CS243488B2 - Herbicide and method of efficient substance production - Google Patents

Description

The present invention relates to a herbicidal composition comprising as active ingredient novel cyclohexanedione carboxylic acid derivatives. The invention further relates to a process for the production of these novel cyclohexanedione carboxylic acid derivatives, as well as to their use for the selective and total control of weeds.

The new cyclohexenedione carboxylic acid derivatives correspond to the above. the general formula

(AND)

a-° - ^ne ^ neN ^R ^R ^, a hydroxyl group, a -NHOR ^ group, or a C 1 -C 4 alkyl or ammonium salt thereof, a C 1 -C 6 alkyl group or a C 3 -C 3 cycloalkyl group; from 1 to 6 carbon ethers optionally substituted by halogen, C1-C4 alkoxy or C1-C4 alkylthio, altered C1-C6 alkyl, C1-C6haloalkyl, C3-C6 alkenyl C halogen-C halogenhaloalkenyl or C až-C el el el alkynyl; independently of one another a hydrogen atom;

(C 1 -C 6) alkyl, (C 1 -C 6) haloalkyl, (C 2 -C 10) alkoxyalkyl, (C 2 -C 10) alkylthioalkyl, (C 3 -C 6) alkenyl, optionally substituted by halogen, alkoxy C 1 -C 4 alkyl or C 1 -C 4 alkylthio, C 3 -C 6 alkynyl, phenyl or benzyl, the phenyl nucleus optionally substituted with halogen, C 1 -C 4 alkyl, C 1 alkoxy up to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a nitro group or a cyano group, together with the nitrogen atom to which they are attached, also represent a 5- to 6-membered heterocyclic ring which may still contain oxygen or sulfur in the ring .

As used herein, alkyl groups include both straight and branched chain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, as well as all stereoisomeric forms of higher homologs. in this case, alkenyl and alkynyl are both straight-chain and branched groups, such as, for example, vinyl, allyl, methallyl, butenyl, methyl and dimethylbutenyl, ethynyl, propynyl, butynyl, methylbutinyl and dimethylbutinyl.

Halogen means fluorine, chlorine, bromine and iodine atoms.

5- to 6-ringed cyclocycles, which are formed by R ^ θ И společně together with the nitrogen atom and which may also contain an oxygen or sulfur atom in the ring, are pyrrole, pyrrolidine, piperidine, morpholine or thiomorpholine residues . Such rings are optionally substituted with methyl groups.

and

and

Salts of these compounds are prepared by treatment with bases. Suitable bases for this purpose are ammonia or quaternary alkylammonium bases containing from 1 to 4 carbon atoms in the alkyl radicals.

The cyclohexanedione carboxylic acid derivatives of the formula I are distinguished by good herbicidal activity and the ability to control the growth of plants. Among the compounds which are particularly advantageous for their action, mention may be made

- cyclohexanedione carboxylic acid derivatives of the following groups: acids of the formula Ia:

in which

A and K are as defined above, as well as their ammonium salts or C 1 -C 4 alkyllemmonium salts;

- derivatives of the formula Ia in which A represents a group -O 'and in which R and ^R _{2 are} as defined above, as well as their ammonium or C 1 -C 4 -alkylemmonium salts thereof;

- derivatives of the formula Ia in which A represents a group -HR1- and in which R5 are as defined above, and also their ammonium salts or C1-C4-alkyllemmonium salts thereof,

- derivatives of the formula Ie in which A is as defined above and in which R represents a C 3 -C 6 cycloalkyl group, as well as their ammonium or C 1 -C 4 -alkylemmonium salts in the alkyl moieties,

- cyclohexanedione carboxylic acid derivatives of general formula 1b

O in which

A, R and R R are as defined above, as well as their ammonium salts or C 1 -C 4 alkyl ammonium salts in the alkyl moieties,

- derivatives of the general formula 1b in which A represents a group of 0¾ and K, R ^ and R ^ are as defined above, as well as their ammonium or C1-C4 alkyl ammonium salts * in the alkyl moieties,

- derivatives of the general formula 1b, in which A represents a group and R, R 6, R 6 and R 6 have

As defined above, as well as their ammonium salts or alkyl ammonium salts of 1 to 4 carbon atoms in the alkyl moieties.

Preferred individual compounds include, but are not limited to: 4-butynyl-3,5-cyclohexanedione carboxylic acid ethyl ester, 4-butyryl-3,5-cyclohexanedione carboxylic acid isobutyl ester, 4- (1-ethoxyarninobutylidene) * 3,5-cyclohexanedione carboxylic acid ethyl ester, 4- (ethyl ester) 1-allyl: (4-cyclohexanedioxybutylidene) -3,5-cyclohexanedioocarbonyl acid, 4- (cyclobroprohydrocarbonylethyl) -3,5-cyclohexa-dibarbocarbonyl-ethyl ester, 4- (1-ethoxyxyamino-4-cyclohexylamide) -dimethyl-1,4-cyclohexyl-dimethylamide; (5-cyclopropanecarbonic acid), as well as their sodium, ammonium and tetrafluoroboronate salts.

