CZ394999A3 - Substituted 2-(3-alkenylbenzoyl)cyclohexane-1,3-diones - Google Patents

Abstract

2- (3-Alkenylbenzoyl) cyldohexane-1,3-dione general formula I, in which R1, R2 are hydrogen, nitro, atom halogen, cyano, thiocyanato, alkyl, haloalkyl, alkoxyalkyl, alkenyl, alkynyl, -OR 6, -OCOR 7, -SH, -S (O) n R 8, -SO 2 OR 6, -SO 2 NR 6 R 9, -NR 9 SO 2 R 7 or -NR 9 CIR 7, R 3 is hydrogen, atomhalogen, alkyl, haloalkyl, alkoxy, alkenyl or alkynyl, Q is unsubstituted or substituted cyclohexane-1,3-dionic ring attached at the 2-position and having the same salts. The use of such derivatives or compositions containing them for controlling undesirable plant growth.

Description

Substituted 2- (3-alkenylbenzoyl) cyclohexane-1,3-diones

Technical field

The present invention relates to 2- (3-alkenylbenzoyl) cyclohexane-1,3-dione of formula I

(I) wherein the substituent symbols have the following meanings:

R ¹ , R ² are hydrogen, nitro, halogen, cyano, thiocyanato, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 8 alkoxy-C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 -alkynyl, -0R ^s -0C0R ^7, -OSO 2 R ^7, thio, -S (O) n R ^e, -SO2OR ^6, -SO ₂ NR ⁶ R ^9,

-NR ⁹ SO ₂ R ⁷ or -NR ⁹ COR ⁷ ,

R ³ is hydrogen, halogen, C -C alkyl, C -C haloalkyl, C -C _g alkoxy, C ₂ -C _g alkenyl, _C2 ~ _Cg alkynyl,

R ^4, R ³ is hydrogen, nitro, halogen, cyano, thiocyanato, C _T -C _g alkyl, • "haloalkyl, C ₃ -C _g cycloalkyl, C ₂ -C ₆ alkenyl, C ₄ ~ _Ce cycloalkenyl, _C2-Cg alkynyl, C _x C _g alkoxy, _C -C alkylthio _g C _g -C haloalkoxy, -COR ^10, -CO-R ^10, -COSR ^10, -CONR ^ R ¹¹ ,

-C (R ¹² ) = NR ¹³ , -PO (OR ¹⁰ ) (OR ¹¹ ), a C 1 -C 4 alkyl group having one of the following groups attached thereto: hydroxyl group, COR ¹⁰ group, -CO_R ¹⁰ , -COSR ¹⁰ -C0NR ^lo R ^L or -C (R ¹²⁾ = NR ^13, heterocyclyl, heterocyclyl-C ^ -C ^ alkyl, phenyl, phenyl-C-C4 alkyl, hetaryl, _hetaryl-C - The C ₄ alkyl group and the last six of these groups may be substituted or

R ⁴ and R ^s together form C ₂ ~ C _g -alkanediyl chain which can be mono- to tetrasubstituted by C, -C ₄ alkyl group and / or may be interrupted by oxygen or sulfur or by a nitrogen which is unsubstituted or substituted by C, -C ₄ alkyl, n is 0, 1 or 2,

R ⁶ is hydrogen, C, -C _g alkyl, C _i -C _e haloalkyl, _{C g} -C -alkoxy-C ₂ -C _g alkyl, _C3 ~ _Cg alkenyl or C ₃ -C _g alkynyl,

^R7 is C, -C _s alkyl or C ₁ -C haloalkyl,

R _e is C _g -C alkyl, C -C haloalkyl, C -C _g -alkoxy-C ₂ -C _g alkyl, C ₃ -C alkenyloxy _g • ·· · · · · · · I • 4 • · · · · 4 · 4 · · · ·

R®

Rl °

RX!

R ^xo a

R ¹² cycloC -C

Fenylonylová 6 alkyl or C ₃ -C _g alkynyl, is hydrogen or C _x -C _g alkyl, is hydrogen, C _x -C _g alkyl, C ₃ -C _g alkyl group C _x -C haloalkyl _g group, an alkenyl group, a C ₃ -C _g alkynyl, weighing or benzyl group and the last two groups from the following list may be partially or fully halogenated and / or can have attached one to three of the following groups: nitro, cyano, C _x -C ₄ alkyl, C -C haloalkyl, C _x -C ₄ alkoxy, C _x -C ₄ haloalkoxy, C _x -C ₄ alkylcarbonyl or C _x -C ₄ alkoxycarbonyl group, a hydrogen atom, a C _x - C _g alkyl, C ₃ -C _alkenyl radical or C ₃ -C _g alkynyl or

R ¹¹ together form a C ₂ -C _g alkanediyl chain which can be mono- to tetrasubstituted by C _x -C ₄ alkyl group and / or may be interrupted by oxygen or sulfur or by a nitrogen which is unsubstituted or substituted by _{C 4} -C alkyl, is hydrogen, C _x -C _g alkyl, C, -C _{x g} haloalkyl, C _x C _g alkoxy, C ₂ -C _g alkoxycarbonyl, _C3-Cg cycloalkyl, C ₂ -C _g alkenyl, C ₂ -C _g alkynyl, phenyl or benzyl, the last two of these groups may be partially or fully halogenated and / or may be connected one to three groups from the following list: nitro, cyano, C ~ _x C ₄ alkyl, CC haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylcarbonyl or C 1 -C ₄ alkoxycarbonyl,

R ¹³ is a C _x -C _g alkyl, C, -C _{x g} haloalkyl, C ₃ -C _g cycloalkyl, C ₃ -C _alkenyl radical, C ₃ -C _g alkynyl, C _x C _g alkoxy, C _x -C _g haloalkoxy, C ₃ -C _g cycloalkyloxy, C ₃ -C _g alkenyloxy, C ₃ -C _g alkynyloxy, phenyl, benzyl, or phenyl-C _x -C ₄ -alkoxy, and the last three of these groups, be partially or fully halogenated and / or may have one to three groups selected from the following list: nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C 4 ₄ haloalkoxy, C ₁ -C ₄ alkylcarbonyl or C ₁ -C ₄ alkoxycarbonyl,

Q is an unsubstituted or substituted cyclohexane-1,3-dione ring which is attached at the 2-position and salts thereof which can be used in agriculture.

The present invention further relates to processes for the preparation of a compound of formula I, to compositions comprising it, and to the use of this compound of formula I and compositions comprising it for controlling harmful plants.

BACKGROUND OF THE INVENTION

WO 93/24446 discloses cyclohexane-1,3 »··

diones which are substituted in the 2-position and which have anthelmintic and nematicidal properties. 2-Benzoylcyclocyclohexane-1,3-diones are also known in the literature, for example EP-A 135 191, EP-A 137 963 and EP-A 319 075. However, the herbicidal properties of these compounds and their crop tolerance are only slightly satisfactory.

SUMMARY OF THE INVENTION

In particular, it is an object of the present invention to find herbicidally active compounds with improved properties.

The present inventors have found that this object can be achieved by 2- (3-alkenylbenzoyl) cyclohexane-1,3-diones of formula I and their herbicidal action.

Furthermore, they find highly effective herbicidal compositions comprising a compound of formula I. In addition, they find methods for preparing such compositions and methods of controlling undesirable vegetation with a compound of formula I.

The present invention also relates to stereoisomers of a compound of formula I. This includes not only pure stereoisomers but also mixtures thereof.

The compound of formula I contains a double bond between carbon atoms and therefore exists in the form of E or Z isomers or isomeric E / Z mixtures. Further, the compound of formula (I) may contain additional double bonds between carbon atoms or between a carbon atom and a nitrogen atom. The present invention relates not only to pure geometric isomers but also to mixtures thereof.

· Ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft

I ftft * · • ♦ • • ft ft

The compound of formula I may also have one or more chiral centers, depending on the type of substitution, and in this case exists as a mixture of enantiomers or diastereomers. The present invention relates not only to pure enantiomers or diastereomers, but also to mixtures thereof.

The compound of formula (I) may also exist in the form of its agriculturally useful salts, and the type of salt is not generally important. In general, salts of those cations or acid addition salts of those acids in which the cations or anions do not adversely affect the herbicidal activity of the compound of formula I are suitable.

Suitable cations are, in particular, alkali metal ions, preferably lithium, sodium and potassium, alkaline earth metals, preferably calcium and magnesium and transition metals, preferably manganese, copper, zinc and iron, as well as ammonium ions, in which case one to four hydrogen atoms C _x -C ₄ alkyl, hydroxy-C₁₋₄ -C ^ alkyl, C _i -C ₄ -alkoxy-C _i -C ₄ -alkyl, hydroxy-C _i -C _{4 -alkoxy-C} -C ₄ -alkyl, phenyl or benzyl, preferably ammonium salts, dimethylammonium salts, diisopropylammonium salts, tetra-methylammonium salts, tetrabutylammonium salts, 2- (2-hydroxyeth-1-oxy) eth-1-ylammonium salts, di - (2-hydroxyeth-1-yl) ammonium salts, trimethylbenzylammonium salts and further phosphonium salts, sulfonium salts, preferably tri (C ₁ -C ₄ -alkyl) sulfonium salts and sulfoxonium salts, preferably tri (C ₁ -C ₄ -alkyl) sulfoxonium salts.

Anions of useful acid addition salts are mainly chloride anion, bromide anion, fluoride anion, hydrogen sulphate anion, sulphate anion, dihydrogenphosphate anion, hydrogenphosphate anion, nitrate anion, hydrogen carbonate anion, carbonate anion, hexafluorsilicate anion, hexafluorsilicate anion, hexafluorsilicate anion alkanoic acids, preferably a formate anion, an acetate anion, a propionate anion and a butyrate anion.

Mention should be made of a compound of the formula I according to the invention in which the variable Q is cyclohexane-1,3.

a dione ring of the general formula II r14 OH AND ^Rl? Rie ^R19

(II) which is attached in position 2 and II may also represent tautomeric formulas II 'and II' '

(II) (II ') • 9 ··

9 ·

in which

R ^14, R ^x, R ¹⁷ and R ¹⁹ are hydrogen or C _x -C ₄ alkyl,

R ¹⁶ is hydrogen, C -C alkyl, C, _X ~ C haloalkyl group or C ₃ -C ₄ cycloalkyl group, and these last three groups may be attached one to three of the following substituents: C _x -C ₄ alkylthio or C _{x C4} alkoxy group, or the substituent is a tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl,

1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2-yl or 1,3-dithian- The 2-yl group and the latter 6 groups may carry one to three C ₁ -C ₄ alkyl groups as substituents,

® R ^x is hydrogen, C _x -C ₄ alkyl or C _x -C _s alkoxycarbonyl or a

R ^x6 and R ^x9 together form a π bond or a three- to six-membered carbocyclic ring fcfc fcfc fcfc fcfc fcfcfcfc fc fc fc ····· · · Fcfc or CR ^ R ^{17 can be} replaced by group C = 0.

The organic radicals described for the substituents R ¹ to R ¹⁹ or as groups on the phenyl, hetaryl and heterocyclyl ring represent common terms for the individual enumerations of the group members. All hydrocarbon chains, i.e. all alkyl, haloalkyl, cycloalkyl alkoxyalkyl groups, alkoxy groups, haloalkoxy groups, cycloalkoxy groups, alkylthio groups, alkylcarbonyl groups, alkoxycarbonyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, alkynyl groups, alkenyloxy groups, alkenyloxy groups, alkenyloxy groups, alkenyloxy groups, alkenyloxy groups. Unless otherwise stated, the halogenated substituents preferably have the same or different halogen atoms in the number of one to five. In each case, halogen atoms are fluorine, chlorine, bromine or iodine.

Examples of other meanings are:

C ₂ -C ₄ alkyl: ethyl, n-propyl, 1-methylethyl, butyl,

1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl,

C ₁ -C ₄ alkyl and C ₁ -C ₄ -alkoxy-C ₄ -C ₄ -alkyl groups, hydroxy-C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl groups, C ₁ -C ₄ alkylcarbonyl groups , heterocyclyl-C ₁ -C ₄ alkyl groups, phenyl-C ₁ -C ₄ -alkyl groups, hetaryl-C ₁ -C ₄ -alkyl groups: a C ₂ -C ₄ alkyl group as described above, and also a methyl group,

C ₂ -C ₆ alkyl and C _x -C _g -alkoxy-C ₂ -C _g -alkyl. A C ₂ -C ₄ alkyl group as described above 99

9 «

9

99

9 9

9 99

9 9

9 9 9

9 9

99 • 9 *

9 9

999 999

9

And also pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2 -dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,

1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,

3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl or

1-ethyl-3-methylpropyl group,

C _i -C _s alkyl group and further -C -alkoxy-C _x -C alkyl groups _with C ₂ -C _g alkyl group as described above, and also methyl, haloalkyl C, -C ₄ alkyl group as described above, which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl , chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,

2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl,

0 0

0

0 ·

0 0 0 0 0

0 0

00 00 »00» 0

0 0

00 is pentafluoroethyl, 2-fluoropropyl,

3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3, 3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2- chloroethyl, 1- (bromomethyl) -2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl,

C _x -C haloalkyl _g CC haloalkyl, as described above, and also 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-jodpentylová group, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl 6-bromo-hexyl, 6-iodo-hexyl, or dodecafluorohexyl,

C ₁ -C ₄ alkoxy radicals and alkoxy-C _i -C _{4 -alkoxy-C L} -C ₄ -alkyl, hydroxy-C _i -C ₄ -alkoxy-C _i -C ₄ alkyl groups _and C - C ₄ alkoxycarbonyl groups: methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy,

2-methylpropoxy or 1,1-dimethylethoxy,

C 1 -C 4 alkoxy- and alkoxy-C 1 -C 4 alkoxy-C 1 -C 4 -alkyl and C ₁ -C ₄ alkoxycarbonyl groups: C ₁ -C ₄ alkoxy as mentioned above, as well as pentoxy, 1-methylbutoxy, 2-methylbutoxy * 9 9 9

999 999 9

98 99 «9

9 ·· ·

9 99

9 · 4 · 9 ·

99'-group, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy,

1-methylpentoxy, 2-methylpentoxy,

3-methylpentoxy, 4-methylpentoxy,

1,1-dimethylbutoxy, 1,2-dimethylbutoxy,

1,3-dimethylbutoxy, 2,2-dimethylbutoxy,

2,3-dimethylbutoxy, 3,3-dimethylbutoxy,

1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy,

C ₄ -C ₄ haloalkoxy: C 1 -C ₄ alkoxy as described above, which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromdifluoromethoxy,

2-fluoroethoxy, 2-chloroethoxy,

2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,

2.2.2- trichloroethoxy, pentafluoroethoxy,

2-fluoropropoxy, 3-fluoropropoxy,

2-chloropropoxy, 3-chloropropoxy,

2-bromopropoxy, 3-bromopropoxy,

2,2-difluoropropoxy, 2,3-difluoropropoxy,

2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy,

1- (Fluoromethyl) -2-fluoroethoxy, 1- (chlorine), (Chlorine) · · · · · · · · · · · · · · · · · · · · · · · · · · · methyl) -2-chloroethoxy, 1- (bromomethyl) -2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nona fluorobutoxy,

