WO2025237868A1

WO2025237868A1 - Aqueous suspension

Info

Publication number: WO2025237868A1
Application number: PCT/EP2025/062835
Authority: WO
Inventors: Andreas Röchling; Joachim Krüger; Hubert Menne
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 2024-05-15
Filing date: 2025-05-12
Publication date: 2025-11-20
Anticipated expiration: 2026-11-15

Abstract

The present invention relates to suspensions comprising herbicidal heterocyclic amide compounds and suitable adjuvants.

Description

Aqueous suspension

The present invention relates to herbicidal aqueous suspensions and their use for controlling harmful plants. Specifically, the present invention relates to suspensions comprising herbicidal heterocyclic amide compounds and suitable adjuvants.

Background

Heterocyclic amide compounds are known in the art to provide for a herbicidal action against a variety of weeds. WO 2014/192936 discloses certain herbicidal heterocyclic amide structures.

Many herbicides, however, require an adjuvant system in order to develop full biological activity. In particular, adjuvants may significantly increase the biological uptake into leaves or retention of the herbicides on the plant structures. On the other hand, an adjuvant system needs to be carefully selected, as it may not be compatible with the chemical nature of the respective herbicide or as it may not adequately contribute to a reduced phytotoxicity of the herbicide to crop plants.

JP2020117496A describes an aqueous emulsion with a suspended agrochemical composition based on the compounds described in WO 2014/192936.

So far, there has, however, not been developed a suitable formulation system for herbicidal heterocyclic amide structures that both enhances the biological activity of the herbicides and provides for a stable composition, while minimizing phytotoxic effects on the relevant crops.

Summary

The above-described problems are at least partially solved by an aqueous suspension comprising a certain class of herbicides as well as an adjuvant system.

Specifically, according to a first aspect, the present disclosure relates to an aqueous suspension comprising a) a compound of formula (1) in form of suspended particles, where Q is an aromatic heterocycle of any one of Q-l to Q-5;

W is an aromatic heterocycle of W-l, W-2, or W-3;

X is an oxygen atom or a sulfur atom;

R^la is a hydrogen atom, a halogen atom, Ci-6 alkyl, (Cue) alkyl optionally substituted with R⁶, C3-6 cycloalkyl (C3 e) cycloalkyl optionally substituted with R⁶, C2-6 alkenyl, C2 6 alkynyl, C3-6 cycloalkenyl, -C(O)R⁸, -C(O)OR¹⁶, cyano, -OR⁹, -S(O)_miR¹⁰, -N(R")R¹², -C(=NR^12b)R^8b, phenyl, phenyl substituted with (R⁷)_P, naphthyl, or any one group of U-l to U-26;

R^lb is a hydrogen atom, Ci-6 alkyl, (Cue) alkyl optionally substituted with R⁶, C3

6 cycloalkyl, (C3 e) cycloalkyl optionally substituted with R⁶, C2-6 alkenyl, C2-6 alkynyl, phenyl, phenyl substituted with (R⁷)_P, naphthyl, 5-6-membered heteroaryl, 5-6- membered heteroaryl (optionally substituted with R²⁸ and R^28a), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^28a);

R^lc is C1-6 alkyl;

R^2a is a halogen atom, Ci-6 alkyl, Ci-6 haloalkyl, -C(O)R¹⁸, -C(O)OR²⁴, cyano, nitro, -OR¹⁹, - S(O)m3R²⁰, -N (R²¹)R²², phenyl, or phenyl substituted with (R⁷)_P; when n is an integer of 2 or more, R^2a are optionally the same as or different from each other, and when two R^2a are adjacent, the two adjacent R^2a optionally form a 6-membered ring together with carbon atoms bonded to each R^2a by forming -CH=CH-CH=CH-;

R^2c is C1-6 haloalkyl;

R³ is a hydrogen atom, Ci-6 alkyl, (Cue) alkyl optionally substituted with R²⁷, C3

6 cycloalkyl, C3-6 halocycloalkyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C2

₆ haloalkynyl, -C(O)R²⁵, or -C(O)OR²⁶;

