AGENTS HERBICIDES SYNERGIQUES CONTENANT DES HERBICIDES DU GROUPES DES BENZOPYRAZOLS

SYNERGISTIC HERBICIDAL COMPOSITIONS COMPRISING HERBICIDES FROM THE GROUP OF THE BENZOYLPYRAZOLES

Abrégé français

Des agents herbicides contenant A) au moins un composé du groupe des benzopyrazoles et B) au moins un composé du groupe d'herbicides actifs contre des plantes nuisibles monocotylédones et/ou dicotylédones. Ces agents présentent une efficacité supérieure par rapport aux herbicides appliqués individuellement.

Abrégé anglais

Herbicidal compositions comprising: A) at least one compound from the group of the benzoylpyrazoles; and B) at least one compound from the group of the herbicides active against monocotyledonous and/or dicotyledonous harmful plants are described. The activity of these compositions is superior to that of the herbicides applied individually.

Revendications

18
CLAIMS:
1. A herbicidal composition, comprising:
(A) at least one compound of the general formula (I), or an
agriculturally acceptable salt, thereof:
<IMG>
in which:
R1 is methyl or ethyl,
R2 is trifluoromethyl, F, Cl, or Br,
R3 is H or methyl,
R4 is methyl or ethyl,
R5 is H, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, phenylsulfonyl,
4-methylphenylsulfonyl, benzyl, benzoylmethyl, nitrobenzoylmethyl or 4-fluoro-
benzoylmethyl, and
n is 0, 1, or 2; and
(B4) at least one compound which is an inhibitor of fatty acid
biosynthesis and is selected from the group consisting of benthiocarb (B4.1),
clodinafop-propargyl (B4.2), diclofop-methyl (B4.3), fenoxaprop-P-ethyl (B4.4)
and
tralkoxydim (B4.5);
wherein the composition comprises (A) and (B4) in a weight ratio of
from 1:2000 to 2000:1.

19
2. The herbicidal composition as claimed in claim 1, wherein the
compound of the general formula (I):
R1 is methyl;
R2 is trifluoromethyl;
R3 is H or methyl;
R4 is methyl or ethyl;
R5 is H; and
n is 2.
3. The herbicidal composition as claimed in claim 1 or 2, wherein the
weight ratio (A):(B4) is in the range from 1:50 to 50:1.
4. The herbicidal composition as claimed in claim 3, wherein the weight
ratio (A):(B4) is in the range from 1:20 to 20:1.
5. The herbicidal composition as claimed in any one of claims 1 to 4,
which comprises 0.1-99% by weight of herbicides (A) and (B4), and 99 to 0.1%
by
weight of a formulating agent customary in crop protection.
6. A method for controlling unwanted vegetation, which comprises
applying one or more herbicides (A) and one or more herbicides (B4) to the
unwanted vegetation, to parts of the unwanted vegetation or to an area under
cultivation, the combination of the herbicides (A) and (B4) being as defined
in any
one of claims 1 to 5.
7. Use of a combination of herbicides (A) and (B4) as defined in any
one of claims 1 to 5, as a herbicidal composition for controlling unwanted
vegetation.

Description

CA 02720498 2010-11-09
28976-244E
1
Description
Synergistic herbicidal compositions comprising herbicides from the group of
the
benzoylpyrazoles
This application is a divisional application of copending application
2,467,976, filed
November 13, 2002.
The invention relates to the technical field of crop protection agents which
can be
used against unwanted vegetation and comprise, as active compounds, a
combination of at least two herbicides.
More specifically, it relates to herbicidal compositions which comprise, as
active
compound, a herbicide from the group of the benzoylpyrazoles in combination
with at
least one further herbicide.
Herbicides of the abovementioned group of the benzoylpyrazoles are known from
numerous documents. Thus, EP-AO 203 428, US 4,643,757, WO 97/23135 and the
German patent application DE 10016116.2, which is of earlier priority but not
prior-
published, describe a number of benzoylpyrazoles having herbicidal action.
However, the use of the benzoylpyrazoles derivatives known from these
publications
frequently entails disadvantages in practice. Thus, the herbicidal activity of
the
known compounds is not always sufficient, or, if the herbicidal activity is
sufficient,
then undesired damage to the useful plants is observed.
The effectiveness of herbicides depends inter alia on the type of herbicide
used, its
application rate, the formulation, the harmful plants to be controlled in each
case,
climatic and soil conditions, etc. A further criterion is the persistency or
the rate at
which the herbicide is degraded. Changes in the susceptibility of harmful
plants to an
active compound which may occur on prolonged use or in specific geographical
areas may also have to be taken into account. Such changes manifest themselves
by a more or less pronounced loss in activity and can only be compensated to a
limited extent by higher herbicide application rates.

