(19)

*EP003876736B1*
(11) EP 3 876 736 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) International Patent Classification (IPC):
of the grant of the patent: A01N 43/90 (2006.01) A01N 43/56 (2006.01)
30.11.2022 Bulletin 2022/48 A01N 25/02 (2006.01) A01N 25/22 (2006.01)
A01P 13/02 (2006.01)
(21) Application number: 20745309.3
(52) Cooperative Patent Classification (CPC):
(22) Date of filing: 17.07.2020 (C-Sets available)
A01N 25/02; A01N 25/22 (Cont.)

(86) International application number:

PCT/IB2020/056720

(87) International publication number:

WO 2021/009716 (21.01.2021 Gazette 2021/03)

(54) STABLE FORMULATION COMPRISING HERBICIDES

STABILE FORMULIERUNG MIT HERBIZIDEN
FORMULATION STABLE COMPRENANT DES HERBICIDES

(84) Designated Contracting States: (74) Representative: ABG Intellectual Property Law,
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB S.L.
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Avenida de Burgos, 16D
PL PT RO RS SE SI SK SM TR Edificio Euromor
Designated Extension States: 28036 Madrid (ES)
BA ME
Designated Validation States: (56) References cited:
MD WO-A1-01/17351 WO-A2-2007/073933
WO-A2-2008/049618 WO-A2-2014/060557
(30) Priority: 18.07.2019 US 201962875608 P AU-A4- 2019 100 546 CN-A- 108 013 066

(43) Date of publication of application: • MICHEL MUEHLEBACH ET AL: "Aryldiones

15.09.2021 Bulletin 2021/37 incorporating a [1,4,5]oxadiazepane ring. Part 2:
Chemistry and biology of the cereal herbicide
(73) Proprietor: Adama Agan Ltd. pinoxaden", PEST MANAGEMENT SCIENCE, vol.
7710201 Ashdod (IL) 67, no. 12, 8 June 2011 (2011-06-08), pages
1499-1521, XP055539325, ISSN: 1526-498X, DOI:
(72) Inventors: 10.1002/ps.2204
• SILBERT, Gilad
7917500 Kibutz Dorot (IL)
• MEIRON, Oren
8502500 Meitar (IL)
• AL SOUSOU, Merna
7221432 Ramla (IL)
EP 3 876 736 B1

• HEVRONI, Liron
8502500 Meitar (IL)

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Processed by Luminess, 75001 PARIS (FR) (Cont. next page)

 EP 3 876 736 B1

(52) Cooperative Patent Classification (CPC): (Cont.)

C-Sets
A01N 25/02, A01N 43/56, A01N 43/90;
A01N 25/22, A01N 43/56, A01N 43/90

2
 EP 3 876 736 B1

Description

FIELD OF THE INVENTION

5 [0001] The present invention relates to the field of agrochemical formulations, more specifically to a stable formulation
comprising an herbicide with 3-hydroxy-pyrazol skeleton containing a substituted phenyl group.

BACKGROUND PRIOR ART

10 [0002] Herbicides are extensively used in the control of grasses and other weeds. Some herbicides display a 3-hydroxy-
pyrazol skeleton containing a substituted phenyl group, for example, pinoxaden, which was disclosed as compound
1.008 in WO 99/47525 A1 (Novartis AG). It has been used together with different co-herbicides; see for example WO
01/17351 A1 (Syngenta Participations AG). Also, liquid formulations have been developed, for example as described
in WO 2008/049618 A2 (Syngenta Participations AG), that required a built-in phosphate adjuvant. Pinoxaden and its
15 herbicidal uses are further disclosed in "Pesticide Chemistry. Crop Protection, Public Health, Environmental Safety" ed.
H. Ohkawa et al., 2007, Wiley, Weinheim, pp. 101-110.

20

25

30 [0003] Pinoxaden has however a problem of stability and its formulations such as oil dispersions (OD), often result in
the rapid degradation of the compound.
[0004] WO 2007/073933 (Syngenta Crop Protection Inc) discloses EC herbicidal formulations comprising pinoxaden
and an alcohol. The alcohol prevents the degradation of pinoxaden. The formulations further comprise a water-insoluble
solvent. In addition to Solvesso 200 ND and an alcohol, Example 5 uses as co-solvent rape oil methyl ester.
35 [0005] Muehlebach et al. "Aryldiones incorporating a [1,4,5]-oxadiazepane ring. Part 2: Chemistry and biology of the
cereal herbicide pinoxaden", Pest Manag. Sci., vol. 67, no. 12, 8 June 2011, pages 1499-1521: discloses on lines 30-42,
right column of page 1509 (section 2.4.2) "... the plants were sprayed at the 3 to 6 lead stage with an aqueous spray
solution (500 L ha-1 carrier volume) prepared by diluting a formulation of the technical active ingredient [pinoxaden] with
water and a with optional addition of [...] Merge® (1% v/v)" or with "Adigor® (0.5%, v/v)", i.e. a tank mixture. Both, Merge
40 and Adigor are used as tank mix adjuvants in the dilution of the formulations immediately before their application in the
field. They are therefore adjuvants intended for the physical stabilization of the diluted tank mix.
[0006] WO 2014/060557 A2 (Syngenta Participations AG) discloses EC formulations wherein the harmful effects of
the heavy aromatic solvents of previous pinoxaden EC formulations are reduced. Also, the document aims to substitute
tetrahydrofurfuryl alcohol (THFA) with a more environmentally friendly alcohol (used as stabilizer).
45 [0007] CN 108 013 066 A (Beijuing Kefa Weiye Pesticide Tech.) discloses synergistic mixtures of pinoxaden and
mesosulfuron in combination with a third herbicide. Example 8 teaches a Dispersable Oil Suspension comprising 49%
of active ingredients and 30% of castor oil (based on machine translation from espacenet). No information is given in
relation of pinoxaden’s stability, or about the pH of the castor oil, or the possible effects of the pH of castor oil on
pinoxaden’s stability.
50 [0008] AU 2019 100 546 B4 (Titan AG Pty Ltd) discloses EC herbicidal formulations comprising pinoxaden and two
solvents selected from the following groups (i), (ii) or (iii): (i) acetophenone; (ii) propylene carbonate and butylene
carbonate; or (iii) N-(C1 to C4 alkyl)pyrrolidone.
[0009] There is therefore in the art a need to provide improved formulations for the herbicide pinoxaden.

55 SUMMARY OF THE INVENTION

[0010] In the search of a more stable formulation, the inventors first tried numerous oils as carriers.
[0011] They were tested to determine which ones provided optimum stability to pinoxaden During the trials it was not

3
 EP 3 876 736 B1

apparent why some oils provided stable compositions, while others, sometimes structurally related, resulted in a rapid
degradation of pinoxaden.
[0012] It was not until the inventors investigated the pH of these oils that the problem could be solved, when realizing
the crucial role that the oil’s pH plays in the stability of pinoxaden and other co-herbicides or safeners that might be
5 present in the mixture.
[0013] It is thus a first aspect of the present invention a formulation for controlling undesired plants comprising

(i) an herbicidal effective amount of a compound of formula (I), stereoisomers, salts or solvates thereof, wherein
said compound of formula (I) is pinoxaden, its stereoisomers, salts or solvates thereof
10

15

20

and
25
(ii) above 50 w/w % to 99 w/w % of an oil carrier;

characterized in that the oil carrier has a pH of 5.0 or more, as measured by a process consisting of the steps of

30 a) making a deionized water mixture having 1 w/w% of oil;

b) stirring the mixture of the previous step with a magnetic stirrer at 1,500 RPM for 10 minutes at 25°C;
c) allowing the phases in the mixture to separate for 10 min at 25°C,
d) collecting into a separate vial the lower aqueous phase;
e) measuring at 25°C the pH of aqueous phase collected using a JENWAY 3510 pH meter, with an AgCl,
35 liquid filled single junction electrode, such that the electrode and the thermocouple of the pH meter are
inserted into the vial containing the aqueous water phase until the measured pH value is stable for 10s;

wherein the water content in the oil is less than 0.2 w/w%, with respect to the total weight of the oil, as measured
by Karl-Fischer titration; and
40
wherein said formulation is an oil dispersion.

