CH677664A5 - - Google Patents

Description

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description

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

The salts of 2-acyl-1,3-cyclohexanedione oxime ethers according to the invention correspond to formula I.

Egg-:

ff FR3

'V \.

n q v

- / »^

cd wherein  a 2-7-membered alkylene bridge, a 3-7-membered alkenylene bridge, which may be mono- or polyunsaturated,

n zero, one or two Ri Ci-C4-alkyl or benzyl

R2 Ci-Cs-alkyl, unsubstituted or substituted by halogen, Ci-C4-alkoxy, Ci-C4-AlkyIthio; C3-C6 cycloalkyl; Phenyl, benzyl or phenylethyl, where the phenyl ring can be substituted by halogen, Ci-C4-alkyl, Gj-C4-alkoxy, Cj-C4-Aik / lthio, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, cyano or nitro ,

Rs Ci-C6-alkyl, Gi-C6-haloalkyl, C3-C6-alkenyl, Cs-Ce-haloalkenyl or C3-C6-alkynyl and t / m Mm® mean the cation equivalent of a metal or ammonium salt.

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 ammonium bases.

In these definitions, the term alkyl itself or as a constituent of another substituent, such as alkoxy, alkylthio, haloalkyl, haloalkylthio, includes both straight-chain and branched radicals, e.g. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sea-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 ice and trans forms, e.g. 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. 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, cycloocta-dienyl and cyclooctatrienyl. These residues can be substituted with methyl groups.

Halogen means fluorine, chlorine, bromine or iodine atoms.

Metals which are suitable for salt formation are the alkali metals, the alkaline earth metals, and zinc, iron, copper, manganese. Cobalt, nickel; Ammonium compounds are ammonium and Ci-C4-alkyl ammonium. Ci-C4-hydroxyalkylammonium,

C2-C4-alkoxyalky! Ammomum and benzylammonium.

The salts of the 2-acyl-1,3-cyclohexanedione oxime ether of the formula I are notable for good herbicidal and plant growth-regulating action. Among the compounds that are particularly notable for their action are the lithium, sodium, potassium, magnesium, calcium, barium, copper and tri- and tetra-C 1 -C 4 -alkylammonium salts of 2-acyl-1,3-cyclohexanedione. oxime ethers of the formula I, in which n is zero,

A is a 2-5 link alkylene chain,

RiCi-C4-AlkyI,

R2 Ca-C4-AIkyI and

R3 mean Ci-Co-alkyl, C3-C6-alkenyl or C3-C6-haloalkenyl.

Among these, in turn, those salts in which n zero,

A is a 2 to 5 chain alkylene chain,

Ri methyl or ethyl,

R2 ethyl or n-propyl and

R3 is ethyl, allyl, buten-2-yl or 3-chloroallyl (ice and trans).

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The triethylammonium, lithium, sodium, potassium, magnesium, calcium, barium and copper salts of (1-methylthiocyclopropan-1-yl) -2- [1 - (trans-3-chloroIlyloximino) -n-propionyl] -cyclohe- work best xan-1,3-dione of the formula

HCCl] fOCH2CH

{No./ SC2H5 ch3s _

V 1 / »rf *

where Vm Mm® means triethylammonium, lithium, sodium, potassium, magnesium, calcium, barium or Rufperion.

The salts according to the invention have good herbicidal and plant growth regulating action, they are suitable, for example for the selective control of grasses in crops.

At low application rates, they are characterized 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 salts of Formula 1 also have good plant growth regulating properties. They also have a much better shelf life and soil stability than the corresponding free oximes. They decompose only slightly during storage, even at higher temperatures, and are also decomposed less quickly after application in the soil.

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

A first process for the preparation of the acyl-cyclohexanedione oxime ether salts of the formula I is characterized in that a 1,3-cyclohexanedione derivative of the formula II is present in an inert organic solvent in the presence of the equimolar amount of a base

/ \

* - * <0) irT? -IsÀ CII)

wherein A, n and Ri have the meaning given under the formula I, with an acid halide or acid anhydride of the formula III

B-2 — C — Ï (III)

wherein Y is a halogen atom or a radical

—0CE.2

means and R2 has the meaning given under formula I, the cyclohexanone ester of the formula IV obtained

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CH 677 664 A5

ff «

\

(IV)

-R2

wherein A, n, Ri and Rg 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 la,

ff ff

(Ia)

wherein A, n, R-t and R2 have the meaning given under the formula I, and this in an inert organic solvent, in the presence of the equimolar amount of a base, with a hydroxylamine • hydrochloride of the formula V

H2NOR3 • HCl (V)

in which R3 has the meaning given under the formula I, to the oxime ether of the formula Ib,

ff P * 3 • •

/ \ / V,

_ _ I Ï 2 (Ib)

ïrÇr'w \ 0

wherein A, n, Rt, Rg and Rs have the meaning given under formula I and this with the equimolar amount of a hydroxide of formula VII

HO-VmM (VII)

reacted where 1 / mM means a metal or an ammonium residue, and the water formed in the salt formation is removed by distillation.

