyl-4-hydroxy-6-chloropyridazine), a compound of
the formula ##STR3## in which
R=4-chloro-2-fluoro-5-(methoxycarbonylmethylthio)phenyl (disclosed
in U.S. Pat. No. 4,671,819),
CGA276854=1-allyloxycarbonyl-1-methylethyl
2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-
-1-yl)-benzoate (=WC9717, disclosed in U.S. Pat. No. 5,183,492) and
4-oxetanyl
2{N-[N-(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]aminosulfonyl}benzoate
(disclosed in EP-A-496701). Details on the obtainable effects, or
effects which have been obtained, cannot be found in the
publication WO-A-98/09525. There are no examples on synergistic
effects or on carrying out the method in specific crops, nor are
there specific combinations of two, three or more herbicides.
[0027] DE-A-2856260 has already disclosed a few herbicide
combinations with glufosinate or L-glufosinate and other herbicides
such as alloxidim, linuron, MCPA, 2,4-D, dicamba, triclopyr,
2,4,5-T, MCPB and others.
[0028] Some herbicide combinations with glufosinate or glyphosate
and other herbicides from the sulfonylurea series such as
metsulfuron-methyl, nicosulfuron, primisulfuron, rimsulfuron and
the like have already been disclosed in WO-A-92/083 53 and EP-A 0
252 237.
[0029] However, the use of the combinations for controlling harmful
plants has been shown in the publications only with reference to a
few plants species or else with reference to no example.
[0030] In our experiments, it has been found, surprisingly, that
there exist large differences between the usefulness of the
herbicide combinations mentioned in WO-A-98/09525 and in the other
references and also of other novel herbicide combinations in crops
of plants.
[0031] According to the invention, herbicide combinations which can
be employed particularly advantageously in tolerant maize crops are
provided.
[0032] The compounds of the formulae (A1) to (A5) are known or can
be prepared analogously to known processes.
[0033] Formula (A1) encompasses all stereoisomers and their
mixtures, in particular the racemate and the particular enantiomer
which has a biological action, for example L-glufosinate and its
salts. Examples of active substances of the formula (A1) are the
following: [0034] (A1.1) glufosinate in the narrow sense, i.e.
D,L-2-amino-4-[hydroxy(methyl)phosphinyl]butanoic acid, [0035]
(A1.2) glufosinate-monoammonium salt, [0036] (A1.3) L-glufosinate,
L- or (2S)-2-amino-4-[hydroxy(methyl)phosphinyl]butanoic acid
(=phosphinothricin), [0037] (A1.4) L-glufosinate monoammonium salt,
[0038] (A1.5) bialaphos (or bilanafos), i.e.
L-2-amino-4-[hydroxy-(methyl)phosphinyl]butanoyl-L-alanyl-L-alanine,
in particular its sodium salt.
[0039] The abovementioned herbicides (A1.1) to (A1.5) are absorbed
via the green parts of the plants and are known as broad-range
herbicides or total herbicides; they are inhibitors of the enzyme
glutamine synthetase in plants; see "The Pesticide Manual" 11th
Edition, British Crop Protection Council 1997, pp. 643-645 and
120-121. While they can be employed post-emergence for controlling
broad-leaved weeds and grass weeds in plantation crops and on
non-crop area and, using specific application techniques, also for
the in-between-rows treatment of agricultural ground crops such as
maize, cotton and the like, the importance of use as selective
herbicides in resistant transgenic crops of plants is
increasing.
[0040] Glufosinate is usually employed in the form of a salt,
preferably of the ammonium salt. The racemate of glufosinate, or
glufosinate-ammonium, alone is usually applied at rates between 200
and 2000 g of a.s./ha (=g of a.i./ha=grams of active substance per
hectare). At such rates, glufosinate is effective mainly when taken
up via the green parts of the plants. However, since it is degraded
microbially in the soil within a few days, it has no long-term
action in the soil. The same also applies to the related active
substance bialaphos sodium (also termed bilanafos-sodium); see "The
Pesticide Manual" 11th Ed., British Crop Protection Council 1997
pp. 120-121. As a rule, markedly less active substance (A1), for
example an application rate in the range of 20 to 800, preferably
20 to 600, grams of active substance of glufosinate per hectare (g
of a.s./ha or g of a.i./ha) is required in the combinations
according to the invention. Similar amounts, preferably amounts
which have been converted into moles per hectare, also apply to
glufosinate-ammonium and bialafos, or bialafos-sodium.
[0041] The combinations with the foliar-acting herbicides (A1) are
expediently employed in maize crops which are resistant or tolerant
to the compounds (A1). Some tolerant maize crops which have been
generated by genetic engineering, are already known and are
employed in practice; cf. the article in the journal "Zuckerrube"
[Sugarbeet], year 47 (1998), p. 217 et seq.; for the generation of
transgenic plants which are resistant to glufosinate, cf.
EP-A-0242246, EP-A-242236, EP-A-257542, EP-A-275957,
EP-A-0513054).
[0042] Examples of compounds (A2) are [0043] (A2.1) glyphosate,
i.e. N-(phosphonomethyl)glycine, [0044] (A2.2)
glyphosate-monoisopropylammonium salt, [0045] (A2.3)
glyphosate-sodium salt, [0046] (A2.4) sulfosate, i.e.
N-(phosphonomethyl)glycine-trimesium
salt=N-(phosphonomethyl)glycine-trimethylsulfoxonium salt.
[0047] Glyphosate is usually employed in the form of a salt,
preferably of the monoisopropylammonium salt or the
trimethylsulfoxonium salt (=trimesium salt=sulfosate). Based on the
free acid glyphosate, the single dose is in the range of 0.5-5 kg
of a.s./ha. Glyphosate is similar to glufosinate with regard to
certain applications, but, in contrast to the latter, it is an
inhibitor of the enzyme 5-enolpyruvylshikimate-3-phosphate synthase
in plants; see "The Pesticide Manual" 11th Ed., British Crop
Protection Council 1997 pp. 646-649. In the combinations according
to the invention, application rates in the range of 20 to 1000,
preferably 20 to 800, g of a.s. glyphosate are, as a rule, required
per ha.
[0048] Also, tolerant plants generated by genetic engineering are
known for compounds (A2) and have been introduced into practice;
cf. "Zuckerrube" year 47 (1998), p. 217 et seq.; cf. also WO
92/00377, EP-A-115673, EP-A409815.
[0049] Examples of imidazolinone herbicides (A3) are [0050] (A3.1)
imazapyr and its salts and esters, [0051] (A3.2) imazethapyr and
its salts and esters, [0052] (A3.3) imazamethabenz and its salts
and esters, [0053] (A3.4) imazamethabenz-methyl, [0054] (A3.5)
imazamox and its salts and esters, [0055] (A3.6) imazaquin and its
salts and esters, for example the ammonium salt, [0056] (A3.7)
imazapic (AC 263,222) and its salts and esters, for example the
ammonium salt.
[0057] The herbicides inhibit the enzyme acetolactate synthase
(ALS) and thus the protein synthesis in plants; they are both
soil-acting and foliar-acting and, in some cases, show
selectivities in crops; cf. "The Pesticide Manual" 11th Ed.,
British Crop Protection Council 1997 pp. 697-699 for (A3.1), pp.
701-703 for (A3.2), pp. 694-696 for (A3.3) and (A3.4), pp. 696-697
for (A3.5), pp. 699-701 for (A3.6) and pp. 5 and 6, reviewed as AC
263,222 (for A3.7). The application rates of the herbicides are
usually between 0.001 and 2 kg of a.s./ha. In the combinations
according to the invention, they are in the range of 10 to 200 g of
a.s./ha.
[0058] The combinations with imidazolinones are expediently
employed in maize crops which are resistant to the imidazolinones.
Such tolerant crops are already known. EP-A-0360750, for example,
describes the generation of ALS-inhibitor-tolerant plants by
selection methods or genetic engineering methods. The herbicide
tolerance of the plants is generated by means of an elevated ALS
content in the plants. U.S. Pat. No. 5,198,599 describes
sulfonylurea- and imidazolinone-tolerant plants which have been
obtained by selection methods.
[0059] Examples of PPO inhibitors (A4) are: [0060] (A4.1)
pyraflufen and its esters, such as pyraflufen-ethyl, [0061] (A4.2)
carfentrazone and its esters, such as carfentrazone-ethyl, [0062]
(A4.3) oxadiargyl [0063] (A4.4) sulfentrazone [0064] (A4.5) WC9717
or CGA276854=1-allyloxycarbonyl-1-methylethyl
2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-
-1-yl)benzoate (disclosed in U.S. Pat. No. 5,183,492).
[0065] The abovementioned azoles are known as inhibitors of the
enzyme protoporphyrinogen oxidase (PPO) in plants; see "The
Pesticide Manual" 11th Ed., British Crop Protection Council 1997
pp. 1048-1049 for (A4.1), pp. 191-193 for (A4.2), pp. 904-905 for
(A4.3) and pp. 1126-1127 for (A4.4). Tolerant crops of plants have
already been described. As a rule, the application rates of the
azoles are in the range of 5 to 200 g of a.s./ha.
[0066] Some plants which are tolerant to PPO inhibitors are already
known.
[0067] Examples of cyclohexanedione herbicides (A5) are: [0068]
(A5.1) sethoxydim ("The Pesticide Manual" 11th Ed., British Crop
Protection Council 1997 (termed "PM" hereinbelow, pp 1101-1103),
i.e.
