HERBICIDAL COMPOSITIONS
The present invention relates to compositions comprising certain herbicidal pyridine
derivatives and a safener and methods for protecting cultivated plants from the damaging
effects of the herbicidal pyridine derivatives.
It is known that when herbicides are used to control the growth of undesired plants,
there may be some damage to the cultivated plants. The amount of damage will depend on a
number of factors but, in some cases, the cultivated plants can be protected from the effect of
the herbicide by using a compound termed a safener.
Surprisingly, it has now been found that certain herbicidal pyridine derivatives can be
safened by N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Accordingly, the present invention provides a composition for protecting crop plants
from the harmful effects of a pyridine derivative herbicide of formula (I)
or a salt or N-oxide thereof wherein
Y is chloro or bromo,
R is hydrogen, Ci_s alkyl, C2-5 alkenyl, C3-5 alkynyl, aryl Ci_2 alkyl-, Ci_4 alkoxy Ci_4
alkyl- or Ci_4 alkoxy Ci_4 alkoxy Ci_2 alkyl-,
R1 is chloro or bromo,
R2 is Ci_2 alkoxy,
R is chloro or fluoro.
and wherein said composition comprises, in addition to the pyridine derivative
herbicide of formula (I), the safener N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide.
"Alkyl" means a linear saturated monovalent hydrocarbon radical of one to eight
carbon atoms or a branched saturated monovalent hydrocarbon radical of three to eight
carbon atoms, e.g. methyl, ethyl, n-propyl, z' -propyl, n-butyl, ec-butyl, z' -butyl, tertbutyl,
and the like. Suitably, linear alkyl groups contain one to eight, one to six, one to five
or one to four carbon atoms, more suitably are selected from methyl, ethyl or n-propyl and,
most suitably, are methyl or ethyl. Suitably, branched alkyl groups contain three to eight,
three to six or three to five carbon atoms and more suitably are selected from z' -propyl, secbutyl,
z' -butyl or tert-butyl. It is noted that this definition applies both when the term is
used alone and when it is used as part of a compound term, such as "haloalkyl" and similar
terms.
"Alkenyl" means a linear monovalent unsaturated hydrocarbon radical of two to five
carbon atoms, or a branched monovalent hydrocarbon radical of three to five carbon atoms
containing at least one double bond, e.g. ethenyl, propenyl and the like. Where appropriate,
an alkenyl group can be of either the (E)- or (Z)-configuration. Suitably, linear alkenyl
groups contain two to five carbon atoms, more suitably two to four carbon atoms and, most
suitably are ethenyl (vinyl), prop-l-enyl (1-propenyl) or prop-2-enyl (allyl). Suitably,
branched alkenyl groups contain three to five carbon atoms, more suitably from three to four
and, most suitably, are 1-methylethenyl ( -propenyl), 1-methylprop-l-enyl, l-methylprop-2-
enyl, 2-methylprop-l-enyl and 2-methylprop-2-enyl (2-methylallyl).
"Alkynyl" means a linear monovalent unsaturated hydrocarbon radical of three to
five carbon atoms, or a branched monovalent hydrocarbon radical of four to five carbon
atoms, containing at least one triple bond e.g. propynyl and the like. Suitably, alkynyl groups
contain three to five carbon atoms and more suitably three to four carbon atoms e.g. prop-1-
ynyl, prop-2-ynyl, but-l-ynyl, but-2-ynyl and but-3-ynyl.
"Alkoxy" means a radical -OR, where R is alkyl as defined above. Alkoxy groups
include, but are not limited to, methoxy, ethoxy, 1-methylethoxy, propoxy, butoxy, 1-
methylpropoxy and 2-methylpropoxy. Preferably alkoxy means methoxy or ethoxy.
"Alkoxyalkyl" means a radical -ROR, where each R is, independently, alkyl as
defined above.
"Alkoxyalkoxyalkyl" means a radical -ROROR, wherein each R is, independently,
alkyl as defined above.
"Aryl" or "aromatic ring" refers to an aromatic substituent which may be a single
ring or multiple rings which are fused together, linked covalently or linked to a common
group such as an ethylene (-CH2-CH2-) or methylene (-CH2-) moiety. Representative
examples of aryl include, for example, phenyl, naphthyl, azulenyl, indanyl, indenyl,
anthracenyl, phenanthrenyl, tetrahydronaphthyl, biphenyl, diphenylmethyl and 2,2-diphenyl-
1-ethyl. Preferred aryl groups are phenyl and naphthyl groups.
"Halo" or "halogen" means fluoro, chloro, bromo or iodo, preferably chloro or
fluoro.
"Arylalkyl" means -R-aryl, wherein R is an alkyl group as defined above.
The compounds of formula I may exist in different geometric or optical isomeric
forms or in different tautomeric forms. One or more centres of chirality may be present, in
which case compounds of the formula I may be present as pure enantiomers, mixtures of
enantiomers, pure diastereomers or mixtures of diastereomers. There may be double bonds
present in the molecule, such as C=C or C=N bonds, in which case compounds of formula I
may exist as single isomers or mixtures of isomers. Centres of tautomerisation may be
present. This invention covers all such isomers and tautomers and mixtures thereof in all
proportions as well as isotopic forms such as deuterated compounds.
Suitable salts include those formed by contact with acids or bases. Suitable salts of
the compounds of formula I thus include those derived from alkali or alkaline earth metals
and those derived from ammonia and amines. Preferred cations include sodium, potassium,
magnesium, and ammonium cations of the formula R'R R1) wherein R1, R", Rk and R1
are independently selected from hydrogen, Ci_ alkyl and Ci_ hydroxyalkyl. Salts of the
compounds of formula I can be prepared by treatment of compounds of formula I with a
metal hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine,
diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine,
cyclododecylamine, or benzylamine. Amine salts are often preferred forms of the
compounds of Formula I because they are water-soluble and lend themselves to the
preparation of desirable aqueous based herbicidal compositions.
Suitable salts of the compounds of formula I also include acid addition salts such as
those with an inorganic acid such as hydrochloric, hydrobromic, sulphuric, nitric or
phosphoric acid, an organic acid such as acetic, butyric, propionic or hexanoic, an organic
carboxylic acid such as citric, fumaric, lactic, maleic, malonic, mandelic, malic, oxalic,
succinic, tartaric, toluic or phthalic acid, or a sulphonic acid such as methane, benzene,
naphthalene, camphor or toluene sulphonic acid.
N-oxides are oxidised forms of tertiary amines or oxidised forms of nitrogen
containing heteroaromatic compounds. They are described in many books for example in
"Heterocyclic N-oxides" by Angelo Albini and Silvio Pietra, CRC Press, Boca Raton,
Florida, 1991.
In particularly preferred embodiments of the invention, the preferred groups for Y, R,
R and R3, in any combination thereof, are as set out below.
In a preferred embodiment, Y is chloro.