C -C haloalkoxy: haloalkoxy as described above and, for example, 5-fluoropentoxy,

5-chloropentoxy, 5-bromopentoxy,

5-iodopentoxy, undecafluoropentoxy,

6-fluorohexoxy, 6-chlorohexoxy,

6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy,

C ₃ -C ₆ cycloalkoxy: cyclopropoxy, cyclobutoxy, cyclopentoxy or cyclohexoxy,

C 1 -C 6 alkylthio: methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio,

2-methylpropylthio or 1,1-dimethylethylthio,

C _x -C _s alkylthio, C _x -C ₄ alkylthio group, as described above, and for example, pentylthio,

1-methylbutylthio, 2-methylbutylthio,

3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio,

1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio,

4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethyl 9, 9, 99, 9, 99, 9, 9 9 9 • 99999 • 9

99 butylthio, 2,2-dimethylbutylthio,

2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio,

1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio or 1-ethyl-2-methylpropylthio,

C ₃ -C _e alkenyl: prop-l-en-l-yl, prop-2-en-l-yl, 1-methylethenylová group, buten-l-yl, buten-2-yl, buten -3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl,

2-methylprop-2-en-1-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methylbut-1-en-1 -yl, 2-methylbut-1-en-1-yl,

3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl a group, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-ene 1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl,

1-ethylprop-2-en-1-yl, hex-1-en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4- en-1-yl, hex-5-en-1-yl, 1-methylpent-1-en-1-yl,

2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl Group, • 9 ·· • 9 9 9

9 9 9 9 9 9 9 9 9 9 9 9

999 999

9

99

2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl group,

2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl a group, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-ene -l-yl group,

1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut -3-en-1-yl, 1,3-dimethylbut-1-en-1-yl,

1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1 -en-1-yl group,

2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2 -en-1-yl group,

1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl,

2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl,

1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl or

1-ethyl-2-methylprop-2-en-1-yl,

C ₂ -C _g alkenyl: _C3-C6 alkenyl group as described above, and also ethenyl,

C ₃ -C _g alkynyl: prop-l-yn-l-yl, prop-2-yn-l-yl, but-l-yn-l-yl, but-l-yn-3-yl but-1-yn-4-yl group;

0 0 0 0 • 0 0 0 0

0 000 000

0 0

000 00 00 • 0 • 00

00 0 0 0 0 0 00 0 0 0 0 0 0 0 00 00 But-2-yn-1-yl, pent-1-yn-1-yl, pent-1-yn-3-yl, pent 1-in-4-yl, pent-1-in-5-yl, pent-2-in-1-yl, pent-2-in-4-yl, pent-2-in-5 -yl group,

3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, hex-1-yn-1-yl, hex-1-yn-3-yl, hex- 1-in-4-yl, hex-1-in-5-yl, hex-1-in-6-yl, hex-2-in-1-yl, hex-2-in-4- yl, hex-2-yn-5-yl, hex-2-yn-6-yl, hex-3-yn-1-yl, hex-3-yn-2-yl, 3-methylpent -1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4 -methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl or 4-methylpent-2-yn-5-yl,

C ₂ -C ₆ alkynyl, C ₃ -C _g alkynyl group as described above, and also ethynyl,

C ₃ -C ₄ cycloalkyl: cyclopropyl or cyclobutyl,

C ₃ -C _e cycloalkyl, C ₃ -C ₄ cycloalkyl group, as described above, and also cyclopentyl or cyclohexyl,

C ₃ -C _{e-alkenyloxy:} for example prop-l-en-l-yloxy, prop-2-en-l-yloxy, 1-methylethenyloxyskupina, butene-l-yloxy, buten-2-yloxy, buten-3-yloxy, 1-methylprop-1-en-1-yloxy, 2-methylprop-1-en-1-yloxy,

1-methylprop-2-en-1-yloxy, 2-methylprop-299 9 9

9 9 9 • 99,999

9 · 99 · 99 · 9 · 99

9 9 • 9 * 9 99

-en-1-yloxy, penten-1-yloxy, penten-2-yloxy, penten-3-yloxy, penten-4-yloxy, 1-methylbut-1-en-1-yloxy,

2-methylbut-1-en-1-yloxy, 3-methylbut-1-en-1-yloxy, 1-methylbut-2-en-1-yloxy,

2-methyl-but-2-en-1-yloxy, 3-methyl-but-2-en-1-yloxy, 1-methyl-but-3-en-1-yloxy,

2-methylbut-3-en-1-yloxy, 3-methylbut-3-en-1-yloxy, 1,1-dimethylprop-2-en-1-yloxy,

1,2-dimethylprop-1-en-1-yloxy, 1,2-dimethylprop-2-en-1-yloxy, 1-ethylprop-1-en-2-yloxy, 1-ethylprop-2-en-1-yloxy, hex-1-en-1-yloxy, hex-2-en-1-yloxy, hex-3-en-1-yloxy, hex-4-en-1-yloxy, hex-5-en-1-yloxy, 1-methylpent-1-en-1-yloxy, 2-methylpent-1-en-1-yloxy,

3-methylpent-1-en-1-yloxy, 4-methylpent-1-en-1-yloxy, 1-methylpent-2-en-1-yloxy,

2-methylpent-2-en-1-yloxy, 3-methylpent-2 -en-1-yloxy, 4-methylpent-2-en-1-yloxy,

1-methylpent-3 -en-1-yloxy, 2-methylpent-3 -en-1-yloxy, 3-methylpent-3 -en-1-yloxy,

4-methylpent-3-en-1-yloxy, 1-methylpent-4 -en-1-yloxy, 2-methylpent-4-en-1-yloxy,

3-methylpent-4-en-1-yloxy, 4-methylpent-4-en-1-yloxy, 1,1-dimethylbut-2-en-1-yloxy, 1,1-dimethylbut-3-en-1- yloxy group,

1,2-dimethylbut-1-en-1-yloxy, 1,2-dimethylbut-2 -en-1-yloxy, 1,2-dimethylbut-3-en-1-yloxy, 1,3-dimethylbut-1-ene -l-yloxy,

1,3-dimethylbut-2-en-1-yloxy, 1,3-dimethylbut-3-en-1-yloxy, 2,2-dimethylbut-3-en-1-yloxy, 2,3-dimethylbut-1-en- l-yloxy,

• ··

2,3-dimethylbut-2-en-1-yloxy, 2,3-dimethylbut-3-en-1-yloxy, 3,3-dimethylbut-1-en-1-yloxy, 3,3-dimethylbut-2- en-1-yloxy,

1-ethylbut-1-en-1-yloxy, 1-ethylbut-2-en-1-yloxy, 1-ethylbut-3-en-1-yloxy,

2-ethylbut-1-en-1-yloxy, 2-ethylbut-2-en-1-yloxy, 2-ethylbut-3-en-1-yloxy,

1,1,2-trimethylprop-2-en-1-yloxy, 1-ethyl-1-methylprop-2-en-1-yloxy, 1-ethyl-2-methylprop-1-en-1-yloxy or 1- ethyl-2-methylprop-2-en-1-yloxy,

C ₃ -C _g alkinylooxyskupina: for example prop-1-yn-l-yl oxy, prop-2-yn-1-yloxy, but-l-yn-l-yloxy, but-1-yn-3-yloxy, but 1-yn-4-yloxy, but-2-yn-1-yloxy, pent-1-yn-1-yloxy, pent-1-yn-3-yloxy, pent-1-yn-4-yloxy, pent 1-yn-5-yloxy, pent-2-yn-1-yloxy, pent-2-yn-4-yloxy, pent-2-yn-5-yloxy, 3-methylbut-1-yn-3- yloxy group,

3-methylbut-1-yn-4-yloxy, hex-1-yn-1-yloxy, hex-1-yn-3-yloxy, hex-1-yn-4-yloxy, hex-1-yn-5- yloxy, hex-1-yn-6-yloxy, hex-2-yn-1-yloxy, hex-2-yn-4-yloxy, hex-2-yn-5-yloxy, hex-2-yn-6- yloxy, hex-3-yn-1-yloxy, hex-3-yn-2-yloxy, 3-methylpent-1-yn-1-yloxy,

3-methylpent-1-yn-3-yloxy, 3-methylpent-1-yn-4-yloxy, 3-methylpent-1-yn-5-yloxy,

4-methylpent-1-yn-1-yloxy, 4-methylpent-2-yn-4-yloxy or 4-methylpent-2-yn-5-yloxy,

C ₄ -C cycloalkenyl: cyclobuten-l-yl • ·

• * 99 9 • « 9 · 9 • • 9 9 • 9 99 · • 9 · 9 9 9 · 9 9 9 9 9 9

cyclobuten-3-yl, cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl or cyclohexen-4-yl, heterocyclyl and heterocyclyl residues in the heterocyclyloxy and heterocyclyl-C 1 -C 4 alkyl groups: 3- to 7-membered, saturated or partially unsaturated, monocyclic or polycyclic heterocycles containing one to three heteroatoms selected from oxygen, nitrogen and sulfur atoms such as oxiranyl, 2-tetrahydrofuranyl, 3 -tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl,

3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl,

5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl,

4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl,

1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazodiazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl,

1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, (·

2,3-dihydrofuran-4-yl, 2,3-dihydrofuran-5-yl, 2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl,

2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,3-dihydrothien-2-yl,

2,3-dihydrothien-3-yl, 2,3-dihydrothien-4-yl, 2,3-dihydrothien-5-yl,

2,5-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,3-dihydropyrrol-2-yl,

2,3-dihydropyrrol-3-yl, 2,3-dihydropyrrol-4-yl, 2,3-dihydropyrrol-5-yl,

2,5-dihydropyrrol-2-yl, 2,5-dihydropyrrol-3-yl, 2,3-dihydroisoxazol-3-yl,

2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl,

4,5-dihydroisoxazol-5-yl, 2,5-dihydroisoxazol-3-yl, 2,5-dihydroisoxazol-4-yl, 2,5-dihydroisoxazol-5-yl,

2,3-dihydroisothiazol-3-yl, 2,3-dihydroisothiazol-4-yl, 2,3-dihydroisothiazol-5-yl, 4,5-dihydroisothiazol-3-yl,

4,5-dihydroisothiazol-4-yl, 4,5-dihydroisothiazol-5-yl, 2,5-dihydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-5-yl yl group,

2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 4,5-dihydropyrazol-3-yl,

4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,5-dihydropyrazol-3-yl, 2,5-dihydropyrazol-4-yl,

2,5-dihydropyrazol-5-yl, 2,3-dihydro-21

oxazol-2-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl,

4,5-dihydrooxazol-2-yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-2-yl, 2,5-dihydrooxazol-4- yl, 2,5-dihydrooxazol-5-yl, 2,3-dihydrothiazol-2-yl,

2,3-dihydrothiazol-4-yl, 2,3-dihydrothiazol-5-yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5- yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl,

2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydroimidazol-2-yl,

4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazol-5-yl, 2,5-dihydroimidazol-2-yl, 2,5-dihydroimidazol-4-yl,

2,5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-tetrahydropyridazinyl,

4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl,

2-tetrahydropyrazinyl, 1,3,5-tetrahydrotriazin-2-yl, 1,2,4-tetrahydrotriazin-3-yl, 1,3-dihydrooxazin-2-yl,

2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothiopyranyl, 3-tetrahydrothiopyranyl, 4-tetrahydrothiopyranyl, ♦ ·

1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl, 1,3-dithiolan-2-yl, 1,3-dithiolan-4-yl, 1,3-dioxan-2- yl group,

1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,3-dithian-2-yl, 1,3-dithian-4-yl, 1,3-dithian-5- yl group,

3,4,5,6-tetrahydropyrid-2-yl, 4H-1,3-thiazin-2-yl, 4H-3,1-benzothiazin-2-yl, 1,1-dioxo-2,3 , 4,5-tetrahydrothien-2-yl, 2H-1,4-benzothiazin-3-yl, 2H-1,4-benzoxazin-3-yl or 1,3-dihydrooxazin-2-yl, hetaryl groups and hetaryl residues in hetaryloxy and hetaryl-C ₁ -C ₄ -alkyl groups: aromatic monocyclic or polycyclic groups which, in addition to the carbon ring members, may contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen atom or one atom sulfur or one oxygen atom or one sulfur atom, for example

2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl,

3-pyrrolyl, 3-isoxazolyl,

4-isoxazolyl, 5-isoxazolyl,

3-isothiazolyl, 4-isothiazolyl,

5-isothiazolyl, 3-pyrazolyl,

4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl,

5-oxazolyl, 2-thiazolyl,

4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl,

1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl,

1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl,

1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2 -pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, or

1,2,4,5-tetrazin-3-yl and the corresponding benzo-fused derivatives,

C ₂ -C _e alkanediyl: for example ethane-1,2-diyl, propane-l, 3-diyl, butane-1, 4-diyl group, pentane-1,5-diyl or hexane-1,6 -diyl group.

All phenyl and hetaryl rings are preferably unsubstituted or have one to three halogen atoms and / or one or two groups selected from the following groups: nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy or methoxycarbonyl.

With respect to the use of the compound of the formula I according to the invention as a herbicide, the substituent symbols preferably have the following meaning, in each case alone or in combination.