R^4a is a hydrogen atom, a halogen atom, Ci-6 alkyl, (Cue) alkyl optionally substituted with R²⁷, C3-6 cycloalkyl, (C3 e) cycloalkyl optionally substituted with R²⁷, C2-6 alkenyl, C2 6 haloalkenyl, C2-6 alkynyl, C2-6 haloalkynyl, C3-6 cycloalkenyl, -NH2, Ci-6 alkylamino, di(Ci 6 alkyl)amino, -NHC(O)R⁸, phenyl, phenyl substituted with (R²⁸)_r, 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^28a), 3-7- membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^28a);

R^4b is a hydrogen atom, a halogen atom, cyano, nitro, Ci-6 alkyl, (Cue) alkyl optionally substituted with R²⁷, C3-6 cycloalkyl, (C3 e) cycloalkyl optionally substituted with R²⁷, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C2-6 haloalkynyl, C3-6 cycloalkenyl, - C(O)OR¹⁶, -OR³⁸, -S(O)_m3R²⁰, -NH₂, CI-₆ alkylamino, di(Ci-₆ alkyl)amino, -NHC(O)R⁸, phenyl, phenyl substituted with (R²⁸)_r, 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^28a), 3-7-membered heterocyclyl, or 3-7- membered heterocyclyl (optionally substituted with R²⁸ and R^28a);

R^4c is a hydrogen atom, a halogen atom, Ci-6 alkyl, (Cue) alkyl optionally substituted with R²⁷, C3-6 cycloalkyl, (C3 e) cycloalkyl optionally substituted with R²⁷, phenyl, phenyl substituted with (R²⁸)_r, 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^28a), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^28a);

R^4d is a hydrogen atom, Ci-6 alkyl, or (Cue) alkyl optionally substituted with R³⁵;

U-l to U-6, U-6a, U-7 to U-10, U-lOa, U-l l, U-l la, U-12, U-12a, U-13, U-13a, U-14 to U-22, U-22a, U-23, U-24, U-25, and U-26 are respective heterocycles of the following structures;

R^5a and R^5b are each independently a hydrogen atom, Ci-6 alkyl, (Ci e) alkyl optionally substituted with R²⁷, C3-6 cycloalkyl, C3-6 halocycloalkyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C2-6 haloalkynyl, C3-6 cycloalkenyl, phenyl, or phenyl substituted with (R²⁸)_r;

R^5c is a hydrogen atom, Ci-6 alkyl, or (Cue) alkyl optionally substituted with R³⁶, or

R^5c optionally forms a 6-membered ring together with a nitrogen atom to which R^5c is bonded and a carbon atom to which R^4d is bonded by forming -(CH2)4- or -CH=CH- CH=CH- with R^4d;

R⁶ is a halogen atom, cyano, C3-6 cycloalkyl, -C(O)R⁸, -C(O)OR¹⁶, -OR¹³, -S(O)_m2R¹⁴, phenyl, or phenyl substituted with (R⁷)_P;

R⁷ is a halogen atom, cyano, nitro, Ci-6 alkyl, (Cue) alkyl optionally substituted with R²⁷, C3-6 cycloalkyl, C3-6 halocycloalkyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C2 6 haloalkynyl, C3-6 cycloalkenyl, Ci-6 alkylcarbonyl, C3-6 cycloalkylcarbonyl, Ci- 6 haloalkylcarbonyl, C3-6 halocycloalkylcarbonyl, Ci-6 alkoxycarbonyl, Ci-

6 haloalkoxycarbonyl, Ci-6 alkylaminocarbonyl, Ci-6 haloalkylaminocarbonyl, di(Cr

6 alkylamino)carbonyl, -OR¹⁵, -S(O)_m3R²⁰, Ci-6 alkylaminosulfonyl, di(Ci-

6 alkyl) aminosulfonyl, -NH2, Ci-6 alkylamino, di(Ci-6 alkyl)amino, 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^28a), 3-7- membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^28a);

R⁸ is a hydrogen atom, Ci-6 alkyl, or -N(R^{l la})R^12a;

R^8b is a hydrogen atom or Ci -6 alkyl;

R⁹ is a hydrogen atom, Ci-6 alkyl, or phenyl; R¹⁰ is a hydrogen atom, Ci-6 alkyl, (Ci e) alkyl optionally substituted with R³⁴, C3

6 cycloalkyl, C3-6 halocycloalkyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, or C2