[0014] The composition of the invention preferably comprises a co-herbicide, preferably a sulphonylurea.
[0015] A second aspect of the invention is a method for the control of an undesired plant (also referred herein as
45 "weed" or "undesired vegetation") comprising dispersing in an aqueous solution the formulation of the invention and
contacting the resulting mixture with the locus of said plant.
[0016] A third aspect is the use of the formulation of the invention for the control of undesired plants.
[0017] US 4,834,908 discloses that certain oil additive combinations can increase the herbicidal activity of compounds
from the class of the cyclohexanediones, benzothiadiazinone dioxides, diphenyl ether herbicides and aryloxyphenoxy
50 herbicides. The document is however silent about the importance of the oil’s pH, nor does it suggest that an oil with a
pH of 5.0 or more could provide a stable formulation of pinoxaden.
[0018] Neither does WO 2011/107741 A1 disclose the importance of the pH of the oil. WO 2011/107741 A1 discloses
herbicidal compositions comprising a mixture of (a) an ALS inhibitor in the form of an aluminum salt and (b) pinoxaden.
EC formulations and other solid formulations are described on pages 26-29, none containing an oil carrier, the latter
55 being taught only in amounts of 0.01 to 10 w/w%, that is, as adjuvants for the tank mix (last paragraph of page 21 and
page 22). See also the mixture of Axial™ and Adigor™ (oil) on lines 32-33 of page 40, wherein the Adigor™ is marked
as "adjuvant".
[0019] WO 01/17351 (Syngenta Participations AG) discloses a composition comprising a) a 3-hydroxy-4-(4-methyl-

4
 EP 3 876 736 B1

phenyl)-5-oxo-pyrazoline (e.g. pinoxaden), b) a safener and c) an oil of vegetable or animal origin, a mineral oil or
derivatives thereof. Preferred oils are those of vegetable origin, and all the examples refer to emulsifiable concentrates
(EC) and other solid formulations (pages 33-36), wherein the oil is again only added as an additive (0.7-1 w/w %) in the
tank mixture (see the biological examples on pages 37-40 or second paragraph of page 12). The oils used are MERGE
5 (an aromatic adjuvant for EC formulations) and Emery 2231, a fatty acid methyl ester derivative. No oils are added as
carriers, nor their pH is considered.
[0020] Thus, the inventors were surprised to find out that the compounds of formula (I) were stable in an oil carrier
having a pH of at least 5.0.

10 DETAILED DESCRIPTION OF THE INVENTION

Definitions

[0021] In the present document the following terms are given the meaning below.
15 [0022] The present document teaches that some of the compounds must be in an "herbicidal effective amount", which
is understood as the amount of that compound that is effective to provide the desired effect when used in combination
with the other components of the formulation. The amount that is "effective" will vary from application to application,
depending on the particular crop to be treated or undesirable plant targeted. Additionally, what amount is considered
effective may vary depending on the particular objective that is being pursued and on the balancing of certain outcomes,
20 such as for example the effectiveness on the weed control versus the damage to crop. Thus, it is not always possible
to specify an exact "effective amount", but in any given situation it may be determined by one of ordinary skill in the art
using routine experimentation.
[0023] This is also true when determining the effective amount of a safener, a compound having antagonistic effects
on the active herbicides present in the formulation, that is used to prevent damage to the crop.
25 [0024] The formulation of the invention is thus useful for the "control of undesired plants", which is given in the present
document its usual meaning in the agrochemical industry, that is, amongst others, the capacity to kill, prevent growth
or reproduction, or to diminish the health of unwanted plants in a given locus, by interfering in the unwanted plant’s
mechanisms, such as metabolism, photosynthesis and/or cell division.
[0025] "Crop" refers to any plant of industrial interest, including whole plants, plant organs (e.g. leaves, stems, twigs,
30 roots, trunks, limbs, shoots, fruits etc.), plant cells, or plant seeds. This term also encompasses plant crops such as
fruits. The term "plant" also includes the propagation material thereof, which may include all the generative parts of the
plant such as seeds and vegetative plant material such as cuttings and tubers, which can be used for the multiplication
of the plant. This includes seeds, tubers, spores, corms, bulbs, rhizomes, sprouts basal shoots, stolons, and buds and
other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after
35 emergence from soil.
[0026] Crop locus are areas of land on which the cultivated plants are already growing or in which the seeds of those
cultivated plants have been sown, also referring to areas of land on which it is intended to grow those cultivated plants.
[0027] Unless otherwise indicated, all weight percentages ("w/w %") are calculated with respect to the total weight of
the formulation: 100x(weight of compound/total weight of formulation).
40 [0028] "Agrochemical acceptable" refers to any molecular entity and composition that is used in the formulation of the
invention to improve any of its properties, such as any chemical, biological or physico-chemical properties approved for
use agrochemistry by a regulatory agency or a state government or other generally recognized pharmacopeia.
[0029] The invention also provides salts of the compounds herein defined. For instance, salts of compounds provided
herein may be acid addition salts, base addition salts or metallic salts, and they can be synthesized from the parent
45 compound which contains a basic or acidic moiety by conventional chemical methods. Generally, such salts are, for
example, prepared by reacting the free acid or base forms of these compounds with a stoichiometric amount of the
appropriate base or acid in water or in an organic solvent or in a mixture of the two. Generally, non-aqueous media like
ether, ethyl acetate, ethanol, isopropanol or acetonitrile are preferred. Examples of the acid addition salts include mineral
acid addition salts such as, for example, hydrochloride, hydrobromide, hydroiodide, sulphate, nitrate, phosphate, and
50 organic acid addition salts such as, for example, acetate, maleate, fumarate, citrate, oxalate, succinate, tartrate, malate,
mandelate, methanesulphonate and p-toluenesulphonate. Examples of the alkali addition salts include inorganic salts
such as, for example, ammonium, and organic alkali salts such as, for example, ethylenediamine, ethanolamine, N,N-
dialkylenethanolamine, triethanolamine, glucamine and basic aminoacids salts. Examples of the metallic salts include,
for example, sodium, potassium, calcium, magnesium, aluminium and lithium salts.
55 [0030] The term "solvate" according to this invention is to be understood as meaning any form of the compound which
has another molecule (most likely a polar solvent) attached to it via noncovalent bonding. Examples of solvates include
hydrates and alcoholates, e.g. methanolate.
[0031] An "stereoisomer" in the present patent application refers to compounds made up of the same atoms bonded

5
 EP 3 876 736 B1

by the same sequence of bonds but having different three-dimensional structures which are not interchangeable.
[0032] The term "about" as used herein specifically includes 610% from the indicated values in the range. In addition,
the endpoints of all ranges directed to the same component or property herein are inclusive of the endpoints, are
independently combinable, and include all intermediate points and ranges.
5 [0033] It is understood that where a parameter range is provided, all integers within that range, and tenths thereof,
are also provided by the invention as if the integers and tenths thereof are expressly described herein. For example,
"between 75 and 99 w/w %" includes 70 0 w/w %, 70 1 w/w %, 70. 2 w/w %, 70. 3 w/w %, etc. up to 99.0 w/w %.

Oil
10
[0034] The oil carrier having a pH of 5.0 or more can be a mineral oil or an oil of vegetable origin such as, for example,
rapeseed oil, olive oil or sunflower oil, an emulsified vegetable oil, or an alkyl ester of an oil of vegetable origin such as,
for example, the methyl or ethyl ester derivatives, or an oil of animal origin such as fish oil or beef tallow.
[0035] Specially preferred oil carriers are mineral oils, whether aromatic or non-aromatic, preferably paraffins, such
15 as isoparaffins. Exemplary isoparaffins comprise C8-C25, for example C10-C20-isoalkanes, i.e. alkanes comprising mostly
linear molecules with a methyl group in one of its penultimate carbon atoms to form a -C(H)(CH3)2 residue. It is for
example preferred that the oil carrier is an isoparaffinic oil comprising at least 20 w/w % of C14-C19-isoalkanes, with
respect to the total weight of the oil, and less than 2 w/w % of aromatic compounds, with respect to the total weight of the oil.
[0036] The inventors have also discovered that the water content of the oil plays an important role in the stability of
20 the formulation. Therefore, the water content in the oil is below 0.2, preferably below 0.18 or below 0.15, for example,
below 0.12 or below 0.10, typically between 0.001 and 0.19, more preferably between 0.01 and 0.12 w/w %, with respect
to the total weight of the oil, as measured by Karl-Fischer titration.
[0037] The pH of the oil as measured according to the process defined above, is preferably 5.5 or more, or 5.8 or
more, typically between 5.0 and 10.0, or between 5.5 and 9.0, or between 5.5 and 8.0, for example, between 5.5 and
25 7.8, or between 5.6 and 7.6, or between 5.8 and 7.5.
[0038] As shown in examples 1 and 2 described herein, the combination of low water content and a pH of at least 5.0
provides excellent stability results. Thus, it is preferable that the water content in the oil carrier is less than 0.20 w/w %,
with respect to the total weight of the oil carrier, as measured by Karl-Fischer titration, and the pH is between 5.5 and
10.0, preferably between 5.5 and 9.0, as measured by the method defined above.
30 [0039] The oil is the carrier, in an oil dispersion formulation (OD), and it is used in amounts preferably above 70 w/w
%, or above 80 w/w %, for example, between 75 w/w % and 99 w/w %, or between 80 and 95 w/w %.

