U.S. patent application number 12/540244 was filed with the patent office on 2010-03-11 for herbicide combination comprising dimethoxytriazinyl-substituted difluoromethanesulfonylanilides.
This patent application is currently assigned to BAYER CROPSCIENCE AG. Invention is credited to Georg Bonfig-Picard, Erwin HACKER, Christopher Hugh Rosinger, Stefan Schnatterer, Shinichi Shirakura, Chieko Ueno, Christian Waldraff.
Application Number | 20100062941 12/540244 |
Document ID | / |
Family ID | 41259049 |
Filed Date | 2010-03-11 |
United States Patent
Application |
20100062941 |
Kind Code |
A1 |
HACKER; Erwin ; et
al. |
March 11, 2010 |
Herbicide Combination Comprising Dimethoxytriazinyl-Substituted
Difluoromethanesulfonylanilides
Abstract
The present invention relates to a herbicide combination
comprising components (A) and (B) where (A) denotes one or more
compounds or salts thereof from the group described by the general
formula (I): ##STR00001## in which R.sup.1 is halogen, preferably
fluorine or chlorine, R.sup.2 is hydrogen and R.sup.3 is hydroxyl
or R.sup.2 and R.sup.3 together with the carbon atom to which they
are attached are a carbonyl group C.dbd.O and R.sup.4 is hydrogen
or methyl; and (B) denotes one or more herbicides from the group of
the pyrimidines consisting of: (B1-1) ancymidol, (B1-2)
flurprimidol, (B1-3) pyrimisulfan, (B2-1) bispyribac-sodium, (B2-2)
pyribenzoxim, (B2-3) pyriminobac-methyl, (B2-4)
pyribambenz-isopropyl, (B2-5) pyribambenz-propyl, (B3-1)
pyriftalid, (B3-2) pyrithiobac-sodium, (B4-1) benzfendizone, (B4-2)
bromacil, (B4-3) butafenacil, (B4-4) lenacil, (B4-5) terbacil,
(B4-6) SYN-523, (B4-7) saflufenacil.
Inventors: |
HACKER; Erwin; (Hochheim,
DE) ; Waldraff; Christian; (Bad Vilbel, DE) ;
Rosinger; Christopher Hugh; (Hofheim, DE) ; Ueno;
Chieko; (Frankfurt, DE) ; Bonfig-Picard; Georg;
(Rodenbach, DE) ; Schnatterer; Stefan;
(Hattersheim, DE) ; Shirakura; Shinichi; (Tochigi,
JP) |
Correspondence
Address: |
Baker Donelson Bearman, Caldwell & Berkowitz, PC
555 Eleventh Street, NW, Sixth Floor
Washington
DC
20004
US
|
Assignee: |
BAYER CROPSCIENCE AG
Monheim
DE
|
Family ID: |
41259049 |
Appl. No.: |
12/540244 |
Filed: |
August 12, 2009 |
Current U.S.
Class: |
504/227 |
Current CPC
Class: |
A01N 43/66 20130101;
A01N 43/66 20130101; A01N 43/66 20130101; A01N 43/54 20130101; A01N
2300/00 20130101 |
Class at
Publication: |
504/227 |
International
Class: |
A01N 43/46 20060101
A01N043/46 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 14, 2008 |
DE |
10 2008 037 631.0 |
Claims
1. A herbicide combination comprising components (A) and (B), where
(A) denotes one or more compounds or salts thereof from the group
described by the general formula (I): ##STR00006## in which R.sup.1
is halogen, preferably fluorine or chlorine, R.sup.2 is hydrogen
and R.sup.3 is hydroxyl or R.sup.2 and R.sup.3 together with the
carbon atom to which they are attached are a carbonyl group C.dbd.O
and R.sup.4 is hydrogen or methyl; and (B) denotes one or more
herbicides from the group of the pyrimidines consisting of: (B1-1)
ancymidol; (B1-2) flurprimidol; (B1-3) pyrimisulfan; (B2-1)
bispyribac-sodium; (B2-2) pyribenzoxim; (B2-3) pyriminobac-methyl;
(B2-4) pyribambenz-isopropyl; (B2-5) pyribambenz-propyl; (B3-1)
pyriftalid; (B3-2) pyrithiobac-sodium; (B4-1) benzfendizone; (B4-2)
bromacil; (B4-3) butafenacil; (B4-4) lenacil; (B4-5) terbacil;
(B4-6) SYN-523; (B4-7) saflufenacil; where the following
combinations are excluded: compounds of the general formula (I)
where R.sup.1 is fluorine, R.sup.2 and R.sup.3 are a carbonyl group
C.dbd.O, R.sup.4 is methyl, and the compound B1-3
(pyrimisulfan).
2. The herbicide combination as claimed in claim 1, comprising as
component (A) one or more of the compounds from the group mentioned
below consisting of: ##STR00007## ##STR00008##
3. The herbicide combination as claimed in claim 1, comprising as
component (B) one or more of the compounds from the group mentioned
below consisting of: (B1-3) pyrimisulfan, (B2-1) bispyribac-sodium,
(B3-1) pyriftalid, (B3-2) pyrithiobac-sodium, (B4-2) bromacil,
(B4-6) SYN-523, (B4-7) saflufenacil; particularly preferably (B1-3)
pyrimisulfan, (B2-1) bispyribac-sodium, (B4-6) SYN-523, (B4-7)
saflufenacil.
4. The herbicide combination as claimed in claim 1, where the
weight ratio (A):(B) of the components (A) and (B) is generally in
the range of from 1:5000 to 500:1, preferably 1:800 to 70:1, in
particular 1:500 to 50:1.
5. The herbicide combination as claimed in claim 1, comprising an
effective amount of components (A) and (B) and/or additionally one
or more further components from the group of agrochemically active
compounds of a different type, formulation auxiliaries and
additives customary in crop protection.
6. A method for controlling unwanted vegetation wherein the
components (A) and (B) of the herbicide combination, defined
according to claim 1, are applied jointly or separately.
7. The method as claimed in claim 6 for controlling unwanted
vegetation in crop plants such as wheat (durum wheat and common
wheat), corn, soybeans, sugar beet, sugar cane, cotton, rice,
beans, flax, barley, oats, rye, triticale, oilseed rape, potatoes,
millet (sorghum), pasture grass, greens/lawns, in fruit plantations
or on non-crop areas, in particular in rice crops.
8. The use of the herbicide combination defined in claim 1 for
controlling unwanted vegetation.
Description
[0001] The present invention is in the technical field of crop
protection compositions which can be used against unwanted
vegetation, for example by the pre-sowing method (with or without
incorporation), by the pre-emergence method or by the
post-emergence method in sown or planted crop plants such as, for
example, in wheat (durum wheat and common wheat), corn, soybeans,
sugar beet, sugar cane, cotton, rice (planted or sown under upland
or paddy conditions using indica or japonica varieties and also
hybrids/mutants/GMOs), beans (such as, for example, bush beans and
broad beans), flax, barley, oats, rye, triticale, oilseed rape,
potatoes, millet (sorghum), pasture grass, greens/lawns, in fruit
plantations (plantation crops) or on non-crop areas (for example
squares of residential areas or industrial sites, rail tracks). In
addition to the single application, sequential applications are
also possible.
[0002] It relates to a herbicide combination comprising at least
two herbicides and to their use for controlling unwanted
vegetation, in particular a herbicide combination comprising
N-{2-[4,6-dimethoxy-(1,3,5)triazine-2-(carbonyl- or
-hydroxymethyl)]-6-halophenyl}difluoromethanesulfonamides or their
N-methyl derivatives and/or their salts, hereinbelow also referred
to as "dimethoxytriazinyl-substituted
difluoromethanesulfonylanilides", and to herbicidally active
compounds from the group of the pyrimidines.
[0003] It is known that cyclicly substituted sulfonamides have
herbicidal properties (for example WO 93/09099 A2, WO 96/41799 A1).
These also include the phenyldifluoromethanesulfonamides, which are
also referred to as difluoromethanesulfonylanilides. The
lastmentioned compounds are, for example, phenyl derivatives which
are mono- or polysubstituted, inter alia by dimethoxypyrimidinyl
(for example WO 00/006553 A1) or dimethoxytriazinyl and also a
further halogen substitution (for example WO 2005/096818 A1, WO
2007/031208 A2).
[0004] However, specific compounds from the group of the
N-{2-[4,6-dimethoxy-(1,3,5)triazine-2(-carbonyl- or
-hydroxymethyl)]-6-halophenyl}difluoromethanesulfonamides, as
described in WO 2005/096818 A1, and their N-methyl derivatives, as
described for the first time in WO 2006/008159 A1 in connection
with fungicides and in WO 2007/031208 A2 and JP 2007-213330
(unpublished) as herbicides, are not entirely satisfactory in all
respects with regard to their herbicidal properties.
[0005] The herbicidal activity of the
dimethoxytriazinyl-substituted difluoromethanesulfonylanilides
against harmful plants (broad-leaved weeds, weed grasses,
Cyperaceae; hereinbelow collectively also referred to as "weed") is
already at a high level, but depends in general on the application
rate, the formulation in question, the harmful plants to be
controlled in each case or the spectrum of harmful plants, the
climatic and soil conditions and the like. Further criteria in this
context are duration of action, or the breakdown rate, of the
herbicide, the general crop plant compatibility and the speed of
action (more rapid onset of action), the activity spectrum and
behavior toward follower crops (replanting problems) or the general
flexibility of application (control of weeds in their various
growth stages). If appropriate, changes in the susceptibility of
harmful plants, which may occur on prolonged use of the herbicides
or in limited geographical regions (control of tolerant or
resistant weed species) may also have to be taken into account. The
compensation of losses in action in the case of individual plants
by increasing the application rates of the herbicides is only
possible to a certain degree, for example because such a procedure
reduces the selectivity of the herbicides or because the action is
not improved, even when applying higher rates.
[0006] Thus, there is frequently a need for targeted synergistic
activity against specific weed species, weed control with better
overall selectivity, generally lower amounts of active compounds
used for equally good control results and for a reduced active
compound input into the environment to avoid, for example, leaching
and carry-over effects. There is also a need for developing
one-shot applications to avoid labor-intensive multiple
applications, and also to develop systems for controlling the rate
of action, where, in addition to an initial rapid control of weeds
there is also a slower, residual control.