The cyclohexanedibiphenylbenzoic acid derivatives of the formula I can be present in various tautomeric forms. Thus, for example, the following forms exist for the methyl ester of 4- (1-methoxyamioobutylidene) -3,5cyclooeexo] -tiborocarboxylic acid:

CnHn hoc ₂ h ₅

The cyclohexanedione carboxylic acid derivatives of formula (I) according to the present invention are prepared by not being a .beta.-cyclohexanedione carboxylic acid derivative of the formula. II

O

II o in which (II)

A is an ester or amide moiety as defined above, acting in an inert organic solvent, in the presence of a base, as an acid-binding agent, an acid halide of the formula IU

Hal-COR (III) wherein

R is as defined above. If B is not a hydroxyl group, the obtained product is treated with a hydroxylamine of formula IV at boiling point in a water-immiscible inert solvent at boiling point.

HONHR, (IV) in which.

R1 is as defined above, and the product obtained is isolated.

Suitable solvents for these reactions are, in particular, aromatic hydrocarbons, such as benzene, toluene, xylene, as well as halogenated hydrocarbons, such as chloroform, dichloroethane, tetrachloroethane.

The temperature range is between room temperature and the boiling point of the reaction mixture. During the addition of the acid chloride, it may be expedient to cool the reaction mixture.

Suitable acid-binding agents are organic and inorganic bases. . Examples include pyridine, 4-aminooyyidine, collidine, triethylamine, smoky carbonate, sodium carbonate, potassium carbonate or calcium carbonate or ammonium hydrogen carbonate, sodium tetrachloride, potassium hydrogen carbonate or calcium hydrogen carbonate. '

Suitable acid halides of the formula (III) are, in particular, acetic acid chloride, propionic acid chloride, butyric acid chloride, tartaric acid chloride, 3-methoxyproic acid chloride, 2-chloropyropionic acid chloride, cycloyioyanoic acid chloride or cyclohexanoic acid chloride, as well as the corresponding bromides.

Suitable hydroxylamines of the formula (IV) are, in particular, dimethylhydroxylamine, ethylhydroxylamine, chloroethylhydroxylamine, yynylhydioxylamine, iso-propylhydroxylamine, butylhydroxylamine, isobutylhydroxylamine, allyydydroxylamine, cycloallylhydroxylamine, cycloallylhydroxylamine, cycloallylhydroxylamine, cycloallylhydroxylamine, cycloallylhydroxylamine, cycloallyl hydroxylamine. they can also be added to the reaction mixture in the form of a salt, for example the hydrochloride.

The starting compounds are prepared by hydrogenating 3,5-dihydroxybenzoic acid with hydrogen in the presence of Raney nickel, followed by esterification or amidation of the residue of cyyelin according to the following scheme:

the keto group optionally having to be protected, for example in the form of an enoleter or in the form of an enamine (cf. also J. Am. Chem. Soc. 28: 4 405 (1956)). ,

On the other hand, however, it is also possible to hydrogenate a 3,5-ditydroxybenzoic acid derivative according to the reaction scheme with hydrogen in the presence of Raney nickel:

OH

(cf. Arch. Pharm. 307. 577 (1974)).

At very low rates of application, the compounds of formula (I) are characterized by good selective plant growth control properties and good selective herbicidal properties which allow their excellent application in crops of useful plants, in particular sugar cane, cereals, cotton, soybean, corn and rice. Weed control also partially kills which have so far only been possible to control with total herbicides.

The type of action of these active substances is unusual. Many of these active substances are trenslockable, i.e. the active substances are taken up by the plant and transported to other sites where their effect is then applied. Thus, for example, the surface treatment of perennial weeds manages to damage these weeds up to their roots. Compared to other herbicides and growth regulators, the novel compounds of formula I are effective even at very low rates of application.

In addition, the compounds of formula I have a considerable ability to control the growth of plants, which may result in an increase in yields of crop plants or harvested products, many of these compounds of formula I also show the ability to control the growth of plants depending on their concentration. With these compounds it is possible to influence the growth of both monocotyledonous and dicotyledonous plants.

Thus, for example, legumes grown in tropical areas often as cover crops in tropical areas can be selectively inhibited by the compounds of formula I, so as not to prevent soil erosion among the crop plants, cover crops competition for cultural plants.

The suppression of vegetative growth allows for more dense planting of many crop plants, so that higher yields can be achieved based on the soil surface.

Another mechanism for increasing yields through plant growth regulators is that nutrients are used more intensively to produce flowers and fruits, while

In monocotyledonous plants, such as grasses or even crop plants, such as cereals, inhibiting vegetative growth is often desirable and advantageous. Such inhibition of growth is of economic importance, inter alia, in grassland, since by inhibiting grass growth, for example, the frequency of mowing in ornamental gardens, parks and sports facilities or on the roadside can be reduced. It is also important to inhibit the growth of herbaceous and woody plants at roadside and near overhead lines or, in general, where strong growth is undesirable.

It is also important to use plant growth regulators to suppress the growth of cereals to a height, as this will reduce or eliminate lodging of the plants before harvest due to the shortening of the stalks. In addition, plant growth regulators can cause cereal thickening in cereals, which also counteracts lodging.

The compounds of formula I are furthermore suitable for preventing the germination of stored potatoes. For potatoes are in storage over the winter often develop sprouts which result in shrinkage · ¹ tubers, loss of weight and rot.