Compounds of formula (I)

35 [0040] The compound of formula (I) is pinoxaden, its stereoisomers, salts or solvates thereof
[0041] The compounds of formula (IA), its stereoisomers, salts or solvates thereof are readily available following the
procedures already taught in the prior art, such as WO 96/21652, WO 01/17351, or WO 01/17352.
[0042] All tautomers of the compounds of formula (I) are included in the scope of the present invention.

40

45

50

[0043] The compound of formula (I) can be added in different amounts, typically between 0.1 w/w % and 70 w/w %,
for example, between 0.1 and 50 w/w % or between 0.5 and 10 w/w % or between 1 and 8 w/w %. The formulation an
55 OD preferably comprising between 0.1 and 15 w/w % of a compound of formula (I) stereoisomers, salts or solvates thereof.

6
 EP 3 876 736 B1

Co-herbicides

[0044] To attend the problem of weed resistance the formulators follow several strategies, most notably the combined
use of two or more herbicides having different Modes of Action (MOA), sometimes also in combination with a safener.
5 Such combinations are ideally administered in a single formulation, but can be added simultaneously in different formu-
lations or added at different times.
[0045] The compositions of the invention may thus comprise at least one co-herbicide, for example one selected from
the group consisting of ALS inhibitors such as sulphonylureas (e.g. mesosulfuron), sulphonyl-carbonyl-triazolinones,
imidazolinones, triazolopyrimidines or pyrimidinyl (thio) benzoates; inhibitors of the photosynthesis at PS II such as
10 nitriles, phenyl-pyridazines, benzothiadiazinones, triazines, triazolinones or triazinones; PS-I-electron diversion such as
bipyridyliums; protoporphyrinogen oxidase inhibitors, such as diphenyl ethers, thiadiazoles, pyrmidinediones, N-phenyl-
phthalimides, oxazolidinediones, tiazolinones, oxadiazoles or phenypyrazoles; PDS inhibitors; 4-HPPD inhibitors; DOXP
synthase inhibitors and other pigment synthesis inhibitors; EPSP synthase inhibitors; glutamine synthase inhibitors;
DHP inhibitors; microtubule assembly inhibitors; microtubule organization inhibitors; VLCFA inhibitors; inhibitors of the
15 synthesis of cellulose; membrane disruptors (uncouplers); non-ACCase inhibitors of lipid synthesis; synthetic auxins; or
auxin transport inhibitors.
[0046] Herbicides that can be used as co-herbicides in the present invention can be for example amidosulfuron,
azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, cinosulfuron, chlorsulfuron, chlorimuron, cyclosulfamuron,
ethametsulfuron-methyl, ethoxysulfuron, fluazasulfuron, flupyrsulfuron, imazosulfuron, iodosulfuron, mesosulfuron-met-
20 sulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, pyrazosulfuron-ethyl, sulfosulfuron, rimsulfuron, imazamox,
imazapyr, pyrithiobac-sodium, pyriminobac, bispyribac-sodium, atrazin, butracil, simazin, simethryne, terbutryne, ter-
buthylazine, trimexyflam, isoproturon, chlortoluron, diuron, dymron, fluometuron, linuron, methabenzthiazuron, glypho-
sate, sulfosate, glufosinate, nitrofen, bifenox, acifluorfen, lactofen, oxyfluorfen, ethoxyfen, fluoroglycofen, fomesafen,
halosafen, azafenidin, benzfendizone, butafenacil, carfentrazone-ethyl, cinidon-ethyl, flumichlorac-pentyl, flumioxazin,
25 fluthiacet-methyl, oxadiargyl, oxadiazon, pentoxazon, sulfentrazone, fluazolate, pyraflufen-ethyl, alachlor, acetochlor,
butachlor, dimethachlor, dimethenamid, S-dimethenamid, metazachlor, metolachlor, S-metolachlor, pretilachlor,
propachlor, propisochlor, thenylchlor, pethoamid, 2,4-D, fluroxypyr, MCPA, MCPP, MCPB, trichlorpyr, mecropop-P,
hexazinon, metamitron, metribuzin, oryzalin, pendimethalin, trifluralin, chloridazon, norflurazon, chlorpropham, des-
medipham, phenmedipham, propham, mefenacet, fluthiacet, butylate, cycloate, diallate, EPTC, esprocarb, molinate,
30 prosulfocarb, thiobencarb, triallate, fentrazamide, cafenstrole, dicamba, picloram, diflufenican, propanil, bromoxynil,
dichlobenil, ioxynil, sulcotrione, mesotrione, isoxaflutole, isoxachlortole, flucarbazone, propoxycarbazone (or its sodium
salt), foramsulfuron, penoxsulam, trifloxysulfuron (or its sodium salt), pyriftalid, trifloxysulfuron (or its sodium salt), py-
riftalid, flufenpyr-ethyl, profluazol, pyraclonil, benfluamid, picolinafen, amicarbazone, flufenpyr-ethyl, profluazol, pyra-
clonil, benfluamid, picolinafen, amicarbazone, chlorasuiam, diclosulam, florasulam, flumetsulam, metosulam, amitrol,
35 benfuresate, bentazone, cinmethylin, clomazone, chlopyralid, difenzoquat, dithiopyr, ethofumesate, flurochloridone, in-
danofane, isoxaben, oxaziclomefone, pyridate, pyridafol, quinchlorac, quinmerac, tridiphane and flamprop.
[0047] Preferably, the formulation of the invention comprises a mixture of a compound of formula (I), its stereoisomers,
salts or solvates thereof and an ALS inhibitor, such as a sulphonylurea.
[0048] Sulphonylureas are a well know family of ALS inhibitors with numerous examples in the pesticide industry. For
40 example, Triasulfuron, tribenuron-methyl, iodosuifuron-methyl (as the sodium salt), mesosulfuron- methyl, and pyrox-
sulam are disclosed in "The Pesticide Manual, ed. C.D.S. Tomlin, 15th edition, 2009, British Crop Production Council,
UK, see entry 494 "iodosulfuron-methyl- sodium" (pp. 658-660), entry 550 "mesosulfuron-methyl" (pp. 733-734), entry
753 "pyroxsulam" (pp. 1001-1002), entry 868 "triasulfuron" (pp. 1150-1151), and entry 873 "tribenuron-methyl" (pp.
1156-1158).
45

50

55 [0049] Preferably, the sulphonylurea herbicide is one selected from the group consisting of amidosulfuron, azimsul-
furon, bensulfuron, chlorimuron, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethoxysulfuron, flaza-
sulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, nicosulfuron, oxasul-
furon, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron,

7
 EP 3 876 736 B1

tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron and alkyl ethers or esters thereof, as well as salts thereof.
[0050] For example, the sulphonylurea herbicide can be one of compound of formula (II), its isomers, stereoisomers,
salts and solvates thereof