R ¹ is nitro, halogen, cyano, thiocyanato, C _i -C ₆ alkyl, C, -C _e haloalkyl, C ^ -C _alkoxy-C -C _g alkyl, C ₂ -C _alkenyl radical, C ₂ -C _g alkynyl • * «• · · · ♦ • 4 · 9

9 9 4 9 9 • • · · ♦ 94, -OR ⁶ or -S (O) nR®, particularly preferably nitro, halogen, such as fluorine, chlorine or bromine, C -C haloalkyl group, -OR ⁶ or -SO2R®,

R ² is hydrogen, nitro, halogen, cyano, thiocyanato, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C 1 -C 8 alkoxy-C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl , -OR ⁶ or -S (O) nR®, particularly preferably hydrogen, nitro, halogen, such as fluorine, chlorine or bromine, C _x -C _g alkyl group, _x C ~ _Cg haloalkyl, -OR ⁶ or -SO 2 R ®, particularly preferably nitro, halogen, for example fluorine, chlorine or bromine, C 1 -C 8 alkyl, for example methyl or ethyl, C 1 -C 8 haloalkyl, for example difluoromethyl or trifluoromethyl a group -OR ⁶ or -SO 2 R ®,

R ³ is hydrogen, halogen, C -C alkyl, C _x -C ₆ haloalkyl, C _x C _g alkoxy, C ₂ -C _alkenyl radical or a C ₂ -C _g alkynyl group, particularly preferably a hydrogen atom a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, a C ₁ -C ₄ alkyl group such as a methyl or ethyl group, a C ₁ -C ₄ haloalkyl group such as a trifluoromethyl group, a C ₁ -C ₄ alkoxy group such as a methoxy group or ethoxy, allyl or propargyl, particularly preferably hydrogen or methyl, ftft ftft ftft ftft ftft ftft ftft ftft ft ftftftft Ftftft ftftft ftft ftft ftft ftft

R ⁴ is hydrogen, nitro, halogen, cyano, thiocyanato, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 4 -C 8 cycloalkenyl, C 2 -C 8 alkynyl , C-C6 alkoxy, C -C alkylthio, C -C haloalkoxy, -COR ^10, -CO ^10, -COSR ^10, -C0NR ^lo R ^l, -C (R ¹²⁾ = NR ^13, -PO ( oR ¹⁰⁾ (oR ^11), _C-C4 alkyl group which has attached thereto one of the following groups: a group COR ^10, -CO 2 R ° ^X, -COSR ^10, -C0NR ^{Lo lx} R or -C (R ¹²⁾ = NR ¹³ , heterocyclyl, heterocyclyl-C 1 -C ₄ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, hetaryl, hetaryl-C ₁ -C ₄ alkyl and the last six of these may be substituted one to three halogen atoms and / or one to three groups of the following groups: nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylcarbonyl, C ₁ -C 4 alkoxycarbonyl,

^R is hydrogen, nitro, halogen, cyano, thiocyanato, C -C alkyl, C -C haloalkyl, C3-Cg cycloalkyl, C2-Cs alkenyl, C4-Ce cycloalkenyl, C2-Cg alkynyl , Cx-Cg alkoxy, Cx-Cs alkylthio, C -C haloalkoxy, -COR ^10, -CO 2 R ° ^X, -COSR ^10, -CONR R ^{xo lx,}

-C (R ¹² ) = NR ¹³ , -PO (OR ^{x 0} ) (OR ¹¹ ), a C 1 -C 4 alkyl group having one of the following groups attached thereto: COR ¹⁰ , -CO 2 R ^X 0, -COSR ¹⁰ , -C0NR ^{lo lux} R, or -C (R ¹²⁾ = NR ^13, heterocyclyl Skupi 9 » '•» • 99 9

9 9 9

9 9 ·

999 999

9a, heterocyclyl-C 1 -C ₄ -alkyl, phenyl, phenyl-C ₁ -C ₄ -alkyl, hetaryl, hetaryl-C ₁ -C ₄ -alkyl and the last six of these groups may be substituted one to three halogen atoms and / or one to three of the following groups: nitro, cyano, C, _X ~ C ₄ alkyl, C -C haloalkyl, C _x -C ₄ alkoxy, C -C haloalkoxy, C _x -C ₄ alkylcarbonyl, C, -C ₄ alkoxycarbonyl group, particularly preferably hydrogen, halogen, cyano, thiocyanato, C _x -C alkyl, C -C _{x g} haloalkyl group,

-COR ^10, -CO R ^10, -COSR ^10, -C0NR ^{lo and R:} or ^L '2

- PO (OR ¹⁰ ) (OR ¹¹ ), or

R ⁴ an

^{6 5} R ⁵ together form a C ₂ -C _g -alkanediyl chain which can be mono- to tetrasubstituted by C, -C ₄ alkyl group and / or may be interrupted by oxygen or sulfur or by a nitrogen which is unsubstituted or substituted by a C _x -C an alkyl group such as butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, 3-oxapentane-1,5-diyl or 3-methyl-3-azapentan-1 , 5-diyl group, a is 0 or 2 is hydrogen, C _x -C _g alkyl, C, -C _{x g} haloalkyl, C _x -C _g -alkoxy-C ₂ -C _g alkyl, C ₃ ~ _Cg alkenyl or C ₃ -C _g alkynyl group is particularly preferably the substituent fc · fc · • • fc fc fc • • • · fcfc fcfc fcfc fc fc fc fc · fcfc fcfcfcfc • fc fc ······ Fcfc fcfc fcfc fcfc

C ₁ -C ₄ alkyl, for example methyl or ethyl, C ₁ -C ₄ haloalkyl, for example trifluoromethyl or difluoromethyl, C 1 -C ₄ alkoxy-C ₁ -C ₄ -alkyl, for example methoxyethyl, allyl or a propargyl group,

R® is a C _x -C _g alkyl, C, -C _{x g} haloalkyl, C _x -C _g -alkoxy-C ₂ -C _g alkyl, C ₃ -C _alkenyl radical or C ₃ -C _g alkynyl group, particularly preferably C, -C ₄ alkyl, for example methyl or ethyl, C _x -C ₄ haloalkyl, such as trifluoromethyl group, difluoromethyl group, C _x -C _{4 -alkoxy-C L} -C ₄ -alkyl , such as methoxyethyl, allyl or propargyl,

R ^1D is hydrogen, C -C alkyl, C -C cycloalkyl, C -C _{x g} haloalkyl, C ₃ -C _alkenyl radical, C ₃ -C _g alkynyl, phenyl or benzyl, particularly preferably the substituent is a hydrogen atom, a C ₁ -C ₄ alkyl group such as a methyl or ethyl group, a C ₁ -C ₄ haloalkyl group such as a trifluoromethyl group, an allyl group, a propargyl group and a benzyl group,

R ¹¹ is hydrogen, C _x -C _g alkyl, _C3 ~ _Cg alkenyl or C ₃ -C _g alkynyl or • * • * 9 9 9 9 9 9 9 • • • 9 · · · · ·

9 «99 • 99 · 9

9 9 9 9 • 9 é 9 · 9 9 9 999

9 9

9 9 99 99

R ¹⁰ and R ¹¹ together form a C ₂ -C _g -alkanediyl chain which can be mono- to tetrasubstituted by

C ₁ -C ₄ alkyl,

R ¹² is hydrogen, C _x C ~ _g alkyl, C, -C _{x g} haloalkyl, C _x -C _e alkoxy group, a C _x -C _g alkoxycarbonyl, C ₃ -C _g cycloalkyl group, a C ₂ -C _g alkenyl, C ₂ -C _g alkynyl, phenyl or benzyl, particularly preferably the substituent is hydrogen, C _x -C ₄ alkyl, for example methyl or ethyl, C _x -C ₄ alkoxycarbonyl, for example methoxycarbonyl a group or ethoxycarbonyl group, a C ₁ -C ₄ haloalkyl group, for example a trifluoromethyl group or a C ₁ -C ₄ alkoxy group, for example a methoxy group or an ethoxy group,

R ¹³ is a C _x -C _g alkyl, C, -C _{x g} haloalkyl, C ₃ -C _g cycloalkyl, C ₃ -C _g alkenyl, _C3 ~ _Cg alkynyl, C _x C _g alkoxy, C _x -C _g haloalkoxy, C ₃ -C _g cycloalkyloxy, _C3-Cg alkenyloxy, _C3-Cg alkynyloxy, phenyl, benzyl or benzyloxy, more preferably C _x -C ₄ alkyl, for example methyl or ethyl, C ₁ -C ₄ alkoxy, for example methoxy or ethoxy, allyloxy, propargyloxy, benzyl or benzyloxy,

R ¹⁴ , R ¹⁵ , R ¹⁷ , R ^{x £?} They are hydrogen _or a _Cl-C4 alkyl, particularly preferably hydrogen, methyl or ethyl,

9 •

9 9 9 9 9 9 9 9 9 9 9 9 9 9

9 «99

9 9 9

9 9 9

999 999 9

99

R ¹⁶ is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₄ cycloalkyl, and the last three groups may have one to three of the following substituents attached thereto: C ₁ -C 4 ₄ alkoxy or C 1 -C 6 alkylthio, tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothipyran-2-yl, tetrahydrothipyran-3-yl, tetrahydrothipyran-4-yl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithian- 2-yl or 1,3-dithiolan-2-yl, and each of the last six groups may have one to three C-alkyl groups attached thereto, particularly preferably methyl, ethyl, cyclopropyl, di (methoxy) methyl, di (ethoxy) methyl, 2-ethylthiopropyl, tetrahydropyran-2-yl, tetr ahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl, 1,3- dioxan-2-yl, 5,5-dimethyl-1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3- dithiolan-2-yl, 5,5-dimethyl-1,3-dithian-2-yl or 1-methylthiocyclopropyl,

® R ¹ is hydrogen, C _x -C ₄ alkyl group _or a _Cl-C4 alkoxycarbonyl group, particularly preferably hydrogen, methyl or methoxycarbonyl group, especially preferably hydrogen or methyl.

• 9 9 9 · 9 98 9 · 9 9 9 9 9 9 9 9 9 9 1 9 9 9 9 9 9 9 9 99 · 999 • • • 9 9 9 9 « 9 * 9 9 ··· 999 9 «99

It may also be advantageous for R ¹⁶ and R ^{19 to} form a π bond so that double bond systems are obtained.

The CR ¹⁶ R ^{1.7 unit} may also advantageously be replaced by a group C = O.

Particularly preferred compounds of the general formula

I are the ones in which

R ¹ is nitro, halogen, cyano, thiocyanato, C, -C ₆ alkyl, C -C haloalkyl, C _i -C ₆ -alkoxy C_ _L -C ₆ -alkyl, C ₂ -C _s alkenyl, C ₂ -C ₆ alkynyl, -OR ^S or -S (O) _n R ®,

R ² is hydrogen or a group as described above under R ^1.

Particularly particularly preferred is a compound of formula I in which

R ¹ is nitro, halogen, for example fluorine, chlorine or bromine, C-haloalkyl, OR ⁶ or SO ₂ R ₈ ,

R ² is nitro, halogen, such as fluorine, chlorine or bromine, C -C alkyl, for example methyl or ethyl, Ci-C6 haloalkyl, OR ^e or SO2R®, such as methylsulfonyl or ethylsulfonyl .

A particularly preferred compound of formula I is also one in which

R ⁴ is hydrogen, nitro, halogen, cyano, thiocyanato, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C 1 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C 4 -C 8 cycloalkenyl, C 2 -C 8 alkynyl , C 1 -C 8 alkoxy, C 1 -C 8 alkylthio, C 1 -C 8 haloalkoxy, -COR ^xo , -CO 2 R ^xo , -COSR ^XO , -CONR ^XO R ^XX ,

-C (R ^{X2) X3} = NR, -PO (0R ^xo) (0R ^xx), C ~ -C4 alkyl group to which is attached one of the following groups: ^xo -COR, -C02R ^xo, -COSR ^XO - CONR R ^{XO XX} or -C (R ^x2) = NR ^X3, heterocyclyl, heterocyclyl-C _x -C ₄ -alkyl, phenyl, phenyl-C _x -C ₄ -alkyl, hetaryl, hetaryl-C _x The -C ₄ -alkyl group and the last six groups may be substituted,

^R is hydrogen, halogen, cyano, thiocyanato, C -C alkyl, C -C haloalkyl, -COR ^{XO, XO} -C02R, -COSR ^{XO, XO} -CONR R ^xx or -PO (OR ^xo) (0R ^xx ) or

R ⁴ and ^R together form a C ₂ -C _g -alkanediyl chain which can be mono- to tetrasubstituted by C _x -C ₄ alkyl group and / or may be interrupted by oxygen or sulfur or by a nitrogen which is unsubstituted or substituted by C _x ~ C ₄ alkyl group.

Equally particularly preferred is a compound of formula (I) wherein:

^Ie R is hydrogen, C _x -C ₄ alkyl, CC haloalkyl, C ₃ -C ₄ cycloalkyl group, and the last three to four groups can be attached two or three of the following substituents: C _x -C ₄ alkylthio or _{C C4} alkoxy.

An equally particularly preferred compound of formula I is one in which

R ⁴ is nitro, halogen, cyano, thiocyanato, C 1 -C 8 haloalkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C 4 -C 8 cycloalkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, CC haloalkoxy, -COR ^10, -CO 2 R ^1D, -COSR ^10, -CONR ¹¹ R, -CONR ¹ ° R ^11, -C (R ¹²⁾ = NR ^13, -PO (OR ¹⁰⁾ (OR ¹¹ ) 0χ-04 alkyl group having attached thereto from the following group: -COR ^10, -CO 2 R ^1D, -COSR ^10, -C0NR ^1o R ^{1: L} or -C (R ¹²⁾ = NR ^13, heterocyclyl, , heterocyclyl-C _i -C ₄ -alkyl, _phenyl-C feny1 -C ₄ -alkyl, hetaryl, hetaryl-C _i -C ₄ -alkyl, and the last six groups to be substituted,

R ⁵ is hydrogen, halogen, cyano, CC alkyl group, a C _x -C _e haloalkyl, -COR ^10, -C02R ^lo; -COSR ^10, -C0NR ^{Lo R1i} or

- PO (OR ^xo ) (OR ¹¹ ) or

R ⁴ and ^R together form a C ₂ -C _g -alkanediyl chain which can be mono- to tetrasubstituted by C _x -C ₄ alkyl group and / or may be interrupted by oxygen or sulfur or by a nitrogen which is unsubstituted or substituted C - C 1-6 alkyl.

A particularly preferred compound of formula (I) is one in which

R ¹ is nitro, halogen, C _x -C _e haloalkyl or C _x -C _e alkylsulphonyl group, in particular nitro, chlorine, trifluoromethyl, methylsulfonyl or ethylsulfonyl,

R ² is nitro, halogen, C -C alkyl, C _x -C _e haloalkyl, C _x -C ₆ alkoxy or C _x -C _e alkylsulphonyl group, in particular nitro, chlorine, methyl, trifluoromethyl, alkyl group, methoxy or methylsulfonyl,

R ³ is a hydrogen atom or a C ₁ -C ₆ alkyl group, in particular a hydrogen atom or a methyl group, preferably a hydrogen atom,

R ⁴ is hydrogen, halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl,

C ^ -C ^ alkoxy, C _x -C ₄ alkylcarbonyl, C _x -C ₄ alkoxycarbonyl group or a -C (R ¹²⁾ = NR ^13, in particular hydrogen, chlorine, bromine, cyano, methyl, ethyl, sku9 99 99

9

9

9,999,999

9 9

991 99 99 • · «« 99

9 9

9 99

9 9

9 9 9

99-pin, 2-hydroxyethyl, methoxy, ethoxy, methylcarbonyl, ethylcarbonyl, methoxycarbonyl, ethoxycarbonyl or -C (R ¹² ) = NR ¹³ ,

R ⁵ is a hydrogen atom, a halogen atom, a C 1 -C ₄ alkyl group or a C ₄ -C ₄ alkoxy group, in particular a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group or an ethoxy group,

R ¹² is a hydrogen atom, a C 1 -C 4 alkyl group or a C 1 -C 10 alkoxy group, in particular a hydrogen atom or a methyl group,

R ¹³ is C ₁ -C ₆ alkyl or C 1 -C ₆ alkoxy, in particular methoxy or ethoxy,

R ³ - ⁴ , R ^{1 S} , R ^{1 S} , R ¹⁷ , R ¹ and R ¹⁹ are hydrogen or C-alkyl, in particular hydrogen or methyl, or the CR ¹⁶ R ¹⁷ can be replaced by C = O and the definitions of R ¹ to R ¹⁹ have particular meaning for the compound of the formula I according to the invention not only in combination with each other, but also in each case separately.

Especially extraordinarily preferred are compounds of formula Ia (= I where R ¹ is attached in position 4 of the phenyl ring and R ² is attached in position 2 of the phenyl ring).