(E,Z)-2-(1-ethoxyiminobutyl)-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2--
enone, [0069] (A5.2) cycloxydim (PM, pp. 290-291), i.e.
2-(1-ethoxyiminobutyl)-3-hydroxy-5-thian-3-ylcyclohex-2-enone,
[0070] (A5.3) clethodim (PM, pp. 250-251), i.e.
2{(E)1-[(E)-3-chloroallyloxyimino]propyl}5-[-2(ethylthio)-propyl]-3-hydro-
xycyclohex-2-enone, [0071] (A5.4) "clefoxidim" or "BAS 625H" (see
AG Chem New Compound Review, Vol. 17, 1999, pp. 26, edited by
AGRANOVA)
(=2-[1-2-(4-chlorophenoxy)propoxyimino)butyl]-3-oxo-5-thion-3-yl-cyclohex-
-1-enol), [0072] (A5.5) tralkoxidim (PM, pp. 1211-1212), i.e.
2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-enone.
[0073] The herbicides inhibit mitosis and thus the fatty acid
synthesis in plants; in particular, they are foliar-acting and, in
some cases, they exhibit selectivities in crops. The application
rates of the herbicides are usually between 0.2 and 1 kg of
a.s./ha. In the combinations according to the invention, they are
in the range of 10 to 1000 g of a.s./ha. The combinations with
cyclohexanediones are expediently employed in maize crops which are
resistant to the cyclohexanediones. Such tolerant crops are already
known.
[0074] Examples of heteroarylphenoxyphenoxypropionic acid
herbicides (A6) are: [0075] (A6.1) "fenoxaprop-P" and its esters,
such as the ethyl ester "fenoxaprop-P-ethyl" (see PM, pp. 519-520)
(=(R)-2-[4-(6-chlorobenzoxyzolyl-2-yloxy)-phenoxy]propionic acid
and its ethyl ester), also in the use form of the racemate
ufenoxapropn and its esters, such as the ethyl ester, and/or [0076]
(A6.2) "quizalofop-P" and its esters, such as the ethyl or tefuryl
ester (see PM, pp. 1089-1092)
(=(R)-2-[4-(6-chloroquinoxalin-2-yloxy)phenoxy]propionic acid or
its ethyl ester or its tetrahydrofurfuryl ester), also in the form
of the racemate "quizalofop" and its esters; cf. also as the
specific ester "propaquizafop" (compound A6.3) and/or [0077] (A6.3)
"propaquizafop" (PM, pp. 1021-1022), the
2-isopropylideneamino-oxyethyl ester of quizalofop-P, and/or [0078]
(A6.4) "fluazifop-P" and its esters, such as the butyl ester (see
PM, pp. 556-557)
(=(R)-2-[4-(5-trifluoromethylpyrid-2-yloxy)-phenoxy]propionic acid
or its butyl ester), also in the use form of the racemate
"fluazifop" and its ester, and/or [0079] (A6.5) "haloxyfop-P" and
its esters, such as the methyl ester (see PM, pp. 660-663)
(=(R)-2-[4-(3-chloro-5-trifluoromethylpyrid-2-yl-oxy)phenoxy]propionic
acid or its methyl ester), also in the use form of the racemate
"haloxyfop" and its esters, such as the methyl or the etotyl ester
and/or [0080] (A6.6) "cyhalofop" and its esters, such as the butyl
ester (PM, pp. 297-298)
(=(R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propionic acid or its
butyl ester and/or [0081] (A6.7) "clodinafop" and its esters, such
as the propargyl ester (PM, pp. 251-252)
(=(R)-2-[4-(5-chloro-3-fluoropyrid-2-yloxy)phenoxy]propionic acid
or its propargyl ester).
[0082] The herbizides (A6) are known as inhibitors of fatty acid
biosynthesis and are usually employed at application rates of 5-500
g of a.s./ha. The application rate in the combinations according to
the invention may be even lower in some cases, for example 1 to 300
g of a.s./ha. The combinations with the herbicides (A6) are
expediently employed in maize crops which are tolerant to the
herbicides; for example, in practice, this is also the case in
those crops which are tolerant to cyclohexanedione herbicides
(A5).
[0083] Examples of suitable components (B) are compounds of
subgroups (B1) to (B4): [0084] (B1) Herbicides which are not only
foliar-acting, but also soil-acting, and which can be employed
selectively in maize against grasses and dicots, for example the
following compounds (of which the common name and the reference in
"The Pesticide Manual" 11th Ed., British Crop Protection Council
1997, abbreviated to "PM"), is given: [0085] (B1.1) cyanazine (PM,
pp. 280-283), i.e.
2-(4-chloro-6-ethylamino-1,3,5-triazin-2-ylamino)-2-methylpropionitrile,
[0086] (B1.2) atrazine (PM, pp. 55-57), i.e.
N-ethyl-N'-isopropyl-6-chloro-2,4-diamino-1,3,5-triazine, [0087]
(B1.3) terbuthylazine (PM, pp. 1168-1170), i.e.
N-ethyl-N'-tert-butyl-6-chloro-2,4-diamino-1,3,5-triazine, [0088]
(B1.4) acetochlor (PM, pp. 10-12), i.e.
2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide,
[0089] (B1.5) metolachlor (PM, pp. 833-834), i.e.
2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)-acetamide-
, [0090] (B1.6) alachlor (PM, pp. 23-24), i.e.
2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide, [0091]
(B1.7) terbutryn (PM, pp. 1170-1172), i.e.
N-(1,1-dimethylethyl)-N'-ethyl-6-methylthio-2,4-diamino-1,3,5-triazine,
[0092] (B1.8) benoxacor (PM, pp. 102-103), i.e.
4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine, [0093]
(B1.9) nicosulfuron (PM, pp. 877-879), i.e.
2-(4,6-dimethoxypyrimidin-2-yl)-3-(3-dimethylcarbamoyl-2-pyridylsulfonyl)-
urea, [0094] (B1.10) rimsulfuron (PM, pp. 1095-1097), i.e.
1-(4,6-dimethoxypyrimidin-2-yl)-3-(3-ethylsulfonyl-2-pyridylsulfonyl)-ure-
a, [0095] (B1.11) primisulfuron and its esters, such as the methyl
ester (PM, pp. 997-999), i.e.
2-[4,6-bis(difluoromethoxy)pyrimidin-2-ylcarbamoylsulfamoyl]benzoic
acid or its methyl ester, [0096] (B1.12) dimethenamid (PM, pp.
409-410), i.e.
2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)aceta-
mide, [0097] (B1.13) fluthiamide (BAY FOE 5043, flufenacet) (PM,
pp. 82-83), i.e.
4'-fluoro-N-isopropyl-2-(5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy)aceta-
nilide, [0098] (B1.14) sulcotrione (PM, pp. 1124-1125), i.e.
2-(2-chloro-4-mesylbenzoyl)cyclohexane-1,3-dione, [0099] (B1.15)
simazin (PM, pp. 1106-1108), i.e.
6-chloro-N,N'-diethyl-2,4-diamino-1,3,5-triazine, [0100] (B1.16)
mesotrione, i.e. 2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione
(ZA1296, cf. Weed Science Society of America (WSSA) in WSSA
Abstracts 1999, Vol. 39, pages 65-66, numbers 130-132), [0101]
(B1.17) penthoxamid, i.e.
2-chloro-N-(2-ethoxyethyl)-N-(2-methyl-1-phenyl-1-propenyl)acetamide
(TKC-94, known from AG Chem New Compound, Review Vol. 17 (1999),
EP-A-206 251), and, if active substances from group (B1) are
present as racemic mixtures, preferably also the particular active
compounds in the form of the pure or enriched active isomer, [0102]
(B2) herbicides which can be employed selectively in maize against
dicots, for example the compounds [0103] (B2.1) pendimethalin (PM,
pp. 937-939), i.e. N-(1-ethylpropyl)-2,6-dinitro-3,4-xylidine,
[0104] (B2.2) pyridate (PM, pp. 1064-1066), i.e.
6-chloro-3-phenylpyridazin-4-yl S-octyl thiocarbonate, [0105]
(B2.3) iodosulfuron (proposed common name) and, preferably, the
methyl ester (cf. WO 96/41537), i.e.
4-iodo-2-(4-methoxy-6-methyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl)benzoic
acid or the methyl ester, disclosed in WO-A-92/13845, [0106] (B2.4)
metosulam (PM, pp. 836-495), i.e.
2',6'-dichloro-5,7-dimethoxy-3'-methyl-[1,2,4]triazolo[1,5a]pyrimidine-2--
sulfonanilide, [0107] (B2.5) isoxaflutole (PM, pp. 737-739), i.e.
(5-cyclopropyl-4-isoxazolyl)[2-(methylsulfonyl)-4-(trifluoromethyl)phenyl-
]-methanone, [0108] (B2.6) metribuzin (PM, pp.
4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one, [0109]
(B2.7) cloransulam and, preferably, the methyl ester (PM, p. 165),
i.e.
3-chloro-2-(5-ethoxy-7-fluoro-[1,2,4]triazolo-[1,5-6]pyrimidin-2-ylsulfon-
amido)benzoic acid or its methyl ester, [0110] (B2.8) flumetsulam
(PM, pp. 573-574), i.e.
