WO1998031226A1 - Herbicidal agent - Google Patents

Abstract

The invention relates to a selective herbicidal agent for combating grasses and weeds in crop plant cultivations, containing: a) a herbicidally active quantity of a herbicide of formula (I), and b) a herbicidally antagonistic quantity of a safener of formula (IIa), a safener of formula (IIb), a safener of formula (IIc), a safener of formula (IId), a safener of formula (IIe), a safener of formula (IIf) or a safener of formula (IIg), wherein the substituents have the meaning assigned to them in claim 1.

Description

Herbicidal agent

The present invention relates to new selective herbicidal compositions for controlling grasses and weeds in crops of useful plants, in particular in crops of cereals, maize,

Rice and soybeans, which contain a herbicide and a safener (antidote, antidote) and which protect the crops, but not the weeds, from the phytotoxic ^" effects of

Preserve herbicides, as well as the use of this herbicide in

Crop crops.

When using herbicides, e.g. Depending on the dose of the herbicide and the type of application, the crop, the soil conditions and the climatic conditions, such as exposure time, temperature and rainfall, the crops are also significantly damaged. In order to counter this and similar problems, various substances have already been proposed as safeners which are capable of antagonizing the damaging effect of the herbicide on the crop, that is to say of protecting the crop from it, but the herbicide action on the weeds to be combated is practically not affected. It has been shown that the proposed safeners often have a very specific effect both with regard to the crop plants and with regard to the herbicide and in some cases also depending on the type of application, that is to say that a particular safener is often only suitable for a particular crop and a particular class of herbicide or a specific herbicide.

It has now been found that known from US-A-4,601,745, EP-A-0 492 366, EP-A-0 094 349, WO 91/7874 and WO 94/987 for protecting crops from the phytotoxic effect of Suitable herbicides are those described in WO 95/25730, DE 4 026 177, WO 91/10653, US-A-5,561,101 and US-A-5,506,192.

The invention thus proposes a selective herbicidal composition which is characterized in that, in addition to customary inert formulation auxiliaries such as carriers, solvents and wetting agents, it is a mixture of active ingredients

a) a herbicidally effective amount of a herbicide of the formula I. / W (l). \

wherein

W the groups

X is the group -C (Q ₁ ) (Q ₂ ) -;

Y represents the group -C (0) -A;

A is hydrogen, hydroxy, O ^" M ⁺ , OR ₂ , NR ₂₈ R ₂₉ or together with Q ₂ -O-;

Q, hydrogen, hydroxy, halogen, cyano. C (0) NH ₂ , -C ₅ alkoxycarbonyl, OR ₅₈ or -

OC (0) -R ₅₇ ;

Q _{2 is} hydrogen, hydroxy or together with Q = 0 or = NH;

M ⁺ Li ⁺ , Na ⁺ , K ⁺ , 1/2 Mg ²⁺ , 1/2 Ca ²⁺ or N ⁺ R ₃₀ R ₃₁ R ₃₂ R ₃₃ ;

R ₂₂ and R ₂₃ independently of one another hydrogen, halogen, CC ₅ -alkyl, trifluoromethyl, -O-

(C -C ₅ ) alkyl or C ₃ -C ₅ cycloalkyl; or

R ₂₂ and R ₂ together form a butadienylene chain which is substituted by halogen, methyl, methoxy,

-S (0) _r CH ₃ , trifluoromethyl or trifluoromethoxy may be substituted and fused at positions 3 and 4;

R ₅₉ and R ₆ o independently of one another are hydrogen, halogen, CC ₅ -alkyl, trifluoromethyl, -O-

(C ₁ -C ₅ ) alkyl, C ₃ -C ₅ cycloalkyl, -S (0) _q -q-C5 alkyl, C ₃ - alkenyl, - -alkynyl, C ₃ -C ₅ -

Cycloalkyl, nitro, amino, cyano, -COO-Q- alkyl, -NH-C C ₅ alkyl, N (-C ₅ alkyl) ₂ , C ₃ -

C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy, benzyloxy, hydroxy, phenyl, thienyl, furyl, pyrazolyl,

Oxazolyl, pyridyl, or by halogen, -C ₄ alkyl, dC ₄ alkoxy, Cι-C ₄ alkylthio, C _T C ^ -

Alkylsulfinyl, -CC ₄ alkylsulfonyl, C ₁ -C ₄ haloalkoxy or trifluoromethyl substituted

Phenyl, thienyl, furyl, pyrazolyl, oxazolyl or pyridyl; or phenyloxy, thienyloxy,

Furyloxy, pyrazolyloxy, oxazolyloxy, pyridyloxy or by halogen, -C ^ alkyl, -C ₄ -

Alkoxy, C C4-alkylthio, C ₁ -C ₄ -alkylsulfinyl, CC ₄ -alkyisulfonyl, -CC -haloalkoxy or

Trifluoromethyl substituted phenyloxy, thienyloxy, furyloxy, pyrazolyloxy, oxazolyloxy or pyridyloxy; or phenylthio, thienylthio, furylthio, pyrazolylthio, oxazolylthio or pyridylthio; or phenylthio, thienylthio, furylthio substituted by halogen, CC ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, GC ₄ - alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, CC ₄ haloalkoxy or trifluoromethyl, Pyrazolylthio, Oxazolylthio or Pyridylthio, or the group Q ₃

(Q), wherein E _{2 is} methine, -C (halogen) - or nitrogen;

R _{64 is} hydrogen, -0- (C ₁ -C ₅ ) alkyl, -O- - -alkenyl, -O- - -alkynyl, CC ₃ -haloalkoxy or Ci-Cs-alkyl;

R ₆₅ C, -C ₃ -alkyl, C ₃ -C ₅ -cycloalkyl, -0- (C) -alkyl, -OQQ-alkenyl, -OQQ-alkinyi, Q-

Cs-haloalkoxy, halogen or trifluoromethyl;

R _{JS is} hydrogen, -0- (QC ₅ ) alkyl, -OQQ-alkenyl, -OQQ-alkynyl, C, -C ₅ -haloalkoxy or QQ-alkyl;

R ₂₆ QQ-alkyl, C ₃ -C ₅ cycloalkyl, -0- (QQ) alkyl, -0-C ₃ -C ₅ alkenyl, -O- - -alkynyl, Q-

Q-haloalkoxy, halogen or trifluoromethyl;

R ₅₈ QQ alkyl, QQ alkenyl, C ₃ -C 5 cycloalkyl, halogen or trifluoromethyl;

R ₂₇ CC ₈ alkyl, C -C ₈ cycloalkyl, QQ alkenyl, QQ alkynyl, benzyl, C 1 -C ₅ haloalkyl,

Q-Q-haloalkenyl,

R _{2g is} hydrogen, -CC-alkyl, QQ-alkenyl or QQ-alkynyl;

R _{29 is} hydrogen, QQ-alkyl, QQ-alkenyl, QQ-alkynyl, or by halogen, cyano,

Cyclopropyl, phenyl, furyl, thienyl, naphthyl, pyridyl, -X ₂ - (CC ₅ -alkyl), hydroxy, amino, -

NH (CC ₅ alkyl), N (CC ₅ alkyl) ₂ or -CH (X ₃ R ₃₄ ) (X ₄ R ₅₆ ) substituted QQ-alkyl, QQ-

Alkenyl or Q-Q-alkynyl; Phenyl, pyridyl or benzyl or by halogen, Q-Q-alkyl, Q-

Q-haloalkyl, -S (0) _p -C-C ₅ alkyl, nitro, cyano or trifluoromethoxy substituted

Phenyl, pyridyl or benzyl; or the group in which

for hydrogen,

QQ-alkyl, QQ-alkenyl, phenyl, benzyl or QQ-alkynyl; R ₆₂ for hydrogen, QQ- Alkyl, or by hydroxy, SCH ₃ , SH, benzyl, indol-3-yl, 4-hydroxybenzyl, COOR ^ ₃ ,

C (0) NH ₂ , amino, or imidazol-5-yl substituted QQ-alkyl; and

R_ ₃ for hydrogen, Q-Cg-alkyl, QQ-alkenyl, QQ-alkynyl, -NH (QQ-alkyl), -N (QQ-

Alkyl) ₂ , phenylamino, the phenyl group being substituted by halogen, QQ-alkyl, QQ-

Haloalkyl,

QQ-alkylthio, QC ₅ -alkylsulfonyl, QQ-alkylsulfinyl, nitro, cyano or trifluoromethoxy may be substituted, morpholino or piperidino;

X ₂ , X ₃ and X ₄ independently of one another oxygen or sulfur; p, q, r, s and t independently of one another 0, 1 or 2;

R ₂₈ and R ₂ 9 together form a QQ alkylene chain which is substituted by halogen, methyl, methoxy,

-S (0) _s CH ₃ , trifluoromethyl or trifluoromethoxy may be substituted and may be interrupted by -O-, -NH- or -N (C ₂ -Q-alkyl) -;

R ₃₄ and R ₅ 0 independently of one another QQ-alkyl; or

R ₃₄ and R ₅ 6 together form a C ₂ -C ₃ alkylene chain;

R ₅₇ QQ-AlkyL Q-Cg-alkoxy, Q-Cg-haloalkyl, Ci-Cg-haloalkoxy, C -C ₈ cycloalkyl,

Q-Q-alkenyl, Q-Q-alkynyl, phenyl or benzyl or by halogen, Q-Q-alkyl, Q-Q-

Haloalkyl, -S (0) _t -QQ-alkyl, nitro, cyano or trifluoromethoxy substituted phenyl or benzyl;