CA 02720498 2010-11-09
28976-244
2
Owing to the large number of possible influencing factors, there is virtually
no
individual active compound which has all the desired properties for different
requirements, in particular with respect to the species of harmful plants and
the
climatic zones- Furthermore, there is the permanent object to achieve the
desired
effect using more and more reduced herbicide application rates. A lower
application
rate reduces not only the amount of active compound required for the
application,
but generally also reduces the amount of formulation of auxiliaries required.
Both
reduce the economic expense and improve the ecological compatibility of the
herbicide treatment.
A frequently used method for improving the use profile of a herbicide is the
combination of the active compound with one or more other active compounds
which
contribute the desired additional properties. WO 01/28341 discloses
combinations of
herbicidally active benzoyl derivatives with other herbicides. Combinations of
herbicidally active benzoyipyrazoles and a number of other herbicides are
known
from WO 97/31535, WO 98/68526, WO 98/54967, WO 00/02703 and WO 00/03591.
However, when two or more active compounds are applied in combination, it is
not
uncommon for phenomena of physical and biological incompatibility to occur,
for
example insufficient stability of a joint formulation, decomposition of an
active
compound or antagonism of the active compounds. What is desired are, in
contrast,
active compound combinations having a favorable activity profile, high
stability and, if
possible, synergistically enhanced activity, thus permitting the application
rate to be
reduced, compared with the individua! application of the active compounds to
be
combined.
The invention provides selected herbicidal compositions, comprising an
effective
amount of

CA 02720498 2010-11-09
3
A) at least one compound of the formula (I) or an agriculturally suitable salt
thereof (component A)
R3 O S(O)nR'
N I I
N 2
OR' R
(I),
in which
R1 is methyl or ethyl;
R2 is trifluoromethyl, fluorine, chlorine or bromine;
R3 is hydrogen or methyl:
R4 is methyl or ethyl;
R' is hydrogen, methylsuifonyl, ethylsulfonyl, n-propylsulfonyl,
phenylsulfonyl,
4-m ethyl phenylsuifonyl, benzyl, benzoylmethyl, nitrobenzoylmethyl or 4-
fluoro-
benzoylmethyl and
n is 0, 1, or 2, and
B) at least one compound (component B) from one of the following groups
BI inhibitors of the biosynthesis of branched amino acids:
amidosulfuron (81.1), bensulfuron (81.2), ethoxysulfuron (81.3), halosuifuron
(131.4),
imazethapyr (B1.5), iodosulfuron-methyl-sodium (81.6), metsulfuron (81.7),
nicosulfuron (B1.8), sulfosulfuron (B1.9), thifensulfuron-methyl (B1.10),
tribenuron
(B1.11), N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonyl-5-
methylsulfonylaminomethylbenzenesulfonamide (mesosulfuron) (81.12) and N-[(4,6-
dimethoxypyrimid in-2-yl)aminocarbonyl]-2-dimethylaminocarbonyl-5-formylamino-
benzenesulfonamide (foramsulfuron) (B1.13), procarbazone sodium (MKH 6561)
(81.14), flucarbazone (MKH 6562) (81.15), amicarbazone (MKH 31866) (61.16),
florasulam (B1.17), flupyrsulfuron-methyl-sodium (BI.18);
B2 inhibitors of the photosynthesis electron transport:

CA 02720498 2010-11-09
28976-244
4
atrazine (B2.1), bromoxynil (82.2), ioxynil (B2.3), isoproturon (B2.4),
metribuzin
(B2.5), propanil (B2.6);
83 synthetic auxins:
MCPA (83.1), 2,4-DP (B3.2), mecoprop (B3.3), dicamba (83.4), diflufenzopyr
(83.5),
fluroxypyr (B3.6), quinclorac (B3.7);
B4 inhibitors of fatty acid biosynthesis:
benthiocarb (B4.1), clodinafop-propargyl (B4.2), diclofop-methyl (B4.3),
fenoxaprop-
P-ethyl (84.4), tralkoxydim (B4.5);
B5 inhibitors of cell division:
acetochlor (B5.1), alachlor (B5.2), anilofos (85.3), flufenacet (B5.4),
metolachlor
(85.5), thenylchlor (85.6), flufenacet (B5.7), mefenacet (B5.8);
86 inhibitors of fatty acid biosynthesisicarotinoid biosynthesis:
diflufenican (86.1), clomazone (B6.2);
87 glyphosate (87.1) and
B8 glufosinate (88.1),
where these compositions comprise the compounds of the formula (I) or salts
thereof
(component A) and the compounds of groups 131 to B8 (component B) in a weight
ratio of from 1:2000 to 2000:1.

CA 02720498 2010-11-09
28976-244E
4a
In one aspect, the parent application relates to a herbicidal
composition, comprising: (A) at least one compound of the general formula (I),
or
an agriculturally acceptable salt, thereof:
R3 0 S(O)nR'
5R2
R'ORS (1),
in which: R1 is methyl or ethyl, R2 is trifluoromethyl, F, Cl, or Br, R3 is H
or methyl,
R4 is methyl or ethyl, R5 is H, methylsulfonyl, ethylsulfonyl, n-
propylsulfonyl,
phenylsulfonyl, 4-methylphenylsulfonyl, benzyl, benzoylmethyl,
nitrobenzoylmethyl
or 4-fluoro-benzoylmethyl, and n is 0, 1, or 2; and (B2) at least one compound
which is an inhibitor of photosynthesis electron transport and is selected
from the
group consisting of atrazine (B2.1), bromoxynil (B2.2), isoproturon (B2.3),
metribuzin (B2.4) and propanyl (B2.5); wherein the composition comprises (A)
and
(B2) in a weight ratio of from 1:2000 to 2000:1.
In one aspect, this divisional application relates to a herbicidal
composition, comprising:
(A) at least one compound of the general formula (I), or an
agriculturally acceptable salt, thereof:
R3 0 S(O)õR'
2
R4/ ORS R
(I),
in which:
R1 is methyl or ethyl,

CA 02720498 2010-11-09
28976-244E
4b
R2 is trifluoromethyl, F, Cl, or Br,
R3 is H or methyl,
R4 is methyl or ethyl,
R5 is H, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, phenylsulfonyl,
4-methylphenylsulfonyl, benzyl, benzoylmethyl, nitrobenzoylmethyl or 4-fluoro-
benzoylmethyl, and
n is 0, 1, or 2; and
(B4) at least one compound which is an inhibitor of fatty acid
biosynthesis and is selected from the group consisting of benthiocarb (B4.1),
clodinafop-propargyl (B4.2), diclofop-methyl (B4.3), fenoxaprop-P-ethyl (B4.4)
and
tralkoxydim (B4.5);
wherein the composition comprises (A) and (B4) in a weight ratio of
from 1:2000 to 2000:1.
The compounds of the formula (1) are known from W001/74785 and
can be prepared, for example, by the processes described therein or the
processes known from DE 25 13 750 and EP-A 0 186 117.

