ZA200504444B

ZA200504444B - Oil suspension concentrate.

Info

Publication number: ZA200504444B
Application number: ZA200504444A
Authority: ZA
Inventors: Roland Deckwer; Detlev Haase; Hans-Peter Krause; Rhard Schnabel
Original assignee: Bayer Crpscience Gmbh
Priority date: 2002-12-13
Filing date: 2005-05-31
Publication date: 2006-02-22
Also published as: UA84858C2; DE10258216A1; CN1722952A; CN101658164A

Description

@® WO 2004/054364 PCT/EP2003/013389

Description

Oil suspension concentrate

The present invention relates to the field of crop protection compositions. In particular, the invention relates to liquid formulations in the form of oil suspension concentrates comprising herbicidally active compounds from the group of the sulfonamides, in particular the phenyisulfonamides and heteroarylsulfonamides.

In general, active compounds for crop protection are not employed in pure form.

Depending on the area of use and the type of use, and on physical, chemical and biological parameters, the active compound is used as an active compound formulation in a mixture with customary auxiliaries and additives. Also known are combinations with further active compounds for widening the activity spectrum and/or for protecting crop plants (for example by safeners, antidotes).

In general, formulations of active compounds for crop protection should have high chemical and physical stability, should be easy to apply and easy to use and have broad biological action combined with high selectivity.

In general, herbicidally active compounds from the group of the sulfonamides, such as sulfonylureas, have high chemical reactivity and tend to be degraded chemically, for example by hydrolysis.

One possibility of formulating chemically unstable active compounds is the preparation of solid formulations. Thus, formulations of active compounds from the group of the sulfonylureas in the form of powders, granules and tablets are known (for example in EP 764404, WO 9834482, WO 9313658). However, the processes for preparing solid formulations, for example in the form of granules and tablets, are generally complicated, in particular when auxiliaries and additives or active compounds having a low melting point are incorporated. Moreover, solid

® 2 formulations are generally more difficult to apply and less user-friendly.

Liquid formulations of sulfonylureas are described, for example, in US 4599412,

US 4683000, US 4671817, EP 0245058, WO 01/82693, EP 0313317, EP 0514768,

EP 0163598 and EP 05147689.

It was an object of the present invention to provide an improved formulation of crop protection agents, which formulation has high chemical stability and high biological effectiveness and crop plant compatibility.

This object is achieved by the specific oil suspension concentrate of the present invention.

Accordingly, the present invention relates to an oil suspension concentrate comprising a) one or more herbicidally active compounds from the group of the sulfonamides in suspended form, b) one or more safeners,

Cc) one or more organic solvents, and d) one or more sulfosuccinates.

Furthermore, the oil suspension concentrate according to the invention may optionally also comprise, as further components: e) one or more agrochemically active compounds different from a) and b) and f) customary auxiliaries and additives.

The term “oil suspension concentrate” (OD) is to be understood as meaning a suspension concentrate based on organic solvents. Here, one or more active compounds are suspended in the organic solvent, further active compounds may be dissolved in the organic solvent. :

In the oil suspension concentrate according to the invention, the sulfonamide a) is present in suspended form in the organic solvent. This means that the major portion (in % by weight) of sulfonamide is present undissolved in finely distributed form, a minor portion of the sulfonamide may be dissolved. Preferably, more than 80% by weight, particularly preferably more than 90% by weight, of the sulfonamide are suspended in the organic solvent, in each case based on the total amount of sulfonamide in the oil suspension concentrate according to the invention.

Preferred sulfonamides a) are phenylsulfonamides and heteroarylsulfonamides and other sulfonamides such as amidosulfuron. Suitable phenylsulfonamides a) are, for example, compounds from the group of the phenylsulfonylaminocarbonyl- triazolinones or the phenylsulfonylureas, preferably from the group of the phenylsulfonylureas. The term “phenylsulfonylurea” is to be understood as including those sulfonylureas in which the phenyl group is attached via a spacer such as CHz,

O or NH to the sulfone group (SO,). Examples of phenyisulfonylaminocarbonyl- triazolinones are flucarbazone or propoxycarbazone and/or salts thereof. The sulfonamides a) are commercially available and/or can be prepared by known processes, as described, for example, in EP-A-7687, EP-A-30138, US 5,057,144 and US 5,534,486.

Suitable phenyisulfonamides are, for example, phenylsulfonamides of the formula (1) and/or salts thereof

R%(A)m-SO-NRP-CO-(NR"),-R® (I) in which

R® is an unsubstituted or substituted phenyl radical, where the phenyl radical including substituents has 1-30 carbon atoms, preferably 1-20 carbon atoms,

RP is a hydrogen atom or an unsubstituted or substituted hydrocarbon radical which, including substituents, has 1-10 carbon atoms, for example unsubstituted or substituted C1-Cs-alkyl, preferably a hydrogen atom or methyl,

RY is a hydrogen atom or an unsubstituted or substituted hydrocarbon radical

® 4 which, including substituents, has 1-10 carbon atoms, for example unsubstituted or substituted C4-Cs-alkyl, preferably a hydrogen atom or methyl,

A is CH2, O or NH, preferably O, m is zero or 1, n is zero or 1, preferably 1, and

R® is a heterocyclic radical, such as a pyridyl radical, a triazinyl radical or a triazolinone radical.