By applying higher doses of the compounds of the invention, all test plants are damaged in their development to the extent that they die.

Accordingly, the present invention provides herbicidal and plant growth control agents which comprise as active ingredient at least one new active ingredient of the formula I or a salt thereof.

The compositions according to the invention can be used for pre-emergence and post-emergence weed control and for inhibiting the growth of monocotyledonous and dicotyledonous plants, in particular grasses, tropical crops, to protect the soil from erosion of 8 tobacco shoots.

The compounds of the formula I are used in unchanged form or preferably in the form of compositions together with auxiliaries which are customary in the preparation of such compositions and are therefore processed, for example, into emulsion concentrates, into solutions which are sprayed directly or diluted before application. for dilute emulsions, wettable powders, soluble powders, dusts, granules also encapsulated, for example in polymeric substances. Methods of application such as spraying, fogging, dusting, sprinkling, or watering are selected, as well as the type of composition, according to the desired objectives and proportions.

Said compositions, i.e. compositions comprising the active compound of the formula I and optionally a solid or liquid additive, concentrates or dosage forms, are prepared in a known manner, for example by thoroughly mixing and / or grinding the active compounds with diluents such as solvents, solid carriers and optionally surfactants (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably 8 to 12 Btomy carbon fractions, such as mixtures of xylenes or substituted n-phthalenes, phthalic acid esters such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, as well as their ethers 8 esters, such as ethanol, ethyl glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or or water.

As solid carriers, for example for dusts and dispersible powders, natural stone flours, such as limestone, talc, kaolin, montmorillonite or attapulgite are generally used. Highly dispersed silicic acid or highly dispersed absorbent polymers may also be added to improve physical properties. Suitable granular adsorptive granule carriers are porous types such as pumice, brick ground, sepiolite or bentoaite; as non-sorptive carriers, for example, limestone or sand. In addition, a wide variety of granular materials of inorganic or organic origin, such as in particular dolomite or comminuted plant residues, may be used.

Suitable surfactants are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. Ternsides are also understood as meaning surfactants.

Suitable snionic surfactants can be both so-called water-soluble media and water-soluble synthetic surfactants.

Examples of alkali metal, alkaline earth metal or, if appropriate, substitute ammonium salts, such as sodium or potassium oleic acid or stearic acid salts of higher fatty acids (C10-22) or mixtures of natural acids, are obtained, for example, from coconut oil or tallow. Mention must also be made of a mixture of methyl laurim with matt acids.

The so-called synthetic surfactants, in particular matt sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkali metal sulfonates, have been used for some years.

Fatty sulphonates or sulphates are replaced. generally in the form of alkali metal, alkaline earth metal or optionally substituted ammonium salts and containing an alkyl radical of 8 to 22 carbon atoms, the alkyl radical may also include an alkyl portion of the acyl radicals, such as the sodium or calcium salt of lignin sulphonic acid , a dodecylsulfuric acid ester, or a mixture of sulfated fatty alcohols which have been made from natural matt cyyelin. Also included are salts of sulfuric acid esters and sulfonic acids with adducts of fatty alcohols with ethylene oxide. Preferred benzimidazole derivatives preferably contain 2 sulfonic acid residues and a C 8 -C 22 meth acid residue. Alkyl aryl sulfonates are, for example, the sodium, calcium or tetrammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or the condensation product of naphthalenesulfonic acid and aldehyde.

They come into consideration. They also contain phosphates, such as, for example, phosphoric acid ester salts of adducts of 4 to 14 moles of ethylene oxide with a polyphenylene or salt.

Suitable surfactants are, in particular, derivatives of pollglycol ethers of aliphatic or cyclic fatty alcohols, saturated or unsaturated fatty acids with C1-4 -phthalts, which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (hydrocarbon residue having 6 to 6 hydrocarbon radicals). up to 18 carbon atoms in the alkyl moiety of the alkenyl moieties.

Other suitable non-ionic surfactants are the water-soluble educts of polyethylene glycol propylene glycol, ethylene glycol propylene glycol having from 1 to 10 carbon atoms in the alkyl chain containing from 20 to 250 toluene groups. Said compounds usually contain from 1 to 5 units of one propylene glycol unit

Examples of non-ionic surfactants include polyethylene polyol ethoxyethiol, polysilketters of castor oil, polypropylene starting materials with triethyltin oxide, tributylthiooxyltetyl ether, and polyethyltethoxyethyltetyl ether.

Also suitable are fatty acid esters of poly (xyl) yl toluene, such as poly (ethyl) ethyl ether (III) trioleate.

The cationic surfactants are in particular quaternary ammonium salts which contain at least one C8 -C22 alkyl radical as non-nitrogen-containing substituents and, as further substituents, lower, optionally halogenated, allyl, benzyl or lower Udrostyalkyl groups ztytky. These salts are precipitated. preferably in the form of the U-halides, methyl sulfate or ethyl sulfates, such as stelryl triellylilino chlorichloria or bennyl-d-2- (2-chloroethyl) et al.

Surfactants common in the preparation of such compositions are described, inter alia, in the following publications:

My Cutcheon's Detergents and Smlssflers Airnual MC PubUshing Corp., Ringewood, New Jersey, 1979.