A second, more direct 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

ff iti-s (o) —t «* -! L ClI ')

"A

wherein A, n and Rt have the meaning given under the formula I, with an acid cyanide of the formula VI

X

R2-C-CN (vi)

wherein R2 has the meaning given under formula I, and the resulting 2-acyl-1,3-cyclohexanedione derivative of the formula la

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(la)

wherein A, n, Ri and Rg 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 the formula V.

HaNORs • HCl (V)

in which R3 has the meaning given under formula I to give the oxime ether of formula Ib in which A, n, R 1, R 2 and R 3 have the meaning given under formula I and react this with the equimolar amount of a hydroxide of formula VII,

HO-VmM (VII)

where VmM represents a metal or an ammonium residue, and the water formed in the salt formation is removed by distillation.

Inert organic solvents for these reactions are mainly aromatics such as benzene, toluene, hydrogen halides such as chloroform, dichloroethane, dichloromethane, carbon tetrachloride, esters such as e.g. Ethyl acetate in question.

The reaction temperatures are advantageously 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.

The preparation of the 2-acyl-1,3-cyclohexanedione oxime ether required for the salts according to the invention is known and is described in the published European patent application EP-A 243 313.

The conversion into their salts takes place by combining them with the equimolar amount of the hydroxide of the salt-forming metal or ammonium.

The reaction is advantageously carried out in an inert water-miscible solvent such as tetrahydrofuran, dioxane or a lower alkanol and at a temperature between room temperature and the boiling point of the solvent. When the solvent evaporates, the water generated during salt formation is removed azeotropically.

The salts according to the invention are also prepared by reacting a 2-acyl-1,3-cyclohexanedione oxime ether with the equimolar amount of a metal alkanolate, the corresponding alkanol serving as solvent and the reaction being carried out at a temperature which is between room temperature and the boiling point of the alkanol becomes. The salt can be obtained in crystalline or amorphous form by evaporation of the alkanol.

The ammonium salts are prepared by dissolving both the 2-acyi-1,3-hexanedione oxime and an excess amount of an amine in an inert organic solvent and then concentrating the solvent, also removing the excess amine.

Alkali metal salts of 2-acyl-1,3-cyclohexanedione oxime ethers can be converted to other alkaline earth metal, iron, zinc, manganese or copper salts by dissolving the alkali metal salts in water and then dissolving the solution with an excess of a heavy metal halide provides. After the ion exchange has taken place, the 2-acyl-1,3-cyclohexane-1,3-dione oxime ether salt is extracted with a water-immiscible organic solvent such as chloroform, methylene chloride while the halide salts remain in the aqueous solution.

The new active ingredients are solids or oils that can be handled easily.

The salts according to the invention have herbicidal activity and are suitable, for example, for the selective control of grasses in crops. The salts of the trans-3-chloroallyloxime ether were particularly effective.

(Ib)

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The salts of formula I also have good plant growth regulating properties.

It has now surprisingly been found that the new salts of the formula I or agents 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 those which are associated with the increase in yield in useful plants, the easier harvesting and the labor savings in measures on plant crops.

Experience has shown that the effect of plant wax 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, among other things, for grasses, because it can e.g. the frequency of grass clippings in ornamental gardens, parks and sports facilities or on the side of the road can be reduced. 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 length growth of cereals, because shortening the stalk reduces or completely eliminates the risk of the plant twisting ("storing") from 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 e.g. more or bigger fruits come to training.

In some cases, yield increases can also be achieved by an intervention in the 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 soybeans 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 secondary pharmaceuticals. One example is the stimulation of 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 apica dominance. This is e.g. Interest in plant propagation. However, it is also possible to inhibit the growth of the rare shoots, e.g. to prevent the formation of side shoots in tobacco plants after decapitation and thus to promote leaf growth.

Growth regulators can also be used to accelerate or delay the ripening of the crop before or after the 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 conditions for e.g. for tobacco, tomatoes or coffee, a complete mechanical or manual harvesting can be carried out in just one operation.

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, e.g. Pineapples or ornamental plants in nurseries, germinate, sprout or bloom at a time when they are usually not ready to do so.

Growth regulators can also be used to delay bud budding or seed germination, e.g. 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.

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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 crop plants by extending the photosythetic activity phase.

Another important area of application for growth inhibitors is their use to inhibit excessive growth in tropical soil cover plants, the so-called cover crops. In tropical and subtropical monocultures, e.g. In palm plantations, cotton, maize fields, etc., in addition to the actual crop plants, land cover plants, in particular legume species, are often planted, which serve to maintain or increase the soil quality (preventing drying out, supply with nitrogen) and preventing 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.