Preferred phenylsulfonamides are phenylsulfonylureas, for example phenylsulfonylureas of the formula (ll) and/or salts thereof

R%-(A)n-SO-NRP-CO-NR"-R® (ll) in which

R* is an unsubstituted or substituted phenyl radical, where the phenyl radical including substituents has 1-30 carbon atoms, preferably 1-20 carbon atoms,

RP is a hydrogen atom or an unsubstituted or substituted hydrocarbon radical which, including substituents, has 1-10 carbon atoms, for example unsubstituted or substituted C4-Ce-alkyl, preferably a hydrogen atom or methyl,

R” is a hydrogen atom or an unsubstituted or substituted hydrocarbon radical which, including substituents, has 1-10 carbon atoms, for example unsubstituted or substituted C4-Cg-alkyl, preferably a hydrogen atom or methyl,

A is CH,, O or NH, preferably O, m is zero or 1, and

R® is a heterocyclic radical, such as a pyridyl radical or a triazinyl radical.

Preference is given to phenylsulfonylureas of the formula (Il) and/or salts thereof

® 5

R4 X 1X =

RS (0) SO,—NH—C-—NR® —4 ya (in) 4

Y in which

R* is C4-C4-alkoxy, preferably C,-Cg4-alkoxy, or CO-R?, where R®is OH,

C,-Cs-alkoxy or NR°RS, where R® and RC are identical or different and independently of one another are H or C4-Cs-alkyl,

R® is halogen, preferably iodine, or (A),-NR®R®, where n is zero or 1, A is a group

CR'R*, where R' and R*" are identical or different and independently of one another are H or C4-C4-alkyl, R? is H or C;-C4-alkyl and R® is an acyl radical, such as formyl, or C4-Cg-alkylsulfonyl, and if R%is C1-Cs-alkoxy, preferably

C,-Cs-alkoxy, R® may also be H,

R® is H or C4-Cs-alkyl, m is zero or 1,

X and Y are identical or different and independently of one another are halogen or

NR’'R", where R‘ and R" are identical or different and are H or C4-Cs-alkyl, or

C1-Cs-alkyl, C1-Cs-alkoxy, C1-Cs-alkylthio, C3-Cs-cycloalkyl, C,-Cs-alkenyl,

C,-Ce-alkynyl, C3-Cg-alkenyloxy or C3-Ce-alkynyloxy, where each of the eight lastmentioned radicals is unsubstituted or substituted by one or more radicals from the group consisting of halogen, C4-C;-alkoxy and C-Cs-alkylthio, preferably C1-Cs-alkyl or C4-Cs-alkoxy, and

Z is CH or N.

Particular preference is given to phenyisulfonylureas of the formula (lil) and/or salts thereof, in which a) R* is CO-(C;-Ca-alkoxy), R® is halogen, preferably iodine, or R® is CH,-NHR®, where R® is an acyl radical, preferably C,-Cs-alkylsulfonyl, and m is zero, b) R* is CO-N(C1-Ca-alkyl),, R® is NHR®, where R% is an acyl radical, preferably formyl, and m is zero, or c) R* is C,-Cq-alkoxy, R¥is H and mis 1.

® 6

Typical phenylsulfonylureas are, inter alia, the compounds listed below and their salts, such as the sodium salts: bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron and its sodium salt, metsulfuron-methyl, oxasulfuron, primisulfuron-methyl, prosulifuron, sulfometuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, tritosulfuron, iodosulfuron-methyl and its sodium salt (WO 92/13845), mesosulfuron-methyl and its sodium salt (Agrow No. 347, March 3, 2000, page 22 (PJB Publications Ltd. 2000)) and foramsulfuron and its sodium salt (Agrow No. 338,

October 15, 1999, page 26 (PJB Publications Ltd. 1999)).

Particularly preferred phenylsulfonamides are: iodosulfuron-methyl (A1.1) and its sodium salt (A1.2), mesosulfuron-methyl (A2.1) and its sodium salt (A2.2), foramsulfuron (A3.1) and its sodium salt (A3.2), flucarbazone (A4.1) and its sodium salt (A4.2), propoxycarbazone (A5.1) and its sodium salt (A5.2) and ethoxysulfuron (A6.1) and its sodium salt (A6.2), metsulfuron-methyl (A7.1) and its sodium salt (A7.2), tribenuron-methyl (A8.1) and its sodium salt (A8.2), chlorsulfuron (AS.1) and its sodium salt (A9.2).

The active compounds listed above are known, for example, from “The Pesticide

Manual®, 12th edition (2000), The British Crop Protection Council, or the literature references given after the individual active compounds.

Suitable heteroarylsulfonamides a) are, for example, compounds from the group of the heteroarylsulfonylaminocarbonyltriazolinones or the heteroaryisulfonylureas, preferably from the group of the heteroarylsulfonylureas. The term “heteroarylsulfonylureas” is to be understood as including those sulfonylureas in which the heteroaryl group is attached via a spacer such as CH, O or NH to the sulfone group (SO,).

Suitable heteroarylsulfonamides are, for example, sulfonamides of the formula (IV) and/or salts thereof,

® 7

R*-(A)m-S02-NRF-CO-(NR"),. - R® (IV) in which

R* is an unsubstituted or substituted heteroaryl radical, where the heteroaryl radical including substituents has 1-30 carbon atoms, preferably 1-20 carbon atoms,

R¥ isa hydrogen atom or an unsubstituted or substituted hydrocarbon radical which, including substituents, has 1-10 carbon atoms, for example unsubstituted or substituted C4-Cs-alkyl, preferably a hydrogen atom or methyl,

R" is a hydrogen atom or an unsubstituted or substituted hydrocarbon radical which, including substituents, has 1-10 carbon atoms, for example unsubstituted or substituted C1-Ceg-alkyl, preferably a hydrogen atom or methyl,

A is CH, O or NH, preferably O, m’ is zero or 1, n is zeroor 1, preferably 1, and

RY is a heterocyclic radical, such as a pyridyl radical, a triazinyl radical or a triazolinone radical.

