Acyl-cyclohexane diones and their oxime ethers exhibiting a herbicidal and plant growth activity

The present invention relates to new 2-acyl-1,3-cyclohexanediones and their oxime ether with herbicidal and plant growth-regulating action, process for the preparation of the 2-acyl-1,3-cyclohexanedione and its oxime ether, agents which contain these derivatives and the use of these derivatives or compositions containing them for weed control and for regulating plant growth.

The new 2-acyl-1,3-cyclohexanediones and their oxime ether correspond to Formula 1<chemistry id="chem0001" num="0001"><img file="EP0243313B1_D0001.tif" /></chemistry>in which A is a 2-7-membered alkylene bridge, a 3-7-membered alkenylene bridge which can be mono- or polyunsaturated,<ul id="ul0001" list-style="none"><li>n zero, one or two</li><li>R₁ CI-C4 alkyl or benzyl</li><li>R₂ C.₁-C₆-Alkyl, unsubstituted or substituted by halogen, Ci-C₄-Alkoxy, C_I.-C₄-Alkyl thio; C.₃-C₆Cycloalkyl; Phenyl, benzyl or phenylethyl, where the phenyl ring by halogen, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₁-C₄-Alkylthio, C₁-C₄Haloalkyl, Ci-C₄-Halogenalkoxy, cyan or nitro can be substituted,</li><li>X oxygen or a residue = NOR₃ and</li><li>Rs C₁-C₆-Alkyl, C₁-C₆-Halogenalkyl, Cs-Cs-alkenyl, Cs-Cs-haloalkenyl or C₃-C₆-Alkynyl</li><li>mean.</li></ul>

The invention also encompasses the isomers, enantiomers and diastereomers of the formula I characterized by the various end forms, and the salts of these compounds with metals and nitrogen bases.

In these definitions, the term alkyl itself or as part of another substituent, such as alkoxy, alkylthio, haloalkyl, haloalkylthio, both straight-chain and branched radicals, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert. Butyl and all stereoisomeric forms of the higher homologues. Alkenyl and alkynyl are also understood to mean straight-chain and branched radicals and their cis and trans forms, for example Allyl, methallyl, butenyl, methyl and dimethylbutenyl, propynyl, butynyl, methylbutinyl, dimethylbutinyl.

Cycloalkyl radicals as substituents R₂ or which are formed by the carbon atom and the alkylene bridge A include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Cycloalkenylene radicals formed by the carbon atom and the alkenylene bridge A can be mono- or polyunsaturated. Examples include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, cycloheptadienyl, cycloheptatrienyl, cyclooctenyl, cyclooctadienyl and cyclooctatrienyl. These residues can be substituted with up to 5 methyl groups.

Halogen means fluorine, chlorine, bromine or iodine atoms.

The 2-acyl-1,3-cyclohexanediones and their oxime ethers of the formula I are notable for good herbicidal and plant growth-regulating effects. The following groups are among the connections that are particularly notable for their effectiveness:<ul id="ul0002" list-style="none"><li>The acylcyclohexanediones of formula 1, in which</li><li>A is a 2-7 membered alkylene bridge,</li><li>n zero, one or two,</li><li>R₁ C.₁-C₄-Alkyl or benzyl,</li><li>R₂ C.₁-C₆-Alkyl, unsubstituted or substituted by halogen, C₁-C₄-Alkoxy or C₁-C₄-Alkyl thio; C.₃-C₈Cycloalkyl; Phenyl, benzyl or phenylethyl, where the phenyl ring by halogen, C₁-C₄-Alkyl, C_I.-C₄-Alkoxy, C₁-C₄-Alkylthio, C₁-C₄Haloalkyl, C₁-C₄-Halogenalkoxy, cyan or nitro can be substituted and</li><li>X is oxygen, among which the compounds</li><li>5- (1-methylthiocydobutan-1-yl) -2- (2,4-dichlorobenzoyl) -cydohexan-1,3-dione,</li><li>5- (1-Methylthiocyclobutan-1-yl) -2-n-butyrylcyclohexan-1,3-dione</li><li>5- (1-methylthiocyclobutan-1-yl) -2-cyclopropylcarbonyl-cyclohexan-1,3-dione,</li><li>5- (1-methylthiocyclobutan-1-yl) -2- (2,3-dichlorobenzoyl) cyclohexane 1,3-dione,</li><li>5- (1-methylsulfonylcyclobutan-1-yl) -2-n-butyrylcyclohexan-1,3-dione,</li><li>5- (1-methylthiocyclopropan-1-yl) -2-propionyl-cyclohexan-1,3-dione,</li><li>5- (1-ethylthiocyclopropan-1-yl) -2-propionylcyclohexan-1,3-dione and</li><li>5- (1 1-methylthiocyclopropan-1-yl) -2-n-butyrylcyclohexan-1,3-dione.</li></ul>