10

15
wherein
R4 is phenyl or heterocyclyl, either optionally substituted by one or two groups selected from the group consisting of
halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, -(C=O)-R7, - (C=O)-O-R7, -(C=O)-N(R7)(R 8), -SO 2-R7, and C1-C6-alkyl-
N(H)-SO2-R7, wherein R7 is selected from the group consisting of C 1-C6-alkyl, C1-C6-alkyl-C6-C10-aryl, and C6-C10-aryl-
20 C1-C6-alkyl; and R8 is selected from the group consisting of hydrogen, C1-C6-alkyl, C1-C6-alkyl-C6-C10-aryl, and
C6-C10-aryl-C 1-C6-alkyl.
[0051] It is preferred that in the compounds of formula (II) R4 is phenyl or piridine, either optionally substituted by one
or two groups selected from the group consisting of halogen, cyano, C1-C6-alkyl, -(C= O)-O-R7, and C1-C3-alkyl-
N(H)-SO2-R7, wherein R7 is selected from the group consisting of C1-C6-alkyl; and R8 is selected from the group consisting
25 of hydrogen, and C1-C6-alkyl.
[0052] More preferably, the compound of formula (II) is mesosulfuron or a mesosulfuron ester, for example mesosul-
furon-methyl.
[0053] The fact that the key to obtain a stable formulation in oil carrier of a mixture comprising a compound of formula
(I) (e.g. pinoxaden) and a compound of formula (II) (e.g. mesosulfuron) was the control of the pH at 5.0 or more was
30 even more surprising, and it has opened the door to stable oil suspensions comprising both, since it could be stablished
that the co-herbicide did not interfere in the stability of the compound of formula (I).
[0054] Combinations of pinoxaden and structural derivatives thereof together with sulphonylureas are known in the
art. WO 2011/107741 A1 discloses herbicidal compositions comprising a mixture of (a) an ALS inhibitor in the form of
an aluminum salt and (b) pinoxaden. The examples include the simultaneous treatment with pinoxaden commercial
35 formulations (including a safener) and with dicamba salts, trisulfuron, tribenuron-methyl commercial formulations. Also,
EC formulations and other solid formulations are mentioned in pages 26-29, although the specific active ingredients in
each case are not mentioned.
[0055] WO 01/17351 (Syngenta Participations AG) discloses a composition comprising a) a 3-hydroxy-4-(4-methyl-
phenyl)-5-oxo-pyrazoline, b) a safener and c) an oil of vegetable or animal origin, a mineral oil or derivatives thereof.
40 Preferred oils are those of vegetable origin, and all the examples refer to emulsifiable concentrates (EC formulations)
and other solid formulations (pages 33-36), wherein the oil is added as an additive (0.7-1 w/w %) in the tank mixture
(see the biological examples on pages 37-40). The oils used are MERGE (an aromatic adjuvant for emulsifiable con-
centrates) and Emery 2231, a fatty acid methyl ester derivative.
[0056] The co-herbicide, preferably a sulphonylurea, can be present in a wide range of concentrations, typically, in
45 an amount from 0.01 to 95 w/w %, typically from 0.1 to 50 w/w %, for example, from 0.2 to 5 w/w %, or from 0.5 to 3
w/w %. Said co-herbicides can even be in lower amounts, for example, between 0.01 and 0.5 w/w %.
[0057] The formulations of the invention may comprise from 0.01 to 95 w/w %, typically from 0.1 to 55 w/w %, of total
active ingredients, for example, from 0.5 to 20 w/w %, or from 1 to 15 w/w % of total active ingredients, considering
active ingredients as the sum of any compounds of formula (I), any co-herbicides and any safeners.
50
Safeners

[0058] When using herbicides, the crops may also suffer damage, depending on, for example, the amount of herbicide
used and the method of application, the nature of the soil or the climatic conditions, for example hours of daylight,
55 temperature and amount of rainfall. Various safeners (previously known as "antidotes") are known to antagonize the
harmful effect of the herbicide on crops and protect them without appreciably impairing the herbicidal action on the
undesirable plants to be controlled.
[0059] These substances are known in the agricultural industry and are taught in different reviews, for example, Délye

8
 EP 3 876 736 B1

C, et al (2017) "Herbicide Safeners Decrease Sensitivity to Herbicides Inhibiting Acetolactate-Synthase and Likely
Activate Non-Target-Site-Based Resistance Pathways in the Major Grass Weed Lolium sp. (Rye-Grass)" Front. Plant
Sci. 8:1310, doi: 10.3389/fpls.2017.01310; Davies, J. "Herbicide safeners - commercial products and tools for agro-
chemical research", Pesticide Outlook, February 2001, p. 10-15 10.1039/b100799h; Jablonkai, I. "Herbicide Safeners:
5 Effective Tools to Improve Herbicide Selectivity" Intech open Science, http://dx.doi.org/10.5772/55168; Rosinger, C.
"Sektion 6: Developments in herbicides - Herbicide Safeners: an overview", 26th German Conference on weed Biology
an Weed Control, March 11-13, 2014, Braunschweig, Germany.
[0060] Exemplary safeners that can be used in the present invention are anhydrides (e.g. 1,8-naphthalic anhydride),
dihydropyrazole-dicarboxylates (e.g. mefenpyr), dihydroisoxazole-carboxylates (e.g. isoxadifen), thiazole carboxylic ac-
10 ids (e.g. flurazole), phenyl-pyrimidines (e.g. fenclorim), 1,2,4-Triazole-carboxylates (e.g. fenchlorazole), dichloroaceta-
mides (e.g. dichlormid), Ureas (e.g. dymron), arylsulfonyl-benzamides (e.g. cyprosulfamide), oxime ethers (e.g. cyo-
metrinil), 8-Quinolinoxy-carboxylic esters (e.g. cloquintocet), dichloromethylketals (e.g. MG-91), or piperidine-1-carboth-
ioates (e.g. Dimepiperate).
[0061] For example, known safeners that can be used in the present application are oxabetrinil, 1,8-naphthalic anhy-
15 dride, metcamifen, mephenate, mefenpyr, jiecaoxi, jiecaowan, isoxadifen, furilazole, fluxofenim, flurazole, fenclorim,
fenchlorazole, dietholate, dicyclonon, dichlormid, cyprosulfamide, cyometrinil, cloquintocet, AD-67, BPCMS, MG-91,
Dymron, benoxacor or salts, solvates or esters thereof.
[0062] A preferred group of safeners in the present invention are the dihydropyrazole-dicarboxylates or the 8-Quino-
linoxy-carboxylic esters. More preferably, the formulation of the invention comprises a safener selected from the group
20 consisting of cloquintocet or a salt thereof, preferably an alkali, alkaline earth, sulfonium or ammonium cation of cloquin-
tocet, cloquintocet-mexyl, mefenpyr or a salt thereof, an alkali, alkaline earth, sulfonium or ammonium cation of mefenpyr,
mefenpyr-diethyl and mixtures thereof, preferably mefenpyr-diethyl.
[0063] A safener in accordance with the invention may, depending on the intended purpose, be used to pre-treat a
seed material of the cultivated plant (dressing the seed or the seedlings) or may be incorporated into the soil before or
25 after sowing. It may, however, also be applied, alone or together with the herbicide and the oil, after the emergence of
the plants. The treatment of the plants or the seeds with the safener can therefore, in principle, be effected independently
of the time at which the herbicide is applied. The treatment of the locus can, however, also be carried out by applying
the herbicide of formula (I), the oil and the safener simultaneously (for example in the form of a tank mixture). In the
present invention it is preferred that the safener is part of the same formulation as the compounds of formula (I) and the
30 oil (and optionally together with a co-herbicide) and is preferably used as post-emergence control. The rate of application
of the safener in relation to the herbicide depends largely on the method of application. For example, the molar ratio of
compound of formula (I):safener is generally from 100:1 to 1:10, preferably from 20:1 to 1:2, for example 3:1 to 1:1.5.
The concentration of the safener in the application can for example be from 0.01 to 95 w/w %, typically from 0.1 to 50
w/w %, for example, from 0.5 to 10 w/w %, or from 1 to 5 w/w %.
35 [0064] In terms of the amounts of safener to be applied, the present invention can use customary amounts, for example,
from 0.001 to 1.0 kg of safener/ha, preferably from 0.001 to 0.25 kg of safener/ha, are generally applied.

Formulations

40 [0065] The formulations of the invention may also comprise further additives commonly used in the field of agrochem-
istry, such as wetting agents, adjuvants, adhesives, neutralizers, antifoams, for example silicone oil, sequestrates,
fertilizers, preservatives or biocides, viscosity regulators, binders, tackifiers, thickeners, stabilizers, buffers or anti-freeze
agents, or surfactants, amongst others. Typical additives that can be used in the formulations of the invention are for
example disclosed in WO 2013/021229. The formulations are prepared in a known manner, for example by intimately
45 mixing and/or grinding the active ingredients or optionally with other solid components, with the oil carrier.
[0066] Said additives are known in the art and the skilled person can find numerous examples in the literature. For
examples, McCutcheon’s, "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ.; or Sisley and Wood,
"Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; provide detailed examples of surfactants
that can be useful. Surfactants can be anionic surfactants of the dodecylbenzylsulfonate type (alkyl benzene sulfonate
50 salts such as Nansa EVM 70/2E)), especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol
ethoxylate type. Examples of commercially available surfactants are the Genapol types (Clariant AG, Muttenz, Switzer-
land). Typical surfactants can also be selected from the group consisting of polyacrylate graft copolymers (e.g. Disper-
sogen PSL 100), phosphated alcohol ethoxylates (e.g. Hostaphat 1306) and star structure polymers (e.g. Atlox 4916).
The concentration of the surface-active substances is generally from 1 to 30 w/w %, preferably between 2 and 10 w/w %.
55 [0067] The antifoams or defoamers useful in the formulations of the invention can be selected from the group consisting
of silicon oil, polyethylene glycol polypropylene glycol copolymers and alkyl polyacrylates.
[0068] The thickeners useful in the formulations of the invention can be selected from the group consisting of organically-
derived hectorite clay (e.g. Bentone 38), polyester block co-polymer (e.g. Atlox Rheostrux 100), organically-derived silica

9
 EP 3 876 736 B1

(e.g. Aerosil R816).