Preferred heteroarylsulfonamides are heteroarylsulfonylureas, for example sulfonylureas of the formula (V) and/or salts thereof,

R*-(A)m-S0O,-NRF-CO-NR" - R® (V) in which

R¥ isa hydrogen atom or an unsubstituted or substituted hydrocarbon radical which, including substituents, has 1-10 carbon atoms, for example unsubstituted or substituted C4-Cg-alkyl, preferably a hydrogen atom or

® : methyl,

R" is a hydrogen atom or an unsubstituted or substituted hydrocarbon radical which, including substituents, has 1-10 carbon atoms, for example unsubstituted or substituted C1-Ce-alkyl, preferably a hydrogen atom or methyl,

A is CHa, O or NH, preferably O, m’ is zero or 1, and

RY is a heterocyclic radical, such as a pyridyl radical or a triazinyl radical.

Particular preference is given to heteroarylsulfonamides of the formula (Vi) below

R*—S0; NH-CO—(NR"");—R?' (Wh) in which

R% is a substituted heteroaryl radical such as substituted pyridyl, thienyl, pyrazolyl or imidazolyl,

R" is H, (C4-Ca)-alkyl, unsubstituted or substituted by halogen (F, C, Br, |) or halo-(C1-C3)-alkoxy, preferably H or methyl, forn'= 1, R* is a pyridyl radical or a triazinyl radical, preferably ~ N Y ~NANr je) eo!

X X and for n' = zero, R* is a triazolinone radical, preferably

® 9

X

\ —— =

OR?

R’ is (C1-C1o)-alkyl, which is unsubstituted or substituted by halogen (F, Cl,

Br, 1) or halo-(C+-Cs)-alkyl,

R® is (C1-C10)-alkyl, which is unsubstituted or substituted by halogen (F, Cl,

Br, 1) or halo-(C4-Cs)-alkyl,

XandY are identical or different and independently of one another are halogen or

NR'R", where R‘ and R* are identical or different and are H or C-Cs-alkyl, or C4-Ce-alkyl, C4-Cg-alkoxy, C4-Cs-alkylthio, C3-Ce-cycloalkyl,

C.-Cs-alkenyl, C,-Cg-alkynyl, C3-Ce-alkenyloxy or C3-Cg-alkynyloxy, where each of the eight lastmentioned radicals is unsubstituted or substituted by one or more radicals from the group consisting of halogen, C;-C4-alkoxy and C1-C4-alkylthio, preferably C4-C4-alkyl or C1-C4-alkoxy.

Particularly preferably, R* is

R® R12 ~ oN B- ? S ’

R14 R13 N R16 7 all

Ti or / N

N —_— ~ 15 R in which

R® is (C1-Ce)-alkyl, (C4-Ce)-alkoxy, (C2-Cg)-alkenyloxy, (C,-Ce)-alkynyloxy, (C,4-Ce)-alkylsulfonyl, (C4-Cs)-alkylcarbonyl, (C-Cg)-alkoxycarbonyl, (C2-Ce)-alkenyloxycarbonyl, (C,-Ce)-alkynyloxycarbonyl, CONR’'R",

® 10 halo-(C1-Ce)-alkyl, halo-(C4-Cs)-alkoxy, halo-(C,-Ce)-alkenyloxy, halo-(C2-Cs)-alkynyloxy, halo-(C4-Cg)-alkylsulfonyl, halo-(C4-Cs)-alkyl- carbonyl, halo-(C4-Cg)-alkoxycarbonyl, halo-(C,-Cs)-alkenyloxycarbonyl, halo-(C,-Ce)-alkynyloxycarbonyl,

R'" is H, (C4-Ca)-alkyl, (C1-Cs)-alkoxy, halo-(C1-Ca)-alkyl, halo-(C-Cs)-alkoxy or halogen (F, CI, Br, 1), is zero or 1,

R" is (C1-Ce)-alkyl, (C4-Cg)-alkoxy, (C2-Cg)-alkenyloxy, (C2-Cs)-alkynyloxy, (C1-Ce)-alkylsulfonyl, (C4-Ce)-alkylcarbonyl, (C4-Ce)-alkoxycarbonyl, (C2-Ce)-alkenyloxycarbonyl, (C.-Cg)-alkynyloxycarbonyl, halo-(C1-Ce)-alkyl, halo-(C4-Cg)-alkoxy, halo-(C2-Ce)-alkenyloxy, halo-(C,-Ce)-alkynyloxy, halo-(C4-Csg)-alkyisulfonyl, halo-(C4-Cg)-alkyl- carbonyl, halo-(C4-Cg)-alkoxycarbonyl, halo-(C,-Cs)-alkenyloxycarbonyl, halo-(C2-Ce)-alkynyloxycarbonyl, CONR'R",

R™ is halogen (F, Cl, Br, 1), (C1-Cg)-alkyl, (C4-Cg)-alkoxy, (C1-Cg)-alkylsulfonyl, (C1-Ce)-alkoxycarbonyl, (C,-Cs)-alkenyloxycarbonyl, (C,-Cs)-alkynyloxy- carbonyl, halo-(C,-Ce)-alkyl, halo-(C4-Cg)-alkoxy halo-(C;-Cg)-alkyl- sulfonyl, halo-(C4-Cg)-alkoxycarbonyl, halo-(C,-Cg)-alkenyloxycarbonyl, halo-(C,-Ce)-alkynyloxycarbonyl,