Furthermore, the oxime ethers of the acylcyclohexanediones of the formula I in which A is a 2-7-membered alkylene bridge, n zero, one or two,<ul id="ul0003" list-style="none"><li>Ri C₁-C₄-Alkyl or benzyl,</li><li>R₂ C.₁-C₆-Alkyl, unsubstituted or substituted by halogen, C_I.-C₄-Alkoxy or C_I.-C₄-Alkylthio,</li><li>X the rest = NOR₃ and</li><li>Rs C₁-C₆-Alkyl, C₃-C₆Haloalkyl, C₃-C₆-Alkenyl, Cs-Cs-haloalkenyl or C₃-C₆-Alkynyl,</li><li>mean, especially the connections</li><li>5- (1-methylthiocyclobutan-1-yl) -2- (1-ethoximino-n-butyry1) cyclohexane-1,3-dione,</li><li>5- (1-methylthiocyclopropan-1-yl) -2- (1-ethoximino-n-butyryl) cyclohexan-1, 3-dione,</li><li>5- (1-methylthiocyclohexan-1-yl) -2- (1-ethoximino-n-butyry1) cyclohexan-1, 3-dione,</li><li>5- (1-Methylthiocyclobutan-1-yl) -2- (1-allyloxyimino-n-butyryl) cyclohexan-1,3-dione and 5- (1-methylthiocyclopentan-1-yl) -2- (1-ethoximino -n-butyryl) -cyclohexane-1,3-dione,</li><li>5- (1-methylthiocyclopropan-1-yl) -2- [1- (trans-3-chloroallyloximino) -n-butyryl] cyclohexan-1, 3-dione,</li><li>5- (1-methylthiocyclopropan-1-yl) -2- [1- (trans-3-chloroallyloximino) propionyl] cyclohexan-1, 3-dione,</li><li>5- (1-Methylthlocyclopropan-1-yl) -2- [1- (cis-3-chloroallyloximino) propionyl] cyclohexan-1,3-dione and</li><li>5- (1-Ethylthiocyclopropan-1-yl) -2- [1- (trans-3-chloroallyloximino) propionyl] cyclohexan-1, 3-dione.</li></ul>

These compounds can also exist in tautomeric forms or as salts. Alkali and alkaline earth metal salts as well as manganese, copper, zinc and iron salts are particularly suitable.

The acyl-cyclohexanediones and their oxime ether according to the invention are prepared in a manner known per se by reacting a 1,3-cyciohexanedione correspondingly substituted in the 5-position by the remainder with an acid chloride or an acid cyanide and optionally further reacting the 2-acyl-1 obtained , 3-cyclohexanedione with a hydroxylamine.

A first process for the preparation of the acyl-cyclohexanediones and their oxime ether of the formula I is characterized in that a 1,3-cyclohexanedione derivative of the formula II in an inert organic solvent in the presence of the equimolar amount of a base<chemistry id="chem0002" num="0002"><img file="EP0243313B1_D0002.tif" /></chemistry>wherein A, n and R₁ have the meaning given under formula I, with an acid halide or acid anhydride of the formula III<chemistry id="chem0003" num="0003"><img file="EP0243313B1_D0003.tif" /></chemistry>wherein Y is a halogen atom or a radical<chemistry id="chem0004" num="0004"><img file="EP0243313B1_D0004.tif" /></chemistry>means and R₂ has the meaning given under formula I, the cyclohexanone ester of formula IV obtained<chemistry id="chem0005" num="0005"><img file="EP0243313B1_D0005.tif" /></chemistry>wherein<ul id="ul0004" list-style="none"><li>A, n, Ri and R₂ which have the meaning given under formula I, rearranged in an inert organic solvent in the presence of a catalyst to give the 2-acyl-1,3-cyclohexanedione derivative of the formula Ia,<chemistry id="chem0006" num="0006"><img file="EP0243313B1_D0006.tif" /></chemistry>where A, n, Ri and R₂ have the meaning given under the formula I, and if desired in an inert organic solvent, in the presence of the equimolar amount of a base, with a hydroxylamine hydrochloride of the formula VH₂NOR₃ HCI (V)</li><li>where R₃ which has the meaning given under the formula, converts to the oxime ether of the formula Ib,<chemistry id="chem0007" num="0007"><img file="EP0243313B1_D0007.tif" /></chemistry>where A, n, R₁, R₂ and R₃ have the meaning given under formula I.</li></ul>

The cyclohexanone esters of formula IV are new compounds. They and their manufacture are the subject of this invention.

A second more direct process for the preparation of the acyl-cyclohexanediones and their oxime ether of the formula I is characterized in that in an inert organic solvent or diluent, in the presence of zinc chloride_Qrid and a nitrogen base a 1,3-cyclohexanedione derivative of the formula II<chemistry id="chem0008" num="0008"><img file="EP0243313B1_D0008.tif" /></chemistry>wherein A, n and R₁ have the meaning given under formula I, with an acid cyanide of the formula VI<chemistry id="chem0009" num="0009"><img file="EP0243313B1_D0009.tif" /></chemistry>where R₂ has the meaning given under the formula I, and the 2-acyl-1,3-cyclohexanedione derivative of the formula Ia obtained<chemistry id="chem0010" num="0010"><img file="EP0243313B1_D0010.tif" /></chemistry>where A, n, R₁ and R₂ have the meaning given under formula I, if desired in an inert organic solvent, in the presence of the equimolar amount of a base with a hydroxylamine • hydrochloride of formula V<ul id="ul0005" list-style="none"><li>H₂NOR₃• HCl (V)</li></ul>where Rs has the meaning given under the formula I, to the oxime ether of the formula Ib<chemistry id="chem0011" num="0011"><img file="EP0243313B1_D0011.tif" /></chemistry>where A, n, Ri, R₂ and Rs di have the meaning given under the formula.