J. end M. Ash, Encyclopedia of Surfactens Vol. I - III, Chernical PubUshing Co., Inc. New York, 1980/81.

The active ingredient-containing compositions generally comprise from 0.1 to 95% by weight of active compound of the formula I, in particular from 0.1 to 80% by weight of active compound of the formula I, from 1 to 99.9% by weight of mono-solid or liquid additives and from 0 to 25%. Moisture, in particular 0.1 to 25% by weight of surfactant.

Preferred compositions have in particular the following composition (% <%):

Ernuugable concentrates:

active ingredient surfactant liquid carrier

Popřeš:

active substance solid carrier

Suspension Concentrate:

active ingredient water surfactant

Wettable powder:

active ingredient surfactant solid carrier

Granulate:

For example, a solid carrier of from about 20% to about 20%, preferably from about 5% to about 10%, from about 5% to about 30%, preferably from about 10% to about 20%, and from about 94% to about 70%. 85%.

0.1 to 10%, preferably 0.1 to 1% 99.9 to 90%, preferably 99.9 to 99% to 75%, preferably 10 to 50 to 94 to 25%, preferably 90 to 30% 40%, preferably 2 to 30%.

0.5 to 90%, preferably 1 to 80%

0.5 to 20%, preferably 1 to 15%, 5 to 95%, preferably 15 to 90%.

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

While concentrated compositions are preferred as commercial goods, the final consumer typically uses dilute compositions. The application foils are diluted to a content of 0.001% of active ingredient. The application rate is generally from 0.001 to 10 kg of active substance / ha, preferably from 0.025 to 5 kg of active substance ηθ 1 ha.

These compositions may also contain longer ingredients, such as stabilizers, compositions

243486

These compositions may also contain other additives, such as stabilizers, antifoams, viscosity regulators, binders, and lubricants, as well as fertilizers or other active ingredients to achieve special effects.

The following examples have been drawn closer, but in no way I can carry her.

Examples illustrating the method of production of active ingredients:

Example 1

Preparation of 4-butyryl-3,5-cyclohexanedione carboxylic acid isobutyl ester

O <j> H. JU ^C - ^C 3 ^H 7.

I 1 (Compound 1.3) isoHgC ₄ OC &

a) 3,5-Cyclohaxaliphenylcarboxylic acid isobutyl ester

Snls of 50 g of 3,5-cyclohexylionic acid, 150 µl of isobutenol, 30 g of 85% phosphoric acid ⁰ 400-toluene were boiled overnight using a water trap. . The solution is then rotated on a rotary evaporator. The residue is taken up in 200 µl of tetrahydrofuran, 100 µl of 1 N hydrochloric acid solution is added and boiled for 2 hours. After cooling, ethyl acetate was added. The organic phase is separated, saturated with sodium chloride solution, dried and gassed. A waxy residue remains, which is recrystallized from ether and hexane and melts at 74-76 ° C.

b) Ia-Utyl-4-bulyryl-3,5-cyclohexeadionkerbroxyl tysalines

To a solution of 60 g of 3,5-cycloheptanedioacsulfonyl ester and 25 n of pyridine in 400 µl of dichloroethane is added dropwise 30 µl of the Butylate chloride and the reaction mixture is stirred for 15 hours at low temperature. hydrochloric acid, dried and concentrated by evaporation. The O-silylated product thus obtained is taken up in 200 µl of dichloromethane, 4 g of 4-dinatyaeninopyridine are added and the reaction mixture is boiled under reflux for 4 hours. The cooled reaction solution was then washed with 1N hydrochloric acid solution, dried, condensed and dried. chronaéoogaphases to malen marriage of ailiksgal · 51 g of isobutyl ester of 4-yr-butyl-3,5-cyclohaxaadionkerbolstrtic tysaline are obtained in a forot of yellow oil having a refractive index of 1,490 7 «

Example 2

Isobutyl Ester Production 4- (1-8LУYloyanniObutylidene) 3355-CycloaeaaNilalcercerblicyl tysalines isoHgCjOC ^{8 4} II

NHOCH ₂ CH = CH 2

C 'С3Н7П o

(compound 2.5)

With 14 g of isobutyl 4-butyryl-3,5-yyclolexylthioacetic acid isobutyl, 6.5 g of O-allyltydroxylanine hydrobromide, 6.5 g of potassium carbonate and 150 ml of chillers are boiled for 6 hours under The reaction solution was then swelled with 1N hydrochloric acid solution, dried, heated, and the silica gel was eluted with a 1: 3 mixture of ethyl acetate and petroleum ether on a small, non-silica gel. evaporation of the solvent yielded 6.9 g of 4- (1-ellyloxyeminobutylidene) -3,5-cyclohexanecarboxylic acid isobutyl ester as a light oil having a refractive index of n ^ ¹ 1,498 9.