[0007] A possible solution to the problems mentioned above may be
to provide herbicide combinations, that is mixtures of a plurality
of herbicides and/or other components from the group of the
agrochemically active compounds of a different type and of
formulation auxiliaries and additives customary in crop protection
which contribute the desired additional properties. However, in the
combined use of a plurality of active compounds, there are
frequently phenomena of chemical, physical or biological
incompatibility, for example lack of stability of a joint
formulation, decomposition of an active compound or antagonism in
the biological activity of the active compounds. For these reasons,
potentially suitable combinations have to be selected in a targeted
manner and tested experimentally for their suitability, it not
being possible to safely discount a priori negative or positive
results.
[0008] Mixtures of non-N-methyl derivatives of the compounds
mentioned above are known in principle (for example WO 2007/079965
A2); however, their effectiveness in mixtures with other herbicides
has only been confirmed in individual cases for
dimethoxypyimidinyl-substituted phenyl derivatives. In addition,
there are also mixtures of selected N-methyl derivatives of the
compounds mentioned above with some combination partners
(PCT/EP2008/000870, unpublished).
[0009] It was the object of the present invention to provide crop
protection compositions as alternatives to the prior art, or as an
improvement thereof.
[0010] Surprisingly, it has now been found that this object can be
achieved by herbicide combinations of
dimethoxytriazinyl-substituted difluoromethanesulfonylanilides in
combination with structurally different herbicides from the group
of the pyrimidines which act together in a particularly favorable
manner, for example when they are used for controlling unwanted
vegetation in sown and/or planted crop plants such as wheat (durum
wheat and common wheat), corn, soybeans, sugar beet, sugar cane,
cotton, rice (planted or sown under upland or paddy conditions
using indica and/or japonica varieties and also
hybrids/mutants/GMOs), beans (such as, for example, bush beans and
broad beans), flax, barley, oats, rye, triticale, oilseed rape,
potatoes, millet (sorghum), pasture grass, greens/lawns, in fruit
plantations (plantation crops) or on non-crop areas (for example
squares of residential areas or industrial sites, rail tracks), in
particular in rice crops (planted or sown under upland or paddy
conditions using indica and/or japonica varieties and also
hybrids/mutants/GMOs).
[0011] Compounds from the group of the pyrimidines are already
known as herbicidally active compounds for controlling unwanted
vegetation; see, for example GB 118623, U.S. Pat. No. 4,002,628, WO
200006553, U.S. Pat. No. 4,906,285, EP 658549, U.S. Pat. No.
5,118,339, WO 2002034724, WO 199105781, U.S. Pat. No. 4,932,999,
U.S. Pat. No. 5,344,812, U.S. Pat. No. 3,325,357, U.S. Pat. No.
5,183,492, U.S. Pat. No. 3,235,360, U.S. Pat. No. 3,235,357, EP
1122244 and the literature cited in the publications mentioned
above
[0012] Accordingly, the present invention provides a herbicide
combination comprising components (A) and (B) where [0013] (A)
denotes one or more compounds or salts thereof from the group
described by the general formula (I):
[0013] ##STR00002## [0014] in which [0015] R.sup.1 is halogen,
preferably fluorine or chlorine, [0016] R.sup.2 is hydrogen and
R.sup.3 is hydroxyl or [0017] R.sup.2 and R.sup.3 together with the
carbon atom to which they are attached are a carbonyl group C.dbd.O
and [0018] R.sup.4 is hydrogen or methyl; and [0019] (B) denotes
one or more herbicides from the group of the pyrimidines consisting
of: [0020] the subgroup of the pyrimidinylcarbinols (subgroup 1)
consisting of: [0021] (B1-1) ancymidol (PM #31), for example
.alpha.-cyclopropyl-.alpha.-(4-methoxyphenyl)-5-pyrimidinemethanol
(application rate: 1-5000 g of AS/ha, preferably 3-4000 g of AS/ha;
weight ratio A:B=1:5000-500:1, preferably 1:800-70:1); [0022]
(B1-2) flurprimidol (PM #403), for example
.alpha.-(1-methylethyl)-.alpha.-[4-(trifluoromethoxy)phenyl]-5-pyrimidine-
methanol, also including its racemate or isomers (application rate:
1-5000 g of AS/ha, preferably 3-4000 g of AS/ha; weight ratio
A:B=1:5000-500:1, preferably 1:800-70:1); [0023] (B1-3)
pyrimisulfan (CPCN), syn. KIH5996, for example
N-[2-[(4,6-dimethoxy-2-pyrimidinyphydroxymethyl]-6-(methoxymethyl)phenyl]-
-1,1-difluoromethanesulfonamide, also including its salts
(derivatives) (application rate: 1-500 g of AS/ha, preferably 3-400
g of AS/ha; weight ratio A:B=1:500-500:1, preferably 1:80-70:1);
[0024] the subgroup of the pyrimidinyloxybenzoic acid derivatives
(subgroup 2), consisting of: [0025] (B2-1) bispyribac-sodium (PM
#85), for example sodium
2,6-bis[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzoate (sodium salt),
also including its acid (for example
2,6-bis(4,6-dimethoxypyrimidin-2-yloxy) benzoic acid) and other
salts (derivatives) (application rate: 1-500 g of AS/ha, preferably
3-400 g of AS/ha; weight ratio A:B=1:500-500:1, preferably
1:80-70:1); [0026] (B2-2) pyribenzoxim (PM #717), syn. LGC 40863,
for example diphenylmethanone,
O-[[2,6-bis(4,6-dimethoxy-2-pyrimidinyl)oxy]benzoyl]oxime
(application rate: 1-500 g of AS/ha, preferably 3-400 g of AS/ha;
weight ratio A:B=1:500-500:1, preferably 1:80-70:1); [0027] (B2-3)
pyriminobac-methyl (PM #727), syn. KIH 6127, for example methyl
2-[(4,6-dimethoxypyrimidin-2-yl)oxy]-6-[1-(methoxyimino)ethyl]benzoate
(methyl ester), also including its acid pyriminobac (for example
2,6-bis(4,6-dimethoxypyrimidin-2-yloxy) benzoic acid) and its salts
and other esters (derivatives) (application rate: 1-500 g of AS/ha,
preferably 3-400 g of AS/ha; weight ratio A:B=1:500-500:1,
preferably 1:80-70:1); [0028] (B2-4) pyribambenz-isopropyl
(published inter alia in WO2005/002338 A1), for example the
isopropyl esters of pyrimidinyloxybenzylaminobenzoic acids,
Chemical Abstract Service Registry Number [CAS RN 420138-41-6],
also including the acid and other esters (derivatives) except for
pyribambenz-propyl (application rate: 1-500 g of AS/ha, preferably
3-400 g of AS/ha; weight ratio A:B=1:500-500:1, preferably
1:80-70:1); [0029] (B2-5) pyribambenz-propyl (published inter alia
in WO2005/002338 A1), for example the propyl esters of
pyrimidinyloxybenzylaminobenzoic acids, Chemical Abstract Service
Registry Number [CAS RN 420138-40-5] (application rate: 1-500 g of
AS/ha, preferably 3-400 g of AS/ha; weight ratio A:B=1:500-500:1,
preferably 1:80-70:1); [0030] the subgroup of the
pyrimidinylthiobenzoic acid derivatives (subgroup 3) consisting of:
[0031] (B3-1) pyriftalid (CPCN), for example
(RS)-7-(4,6-dimethoxypyrimidin-2-ylthio)-3-methyl-2-benzofuran-1(3H)-one,
also including its racemate or isomers (application rate: 3-2000 g
of AS/ha, preferably 5-1500 g of AS/ha; weight ratio
A:B=1:2000-100:1, preferably 1:300-40:1); [0032] (B3-2)
pyrithiobac-sodium (PM #729) for example sodium
2-chloro-6-(4,6-dimethoxypyrimidin-2-ylthio)benzoate (sodium salt),
also including its acid (for example
2-chloro-6-(4,6-dimethoxypyrimidin-2-ylthio)benzoic acid) and other
salts (derivatives) (application rate: 1-500 g of AS/ha, preferably
3-400 g of AS/ha; weight ratio A:B=1:500-500:1, preferably
1:80-70:1); [0033] the subgroup of the pyrimidinediones (subgroup
4) consisting of: [0034] (B4-1) benzfendizone (PM #70), for example
methyl
2-[2-[[4-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimi-
dinyl]phenoxy]methyl]-5-ethylphenoxy]propanoate (application rate:
10-5000 g of AS/ha, preferably 30-4000 g of AS/ha; weight ratio
A:B=1:5000-50:1, preferably 1:800-7:1); [0035] (B4-2) bromacil (PM
#92), for example
5-bromo-6-methyl-3-(1-methylpropyl)-2,4(1H,3H)-pyrimidinedione),
also including its salts, in particular the lithium salt (for
example bromacil-lithium) (application rate: 10-5000 g of AS/ha,
preferably 30-4000 g of AS/ha; weight ratio A:B=1:5000-50:1,
preferably 1:800-7:1); [0036] (B4-3) butafenacil (PM #103), for
example 1,1-dimethyl-2-oxo-2-(2-propenyloxy)ethyl
2-chloro-5-3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-[(2H)-pyrim-
idinyl]benzoate (application rate: 3-2000 g of AS/ha, preferably
5-1500 g of AS/ha; weight ratio A:B=1:2000-100:1, preferably
1:300-40:1); [0037] (B4-4) lenacil (PM #504), for example
3-cyclohexyl-6,7-dihydro-1H-cyclopentapyrimidine-2,4(3H,5H)-dione
(application rate: 10-5000 g of AS/ha, preferably 30-4000 g of
AS/ha; weight ratio A:B=1:5000-50:1, preferably 1:800-7:1); [0038]
(B4-5) terbacil (PM #792), for example
5-chloro-3-(1,1-dimethylethyl)-6-methyl-2,4(1H,3H)-pyrimidinedione
(application rate: 10-5000 g of AS/ha, preferably 30-4000 g of
AS/ha; weight ratio A:B=1:5000-50:1, preferably 1:800-7:1); [0039]
(B4-6) SYN-523 (described in: EP 1122244; Eur. Chem. News, 82 (Feb.
