EP0964866A1

EP0964866A1 - 5-(dioxabicyclohept-6-yl)-cyclohexenone oxime ethers, their preparation and their use

Info

Publication number: EP0964866A1
Application number: EP97954747A
Authority: EP
Inventors: Joachim Rheinheimer; Volker Maywald; Uwe Kardorff; Karl-Otto Westphalen; Ulf Misslitz; Helmut Walter
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1997-01-09
Filing date: 1997-12-19
Publication date: 1999-12-22
Also published as: JP2001508432A; US6107254A; WO1998030565A1; CA2277019A1

Abstract

The invention concerns 5-(dioxabicyclohept-6-yl)-cyclohexenone oxime ethers of formula (I) in which the substituents have the following meanings: R<1> is hydrogen, the equivalent of an agriculturally useful cation, C1-C10 alkylcarbonyl, C1-C10 alkylsulphonyl, C1-C10 alkylphosphonyl, benzoyl, benzene sulphonyl or benzene phosphonyl; R<2> is C1-C6 alkyl; R<3>, in each case independently of each other, is hydrogen or C1-C4 alkyl; Z is a C1-C6 alkylene, C3-C6 alkenylene or C3-C6 alkinylene chain which can carry an exo-methylene substituent (=CH2) and/or in each case a further one to three substituents selected from a group comprising C1-C3 alkyl substituents and halogen atoms; a C3-C6 alkylene or C4-C6 alkenylene chain which can carry between one and three C1-C3 alkyl substituents and which, in addition to methylene or methine units, contains one of the following bridge members: oxygen, sulphur, -SO-, -SO2- or -N(R<i>)-, R<i> standing for hydrogen, C1-C4 alkyl, C3-C6 alkenyl or C3-C6 alkinyl; R<4> is hydrogen, halogen, phenyl, wherein the phenyl group can be unsubstituted, partially or completely halogenated, and, if it is not completely halogenated, can carry between one and three substituents having the meaning given in the claims. The invention also concerns the preparation of these substances and their use.

Description

5- (Dioxabicyclohept-6-yl) cyclohexenone oxime ether, their preparation and use

description

The present invention relates to new 5- (dioxabicyclohept-β-yl) cyclohexenone oxime ethers of the formula I.

in which the substituents have the following meaning:

R ^{1 is} hydrogen, the equivalent of an agriculturally usable cation, Cι-Cιo-alkylcarbonyl, Cι-Cιo-alkylsulfonyl, Cι-Cιo-alkylphosphonyl, benzoyl, benzenesulfonyl or benzene-phosphonyl, where the latter three radicals can still carry 1 to 5 halogen atoms;

R ² -C ₆ alkyl;

R ³ each independently of one another hydrogen or -CC alkyl;

a Ci-C _ß- alkylene, C ₃ -C ₆ -alkenylene or C ₃ -C, ₆ -alkynylene chain, which can carry an exo-methylene substituent (= CH) and / or each one to three substituents, selected from a group consisting of C ₁ -C ₃ -alkyl substituents and halogen atoms,

a C ₃ -C ₆ alkylene or C ₄ -C- ₆ -alkenylene chain which Cι-C ₃ alkyl substituents may carry from one to three, and in addition to methylene or methine units contains one of the following bridgehead members: oxygen, sulfur , -SO-, -S0 ₂ - or - NCR ¹ ) -, wherein R ^{1 is} hydrogen, -CC ₄ alkyl, C ₃ -C ₆ alkenyl or C -C ₆ alkynyl;

R ^{4 is} hydrogen, halogen, phenyl, where the phenyl group can be unsubstituted, partially or completely halogenated and, if it is not fully halogenated, one Cι Cι-C-C can carry one to three substituents selected from the group consisting of nitro, cyano, formyl, halogen, ₄ -alkyl, C ₄ haloalkyl, ₄ -alkoxy, C ₄ haloalkoxy, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyl, CC ₆ ~ alkynyloxy and -NR ⁵ R ⁶ , where

R ⁵ -CC ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl and

R ⁵ Cι-C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, Cι-C ₆ -acyl or benzoyl which may carry from one to three substituents selected from the group consisting of nitro, cyano, halo, Cι-C ₄ -alkyl, C ₄ haloalkyl, _Cι-C4 alkoxy, and Cι-C alkylthio.

The invention also relates to

herbicidal agents and plant growth regulators which contain the compounds I as active substances,

Process for the preparation of the compounds I,

Intermediates of formula II,

Methods for controlling undesired plant growth with the compounds I,

the use of the compounds I as herbicides and for regulating the growth of plants.

Herbicidally active cyclohexenone oxime ethers are already known from the literature which have a tetrahydropyran-4-yl radical in the 5-position on the cyclohexenone ring (EP-A 142 741, DE-A 38 38 309 and EP-A 456 112).

EP-A 230 235 describes herbicidally active 5- (3, 7-dioxabicyclo [4.1.0] hept-1-yl) cyclohexenone oximes which differ from the compounds according to the invention in the linking site 1 instead of 6 on the bicyclus .