In a preferred embodiment, R is hydrogen, Ci_4 alkyl, C3_4 alkenyl, arylmethyl, Ci_4
alkoxy Ci_2 alkyl. In a more preferred embodiment, R is hydrogen or methyl. In a particular
embodiment, when R is hydrogen, there is provided a salt of the compound of formula (I) as
described or listed above. In particular, the salt of the compound of formula (I) may be
derived from an alkali metal, an alkaline earth metal, ammonia or an amine. Preferably, the
salt is a sodium salt, a potassium salt or a triethylammonium salt.
In a preferred embodiment, R1 is chloro.
In a preferred embodiment, R2 is methoxy.
In a preferred embodiment, R is fluoro.
The compounds described below are illustrative of compounds of Formula (I)
featured in the composition of the invention. Table 1 below provides 50 compounds
designated compounds 1-1 to 1-50 respectively, of formula (I).
50 CI CI OCH3 F Et3N salt
These pyridine compounds used in the safened compositions of the present invention
may be made as the skilled man will appreciate by applying and/or adapting as appropriate,
the methods described in the prior art (see for example WO 2007/082098 and
US2010/031 1981).
The safener of the invention is disclosed in EP 0 365 484 A and may be made using
the methods described therein.
Preferably the mixing ratio of compound of formula (I) to safener is from 100:1 to
1:100, especially from 20: 1 to 1:20.
In a further aspect, the present invention provides a method for protecting crops of
useful plants from the harmful effects of a herbicide of formula (I) as defined herein, which
comprises applying to the locus of the useful plants the safener N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide.
In a still further aspect, the present invention provides a method for combating weeds
in crops of useful plants, which comprises treating the useful plants, seeds or cuttings thereof
or the locus of the useful plants simultaneously or at separate times with a herbicidally active
amount of a compound of formula (I) and the safener N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide.
Any method of application to weeds/crop of useful plant, or locus thereof, which is
routinely used in agriculture may be used, for example application by spray or broadcast
method typically after suitable dilution of the composition of the invention.
The term "locus" as used herein includes not only areas where weeds may already be
growing, but also areas where weeds have yet to emerge, and also to areas under cultivation
with respect to crops of useful plants. Areas under cultivation include land on which the
crop plants are already growing and land intended for cultivation with such crop plants.
Crops of useful plants in which compositions of the invention may be used or the
methods of the invention applied include perennial crops, such as citrus fruit, grapevines,
nuts, oil palms, olives, pome fruit, stone fruit and rubber, and annual arable crops, such as
cereals, for example barley and wheat, cotton, oilseed rape, maize (including sweet corn),
rice, sorghum, soy beans, sugar beet, sugar cane, sunflowers, ornamentals and vegetables,
especially cereals and maize. In particular, the compositions of the invention may be used
on maize (including sweet corn), sorghum, sugar cane and rice, more particularly, on maize,
sugar cane and rice and most particularly on maize.
Compositions and methods of the invention may also be used on turf, pasture,
rangeland, rights of way etc. In particular they may be used on golf-courses, lawns, parks,
sports-fields, race-courses and the like.
Crops are to be understood as also including those crops which have been rendered
tolerant to herbicides or classes of herbicides (e.g. ALS-, ACCase-, GS-, EPSPS-, PPO- and
HPPD-inhibitors and synthetic auxins) by conventional methods of breeding or by genetic
engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g.
imazamox, by conventional methods of breeding is Clearfield® summer rape (canola).
Examples of crops that have been rendered tolerant to herbicides by genetic engineering
methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially
available under the trade names RoundupReady® and LibertyLink®.
Crops are also to be understood as being those which have been rendered resistant to
harmful insects by genetic engineering methods, for example Bt maize (resistant to European
corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to
Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK (Syngenta
Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil
bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are
described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073
and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code
for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield
Gard® (maize), NuCOTIN33B ® (cotton), Bollgard® (cotton), NewLeaf® (potatoes),
NatureGard ® and Protexcta®. Plant crops or seed material thereof can be both resistant to
herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events).
For example, seed can have the ability to express an insecticidal Cry3 protein while at the
same time being tolerant to glyphosate.
Crops are also to be understood as being those which are obtained by conventional
methods of breeding or genetic engineering and contain so-called output traits (e.g. improved
storage stability, higher nutritional value and improved flavour).
The term "weeds" as used herein means any undesired plant, and thus includes not
only agronomically important weeds as described below, but also volunteer crop plants.
Compounds of formula (I) may be used against a large number of agronomically
important weeds. The weeds that may be controlled include both monocotyledonous and
dicotyledonous weeds, such as, for example, Alisma spp, Leptochloa chinensis, Stellaria,
Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solarium, Echinochloa,
Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia, Cyperus and
especially Cyperus iria, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea,
Chrysanthemum, Galium, Viola, Veronica, Bidens, Euphorbia, Ischaemum, Polygonum,
Helianthus, Panicum, Eriochloa, Brachiaria, Cenchrus, Commelina, Spermacoce, Senna,
Tridax, Richardia, Chamaesyce, and Conyza spp.
The compositions according to the invention are suitable for all the conventional
methods of application in agriculture, such as, e.g., pre-emergent application, post-emergent
application and seed dressing. Depending on the intended use, the safener can be employed
for pre-treatment of the seed of the crop plant (dressing of the seed or cuttings) or can be
introduced into the soil before or after sowing. However, it can also be applied by itself or
together with the herbicide before or after emergence of the plants. The treatment of the
plants or seed with the safener can therefore in principle be carried out independently of the
time of application of the herbicide. Treatment of the plants by simultaneous application of
the herbicide and safener (e.g, as a tank mix) is as a rule preferred. The application rate of
safener to herbicide to be applied largely depends of the method of use. For field treatment,
as a rule 0.001 to 5.0 kg of safener/ha, preferably 0.01 to 0.5 kg safener/ha and as a rule
between 0.005 to 2 kg of herbicide/ha, but preferably between 0.001 to 1 kg/ha are applied.
For seed dressing, in general 0.001 to 10 g of safener/kg seed, preferably 0.05 to 2g
safener/kg seed are applied. If the safener is applied in liquid form, with soaking of the seed,
shortly before sowing, safener solutions which contain the safener in a concentration of 1 to
10,000, preferably 100 to 1000 ppm are expediently used.
The safened compositions of the present invention can be employed in unchanged
form as a herbicidal composition. However, as a rule the compositions of the invention are
preferably formulated in various ways using formulation adjuvants, such as carriers, solvents
and surface-active substances, for example, as described hereinafter. Accordingly, the
present invention provides a composition of the invention which further comprises at least
one agriculturally acceptable adjuvant or diluent.