6 haloalkynyl;

R” and R¹² are each independently a hydrogen atom, Ci-6 alkyl, (Cue) alkyl optionally substituted with R³⁴, C3-6 cycloalkyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C2 6 haloalkynyl, phenylsulfonyl, phenyl, phenyl substituted with (R⁷)_P, U-7, U-8, U-9, or U-14 to U-19, or R” optionally forms a 3-7-membered ring together with a nitrogen atom to which R” and R¹² are bonded by forming a C2-6 alkylene chain together with R¹², and in this case, the alkylene chain optionally contains one O, S, S(O), S(O)2, or N(R³³) and is optionally substituted with an oxo group or a thioxo group;

R^{l la} and R^12a are each independently a hydrogen atom, Ci-6 alkyl, or phenyl, or R^{l la} optionally forms a 3-7-membered ring together with a nitrogen atom to which R^{l la} and R^12a are bonded by forming a C2-6 alkylene chain together with R^12a, and in this case, the alkylene chain optionally contains one O, S, S(O), S(O)2, or N(R³³) and is optionally substituted with an oxo group or a thioxo group;

R^12b is -OR^19b;

R¹³ is a hydrogen atom, Ci-6 alkyl, (Cue) alkyl optionally substituted with R³⁴, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C2-6 haloalkynyl, -C(O)R⁸, or phenyl;

R¹⁴ is a hydrogen atom, Ci-6 alkyl, (Cue) alkyl optionally substituted with R³⁴, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C2-6 haloalkynyl, or phenyl;

R¹⁵ is a hydrogen atom, Ci-6 alkyl, (Cue) alkyl optionally substituted with R²⁷, C3

6 cycloalkyl, C3-6 halocycloalkyl C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C2

6 haloalkynyl, or C3-6 cycloalkenyl;

R¹⁶ is a hydrogen atom, Ci-6 alkyl, or (Cue) alkyl optionally substituted with R³⁷;

R¹⁸ is a hydrogen atom or Ci-6 alkyl;

R¹⁹ is a hydrogen atom, Ci-6 alkyl, or phenyl;

R^19b is a hydrogen atom or Ci-6 alkyl;

R²⁰ is C1-6 alkyl, Ci-6 haloalkyl, C3-6 cycloalkyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C2-6 haloalkynyl, or C3-6 cycloalkenyl;

R²¹ and R²² are each independently a hydrogen atom, Ci-6 alkyl, or phenyl, or R²¹ optionally forms a 3-7-membered ring together with a nitrogen atom to which R²¹ and R²² are bonded by forming a C2-6 alkylene chain together with R²², and in this case, the alkylene chain optionally contains one O, S, S(O), S(O)2, or N(R³⁹) and is optionally substituted with an oxo group or a thioxo group;

R²⁴ is a hydrogen atom or Ci-6 alkyl; R²⁵ and R²⁶ are each independently a hydrogen atom, Ci-6 alkyl, Ci-6 haloalkyl, C3

6 haloalkynyl, C3-6 cycloalkenyl, or phenyl;

R²⁷ is a halogen atom, cyano, nitro, phenyl, phenyl substituted with (R²⁸)_r, -C(O)OR¹⁶, - OR²⁹, -S(O)m4R³⁰, 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^28a), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^28a);

R²⁸ is a halogen atom, cyano, nitro, Ci-6 alkyl, Ci-6 haloalkyl, C3-6 cycloalkyl, C3

6 halocycloalkyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C2-6 haloalkynyl, (Cr

6 alkoxy) Ci-6 alkyl, -OR³¹, or -S(O)_m4R³⁰; when t2, t3, t4, t5, t7, t8, or t9 is an integer of 2 or more, R²⁸ are optionally the same as or different from each other; further when two R²⁸ are adjacent, the two adjacent R²⁸ optionally form a 6-membered ring together with carbon atoms to which each R²⁸ is bonded by forming -CH=CH-CH=CH-;

R^28a is C1-6 alkyl, Ci-6 haloalkyl, (Ci-6 alkoxy) Ci-6 alkyl, or (Ci-6 alkylthio) Ci-6 alkyl;

R²⁹, R³⁰, and R³¹ are each independently a hydrogen atom, Ci-6 alkyl, Ci-6 haloalkyl, C3