Q the group

Egg methine, -C (halogen) - or nitrogen; or

R ₆ and egg together -CH ₂ -CH ₂ -;

R ₃ o, R ₃ ι, R ₃₂ and R ₃₃ independently of one another hydrogen, QQ-alkyl or QQ-alkyl substituted by hydroxy or methoxy; or

R ₃₀ and R ₃ ι or R ₃₀ , R ₃ ι and R ₃₂ or R ₃₀ , R _{3 l} , R ₂ and R together form a QQ

Alkylene chain, which can be interrupted by -O-, -NH- or -N (QQ-alkyl) - mean; and b) a herbicide-antagonistically effective amount of a safener of the formula Ha

wherein Ri is hydrogen, Ci-Cg-alkyl or QQ-alkyl substituted by QQ-alkoxy or QQ-alkenyloxy and X is hydrogen or chlorine; of a safener of the formula

wherein E is nitrogen or methine;

R ₂ QC ₄ alkyl;

R _{3 is} -CC1 ₃ or phenyl optionally substituted by halogen, and

R ₄ and R _{5 are} independently hydrogen or halogen; a Formula He safener

wherein R ₆ and R _{7 are} independently hydrogen or halogen, and Rg, R9 and R _{10 are} independently C 1 -C ₄ alkyl, a safener of the formula Ild

wherein

A ₂ for a group

stands,

Rι ₃ and Rι independently of one another hydrogen, Ci-Cg-alkyl, C ₃ -C ₈ cycloalkyl, QQ-

Alkenyl, QQ-alkynyl, or by C -C ₄ alkoxy or

substituted QC ₄ alkyl; or Rι ₃ and Rι ₄ form

together a QQ-Alkylenbrückε, which by oxygen, sulfur, SO, S0 ₂ , NH or -

N (Q-Qalkyl) - can be interrupted,

Ri ₅ for hydrogen or QQ alkyl;

Rn for hydrogen, halogen, cyano, trifluoromethyl, nitro, Q-Q-alkyl, Q-Q-alkoxy, Q-

C ₄ -alkylthio, QC ₄ -alkylsulfinyl, -C-C ₄ -alkylsulfonyl, -COOR ,, -CONR _k R _m , -COR _n , -

S0 ₂ NR _k R _m or -OS0 ₂ -QQ-alkyl;

R _g for hydrogen, halogen, cyano, nitro, QQ-alkyl, QQ-haloalkyl, QQ-

Alkylthio, Q-C_t-alkylsulfinyl, -C-C ₄ -alkylsulfonyl, -COOR ,, -CONR _k R _m , -COR _n , -

S0 ₂ NR _k R _m , -OS0 ₂ -Cι-C ₄ alkyl, QQ-alkoxy, or Q-Qalkoxy substituted by QQ- Alkoxy or halogen, QQ-alkenyloxy, or QQ-alkenyloxy substituted by halogen, or QQ-alkynyloxy, or Rn and Rι ₂ together form a QQ-alkylene bridge, which can be substituted by halogen or QQ-alkyl, or form a QQ-alkenylene bridge which may be substituted by halogen or QQ-alkyl, or form a Q-alkadienylene bridge which may be substituted by halogen or QQ-alkyl; Rι ₂ and R _h independently of one another for hydrogen, halogen, QQ-alkyl, trifluoromethyl, QQ-alkoxy, QQ-alkylthio or -COORJ;

R _{c represents} hydrogen, halogen, nitro, QQ-alkyl or methoxy; R _< j for hydrogen, halogen, nitro, QQ-alkyl, QQ-alkoxy, Q-Qalkylthio, QQ-alkylsulfinyl, QQ-alkylsulfonyl, - COOR _j or CONR _k R _m ;

R _e for hydrogen, halogen, QQ-alkyl, -COOR _J5 trifluoromethyl or methoxy, or R _d and R ,, together form a QQ-alkylene bridge; R _{f represents} hydrogen, halogen or QQ alkyl;

R _x and R _y independently of one another for hydrogen, halogen, QQ-alkyl, QQ-alkoxy, Q-Q-alkylthio, -COOR ₁₆ , trifluoromethyl, nitro or cyano; R _j , R and R _{m are} independently hydrogen or QQ alkyl; or R _k and R _m together form a Q-alkylene bridge which can be interrupted by oxygen, NH or -N (Q-Q-alkyl);

R _{n is} QQ-alkyl, phenyl, or phenyl substituted by halogen, QQ-alkyl, methoxy, nitro or trifluoromethyl;

R ₁₆ for hydrogen, Q-Qo-alkyl, QQ-alkoxy-QQ-alkyl, QQ-alkylthio-QQ-alkyl, di-QQ-alkylamino-QQ-alkyl, halogen-QQ-alkyl, C ₂ -C ₈ alkenyl , Halogen-C ₂ -Cg-alkenyl, C ₃ -C ₈ -alkynyl, QQ-cycloalkyl, halogen-C -C ₇ -cycloalkyl, Ci-Cg-alkylcarbonyl, allylcarbonyl, C ₃ -C ₇ -cycloalkylcarbonyl, benzoyl, the is unsubstituted or substituted on the phenyl ring, identically or differently, up to three times by halogen, QQ-alkyl, halogen-QQ-alkyl, halogen-QQ-alkoxy or QQ-alkoxy; or furoyl, thienyl; or QQ-alkyl substituted by phenyl, halophenyl, QQ-alkylphenyl, QQ-alkoxyphenyl, halogen-QQ-alkylphenyl, halogen-QQ-alkoxyphenyl, QQ-alkoxycarbonyl, QQ-alkoxy-Ci-Cg-alkoxycarbonyl, C -C ₈ -alkenoxycarbonyl , C ₃ -Cg-alkynyloxycarbonyl, QQ-- alkylthiocarbonyl, C -Cg-alkenylthiocarbonyl, C -Cg-alkynylthiocarbonyl, carbamoyl, mono-QQ-alkylaminocarbonyl, di-C ₁ -C ₄ -alkylaminocarbonyl; or phenylaminocarbonyl which is unsubstituted or substituted on the phenyl in the same or different way up to three times by halogen, Q-Q-alkyl, halogen-QQ-alkyl, halogen-QQ-alkoxy or QQ-alkoxy or simply by cyano or nitro, or dioxolane 2-yl that is unsubstituted or by one or two Q- ^Q- alkyl radicals, or dioxan-2-yl which is unsubstituted or substituted by one or two QQ-alkyl radicals, or QQ-alkyl which is substituted by cyano, nitro, carboxyl or QQ-alkylthio-QQ- alkoxycarbonyl is substituted; of a safener of the formula Ile

wherein

R ₁₇ and R _{18 are} independently QQ alkyl or QQ alkenyl; or R- ₁₇ and Rι ₈

together for

R ₃ and R _{36 are} independently hydrogen or QQ alkyl;

or R ₁₇ and rig together for

R ₃₇ and R ₈ independently of one another for QQ-alkyl, or R ₃₇ and R ₃₈ together - (CH ₂ ) r;

R 9 for hydrogen, QQ-alkyl or

or R 7 and rig together for

R40, R41, R ₄₂ , ϊl4 ₃ »R44, R45, R46, R ₄₇ , R ₄₈ , R49, R050, R5 ₁ , Rsi, R5 ₃ , R5 ₄ and R ₅₅ independently of one another represent hydrogen or QQ-alkyl; of a safener of Formula Ef

wherein

R _{20 is} hydrogen or chlorine and R _{19 is} cyano or trifluoromethyl, or a safener of the formula Hg

wherein

R _{2] is} hydrogen or methyl.

The pictorial representation of the groups W _, W and W ₃ should be understood in such a way that the point of attachment to the substituent Y is always the upper free valence. For example, in the case of the substituent i, the linkage point to the substituent Y is in the ortho position to the substituent R ₅₉ .

The alkyl groups occurring in the substituent definitions are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl and their branched Isomers. Alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned. The alkenyl and alkynyl radicals can be mono- or polyunsaturated.

Suitable cycloalkyl substituents contain 3 to 6 carbon atoms and are e.g. Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Halogen usually means fluorine, chlorine, bromine or iodine. Haloalkyl and haloalkoxy groups can be substituted one or more times, with fluorine being preferred as halogen. In substituents such as -N (QQ-alkyl) ₂ , the alkyl radicals can be the same or different. They preferably have the same meaning.

If R _{62 is} different from hydrogen, the group has a through *

labeled chiral center, which particularly preferably has the configuration <S> of the naturally occurring L-amino acids.