CA 02720498 2010-11-09
The chemical structures of the active compounds referred to above by their
common
names are known, for example, from "The Pesticide Manual", 12th edition, 2000,
British Crop Protection Council. Foramsulfuron is known as a herbicide from
WO 95/10507, for example, and mesosulfuron is known as a herbicide from
5 WO 95/10507, for example.
Preference is given to herbicidal compositions which, as component (A),
comprise a
compound of the formula (I) which is as defined below:
R3 O S(O)nR'
NX I I 11\
N 2
4 OR5 R
(I)
Nr. R1 R2 R3 R4 R5 n
(Al) CH3 CF3 H CH3 H 2
/A2) CH3 CF3 CH; CH3 H 2
(A3) CH3 CF3 CH3 CH2CH3 H 2
(A4) CH3 CF3 H CH2CH3 H 2
Of particular interest are herbicidal compositions comprising a
synergistically
effective amount of one or more of the following combinations of two compounds
(A)
+ (B):
(A1)+(B1.1), (A1)+(B1.2), (A1)+(B1.3), (A1)+(B1.4), (A1)+(B1.5), (A1)+(B1.6),
(A1)+(B1.7), (A1)+(B1.8), (A1)+(B1.9), (A1)+(B1.10), (A1)+(B1.11),
(A1)+(B1.12),
(A1)+(B1.13), (A1)+(B1.14), (A1)+(61.15), (A1)+(B1.16), (A1)+(B1.17),
(A1)+(B1.18);
(A2)+(B1.1), (A2)+(Bl.2), (A2)+(B1.3), (A2)+(Bl.4), (A2)+(B1.5), (A2)+(B1.6),

CA 02720498 2010-11-09
6
(A2)+(B1.7), (A2)+(B1.8), (A2)+(B1.9), (A2)+(B1.10), (A2)+(B1.11),
(A2)+(B1.12),
(A2)+(B1.13), (A2)+(B1.14), (A2)+(B1.15), (A2)+(61.16), (A2)+(B1.17),
(A2)+(B1.18);
(A3)+(B1.1), (A3)+(B1.2), (A3)+(B1.3), (A3)+(B1.4), (A3)+(B1.5), (A3)+(B1.6),
(A3)+(B1.7), (A3)+(B1.8), (A3)+(Bl.9), (A3)+(B1.10), (A3)+(61.11),
(A3)+(61.12),
(A3)+(B1.13), (A3)+(B1.14), (A3)+(B1.15), (A3)+(B1.16), (A3)+(B1.17),
(A3)+(B1.18);
(A4)+(B1.1), (A4)+(B1.2), (A4)+(B1.3), (A4)+(B1.4), (A4)+(B1.5), (A4)+(B1.6),
(A4)+(B1.7), (A4)+(B1.8), (A4)+(B1.9), (A4)+(B1.10), (A4)+(61.11),
(A4)+(B1.12),
(A4)+(B1.13), (A4)+(B1.14), (A4)+(B1.15), (A4)+(B1.16), (A4)+(B1.17),
(A4)+(B1.18);
(A1)+(B2.1), (A1)+(B2.2), (A1)+(B2.3), (A1)+(B2.4), (Al)+(B2.5);
(A2)+(B2.1), (A2)+(B2.2), (A2)+(B2.3), (A2)+(B2.4), (A2)+(B2.5);
(A3)+(B2.1), (A3)+(B2.2), (A3)+(B2.3), (A3)+(B2.4), (A3)+(B2.5);
(A4)+(B2.1), (A4)+(B2.2), (A4)+(B2.3), (A4)+(B2.4), (A4)+(B2.5);
(A1)+(B3.1), (A1)+(B3.2), (A1)+(B3.3), (A1)+(B3.4), (Al)+(B3.5), (A1)+(B3.6),
(A1)+(B3.7);
(A2)+(B3.1), (A2)+(B3.2), (A2)+(B3.3), (A2)+(B3.4), (A2)+(B3.5), (A2)+(B3.6),
(A2)+(B3.7);
(A3)+(B3.1), (A3)+(B3.2), (A3)+(B3.3), (A3)+(B3.4), (A3)+(B3.5), (A3)+(B3.6),
(A3)+(B3.7);
(A4)+(B3.1), (A4)+(B3.2), (A4)+(B3.3), (A4)+(B3.4), (A4)+(B3.5), (A4)+(B3.6),
(A4)+(B3.7);
(A1)+(B4.1), (A1)+(B4.2), (A1)+(B4.3), (A1)+(B4.4), (A1)'+(B4.5);