2005), p. 27; Farm Chemicals Int. (April 2005), 19 (3), 6; AGROW
2005-02-14.), for example ethyl
[[3-[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-
-pyrimidinyl]-4-fluorophenoxy]-2-pyridinyl]oxy]acetate; Chemical
Abstract Service Registry Number [CAS RN 353292-31-6], also
including its acid and other esters and salts (derivatives)
(application rate: 1-1000 g of AS/ha, preferably 2-800 g of AS/ha;
weight ratio A:B=1:1000-250:1, preferably 1:160-100:1); [0040]
(B4-7) saflufenacil (CPCN), syn. BAS H800, for example
2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-[(2H)-pyri-
midinyl]-4-fluoro-N-[[methyl(1-methylethyl)amino]sulfonyl]benzamide;
Chemical Abstract Service Registry Number [CAS RN 372137-35-4]
(application rate: 1-1000 g of AS/ha, preferably 2-800 g of AS/ha;
weight ratio A:B=1:1000-250:1, preferably 1:160-100:1); except for
the following combinations which are described in PCT/EP2008/000870
(unpublished): [0041] compounds of the general formula (I) where
R.sup.1 is fluorine, R.sup.2 and R.sup.3 are a carbonyl group
C.dbd.O, R.sup.4 is methyl, and [0042] the compound B1-3
(pyrimisulfan);
[0043] The compounds mentioned above in group B are referred to
either by the "common name" according to the International
Organization for Standardization (ISO) or by the chemical name or
by a code number (development code); as known, for example, from
the following sources "The Pesticide Manual", 14.sup.th edition
2006/2007 or "The e-Pesticide Manual", version 4.0 (2006-07), each
published by the British Crop Protection Council (abbreviation: "PM
# . . . " with the respective sequential entry number, and the
literature cited therein, from "The Compendium of Pesticide Common
Names" (abbreviation: "CPCN"; internet URL:
http://www.alanwood.net/pesticides/) and/or other sources. The use
of the names mentioned above, for example in the short form of the
"common names", includes in each case all use forms (derivatives)
such as acids, salts, esters and isomers such as stereoisomers and
optical isomers, unless not already more specifically defined. The
commercial use forms of the herbicides mentioned in group B are
preferred. Here, the abbreviation "AS/ha" above means "active
substance per hectare" and is based on 100% pure active
compound.
[0044] Preferred components (A) are the following compounds (A-1)
to (A-8) of the formulae (A1), (A2), (A3), (A4), (A5), (A6), (A7)
and (A8) or their salts:
##STR00003## ##STR00004##
[0045] Particularly preferred as components (A) are the compounds
(A-1), (A-2) and (A-3).
Compounds preferred as components (B) are: (B1-3) pyrimisulfan,
(B2-1) bispyribac-sodium, (B3-1) pyriftalid, (B3-2)
pyrithiobac-sodium, (B4-2) bromacil, (B4-6) SYN-523, (B4-7)
saflufenacil; particularly preferably (B1-3) pyrimisulfan, (B2-1)
bispyribac-sodium, (B4-6) SYN-523, (B4-7) saflufenacil.
[0046] The herbicide combinations according to the invention may
additionally comprise further components: for example
agrochemically active compounds of a different type and/or
formulation auxiliaries and/or additives customary in crop
protection, or they may be employed together with these.
Hereinbelow, the use of the term "herbicide combination(s)" or
"combination(s)" also includes the "herbicidal compositions" formed
in this manner.
[0047] The compounds of the formula (I) are capable of forming
salts. The salt formation may take place by allowing a base to act
on those compounds of the formula (I) carrying an acidic hydrogen
atom. Suitable bases are, for example, organic amines, such as
trialkylamines, morpholine, piperidine or pyridine, and also
ammonium, alkali metal or alkaline earth metal hydroxides,
carbonates and bicarbonates, in particular sodium hydroxide and
potassium hydroxide, sodium carbonate and potassium carbonate and
sodium bicarbonate and potassium bicarbonate, alkali metal or
alkaline earth metal alkoxides, in particular sodium methoxide,
ethoxide, n-propoxide, isopropoxide, n-butoxide or t-butoxide or
potassium methoxide, ethoxide, n-propoxide, isopropoxide,
n-butoxide or t-butoxide. These salts are compounds in which the
acidic hydrogen is replaced by an agriculturally suitable cation,
for example metal salts, in particular alkali metal salts or
alkaline earth metal salts, especially sodium salts or potassium
salts, or else ammonium salts, salts with organic amines or
quaternary ammonium salts, for example with cations of the formula
[NRR'R''R'''].sup.+in which R to R''' are in each case
independently of one another organic radicals, in particular alkyl,
aryl, arylalkyl or alkylaryl. Also suitable are alkylsulfonium and
alkylsulfoxonium salts, such as (C.sub.1-C.sub.4)-trialkylsulfonium
and (C.sub.1-C.sub.4)-trialkylsulfoxonium salts. By a suitable
inorganic or organic acid, such as, for example, mineral acids such
as, for example, HCl, HBr, H.sub.2SO.sub.4, H.sub.3PO.sub.4 or
HNO.sub.3, or organic acids, for example carboxylic acids such as
formic acid, acetic acid, propionic acid, oxalic acid, lactic acid
or salicylic acid or sulfonic acids, such as, for example,
p-toluenesulfonic acid, forming an adduct with a basic group such
as, for example, amino, alkylamino, dialkylamino, piperidino,
morpholino or pyridino, the compounds of the formula (I) are also
capable of forming salts. These salts then contain the conjugated
base of the acid as anion.
[0048] Hereinbelow, the terms "herbicide(s)", "individual
herbicide(s)", "compound(s)" or "active compound(s)" are also used
synonymously for the term "components(s)" in the context.
[0049] In a preferred embodiment, the herbicide combinations
according to the invention comprise effective amounts of the
herbicides (A) and (B) and/or have synergistic actions. The
synergistic actions can be observed, for example, when applying the
herbicides (A) and (B) together, for example as a coformulation or
as a tank mix; however, they can also be observed when the active
compounds are applied at different times (splitting). It is also
possible to apply the herbicides or the herbicide combinations in a
plurality of portions (sequential application), for example
pre-emergence applications followed by post-emergence applications
or early post-emergence applications followed by medium or late
post-emergence applications. Preference is given here to the joint
or almost simultaneous application of the herbicides (A) and (B) of
the combination in question, and the joint application is
particularly preferred.
[0050] The synergistic effects permit a reduction of the
application rates of the individual herbicides, a higher efficacy
at the same application rate, the control of species which were as
yet uncontrolled (gaps), control of species which are tolerant or
resistant to individual herbicides or to a number of herbicides, an
extension of the period of application and/or a reduction in the
number of individual applications required and--as a result for the
user--weed control systems which are more advantageous economically
and ecologically.
[0051] For example, the combinations according to the invention of
herbicides (A)+(B) allow the activity to be enhanced
synergistically in a manner which, by far and in an unexpected
manner, exceeds the activities which can be achieved using the
individual herbicides (A) and (B).
[0052] The formula (I) mentioned embraces all stereoisomers and
their mixtures, in particular also racemic mixtures, and--if
enantiomers are possible--the respective enantiomer which is
biologically active. This also applies to possible rotamers of the
formula (I).
[0053] The herbicides of group (A) inhibit mainly the enzyme
acetolactate synthase (ALS) and thus the protein biosynthesis in
plants. The application rate of the herbicides (A) can vary within
a wide range, for example between 0.1 g and 1000 g of AS/ha
(hereinbelow, AS/ha means "active substance per hectare"=based on
100% pure active compound). Applied at application rates of from
0.1 g to 1000 g of AS/ha, the herbicides (A), preferably the
compounds (A-1) to (A-8), control, when used in the pre-sowing
pre-planting or the pre- and post-emergence method, a relatively
wide spectrum of harmful plants, for example of annual and
perennial mono- or dicotyledonous broad-leaved weeds, weed grasses
and Cyperaceae, and also of unwanted crop plants. For the
combinations according to the invention, the application rates are
generally lower, for example in the range of from 0.1 g to 500 g of
AS/ha, preferably from 0.5 g to 200 g of AS/ha, particularly
preferably from 1 g to 150 g of AS/ha.
[0054] The herbicides of group (B) have an effect, for example, on
acetohydroxy acid synthase, photosystem II and protoporphyrinogen
oxidase, and they are suitable both for pre-emergence and
post-emergence application. The application rate of the herbicides
(B) can vary within a wide range, for example between 1 g and 5,000
g of AS/ha (hereinbelow, AS/ha means "active substance per
hectare"=based on 100% pure active compound). Applied at
application rates of from 3 g to 4000 g of AS/ha, the herbicides
(B), preferably the compounds (B1-3), (B2-1), (B3-1), (B3-2),
(B4-2), (B4-6) and (B4-7), control, when used in the pre- and
post-emergence method, a relatively wide spectrum of harmful
plants, for example of annual and perennial mono- or dicotyledonous
broad-leaved weeds, weed grasses and Cyperaceae, and also of
unwanted crop plants. For the combinations according to the
invention, the application rates are generally lower, for example
in the range of from 1 g to 5000 g of AS/ha, preferably from 3 g to
4000 g of AS/ha, particularly preferably from 1 g to 3000 g of
AS/ha.
[0055] Preference is given to herbicide combinations of one or more
herbicides (A) and one or more herbicides (B). More preference is
given to combinations of herbicides (A) with one or more herbicides
(B). Here, combinations additionally comprising one or more further
agrochemically active compounds which differ from the herbicides
(A) and (B) but also act as selective herbicides are likewise in
accordance with the invention.
[0056] For combinations of three or more active compounds, the
preferred conditions illustrated below in particular for
two-component combinations according to the invention primarily
also apply, provided they comprise the two-component combinations
according to the invention.