The salts of the formula I are usually used in the form of compositions and can be added to the area or plant to be treated simultaneously or in succession with further active ingredients. 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, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

A preferred method for applying a salt of the formula I or an agrochemical agent which contains at least one of these active ingredients is application to the foliage (foliar application). The number of applications depends on the type of growth influencing. The active compounds of formula I can also get into the plants via the soil through the root system (systemic effect) by soaking the location of the plants with a liquid preparation or 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, e.g. the targeted treatment of plant stems or buds.

The salts of the formula I are used in unchanged form or preferably together with the auxiliaries customary in formulation technology and are therefore, for example to emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules, by encapsulation in e.g. polymeric materials processed in a known manner. The application methods, 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, i.e. The agents, preparations or compositions containing a salt of the formula I according to the invention and optionally a solid or liquid additive are prepared in a known manner, e.g. by intimately mixing and / or grinding the active ingredients with extenders, e.g. with solvents, solid carriers and optionally surface-active compounds (surfactants).

Possible solvents are: Aromatic hydrocarbons, preferably fractions Cb to Oi2, such as Xylene mixtures or substituted naphthalenes, phthalic esters such as di-butyl 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, such as cyclohexanone -Methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oil such as epoxidized coconut oil or soybean oil; or water.

As solid carriers, e.g. natural dust, such as calcite, talc, kaolin, montmorillonite or attapulgite, is generally used for dusts and dispersible powders. To improve the physical properties, highly disperse silica or highly disperse

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absorbent polymers are added. As granular, adsorptive granulate carriers come porous types such as Pumice, broken brick, sepia or bentonite, as non-sorptive substrates e.g. Calcite or sand in question. In addition, a large number of pregranulated materials of inorganic or organic nature, such as, in particular, dolomite or comminuted plant residues can be used.

Nonionic surfactants with good emulsifying, dispersing and wetting properties are suitable as surface-active compounds. 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 (O10-C22), e.g. the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures e.g. can be obtained from coconut or taig oil. Also to be mentioned are the fatty acid methyl taurine salts.

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 usually present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical with 8 to 22 carbon atoms, alkyl also including the alkyl part of acyl radicals, e.g. the Na or Ca salt of 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 sulfonic 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 e.g. the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid / formaldehyde condensation product.

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

Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, the 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 can contain.

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

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

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 with 8 to 22 C atoms as N - substituents and have low, optionally halogenated alkyl, benzyl or low hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. the stearyl trimethyl ammonium chloride or the benzyl di (2-chloroethyl) ethyl ammonium bromide.

The surfactants commonly used in formulation technology include described in the following publications:

"Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood, New Jersey, 1979.

M. and J. Ash, "Encyclopedia of Surfactants" Vol. I-III,

Chemical Publishing Co., Inc. New York, 1981.

H. Stächen «Tensid-Taschenbuch» 2, edition by G. Hanser Verlag, Munich and Vienna 1981.

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

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

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Solutions Active ingredient: Solvent: surfactant: emulatable concentrates Active ingredient surfactant: liquid carrier: dust

Active ingredient:

solid carrier material: suspension concentrates active ingredient water:

surfactant: wettable powders active ingredient:

5 to 95%, preferably 10 to 80% 95 to 5%, preferably 90 to 0% 1 to 30%, preferably 2 to 20%.

10 to 50%, preferably 10 to 40% 5 to 30%, preferably 10 to 20% 20 to 95%, preferably 40 to 80%.

5 to 90%, preferably 10 to 80% and in particular 20 to 60%

5 to 75%, preferably 10 to 50% 94 to 25%, preferably 90 to 30% 1 to 40%, preferably 2 to 30%.

0.5 to 10%, preferably 2 to 8%, 99.5 to 90%, preferably 98 to 92%.

surface-active agent: solid carrier material ". Granules Active agent:

solid carrier material:

0.5 to 20%, preferably 1 to 15% 5 to 90%, preferably 30 to 70%.

0.5 to 30%, preferably 3 to 15%, 99.5 to 70%, preferably 97 to 85%.

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).

Preparation of the sodium salt of 2- [1- (3-trans-chloroallyloxyimino) propyl] -3-oxo-5- (1-methylthio-cy-clopropyl) cyclohex-1-en-1-ol

A solution of 600 mg (0.015 mol) of sodium hydroxide in 3 ml of water is converted into a solution of 5.16 g (0.015 mol) of 2- [1- (3-trans-chloraliyloxyimino) propyl] -3-oxo-5- ( 1-MethyIthio-cyclopropyl) -cyclohex-1-en-l-ol in 10 ml of tetrahydrofuran. The mixture is stirred vigorously for 5 minutes and then evaporated on a rotary evaporator at 30-40 ° C. The residue is dried under high vacuum at 30 ° C. for 6 hours. The title compound remains as a dry foam. The analysis shows that the end product contains about 1/4 molecule of tetrahydrofuran as ligand solvent per molecule of salt.