CA 02720498 2010-11-09
7
(A2)+(B4.1), (A2)+(B4.2), (A2)+(B4.3), (A2)+(B4.4), (A2)+(B4.5);
(A3)+(B4.1), (A3)+(B4.2), (A3)+(B4.3), (A3)+(B4.4), (A3)+(B4.5);
(A4)+(B4.1), (A4)+(B4.2), (A4)+(B4.3), (A4)+(B4.4), (A4)+(B4.5);
(A1)+(B5.1), (A1)+(B5.2), (A1)+(B5.3), (A1)+(B5.4), (A1)+(B5.5), (A1)+(B5.6),
(A1)+(B5.7), (A1)+(B5.8),
(A2)+(B5.1), (A2)+(B5.2), (A2)+(B5.3), (A2)+(B5.4), (A2)+(B5.5), (A2)+(B5.6),
(A2)+(B5.7), (A2)+(B5.8);
(A3)+(B5.1), (A3)+(B5.2), (A3)+(B5.3), (A3)+(B5.4), (A3)+(B5.5), (A3)+(B5.6),
(A3)+(B5.7), (A3)+(B5.8);
(A4)+(B5.1), (A4)+(B5.2), (A4)+(B5.3), (A4)+(B5.4), (A4)+(B5.5), (A4)+(B5.6),
(AM)+(B5,7), (A4) (B5.8);
(A1)+(B6.1), (A1)+(B6.2), (A2)+(B6.1), (A2)+(B6.2), (A3)+(B6.1), (A3)+(B6.2),
(A4)+(B6.1); (A4)+(B6.2);
(A1)+(B7 1), (A2)+(B7.1), (A3)+(B7.1), (A4)+(B7.1);
(A1)+(B8.1), (A2)+(B8.1), (A3)+(B8.1), (A4)+(B8.1).
In the combinations according to the invention, application rates in the range
from 1
to 2000 g, preferably from 10 to 500 g, particularly preferably from 10 to 250
g, of
active ingredient per hectare (ai/ha) of the component A) and from 1 to 2000
g,
preferably from 1 to 500 g, particularly preferably from 5 to 250 g, of the
component
B) are generally required.

CA 02720498 2010-11-09
8
The weight ratios of the components A) to B) to be used can be varied within
wide
ranges. The ratio is preferably in the range from 1:50 to 50:1, in particular
in the
range from 1:20 to 20:1. Optimum weight ratios may depend on the particular
field of
application, on the weed spectrum and the active compound combination used and
can be determined in preliminary experiments.
The compositions according to the invention can be employed for the selective
control of annual and perennial monocotyledonous and dicotyledonous harmful
plants in crops of cereals (for example barley, oats, rye, wheat), corn and
rice and in
crops of transgenic useful plants or crops of useful plants selected by
classical
means which are resistant to active compounds A) and B). Likewise, they can be
employed for controlling undesirable harmful plants in plantation crops such
as oil
palm, coconut palm, Indian-rubber tree, citrus, pineapple, cotton, coffee,
cocoa and
the like, and also in fruit production and viticulture. Owing to their good
compatibility,
they are particularly suitable for use in cereals and corn, especially
cereals.
The compositions according to the invention act against a broad spectrum of
weeds.
They are suitable, for example, for controlling annual and perennial harmful
plants
such as, for example, from the species Abutilon, Alopecurus, Avena,
Chenopodium,
Cynoden, Cyperus, Digitaria, Echinochloa, Elymus, Galium, lpomoea, Kochia,
Lamium, Matricaria, Polygonum, Scirpus, Setaria, Sorghum, Veronica, Viola and
Xanthium.
A further advantage of the compositions according to the invention is their
excellent
action against many harmful plants which have now become resistant to
sulfonylureas, such as, for example, Kochia.
The herbicidal compositions according to the invention are also distinguished
by the
fact that the effective dosages of the components A) and B) used in the
combinations are reduced with respect to an individual dosage, so that it is
possible
to reduce the required active compound application rates (synergistic effect).

