WO2014184072A1

WO2014184072A1 - Herbicidal composition comprising a haloalkylsulphonanilide derivative and a safener

Info

Publication number: WO2014184072A1
Application number: PCT/EP2014/059370
Authority: WO
Inventors: William Guy Whittingham
Original assignee: Syngenta Ltd
Current assignee: Syngenta Ltd
Priority date: 2013-05-14
Filing date: 2014-05-07
Publication date: 2014-11-20
Anticipated expiration: 2015-11-14
Also published as: AR096229A1; GB201308612D0; UY35560A

Abstract

The present invention relates to compositions for protecting crop of useful plants from the harmful effects of certain sulphonanilide derivative herbicides as well as methods for protecting crops of useful plants from the harmful effects of these herbicides and methods for combating weeds in crops of useful plants.

Description

HERBICI DAL COMPOSITION COMPRISING A HALOALKYLSULPHONANI LI DE DERIVATIVE AND A SAFENER

The present invention relates to compositions comprising certain herbicidal sulphonanilide derivatives and a safener and methods for protecting cultivated plants from the damaging effects of the herbicidal sulphonanilide derivatives.

It is known that when herbicides are used to control the growth of undesired plants, there may be some damage to the cultivated plants. The amount of damage will depend on a number of factors but, in some cases, the cultivated plants can be protected from the effect of the herbicide by using a compound termed a safener.

Accordingly, the present invention provides a composition for protecting crop plants from the harmful effects of a sulphonanilide derivative herbicide of formula (I)

or a salt or N-oxide thereof wherein

R¹ is H, Ci_₄alkyl, C₃_₅alkenyl, propargyl, Ci_₄alkoxyCi_₂alkyl, Ci_₄alkoxyCi_

2alkoxyCi_₂alkyl, Ci_₄alkylthioCi_₂alkyl, arylCi_₂alkyl optionally substituted by 1-3 groups R²⁰, heteroarylCi_₂alkyl optionally substituted by 1-3 groups R²⁰, phenylthioCi_₂alkyl, arylCi_ ₂alkoxyCi_₂alkyl optionally substituted by 1-3 groups R²⁰, Ci_₅alkylcarbonyl, C₂_

5alkenylcarbonyl, Ci_₄haloalkylcarbonyl, C₃_6cycloalkylcarbonyl, arylcarbonyl optionally substituted by 1-3 groups R²⁰, Ci_ioalkoxycarbonyl; Ci_₄haloalkoxycarbonyl, C_3- salkenyloxycarbonyl, propargyloxycarbonyl, Ci_₄alkoxyCi_₂alkoxycarbonyl, Ci_

4alkylthiocarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R²⁰, arylCi_ ₂alkoxycarbonyl optionally substituted by 1-3 groups R²⁰, aminocarbonyl, Ci_

4alkylaminocarbonyl, di(Ci_₄alkyl)aminocarbonyl, Ci_₄alkylsulphonyl or Ci_ ₄haloalkylsulphonyl and each R is, independently, halogen, Ci_₄alkyl, Ci_₄haloalkyl, Ci_ ₄alkoxy, Ci_₄haloalkoxy, Ci_₂alkoxyCi_₂alkoxy, hydroxy, phenyl or phenoxy;

R² is halogen or methyl; m is 0, 1 or 2; X is oxygen or CR³R⁴;

R³ and R⁴ are independently H, halogen or Ci_₄ alkyl;

Y is oxygen or CR⁵R⁶;

R⁵ and R⁶ are independently H, halogen, Ci_salkyl, Ci_₄haloalkyl, C3_₆Cycloalkyl, Ci_ ₄alkoxyCi_₄alkyl, Ci_₄alkoxy, Ci_₄alkylthio or aryl optionally substituted by 1-3 groups R²¹ or R⁵ and R⁶ together form a C₂_₅alkylene chain or an oxo group and each R²¹ is, independently, halogen, Ci_₄ alkyl, Ci_₄haloalkyl, Ci_₄alkoxy, Ci_₄haloalkoxy, Ci_₂alkoxyCi_ ₂alkoxy, hydroxy, phenyl or phenoxy;

Z is oxygen, CR⁸R⁹ or NR¹⁰;

R⁸ and R⁹ are independently H, halogen, cyano, Ci_₄alkyl, Ci_₄alkoxy, Ci_₄alkylthio, Ci_₄alkoxycarbonyl or aryl optionally substituted by 1-3 groups R²¹ or R⁸ and R⁹ together form a C₂_₅alkylene chain;

R¹⁰ is H, Ci_₄alkyl, aryl optionally substituted by 1-3 groups R²², arylmethyl optionally substituted by 1-3 groups R²², Ci_₄alkylcarbonyl or Ci_₄alkoxycarbonyl and each R²² is, independently, halogen, Ci_₄alkyl, Ci_₄haloalkyl, Ci_₄alkoxy, Ci_₄haloalkoxy, Ci_ ₂alkoxyCi_₂alkoxy, hydroxy, phenyl or phenoxy;

A is CO or S0₂;

W is oxygen, -C(RⁿR¹²)-, -C(R¹³R¹⁴)C(R¹⁵R¹⁶)-, -OC(R¹⁷R¹⁸)- or -C(R¹⁹R³⁰)O-; R¹¹ is halogen, hydroxy, Ci_₄alkyl or Ci_₄alkoxy; R¹² is H or Ci_₄alkyl; R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹ and R³⁰ are independently H, halogen or Ci_₄alkyl; provided that only one of X, Y and Z is oxygen; and provided that when W is oxygen, -OC(R¹⁷R¹⁸)- or -C(R¹⁹R³⁰)O- neither X nor Y is oxygen; and wherein said composition comprises, in addition to the sulphonanilide derivative herbicide of formula (I), at least one safener selected from the group consisting of benoxacor, cloquintocet-mexyl, cyometrinil, the (Z) isomer of cyometrinil, cyprosulfamide (CAS RN 221667-31-8), dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, isoxadifen- ethyl, mefenpyr-diethyl, naphthalic anhydride (CAS RN 81-84-5), oxabetrinil, N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide, an oxylipin A, R- 29148 (CAS RN 52836-31-4) or a 2,2,4,5 -tetrasubstituted 3-dichloroacetyl-l,3-oxazolidine.

Except where more narrow ranges are stated, in general, "alkyl" means a linear saturated monovalent hydrocarbon radical of one to ten carbon atoms or a branched saturated monovalent hydrocarbon radical of three to ten carbon atoms, e.g. methyl, ethyl, n-propyl, z^'so-propyl, n-butyl, sec-butyl, z^'so-butyl, tert-butyl, neopentyl, and the like. Suitably, linear alkyl groups contain one to five, one to four or one to three carbon atoms, more suitably are selected from methyl, ethyl or n-propyl and, most suitably, are methyl or ethyl. Suitably, branched alkyl groups contain three to five or three to four carbon atoms and more suitably are selected from z^'so-propyl, sec -butyl, z^'so-butyl or tert-butyl. It is noted that this definition applies both when the term is used alone and when it is used as part of a compound term, such as "haloalkyl" and similar terms.

Except where more narrow ranges are stated, in general, "cycloalkyl" means a monovalent cyclic hydrocarbon radical of three to six ring carbons e.g. cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Cycloalkyl groups are fully saturated. Suitably, cycloalkyl groups are cyclopropyl or cyclobutyl.

Except where more narrow ranges are stated, in general, "alkenyl" means a linear monovalent unsaturated hydrocarbon radical of two to five carbon atoms, or a branched monovalent hydrocarbon radical of three to five carbon atoms containing at least one double bond, e.g. ethenyl, propenyl and the like. Where appropriate, an alkenyl group can be of either the (E)- or (Z)-configuration. Suitably, linear alkenyl groups contain two to five carbon atoms, more suitably two to four carbon atoms and, most suitably are ethenyl (vinyl), prop-l-enyl (1-propenyl) or prop-2-enyl (allyl). Suitably, branched alkenyl groups contain three to five carbon atoms, more suitably from three to four and, most suitably, are 1- methylethenyl (2-propenyl), 1-methylprop-l-enyl, l-methylprop-2-enyl, 2-methylprop-l- enyl and 2-methylprop-2-enyl (2-methylallyl).

Except where more narrow ranges are stated, in general, "alkylene" means a linear saturated divalent hydrocarbon radical of one to six carbon atoms or a branched saturated divalent hydrocarbon radical of three to six carbon atoms, e.g. methylene, ethylene, propylene, 2-methylpropylene and the like.

"Alkoxy" means a radical -OR, wherein R is alkyl as defined above. Alkoxy groups include, but are not limited to, methoxy, ethoxy, 1-methylethoxy, propoxy, butoxy, 1- methylpropoxy and 2-methylpropoxy. Preferably alkoxy means methoxy or ethoxy.

"Alkoxyalkyl" means a radical -ROR, wherein each R is, independently, alkyl as defined above.

"Alkoxyalkoxy" means a radical -OROR, wherein each R is, independently, alkyl as defined above.

"Alkoxyalkoxyalkyl" means a radical -ROROR, wherein each R is, independently, alkyl as defined above.

"Aryl" or "aromatic ring" refers to an aromatic substituent which may be a single ring or multiple rings which are fused together, linked covalently or linked to a common group such as an ethylene (-CH₂-CH₂-) or methylene (-CH₂-) moiety. Representative examples of aryl include, for example, phenyl, naphthyl, azulenyl, indanyl, indenyl, anthracenyl, phenanthrenyl, tetrahydronaphthyl, biphenyl, diphenylmethyl and 2,2-diphenyl- 1 -ethyl. Preferred aryl groups are phenyl and naphthyl groups.

"Arylalkyl" means a radical -RAryl, wherein R is alkyl as defined above.