R" is (C4-Cs)-alkoxycarbonyl, (C,-Ce)-alkenyloxycarbonyl, (C2-Ce)-alkynyl- oxycarbonyl, (C4-Ce)-alkyl, (C1-Ce)-alkoxy, (C1-Ce)-alkylsulfonyl, halo-(C4-Ce)-alkoxycarbonyl, halo-(C,-Cs)-alkenyloxycarbonyl, halo-(C,-Ce)-alkynyloxycarbonyl, halo-(C4-Ce)-alkyl, halo-(C1-Cg)-alkoxy, halo-(C1-Cs)-alkylsulfonyl, halogen (F, Cl, Br, 1), CONR'R*, or Ris a heterocyclic ring, which may be saturated, unsaturated or aromatic and which preferably contains 4-6 ring atoms and one or more heteroatoms from the group consisting of N, O and S and which may be unsubstituted or substituted by one or more substituents, preferably from the group consisting of (C4-C3)-alkyl, (C1-C3)-alkoxy, halo-(C1-C3)-alkyl, = halo-(C4-Cs)-alkoxy and halogen, particularly preferably

_ T

CH a 3

N=N

R' is H, halogen (F, C, Br, I), (C1-Ce)-alkyl, halo-(C-Cg)-alkyl,

R'® is H, (C4-Cg)-alkyl, halo-(C4-Cs)-alkyl,

R'® is (C41-Cs)-alkyl, (C1-Cs)-alkoxy, (C,-Cg)-alkenyloxy, (C,-Cs)-alkynyloxy, (C4-Cg)-alkylsulfonyl, (C1-Ce)-alkylcarbonyl, (C4-Cg)-alkoxycarbonyl, (C2-Ce)-alkenyloxycarbonyl, (C,-Ce)-alkynyloxycarbonyl, halo-(C4-Csg)-alkyl, halo-(C1-Cg)-alkoxy, halo-(C,-Cg)-alkenyloxy, halo-(C,-Cs)-alkynyloxy, halo-(C4-Cg)-alkylsulfonyl, halo-(C4-Cg)-alkyl- carbonyl, halo-(C1-Cg)-alkoxycarbonyl, halo-(C,-Cg)-alkenyloxycarbonyl, halo-(C,-Ce)-alkynyloxycarbonyl, CONR’'R", in particular SO-ethyl, and

R" and R" independently of one another are H, (C1-Cs)-alkyl, halo-(C1-Cs)-alkyl, (C2-Ce)-alkenyl, (C2-Ce)-haloalkenyl, (C2-Ce)-alkynyl, (C,-Cs)-haloalkynyl, or NR'R" forms a heterocyclic ring which may be saturated, unsaturated “or aromatic and which preferably contains 4-6 ring atoms and one or more heteroatoms from the group consisting of N, O and S and which may be unsubstituted or substituted by one or more substituents, preferably from the group consisting of (C4-Cj)-alkyl, (C1-C3)-alkoxy, halo-(C1-C3)-alkyl, halo-(C+-C3)-alkoxy and halogen.

Particularly preferred heteroarylsulfonylureas are, for example, nicosulfuron (A10.1) and its salts, such as the sodium salt (A10.2), rimsulfuron (A11.1) and its salts, such as the sodium salt (A11.2), thifensulfuron-methyl (A12.1) and its salts, such as the sodium salt (A12.2), pyrazosulfuron-ethyl (A13.1) and its salts, such as the sodium salt (A13.2), flupyrsulfuron-methyl (A14.1) and its salts, such as the sodium salt (A14.2), sulfosulfuron (A15.1) and its salts, such as the sodium salt (A15.2), trifloxysulfuron (A16.1) and its salts, such as the sodium salt (A16.2), azimsulfuron (A17.1) and its salts, such as the sodium salt (A17.2), flazasulfuron (A18.1) and its salts, such as the sodium salt (A18.2), and flucetosulfuron (1-[3-[[[[(4,6-dimethoxy- 2-pyrimidinyl)amino]carbonyl}lamino]sulfonyl}-2-pyridinyl]-2-fluoropropyl methoxyacetate, (A19.1)) and its salts, such as the sodium salt (A 19.2).

Particularly preferred heteroarylsulfonylaminocarbonyltriazolinones are the compounds of the formula (VII) mentioned below which are known, for example, from

WO 03/026427. 0 O

R18 )& J 20 i 0 I \ na

SO, 19 (Vi)

Rs

S CH, fz om | Wa | ook | om

Eo | Wa | ooh | oh

Ez om | Na | oom | oh mz | oh | ta | oom | oh fez | om | Na | ooh | odowon a NS LC I NY

Ez | oh | Na | oo | oon rz | oh | Ma | Oo | adoro oc LC NC ICCC 2 CO ILC IC EC 2 oR | Ne [om [on

EE NC ILC I IC

Rez Om | We | oom | oh a EL NC

Fez [om |W | oom | om

LE I HC I

EE IS LC BE CCN

The active compounds listed above are known, for example, from “The Pesticide

Manual“, 12th edition (2000) (PM) and 13th edition (2003), The British Crop

Protection Council or the literature references given after the individual active compounds.

For the purpose of the present invention, the sulfonamides a) contained as a component in the oil suspension concentrates according to the invention are in each case to be understood as meaning all use forms, such as acids, esters, salts and isomers. such as stereoisomers and optical isomers. Thus, in addition to neutral compounds, their saits with inorganic and/or organic counterions are in each case meant to be included. Thus, sulfonamides are capable of forming salts, for example,

® 14 in which the hydrogen of the -SO,-NH group is replaced by an agriculturally suitable cation. These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or else ammonium salts or salts with organic amines. Salt formation may also take place by addition of an acid to basic groups, such as, for example, amino and alkylamino.

Acids suitable for this purpose are strong inorganic and organic acids, for example

HCI, HBr, H2S04 or HNOs. Preferred esters are the alkyl esters, in particular the

C,-Cqo-alkyl esters, such as methyl esters.

Whenever the term “acyl radical” is used in this description, this means the radical of an organic acid which is formally formed by removing an OH group from the organic acid, for example the radical of a carboxylic acid and radicals of acids derived therefrom, such as thiocarboxylic acid, unsubstituted or N-substituted iminocarboxylic acids or the radicals of carbonic monoesters, unsubstituted or

N-substituted carbaminic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.