[0057] Ranges of suitable ratios of the compounds (A) and (B) can
be found, for example, by looking at the application rates
mentioned for the individual compounds. In the combinations
according to the invention, the application rates can generally be
reduced. Preferred mixing ratios of the combined herbicides (A):(B)
in the combinations according to the invention are characterized by
the following weight ratios:
[0058] The weight ratio (A):(B) of the components (A) and (B) is
generally in the range of from 1:5000 to 500:1, preferably 1:800 to
70:1, in particular 1:500 to 50:1.
[0059] Of particular interest is the use of herbicide combinations
having a content of the following compounds (A)+(B):
(A-1)+(B1-1), (A-1)+(B1-2), (A-1)+(B1-3), (A-1)+(B2-1),
(A-1)+(B2-2), (A-1)+(B2-3), (A-1)+(B2-4), (A-1)+(B2-5),
(A-1)+(B3-1), (A-1)+(B3-2), (A-1)+(B4-1), (A-1)+(B4-2),
(A-1)+(B4-3), (A-1)+(B4-4), (A-1)+(B4-5), (A-1)+(B4-6),
(A-1)+(B4-7); (A-2)+(B1-1), (A-2)+(B1-2), (A-2)+(B1-3),
(A-2)+(B2-1), (A-2)+(B2-2), (A-2)+(B2-3), (A-2)+(B2-4),
(A-2)+(B2-5), (A-2)+(B3-1), (A-2)+(B3-2), (A-2)+(B4-1),
(A-2)+(B4-2), (A-2)+(B4-3), (A-2)+(B4-4), (A-2)+(B4-5),
(A-2)+(B4-6), (A-2)+(B4-7); (A-3)+(B1-1), (A-3)+(B1-2),
(A-3)+(B1-3), (A-3)+(B2-1), (A-3)+(B2-2), (A-3)+(B2-3),
(A-3)+(B2-4), (A-3)+(B2-5), (A-3)+(B3-1), (A-3)+(B3-2),
(A-3)+(B4-1), (A-3)+(B4-2), (A-3)+(B4-3), (A-3)+(B4-4),
(A-3)+(B4-5), (A-3)+(B4-6), (A-3)+(B4-7); (A-4)+(B1-1),
(A-4)+(B1-2), (A-4)+(B1-3), (A-4)+(B2-1), (A-4)+(B2-2),
(A-4)+(B2-3), (A-4)+(B2-4), (A-4)+(B2-5), (A-4)+(B3-1),
(A-4)+(B3-2), (A-4)+(B4-1), (A-4)+(B4-2), (A-4)+(B4-3),
(A-4)+(B4-4), (A-4)+(B4-5), (A-4)+(B4-6), (A-4)+(B4-7);
(A-5)+(B1-1), (A-5)+(B1-2), (A-5)+(B1-3), (A-5)+(B2-1),
(A-5)+(B2-2), (A-5)+(B2-3), (A-5)+(B2-4), (A-5)+(B2-5),
(A-5)+(B3-1), (A-5)+(B3-2), (A-5)+(B4-1), (A-5)+(B4-2),
(A-5)+(B4-3), (A-5)+(B4-4), (A-5)+(B4-5), (A-5)+(B4-6),
(A-5)+(B4-7); (A-6)+(B1-1), (A-6)+(B1-2), (A-6)+(B1-3),
(A-6)+(B2-1), (A-6)+(B2-2), (A-6)+(B2-3), (A-6)+(B2-4),
(A-6)+(B2-5), (A-6)+(B3-1), (A-6)+(B3-2), (A-6)+(B4-1),
(A-6)+(B4-2), (A-6)+(B4-3), (A-6)+(B4-4), (A-6)+(B4-5),
(A-6)+(B4-6), (A-6)+(B4-7); (A-7)+(B1-1), (A-7)+(B1-2),
(A-7)+(B1-3), (A-7)+(B2-1), (A-7)+(B2-2), (A-7)+(B2-3),
(A-7)+(B2-4), (A-7)+(B2-5), (A-7)+(B3-1), (A-7)+(B3-2),
(A-7)+(B4-1), (A-7)+(B4-2), (A-7)+(B4-3), (A-7)+(B4-4),
(A-7)+(B4-5), (A-7)+(B4-6), (A-7)+(B4-7); (A-8)+(B1-1),
(A-8)+(B1-2), (A-8)+(B1-3), (A-8)+(B2-1), (A-8)+(B2-2),
(A-8)+(B2-3), (A-8)+(B2-4), (A-8)+(B2-5), (A-8)+(B3-1),
(A-8)+(B3-2), (A-8)+(B4-1), (A-8)+(B4-2), (A-8)+(B4-3),
(A-8)+(B4-4), (A-8)+(B4-5), (A-8)+(B4-6), (A-8)+(B4-7);
[0060] The herbicide combinations according to the invention may
furthermore comprise, as additional further components, various
agrochemically active compounds, for example from the group of the
safeners, fungicides, insecticides, acaricides, nematicides, bird
repellants, soil structure improvers, plant nutrients
(fertilizers), and herbicides which differ structurally from
herbicides (A) and (B), and plant growth regulators, or from the
group of the formulation auxiliaries and additives customary in
crop protection.
[0061] Thus, suitable further herbicides are, for example, the
following herbicides which differ structurally from the herbicides
(A) and (B), preferably herbicidally active compounds whose action
is based on inhibition of, for example, acetolactate synthase,
acetyl coenzyme A carboxylase, cellulose synthase, enol
pyruvylshikimate 3-phosphate synthase, glutamine synthetase,
p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase,
photosystem I, photosystem II, protoporphyrinogen oxidase, as
described, for example, in Weed Research 26 (1986) 441-445 or "The
Pesticide Manual", 13.sup.th edition 2003 or 14.sup.th edition
2006/2007, or in the corresponding "The e-Pesticide Manual",
version 4.0 (2006-07), all published by the British Crop Protection
Council, and the literature cited therein, can be used. Lists of
common names are also available in "The Compendium of Pesticide
Common Names" on the internet. Here, the herbicides are referred to
either by the "common name" in accordance with the International
Organization for Standardization (ISO) or by the chemical name or
by the code number, and in each case include all use forms, such as
acids, salts, esters and isomers, such as stereoisomers and optical
isomers. Here, by way of example, one and in some cases a plurality
of use forms are mentioned:
acetochlor, acibenzolar, acibenzolar-S-methyl, acifluorfen,
acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim,
alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron,
aminocyclopyrachlor, aminopyralid, amitrole, ammoniumsulfamat,
anilofos, asulam, atrazine, azafenidin, azimsulfuron, aziprotryn,
BAH-043, BAS-140H, BAS-693H, BAS-714H, BAS-762H, BAS-776H,
beflubutamid, benazolin, benazolin-ethyl, bencarbazone,
benfluralin, benfuresate, bensulide, bensulfuron-methyl, bentazone,
benzobicyclon, benzofenap, benzofluor, benzoylprop, bifenox,
bilanafos, bilanafos-sodium, bromobutide, bromofenoxim, bromoxynil,
bromuron, buminafos, busoxinone, butachlor, butamifos, butenachlor,
butralin, butroxydim, butylate, cafenstrole, carbetamide,
carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chloramben,
chlorazifop, chlorazifop-butyl, chlorbromuron, chlorbufam,
chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol,
chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl,
chlormequat chloride, chlornitrofen, chlorophthalim,
chlorthal-dimethyl, chlorotoluron, chlorsulfuron, cinidon,
cinidon-ethyl, cinmethylin, cinosulfuron, clethodim, clodinafop
clodinafop-propargyl, clofencet, clomazone, clomeprop, cloprop,
clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide,
cyanazine, cyclanilide, cycloate, cyclosulfamuron, cycloxydim,
cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyprazine,
cyprazole, 2,4-D, 2,4-DB, daimuron/dymron, dalapon, daminozide,
dazomet, n-decanol, desmedipham, desmetryn, detosyl-pyrazolate
(DTP), diallate, dicamba, dichlobenil, dichlorprop, dichlorprop-P,
diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam,
diethatyl, diethatyl-ethyl, difenoxuron, difenzoquat, diflufenican,
diflufenzopyr, diflufenzopyr-sodium, dimefuron, dikegulac-sodium,
dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid,
dimethenamid-P, dimethipin, dimetrasulfuron, dinitramine, dinoseb,
dinoterb, diphenamid, dipropetryn, diquat, diquat dibromide,
dithiopyr, diuron, DNOC, eglinazine-ethyl, endothal, EPTC,
esprocarb, ethalfluralin, ethametsulfuron-methyl, ethephon,
ethidimuron, ethiozin, ethofumesate, ethoxyfen, ethoxyfen-ethyl,
ethoxysulfuron, etobenzanid, F-5331, i.e.
N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol--
1-yl]phenyl]ethanesulfonamide, fenoprop, fenoxaprop, fenoxaprop-P,
fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentrazamide, fenuron,
flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron,
florasulam, fluazifop, fluazifop-P, fluazifop-butyl,
fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazone-sodium,
flucetosulfuron, fluchloralin, flufenacet (thiafluamide),
flufenpyr, flufenpyr-ethyl, flumetralin, flumetsulam, flumiclorac,
flumiclorac-pentyl, flumioxazin, flumipropyn, fluometuron,
fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, flupoxam,
flupropacil, flupropanate, flupyrsulfuron,
flupyrsulfuron-methyl-sodium, flurenol, flurenol-butyl, fluridone,
fluorochloridone, fluoroxypyr, fluoroxypyr-meptyl, flurtamone,
fluthiacet, fluthiacet-methyl, fluthiamide, fomesafen,
foramsulfuron, forchlorfenuron, fosamine, furyloxyfen, gibberellic
acid, glufosinate, glufosinate-ammonium, glufosinate-P,
glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate,
glyphosate-isopropylammonium, H-9201, halosafen, halosulfuron,
halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl,
haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl,
hexazinone, HNPC-9908, HW-02, imazamethabenz,
imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin,
imazethapyr, imazosulfuron, inabenfide, indanofan, indoleacetic
acid (IAA), 4-indol-3-ylbutyric acid (IBA), iodosulfuron,
iodosulfuron-methyl-sodium, ioxynil, ipfencarbazone, isocarbamid,
isopropalin, isoproturon, isouron, isoxaben, isoxachlortole,
isoxaflutole, isoxapyrifop, KUH-043, KUH-071, karbutilate,
ketospiradox, lactofen, linuron, maleic hydrazide, MCPA, MCPB,
MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium,
mecoprop-butotyl, mecoprop-P-butotyl, mecoprop-P-dimethylammonium,
mecoprop-P-2-ethylhexyl, mecoprop-P-potassium, mefenacet,
mefluidide, mepiquat chloride, mesosulfuron, mesosulfuron-methyl,
mesotrione, methabenzthiazuron, metam, metamifop, metamitron,
metazachlor, methazole, methoxyphenone, methyldymron,
1-methylcyclopropene, methyl isothiocyanate, metobenzuron,
metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron,
metribuzin, metsulfuron, metsulfuron-methyl, molinate, monalide,
monocarbamide, monocarbamide dihydrogensulfate, monolinuron,
monosulfuron, monuron, MT 128, MT-5950, i.e.