Since the herbicidal properties of the known compounds, with regard to their activity and in particular with regard to their selectivity against grass weed in grassy crop plants, are not always fully satisfactory, it was the object of the present invention to find new, herbicidally active cyclohexenone oximes. The The task also extended to the provision of new growth regulatory connections.

We have found that this object is achieved by the novel 5- (dioxabicyclohept-6-yl) cyclohexenone oxime ether I defined at the outset. Furthermore, herbicidal and growth regulating agents have been found which contain them. Processes for the preparation of the compounds I and the intermediates of the formula II required for their preparation have been found. A method for controlling undesired plant growth with the compounds I was found. Furthermore, the use of the compounds I as herbicides and growth regulators has been found.

Depending on the substitution pattern, the compounds of the formula I can contain one or more chiral centers. They are then present as mixtures of enantiomers or diastereomers. The invention relates both to the pure enantiomers or diastereomers and to their mixtures.

The molecular parts mentioned in the definition of the radicals R ¹ to R ⁶ and Z or as substituents for alkyl, alkenyl, alkynyl and phenyl represent collective terms for individual lists of the individual group members. The radicals alkyl, alkylthio, alkoxy, alkylcarbonyl, alkylsulfonyl, Alkylphosphonyl, alkenyl, alkenyloxy, alkynyl, alkynyloxy can be straight-chain or branched. The unsubstituted alkylene, alkenylene, alkynylene chains are straight-chain. Halogenated substituents preferably carry one to three identical or different halogen atoms. Halogen means bromine, iodine, and especially fluorine or chlorine.

Furthermore, for example:

C ₁ -C ₄ -Alkyl, and the alkyl parts of -C-C ₄ -alkylthio: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1, 1-dimethylethyl;

-C ₆ alkyl:

C ₁ -C ₄ alkyl, as mentioned above, and pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl,

1-Et ylpropyl, 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-l-methylpropyl and l-ethyl-3-methylpropyl; _{Cι-C4-haloalkyl:} a Cι-C ₄ -alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, eg chloromethyl, dichloromethyl, tri- chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl , Chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2, 2 -difluoroethyl, 2, 2, 2 -trifluoroethyl, 2 -chloro-2-luorethyl, 2-chloro -2 , 2-difluoroethyl, 2, 2 -dichloro-2-fluoroethyl, 2, 2, 2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoro-propyl, 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-bromethyl,

4 - fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl;

C 1 -C ₄ alkoxy: methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1, 1-dimethylethoxy;

C ₁ -C ₄ haloalkoxy: a C ₁ -C ₄ alkoxy radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromdi - fluoromethoxy, 2-fluoroethoxy, 2 -chloroethoxy, 2 -bromomethoxy, 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- (chloromethyl) -2-chloroethoxy, 1- (bromomethyl) -2 -bromethoxy, 4 -fluorobutoxy, - Chlorobutoxy, 4-bromobutoxy and nonaflupr-butoxy;

C ₁ -C ₁₀ alkyl of the alkyl parts of Cx-Cio-alkylcarbonyl, Cι-Cιo-alkylsulfonyl and Cι-Cι ₀ -alkylphosphonyl: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1st , 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 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, 2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl, Heptyl, octyl, 2-ethylhexyl, nonyl, decyl;

Agricultural usable cation: alkali metal salts, in particular the sodium or potassium salt, alkaline earth metal salts, in particular the calcium, magnesium or barium salt, manganese, copper, zinc or iron salt and ammonium, phosphonium, sulfonium or sulfoxonium salts, for example ammonium salts, Tetraalkylammonium salts, benzyltrialkylammonium salts, trialkylsulfonium salts or trialkylsulfoxonium salts;

C -C ₆ alkenyl, and the alkenyl parts of C ₃ -C ₆ alkenyloxy:

Prop-1-en-l-yl, prop-2-en-l-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl, 1-methyl-prop-l- en-l-yl, 2-methyl-prop-1-en-l-yl, l-methyl-prop-2-en-l-yl and 2-methyl-prop-2-en-l-yl, pentene 1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methyl-but-l-en-l-yl, 2-methyl-but-l-en-l-yl, 3-methyl-but-l-en-l-yl, l-methyl-but-2-en-l-yl, 2-methyl-but-2-en-l-yl, 3-methyl-but-2- en-l-yl, 1-methyl-but-3-en-l-yl, 2-methyl-but-3-en-l-yl, 3-methyl-but-3-en-l-yl, 1, l-dimethyl-prop-2-en-l-yl, 1, 2-dimethyl-prop-1-en-l-yl, l, 2-dimethyl-prop-2-en-l-yl, 1-ethyl prop-l-en-2-yl, l-ethyl-prop-2-en-l-yl, hex-1-en-l-yl, hex-2-en-l-yl, hex-3-en- l-yl, hex-4-en-l-yl, hex-5-en-l-yl, 1-methyl-pent-l-en-l-yl, 2-methyl-pent-1-en-l- yl, 3-methyl-pent-1-en-l-yl, 4-methyl-pent-l-en-l-yl, l-methyl-pent-2-en-l-yl, 2-methyl-pent 2-en-l-yl, 3-methyl-pent-2-en-l-yl, 4-methyl-pent-2-en-l-yl, l-methyl-pent-3-en-l-yl, 2-methyl-pent-3-en-l-yl, 3-methyl-pent-3-en-l-yl, 4-methyl-pent-3-en-l-yl, l-methyl-pent-4- e n-1-yl, 2-methyl-pent-4-en-1-yl, 3-methyl-pent-4-en-1-yl, 4-methyl-pent-4-en-1-yl,