"Arylalkoxyalkyl" means a radical -RORAryl, wherein each R is, independently, alkyl as defined above. "Heteroaryl" means a ring system consisting either of a single aromatic ring or of two or more fused rings, at least one of which is aromatic, the other or others independently being saturated, unsaturated or aromatic, containing one, two, three or four ring heteroatoms selected, independently, from N, O or S, the remaining ring atoms being carbon. Examples of heteroaryl groups include, but are not limited to pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl. Examples of bicyclic groups are benzothiophenyl, benzimidazolyl, benzothiadiazolyl, quinolinyl, cinnolinyl, quinoxalinyl and pyrazolo[l,5-a]pyrimidinyl. Preferred heteroaryl groups include pyridyl, pyrimidinyl, furanyl, thiophenyl, thiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, benzothiophenyl, benzimidazolyl and quinolinyl.

"Heteroarylalkyl" means a radical -RHeteroaryl, wherein R is alkyl as defined above.

"Alkylthio" means a radical -SR, wherein R is alkyl as defined above. Alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, tert-butylthio, and the like.

"Alkylthioalkyl" means a radical -RSR, wherein each R is, independently, alkyl as defined above.

"Phenylthioalkyl" means a radical -RSPhenyl, wherein R is alkyl as defined above. "Alkylcarbonyl" means a radical -C(0)R, wherein R is alkyl as defined above. "Alkylthiocarbonyl" means a radical -C(0)SR, wherein R is alkyl as defined above.

"Alkenylcarbonyl" means a radical -C(0)R, wherein R is alkenyl as defined above. "Cycloalkylcarbonyl" means a radical -C(0)R, wherein R is cycloalkyl as defined above.

"Alkoxycarbonyl" means a radical -C(0)OR, wherein R is alkyl as defined above. "Alkenyloxycarbonyl" means a radical -C(0)OR, wherein R is alkenyl as defined above.

"Propargyloxycarbonyl" means a radical -C(0)OR, wherein R is propargyl. "Alkoxyalkoxycarbonyl" means a radical -C(0)OROR, wherein each R is, independently, alkyl as defined above.

"Arylcarbonyl" means a radical -C(0)Aryl.

"Aryloxycarbonyl" means a radical -C(0)OAryl.

"Arylalkoxycarbonyl" means a radical -C(0)ORAryl, wherein R is alkyl as defined above.

"Aminocarbonyl" means a radical -C(0)NH₂.

"Alkylaminocarbonyl" means a radical -C(0)NRH, wherein R is alkyl as defined above.

"Dialkylaminocarbonyl" means a radiacal -C(0)NRR, wherein each R is, independently, alkyl as defined above.

"Alkylsulphonyl" means a radical -S(0)₂R, wherein R is alkyl as defined above.

"Halo" or "halogen" means fluoro, chloro, bromo or iodo, preferably chloro or fluoro.

"Haloalkyl" means alkyl as defined above substituted with one or more of the same or different halo atoms. Examples of haloalkyl groups include, but are not limited to chloromethyl, fluoromethyl, dichloromethyl, difluoromethyl, trichloromethyl,

trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1 ,2-difluoroethyl, 2,2- dif uoroethyl, pentafluoroethyl, 2-chloroethyl, 3-fluoropropyl, 3-chloropropyl, 2,2,2- trifluoro-l-chloroethyl and heptaf uoropropyl.

"Haloalkoxy" means a radical -OR, wherein R is haloalkyl as defined above.

"Haloalkylcarbonyl" means -C(0)R, wherein R is haloalkyl as defined above.

"Haloalkoxycarbonyl" means -C(0)OR, wherein R is haloalkyl as defined above.

"Haloalkylsulphonyl" means -S(0)₂R, wherein R is haloalkyl as defined above.

"Hydroxy" or "hydroxy 1" means an -OH group. "Oxo" means the group =0.

The compounds of formula I may exist in different geometric or optical isomeric forms or in different tautomeric forms. One or more centres of chirality may be present, in which case compounds of the formula I may be present as pure enantiomers, mixtures of enantiomers, pure diastereomers or mixtures of diastereomers. There may be double bonds present in the molecule, such as C=C bonds, in which case compounds of formula I may exist as single isomers or mixtures of isomers. Centres of tautomerisation may be present. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds. Suitable salts include those formed by contact with bases. Suitable salts of the compounds of formula I thus include those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and ammonium cations of the formula N^R'PjR^kR¹) wherein R¹, R", R^k and R¹ are independently selected from hydrogen, Ci_₆ alkyl and Ci_₆ hydroxyalkyl. Salts of the compounds of formula I can be prepared by treatment of compounds of formula I with a metal hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine. Amine salts are often preferred forms of the

compounds of Formula I because they are water-soluble and lend themselves to the preparation of desirable aqueous based herbicidal compositions.

N-oxides are oxidised forms of tertiary amines or oxidised forms of nitrogen containing heteroaromatic compounds. They are described in many books for example in "Heterocyclic N-oxides" by Angelo Albini and Silvio Pietra, CRC Press, Boca Raton, Florida, 1991. In a preferred embodiment, the preferred groups for R¹, R², R³, R⁴, R⁵, R⁶, R⁸, R⁹,

R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R³⁰, R²⁰, R²¹, R²², W, X, Y, Z and A as well as the preferred values for m, in any combination thereof, are as set out below.

In a preferred embodiment, R¹ is as described above and R²⁰ is halogen, Ci_₂alkyl or Ci_₂haloalkyl. In a further preferred embodiment, R¹ is H, Ci_₅alkoxycarbonyl, Ci_ ₄haloalkoxycarbonyl, Ci_₅alkylcarbonyl or trifluoromethylsulphonyl. Most preferably, R¹ is H.

In a preferred embodiment, m is 0. In one embodiment, X is O.

In another embodiment, X is CR³R⁴, and R³ and R⁴ are as defined above. Preferably, R³ is H or Ci_₂alkyl. Preferably, R⁴ is H or Ci_₂alkyl. In this embodiment, most preferably, X is CH₂.

In one embodiment, Y is O. In another embodiment, Y is CR⁵R⁶ and R⁵ and R⁶ are as defined above. Preferably,

R⁵ is H, Ci_₄alkyl, Ci_₂haloalkyl, Ci_₄alkoxy or cyclopropyl. Preferably, R⁶ is H, Ci_₄alkyl or aryl optionally substituted by 1-3 groups R²¹, wherein R²¹ is as described above or, preferably, R²¹ is halogen, Ci_₂alkyl or Ci_₂haloalkyl. Alternatively, R⁵ and R⁶ together form a C₂_₅alkylene chain. In this embodiment, most preferably, Y is CH₂. In one embodiment, Z is O.

In another embodiment, Z is CR⁸R⁹, and R⁸ and R⁹ are as defined above. Preferably, R⁸ is H, halogen or Ci_₂alkyl. Preferably, R⁹ is H, halogen, Ci_₂alkyl or Ci_₂alkylthio. In this embodiment, most preferably, Z is CH₂.

In another embodiment, Z is NR¹⁰ and R¹⁰ is as defined above. Preferably, R¹⁰ is H, Ci_₂alkyl or Ci_₄alkoxycarbonyl.

In one embodiment, W is O.

11 12 11 12

In another embodiment, W is CR R and R and R are as defined above. Preferably, R¹¹ is Ci_₂alkyl. Preferably, R¹² is H or Ci_₂alkyl.

In another embodiment, W is -C(R¹³R¹⁴)C(R¹⁵R¹⁶)- and R¹³, R¹⁴, R¹⁵ and R¹⁶ are as defined above. Preferably, R¹³ is H. Preferably, R¹⁴ is H. Preferably R¹⁵ is H. Preferably, R¹⁶ is H. In this embodiment, most preferably, W is CH₂CH₂. 17 18 17 18

In another embodiment, W is -OCCR 'R¹⁰)- and R and R are as defined above. Preferably, R¹⁷ is H. Preferably, R¹⁸ is H.

In another embodiment, W is -C(R¹⁹R³⁰)O- and R¹⁹ and R³⁰ are as defined above. Preferably, R¹⁹ is H. Preferably R³⁰ is H.

In one embodiment, the invention provides a composition for protecting crop plants from the harmful effects of a sulphonanilide derivative herbicide of formula (I)

or a salt or N-oxide thereof wherein X is oxygen or CR³R⁴;

R³ and R⁴ are independently H, halogen or Ci_₄alkyl; Y is oxygen or CR⁵R⁶;

R⁵ and R⁶ are independently H, halogen, Ci_salkyl, Ci_₄haloalkyl, C3_₆cycloalkyl, Ci_ ₄alkoxyCi_₄alkyl, Ci_₄alkoxy, Ci_₄alkylthio or aryl optionally substituted by 1-3 groups R²¹ or R⁵ and R⁶ together form a C₂_₅alkylene chain or an oxo group and each R²¹ is,

independently, halogen, Ci_₄alkyl, Ci_₄haloalkyl, Ci_₄alkoxy, Ci_₄haloalkoxy, Ci_₂alkoxyCi_ ₂alkoxy, hydroxy, phenyl or phenoxy;

Z is oxygen or CR⁸R⁹;

R⁸ and R⁹ are independently H, halogen, cyano, Ci_₄alkyl, Ci_₄alkoxy, Ci_₄alkylthio, Ci_₄alkoxycarbonyl or aryl optionally substituted by 1-3 groups R²¹ or R⁸ and R⁹ together form a C₂_₅alkylene chain; W is -C(RⁿR¹²)- or -C(R¹³R¹⁴)C(R¹⁵R¹⁶)-;

R¹¹ is halogen, hydroxy, Ci_₄alkyl or Ci_₄alkoxy;

R¹² is H or Ci_₄alkyl;

R¹³, R¹⁴, R¹⁵, R¹⁶, are independently H, halogen or Ci_₄alkyl; provided that only one of X, Y and Z is oxygen; and wherein said composition comprises, in addition to the sulphonanilide derivative herbicide of formula (I), at least one safener selected from the group consisting of benoxacor, cloquintocet-mexyl, cyometrinil, the (Z) isomer of cyometrinil, cyprosulfamide (CAS RN 221667-31-8), dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, isoxadifen- ethyl, mefenpyr-diethyl, naphthalic anhydride (CAS RN 81-84-5), oxabetrinil, N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide, an oxylipin A, R- 29148 (CAS RN 52836-31-4) or a 2,2,4,5 -tetrasubstituted 3-dichloroacetyl-l,3-oxazolidine.