N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide, NGGC-011,
naproanilide, napropamide, naptalam, NC-310, i.e.
4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole, neburon,
nicosulfuron, nipyraclofen, nitralin, nitrofen,
nitrophenolate-sodium (isomer mixture), nitrofluorfen, nonanoic
acid, norflurazon, orbencarb, orthosulfamuron, oryzalin,
oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen,
paclobutrazol, paraquat, paraquat dichloride, pelargonic acid
(nonanoic acid), pendimethalin, pendralin, penoxsulam,
pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham,
phenmedipham, phenmedipham-ethyl, picloram, picolinafen, pinoxaden,
piperophos, pirifenop, pirifenop-butyl, pretilachlor,
primisulfuron, primisulfuron-methyl, probenazole, profluazol,
procyazine, prodiamine, prifluraline, profoxydim, prohexadione,
prohexadione-calcium, prohydrojasmone, prometon, prometryn,
propachlor, propanil, propaquizafop, propazine, propham,
propisochlor, propoxycarbazone, propoxycarbazone-sodium,
propyzamide, prosulfalin, prosulfocarb, prosulfuron, prynachlor,
pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole,
pyrazolynate (pyrazolate), pyrazosulfuron-ethyl, pyrazoxyfen,
pyributicarb, pyridafol, pyridate, pyroxasulfone, pyroxsulam,
quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl,
quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl,
rimsulfuron, secbumeton, sethoxydim, siduron, simazine, simetryn,
SN-106279, sulcotrione, sulfallate (CDEC), sulfentrazone,
sulfometuron, sulfometuron-methyl, sulfosate
(glyphosate-trimesium), sulfosulfuron, SYN-449, SYP-249, SYP-298,
SYP-300, tebutam, tebuthiuron, tecnazene, tefuryltrione,
tembotrione, tepraloxydim, terbucarb, terbuchlor, terbumeton,
terbuthylazine, terbutryn, TH-547, thenylchlor, thiafluamide,
thiazafluoron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone,
thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl,
thiobencarb, tiocarbazil, topramezone, tralkoxydim, triallate,
triasulfuron, triaziflam, triazofenamide, tribenuron,
tribenuron-methyl, trichloroacetic acid (TCA), triclopyr,
tridiphane, trietazine, trifloxysulfuron, trifloxysulfuron-sodium,
trifluralin, triflusulfuron, triflusulfuron-methyl, trimeturon,
trinexapac, trinexapac-ethyl, tritosulfuron, tsitodef, uniconazole,
uniconazole-P, vernolate, ZJ-0166, ZJ-0270, ZJ-0543, ZJ-0862 and
the following compounds
##STR00005##
[0062] Of particular interest is the selective control of harmful
plants in crops of useful plants and ornamental plants. Although
the herbicides (A) and (B) have already demonstrated very good to
sufficient selectivity in a large number of crops, in principle, in
some crops and in particular also in the case of mixtures with
other, less selective herbicides, phytotoxicities on the crop
plants may occur. In this respect, combinations of herbicides (A)
and (B) comprising the herbicidally active compounds combined
according to the invention and one or more safeners are of
particular interest. The safeners, which are used in an
antidotically effective amount, reduce the phytotoxic side effects
of the herbicides/pesticides employed, for example in economically
important crops, such as cereals (wheat, barley, rye, oats, corn,
rice, millet), sugar beet, sugar cane, oilseed rape, cotton,
soybeans or in fruit plantations (plantation crops), preferably
cereals, in particular rice.
[0063] The following groups of compounds are, for example, suitable
as safeners (including possible stereoisomers and agriculturally
customary esters or salts):
benoxacor cloquintocet (-mexyl) cyometrinil cyprosulfamide
dichlormid dicyclonon dietholate disulfoton (.dbd.O,O-diethyl
S-2-ethylthioethyl phosphordithioate) fenchlorazole (-ethyl)
fenclorim flurazole fluxofenim furilazole isoxadifen (-ethyl)
mefenpyr (-diethyl) mephenate naphthalic anhydride oxabetrinil
"R-29148" (=3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine),
"R-28725" (=3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine),
"PPG-1292"
(.dbd.N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide),
"DKA-24"
(.dbd.N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide),
"AD-67" or "MON 4660"
(=3-dichloroacetyl-1-oxa-3-azaspiro[4,5]decane), "T1-35"
(=1-dichloroacetylazepane), "dimepiperate" or "MY-93"
(.dbd.S-1-methyl-1-phenylethyl piperidine-1-thiocarboxylate),
"daimuron" or "SK 23" (=1-(1-methyl-1-phenylethyl)-3-p-tolylurea),
"cumyluron"="JC-940"
(=3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethypurea),
"methoxyphenon" or "NK 049" (=3,3'-dimethyl-4-methoxybenzophenone),
"CSB" (=1-bromo-4-(chloromethylsulfonyl)benzene) "CL-304415"
(=4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid; CAS reg no:
31541-57-8) "MG-191" (=2-dichloromethyl-2-methyl-1,3-dioxolane)
"MG-838" (=2-propenyl 1-oxa-4-azaspiro[4.5]decane-4-carbodithioate;
CAS reg no: 133993-74-5) methyl(diphenylmethoxy)acetate (CAS reg
no: 41858-19-9 from WO-A-1998/38856)
methyl[(3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate
(CAS reg no: 205121-04-6 from WO-A-1998/13361)
1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone
(CAS reg no: 95855-00-8 from WO-A-1999/000020).
[0064] Some of the safeners are already known as herbicides and
accordingly, in addition to the herbicidal action against harmful
plants, also act by protecting the crop plants.
[0065] The weight ratios of herbicide combination to safener
generally depend on the herbicide application rate and the
effectiveness of the safener in question and may vary within wide
limits, for example in the range from 90 000:1 to 1:5000,
preferably from 7000:1 to 1:1600, in particular from 3000:1 to
1:500. The safeners may be formulated analogously to the compounds
of the formula (I) or their mixtures with other
herbicides/pesticides and be provided and used as a finished
formulation or as a tank mix with the herbicides or separately be
applied as a seed, soil or foliar application.
[0066] The herbicide combinations according to the invention
(=herbicidal compositions) have excellent herbicidal activity
against a broad spectrum of economically important monocotyledonous
and dicotyledonous harmful plants, such as broad-leaved weeds, weed
grasses or Cyperaceae, including species which are resistant to
herbicidally active compounds such as glyphosate, glufosinate,
atrazine, imidazolinone herbicides, sulfonylureas,
(hetero)aryloxyaryloxyalkylcarboxylic acids or
-phenoxyalkylcarboxylic acids (`fops`), cyclohexanedione oximes
(`dims`) or auxin inhibitors. The active compounds also act
efficiently on perennial weeds which produce shoots from rhizomes,
root stocks and other perennial organs and which are difficult to
control. Here, the substances can be applied, for example, by the
pre-sowing method, the pre-emergence method or the post-emergence
method, for example jointly or separately. Preference is given, for
example, to application by the post-emergence method, in particular
to the emerged harmful plants.
[0067] Specific 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 restricted to certain species.
[0068] Examples of weed species on which the herbicidal
compositions act efficiently are, from amongst the monocotyledonous
weed species, Avena spp., Alopecurus spp., Apera spp., Brachiaria
spp., Bromus spp., Digitaria spp., Lolium spp., Echinochloa spp.,
Leptochloa spp., Fimbristylis spp., Panicum spp., Phalaris spp.,
Poa spp., Setaria spp. and also Cyperus species from the annual
group, and, among the perennial species, Agropyron, Cynodon,
Imperata and Sorghum and also perennial Cyperus species.
[0069] In the case of the dicotyledonous weed species, the spectrum
of action extends to genera such as, for example, Abutilon spp.,
Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp.,
Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharbitis
spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp.,
Stellaria spp., Veronica spp. Eclipta spp., Sesbania spp.,
Aeschynomene spp. and Viola spp., Xanthium spp. among the annuals,
and Convolvulus, Cirsium, Rumex and Artemisia in the case of the
perennial weeds.
[0070] If the active compounds of the herbicide combinations
according to the invention are applied to the soil surface before
germination, the weed seedlings are either prevented completely
from emerging or else the weeds grow until they have reached the
cotyledon stage, but then their growth stops, and, eventually,
after two to four weeks have elapsed, they die completely.
[0071] If the active compounds 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
very early and in a sustained manner. In the case of rice, the
active compounds can also be applied into the water, and they are
then taken up via soil, shoot and roots.
[0072] The herbicidal compositions according to the invention are
distinguished by a rapidly commencing and long-lasting herbicidal
action. As a rule, the rainfastness of the active compounds in the
combinations according to the invention is favorable. A particular
advantage is that the dosages used in the combinations and the
effective dosages of compounds (A) and (B) can be adjusted to such
a low level that their soil action is optimally low. This does not
only allow them to be employed in sensitive crops in the first
place, but ground water contaminations are virtually avoided. The
combinations according to the invention of active compounds allow
the required application rate of the active compounds to be reduced
considerably.
[0073] In a preferred embodiment, the herbicide combinations
according to the invention of the herbicides (A) and (B) are highly
suitable for the selective control of harmful plants in rice crops.