2',6'-dichloro-5-methyl-[1,2,4]triazolo[1,5a]pyrimidine-2-sulfonanilide
and [0111] (B2.9) linuron (PM, pp. 751-753), i.e.
3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea and [0112] (B2.10)
florasulam, i.e.
N-(2,6-difluorophenyl)-8-fluoro-5-methoxy-1,2,4-triazolo[1,5C]-pyrimidine-
-2-sulfonamide (DE-570, cf. Zeitschrift Pfl. Krankh. PflSchutz,
Special Issue XVI, 527-534 81998), [0113] (B2.11) isoxachlortole,
i.e. (4-chloro-2-(methylsulfonyl)phenyl) 5-cyclopropyl-4-isoxazolyl
ketone, EP-A-470856) and, if abovementioned active substances from
group (B2) exist as racemic mixtures, preferably also the
particular active substance in the form of the pure or enriched
effective isomer, [0114] (B3) herbicides which are foliar-acting
and soil-acting and which can be employed selectively in maize,
predominantly against dicotyledonous harmful plants, for example
the compounds: [0115] (B3.1) bromoxynil (PM, pp. 149-151), i.e.
3,5-dibromo-4-hydroxybenzonitrile, [0116] (B3.2) dicamba (PM, pp.
356-357), i.e. 3,6-dichloro-o-anisic acid and its salts, [0117]
(B3.3) 2,4-D (PM, pp. 323-327), i.e. 2,4-dichlorophenoxyacetic acid
and its salts and esters, [0118] (B3.4) clopyralid (PM, pp.
260-263), i.e. 3,6-dichloro-2-pyridinecarboxylic acid and its salts
and esters, [0119] (B3.5) prosulfuron (PM, pp. 1041-1043), i.e.
1-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-3-[2-(3,3,3-trifluoropropyl)phe-
nylsulfonyl]urea, [0120] (B3.6) thifensulfuron and its esters,
preferably the methyl ester (PM, pp. 1188-1190), i.e.
3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfony-
l]-2-thiophenecarboxylic acid or its methyl ester, [0121] (B3.7)
carfentrazone and its salts and esters, preferably the ethyl ester
(PM, pp. 191-193), i.e.
2-chloro-3-[2-chloro-5-(difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,-
4-triazol-1-yl).sub.4-fluorophenyl]propionic acid and its ethyl
ester, [0122] where combinations with compound (A4.2) according to
the definition do not constitute herbicide combinations of
different herbicide active substances A and B and are therefore
excepted, [0123] (B3.8) Lab271272 (=tritosulfuron, CAS Reg. No.
142469-14-5; see AG Chem New Compound Review, Vol. 17, 1999, p. 24,
edited by AGRANOVA), i.e.
N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl)amino]-carbonyl]-2--
(trifluoromethyl)benzenesulfonamide), and [0124] (B3.9) MCPA (PM,
pp. 767-769), i.e. (4-chloro-2-methylphenoxy)acetic acid, and its
salts and esters, [0125] (B3.10) halosulfuron and its esters, such
as the methyl ester (PM, p. 657-659), i.e. methyl
3-chloro-5-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-1-methylpyrazo-
lecarboxylate, also in its salt form, [0126] (B3.11) diflufenzopyr
(BASF 654 00H) (PM, pp. 81-82), i.e.
2-{1-[4-(3,5-difluorophenyl)semi-carbazone]ethyl}nicotinic acid,
and its salts, [0127] (B3.12) sulfosulfuron (PM, pp. 1130-1131),
i.e.
1-(4,6-dimethoxypyrimidin-2-yl)-3-(2-ethylsulfonylimidazo[1,2-a]-pyridin--
3-ylsulfonyl)urea [0128] and, if abovementioned active substances
from group (B3) exist as racemic mixtures, preferably also the
particular active compound in the form of the pure or enriched
effective isomer.
[0129] In the case of active substances based on carboxylic acids
or other active substances which form salts or esters, the
specification of the herbicides by the common name of the acid is
also intended to encompass the salts and esters, preferably the
commercially available salts and esters, in particular the current
commercial form of the active substance.
[0130] The application rates of the herbicides (B) may vary greatly
from herbicide to herbicide. The following ranges are rules of
thumb: [0131] Compounds (B0): 1-3000 g a.s./ha, preferably 5-2000 g
a.s./ha (cf. the information on the group of the compounds (A)),
[0132] Compounds (B1): 0.1-5000 g a.s./ha, preferably 1-5000 g
a.s./ha, [0133] Compounds (B2): 0.1-5000 g a.s./ha, preferably
1-3000 g a.s./ha [0134] Compounds (B3): 0.5-5000 g a.s./ha,
preferably 1-3000 g a.s./ha
[0135] The following specific application rates are preferred (in g
of a.s./ha):
(B1.1) to (B1.8) 100-5000 g, preferably 200-4000, in particular
300-3500,
(B1.9) to (B1.11) 0.1-120, preferably 1-90,
(B1.12) 50-5000, preferably 1004000, in particular 300-3500,
(B1.13) 100-2000, preferably 200-1500, in particular 300-1200,
(B1.14) 50-1000, preferably 100-600, in particular 200-500,
(B1.15) 100-5000, preferably 200-4000, in particular 300-3500,
(B1.16) 10-500, preferably 25-300, in particular 50-200,
(B1.17) 5-1500, preferably 10-1000, in particular 20-800,
(B2.1) 100-3000, preferably 200-2500, in particular 300-2000,
(B2.2) 100-2500, preferably 200-2000, in particular 300-1500,
(B2.3) 0.1-100, preferably 0.2-20, in particular 0.5-15,
(B2.4) 1-200, preferably 5-150, in particular 10-100,
(B2.5) 5-300, preferably 10-200, in particular 20-150,
(B2.6) 10-1500, preferably 25-1000, in particular 50-800,
(B2.7) 2-200, preferably 2.5-100, in particular 5-80,
(B2.8) 5-500, preferably 10-300, in particular 20-200,
(B2.9) 50-2500, preferably 100-2000, in particular 200-1000,
(B2.10) 0.5-100, preferably 1-20, in particular 3-15,
(B2.11) 5-300, preferably 10-200, in particular 20-150,
(B3.1) 50-1000, preferably 100-600, in particular 200-500,
(B3.2) 5-2500, preferably 10-2000, in particular 200-1500,
(B3.3) 50-3000, preferably 100-2000, in particular 200-1500,
(B3.4) 10-300, preferably 20-250, in particular 40-200,
(B3.5) 1-100, preferably 2-70, in particular 5-50,
(B3.6) 0.5-100, preferably 1-50, in particular 240,
(B3.7) 1-250, preferably 5-120, in particular 10-100,
(B3.8) 1-200, preferably 5-150, in particular 10-120,
(B3.9) 50-3000, preferably 100-2000, in particular 200-1500,
(B3.10) 1-200, preferably 5-150, in particular 10-50,
(B3.11) 5-1000, preferably 10-500, in particular 20-80,
(B3.12) 1-150, preferably 5-100, in particular 5-80.
[0136] The ratios of compounds (A) and (B) can be deduced from the
abovementioned application rates for the individual substances, for
example the following ratios are of particular interest: [0137]
(A):(B) in the range of 18,000:1 to 1:5000, preferably 2000:1 to
1:1000, in particular 200:1 to 1:100, [0138] (A):(B0) in the range
of 1000:1 to 1:400, preferably 400:1 to 1:400, in particular 200:1
to 1:200, [0139] (A1):(B1) in the range of 1500:1 to 1:300,
preferably 400:1 to 1:250, in particular 200:1 to 1:100, [0140]
(A1):(B2) in the range of 10,000:1 to 1:300, preferably 1500:1 to
1:250, in particular 1000:1 to 1:100, particularly preferably 200:1
to 1:100, [0141] (A1):(B3) in the range of 2000:1 to 1:300,
preferably 1500:1 to 1:250, in particular 200:1 to 1:100, [0142]
(A2):(B1) in the range of 2500:1 to 1:100, preferably 2000:1 to
1:50, in particular 300:1 to 1:20, [0143] (A2):(B2) in the range of
18,000:1 to 1:100, preferably 2000:1 to 1:50, in particular 300:1
to 1:20, [0144] (A2):(B3) in the range of 3000:1 to 1:100,
preferably 2000:1 to 1:50, in particular 300:1 to 1:20, [0145]
(A3):(B1) in the range of 1000:1 to 1:1000, preferably 200:1 to
1:500, in particular 100:1 to 1:200, [0146] (A3):(B2) in the range
of 5000:1 to 1:1000, preferably 800:1 to 1:500, in particular 200:1
to 1:500, particularly preferably 100:1 to 1:200, [0147] (A3):(B3)
in the range of 500:1 to 1:800, preferably 200:1 to 1:500, in
particular 100:1 to 1:200, [0148] (A4):(B1) in the range of 1000:1
to 1:5000, preferably 200:1 to 1:1000, in particular 100:1 to
1:250, [0149] (A4):(B2) in the range of 10,000:1 to 1:5000,
preferably 2000:1 to 1:1000, in particular 1000:1 to 1:400, in
particular 500:1 to 1:250, [0150] (A4):(B3) in the range of 1000:1
to 1:2000, preferably 200:1 to 1:1000, in particular 100:1 to
1:250, [0151] (A5):(B1) in the range of 1500:1 to 1:1000,
preferably 1000:1 to 1:500, in particular 200:1 to 1:100, [0152]
(A5):(B2) in the range of 10,000:1 to 1:2000, preferably 1000:1 to
1:500, in particular 200:1 to 1:100, [0153] (A5):(B3) in the range
of 1500:1 to 1:1000, preferably 1000:1 to 1:500, in particular
200:1 to 1:100, [0154] (A6):(B1) in the range of 2000:1 to 1:2000,
preferably 1000:1 to 1:1000, in particular 200:1 to 1:200, [0155]
(A6):(B2) in the range of 5000:1 to 1:2000, preferably 2000:1 to
1:1000, in particular 200:1 to 1:100, [0156] (A6):(B3) in the range
of 1000:1 to 1:1000, preferably 500:1 to 1:500, in particular 100:1
to 1:100.