1, l-dimethyl-but-2-en-l-yl, 1, l-dimethyl-but-3-en-l-yl, 1, 2-dimethyl-but-l-en-l-yl, 1, 2-dimetyl-but-2-en-l-yl, 1, 2-dimethyl-but-3-en-l-yl, 1, 3-dimetyl-but-l-en-l-yl, 1, 3- Dimethyl-but-2-en-l-yl, 1, 3-dimetyl-but-3-en-l-yl, 2,2-dimethyl-but-3-en-l-yl, 2, 3-dimethyl but-l-en-l-yl,

2,3-dimethyl-but-2-en-l-yl, 2,3-dimethyl-but-3-en-l-yl,

3,3-dimethyl-but-l-en-l-yl, 3,3-dimethyl-but-2-en-l-yl, 1-ethyl-but-l-en-l-yl, l-ethyl but-2-en-l-yl, 1-ethyl-but-3-en-l-yl, 2-ethyl-but-l-en-l-yl, 2-ethyl-but-2-en-l- yl, 2-ethyl-but-3-en-l-yl, 1, 1, 2-trimethyl-prop-2-en-l-yl, l-ethyl-l-methyl-prop-2-en-l-yl, l-ethyl-2-methyl-prop-1-en-l-yl and l-ethyl-2-methyl-prop-2-en- l-yl;

C ₆ -C ₆ alkynyl, and the alkynyl radicals of C ₆ -C ₆ alkynyloxy: prop-1-in-1-yl, prop-2-in-1-yl, but-1-in-1-yl, but- l-in-3-yl, but-l-in-4-yl and but-2-in-l-yl; Pent-1-in-l-yl, Pent-1-in-3-yl, Pent-1-in-4-yl, Pent-1-in-5-yl, Pent-2-in-1-yl, Pent-2-yn-4-yl, pent-2-yn-5-yl, 3-methylbut-l-yn-3-yl, 3-methylbut-l-yn-4-yl, hex 1-in-l-yl, hex-l-in-3-yl, hex-l-in-4-yl, hex-l-in-5-yl, hex-l-in-6-yl, hex 2-in-l-yl, hex-2-in-4-yl, hex-2-in-5-yl, hex-2-in-6-yl, hex-3-in-l-yl, hex 3-in-2-yl, 3-methyl-pent-1-in-1-yl, 3-methyl-pent-1-in-3-yl, 3-methyl-pent-1-in-4-yl, 3-methyl-pent-l-in-5-yl, 4-methyl-pent-1-in-l-yl, 4-methyl-pent-2-in-4-yl and 4-methyl-pent-2-yl in-5-yl;

C ₁ -C ₆ -alkylene: the straight-chain alkylene chains methylene, ethylene, propylene, butylene, pentylene and hexylene, these chains being able to carry an exo-methylene substituent and / or in each case also one to three substituents, selected from a group consisting of C 1 -C -Alkyl substituents and halogen atoms;

C ₃ -C ₆ alkenylene: the straight-chain alkenylene chains such as, for example, 2-propenylene, 2-butenylene, 3-butenylene, 2-pentenylene, these chains being able to carry an exo-methylene substituent and / or in each case also one to three substituents a group consisting of -CC alkyl substituents and halogen atoms;

C ₃ -C ₆ -alkynylene: the straight-chain alkynylene chains such as 2-propynylene, 2-butynylene, 3-butynylene, 2-pentynylene, where these chains can carry an exo-methylene substituent and / or each one or three substituents a group consisting of -CC alkyl substituents and halogen atoms;

a C ₃ -Cg alkylene chain which, in addition to methylene units, contains one of the following link members: oxygen, sulfur, -SO-, -S0- or -N (R ¹ ) -: 3-oxapropylene, 3-azapropylene, 3-thiapropylene, 3 -Tiapropylene-3-oxide, 3-thia-propylene-3, 3-dioxide, 3-oxabutylene, 3-azabutylene, 3-thia-butylene, 3-thiabutylene-3-oxide, 3-thiabutylene-3, 3-dioxide , 4-oxabutylene, 4-azabutylene, 4-thiabutylene, 4-thia-butylene-4-oxide, 4-thiabutylene-4, 4-dioxide, 3-oxapentylene,

3-azapentylene, 3-thiapentylene, 3-thiapentylene-3-oxide, 3-thia-pentylene-3, 3-dioxide, 4-oxapentylene, 4-azapentylene, 4-thia- pentylene, 4-thiapentylene-4-oxide, 4-thiapentylene-4, 4-dioxide, 5-oxapentylene, 5-azapentylene, 5-thiapentylene, 5-thiapentylene-5-oxide, 5-thiapentylene-5, 5- dioxide.