In this embodiment, preferably,

X is oxygen or CR³R⁴; R³ and R⁴ are independently H, halogen or Ci_₄alkyl;

Y is CR⁵R⁶;

Z is CR⁸R⁹;

R⁸ and R⁹ are independently H, halogen, cyano, Ci_₄alkyl, Ci_₄alkoxy, Ci_₄alkylthio, Ci_₄alkoxycarbonyl or aryl optionally substituted by 1-3 groups R²¹ or R⁸ and R⁹ together form a C₂_salkylene chain;

W is -C(RⁿR¹²)- or -C(R¹³R¹⁴)C(R¹⁵R¹⁶)-; R¹¹ is halogen, hydroxy, Ci_₄alkyl or Ci_₄alkoxy; R¹² is H or Ci_₄alkyl;

R¹³, R¹⁴, R¹⁵, R¹⁶, are independently H, halogen or Ci_₄alkyl; More preferably, X is oxygen or CH₂; Y is CH₂; Z is CH₂; and

W is -CH(CH₃)- or -CH₂CH₂-.

In another embodiment, the invention provides a composition for protecting crop plants from the harmful effects of a sulphonanilide derivative herbicide of formula (I)

or a salt or N-oxide thereof wherein X is oxygen or CR³R⁴;

R⁵ and R⁶ are independently H, halogen, Ci_salkyl, Ci_₄haloalkyl, C₃_₆cycloalkyl, Ci_ ₄alkoxyCi_₄alkyl, Ci_₄alkoxy, Ci_₄alkylthio or aryl optionally substituted by 1-3 groups R²¹ or R⁵ and R⁶ together form a C₂_₅alkylene chain or an oxo group and each R²¹ is, independently, halogen, Ci_₄alkyl, Ci_₄haloalkyl, Ci_₄alkoxy, Ci_₄haloalkoxy, Ci_₂alkoxyCi_ ₂alkoxy, hydroxy, phenyl or phenoxy;

Z is oxygen or CR⁸R⁹;

W is -C(RⁿR¹²)- or -C(R¹³R¹⁴)C(R¹⁵R¹⁶)-;

R¹¹ is halogen, hydroxy, Ci_₄alkyl or Ci_₄alkoxy;

R¹² is H or Ci_₄alkyl;

In this embodiment, preferably,

X is oxygen or CR³R⁴;

R⁵ and R⁶ are independently H, halogen, Ci_salkyl, Ci_₄haloalkyl, C3_₆Cycloalkyl, Ci_ ₄alkoxyCi_₄alkyl, Ci_₄alkoxy, Ci_₄alkylthio or aryl optionally substituted by 1-3 groups R²¹ or R⁵ and R⁶ together form a C₂_₅alkylene chain or an oxo group and each R²¹ is, independently, halogen, Ci_₄alkyl, Ci_₄haloalkyl, Ci_₄alkoxy, Ci_₄haloalkoxy, Ci_₂alkoxyCi_ ₂alkoxy, hydroxy, phenyl or phenoxy;

Z is CR⁸R⁹;

W is -C(RⁿR¹²)- or -C(R¹³R¹⁴)C(R¹⁵R¹⁶)-;

R¹¹ is halogen, hydroxy, Ci_₄alkyl or Ci_₄alkoxy;

R¹² is H or Ci_₄alkyl;

R¹³, R¹⁴, R¹⁵, R¹⁶, are independently H, halogen or Ci_₄alkyl; More preferably, X is oxygen or CH₂; Y is oxygen or CH₂; Z is CH₂; and

W is -CH(CH₃)- or -CH₂CH₂-.

The compounds described below are illustrative of compounds for use in the novel safened compositions of the invention. Table 1 below provides 96 compounds designated compounds 1 to 96 respectively, of formula (I).