These include all possible forms of rice cultivation under the most
diverse conditions, such as upland cultivation, dry cultivation or
paddy cultivation, where the irrigation may be natural (rainfall)
and/or artificial (irrigated, flooded). The rice used for this
purpose may be conventionally cultivated seed, hybrid seed, or else
resistant, at least tolerant, seed (obtained by mutagenesis or
transgenically) which can be derived from the indica or japonica
variety or from crossbreeds thereof.
[0074] The herbicide combinations according to the invention can be
applied by all application methods customary for rice herbicides.
Particularly preferably, they are applied by spray application
and/or by submerged application. In the submerged application, the
paddy water already covers the ground by up to 3-20 cm at the time
of the application. The herbicide combinations according to the
invention are then directly placed in the paddy water, for example
in the form of granules. Worldwide, the spray application is used
predominantly with direct seeded rice and the submerged application
is used predominantly with transplanted rice.
[0075] The herbicide combinations according to the invention cover
a broad weed spectrum which is specific in particular for rice
crops. From among the monocotyledonous weeds, genera such as, for
example, Echinochloa spp., Panicum spp., Poa spp., Leptochloa spp.,
Brachiaria spp., Digitaria spp., Setaria spp. Cyperus spp.,
Monochoria spp., Fimbristylis spp., Sagittaria spp., Eleocharis
spp., Scirpus spp., Alisma spp., Aneilema spp., Blyxa spp.,
Eriocaulon spp., Potamogeton spp. and the like are controlled well,
in particular the species Echinochloa oryzicola, Monochoria
vaginalis, Eleocharis acicularis, Eleocharis kuroguwai, Cyperus
difformis, Cyperus serotinus, Sagittaria pygmaea, Alisma
canaliculatum, Scirpus juncoides. In the case of the dicotyledonous
weeds, the activity spectrum extends to genera such as, for
example, Polygonum spp., Rorippa spp., Rotala spp., Lindernia spp.,
Bidens spp., Sphenoclea spp., Dopatrium spp., Eclipta spp., Elatine
spp., Gratiola spp., Lindernia spp., Ludwigia spp., Oenanthe spp.,
Ranunculus spp., Deinostema spp. and the like. In particular
species such as Rotala indica, Sphenoclea zeylanica, Lindernia
procumbens, Ludwigia prostrate, Potamogeton distinctus, Elatine
triandra, Oenanthe javanica are controlled well.
[0076] When herbicides of group (A) and those of group (B) are
applied jointly, there are preferably superadditive (=synergistic)
effects. Here, the activity in the combinations is higher than the
expected sum of the activities of the individual herbicides
employed. The synergistic effects allow the application rate to be
reduced, a broader spectrum of broad-leaved weeds, weed grasses and
Cyperaceae to be controlled, a more rapid onset of the herbicidal
action, a longer persistency, a better control of the harmful
plants with only one or a few applications and a widening of the
application period possible. To some extent, by using the
compositions, the amount of harmful ingredients, such as nitrogen
or oleic acid, and their introduction into the soil are likewise
reduced.
[0077] The abovementioned properties and advantages are necessary
for weed control practice to keep
agricultural/forestry/horticultural crops or green land/meadows
free of unwanted competing plants, and thus to ensure and/or
increase yield levels from the qualitative and quantitative angle.
These novel herbicide combinations markedly exceed the technical
state of the art with a view to the properties described.
[0078] Owing to their herbicidal and plant growth-regulatory
properties, the herbicide combinations according to the invention
can be employed for controlling harmful plants in known plant crops
or in tolerant or genetically modified crop and energy plants still
to be developed. In general, the transgenic plants (GMOs) are
distinguished by specific advantageous properties, in addition to
resistances to the herbicide combinations according to the
invention, for example, by resistances to plant diseases or the
causative organisms of plant diseases such as certain insects or
microorganisms, such as fungi, bacteria or viruses. Other specific
characteristics relate, for example, to the harvested material with
regard to quantity, quality, storability, and the composition of
specific constituents. Thus, transgenic plants are known whose
starch content is increased, or whose starch quality is altered, or
those where the harvested material has a different fatty acid
composition, or increased vitamin content or energetic properties.
In the same manner, owing to their herbicidal and plant
growth-regulatory properties, the active compounds can also be used
for controlling harmful plants in crops of known plants or plants
still to be developed by mutant selection, and also crossbreeds of
mutagenic and transgenic plants.
[0079] 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 recombinant methods
(see, for example, EP-A-0221044, EP-A-0131624). For example, the
following have been described in several cases: [0080] the
modification, by recombinant technology, of crop plants with the
aim of modifying the starch synthesized in the plants (for example
WO 92/11376, WO 92/14827, WO 91/19806), [0081] transgenic crop
plants which exhibit resistances to herbicides, for example to
sulfonylureas (EP-A-0257993, U.S. Pat. No. 5,013,659), [0082]
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), [0083] transgenic
crop plants with a modified fatty acid composition (WO
91/13972).
[0084] A large number of techniques in molecular biology are known
in principle with the aid of which novel transgenic plants with
modified properties can be generated; see, for example, Sambrook et
al., 1989, Molecular Cloning, A Laboratory Manual, 2.sup.nd
Edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor,
N.Y.; or Winnacker "Gene and Klone", VCH Weinheim 2.sup.nd Edition
1996 or Christou, "Trends in Plant Science" 1 (1996) 423-431). To
carry out such recombinant manipulations, nucleic acid molecules
which allow mutagenesis or sequence changes by recombination of DNA
sequences can be introduced into plasmids. For example, the
above-mentioned standard methods allow base exchanges to be carried
out, subsequences to be removed, or natural or synthetic sequences
to be added. To connect the DNA fragments to each other, adapters
or linkers may be added to the fragments.
[0085] 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
above-mentioned gene product.
[0086] To this end, it is possible to use DNA molecules which
encompass the entire coding sequence of a gene product inclusive of
any flanking sequences which may be present, and also DNA molecules
which only encompass portions of the coding sequence, it being
necessary for these portions to be long enough to have an antisense
effect in the cells. The use of DNA sequences which have a high
degree of homology to the coding sequences of a gene product, but
are not completely identical to them, is also possible.
[0087] 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 coding 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).
[0088] The transgenic plant cells can be regenerated by known
techniques to give rise to entire plants. In principle, the
transgenic plants can be plants of any desired plant species, i.e.
not only monocotyledonous, but also dicotyledonous, plants. 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.
[0089] The present invention furthermore provides a method for the
selective control of unwanted plants, preferably in crop plants, in
particular in rice crops (planted or sown under upland or paddy
conditions using indica and/or japonica species and/or
hybrids/mutants/GMOs), which comprises applying the herbicides as
components (A) and (B) of the herbicide combinations according to
the invention to the plants (for example harmful plants, such as
monocotyledonous or dicotyledonous broad-leaved weeds, weed
grasses, Cyperaceae or unwanted crop plants), the seed (for example
grains, seeds or vegetative propagation organs, such as tubers or
shoot parts with buds) or to the area in which the plants grow (for
example the area under cultivation, which may also be covered by
water), for example together or separately. One or more herbicides
(A) may be applied before, after or simultaneously with the
herbicide(s) (B) to the plants, the seed or the area in which the
plants grow (for example the area under cultivation).
[0090] Unwanted plants are to be understood as meaning all plants
which grow in locations where they are unwanted. These can, for
example, be harmful plants (for example monocotyledonous or
dicotyledonous weeds, weed grasses, Cyperaceae or unwanted crop
plants), including, for example, those which are resistant to
certain herbicidally active compounds, such as glyphosate,
glufosinate, atrazine, imidazolinone herbicides, sulfonylureas,
(hetero)aryloxyaryloxyalkylcarboxylic acids or
-phenoxyalkylcarboxylic acids (`fops`), cyclohexanedione oximes
(`dims`) or auxin inhibitors.
[0091] The herbicide combinations according to the invention are
employed selectively for controlling unwanted vegetation, for
example in crop plants such as farm crops, for example
monocotyledonous farm crops, such as cereals (for example wheat,
barley, rye, oats, rice, corn, millet), or dicotyledonous farm
crops, such as sugar beet, sugar case, oilseed rape, cotton,
sunflowers and leguminous plants, for example of the genera Glycine
(for example Glycine max. (soybean), such as non-transgenic Glycine
max. (for example conventional cultivars, such as STS cultivars) or
transgenic Glycine max. (for example RR-soybean or LL-soybean) and
crossbreeds thereof), Phaseolus, Pisum, Vicia and Arachis, or
vegetable crops from various botanical groups, such as potato,
leek, cabbage, carrot, tomato, onion, in fruit plantations
(plantation crops), greens, lawns and pasture areas, or on non-crop
areas (for example squares of residential areas or industrial
sites, rail tracks) in particular in rice crops (planted or sown
under upland or paddy conditions using indica or japonica varieties
and also hybrids/mutants/GMOs). The application is preferably
carried out both prior to the emergence of the harmful plants and
to the emerged harmful plants (for example broad-leaved weeds, weed
grasses, Cyperaceae or unwanted crop plants), independently of the
stage of the sown/planted crop.
[0092] The invention also provides the use of the herbicide
combinations according to the invention for selectively controlling
unwanted vegetation, preferably in crop plants, in particular in
rice crops (planted or sown under upland or paddy conditions using
indica or japonica varieties and also hybrids/mutants/GMOs).
[0093] The herbicide combinations according to the invention can be
prepared by known processes, for example as mixed formulations of
the individual components, if appropriate with further active
compounds, additives and/or customary formulation auxiliaries,
which combinations are then applied in a customary manner diluted
with water, or as tank mixes by joint dilution of the components,
formulated separately or formulated partially separately, with
water. Also possible is the split application of the separately
formulated or partially separately formulated individual
components. It is also possible to use the herbicides or the
herbicide combinations in a plurality of portions (sequential
application), for example after application as seed dressing or
pre-sowing/planting treatment or pre-emergence applications
followed by post-emergence applications or early post-emergence
applications followed by medium or late post-emergence
applications. Preference is given here to the joint or almost
simultaneous use of the active compounds of the combination in
question, and the joint use is particularly preferred.