Inert organic solvents for these reactions are in particular aromatics such as benzene, toluene, hydrogen halides such as chloroform, dichloroethane, dichloromethane, carbon tetrachloride, esters such as, for example, ethyl acetate.

The reaction temperatures are between room temperature and the boiling point of the reaction mixture. Cooling of the reaction vessel may be indicated during the addition of acid chloride.

Suitable bases are organic and inorganic. Examples are pyridine, 4-aminopyridine, 4-dimethylaminopyridine, collidine, triethylamine, ammonium, sodium, potassium or calcium carbonate or the corresponding bicarbonates.

Such implementations are known. The reaction with the acid halide or acid anhydride of the formula III is described in Tetrahedron Letters 29 (1973) 249 or in Synthesis 1978, 925, the reaction with the acid cyanide of the formula V in EP-A 90 262.

The rearrangement of the cyclohexanone ester of the formula IV to the 2-acyl-cyclohexanedione derivative of the formula Ia is carried out, for example, by treatment in an inert organic solvent in the presence of a catalyst or in an organic base as solvent. Examples of suitable catalysts are pyridine, 4-aminopyridine, 4- (dimethylamino) pyridine, aluminum (III) chloride in methylene chloride, collidine, lutidine, cyanohydrins together with nitrogen bases such as triethylamine.

The cyclohexanediones of the formula II required as starting products are prepared in a multi-stage process.

An unsaturated methyl ketone of formula VII<chemistry id="chem0012" num="0012"><img file="EP0243313B1_D0012.tif" /></chemistry>wherein A, n and R_i which have the meaning given under the formula, is reacted in an absolute, inert organic solvent in the presence of alkali metal methylate at the reflux temperature of the solvent with a malonic diester of the formula VIII<chemistry id="chem0013" num="0013"><img file="EP0243313B1_D0013.tif" /></chemistry>where R is a C₁-C₆-Alkylrest or benzyl means to the cyclohex-1-en-2-ol-4-one ester of the formula IX<chemistry id="chem0014" num="0014"><img file="EP0243313B1_D0014.tif" /></chemistry>wherein A, n and R₁ has the meaning given under formula I, R is a C₁-C₆-Alkylrest or benzyl and MeΦ means an alkali metal ion, this ester saponified in the presence of sodium or potassium hydroxide solution and washed with acid, the 2,4-cyclohexanedioic acid derivative of the formula X obtained<chemistry id="chem0015" num="0015"><img file="EP0243313B1_D0015.tif" /></chemistry>wherein A, n and Ri have the meaning given under the formula, then decarboxylated in an inert solvent and the cyclohexanedione of the formula II required as the starting product<chemistry id="chem0016" num="0016"><img file="EP0243313B1_D0016.tif" /></chemistry>wherein A, n and R₁ the meaning given under the formula has been isolated from the reaction mixture.

The reaction of the unsaturated methyl ketone of the formula VII with the malonic diester of the formula VIII is carried out in an absolute solvent in the presence of preferably sodium or potassium methylate. The ethyl and methyl esters are preferred as malonic esters. The saponification and the subsequent precipitation of the acid takes place in an aqueous medium. The 2,4-cyclohexanedione-1-carboxylic acid derivative of the formula X is then in a solvent, such as Water, toluene, xylene or boiled in a chlorine-containing solvent such as methylene chloride or chloroform until no more carbon dioxide is produced.

Another way of producing the 1,3-cyclohexanedione derivatives of the formula II is to use an aldehyde of the formula XI<chemistry id="chem0017" num="0017"><img file="EP0243313B1_D0017.tif" /></chemistry>wherein A, n and R₁ the meaning given under formula 1 have condensed in a basic solvent with malonic acid to give the unsaturated acid of formula XII,<chemistry id="chem0018" num="0018"><img file="EP0243313B1_D0018.tif" /></chemistry>wherein A, n and R₁ have the meaning given under Formula 1. This acid is then in a known manner with an alkanol R-OH, wherein RC₁-C₆-Alkyl or benzyl, esterified and the ester of the formula XIV in an absolute solvent, in the presence of sodium methylate or potassium methylate ring-closed with an alkyl acetoacetate of the formula XV, according to the formula scheme:<chemistry id="chem0019" num="0019"><img file="EP0243313B1_D0019.tif" /></chemistry><chemistry id="chem0020" num="0020"><img file="EP0243313B1_D0020.tif" /></chemistry>

The condensation of the aldehyde of the formula XI with malonic acid takes place either in a basic solvent such as pyridine, collidine, lutidine or in an absolute alkanol, for example ethanol or methanol in the presence of sodium ethylate or sodium methylate.

The 1,3-cyclohexanedione derivatives of the formula II are new products and their preparation form an object of this invention.

The methyl ketones of the formula VII required as starting material are obtained by condensation of aldehydes of the formula XI with acetone and subsequent elimination of water from the β-hydroxy ketone obtained as the condensation product.

The reaction can be represented by the following scheme:<chemistry id="chem0021" num="0021"><img file="EP0243313B1_D0021.tif" /></chemistry>

The condensation takes place in an aqueous medium in the presence of a base, for example sodium or potassium hydroxide solution, advantageously at a higher temperature, for example the boiling point of the reaction mixture.