TABLE 1

Cpd R¹ A m w X Y Z

No

1 H CO 0 0 CH₂ CH₂ CH₂

2 EtOCO CO 0 0 CH₂ CH₂ CH₂

3 'BuOCO CO 0 0 CH₂ CH₂ CH₂ 'BuCHzOCO CO 0 0 CH₂ CH₂ CH₂

EtCO CO 0 0 CH₂ CH₂ CH₂

F₃CS0₂ CO 0 0 CH₂ CH₂ CH₂

H CO 0 0 CH₂ CH Et 0

EtOCO CO 0 0 CH₂ CH Et 0

'BuOCO CO 0 0 CH₂ CH Et 0

'BUCHZOCO CO 0 0 CH₂ CH Et 0

EtCO CO 0 0 CH₂ CH Et 0

F₃CS0₂ CO 0 0 CH₂ CH Et 0

H CO 0 CHMe 0 CH₂ CH₂

EtOCO CO 0 CHMe 0 CH₂ CH₂

'BuOCO CO 0 CHMe 0 CH₂ CH₂ ^tBuCH₂OCO CO 0 CHMe 0 CH₂ CH₂

EtCO CO 0 CHMe 0 CH₂ CH₂

F₃CS0₂ CO 0 CHMe 0 CH₂ CH₂

H CO 0 CHMe 0 CMe₂ CH₂

EtOCO CO 0 CHMe 0 CMe₂ CH₂

'BuOCO CO 0 CHMe 0 CMe₂ CH₂

'BUCHZOCO CO 0 CHMe 0 CMe₂ CH₂

EtCO CO 0 CHMe 0 CMe₂ CH₂

F₃CS0₂ CO 0 CHMe 0 CMe₂ CH₂

H CO 0 CHMe CH₂ 0 CH₂

EtOCO CO 0 CHMe CH₂ 0 CH₂

'BuOCO CO 0 CHMe CH₂ 0 CH₂

'BUCHZOCO CO 0 CHMe CH₂ 0 CH₂ EtCO CO 0 CHMe CH₂ O CH₂

F₃CS0₂ CO 0 CHMe CH₂ O CH₂

H CO 0 CHMe CH₂ CH₂ CH₂

EtOCO CO 0 CHMe CH₂ CH₂ CH₂

'BuOCO CO 0 CHMe CH₂ CH₂ CH₂

'BUC^OCO CO 0 CHMe CH₂ CH₂ CH₂

EtCO CO 0 CHMe CH₂ CH₂ CH₂

F₃CS0₂ CO 0 CHMe CH₂ CH₂ CH₂

H CO 0 CHMe CH₂ CMe₂ CH₂

EtOCO CO 0 CHMe CH₂ CMe₂ CH₂

'BuOCO CO 0 CHMe CH₂ CMe₂ CH₂ ^tBuCH₂OCO CO 0 CHMe CH₂ CMe₂ CH₂

EtCO CO 0 CHMe CH₂ CMe₂ CH₂

F₃CS0₂ CO 0 CHMe CH₂ CMe₂ CH₂

H CO 0 OCH₂ CH₂ CMe₂ CH₂

EtOCO CO 0 OCH₂ CH₂ CMe₂ CH₂

'BuOCO CO 0 OCH₂ CH₂ CMe₂ CH₂

'BUCHZOCO CO 0 OCH₂ CH₂ CMe₂ CH₂

EtCO CO 0 OCH₂ CH₂ CMe₂ CH₂

F₃CS0₂ CO 0 OCH₂ CH₂ CMe₂ CH₂

H CO 0 CH₂CH₂ O CH₂ CH₂

EtOCO CO 0 CH₂CH₂ O CH₂ CH₂

'BuOCO CO 0 CH₂CH₂ O CH₂ CH₂

'BUCHZOCO CO 0 CH₂CH₂ O CH₂ CH₂

EtCO CO 0 CH₂CH₂ O CH₂ CH₂ F₃CS0₂ CO 0 CH₂CH₂ 0 CH₂ CH₂

H CO 0 CH₂CH₂ CH₂ CH₂ 0

EtOCO CO 0 CH₂CH₂ CH₂ CH₂ 0

'BuOCO CO 0 CH₂CH₂ CH₂ CH₂ 0

'BUCHZOCO CO 0 CH₂CH₂ CH₂ CH₂ 0

EtCO CO 0 CH₂CH₂ CH₂ CH₂ 0

F₃CS0₂ CO 0 CH₂CH₂ CH₂ CH₂ 0

H CO 0 CH₂CH₂ CHMe CH₂ 0

EtOCO CO 0 CH₂CH₂ CHMe CH₂ 0

'BuOCO CO 0 CH₂CH₂ CHMe CH₂ 0

'BUCHZOCO CO 0 CH₂CH₂ CHMe CH₂ 0

EtCO CO 0 CH₂CH₂ CHMe CH₂ 0

F₃CS0₂ CO 0 CH₂CH₂ CHMe CH₂ 0

H CO 0 CH₂CH₂ CMe₂ CH₂ 0

EtOCO CO 0 CH₂CH₂ CMe₂ CH₂ 0

'BuOCO CO 0 CH₂CH₂ CMe₂ CH₂ 0

'BUCHZOCO CO 0 CH₂CH₂ CMe₂ CH₂ 0

EtCO CO 0 CH₂CH₂ CMe₂ CH₂ 0

F₃CS0₂ CO 0 CH₂CH₂ CMe₂ CH₂ 0

H CO 0 CH₂CH₂ CH₂ CH₂ NH

EtOCO CO 0 CH₂CH₂ CH₂ CH₂ NH

'BuOCO CO 0 CH₂CH₂ CH₂ CH₂ NH

'BUCHZOCO CO 0 CH₂CH₂ CH₂ CH₂ NH

EtCO CO 0 CH₂CH₂ CH₂ CH₂ NH

F₃CS0₂ CO 0 CH₂CH₂ CH₂ CH₂ NH 79 H CO 0 CH₂CH₂ CH₂ CH₂ CH₂

80 EtOCO CO 0 CH₂CH₂ CH₂ CH₂ CH₂

81 'BuOCO CO 0 CH₂CH₂ CH₂ CH₂ CH₂

82 'BUCHZOCO CO 0 CH₂CH₂ CH₂ CH₂ CH₂

83 EtCO CO 0 CH₂CH₂ CH₂ CH₂ CH₂

84 F₃CS0₂ CO 0 CH₂CH₂ CH₂ CH₂ CH₂

85 H CO 0 CH₂CH₂ CHMe CH₂ CH₂

86 EtOCO CO 0 CH₂CH₂ CHMe CH₂ CH₂

87 'BuOCO CO 0 CH₂CH₂ CHMe CH₂ CH₂

88 'BuCHzOco CO 0 CH₂CH₂ CHMe CH₂ CH₂

89 EtCO CO 0 CH₂CH₂ CHMe CH₂ CH₂

90 F₃CS0₂ CO 0 CH₂CH₂ CHMe CH₂ CH₂

91 H CO 0 CH₂CH₂ CMe₂ CH₂ CH₂

92 EtOCO CO 0 CH₂CH₂ CMe₂ CH₂ CH₂

93 'BuOCO CO 0 CH₂CH₂ CMe₂ CH₂ CH₂

94 ^tBuCH₂OCO CO 0 CH₂CH₂ CMe₂ CH₂ CH₂

95 EtCO CO 0 CH₂CH₂ CMe₂ CH₂ CH₂

96 F₃CS0₂ CO 0 CH₂CH₂ CMe₂ CH₂ CH₂

Preferably, the compound of formula (I) is selected from compound 13, compound 31 or compound 79.

In a preferred embodiment, the safener is selected from benoxacor, cloquintocet- mexyl, isoxadifen-ethyl, cyprosulfamide, fenchlorazole-ethyl, fluxofenim, mefenpyr-diethyl, dichlormid, naphthalic anhydride and N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide. In a more preferred embodiment, the safener is selected from benoxacor,

cloquintocet-mexyl, isoxadifen-ethyl, cyprosulfamide, fluxofenim, mefenpyr-diethyl, dichlormid, naphthalic anhydride and N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide. In a more preferred embodiment, the safener is N-(2-methoxybenzoyl)-4-

[(methylaminocarbonyl)amino]benzenesulfonamide.

In a further more preferred embodiment, the safener is cloquintocet-mexyl.

In a further more preferred embodiment, the safener is benoxacor.

These sulphonanilide compounds used in the safened compositions of the present invention may be made as the skilled man will appreciate by applying and/or adapting as appropriate, the methods described in the prior art (see for example EP2085392, EP1852425, WO2008/102908, EP2336104 and WO2010/119906).

The safeners of the invention are described in The Pesticide Manual, 14^th Edition, 2006. It is noted that the safeners for use in the compositions of the invention may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14^th Edition supra. Thus, the reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO02/34048, etc. N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide is disclosed in EP 0 365 484 A and may be made using the methods described therein. Oxylipins A and methods for their preparation are disclosed in WO 2011/134539 and include oxophytodienoic acids, phytoprostane type I and type II series, cyclopentanones, fatty acid hydroperoxides, mono-, di- and tri-hydroxy fatty acids, keto- or ω-οχο fatty acids, epoxy alcohols of unsaturated fatty acids, fatty acids containing ketodiene and ketotriene groups, alkenals and hydroxyalkenals, fatty acids containing a- and γ-ketol groups and fatty acids containing divinyl ether groups, including salts thereof. 2,2,4,5-tetrasubstituted 3-dichloroacetyl-l,3-oxazolidines and methods for making them are disclosed in Fu et al., Heterocycles, Vol 83(11), 2011, pp. 2607 to 2613.

Preferably the mixing ratio of compound of formula (I) to safener is from 100: 1 to 1 : 100, especially from 20: 1 to 1 :20. In a further aspect, the present invention provides a method for protecting crops of useful plants from the harmful effects of a herbicide of formula (I) as defined herein, which comprises applying to the locus of the useful plants at least one safener selected from the group consisting of benoxacor, cloquintocet-mexyl, cyometrinil, the (Z) isomer of cyometrinil, cyprosulfamide (CAS RN 221667-31-8), dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride (CAS RN 81-84-5), oxabetrinil, N-(2-methoxybenzoyl)-4-

[(methylaminocarbonyl)amino]benzenesulfonamide, an oxylipin A, R-29148 (CAS RN 52836-31-4) or a 2,2,4,5-tetrasubstituted 3-dichloroacetyl-l,3-oxazolidine.

In a still further aspect, the present invention provides a method for combating weeds in crops of useful plants, which comprises treating the useful plants, seeds or cuttings thereof or the locus of the useful plants simultaneously or at separate times with a herbicidally active amount of a compound of formula (I) and at least one safener selected from the group consisting of benoxacor, cloquintocet-mexyl, cyometrinil, the (Z) isomer of cyometrinil, cyprosulfamide (CAS RN 221667-31-8), dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride (CAS RN 81-84-5), oxabetrinil, N-(2-methoxybenzoyl)-4-

Any method of application to weeds/crop of useful plant, or locus thereof, which is routinely used in agriculture may be used, for example application by spray or broadcast method typically after suitable dilution of the composition of the invention.

The term "locus" as used herein includes not only areas where weeds may already be growing, but also areas where weeds have yet to emerge, and also to areas under cultivation with respect to crops of useful plants. Areas under cultivation include land on which the crop plants are already growing and land intended for cultivation with such crop plants.

Crops of useful plants in which compositions of the invention may be used or the methods of the invention applied include perennial crops, such as citrus fruit, grapevines, nuts, oil palms, olives, pome fruit, stone fruit and rubber, and annual arable crops, such as cereals, for example barley and wheat, cotton, oilseed rape, maize (including sweet corn), rice, sorghum, soy beans, sugar beet, sugar cane, sunflowers, ornamentals and vegetables, especially cereals and maize. Preferred crops are cereals, maize, soy bean and rice. More preferred are barley, wheat, maize, sweet corn, rice and soy bean. Most preferred are wheat, maize, rice and soy bean.

Preferred safeners for use in maize are benoxacor, cloquintocet-mexyl, isoxadifen- ethyl, cyprosulfamide, fluxofenim, mefenpyr-diethyl, dichlormid, naphthalic anhydride and N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide. A

particularly suitable safener for use in maize is N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide. A further preferred safener for use in maize is benoxacor.

Preferred safeners for use in wheat are cloquintocet-mexyl, fenchlorazole-ethyl, isoxadifen-ethyl, N-(2-methoxybenzoyl)-4-

[(methylaminocarbonyl)amino]benzenesulfonamide and mefenpyr-diethyl. A particularly suitable safener for use in wheat is cloquintocet-mexyl.

Preferred safeners for use in soy bean are benoxacor, cloquintocet-mexyl, isoxadifen- ethyl, cyprosulfamide, fluxofenim, mefenpyr-diethyl, dichlormid, naphthalic anhydride and N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide. Particularly suitable safeners for use in maize are benoxacor, fluxofenim, mefenpyr-diethyl, dichlormid, naphthalic anhydride and N-(2-methoxybenzoyl)-4-

[(methylaminocarbonyl)amino]benzenesulfonamide. Most preferred are benoxacor or N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.

A preferred safener for use in rice is N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide.

Compositions and methods of the invention may also be used on turf, pasture, rangeland, rights of way etc. In particular they may be used on golf-courses, lawns, parks, sports-fields, race-courses and the like.

Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, ACCase-, GS-, EPSPS-, PPO- and HPPD-inhibitors and synthetic auxins) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield^® summer rape (canola).

Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady^® and LibertyLink^®.

Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK^® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut^® (maize), Yield Gard^® (maize), NuCOTIN33B^® (cotton), Bollgard^® (cotton), NewLeaf^® (potatoes),

NatureGard^® and Protexcta^®. Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate. Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).

The term "weeds" as used herein means any undesired plant, and thus includes not only agronomically important weeds as described below, but also volunteer crop plants. Compounds of formula (I) may be used against a large number of agronomically important weeds. The weeds that may be controlled include both monocotyledonous and dicotyledonous weeds, such as, for example, Alisma spp, Leptochloa chinensis, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solarium, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia, Cyperus and especially Cyperus iria, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola, Veronica, Bidens, Euphorbia, Ischaemum, Polygonum, Helianthus, Panicum, Eriochloa, Brachiaria, Cenchrus, Commelina, Spermacoce, Senna, Tridax, Richardia, Chamaesyce, and Conyza spp.