[0094] The herbicides (A) and (B) can be converted jointly or
separately into customary formulations, such as solutions,
emulsions, suspensions, powders, foams, pastes, granules, aerosols,
natural and synthetic materials impregnated with active compound
and microencapsulations in polymeric materials. Mention may also be
made of formulations specific for the cultivation of rice, such as,
for example, granules for scattering, jumbo granules, floating
granules, floating suspoemulsions applied via shaker bottles and
dissolved in and distributed via the paddy water. The formulations
may comprise the customary auxiliaries and additives.
[0095] These formulations are produced in a known manner, for
example by mixing the active compounds with extenders, that is,
liquid solvents, liquefied gases under pressure, and/or solid
carriers, optionally with the use of surfactants, that is
emulsifiers and/or dispersants, and/or foam formers.
[0096] If the extender used is water, it is also possible to
employ, for example, organic solvents as auxiliary solvents.
Essentially, suitable liquid solvents are: aromatics such as
xylene, toluene or alkylnaphthalenes, chlorinated aromatics and
chlorinated aliphatic hydrocarbons such as chlorobenzenes,
chloroethylenes or methylene chloride, aliphatic hydrocarbons such
as cyclohexane or paraffins, for example mineral oil fractions,
mineral and vegetable oils, alcohols such as butanol or glycol and
their ethers and esters, ketones such as acetone, methyl ethyl
ketone, methyl isobutyl ketone or cyclohexanone, strongly polar
solvents such as dimethylformamide and dimethyl sulfoxide, and also
water.
[0097] Suitable solid carriers are: for example ammonium salts and
ground natural minerals such as kaolins, clays, talc, chalk,
quartz, attapulgite, montmorillonite or diatomaceous earth, and
ground synthetic minerals such as highly-disperse silica, alumina
and silicates; suitable solid carriers for granules are: for
example crushed and fractionated natural rocks such as calcite,
marble, pumice, sepiolite and dolomite, and also synthetic granules
of inorganic and organic meals, and granules of organic material
such as sawdust, coconut shells, maize cobs and tobacco stalks;
suitable emulsifiers and/or foam-formers are: for example nonionic
and anionic emulsifiers, such as polyoxyethylene fatty acid esters,
polyoxyethylene fatty alcohol ethers, for example alkylaryl
polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl
sulfonates, and also protein hydrolysates; suitable dispersants
are: for example lignosulphite waste liquors and methyl
cellulose.
[0098] Tackifiers, such as carboxymethyl cellulose, natural and
synthetic polymers in the form of powders, granules or latices,
such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and
also natural phospholipids, such as cephalins and lecithins, and
synthetic phospholipids can be used in the formulations. Other
possible additives are mineral and vegetable oils.
[0099] The herbicidal action of the herbicide combinations
according to the invention can be improved, for example, by
surfactants, preferably by wetting agents from the group of the
fatty alcohol polyglycol ethers. The fatty alcohol polyglycol
ethers preferably comprise 10-18 carbon atoms in the fatty alcohol
radical and 2-20 ethylene oxide units in the polyglycol ether
moiety. The fatty alcohol polyglycol ethers may be present in
nonionic form, or ionic form, for example in the form of fatty
alcohol polyglycol ether sulfates, which may be used, for example,
as alkali metal salts (for example sodium salts and potassium
salts) or ammonium salts, or even as alkaline earth metal salts,
such as magnesium salts, such as C.sub.12/C.sub.14-fatty alcohol
diglycol ether sulfate sodium (Genapol.RTM. LRO, Clariant GmbH);
see, for example, EP-A-0476555, EP-A-0048436, EP-A-0336151 or U.S.
Pat. No. 4,400,196 and also Proc. EWRS Symp. "Factors Affecting
Herbicidal Activity and Selectivity", 227-232 (1988). Nonionic
fatty alcohol polyglycol ethers are, for example,
(C.sub.10-C.sub.18)-, preferably (C.sub.10-C.sub.14)-fatty alcohol
polyglycol ethers (for example isotridecyl alcohol polyglycol
ethers) which comprise, for example, 2-20, preferably 3-15,
ethylene oxide units, for example those from the Genapol.RTM.
X-series, such as Genapol.RTM. X-030, Genapol.RTM. X-060,
Genapol.RTM. X-080 or Genapol.RTM. X-150 (all from Clariant
GmbH).
[0100] The present invention further comprises the combination of
components (A) and (B) with the wetting agents mentioned above from
the group of the fatty alcohol polyglycol ethers which preferably
contain 10-18 carbon atoms in the fatty alcohol radical and 2-20
ethylene oxide units in the polyglycol ether moiety and which may
be present in nonionic or ionic form (for example as fatty alcohol
polyglycol ether sulfates). Preference is given to
C.sub.12/C.sub.14-fatty alcohol diglycol ether sulfate sodium
(Genapol.RTM. LRO, Clariant GmbH) and isotridecyl alcohol
polyglycol ether having 3-15 ethylene oxide units, for example from
the Genapol.RTM. X-series, such as Genapol.RTM. X-030, Genapol.RTM.
X-060, Genapol.RTM. X-080 and Genapol.RTM. X-150 (all from Clariant
GmbH).
[0101] Furthermore, it is known that fatty alcohol polyglycol
ethers, such as nonionic or ionic fatty alcohol polyglycol ethers
(for example fatty alcohol polyglycol ether sulfates) are also
suitable for use as penetrants and activity enhancers for a number
of other herbicides (see, for example, EP-A-0502014). Accordingly,
the present invention also embraces the combination with suitable
penetrants and activity enhancers, preferably in commercially
available form.
[0102] The herbicide combinations according to the invention can
also be used together with vegetable oils. The term vegetable oils
is to be understood as meaning oils of oleaginous plant species,
such as soybean oil, rapeseed oil, corn oil, sunflower oil,
cottonseed oil, linseed oil, coconut oil, palm oil, thistle oil or
castor oil, in particular rapeseed oil, and also their
transesterification products, for example alkyl esters, such as
rapeseed oil methyl ester or rapeseed oil ethyl ester.
[0103] The vegetable oils are preferably esters of
C.sub.10-C.sub.22-, preferably C.sub.12-C.sub.20-, fatty acids. The
C.sub.10-C.sub.22-fatty acid esters are, for example, esters of
unsaturated or saturated C.sub.10-C.sub.22-fatty acids, in
particular those having an even number of carbon atoms, for example
erucic acid, lauric acid, palmitic acid and in particular
C.sub.18-fatty acids, such as stearic acid, oleic acid, linoleic
acid or linolenic acid.
[0104] Examples of C.sub.10-C.sub.22-fatty acid esters are esters
obtained by reacting glycerol or glycol with the
C.sub.10-C.sub.22-fatty acids contained, for example, in oils of
oleaginous plant species, or
C.sub.1-C.sub.20-alkyl-C.sub.10-C.sub.22-fatty acid esters which
can be obtained, for example, by transesterification of the
aforementioned glycerol- or glycol-C.sub.10-C.sub.22-fatty acid
esters with C.sub.1-C.sub.20-alcohols (for example methanol,
ethanol, propanol or butanol). The transesterification can be
carried out by known methods as described, for example, in Rompp
Chemie Lexikon, 9th edition, Volume 2, page 1343, Thieme Verlag
Stuttgart.
[0105] Preferred C.sub.1-C.sub.20-alkyl-C.sub.10-C.sub.22-fatty
acid esters are methyl esters, ethyl esters, propyl esters, butyl
esters, 2-ethylhexyl esters and dodecyl esters. Preferred glycol-
and glycerol-C.sub.10-C.sub.22-fatty acid esters are the uniform or
mixed glycol esters and glycerol esters of C.sub.10-C.sub.22-fatty
acids, in particular fatty acids having an even number of carbon
atoms, for example erucic acid, lauric acid, palmitic acid and, in
particular, C.sub.18-fatty acids, such as stearic acid, oleic acid,
linoleic acid or linolenic acid.
[0106] In the herbicidal compositions according to the invention,
the vegetable oils can be present, for example, in the form of
commercially available oil-containing formulation additives, in
particular those based on rapeseed oil, such as Hasten.RTM.
(Victorian Chemical Company, Australia, hereinbelow referred to as
Hasten, main ingredient: rapeseed oil ethyl ester), Actirob.RTM.B
(Novance, France, hereinbelow referred to as ActirobB, main
ingredient: rapeseed oil methyl ester), Rako-Binol.RTM. (Bayer AG,
Germany, hereinbelow referred to as Rako-Binol, main ingredient:
rapeseed oil), Renol.RTM. (Stefes, Germany, hereinbelow referred to
as Renol, vegetable oil ingredient: rapeseed oil methyl ester) or
Stefes Mero.RTM. (Stefes, Germany, hereinbelow referred to as Mero,
main ingredient: rapeseed oil methyl ester).
[0107] In a further embodiment, the present invention also
comprises combinations with the vegetable oils mentioned above,
such as rapeseed oil, preferably in the form of commercially
available oil-containing formulation additives, in particular those
based on rapeseed oil, such as Hasten.RTM. (Victorian Chemical
Company, Australia, hereinbelow referred to as Hasten, main
ingredient: rapeseed oil ethyl ester), Actirob.RTM.B (Novance,
France, hereinbelow referred to as ActirobB, main ingredient:
rapeseed oil methyl ester), Rako-Binol.RTM. (Bayer AG, Germany,
hereinbelow referred to as Rako-Binol, main ingredient: rapeseed
oil), Renol.RTM. (Stefes, Germany, hereinbelow referred to as
Renol, vegetable oil ingredient: rapeseed oil methyl ester) or
Stefes Mero.RTM. (Stefes, Germany, hereinbelow referred to as Mero,
main ingredient: rapeseed oil methyl ester).
[0108] It is possible to use colorants such as inorganic pigments,
for example iron oxide, titanium oxide and Prussian Blue, and
organic colorants such as alizarin colorants, azo colorants and
metal phthalocyanine colorants, and trace nutrients such as salts
of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
[0109] In general, the formulations comprise between 0.1 and 95% by
weight of active compound, preferably between 0.5 and 90% by
weight.