The formulated compositions can be in various physical forms, e.g. in the form of
dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible
tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oilin-
water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions,
capsule suspensions, suspension concentrates, emulsifiable granules, soluble liquids, watersoluble
concentrates (with water or a water-miscible organic solvent as carrier), impregnated
polymer films or in other forms known e.g. from the Manual on Development and Use of
FAO Specifications for Plant Protection Products, 5th Edition, 1999. The formulated
compositions can be in the form of concentrates which are diluted prior to use, although
ready-to-use formulations can also be made. The dilutions can be made, for example, with
water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
The formulated compositions can be prepared e.g. by mixing the active ingredient
and safener combination with the formulation adjuvants in order to obtain compositions in
the form of finely divided solids, granules, solutions, dispersions or emulsions. The active
ingredients can also be formulated with other adjuvants, such as finely divided solids,
mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin,
organic solvents, water, surface-active substances or combinations thereof. The active
ingredients can also be contained in very fine microcapsules consisting of a polymer.
Microcapsules usually have a diameter of from 0.1 to 500 microns. Typically, they will
contain active ingredients in an amount of about from 25 to 95% by weight of the capsule
weight. The active ingredients can be in the form of a monolithic solid, in the form of fine
particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating
membranes comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene
copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane
or chemically modified polymers and starch xanthates or other known polymers.
Alternatively, very fine microcapsules can be formed in which the active ingredient is
contained in the form of finely divided particles in a solid matrix of base substance, but the
microcapsules are not themselves encapsulated.
The formulation adjuvants that are suitable for the preparation of compositions
according to the invention are known per se. As liquid carriers there may be used: water,
toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone,
cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone,
butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid
(e.g. butyl acetate, ethyl acetate, isoamyl acetate, amyl acetate), diacetone alcohol, 1,2-
dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol
abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol
methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol,
dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone,
2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, dlimonene,
ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl
ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate,
hexadecane, hexylene glycol, isobornyl acetate, isooctane, isophorone, isopropylbenzene,
isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl
isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate,
methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine
acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG), propionic acid,
propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, pxylene,
toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral
oil, trichloroethylene, perchloroethylene, methanol, ethanol, isopropanol, and alcohols of
higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol,
N-methyl-2-pyrrolidone and the like. Water is generally the carrier of choice for diluting the
concentrates. Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite
clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium
montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground
walnut shells, lignin and similar substances, as described, for example, in CFR 180.1001. (c)
& (d).
A large number of surface-active substances may advantageously be used in the
formulations, especially in those formulations designed to be diluted with a carrier prior to
use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can
be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical
surface-active substances include, for example, salts of alkyl sulfates, such as
diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium
dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol
ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate;
soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium
dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-
ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as
lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as
polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and
salts of mono- and di-alkylphosphate esters; and also further substances described e.g. in
"McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New
Jersey, 1981.
Further adjuvants that can usually be used in such formulations include crystallisation
inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light
absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying
substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers,
micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes,
microbicides, and also liquid and solid fertilisers. An example of such an adjuvant is
ammonium sulphate.
The formulated compositions according to the invention can additionally include an
additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such
oils or mixtures of such oils and oil derivatives. The amount of oil additive in the
composition according to the invention is generally from 0.01 to 10%, based on the spray
mixture. For example, the oil additive can be added to the spray tank in the desired
concentration after the spray mixture has been prepared. Preferred oil additives comprise
mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil,
emulsified vegetable oil, such as AMIGO ® (Rhone-Poulenc Canada Inc.), alkyl esters of oils
of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as
fish oil or beef tallow. A preferred additive contains, for example, as active components
essentially 80% by weight alkyl esters of fish oils and 15%> by weight methylated rapeseed
oil, and also 5% by weight of customary emulsifiers and pH modifiers. Especially preferred
oil additives comprise alkyl esters of C 22 fatty acids, especially the methyl derivatives of
C12-18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid,
being of importance. Those esters are known as methyl laurate (CAS-1 11-82-0), methyl
palmitate (CAS-1 12-39-0) and methyl oleate (CAS-1 12-62-9). A preferred fatty acid methyl
ester derivative is Emery ® 2230 and 2231 (Cognis GmbH). Those and other oil derivatives
are also known from the Compendium o f Herbicide Adjuvants, 5th Edition, Southern Illinois
University, 2000. Another preferred adjuvant is Adigor ® (Syngenta AG) which is a
methylated rapeseed oil-based adjuvant.
The application and action of the oil additives can be further improved by
combination with surface-active substances, such as non- ionic, anionic or cationic
surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on
pages 7 and 8 of W097/34485. Preferred surface-active substances are anionic surfactants
of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic
surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated
C12-22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of
commercially available surfactants are the Genapol types (Clariant AG). Also preferred are
silicone surfactants, especially polyalkyl-oxide-modified heptamethyltriloxanes which are
commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants. The
concentration of the surface-active substances in relation to the total additive is generally
from 1 to 30% by weight. Examples of oil additives consisting of mixtures of oil or mineral
oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Syngenta
AG, CH) or ActipronC (BP Oil UK Limited, GB).
If desired, it is also possible for the mentioned surface-active substances to be used in
the formulations on their own, that is to say, without oil additives.
Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture
may contribute to an additional enhancement of action. Suitable solvents are, for example,
Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation). The concentration of such
solvents can be from 10 to 80% by weight of the total weight. Oil additives that are present
in admixture with solvents are described, for example, in US-A-4,834,908. A commercially
available oil additive disclosed therein is known by the name MERGE® (BASF
Corporation). A further oil additive that is preferred according to the invention is SCORE®
(Syngenta Crop Protection Canada).
In addition to the oil additives listed above, for the purpose of enhancing the action of
the compositions according to the invention it is also possible for formulations of
alkylpyrrolidones (e.g. Agrimax®) to be added to the spray mixture. Formulations of
synthetic lattices, e.g. polyacrylamide, polyvinyl compounds or poly-l-p-menthene (e.g.
Bond®, Courier® or Emerald®) may also be used. It is also possible for solutions that contain
propionic acid, for example Eurogkem Pen-e-trate®, to be added to the spray mixture as
action-enhancing agent.
Formulated compositions of the invention generally comprise from 0.1 to 99% by
weight, especially from 0.1 to 95% by weight, of active compound mixture of the compound
of formula (I) with a safener and from 1 to 99.9% by weight of a formulation adjuvant which
preferably includes from 0 to 25% by weight of a surface-active substance. Whereas
commercial products will preferably be formulated as concentrates, the end user will
normally employ dilute formulations.
Various methods and techniques are suitable for using safeners or compositions
containing them for protecting crop plants from the harmful actions of herbicides of formula
I, such as, for example, the following:
i) Seed dressing
a) Dressing of the seed with the safener formulated as a wettable powder by
shaking in a vessel until uniform distribution over the seed surface is
achieved (dry dressing). About 1 to 500g of safener (4g to 2kg of
wettable powder) per 100 kg of seed are used here.
b) Dressing of the seed with an emulsion concentrate of the safener by
method a) (wet dressing).
c) Dressing by immersing the seed in a liquor with 100-1000 ppm of safener
for 1 to 72 hours and optionally subsequent drying of the seed (immersion
dressing).