3-Oxapropylene, 3-Oxabutylene and are particularly preferred

4-oxabutylene, which, like the other alkylene chains mentioned above, can carry one to three C 1 -C 4 -alkyl substituents, in particular one to three methyl substituents;

- A C ₄ -C ₆ alkenylene chain which, in addition to methine units, contains one of the following link members: oxygen, sulfur, -SO-, -S0- or -NtR ¹ ) - such as: 5-oxapent-3-enylene, 5-aza - Pent-3-enylene, 5-thiapent-3-enylene, where these chains can carry one to three C ₁ -C ₃ -alkyl substituents, in particular one to three methyl substituents;

With regard to the herbicidal activity of the 5- (dioxabicyclohept-6-yl) cyclohexenone oxime ether I, the following meanings of the substituents, in each case individually or in combination, are particularly preferred:

R ^{1 is} hydrogen or the equivalent of an agriculturally useful cation, particularly preferably hydrogen, sodium, potassium, lithium or ammonium;

R ^{2 is} ethyl or n-propyl;

R ^{3 is} hydrogen or methyl;

Z is a C ₁ -C ₆ -alkylene, C ₃ -C ₆ -alkenylene or C ₃ -C ₆ -alkynylene chain, each of which can also carry a C ₁ -C ₃ -alkyl substituent,

a CC ₆ -alkylene or C ₄ -C ₆ -alkenylene chain, which can optionally carry one to three -CC alkyl substituents, and which optionally contain an oxygen atom as a bridging link in addition to methylene or methine units;

R ^{4 is} hydrogen, halogen, phenyl, where the phenyl group can also carry one to three substituents, selected from a group consisting of nitro, cyano, formyl, halogen, C 1 -C ₄ alkyl, C 1 -C ₄ haloalkyl, C 1 -C ₄ -Alkoxy, -CC ₄ -haloalkoxy, C-C6-alkenyl, CC ₆ -alkenoxy, C -C ₆ -alkynyl, CC ₆ -alkynyloxy and -NR ⁵ R ⁶ , wherein

R ^{5 is} hydrogen, -CC ₄ alkyl, C ₃ -Cg alkenyl or C -C ₆ alkynyl and R ^{6 is} hydrogen, -CC alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl,

Cι-C ~ ₆ acyl or benzoyl which may carry one to three substituents selected from the group consisting of nitro, cyano, halo, Cι-C ₄ -alkyl, C ₄ haloalkyl, Cι-C ₄ alkoxy and -CC ₄ alkylthio mean.

Particularly preferred, individually or in combination, are:

R ^{3 is} hydrogen;

Z ethylene, propylene, 2-propenylene, 3-oxapropylene,

2-methyl-3-oxapropylene, 3-oxabutylene and 4-oxabutylene;

R ^{4 is} hydrogen, halogen or phenyl, which can be halogenated once or twice, for example chlorinated or fluorinated.

The 5- (dioxabicyclohept-6-yl) cyclohexenone oxime ethers of the formula I, where R ^{1 is} hydrogen, can be written in several tautomeric forms, all of which are encompassed by the invention (cf. formula I '):

The 5- (dioxabicyclohept-6-yl) cyclohexenone oxime ethers I are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides. In general, they are contractual and therefore selective in broad-leafed crops and in monocotyledonous (monocotyledonous) crops, which do not count towards the Gramineae. Some of the cyclohexenone oxime ethers I according to the invention are also suitable for the selective control of undesired grassers in grenade cultures. This effect occurs especially at low application rates. Depending on the particular application method, the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants. The following crops are considered, for example:

Allium cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaπs spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tmctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica sativus), Cucumisis , Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoealinarisisis - mum, Lycopersicon lycopersicum, Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisum sativu, Prunus avium, Prunus persica, Pyrus communis, Ribes sylestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (see vulgar), Theobro a cacao, Trifolium pra tense, Triticu aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.

In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.

The cyclohexenone oxime ethers I or the herbicidal compositions comprising them can be sprayed, atomized, for example in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oldispersions, pastes, dusting agents, scattering agents or granules , Dusting, scattering or pouring. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

The following are essentially considered to be inert additives: mineral oil fractions with a medium to high boiling point, such as kerosene or diesel oil, also coal tarols and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, e.g. B. 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 adding water. For the production of emulsions, pastes or old dispersions, the substrates as such or dissolved in a oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. But it can also be made from an active substance, wetting, adhesive, dispersing or emulsifying agent and possibly solvents or existing concentrates that are suitable for dilution with water.