[0110] As such or in their formulations, the herbicides (A) and (B)
can also be used as a mixture with other agrochemically active
compounds, such as known herbicides, for controlling unwanted
vegetation, for example for controlling weeds or for controlling
unwanted crop plants, finished formulations or tank mixes, for
example, being possible.
[0111] Mixtures with other known active compounds, such as
fungicides, insecticides, acaricides, nematicides, safeners, bird
repellents, plant nutrients and agents which improve soil
structure, are also possible.
[0112] The herbicides (A) and (B) can be used as such, in the form
of their formulations or in the use forms prepared therefrom by
further dilution, such as ready-to-use solutions, suspensions,
emulsions, powders, pastes and granules. They are used in a
customary manner, for example by watering, spraying, atomizing or
broadcasting.
[0113] The active compounds can be applied to the plants (for
example harmful plants, such as monocotyledonous or dicotyledonous
broad-leaved weeds, weed grasses, Cyperaceae or unwanted crop
plants), the seed (for example grains, seeds or vegetative
propagation organs, such as tubers or shoot parts with buds) or the
area under cultivation (for example the soil), preferably to the
green plants and parts of plants and, if appropriate, additionally
the soil. One possible use is the joint application of the active
compounds in the form of tank mixes, where the optimally formulated
concentrated formulations of the individual active compounds are,
together, mixed in a tank with water, and the spray liquor obtained
is applied.
[0114] A joint herbicidal formulation of the combination according
to the invention of herbicides (A) and (B) has the advantage that
it is easier to apply, since the amounts of the components are
already in an optimum ratio. Moreover, the auxiliaries in the
formulation can be adjusted optimally to one another.
BIOLOGICAL EXAMPLES
Post-Emergence Action Against Weeds
Method
[0115] Seeds or rhizome pieces of mono- and dicotyledonous harmful
and useful plants were placed in peat pots (diameter 4 cm) filled
with sandy loam and then covered with soil. The pots were kept in a
greenhouse under optimum conditions. In addition, harmful plants
encountered in paddy rice cultivation were cultivated in pots with
a water level 2 cm above the soil surface.
[0116] About three weeks after the start of the cultivation, the
test plants were treated at the 2- to 3-leaf stage. The herbicides,
formulated as powder or liquid concentrates, were, either alone or
in the combinations according to the invention, sprayed in various
dosages on to the green parts of the plants using an application
rate of 600 l of water/ha (converted). For further cultivation of
the plants, the pots were then again kept under optimum conditions
in a greenhouse.
[0117] The visual scoring of the herbicidal effects was carried out
in intervals up to 21 days after the treatment. Scoring was carried
out in percent in comparison to the untreated control plants. 0%=no
herbicidal activity, 100%=complete herbicidal activity=complete
kill.
[0118] The percentages from the treatments with the herbicides
alone (=individual application) and with the combinations according
to the invention (=mixtures) were employed to calculate
interactions using the method of Colby. When the observed
efficacies of the mixtures exceed the formal sum of the values of
the tests with individual applications, they also exceed the
expected value according to Colby, which is calculated using the
formula below (cf. S. R. Colby; in Weeds 15 (1967) pp. 20 to
22):
E=A+B-(A.times.B/100)
Here:
[0119] A, B=activity of components A and B in percent at a dosage
of a and b g of ai/ha (=gramm of active substance per hectare),
respectively. [0120] E=expected value in % at a dosage of a+b g of
ai/ha.
Results
[0121] The combinations according to the invention of herbicides
from group (A) with herbicides from group (B) were tested on a
broad spectrum of important harmful plants (weed grasses,
broad-leaved weeds/Cyperaceae) and useful plants: Triticum aestivum
(TRZAS), Stellaria media (STEME), Lolium multiflorum (LOLMU),
Veronica persica (VERPE), Alopecurus myosuroides (ALOMY),
Matricaria inodora (MATIN), Brassica napus (BRSNW), Viola tricolor
(VIOTR), Avena fatua (AVEFA), Amaranthus retroflexus (AMARE), Zea
mays (ZEAMX), Pharbitis purpurea (PHBPU), Setaria viridis (SETVI),
Fallopia (ex Polygonum) convolvulus (POLCO), Echinochloa crusgaffi
(ECHCG), Abuthilon theophrasti (ABUTH), Cyperus esculentus (CYPES),
Oryza sativa (ORYSA).
[0122] Of particular interest are the results shown in the tables
(Tab.) below, where the following key is used: [0123] (1) EPPO code
(former Bayer code) for the treated plant (see above) [0124] (2)
Time of scoring: DAT (days after treatment) [0125] (3) Component A
tested (identifying number) [0126] (4) Component B tested
(identifying number) [0127] (5) Dosage component A [g of ai/ha]
[0128] (6) Dosage component B [g of ai/ha] [0129] (7) % activity
found [0130] (8) E value (calculated according to Colby; see above)
[0131] (9) Comments: "SYNERGY"=synergistic interaction (E value
<% activity found); "SAFENING"=safener action on useful plant (E
value >% activity found)
TABLE-US-00001 [0131] TABLE 1 (1) LOLMU - (2) 10 DAT - (3) A-1 -
(4) B2-1 (5) (6) (7) (8) (3) 12 -- 10 -- 4 -- 0 -- (4) -- 12 40 --
(3) + (4) 12 12 70 46 4 12 70 40 (9) SYNERGY
TABLE-US-00002 TABLE 2 (1) ZEAMX - (2) 10 DAT - (3) A-1 - (4) B2-1
(5) (6) (7) (8) (3) 12 -- 0 -- 4 -- 0 -- (4) -- 36 40 -- -- 12 40
-- (3) + (4) 12 36 70 40 12 12 60 40 4 36 50 40 4 12 50 40 (9)
SYNERGY
TABLE-US-00003 TABLE 3 (1) LOLMU - (2) 21 DAT - (3) A-1 - (4) B2-1
(5) (6) (7) (8) (3) 4 -- 0 -- (4) -- 36 70 -- -- 12 20 -- (3) + (4)
4 36 80 70 4 12 60 20 (9) SYNERGY
TABLE-US-00004 TABLE 4 (1) LOLMU - (2) 21 DAT - (3) A-1 - (4) B2-1
(5) (6) (7) (8) (3) 12 -- 10 -- (4) -- 12 20 -- (3) + (4) 12 12 70
28 (9) SYNERGY
TABLE-US-00005 TABLE 5 (1) ZEAMX - (2) 21 DAT - (3) A-1 - (4) B2-1
(5) (6) (7) (8) (3) 12 -- 0 -- 4 -- 0 -- (4) -- 36 0 -- -- 12 0 --
(3) + (4) 12 36 50 0 12 12 40 0 4 36 20 0 4 12 10 0 (9) SYNERGY
TABLE-US-00006 TABLE 6 (1) ORYSA - (2) 21 DAT - (3) A-1 - (4) B2-1
(5) (6) (7) (8) (3) 12 -- 10 -- 4 -- 0 -- (4) -- 36 70 -- (3) + (4)
12 36 60 73 4 36 50 70 (9) SAFENING
TABLE-US-00007 TABLE 7 (1) TRZAS - (2) 10 DAT - (3) A-1 - (4) B4-6
(5) (6) (7) (8) (3) 12 -- 0 -- 4 -- 0 -- (4) -- 9 50 -- (3) + (4)
12 9 60 50 4 9 60 50 (9) SYNERGY
TABLE-US-00008 TABLE 8 (1) VIOTR - (2) 10 DAT - (3) A-1 - (4) B4-6
(5) (6) (7) (8) (3) 4 -- 20 -- (4) -- 9 85 -- -- 3 10 -- (3) + (4)
4 9 100 88 4 3 95 28 (9) SYNERGY
TABLE-US-00009 TABLE 9 (1) VIOTR - (2) 10 DAT - (3) A-1 - (4) B4-6
(5) (6) (7) (8) (3) 12 -- 20 -- (4) -- 3 10 -- (3) + (4) 12 3 90 28
(9) SYNERGY
TABLE-US-00010 TABLE 10 (1) ZEAMX - (2) 10 DAT - (3) A-1 - (4) B4-6
(5) (6) (7) (8) (3) 12 -- 0 -- (4) -- 3 40 -- (3) + (4) 12 3 60 40
(9) SYNERGY
TABLE-US-00011 TABLE 11 (1) ORYSA - (2) 10 DAT - (3) A-1 - (4) B4-6
(5) (6) (7) (8) (3) 12 -- 10 -- 4 -- 10 -- (4) -- 9 40 -- -- 3 40
-- (3) + (4) 12 9 30 46 12 3 30 46 4 9 20 46 4 3 20 46 (9)
SAFENING
TABLE-US-00012 TABLE 12 (1) TRZAS - (2) 21 DAT - (3) A-1 - (4) B4-6
(5) (6) (7) (8) (3) 12 -- 0 -- (4) -- 3 30 -- (3) + (4) 12 3 40 30
(9) SYNERGY
TABLE-US-00013 TABLE 13 (1) MATIN - (2) 21 DAT - (3) A-1 - (4) B4-6
(5) (6) (7) (8) (3) 4 -- 50 -- (4) -- 9 80 -- (3) + (4) 4 9 100 90
(9) SYNERGY
TABLE-US-00014 TABLE 14 (1) AVEFA - (2) 21 DAT - (3) A-1 - (4) B4-6
(5) (6) (7) (8) (3) 12 -- 30 -- 4 -- 10 -- (4) -- 3 0 -- (3) + (4)
12 3 40 30 4 3 40 10 (9) SYNERGY
TABLE-US-00015 TABLE 15 (1) ZEAMX - (2) 21 DAT - (3) A-1 - (4) B4-6
(5) (6) (7) (8) (3) 12 -- 0 -- (4) -- 3 30 -- (3) + (4) 12 3 40 30
(9) SYNERGY
TABLE-US-00016 TABLE 16 (1) CYPES - (2) 21 DAT - (3) A-1 - (4) B4-6
(5) (6) (7) (8) (3) 4 -- 80 -- (4) -- 9 20 -- (3) + (4) 4 9 98 84
(9) SYNERGY
* * * * *
References