ΦΦ φ • · φ φ φ φ φ φ • • φ φ φ • • • • • · · · · · · · φ φ φ φ φ φ φ φ φ φ φ

da)

Particularly particularly preferred is the compound IaI (=

I wherein R ¹ is chlorine, R ^14, R ^13, R ^16, R ^17, R ^1S, R ¹⁹ is hydrogen, R ¹ is bound at position 4 of the phenyl ring and R ² is bound in the 2-position of the phenyl ring) especially the compounds of table 1, and the definitions of R ² and R ^s are not special for the compounds of this invention in combination, but also in any case by themselves.

(ial) · te te 9 9 9 9 9 9 9 9 9

9 99 · · · · a ··

Table 1

C. R2 R ³ R ⁴ R ⁵ Ial.OOl Cl H H H lal.002 Cl H CH ₃ H lal.003 Cl H ch ₃ ch ₃ íal.004 Cl H c ₂ h ₅ H lal.005 Cl H nC ₃ H ₇ H lal.006 Cl H n-C4Hg H Ial.007 Cl H CH _{(CH3) 2} H lal.008 Cl H cyclo-C ₃ Hs H Ial.009 Cl H cyclo-C4H7 H Ial.010 Cl H cyclo -C5H9 H Ial.Oll Cl H cyclo -C6Hh H Ial.012 Cl H c ₆ h ₅ H Ial.O13 Cl H ch ₂ -c ₆ h ₅ H Ial.O14 Cl H 2-furyl H Ial.015 Cl H 3-furyl H Ial.016 Cl H 2-thienyl H Ial.017 Cl H 3-thienyl H Ial.018 Cl H 1,3-dioxan-2-yl H lal.019 Cl H CHO H lal.020 Cl H coch ₃ H Ial.021 Cl H cooch ₃ H lal.022 Cl H cooc ₂ h ₅ H Ial.023 Cl H och ₃ H Ial.024 Cl H CN H Ial.025 Cl H sch ₃ H Ial.026 Cl H cocf ₃ H Ial.O27 Cl H COC ₆ H ₅ H Ial.O28 Cl H ch = noch ₃ H Ial.029 Cl H ch = night ₂ h ₅ H Ial.030 Cl H C (CH ₃₎ = NOCH ₃ H Ial.031 ch ₃ H H H Ial.032 ch ₃ H ch ₃ H

0 «>

* «

0 ··

00 0 · 0 0 0 0 0

000 000 0 ·

00 • t

000

C. R ² R ³ R ⁴ R ⁵ Ial.033 ch ₃ H ch ₃ CH ₃ Ial.034 ch ₃ H c ₂ h ₅ H Ial.035 ch ₃ H nC ₃ H ₇ H Ial.036 ch ₃ H n = C4H9 H Ial.037 ch ₃ H CHO H Ial.038 ch ₃ H C0CH ₃ H Ial.039 ch ₃ H cooch ₃ H Ial.040 ch ₃ H och ₃ H lal.041 ch ₃ H C ₆ H ₅ H Ial.042 ch ₃ H c ₆ h ₅ ch ₃ Ial.043 ch ₃ H c ₆ h ₅ c ₂ h ₅ Ial.044 ch ₃ H ch ₂ -cho H Ial.045 ch ₃ H cooch ₂ c ₆ h ₅ H Ial.046 ch ₃ Cl ch ₃ H Ial.047 ch ₃ ch ₃ ch ₃ H Ial.048 ch ₃ c ₂ h ₅ ch ₃ H Ial.049 ch ₃ cf ₃ ch ₃ H Ial.050 ch ₃ och ₃ ch ₃ H Ial.051 ch ₃ oc ₂ h ₅ ch ₃ H Ial.052 ch ₃ CH ₂ -CbCH ch ₃ H Ial.053 ch ₃ ch ₂ -ch = ch ₂ ch ₃ H Ial.054 ch ₃ Cl c ₂ h ₅ H Ial.055 ch ₃ ch ₃ c ₂ h ₅ H Ial.056 ch ₃ cf ₃ C2H5 H Ial.057 ch ₃ och ₃ C ₂ H ₅ H Ial.058 ch ₃ oc ₂ h ₅ c ₂ h ₅ H Ial.059 ch ₃ ch ₂ -c »ch C2H5 H Ial.060 ch ₃ ch ₂ -ch = ch c ₂ h ₅ H Ial.061 och ₃ H H H Ial.062 och ₃ H ch ₃ H Ial.063 och ₃ H C ₂ H ₅ H Ial.064 och ₃ H nC ₃ H ₇ H Ial.065 och ₃ H n-Cl2Hg H Ial.066 och ₃ H CHO H Ial.067 och ₃ H COCH ₃ H Ial.068 och ₃ H COOCH3 H Ial.069 och ₃ H och ₃ H Ial.070 och ₃ H c ₆ h ₅ H Ial.071 och ₃ H ch = noch ₃ H

fc • · · · f · fcfc · t · fc

C. R2 R ³ R ⁴ R ⁵ Ial.072 OCH ₃ H C (CH ₃₎ = NOCH ₃ H Ial.073 OCH3 ch ₃ 2-Cl-C ₆ H ₄ H Ial.074 OCH3 ch ₃ 3-Br-C ₆ H ₄ H Ial.075 OCH3 ch ₃ 4-FC ₆ H ₃ H Ial.076 OCH ₃ ch ₃ 2,4-Cl ₂ -C ₆ H ₃ H Ial.077 OCH ₃ ch ₃ 2-NO ₂ -C ₆ H ₄ H Ial.078 OCH ₃ ch ₃ 3-CN-C ₆ H ₄ H lal.079 OCH ₃ ch ₃ 4-CH ₃ -C ₆ H ₄ H Ial.080 OCH ₃ ch ₃ 2-OCH ₃ -C ₆ H ₄ H Ial.081 OCH ₃ ch ₃ 3-CF ₃ -C ₆ H ₄ H Ial.082 OCH3 ch ₃ 4-OCF ₃ -C ₆ H ₄ H Ial.083 OCH3 ch ₃ 2-CH ₃ -C ₆ H ₄ H Ial.084 OCH3 ch ₃ 3-CH ₃ -C ₆ H ₄ H Ial.085 OCH ₃ ch ₃ 2-COCH ₃ -C ₆ H ₄ H Ial.086 OCH ₃ ch ₃ 3-COOCH ₃ -C ₆ H ₄ H Ial.087 OCH3 ch ₃ 4-CF ₃ -C ₆ H ₄ H Ial.088 OCH3 ch ₃ 2-CF ₃ -C ₆ H ₄ H Ial.089 OCH3 ch ₃ 3-OCH ₃ -C ₆ H ₄ H Ial.090 och ₃ ' ch ₃ 4-OCH ₃ -C ₆ H ₄ H Ial.091 cf ₃ H H H Ial.092 cf ₃ H ch ₃ H Ial.093 cf ₃ H c ₂ h ₅ H Ial.094 cf ₃ H nC ₃ H ₇ H Ial.095 cf ₃ H nC ₄ Hg H Ial.096 cf ₃ H CHO H Ial.097 cf ₃ H coch ₃ H Ial.098 CF ₃ H cooch ₃ H Ial.099 cf ₃ H och ₃ H Ial.100 cf ₃ H c ₆ h ₅ H Ial.lOl cf ₃ H ch = noch ₃ H Ial.102 cf ₃ H C (CH ₃₎ = NOCH ₃ H Ial.103 cf ₃ H 2-furyl CH ₃ Ial.104 cf ₃ H 3-furyl ch ₃ Ial.105 cf ₃ H 2-thienyl ch ₃ Ial.106 cf ₃ H 3-thienyl ch ₃ Ial.107 CF ₃ H 2-pyridyl ch ₃ Ial.108 cf ₃ H 3-pyridyl ch ₃ Ial.109 CF ₃ H 4-pyridyl ch ₃ Ial.llO cf ₃ H 2-thiazazolyl ch ₃

9 • 9

9 * 9 • 9

C. R ² R ³ R ⁴ R ⁵ Ial.lll cf ₃ H 4-thiazolyl ch ₃ Ial.112 cf ₃ H 5-thiazolyl ch ₃ Ial.113 cf ₃ H 2-pyrrolyl ch ₃ Ial.114 cf ₃ H 3-pyrrolyl ch ₃ Ial.115 cf ₃ H 4-pyrrolyl ch ₃ Ial.116 cf ₃ H 3-isoxazolyl ch ₃ Ial.117 cf ₃ H 4-isoxazolyl ch ₃ Ial.118 cf ₃ H 5-isoxazolyl ch ₃ Ial.119 cf ₃ H 2-oxazolyl ch ₃ lal.120 cf ₃ H 4-oxazolyl ch ₃ Ial.121 Sat ₂ ch ₃ H H H Ial.122 Sat ₂ ch ₃ H ch ₃ H Ial.123 Sat ₂ ch ₃ H c ₂ h ₅ H Ial.124 SO ₂ CHy H n-C ₃ H ₇ H Ial.125 Sat ₂ ch ₃ H n = C4H9 H Ial.126 Sat ₂ ch ₃ H CHO H Ial.127 Sat ₂ ch ₃ H coch ₃ H Ial.128 Sat ₂ ch ₃ H cooch ₃ H Ial.129 Sat ₂ ch ₃ H och ₃ H Ial.130 Sat ₂ ch ₃ H c ₆ h ₅ H Ial.131 Sat ₂ ch ₃ H ch = noch ₃ H Ial.132 Sat ₂ ch ₃ H C (CH ₃₎ = NOCH ₃ H Ial.133 Sat ₂ ch ₃ c ₂ h ₅ 5-oxazolyl H Ial.134 Sat ₂ ch ₃ c ₂ h ₅ 3-pyrazolyl H Ial.135 Sat ₂ ch ₃ c ₂ h ₅ 4-pyrazolyl H Ial.136 Sat ₂ ch ₃ c ₂ h ₅ 5-pyrazolyl H Ial.137 Sat ₂ ch ₃ c ₂ h ₅ 2-imidazolyl H Ial.138 Sat ₂ ch ₃ c ₂ h ₅ 4-imidazolyl H Ial.139 Sat ₂ ch ₃ c ₂ h ₅ 5-imidazolyl H Ial.140 Sat ₂ ch ₃ c ₂ h ₅ 2-pyrimidinyl H Ial.141 Sat ₂ ch ₃ c ₂ h ₅ 4-pyrimidinyl H Ial.142 Sat ₂ ch ₃ c ₂ h ₅ 5-pyrimidinyl H Ial.143 Sat ₂ ch ₃ c ₂ h ₅ 1,3-dioxolane-2-yl H Ial.144 Sat ₂ ch ₃ c ₂ h ₅ 1,3-dioxolane-4-yl H Ial.145 Sat ₂ ch ₃ c ₂ h ₅ 1,3-dioxan-2-yl H Ial.146 Sat ₂ ch ₃ c ₂ h ₅ 3-pyridazinyl H Ial.147 Sat ₂ ch ₃ C ₂ H5 4-pyridazinyl H Ial.148 Sat ₂ ch ₃ C ₂ H ₅ 2-pyrazinyl H Ial.149 Sat ₂ ch ₃ C ₂ H ₅ 2-pyridyl H

9 9 99 9

9 9 9 · 9 999 »99

9 • 99 99 99

C. R2 R ³ R ⁴ R ⁵ Ial.150 Sat ₂ ch ₃ c ₂ h ₅ 2-N-methylpyrrolyl H Ial.151 no ₂ H H H Ial.152 no ₂ H ch ₃ H Ial.153 no ₂ H c ₂ h ₅ H Ial.154 no ₂ H nC ₃ H ₇ H Ial.155 no ₂ H nC ₄ H ₉ H Ial.156 no ₂ H CHO H Ial.157 no ₂ H coch ₃ H Ial.158 no ₂ H cooch ₃ H Ial.159 no ₂ H och ₃ H Ial.160 no ₂ H c ₆ h ₅ H Ial.161 no ₂ H ch = noch ₃ H Ial.162 no ₂ H C (CH ₃₎ = NOCH ₃ H Ial.163 no ₂ H COOH c ₂ h ₅ Ial.164 no ₂ H COOMe c ₂ h ₅ Ial.165 no ₂ H COOC ₂ H ₅ c ₂ h ₅ Ial.166 no ₂ H COOCH ₂ C ₆ H ₅ c ₂ h ₅ Ial.167 no ₂ H COOC (CH3) ₃ c ₂ h ₅ Ial.168 no ₂ H ch = noch ₃ c ₂ h ₅ Ial.169 no ₂ H ch = night ₂ h ₅ c ₂ h ₅ Ial.170 no ₂ H ch = noch ₂ c ₆ h ₅ c ₂ h ₅ Ial.171 no ₂ H CH = NOCH _{(CH3) 2} c ₂ h ₅ Ial.172 no ₂ H C (CH ₃₎ = NOCH ₃ c ₂ h ₅ Ial.173 no ₂ H C (CH ₃ ) = NOC ₂ H ₅ c ₂ h ₅ Ial.174 no ₂ H C (CH ₃ ) = NOCH (CH ₃ ) ₂ c ₂ h ₅ Ial.175 no ₂ H C (CH ₃ ) = NOCH ₂ C ₆ H ₅ C ₂ H ₅ Ial.176 no ₂ H ch = noch ₂ -ch = ch ₂ c ₂ h ₅ Ial.177 no ₂ H CH = NOCH ₂ -CsCH c ₂ h ₅ Ial.178 no ₂ . H ch ₂ -cho c ₂ h ₅ Ial.179 no ₂ H ch ₂ -ch = noch ₃ c ₂ h ₅ Ial.180 no ₂ H ch ₂ -ch = night ₂ h ₅ c ₂ h ₅

Ftft ftftft ftft ftft ftft ftft ftft

Equally particularly preferred are compounds Ia2, especially compounds Ia2.0001 to Ia2.180, which differ from the corresponding compounds Ia.001 to

Ial.180 fact that R is a methyl group ^ie:

• ftft • ftftft

(Ia2)

Also especially extraordinarily preferred are the compounds of a3, in particular the compounds Ia3.001 to Ia3.180, which differ from the corresponding compounds Ial.001 Ial.180 to the fact that R ¹⁶ and R ¹⁷ are in each case methyl:

(Ia3)

9

Also particularly preferred are compounds Ia4, in particular compounds Ia4.001 to Ia4.180, which differ from the corresponding compounds Ia.001 to

Ial.180 that R ¹⁸ and R ¹⁹ are in each case methyl groups:

9 9 9

9 9 «

9 9 9 9 9 9 9

99

9 9 9

9 9 9

999 999

9

9 »99

(Ia4)

Also particularly particularly preferred are compounds Ia5, in particular compounds Ia5.001 to Ia5.180, which differ from the corresponding compounds Ia.001 to Ia.180 by the fact that the group CR ^ie R ^{: L} ' ^{7 is} replaced by the group C = O:

(Ia5) • φ • ·; p.