The 1-Aikyithio- resp. 1-Alkylsulfinyl- or 1-alkylsulfonyl-cycloalkyl-carbaldehydes of the formula IX are known; their preparation is described, for example, in DE-A 2,120,908 or can be implemented in analogy to DE-A 2,403,236.

The unsaturated methyl ketones of formula VII are new products. They and their manufacture are the subject of this invention.

The process for the preparation of the unsaturated methyl ketones of formula VII<chemistry id="chem0022" num="0022"><img file="EP0243313B1_D0022.tif" /></chemistry>wherein A, n and Ri have the meaning given under the formula, is characterized in that an aldehyde of the formula XI<chemistry id="chem0023" num="0023"><img file="EP0243313B1_D0023.tif" /></chemistry>wherein A, n and R₁ have the meaning given under formula I, condensed in a basic aqueous medium with acetone, then boiled under reflux for several hours and then isolated from the reaction mixture.

A similar process for the production of unsaturated ketones is described, for example, in Agr. Biol. Chem. 37 (1973) 261.

The manufacturing methods described, including all partial cuts, are an important part of the present invention. The new active ingredients are solids or oils that can be handled easily.

The compounds of the formula I have herbicidal and plant growth regulating action, they are suitable, for example, for the selective control of grasses in crops of useful plants. The trans-3-chloroallyloxime ether compounds were particularly effective.

At low application rates, the compounds of the formula are distinguished by good growth-inhibiting and selective herbicidal properties which make them excellent for use in crops of useful plants, in particular in sugar beets, cereals, cotton, soybeans, corn and rice. Weeds are sometimes damaged, which previously could only be dealt with with total herbicides.

The compounds of formula 1 also have good plant growth regulating properties.

It has now surprisingly been found that the new active compounds of the formula 1 or compositions which contain these active compounds are distinguished above all by the fact that they specifically intervene in the metabolism of the plants. This targeted intervention in the physiological processes of plant development makes the active ingredients of the formula I usable for various purposes, in particular for those which are associated with the increase in yield in useful plants, the easier harvesting and the labor savings in measures on plant crops.

According to previous experience, the principle of action of plant growth regulators is that an active ingredient can have one or more different effects on plants. The effects of the substances essentially depend on the time of use, based on the development stage of the seed or the plant, on the amounts of active ingredient applied to the plants or their environment and on the type of application. In any case, growth regulators should have a positive influence on the crop plants in the desired manner.

Plant growth regulating substances can be used, for example, to inhibit vegetative plant growth. Such inhibition of growth is of economic interest, inter alia, in the case of grasses, since it can, for example, reduce the frequency of grass cuts in ornamental gardens, park and sports facilities or on the side of the road. It is also important to inhibit the growth of herbaceous and woody plants on the side of the road and in the vicinity of overhead lines or in general in areas where heavy growth is undesirable.

It is also important to use growth regulators to inhibit the growth in length of cereals, because shortening the stalk reduces or completely eliminates the risk of the plant twisting ("storing") from the harvest. In addition, growth regulators in cereals can cause stalk reinforcement, which also counteracts storage.

An inhibition of vegetative growth allows a denser cultivation of the crop in many crop plants, so that an additional yield, based on the soil area, can be achieved.

Another mechanism of increasing yield with growth inhibitors is based on the fact that the nutrients benefit the bloom and fruit formation to a greater extent, while vegetative growth is restricted.

Growth regulators can often also be used to promote vegetative growth. This is of great benefit when the vegetative parts of the plant are harvested. A promotion of vegetative growth can also lead to a promotion of generative growth, so that, for example, more or larger fruits are formed.

In some cases, increases in yield can also be achieved by intervening in plant metabolism without any changes in vegetative growth being noticeable. Growth regulators can also cause a change in the composition of the plants, so that a better quality of the harvested products is brought about. For example, it is possible to increase the sugar content in sugar beet, sugar cane, pineapple and citrus fruits or to increase the protein content in soy or cereals.

Parthenocarpic fruits can develop under the influence of growth regulators. The gender of the flowers can also be influenced.

Growth regulators can also have a positive impact on the production or outflow of phytochemicals. One example is the stimulation of the latex flow in rubber trees.

While the plant is growing, growth regulators can also be used to increase the lateral branching by chemically breaking the apical dominance. This is of interest, for example, in the propagation of cuttings from plants. However, it is also possible to inhibit the growth of the side shoots, for example to prevent the formation of side shoots in tobacco plants after decapitation and thus to promote leaf growth.

Growth regulators can also accelerate or delay the ripening of the crop before or after harvest. This is particularly advantageous because it can be optimally adapted to the needs of the market. Furthermore, growth regulators can improve fruit coloration in some cases. In addition, growth regulators can also be used to concentrate the maturity over time. This creates the prerequisites for complete mechanical or manual harvesting in a single operation, for example with tobacco, tomatoes or coffee.

The use of growth regulators can also influence the rest of the seeds or buds of the plants, i.e. the endogenous annual rhythm, so that the plants, such as pineapples or ornamental plants in nurseries, germinate, sprout or bloom at a time when they normally do so show no willingness.