The dressing of the seed or the treatment of the sprouted seed are
preferred methods of application, because the treatment with the safener is
directed entirely at the target crop. As a rule, 1 to lOOOg of safener,
preferably 5 to 250g of safener are used per 100 kg of seed, it being
possible to deviate upwards or downwards from the limit concentrations
stated (repeat dressing), depending on the methods, which also allows the
addition of other active compounds or micronutrients.
ii) Application as a tank mix
A liquid processed mixture of safener and herbicide of formula I (reciprocal
ratio of amounts between 10:1 and 1:100) is used, the application rate of
herbicide being 0.005 to 5.0 kg per hectare, alternatively from 0.001 to 1.0 kg
per hectare. Such tank mixes are applied before or after sowing.
iii) Application into the seed furrow
The safener is introduced into the open sown seed furrow as an emulsion
concentrate, wettable powder or as granules. After the seed furrow has been
covered, the herbicide is applied by the pre-emergent method in a
conventional method.
iv) Controlled release of the safener
The safener is absorbed in solution on to mineral carrier granules or
polymerised granules (urea/formaldehyde) and dried. A coating which allows
the safener to be released over a certain period of time can optionally be
applied (coated granules).
In particular, preferred formulations have the following composition (% = per cent by
weight; active mixture of active compounds means the mixture of a compound of formula I
with a safener):
Emulsifiable concentrates
Active mixture of active compounds: 1 to 95%, preferably 60 to 90%
Surface-active agent: 1 to 30%>, preferably 5 to 20%>
Liquid carrier: 1 to 80%>, preferably 1 to 35%
Dusts
Active mixture of active compounds: 0.1 to 10%, preferably 0.1 to 5%
Solid carrier: 99.9% to 90%, preferably 99.9 to 99%
Suspension concentrates
Active mixture of active compounds: 5 to 75%, preferably 10 to 50%
Water: 94 to 24%, preferably 88 to 30%
Surface-active agent: 1 to 40%, preferably 2 to 30%
Wettable powders
Active mixture of active compounds: 0.5 to 90%, preferably 1 to 80%
Surface-active agent: 0.5 to 20%, preferably 10 to 15%
Solid carrier: 5 to 95%, preferably 15 to 90%
Granules
Active mixture of active compounds: 0.1 to 30%, preferably 0.1 to 15%
Solid carrier: 99.5 to 70%, preferably 97 to 85%
Formulation examples for mixtures of herbicides of formula (I) with safeners (% =% by
weight; EO = ethylene oxide)
Fl. Emulsifiable concentrates a) b) c) d)
active compound mixture 5% 10% 25% 50%
calcium dodecylbenzenesulfonate 6% 8% 6% 8%
castor oil polyglycol ether (36 mol of EO) 4% - 4% 4%
octylphenol polyglycol ether (7-8 mol of EO) - 4% - 2%
N-methyl pyrrolidone - - 10% 20%
arom. hydrocarbon mixture (C9-C12) 85% 78% 55% 16%
Emulsions of any desired concentration can be obtained from such concentrates by dilution
with water.
F2. Solutions a) b) c) d)
active compound mixture 5% 10% 50% 90%
l-methoxy-3-(3-methoxy-propoxy)-propane - 20% 20%
polyethylene glycol MW 400 20% 10% -
NMP - - 30% 10%
arom. hydrocarbon mixture (C9-C12) 75% 60%
The solutions are suitable for use in the form of microdrops.
F3. Wettable powders a) b) c) d)
active compound mixture 5% 25% 50% 80%
sodium lignosulfonate 4% - 3%
sodium lauryl sulphate 2% 3% - 4%
sodium diisobutylnaphthalene-sulfonate - 6% 5% 6%
octylphenol polyglycol ether (7-8 mol EO) - 1% 2%
highly dispersed silicic acid 1% 3% 5% 10%
kaolin 88% 62% 35% -
The active compound mixture is mixed thoroughly with the adjuvants and the resulting
mixture is thoroughly ground in a suitable mill, affording wettable powders which can be
diluted with water to give suspensions of any desired concentration.
F4. Coated granules a) b) c)
active compound mixture 0.1% 5% 15%
highly dispersed silicic acid 0.9% 2% 2%
inorganic carrier (diameter 0.1-1 mm) e.g. CaC0 3 or Si0 2 99.0% 93% 83%
The active compound mixture is dissolved in methylene chloride and applied to the carrier
by spraying, and the solvent is then evaporated off in vacuo.
F5. Coated granules a) b) c)
active compound mixture 0.1% 5% 15%
polyethylene glycol MW 200 1.0% 2% 3%
highly dispersed silicic acid 0.9% 1% 2%
inorganic carrier (diameter 0.1-1 mm) e.g. CaC0 3 or Si0 2 98.0% 92% 80%
The finely ground active compound mixture is uniformly applied, in a mixer, to the carrier
moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
F6. Extruded granules a) b) c) d)
active compound mixture 0.1% 3% 5% 15%
sodium lignosulfonate 1.5% 2% 3% 4%
carboxymethylcellulose 1.4% 2% 2% 2%
kaolin 97.0% 93% 90% 79%
The active compound mixture is mixed and ground with the adjuvants, and the mixture is
moistened with water. The mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) c)
active compound mixture 0.1% 1% 5%
talcum 39.9% 49% 35%
kaolin 60.0% 50% 60%
Ready-to-use dusts are obtained by mixing the active compound mixture with the carriers
and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d)
active compound mixture 3% 10% 25% 50%
ethylene glycol 5% 5% 5% 5%
nonylphenol polyglycol ether (15 mol EO) - 1% 2% -
sodium lignosulfonate 3% 3% 4% 5%
carboxymethylcellulose 1% 1% 1% 1%
37% aqueous formaldehyde solution 0.2 % 0.2% 0.2% 0.2%
silicone oil emulsion 0.8% 0.8% 0.8% 0.8 %
water 87% 79% 62% 38%
The finely ground active compound mixture is intimately mixed with the adjuvants, giving a
suspension concentrate from which suspensions of any desired concentration can be obtained
by dilution with water.
It is often more practical to formulate the active compound of formula I and the
safener individually and then to bring them together as a 'tank mix' in water in the
application in the desired mixing ratio shortly before application.
The compositions of the present invention can also be used in combination with other
active ingredients, e.g. other herbicides, and/or insecticides, and/or acaricides, and/or
nematocides, and/or molluscicides, and/or fungicides, and/or plant growth regulators. Such
mixtures, and the use of such mixtures to control weeds and/or undesired plant growth form
yet further aspects of the invention. For the avoidance of doubt, mixtures of invention also
include mixtures of two or more different compounds of formula (I). In particular, the
present invention also relates to a composition of the invention which comprises at least one
further herbicide in addition to the compound of formula (I) and the safener.