• φ φ φ φ φ · · · · φ φ

Also especially extraordinarily preferred are the compounds IA6, in particular the compounds Ia6.001 to Ia6.180, which differ from the corresponding compounds Ial.001 Ial.180 to the fact that the groups R ^14, R ¹ ® and R ¹⁹ are in each case methyl and the unit CR ^ R ¹⁷ is replaced by the group C = 0:

(Ia6)

Also particularly particularly preferred are compounds Ia7, in particular compounds Ia7.001 to Ia7.180, which differ from the corresponding compounds Ia.001 to Ia.180 by the fact that R ^X4 , R ¹⁵ , R ^x ® and R ¹⁹ are in each case methyl groups and CR ^{x e} R ¹⁷ are replaced by C = 0:

(Ia7) t · I I I I I I I I I I I I I I I

Also particularly particularly preferred are compounds Ia8, in particular compounds Ia8.001 to Ia8.180, which differ from the corresponding compounds Ia.001 to Ia.180 by the fact that R ¹ is a nitro group:

(Ia8)

Also especially extraordinarily preferred are the compounds Ia9, in particular the compounds Ia9.001 to Ia9.180, which differ from the corresponding compounds lal.001 Ial.180 to the fact that R @ ¹ is nitro and R ¹⁶ is a methyl group:

(Ia9)

99

9 9 9

9 9 9

999 999

9 ·· • 99

Also particularly preferred are the IalO compounds, in particular the IalO compounds.

Ial.180 the fact that R ¹ is nitro and R ¹ ® and R ¹⁹ are in each case methyl groups:

9 9 9 9 9

(IalO)

Also especially extraordinarily preferred are the compounds Iall especially to compounds Iall.001 Iall.180 which differ from the corresponding compounds Ial.001 Ial.180 to the fact that R @ ¹ is nitro and R ^1B and R ^X9 are in each case methyl :

(Iall) «♦ • 0 0 I · 0

00

Also particularly preferred are the compounds Ia12, in particular Ia12.001 to Ia1280, which differ from the corresponding Ia1200 to Ia1201 compounds.

Ial.180 the fact that R ^x is a nitro group and a unit

CR ^ie R ^x ' ⁷ is replaced by the group C = O:

(Ial2)

Also especially extraordinarily preferred are the compounds Ial3 especially to compounds Ial3.001 Ial3.180 which differ from the corresponding compounds Ial.001 Ial.180 to the fact that R @ ¹ is nitro, R @ ^14, R @ ¹ and R @ ® ¹⁹ are in each case the methyl group and the CR ¹⁶ R ^{17 unit} are replaced by the group C = 0:

(Ial3) • * φ

W w w w w w 99 99 99 99 99 99 99 99 99 99

Also particularly particularly preferred are the compounds Ia14, in particular the compounds Ia14.001 to Ia1480, which differ from the corresponding compounds Ia.001 to Ia1880 in that R @ ¹ is nitro, R @ ¹⁴ ,

R ^1S , R ^x ® and R ¹ ® are in each case methyl groups and the CR ¹⁶ R ^{: L} ' ^{7 unit} is replaced by C = 0:

(Ial4)

Also particularly particularly preferred are the compounds Ia15, in particular the compounds Ia15.001 to Ia1580, which differ from the corresponding compounds Ia.001 to Ia1880 in that R @ ¹ is a methylsulfonyl group:

(Ial5) 99 99 «9 4 99 9

9

9 9 «· 9 9 9

9 9

499 99 99

- 48 • 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 4 9 9

Also especially extraordinarily preferred are the compounds Ial6 especially to compounds Ial6.001 Ial6.l80 which differ from the corresponding compounds Ial.001 Ial.180 to the fact that R, ^is methylsulfonyl and R @ ¹⁶ is methyl:

(Ial6)

Particularly particularly preferred are the compounds Ia17, in particular Ia17.001 to Ia1780, which differ from the corresponding Ia.001 to Ia1700 compounds.

Ial.180 that R ¹ is a methylsulfonyl group and R ¹⁶ and R ¹⁷ are in each case a methyl group: OH o R2 R ³ 1 ll 1 R ⁴ I JJ. ΓίΓιΓ 'IN H ₃ C - / 0 \ R ⁵ ch ₃ Sat ₂ ch ₃

(Ial7)

• «

Also especially extraordinarily preferred are the compounds Ial8 especially to compounds Ial8.001 Ial8.180 which differ from the corresponding compounds Ial.001 Ial.180 to the fact that R, ^is methylsulfonyl and R ^x and R ^{x £} * are in each in the case of a methyl group:

OH

OR ² r3 ^h 3C ch ₃ with ₂ ch ₃ (Ial8)

Also especially extraordinarily preferred are the compounds Ial9 especially to compounds Ial9.001 Ial9.180 which differ from the corresponding compounds Ial.001 Ial.180 to the fact that ^{R, is} methylsulfonyl and the CR ^XS R ^X7 is replaced with a C = 0:

OH OR ² R ³

O

SO ₂ CH ₃ (Ial9)

· · * * * * * * * * · · · · ·

Also especially extraordinarily preferred are the compounds Ia20, in particular to the compounds Ia20.001 Ia20.l80 which differ from the corresponding compounds Ial.001 Ial.180 to the fact that R @ ¹ is methylsulfonyl, R @ ^14, R @ ® ¹ and R ¹⁹ are in each case, the methyl group and the CR 6 R ^{17 unit} are replaced by C = O:

(Ia20)

Also particularly particularly preferred are the compounds Ia21, especially the compounds Ia1.001 to Ia21.180, which differ from the corresponding compounds Ia.001 to Ia.180 by the fact that R ¹ is a methylsulfonyl group, R ¹⁴ , R ¹⁵ , R ^x ® and R ¹⁹ are in each case methyl groups and the CR ¹⁶ R ^{X 7 unit} is replaced by C = O:

(Ia21) · · Φ Φ Φ Φ Φ • • •

ΦΦ «Φ ·

•

Φ

Φ Φ • · φ φ φ φ φ φ φ φ

Also especially extraordinarily preferred are the compounds Ia22, in particular the compounds Ia22.001 to Ia22.180, which differ from the corresponding compounds Ial.001 Ial.180 to the fact that R @ ¹ is trifluoromethyl:

(la22)

Also especially extraordinarily preferred are the compounds Ia23, in particular the compounds Ia23.001 to Ia23.180, which differ from the corresponding compounds Ial.001 Ial.180 to the fact that R ^x is trifluoromethyl, and R 5 ^{e 16} methyl group:

(Ia23) · ♦ I I

Also particularly particularly preferred are compounds Ia24, in particular compounds Ia24.001 to Ia24.180, which differ from the corresponding compounds Ia.001 to Ia.180 by the fact that R ^x is a trifluoromethyl group and R ^xe and R ¹⁷ are in each case methyl Groups:

(Ia24)

Also particularly particularly preferred are the compounds Ia25, in particular the compounds Ia25.001 to Ia25.180, which differ from the corresponding compounds Ia.001 to Ia.180 by the fact that R ¹ is a trifluoromethyl group and R ¹ ® and R ¹⁹ are in each case methyl groups:

(Ia25)

99

9 9 9

9 9 • 9 9 9 9 • 9 9 9

9 «99 • 9

9 9 • 9 9 999

999 «·

Also particularly particularly preferred are compounds Ia26, in particular compounds Ia26.001 to la26.180, which differ from the corresponding compounds Ia.001 to Ia.180 by the fact that R ^x is a trifluoromethyl group and the CR ^XS unit R ^X7 is replaced by C = 0:

(Ia26)

Also particularly particularly preferred are compounds Ia27, in particular compounds Ia27.001 to Ia27.180, which differ from the corresponding compounds Ia.001 to Ia.180 by the fact that R ^x is a trifluoromethyl group, R ¹⁴ , R ^xe and R ¹⁹ are in each case the methyl group and the CR ^X6 R ^{X7 unit} are replaced by the group C = 0:

(Ia27) »

· •!!!!!!!

• · »· · 9 · 9 ·

Also particularly particularly preferred are compounds Ia28, in particular compounds Ia28.001 to I28.80 which differ from the corresponding compounds Ia.001 to Ia.180 by the fact that R ^x is a trifluoromethyl group, R ^{x 4} , R ^xs , R ^xe and R x ^x9 are in each case methyl and CR ^X6 R ^X7 is replaced by C = 0:

(Ia28)

Also particularly particularly preferred are compounds of formula I in which

R ^x is a halogen atom such as a chlorine atom or a bromine atom, a C ₁ -C ₆ alkylsulfonyl group such as a methylsulfonyl group or an ethylsulfonyl group, particularly preferred is a chlorine atom or a methylsulfonyl group,

R ² is halogen atom such as chlorine or bromine, especially preferred is a chlorine atom,

R ³ is a hydrogen atom,

49 · 9 9 • 9 99 * 9 99 9 9

I 9 9 4 9 9

49

- R ⁴ is hydrogen, cyano, C 1 -C 6 alkyl such as methyl, propyl, 2-methylethyl, butyl or pentyl, C 1 -C 6 alkoxy such as methoxy, ethoxy, C 1 -C 6 alkylthio , such as methylthio or ethylthio, formyl, C 1 -C 6 alkylcarbonyl, such as methylcarbonyl or ethylcarbonyl, C 1 -C 8 alkoxycarbonyl, such as methoxycarbonyl or ethoxycarbonyl, -C (R ¹² ) = NR ¹³ , heterocyclyl the group, heterocyclyl-C 1 -C ₄ alkyl, phenyl, hetaryl and the last four mentioned may be substituted with one to three halogen atoms and / or two to three groups selected from: nitro, cyano, C ₁ -C ₄ alkyl C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C 4 alkylcarbonyl, C -C alkoxycarbonyl, especially C ₁ -C ₄ alkyl, particularly preferred are hydrogen, cyano, methyl,

2-methylethyl, pentyl, methoxy, methylthio, formyl, methylcarbonyl, ethoxycarbonyl, -C (R ^{X 2} ) = NR ¹³ , 2-methyl-1,3-dioxolan-4-yl, 2,2 -dimethyl-1,3-dioxolan-4-yl

1,3-dioxan-2-yl, 1,3-dioxan-2-ylmethyl, phenyl, 2-furyl,

3-furyl, 2-thienyl,

3-thienyl, is a hydrogen atom, a halogen atom such as a chlorine atom;

♦ · · 9 <<9 9 9 9 9 · 9 «« ·

Or a bromine atom, or a C-C alkoxy group such as a methoxy or ethoxy group, in particularly preferred cases a hydrogen atom, a chlorine atom or an ethoxy group,

R ¹² is hydrogen, C _x -C _g alkyl group such as methyl group or ethyl group, _or a _Cl-C6 alkoxycarbonyl, such as methoxycarbonyl group or ethoxycarbonyl group, especially preferred is hydrogen, methyl or methoxycarbonyl ,

R ^14, R ^X, R ^{X 6,} R ^x, R ^x and R ^x ® ^£ * are hydrogen or C _x -C ₄ alkyl group such as methyl group or ethyl group, especially preferred is hydrogen or methyl or can be replace the unit C ^X6 R ^X ' ⁷ with group C = 0.

The 2- (3-alkenylbenzoyl) cyclohexane-1,3-diones of the formula I can be obtained in various ways, for example as follows:

Reaction of the cyclohexanediones of formula II with activated carboxylic acid IIIa or carboxylic acid β, which is preferably carried out in situ to give the acylation product IV followed by a rearrangement reaction.

·· φ φ φ φ φ φ φ φ φ «φ φ φ φ • • φ φ φ φ φ

φ φφφ

ΦΦ φ φ · • • · · · · ·

L is a leaving group which can be displaced by a nucleophilic reaction such as a halogen atom, for example bromine, chlorine, a hetaryl group, for example an imidazolyl group, a pyridyl group, a carboxylate group, for example an acetyl group, e.g. t · ·;

9 10 «« 9 ··

99,999,999, trifluoroacetate, and the like.

The activated carboxylic acid can be obtained directly, as is the case with carboxylic acid halides, or prepared in situ, for example by reaction with dicyclohexylcarbodiimide, triphenylphosphine / azodicarboxylic acid ester, 2-pyridinedisulfide / triphenylphosphine, carbonyldiimidazole and the like.

In suitable cases, an acylation reaction in the presence of a base may be advantageously performed. The reactants and the auxiliary base are preferably used in equimolar amounts. In certain circumstances, it may be advantageous to use a small excess of the auxiliary base, for example 1.2 to 1.5 molar equivalents relative to II.

Suitable auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates. Examples of solvents that can be used are chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane, aromatic hydrocarbons such as toluene, xylene, chlorobenzene, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, polar aprotic solvents such as acetonitrile, dimethylformamide, dimethylsulfoxide or esters such as ethyl acetate or mixtures thereof.

If carboxylic acid halides are used as the activated carboxylic acid component, it may be advantageous to cool the reaction mixture to 0-10 ° C when adding the reactant. The reaction mixture is subsequently stirred at 20 to 100 ° C, preferably at 25 to 50 ° C, until the reaction is complete. The work-up is carried out in a conventional manner, for example the reaction mixture is poured into water and the desired product is ftft ftft ftft ftft ftft ftft ftft ftft ftft ftft ftft ftft ft ft ft ft ft ft ft ft ft ft ft ft extracts. Particularly preferred solvents for this purpose are methylene chloride, diethyl ether and ethyl acetate. After drying of the organic phase and removal of the solvent, the enol ester of formula IV is purified, preferably by chromatography. However, it is also possible to use the crude enol ester of formula IV in the rearrangement reaction without further purification.

The rearrangement of the enol ester of formula IV to give a compound of formula I is preferably carried out at temperatures from 20 to 40 ° C in a solvent and in the presence of an auxiliary base with or without the use of a cyano compound as a catalyst.

Examples of solvents that can be used are acetonitrile, methylene chloride, 1,2-dichloroethane, ethyl acetate, toluene or mixtures thereof. A preferred solvent is acetonitrile.

Suitable auxiliary bases are tertiary amines, such as triethylamine, pyridine or alkali metal carbonates, such as sodium carbonate or potassium carbonate, which are preferably used in equimolar or up to four times the amount of enol ester. Preferably, triethylamine is used, preferably in triethylamine. twice the equimolar ratio with respect to the amount of enol ester.

Suitable rearrangement catalysts are inorganic cyanides such as sodium cyanide or potassium cyanide and organic cyano compounds such as acetone cyanohydrin or trimethylsilyl cyanide. They are normally used in an amount of from 1 to 50 mole% based on the amount of enol ester. Preferred substances are acetone cyanohydrin or trimethylsilyl cyanide, in an amount of, for example, from 5 to 15, preferably

til •

Up to 10 mole% based on the amount of enol ester.

The processing may be carried out in any known manner. For example, the reaction mixture is acidified with a dilute mineral acid such as 5% hydrochloric acid or sulfuric acid and extracted with an organic solvent such as methylene chloride or ethyl acetate. The organic extract can be extracted with a 5-10% solution of an alkali metal carbonate such as sodium carbonate or potassium carbonate. The aqueous phase is acidified and the precipitate formed is suction filtered and / or extracted with methylene chloride or ethyl acetate, dried and evaporated.

(Examples of the preparation of enol esters from cyclohexane-1,3-diones and cyanide catalyzed enol ester rearrangements are given, for example, in EP-A 186 118, US 4 780 127).