Example 1 :

II

\ / \

'ONa

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Example 2:

Preparation of the lithium salt of 2- [1- (3-trans-chloroallyloxyimino) propyl] -3-oxo-5- (1-methylthio-cy-cyclopropyl) cyclohex-1-en-1-ol ff F ^ CH

/ \ / \ HÖC1

{c2H5 ch3-s—. .

• —— • • OLx

A mixture of 4127 mg of 2- [1- (3-trans-chloroallyloxyimino) propyl] 3-oxo-5- (1-methylthio-cyclo-propyl) -cyclohex-1-en-1-ol and 504 mg of lithium hydroxide ( LiOH-HaO) in 70 ml of water is stirred for 1 hour. This creates an almost clear solution. This is deep-frozen and freeze-dried (lyophilized) for 48 hours under high vacuum. The crystalline residue is suspended in ether, filtered and dried at room temperature under a high vacuum. A powder is obtained which melts at over 150 ° with decomposition.

Example 3:

Preparation of the lithium salt of 2 - [- 1- (3-trans-chloroallyloxyimino) propylJ-3-oxo-5- (1-methylthio-cy-clopropyl) cyclohex-1-en-1-ol ff I0CH ^

• - HÒC1

i Y C2lî5

c ^ 3_s 7 "\ * \ / \ nT.

• • OLx

A solution of 4127 mg (12 mmol) of 2- [1- (3-trans-chloroalyloxyimino) propyl] -3-oxo-5- (1-methylthio-cy-clopropyl) cyclohex-1-en-1-ol in 40 ml of dioxane is mixed with a solution of 504 mg of lithium hydroxide (LÌOH H2O) in 20 ml of water and stirred vigorously for 10 minutes. The reaction mixture is then filtered, deep-frozen and freeze-dried (lyophilized) under high vacuum for 20 hours. The dry residue is suspended in ether, filtered and dried for 3 hours at room temperature in a high vacuum. 4 g of lithium salt remain as a crystalline, colorless powder. The crystals melt at over 170 ° with decomposition. The analysis shows that the product still contains 0.44 mol of dioxane as ligand solvent per molecule.

Example 4:

Preparation of the magnesium salt of 2- [1- (3-trans-chloroallyloxyimino) propyl] -3-oxo-5- (1-methylthio-cyclopropyl) -cyclohex-1-en-1 -ol ff

• • 1

Ï lì C2lis

CH3S _._.

• »» O ^ / zMg

147 mg of magnesium chips (6.046 mmol) are added to 30 ml of methanol and the mixture is stirred until the magnesium chips have dissolved and a milky solution of magnesium methylate, Mg (OCH3) s has formed. Then 4158 mg (12.092 mmol) of 2- [1 - (3-trans-chloroallyloxyimino) propyl] -3-oxo-5- (1-methylthio-cyclopropyl) cyclohex-1-en-1-ol are added in portions and continue stirring for 15 minutes. Then the reaction mixture is filtered, the filtrate is frozen and freeze-dried under high vacuum for 20 hours (lyophilized). The resulting dry foam is suspended in ether, filtered and dried under high vacuum at room temperature for 3 hours. The magnesium salt obtained melts at over 130 ° with decomposition and still contains 1/3 equivalent of methanol as ligand solvent per molecule.

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Example 5:

Preparation of the copper (II) salt of 2- [1- (3-trans-chloroallyloxyimino) propyl] -3-oxo-5- (1-methylthio-cyclopropyl) cyclohex-1-en-1-ol

3610 mg of 2- [1 - (3-trans-chloroallyloxyimino) propyl] -3-oxo-5- (1-methyIthio-cyclopropyI) -cyclohex- are added in portions to a solution of 420 mg of sodium hydroxide in 30 ml of water with stirring. 1 -en-1 -ol and keep stirring until everything is dissolved. Then, in portions, add 1310 mg of copper sulfate CUSO45H2O to stirring for 30 minutes and then add 50 ml of methylene chloride, CH2CI2. After another 90 minutes the reaction mixture is filtered, the dark green colored methyl chloride layer is separated, dried over sodium sulfate and evaporated. The residue, a dark green solid, is suspended in ether and filtered. There remains 0.6 g of green copper salt, which melts at over 175 ° with decomposition.

The following salts are prepared analogously to these examples. The temperatures are given in degrees Celsius. Z means decomposition.

I H

ch3-S-

- • ^ O »1 / zCu (H)

ff FRs / \ / v

î ß-Z

1] e.g.