With growth regulators it is also possible to delay the bud budding or the germination of seeds, for example in order to avoid damage from late frosts in areas at risk of frost. On the other hand, it is possible to stimulate root growth and / or the formation of sprouts, so that growth can be restricted to a shorter period of time.

Growth regulators can also produce halophilia in crops. This creates the conditions for cultivating plants on saline soils.

Frost and drought resistance can also be induced in plants with growth regulators.

Under the influence of growth regulators, the aging (senescence) of plants or parts of plants can be inhibited or delayed. Such an effect can be of great economic interest in that, in the case of treated parts of plants or whole plants such as fruit, berries, vegetables, lettuce or ornamental plants, their storage stability after harvest can be improved or extended. Likewise, a considerable increase in yield can be achieved by treating crops by extending the photosythetic activity phase.

Another important area of ​​application for growth inhibitors is their use to inhibit excessive growth in tropical ground cover plants, the so-called cover crops. In tropical and subtropical monocultures, such as in palm plantations, cotton, corn fields, etc. In addition to the actual crop plants, soil covering plants, in particular legume species, are often planted, which serve to maintain or increase the soil quality (prevention of dehydration, supply with nitrogen) and to prevent erosion (erosion by wind and water). By applying the active compounds according to the invention, the growth of these cover crops can now be controlled and the growth height of these ground covering plants can thus be kept at a low level, so that healthy growth of the crop plants and the maintenance of a favorable soil quality is ensured.

Active substances of the formula I are usually used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with further active substances. These further active ingredients can be both fertilizers, trace element mediators or other preparations which influence plant growth; but it can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, together with any other carriers, surfactants or other application-promoting additives customary in formulation technology.

Suitable carriers and additives can be solid or liquid and correspond to the substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

A preferred method for applying an active ingredient of the formula I or an agrochemical composition which contains at least one of these active ingredients is application to the foliage (leaf application). The number of applications depends on the type of growth influencing. The materials of formula I can also get into the plants through the roots through the root system (systemic effect) by soaking the location of the plants with a liquid preparation or by introducing the substances into the soil in solid form, e.g. in the form of granules (Floor application). However, the compounds of the formula I can also be applied to seeds (coating) by either impregnating the grains with a liquid preparation of the active ingredient or coating them with a solid preparation. In addition, other types of application are possible in special cases, such as the targeted treatment of plant stems or buds.

The compounds of the formula I are used in unchanged form or preferably together with the auxiliaries customary in formulation technology and are therefore used, for example, to give emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules Encapsulations in, for example, polymeric materials processed in a known manner. The methods of application such as spraying, atomizing, dusting, scattering, brushing or pouring are selected in the same way as the type of agent, in accordance with the intended objectives and the prevailing conditions. Favorable application rates are generally 10 g to 5 kg of active ingredient (AS) per ha; preferably 100 g to 3 kg ai / ha, in particular at 200 g to 1000 g ai / ha.

The formulations, ie the agents, preparations or compositions containing the active ingredient of the formula I and optionally a solid or liquid additive, are prepared in a known manner, for example by intimately mixing and / or grinding the active ingredients with extenders, such as, for example, with solvents, solid carriers and optionally surface-active compounds (surfactants).

Possible solvents are: Aromatic hydrocarbons, preferably the fractions Ce to C.₁₂, such as Xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or - ethyl ether, ketones such as cyclohexanone, strong, such as cyclohexanone -2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oil such as epoxidized coconut oil or soybean oil; or water.

Natural rock flours, such as calcite, talc, kaolin, montmorillonite or attapulgite, are generally used as solid carriers, for example for dusts and dispersible powders. To improve the physical properties, highly disperse silica or highly disperse absorbent polymers can also be added. Porous types such as pumice, broken brick, sepiolite or bentonite come as granular, adsorptive granulate carriers, and non-sorptive carrier materials, for example Calcite or sand in question. In addition, a large number of pregranulated materials of an inorganic or organic nature, such as, in particular, dolomite or comminuted plant residues can be used.

Depending on the nature of the active ingredient of formula 1 to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants are also to be understood as mixtures of surfactants.

Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

The soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C_loC₂₂), such as the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut or tallow oil. The fatty acid methyl taurine salts should also be mentioned.

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

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

Corresponding phosphates, such as, for example, salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct, are also suitable.

Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols .

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

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

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

The cationic surfactants are primarily quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as N substituents and, as further substituents, have low, optionally halogenated alkyl, benzyl or low hydroxyalkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) ethylammonium bromide.

The surfactants commonly used in formulation technology are described in the following publications:<ul id="ul0006" list-style="none"><li>"Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood, New Jersey, 1979.</li><li>M. and J. Ash, "Encyclopedia of Surfactants" Vol. 1-111, Chemical Publishing Co., Inc. New York, 1981.</li><li>H. Stache "Tensid-Taschenbuch" 2nd edition C. Hanser Verlag, Munich and Vienna 1981</li></ul>

These preparations generally contain 0.1 to 99%, in particular 0.1 to 95%, active ingredient of the formula 1, 1 to 99% of a solid or liquid additive and 0 to 25%, in particular 0.1 to 25%, of one Surfactants.