[0157] The use of the following combinations is of particular
interest:
[0158] (A1.1)+(B1.1), (A1.1)+(B1.2), (A1.1)+(B1.3), (A1.1)+(B1.4),
(A1.1)+(B1.5), (A1.1)+(B1.6), (A1.1)+(B1.7), (A1.1)+(B1.8),
(A1.1)+(B1.9), (A1.1)+(B1.10), (A1.1)+(B1.11), (A1.1)+(B1.12),
(A1.1)+(B1.13), (A1.1)+(B1.14), (A1.1)+(B1.15), (A1.1)+(B1.16),
(A1.1)+(B.17),
[0159] (A1.2)+(B1.1), (A1.2)+(B1.2), (A1.2)+(B1.3), (A1.2)+(B1.4),
(A1.2)+(B1.5), (A1.2)+(B1.6), (A1.2)+(B1.7), (A1.2)+(B1.8),
(A1.2)+(B1.9), (A1.2)+(B1.10), (A1.2)+(B1.11), (A1.2)+(B1.12),
(A1.2)+(B1.13), (A1.2)+(B1.14), (A1.2)+(B.1.15), (A1.2)+(B.1.16),
(A1.2)+(B1.17),
(A1.1)+(B2.1), (A1.1)+(B2.2), (A1.1)+(B2.3), (A1.1)+(B2.4),
(A1.1)+(B2.5), (A1.1)+(B2.6), (A1.1)+(B2.7), (A1.1)+(B2.8),
(A1.1)+(B2.9), (A1.1)+(B2.10), (A1.1)+(B2.11),
(A1.2)+(B2.1), (A1.2)+(B2.2), (A1.2)+(B2.3), (A1.2)+(B2.4),
(A1.2)+(B2.5), (A1.2)+(B2.6), (A1.2)+(B2.7), (A1.2)+(B2.8),
(A1.2)+(B2.9),
(A.1.2)+(B2.10), (A1.2)+(B2.11),
(A1.1)+(B3.1), (A1.1)+(B3.2), (A1.1)+(B3.3), (A11.1)+(B3.4),
(A1.1)+(B3.5), (A1.1)+(B3.6), (A1.1)+(B3.7), (A1.1)+(B3.8),
(A1.1)+(B3.9), (A1.1)+(B3.10), (A1.1)+(B3.11), (A1.1)+(B3.12),
(A1.1)+(B3.13),
(A1.2)+(B3.1), (A1.2)+(B3.2), (A1.2)+(B3.3), (A1.2)+(B3.4),
(A1.2)+(B3.5), (A1.2)+(B3.6), (A1.2)+(B3.7), (A1.2)+(B3.8),
(A1.2)+(B3.9), (A.1.2)+(B3.10), (A1.2)+(B3.11), (A1.2)+(B3.12),
(A1.2)+(B3.13),
[0160] (A2.2)+(B1.1), (A2.2)+(B1.2), (A2.2)+(B1.3), (A2.2)+(B1.4),
(A2.2)+(B1.5), (A2.2)+(B1.6), (A2.2)+(B1.7), (A2.2)+(B1.8),
(A2.2)+(B1.9), (A2.2)+(B1.10), (A2.2)+(B1.11), (A2.2)+(B1.12),
(A2.2)+(B1.13), (A2.2)+(B1.14), (A2.2)+(B1.15), (A2.2)+(B1.16),
(A2.2)+(B1.17),
(A2.2)+(B2.1), (A2.2)+(B2.2), (A2.2)+(B2.3), (A2.2)+(B2.4),
(A2.2)+(B2.5), (A2.2)+(B2.6), (A2.2)+(B2.7), (A2.2)+(B2.8),
(A2.2)+(B2.9), (A2.2)+(B2.10), (A2.2)+(B2.11),
(A2.2)+(B3.1), (A2.2)+(B3.2), (A2.2)+(B3.3), (A2.2)+(B3.4),
(A2.2)+(B3.5), (A2.2)+(B3.5), (A2.2)+(B3.6), (A2.2)+(B3.7),
(A2.2)+(B3.8), (A2.2)+(B3.9), (A2.2)+(B3.10), (A2.2)+(B3.11),
(A2.2)+(B3.12), (A2.2)+(B3.13).
[0161] In the case of the combination of a compound (A) with one or
more compounds (B0), this is, according to the definition, a
combination of two or more compounds from group (A). Because of the
broad-spectrum herbicides (A), the condition for such a combination
is that the transgenic plants or mutants show cross-resistance to
various herbicides (A). Such cross-resistances in transgenic plants
have already been disclosed; cf. WO-A-98/20144.
[0162] In individual cases, it may be meaningful to combine one or
more of the compounds (A) with more than one compound (B),
preferably from amongst classes (B1), (B2) and (B3).
[0163] Moreover, the combinations according to the invention can be
employed together with other active substances, for example from
the group of the safeners, fungicides, insecticides and plant
growth regulators, or from the group of the additives and
formulation auxiliaries conventionally used in crop protection.
[0164] Additives are, for example, fertilizers and colors.
[0165] Preferred are herbicide combinations of one or more
compounds (A) with one or more compounds from the group (B1) or
(B2) or (B3).
[0166] Also preferred are combinations of one or more compounds
(A), for example (A1.2)+(A2.2), preferably of a compound (A), with
one or more compounds (B) as shown in the scheme:
(A)+(B1)+(B2), (A)+(B1)+(B3), (A)+(B2)+(B3).
[0167] Combinations to which one or more other active substances of
a different structure [active substances (C)] are added are also
according to the invention, for example
(A)+(B1)+(C), (A)+(B2)+(C) or (A)+(B3)+(C),
(A)+(B1)+(B2)+(C) or (A)+(B1)+(B3)+(C) or (A)+(B2)+(B3)+(C).
[0168] The preferred conditions illustrated hereinbelow also apply
to combinations of the last-mentioned type with three or more
active substances, in particular to two-way-combinations according
to the invention, mainly when they contain the two-way-combinations
according to the invention. Preferred active substances (C) are
those which show a safener effect on the maize crop, specifically
safeners which, in combination with the herbicides (B) reduce or
avoid phythotoxic side-effects of the herbicides in maize
plants.
[0169] The use according to the invention of the combinations with
one or more herbicides from the group (A), preferably (A1.2) or
(A2.2), in particular (A1.2), and with one or more herbicides,
preferably one herbicide, from the group mentioned hereinbelow is
also of particular interest:
(B1') cyanazine, acetochlor, alachlor, terbutryn, benoxacor,
fluthiamide, sulcotrione, mesotrione and penthoxamid or
(B2') pendimethalin, iodosulfuron, metosulam, isoxaflutole,
metribuzin, cloransulam, flumetsulam and also florasulam and
isoxachlortole or
(B3') bromoxynil, clopyralid, carfentrazone and Lab271272 and also
halosulfuron, diflufenzopyr and sulfosulfuron, or
herbicides of more than one of groups (B1') to (B3').
[0170] Preferred are the combinations of the particular component
(A) with one or more herbicides of group (B1'), (B2') or (B3').
[0171] Also preferred are the combinations (A)+(B1')+(B2'),
(A)+(B1')+(B3') or (A)+(B2')+(B3').
[0172] The combinations according to the invention (=herbicidal
compositions) have an outstanding herbicidal activity against a
broad spectrum of economically important monocotyledonous and
dicotyledonous harmful-plants. The active substances also act
efficiently on perennial weeds which produce shoots from rhizomes,
rootstocks or other perennial organs and which are difficult to
control. In this context, it does not matter whether the substances
are applied before sowing, pre-emergence or post-emergence.
Postemergence application, or early post-sowing pre-emergence
application, is preferred.
[0173] Specifically, examples may be mentioned of some
representatives of the monocotyledonous and dicotyledonous weed
flora which can be controlled by the compounds according to the
invention, without the enumeration being a restriction to certain
species. Examples of weed species on which the herbicidal
compositions act efficiently are, from amongst the monocots,
Echinochloa spp., Setaria spp., Digitaria spp., Brachiaria spp.,
Panicum spp., Agropyron spp., wild cereal forms and Sorghum spp.,
but also Avena spp., Alopecurus spp., and Cynodon spp, Lolium spp.,
Phalaris spp., Poa spp., and Cyperus species and Imperata.