The cyclohexane-1,3-diones of the general formula II which are used as starting materials and which are not known can be prepared by known methods (e.g. EP-A 71 707, EP-A 142 741, EP-A 243 313, US 4,249) 937, WO 92/13821).

Activated carboxylic acids IIIa, which are not prepared in situ, can be prepared in a known manner as such. For example, carboxylic acid halides of formula IIIa (where L is a halogen atom) can be prepared by methods similar to those known in the literature [cf. L.G. Fieser, M. Fieser Reagents for Organic Synthesis, Vol. I, pp. 767-769 (1967)] by reacting benzoic acids of the formula HIS with halogenating agents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride or oxalyl bromide.

3-Alkenylbenzoové acid of formula • · IIS are known from the literature or may be obtained by methods similar to those known from the literature, inter alia by hydrolysis of the corresponding 3-alkenylbenzoových esters {wherein M = C _x C _g alkoxy) of formula Illgama .

3-Alkenylbenzoové esters (where M = C _x C _g alkoxy) Illgama formula are also known from the literature or can be obtained in various ways, for example in the following ways:

· 9 9 ·························· · 9 · ·

99 99 99 99 99

ΐΐΐΐΐΐ · · ·

The compound of formula Illgama can be obtained by subjecting the phosphonium salt of formula VI to Wittig reaction with aldehydes or ketones (VII) in a known manner (J. March, Advanced Organic Chemistry, 3rd ed., P. 864 et al.

Wiley-Interscience Publication, 1985).

• 9 * 0 • 9 * 0 · 9 · 0 · 9 · 0 · 9 · 0

The phosphonium salts of formula VI can be obtained from a bromine compound of formula V in a known manner (J. March, Advanced Organic Chemistry, 3rd ed., P. 377 et al., Wiley-Interscience Publication, 1985).

(B)

my tt 9 9 * • 9 9 *

9 9

9 9 9

A compound of formula Illgama can also be obtained by subjecting aldehydes or ketones of formula VIII to a Wittig reaction or a Horner-Emmons reaction with a phosphonium salt IXa (see also A) or a phosphonate IXb (J. March, Advanced Organic Chemistry, 3rd ed., P. 867) and more,

Wiley-Interscience Publication, 1985).

The compound of formula VIII is accessible in a known manner by oxidation of a bromine compound of formula V (J. March, Advanced Organic Chemistry, 3rd ed., P. 1105 et al., Wiley-Interscience Publication, 1985).

C)

The compound of formula Illgama can also be obtained in a known manner by subjecting the aldehydes or ketones of formula VIII to an aldol condensation reaction and related reactions (J. March, Advanced Organic Chemistry, 3rd Ed., P. 849 et al., Wiley-Interscience Publication, 1985).

DETAILED DESCRIPTION OF THE INVENTION

• 9 ·· • · 99 99 • 9 • • • · 9 9 9 9 9 1 • • • · · • 9 9 9 9 9 9 • • • 9 • 9 9 9 • · • 9 • · 9 9 9 9 9 · 9 9

Examples of preparation methods

2- [2 ', 4'-Dichloro-3' - (prop-1''-en-1''-yl) benzoyl] -1,3-cyclohexanedione (Compound 2.1) g (16 mmol) cyclohexanedione and 2, 2 ml (16 mmol) of triethylamine is added to a solution of 4.0 g (16 mmol)

2,4-dichloro-3- (prop-1'-en-1'-yl) benzoyl chloride in 50 mL acetonitrile. The mixture was stirred for 12 h at room temperature and then poured into 500 mL of water and extracted three times with ethyl acetate. After drying the mixture with sodium sulfate, the solvent was evaporated in vacuo and the residue was purified by silica gel chromatography (cyclohexane / ethyl acetate = 9/1). The resulting enol ester was dissolved in 100 mL of acetonitrile and treated with 1.0 g (10 mmol) of trimethylsilyl cyanide and 1.3 mL of triethylamine. The mixture was stirred at room temperature for 12 h, then evaporated in vacuo and the residue was poured into 200 mL of 10% sodium carbonate solution. It was then extracted once with methyl tert-butyl ether and the pH of the aqueous phase was adjusted to pH 3 with 10% hydrochloric acid. After extraction of the mixture with ethyl acetate and drying over sodium sulfate, the solvent is removed in vacuo. 0.6 g of a pale yellow powder remained, m.p. 115-120 ° C.

¹ H NMR (CDCl ₃ / δ in ppm): 17.0 (IH), 7.45 (IH), 6.95 (IH), 6.30 (IH), 6.15 (IH), 2.75 (2H), 2.45 (2H), 2.05 (2H), 1.90 (3H).

2- [2 ', 4'-Dichloro-3' - (2 '' - methoxyethen-1 '' - yl) benzoyl] -1,3-cyclohexanedione (Compound 2.7)

2.5 g (10 mmol) of 2,4-dichloro-3- (2'-methoxyethen-1'-yl) benzoic acid are suspended in 50 ml of acetonitrile under nitrogen and the suspension is treated with 11 g (10 mmol).

cyclohexanedione and 2.1 g (10 mmol) of dicyclohexylcarbodiimide. The mixture was stirred for 12 h at room temperature, the urea that precipitated was filtered off using suction and the solvent was evaporated in vacuo. The residue was purified by silica gel chromatography (cyclohexane / ethyl acetate = 9/1). The resulting enol ester was dissolved in 50 mL of acetonitrile and treated with 0.4 g (4.4 mmol) of trimethylsilyl cyanide and 0.4 g (4.4 mmol) of triethylamine. The mixture is stirred for 3 h at room temperature, evaporated to one third of its volume and poured into 200 ml of 5% sodium carbonate solution. Then the mixture was extracted with one small amount of methyl tert-butyl ether and the pH was adjusted to 3 with 10% hydrochloric acid. After extraction with ethyl acetate and evaporation in vacuo, 1.0 g of yellow resin remained.

¹ H NMR (CDCl ₃ /? In ppm): 17.0 (IH), 7.35 (IH), 7.10 (IH), 6.90 (IH), 5.80 (IH), 3.75 (3H), 2.80 (2H), 2.40 (2H), 2.05 (2H).

In addition to the 2- (3-alkeynylbenzoyl) cyclohexane-1,3-diones of formula (I) described above, the following are similarly prepared as shown in Table 2 below:

φ · · · ·

Φ · · φ

φ φ φ φ ··

77 • 8 ... ο. ' ³ U'ί' ν li Ζ 115-120 17.0 (1H); 7.6-7.0 (9H); 2.75 (2H); 2.45 (2H); 2.05 (2H) 77 -107 67-77 oily liquid cis / trans 35:65 7.40 (1H); 7.10 (1H); 6.85 (1H); 4.35 (2H): 3.85 (2 H); 2.80 (2H): 2.45 (2H); 2.05 (2H): 1.40 (3 H); 1.15 (3H) Ο 0I 33 X X X X X 00 οί 33 X X X X X r- Oí X X X X X X Ό Oí X X X X X X «Η Oí X X X X X X Xt Oí X X X X X X in*" Oí X X •in ► * 4 X VD X (N O X xt Oí m X at phenyl ί 3-furyl 2-thienyl ΜΊ X CM at O O at (1,3-dioxan-2-yl) methyl cn Oí X X X X X X cm Oí at at υ O ϋ at 0 < 0 O 0 at 0 O * 5 2.1 2.2 2.3 2.4 2-5 kO CM

• φ ι »ι ι ι ι ι ι ι

Physical data temp. m.p. [° C]; 'NMR [ppm] 17.00 (1H); 7.35 (1H); 7.10 (1H); 6.90 (1H); 5.80 (1H); 3.75 (3H); 2.80 (2 H); 2.40 (2H); 2.05 (2H) 86-106 17.00 (1H); 7.40-7.30 (4 H); 7.10-6.90 (3H); 2.80 (2H); 2.45 (2H); 2.05 (2H) mixture of isomers CN r- CN O 64-74 54-74 oily liquid 16.90 (1H); 7.80 (1H); 7.40 (1H); 7.10 (1H); 4.40 (2H); 2.80 (2H); 2.50 (2H), 2.05 (2H); 1.40 (3H) O\ CZ TO and tn and υ and and and and and and m and at and and 00 Oí and and m and υ and and and and and and tn and at and and and and O II and and and and tn and at and O II and and Ό o £ and and and and and and tn and O m and O and and vn Oí and and tn and O tn and O and and m and at and and tn and at and and Tf Qa and and tn and O tn and <> and and m and at and and tn and at and and vn & and and and and and and and and and and and G N ^- oi tn and at O «2 whose Tn at. «2 1 ΓΊ Tn Um <2 1 m tí £ ΓΌ T \ 1 Μ- ι C «J O X .2 * 3 1 cn »- ( * £ 3 E CN ff <a ff <2 ff CN 1 C rt X O R-H 73 1 πγ vn and n at O O at tn & and and and and and and and and and and and and <N Ďí 0 0 G □ G 0 G G G G G G the 0 G G G 0 G G G G G G G 1 • CN 00 CN cn CN O t — 1 CN r = 4 rH CN CN rM CN cn r — 4 CN nr r ~ 4 CN tn τ — 4 CN it <~ 4 CN Γ T — 1 CN 00 CN

»♦ *

- 67 «· · ··· · * ♦«

Physical data temp. m.p. [° C]; Ή NMR [ppm] oily liquid 16.50 (1 H); 7.60 (1H); 7.40 (1 H); 6.95 (1H); 6.50 (1 H); 3.95 (6H); 2.80 (2H); 2.55 (2H); 2.05 (2H) 17.00 (1H); 7.35 (2H); 7.00 (2H); 6.85 (2 H); 3.95 (3H); 2.55 (4H); 2.05 (3H); 1.95 (2H) 96-100 oily liquid resin resin resin oS X X X X X X X X X X X X O X X X X 00 □ S X X X X X X X X X X X it X O X X X X Γ * »-« PS X X X X X X X X X m X O X O II ro X O X X X MO PS X X X X X X X X X X at X O X O X X X m PS X X X X X X X X m X O X X ro X at X m X O X X r! 4 X X X X X X X X X O X X ro X O X m X O X X PS X X X X X X X X X X X X X X X ro X at 0 $ of at tn X at (OF) m X at O O O X υ m X at CM O at m X O O of JL at fO X O tn X at O of at X X at O of ï "and <a and? <8 "and δ * <a m X O O ΓΊ X i.e CM it X at X O ro X at m PS X X X X X X X X X X X X X X X X CM aS G G G 0 D G G G G G G G G G G G oí □ C G »- <u D G G X at n O 00 ro X at N O WHAT ΓΊ X at (N O 00 CH X at n O CZ) fC X at Ol O 00 0 0 G D "O Ch rH CM O cm CM rM CM CM CM CM CM m CM CM CM CM in CM CM \ £> CM CM Γ- CM CM 00 CM CM ch CM CM O ro CM ro CM CM WHAT CM ro ro CM ro CM

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9 9 9 9

9999 99

9 99 9

9 9 9 9 ·

9

99,999 • 99,99 ·· 9 9 # 9

9

9,999,999

9 9 «99 99 99

The preparation of some starting materials is described below.

2-Chloro-4-methylsulfonyl-3- (2'-phenylethen-1'-yl) benzoic acid (Compound 3.02)

Step a)

2-Chloro-4-methylsulfonyl-3- (2'-phenylethen-1'-yl) benzoic acid methyl ester (Compound 3.01)

10.1 g (90 mmol) of potassium tert-butoxide was added to a solution of 52.0 g (120 mmol) of benzyltriphenylphosphonium bromide in 400 ml of tetrahydrofuran. The mixture was stirred for 30 min at room temperature and then 16.6 g (60 mmol) of 2-chloro-3-formyl-4-methylsulfonylbenzoic acid methyl ester in 100 mL of tetrahydrofuran was added dropwise and stirring was continued for 3 h at temperature. rooms. The reaction mixture was then added with stirring to 500 ml of water and extracted with methyl tert-butyl ether. The solvent is removed in vacuo, the residue is treated with diethyl ether and the triphenylphosphine oxide precipitated is filtered off with suction. The residue is purified by chromatography on silica gel (cyclohexane / ethyl acetate = 95/5 to 1/1). Yield: 10.9 g (52% of theory) of a pale yellow oil which solidifies slowly.

¹ H NMR (CDCl ₃ / δ in ppm): 8.15 (1H), 7.70 (1H), 7.60-7.30 (7H), 7.00 (1H), 4.00 (3H) , 3.10 (3H).

Step b)

99

9 9

9

999 9

99

9 9 9

9 99

9 9 9

9 9 ·

9 9

9 9 • 9 9

999

99

2-Chloro-4-methylsulfonyl-3- (2'-phenylethen-1'-yl) benzoic acid

10.0 g (28 mmol) of 2-chloro-3- (2'-phenylethen-1'-yl) -4-methylsulfonylbenzoate are dissolved in 200 ml of tetrahydrofuran / methanol (1/1) and the solution is treated with 35 g of ethyl acetate. 2 g of a 10% sodium hydroxide solution. The mixture was stirred for 12 h at room temperature and the solvent was then evaporated in vacuo. The residue was treated with 400 mL of water and washed with ethyl acetate. The pH was then adjusted to 11 with 10% hydrochloric acid and the precipitate formed was filtered off with suction. After drying, 9.4 g (97% of th.) Of a white powder are obtained, m.p. 232 DEG-233 DEG.

¹ H NMR (CDCl ₃ / δ in ppm): 8.20 (1H), 7.90 (1H), 7.55 (2H), 7.40 (4H), 7.00 (1H), 3.10 (3H).

2,4-Dichloro-3 - [(2 '' - furyl) ethen-1'-yl]) benzoic acid methyl ester (Compound 3.05)

Step a)

2,4-Dichloro-3-methylacetophenone

235.0 g (3.0 mol) of acetyl chloride is added dropwise with stirring at 100 ° C over 2 h to a solution of 502.0 g (3.12 mol) of 2,6-dichlorotoluene and 408.0 g (3, 06 mol) of aluminum chloride. The mixture was stirred at 100-105 ° C for 2 h, then cooled and poured into 3 L of ice and 1 L of water. The solid which precipitates is filtered off using suction and washed with water until neutral. After drying at 40 ° C, 500.0 ftft ftft ftft ft ft · ftft ftft ftft ftft ft ftft ftft ftft ftft ftft ftft ftftft ftft 2,4-dichloro-3 -methylacetophenone as a crude product and then distilled under high vacuum.

[Boiling point: 121-128 ° C at 4 mbar].

Step b)

2,4-Dichloro-3-methylbenzoic acid

First 655.2 g (4.1 mol) of bromine and then 203.0 g (1.0 mol) of 2,4-dichloro-3-methylacetophenone in 1300 ml of 1,4-dioxane are added dropwise at 0-10 ° C to a solution of 520.0 g (13 mol) of sodium hydroxide in 2600 ml of water. After stirring the mixture for 12 h, the organic phase is separated, the aqueous phase is treated with a 30¾ solution of sodium metabisulphite in water and the pH is adjusted to 1 with hydrochloric acid. The precipitate formed is filtered off with suction, washed with water and dried under vacuum at 60 ° C. 197.0 g of acid are thus obtained

2,4-dichloro-3-methylbenzoic acid.