The compositions according to the invention are suitable for all the conventional methods of application in agriculture, such as, e.g., pre-emergent application, post-emergent application and seed dressing. Depending on the intended use, the safener can be employed for pre-treatment of the seed of the crop plant (dressing of the seed or cuttings) or can be introduced into the soil before or after sowing. However, it can also be applied by itself or together with the herbicide before or after emergence of the plants. The treatment of the plants or seed with the safener can therefore in principle be carried out independently of the time of application of the herbicide. Treatment of the plants by simultaneous application of the herbicide and safener (e.g, as a tank mix) is as a rule preferred. The application rate of safener to herbicide to be applied largely depends of the method of use. For field treatment, as a rule 0.001 to 5.0 kg of safener/ha, preferably 0.01 to 0.5 kg safener/ha and as a rule between 0.005 to 2 kg of herbicide/ha, but preferably between 0.01 to 1 kg/ha are applied. For seed dressing, in general 0.001 to 10 g of safener/kg seed, preferably 0.05 to 2g safener/kg seed are applied. If the safener is applied in liquid form, with soaking of the seed, shortly before sowing, safener solutions which contain the safener in a concentration of 1 to 10,000, preferably 100 to 1000 ppm are expediently used.

The safened compositions of the present invention can be employed in unchanged form as a herbicidal composition. However, as a rule the compositions of the invention are preferably formulated in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances, for example, as described hereinafter. Accordingly, the present invention provides a composition of the invention which further comprises at least one agriculturally acceptable adjuvant or diluent.

The formulated compositions can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil- in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, suspension concentrates, emulsifiable granules, soluble liquids, water- soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. The formulated compositions can be in the form of concentrates which are diluted prior to use, although ready-to-use formulations can also be made. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

The formulated compositions can be prepared e.g. by mixing the active ingredient and safener combination with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof. The active ingredients can also be contained in very fine microcapsules consisting of a polymer.

Microcapsules usually have a diameter of from 0.1 to 500 microns. Typically, they will contain active ingredients in an amount of about from 25 to 95% by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other known polymers.

Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.

The formulation adjuvants that are suitable for the preparation of compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone,

cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid (e.g. butyl acetate, ethyl acetate, isoamyl acetate, amyl acetate), diacetone alcohol, 1,2- dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, Ν,Ν-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d- limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG), propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p- xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, N-methyl-2-pyrrolidone and the like. Water is generally the carrier of choice for diluting the concentrates. Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances, as described, for example, in CFR 180.1001. (c) & (d).

A large number of surface-active substances may advantageously be used in the formulations, especially in those formulations designed to be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as

diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium

dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkylphosphate esters; and also further substances described e.g. in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981.

Further adjuvants that can usually be used in such formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and also liquid and solid fertilisers. An example of such an adjuvant is ammonium sulphate.

The formulated compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10%, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO^® (Rhone-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as active components essentially 80% by weight alkyl esters of fish oils and 15%> by weight methylated rapeseed oil, and also 5%> by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of Cs_22 fatty acids, especially the methyl derivatives of C12-18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being of importance. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery^® 2230 and 2231 (Cognis GmbH). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000. Another preferred adjuvant is Adigor (Syngenta AG) which is a methylated rapeseed oil-based adjuvant.

The application and action of the oil additives can be further improved by

combination with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of W097/34485. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C12-22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol types (Clariant AG). Also preferred are silicone surfactants, especially polyalkyl-oxide -modified heptamethyltriloxanes which are commercially available e.g. as Silwet L-77^®, and also perfluorinated surfactants. The concentration of the surface-active substances in relation to the total additive is generally from 1 to 30% by weight. Examples of oil additives consisting of mixtures of oil or mineral oils or derivatives thereof with surfactants are Edenor ME SU^®, Turbocharge^® (Syngenta AG, CH) or ActipronC (BP Oil UK Limited, GB).

If desired, it is also possible for the mentioned surface-active substances to be used in the formulations on their own, that is to say, without oil additives.

Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture may contribute to an additional enhancement of action. Suitable solvents are, for example, Solvesso^® (ESSO) or Aromatic Solvent^® (Exxon Corporation). The concentration of such solvents can be from 10 to 80% by weight of the total weight. Oil additives that are present in admixture with solvents are described, for example, in US-A-4,834,908. A commercially available oil additive disclosed therein is known by the name MERGE^® (BASF

Corporation). A further oil additive that is preferred according to the invention is SCORE^® (Syngenta Crop Protection Canada).

In addition to the oil additives listed above, for the purpose of enhancing the action of the compositions according to the invention it is also possible for formulations of

alkylpyrrolidones (e.g. Agrimax^®) to be added to the spray mixture. Formulations of synthetic lattices, e.g. polyacrylamide, polyvinyl compounds or poly-l-p-menthene (e.g. Bond , Courier® or Emerald ) may also be used. It is also possible for solutions that contain propionic acid, for example Eurogkem Pen-e-trate^®, to be added to the spray mixture as action-enhancing agent.

Formulated compositions of the invention generally comprise from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of active compound mixture of the compound of formula (I) with a safener and from 1 to 99.9% by weight of a formulation adjuvant which preferably includes from 0 to 25% by weight of a surface-active substance. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

Various methods and techniques are suitable for using safeners or compositions containing them for protecting crop plants from the harmful actions of herbicides of formula I, such as, for example, the following: i) Seed dressing a) Dressing of the seed with the safener formulated as a wettable powder by shaking in a vessel until uniform distribution over the seed surface is achieved (dry dressing). About 1 to 500g of safener (4g to 2kg of wettable powder) per 100 kg of seed are used here. b) Dressing of the seed with an emulsion concentrate of the safener by

method a) (wet dressing). c) Dressing by immersing the seed in a liquor with 100-1000 ppm of safener for 1 to 72 hours and optionally subsequent drying of the seed (immersion dressing).

The dressing of the seed or the treatment of the sprouted seed are of course the preferred methods of application, because the treatment with the safener is directed entirely at the target crop. As a rule, 1 to lOOOg of safener, preferably 5 to 250g of safener are used per 100 kg of seed, it being possible to deviate upwards or downwards from the limit concentrations stated (repeat dressing), depending on the methods, which also allows the addition of other active compounds or micronutrients. ii) Application as a tank mix

A liquid processed mixture of safener and herbicide of formula I (reciprocal ratio of amounts between 10: 1 and 1 : 100) is used, the application rate of herbicide being 0.005 to 5.0 kg per hectare. Such tank mixes are applied before or after sowing. iii) Application into the seed furrow

The safener is introduced into the open sown seed furrow as an emulsion concentrate, wettable powder or as granules. After the seed furrow has been covered, the herbicide is applied by the pre-emergent method in a

conventional method. iv) Controlled release of the safener

The safener is absorbed in solution on to mineral carrier granules orpolymerised granules (urea/formaldehyde) and dried. A coating which allows the safener to be released over a certain period of time can optionally be applied (coated granules).

In particular, preferred formulations have the following composition (% = per cent by weight; active mixture of active compounds means the mixture of a compound of formula I with a safener):

Emulsifiable concentrates

Active mixture of active compounds: 1 to 95%, preferably 60 to 90%

Surface-active agent: 1 to 30%>, preferably 5 to 20%>

Liquid carrier: 1 to 80%>, preferably 1 to 35%

Dusts

Active mixture of active compounds: 0.1 to 10%, preferably 0.1 to 5%

Solid carrier: 99.9% to 90%, preferably 99.9 to 99% Suspension concentrates

Active mixture of active compounds: 5 to 75%, preferably 10 to 50%>

Water: 94 to 24%, preferably 88 to 30%

Surface-active agent: 1 to 40%>, preferably 2 to 30%> Wettable powders

Active mixture of active compounds: 0.5 to 90%>, preferably 1 to 80%>

Surface-active agent: 0.5 to 20%>, preferably 10 to 15%

Solid carrier: 5 to 95%, preferably 15 to 90%

Granules Active mixture of active compounds: 0.1 to 30%, preferably 0.1 to 15%

Solid carrier: 99.5 to 70%, preferably 97 to 85%

Formulation examples for mixtures of herbicides of formula (I) with safeners (% =% by weight; EO = ethylene oxide)

Fl . Emulsifiable concentrates a) b) c) d) active compound mixture 5% 10% 25% 50%

calcium dodecylbenzenesulfonate 6% 8% 6% 8%

castor oil polygly col ether (36 mol of EO) 4% - 4% 4%

octylphenol polyglycol ether (7-8 mol of EO) - 4% - 2%

N-methyl pyrrolidone - - 10% 20%

arom. hydrocarbon mixture (C₉-C 12) 85% 78% 55% 16%

Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.

F2. Solutions a) b) c) d) active compound mixture 5% 10% 50% 90%

l-methoxy-3-(3-methoxy-propoxy)-propane - 20% 20%

polyethylene glycol MW 400 20% 10% -

NMP - - 30% 10% arom. hydrocarbon mixture (C9-C 12) 75% 60%

The solutions are suitable for use in the form of microdrops.

F3. Wettable powders a) b) c) d) active compound mixture 5% 25% 50% 80%

sodium lignosulfonate 4% - 3%

sodium lauryl sulphate 2% 3% - 4%

sodium diisobutylnaphthalene- sulfonate - 6% 5% 6%

octylphenol polyglycol ether (7-8 mol EO) - 1% 2%

highly dispersed silicic acid 1% 3% 5% 10%

kaolin 88% 62% 35% -

The active compound mixture is mixed thoroughly with the adjuvants and the resulting mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

F4. Coated granules a) b) c) active compound mixture 0.1% 5 % 15 %

highly dispersed silicic acid 0.9% 2% 2%

inorganic carrier (diameter 0.1-1 mm) e.g. CaC0₃ or Si0₂ 99.0% 93% 83%

The active compound mixture is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo. F5. Coated granules a) b) c) active compound mixture 0.1% 5 % 15 %

polyethylene glycol MW 200 1.0% 2% 3%

highly dispersed silicic acid 0.9% 1% 2%

inorganic carrier (diameter 0.1-1 mm) e.g. CaC0₃ or Si0₂ 98.0% 92% 80% The finely ground active compound mixture is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. F6. Extruded granules a) b) c) d) active compound mixture 0.1% 3% 5% 15%

sodium lignosulfonate 1.5% 2% 3% 4%

carboxymethylcellulose 1.4% 2% 2% 2%

kaolin 97.0% 93% 90% 79%

The active compound mixture is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

F7. Dusts a) b) c) active compound mixture 0.1 % 1 % 5 %

talcum 39.9% 49% 35%

kaolin 60.0% 50% 60%

Ready-to-use dusts are obtained by mixing the active compound mixture with the carriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) c) d) active compound mixture 3% 10% 25% 50%

ethylene glycol 5% 5% 5% 5%

nonylphenol polygly col ether (15 mol EO) - 1% 2%

sodium lignosulfonate 3% 3% 4% 5%

carboxymethylcellulose 1% 1% 1% 1%

37% aqueous formaldehyde solution 0.2 % 0.2% 0.2% 0.2%

silicone oil emulsion 0.8% 0.8% 0.8% 0.8 %

water 87% 79% 62% 38%

The finely ground active compound mixture is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water. It is often more practical to formulate the active compound of formula I and the safener individually and then to bring them together as a 'tank mix' in water in the application equipment in the desired mixing ratio shortly before application.