[0174] In the case of the dicotyledonous weed species, the spectrum
of action extends to species such as, for example, Chenopodium
spp., Amaranthus spp., Solanum spp., Datura spp., Abutilon spp.,
Ipomoea spp., Polygonum spp., Xanthium spp., Stellaria spp., Kochia
spp. and Viola spp., but also Chrysanthemum spp., Matricaria spp.,
Veronica spp., Anthemis spp., Thlaspi spp., Galium spp., Lamium
spp., Pharbitis spp., Sida spp., Sinapis spp., Cupsella spp.,
Cirsium spp., Convolvulus spp., Rumex and Artemisia.
[0175] If the compounds according to the invention are applied to
the soil surface before germination, then the weed seedlings are
either prevented completely from emerging, or the weeds grow until
they have reached the cotyledon stage but then their growth stops,
and, eventually, after three to four weeks have elapsed, they die
completely.
[0176] If the active substances are applied post-emergence to the
green parts of the plants, growth likewise stops drastically a very
short time after the treatment and the weed plants remain at the
growth stage of the point of time of application, or they die
completely after a certain time, so that in this manner competition
by the weeds, which is harmful to the crop plants, is eliminated at
a very early point in time and in a sustained manner.
[0177] In comparison with the individual preparations, the
herbicidal compositions according to the invention are
distinguished by a more rapidly commencing and longer lasting
herbicidal action. As a rule, the rainfastness of the active
substances in the combinations according to the invention is
advantageous. A particular advantage is that the dosages of the
compounds (A) and (B), which are used in the combinations and are
effective, can be adjusted to such a low quantity that their soil
action is optimal. This does not only allow them to be employed in
sensitive crops in the first place, but groundwater contaminations
are virtually avoided. The active-substance-combination according
to the invention allows the application rate of the active
substances required to be reduced considerably.
[0178] When herbicides of the type (A)+(B) are used jointly,
superadditive (=synergistic) effects are observed. This means that
the effect in the combinations exceeds the expected total of the
effects of the individual herbicides employed. The synergistic
effects allow the application rate to be reduced, a broader
spectrum of broad-leaved weeds and grass weeds to be controlled,
the herbicidal effect to take place more rapidly, the duration of
action to be longer, the harmful plants to be controlled better
while using only one, or few, applications, and the application
period which is possible to be extended. In some cases, uptake of
the compositions also reduces the amount of harmful constituents in
the crop plant, such as nitrogen or oleic acid. The abovementioned
properties and advantages are necessary under practical weed
control conditions to keep agricultural crops free from undesired
competing plants and thus to guarantee and/or increase the yields
from the qualitative and quantitative point of view. These novel
combinations markedly exceed the technical state of the art with a
view to the properties described.
[0179] While the compounds according to the invention have an
outstanding herbicidal activity against monocotyledonous and
dicotyledonous weeds, the tolerant, or cross-tolerant, maize plants
are damaged only to a minor extent, or not at all.
[0180] Moreover, some of the compositions according to the
invention have outstanding growth-regulatory properties on the
maize plants. They engage in the plants' metabolism in a regulatory
manner and can thus be employed for provoking directed effects on
plant constituents. Moreover, they are also suitable for the
general control and inhibition of undesired vegetative growth
without simultaneously destroying the plants. An inhibition of
vegetative growth is very important in a large number of
monocotyledonous and dicotyledonous crops since lodging can thus be
reduced, or prevented completely.
[0181] Owing to their herbicidal and plant-growth-regulatory
properties, the compositions can be employed for controlling
harmful plants in known tolerant or cross-tolerant maize crops, or
in tolerant or genetically engineered maize crops still to be
developed. As a rule, the transgenic plants are distinguished by
particular, advantageous properties, in addition to resistances to
the compositions according to the invention, for example, by
resistances to plant diseases or pathogens of plant diseases such
as particular insects or microorganisms such as fungi, bacteria or
viruses. Other particular properties relate, for example, to the
harvested material with regard to quantity, quality, storability,
composition and specific constituents. Thus, transgenic plants are
known whose oil content is increased or whose quality is altered,
for example where the harvested material has a different fatty acid
composition.
[0182] Conventional methods of generating novel plants which have
modified properties in comparison to plants occurring to date
consist, for example, in traditional breeding methods and the
generation of mutants. Alternatively, novel plants with altered
properties can be generated with the aid of genetic engineering
methods (see, for example, EP-A0221044, EP-A-0131624). For example,
the following were described in several cases: [0183] the
modification, by genetic engineering, of crop plants with the aim
of modifying the starch synthesized in the plant (for example WO
92/11376, WO 92/14827, WO 91/19806), [0184] transgenic crop plants
which exhibit resistances to other herbicides, for example to
sulfonylureas (EP-A-0257993, U.S. Pat. No. 5,013,659), [0185]
transgenic crop plants with the capability of producing Bacillus
thuringiensis toxins (Bt toxins), which make the plants resistant
to certain pests (EP-A-0142924, EP-A-0193259), [0186] transgenic
crop plants with a modified fatty acid composition (WO 91/13972). A
large number of techniques in molecular biology with the aid of
which novel transgenic plants with modified properties can be
generated are known in principle; see, for example, Sambrook et
al., 1989, Molecular Cloning, A Laboratory Manual, 2nd Edition,
Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y.; or
Winnacker "Gene und Klone" [Genes and Clones], VCH Weinheim 2nd
Edition 1996 or Christou, "Trends in Plant Science" 1(1996)
423-431.
[0187] To carry out such genetic engineering manipulations, nucleic
acid molecules which allow mutagenesis or sequence changes by
recombination of DNA sequences can be introduced in plasmids. For
example, the abovementioned standard methods allow base changes to
be carried out, subsequences to be removed, or natural or synthetic
sequences to be added. To connect the DNA fragments to each other,
adaptors or linkers may be added to the fragments.
[0188] For example, the generation of plant cells with a reduced
activity of a gene product can be achieved by expressing at least
one corresponding antisense RNA, a sense RNA for achieving a
cosuppression effect or by expressing at least one suitably
constructed ribozyme which specifically cleaves transcripts of the
abovementioned gene product.
[0189] To this end, it is possible to use, on the one hand, DNA
molecules which encompass the entire encoding sequence of a gene
product inclusive of any flanking sequences which may be present,
as well as DNA molecules which only encompass portions of the
encoding sequence, it being necessary for these portions to be long
enough to have an antisense effect on the cells. The use of DNA
sequences which have a high degree of homology to the encoding
sequences of a gene product, but are not completely identical to
them, is also possible.
[0190] When expressing nucleic acid molecules in plants, the
protein synthesized can be localized in any desired compartment of
the plant cell. However, to achieve localization in a particular
compartment, it is possible, for example, to link the encoding
region with DNA sequences which ensure localization in a particular
compartment. Such sequences are known to those skilled in the art
(see, for example, Braun et al., EMBO J. 11(1992), 3219-3227;
Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850;
Sonnewald et al., Plant J. 1 (1991), 95-106).
[0191] The transgenic plant cells can be regenerated by known
techniques to give rise to whole plants. In principle, the
transgenic plants can be plants of any desired plant species, i.e.
not only monocotyledonous, but also dicotyledonous, plants.
[0192] Thus, transgenic plants can be obtained whose properties are
altered by overexpression, suppression or inhibition of homologous
(=natural) genes or gene sequences or the expression of
heterologous (=foreign) genes or gene sequences.
[0193] The invention therefore also relates to a method of
controlling undesired vegetation in tolerant maize crops, which
comprises applying one or more herbicides of the type (A) and one
or more herbicides of the type (B) to the harmful plants, parts of
these plants, or the area under cultivation.
[0194] The invention also relates to the novel combinations of
compounds (A)+(B) and to herbicidal compositions comprising
them.
[0195] The active substance combinations according to the invention
can exist not only as formulation mixes of the two components, if
appropriate together with other active substances, additives and/or
conventional formulation auxiliaries, which are then applied in the
customary manner after dilution with water, but also as so-called
tank mixes by jointly diluting the separately formulated, or
partially separately formulated, components with water.
[0196] Compounds (A) and (B) or their combinations can be
formulated in different ways, depending on the biological and/or
chemico-physical parameters which prevail. The following are
examples of general possibilities for formulations: wettable
powders (WP), emulsifiable concentrates (EC), aqueous solutions
(SL), emulsions (EW) such as oil-in-water and water-in-oil
emulsions, sprayable solutions or emulsions, oil- or water-based
dispersions, suspoemulsions, dusts (DP), seed-dressing materials,
granules for soil application or for broadcasting, or water
dispersible granules (WG), ULV formulations, microcapsules or
waxes.
[0197] The individual formulation types are known in principle and
are described, for example, in: Winnacker-Kuchler "Chemische
Technologie" [Chemical engineering], Volume 7, C. Hauser Verlag
Munich, 4th Edition, 1986; van Valkenburg, "Pesticide
Formulations", Marcel Dekker N.Y., 1973; K. Martens, "Spray Drying
Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.
[0198] The formulation auxiliaries required, such as inert
materials, surfactants, solvents and other additives are also known
and are described, for example, in Watkins, "Handbook of
Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books,
Caldwell N.J.; H. v. Olphen, "Introduction to Clay Colloid
Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y. Marsden, "Solvents
Guide", 2nd Ed., Interscience, N.Y. 1950; McCutcheon's, "Detergents
and Emulsifiers Annual", MC Publ. Corp., Ridegewood N.J.; Sisley
and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co.