CA 02720498 2010-11-09
9
The invention also provides a method for controlling unwanted vegetation,
which
comprises applying one or more herbicides A) and one or more herbicides B) to
the
harmful plants, to parts of the harmful plants or to the area under
cultivation.
When herbicides of type A) and B) are applied jointly, superadditive (=
synergistic)
effects are observed. The activity in the combinations is more pronounced than
the
expected sum of the activities of the individual herbicides employed and the
activity
of the particular individual herbicide A) and B). The synergistic effects
permit the
application rate to be reduced, a broader spectrum of broad-leaved weeds and
weed
grasses to be controlled, more rapid onset of the herbicidal action, a more
prolonged
action, better control of the harmful plants by only one application, or few
applications, and widening of the period of time within which the product can
be
used. These properties are required in weed control practice to keep
agricultural
crops free from undesirable competing plants and thus to ensure and/or to
increase
quality and quantity of the yields. These novel combinations markedly surpass
the
prior art with respect to the described properties.
The active compound combinations according to the invention can either be
present
as mixed formulations of the components A) and B), if appropriate together
with
other customary formulation auxiliaries, which mixed formulations are then
applied in
the usual manner in the form of a dilution with water, or else they can be
prepared in
the form of so-called tank mixes by joint dilution with water of the
components which
are formulated separately, or partly separately.
The components A) and B) can be formulated in various ways, depending on the
prevailing biological and/or physicochemical parameters. Suitable general
possibilities for formulations are, for example: 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 products, granules for
soil
application or for broadcasting or water-dispersible granules (WG), ULV
formulations, microcapsules or waxes.

CA 02720498 2010-11-09
The individual types of formulation are known in principle and are described,
for
example, in: Winnacker-Kuchler, "Chemische Technologie" [Chemical Technology],
Vol. 7, C. Hauser Verlag Munich, 4th Ed. 1986; van Valkenburg, "Pesticides
5 Formulations", Marcel Dekker N.Y., 1973; K. Martens, "Spray Drying
Handbook", 3rd
Ed. 1979, G. Goodwin Ltd. London. 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
10 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., Ridgewood 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"
[Chemical Technology], Vol. 7, C. Hauser Verlag Munich, 4th Ed. 1986.
Based on these formulations, it is also possible to prepare combinations with
other
pesticidally active substances, such as other herbicides, fungicides or
insecticides,
and also safeners, fertilizers and/or growth regulators, for example in the
form of a
ready mix or tank mix.
Wettable powders are preparations which are uniformly dispersible in water and
which, besides the active compound, also comprise ionic or nonionic
surfactants
(wetting agents, dispersants), for example polyethoxylated alkyiphenols,
polyethoxylated fatty alcohols or fatty amines, alkanesulfonates or
alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-
6,6'-
disulfonate, sodium dibutylnaphthalenesulfonate or else sodium
oleoylmethyltaurinate, in addition to a diluent or an inert substance.
Emulsifiable concentrates are prepared by dissolving the active compound in an
organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene
or