6 haloalkynyl, C3-6 cycloalkenyl, or phenyl;

R³³ is a hydrogen atom or Ci-6 alkyl;

R³⁴ is a halogen atom, cyano, C3-6 cycloalkyl, -C(O)R⁸, -C(O)OR¹⁶, -OR³³, -S(O)_meR³³, phenyl, phenyl substituted with (R⁷)_P, U-l, U-3, U-7, U-8, U-9, or U-14 to U-25;

R³⁵ is a halogen atom or Ci-6 alkoxy;

R³⁶ is a halogen atom or Ci-6 alkoxy;

R³⁷ is C1-6 alkoxy,

R³⁸ is C1-6 alkyl, (Cue) alkyl optionally substituted with R³⁴, C3-6 cycloalkyl, C3

6 halocycloalkyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C2-6 haloalkynyl, C3

6 cycloalkenyl, or phenyl;

R³⁹ is a hydrogen atom or Ci-6 alkyl; tl is an integer of 0 or 1; ml, m2, m3, m4, m6, and t2 are each independently an integer of 0, 1, or 2; n and t3 are each independently an integer of 0, 1, 2, or 3; p and r are each independently an integer of 1, 2, 3, 4, or 5; t4 is an integer of 0, 1, 2, 3, or 4; t5 is an integer of 0, 1, 2, 3, 4, or 5; t7 is an integer of 0, 1, 2, 3, 4, 5, 6, or 7; t8 is an integer of 0, 1, 2, 3, 4, 5, 6, 7, or 8; and t9 is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; or a salt thereof; b) tris(2-ethylhexyl) phosphate, and c) a non-ionic tenside, characterized in that the weight ratio of tris(2-ethylhexyl) phosphate to the non-ionic tenside is between 1.5:0.6 and 0.6:1.5.

The compound of formula (1) can be synthesized as described in WO 2014/192936.

The weight ratio of tris(2-ethylhexyl) phosphate to the non-ionic tenside is preferably between 1.4:0.7 and 0.7:1.4, further preferably 1.2:0.8 and 0.8:1.2.

Tris(2-ethylhexyl) phosphate (commonly abbreviated as TEHP) is a known adjuvant for herbicides, such as pinoxaden (W02008049618A2).

The inventors of the present invention found that TEHP in combination with compounds of formula (1) does not provide for a sufficient increase in herbicidal efficacy in combination with an acceptable level of phytotoxicity of relevant crops, such as rice. Surprisingly, however, a specific combination of compounds of formula (1) with TEHP and a non-ionic tenside, the latter two components in a specific weight ratio, significantly improves herbicidal efficacy while minimizing phytotoxic effects.

Preferably, the compound of formula (1) is 3-[(isopropylsulfonyl)methyl]-N-(5-methyl-l,3,4-oxadiazol- 2-yl)-5-(trifluoromethyl)-[l,2,4]triazolo[4,3-a]pyridine-8-carboxamide (common name: iptriazopyrid; CAS 1994348-72-9). This compound demonstrates a high level of weed control, in particular in rice fields.

Preferably, the non-ionic tenside is selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene polyoxypropylene sorbitan fatty acid esters and alkoxylated 2-ethyl- hexanol, preferably 2-ethylhexanol propoxylated ethoxylated polymer.

Polyoxyethylene sorbitan fatty acid esters refer to a series of synthetic nonionic surfactants commonly known as polysorbates, such as polysorbate 20 (polyoxyethylene (20) sorbitan monolaurate), polysorbate 21 (polyoxyethylen-(4)-sorbitanmonolaurate), polysorbate 40 (polyoxyethylene (20) sorbitan monopalmitate), polysorbate 60 (polyoxyethylene (20) sorbitan monostearate) and polysorbate 80 (polyoxyethylene (20) sorbitan monooleate).

Polyoxyethylene polyoxypropylene sorbitan fatty acid esters complement above sorbitans, by including ethylene and propylene oxides, such as polyoxyethylene polyoxypropylene sorbitan monolaurate (Tween L-1505).

2-Ethylhexanol propoxylated ethoxylated polymer is described in European patent application EP1139739A1, and refers to the following chemical structure: wherein m and n are average numbers, and wherein m is an average number between 6 and 10, preferably 8, and wherein n is an average number between 4 and 8, more preferably 5 to 6, e.g. 5 or 6.