The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalene sulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols as well as of fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonyl phenol, alkylphenyl, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl ethoxylate, ethoxylate, ethoxylate, ethoxylate, ethoxylate, ethoxylate, ethoxylate, ethoxylate, ethoxylate, ethoxylate, ethoxylate, ethoxylate, ethoxylate, ethoxylate, ethoxylate, and , Laurylalkoholpolyglykoletherace- tat, sorbitol ester, lignin sulfite waste or methyl cellulose into consideration.

Powders, materials for spreading and dusting can be produced by mixing or grinding the active substances together with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urine and vegetable products such as flour, tree bark, Wood and nutshell flour, cellulose powder or other solid carriers.

The concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range. The formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

The compounds I according to the invention can be formulated, for example, as follows:

I 20 parts by weight of compound No. 1 are dissolved in a mixture which alkylated from 80 parts by weight

Benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor sol. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

II 20 parts by weight of compound no. 5 are in one

Dissolved mixture, which consists of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of ricinusol. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

III 20 parts by weight of compound no. 13 are in one

Dissolved mixture, which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of ricinusol. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

IV 20 parts by weight of compound no. 15 are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalenesulfonic acid, 17 parts by weight of the sodium salt of a ligmene sulfonic acid from a sulfite waste liquor and 60 parts by weight. parts of powdered silica gel mixed well and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray broth is obtained which contains 0.1% by weight of the active ingredient.

V 3 parts by weight of compound no. 9 are mixed with 97 parts by weight of finely divided kaolin. In this way, a dusting agent is obtained which contains 3% by weight of the active ingredient.

VI 20 parts by weight of compound no. 27 are mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid,

8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.

VII 1 part by weight of compound no. 1 is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained.

VIII 1 part by weight of compound no. 5 is dissolved in a mixture consisting of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol® EM 31 (non-ionic emulsifier based on ethoxylated castor oil sol). A stable emulsion concentrate is obtained.

The herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less contractual for certain crop plants, application techniques can be used in which the herbicides are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit wherever possible, while the active ingredients grow more rapidly on the leaves below unwanted plants or the uncovered floor area (post-directed, lay-by).

To broaden the spectrum of activity and to achieve synergistic effects, the cyclohexenone oxime ethers I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together. For example, 1, 2, 4-thiadiazoles, 1, 3, 4-thiadiazoles, amides, aminophosphoric acid and their derivatives, ammotriazoles, anilides, (het) -aryloxyalkanoic acid and their deri- vate, benzoic acid and its derivatives, benzothiadiazinones, 2-aroyl-l, 3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinoline acid and their derivatives, chloroacetanilides, 3- cyclohexan-1, diondeπvate, diazines, dichloropropionic acid and its derivatives, dihydrobenzofuran, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidone- noles, imidazoline, imidazoline, imidazoline, imidazoline 3, 4, 5, 6-tetrahydrophthalimide, oxadiazole, oxirane, phenol, aryloxy- or heteroaryloxyphenoxypropionic acid ester, phenyl acetic acid and its derivative, phenylpropionic acid and its derivative, pyrazole, phenylpyrazole, pyridazine, pyridinecarbonamide, sulfonyl amide, sulfonyl amide, sulfonyl amide and sulfonyl derivative, substances, triazines, triazinones, triazolinones, triazolecarboxamides, uraciles.

It may also be useful to apply the compounds I alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.

The application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.s.), depending on the target, season, target plants and growth stage.

The compounds of formula I according to claim 1 can be prepared, for example, by reacting a hydroxylamine of formula III with a ketone of formula II. The ketones II in turn are accessible by oxidation (epoxidation) of a dihydropyran of the formula IV.

The known hydroxylamines III can be prepared as described in Houben-Weyl (1971) 10/1 p.1181 or as described in EP-A 465 089 and DE-A 42 04 203. The dihydropyrans IV are accessible analogously to the procedure given in synthesis examples la) and lb). A general overview of synthetic routes to cyclohexane-1,3-dions substituted in the 5-position is presented in EP 142 741.

The reaction of the ketones II to the oximes I can take place with or without a solvent. The choice of solvent is usually not critical and most common solvents can be used. Are u. a. Alcohols such as methanol or ethanol or ethers such as tetrahydrofuran or methyl tert. -butyl ether.

Instead of the free hydroxylamines, it is also possible to use their salts, in particular the hydrochloride. In this case, the addition of 0.5 to 2 equivalents of base requires conversion.

As bases come z. B. alkali metal carbonates, hydrogen carbonates or hydroxides or tertiary amines such as. B. triethylamine, morpholine or pyridine in question. In order to obtain a homogeneous reaction mixture, water can optionally be added as a co-solvent.

The reaction temperature is generally -20 to 100 ° C, preferably 15 to 70 °.

0.7 to 5 equivalents and preferably 1 to 2 equivalents of hydroxylamine III are generally used per equivalent of ketone II.

