EP3359524A1

EP3359524A1 - New alkynyl-substituted 3-phenylpyrrolidine-2,4-diones and use thereof as herbicides

Info

Publication number: EP3359524A1
Application number: EP16775710.3A
Authority: EP
Inventors: Alfred Angermann; Stefan Lehr; Reiner Fischer; Guido Bojack; Hendrik Helmke; Dirk Schmutzler; Hansjörg Dietrich; Elmar Gatzweiler; Christopher Hugh Rosinger
Original assignee: Bayer CropScience AG
Current assignee: Bayer CropScience AG
Priority date: 2015-10-06
Filing date: 2016-10-04
Publication date: 2018-08-15
Also published as: UY36930A; CA3000768A1; AU2016336175A1; BR112018007013B1; US11178868B2; UA123214C2; AU2020277157A1; WO2017060204A1; AR106257A1; EP3359525A1; EA035255B1; WO2017060203A1; AU2016336174A1; EP3795557A2; CN108349888B; AU2016336174B2; CA3000769A1; CN108349888A; CN108349889A; UY36929A

Abstract

The invention relates to novel effective alkinyl-substituted 3-phenylpyrrolidine-2,4-diones according to the general formula (I) or agrochemically acceptable salts thereof,(I) wherein X = C₁-C₄ alkyl, C₁-C₄ haloalkyl or C₃-C₆ cycloalkyl, Y = C₁-C₄ alkyl or C₃-C₆ cycloalkyl, R¹ = hydrogen, C₁-C₆ alkyl, or C₃-C₆ cycloalkyl, R² = hydrogen or methyl, R³ = C₁-C₆ alkyl or C₁-C₆ alkoxy-C₂-C₆alkyl, G = hydrogen, a group L that can be split or a cation E, wherein R³ is not methyl, if R¹ = methyl and R³ is not C₁-C₃ alkyl, R¹ = H. The invention further relates to a herbicide composition containing a compound of the general formula (I) and to the use of the compounds according to the invention for combating weeds and weed grasses in useful plant crops.

Description

Novel alkynyl-substituted 3-phenylpyrrolidine-2,4-diones and their use as herbicides Description

The present invention relates to novel herbicidally active alkynyl-substituted 3-phenylpyrrolidine-2,4-diones according to the general formula (I) or agrochemically acceptable salts thereof, as well as their use for controlling weeds and grass weeds in crops.

The class of 3-arylpyrrolidine-2,4-diones and their preparation and use as herbicides are well known in the art. In addition, bicyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-355 599, EP-A-415 211 and JP-A-12-053 670 ff.) And substituted monocyclic 3-aryl are also -pyrrolidine-2,4-dione derivatives (EP-A-377 893 and EP-A-442 077 et seq.) having herbicidal, insecticidal or fungicidal activity. Alkynyl-substituted-N-phenylpyrrolidine-2,4-diones with herbicidal activity are also known from WO 96/82395, WO 98/05638, WO 01/74770, WO 14/032702 or WO15 / 040114.

The effectiveness of these herbicides against harmful plants depends on numerous parameters, for example on the application rate used, the formulation (formulation), the respective harmful plants to be controlled, the harmful plant spectrum, the climate and soil conditions and the duration of action or rate of degradation of the herbicide. Numerous herbicides from the group of 3-arylpyrrolidine-2,4-diones require, in order to develop a sufficient herbicidal action, high application rates and / or narrow harmful plant spectra, which makes their application economically unattractive. There is therefore a need for alternative herbicides which have improved properties as well as being economically attractive and at the same time efficient. The object of the present invention is consequently to provide novel compounds which do not have the disadvantages mentioned.

The present invention therefore relates to novel alkynyl-substituted-N-phenylpyrrolidine-2,4-diones of the general formula (I)

or an agrochemically acceptable salt thereof, wherein

X = _Ci-C4-alkyl, Ci-C ₄ haloalkyl or C ₃ -C ₆ cycloalkyl,

Y is C ₁ -C ₄ -alkyl or C ₃ -C ₆ -cycloalkyl,

R ¹ = hydrogen, Ci-C ₆ alkyl, or C ₃ -C ₆ cycloalkyl,

R ² = hydrogen or methyl,

R ³ = C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy-C 2 -C ₆ -alkyl,

G = hydrogen, a leaving group L or a cation E; in which

L = one of the following radicals

wherein

R 4 = C 1 -C ₄ -alkyl or C ₁ -C ₃ -alkoxy-C ₁ -C ₄ -alkyl,

R ⁵ = C 1 -C ₄ -alkyl,

R ⁶ = C 1 -C ₄ -alkyl, an unsubstituted phenyl or a mono- or polysubstituted with halogen, C 1 -C ₄ -alkyl, C 1 -C ₄ -haloalkyl, C 1 -C ₄ -alkoxy, C 1 -C ₄ -haloalkoxy, nitro or cyano substituted phenyl,

R ⁷ , R ⁷ '= independently of one another methoxy or ethoxy, R ⁸ and R ⁹ = each independently represent methyl, ethyl, phenyl or together form a saturated 5-, 6- or 7-membered ring, or together form a saturated 5-, 6-, or 7-membered heterocycle with an oxygen or Form sulfur atom,

E = an alkali metal ion, an ionic equivalent of an alkaline earth metal, an ionic equivalent of aluminum, an ionic equivalent of a transition metal, a magnesium-halogenated cation, or

an ammonium ion in which optionally one, two, three or all four hydrogen atoms by identical or different radicals from the groups hydrogen, Ci-Cs-alkyl, Ci-Cs-alkoxy or C3-C7-cycloalkyl, each with one or more times with Fluorine, chlorine, bromine, cyano, hydroxy or may be interrupted by one or more oxygen or sulfur atoms, or

a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, for example morpholinium, thiomorpholinium, piperidinium, pyrrolidinium, or in each case protonated l, 4-diazabicyclo [1.1.2] octane (DABCO) or l, 5-diazabicyclo [4.3.0] undec-7 -EN (DBU), or a heterocyclic ammonium cation, for example, in each case protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5- Ethyl 2-methylpyridine, pyrrole, imidazole, quinoline, quinoxaline, 1, 2-dimethylimidazole, 1, 3-dimethylimidazolium methylsulfate, stands, or further for a sulfonium ion, wherein R ^{3 is} other than methyl when R ¹ = methyl and R ³ unlike Ci-C3-alkyl, when R ¹ = H.