Inc., N.Y. 1964; Schonfeldt, "Grenzflachenaktive
Athylenoxidaddukte" [Surface-active ethylene oxide adducts], Wiss.
Verlagsgesellschaft, Stuttgart 1976, Winnacker-Kuchler, "Chemische
Technologie", Volume 7, C. Hauser Verlag Munich, 4th Edition
1986.
[0199] Based on these formulations, combinations with other
pesticidally active substances, such as other herbicides,
fungicides or insecticides, and with safeners, fertilizers and/or
growth regulators, may also be prepared, for example in the form of
a readymix or a tank mix.
[0200] Wettable powders (sprayable powders) are products which are
uniformly dispersible in water and which, besides the active
substance, also comprise ionic or non-ionic surfactants (wetters,
dispersants), for example polyoxethylated alkylphenols,
polyethoxylated fatty alcohols or fatty amines, alkanesulfonates or
alkylbenzenesulfonates, sodium lignosulfonate, sodium
2,2'-dinaphthylmethane-6,6'-disulfonate, sodium
dibutyinaphthalenesulfonate or else sodium oleoylmethyltauride, in
addition to a diluent or inert material.
[0201] Emulsifiable concentrates are prepared by dissolving the
active substance in an organic solvent, for example butanol,
cyclohexanone, dimethylformamide, xylene or else higher-boiling
aromatic or hydrocarbons with addition of one or more ionic or
non-ionic surfactants (emulsifiers). Examples of emulsifiers which
may be used are: calcium salts of alkylarylsulfonic acids, such as
calcium dodecylbenzene sulfonate, or nonionic emulsifiers such as
fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty
alcohol polyglycol ethers, propylene oxide/ethylene oxide
condensates, alkyl polyethers, sorbitan fatty acid esters,
polyoxyethylene sorbitan fatty acid esters or polyoxethylene
sorbitol esters.
[0202] Dusts are obtained by grinding the active substance with
finely divided solid materials, for example talc, natural clays
such as kaolin, bentonite and pyrophyllite, or diatomateous
earth.
[0203] Granules can be prepared either by spraying the active
substance onto adsorptive, granulated inert material or by applying
active substance concentrates to the surface of carriers such as
sand, kaolites or granulated inert material with the aid of
binders, for example polyvinyl alcohol, sodium polyacrylate or else
mineral oils. Suitable active substances may also be granulated in
the manner conventionally used for the production of fertilizer
granules, if desired in a mixture with fertilizers. As a rule,
water-dispersible granules are prepared by processes such as spray
drying, fluidized-bed granulation, disk granulation, mixing with
high-speed mixers and extrusion without solid inert material.
[0204] As a rule, the agrochemical preparations comprise 0.1 to 99
percent by weight, in particular 2 to 95% by weight, of active
substances of the types A and/or B, the following concentrations
being customary, depending on the type of formulation: The active
substance concentration in wettable powders is, for example,
approximately 10 to 95% by weight, the remainder to 100% by weight
being composed of customary formulation constituents. In the case
of emulsifiable concentrates, the active substance concentration
may amount to, for example, 5 to 80% by weight.
[0205] Formulations in the form of dusts comprise, in most cases, 5
to 20% by weight of active substance, sprayable solutions
approximately 0.2 to 25% by weight of active substance.
[0206] In the case of granules such as dispersible granules, the
active substance content depends partly on whether the active
compound is present in liquid or solid form and on which
granulation auxiliaries and fillers are being used. As a rule, the
content amounts to between 10 and 90% by weight in the case of the
water-dispersible granules.
[0207] In addition, the abovementioned active substance
formulations may comprise, if appropriate, the conventional
adhesives, wetters, dispersants, emulsifiers, preservatives,
antifreeze agents, solvents, fillers, colors, carriers, antifoams,
evaporation inhibitors, pH regulators or viscosity regulators.
[0208] For example, it is known that the effect of
glufosinate-ammonium (A1.2) and of its L-enantiomer can be improved
by surfactants, preferably by wetters from the series of the alkyl
polyglycol ether sulfates which contain, for example, 10 to 18
carbon atoms and which are used in the form of their alkali metal
salts or ammonium salts, but also as the magnesium salt, such as
sodium C.sub.12/C.sub.14-fatty alcohol diglycol ether sulfate
(.RTM.Genapol LRO, Hoechst); see EP-A-0476555, EP-A-0048436,
EP-A-0336151 or U.S. Pat. No. 4,400,196 and Proc. EWRS Symp.
"Factors Affecting Herbicidal Activity and Selectivity", 227-232
(1988). Moreover, it is known that alkyl polyglycol ether sulfates
are also suitable as penetrants and synergists for a series of
other herbicides, inter alia also herbicides from the series of the
imidazolinones; see EP-A-0502014.
[0209] For use, the formulations, which are present in commercially
available form, are optionally diluted in the customary manner, for
example using water in the case of wettable powders, emulsifiable
concentrates, dispersions and water-dispersible granules.
Preparations in the form of dusts, soil granules, granules for
broadcasting and sprayable solutions are usually not diluted
further prior to use with other inert substances.
[0210] The active substances can be applied to the plants, parts of
the plants, seeds of the plants or the area under cultivation (soil
of a field), preferably to the green plants and parts of the plants
and, if appropriate, additionally to the soil of the field.
[0211] One possible use is the joint application of the active
substances in the form of tank mixes, the concentrated formulations
of the individual active substances, in optimal formulations,
jointly being mixed with water in the tank and the resulting spray
mixture being applied.
[0212] A joint herbicidal formulation of the combination according
to the invention of the active substances (A) and (B) has the
advantage of being easier to apply since the quantities of the
components are already presented in the correct ratio to each
other. Moreover, the adjuvants in the formulation can be matched
optimally to each other, while a tank mix of different formulations
may lead to undesired combinations of adjuvants.
A. GENERAL FORMULATION EXAMPLES
[0213] a) A dust is obtained by mixing 10 parts by weight of an
active substance/active substance mixture and 90 parts by weight of
talc as inert material and comminuting the mixture in a hammer
mill. [0214] b) A wettable powder which is readily dispersible in
water is obtained by mixing 25 parts by weight of an active
substance/active substance mixture, 64 parts by weight of
kaolin-containing quartz as inert material, 10 parts by weight of
potassium lignosulfonate and 1 part by weight of sodium
oleoylmethyltaurinate as wetter and dispersant, and grinding the
mixture in a pinned-disk mill. [0215] c) A dispersion concentrate
which is readily dispersible in water is obtained by mixing 20
parts by weight of an active substance/active substance mixture
with 6 parts by weight of alkylphenol polyglycol ether (.RTM.Triton
X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO)
and 71 parts by weight of paraffinic mineral oil (boiling range for
example approx. 255 to 277.degree. C.), and grinding the mixture in
a ball mill to a fineness of below 5 microns. [0216] d) An
emulsifiable concentrate is obtained from 15 parts by weight of an
active substance/active substance mixture, 75 parts by weight of
cyclohexanone as solvent and 10 parts by weight of oxethylated
nonylphenol as emulsifier. [0217] e) Water-dispersible granules are
obtained by mixing [0218] 75 parts by weight of an active
substance/active substance mixture, [0219] 10 parts by weight of
calcium lignosulfonate, [0220] 5 parts by weight of sodium lauryl
sulfate, [0221] 3 parts by weight of polyvinyl alcohol and [0222] 7
parts by weight of kaolin, [0223] grinding the mixture on a
pinned-disk mill and granulating the powder in a fluidized bed by
spraying on water as granulation liquid. [0224] f)
Water-dispersible granules are also obtained by homogenizing and
precomminuting, on a colloid mill, [0225] 25 parts by weight of an
active substance/active substance mixture, [0226] 5 parts by weight
of sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, [0227] 2 parts
by weight of sodium oleoylmethyltaurinate, [0228] 1 part by weight
of polyvinyl alcohol, [0229] 17 parts by weight of calcium
carbonate and [0230] 50 parts by weight of water, [0231]
subsequently grinding the mixture in a bead mill and atomizing and
drying the resulting suspension in a spray tower by means of a
single-substance model.
BIOLOGICAL EXAMPLES
[0231] 1. Pre-Emergence Effect on Weeds
[0232] Seeds or rhizome pieces of monocotyledonous and
dicotyledonous weed plants are placed in sandy loam soil in plastic
pots and covered with soil. The compositions which are formulated
in the form of concentrated aqueous solutions, wettable powders or
emulsion concentrates are then applied to the surface of the soil
cover in the form of an aqueous solution, suspension or emulsion at
an application rate of 600 to 800 of l water/ha (converted), in
various dosages. After the treatment, the pots are placed in a
greenhouse and kept under good growth conditions for the weeds.
After the test plants have emerged, the damage to the plants or the
negative effect on the emergence is scored visually after a test
period of 3 to 4 weeks by comparison with untreated controls. As
shown by the test results, the compositions according to the
invention have a good herbicidal pre-emergence activity against a
broad spectrum of grass weeds and dicotyledonous weeds.
[0233] Frequently, effects of the combinations according to the
invention are observed which exceed the formal total of the effects
when applying the herbicides individually (=synergistic
effect).