CA 02720498 2010-11-09
11
else higher-boiling aromatics or hydrocarbons, with the addition of one or
more ionic
or nonionic surfactants (emulsifiers). Examples of emulsifiers which can be
used are:
calcium alkylarylsulfonates, such as calcium dodecylbenzenesulfonate, 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
polyoxyethylene sorbitol esters.
Dusts are obtained by grinding the active compound with finely divided solid
materials, for example talc, natural clays, such as kaolin, bentonite and
pyrophyllite,
or diatomaceous earth.
Granules can be prepared either by spraying the active compound onto
absorptive,
granulated inert material, or by applying active compound concentrates to the
surface of carriers, such as sand, kaolinite or granulated inert material,
with the aid
of binders, for example polyvinyl alcohol, sodium polyacrylate or else mineral
oils.
Suitable active compounds can also be granulated in the manner customary for
the
preparation of fertilizer granu(es, if desired as a mixture with fertilizers.
Water-
dispersible granules are, in general, prepared by processes such as spray-
dying,
fluidized-bed granulation, disk granulation, mixing using high-speed mixers,
and
extrusion without solid inert material.
The agrochemical preparations generally comprise from 0.1 to 99 percent by
weight,
in particular from 0.2 to 95% by weight, of active compounds of types A) and
B), the
following concentrations being customary, depending on the type of
formulation: In
wettable powders, the active compound concentration is, for example,
approximately
10 to 95% by weight, the remainder to 100% by weight being composed of
customary formulation components. In the case of emulsifiable concentrates,
the
active compound concentration can be, for example, from 5 to 80% by weight.
Formulations in the form of dusts in most cases comprise from 5 to 20% by
weight of
active compound, sprayable solutions approximately 0.2 to 25% by weight of
active
compound. In the case of granules, such as dispersible granules, the active

CA 02720498 2010-11-09
12
compound content depends partly on whether the active compound is in liquid or
solid form and on which granulation auxiliaries and fillers are used. In
general, the
content in the water-dispersible granules amounts to between 10 and 90% by
weight. In addition, the active compound formulations mentioned comprise, if
appropriate, the tackifiers, wetting agents, dispersants, emulsifiers,
preservatives.
antifreeze agents, solvents, fillers, colorants, carriers, antifoams,
evaporation
inhibitors and pH or viscosity regulators which are customary in each case.
For use. the formulations, which are in commercially available form, are., if
appropriate, diluted in a 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
spreading and
sprayable solutions, are conventionally not diluted any further with other
inert
substances prior to use.
The active compounds can be applied to the plants, parts of the plants, seeds
of the
plants or the area under cultivation (tilled soil), preferably to the green
plants and
part3 of the-olants and, if desired, additional!y to the tilled soil.
A possible use is the joint application of the active compounds in the form of
tank
mixes, where the concentrated formulations of the individual active
substances, in
the form of their optimal formulations, are mixed jointly with water in the
tank, and the
spray mixture obtained is applied.
'A joint herbicidal formulation of the combination according to the invention
of the
components A) and B) has the advantage that it can be applied more easily
because
the amounts of the components have already been adjusted with respect to one
another to the correct ratio. Moreover, the auxiliaries of the formulation can
be
selected to suit each other in the best possible way, while a tank mix of
various
formulations may result in undesirable combinations of auxiliaries.
A. Formulation examples

CA 02720498 2010-11-09
28976-244
13
a) A dust (WP) is obtained by mixing 10 parts by weight of an active
compound/active compound mixture and 90 parts by weight of talc as inert
substance and comminuting the mixture in a hammer mill.
b) A wettable powder (LNG) which is readily dispersible in water is obtained
by
mixing 25 parts by weight of an active compound/active compound mixture, 64
parts
by weight of kaolin-containing quartz as inert substance, 10 parts by weight
of
potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurinate
as
wetting agent and dispersant, and grinding the mixture in a pinned-disk mill.
c) A dispersion concentrate which is readily dispersible in water is obtained.
by
mixing 20 parts by weight of an active compound/active compound mixture with 6
parts by weight. of alkylphenol polyglycol ether (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 approximately 255 to 277 C) and grinding the
mixture in a
ball mill to a fineness of below 5 microns.
d) An emulsifiable concentrate (EC) is obtained from 15 parts by weight of an
active compound/active compound mixture, 75 parts by weight of cyclohexanone
as
solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.
e) Water-dispersible granules are obtained by mixing
75 parts by weight of an active compound/active compound .mixture,
10 parts by weight of calcium lignosulfonate,
5 parts by weight of sodium lauryl sulfate,
3 parts by weight of polyvinyl alcohol and
7 parts by weight of kaolin
grinding the mixture in a pinned-disk mill and granulating the powder in a
fluidized
bed by spraying on water as granulation liquid.
f) Water-dispersible granules are also obtained by homogenizing and
precomminuting, in a colloid mill,