Methods

5 [0069] The compositions according to the invention are suitable for all methods of application that are customary in
agriculture, for example pre-emergence application, post-emergence application and seed dressing.
[0070] Pinoxaden and derivatives thereof of formula (I), stereoisomers , salts or solvates thereof are known to be
suitable for use on non-oat cereals such as wheat, and on barley, rye and/or triticale, especially wheat and/or barley
(i.e. is selective for non-oat cereals), and is typically applied post-emergence for control of grassy weeds such as
10 Alopecurus, Apera, Avena, Lolium, Phalaris or Setaria species, e.g. at application rates of from 30 to 60 g/ha (ha =hectare).
[0071] The invention thus relates also to a method for the control of an undesired plant comprising dispersing in an
aqueous solution the formulation of the invention, optionally in the presence of one or more adjuvants, and contacting
the resulting mixture with the locus of said plant.
[0072] Crops are to be understood as including those that have been made tolerant to herbicides or classes of herbicides
15 by means of conventional breeding or genetic engineering methods.
[0073] The undesired plants to be controlled may include one or more of Alfalfa (Medicago sativa), Amsinckia (Am-
sinckia spp.), Capeweed (Arctotheca calendula), Charlock (wild mustard, Sinapis arvensis), Chickweed (Stellaria media),
Corn gromwell (sheepweed, white ironweed) (Buglossoides arvensis), Common couchgrass (Agropyron repens), Corn
mint {Mentha arvensis), Crassula (Crassula spp.), Creeping thistle (Cirsium arvense), False bindweed (Calystegia se-
20 pium), False mayweed (Tripleurospermum maritimum), Field bindweed (Convolvulus arvensis), Fool’s parsley (Aethusa
cynapium), Gallant soldier (Galinsoga parviflora), Henbit deadnettle (Lamium amplexicaule), Hedge mustard (Sisymbri-
um officinale), Hyssop loosestrife (Lythrum hyssopifolia), Indian hedge mustard (Sisymbrium orientale), Italian rye-grass
(Lolium multiflorum), Marshmallow (Malva parviflora), Sticky mouse-eared chickweed (Cerastium glomeratum), Night-
scented stock (Matthiola longipetala), Paterson’s curse (Salvation Jane) (Echium plantagineum), Pheasant’s eye (Adonis
25 microcarpa), Pineapple weed (Matricaria discoidea), Poinsettia (Euphorbia pulcherrima), Prickly lettuce (Lactuca serri-
ola), Purple deadnettle (Lamium purpureum), Rough poppy (Papaver hybridum), Shepherd’s purse (Capsella bursa-
pastoris), Skeletonweed (Chondrilla juncea), Sorrel (Rumex acetosella), Ivy-leaved Speedwell (Veronica hederifolia),
Dwarf nettle (Stinging nettle) (Urtica urens), Toad rush (Juncus bufonius), Turnipweed (Rapistrum rugosum), Wild radish
(Raphanus raphanistrum), Wild turnip (Brassica tournefortii), Knotgrass {Polygonum aviculare), Annual mercury (Mer-
30 curialis annua), False castor oil (thomapples) (Datura ferox), Ball mustard (Neslia paniculata), Barnyard grass (Echin-
ochloa crusgalli), Beta vulgaris, Black Bindweed (Fallopia convolvulus), Blackgrass (Alopecurus myosuroides), Black
pigweed (Trianthema portulacastrum), Buchan weed (Hirschfeldia incana), Bull’s head (Tribulus terrestris), Buttonweed
(Abutilon theophrasti), Catsear (Hypochaeris radicata), Cleavers (Galium aparine), Common bugloss (Anthusa arvensis),
Common borage (Boragio officinales), Common cotula (Cotula australis), Common groundsel (Senecio vulgaris), Com-
35 mon hempnettle (Galeopsis tetrahit), Common nettle (Urtica dioica), Corn spurry (Spergula arvensis), Creeping speedwell
(Veronica filiformis), Crown beard (dogweed) (Verbesina encelioides), Crowsfoot grass (Eleusine indica), Dock (Rumex
spp.), Doublegee (Emex australis), Fat hen (Atriplex prostrata), Field madder (Sherardia arvensis), Field Pansy (Viola
arvensis), Field oennycress (Thlaspi arvense), Fog grass (Holcus lanatus), Fumitory (Fumaria spp.), Fumaria officinalis,
Geranium (Geranium spp.), Geranium dissectum, Great brome (Bromus diandrus), Greater plantain (Plantago major),
40 Green summer grass (Digitaria ciliaris), Hare’s ear (treacle mustard) (Conringia orientalis), Heliotrope (Heliotr opium
spp.), Hempnettle (Galeopsis sp.), Horehound (Marrubium vulgare), Indian hedge mustard (Sisymbrium orientale), Less-
er swinecress (Coronopus didymus), Matricaria spp., Scented mayweed (Matricaria recutita), Scentless mayweed (Mat-
ricaria inodora), Mountain sorrel (purple calandrinia) (Calandrinia ciliata), Mustard, Nettle, Urtica spp., Nightshade (Sola-
num nigrum), Pale persicaria (Persicaria lapathifolia), Perennial sowthistle (Sonchus arvensis), Persian speedwell (Ve-
45 ronica persica), Chenopodium sp., Pigweed (Chenopodium albu ), Powell’s amaranth (Amaranthus powellii), Red hemp-
nettle (Galeopsis intermedia), Redshank (Persicaria maculosa), Redroot pigweed (Amaranthus retroflexus), Scarlet
pimpernel (Anagallis arvensis), Scrub nettle (stinging nettle) (Urtica incisa), Annual sowthistle (Sonchus oleraceus),
Spiny emex (Three cornered jack) (Emex australis), Spreading orache (Atriplex patula), Stagger weed (Stachys arvensis),
Storksbill (Erodium cicutarium), Summer grass, Sun spurge (Euphorbia helioscopia), Toad rush (Juncus bufonius), Black
50 bindweed (Polygonum convolvulus), Polygonum spp., Wild Pansy (Viola tricolor), Winter grass (annual meadow grass)
(Poa Annua), Wild oat (Avena fatua), Winter rape (Brassica napus) and Yellow burrweed (Amsinckia calycina).
[0074] Preferably, the undesirable weeds to be controlled are monocotyledonous weeds, for example the monocoty-
ledonous weeds Avena, Agrostis, Phalaris, Lolium, Bromus, Alopecurus, Setaria, Digitaria, Brachiaria, Echinochloa,
Panicum, Sorghum hal./bic., Rottboellia, Cyperus, Brachiaria, Echinochloa, Scirpus, Monochoria and Sagittaria and the
55 dicotyledonous weeds Sinapis, Chenopodium, Stellaria, Galium, Viola, Veronica, Matricaria, Papaver, Solanum, Abutilon,
Sida, Xanthium, Amaranthus, Ipomoea and Chrysanthemum.
[0075] The rate of application of the compound of formula (I) is generally from 0.001 to 2 kg/ha, but preferably from
0.005 to 1 kg/ha.

10
 EP 3 876 736 B1

[0076] The nature of the different possible compounds of formula (I), stereoisomers, salts or solvates thereof, or co-
herbicides, or oil carriers or safeners, as well as their amounts, can be combined to create different combinations. Thus,
for example, a formulation of the invention may comprise

5 (i) between 0.2 and 15 w/w% of pinoxaden;

(ii) between 0.1 and 10 w/w % of mesosulfuron-methyl; and

(iii) 60 to 97 w/w % of a paraffinic oil carrier having a pH of 5.0 or more, having a water content of 0.01 to 0.19 w/w
10 %, preferably 0.05 to 0.15 w/w %, with respect to the weight of the oil carrier, as measured by Karl-Fischer titration.

[0077] Alternatively, the formulation of the invention may comprise

(i) between 0.2 and 15 w/w% of pinoxaden;

15
(ii) between 0.1 and 10 w/w % of mesosulfuron-methyl;

(iii) between 60 and 97 w/w % of a paraffinic oil carrier having a pH of 5.0 or more, having a water content of 0.01
to 0.19 w/w %, preferably 0.05 to 0.15 w/w %, with respect to the weight of the oil carrier, as measured by Karl-
20 Fischer titration; and

(iv) between 1 and 15 w/w % of a surfactant system.