In preferred agents according to the invention means

A is hydrogen, hydroxy, O ^' M ", OR ₂₇ , NR ₂₈ R ₂ or together with Q ₂ -O-;

Q, hydrogen, hydroxy, halogen, cyano, C (0) NH ₂ , OR ₅₈ or -OC (0) -R ₅₇ ;

Q _{2 is} hydrogen, hydroxy or together with Qi = 0;

M ⁺ Li ⁺ , Na ⁺ , K ⁺ , 1/2 Mg ²⁺ , 1/2 Ca ²⁺ or N ⁺ R ₃₀ R ₃ ιR ₃₂ R ₃₃ ;

R ₂₂ and R ₂₃ independently of one another hydrogen, halogen, QQ-alkyl, trifluoromethyl, -O-

(QC ₅ ) alkyl or QQ cycloalkyl; or R ₂₂ and R ₂₃ together form a butadienylene chain which is substituted by halogen, methyl, methoxy,

-S (0) _r CH, trifluoromethyl or trifluoromethoxy may be substituted and fused at positions 3 and 4;

R ₅₉ and R ₆₀ independently of one another are hydrogen, halogen, QQ-alkyl, trifluoromethyl, -0- (QQ) -alkyl or QQ-cycloalkyl;

R _{25 is} hydrogen, -0- (QQ) -alkyl, -OQQ-alkenyl, -OQQ-alkynyl, difluoromethoxy or

Trifluoromethoxy;

R ₂₆ QQ-alkyl, QQ-cycloalkyl, -0- (GQ) -alkyl, -OQQ-alkenyl, -OQQ-alkynyl,

Difluoromethoxy, trifluoromethoxy, halogen or trifluoromethyl; R ₅₈ independently of one another are QQ-alkyl, QQ-cycloalkyl, -0- (QQ) -alkyl, -OQQ-alkenyl, -OQQ-alkynyl, halogen or trifluoromethyl; or R_ ₆ and Ei together -CH ₂ -CH ₂ -;

R ₂₇ Ci-Cg-alkyl, QQ-cycloalkyl, QQ-alkenyl, QQ-alkynyl, benzyl, QQ-haloalkyl, Q -Q-haloalkenyl,

R _{28 is} hydrogen, QC ₅ alkyl, QQ alkenyl or QQ alkynyl;

R _{29 is} hydrogen, Q-Cg-alkyl, QQ-alkenyl, QQ-alkynyl, or by halogen, -X ₂ - (QQ-alkyl), hydroxy, amino, -NH (QQ-alkyl), N (QQ-alkyl) ₂ or -CH (X ₃ R ₃₄ ) (X ₄ R ₅ 6) substituted Q-Cg-alkyl, QQ-alkenyl or QQ-alkynyl; Phenyl, pyridyl or benzyl or phenyl, pyridyl or benzyl substituted by halogen, QQ-alkyl, QQ-haloalkyl, -S (0) _p -QQ-alkyl, nitro, cyano or trifluoromethoxy; or the group

, where R _{ό1 is} hydrogen, Q-Cg-alkyl, QQ-alkenyl or QQ-

Alkynyl; R ₆₂ for hydrogen, QQ-alkyl, or QC substituted by hydroxy, SCH ₃ , SH, benzyl, indol-3-yl, 4-hydroxybenzyl, COOR, C (0) NH ₂ , amino or imidazol-5-yl ₅ alkyl; and R _{63 represents} hydrogen, Ci-Cg-alkyl, QQ-alkenyl or QQ-alkynyl; X ₂ , X ₃ and X4 independently of one another oxygen or sulfur; p, r, s and t independently of one another 0, 1 or 2;

R ₂₈ and R ₂₉ together form a QQ alkylene chain which can be substituted by halogen, methyl, methoxy, -S (0) _s CH, trifluoromethyl or trifluoromethoxy and by -O-, -NH- or -N (QQ-alkyl) - can be interrupted;

R ₃₄ and R _{56 are} independently QQ alkyl; or R ₃₄ and R ₅₆ together form a QQ alkylene chain; R ₅₇ QQ-alkyl, QQ-cycloalkyl, QQ-alkenyl, QQ-alkynyl, phenyl or benzyl or substituted by halogen, QQ-alkyl, QQ-haloalkyl, -S (0) _t -QQ-alkyl, nitro, cyano or trifluoromethoxy Phenyl or benzyl;

Q the group

'26

Egg methine, -C (halogen) - or nitrogen; R ₃₀ , R ₃ ι, R and R ₃₃ independently of one another hydrogen, QQ-alkyl or QQ-alkyl substituted by hydroxy or methoxy; or R ₃₀ and R _3] or R ₃₀ , R ₃ ι and R ₃₂ or R ₃₀ , ₃ ι, 3 ₂ and R ₃₃ together form a QQ alkylene chain which can be replaced by -O-, -NH- or -N (QQ- Alkyl) - can be interrupted.

In further preferred agents of the present invention, the compounds of

Formula I Ei for methine, R ₂₂ and R ₂₃ and for hydrogen and R ₁₅ and R ₂₆ each for methoxy, with particular preference

W stands for W;

R ₅ 9 is hydrogen, fluorine, chlorine or methoxy;

R _{50 is} hydrogen, fluorine, or chlorine;

A hydroxy, O ^" M ⁺ , NR ₂₈ R ₂₉ or together with Q ₂ -O-;

Qi is hydrogen, hydroxy, OR ₅₈ or -OC (0) -R ₅₇ , and

R57 QQ-alkyl ₅ QQ-alkenyl or QQ-alkynyl mean.

From this group of agents according to the invention, those in which a) R _{28 is} hydrogen or methyl and R _{29 is} QQ-alkyl, QQ-alkenyl, QQ-alkynyl, or by halogen, -X ₂ - (QQ-alkyl), hydroxy, Amino, -NH (QQ-alkyl), N (QQ-alkyl) ₂ or

-CH (X ₃ R ₃₄ ) (X ₄ R ₅ 6) substituted Q-Cg-alkyl, QQ-alkenyl or QQ-alkynyl; Phenyl,

Pyridyl or benzyl or by halogen, QQ-alkyl, QQ-haloalkyl, -S (0) _p -QQ-

Alkyl, nitro, cyano or trifluoromethoxy substituted phenyl, pyridyl or benzyl; or the

Group in which R≤i is hydrogen, Q-Q-alkyl, Q-Q-alkenyl or Q-

Q-alkynyl; R ₆₂ for hydrogen, QQ-alkyl, or QQ substituted by hydroxy, SCH ₃ , SH, benzyl, indol-3-yl, 4-hydroxybenzyl, CO0R ₆₃ , C (0) NH ₂ , amino, or imidazol-5-yl - alkyl; and R _{6 represents} hydrogen, QQ-alkyl, QQ-alkenyl or QQ-alkynyl; or b) R _{5S is} chlorine; Rβo hydrogen; AO ^' M ⁺ or together with Q ₂ -O-; Qi is hydrogen, hydroxy or -OC (O) - Q-Cg-alkyl; and

M is Li ⁺ , Na ⁺ , K ⁺ , NH ₃ ⁺ C-Cg-alkyl or NH ₂ ⁺ (C ₁ -C ₈ alkyl) ₂ .

Particularly preferred agents according to the invention contain a safener of the formula Ha, wherein Xi very particularly preferably represents chlorine and Ri represents -CH (CH ₃ ) QHn (n).

The invention also relates to a process for the selective control of weeds in crops, which consists in that the crops, their seeds or cuttings or their cultivated area are treated simultaneously or separately with a herbicidally active amount of the herbicide of the formula I and a herbicidally antagonistically effective amount of the safener of the formulas Ha to Hg. Cereals, maize, soybeans and rice, preferably cereals, are particularly suitable as crop plants which can be protected against the damaging action of the herbicides mentioned by the safeners of the formulas Ha to Ilg. Cultures are also to be understood as those which have been made tolerant to herbicides or classes of herbicides by means of conventional breeding or genetic engineering methods. The weeds to be combated can be both monocot and dicot weeds, such as Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.

The cultivated areas are the soil areas already overgrown with the crop plants or filled with the seeds of these crop plants, as well as the soils intended for cultivation with these crop plants.

Depending on the intended use, a safener of the formula II can be used for the pretreatment of the seed of the crop (dressing the seed or the cuttings) or can be added to the soil before or after the seed. However, it can also be applied on its own or together with the herbicide after the plants have emerged. The treatment of the plants or the seed with the safener can therefore in principle be carried out independently of the time of application of the herbicide. However, the treatment of the plant can also be carried out by simultaneous application of herbicide and safener (for example as a tank mix). The application rate of safener to herbicide largely depends on the type of application. In the case of field treatment, which is carried out either using a tank mixture with a combination of safener and herbicide or by separate application of safener and herbicide, the ratio of herbicide to safener is generally from 100: 1 to 1:10, in particular from 10: 1 to 1: 1, preferably 5: 1 to 1: 1. As a rule, 0.001 to 5.0 kg of safener / ha, preferably 0.001 to 0.5 kg of safener / ha, are applied in the field treatment. The application rates of herbicide are generally between 0.001 to 4 kg / ha, but preferably between 0.005 to 1 kg / ha.

The agents according to the invention are suitable for all application methods customary in agriculture, e.g. preemergent application, postemergent application and seed dressing suitable.

In the seed dressing, 0.001 to 10 g safener / kg seed, preferably 0.05 to 2 g safener / kg seed, are generally applied. If the safener is applied in liquid form shortly before sowing with seed swelling, then safener solutions are advantageously used which contain the active compound in a concentration of 1 to 10,000, preferably 100 to 1000 ppm.

For application, the safeners of the formula II or combinations of these safeners with the herbicides of the formula I are expediently processed together with the auxiliaries customary in formulation technology, for example to emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. The formulations are prepared in a known manner, e.g. by intimately mixing and / or grinding the active ingredients with liquid or solid formulation auxiliaries, e.g. Solvents or solid carriers. Furthermore, surface-active compounds (surfactants) can also be used in the preparation of the formulations.