For the oxidation of the dihydropyrans IV to the ketones II, the oxidizing agents described in the literature for epoxidations come into consideration (cf., for example, Organikum, Barth Verlagsgesellschaft, 19th edition, 1993, p. 272).

For example, peroxides such as metachloroperbenzoic acid, peracetic acid, performic acid or hydrogen peroxide are suitable.

In principle, all solvents can be used that do not themselves participate in the reaction in a disruptive manner. So are z. B. halogenated hydrocarbons such as methylene chloride, dichloroethane or chloroform. Organic acids such as acetic acid or formic acid can also be used.

The reaction temperature can be between -20 ° C and 140 ° C, preferably between 10 ° C and 100 ° C.

As a rule, 1 to 5 equivalents of the oxidizing agent are used per equivalent of dihydropyran IV and preferably 1 to 2 equivalents. In particular, equimolar amounts of the oxidizing agent are used.

The conversion of compounds I, in which R ^{1 is} hydrogen, into salts with agriculturally useful cations is described, for example, in EP-A 728 753.

The esterification of the compounds I, in which R ^{1 is} hydrogen, with alkylcarboxylic acids, alkylsulfonic acids and alkylphosphonic acids can be carried out in the customary manner (cf., for example, Organikum, Barth Verlagsgesellschaft, 19th edition, 1993, pages 419-424).

The 5- (dioxabicyclohept-6-yl) cyclohexenone oxime ether I fall in the manufacture as a rule as (R- / S-) enantiomer or diasterereomer mixtures, eg. Partly as E- / Z-isomer mixtures. The isomer mixtures can, if appropriate, be separated by the methods customary for this, for example by chromatography or by crystallization. Synthesis examples:

1) 2- [1- ((E) -3-chloroallyloxyimino) propyl] -5- (3, 6-dihydro-2H-pyran-4-yl) -3-hydroxycyclohex-2-enone (Tab. l, No. 15) 5 a) 4- (3, 6-dihydro-2H-pyran-4-yl) -but-3-en-2-one: 59.4 g (0.31 mol) (2- Oxopropyl) -phosphonic acid diethyl ester was 69.0 g

(0.50 mol) of potassium carbonate in 75 ml of water and 40.0 g (0.25 mol) of 3,6-dihydro-2H-pyran-4-carbaldehyde (69%) added dropwise at room temperature. After 24 hours of stirring, water was added, the phases were separated and the aqueous phase was extracted several times with methylene chloride. After drying over magnesium sulfate, the combined organic phases were concentrated in vacuo and fractionally distilled. 19.3 g of 4- (3, 6-dihydro-2H-15 pyran-4-yl) but-3-en-2-one were obtained. Boiling point: 82 ° C (0.2 mbar).

b) 2- (1-Oxopropyl) -5- (3, 6-dihydro-2H-pyran-4-yl) -3-hydroxycyclohex-2-enone: 17.0 g (0.11 Mole)

4- (3, 6-Dihydro-2H-pyran-4-yl) -but-3-en-2-one in 100 ml of toluene

20 and 14.5 g (0.11 mol) of diethyl malonate were added at room temperature. Then 19.8 g (0.11 mol) of a 30% solution of sodium methylate in methanol were added dropwise and the mixture was stirred at 60 ° C. for 2 h. The following distillation of an azeotropic mixture of methanol and toluene was used

25 complete removal of the methanol, the temperature is increased until the transition temperature of pure toluene (approx. 110 ° C.) is reached. After cooling to 60 ° C., 1.2 g (10 mmol) of 4- (N, N-dimethylamino) pyridine and 10.2 g (0.11 mol) of propionyl chloride were added and the mixture was stirred at 80 ° C. for 7 h touched. After cooling down

30 30 ° C was washed with 50 ml of 2.5% sulfuric acid and then the product extracted with 100 g (0.25 mol) of 10% sodium hydroxide solution. The aqueous extract was stirred at 40-45 ° C. for 2 hours and, after adding 75 ml of toluene, acidified to a pH of 2 with concentrated sulfuric acid. After two hours of stirring at 45-50 ° C

35 the organic phase is separated off and washed with a little dilute sodium hydrogen carbonate solution.

The solution obtained was either directly reacted further with the desired hydroxylamines or concentrated in vacuo to isolate the product.

c) 2- (l-Oxopropyl) -5- (3, 7-dioxabicyclo [4.1.0] hept-6-yl) -3-hydroxycyclohex-2-enone: 20 g (80 mmol) 2- (1-oxopropyl ) -5- (3, 6-di-hydro-2H-pyran-4-yl) -3-hydroxycyclohex-2-enone in 150 ml of methyl

45 l of chloride were mixed with 32.6 g (0.10 mol) of 55% metachloroperbenzoic acid and stirred for 3 days at room temperature. After concentration in vacuo at room temperature, silica gel was added Chromatographed cyclohexane / ethyl acetate. Yield 14.8 g. ⁱ H-NMR (CDC1 ₃ ): δ = 1.15 (t); 1.95 (m); 2.30-2.80 (m); 3.07 (q); 3.13 (m); 3.50 (m); 3.98 (); 18.2 (s).