The preferred 2-ethylhexanol propoxylated ethoxylated polymer may be provided by the following structure (denoted pl): with P being

E being -CH2-CH2- , and the numbers 8 and 6 represent average values.

Alternatively, the preferred 2-ethylhexanol propoxylated ethoxylated polymer may be provided by the following structure (denoted p2): with P being

E being -CH2-CH2- , and the numbers 8 and 5 represent average values.

Alternatively, the preferred 2-ethylhexanol propoxylated ethoxylated polymer may be a mixture of above structures pl and p2.

Throughout the present disclosure, the preferred compounds pl and p2 (alone or in mixture) are also called Lucramul Hot 5902.

In a further embodiment, the weight ratio of tris(2-ethylhexyl) phosphate to the non-ionic tenside is between 1.1:0.9 and 0.9: 1.1, preferably the ratio is approximately 1:1, or the ratio is 1:1. Preferably, the compound of formula (1), and more preferably iptriazopyrid, is comprised in a concentration of at least 0.1 wt.%, based on the based on the total weight of the suspension.

Further preferably, the compound of formula (1), and more preferably iptriazopyrid, is comprised in a concentration of at least 0.5 wt.%, or 1 wt.%, or 1.5 wt.% or 2 wt.%, or 2.5 wt.%, based on the based on the total weight of the suspension.

Preferably, the compound of formula (1), and more preferably iptriazopyrid, is comprised in a concentration of at most 6 wt.%, based on the based on the total weight of the suspension.

Further preferably, the compound of formula (1), and more preferably iptriazopyrid, is comprised in a concentration of at most 5.5 wt.%, or 5 wt.%, or 4.5 wt.% or 4 wt.%, based on the total weight of the suspension.

Preferably, the combined concentration of tris(2-ethylhexyl) phosphate and the non-ionic tenside is at least 25 wt.% based on the total weight of the suspension, more preferably at least 30 wt.% based on the total weight of the suspension, further preferably at least 35 wt.% based on the total weight of the suspension.

Preferably, the combined concentration of tris(2-ethylhexyl) phosphate and the non-ionic tenside is at most 60 wt.% based on the total weight of the suspension, more preferably at most 50 wt.% based on the total weight of the suspension, further preferably at most 45 wt.% based on the total weight of the suspension.

Preferably, the aqueous suspension comprises a further herbicidal compound selected from oxadiazon (CAS 19666-30-9), bentazone (CAS 25057-89-0), propanil (CAS 709-98-8) and triafamone (CAS 874195-61-6).

Further preferably, the further herbicidal compound is triafamone.

In a further embodiment, the aqueous suspension comprises a) iptriazopyrid in form of suspended particles, b) tris(2-ethylhexyl) phosphate, c) a non-ionic tenside selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene polyoxypropylene sorbitan fatty acid esters and alkoxylated 2-ethyl- hexanol, preferably 2-ethylhexanol propoxylated ethoxylated polymer, or mixtures thereof, wherein the weight ratio of tris(2-ethylhexyl) phosphate to the non-ionic tenside is between 1.4:0.7 and 0.7: 1.4, d) optionally a further herbicide selected from selected from oxadiazon, bentazone, propanil, and triafamone, preferably triafamone, e) optionally one or more organic water-miscible solvents, f) optionally one or more nonionic surfactants, g) optionally one or more antifoam agents, h) optionally one or more rheological modifiers or thickeners, i) optionally one or more preservatives, j) optionally one or more pH adjusters.

Suitable organic water-miscible solvents by way of example are linear or cyclic alkyl carbonates, such methyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and isomers thereof, propylene carbonate, glycerol- 1 ,2-carbonate and butylene carbonate, or alkanols, such as monohydric or dihydric alkanols, e.g. ethylene glycol or 1 ,2-propylene glycol.

Preferably, the organic water-miscible solvent is an alkanol, further preferably 1 ,2-propylene glycol.