In particular, preferred formulations are composed as follows: (% = weight percent)

Solutions

<ul id="ul0007" list-style="none"><li>Active ingredient: 5 to 95%, preferably 10 to 80%</li><li>Solvent: 95 to 5%, preferably 90 to 0%</li><li>surfactant: 1 to 30%, preferably 2 to 20%.</li></ul>

Emulsifiable concentrates

<ul id="ul0008" list-style="none"><li>Active ingredient 10 to 50%, preferably 10 to 40%</li><li>surfactant: 5 to 30%, preferably 10 to 20%</li><li>liquid carrier: 20 to 95%, preferably 40 to 80%.</li></ul>

Dusts

<ul id="ul0009" list-style="none"><li>Active ingredient: 0.5 to 10%, preferably 2 to 8%</li><li>solid carrier material: 99.5 to 90%, preferably 98 to 92%.</li></ul>

Suspension concentrates

<ul id="ul0010" list-style="none"><li>Active ingredient 5 to 75%, preferably 10 to 50%</li><li>Water: 94 to 25%, preferably 90 to 30%</li><li>surfactant: 1 to 40%, preferably 2 to 30%.</li></ul>

Wettable powder

More active <ul id="ul0011" list-style="none"><li>Active ingredient: 5 to 90%, preferably 10 to 80%</li><li>and in particular 20 to 60%</li><li>surfactant: 0.5 to 20%, preferably 1 to 15%</li><li>solid carrier material: 5 to 90%, preferably 30 to 70%.</li></ul>

Granules

<ul id="ul0012" list-style="none"><li>Active ingredient: 0.5 to 30%, preferably 3 to 15%</li><li>solid carrier: 99.5 to 70%, preferably 97 to 85%.</li></ul>

While concentrated agents are preferred as a commodity, the end user generally uses diluted agents. The use forms can be diluted down to 0.001% of active ingredient.

The agents can also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active ingredients to achieve special effects.

Such agrochemicals are part of the present invention.

The following examples serve to explain the invention in more detail without restricting it. Temperatures are given in degrees Celsius, pressures in millibars (mbar).

Example 1

Preparation of 1- (trans-but-3-en-2-one-4-yl) -1-methylthio-cyclobutane (intermediate)

<chemistry id="chem0024" num="0024"><img file="EP0243313B1_D0024.tif" /></chemistry>

A solution of 39 g of cyclobutane-1-methylthio-1-carbaldehyde in 400 ml of acetone is added dropwise with stirring at 50_°C 140 ml of aqueous 2N sodium hydroxide solution for 5 minutes. The mixture is then stirred for 15 hours at room temperature and 8 hours under reflux. Then the reaction mixture is evaporated, the residue taken up in ether, washed with water and brine, dried and the ether evaporated. The remaining oil is distilled at 0.013 mbar. 41.5 g of a clear oil are obtained, which at 58_°/ 0.013 mbar boils and has a title product content of 96.5% (gas chromatography).

In an analogous manner to this example, the methyl ketones of the formula VII listed in Table 1, which serve as intermediates, are prepared.<chemistry id="chem0025" num="0025"><img file="EP0243313B1_D0025.tif" /></chemistry><tables id="tabl0001" num="0001"><img file="EP0243313B1_D0026.tif" /></tables>

Example 2

Preparation of 5- (1-methylthio-cyclobutan-1-yl) cyclohexan-1,3-dione (intermediate)

<chemistry id="chem0026" num="0026"><img file="EP0243313B1_D0027.tif" /></chemistry>

41 g of 1- (trans-but-3-en-2-one-1-) are added dropwise to a stirred suspension of 33.5 g of dimethyl malonate and 47 g of sodium methylate (30.8% in methanol) in 900 ml of absolute toluene over 15 minutes. yl) -1-methylthio-cyclobutane. The slurry-like reaction mixture is then heated to reflux within 5 hours. Methanol is distilled off until a distillation temperature of 110 ° is reached. The reaction mixture, which is initially difficult to stir, then turns into a fine suspension. After cooling, evaporate to dryness and wash the residue with hexane. This gives 70 g of sodium salt of 5- (1-methylthio-cyclobutan-1-yl) -6-methoxycarbonyl-cyclohex-6-en-3-one-1-ol's of the formula<chemistry id="chem0027" num="0027"><img file="EP0243313B1_D0028.tif" /></chemistry>as an intermediate.

This is dissolved in 250 ml of aqueous 2N potassium hydroxide solution and at 80 for 1 ¼ hours_°C stirred. Then let cool and start at 70_° slowly add 80 ml of concentrated hydrochloric acid. After cooling, the product precipitates out in crystalline form. It is filtered off, washed with water until the wash water is neutral and dried at 40-50_°C in the desiccator. Yield 48 g. Melting point after recrystallization from ethanol / water 141-143_°.

In an analogous manner to this example, the 1,3-cyclohexanedione derivatives listed in Table 2, which are required as intermediates, are obtained.<chemistry id="chem0028" num="0028"><img file="EP0243313B1_D0029.tif" /></chemistry><tables id="tabl0002" num="0002"><img file="EP0243313B1_D0030.tif" /></tables>

Example 3

Preparation of 5- (1-methylthio-cyclobutan-1-yl) -3-n-butyryloxycyclohex-2-en-1-one (intermediate)

<chemistry id="chem0029" num="0029"><img file="EP0243313B1_D0031.tif" /></chemistry>A mixture of 13.8 g of cyclohexane-1,3-dione, 8.7 g of butyryl chloride and 11.3 g of potassium carbonate in 250 ml of tetrahydrofuran is stirred for 4 hours at room temperature. Then the reaction mixture is evaporated, taken up in ether, washed twice with water and once with brine and dried. The ether is evaporated off, and the remaining oil is chromatographed with ether-hexane 1: 2 on a silica gel flash column. After evaporation of the eluate, 10.2 g of a colorless oil n remain²⁶_D 1.275..