Example 3

Preparation of 4- (1-ethoxyaminobutylidene) -3,5-cyclohexanedione carboxylic acid di-methyleaid

(Compound 2.72)

(a) A solution of 15.6 g of cyclohexanedicarboxylic acid is added dropwise with stirring to 18.4 ml of dimethylcarbamorl chloride, and the reaction mixture is then further stirred for 12 hours at room temperature and 2 hours at reflux. After cooling, the reaction mixture was removed

400 ml of ethyl acetate, the organic phase was washed four times with brine, dried over magnesium sulphate and concentrated. The residue consists of 13.2 g of crude 3- (N, N-dimethylcarbamoyl) -5-oxo-cyclohex-3-enecarboxylic acid dimethylamide · This product is dissolved in 300 ml of tetrahydrofuran, 8 ml of concentrated hydrochloric acid is added and the mixture is stirred 2 hours at room temperature. The reaction mixture was then washed with brine, dried over magnesium sulfate and concentrated. 13.2 g of 3,5-cyclohexanedione carboxylic acid dimethylamide remains as a gum which is purified by chromatography on a silica gel column using hexane / ether as the eluent. Mp 152-155 ° C.

b) 13.2 g of 3,5-cyclohexanedione carboxylic acid dimethylamide are dissolved together with 6.9 ml of pyridine in 100 ml of ethylene chloride. It is then added dropwise to this solution with stirring

8.5 ml of butyric acid chloride causing a slightly exothermic reaction. The resulting yellow suspension was stirred for 14 hours at room temperature, then washed with 1N hydrochloric acid solution and brine, dried over magnesium sulfate and concentrated. The residue is dissolved in 100 ml of dichloroethane and refluxed together with 0.1 ml of butyric acid chloride and 0.5 g of 4-dimethylaminopyridine for 2 hours. After cooling, the reaction mixture was washed with 10 N hydrochloric acid saturated with sodium chloride, dried over magnesium sulfate and evaporated. The residue was purified by silica gel column chromatography using ethyl acetate as eluent. There was thus obtained 4-butyryl-3,5-cyclohexenedione carboxylic acid dimethylamide (7.8 g) as a light oil.

c) A mixture of 4.3 g of 4-butyryl-3-cyclohexanedione carboxylic acid dimethylamide, 1.9 g of ethoxyamine hydrochloride, 1.4 g of potassium carbonate in 50 ml of chloroform and 5 ml of methanol is stirred for 24 hours at room temperature. . The reaction mixture was then washed with 1N hydrochloric acid solution, dried over magnesium sulfate and concentrated. An oil is obtained as a residue which is purified by chromatography on a silica gel column using ethyl acetate as the eluent. After evaporation of the solvent an oil remains which crystallizes on standing. 2 g of the title compound of melting point 54-58 ° C are obtained.

Example 4

Preparation of 4- (ethoxyaminobutylidene) -3,5-cyclohexanedione carboxylic acid benzylamide

nhoc ₂ h ₅ С “C ^ H ^ n (compound 2.47)

a) A solution of 107 g of 3,5-cyclo-irioicarboxylic acid ⁸ L of concentrated sulfuric acid in 400 L of methanol and stirred for 3 hours at m.p. Ether (400 mL) was added, whereupon the 3-methoxy-β-5-oxocyclohex-3-excerceryl tyrosine precipitated in crystalline form. After filtration and drying in a desiccator, 120 g of product are obtained.

b) 34 g of 3-methoxy-5'-oxocyclohex-3-eeicarboxylic acid, 33 g of M, N &apos; -dioxideimidazole and 300 mL of dichloroethane are mixed and the suspension obtained is stirred at room temperature for 1 hour. tníítnesti. Then, 22 mL of bensydemine was added dropwise and the reaction was allowed to stir for an additional 14 hours (overnight) at temperatures. míítinssi. The hydrochloric acid solution is then added until the pH of the reaction mixture reaches 3-4. The organic phase is separated, washed with brine, dried over magnesium sulphate and concentrated. This yields 43.6 g of benamidid 3-netcl-5-oxycyclohex-e-oxylic acid in the foro! holy oil.

c) 42 g of this 3-methoxy-5-oxycyclshex-3-ethoxycarbonic acid benzylemide is dissolved in 500 mL of tetrahydrofuran. Concentrated hydrochloric acid (0.5 mL) and water (10 mL) were added and the reaction mixture was further stirred at room temperature for 5 hours. room. While drying the solution using a modular sieve, 16.6 g of 3,5-chlorobenzene hexosulfonic acid are prepared. An additional 17.8 g of product could be obtained by concentrating the liquor. Mined ^to 34.4 ^g. I mp ^78-18 ° C 1.

(d) 29 g of 3,5-cyclopenthoxysio-oxio-thiocarboxylic acid beezamide were reacted in an analogous manner as described in Example 3b in ethyl ethyl chloride in the presence of a small amount of pyridine with pentachloride chloride. After the reaction mixture had passed through, the benzyl amide of 4-styryl-3,5-cyclohexylphenylcarboxylic acid was isolated as a waxy mass which was painted from a mixture of ether and hexane. Yield 15 g. M.p. 126-128 ° C.

e) 6 g of 4-butyl-3,5-cyclohexanedioic acid are reacted according to Example 3c in chloroform in the presence of potassium metabisulphate and hydrochloride ethoxyamine. After working up the reaction mixture, 2.3 g of beesamidamide 1- (1-oxysysiumsulfide) -3,5-cyclohexylcarbonyl acid are obtained in ctymadic form. Mp 88-90 ° C.