Suitable nonionic surfactants by way of example are alkylphenolethoxylates, alkoxylated tristyrylphenols, alkoxylated tributylphenols, alkylamine thoxylates, ethoxylated vegetable oils including their hydrogenates, polyadducts of ethylene oxide and propylene oxide (e.g. polyoxyethylenepoly oxypropylene block copolymers and their derivatives), ethoxylated fatty acids, nonionic polymeric surfactants (e.g. polyvinylalcohol, polyvinylpyrrolidone, polymethacrylates and their derivatives), propylene glycol esters of fatty acids and polyglycerol esters. Preferred are ethoxylated polymethacrylates and polyoxide blends, and mixtures thereof.

The one or more nonionic surfactants f) are preferably different from the non-ionic tenside c).

Suitable rheological modifiers or thickeners by way of example are polysaccharides including xanthan gum, guar gum and hydroxyethyl cellulose. Examples are Kelzan®, Rhodopol® G and 23, Satiaxane® CX911 and Natrosol® 250 range; clays including montmorillonite, bentonite, sepiolite, attapulgite, laponite, hectorite. Examples are Veegum® R, Van Gel® B, Bentone® CT, HC, EW, Pangel® M100, M200, M300, S, M, W, Attagel® 50, Laponite® RD; fumed and precipitated hydrophylic silica, examples are Aerosil® 200, Aerosil® 380, Sipernat® 22; fumed and precipitated hydrophobic silica, examples are Aerosil® R812, Aerosil® R812S, Aerosil® R972.

Suitable antifoams by way of example are silicone antifoams and magnesium stearate, silicone oils, silicone oil preparations, particularly nonionic aqueous polydimethylsiloxane -based emulsions (dimethyl siloxanes and silicones, CAS No. 63148-62-9). Examples are Silcolapse® 426 and 432 from Bluestar Silicones, Silfoam® SRE and SC132 from Wacker, SAG 1572 and SAG 30 from Momentive. Suitable preservatives are by way of example e.g. dichlorophene and benzyl alcohol hemiformal, 5- chloro-2-methyl-4-isothiazolin-3-one [CAS-No. 26172-55-4], 2-methyl-4-isothiazolin-3-one [CAS-No. 2682-20-4] or 1.2-benzisothiazol-3(2H)-one [CAS-No. 2634-33-5]. Examples which may be mentioned are Preventol® D7 (Lanxess), Kathon® CG/ICP (Dow), Acticide® SPX (Thor GmbH) and Proxel® GXL (Arch Chemicals).

Suitable pH adjusters by way of example are acids and bases, such as, for example, hydrochloric acid, sulfuric acid, citric acid or sodium hydroxide and potassium hydroxide; buffers, e.g. suitable combinations of phosphate salts, or of citrate salts known in the literature to stabilize a concrete pH range.

In a further embodiment, the aqueous suspension comprises a) iptriazopyrid in form of suspended particles in a concentration of between 2 and 5 wt.%, preferably between 3 and 4 wt.%, b) tris(2-ethylhexyl) phosphate in a concentration of between 10 and 30 wt.%, preferably between 15 and 25 wt.%, c) a non-ionic tenside selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene poly oxypropylene sorbitan fatty acid esters and alkoxylated 2-ethyl- hexanol, preferably 2-ethylhexanol propoxylated ethoxylated polymer, or mixtures thereof, in a concentration of between 10 and 30 wt.%, preferably between 15 and 25 wt.%, wherein the weight ratio of tris(2-ethylhexyl) phosphate to the non-ionic tenside is between 1.4:0.7 and 0.7: 1.4, d) optionally triafamone in a concentration of between 1 and 4 wt.%, preferably between 2 and 3 wt.%, e) one or more organic water-miscible solvents in a concentration of between 2 and 8 wt.%, preferably between 4 and 6 wt.%, f) one or more nonionic surfactants in a concentration of between 2 and 8 wt.%, preferably between 4 and 6 wt.%, g) one or more antifoam agents in a concentration of between 0.1 and 1 wt.%, preferably between 0.2 and 0.8 wt.%, h) one or more rheological modifiers or thickeners in a concentration of between 0.1 and 2 wt.%, preferably between 0.2 and 0.8 wt.%, i) one or more preservatives in a concentration of between 0.05 and 1 wt.%, preferably 0.05 and 0.5 wt.%, or between 0.1 and 1 wt.%, preferably between 0.2 and 0.8 wt.%, i) one or more pH adjusters in a concentration of between 0.05 and 1 wt.%, preferably between 0.05 and 0.5 wt. %, or between 0.1 and 1 wt.%, preferably between 0.2 and 0.8 wt.%. The non-ionic surfactants f) are preferably different from the non-ionic tenside c).