In an analogous manner to this example, the cyclohexanone esters of the formula IV listed in Table 3, which are required as intermediates, are obtained.<chemistry id="chem0030" num="0030"><img file="EP0243313B1_D0032.tif" /></chemistry><tables id="tabl0003" num="0003"><img file="EP0243313B1_D0033.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0243313B1_D0034.tif" /></tables>

Example 4

Preparation of 5- (1-methylthiooyclobutan-1-yl) -2-n-butyryl-cyclohexan-1,3-dione

<chemistry id="chem0031" num="0031"><img file="EP0243313B1_D0035.tif" /></chemistry>A solution of 10.0 g of 5- (1-methylthio-cyclobutan-1-yl) -3-n-butyryloxy-cyclohex-2-en-1-one (Example 3) and 0.5 g of 4- (N, N-Dimethylamino) -pyridine are at a temperature of 100-110 for 3 days _°C stirred. The reaction mixture is then evaporated. The remaining oil is chromatographed on a silica gel column which contains 300 g of silica gel and on top of it a 1 cm layer of "aluminum oxide acid" with ether / hexane 1: 5. After evaporation of the eluate, 8.1 g of the title product remain as yellow oil n351.5498.

Example 5

Preparation of 5- (1-methylthiocyclobutan-1-yl) -2- (2,4-dichlorobenzoyl-cyclohexan-1,3-dione

<chemistry id="chem0032" num="0032"><img file="EP0243313B1_D0036.tif" /></chemistry>

To a mixture of 3.71 g of 5- (1-methylthiocyclobutan-1-yl) cyclohexane-1,3-dione (Example 2), 3.85 g of 2,4-dichlorobenzoyl cyanide and 2.62 g of zinc chloride in 100 ml Methylene chloride is added dropwise 1.94 g of triethylamine while cooling in an ice bath and stirring. The reaction mixture is then allowed to warm to room temperature and is stirred for a further 20 hours. Then it is poured onto a mixture of ice and concentrated hydrochloric acid 1: 1, methylene chloride is added and the organic phase is separated off. This is washed twice with water, dried and evaporated. The residue is chromatographed with ethyl acetate / hexane 1: 1 over a 150 g silica gel column, onto which a 1 cm thick layer of aluminum oxide (Alox I acid) has been added. The eluate is evaporated and the residue is taken up in ether. Insoluble residue is filtered off. After the ether has evaporated, a viscous oil remains, which solidifies on standing. It is triturated in hexane to give 3.4 g of crystalline material. Melting point 82-83 °.

The 2-acyl-1,3-cyclohexanediones of the formula Ia listed in Table 4 are prepared in an analogous manner to Examples 4 and 5.<chemistry id="chem0033" num="0033"><img file="EP0243313B1_D0037.tif" /></chemistry><tables id="tabl0005" num="0005"><img file="EP0243313B1_D0038.tif" /></tables><tables id="tabl0006" num="0006"><img file="EP0243313B1_D0039.tif" /></tables>

Example 6

Preparation of 5- (1-methylthiocyclobutan-1-yl) -2- (3-oxa-4-aza-oct-4-en-5-yl) cyclohexane-1,3-dione [5- (1-methylthiocyclobutane -1-yl) -2- (1-ethoximino-butyryl) cyclohexane-1,3-dioneJ<chemistry id="chem0034" num="0034"><img file="EP0243313B1_D0040.tif" /></chemistry>

A mixture of 3.0 g of 5- (1-methylthiocyclobutan-1-yl) -2-n-butyrylcyclohexan-1,3-dione (Example 4), 1.15 g of O-ethylhydroxylamine hydrochloride and 1.5 g of potassium carbonate in 30 ml of chloroform and 3 ml of methanol is stirred for 3 days at room temperature. The reaction mixture is then evaporated to dryness, the residue is taken up in ether and the ether layer is washed first with water and then with 1N hydrochloric acid. The ether layer is then cold extracted with 2N potassium hydroxide solution and the aqueous layer is washed with ether. The basic aqueous extract is placed in a cold place and ice-cold semi-conc. Neutralized hydrochloric acid up to pH 5.5. The mixture is then extracted again with ether, the ether layer is dried over sodium sulfate, filtered, evaporated and the residue is taken up in pentane. The pentanol solution is treated with activated carbon, filtered and evaporated. This gives 2.5 g of the title product as a colorless oil. N³⁰_D 1.5428.