The following compounds are also prepared in an analogous manner to those described above:

OH (M ⁺ )

Table 1 number AND R £ 9Physical data 1.1 OCHj C ^ n n * ⁷ 1.506 0 1.2 ^0C 2 ^H 5 63 ^ 0 1.3 O 2 CH iso W ng ⁷ 1 »490 7 (example 1) 1.4 OC ^ SCUj W ⁿ g ⁵ 1 ^, 519 3 1.5 ^C3H ? N 1.6 oc ₂ hr ₄ ocHj CHjn 1.7 Ο ₃ Ηγ1 CjHyB n ⁵ 1 ^, 499 8 1.8 OC-Cl = Cl C3 &? N 1.9 OCHg— CjHjn 1.10 OCHg— 0CH3 C ₃ H ⁿ 1.11 OCEgClH-CHg C ₃ Hn 1.12 OCIHgCCI-CHg 03 ^ 0 1.13 OCHgCNCH W 1.14 OCiLj ^C 6 ^H 13 ⁿ 1,533 0 1.15 OC ^ cyllopropyl 1.16 0CH ₃ cyclohaxrl 1.17 ^0G 6 ^H 13 CH3 1.18 0CH ₂ SCH ₃ ch ₃ 1.19 OC ₂ H ₅ : CH ₂ SCHj 1.20 °° 2 ^Й 5 C ₂ H ₄ OCH ₃ 1.21 ДО ₄ Нн-1егс. CHCICHj 1.22 nh ₂ OjHpn m.p. Mp 167-169 ° C 1.23 nh ₂ C ₂ H ₅ n 1.24 • «OJ 03 ^ “ 1.25 N _{(CH3) 2} W 1.26 NE ^ iso C, H, n; m.p. Mp 126-128 ° C 1.27 NE ^ iso CH3 1.28 n (ch ₂ -ch ₂ ) ₂ cyclopropyl 1.29 Our ^C oCH СН ₂ 0СНз 1.30 MHOH 2 -HH Ο ^ η 1.31 NHCH 3 - NO ₂ c ₂ h ₄ ci

T e b u 1 k & 1 continued

number AND N ^{L t3} physical data 1.32 MÍCHjJCHj — СУ C ₂ H ₄ OC ₂ ^H 5 1.33 HHC ₂ H ₄ SC ₂ H ₅ C ₄ H ₁₈ N ₃ O ₄ 1.34 piparidi.no C ^^ iso 1.35 morfoll.no ^C 6 ^{H 13n} 1.36 °° л. W On* 1.37 ^O C * 5 W mh ₄ * 1.38 OC ^ H ¹ · ⁰ C ^ n and*· 1.40 N (CH3) ₃ C ^ n 0 (003) 3 * 1.42 oc ₂ H ₅ 0¾ tt 49.66 ^{e e} 1.43 oc ₂ H ₅ eyclobutyl 1.44 00¾ cyclobityl 1.45 ^o a cyclopantyl - ' 1.46 00¾ cyclopantyl 1.47 OCjgHj cyclohexyl 1.48 00¾ cyclohexyl 1.49 M (CH ₃ ) ₂ cyclopropyl m.p. 109 to 112 ° C (wax) 1.50 NHCHj— cyclopropyl m.p. Mp 130-144 ° C (wax) 1.51 "-O cyclopropyl 1.52 -Q cyclopropyl CF3 1.53 N (CH 3) (CH ₃ C3H? N oil 1.54 N (3 3> OCH 3) ^C 2 ^H 5 1.55 -O m.p. Mp 123-127 ° C 1.56 NH— ch ₃ 1.57 mh —— fyy ^C 6 ^H13 » 1.58 ^m ~ O C ₂ H ₄ CH (CH ₃ ) ₂

Table 1 continued

number AND R physical data 1.59 NH - CF ₃ C ^ n 1.60 НН — РУ — OCH ₃ 0 ₃ Ηγη 1 .61 NH —-- Cl CHj 1.62 CjHjn oil ' 1.63 NHCH} C-J ^ n 1.64 - “зЮ 1.65 cyclopropylanlno Ο ^ ΗγΠ 1.66 MHC ₆ H _u n Cý ^ n 1., 67 NHCl 3 SO 3 ° 3 * 7 ^N wax 1.68 NHC ^ SCH} ^C 2 ^H 5 1.69 NHCl 2 SC 3 CjHyn 1.79 □ wax 1.71 KCCHjOOCHpj 0 ₃ ΗγΠ oil 1 * 72 stir cyclobutyl 1.73 N _{(CH3) 2} ^c 6 ^{H 13 n} 1 * 74 _{»(CH3) 2} ^C 2 ^H 5 m.p. Mp 82-83 ° C 1.75 KHCHj c ₅ H _n n 1.76 щснрс ^ W 1.77 MÍCHpCjHj 03 ^! 1.78 MÍCHjJCjHj * cyclopropyl 1.79 «°« 3> 3 c ₅ H _u n m.p. 70-72 ° C