The aqueous suspension according to the present invention may further comprise stabilizers, dyes or pigments, or other typical ingredients for agrochemical formulations.

A second aspect of the present disclosure relates to a method for controlling undesirable vegetation which comprises contacting the vegetation or the place of vegetation with, or applying to the soil or water, to prevent the appearance or growth of vegetation, a herbicidally effective amount of the aqueous emulsion suspension according to the first aspect of the present disclosure.

Preferably, iptriazopyrid is applied in a concentration of between 15 and 80 g ai/ha.

Preferably, the aqueous emulsion suspension comprises iptriazopyrid and triafamone, and wherein iptriazopyrid is applied in a concentration of between 15 and 80 g ai/ha, and triafamone is applied in a concentration of between 8 and 50 g ai/ha.

Preferably, the undesirable vegetation is controlled in a rice field.

The aqueous suspension can also be considered as an aqueous emulsion suspension as the adjuvants are emulsified within the suspension.

Detailed description

The present invention relates to a specific formulation comprising an herbicidal heterocyclic amide compound, TEHP and a non-ionic tenside. TEHP and the non-ionic tenside are to be formulated in a specific ratio to provide for a surprisingly strong herbicidal efficacy and minimal phytotoxicity of the herbicide.

It has been in particular found that a combination of TEHP with a non-ionic tenside selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene polyoxypropylene sorbitan fatty acid esters and alkoxylated 2-ethyl-hexanol, preferably 2-ethylhexanol propoxylated ethoxylated polymer, provides for a strong herbicidal activity while reducing the phytotoxicity of the herbicide iptriazopyrid.

Examples

The examples are meant to illustrate the invention and do not limit it to the processes and compounds described therein.

Starting materials: The compounds used in the examples are hereafter specified in Table 1.

Table 1: Chemicals used in the examples.

The following suspension concentrates, comprising emulsified adjuvants, have been prepared as follows: All liquid formulation inerts were first provided in in water, followed by adding the solid inerts and then the active ingredients. The obtained suspension was pre-milled with a rotor-stator, followed by milling with a bead-mill to achieve particle-size of d 90 < 10 pm for the suspended particles. Then, the liquid adjuvants were added and emulsified after milling. Finally, thickener and biocides were added as appropriate, and the pH was adjusted. Table 2: Formulation examples.

*not according to the invention

Glasshouse screening:

The formulations were tested in terms of crop damage against rice (ORYSA - Oryza sativa), and in terms of weed efficacy against the following weeds: BRAPP (Brachiaria platyphylla) / CYPES (Cyperus esculentus) / CYPIR (Cyperus iria) / ECHCO (Echinochloa colona) / PHBPU (Ipomoea purpurea) / SEBEX (Sesbania exaltata).

Testing conditions:

Plants were grown in pots with silty sand and applied at growth stages of BBCH 12-14 of the crop and grass species. The application was done with a flat-fan nozzle and an application volume corresponding to 3001/ha.

The following dose rates were tested: 40+25, 20+12.5 and 10+6.25 (each Iptriazopyrid + Triafamone) g ai/ha.

The treated pots were grown under glasshouse condition of 24°C during the day and 16°C at night. The pots were regularly irrigated to keep paddy conditions from two days after application until the assessment.

The assessment of crop damage and weed efficacy was analyzed 21 days after application.

The assessment was done visually, with the weed efficacy average over all 6 weed species tested.

A variation of > 5% in mean values show a significant difference between treatments. The weed efficacy should be at least 80 % to provide sufficient control. Table 3: Phytotoxicity against ORYSA and weed efficacy against BRAPP / CYPES / CYPIR / ECHCO /

PHBPU / SEBEX

Example 1 confers no damage on ORYSA, however the weed efficacy is low (75%). Examples 2 and 3 provide for a sufficient weed efficacy (83%), however, the damage to ORYSA is significant (10%).