An acyl radical is preferably formyl or acyl from the group consisting of CO-R?,

CS-R? CO-0OR?, CS-OR?, CS-SR?, SOR? and SO,R?, where R? is in each case a C4-Cyo-hydrocarbon radical, such as C4-Cqp-alkyl or Ce-Cio-aryl, which is unsubstituted or substituted, for example by one or more substituents from the group consisting of halogen, such as F, Cl, Br, |, alkoxy, haloalkoxy, hydroxyl, amino, nitro, cyano and alkylthio, or R? is aminocarbonyl or aminosulfonyl, where the two lastmentioned radicals are unsubstituted, N-monosubstituted or N,N-disubstituted, for example by substituents from the group consisting of alkyl and aryl.

Acyl is, for example, formyl, haloalkylcarbonyl, alkylcarbonyl, such as (C1-C4)-alkyl- carbonyl, phenylcarbonyl, where the phenyl ring may be substituted, or alkyloxy- carbonyl, such as (C4-C4)-alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, such as (C4-C)-alkylsulfonyl, alkylsulfinyl, such as C1-Cs-(alkylsulfinyl),

N-alkyl-1-iminoalkyl, such as N-(C4-C,4)-1-imino-(C1-C4)-alkyl, and other radicals of organic acids.

A hydrocarbon radical is a straight-chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon radical, for example alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl.

A hydrocarbon radical has preferably 1 to 40 carbon atoms, with preference 1 to 30 carbon atoms; with particular preference, a hydrocarbon radical is alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl.

Aryl is a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl.

A heterocyclic radical or ring (heterocyclyl) can be saturated, unsaturated or heteroaromatic and unsubstituted or substituted; it preferably contains one or more heteroatoms in the ring, preferably from the group consisting of N, O and S; itis preferably an aliphatic heterocyclyl radical having 3 to 7 ring atoms or a heteroaromatic radical having 5 or 6 ring atoms and contains 1, 2 or 3 heteroatoms.

The heterocyclic radical can, for example, be a heteroaromatic radical or ring (heteroaryl), such as, for example, a mono-, bi- or polycyclic aromatic system in which at least one ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or itis a partially or fully hydrogenated radical, such as oxiranyl, oxetanyl, pyrrolidyl, piperidyl, piperazinyl, triazolyl, dioxolanyl, morpholinyl, tetrahydrofuryl. Preference is given to pyrimidinyl and triazinyl. Suitable substituents for a substituted heterocyclic radical are the substituents mentioned further below, and additionally also oxo. The oxo group may also be present at the hetero ring atoms, which may exist in different oxidation states, for example in the case of N and

S.

Substituted radicals, such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heterocyclyl or heteroaryl, are, for example, a substituted radical which is derived from an unsubstituted parent compound, where the substituents are, for example, one or more, preferably 1, 2 or 3, radicals from the group consisting of halogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylisulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl, and unsaturated aliphatic radicals which correspond to the saturated hydrocarbon-containing radicals mentioned, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy, etc. Among the radicals with carbon atoms, preference is given to those having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms.

Preference is generally given to substituents from the group consisting of halogen, for example fluorine and chlorine, (C,-Cs)-alkyl, preferably methyl or ethyl, (C4-C4)-haloalkyl, preferably trifluoromethyl, (C-C,)-alkoxy, preferably methoxy or ethoxy, (C1-C4)-haloalkoxy, nitro and cyano. Particular preference is given here to the substituents methyl, methoxy and chlorine.

Unsubstituted or substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably substituted up to three times, by identical or different radicals, preferably from the group consisting of halogen, (C;-C4)-alkyl, (C4-Cy)-alkoxy, (C1-Cs)-haloalkyl, (C4-C4)-haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.

Cycloalkyl is a carbocyclic saturated ring system having preferably 3-6 carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

The carbon skeleton of the carbon-containing radicals, such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and/or substituted radicals in each case be straight-chain or branched. in these radicals, preference is given to the lower carbon skeletons having, for example, 1 to 6 carbon atoms and, in the case of unsaturated groups, 2 to 6 carbon atoms, unless specified otherwise. Alkyl radicals, also in the composite meanings such as alkoxy,

® 17 haloalkyl, etc., are, for example, methyl, ethyl, n- or isopropyl, n-, iso-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, isohexyl and 1,3-dimethylbutyl, heptyls, such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl; alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals which correspond to the alkyl radicals; alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methyl-but-3-en-1-yl and 1-methyl-but-2-en-1-yl; alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methyl-but-3-yn-1-yl.

Halogen is, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl is alkyl, alkenyl and alkynyl, respectively, which is partially or fully substituted by halogen, preferably by fluorine, chlorine and/or bromine, in particular by fluorine or chlorine, for example CF, CHF,, CHyF, CF3CF,, CH,FCHCI, CCl3,

CHCI,, CH,CH,CI; haloalkoxy is, for example, OCF3, OCHF,, OCH,F, CF3CF20,

OCH,CF3 and OCH2CH,CI; this applies correspondingly to haloalkenyl and other halogen-substituted radicals.

The oil suspension concentrates according to the invention comprise the herbicidally active compounds a) from the group of the sulfonamides in general in amounts of from 0.01 to 50% by weight, preferably from 0.1 to 30% by weight; here and in the entire description, the term “% by weight” refers to the relative weight of the component in question based on the total weight of the formulation, unless defined otherwise.

The oil suspension concentrates according to the invention comprise, as component b), safeners which are suitable for reducing or preventing damage to the crop plant. Suitable safeners are known, for example, from WO-A-96/14747 and the literature cited therein. In the organic solvent, the safeners can be present in suspended and/or dissolved form, preferably in dissolved form.