d) 2- (1- ((E) -3-chloro-2-propenyloxyimino) propyl) -5- (3, 7-dioxabicyclo [4.1.0] hept-6-yl) -3-hydroxycyclohex- 2-enone: 7.9 g (29.5 mmol) of 2- (l-oxopropyl) -5- (3, 7-dioxabicyclo [4.1.0] - hept-6-yl) -3-hydroxycyclohex-2-enone 3.5 g (32.4 mmol) of 0- ((E) -3-chloro-2-propenyl) hydroxylamine were added to 20 ml of methanol at room temperature and the mixture was stirred for about 10 hours. After concentration in vacuo, an oil remained in quantitative yield. It could be purified by chromatography on silica gel using cyclohexane / ethyl acetate. Yield 6.6 g. ^X H NMR (CDCI ₃ ): δ = 1.13 (t); 1.93 (m); 2.20-2.75 (m); 2.90 (m); 3.13 (m); 3.50 (m); 3.98 (m); 4.52 (d); 6.10 (m); 6.35 (d); 14.3 (s).

2) 2- (1- (2- (4-chlorophenoxy) ethoxyimino) propyl) -5- (3, 7-dioxabicyclo [4.1.0] hept-6-yl) -3-hydroxycyclohex-2- enon (Tab. 1, No. 1)

Phys. Data: ⁱ H-NMR (CDC1 ₃ ): δ = 1.10 (t); 1.95 (t); 2.25-2.75 (m); 2.90 (m); 3.15 (m); 3.55 (m); 4.00 (m); 4.23 (t); 4.45 (t); 6.88 (d); 7.25 (d).

3) 2- (1- (2- (4-chlorophenoxy) propoxyimino) propyl) -5- (3, 7-dioxabicyclo [4.1.0] hept-6-yl) -3-hydroxycyclohex-2- enon (Tab. 1, No. 5)

Phys. Data: ⁱ H-NMR (CDC1 ₃ ): δ = 1.10 (t); 1.37 (d); 1.95 (t); 2.20-2.75 (m); 2.85 (m); 3.15 (m); 3.55 (m); 4.00 (m); 4.23 (m); 4.68 (m); 6.88 (d); 7.25 (d).

4) 2- (1- (Ethoxyimino) propyl) -5- (3, 7-dioxabicyclo [4.1.0] - hept-6-yl) -3-hydroxycyclohex-2-enone (Tab. 1, No. 9 )

Phys. Data: ⁱ H NMR (CDC1 ₃ ): δ = 1.13 (t); 1.33 (t); 1.95 (t); 2.25-2.75 (m); 2.95 (m); 3.15 (m); 3.54 (m); 3.98 (m); 4.12 (q).

5) 2- (1- (3-propenyloxyimino) propyl) -5- (3, 7-dioxabicyclo- [4.1.0] hept-6-yl) -3-hydroxycyclohex-2-enone (Tab. 1, No. . 13)

Phys. Data: ^X H NMR (CDCI ₃ ): δ = 1.13 (t); 1.95 (t);

2.25-2.75 (m); 2.93 (m); 3.13 (m); 3.55 (m); 3.98 (m); 4.53 (d); 5.38 (m); 5.95 (m).

6) 2- (l- (2- (2,4-difluorophenoxy) propoxyimino) propyl) -5- (3,7-dioxabicyclo [4.1.0] hept-6-yl) -3-hydroxycyclo- hex-2-enone (Tab. 1, No. 27) Phys. Data: ⁱ H-NMR (CDCI3): δ = 1.11 (t); 1.35 (d); 1.95 (t); 2.20-2.70 (m); 2.85 (m); 3.13 (m); 3.50 (m); 4.00 (m); 4.23 (m); 4.55 (m); 6.70-7.05 (m).

The following table lists further cyclohexenone oxime ethers of the formula 1 which were prepared or can be prepared in the same way:

Table 1

Examples of use

The herbicidal activity of 5- (dioxabicyclohept-6-yl) cyclohexenonoximether I was demonstrated by greenhouse experiments:

Plastic pots with loamy sand with about 3.0% humus served as the culture vessels. The seeds of the test plants were sown separately according to species.

In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The tubes were lightly sprinkled to promote germination and growth, and then covered with clear plastic covers until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.

For the purpose of post-emergence treatment, the test plants, depending on the growth habit, were first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.

The plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated. Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.

example 1

Selective herbicidal activity in post-emergence applications in the greenhouse.

The application rate was 62.5g / ha a.S.

The plants used in the greenhouse experiments are composed of the following types:

Latin name German name English name

Crop plant Glycine max Soy without soybeans

Harmful plants Echinochloa crus-galli millet barnyardgrass

Setaria faberii millet giant foxtail

The result showed that the above-mentioned grasses were combated very effectively with compounds No. 15 (> 90% damage to the plants), while the crop plant soybean suffered no visible damage from the treatment.