11

5

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15

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25th

30th

35

40

45

50

55

60

65

CH 677 664 A5

Table 1

No

Ri

A

R2

Ra

physical data

1.01

CH3

(CH2) 2

C2H5

CH2CH = CHCi trans

HN (c2h5) 3

viscous oil

1.02

CHa

(CH2) 2

C2H5

CH2CH = CHCI trans

U

Symp> 170 ° Z (THF)

1.03

CHs

(CH2) 2

C2H5

CH2CH = CHCI trans

LÌ

Syrap> 150 ° Z

1.04

ch3

(CH2) 2

C2H5

CH2ÛH = CHCi trans

Li

Symp> 160 ° Z (MeOH)

1.05

CHs

(CH2} 2

C2H5

ch2ch = chc1 trans

Li

Symp> 170 ° Z (dioxane)

1.06

CHâ

(CH2) 2

C2H5

CH2CH = CHCI trans

Solid foam (tHF)

1.07

CHs

(CH2) 2

C2H5

CH2CH = CHCI trans

Solid foam

1.08

CHs

(CH2) 2

C2H5

CH2CH = CHCI trans

K

firm foam

1.09

CHs

(CH2) 2

C2H5

CH2CH = CHCl trans

1 / 2Ba

Symp> 120 ° Z

1.10

CHs

(CH2) 2

G2H5

CH2CH = CHC! trans

1 / 2Ca

Symp> 140 ° Z (THF)

1.11

CHs

(CH2) 2

C2H5

CH2CH = CHCl trans

1 / 2Mg

Symp> 1305Z (MeOH)

1.12

CHa

(CHa) 2

C2H5

CH2CH = CHCI trans

1 / 2Cu (ll)

Symp> 175 ° Z

1.13

C2Hs

(CH2) 2

G2HS

CH2CH = CHCI trans

Li

1.14

CH3

(CH2) 2

C3H7-n

CH2CH = CHCI trans

U

1.15

C2H5

(CH2} 2

C2H5

CH2CH = CHCH3

Li

1.16

CHa

(CH2) 2

C2H5

CH2CH = CHCH3

1 / 2Mg

1.17

CHa

(CH2) 2

c2h5

CH2CH = chch3

1 / 2Ca

1.18

c2h5

(CH2) 2

C3H7-n

CH2CH = CHCI trans

Li

1.19

CHa

(CH2) 2

C2Hs

CH2CH = CH2

U

1.20

ch3

(CH2) 2

C3H7-n

CH2CH = ch2

Li

1.21

C3H7-n

(CH2) 2

C2H5

CH2CH = CHCI trans

Li

1.22

CHs

(CH2) 2

C2H5

ch2ch = chch3

1 / 2Cu (ll)

1.23

c2h5

(CH2) 2

C2H5

CH2CH = CHCI trans

1.24

C2H5

(CH2) 2

C2H5

CH2CH = CHCH3

1 / 2Cu (ll)

1.25

CHs

(ch2) 3

C2H5

CH2CH = CHCI trans

U

'

1.26

CHs

(CH2) s

C2H5

CH2CH = CHCI trans

1 / 2Mg

1.27

CHa

(CH2) 3

C2H5

CH2CH = CHCl trans

1 / 2Óa

1.28

CHs

(CH2) 3

c2h5

CH2CH = CHCI trans

VzCuCH)

1.29

ch3

(CH2) 3

C2H5

CH2CH = CHCH3

Li

1.30

ch3

(CH2) 3

C3Ht-ti

CH2CH = CHCI trans

Li

1.31

c2h5

(CH2) s c2h5

CH2CH = CHCI trans

Li

1.32

ch3

(CH2) 3

C3H7-n

CH2GH = CHCH3

U

1.33

CHa

(CH2) 3

C2H5

C2HS

Li

1.34

ch3

(ch2) 4

c2h5

CH2CH = CHCI trans

Li

1.35

ch3

(CH2) s

C2H5

CH2CH = CHCI trans

Li

1.36

CHs

(CH2) 3

C2Hs

CH2CH = CHCH3

V2Mg

1.37

CHa

(CH2) a c2h5

CH2CH = CHCH3

V2Cu (ll)