Possible solvents are: Aromatic hydrocarbons, preferably the fractions Cg to Q ₂ , such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and their ethers and esters such as ethanol Ethylene glycol Ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or N, N-dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

As solid carriers, e.g. natural dust, such as calcite, talc, kaolin, montmorillonite or attapulgite, is generally used for dusts and dispersible powders. To improve the physical properties of the formulation, it is also possible to add highly disperse silica or highly disperse absorbent polymers. As granular, adsorptive granulate carriers come porous types such as Pumice stone, broken brick, sepiolite or bentonite, as non-sorptive carrier materials e.g. Calcite or sand in question. In addition, a large number of pregranulated materials of inorganic or organic nature, such as in particular dolomite or comminuted plant residues, can be used.

Depending on the type of active substance to be formulated, nonionic, cationic and / or anionic surfactants and surfactant mixtures with good emulsifying, dispersing and wetting properties are suitable as surface-active compounds. Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds. The soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (Qo-C ₂₂ ), such as the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures, for example from coconut or Tallow oil can be extracted. The fatty acid methyl taurine salts should also be mentioned.

However, so-called synthetic surfactants are used more frequently, in particular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty alcohol sulfonates or sulfates are generally present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical with 8 to 22 C atoms, alkyl also including the alkyl part of acyl radicals, for example the Na or Ca salt lignin sulfonic acid, dodecyl sulfuric acid ester or a fatty alcohol sulfate mixture made from natural fatty acids. This subheading also includes the salts of sulfuric acid esters and sulphonic acids from fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid residue with 8-22 carbon atoms. Alkylarylsulfonates are, for example, the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid / formaldehyde condensation product.

Corresponding phosphates such as e.g. Salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct or phospholipids in question.

Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylene phenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 10 carbon atoms in the alkyl radical of the alkylphenols.

Other suitable nonionic surfactants are the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups on polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are also suitable.

The cationic surfactants are primarily quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as N substituents and have low, optionally halogenated alkyl, benzyl or low hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyl trimethyl ammonium chloride or benzyl di (2-chloroethyl) ethyl ammonium bromide. The surfactants customary in formulation technology, which can also be used in the agents according to the invention, are described, inter alia, in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stächen, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich / Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol I-IH, Chemical Publishing Co., New York, 1980-81.

The herbicidal formulations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active compound mixture from the compound of the formula I with the compounds of the formulas Ha, üb, He, Ild, He, Ilf or Hg 1 to 99.9% by weight of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight of a surfactant. While concentrated agents are usually preferred as commercial goods, the end user generally uses diluted agents. The agents can also contain other additives such as stabilizers e.g. optionally epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), defoamers, e.g. Contain silicone oil, preservatives, viscosity regulators, binders, adhesives as well as fertilizers or other active ingredients. Various methods and techniques can be used for the use of safeners of the formula II or compositions containing them to protect crop plants against the harmful effects of herbicides of the formula I, for example the following:

i) Seed dressing a) Dressing the seeds with an active ingredient of the formula II formulated as a wettable powder by shaking in a vessel until uniform distribution on the seed surface (dry dressing). About 1 to 500 g of active ingredient of the formula Ha, üb, He, Ild, Ile, Ilf or Hg (4 g to 2 kg of wettable powder) are used per 100 kg of seed.

b) dressing the seeds with an emulsion concentrate of the active ingredient of the formula Ha, Eb, He, Ild, Ile, Ilf or Hg according to method a) (wet dressing).

c) Dressing by immersing the seed in a broth with 100-1000 ppm of active ingredient of the formula Ha, üb, He, Ild, He, Ilf or Hg for 1 to 72 hours and, if appropriate, subsequently drying the seeds (immersion dressing).

The dressing of the seeds or the treatment of the germinated seedlings are naturally the preferred methods of application because the active ingredient treatment is completely based on the Target culture is aimed. As a rule, 1 to 1000 g antidote, preferably 5 to 250 g antidote, are used per 100 kg of seed, depending on the method, which also allows the addition of other active substances or micronutrients, to deviate upwards or downwards from the specified limit concentrations ( Repeat stain).

ii) Application as a tank mix

A liquid processing of a mixture of antidote and herbicide (mutual ratio between 10: 1 and 1: 100) is used, the amount of herbicide applied being 0.005 to 5.0 kg per hectare. Such tank mixes are applied before or after sowing.

iii) Application in the seed furrow

The safener is introduced into the open seeded furrow as an emulsion concentrate, wettable powder or as granules. After covering the furrow, the herbicide is applied in the pre-emergence process in the usual way.

iv) Controlled drug delivery

The active substance of the formula Ha, üb, He, Ild, Ile, Ilf or Hg is applied in solution to mineral granulate carriers or polymerized granules (urea / formaldehyde) and dried. If necessary, a coating can be applied (coating granules), which allows the active ingredient to be dispensed in doses over a certain period of time.

In particular, preferred formulations are composed as follows:

(% = Weight percent)

Emulsifiable concentrates:

Active ingredient mixture: 1 to 90%, preferably 5 to 20% surface-active agent: 1 to 30%, preferably 10 to 20% liquid carrier: 5 to 94%, preferably 70 to 85%

Dusts:

Active ingredient mixture: 0.1 to 10%, preferably 0.1 to 5% solid carrier: 99.9 to 90%, preferably 99.9 to 99% suspension concentrates:

Active ingredient mixture: 5 to 75%, preferably 10 to 50% Water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30%

Wettable powders:

Active ingredient mixture: 0.5 to 90%, preferably 1 to 80% surface-active agent: 0.5 to 20%, preferably 1 to 15% solid carrier material: 5 to 95%, preferably 15 to 90%

Granules:

Active ingredient mixture: 0.1 to 30%, preferably 0.1 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%

The following examples further illustrate the invention without restricting it.

Formulation examples for mixtures of herbicides of the formula I and safeners of the formula Ha. Hb. He, Ed. Ile. Ilf or H (% = weight percent)

Fl. Emulsion concentrates a) b) c) d)

Active ingredient mixture

I with Ea, üb, Ec, Ild

Ee, πf or Eg 5% 10% 25% 50%

Ca-dodecylbenzenesulfonate 6% 8% 6% 8%

Castor oil polyglycol ether 4% _ 4% 4%

(36 moles of EO)

Octylphenol polyglycol ether - 4% - 2%

(7-8 mol EO)

Cyclohexanone - - 10% 20%

Aroma. Hydrocarbon- 85% 78% 55% 16% blended QQ ₂

Such concentrates can be used to prepare emulsions of any desired concentration by dilution with water. F2. Solutions a) b) c) d)

Active ingredient mixture

I with Ea, Eb, Ec, Ed,

Ee, Ef or g 5% 10% 50% 90% l-methoxy-3- (3-methoxy-propoxy) propane - 20% 20%

Polyethylene glycol MG 400 20% 10%

N-methyl-2-pyrrolidone - - 30% 10%

Aroma. Hydrocarbon 75% 60% blend QQ ₂

The solutions are suitable for use in the form of tiny drops.

F3. Spray powder a) b) c) d)

Active ingredient mixture

I with Ea, Eb, Ec, Ed,

Eε, Ef or Eg 5% 25 ° Λ 5 500 ι %% 80 ^« %

Na lignin sulfonate 4% - 3 3%% -

Na lauryl sulfate 2% 3 3% o // o - 4%

Na-Diisobutvl-naphthalinsu ilfonat - 6 6% o // o 5 5%% 6%

Octylphenol polyglycol ether 1 / o 2%

(7-8 mol EO)

Fumed silica 1% 33% / o 55 %% 10%

Kaolin 88% 52 / o 35%

The active ingredient is mixed well with the additives and ground well in a suitable grinder. Spray powder is obtained which can be mixed with water to form any desired suspension

Allow concentration to be diluted.

F4. Coating granules a) b) c)

Active ingredient mixture

I with Ea, Eb, Ec, Ed,

Ee, Ef or Eg 0.1% 5% 15%

Fumed silica 0.9% 2% 2%

Inorg. Backing material 99.0% 93% 83%

{JE 0.1 - 1 mm) such as CaC0 ₃ or Si0 The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated off in vacuo.

F5. Coating granules a) b) c)

Active ingredient mixture

I with Ea, Eb, Ec, Ed,

Ee, Ef or Eg 0.1% 5% 15%

Polyethylene glycol MG 200 1.0% 2% 3%

Fumed silica 0.9% 1% 2%

Inorg. Backing 98.0% 92% 80%

{JE 0.1 - 1 mm) such as CaC0 or Si0 ₂

The finely ground active ingredient is evenly applied in a mixer to the carrier material moistened with polyethylene glycol. In this way you get dust-free

Coating granules.

F6. Extruder granules a) b) c) d)

Active ingredient mixture

I with Ea, Eb, Ec, Ed,

Ee, Ef or Eg 0.1% 3% J / o 15%

Na lignin sulfonate 1.5% 2% 3% 4%

Carboxymethyl cellulose 1.4% 2% T 0 // o 2%

Kaolin 97.0% 93% 90% 79%

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.