The compounds of the invention are generally defined by the formula (I). Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below:

In formula (I) and all subsequent formulas, alkyl radicals having more than two carbon atoms may be straight-chain or branched. Examples of alkyl radicals are methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls such as n-pentyl, 2,2-dimethylpropyl and Methylbutyl. Cycloalkyl means a carbocyclic, saturated ring system having three to six carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Halogen is fluorine, chlorine, bromine or iodine.

The compounds of the formula (I) may, depending on the nature of the substituents, be present as geometric and / or optical isomers or mixtures of isomers in different compositions, for example also in cis or trans form, which are defined as follows:

trans-form cis-form

The optionally obtained in the synthesis isomer mixtures can be separated by the usual technical methods. Both the pure isomers and the Tautomeren- and Isomerenrengemische, their preparation and use and compositions containing them are the subject of the present invention. However, in the following, for the sake of simplicity, reference will always be made to compounds of the formula (I), although both the pure compounds and optionally mixtures with different proportions of isomeric and tautomeric compounds are meant.

Preference is given to compounds in which

X is C ₁ -C ₄ -alkyl or C ₃ -C ₆ -cycloalkyl,

Y is C ₁ -C ₄ -alkyl or C ₃ -C ₆ -cycloalkyl,

R ¹ = hydrogen, methyl, ethyl, isopropyl or cyclopropyl,

R ² = hydrogen or methyl,

R ³ = Ci-Ce-alkyl or Ci-C ₄ -alkoxy-C ₂ -C ₄ alkyl,

G = hydrogen, a leaving group L or a cation E in which L is one of the following radicals wherein

R ⁴ = C 1 -C ₄ -alkyl,

R ⁵ = C 1 -C ₄ -alkyl,

R ⁶ = C 1 -C ₄ -alkyl, an unsubstituted phenyl or a phenyl substituted by halogen, C 1 -C ₄ -alkyl or C 1 -C ₄ -alkoxy,

R ⁷ , R ^{7 '} = independently of one another methoxy or ethoxy,

E = an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminum or an ion equivalent of a transition metal, or

an ammonium ion in which optionally one, two, three or all four hydrogen atoms by identical or different radicals from the groups hydrogen or Ci-Cs-alkyl, or a tertiary aliphatic or heteroaliphatic ammonium ion, or a heterocyclic ammonium cation, for example, in each case protonated pyridine, quinoline , Quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methylsulfate, stands, or furthermore represents a sulfonium ion, where R ^{3 is} other than methyl, if R ¹ = methyl and R ^{3 is} other than C ¹ -C ³ -alkyl, when R ^{1 is} hydrogen.

Particular preference is given to compounds of the general formula (I) in which

X = methyl, ethyl or cyclopropyl,

Y = methyl or ethyl,

R ¹ = hydrogen, methyl, ethyl, isopropyl or cyclopropyl,

R ² = hydrogen,

R ³ = C 1 -C ₄ -alkyl, G = hydrogen, a leaving group L or a cation E in which

L = one of the following radicals wherein

= C 1 -C ₄ -alkyl,

E = an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminum, an ion equivalent of a transition metal or a magnesium-halogen cation, a tetra-Ci-Cs-alkylammonium cation or a heterocyclic ammonium cation, for example each protonated pyridine or quinoline, or continues for a sulfonium ion, where R ³ is equal to methyl when R ¹ = methyl and R ³ is not equal to Ci-C3-alkyl when R ¹ is hydrogen, and compounds of the general formula (I) in which X = Methyl, ethyl or cyclopropyl,

Y = methyl or ethyl,

R ¹ = hydrogen, methyl, ethyl, isopropyl or cyclopropyl,

R ² = hydrogen,

R ³ = _{Ci-C4-alkoxy-C} ₂ -C ₄ alkyl,

G = hydrogen, a leaving group L or a cation E in which

L is one of the following radicals

wherein

C 1 -C ₄ -alkyl,

C 1 -C ₄ -alkyl, E = an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminum, an ion equivalent of a transition metal or a magnesium-halogen cation, a tetra-Ci-Cs-alkylammonium cation or a heterocyclic ammonium cation, for example each protonated pyridine or quinoline, or in which R ³ is methyl and R ^{3 is} other than C ¹ -C ³ -alkyl when R ^{1 is} hydrogen.

Very particular preference is given to compounds of the formula (I) in which

X = methyl or ethyl

Y = methyl or ethyl,

R ¹ = hydrogen, methyl or cyclopropyl,

R ² = hydrogen,

R ³ = C 1 -C ₄ -alkyl,

G = hydrogen, a leaving group L or a cation E in which

L = one of the following radicals

wherein

= Methyl, ethyl or isopropyl,

= Methyl or ethyl,

E = a sodium, potassium, trimethylammonium, pyridinium, quinolinium or trimethylsulfonium cation or an ion equivalent of calcium or magnesium, where R ^{3 is} different from methyl, if R ¹ = methyl and R ³ other than C 1 -C ³ Alkyl is when R ^{1 is} hydrogen, and compounds of the general formula (I) in which

X = methyl or ethyl

Y = methyl or ethyl,

R ¹ = hydrogen, methyl or cyclopropyl,

R ² = hydrogen,

R ³ = C 1 -C ₄ -alkoxy-C ₂ -C ₄ -alkyl,

G = hydrogen, a leaving group L or a cation E in which

L = one of the following radicals

wherein

R ⁴ = methyl, ethyl or isopropyl,

R ⁵ = methyl or ethyl,

E = a sodium, potassium, trimethylammonium, pyridinium, quinolinium or trimethylsulfonium cation or an ion equivalent of calcium or magnesium, where R ^{3 is} not the same as methyl, if R ¹ = methyl and R ³ other than C 1 -C 4 Alkyl is when R ^{1 is} hydrogen.