Where a composition of the invention is combined with at least one additional
herbicide, the following mixtures of the composition of the invention are particularly
preferred: composition of the invention + acetochlor, composition of the invention +
acifluorfen, composition of the invention + acifluorfen-sodium, composition of the invention
+ aclonifen, composition of the invention + acrolein, composition of the invention +
alachlor, composition of the invention + alloxydim, composition of the invention + allyl
alcohol, composition of the invention + ametryn, composition of the invention +
amicarbazone, composition of the invention + amidosulfuron, composition of the invention +
aminocyclopyrachlor, composition of the invention + aminopyralid, composition of the
invention + amitrole, composition of the invention + ammonium sulfamate, composition of
the invention + anilofos, composition of the invention + asulam, composition of the
invention + atrazine, composition of the invention + aviglycine, composition of the invention
+ azafenidin, composition of the invention + azimsulfuron, composition of the invention +
BCPC, composition of the invention + beflubutamid, composition of the invention +
benazolin, composition of the invention + bencarbazone, composition of the invention +
benfluralin, composition of the invention + benfuresate, composition of the invention +
bensulfuron, composition of the invention + bensulfuron-methyl, composition of the
invention + bensulide, composition of the invention + bentazone, composition of the
invention + benzfendizone, composition of the invention + benzobicyclon, composition of
the invention + benzofenap, composition of the invention + bifenox, composition of the
invention + bilanafos, composition of the invention + bispyribac, composition of the
invention + bispyribac-sodium, composition of the invention + borax, composition of the
invention + bromacil, composition of the invention + bromobutide, composition of the
invention + bromophenoxim, composition of the invention + bromoxynil, composition of the
invention + butachlor, composition of the invention + butafenacil, composition of the
invention + butamifos, composition of the invention + butralin, composition of the invention
+ butroxydim, composition of the invention + butylate, composition of the invention +
cacodylic acid, composition of the invention + calcium chlorate, composition of the
invention + cafenstrole, composition of the invention + carbetamide, composition of the
invention + carfentrazone, composition of the invention + carfentrazone-ethyl, composition
of the invention + CDEA, composition of the invention + CEPC, composition of the
invention + chlorflurenol, composition of the invention + chlorflurenol-methyl, composition
of the invention + chloridazon, composition of the invention + chlorimuron, composition of
the invention + chlorimuron-ethyl, composition of the invention + chloroacetic acid,
composition of the invention + chlorotoluron, composition of the invention + chlorpropham,
composition of the invention + chlorsulfuron, composition of the invention + chlorthal,
composition of the invention + chlorthal-dimethyl, composition of the invention + cinidonethyl,
composition of the invention + cinmethylin, composition of the invention +
cinosulfuron, composition of the invention + cisanilide, composition of the invention +
clethodim, composition of the invention + clodinafop, composition of the invention +
clodinafop-propargyl, composition of the invention + clomazone, composition of the
invention + clomeprop, composition of the invention + clopyralid, composition of the
invention + cloransulam, composition of the invention + cloransulam-methyl, composition of
the invention + CMA, composition of the invention + 4-CPB, composition of the invention +
CPMF, composition of the invention + 4-CPP, composition of the invention + CPPC,
composition of the invention + cresol, composition of the invention + cumyluron,
composition of the invention + cyanamide, composition of the invention + cyanazine,
composition of the invention + cycloate, composition of the invention + cyclosulfamuron,
composition of the invention + cycloxydim, composition of the invention + cyhalofop,
composition of the invention + cyhalofop-butyl, composition of the invention + 2,4-D,
composition of the invention + 3,4-DA, composition of the invention + daimuron,
composition of the invention + dalapon, composition of the invention + dazomet,
composition of the invention + 2,4-DB, composition of the invention + 3,4-DB, composition
of the invention + 2,4-DEB, composition of the invention + desmedipham, composition of
the invention + desmetryn, composition of the invention + dicamba, composition of the
invention + dichlobenil, composition of the invention + ortho-dichlorobenzene, composition
of the invention + para-dichlorobenzene, composition of the invention + dichlorprop,
composition of the invention + dichlorprop-P, composition of the invention + diclofop,
composition of the invention + diclofop-methyl, composition of the invention + diclosulam,
composition of the invention + difenzoquat, composition of the invention + difenzoquat
metilsulfate, composition of the invention + diflufenican, composition of the invention +
diflufenzopyr, composition of the invention + dimefuron, composition of the invention +
dimepiperate, composition of the invention + dimethachlor, composition of the invention +
dimethametryn, composition of the invention + dimethenamid, composition of the invention
+ dimethenamid-P, composition of the invention + dimethipin, composition of the invention
+ dimethylarsinic acid, composition of the invention + dinitramine, composition of the
invention + dinoterb, composition of the invention + diphenamid, composition of the
invention + dipropetryn, composition of the invention + diquat, composition of the invention
+ diquat dibromide, composition of the invention + dithiopyr, composition of the invention +
diuron, composition of the invention + DNOC, composition of the invention + 3,4-DP,
composition of the invention + DSMA, composition of the invention + EBEP, composition
of the invention + endothal, composition of the invention + EPTC, composition of the
invention + esprocarb, composition of the invention + ethalfluralin, composition of the
invention + ethametsulfuron, composition of the invention + ethametsulfuron-methyl,
composition of the invention + ethephon, composition of the invention + ethofumesate,
composition of the invention + ethoxyfen, composition of the invention + ethoxysulfuron,
composition of the invention + etobenzanid, composition of the invention + fenoxaprop,
composition of the invention + fenoxaprop-P, composition of the invention + fenoxapropethyl,
composition of the invention + fenoxaprop-P-ethyl, composition of the invention +
fenoxasulfone, composition of the invention + fentrazamide, composition of the invention +
ferrous sulfate, composition of the invention + flamprop-M, composition of the invention +
flazasulfuron, composition of the invention + florasulam, composition of the invention +
fluazifop, composition of the invention + fluazifop-butyl, composition of the invention +
fluazifop-P, composition of the invention + fluazifop-P-butyl, composition of the invention +
fluazolate, composition of the invention + flucarbazone, composition of the invention +
flucarbazone-sodium, composition of the invention + flucetosulfuron, composition of the
invention + fluchloralin, composition of the invention + flufenacet, composition of the
invention + flufenpyr, composition of the invention + flufenpyr-ethyl, composition of the
invention + flumetralin, composition of the invention + flumetsulam, composition of the
invention + flumiclorac, composition of the invention + flumiclorac-pentyl, composition of
the invention + flumioxazin, composition of the invention + flumipropin, composition of the
invention + fluometuron, composition of the invention + fluoroglycofen, composition of the
invention + fluoroglycofen-ethyl, composition of the invention + fluoxaprop, composition of
the invention + flupoxam, composition of the invention + flupropacil, composition of the
invention + flupropanate, composition of the invention + flupyrsulfuron, composition of the
invention + flupyrsulfuron-methyl-sodium, composition of the invention + flurenol,
composition of the invention + fluridone, composition of the invention + flurochloridone,
composition of the invention + fluroxypyr, composition of the invention + flurtamone,
composition of the invention + fluthiacet, composition of the invention + fluthiacet-methyl,
composition of the invention + fomesafen, composition of the invention + foramsulfuron,
composition of the invention + fosamine, composition of the invention + glufosinate,
composition of the invention + glufosinate-ammonium, composition of the invention +
glyphosate, composition of the invention + halosulfuron, composition of the invention +
halosulfuron-methyl, composition of the invention + haloxyfop, composition of the invention
+ haloxyfop-P, composition of the invention + HC-252, composition of the invention +
hexazinone, composition of the invention + imazamethabenz, composition of the invention +
imazamethabenz-methyl, composition of the invention + imazamox, composition of the
invention + imazapic, composition of the invention + imazapyr, composition of the invention