[0078] Alternatively, the formulation of the invention consists of

25
(i) between 0.2 and 15 w/w% of pinoxaden;

(ii) between 0.1 and 10 w/w % of a sulfonylurea herbicide, for example, mesosulfuron-methyl;

30 (iii) 60 to 97 w/w % of a paraffinic oil carrier having a pH of 5.0 or more, having a water content of 0.01 to 0.19 w/w
%, preferably 0.05 to 0.15 w/w %, with respect to the weight of the oil carrier; and

optionally, at least one agrochemical acceptable additive.

[0079] Each embodiment disclosed herein is contemplated as being applicable to each of the other disclosed embod-
35 iments. Thus, all combinations of the various elements described herein are within the scope of the invention. In addition,
the elements recited in the formulation embodiments can be used in the method and use embodiments described herein
and vice versa.

EXAMPLES
40
[0080] Different mixtures were prepared by grinding the solid materials and intimately mixing them with the oil carrier.
The mixtures included individual mixtures of a compound of formula (I), namely pinoxaden, and of a co-herbicide (e.g.
mesosulfuron), for which the stability was tested. Also, the stability was tested for a mixture of pinoxaden, mesosulfuron
and mefenpyr-diethyl.
45
Example 1: Stability test

[0081] The stability of pinoxaden suspended in different oils was tested following standard conditions (1 week or 2
weeks in the oven at 54°C). The results are shown in Table 1. If the percentage of pinoxaden present in the solution
50 after 1 week and after 2 weeks was above 95%, the stability was considered "Excellent". If the stability after 1 week and
2 weeks was above 90%, but below 95%, the stability was considered "Acceptable". All other experiments were considered
failures and were marked as "Unstable".

55

11
 EP 3 876 736 B1

Table 1: Stability tests of pinoxaden

chemical stability pinoxaden w/w% in the solution
(% amount of pinoxaden with respect to start)
5 pH water
oil name start 1 week 54°C 2 weeks 54°C
(1%) content [%]
Safflower oil 4.63 0.23 6.5 5.8 (89%) 5.9 (91%) Unstable
Ednor ME SU/
4.68 0.26 5.7 4.3 (75%) 3.2 (56%) Unstable
10 RADIA 7961
Pine oil 5.83 1.14 5.8 5.6 (97%) 5.4 (93%) Acceptable
Isopar V 6.4 0.09 6 5.8 (97%) 6.2 (103%) Excellent
Isopar V 6.4 0.09 5.9 5.7 (97%) 5.7 (97%) Excellent
15
Linseed oil 6.66 0.25 5.7 5.6 (98%) 5.3 (93%) Acceptable
canola oil (food
7.1 0.23 6.1 5.7 (93%) 5.7 (93%) Acceptable
grade)
Petrol D60 -
20 7.58 0.22 4.7 4.4 (94%) 4.5 (96%) Acceptable
SHELL
canola oil (Croda) 8.23 0.16 6.1 5.9 (97%) 5.9 (97%) Excellent

[0082] The results of Table 1 prove that whenever the pH of the oil used in the formulation is 5.0 or more, the stability
25
of pinoxaden was acceptable or excellent. If additionally, the water content in the oil is below 0.2 w/w%, the stability in
all cases was excellent.
[0083] The same experiments were repeated for mesosulfuron, which was in all cases stable.
[0084] The pH of the oil was measured following the procedure of:

30
a) making a deionized water mixture having 1 w/w% of oil;
b) stirring the mixture of the previous step with a magnetic stirrer at 1,500 RPM for 10 minutes at 25°C;
c) allowing the phases in the mixture to separate for 10 min at 25°C,
d) collecting into a separate vial the lower aqueous phase;
e) measuring at 25°C the pH of aqueous phase collected using a JENWAY 3510 pH meter, with an AgCl, liquid
35
filled single junction electrode, such that the electrode and the thermocouple of the pH meter are inserted into the
vial containing the aqueous water phase until the measured pH value is stable for 10s.

Example 2: Stability test of a mixture of pinoxaden, mesosulfuron and mephenpyr-diethyl

40
[0085] Following the same conditions as in Example 1, the stability of a mixture of pinoxaden, mesosulfuron and
mefenpyr-diethyl in Isopar V (mineral oil with pH of 6.4 and water content of 0.09 w/w %) was tested. The mixture was
also tested for an additional week at 54°C. The composition of the mixture is summarized on Table 2 and the results of
the stability test on Table 3.

45
Table 2: Mixture composition
Component type Name w/w %
Active Ingredient Mesosulfuron methyl 1.31%
Active Ingredient Pinoxaden 6.36%
50
Safener Mefenpyr diethyl 3.75%
Solvent Isopar V 88.58%

55

12
 EP 3 876 736 B1

Table 3: Stability of Mixture

Time 0 1 week 54°C 2 weeks 54°C
Pinoxaden 6.30% 6.50% 6.40%
5
Mesosulfuron 1.40% 1.30% 1.40%
Mefenpyr 3.90% 3.60% 3.80%

[0086] The results prove that all three components displayed an excellent stability in an oil having a pH above 5.0 and
10
a water content below 0.2 w/w%, with respect to the total weight of the oil carrier.

Claims

15
1. A formulation for controlling undesired plants comprising

(i) pinoxaden, its stereoisomers, salts or solvates thereof and

(ii) above 50 w/w% to 99 w/w % of an oil carrier;

20
characterized in that the oil carrier has a pH of 5.0 or more, as measured by a process consisting of the
steps of

a) making a deionized water mixture having 1 w/w% of oil;

b) stirring the mixture of the previous step with a magnetic stirrer at 1,500 RPM for 10 minutes at 25°C;
25
c) allowing the phases in the mixture to separate for 10 min at 25°C,
d) collecting into a separate vial the lower aqueous phase;
e) measuring at 25°C the pH of aqueous phase collected using a JENWAY 3510 pH meter, with an
AgCl, liquid filled single junction electrode, such that the electrode and the thermocouple of the pH
meter are inserted into the vial containing the aqueous water phase until the measured pH value is
30
stable for 10s;

wherein the water content in the oil is less than 0.2 w/w%, with respect to the total weight of the oil, as
measured by Karl-Fischer titration; and
wherein said formulation is an oil dispersion.
35

2. The formulation according to claim 1, wherein the pH is comprised between 5.0 and 10.0.

3. The formulation according to any of the previous claims, comprising a sulphonylurea herbicide.

40
4. The formulation according to claim 3, wherein the sulphonylurea herbicide is a compound of formula (II), its isomers,
stereoisomers, salts and solvates thereof

45

50

wherein
55
R4 is phenyl or heterocyclyl, either optionally substituted by one or two groups selected from the group consisting
of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, -(C= O)-R7, - (C= O)-O-R7, -(C= O)-N(R7)(R8), -SO2-R7, and
C1-C6-alkyl-N(H)-SO2-R7, wherein R7 is selected from the group consisting of C1-C6-alkyl, C1-C6-alkyl-C6-C10-aryl,

13
 EP 3 876 736 B1

and C6-C10-aryl-C1-C6-alkyl; and R8 is selected from the group consisting of hydrogen, C1-C6-alkyl, C1-C6-alkyl-
C6-C10-aryl, and C6-C10-aryl-C1-C6-alkyl.

5. The formulation according to any of the previous claims, wherein the water content of the oil is less than 0.20 w/w
5 %, with respect to the total weight of the oil carrier, as measured by Karl-Fischer titration, and the pH is between
5.5 and 10.0, as measured by the method defined in claim 1.

6. The formulation according to any of the previous claims, wherein said oil is paraffinic oil.

10 7. The formulation according to any of the previous claims, wherein the formulation comprises an effective amount of
one or more safeners.

8. The formulation according to claim 7, wherein the safener is selected from the group consisting of effective amount
of a safener selected from cloquintocet, a salt of cloquintocet, cloquintocet-mexyl, mefenpyr, a salt of mefenpyr,
15 mefenpyr-diethyl and mixtures thereof.

9. The formulation according to any of claims 7 or 8, wherein the safener is mefenpyr-diethyl.

10. The formulation according to any of the previous claims, wherein the herbicidal effective amount of pinoxaden, its
20 stereoisomers, salts or solvates thereof is between 1 and 8 w/w %.

11. The formulation according to claim 3, for the control of undesired plants comprising

(i) between 0.2 and 15 w/w% of pinoxaden;

25 (ii) between 0.1 and 10 w/w % of mesosulfuron-methyl; and
(iii) 60 to 97 w/w % of a paraffinic oil carrier having a pH of 5.0 or more, having a water

content of 0.01 to 0.19 w/w %, with respect to the weight of the oil carrier, as measured by Karl-Fischer titration.