In detail, the following erfindungsgmäßen compounds are illustrative:

Table 1: Example numbers 1.22-1.35 with R ¹

Table 2: Example numbers 2.01-2.31 with R ¹ = CH ₃

Example No. R ³ XY

2.01 Et H Me

2.02 Et H Et

2.03 Et Me Me

2.04 Et Me Et

2.05 Et Et Et

2.06 Et Cyclopropyl Me

2.07 Et Cyclopropyl Et

2.08 n-propyl H Me

2.09 n-Propyl H Et

2.09 n-propyl Me Me

2.09 n-propyl Me Et

2.09 n-Propyl Et Et

2.10 n-Propyl cyclopropyl Me

2.11 n-propyl cyclopropyl Et

2.12 i-Propyl H Me

2.13 i-Propyl H Et

2.14 i-Propyl Me Me

2.15 i-Propyl Me Et

2.16 i-Propyl Et Et

2.17 i-Propyl cyclopropyl Me

2.18 i-Propyl cyclopropyl Et

2.19 n-butyl H Me

2.20 n-butyl H Et

2.21 n-butyl Me Me

2.31 CH 3 OCH 2 CH 2 O- cyclopropyl Et

Table 3: Example numbers 3.01-3.39 with R ¹

Example No., R ³ XY

3.01 Me H Me

3.02 Me H Et

3.03 Me Me Me

3.04 Me Me Et

3.05 Me Et Et

3.06 Me cyclopropyl Me

3.07 Me Cyclopropyl Et

3.08 Et H Me

3.09 Et H Et

3.09 Et Me Me

3.09 Et Me Et Table 4: Example numbers 4.01 - 4.39 with R ¹ C3H7

Example Nos. 4.01 - 4.39, where R ³ , X and Y are identical to those in Table 3

Table 5: Example numbers 5.01-5.39 with R ¹ = isopropyl

Example numbers 5:01 to 5:39, wherein R ^3, X and Y are identical to those in Table 3

Table 6: Example numbers 6.01-6.39 with R ¹ = cyclopropyl

Example numbers 6.01-6.39, where R ³ , X and Y are identical to those in Table 3

The preparation of the compounds of the general formula () according to the invention is known in principle or can be carried out in accordance with methods known from the literature, for example by a) a compound of general formula (II)

in which X, Y, R ¹ , R ² and R ^{3 have} the meanings given above, and R ^{10 is} alkyl, preferably methyl or ethyl, optionally in the presence of a suitable solvent or diluent, with a suitable base with formal cleavage the group R ¹⁰ OH cyclized, or b) a compound of general formula (Ia),

in which X, Y, R ¹ , R ² and R ^{3 have} the meanings given above, with a compound of the general formula (III),

Hal-L (III) in which L has the abovementioned meaning and Hai can be a halogen, preferably chlorine or bromine or a sulfonic acid group, if appropriate in the presence of a suitable solvent or diluent and a suitable base, brings to reaction,

(c) by reacting compounds of general formula (IV), in which X, Y, R ² and R ³ and G have the abovementioned meanings, and U represents a suitable leaving group such as, for example, iodine, bromine, triflate or nonafiat, with a suitable alkynyl reagent of the general formula (V),

W = R

(V) in which R ^{1 has} the abovementioned meaning and W is hydrogen or a suitable leaving group, if appropriate in the presence of suitable catalysts and a suitable base, is reacted. As leaving group W are, for example, halogen atoms such as chlorine, bromine or iodine, Alkylsulfonestergruppen such as triflate, mesylate or nonafiat, magnesium chloride, zinc chloride, a Trialkylzinnrest and boric acid radicals such as - B (OH) ₂ or -B (OAlkyl) ₂ into consideration. As catalysts, in particular Pd ° complexes are very well suited, and in many cases, the addition of Cu® salts can be very beneficial.

The methodology described is state of the art and, incidentally, also known from the literature under the heading "palladium-catalyzed cross-coupling", "Sonogashira, Negishi, Suzuki, Stille or Kumada coupling". Alternatively, a compound of the general formula (IV) can also be reacted with an alkynyl reagent of the general formula (VI) in analogous application of the coupling methodology described above, then cleaved in ethynyl compounds of the general formula (VIII) and finally with a suitable alkylating reagent in the compound (I) according to the invention are converted, wherein in each case X, Y, R ¹ , R ² , R ³ , G, U and W have the meaning described and the leaving group R ¹¹ , for example, a group (Ci) C4-alkyl) ₂ C-OH.

This technique, which is likewise known from the literature, is explained in greater detail in, for example, Beilstein Journal of Organic Chemistry 2011, 7 (55), 426-431 and Catalysis Communications 2015, 60, 82-87.

In the event that the radical R ¹ in the general formula (Ia) is methyl and X, Y, R ² , R ³ and G, U and W have the meaning described above, a further alternative is to use a compound of general formula (IV) with an alkyne reagent of general formula (IX) in analogous application of the coupling methodology described above, to convert a compound of general formula (X). Subsequently, the group R ¹² can be cleaved under suitable conditions and compounds of the formula (I) according to the invention with W = Me are obtained, all other substituents in each case having the meaning described. R ¹² is, for example, a C 1 -C 4 trialkylsilyl radical.

This literature known technique is described for example in the Journal of Medicinal Chemistry 2007, 50 (7), 1627-1634.

The required precursors of the general formula (II) may in analogy to known methods, for example by reacting an amino acid ester of the general formula (XI) with a phenylacetic acid of the general formula (XII), wherein X, Y, R ¹ , R ² and R ³ and R ^{10 have} the meaning described above, optionally by adding a dehydrating agent and optionally in the presence of a suitable solvent or diluent, are prepared.

A further variant for the preparation of compounds of the general formula (II) consists, inter alia, in that a compound of the general formula (XIII) in which X, Y, R ² , R ³ , R ¹⁰ and U are those indicated above have the meaning according to the above-described cross-coupling methodology with a compound of general formula (V) or (VI) in which, R ³ and R ^{1 1} have W as defined above, is reacted:

(XIII)

Phenylacetic acids of general formula (XII) - namely 2,6-dimethyl-4-propargylphenylacetic acid - are mentioned in principle in WO 2015/0401 14, but no access route to these compounds is described.

However, they can be prepared on the basis of methods known from the literature, for example by reacting a compound of the general formula (XIV) where X, Y, U are as defined above and R is C 1 -C 4 -alkyl, again as already described above technology with reagents of the general formula (V) or (VI), wherein W, R ¹ and R ^{11 are} as defined above.