1.38

CHa

(CH2) 2

c2h5

CH2CH = CHCI trans nh4

1.39

CHa

(CH2) 2

C2H5

CH2CH = CHCI trans

NH3CH3

1.40

CHa

(CH2) 2

c2h5

CH2CH = CHCI trans

NH2 (CH3) 2

1.41

CHa

(CH2) 2

c2h5

CH2CH = CHC! trans

NH2 (C2H5) 2

1.42

ch3

(CH2) 2

C2H5

CH2CH = CHCI trans

NH3C2H5

1.43

ch3

(CH2) 2

C2H5

CH2CH = CHCl trans

NH2 (C3H7iso) 2

1.44

CHa

(CH2) 2

c2h5

CH2CH = CHCI trans

N (CH3) 3C2H4OH

1.45

CHa

(CH2) 2

C2H5

CH2CH = CHCl trans

1 / 2Zn

1.46

ch3

(CH2) 2

c2h5

CH2CH = CHCI trans

NH3C3H7Ì so

1.47

CHa

(CH2) 2

c2h5

CH2CH = CHCI trans

NH3C3H7-n

1.48

CHs

(CH2) 2

C3H7-n

CH2CH = CHCl trans

N / A

1.49

CHa

(CH2) 2

C3H7-n

C2H5

N / A

1.50

C2H5

(CH2) 2

C2H5

c2h5

N / A

1.51

CHa

(CH2) 2

C2H5

CH2CH = CHCI trans

N (CH3) 3benzyI

12

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50

55

60

65

CH 677 664 AS

Example 7:

Formulation examples for active ingredients of formula I (% = weight percent)

a) Spray powder

a)

b)

c)

Salt according to table 1

20%

60%

0.5%

Na lignin sulfonate

5%

5%

5%

Na lauryl sulfate

3%

-

-

Na dlisobutylnaphthalenesulfonate

-

6%

6%

Octylphenolpolyäthyienglykoläther (7-8 mol AeO)

-

2%

2%

Fumed silica

5%

27%

27%

kaolin

67%

-

-

Sodium chloride

-

-

59.5%

The active ingredient is mixed well with the additives and ground well in a suitable mill. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.

b) emulsion concentrate

a)

b)

Salt according to table 1

10%

1%

Octylphenol polyethylene glycol ether (4-5 mol AeO)

3%

3%

Ca-dodecylbenzenesulfonate

3%

3%

Castor oil polyglycol ether (36 mol AeO)

4%

4%

Cyclohexanone

30%

10%

Xylene mixture

50%

79%

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

c) dusts

a)

b)

Salt according to table 1

0.1%

1%

talc

99.9%

-

kaolin

-

99%

Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding it in a suitable mill.

d) extruder granules a) b)

Salt according to table 1

10%

1%

Na lignin sulfonate

2%

2%

Carboxymethyl cellulose

1%

1%

kaolin

87%

96%

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

13

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45

50

55

60

65

CH 677 664 A5

e) coating granules

Salt according to table 1 3%

Polyethylene glycol (MG 200) 3%

Kaolin 94%

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,

f) suspension concentrate

a)

b)

Salt according to table 1

40%

5%

Ethylene glycol

10%

10%

Nonylphenol polyethylene glycol ether (15 mol AeO)

6%

1%

Na lignin sulfonate

10%

5%

Garboxymethyl cellulose

1%

1%

37% aqueous formaldehyde solution

0.2%

0.2%

Silicone oil in the form of a 75% aqueous emulsion

0.8%

0.8%

water

32%

77%

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.

g) saline

Salt according to table 1 5%

Isopropytamine 1%

Octylphenol polyethylene glycol ether (78 mol AeO) 3% water 91%

Example 7:

Herbic acid before the plants emerge

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 250 g salt per hectare is used. The pots are then kept 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 salts tested in Table 1 show good activity primarily against the monocotyledonous test plants,

The effect of salt 1.02 is shown in the following table. The number 1 means that the plant has died, the number 2 means serious damage, while the number 9 indicates normal growth, as in untreated plants.

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CH677 664 A5

Table 2

Plant herbicidal coil

Barley 1

Wheat 1

Millet 1

Corn 1

Rice 1

Soy 9

Cotton 9

Sunflower 9

Sugar beet 9_

Avena fatua 1

Bromustectorum 1

Lolium perenne 1

Alopecurus myosuroides 1

Digitarla sanguinali ^ 1

Echinochloacrus galli 1

Sorghum halepense 1

Rottboelliaexaltata 2

Example 8:

Herbicidal effect when the active ingredients 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 substance emulsions (obtained from the 25% emulsion concentrate) at a dosage of 4 kg / ha. The treated plants are then kept under optimal conditions of light, regular watering, 22-25 ° C temperature and 50-70% relative humidity. The test is evaluated 15 days after the treatment. The tested salts show good effects in this test.

Example 9:

Growth inhibition in tropical groundcover leauminoses (cover cropsì.

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 salt is sprayed as an aqueous emulsion. The test plants are kept at 70% relative air humidity and 6000 lux artificial light, 14 hours a day, at temperatures of 27 ° during the day and 21 ° C 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 test, the plants treated with the salts tested in Table 1 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 10:

Growth reaction on soybeans

“Hark” soybeans are sown in plastic containers with a soil-peat-sand mixture in a ratio of 6: 3: 1 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 one of the salts in Table 1 until they are thoroughly wetted. The active ingredient concentration is up to 2000 g ai / ha. The evaluation takes place about 5 weeks after the application of the host material. Compared to untreated

15

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40

45

50

55

60

65

CH 677 664 A5

Control plants show the plants treated with the salts of table 1 according to the invention a marked increase in the number and weight of the pods.