+ imazaquin, composition of the invention + imazethapyr, composition of the invention +
imazosulfuron, composition of the invention + indanofan, composition of the invention +
indaziflam, composition of the invention + iodomethane, composition of the invention +
iodosulfuron, composition of the invention + iodosulfuron-methyl-sodium, composition of
the invention + ioxynil, composition of the invention + ipfencarbazone, composition of the
invention + isoproturon, composition of the invention + isouron, composition of the
invention + isoxaben, composition of the invention + isoxachlortole, composition of the
invention + isoxaflutole, composition of the invention + isoxapyrifop, composition of the
invention + karbutilate, composition of the invention + lactofen, composition of the
invention + lenacil, composition of the invention + linuron, composition of the invention +
MAA, composition of the invention + MAMA, composition of the invention + MCPA,
composition of the invention + MCPA-thioethyl, composition of the invention + MCPB,
composition of the invention + mecoprop, composition of the invention + mecoprop-P,
composition of the invention + mefenacet, composition of the invention + mefluidide,
composition of the invention + mesosulfuron, composition of the invention + mesosulfuronmethyl,
composition of the invention + mesotrione, composition of the invention + metam,
composition of the invention + metamifop, composition of the invention + metamitron,
composition of the invention + metazachlor, composition of the invention + metazosulfuron,
composition of the invention + methabenzthiazuron, composition of the invention +
methazole, composition of the invention + methylarsonic acid, composition of the invention
+ methyldymron, composition of the invention + methyl isothiocyanate, composition of the
invention + metobenzuron, composition of the invention + metobromuron, composition of
the invention + metolachlor, composition of the invention + S-metolachlor, composition of
the invention + metosulam, composition of the invention + metoxuron, composition of the
invention + metribuzin, composition of the invention + metsulfuron, composition of the
invention + metsulfuron-methyl, composition of the invention + MK-616, composition of the
invention + molinate, composition of the invention + monolinuron, composition of the
invention + monosulfuron, composition of the invention + monosulfuron-ester, composition
of the invention + MSMA, composition of the invention + naproanilide, composition of the
invention + napropamide, composition of the invention + naptalam, composition of the
invention + NDA-402989, composition of the invention + neburon, composition of the
invention + nicosulfuron, composition of the invention + nipyraclofen, composition of the
invention + n-methyl glyphosate, composition of the invention + nonanoic acid, composition
of the invention + norflurazon, composition of the invention + oleic acid (fatty acids),
composition of the invention + orbencarb, composition of the invention + orthosulfamuron,
composition of the invention + oryzalin, composition of the invention + oxadiargyl,
composition of the invention + oxadiazon, composition of the invention + oxasulfuron,
composition of the invention + oxaziclomefone, composition of the invention + oxyfluorfen,
composition of the invention + paraquat, composition of the invention + paraquat dichloride,
composition of the invention + pebulate, composition of the invention + pendimethalin,
composition of the invention + penoxsulam, composition of the invention +
pentachlorophenol, composition of the invention + pentanochlor, composition of the
invention + pentoxazone, composition of the invention + pethoxamid, composition of the
invention + petrolium oils, composition of the invention + phenmedipham, composition of
the invention + phenmedipham-ethyl, composition of the invention + picloram, composition
of the invention + picolinafen, composition of the invention + pinoxaden, composition of the
invention + piperophos, composition of the invention + potassium arsenite, composition of
the invention + potassium azide, composition of the invention + pretilachlor, composition of
the invention + primisulfuron, composition of the invention + primisulfuron-methyl,
composition of the invention + prodiamine, composition of the invention + profluazol,
composition of the invention + profoxydim, composition of the invention + prohexadionecalcium,
composition of the invention + prometon, composition of the invention +
prometryn, composition of the invention + propachlor, composition of the invention +
propanil, composition of the invention + propaquizafop, composition of the invention +
propazine, composition of the invention + propham, composition of the invention +
propisochlor, composition of the invention + propoxycarbazone, composition of the
invention + propoxycarbazone-sodium, composition of the invention + propyzamide,
composition of the invention + prosulfocarb, composition of the invention + prosulfuron,
composition of the invention + pyraclonil, composition of the invention + pyraflufen,
composition of the invention + pyraflufen-ethyl, composition of the invention +
pyrasulfotole, composition of the invention + pyrazolynate, composition of the invention +
pyrazosulfuron, composition of the invention + pyrazosulfuron-ethyl, composition of the
invention + pyrazoxyfen, composition of the invention + pyribenzoxim, composition of the
invention + pyributicarb, composition of the invention + pyridafol, composition of the
invention + pyridate, composition of the invention + pyriftalid, composition of the invention
+ pyriminobac, composition of the invention + pyriminobac-methyl, composition of the
invention + pyrimisulfan, composition of the invention + pyrithiobac, composition of the
invention + pyrithiobac-sodium, composition of the invention + pyroxasulfone, composition
of the invention + pyroxulam, composition of the invention + quinclorac, composition of the
invention + quinmerac, composition of the invention + quinoclamine, composition of the
invention + quizalofop, composition of the invention + quizalofop-P, composition of the
invention + quizalofop-ethyl, composition of the invention + quizalofop-P-ethyl,
composition of the invention + rimsulfuron, composition of the invention + saflufenacil,
composition of the invention + sethoxydim, composition of the invention + siduron,
composition of the invention + simazine, composition of the invention + simetryn,
composition of the invention + SMA, composition of the invention + sodium arsenite,
composition of the invention + sodium azide, composition of the invention + sodium
chlorate, composition of the invention + sulcotrione, composition of the invention +
sulfentrazone, composition of the invention + sulfometuron, composition of the invention +
sulfometuron-methyl, composition of the invention + sulfosate, composition of the invention
+ sulfosulfuron, composition of the invention + sulfuric acid, composition of the invention +
tar oils, composition of the invention + 2,3,6-TBA, composition of the invention + TCA,
composition of the invention + TCA-sodium, composition of the invention + tebutam,
composition of the invention + tebuthiuron, composition of the invention + tefuryltrione,
composition of the invention + tembotrione, composition of the invention + tepraloxydim,
composition of the invention + terbacil, composition of the invention + terbumeton,
composition of the invention + terbuthylazine, composition of the invention + terbutryn,
composition of the invention + thenylchlor, composition of the invention + thiazafluron,
composition of the invention + thiazopyr, composition of the invention + thifensulfuron,
composition of the invention + thiencarbazone, composition of the invention +
thifensulfuron-methyl, composition of the invention + thiobencarb, composition of the
invention + tiocarbazil, composition of the invention + topramezone, composition of the
invention + tralkoxydim, composition of the invention + triafamone, composition of the
invention + tri-allate, composition of the invention + triasulfuron, composition of the
invention + triaziflam, composition of the invention + tribenuron, composition of the
invention + tribenuron-methyl, composition of the invention + tricamba, composition of the
invention + triclopyr, composition of the invention + trietazine, composition of the invention
+ trifloxysulfuron, composition of the invention + trifloxysulfuron-sodium, composition of
the invention + trifluralin, composition of the invention + triflusulfuron, composition of the
invention + triflusulfuron-methyl, composition of the invention + trifop, composition of the
invention + trifop-methyl, composition of the invention + trihydroxytriazine, composition of
the invention + trinexapac-ethyl, composition of the invention + tritosulfuron, composition
of the invention + [3-[2-chloro-4-fluoro-5-(l-methyl-6-trifluoromethyl-2,4-dioxo-l,2,3,4-
tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS R 353292-
31-6), composition of the invention + 4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-
(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one (CAS R 352010-68-
5) and composition of the invention + 4-hydroxy-3-[[2-(3-methoxypropyl)-6-
(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one.