(X)

The compounds of the formula (I) according to the invention and / or their salts, together referred to as "compounds according to the invention", have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants from rhizomes, rhizomes or other permanent organs, are well detected by the active ingredients.

The present invention therefore also provides a method for controlling undesirable plants or for regulating the growth of plants, preferably in plant crops, wherein one or more compounds of the invention are applied to the plants (eg harmful plants such as monocotyledonous or dicotyledonous weeds or undesired crop plants), the seeds (eg grains, seeds or vegetative propagules such as tubers or sprout parts with buds) or the area on which the plants grow (eg the acreage) are applied. The compounds according to the invention can be applied, for example, in pre-sowing (optionally also by incorporation into the soil), pre-emergence or postemergence process. Specifically, by way of example, some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned, which can be controlled by the compounds according to the invention, without it being intended to restrict them to certain species. Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera , Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum. Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis Galinsoga Galium Hibiscus Ipomoea Kochia Lamium Lepidium Lindernia Matricaria Mentha Mercurialis Mullugo Myosotis Papaver Pharbitis Plantago Polygonum Portulaca Ranunculus Raphanus Rorippa Rotala Rumex , Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium. If the compounds according to the invention are applied to the surface of the earth before germination, then either the emergence of the weed seedlings is completely prevented or the weeds grow up to the cotyledon stage, but then cease their growth and finally die off completely after a lapse of three to four weeks. Upon application of the active ingredients to the green parts of the plant postemergence, growth stops after the treatment and the harmful plants remain in the growth stage existing at the time of application or die completely after a certain time, so that in this way harmful to the crops weed competition very early and sustainably eliminated.

Although the compounds of the present invention have excellent herbicidal activity against mono and dicotyledonous weeds, crops of economically important crops, e.g. dicotyledonous cultures of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledonous cultures of the genera Allium, Pineapple, Asparagus , Avena, Hordeum, Oryza, Panicum, Saccharum, Seeal, Sorghum, Triticale, Triticum, Zea, in particular Zea and Triticum, depending on the structure of the respective compound of the invention and their application rate only insignificantly or not at all damaged. For these reasons, the present compounds are very well suited for the selective control of undesired plant growth in crops such as agricultural crops or ornamental plants.

Moreover, the compounds of the invention (depending on their respective structure and the applied application rate) have excellent growth-regulatory Properties on crops. They regulate the plant's metabolism and can thus be used to specifically influence plant ingredients and facilitate harvesting, eg by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of unwanted vegetative growth, without killing the plants. Inhibition of vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, for example, as a result of which storage formation can be reduced or completely prevented. Due to their herbicidal and plant growth regulatory properties, the active compounds can also be used to control harmful organisms in crops of genetically engineered or conventional mutagenized plants. The transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties relate to z. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients. Thus, transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known.

Preferred with respect to transgenic crops is the use of the compounds of the invention in economically important transgenic crops of useful and ornamental plants, eg. As cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn or cultures of sugar beet, cotton, soy, rape, potato, tomato, pea and other vegetables. The compounds according to the invention can preferably be employed as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant. Conventional ways of producing new plants which have modified properties in comparison to previously occurring plants consist, for example, in classical breeding methods and the production of mutants. Alternatively, new plants with altered properties can be generated using genetic engineering techniques (See, for example, EP-A-0221044, EP-A-0131624). For example, genetic modifications of crop plants have been described in several cases for the purpose of modifying the starch synthesized in the plants (eg WO 92/11376, WO 92/14827, US Pat.

WO 91/19806),

transgenic crop plants which are resistant to certain glufosinate-type herbicides (cf., for example, EP-A-0242236, EP-A-242246) or glyphosate (WO 92/00377) or the sulfonylureas (EP-A-0257993, US Pat -5013659) are resistant,

- Transgenic crops, such as cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins), which make the plants resistant to certain pests (EP-A-0142924, EP-A-0193259).

Transgenic crop plants with modified fatty acid composition (WO 91/13972). genetically modified crops with new content or secondary substances z. B. new phyto-alexins, which cause increased disease resistance (EPA 309862,

EPA0464461)

genetically modified plants with reduced photorespiration, which have higher yields and higher stress tolerance (EPA 0305398).

Transgenic crop plants that produce pharmaceutically or diagnostically important proteins ("molecular pharming")

Transgenic crops that are characterized by higher yields or better quality

transgenic crops characterized by a combination z. B. the o. G. characterize new properties ("gene stacking")

Numerous molecular biological techniques that can be used to produce novel transgenic plants with altered properties are known in principle. B. I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, or Christou, "Trends in Plant Science" 1 (1996) 423-431).

For such genetic engineering, nucleic acid molecules can be introduced into plasmids that allow mutagenesis or sequence alteration by recombination of DNA sequences. With the help of standard methods z. B. Base exchanges made, partial sequences removed or natural or synthetic sequences added. For the connection of the DNA fragments with one another adapters or linkers can be attached to the fragments, see, for example, US Pat. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 1st ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY, or Winnacker "Genes and Clones", VCH Weinheim 1st Edition, 1996

The production of germ cells with a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a co-suppression effect or the expression of at least one appropriately engineered ribozyme which specifically cleaves transcripts of the above gene product. For this purpose, DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical.

In the expression of nucleic acid molecules in plants, the synthesized protein may be located in any compartment of the plant cell. But to achieve the localization in a particular compartment, z. For example, the coding region can be linked to DNA sequences that ensure localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227, Wolter et al., Proc. Natl. Acad., U.S.A. 85 (1988), 846-850, Sonnewald et al , Plant J. 1 (1991), 95-106). The expression of the nucleic acid molecules can also take place in the organelles of Pfianzenzellen.

The transgenic Pfianzenzellen can be regenerated by known techniques to whole plants. The transgenic plants may, in principle, be plants of any plant species, that is, both monocotyledonous and dicotyledonous plants.

Thus, transgenic plants are available which have altered properties by overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or expression of heterologous (= foreign) genes or gene sequences. Preferably, the compounds of the invention can be used in transgenic cultures which are resistant to growth factors, such as. B. Dicamba or against herbicides, the essential plant enzymes, eg. As acetolactate synthases (ALS), EPSP synthases, glutamine synthase (GS) or hydroxyphenylpyruvate dioxygenases (HPPD) inhibit or herbicides from the group of sulfonylureas, the glyphosate, glufosinate or benzoylisoxazole and analogues, resistant.