(Melting point: 173-175 ° C).

Step c)

Methyl 2,4-dichloro-3-methylbenzoate methyl ester ml of concentrated sulfuric acid is added dropwise to a solution of 424.0 g (2 mol) of 2,4-dichloro-3-methylbenzoic acid and 1500 ml of methanol. The reaction mixture was refluxed for 5 h, cooled, evaporated in vacuo and the residue taken up in 1000 mL of methylene chloride. The organic phase is washed with water, then with a 5% solution of hydrogen carbonate. 401.0 g of 2,4-dichloro-3-methylbenzoic acid methyl ester are obtained.

[Boiling point: 103 to 107 ° C at 1 to 1.5 mbar]].

Step d)

3-Bromomethyl-2,4-dichlorobenzoic acid methyl ester

1.0 g of azobisisobutyronitrile was added to a solution of 84.0 g (0.38 mol) of 2,4-dichloro-3-methylbenzoic acid methyl ester and 67.6 g (0.38 mol) of N-bromosuccinimide in 380 ml of carbon tetrachloride. The reaction mixture was refluxed for 3.5 h, cooled and the precipitate that formed was filtered off with suction. The filtrate was evaporated in vacuo and the resulting residue was extracted by stirring with methyl tert-butyl ether. This gave 108.0 g of 3-bromomethyl-2,4-dichlorobenzoic acid methyl ester.

(Melting point: 51-54 ° C).

Step e) (2,6-Dichloro-3-methoxycarbonyl) benzyltriphenylphosphonium bromide

80.65 g (262 mmol) of methyl 3-bromomethyl-2,4-dichlorobenzoate were dissolved in 800 ml of toluene and treated with 68.7 g (262 mmol) of triphenylphosphine. After the stirred mixture was refluxed for 9 h, the mixture was cooled and the precipitate formed was filtered off with suction. After drying, there are 129.0 g (89% of theory) remaining. Ftft. Ftft. Ftft. Ftft. Ftft. Ftft. Ftft. · •

ft • ftft • ft • ft of light beige powder.

(Melting point: 238-239 ° C).

Step f)

2,4-Dichloro-3 - [(2 '- (2' '- furyl) ethen-1'-yl) benzoic acid methyl ester

28.0 g (50 mmol) of (2,6-dichloro-3-methoxycarbonyl) benzyltriphenylphosphonium bromide are suspended in 200 ml of tetrahydrofuran and the suspension is treated with 5.6 g (50 mmol) of potassium tert-butylate at 0 ° C. The reaction mixture was then cooled to -20 ° C and a solution of 6.2 g (65 mmol) of furfurol in 50 mL of tetrahydrofuran was added dropwise. The mixture was warmed to room temperature and stirred for an additional 12 h. The reaction mixture was added with stirring to 200 mL of water and extracted with methyl tert-butyl ether. After evaporation of the solvent in vacuo, the residue is treated with diethyl ether and the precipitated triphenylphosphine oxide is filtered off with suction. The residue was purified by silica gel chromatography (cyclohexane / ethyl acetate = 98/2 to 90/10). Thus, 8.2 g (55% of theory) of a yellow oil are obtained.

¹ H NMR (CDCl ₃ , δ in ppm): 7.55 (1H), 7.50 (1H), 7.40 (1H), 7.05 (1H), 6.95 (1H), 6.45 (2H), 3.95 (3H).

2,4-Dichloro-3- (3'-methoxycarbonyl-3'-methoxyiminoprop-1'-en-1'-yl) benzoic acid methyl ester (Compound 3.13)

1.9 g (75 mmol) of sodium hydride was added to 17.9 g (75 mmol) of 2-methoxycarbonyl-2-methoxyiminoethyl dimethyl dimethyl.

Φ 4 Φ Φ «1 2 3 4

Φ ΦΦΦ Φ Φ

ΦΦ ΦΦ φ φ φ φ

φ φ

Phosphonate in 150 ml tetrahydrofuran and stirred for 2 h at room temperature. Then, 11.7 g (50 mmol) of 2,4-dichloro-3-formylbenzoic acid methyl ester in 50 ml of tetrahydrofuran is added dropwise and the mixture is stirred for a further 12 h at room temperature. After the reaction mixture is taken up with water, extraction is carried out with methyl tert-butyl ether, the organic phase is dried and the solvent is evaporated off under vacuum. The residue was treated with diethyl ether and the precipitate was filtered off. After drying, 11.3 g (65% of theory) of a white powder are obtained.

(Melting point: 96-97 ° C).

In addition to the compounds described above, other benzoic acid derivatives of formula IIIa which have been prepared or can be prepared in a similar manner are shown in Table 3 below.

Table 3

R2 JLA R ³ R ^{4 r20} ^ [Tj ^] f R ⁵ R ¹ (lila) (= III with R ¹ attached to position and R ² ° = L ^x , OH or M) 4, R ² connected to position 2

99

9 9 9

9 9 9

·· 99

9

9 99

9

4 9 9

99 9

R ^x R ² R ³ R ⁴ R ^s r2 ° Temp. melting point [° C] Sat ₂ ch ₃ Cl H phenyl H OCH 3 97-99 Sat ₂ ch ₃ Cl H phenyl H OH 232-233 Cl Cl H phenyl H OCH 3 oily liquid Cl Cl H phenyl H OH 161-166 Cl Cl H 2-furyl H OCH 3 oily liquid Cl Cl H 2-furyl H OH 171-172 Cl Cl H COCH 3 H OCH 3 38 - 39 Cl Cl H COCH 3 H OH Cl Cl H 2-thienyl H OCH 3 oily liquid Cl Cl H 2-thienyl H OH 134-143 Cl Cl H 3-furyl H OCH 3 62-64 Cl Cl H 3-furyl H OH 167-168 Cl Cl H C (= noch ₃ ) -CO 2 CH 3 H OCH 3 96-97 Cl Cl H -C (= NOCH) - H OH 161 -CO CH 2 3 Cl Cl H 3-thienyl H OCH 3 oily liquid Cl Cl H 3-thienyl H OH Cl Cl H 3-isopropyl and soxa- zol-5-yl H OCH 3 oily liquid Cl Cl H 3-isopropyl and soxa- zol-5-yl H OH Cl Cl H CN H OCH 3 50 - 53 Cl Cl H CN H OH Cl Cl H OCH 3 H OCH 3 38 - 40 Cl Cl H OCH 3 H OH Cl Cl Cl COOCH 3 H OCH 3 oily liquid Cl Cl Cl COOCH 3 H OH

R ² ° Temp. melting point [° C] • 9 · 99 · 9 · 9 9 • 9 99 · 9 9999 •• 999 9 99 999 999

9999 9 9 99

99 99 99 99 99

C. R ¹ R ² R ³ R ⁴ R ^: 3.25 Cl Cl H 1,3-dioxan-2-yl H 3.26 Cl Cl H 1,3-dioxan-2-yl H 3.27 Cl Cl H (1,3-dio- xan-2-yl) - methyl H 3.28 Cl Cl H (1,3-dio- xan-2-yl) - methyl H 3.29 Cl Cl oc ₂ H COOC H 5 2 5 H 3.30 Cl Cl oc ₂ H COOC H 5 2 5 H 3.31 Cl Cl H 2-methyl- -1,3-dio- xolan-4-yl H 3.32 Cl Cl H 2-methyl- -1,3-dio- xolan-4-yl H 3.33 Cl Cl H CHO H 3.34 Cl Cl H CHO H 3.35 Cl Cl H CH -CHO 2 H 3.36 Cl Cl H CH CHO 2 H

OCH 3 51 - 52 OH 93-102 OCH 3 oily liquid OH OCH 3 oily liquid OH OCH 3 oily liquid

OH

OCH 66-68

OH

OCH ₃ oily liquid OH

The 2- (3-alkenylbenzoyl) cyclohexane-1,3-diones of the formula I and their agriculturally useful salts are suitable as herbicides both in the form of isomeric mixtures and in the form of pure isomers. The herbicidal compositions containing the compound of formula I allow very good vegetation control in crop-free areas, especially at high application rates.

For crops such as wheat, rice, corn, soybean and cotton pea · ··

9 9 · 9 9 999 «999 99 * ·

9 9 9 9 9 9 9 9

9 · · <9 ·· act against broad-leafed weeds and grassy weeds without significant crop damage. This effect is particularly observed at low application rates.

In addition, depending on the mode of administration, the compound of formula (I) or the formulations containing it can be used in a number of other crops to eliminate undesirable plants. The following are examples of suitable crops.

Allium cepa, Pineapple comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. Silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica); arboreum (Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Medus spec. Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus aviaum, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, , Solanum tuberosum, Sorghum bicolor (s. Vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

In addition, the compound of formula (I) may also be used in crops that tolerate the action of herbicides due to breeding.

· «·· including methods of genetic engineering.

The compound of formula (I) or herbicidal compositions containing it can be used, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, including highly concentrated aqueous oily or other suspensions or dispersions, emulsions, oily dispersions, pastes, dusts, spray materials or granules by spraying, atomizing, dusting, spreading or pouring. The forms of use depend on the intended purposes. In any case, they should guarantee the finest possible distribution of the active ingredients of the present invention.

The herbicidal compositions comprise a herbicidally effective amount of at least one compound of formula (I) or an agriculturally useful salt thereof and adjuvants conventionally used in the preparation of crop protection products.

It is important to use suitable inert additives such as: medium to high melting point mineral oil fractions such as kerosene and diesel, coal tar oils and vegetable or animal oils, aliphatic cyclic and aromatic hydrocarbons such as paraffin, tetrahydronaphthalene, alkylated naphthalenes and derivatives thereof, alkylated benzenes and derivatives thereof, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone, or strongly polar solvents such as amines such as N-methylpyrrolidone or water.

Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by the addition of water. 2- (3-alkenylbenzoyl) may be used to prepare emulsions, pastes or oily dispersions.

9 9 9

The cyclohexane-1,3-diones, as such or diluted in oil or solvent, are homogenized in water by means of a wettable agent, an adhesive agent, a dispersant or an emulsifier. However, it is also possible to prepare concentrates containing the active ingredient, a wetting agent, a tackifier, a dispersant or an emulsifier and, if appropriate, a solvent or an oil, and these concentrates are suitable for dilution with water.

Suitable surfactants are alkali metal, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids such as ligno-, phenol-, naphthalene- and dibutylnaphthalenic acids and fatty acids, alkyl- and alkylarylsulfonates, alkylsulfates, lauryl ether sulfates and sulfonated fatty alcohol salts. hexa-, hepta- and octadecanols and glycol ethers of fatty alcohols, sulfonated naphthalene condensates and their derivatives with formaldehyde, naphthalene or naphthalenesulfonic acid condensates with phenol and formaldehyde, polyoxyethylene-octylphenyl ether, ethoxylated isooctyl-alkyl, poly-octyl-phenylphenolylphenyl or nylphenyl- polyether alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene-alkyl ethers or polyoxypropylene-alkyl ethers, lauryl alcohol-polyglycol ether acetate, sorbitol esters, lignin-sulphite waste liquors or methylcellulose.

Powders, spreading agents and dusts can be prepared by mixing or concomitantly grinding the active ingredients with a solid carrier.

Granules, such as coated granules, impregnated with 9 granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silicas, silica, silicates, talc, kaolin, limestone, lime, chalk, red clay, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, crushed synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of plant origin such as cereal flour, tree bark meal, wood meal and nut shell meal, cellulose powders or other solid carriers.

The concentration of the compound of formula (I) in the ready-to-use products may vary within wide ranges. In general, the compositions contain from 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are employed in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

The compound of the formula I according to the invention can be formulated, for example, as follows:

I. 20 parts by weight of compound 2.2 are dissolved in a mixture containing 80 parts by weight of alkylated benzene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate. 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it provides an aqueous dispersion containing 0.02% by weight of the active ingredient.

· 4 4 • 4 · 4

444 444 • 4 9 • 4 99 • 99 99 · · ·

9 9 * • 5 · «

II. 20 parts by weight of compound 2.3 are dissolved in a mixture containing 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the product of addition of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 10 parts by weight of the product of addition of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it provides an aqueous dispersion containing 0.02% by weight of the active ingredient.

III. 20 parts by weight of the active ingredient No. 2.4 are dissolved in a mixture comprising 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction boiling at 210 DEG-280 DEG C. and 10 parts by weight of an addition product of 40 moles of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight and finely distributing it provides an aqueous dispersion containing 0.02% by weight of the active ingredient.

IV. 20 parts by weight of the active ingredient No. 2.5 are intimately mixed with 3 parts by weight of sodium diisobutylnaphthalenesulfonate, 17 parts by weight of sodium lignosulfonic acid from sulphite waste liquor and 60 parts by weight of powdered silica gel and the mixture is ground in a hammer mill. Fine dispersion of the mixture in 20,000 parts by weight of water provides a spray mixture containing 0.1% by weight of the active ingredient.

parts by weight of active ingredient No. 2.1 are mixed with 97 parts by weight of finely divided kaolin. This yields dust containing 3 parts by weight of the active ingredient.

IN.

• ft *

VI. 20 parts by weight of active ingredient No. 2.6 are mixed intimately with 2 parts by weight of calcium dodecylbenzene sulfonate, 8 parts by weight of polyglycol ether of fatty alcohol, 2 parts by weight of sodium phenol / urea / formaldehyde condensate and 68 parts by weight of paraffin mineral oil. This gives a stable oily dispersion.

Vil. 1 part by weight of compound No. 2.11 is dissolved in a mixture containing 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. This provides a stable emulsion concentrate.

VIII. 1 part by weight of compound No. 2.23 is dissolved in a mixture containing 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol ^R EM 31 (non-ionic emulsifier based on ethoxylated castor oil). This gives a stable emulsion concentrate.

The active ingredients of the formula I or their herbicidal preparations can be applied before or after emergence. If the active ingredients are less tolerated by some crops, application methods can be used in which the herbicidal compositions are sprayed by means of a spraying device in such a way that they come into contact as little as possible or do not come into contact with leaves of sensitive crops on the lower floor or sprayed on bare soil (post-directed, lay-by).

In order to broaden the spectrum of action and to achieve synergistic effects, the compounds of the formula I can be mixed and used

9 9 9 • 9 9 · 9

99 and 99 99

9 99 9 9 λ 9 9 9 9 9 9

9 9 · 9 9

99,999,999 herj are praising along with a large number of other groups of bicycles or growth regulators. Suitable components in mixtures, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy- / hetaryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones,

2- (aroyl / hetaroyl) -1,3-cyclohexanediones, hetaryl-arylketones, benzylisoxazolidinones, meta-CF ₃ -phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexenone oxime ether derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzoic acid , dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones,

N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- or hetaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.

In addition, it may be advantageous to apply the compound of the formula alone or in combination with other herbicides in the form of a mixture with other crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are used for treatment due to lack of nutrients and trace elements. Non-phytotoxic oils and oil concentrates may also be added.

Depending on the intended objective of the control measures, the season, the target plants and the growth stages, the rates of application of the active ingredient are from 0.001 to 3.0, preferably from 0.01 to 3.0.