Example 11:

Growth inhibition in cereals

The cereals Hordeum vulgare (summer barley) and Secate (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 a salt from Table 1. 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. Compared to untreated controls, the treated plants show a reduction in new growth (60-90% of the control), and in some cases an increase in stem diameter.

Example 12:

Growth inhibition in grasses

The grasses Lolium perenne, Poa pratensis, Festuca ovina, Dactylis glomerate and Cynodon dactylon are sown in plastic trays with a 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 a salt of Table 1 approximately 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 salts tested in Table 1 bring about a 10-30% reduction in new growth compared to the untreated control.

Example 13:

Stability investigation of salts according to the invention

Salt samples were stored for 1 month in the dark and at temperatures of -18 ° C, room temperature and + 54 ° C. Then the content of undecomposed active substance was determined by means of high pressure chromatography (HPLC). The samples stored at -18 ° C were assumed to be 100%. The active substance content of the other samples was based on these samples and shows the extent of the decomposition. As a comparison, the stability of the free 2- [1- (3-trans-chlora (lyioxyimino) propyi] -3-oxo-5- (1-methylthiocycIopropyI) -cycIohex-l-en-1-ol was also determined.

The results are summarized in the following table.

CH3S-

16

5

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15

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30th

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40

45

50

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60

65

CH677 664 A5

Table 3

No

1 / mMm®

pillar

Mobile phase acetonitrile water acetic acid

Solvent acetonitrile water acetic acid

Undecomposed salinity after 1 month storage at room temperature 54 ° C

1.01

HN (c2h5) 3

LC-RP

650: 400; 1

100: 0: 0.1

53.6%

0%

1.02

Li

LC-RP

600: 400: 1

100: 0: 0.1

100%

100%

1.03

Li

LC-RP

600: 400: 1

100: 0: 0.1

100%

95%

1.04

Li

LC-RP

600: 400: 1

100: 0: 0

100%

100%

1.05

Li

LC-RP

600: 400: 1

100: 0: 0

100%

100%

1.06

N / A

LC-RP

600: 400: 1

80: 20: 1

100%

17.4%

1.07

N / A

LC-RP

600: 400: 1

100: 0: 0.1

90.6%

17.2%

1.08

K

LC-RP

600: 400: 1

100: 0: 0.1

98.6%

67%

1.09

Ba

LC-RP

600: 400: 1

100: 0: 0.1

98.1%

0%

1.10

Approx

LC-RP

600: 400: 1

100: 0: 0.1

94.5%

79.1%

1.11

Mg

LC-RP

600: 400: 1

100: 0: 0.1

92.8%

46.2%

1.12

Cu (ll)

LC-S!

*

Tetrahydrofuran

92.4%

92.9%

K **

-

LC-RP

600: 400: 1

Acetonitrile

92.6%

20.5%

* Eluent ** control 1-en-1-ol is heptane: dioxane: acetic acid 900: 100: 1

= free 2- [1 - (3-trans chloroallyloxyimino) propyl] -3-oxo-5- (1-methylthio-cyclopropyl) cyclohex

Claims (1)