In the application of the active compounds according to the invention in transgenic crops, in addition to the effects observed in other crops on harmful plants, effects which are specific for the application in the respective transgenic crop often occur, for example a modified or specially extended weed spectrum which can be controlled Application rates that can be used for the application, preferably good combinability with the herbicides to which the transgenic culture is resistant, and influencing growth and yield of the transgenic crops.

The invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants. In a preferred embodiment of the present invention, the compounds of general formula (I) may also contain such harmful plants, e.g. from the group Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Digitaria, Echinochloa, Eleusine, Eriochloa, Leptochloa, Lolium, Ottochloa, Panicum, Pennisetum, Phalaris, Poa, Rottboellia, Setaria and / or Sorghum weeds; especially Alopecurus, Apera, Avena, Brachiaria, Bromus, Digitaria, Echinochloa, Eriochloa, Lolium, Panicum, Phalaris, Poa, Setaria and / or Sorghum weeds are combated,

which are resistant to one or more of the enzyme acetyl-CoA-carboxylase (ACCase) inhibiting herbicides. ACCase inhibiting herbicides include i.a. Pinoxaden, Clodinafop-propargyl, Fenoxaprop-P-ethyl, Diclopo-methyl, Fluazifop-P-butyl, Haloxyfop-P-methyl, Quizalofop-P-ethyl, Propaquizafop, Cyhalofop-butyl,

Clethodim, sethoxydim, cycloxydim, tralkoxydim or butroxydim are resistant; and / or are resistant to glyphosate,

and / or against one or more acetolactate synthase (ALS) inhibiting herbicides, such as one or more sulfonylurea herbicides (eg Iodosulfuron-methyl, mesosulfuron-methyl, tribenuron-methyl, triasulfuron, prosulfuron, sulfosulfuron, pyrazosulfuron-ethyl, bensulfuron-methyl, nicosulfuron, flazasulfuron, iofensulfuron, metsulfuron-methyl, or any other sulfonylurea described in The Pesticide Manual, 15 Issue (2009) or 16th Issue (2012), CDS Tomlin, British Crop Protection Council is disclosed and / or one or more

Triazolopyrimidine herbicides (eg florasulam, pyroxsulam or penoxsulam) and / or one or more pyrimidinyl (thio or oxy) benzoate herbicides (eg bispyribac sodium or pyriftalid) and / or one or more sulfonylaminocarbonyltriazolinone herbicides (eg thiencarbazone methyl, Propoxycarbazone sodium or flucarbazone sodium) and / or imidazolinone herbicides (eg

Imazamox) are resistant.

Specific examples of such against ACCase and / or ALS inhibitors and / or glyphosate-resistant grass weeds include Alopecurus myosuroides, Apera spicaventi, Avena fatua, Avena sterilis, Brachiaria decumbens, Brachiaria plantaginea, Digitatia horizontalis, Digitaria insularis, Digitaria sanguinalis, Echinochloa colona, Echinochloa crus-galli, Eleusine indica, Lolium multiflorum, Lolium rigidum, Lolium perenne, Phalaris minor, Phalaris paradoxa, Setaria viridis, Setaria faberi or Setaria glauca. In a particularly preferred embodiment of the present invention, the compounds of general formula (I) according to the invention can be used against harmful plants,

the one or more ACCase inhibiting herbicides (e.g., selected from the list above) are resistant, at least in part, due to mutations (e.g., substitution) of one or more amino acids in the ACCase

Targetsite of the harmful plant (see, for example, S.B. Powles and Qin Yu, "Evolution in Action: Plants Resistant to Herbicides", Annu., Rev. Plant Biol, 2010, 61, pp. 317-347); and / or which are resistant to glyphosate, at least in part due to mutation (e.g., substitution) of one or more amino acids on the EPSPS target site in the particular weed to which glyphosate is directed; and or

which are resistant to one or more ALS-inhibiting herbicides (eg selected from the above list of ALS-inhibiting herbicides), at least in part due to mutations (eg substitution) of one or more amino acids in the ALS target site in the particular weed (cf. eg SB Powles and Qin Yu, "Evolution in Action: Plants Resistant to Herbicides," Annu. Rev. Plant Biol, 2010, 61, pp. 317-347); and or

which are resistant to one or more ACCase-inhibiting herbicides (eg selected from the list above) and / or to glyphosate and / or to one or more ALS-inhibiting herbicides (eg selected from the list above), at least in part by a metabolically-induced Herbicide resistance, e.g. At least in part by cytochrome P450-mediated metabolism (see, e.g., S. B. Powles and Qin Yu, "Evolution in Action: Plants Resistant to Herbicides", Annu., Rev. Plant Biol, 2010, 61, pp. 317-347).

The compounds according to the invention show superior properties compared to the compounds of the prior art, for example WO 2015/040114, compound 41.03 (see also the comparative data in Tables 9 and 10). The compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations. The invention therefore also relates to herbicidal and plant growth-regulating agents which contain the compounds according to the invention.

The compounds according to the invention can be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined. Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil in water and water in oil emulsions, sprayable solutions, suspension concentrates (SC), Oil or water based dispersions, oil miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for litter and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water dispersible granules (WG), water soluble Granules (SG), ULV formulations, microcapsules and waxes. These individual formulation types are known in principle and are described, for example, in: Winnacker Kuchler, "Chemische Technologie", Volume 7, C. Hanser Verlag Munich, 4th ed. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY, 1973, K. Martens, "Spray Drying" Handbook, 3rd ed. 1979, G. Goodwin Ltd. London. The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticides Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ, Hv Olphen, "Introduction to Clay Colloid Chemistry, 2nd Ed., J. Wiley & Sons, NY, C. Marsden, "Solvents Guide", 2nd Ed., Interscience, NY 1963, McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ , Sisley and Wood, "Encyclopaedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964, Schonfeldt, "Border-Active Ethylene Oxide Adducts", Wiss. Verlagsgesell., Stuttgart 1976, Winnacker Küchler, "Chemical Technology", Volume 7, C. Hanser Verlag Munich, 4th ed. 1986.