1.0 kg / ha.

Examples of use

The herbicidal action of the 2- (3-alkenylbenzoyl) cyclohexane-1,3-diones of formula I is shown by greenhouse experiments.

The cultivation containers used are plastic pots containing clay sand with about 3.0% humus as a substrate. Seeds of test plants are sown separately for each species.

For pre-emergence treatment, the active ingredients suspended or emulsified in water are applied directly after sowing using finely sprayed nozzles. The pots are gently irrigated to promote germination and growth and then covered with translucent plastic covers to plant roots. This cover allows uniform germination of the test plants without being adversely affected by the active ingredients.

For post-emergence treatment, the test plants are grown to a plant height of from 3 to 15 cm depending on the plant growth pattern and then treated with the active ingredients suspended or emulsified in water. To this end, the test plants are either sown directly and grown in the same containers or first grown separately as seedlings and transplanted into the test containers a few days before treatment. The rate of application of the post-emergence treatment is 0.5-0.25 kg / ha of active ingredient.

Depending on the species, the plants are maintained at temperatures of from 10 to 25 ° C and from 20 to 35 ° C, respectively. Testing 9 # · 9 9 ·· 9 9 • 9 9 9 9 · · · 9 99 9

99 9 9 999 «

99 99 9 · 9 9 · · 9 9 9

9999 98 99

9 «9 999 999 99 99 The period lasts 2 to 4 weeks. During this time the plants are grown and their response to individual treatment is evaluated.

Evaluation is carried out using a scale of 0 to 100. 100 means no plant emergence or complete destruction of at least the above-ground portions and 0 means no damage or normal growth.

The plants used in greenhouse experiments belonged to the following species:

Scientific name

Common name

Chenopodium album Polygonum persicaria Sinapis alba Solanum nigrum Goosefoot Gooseberry Mustard White Aubergine Black

Compound 2.1 applied after emergence at 0.5 or 0.25 kg / ha of active ingredient causes very good weed control.

Claims (11)

PATENT CLAIMS 13 R to R are as described in claim 1 a L is a nucleophilically displaceable leaving group and, if desired, subjecting the rearrangement acylation product to a: · · · · · · · · · · · · · · · · · · · · · · · · · · A 1,3-dithiolan-2-yl group or a 1,3-dithian-2-yl group, and the last 6 groups mentioned may carry one to three C ₁ -C ₄ alkyl groups as substituents, R ^x ® is hydrogen, C 1 -C 6 alkyl or C 1 -C 6 alkyl 14 X 6 alkoxycarbonyl or R ^ie and R ¹⁹ together form a π bond or a three- to six-membered carbocyclic ring or can be a unit CR ^xe R ^{1 '7} replaced by C = 0th 2- (3-Alkenylbenzoyl) cyclohexane-1,3-dione of formula I R ⁴ (I) wherein the substituent symbols have the following meanings: R ^x , R ² are hydrogen, nitro, halogen, cyano, thiocyanato, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C6 alkynyl, -OR ⁶ , -OCOR ⁷ , -OSO R ⁷ , thio, -S (O) n R ^a , -SO 2 OR ^e , -SO ² NR ⁶ R ⁹ , -NR ⁹ SO R ⁷ or -NR ⁹ COR ⁷ , R ³ is hydrogen, halogen, C _{x Ce} alkyl, _Ci-C6 haloalkyl, CC alkoxy, C ₂ -C _g alkenyl, C ₂ -C _g alkynyl, R ^4, R ^s is hydrogen, nitro, halogen, cyano, thiocyanato, C, -C _s alkyl group, a C _i -C _e haloalkyl, C ₃ -C _s cycloalkyl, C ₂ -C _e alkenyl, C ₄ -C _e cycloalkenyl, C ₂ -C _G alkynyl, C? -C _r alko89 • • · · · · · · β • ft · ftft ftft • • «· •« ftft »• ft ft • ftft ftft · ft • • ftft ftft ftftft ft · xyskupina, _{C g} -C alkylthio, _C -C haloalkoxy _g, -COR ^10, -C02R ^10, -COSR ^10, -C0NR ^lo R ^{and L,} -C (R ¹²⁾ = NR ^13, -PO (OR ¹⁰⁾ (OR ^11), C 1 -C ₄ alkyl group which has attached thereto one of the following groups: hydroxyl, -COR ^10, -CO 2 R ^10, -COSR ^10, -C0NR ^{lo R1i} or -C (R ¹²⁾ = NR ^13, heterocyclyl, heterocyclyl-C ^ -C ^ alkyl, phenyl, phenyl-C ^ -C ^ -alkyl, hetaryl, hetaryl The C 1 -C ₄ -alkyl group and the last six of these may be substituted or R ⁴ and ^R together form a C ₂ -C _g alkanediyl chain which can be mono- to tetrasubstituted by C, -C ₄ alkyl group and / or may be interrupted by oxygen or sulfur or by a nitrogen which is unsubstituted or substituted by _C ~ C ₄ alkyl, n is 0, 1 or 2, R * ³ is hydrogen, C -C alkyl, C -C haloal1 6 1 6 alkyl group, a C _x -C _g -alkoxy-C ₂ -C _g alkyl, C ₃ -C _alkenyl radical or C ₃ -C _g alkynyl, R ⁷ is a C _x -C _g alkyl or C -C haloalkyl, _And R is _C -C _g alkyl, C, -C _{x g} haloalkyl, C _x C _g alkoxy-C ₂ -C _g alkyl, _C3 ~ _Cg alkenyl or C ₃ -C _g alkynyl, R ⁹ is hydrogen or _C -C _g alkyl, I ΦΦ ΦΦ • φ · φ! · Φφφ, Φ Φ 4 4Ί · Φ Φ Φ I 4 Φ Φ Φ Φ · · · · ΦΦΦ ΦΦΦ 90 10 is hydrogen, C - ^ - Cg The alkyl group, a C ₃ -C ^ pykioalkylová group, a C ^ -Cg haloalkyl, C ₃ -C ₆ alkenyl, C ₃ -Cg alkynyl, phenyl or benzyl and last |! Dye group from the following list may be partially or fully halogenated and / or can have attached one to three of the following groups: nitro, cyano, ^C l ^"C 4 alkyl, C-C ^ haloalkyl, ^C l" ^C 4 alkoxy, C 1 -C 4 haloalkoxy, C 2 -C ₄ alkylcarbonyl or O 2-04 alkoxycarbonyl, R ¹¹ is hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl or R and R together form a C ₂ -C ₆ -alkanediyl chain which can be mono- to tetrasubstituted by C 2 -C 4 alkyl group and / or may be interrupted by oxygen or sulfur or by a nitrogen which is unsubstituted or substituted C2-C4 alkyl, • io R is hydrogen, C ^ Cg alkyl, C ^ -Cg haloalkyl, C ^ -Cg alkoxy, C ₂ -Cg alkoxycarbonyl, C ₃ -Cg cycloalkyl, ^C 2 ^'C 6 alkenyl, C ₂ - The C8 alkynyl group, the phenyl group or the benzyl group and the last two of these groups may be partially or fully halogenated and / or may have one to three groups attached from the following list: nitro, cyano, C1-C4 alkyl, C2-C4 a haloalkyl group, a 02-04 alkoxy group, a C2-C4 haloalkoxy group, a C2-C4 alkylcarbonyl group, or an alkoxycarbonyl group, • te tete • et · t · et ·· · et ··· · · Te · tet «· tet tet tet tet tet tet tet tet tet tet tet tet tet tet tet tet tet - 91 R ¹³ is a C - ^ - Cg alkyl, ^{C -} Cg haloalkyl, C3-C6 cycloalkyl, C3-Cg alkenyl, C3-Cg alkynyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, C3 C8 cycloalkyloxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, phenyl, benzyl or phenyl-C1-C4 alkoxy and the last three of these may be partially or fully halogenated and / or may have one to three groups attached from the following list : nitro, cyano, ^C l ^-C 4 alkyl, ^C ^ ^-C 4 haloalkyl, ^C l ^-C 4 alkoxy, C 1 -C ₄ haloalkoxy, C ₁ -C ₄ alkylcarbonyl or C ^ -C ^ alkoxycarbonyl, Q is an unsubstituted or substituted cyclohexane-1,3-dione ring which is attached at the 2-position, or a salt thereof suitable for agriculture. 2 1 R is hydrogen or the group described above for R- ¹ . 2- (3-Alkenylbenzoyl) cyclohexane-1,3-dione of formula I, according to claim 1, wherein Q is a cyclohexane-1,3-dione ring of formula II which is attached at the 2-position, wherein: ΦΦ, φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ R ^14, R ^1S, R ¹⁷ and R ¹⁹ are hydrogen or a CC alkyl group, R ^x ® is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₃ -C ₄ cycloalkyl, and the last three groups may have one to three of the following substituents: C ₁ -C ₄ alkylthio or C ₁ -C ₄ alkoxy or the substituent is tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydro thiopyran -4-yl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 2- (3-Alkenylbenzoyl) cyclohexane-1,3-dione of formula (I) according to claim 1 or 2, wherein: Λ C R, R are hydrogen, nitro, halogen, cyano, thiocyanato, C ₁ -C ₆ alkyl, C ₃ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₄ -C 6 ₆ cycloalkenyl, C ₂ -Cg alkynyl, Cj-Cg alkoxy, C ^ -Cg alkylthio, C ^ Cg haloalkoxy, -COR ^10, -CO 2 R ^10, -COSR ^10, -CONR ¹⁰ R ^{i: l} - C (R ¹² ) = NR ¹³ , -PO (OR ¹⁰ ) (OR ¹¹ ), an O 1-4 alkyl group having one of the following groups attached thereto: COR ¹⁰ , -CO ² R ¹⁰ , -COSR ¹⁰ , -CONR ¹⁰ R ¹¹ or -C (R ¹² ) = NR ¹³ , heterocyclyl, heterocyclyl-C ₁ -C ₄ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, hetaryl, hetaryl-C ₁ - The C ₄ alkyl group and the last six of these groups may be substituted or 2- (3-Alkenylbenzoyl) cyclohexane-1,3-dione of formula I according to any one of claims 1 to 3, wherein: R ¹ is nitro, halogen, cyano, thiocyanato, C ^^ - Cg alkyl, C ^ -Cg haloalkyl, C ^ -Cg alkoxy-Cl-Cg alkyl, ^C2-C6 alkenyl, C2-Cg alkynyl, -OR ^6, or -S (O) n R ^8a 4 c R and R together form a C ₂ -C 8 alkanediyl chain which may be mono- to tetrasubstituted with a C 1-4 alkyl group and / or may be interrupted by an oxygen or sulfur atom or a nitrogen atom which is unsubstituted or substituted with a C 1 -C ₄ alkyl group , Ί 3 R is C 1 -C 8 alkyl, C ₁ -C 8 haloalkyl, C 1 -C 8 cycloalkyl, C ₃ -C 8 alkenyl, C ₃ -C 8 alkynyl, C 1 -C 8 alkoxy, C 1 -C 8 haloalkoxy, C ₃ -C ₆ cycloalkyloxy, C ₃ -Cg alkenyloxy, C ₃ -C ₆ alkynyloxy, phenyl, benzyl or benzyloxy, and the last three of these groups may be partially or fully halogenated and / or may have připo94 only one to three groups from of the following list: nitro, cyano, C ^ -C ^ alkyl, ^C, l ^"C 4 haloalkyl, C ₁ -C ₄ alkoxy, C 1 -C ₄ haloalkoxy, alkylcarbonyl or C 1 -C 4 alkoxycarbonyl. 4 44 4 · 44 444 444 4 4 44 9 4 • · «· 4 4 · · · · 2- (3-Alkenylbenzoyl) cyclohexane-1,3-dione of formula I according to any one of claims 1 to 4, wherein: R ⁴ is hydrogen, nitro, halogen, cyano, thiocyanato, C ^ Cg alkyl group, a ^C l ^-C 6 haloalkyl, C3-Cg cycloalkyl, C2-Cg alkenyl, C4-Cg cycloalkenyl, C2 Cg alkynyl, ^{C -} C alkoxy, C -C alkylthio, C - ^ - Cg haloalkoxy, -COR ^10, -CO 2 R ^10, -COSR ^10, -CONR ¹⁰ R ^{1: L,} -C ^(R12) = NR ¹³ , -PO (OR ¹⁰ ) (OR ¹¹ ), a C 1 -C 4 alkyl group to which any of the following groups are attached: -COR ¹⁰ , -CO ² R ¹⁰ , -COSR ¹⁰ , -ΟΟΝΚ ¹ ^ ¹¹ or -C (R ¹² ) = NR ¹³ , furthermore is a heterocyclyl group, ftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftft Heterocyclyl-C ₁ -C ₄ alkyl, phenyl, phenyl-C ₁ -C ₄ -alkyl, hetaryl, hetaryl-C ₁ -C ₄ -alkyl and the latter six may be substituted , ^R is hydrogen, halogen, cyano, thiocyanato, C-C6 alkyl, Cx-Cg haloalkyl, -COR ^10, -CO 2 R ° ^X, -COSR ^10, -CONR R ^{XO XX} or -PO (OR ^XO ) (0R ^xx ) or R ⁴ and ^R together are C ₂ -C _g -alkanediyl chain which can be mono- to tetrasubstituted by C -C alkyl group and / or may be interrupted by oxygen or sulfur or by a nitrogen which is unsubstituted or substituted by C -C alkyl group. 2- (3-Alkenylbenzoyl) cyclohexane-1,3-dione of the formula Ia, (Ia) in which the variables R ^x to R ⁵ and Q have the same meanings as in claims 1 to 5. • 9 99 99 • 9 9 9 9 9 A process for the preparation of 2- (3-alkenylbenzoyl) cyclohexane-1,3-dione of the formula I according to any one of claims 1 to 6, characterized in that it comprises acylation of an unsubstituted or substituted cyclohexane-1,3-dione Q with activated carboxylic acid or a carboxylic acid of formula β R ⁴ (IIIa) in which variables 8. A composition characterized in that it comprises a herbicidally effective amount of at least one merged Nina formula I or salts thereof useful in agriculture _n according to any of claims 1 to 6 and auxiliaries usually used for * the formulation of crop protection products. A process for the preparation of a herbicidally active composition according to claim 8, characterized in that the herbicidally effective amount of at least one compound of the formula I or an agriculturally acceptable salt thereof according to any one of claims 1 to 6 is mixed with auxiliaries usually used in crop protection agents. . The presence of a catalyst gives a compound of formula (I). 9 4 995 9 9 4 9 99 99 99 99 999 999 · 9 99 - 96 9 9 9 9 · · · · ··· ··· 9 · 99. · 9 9 9 9 9 9 4 4 4 49 4 443 4 4 4 4 9 4 9 4 A method of controlling undesirable vegetation, characterized in that a herbicidally effective amount of at least one compound of formula (I) or an agriculturally acceptable salt thereof according to any one of claims 1 to 6 is left to act on the plants, their environment and / or seeds. . Use of a compound of formula (I) or τ salt thereof suitable for agriculture according to any one of claims 1 to 11