Claims 1. Salts of 2-acyl-1,3-cyclohexanedione oxime ethers of the formula I / V \ » Ri-S (0) —tCT— • • / m M .m © (I) in which A is a 2-7-membered alkylene bridge, a 3-7-membered alkenylene bridge which can be mono- or polyunsaturated, n zero, one or two Rt Ci-C4-alkyl or benzyl R2 Ci-C8-alkyl, unsubstituted or substituted by halogen, Ci-C4-alkoxy, CHVAIkylthio; C3-C6 cycloalkyI; Phenyl, benzyl or phenyethyl, where the phenyl ring can be substituted by halogen, Ct-C4-alkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkyl, Ci-C ^ -haloalkoxy, cyano or nitro, R3 Ci-Cß-alkyl, Ci-C6-haloalkyl, C3-C6-alkenyl, C3-Ce-haloalkenyl or C3-C6-alkynyl and Vm Mm® mean the cation equivalent of a metal or ammonium salt. 2. Salts of 2-acyl-1,3-cyclohexanedione oxime ethers of the formula I according to claim 1, wherein M lithium, sodium, potassium, magnesium, calcium, barium, zinc, iron, copper, manganese, cobalt, nickel, Ammonium Ci-C4-alkylammonium, Ci-C4-HydroxyaikyIammonium, C2-C4-Alkoxyalkylammonium or Benzylammonium and m are the valence of M while n, A, Ri, R2 and Rs have the meaning given in claim 1. 3. salts of 2-acyl-1,3-cyclohexanedione oxime ethers of the formula I according to claim 1, in which n is zero, A is a 2- to 5-membered alkylene chain, Ri Ci-C4-alkyl, R2 C2-C4-alkyl, R3 Ci-C6-alkyl, C3-C6-alkenyl or C3-C6-haloalkenyl, 17th s 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH 677 664 AS M is lithium, sodium, potassium, magnesium, calcium, barium, copper, ammonium or a Ci-c4-alkylammonium residue and m is the valency of M. 4. salts of 2-acyl-1,3-cyclohexanedione oxime ethers of the formula I according to claim 1, in which n is zero, A is a 2- to 5-membered alkylene chain, Rt methyl or ethyl, Ra ethyl or n-propyl, R3 ethyl, allyl, buten-2-yl or 3-chlorally! (ice and trans) M is lithium, sodium, potassium, magnesium, calcium, barium, copper or Ci-c4-alkylammonium and m is the valency of M. 5. The lithium, sodium, potassium, magnesium, calcium, barium and copper salts of 2-i1- (3-trans-chloroalyloxyimino) propyl] -3-oxo-5- (1 ~ methylthio-cyclopropyl) -cyclohex-1- en-1-oI according to claim 1. 6. A process for the preparation of the salts of acyl-cyclohexanedione oxime ethers of the formula I according to claim 1, characterized in that a 1,3-cyclohexanedioene derivative of the formula II in an inert organic solvent in the presence of the equimolar amount of a base wherein A, n and Rt have the meaning given in claim 1, with an acid halide or acid anhydride of the formula III R2 — C — Y (III) wherein Y is a halogen atom or a radical -oc-r2 means and R2 has the meaning given in claim 1, the cyclohexanone ester of the formula IV obtained / \ • • Rl-SCO — rCy-i " a • o-e-rz in which A, n, Ri and R2 have the meaning given in claim 1, 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, ri-s (o) ff ff / \ \ 1 i 2 da) n (a) n / ^ 0 wherein A, n, Rt and R2 have the meaning given in claim 1, and this in an inert organic solvent, in the presence of the equimolar amount of a base, with a hydroxylamine • hydrochloride of the formula V. H2NOR3 - HCl (V) wherein R3 has the meaning given in claim 1, to the oxime ether of the formula Ib, 18th 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH677 664 A5 f ^ ° ^ r \ X0 (Ib) wherein A, n, Ri, R2 and r3 have the meaning given in claim 1 and this with the equimolar amount of a hydroxide of formula VII HO-VmM (VII) where M has the meaning given in claim 1, and the water formed in the salt formation is removed by distillation. 7. A process for the preparation of the salts of acyl-cyclohexanedione oxime ethers of Formet I, according to claim 1, characterized in that a 1,3-cyclohexanedione derivative of the in an inert organic solvent or diluent, in the presence of zinc chloride and a nitrogen base Formula II « (II) wherein A, n and Ri have the meaning given in claim 1, with an acid cyanide of the formula VI Rz-C-CN (VI) wherein R2 has the meaning given in claim 1, and the 2-acyl-1,3-cyclohexanedione derivative of formula la obtained ? ? El_s (0) _, ris.; ^ V (ia> wherein A, n, Rt and R2 have the meaning given in claim 1, in an inert organic solvent, in the presence of the equimolar amount of a base with a hydroxyiamine • hydrochloride of the formula V. h2nor3 • HCl (V) wherein R3 has the meaning given in claim 1, to the oxime ether of the formula Ib ff ÌP3 • • / \ / V. Rl_s (o) __ c—! ! (Ib) Ra SCO) - ^ N / ^ in which A, n, Rt, Rz and r3 have the meaning given in claim 1 and react this with the equimolar amount of a hydroxide of the formula VII, HO-VmM (VII) wherein M has the meaning given in claim 1, and the water formed in the salt formation, if desired, removed by distillation. 19th 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH677 664 A5 8. A herbicidal and plant growth-regulating agent, characterized in that it contains as the active ingredient a salt of an acyl-cyclohexanedione oxime ether of Formet I, according to claim 1. 9. A method for the selective pre- or post-emergence control of weeds and weeds in crops of useful plants, characterized in that the crop plants or their cropland with an effective amount of a salt of an acyl-cyclohexanedione oxime ether of the formula I, according to claim 1, or with a treated such a salt-containing agent. 10. A method for regulating plant growth, characterized in that plants, parts of plants or seeds are treated with an effective amount of a salt of an acyl-cyclohexanedione oxime ether of the formula 1, according to claim 1, or with an agent containing such a salt. 20th