Suitable safeners are, for example, the following groups of compounds: 1) Compounds of the type of dichlorophenylpyrazoline-3-carboxylic acid (S1), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-(ethoxy-

® 18 carbonyl)-5-methyl-2-pyrazoline-3-carboxylate (S1-1, mefenpyr-diethyl,

PM pp. 781-782), and related compounds, as described in WO 91/07874. 2) Derivatives of dichlorophenylpyrazolecarboxylic acid, preferably compounds such as ethyl 1-(2,4-dichiorophenyl)-5-methylpyrazole-3-carboxylate (S1-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S1-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (S1-4), ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5) and related compounds, as described in EP-A-333 131 and EP-A-269 806. 3) Compounds of the type of the triazolecarboxylic acids (S1), preferably compounds such as fenchlorazole, i.e. ethyl 1-(2,4-dichlorophenyl)-5-trichloro- methyl-(1H)-1,2,4-triazole-3-carboxylate (S1-6, fenchlorazole-ethyl,

PM pp. 385-386), and related compounds (see EP-A-174 562 and

EP-A-346 620). 4) Compounds of the type of the 5-benzyl- or 5-phenyl-2-isoxazoline- 3-carboxylic acid, or the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid, preferably compounds such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline- 3-carboxylate (S1-7) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S1-8) and related compounds, as described in WO 91/08202, or ethyl 5,5-diphenyl- 2-isoxazolinecarboxylate (S1-9, isoxadifen-ethyl) or n-propyl ester (S1-10) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S1-11), as described in the patent application (WO-A-95/07897). 5) Compounds of the type of the 8-quinolineoxyacetic acid (S2), preferably 1-methylhex-1-yl (5-chloro-8-quinolineoxy)acetate (S2-1, cloquintocet-mexyl,

PM pp. 263-264), : 1,3-dimethylbut-1-yl (6-chloro-8-quinolineoxy)acetate (S2-2), 4-allyloxybutyl (5-chloro-8-quinolineoxy)acetate (S2-3), 1-allyloxyprop-2-yl (5-chloro-8-quinolineoxy)acetate (S2-4), ethyl (5-chloro-8-quinolineoxy)acetate (S2-5), methyl (5-chloro-8-quinolineoxy)acetate (S2-6), allyl (5-chloro-8-quinolineoxy)acetate (S2-7), 2-(2-propylideneiminooxy)-1-ethyl (5-chloro-8-quinolineoxy)acetate (S2-8), 2-oxoprop-1-yl (5-chioro-8-quinolineoxy)acetate (S2-9)

and related compounds, as described in EP-A-86 750, EP-A-94 349 and

EP-A-191 736 or EP-A-0 492 366. 6) Compounds of the type of the (5-chloro-8-quinolineoxy)malonic acid, preferably compounds such as diethyl (5-chloro-8-quinolineoxy)malonate, diallyi (5-chloro-8-quinolineoxy)malonate, methyl ethyl (5-chloro-8-quinoline- oxy)malonate and related compounds, as described in EP-A-0 582 198. 7) Active compounds of the type of the phenoxyacetic or -propionic acid derivatives or the aromatic carboxylic acids, such as, for example, 2,4-dichlorophenoxyacetic acid (esters) (2,4-D), 4-chloro-2-methylphenoxy- propionic esters (mecoprop), MCPA or 3,6-dichloro-2-methoxybenzoic acid (esters) (dicamba). 8) Active compounds of the type of the pyrimidines, such as “fenclorim” (PM, pp. 512-511) (= 4,6-dichloro-2-phenylpyrimidine). 9) Active compounds of the type of the dichloroacetamides, which are frequently used as pre-emergence safeners (soil-acting safeners), such as, for example, "dichlormid” (PM, pp. 363-364 (= N,N-diallyl-2,2-dichloroacetamide), "R-29148" (= 3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidone from Stauffer), "benoxacor” (PM, pp. 102-103) (= 4-dichloroacetyl-3,4-dihydro-3-methyl- 2H-1,4-benzoxazine), "PPG-1292" (= N-allyl-N-[(1,3-dioxolan-2-ylymethylldichloroacetamide from

PPG Industries), "DK-24" (= N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide from

Sagro-Chem), "AD-67" or "MON 4660" (= 3-dichloroacetyl-1-oxa-3-azaspiro[4,5]decane from

Nitrokemia or Monsanto), "dicyclonon" or "BAS145138" or "LAB145138" (=(= 3-dichloroacetyl-2,5,5-tri- methyl-1,3-diazabiclyco[4.3.0]Jnonane from BASF) and "furilazol" or "MON 13900" (see PM, 637-638) (= (RS)-3-dichloroacetyl- 5-(2-furyl)-2,2-dimethyloxazolidone). 10) -Active compounds of the type of the dichloroacetone derivatives, such as, for example, "MG 191" (CAS-Reg. No. 96420-72-3) (= 2-dichloromethyl-2-methyl-

® 20 1,3-dioxolane from Nitrokemia).

11) Active compounds of the type of the oxyimino compounds, which are known as seed dressings, such as, for example,

"oxabetrinil" (PM, pp. 902-903) (= (Z)-1,3-dioxolan-2-yimethoxyimino- (phenyl)acetonitrile), which is known as seed dressing safener against metolachior damage,

"fluxofenim” (PM, pp. 613-614) (= 1-(4-chlorophenyl)-2,2,2-trifluoro-

1-ethanone O-(1,3-dioxolan-2-ylmethyl) oxime which is known as seed dressing safener against metolachlor damage, and

"cyometrinil" or "CGA-43089" (PM, p. 1304) (= (Z)-cyanomethoxyimino- (phenyl)acetonitrile), which is known as seed dressing safener against metolachlor damage.