[0234] If the data of the effects observed already exceed the
formal total of the data of the experiments with individual
applications, then they also exceed Colby's expected value, which
is calculated by the formula which follows and which is also
considered to be suggestive of synergism (cf. S. R. Colby; in Weeds
15 (1967) pp. 20 to 22): E=A+B-(AB/100)
[0235] A, B denote the effect of the active substances A, or in %,
for a or b g of a.s./ha; E denotes the expected value in % for a+b
g a.s./ha.
[0236] At suitable low dosages, the observed data of the
experiments show an effect of the combinations above Colby's
expected values.
2. Post-Emergence Effect on Weeds
[0237] Seeds or rhizome pieces of monocotyledonous and
dicotyledonous weeds are placed in sandy loam soil in cardboard
pots, covered with soil and grown in the greenhouse under good
growth conditions. Three weeks after sowing, the test plants in the
three-leaf stage are treated with the compositions according to the
invention. The compositions according to the invention which are
formulated as wettable powders or as emulsion concentrates are
sprayed in various dosages on the green parts of the plants at an
application rate of 600 to 800 l of water/ha (converted). After the
test plants have remained in the greenhouse for about 3 to 4 weeks
under optimal growth conditions, the effect of the products is
scored visually by comparison with untreated controls. When applied
post-emergence, too, the compositions according to the invention
have a good herbicidal activity against a broad spectrum of
economically important grass weeds and broad-leaved weeds.
[0238] Frequently, effects of the combinations according to the
invention are observed which exceed the formal total of the effects
when applying the herbicides individually.
[0239] At suitable low dosages, the observed data of the
experiments show an effect of the combinations above Colby's
expected values.
[0240] (cf. score figures in Example 1).
3. Herbicidal Effect and Tolerance by Crop Plants (Field Trial)
[0241] Transgenic maize plants with a resistance to one or more
herbicides (A) together with typical weed plants were grown in the
open on 2.times.5 m plots under natural field conditions;
alternatively, weed infestation occurred naturally when the maize
plants were grown. The treatment with the compositions according to
the invention and, as control, separately by only applying the
active substances of the components, was carried out under standard
conditions with a plot sprayer at an application rate of 200-300
liters of water per hectare in parallel tests as can be seen from
the scheme in Table 1, i.e. pre-sowing pre-emergence, post-sowing
preemergence or post-emergence in the early, medium or late stage.
TABLE-US-00001 TABLE 1 Use scheme - examples Application Pre- of
emergence Post- Post- Post- the active Pre- post- emergence
emergence emergence substances sowing sowing 1-2-leaf 2-4-leaf
6-leaf combination (A) + (B) '' (A) + (B) '' (A) + (B) '' (A) + (B)
'' (A) + (B) sequential (A) (B) '' (A) (B) '' (A) (B) '' (A) (A)
(B) '' (A) (B) (B) '' (A) (A) + (B) '' (B) (A) '' (B) (A) + (B) ''
(A) + (B) (A) + (B) '' (A) + (B) (A) + (B) (A) + (B) '' (A) + (B)
(A) + (B) '' (A) + (B) (A) + (B) (A) + (B) '' (A) + (B) (A) + (B)
(A) + (B) (A) + (B) '' (A) + (B) (A) + (B) '' (A) + (B) (A) + (B)
(A) + (B) '' (A) + (B) (A) + (B)
[0242] 2, 4, 6 and 8 weeks after the application, the herbicidal
activity of the active substances or active substance mixtures was
scored visually with reference to the treated plots in comparison
to untreated control plots. The damage to, and the development of,
all aerial parts of the plants was recorded. Scoring was done on
the basis of a percentage sale (100% action=all plants destroyed;
50% action=50% of the plants and green parts of the plants
destroyed; 0% action=no recognizable effect=like control plot. The
mean of the score values of in each case 4 plots was
calculated.
[0243] The comparison demonstrated that the herbicidal effect of
the combinations according to the invention was usually higher, in
some cases considerably higher, than the total of the effects of
the individual herbicides (=E.sup.A). In essential periods of the
period of scoring, the effects were greater than Colby's expected
values (=E.sup.C) (cf. scoring in Example 1) and therefore suggest
a synergism. In contrast, the maize plants were not damaged owing
to the treatments with the herbicidal compositions, or were only
damaged to a negligible extent.
[0244] Other test results are compiled in the tables which
follow.
[0245] Abbreviations generally used in the tables: [0246] g of
a.s./ha=gram of active substance (100% active substance) per
hectare [0247] E.sup.A=Total of the herbicidal effects of the
individual applications [0248] E.sup.C=Colby's expected value (cf.
scoring in Table 1)
[0249] "Mais LL"=.RTM.Liberty-Link-Mais, maize which is tolerant or
resistant to glufosinate-ammonium, TABLE-US-00002 TABLE 2
Herbicidal effect in field trials with maize Damage Herbicidal
action.sup.2) Dose.sup.1) to (%) against Active in g of Mais
LL.sup.3) Digitaria Panicum substance(s) a.s./ha in % sanguinalis
dichotomiflorum (A1.2) 200 2 0 8 400 4 15 50 600 3 30 92 (B3.2) 300
0 88 0 (A1.2) + 200 + 300 3 94 75 (B3.2) (E.sup.A = 88) (E.sup.A =
8) 400 + 300 4 100 92 (E.sup.C = 89) (E.sup.A = 50) Abbreviations
for Table 2: .sup.1)= Application in the 5-6-leaf stage .sup.2)=
Scoring 11 days after application .sup.3)= .RTM. Liberty-Link-Mais
= maize which is resistant to glufosinate-ammonium, (A1.2) =
glufosinate-ammonium (B3.2) = dicamba
[0250] TABLE-US-00003 TABLE 3 Herbicidal effect in field trials
with maize Dose.sup.1) Active in g of Herbicidal action.sup.2) (%)
against Damage to substance(s) a.s./ha AGRRE SETVI AMARE Mais LL in
% (A1.2) 200 0 72 65 3 300 0 72 84 2 400 11 69 82 5 600 15 69 87 3
1000 74 74 85 4 (B1.2) 1500 26 53 3 0 (A1.2) + (B1.2) 200 + 1500 32
95 (E.sup.C = 89) 87 (E.sup.A = 68) 3 400 + 1500 68 97 (E.sup.C =
75) 88 (E.sup.A = 85) 4 Abbreviations for Table 3: .sup.1)=
Application in the 2-4-leaf stage .sup.2)= Scoring 3 weeks after
application (A1.2) = glufosinate-ammonium (B1.2) = atrazine
[0251] TABLE-US-00004 TABLE 4 Herbicidal effect in field trials
with maize Dose.sup.1) Herbicidal action.sup.2) Damage Active in g
of (%) against to Mais LL substance(s) a.s./ha EPHHL in % (A1.2)
600 55 0 300 45 0 (B1.16) 50 60 0 100 58 0 150 70 0 (A1.2) +
(B1.16) 300 + 50 83 10 (E.sup.C = 78) 300 + 100 95 10 (E.sup.C =
77) Abbreviations for Table 4: .sup.1)= Application in the 4-leaf
stage .sup.2)= Scoring 6 weeks after application (A1.2)=
glufosinate-ammonium (B1.16) = mesotrione EPHHL = Euphorbia
heterophylla
[0252] TABLE-US-00005 TABLE 5 Herbicidal effect in field trials
with maize Dose.sup.1) Damage Herbicidal action.sup.2) Active in g
of to Mais (%) against substance(s) a.s./ha LL in % Euphorbia
heterophylla (A1.2) 400 0 60 200 0 50 100 0 37 (B1.14) 400 0 75 300
0 68 200 0 60 (A1.2) + (B1.14) 100 + 200 0 99 (E.sup.A = 97) 400 +
200 0 99 (E.sup.C = 84) Abbreviations for Table 5: .sup.1)=
Application in the 6-leaf stage .sup.2)= Scoring 44 days after
application (A1.2) = glufosinate-ammonium (A1.14) = sulcotrione
[0253] TABLE-US-00006 TABLE 6 Herbicidal effect in field trials
with maize Herbicidal action.sup.1) Dose.sup.1) (%) against Active
in g of Fagopyron Lolium substance(s) a.s./ha esculentum
multiflorum (A1.2) 500 55 78 330 20 15 200 10 0 (B2.3) 2.5 85 84
(A1.2) + (B2.3) 330 + 2.5 93 90 (E.sup.C = 88) (E.sup.C = 87)
Abbreviations for Table 6: .sup.1)= Application in the 2- to 4-leaf
stage .sup.2)= Scoring 26 days after application (A1.2) =
glufosinate-ammonium (B2.3) = iodosulfuron-methyl.