The compositions of the present invention can also be used in combination with other active ingredients, e.g. other herbicides, and/or insecticides, and/or acaricides, and/or nematocides, and/or molluscicides, and/or fungicides, and/or plant growth regulators. Such mixtures, and the use of such mixtures to control weeds and/or undesired plant growth form yet further aspects of the invention. For the avoidance of doubt, mixtures of invention also include mixtures of two or more different compounds of formula (I). In particular, the present invention also relates to a composition of the invention which comprises at least one further herbicide in addition to the compound of formula (I) and the safener.

Where a composition of the invention is combined with at least one additional herbicide, the following mixtures of the composition of the invention are particularly preferred: composition of the invention + acetochlor, composition of the invention + acifluorfen, composition of the invention + acifluorf en-sodium, composition of the invention + aclonifen, composition of the invention + acrolein, composition of the invention + alachlor, composition of the invention + alloxydim, composition of the invention + allyl alcohol, composition of the invention + ametryn, composition of the invention +

amicarbazone, composition of the invention + amidosulfuron, composition of the invention + aminocyclopyrachlor, composition of the invention + aminopyralid, composition of the invention + amitrole, composition of the invention + ammonium sulfamate, composition of the invention + anilofos, composition of the invention + asulam, composition of the invention + atrazine, composition of the invention + aviglycine, composition of the invention + azafenidin, composition of the invention + azimsulfuron, composition of the invention + BCPC, composition of the invention + beflubutamid, composition of the invention + benazolin, composition of the invention + bencarbazone, composition of the invention + benfluralin, composition of the invention + benfuresate, composition of the invention + bensulfuron, composition of the invention + bensulfuron-methyl, composition of the invention + bensulide, composition of the invention + bentazone, composition of the invention + benzfendizone, composition of the invention + benzobicyclon, composition of the invention + benzofenap, composition of the invention and bicyclopyrone, composition of the invention + bifenox, composition of the invention + bilanafos, composition of the invention + bispyribac, composition of the invention + bispyribac-sodium, composition of the invention + borax, composition of the invention + bromacil, composition of the invention + bromobutide, composition of the invention + bromophenoxim, composition of the invention + bromoxynil, composition of the invention + butachlor, composition of the invention + butafenacil, composition of the invention + butamifos, composition of the invention + butralin, composition of the invention + butroxydim, composition of the invention + butylate, composition of the invention + cacodylic acid, composition of the invention + calcium chlorate, composition of the invention + cafenstrole, composition of the invention + carbetamide, composition of the invention + carfentrazone, composition of the invention + carfentrazone-ethyl, composition of the invention + CDEA, composition of the invention + CEPC, composition of the invention + chlorflurenol, composition of the invention + chlorflurenol-methyl, composition of the invention + chloridazon, composition of the invention + chlorimuron, composition of the invention + chlorimuron-ethyl, composition of the invention + chloroacetic acid, composition of the invention +

chlorotoluron, composition of the invention + chlorpropham, composition of the invention + chlorsulfuron, composition of the invention + chlorthal, composition of the invention + chlorthal-dimethyl, composition of the invention + cinidon-ethyl, composition of the invention + cinmethylin, composition of the invention + cinosulfuron, composition of the invention + cisanilide, composition of the invention + clethodim, composition of the invention + clodinafop, composition of the invention + clodinafop-propargyl, composition of the invention + clomazone, composition of the invention + clomeprop, composition of the invention + clopyralid, composition of the invention + cloransulam, composition of the invention + cloransulam-methyl, composition of the invention + CMA, composition of the invention + 4-CPB, composition of the invention + CPMF, composition of the invention + 4- CPP, composition of the invention + CPPC, composition of the invention + cresol, composition of the invention + cumyluron, composition of the invention + cyanamide, composition of the invention + cyanazine, composition of the invention + cycloate, composition of the invention + cyclosulfamuron, composition of the invention + cycloxydim, composition of the invention + cyhalofop, composition of the invention + cyhalofop-butyl, composition of the invention + 2,4-D, composition of the invention + 3,4-DA, composition of the invention + daimuron, composition of the invention + dalapon, composition of the invention + dazomet, composition of the invention + 2,4-DB, composition of the invention + 3,4-DB, composition of the invention + 2,4-DEB, composition of the invention +

desmedipham, composition of the invention + desmetryn, composition of the invention + dicamba, composition of the invention + dichlobenil, composition of the invention + ortho- dichlorobenzene, composition of the invention + para-dichlorobenzene, composition of the invention + dichlorprop, composition of the invention + dichlorprop-P, composition of the invention + diclofop, composition of the invention + diclofop-methyl, composition of the invention + diclosulam, composition of the invention + difenzoquat, composition of the invention + difenzoquat metilsulfate, composition of the invention + diflufenican, composition of the invention + diflufenzopyr, composition of the invention + dimefuron, composition of the invention + dimepiperate, composition of the invention + dimethachlor, composition of the invention + dimethametryn, composition of the invention +

dimethenamid, composition of the invention + dimethenamid-P, composition of the invention + dimethipin, composition of the invention + dimethylarsinic acid, composition of the invention + dinitramine, composition of the invention + dinoterb, composition of the invention + diphenamid, composition of the invention + dipropetryn, composition of the invention + diquat, composition of the invention + diquat dibromide, composition of the invention + dithiopyr, composition of the invention + diuron, composition of the invention + DNOC, composition of the invention + 3,4-DP, composition of the invention + DSMA, composition of the invention + EBEP, composition of the invention + endothal, composition of the invention + EPTC, composition of the invention + esprocarb, composition of the invention + ethalfluralin, composition of the invention + ethametsulfuron, composition of the invention + ethametsulfuron-methyl, composition of the invention + ethephon, composition of the invention + ethofumesate, composition of the invention + ethoxyfen, composition of the invention + ethoxysulfuron, composition of the invention + etobenzanid, composition of the invention + fenoxaprop, composition of the invention + fenoxaprop-P, composition of the invention + fenoxaprop-ethyl, composition of the invention + fenoxaprop-P-ethyl, composition of the invention + fenoxasulfone, composition of the invention + fentrazamide, composition of the invention + ferrous sulfate, composition of the invention + flamprop-M, composition of the invention + flazasulfuron, composition of the invention + florasulam, composition of the invention + fluazifop, composition of the invention + fluazifop-butyl, composition of the invention + fluazifop-P, composition of the invention + fluazifop-P-butyl, composition of the invention + fluazolate, composition of the invention + flucarbazone, composition of the invention + flucarbazone-sodium, composition of the invention + flucetosulfuron, composition of the invention + fluchloralin, composition of the invention + flufenacet, composition of the invention + flufenpyr, composition of the invention + flufenpyr-ethyl, composition of the invention + flumetralin, composition of the invention + flumetsulam, composition of the invention + flumiclorac, composition of the invention + flumiclorac-pentyl, composition of the invention + flumioxazin, composition of the invention + flumipropin, composition of the invention + fluometuron, composition of the invention + fluoroglycofen, composition of the invention + fluoroglycofen-ethyl, composition of the invention + fluoxaprop, composition of the invention + flupoxam, composition of the invention + flupropacil, composition of the invention + flupropanate, composition of the invention + flupyrsulfuron, composition of the invention + flupyrsulfuron-methyl-sodium, composition of the invention + flurenol, composition of the invention + fluridone, composition of the invention + flurochloridone, composition of the invention + fluroxypyr, composition of the invention + flurtamone, composition of the invention + fluthiacet, composition of the invention + fluthiacet-methyl, composition of the invention + fomesafen, composition of the invention + foramsulfuron, composition of the invention + fosamine, composition of the invention + glufosinate, composition of the invention + glufosinate- ammonium, composition of the invention + glyphosate, composition of the invention + halosulfuron, composition of the invention + halosulfuron-methyl, composition of the invention + haloxyfop, composition of the invention + haloxyfop-P, composition of the invention + HC-252, composition of the invention + hexazinone, composition of the invention + imazamethabenz, composition of the invention + imazamethabenz-methyl, composition of the invention + imazamox, composition of the invention + imazapic, composition of the invention + imazapyr, composition of the invention + imazaquin, composition of the invention + imazethapyr, composition of the invention + imazosulfuron, composition of the invention + indanofan, composition of the invention + indaziflam, composition of the invention + iodomethane, composition of the invention + iodosulfuron, composition of the invention + iodosulfuron-methyl-sodium, composition of the invention + ioxynil, composition of the invention + ipfencarbazone, composition of the invention + isoproturon, composition of the invention + isouron, composition of the invention + isoxaben, composition of the invention + isoxachlortole, composition of the invention + isoxaflutole, composition of the invention + isoxapyrifop, composition of the invention + karbutilate, composition of the invention + lactofen, composition of the invention + lenacil, composition of the invention + linuron, composition of the invention + MAA, composition of the invention + MAMA, composition of the invention + MCPA, composition of the invention + MCPA-thioethyl, composition of the invention + MCPB, composition of the invention + mecoprop, composition of the invention + mecoprop-P, composition of the invention + mefenacet, composition of the invention + mefluidide, composition of the invention + mesosulfuron, composition of the invention + mesosulfuron-methyl, composition of the invention + mesotrione, composition of the invention + metam, composition of the invention + metamifop, composition of the invention + metamitron, composition of the invention + metazachlor, composition of the invention + metazosulfuron, composition of the invention + methabenzthiazuron, composition of the invention + methazole, composition of the invention + methylarsonic acid, composition of the invention + methyldymron, composition of the invention + methyl isothiocyanate, composition of the invention + metobenzuron, composition of the invention + metobromuron, composition of the invention + metolachlor, composition of the invention + S-metolachlor, composition of the invention + metosulam, composition of the invention + metoxuron, composition of the invention + metribuzin, composition of the invention + metsulfuron, composition of the invention + metsulfuron-methyl, composition of the invention + MK-616, composition of the invention + molinate, composition of the invention + monolinuron, composition of the invention + monosulfuron, composition of the invention + monosulfuron-ester, composition of the invention + MSMA, composition of the invention + naproanilide, composition of the invention + napropamide, composition of the invention + naptalam, composition of the invention + NDA-402989, composition of the invention + neburon, composition of the invention + nicosulfuron, composition of the invention + nipyraclofen, composition of the invention + n-methyl glyphosate, composition of the invention + nonanoic acid, composition of the invention + norflurazon, composition of the invention + oleic acid (fatty acids), composition of the invention + orbencarb, composition of the invention + orthosulfamuron, composition of the invention + oryzalin, composition of the invention + oxadiargyl, composition of the invention + oxadiazon, composition of the invention + oxasulfuron, composition of the invention + oxaziclomefone, composition of the invention + oxyfluorfen, composition of the invention + paraquat, composition of the invention + paraquat dichloride, composition of the invention + pebulate, composition of the invention + pendimethalin, composition of the invention + penoxsulam, composition of the invention +