30 12. The formulation according to claim 1, for the control of undesired plants consisting of

(i) pinoxaden, its stereoisomers, salts or solvates thereof; and

(ii) above 50 w/w% to 99 w/w % of an oil carrier;
characterized in that the oil has a pH of 5.0 or more, having a water content of 0.01 to 0.19 w/w %, with respect
35 to the weight of the oil carrier, as measured by Karl-Fischer titration; and
optionally, at least one agrochemical acceptable additive.

13. The formulation according to claim 3, for the control of undesired plants consisting of

40 (i) between 0.2 and 15 w/w% of pinoxaden;

(ii) between 0.1 and 10 w/w % of a sulfonylurea herbicide, for example, mesosulfuron-methyl;
(iii) 60 to 97 w/w % of a paraffinic oil carrier having a pH of 5.0 or more, having a water content of 0.01 to 0.19
w/w %, with respect to the weight of the oil carrier; and

45 optionally, at least one agrochemical acceptable additive.

14. A method for the control of an undesired plant comprising dispersing in an aqueous solution the formulation as
defined in any of the previous claims and contacting the resulting mixture with the locus of said plant.

50 15. Use of the formulation defined in any of claims 1 to 13 for the control of undesired plants.

Patentansprüche

55 1. Eine Formulierung zur Bekämpfung unerwünschter Pflanzen, umfassend

(i) Pinoxaden, seine Stereoisomere, Salze oder Solvate davon

und

14
 EP 3 876 736 B1

(ii) über 50 Gew./Gew.-% bis 99 Gew./Gew.-% eines Ölträgers;

dadurch gekennzeichnet, dass der Ölträger einen pH-Wert von 5,0 oder mehr aufweist, gemessen durch
ein Verfahren, das aus den folgenden Schritten besteht;
5
a) Herstellen eines Gemischs aus entionisiertem Wasser mit 1 Gew./Gew.-% Öl;
b) Rühren der Mischung aus dem vorherigen Schritt mit einem Magnetrührer bei 1.500 U/min für 10
Minuten bei 25°C;
c) Trennenlassen der Phasen in der Mischung für 10 Minuten bei 25°C,
10 d) Auffangen der unteren wässrigen Phase in einem separaten Fläschchen;
e) Messen des pH-Wertes der gesammelten wässrigen Phase bei 25°C mit einem JENWAY 3510 pH-
Meter mit einer flüssigkeitsgefüllten Einzelsperrschicht AgCl-Eleklrode, wobei die Elektrode und das
Thermoelement des pH-Meters in das Fläschchen, das die wässrige Phase enthält, eingeführt werden,
bis der gemessene pH-Wert 10 Sekunden lang stabil ist;
15
wobei der Wassergehalt in dem Öl weniger als 0,2 Gew./Gew.-%, bezogen auf das Gesamtgewicht des
Öls, beträgt, gemessen durch Karl-Fischer-Titration; und
wobei die Formulierung eine Öldispersion ist.

20 2. Die Formulierung nach Anspruch 1, wobei der pH-Wert zwischen 5,0 und 10,0 liegt.

3. Die Formulierung nach einem der vorhergehenden Ansprüche, die ein Sulfonylharnstoff-Herbizid umfasst.

4. Die Formulierung nach Anspruch 3, wobei es sich bei dem Sulfonylharnstoff-Herbizid um eine Verbindung der
25 Formel (II), seine Isomere, Stereoisomere, Salze und Solvate davon handelt

30

35

wobei
R4 Phenyl oder Heterocyclyl ist, jeweils gegebenenfalls substituiert durch eine oder zwei Gruppen, ausgewählt aus
40 der Gruppe bestehend aus Halogen, Cyano, C1-C6-Alkyl, C1-C6-Haloalkyl, -(C= O)-R7, -(C= O)-O-R7,
-(C=O)-N(R7)(R8), -SO2-R 7, und C1-C6-Alkyl-N(H)-SO2-R7, wobei R7 ausgewählt ist aus der Gruppe bestehend aus
C1-C6-Alkyl, C1-C6-Alkyl-C6-C10-Aryl, und C6-C10-Aryl-C1-C6-Alkyl; und R8 ausgewählt ist aus der Gruppe beste-
hend aus Wasserstoff, C1-C6-Alkyl, C1-C6-Alkyl-C6-C10-Aryl, und C6-C10-Aryl-C1-C6-Alkyl.

45 5. Die Formulierung nach einem der vorhergehenden Ansprüche, wobei der Wassergehalt des Öls weniger als 0,20
Gew./ Gew.-%, bezogen auf das Gesamtgewicht des Ölträgers, beträgt, gemessen durch Karl-Fischer-Titration,
und der pH-Wert zwischen 5,5 und 10,0 liegt, gemessen nach dem in Anspruch 1 definierten Verfahren.

6. Die Formulierung nach einem der vorhergehenden Ansprüche, wobei das Öl paraffinisches Öl ist.
50
7. Die Formulierung nach einem der vorhergehenden Ansprüche, wobei die Formulierung eine wirksame Menge eines
oder mehrerer Safener enthält.

8. Die Formulierung nach Anspruch 7, wobei der Safener ausgewählt ist aus der Gruppe bestehend aus einer wirksamen
55 Menge eines Safeners, ausgewählt aus Cloquintocet, einem Salz von Cloquintocet, Cloquintocet-Mexyl, Mefenpyr,
einem Salz von Mefenpyr, Mefenpyr-Diethyl und Mischungen davon.

9. Die Formulierung nach einem der Ansprüche 7 oder 8, wobei der Safener Mefenpyr-Diethyl ist.

15
 EP 3 876 736 B1

10. Die Formulierung nach einem der vorhergehenden Ansprüche, wobei die herbizid wirksame Menge an Pinoxaden,
seinen Stereoisomeren, Salzen oder Solvaten davon zwischen 1 und 8 Gew./ Gew.-% liegt.

11. Die Formulierung nach Anspruch 3 zur Bekämpfung von unerwünschten Pflanzen, umfassend
5
(i) zwischen 0,2 und 15 Gew./Gew.-% Pinoxaden;
(ii) zwischen 0,1 und 10 Gew./Gew.-% Mesosulfuron-Methyl; und
(iii) 60 bis 97 Gew./Gew.-% eines paraffinischen Ölträgers mit einem pH-Wert von 5,0 oder mehr, der einen
Wassergehalt von 0,01 bis 0,19 Gew./Gew.-%, bezogen auf das Gewicht des Ölträgers, gemessen durch Karl-
10 Fischer-Titration, aufweist.

12. Die Formulierung nach Anspruch 1 zur Bekämpfung unerwünschter Pflanzen, bestehend aus

(i) Pinoxaden, seinen Stereoisomeren, Salzen oder Solvaten davon;

15 und
(ii) über 50 Gew./Gew.-% bis 99 Gew./Gew.-% eines Ölträgers;

dadurch gekennzeichnet, dass das Öl einen pH-Wert von 5,0 oder mehr aufweist, mit einem Wassergehalt
von 0,01 bis 0,19 Gew./Gew.-%, bezogen auf das Gewicht des Ölträgers, gemessen durch Karl-Fischer-
20 Titration; und
gegebenenfalls mindestens ein agrochemisch akzeptables Additiv.

13. Die Formulierung nach Anspruch 3 zur Bekämpfung von unerwünschten Pflanzen, bestehend aus

25 (i) zwischen 0,2 und 15 Gew./Gew.-% Pinoxaden;

(ii) zwischen 0,1 und 10 Gew./Gew.-% eines Sulfonylharnstoff-Herbizids, beispielsweise Mesosulfuron-Methyl;
(iii) 60 bis 97 Gew./Gew.-% eines paraffinischen Ölträgers mit einem pH-Wert von 5,0 oder mehr, der einen
Wassergehalt von 0,01 bis 0,19 Gew./Gew.-%, bezogen auf das Gewicht des Ölträgers, aufweist; und

30 gegebenenfalls mindestens ein agrochemisch akzeptables Additiv.

14. Ein Verfahren zur Bekämpfung einer unerwünschten Pflanze, umfassend das Dispergieren der in einem der vor-
hergehenden Ansprüche definierten Formulierung in einer wässrigen Lösung und das In-Kontakt-Bringen der re-
sultierenden Mischung mit dem Standort der Pflanze.
35
15. Verwendung der in einem der Ansprüche 1 bis 13 definierten Formulierung zur Bekämpfung unerwünschter Pflanzen.