On the basis of these formulations, combinations with other pesticidally active substances, e.g. Insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a ready-made formulation or as a tank mix. Suitable safeners are e.g. Mefenpyr-diethyl, cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and dichloromid.

Injectable powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, also contain surfactants of an ionic and / or nonionic type (wetting agent, dispersant) in addition to a diluent or inert substance, e.g. polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ethersulfate, alkanesulfonates, alkylbenzenesulfonates, lignosulfonate sodium, 2,2 'dinaphthylmethane 6,6' disulfonic acid sodium, dibutylnaphthalene sulfonic acid sodium or oleoylmethyltauric acid. To prepare the wettable powders, the herbicidal active compounds are finely ground, for example, in customary apparatus such as hammer mills, blower mills and air-jet mills and mixed simultaneously or subsequently with the formulation auxiliaries.

Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent such as butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more ionic and / or nonionic surfactants (emulsifiers). Examples of emulsifiers which may be used are: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ether, fatty alcohol polyglycol ethers, propylene oxide ethylene oxide

Condensation products, alkyl polyethers, sorbitan esters, e.g. Sorbitan fatty acid esters or polyoxethylenesorbitan esters such as e.g. Polyoxyethylene.

Dusts are obtained by milling the active ingredient with finely divided solids, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates may be water or oil based. They can be prepared, for example, by wet grinding by means of commercial bead mills and, if appropriate, addition of surfactants, as described, for example, in US Pat. are already listed above for the other formulation types.

Emulsions, e.g. Oil-in-water emulsions (EW) can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants such as those described e.g. listed above for the other formulation types.

Granules can either be prepared by atomizing the active ingredient on adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the production of fertilizer granules, if desired when mixed with fertilizers.

Water-dispersible granules are generally prepared by the usual methods such as spray-drying, fluidized-bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material. For the preparation of plates, fluidized bed, extruders and spray granules, see for example methods in "Spray Drying Handbook" 3rd Ed. 1979, G. Goodwin Ltd., London, JE Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 et seq., "Perry's Chemical Engineer's Handbook, 5th Ed., McGraw Hill, New York 1973, p. 8 57. See, for example, GC Klingman, "Weed Control as a Science," John Wiley and Sons, Inc., New York, 1961, pp. 81-96, and JD Freyer, SA Evans, "Weed Control Handbook," 5th for further details on pesticide formulation Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

As a rule, the agrochemical preparations contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention.

In wettable powders, the drug concentration is e.g. about 10 to 90% by weight, the remainder to 100% by weight consists of customary formulation constituents. In the case of emulsifiable concentrates, the active substance concentration may be about 1 to 90, preferably 5 to 80,% by weight. Contain dusty formulations

1 to 30 wt.% Active ingredient, preferably usually 5 to 20 wt.% Of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt.% Active ingredient. In the case of water-dispersible granules, the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used. In the case of the water-dispersible granules, the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, the active substance formulations mentioned optionally contain the customary adhesive, wetting, dispersing, emulsifying, penetrating, preserving, antifreezing and solvent, filling, carriers and dyes, antifoams, evaporation inhibitors and the pH and viscosity-influencing agents.

On the basis of these formulations, combinations with other pesticidally active substances, e.g. Insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a ready-made formulation or as a tank mix.

For use, the formulations present in commercially available form are optionally diluted in customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Powdery Preparations, soil or spreading granules and sprayable solutions are usually no longer diluted with other inert substances before use.

With the external conditions such as temperature, humidity, the type of herbicide used, u.a. varies the required application rate of the compounds of formula (I). It can vary within wide limits, e.g. between 0.001 and 1.0 kg / ha or more of active substance, but is preferably between 0.005 and 750 g / ha.

The following examples additionally illustrate the present invention.

A. Chemical examples

Example Di: cis-3- [4- (cyclopropylethynyl) -2,6-dimethylphenyl] -4-hydroxy-8-methoxy-1-azaspiro [4.5] dec-3-ene-2-one

1.46 g (3.67 mmol) of cis-methyl-1- ({[4- (cyclopropylethynyl) -2,6-dimethylphenyl] acetyl} -amino) -4-methoxycyclohexanecarboxylate in 10 ml of DMF became a solution within 30 min at room temperature of 1.03 g of potassium t-butylate (9.18 mmol) in 5 ml of DMF was added dropwise and stirred for 18 h at this temperature. Subsequently, the contents of the flask were added to water, acidified to pH 1 with 2N hydrochloric acid, stirred for 10 minutes and the resulting precipitate was filtered off with suction. After drying, 1.29 g (96%) of the

Title compound in the form of colorless crystals. Table 7: Example numbers D4-D11

In analogy to Example A1 and according to the general information on the preparation, the following compounds according to the invention are obtained

Table 8: Example numbers P5-P15

In analogy to Example PI and in accordance with the general information on the preparation, the following compounds according to the invention are obtained:

Example S5: Sodium cis-8-ethoxy-3- [2-ethyl-6-methyl-4- (prop-1-yn-1-yl) phenyl] -2-oxo-1-azaspiro [4.5] decane 3-en-4-olate

100 mg (0.27 mmol) of cis-8-ethoxy-3- [2-ethyl-6-methyl-4- (prop-1-yn-1-yl) phenyl] -4-hydroxy-1-azaspiro [4.5] dec 3-en-2-one in 1 ml of methanol are mixed with 60 mg of sodium methoxide and stirred at 40 ° C for 1 h. Thereafter, the solvent is distilled off and the residue is dried in vacuo. This gives 102 mg of the desired compound in the form of colorless crystals.