pentachlorophenol, composition of the invention + pentanochlor, composition of the invention + pentoxazone, composition of the invention + pethoxamid, composition of the invention + petrolium oils, composition of the invention + phenmedipham, composition of the invention + phenmedipham-ethyl, composition of the invention + picloram, composition of the invention + picolinafen, composition of the invention + pinoxaden, composition of the invention + piperophos, composition of the invention + potassium arsenite, composition of the invention + potassium azide, composition of the invention + pretilachlor, composition of the invention + primisulfuron, composition of the invention + primisulfuron-methyl, composition of the invention + prodiamine, composition of the invention + profluazol, composition of the invention + profoxydim, composition of the invention + prohexadione- calcium, composition of the invention + prometon, composition of the invention + prometryn, composition of the invention + propachlor, composition of the invention + propanil, composition of the invention + propaquizafop, composition of the invention + propazine, composition of the invention + propham, composition of the invention + propisochlor, composition of the invention + propoxycarbazone, composition of the invention + propoxycarbazone-sodium, composition of the invention + propyzamide, composition of the invention + prosulfocarb, composition of the invention + prosulfuron, composition of the invention + pyraclonil, composition of the invention + pyraflufen, composition of the invention + pyraflufen-ethyl, composition of the invention +

pyrasulfotole, composition of the invention + pyrazolynate, composition of the invention + pyrazosulfuron, composition of the invention + pyrazosulfuron-ethyl, composition of the invention + pyrazoxyfen, composition of the invention + pyribenzoxim, composition of the invention + pyributicarb, composition of the invention + pyridafol, composition of the invention + pyridate, composition of the invention + pyriftalid, composition of the invention + pyriminobac, composition of the invention + pyriminobac-methyl, composition of the invention + pyrimisulfan, composition of the invention + pyrithiobac, composition of the invention + pyrithiobac-sodium, composition of the invention + pyroxasulfone, composition of the invention + pyroxulam, composition of the invention + quinclorac, composition of the invention + quinmerac, composition of the invention + quinoclamine, composition of the invention + quizalofop, composition of the invention + quizalofop-P, composition of the invention + quizalofop-ethyl, composition of the invention + quizalofop-P-ethyl, composition of the invention + rimsulfuron, composition of the invention + saflufenacil, composition of the invention + sethoxydim, composition of the invention + siduron, composition of the invention + simazine, composition of the invention + simetryn, composition of the invention + SMA, composition of the invention + sodium arsenite, composition of the invention + sodium azide, composition of the invention + sodium chlorate, composition of the invention + sulcotrione, composition of the invention + sulfentrazone, composition of the invention + sulfometuron, composition of the invention + sulfometuron-methyl, composition of the invention + sulfosate, composition of the invention + sulfosulfuron, composition of the invention + sulfuric acid, composition of the invention + tar oils, composition of the invention + 2,3,6-TBA, composition of the invention + TCA, composition of the invention + TCA-sodium, composition of the invention + tebutam, composition of the invention + tebuthiuron, composition of the invention + tefuryltrione, composition of the invention + tembotrione, composition of the invention + tepraloxydim, composition of the invention + terbacil, composition of the invention + terbumeton, composition of the invention + terbuthylazine, composition of the invention + terbutryn, composition of the invention + thenylchlor, composition of the invention + thiazafluron, composition of the invention + thiazopyr, composition of the invention + thifensulfuron, composition of the invention + thiencarbazone, composition of the invention +

thifensulfuron-methyl, composition of the invention + thiobencarb, composition of the invention + tiocarbazil, composition of the invention + topramezone, composition of the invention + tralkoxydim, composition of the invention + triafamone, composition of the invention + tri-allate, composition of the invention + triasulfuron, composition of the invention + triaziflam, composition of the invention + tribenuron, composition of the invention + tribenuron-methyl, composition of the invention + tricamba, composition of the invention + triclopyr, composition of the invention + trietazine, composition of the invention + trifloxysulfuron, composition of the invention + trifloxysulfuron-sodium, composition of the invention + trifluralin, composition of the invention + triflusulfuron, composition of the invention + triflusulfuron-methyl, composition of the invention + trifop, composition of the invention + trifop-methyl, composition of the invention + trihydroxytriazine, composition of the invention + trinexapac-ethyl, composition of the invention + tritosulfuron, composition of the invention + [3-[2-chloro-4-fluoro-5-(l-methyl-6-trifluoromethyl-2,4-dioxo-l,2,3,4- tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy] acetic acid ethyl ester (CAS R 353292- 31-6).

Whilst compositions comprising a safener and a two-way mixture of a compound of formula (I) and another herbicide are explicitly disclosed above, the skilled man will appreciate that the invention extends to three-way, and further multiple combinations comprising the above two-way mixtures.

Particularly preferred mixture partners for use in the compositions of the invention are: acetochlor, ametryn, amicarbazone, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)-2-pyridinecarboxylic acid methyl ester, atrazine, bicyclopyrone, clethodim, clodinafop, clodinafop-propargyl, clomazone, 2,4-D, dicamba, diflufenican, dimethachlor, dimethenamid, dimethenamid-P, diuron, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, flucarbazone, flucarbazone-sodium, flufenacet, flumetsulam, flumioxazin, fomesafen, foramsulfuron, glufosinate, glufosinate- ammonium, glyphosate, halauxifen, halauxifen-methyl, haloxyfop, haloxyfop-P, hexazinone, imazamethabenz, imazamethabenz -methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, iodosulfuron, iodosulfuron-methyl-sodium, ipfencarbazone, isoxaflutole, mesosulfuron, mesosulfuron-methyl, mesotrione, metazachlor, metolachlor, S-metolachlor, metribuzin, metsulfuron, metsulfuron-methyl, nicosulfuron, oxyflurfen, paraquat, paraquat dichloride, pinoxaden, prosulfocarb, pyroxasulfone, quizalofop, quizalofop-P, quizalofop- ethyl, quizalofop-P-ethyl, rimsulfuron, saflufenacil, simazine, sulfentrazone, tebuthiuron, tembotrione, terbuthylazine, thiencarbazone, and triasulfuron.

More particularly preferred mixture partners for use in the compositions of the invention are: acetochlor, ametryn, atrazine, bicyclopyrone, glufosinate, glufosinate- ammonium, glyphosate, isoxaflutole, mesotrione, metolachlor, S-metolachlor,

pyroxasulfone, tembotrione, terbuthylazine and topramezone.

For the avoidance of doubt, even if not explicitly stated above, the mixing partners may also be in the form of any suitable agrochemically acceptable ester or salt, as mentioned e.g. in The Pesticide Manual, Thirteenth Edition, British Crop Protection Council, 2003. The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1 : 500 to 1000: 1.

Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example. It will be appreciated that modification of detail may be made without departing from the scope of the invention. For the avoidance of doubt, where a literary reference, patent application, or patent, is cited within the text of this application, the entire text of said citation is herein incorporated by reference.

EXAMPLES

EXAMPLE 1 Pre-Emergence Crop Safening

Maize (variety Garland), rice (variety IR64), soya (variety Nikko) and winter wheat (variety Hereward) seeds were sown into standard soil in pots.

24 Hours after the seeds were sown they were sprayed with an aqueous spray solution containing a compound of formula (I) alone and in combination with a number of different herbicide safeners. All the compounds used for the spray solution were present as technical material and the safeners were either an EC, SC or WP formulation respectively or technical material.

The spray solution was applied with a cabinet tracksprayer with a flat fan nozzle (Teejet 1 1002VS) and an application volume of 200L/ha (at 2 bar).