Examples 4 to 6 provide for a high weed efficacy of at least 80%, while limiting the damage to ORYSA to at most 5 %.

Claims

Claims:

1. Aqueous suspension comprising a) iptriazopyrid in form of suspended particles, b) tris(2-ethylhexyl) phosphate, and c) a non-ionic tenside selected from the group consisting of polyoxyethylene sorbitan fatty acid esters and alkoxylated 2-ethyl-hexanol, characterized in that the weight ratio of tris(2-ethylhexyl) phosphate to the non-ionic tenside is between 1.4:0.7 and 0.7: 1.4.

2. Aqueous suspension according to claim 1 , characterized in that the weight ratio of tris(2- ethylhexyl) phosphate to the non-ionic tenside is between 1.2:0.8 and 0.8:1.2.

3. Aqueous suspension according to claim 1 or 2, wherein the non-ionic tenside is 2-ethylhexanol propoxylated ethoxylated polymer.

4. Aqueous suspension according to any one of the preceding claims, wherein iptriazopyrid is comprised in a concentration of at least 0.1 wt.%, or 1 wt.%, or 1.5 wt.% or 2 wt.%, or 2.5 wt.%, based on the based on the total weight of the suspension.

5. Aqueous suspension according to any one of the preceding claims, wherein iptriazopyrid is comprised in a concentration of at most 6 wt.%, or 5.5 wt.%, or 5 wt.%, or 4.5 wt.% or 4 wt.%, based on the based on the total weight of the suspension.

6. Aqueous suspension according to any one of the preceding claims, wherein the combined concentration of tris(2-ethylhexyl) phosphate and the non-ionic tenside is at least 25 wt.% based on the total weight of the suspension, preferably at least 30 wt.% based on the total weight of the suspension, further preferably at least 35 wt.% based on the total weight of the suspension.

7. Aqueous suspension according to any one of the preceding claims, wherein the combined concentration of tris(2-ethylhexyl) phosphate and the non-ionic tenside is at most 60 wt.% based on the total weight of the suspension, preferably at most 50 wt.% based on the total weight of the suspension, further preferably at most 45 wt.% based on the total weight of the suspension.

8. Aqueous suspension according to any one of the preceding claims, comprising a further herbicidal compound selected from oxadiazon, bentazone, propanil and triafamone.

9. Aqueous suspension according to the preceding claim, wherein the further herbicidal compound is triafamone.

10. Aqueous suspension according to any one of the preceding claims, wherein the weight ratio of tris(2-ethylhexyl) phosphate to the non-ionic tenside is between 1.1:0.9 and 0.9: 1.1, preferably about 1:1.

11. Aqueous suspension according to any one of the preceding claims, comprising a) iptriazopyrid in form of suspended particles, b) tris(2-ethylhexyl) phosphate, c) a non-ionic tenside selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene polyoxypropylene sorbitan fatty acid esters and alkoxylated 2- ethyl-hexanol, preferably 2-ethylhexanol propoxylated ethoxylated polymer, or mixtures thereof, wherein the weight ratio of tris(2-ethylhexyl) phosphate to the non-ionic tenside is between 1.4:0.7 and 0.7: 1.4, d) optionally a further herbicide selected from oxadiazon, bentazone, propanil and triafamone, preferably triafamone, e) optionally one or more water-miscible solvents, f) optionally one or more nonionic surfactants, g) optionally one or more antifoam agents, h) optionally one or more rheological modifiers or thickeners, i) optionally one or more preservatives, j) optionally one or more pH adjusters.

12. Method for controlling undesirable vegetation which comprises contacting the vegetation or the place of vegetation with, or applying to the soil or water, to prevent the appearance or growth of vegetation, a herbicidally effective amount of the aqueous suspension of claims 1 to 11.

13. Method according to the preceding claim, wherein iptriazopyrid is applied in a concentration of between 15 and 80 g/ha.

14. Method according to claim 12 or 13, wherein the aqueous emulsion suspension comprises iptriazopyrid and triafamone, and wherein iptriazopyrid is applied in a concentration of between 15 and 80 g/ha, and wherein triafamone is applied in a concentration of between 8 and 50 g/ha.

15. Method according to any one of claims 12 to 14, wherein the undesirable vegetation is controlled in a rice field.