Example 2

Comparison test with EP-A 230 235

In a further test, the herbicidal activity of compound No. 15 according to the invention was compared to that of compound A known from EP-A 230 235 (see Table 4, Example 401

examined. The application rates in the post-emergence process were 31.2 g / ha aS and 15.6 g / ha aS

In addition to the plants listed in Application Example 1, this experiment also included:

used.

Table 2: Comparison of results from greenhouse tests

As can be seen in Table 2, compound no. 15 shows a significantly higher activity against the harmful plants mentioned than comparative substance A.

Claims

claims

1. 5- (Dioxabicyclohept-6-yl) cyclohexenone oxime ether of the formula I.

in which the substituents have the following meaning:

R ^{1 is} hydrogen, the equivalent of an agriculturally useful cation, -CC-alkylcarbonyl, -CC-alkyl-sulfonyl, -CC-alkylphosphonyl, benzoyl, benzenesulfonyl or benzenephosphonyl, where the last three radicals can still carry 1 to 5 halogen atoms;

R ² Cx-Ce alkyl;

R ³ each independently of one another is hydrogen or C 1 -C ₄ -alkyl;

Z is a Ci-Ce alkylene, C ₃ -C ₆ alkenylene or

C ₃ -C ₆ alkynylene chain, which can carry an exo-methylene substituent (= CH ₂ ) and / or in each case also one to three substituents, selected from a group consisting of C ₁ -C ₃ -alkyl substituents and halogen atoms,

a C ₃ -C ₆ alkylene or C ₄ -C ₆ alkenylene chain, which can carry one to three -C-C ₃ alkyl substituents, and which contains one of the following bridging elements in addition to methylene or methine units: oxygen, sulfur, -SO -, -S0 ₂ - or -NfR ¹ ) -, where R ^{1 is} hydrogen, -CC ₄ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;

R ^{4 is} hydrogen, halogen, phenyl, where the phenyl group can be unsubstituted, partially or completely halogenated and, if it is not completely halogenated, can carry one to three substituents, selected from the group consisting of nitro, cyano, formyl, halogen, C ₁ -C ₄ -alkyl, -C-C ₄ -haloalkyl, -C-C ₄ -alkoxy, Cι-C ₄ -haloalkoxy, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkenyloxy, C ₃ -C ₆ alkynyl, C ₃ -C 6 alkynyloxy ~ and -NR ⁵ R ^6, wherein

R ^{5 is} C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl and

R ^{6 is} C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₁ -C ₆ acyl or benzoyl, which can also carry one to three substituents, selected from the group consisting of from nitro, cyano, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C alkoxy and C ₁ -C ₄ alkylthio.

5- (Dioxabicyclohept-6-yl) cyclohexenone oxime ether of the formula I in which

R ^{1 is} hydrogen or the equivalent of an agriculturally useful cation;

R ^{2 is} ethyl or n-propyl and

R ^{3 is} hydrogen.

3. 5- (Dioxabicyclohept-6-yl) cyclohexenone oxime ether of the formula I, in which

Z is a C ₂ -C ₆ alkylene or C ₄ -C ₆ alkenylene chain which can carry one to three Cχ-C ₃ alkyl substituents, and which in the case of a C ₃ -C ₆ alkylene or C ₄ -C ₆ -Alkenylene chain optionally contains an oxygen atom as a bridge link in addition to methylene or methine units;

R ^{4 is} hydrogen, halogen or phenyl, which can be halogenated once or twice.

4. Agent containing a herbicidally effective amount of at least one 5- (dioxabicyclohept-6-yl) cyclohexenone oxime ether of the formula I according to claim 1 and at least one inert liquid and / or solid carrier and optionally at least one surface-active substance.

5. Agent containing a growth-regulating amount of at least one 5- (dioxabicyclohept-6-yl) cyclohexenone oxime ether of the formula I according to claim 1 and at least one inert liquid and / or solid carrier and optionally at least one surface-active substance.

6. A process for the preparation of 5- (dioxabicyclohept-6-yl) cyclohexenone oxime ethers of the general formula I according to claim 1, characterized in that a hydroxylamine of the formula III H ₂ N0-ZR ⁴ II I

with a ketone of formula II

implements.

7. A process for the preparation of the ketones of the formula II according to claim 6, characterized in that an oxidizing agent suitable for the epoxidation on the dihydropyrans of the formula IV

can act.

Ketones of the formula II in which R ¹ to R ^{3 have} the meaning given in claim 1.

9. A method for controlling undesirable plant growth, characterized in that a herbicidally effective amount of a 5- (dioxabicyclohept-6-yl) cyclohexenone oxime ether of the formula I according to claim 1 is allowed to act on the plants and / or their habitat.

10. Use of a 5- (dioxabicyclohept-6-yl) cyclohexenonoxime ether of the general formula I according to claim 1 as a herbicide or for regulating the growth of plants.