The test plants were then grown on in a glasshouse under controlled conditions (at 24/18 °C day/night; 16 hours light; 65% humidity) and watered twice a day. After 21 days the test was evaluated for general crop injury (100% equals total damage to plant; 0%> equals no damage to plant). Results are shown below in Tables 2-5 as the mean % visual phytotoxicity of two replicates. TABLE 2 Percentage damage caused to maize by compounds of formula (I) alone and in the presence of a number of safeners

*Safener A is N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide **Concep III contains 74.3% fluxofenim.

TABLE 3 Percentage damage caused to rice by compounds of formula (I) alone and in the presence of a number of safeners

50g/ha Cloquintocet-mexyl + 7.5 20 0

50g/ha Safener A*

TABLE 4 Percentage damage caused to soya by compounds of formula (I) alone and in the presence of a number of safeners

*Safener A is N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide ** Concep III contains 74.3% fluxofenim.

TABLE 5 Percentage damage caused to wheat by compounds of formula (I) alone and in the presence of a number of safeners

Compound Compound 13 Compound 31

Rate 200 g/ha 1000 g/ha

Safener

None 12.5 70 100 g/ha Benoxacor 10 52.5 lOOg/ha Cloquintocet-mexyl 0 12.5

lOOg/ha Isoxadifen-ethyl 10 30

lOOg/ha Cyprosulfamide 5 45

lOOg/ha Safener A* 5 17.5 lOOg/ha Concep IIP* 0 30

lOOg/ha Mefenpyr-diethyl 5 40

lOOg/ha Dichlormid 10 52.5 lOOg/ha Naphthalic 10 22.5 anhydride

50g/ha Cloquintocet-mexyl + 0 10

50g/ha Safener A*

Claims

1. A composition for protecting crop plants from the harmful effects of a sulphonanilide derivative herbicide of formula (I)

o o

or a salt or N-oxide thereof wherein

2alkoxyCi_₂alkyl, Ci_₄alkylthioCi_₂alkyl, arylCi_₂alkyl optionally substituted by 1-3 groups R²⁰, heteroarylCi_₂alkyl optionally substituted by 1-3 groups R²⁰,

phenylthioCi_₂alkyl, arylCi_₂alkoxyCi_₂alkyl optionally substituted by 1-3 groups R²⁰, Ci.salkylcarbonyl, C₂_salkenylcarbonyl, Ci_₄haloalkylcarbonyl, C3_

6cycloalkylcarbonyl, arylcarbonyl optionally substituted by 1-3 groups R²⁰, Ci_ i oalkoxycarbonyl; C i _₄haloalkoxycarbonyl, C3_₅alkenyloxycarbonyl,

propargyloxycarbonyl, C i _₄alkoxyC i _₂alkoxycarbonyl, C i _₄alkylthiocarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R²⁰, arylCi_₂alkoxycarbonyl optionally substituted by 1-3 groups R²⁰, aminocarbonyl, Ci_₄alkylaminocarbonyl, di(Ci_₄alkyl)aminocarbonyl, Ci_₄alkylsulphonyl or Ci_₄haloalkylsulphonyl and each R²⁰ is, independently, halogen, Ci_₄alkyl, Ci_₄haloalkyl, Ci_₄alkoxy, Ci_₄haloalkoxy, Ci_₂alkoxyCi_₂alkoxy, hydroxy, phenyl or phenoxy;

R² is halogen or methyl; m is 0, 1 or 2;

X is oxygen or CR³R⁴;

R⁵ and R⁶ are independently H, halogen, Ci_salkyl, Ci_₄haloalkyl, C3_₆cycloalkyl, Ci_ ₄alkoxyCi_₄alkyl, Ci_₄alkoxy, Ci_₄alkylthio or aryl optionally substituted by 1-3 groups R²¹ or R⁵ and R⁶ together form a C₂_₅alkylene chain or an oxo group and each R²¹ is, independently, halogen, Ci_₄alkyl, Ci_₄haloalkyl, Ci_₄alkoxy, Ci_₄haloalkoxy, Ci_₂alkoxyCi_₂alkoxy, hydroxy, phenyl or phenoxy;

Z is oxygen, CR⁸R⁹ or NR¹⁰;

R¹⁰ is H, Ci_₄alkyl, aryl optionally substituted by 1-3 groups R²², arylmethyl optionally substituted by 1-3 groups R²², Ci_₄alkylcarbonyl or Ci_₄alkoxycarbonyl and each R²² is, independently, halogen, Ci_₄alkyl, Ci_₄haloalkyl, Ci_₄alkoxy, Ci_ ₄haloalkoxy, Ci_₂alkoxyCi_₂alkoxy, hydroxy, phenyl or phenoxy;

A is CO or S0₂;

W is oxygen, -C(RⁿR¹²)-, -C(R¹³R¹⁴)C(R¹⁵R¹⁶)-, -OC(R¹⁷R¹⁸)- or -C(R¹⁹R³⁰)O-; R¹¹ is halogen, hydroxy, Ci_₄alkyl or Ci_₄alkoxy; R¹² is H or Ci_₄alkyl;

R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹ and R³⁰ are independently H, halogen or Ci_₄alkyl; provided that only one of X, Y and Z is oxygen; and provided that when W is oxygen, -OC(R¹⁷R¹⁸)- or -C(R¹⁹R³⁰)O- neither X nor Y is oxygen; and wherein said composition comprises, in addition to the sulphonanilide derivative herbicide of formula (I), at least one safener selected from the group consisting of benoxacor, cloquintocet-mexyl, cyometrinil, the (Z) isomer of cyometrinil, cyprosulfamide (CAS RN 221667-31-8), dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride (CAS R 81-84-5), oxabetrinil, N-(2-methoxybenzoyl)-4-

[(methylaminocarbonyl)amino]benzenesulfonamide, an oxylipin A, R-29148 (CAS RN 52836-31-4) or a 2,2,4, 5-tetrasubstituted 3-dichloroacetyl-l,3-oxazolidine.

2. The composition of claim 1, wherein R²⁰ is halogen, Ci_₂alkyl or Ci_₂haloalkyl.

3. The composition of claim 1, wherein R¹ is H, Ci_salkoxycarbonyl, Ci_ 4haloalkoxycarbonyl, Ci_salkylcarbonyl or trifluoromethylsulphonyl.

4. The composition of any one of the preceding claims, wherein m is 0.

5. The composition of any one of the preceding claims, wherein X is O.

6. The composition of any one of claims 1 to 4, wherein X is CR³R⁴.

7. The composition of claim 6, wherein R³ is H or Ci_₂alkyl.

8. The composition of claim 6 or claim 7, wherein R⁴ is H or Ci_₂alkyl.

9. The composition of any one of the preceding claims, wherein Y is O.

10. The composition of any one of claims 1 to 8, wherein Y is CR⁵R⁶.

11. The composition of claim 10, wherein R⁵ is H, Ci_₄alkyl, Ci_₂haloalkyl, Ci_₄alkoxy or cyclopropyl.

12. The composition of claims 10 or claim 11, wherein R⁶ is H, Ci_₄alkyl or aryl optionally substituted by 1-3 groups R²¹.

13. The composition of claim 12, wherein R²¹ is halogen, Ci_₂alkyl or Ci_₂haloalkyl.

14. The composition of claim 10, wherein R⁵ and R⁶ together form a C₂_₅alkylene chain.

15. The composition of any one of claims 1 to 14, wherein Z is CR⁸R⁹.

16. The composition of claim 15, wherein R⁸ is H, halogen or Ci_₂alkyl.

17. The composition of claim 15 or 16, wherein R⁹ is H, halogen, Ci_₂alkyl or Ci_ 2alkylthio.

18. The composition of any one of claims 1 to 17, wherein W is CRⁿR¹² or - C(R¹³R¹⁴)C(R¹⁵R¹⁶)-.

19. The composition of claim 18, wherein R¹¹ is Ci_₂alkyl.

20. The composition of claim 19, wherein R¹² is H or Ci_₂alkyl.

21. The composition of claim 18, wherein R¹³, R¹⁴, R¹⁵, R¹⁶ are each H.

22. The composition of any one of claims 1 to 21, wherein the safener is benoxacor, cloquintocet-mexyl or N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide.

23. A method for protecting crops of useful plants from the harmful effects of a herbicide of formula (I) as defined in any one of claims 1 to 35, which comprises applying to the locus of the useful plants at least one safener selected from the group consisting of benoxacor, cloquintocet-mexyl, cyometrinil, the (Z) isomer of cyometrinil, cyprosulfamide (CAS RN 221667-31-8), dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride (CAS RN 81-84-5), oxabetrinil, N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide, an oxylipin A, R-29148 (CAS RN 52836-31-4) or a 2,2,4,5 -tetrasubstituted 3-dichloroacetyl-l,3-oxazolidine.

24. A method for combating weeds in crops of useful plants, which comprises treating the useful plants, seeds or cuttings thereof or the locus of the useful plants simultaneously or at separate times with a herbicidally active amount of a compound of formula (I) as defined in any one of claims 1 to 35 and at least one safener selected from the group consisting of benoxacor, cloquintocet-mexyl, cyometrinil, the (Z) isomer of cyometrinil, cyprosulfamide (CAS RN 221667-31-8), dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride (CAS RN 81-84-5), oxabetrinil, N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide, an oxylipin A, R-29148 (CAS RN 52836-31-4) or a 2,2,4,5 -tetrasubstituted 3-dichloroacetyl-l,3-oxazolidine.

25. The method of claim 23 or 24, wherein the safener is is benoxacor, cloquintocet-mexyl or N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.

26. The method of any one of claims 23 to 25, wherein the crop is maize, rice, soya or wheat.