F7. Dusts a) b) c)

Active ingredient mixture

I with Ea, Eb, Ec, Ed,

Ee, Ef or Eg 0.1% 1% 5%

Talc 39.9% 49% 35%

Kaolin 60.0% 50% 60%

Ready-to-use dusts are obtained by mixing the active ingredient with the carrier substances and grinding them in a suitable mill. F8. Suspension concentrates a) b) c) d)

Active ingredient mixture I with Ea, Eb, Ec, Ed, Ee, Ef or Eg 3% 10% 25% 50% Erhylenglykol 5% 5% 5% 5%

Nonylphenol polyglycol ether - 1% 2% - (15 mol EO) Na lignin sulfonate 3% 3% 4% 5% carboxymethyl cellulose 1% 1% 1% 1% 37% aqueous formaldehyde 0.2% 0.2% 0.2% 0.2% solution

Silicone oil emulsion 0.8% 0.8% 0.8% 0.8% water 87% 79% 62% 38%

The finely ground active ingredient is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water. It is often more practical to individually formulate the active ingredient of formula I and the mixing partner of the formula Ea, Eb, Ec, Ed, Ee, Ef or Eg and then bring them together in the desired mixing ratio in the applicator as a "tank mixture" in water shortly before application .

In Tables 1 and 2 below, the substituents R ₂₂ and R ^ each denote hydrogen.

Table 1: Herbicides of the formula Ia

O w o

(Ia)

? ^' ^? CH, CH '. 3 where W for the groups

W ₂ ) or (W ₃ ) stands:

Verb.Nr. R59 Rßo Q1 W mp. [° C]

1.004 H H OCOMe Wi

1.005 HH OCOCH =: CHCH _{3 t}

1.008 F H OCOEt W,

1,011 F Cl OH w ₇

1,014 Cl H OCOMe Wi

1,015 Cl H OCO-cyc-Propyl Wi

1,018 Me H OCO-nPr _t

1,019 Me H OCO-i-butyl W,

Verb.Nr. RR ₅ 5 ₉ 9 RR ₆ Ö ₀ O QQ, i W mp. [° C]

1,023 OMe H OCO-n-Pentyl Wi

1,026 Cl F OCO-n-butyl Wi

1-027 C Cll C Cll O OHH W Wii 199-200

1,028 Cl Cl H,

1-029 C Cll C Cll O OCCOO - nn - HHeexxyyll W Wii 90-92

1,030 - HH w ₂

1,031 H - OH w ₃

1,032 (1-thienyl) - CN w ₃

1,033 (1-furyl) - CN w ₃

1,034 (1-furyl) - OH w ₃

1,035 phenyl - CN w ₃

1,036 phenyl - OH w ₃

1,037 phenyl - H w ₃

1,038 (4-F-phenyl) - OH w ₃

1,039 (4-Cl-phenyl-OH w ₃

1,040 (4-Br-phenyl) - OH w ₃

1.041 (4-C1-1- - COOEt w ₃

1,042 Cl H OCO-n-hexyl Wi

1,044 Cl Cl OCOCH ₃ Wi

1-045 C Cll C Cll O OCCOO - nn - PPeennttyyll W Wii 89-91

1,046 Cl Cl OCO-cycl.-Propyl Wi

1,047 Cl Cl OCOCH = CH-CH ₃ W,

1,048 Cl Cl OCH ₂ CH = CH ₂ Wi

1-049 C Cll C Cll FF _t i 185-186

1,050 OCH ₃ Cl H w, Labeile 2: Herbicides of the formula Ib

where W for the groups (W ₂ ) or

(W ₃ ) stands:

Verb.Nr R59 βo Qi Q2 WA mp. [° C]

2,002 H - HH w ₃ OH

2.005 Me HHHW _T O-benzyl 2.006 HH CN H _I OH

2.009 HH CONH2 HW, OMe 2.010 HH COOEt H i COOEt

Verb. R RS9 ÖO Qi Q ₂ w A mp. [° C]

2,015 OMe H = 0 w. OMe

2,016 Cl F = 0. OMe

2,017 Cl Cl = 0 w, OMe

2,018 - H = 0 w ₂ OMe

2,019 HH = 0 w OEt

2,021 Cl H = 0 w, O-n-Pr

Verb.R59 ÖO Qi Q ₂ w A Smp

No. . [° C]

2,024 HH = 0 W, 0-CH (CH ₃ ) CH = CH ₂

2,027 Me H = 0 Wi O-benzyl

2,028 OMe H = 0 i 0-CH ₂ CCH

2,030 - H = 0 w ₂ . Os Bu 1

2,031 - H = 0 w ₂ O-Li ^* 210

278

2,035 Me H = 0 _! 0-Li ⁺

2,039 H - = 0 w ₃ 0-Li ⁺

2,042 Cl H OH H Wi 0-Li ⁺ 205-208

2,044 OMe H OH HW, 0-Na ⁺

2,046 H - OH H w ₃ o-κ ⁺

2,047 - H OH H w ₂ o-κ ⁺

Verb. R 59 R, 60 w mp.

No. [° C]

2,050 Cl H o, 0-Na ⁺

2,054 Cl Cl o W, 0-Na ⁺ 260 264

2,055 H - ow ₃ 0-Na ⁺ 2,056 H - ow ₃ 0-Na ⁺ 2,057 - H ow ₂ 0-Caι _{/ 2} ⁺ 2,058 HH o Wi 0- ⁺ NH ₃ CH (CH ₃ ) ₂ 179 (dec

2,059 FH o Wi 0 ^"+ NH ₂ (CH (CH ₃ ) ₂ ) ₂ 2,060 Cl H o Wi 0 ^{" +} NH ₂ (CH ₃ ) ₂ 2,061 Me H o Wi 0- ⁺ NH ₂ (CH ₂ CH ₂ ) ₂ 2,062 OMe H o Wi 0 ⁺ NH ₃ CH ₂ CH ₂ CH ₃ 2,063 Cl F o W, 0 ⁺ NH ₃ CH (CH ₂ ) ₂ 2,064 F Cl o Wi 0 ⁺ NH ₃ (CH ₂ ) ₃ CH ₃ 2,065 Cl Cl o Wi 0 ^"+ NH ₃ CH (CH ₃ ) ₂ 194-196 2,066 H = o W ₂ 0 ⁺ NH ₃ (n-hexyl)

2,067 HH = o W _Ϊ NH-phenyl

2,068 Cl H = oi NHCH ₃ resin

Verb. R ^■ 59 Rso w Smp.

No. [° C]

2,070 OMe H: 0 Wi N (CH ₂ CH ₃ ) ₂ 2,071 Cl F = o Wi NHCH (CH ₃ ) ₂

2,073 - H OH H w ₂ NH ₂ 2,074 - H OH H w ₂ NHCH ₃ 127-129

2,075 - H OH H w ₂ N (CH ₃ ) ₂ 2,076 - H: 0 w ₂ NHCH ₂ CH ₃ 2,077 - H rO w ₂ N (CH ₃ ) CH ₂ CCH 2,078 - H OH H w ₂ NH- (n- Propyl) 2.079 - H OH HW ₂ NH- (n-hexyl) 2.080 - H OH HW ₂ NH- (3-OMe-benzyl) 2.081 - H OH H w ₂ NH- (4-iPr-phenyl) 2.082 - H = o W ₂ N (CH ₃ ) phenyl 2,083 - H OH HW ₂ NHNHC (CH ₃ ) ₃ 109-110

2,084 - H OH HW ₂ NHNH (4-Cl-phenyl) 149-150

2,085 - H OH H w ₂ NHNH (2,4-F, 2-phenyl)

2,086 - H OH H w ₂ NHCH ₂ C (CH ₃ ) CH ₃ 2,087 - H OH H w ₂ NHCH (CH ₃ ) CH ₂ 0 Me

2,088 - H = ow ₂ N (CH ₃ ) CH ₂ COOEt 2,089 - H = ow ₂ N (CH ₃ ) CH ₂ CONH ₂ 2,090 H - HH w ₃ NHCH (CH ₃ ) COOEt 97 <S> form 59 R≤o Qi Q2 WA Smp

No. [° C]

2,091 HHH w ₃ NHCH (Et) COO resin tBu

2,092 phenyl CN H ₃ OCH ₃

2,093 (4-OMe- CN H w ₃ OCH ₃ phenyl)

2,094 (1-thienyl) CN H w ₃ OCH ₃

2,095 (1-furyl) CN H w ₃ OCH ₃

2,096 phenyl CN OH w ₃ OCH ₃

2,097 (4-C1-COOEt OH w ₃ OCH ₂ CH ₃

1 -thienyl)

2,098 (1-furyl) = 0 w ₃ OCH ₃

2,099 phenyl = 0 w ₃ OCH ₃

2,100 phenyl = 0 w ₃ OCH ₂ CH ₃

2,101 phenyl = 0 w ₃ O-nPr

2,102 phenyl = 0 ₃ On-Bu

2,103 phenyl = 0 w ₃ O-benzyl

2,104 (4-Cl-l-thienyl) - = 0 w ₃ O-nPr

2,105 (4-Cl-l-thienyl) - = 0 • W ₃ O-iPr

2,106 (4-F-phenyl) = 0 w ₃ OCH ₂ CH ₃

2,107 (4-F-phenyl) = 0 w ₃ O-nPr

2,108 (4-F-phenyl) = 0 w ₃ Oi Pr

2,109 (4-F-phenyl) = 0 w ₃ O-allyl

2,110 (4-F-phenyl) = 0 w ₃ N (CH ₂ CH ₃ ) ₂ Verb.R59 Rβo Qi Q2 WA Smp

No. [° C]

2,111 (4-Cl-phenyl) - = 0 w ₃ OCH ₂ CH ₃

2,112 (4-Cl-phenyl) - = 0 w ₃ O-nPr

2,113 (4-Cl-phenyl) - = 0 w ₃ Oi-Pr

2,114 (4-Cl-phenyl) - = 0 w ₃ O-allyl

2,115 (4-Cl-phenyl) - = 0 w ₃ S-CH ₂ CH ₃

2,116 (4-Br-phenyl) - = 0 w ₃ O CH ₂ CH ₃

2,117 (4-OMe-phenyl) - = 0 w ₃ O CH ₂ CH ₃

2,118 (4-OMe-phenyl) - = 0 w ₃ O-nPr

2,119 (4-OMe-phenyl) - = 0 w ₃ Oi-Pr

2,120 - H OH H w ₂ O Li ⁺ 250

2,121 - H = 0 w ₂ NHCH ₂ - C (CH ₃ ) = CH ₂

2,122 - H = 0 w ₂ N (CH ₃ ) ₂ 124-126

2,123 - H = 0 w ₂ N (CH ₃ ) -CH ₂ - CH ₃

2,124 - H = 0 w ₂ NH-NH-phenyl

Safeners which are particularly suitable for use in the agents according to the invention are listed in the following tables.