Revendications
40
1. Formulation pour réguler des plantes indésirables comprenant

(i) du pinoxaden, ses stéréoisomères, sels ou solvates de celui-ci

et
45 (ii) plus de 50 % en poids à 99 % en poids d’un support d’huile ;

caractérisée en ce que le support d’huile a un pH de 5,0 ou plus, tel que mesuré par un procédé constitué
de les étapes suivantes

50 a) préparer un mélange d’eau désionisée contenant 1 % en poids d’huile ;

b) agiter le mélange de l’étape précédente avec un agitateur magnétique à 1500 tours par minute
pendant 10 minutes à 25°C ;
c) laisser les phases du mélange se séparer pendant 10 minutes à 25°C,
d) recueillir dans un flacon séparé la phase aqueuse inférieure ;
55 e) mesurer à 25°C le pH de la phase aqueuse recueillie à l’aide d’un pH-mètre JENWAY 3510, avec
une électrode AgCl à simple jonction remplie de liquide, de telle sorte que l’électrode et le thermocouple
du pH-mètre soient insérés dans le flacon contenant la phase aqueuse jusqu’à ce que la valeur du pH
mesurée soit stable pendant 10 s ;

16
 EP 3 876 736 B1

dans laquelle la teneur en eau dans l’huile est inférieure à 0,2 % en poids, par rapport au poids total de
l’huile, comme mesuré par titrage selon la méthode de Karl-Fischer ; et
dans laquelle ladite formulation est une dispersion d’huile.

5 2. Formulation selon la revendication 1, dans laquelle le pH est compris entre 5,0 et 10,0.

3. Formulation selon l’une quelconque des revendications précédentes, comprenant un herbicide sulfonylurée.

4. Formulation selon la revendication 3, dans laquelle l’herbicide sulfonylurée est un composé de formule (II), ses
10 isomères, stéréoisomères, sels et solvates de celui-ci

15

20

25 dans laquelle
R4 est un phényle ou un hétérocyclyle, l’un ou l’autre étant optionnellement substitué par un ou deux groupes choisis
dans le groupe constitué d’un halogène, un cyano, un alkyle en C 1-C6, un halogénoalkyle en C1-C6, - (C=O)-R7,
-(C=O)-O-R 7, -(C=O)-N(R7)(R8), -SO 2-R7, et un alkyle en C1-C6-N(H)-SO2-R7, où R7 est choisi dans le groupe
constitué par un alkyle en C1-C6, un alkyle en C1-C 6-aryle en C6-C10, et un aryle en C6-C10-alkyle en C1-C6 ; et
30 R8est choisi dans le groupe constitué de l’hydrogène, un alkyle en C1-C6, un alkyle en C1-C6-aryle en C6-C10, et
un aryle en C6-C10-alkyle en C1-C6.

5. Formulation selon l’une quelconque des revendications précédentes, dans laquelle la teneur en eau de l’huile est
inférieure à 0,20 % en poids, par rapport au poids total du support d’huile, telle que mesurée par titrage selon la
35 méthode de Karl-Fischer, et le pH est compris entre 5,5 et 10,0, tel que mesuré par le procédé défini dans la
revendication 1.

6. Formulation selon l’une quelconque des revendications précédentes, dans laquelle ladite huile est une huile paraf-
finique.
40
7. Formulation selon l’une quelconque des revendications précédentes, dans laquelle la formulation comprend une
quantité efficace d’un ou plusieurs phytoprotecteurs.

8. Formulation selon la revendication 7, dans laquelle le phytoprotecteur est choisi dans le groupe constitué d’une
45 quantité efficace d’un phytoprotecteur choisi parmi le cloquintocet, un sel de cloquintocet, le cloquintocet-mexyl, le
méfenpyr, un sel de méfenpyr, le méfenpyr-diéthyle et des mélanges de ceux-ci.

9. Formulation selon l’une quelconque des revendications 7 ou 8, dans laquelle le phytoprotecteur est du méfenpyr-
diéthyle.
50
10. Formulation selon l’une quelconque des revendications précédentes, dans laquelle la quantité efficace herbicide
de pinoxaden, ses stéréoisomères, sels et solvates de celui-ci est comprise entre 1 et 8 % en poids.

11. Formulation selon la revendication 3, pour la régulation de plantes indésirables comprenant

55
(i) entre 0,2 et 15 % en poids de pinoxaden ;
(ii) entre 0,1 et 10 % en poids de mésosulfuron-méthyle ; et
(iii) 60 à 97 % en poids d’un support d’huile paraffinique ayant un pH de 5,0 ou plus, ayant une teneur en eau

17
 EP 3 876 736 B1

de 0,01 à 0,19 % en poids, par rapport au poids du support d’huile, telle que mesurée par titrage selon la
méthode de Karl-Fischer.

12. Formulation selon la revendication 1, pour la régulation de plantes indésirables constituée de

5
(i) pinoxaden, ses stéréoisomères, sels ou solvates de celui-ci ;
et
(ii) plus de 50 % en poids à 99 % en poids d’un support d’huile ;

10 caractérisée en ce que l’huile a un pH de 5,0 ou plus, ayant une teneur en eau de 0,01 à 0,19 % en poids,
par rapport au poids du support d’huile, telle que mesurée par titrage selon la méthode de Karl-Fischer ; et
optionnellement, au moins un additif agrochimiquement acceptable.

13. Formulation selon la revendication 3, pour la régulation de plantes indésirables constituée de

15
(i) entre 0,2 et 15 % en poids de pinoxaden ;
(ii) entre 0,1 et 10 % en poids d’un herbicide sulfonylurée, par exemple du mésosulfuron-méthyle ;
(iii) 60 à 97 % en poids d’un support d’huile paraffinique ayant un pH de 5,0 ou plus, ayant une teneur en eau
de 0,01 à 0,19 % en poids, par rapport au poids du support d’huile ; et
20
optionnellement, au moins un additif agrochimiquement acceptable.

14. Procédé de régulation d’une plante indésirable comprenant la dispersion dans une solution aqueuse de la formulation
telle que définie dans l’une quelconque des revendications précédentes et la mise en contact du mélange résultant
25 avec les locus de ladite plante.

15. Utilisation de la formulation définie dans l’une quelconque des revendications 1 à 13 pour la régulation de plantes
indésirables.

30

35

40

45

50

55

18
 EP 3 876 736 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• WO 9947525 A1 [0002] • US 4834908 A [0017]

• WO 0117351 A1 [0002] • WO 2011107741 A1 [0018] [0054]
• WO 2008049618 A2 [0002] • WO 0117351 A [0019] [0041] [0055]
• WO 2007073933 A [0004] • WO 9621652 A [0041]
• WO 2014060557 A2 [0006] • WO 0117352 A [0041]
• CN 108013066 A [0007] • WO 2013021229 A [0065]
• AU 2019100546 B4 [0008]

Non-patent literature cited in the description

• Pesticide Chemistry. Crop Protection, Public Health, • Herbicide safeners - commercial products and tools
Environmental Safety. Wiley, 2007, 101-110 [0002] for agrochemical research. DAVIES, J. Pesticide
• MUEHLEBACH et al. Aryldiones incorporating a Outlook. February 2001, 10-15 [0059]
[1,4,5]-oxadiazepane ring. Part 2: Chemistry and bi- • JABLONKAI, I. Herbicide Safeners: Effective Tools
ology of the cereal herbicide pinoxaden. Pest Manag. to Improve Herbicide Selectivity. Intech open Sci-
Sci., 08 June 2011, vol. 67 (12), 1499-1521 [0005] ence, http://dx.doi.org/10.5772/55168 [0059]
• The Pesticide Manual. British Crop Production Coun- • ROSINGER, C. Sektion 6: Developments in herbi-
cil, 2009 [0048] cides - Herbicide Safeners: an overview. 26th Ger-
• iodosulfuron-methyl- sodium, 658-660 [0048] man Conference on weed Biology an Weed Control,
• mesosulfuron-methyl, 733-734 [0048] 11 March 2013 [0059]
• pyroxsulam, 1001-1002 [0048] • MCCUTCHEON’S. Detergents and Emulsifiers An-
• triasulfuron, 1150-1151 [0048] nual. MC Publ. Corp, [0066]
• tribenuron-methyl, 1156-1158 [0048] • SISLEY ; WOOD. Encyclopedia of Surface Active
• DÉLYE C et al. Herbicide Safeners Decrease Sen- Agents. Chem. Publ. Co. Inc, 1964 [0066]
sitivity to Herbicides Inhibiting Acetolactate-Synthase
and Likely Activate Non-Target-Site-Based Resist-
ance Pathways in the Major Grass Weed Lolium sp.
(Rye-Grass). Front. Plant Sci., 2017, vol. 8, 1310
[0059]

19