CA 02720498 2010-11-09
14
25 parts by weight of an active compoundlactive compound mixture,
parts by weight of sodium 2,2'-dinaphthylmethane-6,6'-disulfonate,
2 parts by weight of sodium oleoylmethyltaurinate,
1 part by weight of polyvinyl alcohol,
5 17 parts by weight of calcium carbonate and
50 parts by weight of water,
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 nozzle.
B. Biological Examples
Outdoors, crop plants were grown on plots of a size of from 5 to 10 m2 on
various
soils and under various climatic conditions, and the natural presence of
harmful
plants and/or their seeds in the soil was utilized for the experiments. The
treatment
with the compositions according to the invention or the herbicides A) and B)
applied
individually was carried out after emergence of the harmful and the crop
plants, in
general at the 2- to 4-leaf stage. The active compounds or active compound
combinations, formulated as WC, WP or EC, was carried out by the post-
emergence
method. After 2 to 8 weeks, visual evaluation was carried out in comparison
with an
untreated comparative group. It was found that the compositions according to
the
invention have synergistic herbicidal action against economically important
mono-
and dicotyledonous harmful plants, i.e. that most of the compositions
according to
the invention have higher, some considerably higher, herbicidal activity than
the sum
of the activities of the individual herbicides. In addition, the herbicidal
activities of the
compositions according to the invention exceed the expected values according
to
Colby. In contrast, the treatment caused insignificant, if any, damage to the
crop
plants.
If the observed activity values of the mixtures already exceed the formal sum
of the
values for the trials with individual applications, they also exceed the
expected value
according to Colby which is calculated using the following formula (cf. S. R.
Colby; in
Weeds 15 (1967) pp. 20 to 22):

CA 02720498 2010-11-09
E=A+B- AxB
100
The figures denote:
5 A, B = Activity of components A and B in percent, at a dosage of a and b
gram of
ai/ha, respectively.
E = Expected value in % at a dosage of a+b gram of ai/ha.
The values observed in the experimental examples below exceed the expected
10 values according Colby. Table 1 shows the components (A) and (B) used in
the
experiments. Tables 2 to 4 show the herbicidal actions of the individual
components
(A) and (B), that of the mixtures according to the invention and the
theoretical value
according to Colby.
15 Table 1:
H C 0 SO2CH3 OCH
3
E N / \ CGZCH3 N'- i
\~N
OH CF3 J:~SO-N--CO--N H C I t~! CH3
3 Na*
A2 B1.6
O/CH3 O/CH3
COZCH3 N\ N /\ COZCH3 N
~ CH
SOZNH-CO-N N O SOZNH-CO-~" N C 3
" I I
NHSO2CH3 CH3 CH3 iN
H SOZCH3
61.12 B1.13

CA 02720498 2010-11-09
16
CN NH2
cl cl R: CH3(CHZ)30CHZCH(CH3)
I or
F N OCHZCOZR CH3(CH2)SCH(CH3)
Bra Br
OH
B2.2 B3.6
CI 0
ftL,N`r0~~ \-CO2CH2CH.
.
H3C
B4.4
Table 2:
Imo' Herbicide Dosage Herbicidal action Value
against POLCO according to
Colby
A2 75 90%
B1.6 2.5 56%
B1.12 7.5 70%
A2 + B1.6 75 + 2.5 99% 96%
A2 + B1.12 75 + 7.5 99% 96%

CA 02720498 2010-11-09
17
Table 3:
Herbicide Dosage Herbicidal action Value
against AVEFA according to
Colby
A2 75 20%
B1.12 7.5 70%
B4.4 60 80%
A2 + B1.12 75 + 7.5 85% 76%
A2 + B4.4 75 + 60 L 90% 84%
Table 4:
Herbicide Dosage Herbicidal action Value
1 -1 against GALAP according to
Colby
A2 75 84%
B2.2 280 61%
A2 + B2.2 75 + 280 99% 949