Table 3: Safeners of Formula Ila:

Verb.No. Xi Ri

3.01 Cl -CH (CH ₃ ) -C ₅ Hιι-n 3.02 Cl -CH (CH ₃ ) -CH ₂ OCH ₂ CH = CH ₂ 3.03 Cl H

Table 4: Safener of the formula

Verb.No.R ₂ R ₃ R4 R

4.01 CH ₃ phenyl 2-Cl H CH 4.02 CH ₃ phenyl 2-Cl 4-C1 CH 4.03 CH ₃ phenyl 2-FH CH 4.04 CH ₃ 2-chlorophenyl 2-FH CH 4.05 C ₂ H ₅ CC1 ₃ 2-Cl 4- C1 N 4.06 CH ₃ phenyl 2-Cl 4-CF ₃ N 4.07 CH ₃ phenyl 2-Cl 4-CF ₃ N 4.08 CH ₃ 2-fluorophenyl 2-Cl H CH

Table 5: Formula He safeners:

Verb.No.R ₉ R 10 R ₈ R _fi R ₇

5.01 CH ₃ CH ₃ CH ₃ 2-Cl 4-C1 5.02 CH ₃ C ₂ H5 CH ₃ 2-Cl 4-C1 5.03 CH ₃ C ₂ Hs C ₂ H ₅ 2-Cl 4-C1

Table 6: Safeners of the formula πh:

Verb.No.Rl4

Table 7: Safeners of Formula Ee:

Verb.No.R 17 Rl8 Rι + Ri8

7.001 CH ₂ = CHCH ₂ CH ₂ = CHCH ₂

CH,

7.003

CH, CH,

Verb.No.R ₁₇ Rι ₈ R17 + R ₁ 8

Table 8: Safeners of Formula Ef:

No. R ₂₀ R19

8.01 H CN

8.02 Cl CF ₃

Table 9: Safeners of Formula Eg:

Verb.R _: 21

9.01 H

9.02 CH ₃

Particularly preferred agents according to the invention contain the compound no. 3.01 as safener and a compound selected from the compounds 2,090, 2,091, 2,065, 1,020, 1,013, 1,012, 2,054, 2,120, 2,122, 1,045, 2,034 and 2,042 as herbicide.

The safeners listed in Tables 3 to 9 and their preparation are e.g. B. from EP-A-492 366, WO 91/7874 and WO 94/987. The ability of safeners of the formula Ea, Eb, Ec, The following examples illustrate Ed, Ee, Ef or Eg to protect crop plants from the phytotoxic action of herbicides of the formula I.

Biological examples

Example B1: Postemergent phytotoxic effect of the herbicides of the formula I and the mixtures of the herbicides with the safeners of the formula E on wheat: Wheat is grown in plastic pots up to the 4-leaf stage under greenhouse conditions. At this stage, the herbicides alone and the mixtures of the herbicides with the safeners are applied to the test plants. Application is carried out as an aqueous suspension of the test substances according to Example F8 with 500 l of water / ha. The application rates for the herbicides are 4000, 2000, 1000 and 500 g / ha, the application rate for the safeners is 60 g / ha. A percentage scale is used 14 days after the application. 100% means test plant is dead, 0% means no phytotoxic effect. The results show that the safeners significantly reduce the damage to the crop caused by the herbicides. Examples of the reduction in the phytotoxic action of the herbicides by the safeners of the formulas Ea to Ee are given in the following Table B1:

Table B1: Post-emergence phytotoxic effect on wheat:

The application rate of the safener in the following table is 60 g ai / ha.

Herbicide application rate safener phytotoxic effect in%

Verb.Nr. Herbicide [g / ha] Verb.Nr,

1.002 4000-30

1.002 4000 3.01 0

1.002 2000-15

1.002 2000 3.01 0

1.002 1000 - 5

1.002 1000 3.01 0

1.002 500 - 0

1.002 500 3.01 0

1.003 4000-45

1.003 4000 3.01 10 1.003 2000 30

1.003 2000 3.01 0

1.003 1000 20

1.003 1000 3.01 0

1,003,500 5

1.003 500 3.01 0

The same results are obtained if the compounds of the formula I are formulated according to Examples F1 to F7.

Claims

Claims:

1. Selective herbicidal agent, characterized in that it is in addition to customary inert

Formulation aids as an active ingredient, a mixture of a) a herbicidally effective amount of a herbicide of the formula I.

Y

/ W (0. \

X— Q

wherein

W the groups

X is the group -C (Qι) (Q ₂ ) -;

Y represents the group -C (0) -A;

A is hydrogen, hydroxy, O ^" M ^* , OR ₂₇ , NR ₂₈ R ₂ 9 or together with Q ₂ -O-;

Qi is hydrogen, hydroxy, halogen, cyano, C (0) NH ₂ , -CC ₅ alkoxycarbonyl, OR ₅₈ or -

OC (0) -R ₅₇ ;

Q _{2 is} hydrogen, hydroxy or together with Qi = 0 or = NH;

M ⁺ Li ⁺ , Na ⁺ , K ⁺ , 1/2 Mg ² \ 1/2 Ca ²⁺ or N ⁺ R ₃₀ R ₃ ιR ₃₂ R ₃₃ ;

R ₂₂ and R ₂₃ independently of one another hydrogen, halogen, -CC ₅ alkyl, trifluoromethyl, -O-

(-C-C ₅ ) alkyl or C ₃ -C ₅ cycloalkyl; or

R ₂₂ and R ₂₃ together form a butadienylene chain which is substituted by halogen, methyl, methoxy,

-S (0) _r CH, trifluoromethyl or trifluoromethoxy may be substituted and fused at positions 3 and 4;

R ₅₉ and R ₆ o independently of one another hydrogen, halogen, -CC ₅ alkyl, trifluoromethyl, -O-

(C _r C ₅ ) alkyl, C ₃ -C ₅ cycloalkyl, -S (0) _q -Cι-C ₅ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ - C ₅ -

Cycloalkyl, nitro, amino, cyano, -COO-dC ₅ -alkyl, -NH-Cι-C ₅ -alkyl, N (Cι-C ₅ -alkyl) ₂ , C ₃ -

C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy, benzyloxy, hydroxy, phenyl, thienyl, furyl, pyrazolyl, Oxazolyl, pyridyl, or phenyl, thienyl, furyl, pyrazolyl, oxazolyl or pyridyl substituted by halogen, CC ₄ -alkyl, QQ-alkoxy, QQ-alkylthio, QQ-alkylsulfinyl, Cι-C ₄ -alkylsulfonyl, QQ-haloalkoxy or trifluoromethyl; or phenyloxy, thienyloxy, furyloxy, pyrazolyloxy, oxazolyloxy, pyridyloxy or phenyloxy, thienyloxy, furyloxy, pyyloxy, furyloxy, substituted by halogen, QQ-alkyl, QQ-alkoxy, QQ-alkylthio, QQ-alkylsulfinyl, QQ-alkylsulfonyl, QQ-haloalkoxy or trifluoromethyl Oxazolyloxy or pyridyloxy; or phenylthio, thienylrhio, furylthio ^ pyrazolylthio, oxazolylthio or pyridylthio; or phenylthio, thienylthio, furylthio, pyrazolylthio, oxazolylthio or pyridylthio substituted by halogen, QQ-alkyl, QQ-alkoxy, QQ-alkylthio, QQ-alkylsulfinyl, QQ-alkylsulfonyl, QQ-haloalkoxy or trifluoromethyl, or the group Q ₃

(Q ₃ ), wherein E _{2 is} methine, -C (halogen) - or nitrogen;

65

R _{64 is} hydrogen, -0- (QC ₅ ) alkyl, -OQQ-alkenyl, -OQQ-alkynyl, QQ-haloalkoxy or QQ-alkyl;

R ₆₅ -CC ₅ alkyl, QQ-cycloalkyl, -0- (QQ) alkyl, -OQQ-alkenyl, -OQQ-alkynyl, Q-Q-haloalkoxy, halogen or trifluoromethyl;

R ₂ 5 is hydrogen, -0- (QQ) alkyl, -OQQ-alkenyl, -0-C ₃ -C ₆ -alkynyl, QC ₅ -haloalkoxy or QQ-alkyl;