In an analogous manner to Example 6, the oxime ethers of 2-acyl-1,3-cyclohexanediones of the formula Ib which are listed in Table 5 are prepared.<chemistry id="chem0035" num="0035"><img file="EP0243313B1_D0041.tif" /></chemistry><tables id="tabl0007" num="0007"><img file="EP0243313B1_D0042.tif" /></tables><tables id="tabl0008" num="0008"><img file="EP0243313B1_D0043.tif" /></tables><tables id="tabl0009" num="0009"><img file="EP0243313B1_D0044.tif" /></tables><tables id="tabl0010" num="0010"><img file="EP0243313B1_D0045.tif" /></tables><tables id="tabl0011" num="0011"><img file="EP0243313B1_D0046.tif" /></tables><tables id="tabl0012" num="0012"><img file="EP0243313B1_D0047.tif" /></tables>

Example 7: Formulation examples for active compounds of the formula I (% = percent by weight)

<tables id="tabl0013" num="0013"><img file="EP0243313B1_D0048.tif" /></tables>

The active ingredient is mixed well with the additives and in a suitable medium. Spray powder is obtained which can be diluted with water to give any desired suspension. cool well-minted concentration

<tables id="tabl0014" num="0014"><img file="EP0243313B1_D0049.tif" /></tables>

Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.

Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding it in a suitable mill.<tables id="tabl0015" num="0015"><img file="EP0243313B1_D0050.tif" /></tables><tables id="tabl0016" num="0016"><img file="EP0243313B1_D0051.tif" /></tables>

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.<tables id="tabl0017" num="0017"><img file="EP0243313B1_D0052.tif" /></tables>

The finely ground active ingredient is applied evenly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.<tables id="tabl0018" num="0018"><img file="EP0243313B1_D0053.tif" /></tables>

The finely ground active ingredient is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.<tables id="tabl0019" num="0019"><img file="EP0243313B1_D0054.tif" /></tables>

Example 8: Herbicidal action before emergence of the plants

In the greenhouse, plant seeds are sown in flower pots 11 cm in diameter. Immediately afterwards, the surface of the earth is treated with an aqueous emulsion of the active ingredients. A concentration of 4 kg of active ingredient per hectare is used. The pots are then in the greenhouse at a temperature of 22-25_°C and 50-70% relative humidity. After 3 weeks, the test is evaluated and the effect on the test plants is assessed. The tested compounds of Tables 4 and 5 show good activity primarily against the monocotyledonous test plants.

Example 9: Herbicidal action when the active compounds are applied after the plants have emerged

Various crops and weeds are grown from the seeds in pots in the greenhouse until they reach the 4 to 6 leaf stage. Then the plants are sprayed with aqueous active ingredient emulsions (obtained from the 25% emulsion concentrate) at a dosage of 4 kg / ha. The treated plants are then under optimal conditions of light, regular watering, 22-25_°C temperature and 50-70% relative humidity maintained. The test is evaluated 15 days after the treatment. The tested compounds show good effects in this test.

Example 10: Inhibition of growth in tro

p

ground cover legumes (cover cro

p

s).

The test plants (centrosema plumieri and centrosema pubescens) are grown to the fully grown stage and cut back to a height of 60 cm. After 7 days, the active ingredient is injected as an aqueous emulsion. The test plants are grown at 70% relative humidity and 6000 lux artificial light, 14 hours a day, at temperatures of 27_° by day and 21 _°C held at night. The test is evaluated 4 weeks after the application. The new growth compared to the control is estimated and weighed and the phytotoxicity is assessed. In this experiment, the plants treated with the active ingredients in Tables 4 and 5 show a significant reduction in new growth (less than 20% of the new growth in untreated control plants) without the test plants being damaged in the process.

Example 11: Growth regulation on soybeans

"Hark" soybeans are sown in plastic containers with a 6: 3: 1 soil-peat-sand mixture and placed in a climatic chamber. Through optimal temperature selection, lighting, adding fertilizer and irrigation, the plants develop after about 5 weeks until the 5-6 trifolia leaf stage. At this point, the plants are sprayed with the aqueous broth of an active ingredient of the formula I until thoroughly wetted. The active ingredient concentration is up to 2000 g ai / ha. The evaluation takes place about 5 weeks after application of the active ingredient. Compared to untreated control plants, the plants treated with the active substances according to the invention in Tables 4 and 5 show a noticeable increase in the number and weight of the pods.

Example 12: Inhibition of growth in cereals

The cereals Hordeum vulgare (summer barley) and Secale (summer rye) are sown in plastic pots with sterilized soil in the greenhouse and watered as required. The sprouts are sprayed about 21 days after sowing with the aqueous spray mixture of an active ingredient of the formula I. The amount of active ingredient is up to 3000 g of active ingredient per hectare. The growth of the grain is assessed 21 days after application. In comparison to untreated controls, the treated plants show a reduction in new growth (60-90% of the control), and in some cases an increase in the stem diameter.

Example 13: Growth inhibition in grasses

The grasses Lolium perenne, Poa pratensis, Festuca ovina, Dactylis glomerate and Cynodon dactylon are sown in plastic trays with soil-peat-sand mixture (6: 3: 1) in the greenhouse and watered as required. The accumulated grasses are cut back weekly to a height of 4 cm and sprayed with the aqueous spray mixture of an active ingredient of the formula I about 50 days after sowing and one day after the last cut. The amount of active ingredient is equivalent to up to 3000 g of active ingredient per hectare. The growth of the grass is assessed 21 days after application. The tested compounds in Tables 4 and 5 bring about a 10-30% reduction in new growth compared to the untreated control.