Whilst compositions comprising a safener and a two-way mixture of a compound of
formula (I) and another herbicide are explicitly disclosed above, the skilled man will
appreciate that the invention extends to three-way, and further multiple combinations
comprising the above two-way mixtures.
Particularly preferred mixture partners for use in the compositions of the invention
are: 2,4-D, acetochlor, aminocyclopyrachlor, aminopyralid, atrazine, azimsulfuron,
bensulfuron, bensulfuron-methyl, bentazon, benzobicyclon, bispyribac, bispyribac-sodium,
bromobutide, bromoxynil, butachlor, butafenacil, cafenstrole, carfentrazone, cinosulfuron,
clodinafop-propargyl, clomazone, clomeprop, clopyralid, cyclosulfamuron, cycloxydim,
cyhalofop, cyhalofop-butyl, daimuron, dicamba, diclofop-methyl, diflufenzopyr-Na,
dimethenamid, dimethenamid-P, diquat, diquat dibromide, esprocarb, ethoxysulfuron,
fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentrazamide, fenoxasulfone, florasulam, fluazifopbutyl,
fluazifop-P-butyl, flufenacet, flumiclorac, flumioxazin, fluroxypyr, flumetsulam,
fluthiacet, fomesafen, foramsulfuron, glufosinate, glufosinate-ammonium, glyphosate,
halosulfuron, halosulfuron-methyl, haloxyfop-methyl, haloxyfop-P-methyl,
imazamethabenz-methyl, imazamox, imazosulfuron, indanofan, iodosulfuron-methylsodium,
ipfencarbazone, isoxaflutole, MCPA, mecoprop, mecoprop-P, mefenacet,
mesosulfuron-methyl, mesotrione, metamifop, metazosulfuron, metolachlor, s-metolachlor,
metribuzin, metsulfuron, metsulfuron-methyl, MK-616, molinate, monosulfuron-ester,
naptalam, nicosulfuron, orthosulfamuron, oxadiargyl, oxadiazon, oxaziclomefone, paraquat,
paraquat dichloride, pendimethalin, penoxsulam, pentoxazone, pinoxaden, pretilachlor,
primisulfuron-methyl, profoxydim, propanil, propaquizafop, prosulfuron, pyrachlonil,
pyrazolynate, pyrazosulfuron, pyrazosulfuron-ethyl, pyroxsulam, pyrazoxyfen,
pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyroxasulfone, quinclorac,
quizalofop-ethyl, quizalofop-P-ethyl, rimsulfuron, saflufencil, sethoxydim, simazine,
tefuryltrione, tembotrione, terbuthylazine, thifensulfuron, topramezone, tralkoxydim,
triafamone, triasulfuron, tribenuron-methyl, tritosulfuron and trifop-methyl.
In particular, when the composition of the invention is to be used on corn, the
following mixing partners are preferred: 2,4-D, acetochlor, aminocyclopyrachlor,
aminopyralid, atrazine, bentazon, bromoxynil, butafenacil, carfentrazone, clodinafoppropargyl,
cycloxydim, dicamba, diflufenzopyr-Na, dimethenamid, dimethenamid-P,
fenoxaprop-ethyl, fenoxaprop-P-ethyl, florasulam, fluazifop-butyl, fluazifop-P-butyl,
flufenacet, flumiclorac, fluroxypyr, flumetsulam, flumioxazin, fluthiacet, fomesafen,
foramsulfuron, glufosinate, glyphosate, haloxyfop-methyl, haloxyfop-P-methyl,
iodosulfuron-methyl-sodium, isoxaflutole, mesotrione, metolachlor, s-metolachlor,
metribuzin, nicosulfuron, paraquat, pendimethalin, primisulfuron-methyl, propaquizafop,
prosulfuron, pyroxasulfone, quizalofop-ethyl, quizalofop-P-ethyl, rimsulfuron, saflufencil,
sethoxydim, simazine, tembotrione, terbuthylazine, topramezone and tritosulfuron.
In particular, when the composition of the invention is to be used on rice, the
following mixing partners are preferred: 2,4-D, azimsulfuron, bensulfuron, bensulfuronmethyl,
benzobicyclon, bispyribac, bispyribac-sodium, butachlor, cafenstrole, cinosulfuron,
clomazone, clomeprop, clopyralid, cyclosulfamuron, cyhalofop, cyhalofop-butyl, daimuron,
dicamba, diquat, diquat dibromide, esprocarb, ethoxysulfuron, fenoxaprop-P, fenoxaprop-Pethyl,
fentrazamide, florasulam, glufosinate-ammonium, halosulfuron, halosulfuron-methyl,
imazamethabenz-methyl, imazamox, imazosulfuron, MCPA, mefenacet, metamifop,
metsulfuron, metsulfuron-methyl, MK-616, molinate, glyphosate, orthosulfamuron,
oxadiargyl, oxadiazon, paraquat dichloride, pendimethalin, penoxsulam, pretilachlor,
profoxydim, propanil, pyrazolynate, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen,
pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, quinclorac, tefuryltrione,
triasulfuron, trinexapac-ethyl, fenoxasulfone, ipfencarbazone, metazosulfuron, triafamone,
mesotrione, indanofan, oxaziclomefone, bromobutide, pentoxazone and pyrachlonil.
In particular, when the composition of the invention is to be used on sugar cane, the
following mixing partners are preferred: atrazine, ametryn, bicyclopyrone, 2,4-D, diuron,
halosulfuron, mesotrione, pendimethalin and trifloxysulfuron.
For the avoidance of doubt, even if not explicitly stated above, the mixing partners
may also be in the form of any suitable agrochemically acceptable ester or salt, as mentioned
e.g. in The Pesticide Manual, Thirteenth Edition, British Crop Protection Council, 2003.