Table 9: Example numbers S3-S5

In analogy to Example S5 and according to the general information on the preparation, the following compounds according to the invention are obtained:

B. Preparation Examples (Starting Materials)

Example G1: Methyl cis-1 - ({[2,6-dimethyl-4- (prop-1-yn-1-yl) phenyl] acetyl} amino) -4-ethoxycyclohexanecarboxylate

1.00 g (4.9 mmol) of 2,6-dimethyl-4-propynylphenylacetic acid were dissolved in 20 ml of dichloromethane and admixed with one drop of DMF. 1.25 g (9.88 mmol) of oxalyl chloride were added and the mixture was heated to reflux until gas evolution ceased. Subsequently, the reaction solution was concentrated, added twice more with 20 ml of dichloromethane and concentrated again to finally take up in 4 ml of dichloromethane (solution 1). 1.06 g (5 mmol) of cis-4-ethoxy-1- (methoxycarbonyl) cyclohexanaminium chloride and 1 g of triethylamine were dissolved in 20 ml of dichloromethane and solution 1 was added dropwise within 90 min. After stirring for 18 h, 50 ml of water were added, and the organic phase was separated, concentrated and purified by column chromatography (silica gel, gradient of ethyl acetate / n-heptane). 1.84 g (94%) of the desired target compound were obtained.

Table 10: Example numbers G1-G8

In analogy to Example Gl and according to the general information on the preparation, the following compounds are obtained

C. Formulation Examples a) A dust is obtained by mixing 10 parts by weight of a compound of the formula (I) and / or salts thereof and 90 parts by weight of talc as an inert substance and comminuting it in a hammer mill. b) A wettable powder readily dispersible in water is obtained by reacting 25 parts by weight of a compound of the formula (I) and / or its salts, 64 parts by weight of kaohnhaltigen quartz as inert material, 10 parts by weight lignosulfonate potassium and 1 part by weight of oleoylmethyltaurine sodium as a wetting and dispersing agent and grinding in a pin mill. c) A dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of a compound of the formula (I) and / or salts thereof with 6 parts by weight of alkylphenol polyglycol ether (© Triton X 207), 3 parts by weight of isotridecanol polyglycol ether ( 8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to more than 277 ° C) mixed and ground in a ball mill to a fineness of less than 5 microns. d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I) and / or salts thereof, 75 parts by weight of cyclohexanone as solvent and 10% by weight.

Share oxethylated nonylphenol as emulsifier. e) A water-dispersible granules are obtained by

75 parts by weight of a compound of the formula (I) and / or salts thereof,

10 parts by weight of lignosulfonic acid calcium,

5 parts by weight of sodium lauryl sulfate,

3 parts by weight of polyvinyl alcohol and

7 parts by weight kaolin

milled, ground on a pin mill and granulated the powder in a fluidized bed by spraying water as Granulierflüssigkeit. f) A water-dispersible granules are also obtained by

25 parts by weight of a compound of the formula (I) and / or salts thereof, 5 parts by weight of 2,2 'dinaphthylmethane 6,6' disulfonic acid sodium,

2 parts by weight of oleoylmethyltaurine sodium,

1 part by weight of polyvinyl alcohol,

17 parts by weight of calcium carbonate and

50 parts by weight of water

Homogenized on a colloid mill and pre-crushed, then grinded on a bead mill and the suspension thus obtained in a spray tower by means of a Einstoffdüse atomized and dried.

Biological data

1. Pre-emergence herbicidal action

Seeds of monocotyledonous or dicotyledonous weed or crop plants are laid out in sandy loam in wood fiber pots and covered with soil. The compounds of the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then applied to the surface of the cover soil as an aqueous suspension or emulsion having a water application rate of 600 to 800 l / ha with the addition of 0.2% wetting agent applied.

After the treatment, the pots are placed in the greenhouse and kept under good growth conditions for the test plants. The visual assessment of the damage to the test plants is carried out after a test period of 3 weeks in comparison to untreated controls (herbicidal action in percent (%): 100% effect = plants have died, 0% effect = like control plants).

Unwanted plants / weeds:

ALOMY: Alopecurus myosuroides SET VI: Setaria viridis

AMARE: Amaranthus retroflexus AVEFA: Avena fatua

CYPES: Cyperus esculentus ECHCG: Echinochloa crus-galli

LOLMU: Lolium multiflorum STEME: Stellaria media

VERPE: Veronica persica VIOTR: Viola tricolor POLCO: Polygonum convolvulus LOLRI Lolium rigidium

Hormu Hordeum murinum

Table 5: Pre-emergence effect

Table 6: Pre-run effect

As the results from Tables 5 and 6 show, the compounds of the invention have a good herbicidal pre-emergence activity against a broad spectrum of grass weeds and weeds. For example, the compounds D1, D2, D4, D6, D7, P3-P10, S1, S3 and S4 each show an 80-100% action against Alopecurus myosuroides, Avena fatua, Cyperus esculentus at an application rate of 320 g / ha. Echinochloa crus galli, Lolium rigidium, Seraria viridis and Hordewn murinum. Furthermore, the compounds D10, Di l, P14 and P15 at an application rate of 320 g / ha each have an 80-100% action against Alopecurus myosuroides, Avena fatua, Echinochloa crus-galli, Lolium multiflorum and Setaria viridis. The compounds according to the invention are therefore suitable in the pre-emergence process for controlling unwanted plant growth.

2. Post-emergence herbicidal action

Seeds of monocotyledonous or dicotyledonous crops are laid out in sandy loam soil in wood fiber pots, covered with soil and grown in the greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated in the single leaf stage. The compounds of the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then sprayed onto the green parts of plants as an aqueous suspension or emulsion having a water application rate of 600 to 800 l / ha with the addition of 0.2% wetting agent , After about 3 weeks life of the test plants in the greenhouse under optimal Growth conditions, the effect of the preparations is scored visually compared to untreated controls (herbicidal action in percent (%): 100% effect = plants are dead, 0% effect = like control plants). Table 7: Tracking effect

Table 8: Follow-up effect

As the results from Tables 7 and 8 show, compounds of the invention have good post-emergence herbicidal activity against a broad spectrum of weeds and weeds. For example, the compounds D2, D4, D6, D7, P3-P10, S3 and S4 at an application rate of 80 g / ha each have an 80-100% action against Alopecurus myosuroides, Avena fatua, Echinochloa crus-gaüi, Lolium multiflorum and Setaria viridis. The compounds D1, D10, DiI PI 4, P15 and Sl show a 90-100% action against Alopecurus myosuroides, Echinochloa crus-galli and Setaria viridis even at an application rate of only 80 g ai / ha. The compounds according to the invention are therefore suitable post-emergence for the control of undesired plant growth.