IJlORn

C-R

A — C

II o

243466

Table 2

6íalo AND в ^and i & fJaiXal data 2.1 OCHj ^С 3 ^Н 7 ^П ° 2 ^H 6 1,500 2 2.2 OC ^ ₅ W ^C A 2.3 OCjHj Cjltp CHjCttBCK, ng ⁷ 1.511 2 2.4 OC2H3O4 W ^C A ng ⁷ 1,492 9 2.5 OC ^ lto W O = CH-CH3 ng ^T 1.498 9 pMkl.4 2 2.6 och ₂ sch ₃ W ° a og ⁵ 1.518 8 2.7 Ο ^ ΗγΒ CH3-eeCK 2.8 C ₃ ^ n ^C 2 «5 ⁵ '» ^{500 3} 2.9 OC1 ^C ^ 7 ⁿ CH2-CH-CH2 ng ⁵ 1.508 8 2.10 OCjUjiao W CH ₂ CC ₁ CH ₂ 2.11 OC ₂ H ₄ SCH ₃ ^С Я ^{Л C} A 2.12 0C ₂ K ₄ SO ₃ W CH2-CH-CH2 2.13 OCjHjSCKj ^ΰ 3 * Ί ^α C 8 H 11 Cl 2.15 OC ₂ H ₄ OCH ^с Я ^а c ₂ H ₅ 2.16 O.HgCl 3 ° * ^Ί Λ ^C 2 «5 2.17 0CH ₂ - <^ Jy> W ^C 2 «5 2.18 ^C 3 «7“ CH ₂ CCH ₂ 2.19 OCH ₂ -OCH ₃ W ^c 6 ^{H 13 n} 2.20 OCH ₂ CąCK ₂ W C ₆ H _J3 n 2.21 OCH ₂ CH »CH ₂ Ο ^ Ηγϋ 0¾ 2.22 OC ₂ H ₄ C1 w CH ₂ -CSCH ₂ 2.23 OCH ₂ CCL - CH ₂ ^С Л ^П C ₂ H ₄ Cl 2.24 OCH-OCH W ^C 6 ^H 13 ^tM 2.25 OCH ₃ ^c 6 ^H 13 ^{n C} 2 ^H 5

Tabu lk and 2 continued SÍBlo AND R ^K 1 physical data 2.26 oc ₂ H ₅ cyclo. propyl CH2-CH-CH2 2.27 OCK) cyclohexyl ° A 2.28 0 ° 6 ^H 13 ⁿ ch ₃ С4Н9П 2.29 OCHjSCH} CH ₃ CA-aek. 2.30 ^ 5 C ^ SCH ^ C2H5 2.31 C 2 H ₄ OCH ₃ CH2-OCH 2.32 O ^ H ^ -terc. CHCl-Cl2 ^C 2H5 2.33 KH2 W ^C 2H5 2.34 “2 W C ^-CHaCl ^ m.p. 127 DEG-129 DEG 2.35 «“ 2 ^c 2% ^C 2 ^H 5 2.36 NHj C2H5 CH2 CC1 _«CH2 2.37 K (CH3) 2 ° Л- ^C A m.p. Mp 54-58 ° C 2.38 H (CH ₃₎ 2 C ₃ H ₇ n CH2-CHHCH2 m.p. Mp 59-65 ° C 2.39 ' K (CH ₃ > 2 W CHj 2.40 C _(CH3) 2 W C ^ Bt 2.41 №0 ^ 1 «© W ^C 2H ₅ m.p. Mp 88-90 ° C 2.42 NO ^ iao C3V GH ₃ 2.43 MH + -lao W C ^CH CHC ^ m.p. Mp 100-102 ° C 2.44 U = CH-lao CH3 ch ₂ csch 2.45 Ν (0-2-Ή0Η ₂ ) 2 cyclopropyl ^C 2 ^H 5 2.46 ЖиИ.-СН »СН ch ₂ cch ₃ ^c ₅ H _n -s · *. 2.47 ЖМр — ОУ W ^C 2 ^H 5 m.p. Mp 116-119 ° C

example 14

\ c, h ₄ <: i ^C 2 ^H 4 ^F

NOo

Table 2 continued

number ▲ H «1 fiscal d.te 2.50 MHC ₂ H ₄ OCH w 2.51 MHG 2 CH 3 CHj 2.52 p: Lparldinl W Clt-CJHpCHg 2.53 пог ^ Ит ^C ₆ H _I3 ° A 2.57 OC = Hg = 10 W CHg-CH-CHg ми ₄ ⁺ 2.59 №2 CjHj C 1 -C 4 Cl 2 «(C ^ n) / 2.60 ° 0ft CH3 ^C A - 1 ^, 508 7 2.61 NCCHjlOCH} 0 ₃ ΗγΠ ^C A n £ ⁵ 1 ^, 512 2 2.62 N (CH3) OCH3 C, H, n; CHgCH-CHg 2.63 N (CH) ₃ OCH W CH 2 CH 2 CHCl oil 2.64 N ^ 5) 2 CH ⁿ C ₂ »5 wax 2.65 ЖС ^ ОД C3H? N CUgCHaCHg 2.66 N (CH3) 2 cyclopropyl ^C A 2.67 NH— cyclopropyl CH 2 dH> CHg 2.68 N (CH 3) OCH ₃ ° 2 «5 C2 * 5 2.69 ^MH , -O C12 -eo ^ ⁵ 2.70 NHCH ₂ —УУУ cyclopropyl CHgClH-CHg 2.71 CHn ^C 2 ^H 5 m.p. 173 en 176 ° C 2.72 NH— C, H, n; CH-CH 2 CH ₉ 2 z wax example 3 2.73 NH— CH3 ch ₂ ch-ch ₂ 2.74 NH-? Q C ₆ H ₁₃ n ^C 2 ^H 2 2.75 nh-Q , ^C 3 ^H Z ⁿ ^ ⁵