R _{2a -QC 5} alkyl, C ₃ -C ₅ cycloalkyl, -0- (QQ) alkyl, -OQQ alkenyl, -OQQ alkynyl, Q- Q haloalkoxy, halogen or trifluoromethyl;

R ₅₈ QQ-alkyl, QQ-alkenyl, QQ-cycloalkyl, halogen or trifluoromethyl; R ₂₇ QQ-alkyl, QQ-cycloalkyl, QQ-alkenyl, QQ-alkynyl, benzyl, QQ-haloalkyl, QQ-haloalkenyl,

R _{2S is} hydrogen, QQ-alkyl, QQ-alkenyl or QQ-alkynyl;

R _{29 is} hydrogen, QQ-alkyl, QQ-alkenyl, C -C ₆ -alkynyl, or by halogen, cyano, cyclopropyl, phenyl, furyl, thienyl, naphthyl, pyridyl, -X ₂ - (QQ-alkyl), hydroxy, amino , - NH (QQ-alkyl), N (QQ-alkyl) ₂ or -CH (X ₃ R ₃₄ ) (X ₄ R _{5 <} _) substituted Q-Cg-alkyl, QQ-alkenyl or QQ-alkynyl; Phenyl, pyridyl or benzyl or by halogen, QQ-alkyl, Q- Cs-haloalkyl, -S (0) _p -QQ-alkyl, nitro, cyano or trifluoromethoxy substituted

Phenyl, pyridyl or benzyl; or the group in which R _{OI is} hydrogen,

Q-Cg-alkyl, QQ-alkenyl, phenyl, benzyl or QQ-alkynyl; R «; ₂ for hydrogen, QQ-alkyl, or by hydroxy, SCH, SH, benzyl, indol-3-yl, 4-hydroxybenzyl, COOR <; ₃ , C (0) NH ₂ , amino, or imidazol-5-yl substituted C -C ₅ alkyl; and

R ₆₃ for hydrogen, Q-Cg-alkyl, QQ-alkenyl, QQ-alkynyl, -NH (QQ-alkyl), -N (QQ-alkyl) ₂ , phenylamino, the phenyl group being substituted by halogen, QQ-alkyl, QQ- Haloalkyl,

QQ-alkylthio, QQ-alkylsulfonyl, QQ-alkylsulfinyl, nitro, cyano or trifluoromethoxy may be substituted, morpholino or piperidino; X ₂ , X ₃ and X ₄ independently of one another oxygen or sulfur; p, q, r, s and t independently of one another 0, 1 or 2;

R ₂ g and R ₂ together form a QQ alkylene chain which can be substituted by halogen, methyl, methoxy, -S (0) _s CH, trifluoromethyl or trifluoromethoxy and by -O-, -NH- or -N (C ₂ - Q-alkyl) - can be interrupted; R ₃₄ and Rsβ are independently QQ alkyl; or R ₃₄ and R 6 together form a QQ alkylene chain;

R ₅₇ QQ-alkyl, QQ-alkoxy, QQ-haloalkyl, Ci-Cg-haloalkoxy, QQ-cycloalkyl, QQ-alkenyl, QQ-alkynyl, phenyl or benzyl or by halogen, QQ-alkyl, QQ-haloalkyl, -S ( 0) _t -QQ-alkyl, nitro, cyano or trifluoromethoxy substituted phenyl or benzyl;

Q the group

Egg methine, -C (halogen) - or nitrogen; or

R ₂₆ and egg together -CH ₂ -CH ₂ -;

R ₃ o, R ₃ ι, ₃₂ and R ₃ independently of one another hydrogen, QQ-alkyl or QQ-alkyl substituted by hydroxy or methoxy; or R o and R ι or R ₃ o, R ₃ ι and R ₃₂ or R ₃ o, R ₃ ι, R ₃₂ and R ₃ together form a QQ- alkylene chain, which by -O-, -NH- or -N (QQ -Alkyl) - may be interrupted; and b) a herbicide-antagonistically effective amount of a safener of the formula Ea

wherein

Ri is hydrogen, Q-Q-alkyl or substituted by Q-Q-alkoxy or Q-Q-alkenyloxy

Q-Q alkyl and

Xi is hydrogen or chlorine; of a safener of the formula Eb

wherein

E nitrogen or methine,

R _{2 is} C 1 -C ₄ alkyl,

R _{3 is} -CC1 or phenyl optionally substituted by halogen, and

R and R5 are independently hydrogen or halogen; a safener of the formula Ec

wherein

R ₆ and R _{7 are} independently hydrogen or halogen, and R ₈ , R ₉ and Rio are independently QQ-alkyl, of a safener of the formula Ed

wherein

A ₂ for a group

stands, R ₁ and R _M independently of one another hydrogen, Q-Cg-alkyl, QQ-cycloalkyl, QQ-

Alkenyl, QQ-alkynyl, or by QQ-alkoxy or

substituted QQ alkyl; or Rι ₃ and Rι ₄ form

together a QQ-alkylene bridge, which can be interrupted by oxygen, sulfur, SO, S0 ₂ , NH or - N (Q-Qalkyl) -, Ri ₅ for hydrogen or QQ-alkyl;

Rn for hydrogen, halogen, cyano, trifluoromethyl, nitro, QQ-alkyl, QQ-alkoxy, Q-Q-alkylthio, QQ -alkylsulfinyl, C ₁ -C ₄ -alkylsulfonyl, -COOR _j , -CONR _k R _m , -COR _n , - S0 ₂ NR _k R _m or -OS0 ₂ -QQ-alkyl;

R _g for hydrogen, halogen, cyano, nitro, QQ-alkyl, QQ-haloalkyl, QQ-alkylthio, QQ-alkylsulfonyl, QQ-alkylsulfonyl, -COOR _j , -CONR R _m , -COR _n , - S0 ₂ NR _k R _m , -OS0 -Cι-alkyl, QQ-alkoxy, or Q-Qalkoxy substituted by QQ-alkoxy or halogen, QQ-alkenyloxy, or QQ-alkenyloxy substituted by halogen, or QQ-alkynyloxy, or Rn and R ₂ together form a QQ-alkylene bridge which can be substituted by halogen or QQ-alkyl, or form a QQ-alkenylene bridge which can be substituted by halogen or QQ-alkyl or form a Q-alkadienylene bridge which is substituted by halogen or QQ-alkyl can be; Rι ₂ and R _h independently of one another for hydrogen, halogen, QQ-alkyl, trifluoromethyl, QQ-alkoxy, QQ-alkylthio or -COORJ;

R _{c represents} hydrogen, halogen, nitro, QQ-alkyl or methoxy; R _d for hydrogen, halogen, nitro, QQ-alkyl, QQ-alkoxy, Q-G_alkylthio, QQ-alkylsulfinyl, QQ-alkylsulfonyl, - COOR, or CONR _k R _m ;

R _c for hydrogen, halogen, QQ-alkyl, -COOR ,, trifluoromethyl or methoxy, or Rj and R _f together form a QQ-alkylene bridge; R _{f represents} hydrogen, halogen or QQ alkyl;

R _x and R _γ independently represent hydrogen, halogen, alkyl QQ, QQ-alkoxy, QQ-alkylthio, -COOR ₁ 6, trifluoromethyl, nitro or cyano; R "R _k and R _m independently of one another for hydrogen or QQ-alkyl; or R _k and R _m together form a Q-Qalkylene bridge, which can be interrupted by oxygen, NH or -N (Q- C ₄ alkyl);

R _{n is} QC ₄ alkyl, phenyl, or phenyl substituted by halogen, QQ alkyl, methoxy, nitro or trifluoromethyl;

R ₁₆ for hydrogen, QQ ₀ -alkyl, QQ-alkoxy-QQ-alkyl, QQ-alkylthio-QQ-alkyl, di- QC ₄ -alkylamino -CC-C ₄ -alkyl, halogen-Ci-Cg-alkyl, C ₂ -Cg-alkenyl, halogen-QQ-alkenyl, C ₃ -C ₈ -alkynyl, C -C ₇ -cycloalkyl, halogen-C ₃ -C ₇ -cycloalkyl, Ci-Cg-alkylcarbonyl, allylcarbonyl, C ₃ -C ₇ - Cycloalkylcarbonyl, benzoyl, which is unsubstituted or substituted on the phenyl ring in the same or different way up to three times by halogen, QQ-alkyl, halogen-QQ-alkyl, halogen-QQ-alkoxy or QQ-alkoxy; or furoyl, thienyl; or QQ-alkyl substituted by phenyl, halophenyl, QQ-alkylphenyl, QQ-alkoxyphenyl, halogen-QQ-alkylphenyl, halogen-QQ-alkoxyphenyl, QQ-alkoxycarbonyl, QQ-alkoxy-C -Cg-alkoxycarbonyl, QQ-alkenyloxycarbonyl, C ₃ -Cg-alkynyloxycarbonyl, QQ-- alkylthiocarbonyl, C ₃ -C ₈ -alkenylthiocarbonyi, QQ-alkynylthiocarbonyl, carbamoyl, mono-C ₁ -C ₄ -alkylaminocarbonyl, di-QC ₄ -alkylaminocarbonyl; or phenylaminocarbonyl which is unsubstituted or substituted on the phenyl in the same or different manner up to three times by halogen, Q-Q-alkyl, halogen-QQ-alkyl, halogen-QQ-alkoxy or QQ-alkoxy or simply by cyano or nitro, or dioxolane 2-yl which is unsubstituted or substituted by one or two QQ-alkyl radicals, or dioxan-2-yl which is unsubstituted or substituted by one or two QQ-alkyl radicals, or QQ-alkyl which is substituted by cyano, nitro, Carboxyl or QQ-alkylthio-QQ-alkoxycarbonyl is substituted; of a safener of Formula Ee

wherein R17 and Rι ₈ independently of one another for QQ-alkyl or QQ-alkenyl; or

R ₁₇ and Rig together for

R ₃₅ and R _{36 are} independently hydrogen or QQ alkyl;

or R ₁ 7 and R g together for

R ₃₇ and R ₈ independently of one another for QQ-alkyl, or R ₃₇ and R ₃₈ together (CH ₂ ) ₅ -;

or R ₁ 7 and rig together for

R4O, R41, R ₄₂ , R4, R44, R45, R46, R47, R48, R49, Rθ50 ₅ 51, 52> 5 ₃ , R54 and R55 independently of one another represent hydrogen or QQ-alkyl; of a safener of Formula Ef

wonn

R _{20 is} hydrogen or chlorine and R _{19 is} cyano or trifluoromethyl, or a safener of the formula Eg

wherein

R _{2 is} hydrogen or methyl.