Claims

claims

1. Alkynyl-substituted 3-phenylpyrrolidine-2,4-diones of the formula (I)

or an agrochemically acceptable salt thereof, wherein

X = _Ci-C4-alkyl, Ci-C ₄ haloalkyl or C ₃ -C ₆ cycloalkyl,

Y is C ₁ -C ₄ -alkyl or C ₃ -C ₆ -cycloalkyl,

R ¹ = hydrogen, Ci-C ₆ alkyl or C ₃ -C ₆ cycloalkyl,

R ² = hydrogen or methyl,

R ³ = C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy-C 2 -C ₆ -alkyl,

G = hydrogen, a leaving group L or a cation E; in which

L = one of the following radicals wherein

R ⁴ = C 1 -C ₄ -alkyl or C ₁ -C ₃ -alkoxy-C ₁ -C ₄ -alkyl,

R ⁵ = C 1 -C ₄ -alkyl,

R ⁷ , R ⁷ '= independently of one another methoxy or ethoxy,

R ⁸ and R ⁹ = each independently represent methyl, ethyl, phenyl or together form a saturated 5-, 6- or 7-membered ring, or together form a saturated 5-, 6-, or 7-membered heterocycle with an oxygen or Form sulfur atom, E = an alkali metal ion, an ionic equivalent of an alkaline earth metal, an ionic equivalent of aluminum, an ionic equivalent of a transition metal, a magnesium-halogenated cation, or

an ammonium ion in which optionally one, two, three or all four hydrogen atoms are represented by identical or different radicals from the groups

Hydrogen, Ci-Cs-alkyl, Ci-Cs-alkoxy or C3-C7-cycloalkyl, which may each be mono- or polysubstituted by fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulfur atoms , or

a cyclic secondary or tertiary aliphatic or heteroaliphatic

Ammonium ion, for example, morpholinium, thiomorpholinium, piperidinium, pyrrolidinium, or each protonated l, 4-diazabicyclo [1.1.2] octane (DABCO) or l, 5-diazabicyclo [4.3.0] undec-7-ene (DBU), or a heterocyclic ammonium cation, for example, in each case protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-

Dimethyl pyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methylsulfate, is, or

is a sulfonium ion wherein R ^{3 is} other than methyl when R ¹ = methyl and R ^{3 is} other than C ¹ -C ³ -alkyl when R ¹ = H.

2. A compound according to claim 1, wherein

X is C ₁ -C ₄ -alkyl or C ₃ -C ₆ -cycloalkyl,

R ¹ = hydrogen, methyl, ethyl, isopropyl or cyclopropyl,

R ² = hydrogen or methyl,

R ³ = Ci-Ce-alkyl or Ci-C ₄ -alkoxy-C ₂ -C ₄ alkyl,

G = hydrogen, a leaving group L or a cation E in which

L = one of the following radicals wherein

R ⁴ = C 1 -C ₄ -alkyl,

R ⁵ = C 1 -C ₄ -alkyl,

R ⁶ = C 1 -C ₄ -alkyl, an unsubstituted phenyl or a halogen, C 1 -C ₄ -

Alkyl or C 1 -C ₄ -alkoxy-substituted phenyl,

R ⁷ , R ^{7 '} = independently of one another methoxy or ethoxy,

an ammonium ion in which optionally one, two, three or all four hydrogen atoms by identical or different radicals from the groups hydrogen or Ci-Cs-alkyl, or a tertiary aliphatic or heteroaliphatic ammonium ion, or a heterocyclic ammonium cation, for example, in each case protonated pyridine, quinoline Quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methylsulfate, or is a sulfonium ion wherein R ^{3 is} other than methyl when R ¹ = methyl, and R ^{3 is} other than C ¹ -C ³ -alkyl when R ¹ = H is.

3. A compound according to any one of claims 1 or 2, wherein R ^{1 is} methyl, ethyl, isopropyl or cyclopropyl.

4. A compound according to any one of claims 1 to 3, wherein R ² = hydrogen.

5. A compound according to any one of claims 1 to 4, wherein R ³ = Ci-C ₄ alkyl.

6. A compound according to any one of claims 1 to 5, wherein R ³ is Ci-C ₄ alkoxy-C2-C ₄ - alkyl. A compound according to any one of claims 1 to 6, wherein R ¹ = methyl and R ³ = C ₁ -C ₆ -alkyl.

A compound according to any one of claims 1 to 7, wherein X = methyl, ethyl or cyclopropyl, Y = methyl or ethyl, and R ² = hydrogen.

A compound according to any one of claims 1 to 8, wherein G = hydrogen, a leaving group L or a cation E, wherein

L = one of the following radicals

With

R ⁴ = methyl, ethyl or isopropyl,

R ⁵ = methyl or ethyl, and

E = a sodium, potassium, trimethylammonium, pyridinium, quinolinium or trimethylsulfonium cation or an ion equivalent of calcium or magnesium.

A herbicidal composition comprising a compound of general formula (I) according to any one of claims 1 to 9 or an agrochemically acceptable salt thereof, and optionally an agrochemically acceptable carrier, diluent and / or solvent.

11. A herbicidal composition according to claim 10, comprising at least one further agrochemically active substance from the group of insecticides, acaricides, herbicides, fungicides, safeners and growth regulators.

12. A herbicidal composition according to claim 11 containing a safener.

A herbicidal composition according to any one of claims 10 to 12 containing a further herbicide.

14. A method for controlling unwanted plant growth, wherein the compound according to any one of claims 1 to 9, applied to the plant to be controlled, plant parts, plant seeds or the area on which the unwanted plant growth takes place.

The method of claim 14, wherein the undesired plant growth is selected from grassy monocotyledonous weeds.

A method according to claim 14 or 15, wherein the plant growth of resistant grasses in crops is controlled, and wherein the herbicidal composition according to claims 10 to 12 is applied to the weed to be controlled.

The method of claim 16, wherein the crop is selected from wheat, barley, rye, oats, rice, sugar beet, soybean, rapeseed, sunflower and corn.

Use of compounds of the formula (I) or an agrochemically acceptable salt thereof according to Claims 1 to 9 for controlling harmful plants.

Use according to claim 18, characterized in that the compound of formula (I) or an agrochemically acceptable salt thereof is used for controlling harmful plants in crops of crops.

Use according to claim 19, characterized in that the useful plants are transgenic crops.