12) Active compounds of the type of the thiazolecarboxylic esters, which are known as seed dressings, such as, for example,

"flurazole" (PM, pp. 590-591) (= benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole- 5-carboxylate), which is known as seed dressing safener against alachlor and metolachlor damage.

13) Active compounds of the type of the naphthalenedicarboxylic acid derivatives, which are known as seed dressings, such as, for example,

"naphthalic anhydride" (PM, p. 1342) (= 1,8-naphthalenedicarboxylic anhydride), which is known as seed dressing safener for corn against thiocarbamate herbicide damage.

14) Active compounds of the type of the chromanacetic acid derivatives, such as, for example,

"CL 304415" (CAS-Reg.

No. 31541-57-8) (= 2-84-carboxychroman-4-yl)acetic acid from American Cyanamid).

15) Active compounds which, in addition to a herbicidal action against harmful plants, also have safener action on crop plants such as, for example, "dimepiperate" or "MY-93" (PM, pp. 404-405) (= S-1-methyl-1-phenylethyi piperidine-1-thiocarboxylate),

"daimuron" or "SK 23" (PM, p. 330) (= 1-(1-methyl-1-phenylethyl)-3-p-tolyl- urea),

® 21 "cumyluron" = "JC-940" (= 3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenyl- ethyl)urea, see JP-A-60087254), "methoxyphenone” or "NK 049" (= 3,3'-dimethyl-4-methoxybenzophenone), "CSB" (= 1-bromo-4-(chloromethylsulfonyl)benzene) (CAS-Reg No. 54091- 06-4 from Kumiai).

Compounds of the type of the acylsulfamoylbenzamides, for example of formula (VIII) below, which are known, for example, from WO 99/16744.

R21

A i R2

Componate | mw

Preferred safeners are mefenpyr, fenchlorazole, isoxadifen, cloquintocet and their

C4-Cio-alkyl esters, in particular mefenpyr-diethyl (S1-1), fenchlorazole-ethyl (S1-6), isoxadifen-ethyl (S1-9), cloquintocet-mexyl (S2-1) and (S3-1).

The oil suspension concentrates according to the invention generally comprise the safeners b) in amounts of from 0.1 to 60% by weight, in particular from 2 to 40% by weight.

The weight ratio of component a) to component b) can vary within a wide range and is generally between 1:100 and 100:1, preferably between 1:10 and 10:1.

® 22

Suitable agrochemically active compounds e), which may be present or not, are, for example, agrochemically active compounds different from components a) and b), such as herbicides, fungicides, insecticides, plant growth regulators and the like. The agrochemically active compounds e) can be present in the organic solvent in ‘5 suspended and/or dissolved form.

Suitable active compounds different from components a) and b) and optionally present as component e) in the oil suspension concentrates according to the invention are preferably herbicidally active compounds, for example:

A) herbicides of the type of the phenoxyphenoxy- and heteroaryloxyphenoxycarboxylic acid derivatives, such as

A1) phenoxyphenoxy- and benzyloxyphenoxycarboxylic acid derivatives, for example methyl 2-(4-(2,4-dichlorophenoxy)phenoxy)propionate (diclofop-methyl), methyl 2-(4-(4-bromo-2-chlorophenoxy)phenoxy)propionate (DE-A 26 01 548), methyl 2-(4-(4-bromo-2-fluorophenoxy)phenoxy)propionate (US-A 4,808,750), methyl 2-(4-(2-chloro-4-trifluoromethylphenoxy)phenoxy)propionate (DE-A 24 33 067), methyl 2-(4-(2-fluoro-4-trifluoromethylphenoxy)phenoxy)propionate (US-A 4,808,750), methyl 2-(4-(2,4-dichlorobenzyl)phenoxy)propionate (DE-A 24 17 487), ethyl 4-(4-(4-trifluoromethylphenoxy)phenoxy)pent-2-enoate, methyl 2-(4-(4-trifluoromethylphenoxy)phenoxy)propionate (DE-A 24 33 067);

A2) "monocyclic" heteroaryloxyphenoxyalkanecarboxylic acid derivatives, for example ethyl 2-(4-(3,5-dichloropyridyl-2-oxy)phenoxy)propionate (EP-A 0 002 925), propargyl 2-(4-(3,5-dichloropyridyl-2-oxy)phenoxy)propionate (EP-A 0 003 114), methyl 2-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy)propionate (EP-A 0003 890), ethyl 2-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy)propionate (EP-A 0 003 890),

® 23 propargyl 2-(4-(5-chloro-3-fluoro-2-pyridyloxy)phenoxy)propionate (EP-A 0 191 736), butyl 2-(4-(5-trifluoromethyl-2-pyridyloxy)phenoxy)propionate (fluazifop-butyl);

A3) bicyclic" heteroaryloxyphenoxyalkanecarboxylic acid derivatives, for example methyl and ethyl 2-(4-(6-chloro-2-quinoxalyloxy)phenoxy)propionate (quizalofopmethyl and quizalofopethyl), methyl 2-(4-(6-fluoro-2-quinoxalyloxy)phenoxy)propionate (see J. Pest. Sci. Vol. 10, 61 (1985)), 2-isopropylideneaminooxyethyl 2-(4-(6-chloro-2-quinoxalyloxy)phenoxy)propionate (propaquizafop), ethyl 2-(4-(6-chlorobenzoxazol-2-yloxy)phenoxy)propionate (fenoxaprop-ethyl), its

D(+) isomer (fenoxaprop-P-ethyl EX) and ethyl 2-(4-(6-chlorobenzothiazol-2-yloxy)- phenoxy)propionate (DE-A 26 40 730), tetrahydro-2-furylmethyl 2-(4-(6-chloroquinoxalyloxy)phenoxy)propionate (EP-A 0 323 727);