[0254] TABLE-US-00007 TABLE 7 Herbicidal effect in field trials
with maize Herbicidal action.sup.2) Dose.sup.1) (%) against Active
in g of Avena Portulaca substance(s) a.s./ha fatua oleracea (A1.2)
450 50 50 300 48 43 (B1.5) 1680 40 35 (A1.2) + (B1.5) 300 + 1680 98
(E.sup.A = 88) 95 (E.sup.A = 78) (B1.1) 2242 35 45 (A1.2) + (B1.1)
300 + 2242 86 (E.sup.A = 83) 93 (E.sup.A = 88) (B3.1) 360 10 25
(A1.2) + (B3.1) 300 + 360 63 (E.sup.A = 58) 65 (E.sup.A = 60)
Abbreviations for Table 7: .sup.1)= Application in the 2- to 4-leaf
stage .sup.2)= Scoring 28 days after application (A1.2) =
glufosinate-ammonium (B1.5) = metolachlor (B3.1) = bromoxynil
[0255] TABLE-US-00008 TABLE 8 Herbicidal effect in field trials
with maize Active Dose.sup.1) Herbicidal action.sup.2) (%) against
substance(s) in g of a.s./ha Sorghum halepense (A1.2) 500 53 300 15
(B1.11) 20 93 10 62 (A1.2) + (B1.11) 300 + 10 78 (E.sup.A = 77)
Abbreviations for Table 8: .sup.1)= Application in the 4-leaf stage
.sup.2)= Scoring 28 days after application (A1.2) =
glufosinate-ammonium (B1.11) = primisulfuron-methyl
[0256] TABLE-US-00009 TABLE 9 Herbicidal effect in field trials
with maize Dose.sup.1) Herbicidal action.sup.2) Active in g of (%)
against substance(s) a.s./ha Cassia obtusifolia (A1.2) 400 60
(B2.1) 925 0 (A1.1) + (B2.1) 400 + 925 88 (E.sup.A = 60)
Abbreviations for Table 9: .sup.1)= Application in the 3-leaf stage
.sup.2)= Scoring 21 days after application (A1.2) =
glufosinate-ammonium (B2.1) = pendimethalin
[0257] TABLE-US-00010 TABLE 10 Herbicidal effect in field trials
with maize Active Dose.sup.1) Herbicidal action.sup.2) (%) against
substance(s) in g of a.s./ha Brachiaria plantaginea (A1.2) 600 70
300 45 150 5 (B1.5) 1500 70 (1.2) + (B1.5) 150 + 1500 95 (E.sup.A =
75) Abbreviations for Table 10: .sup.1)= Application in the 2-leaf
stage .sup.2)= Scoring 28 days after application (A1.2) =
glufosinate-ammonium (B1.5) = metolachlor
[0258] TABLE-US-00011 TABLE 11 Herbicidal effect in field trials
with maize Dose.sup.1) Herbicidal action.sup.2) (%) Active in g of
against substance(s) a.s./ha Mais LL Commelina benghalensis (A1.2)
600 0 82 300 0 63 200 0 60.0 100 0 43 (A3.2) 100 0 73 (A1.2) +
(A3.2).sup.3) 100 + 100 0 92 (E.sup.A = 86) (B1.6) 1920 0 37 (A1.2)
+ (B1.6) 100 + 1920 0 83 (E.sup.A = 80) Abbreviations for Table 11:
.sup.1)= Application in the 3-leaf stage .sup.2)= Scoring 42 days
after application .sup.3)= Second active substance applied 10 days
after the first active substance (A1.2) = glufosinate-ammonium
(A3.2) = imazethapyr (B1.6) = alachlor
[0259] TABLE-US-00012 TABLE 12 Herbicidal effect in field trials
with maize Active Dose.sup.1) Herbicidal action.sup.2) (%) against
substance(s) in g of a.s./ha Portulaca oleracea (A1.2) 500 60 250
35 (B3.1) 360 25 (A1.2) + (B3.1) 250 + 360 65 (E.sup.A = 60)
Abbreviations for Table 12: .sup.1)= Application in the 6-leaf
stage .sup.2)= Scoring 26 days after application (A1.2)=
glufosinate-ammonium (B3.1)= bromoxynil
[0260] TABLE-US-00013 TABLE 13 Herbicidal effect in field trials
with maize Herbicidal action.sup.2) Active Dose.sup.1) (%) against
substance(s) in g of a.s./ha Sinapis arvensis (A1.2) 350 75 230 45
(B3.6) 15 73 (A1.2) + (B3.6) 230 + 15 99 (E.sup.C = 85)
Abbreviations for Table 13: .sup.1)= Application in the 4-to 5-leaf
stage .sup.2)= Scoring 28 days after application (A1.2) =
glufosinate-ammonium (B3.6) = thifensulfuron-methyl
[0261] TABLE-US-00014 TABLE 14 Herbicidal effect in field trials
with maize Dose.sup.1) Herbicidal action.sup.2) (%) Active in g of
against substance(s) a.s./ha Mais LL Echinochloa crus-galli (A1.2)
400 8 68 200 0 35 (B2.8) 70 8 65 50 5 40 (A1.2) + (B2.8) 200 + 50 6
85 (E.sup.A = 75) (B3.4) 100 0 15 (A1.2) + (B3.4) 200 + 100 1 65
(E.sup.A = 50) Abbreviations for Table 14: .sup.1)= Application in
the 3-leaf stage .sup.2)= Scoring 21 days after application (A1.2)
= glufosinate-ammonium (B3.4) = clopyralid (B2.8) = flumetsulam
[0262] TABLE-US-00015 TABLE 15 Herbicidal effect in field trials
with maize Herbicidal action.sup.2) Dose.sup.1) (%) against Active
in g of Galium Fagopyrum substance(s) a.s/ha aparine esculentum
(A1.2) 500 65 55 250 45 20 125 30 10 (B3.8) 60 85 78 30 65 60 15 45
30 (A1.2) + (B3.8) 250 + 15 85 (E.sup.C = 72) 65 (E.sup.A = 50) 125
+ 30 83 (E.sup.C = 75) 75 (E.sup.A = 70) Abbreviations for Table
15: .sup.1)= Application in the 3-to 4-leaf stage .sup.2)= Scoring
24 days after application (A1.2) = glufosinate-ammonium (B3.6) =
tritosulfuron
[0263] TABLE-US-00016 TABLE 16 Herbicidal effect in field trials
with maize Active Dose Herbicidal action.sup.3) (%) against
substance(s) in g of a.s./ha Sorghum bicolor (B2.5).sup.1) 100 75
50 40 25 20 (A1.2).sup.2) 500 85 250 50 125 30 (B2.5).sup.1) +
(A1.2).sup.2) 50 + 250 95 (E.sup.A = 90) 25 + 250 80 (E.sup.A = 70)
Abbreviations for Table 16: .sup.1)= Pre-emergence application
.sup.2)= Application in the 4-leaf stage 18 days after the
pre-emergence application of.sup.1) .sup.3)= Scoring 46 days after
pre-emergence application, or 28 days after post-emergence
application (B2.5) = isoxaflutole (A1.2) = glufosinate-ammonium
[0264] TABLE-US-00017 TABLE 17 Herbicidal effect in field trials
with maize Active Dose.sup.1) Herbicidal action.sup.2) (%) against
substance(s) in g of a.s./ha Echinochloa crus-galli (A1.2) 500 74
250 45 125 25 (B1.13) 500 55 250 30 125 25 (A1.2) + (B1.13) 250 +
125 85 (E.sup.A = 55) 500 + 125 100 (E.sup.A = 98) 125 + 500 93
(E.sup.A = 80) Abbreviations for Table 17: .sup.1)= Application in
the 3-leaf stage .sup.2)= Scoring 28 days after application (A1.2)
= glufosinate-ammonium (B1.13) = fluthiamide
[0265] TABLE-US-00018 TABLE 18 Herbicidal effect in field trials
with maize Active Dose.sup.1) Herbicidal action.sup.2) (%) against
substance(s) in g of a.s./ha Echinochloa crus-galli (A1.2) 500 78
250 65 125 45 (B1.4) 1500 45 750 40 375 10 (A1.2) + (B1.4) 125 +
750 93 (E.sup.A = 85) 125 + 1500 97 (E.sup.A = 90) 500 + 375 92
(E.sup.A = 88) Abbreviations for Table 18: .sup.1)= Application in
the 3- to 4-leaf stage .sup.2)= Scoring 42 days after application
(A1.2) = glufosinate-ammonium (B1.4) = acetochlor
[0266] TABLE-US-00019 TABLE 19 Herbicidal effect in field trials
with maize Active Dose.sup.1) Herbicidal action.sup.2) (%) against
substance(s)0 in g of a.s./ha Lamium amplexicaule (A2.1) 600 90 400
75 (B2.3) 2.5 55 (A2.1) + (B2.3) 400 + 2.5 93 (E.sup.C = 88)
Abbreviations for Table 19: .sup.1)= Application in the 1-leaf
stage .sup.2)= Scoring 17 days after application (A1.2) =
glyphosate-isopropylammonium (B2.3) = iodosulfuron-methyl
[0267] TABLE-US-00020 TABLE 20 Herbicidal effect in field trials
with maize Dose.sup.1) Active in g of Herbicidal action.sup.2) (%)
against substance(s) a.s./ha Convolvulus arvensis (A1.2) 400 20 200
0 (B3.3) 500 20 (A1.2) + (B3.3) 400 + 500 50 (E.sup.A = 40) (B3.9)
500 60 (A1.2) + (B3.9) 200 + 500 75 (E.sup.A = 60) (B2.2) 900 40
(A1.2) + (B2.2) 200 + 900 73 (E.sup.A = 40) (B1.12) 900 30 (A1.2) +
(B1.12) 200 + 900 65 (E.sup.A = 30) Abbreviations for Table 20:
.sup.1)= Application in the 3- to 4-leaf stage .sup.2)= Scoring 28
days after application (A1.2) = glyphosate-isopropylammonium (B3.3)
= 2,4-D (B3.9) = MCPA (B2.2) = pyridate (B1.12) = dimethenamide
* * * * *