The mixing ratio of the compound of formula (I) to the mixing partner is preferably
from 1: 500 to 1000:1.
Various aspects and embodiments of the present invention will now be illustrated in
more detail by way of example. It will be appreciated that modification of detail may be
made without departing from the scope of the invention.
For the avoidance of doubt, where a literary reference, patent application, or patent, is
cited within the text of this application, the entire text of said citation is herein incorporated
by reference.
EXAMPLES
EXAMPLE 1 Safening on Corn
Maize seeds were sown into standard soil in pots and cultivated under controlled
conditions in a glasshouse (at 24/18 °C day/night; 16 hours light; 65% humidity).
When the plants were at the vegetative stage of 3 leaves they were sprayed with an
aqueous spray solution containing a compound of formula (I) alone and in combination with
a number of different herbicide safeners. All the compounds used for the spray solution were
present as an EC or SC formulation respectively. In addition a non-ionic surfactant (X-77
Spreader) was added to form a 0.2%> v/v solution.
The spray solution was applied with a cabinet tracksprayer with a flat fan nozzle
(Teejet 11002VS) and an application volume of 200L/ha (at 2 bar).
The test plants were then grown on in a glasshouse under controlled conditions (at
24/18 °C day/night; 16 hours light; 65%> humidity) and watered twice a day. After 2 1 days
the test was evaluated for general crop injury (100% equals total damage to plant; 0%> equals
no damage to plant).
Results are shown below in Table 1 as the mean % visual phytotoxicity of two
replicates.
TABLE 1 Percentage damage caused to corn by compounds of formula (I) alone
and in the presence of a number of safeners including N-(2-
methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide
(Safener A).
EXAMPLE 2 Safening on Corn and Sweetcorn
Sweetcorn and Maize seeds were sown into standard soil in troughs and cultivated
under controlled conditions in a glasshouse (at 24/18°C day/night; 16 hours light, 65%
humidity).
When the plants were at the vegetative stage of 2 leaves they were sprayed with an
aqueous spray solution containing a compound of formula (I) alone and in combination with
a number of different herbicide safeners. All the compounds used for the spray solution
were present as technical material. In addition a non-ionic surfactant (X-77 Spreader) was
added to a 0.2%> v/v solution.
The spray solution was applied with a cabinet tracksprayer with a flat fan nozzle
(Teeject 11002VS) and an application volume of 200L/ha (at 2 bar).
The test plants were then grown on in a glasshouse under controlled conditions (at
24/1 8°C day/night; 16 hours light; 65% humidity) and watered twice a day. After 2 1 days
the test was evaluated for general crop injury (100% equals total damage to plant; 0%> equals
no damage to plant).
Results are shown below in Tables 2 and 3 as the mean % visual phytotoxicity of
three replicates.
TABLE 2 Percentage damage caused to corn (variety Claxxon) by compounds of
formula (I) alone and in the presence of a number of safeners including
N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide (Safener A).
*Concep III contains 74.3% fluxofenim.
TABLE 3 Percentage damage caused to sweetcorn (variety Sundance) by
compounds of formula (I) alone and in the presence of a number of
safeners including N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide (Safener A).
*Concep III contains 74.3% fluxofenim.
EXAMPLE 3 Safening on Sugarcane (variety SP803280)
Sugarcane stem sections were sown into standard soil in troughs and cultivated under
controlled conditions in a glasshouse (at 30/20°C day/night; 18 hours light, 75% humidity).
When the plants were at the vegetative stage of 3-4 leaves they were sprayed with an
aqueous spray solution containing a compound of formula (I) alone and in combination with
a number of different herbicide safeners. All the compounds used for the spray solution
were present as technical material. In addition a non-ionic surfactant (X-77 Spreader) was
added to a 0.2% v/v solution.
The spray solution was applied with a cabinet tracksprayer with a flat fan nozzle
(Teeject 11002VS) and an application volume of 200L/ha (at 2 bar).
The test plants were then grown on in a glasshouse under controlled conditions (at
30/20°C day/night; 18 hours light; 75% humidity) and watered twice a day. After 26 days
the test was evaluated for general crop injury (100% equals total damage to plant; 0% equals
no damage to plant).
Results are shown below in Table 4 as the mean % visual phytotoxicity of four
replicates.
TABLE 4 Percentage damage caused to sugarcane (variety SP803280) by
compounds of formula (I) alone and in the presence of a number of
safeners including N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide (Safener A).
*Concep III contains 74.3% fluxofenim.
Although the invention has been described with reference to preferred embodiments
and examples thereof, the scope of the present invention is not limited only to those
described embodiments. As will be apparent to persons skilled in the art, modifications and
adaptations to the above-described invention can be made without departing from the spirit
and scope of the invention, which is defined and circumscribed by the appended claims. All
publications cited herein are hereby incorporated by reference in their entirety for all
purposes to the same extent as if each individual publication were specifically and
individually indicated to be so incorporated by reference.
CLAIMS
1. A composition for protecting crop plants from the harmful effects of a pyridine
derivative herbicide of formula (I)
or a salt or N-oxide thereof wherein Y is chloro or bromo, R is hydrogen, Ci_8 alkyl,
C2-5 alkenyl, C3_ alkynyl, aryl Ci_2 alkyl, Ci_4 alkoxy Ci_4 alkyl or Ci_4 alkoxy Ci_4
alkoxy Ci_2 alkyl, R 1 is chloro or bromo, R2 is Ci_2 alkoxy and R is chloro or fluoro
and wherein said composition comprises, in addition to the pyridine derivative
herbicide of formula (I), the safener N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide.
2. The composition according to claim 1, wherein Y is chloro.
3. The composition according to claim 1 or claim 2, wherein R 1 is chloro.
4. The composition according to any one of claims 1 to 3, wherein R2 is methoxy.
5. The composition according to any one of claims 1 to 4, wherein R is fluoro.
6. The composition according to any one of claims 1 to 5, wherein R is hydrogen, Ci_4
alkyl, C3_4 alkenyl, arylmethyl or Ci_4 alkoxy Ci_2 alkyl.
7. The composition according to claim 6, wherein R is hydrogen or methyl.
8. The composition according to claim 7, wherein R is hydrogen.
9. The composition according to claim 8, wherein the compound of formula (I) is present
as an alkali metal, an alkaline earth metal, ammonia or amine salt.
10. A method for protecting crops of useful plants from the harmful effects of a herbicide
of formula (I) as defined in any one of claims 1 to 9, which comprises applying to the
locus of the useful plants the safener N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide.
11. The method of claim 10, wherein the useful plant is selected from the group consisting
of maize, rice and sugar cane.
12. A method for combating weeds in crops of useful plants, which comprises treating the
useful plants, seeds or cuttings thereof or the locus of the useful plants simultaneously
or at separate times with a herbicidally active amount of a compound of formula (I)
and the safener N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]
benzenesulfonamide.
13. The method of claim 12, wherein the useful plant is selected from the group consisting
of maize, rice and sugar cane.