B) chloroacetanilides, for example

N-methoxymethyl-2,6-diethyl-chloroacetanilide (alachlor),

N-(3-methoxyprop-2-yl)-2-methyl-6-ethylchloroacetanilide (metolachlor), 2,6-dimethyl-N-(3-methyl-1,2,4-oxadiazol-5-ylmethyl)chloroacetanilide,

N-(2,6-dimethylphenyl)-N-(1-pyrazolylmethyl)chloroacetamide (metazachlor); 0) thiocarbamates, for example

S-ethyl N,N-dipropylthiocarbamate (EPTC),

S-ethyl N,N-diisobutylthiocarbamate (butylate);

D) cyclohexanedione oximes, for example methyl 3-(1-allyloxyiminobutyl)-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-ene- carboxylate (alloxydim),

® 2 2-(1-ethoxyiminobutyl)-5-(2-ethyithiopropyl)-3-hydroxycyclohex-2-ene-1-one (sethoxydim), 2-(1-ethoxyiminobutyl)-5-(2-phenylthiopropyl)-3-hydroxycyclohex-2-ene-1-one (cloproxydim), 2-(1-(3-chloroallyloxy)iminobutyl)-5-(2-ethylthiopropyl)-3-hydroxycyclohex-2-ene- 1-one, 2-(1-(3-chioroallyloxy)iminopropyl)-5-(2-ethylthiopropyl)-3-hydroxycyclohex-2-ene- 1-one (clethodim), 2-(1-ethoxyiminobutyl)-3-hydroxy-5-(thian-3-yl)cyclohex-2-enone (cycloxydim), 2-(1-ethoxyiminopropyl)-5-(2,4,6-trimethylphenyl)-3-hydroxycyclohex-2-ene-1-one (tralkoxydim);

E) benzoylcyclohexanediones, for example 2-(2-chloro-4-methylsulfonylbenzoyl)cyclohexane-1,3-dione (SC-0051, EP-A 0137 963), 2-(2-nitrobenzoyl)-4,4-dimethylcyclohexane-1,3-dione (EP-A 0 274 634), 2-(2-nitro-4-methylsulfonylbenzoyl)-4,4-dimethylcyclohexane-1,3-dione (WO 91/13548 mesotrione);

F) S-(N-aryl-N-alkylcarbamoylmethyl) dithiophosphonates, such as S-[N-(4-chlorophenyl)-N-isopropylcarbamoyimethyl] O,O-dimethyl dithiophosphate (anilophos);

G) alkylazines, such as, for example, described in WO-A 97/08156,

WO-A-97/31904, DE-A-19826670, WO-A-98/15536, WO-A-8/15537,

WO-A-98/15538, WO-A-98/15539 and also DE-A-19828519, WO-A-98/34925,

WO-A-98/42684, WO-A-99/18100, WO-A-99/19309, WO-A-99/37627 and

WO-A-99/65882, preferably those of the formula (G)

Claims

@® WO 2004/054364 PCT/EP2003/013389 Claims

1. An oil suspension concentrate, comprising a) one or more herbicidally active compounds from the group of the sulfonamides in suspended form, b) one or more safeners, C) one or more organic solvents, and d) one or more sulfosuccinates.

2. The oil suspension concentrate as claimed in claim 1 which comprises, as component a), one or more herbicidally active compounds from the group of the phenylsulfonamides, preferably the phenylsulfonylaminocarbonyltriazolinones and phenylsulfonylureas, or of the heteroarylsulfonamides, preferably the heteroarylulfonylaminocarbonyltriazolinones and heteroarylsulfonylureas.

3. The oil suspension concentrate as claimed in claim 1 or 2 which comprises, as component b), one or more safeners from the group consisting of dichlorophenylpyrazoline-3-carboxylic acid and its esters, 5,5-diphenyl-2-isoxazoline- 3-carboxylic acid its esters and 8-quinolineoxyacetic acid and its esters.

4. The oil suspension concentrate as claimed in one or more of claims 1 to 3 which comprises, as component c), one or more solvents from the group consisting of unsubstituted or substituted hydrocarbons, aprotic polar solvents and fatty acid esters.

5. The oil suspension concentrate as claimed in one or more of claims 1 to 4 which comprises, as component d), one or more sulfosuccinatees from the group of the mono- and diesters of sulfosuccinic acid.

6. The oil suspension concentrate as claimed as claimed in one or more of claims 1 to 5, which additionally comprises e) one or more agrochemically active compounds different from a) and b) and/or f) customary auxiliaries and additives.

® 100

7. A process for preparing an oil suspension concentrate as claimed in one or more of claims 1 to 6, which comprises mixing and, if appropriate, grinding the components.

8. A method for controlling harmful plants, which comprises applying an effective amount of an oil suspension concentrate as claimed in one or more of claims 1 to 6 to the harmful plants, to parts of the plants, to plant seeds and/or to the area on which the plants grow.

9. The use of an oil suspension concentrate as claimed in one or more of claims 1 to 6 for controlling harmful plants.

10. The use of an oil suspension concentrate as claimed in one or more of claims 1 to 6 for preparing a herbicidal composition.

11. The use as claimed in claim 10 wherein the herbicidal composition is a suspension, an emulsion, a suspoemulsion or a solution.

12. A herbicidal composition, comprising an oil suspension concentrate as claimed in one or more of claims 1 to 6.

13. A method for controlling harmful plants which comprises applying an effective amount of a herbicidal composition as claimed in claim 12 to the harmful plants, to parts of the plants, to plant seeds and/or to the area on which the plants grow.

14. The use of a herbididal composition as claimed in claim 12 for controlling harmful plants.