2. Composition according to claim 1, characterized in that A is hydrogen, hydroxy, O ^" M ⁺ , OR ₂₇ , NR ₂₈ R ₂₉ or together with Q ₂ -O-; Qi is hydrogen, hydroxy, halogen, cyano, C (0) NH ₂ , OR ₅₈ or -OC (0) -R ₅₇ ; Q _{2 is} hydrogen, hydroxy or together with Qi = 0; M ⁺ Li ⁺ , Na ⁺ , K ⁺ , 1/2 Mg ²⁺ , 1/2 Ca ^{2 *} or N ⁺ R ₃₀ R ₃ ιR ₃₂ R ₃₃ ; R ₂₂ and R ₂₃ independently of one another hydrogen, halogen, QQ-alkyl, trifluoromethyl, -0- (QQ) alkyl or C ₃ -C ₅ cycloalkyl; R ₅₉ and R ₆₀ independently of one another is hydrogen, halogen, QQ-alkyl, trifluoromethyl, -0- (Q-Q) -alkyl or C -C ₅ -cycloalkyl; or

R ₂₂ and R ₂ together form a butadienylene chain which can be substituted by halogen, methyl, methoxy, -S (0) _r CH ₃ , trifluoromethyl or trifluoromethoxy and fused to positions 3 and 4;

R _{25 is} hydrogen, -0- (QQ) alkyl, -OQQ-alkenyl, -OQQ-alkynyl, difluoromethoxy or trifluoromethoxy;

R ₂₆ QQ-alkyl, QQ-cycloalkyl, -0- (QQ) alkyl, -OQQ-alkenyl, -OQQ-alkynyl, difluoromethoxy, trifluoromethoxy, halogen or trifluoromethyl; R ₅₈ independently of one another QQ-alkyl, QQ-cycloalkyl, -0- (QQ) -alkyl, -OQ-Q-alkenyl, -OQQ-alkynyl, halogen or trifluoromethyl; or R ₂₆ and egg together -CH ₂ -CH -; R ₂₇ Q-Cg-alkyl, QQ-cycloalkyl, QQ-alkenyl, QQ-alkynyl, benzyl, QQ-haloalkyl,

Q-Q-haloalkenyl,

R _{28 is} hydrogen, QQ-alkyl, QQ-alkenyl or QQ-alkynyl;

R _{29 is} hydrogen, QQ-alkyl, QQ-alkenyl, QQ-alkynyl, or by halogen, -X ₂ - (QQ-

Alkyl), hydroxy, amino, -NH (QQ-alkyl), N (QC ₅ -alkyl) ₂ or -CH (X ₃ R ₃₄ ) (X4R5 _< _) substituted QQ-alkyl, QQ-alkenyl or QQ-alkynyl; Phenyl, pyridyl or benzyl or by halogen, QQ-alkyl, QQ-haloalkyl, -S (0) _p -QQ-alkyl, nitro, cyano or

Trifluoromethoxy substituted phenyl, pyridyl or benzyl; or the group

in which R 1 is hydrogen, Q-Cg-alkyl, Q-Q-alkenyl or Q-Q-

Alkynyl; Rέ ₂ for hydrogen, QQ-alkyl, or by hydroxy, SCH ₃ , SH, benzyl, indol-3-yl,

4-hydroxybenzyl, COOR6 ₃ , C (0) NH ₂ , amino, or imidazol-5-yl substituted QQ-alkyl; and R _{63 represents} hydrogen, Q-Cg-alkyl, QQ-alkenyl or QQ-alkynyl;

X ₂ , X and X4 independently of one another oxygen or sulfur; p, r, s and t independently of one another 0, 1 or 2;

R ₂₈ and R ₂ together form a QQ alkylene chain which is substituted by halogen, methyl, methoxy,

-S (0) _s CH ₃ , trifluoromethyl or trifluoromethoxy may be substituted and may be interrupted by -O-, -NH- or -N (QQ-alkyl) -;

R ₃₄ and R50 are independently QQ alkyl; or

R ₃₄ and R56 together form a QQ alkylene chain;

R ₅₇ QQ-alkyl, QQ-cycloalkyl, QQ-alkenyl, QQ-alkynyl, phenyl or benzyl or by halogen, QQ-alkyl, QQ-haloalkyl, -S (0) _t -QQ-alkyl, nitro, cyano or

Trifluoromethoxy substituted phenyl or benzyl;

Q the group

Egg methine, -C (halogen) - or nitrogen; R ₃₀ , R ι, R ₃₂ and R ₃₃ independently of one another hydrogen, QQ-alkyl or QQ-alkyl substituted by hydroxy or methoxy; or

R ₃₀ and R ₃ ι or R ₃₀ , R ₃ ι and R ₃₂ or R ₃₀ , R, R ₃₂ and R ₃₃ together form a QQ- alkylene chain which is represented by -O-, -NH- or -N (QQ-alkyl) - can be interrupted.

3. Composition according to claim 1, characterized in that in the compounds of formula I Ei stands for methine, R ₂₂ and R_3 are hydrogen and R_s and R _{26 are} methoxy.

4. Means according to claim 3, characterized in that W stands for Wi; R59 is hydrogen, fluorine, chlorine or methoxy; R ₆ o is hydrogen, fluorine, or chlorine;

A hydroxy, 0 ^" M ⁺ , NR ₂₈ R ₂₉ or together with Q ₂ -O-; Qi hydrogen, hydroxy, OR ₅₈ or -OC (0) -R ₅₇ , and R ₅₇ QQ-alkyl, QQ-alkenyl or QQ Mean alkynyl.

5. Composition according to claim 4, characterized in that R _{28 is} hydrogen or methyl and R ₂₉ QC ₈ alkyl, QQ-alkenyl, QQ-alkynyl, or by halogen, -X ₂ - (QQ-alkyl), hydroxy, amino, -NH (QQ-alkyl), N (QQ-alkyl) ₂ or -CH (X ₃ R ₃₄ ) (X ₄ R ₅₆ ) substituted QQ-alkyl, QQ-alkenyl or QQ-alkynyl; Phenyl, pyridyl or benzyl or by halogen, Q-Q-alkyl, QQ-haloalkyl, -S (0) _p -QQ-alkyl, nitro, cyano or trifluoromethoxy

substituted phenyl, pyridyl or benzyl; or the group in which Rβi is

Hydrogen, QQ-alkyl, QQ-alkenyl or QQ-alkynyl; R ₆₂ for hydrogen, QQ-alkyl, or CC substituted by hydroxy, SCH ₃ , SH, benzyl, indol-3-yl, 4-hydroxybenzyl, COOR ^, C (0) NH ₂ , amino, or imidazol-5-yl ₅ alkyl; and R _{63 represents} hydrogen, Ci-Cg-alkyl, QQ-alkenyl or QQ-alkynyl; mean.

6. Composition according to claim 4, characterized in that R ₅₉ chlorine; Rgo hydrogen;

AOM ⁺ or together with Q ₂ -O-; Qi is hydrogen, hydroxy or -OC (O) - Ci-Cg-alkyl; and M is Li ⁺ , Na ⁺ , K ⁺ , NH ₃ ⁺ C-Cg-alkyl or NH ₂ ⁺ (QQ-alkyl) ₂ .

7. Composition according to claim 1, characterized in that it contains a safener of the formula Ea.

8. Composition according to claim 7, characterized in that in the formula Ea Xi for chlorine and R, for -CH (CH ₃ ) QH "(n).

9. A process for the selective control of weeds and grasses in crops, characterized in that the crop plants, their seeds or stems or their cultivated area are used simultaneously or separately with a herbicidally active amount of a herbicide of the formula I and a herbicide-antagonistically effective amount of a safener of the formulas Ea to Eg.

10. The method according to claim 9, characterized in that crops or crop areas for crops with 0.001 to 4 kg / ha of a herbicide of the formula I according to claim 1 and an amount of 0.001 to 0.5 kg / ha of a safener of the formulas Ea to Eg treated according to claim 1.

11. The method according to claim 9, characterized in that it is in the crops of cereals, corn, rice or soy.