Table 2 continued number A R S m + physical det

2.76 0CH3 ^C 6 ^H 13 “ ^C 2 ^H 5 2.77 »-0— ^{c |} C6 ^H 13n CH2CH2CH2 2.78 N (015) —y-y ^C 6 ^H U ⁿ CHgCH-CHg 2.79 cyclopropylarnno C6H _B n C2 «5 2.80 ' MHC6H13B CH ₃ C2H ₅ 2.81 HH— 5¾ ° CH ₂ CH ₃ CH 31 2.82 N (CH) ₂ CH ⁿ _CH2 CHeClH31 2.83 “HiCHjJHH 03 ^ CH 2 CH-CHCl 2.84 NHCl ₃ S ^c Ch ^C 3 ^H 7 ⁿ CA 2.85 HHC3 SCH3 ^C 3V ⁿ CHgCHnCHj 2.86 HHC3 SCH3 C3H? N C ^ CHHaCOCCCli 2.87 NÍCHjJj cyclopropyl CIt > CCHCCs 2.88 Н (СНз) ₂ CjHsn CHCCHSCHg 2.89 Н (СНз) ₂ 03 ^ 0 C4H9n 2.90 Н (СНз) ₂ ° Л C6H _u n 2.91 N (CH 3> ₂ C2 ^{H5 C} A 2.92 H (CH _{3) 2} ^C 2 ^H 5 C ^CH CH ^ ^ 2.93 M (CH & gt _{; a} C2H ₅ 2.94 M (CH 3> 2 C5 ^H 11n c ^ chmc ^ 2.95 C 03 ^ ^C A 2.96 € CHn CH2-CH = CH2 2.97 C CHn CH 2 -CH 2 CHCl 2.98 NHCH3 CHn ^c ₂ H ₅ 2.99 NHCH ₃ 03ΗγΠ CH 2 CH »CH ₂ 2.100 NHCH ₃ 03θγΠ CH ₃

m.p. 61 to 67 ° C oil

m.p. 67 DEG-70 DEG

m.p. 65 to 68 ° C oil

m.p. Mp 82-83 ° C

m.p. Mp 64-66 ° C

m.p. 77 to 85 ° C (wax)

m.p. 138 DEG-140 DEG

m.p. 139 DEG-141 DEG

AND

243498 20

T a b u 1 k and 2 suppression number AND R »1 physical data 2.101 W CHgClHCHg 4 m.p. 52 to 56 ° C 2.102 «> -0 ° 2 ^H 6 t, t. 93 Si 95 ®C 2.103 lUCHgCH-CHgJg ° A 2.104 N (CH ₂ CH ₂ CH ₂ - ₂₎ oil 2.105 NCC-CH-CH3g C ^ HyQ C ^ CHCHaCBCl oil 2.106 K (CH ₂ CH ₂ CH ₂ - ₂₎ ^C 3®7 ⁿ 0¾ 2.107 NHCHj 03 ^ 2.108 HHCH3 C4H $ n 2.109 NHCHj ^C 5 ^H n ^B ^ ΟΗι ^ 2.110 NHCH ₃ ^c 6 ^H 13 ⁿ C4H9n 2.111 NHC ₂ H 48 CH ₃ CA 2.112 MH + SC + 1 ^C 3 “7“ CH 2 Cl 2 Hg 2.113 racC1sCiH ?! W » And ^a 2.114 MťCHpCjjHj C3H? N «^ СН-иЗ ^ 2.115 M (CH ₃ -C ₂ H ₅ W CM 2.116 N (CH ₃ -C ₂ H ₅₎ сап CH3 and WCCH3 2.117 2) ^C 5 ^H n ⁿ AND 2.118 OCH3 CH3 C2 «5 n £ · 1,507 7 2.119 N (CH3-2 W CH3CCHCHCl olaj 2.120 Η3ΗγΒ ^C ₄ ^Hg n ola j 2.1221 H (CH3-2 ca m.p. 59. ° C 63 ° C 2.122 Ν (ΟΗ ₃ ) - ^ => AND" С ₄ И * П oil 2.123 N (? 3-2 AND" C4H ^ n oil 2.124 OH A ⁿ C ^ n olaj

Table 2 continued number * 1

M® physical data

2.125

K (CH ₃ ) ₂ ^C 2 ^H 5

CH ₂ CH · CHCl

mp ° c

2.126

H ₂ H ₅ ) ₂ ^C 2 ^H 5 c ₂ H ₅

mp to ° C

2.127

N (C ₂ H ₅ ) ₂ ^C 2 ^and 5

CH ₂ CH ₂ CH ₂

m.p.

2.128

c ₂ H ₅ c ₂ h ₅

mp to ° C

Г

2.129 VJ g ₂ h ₅ СН ₂ СЯ * СН ₂ m.p. 70 to 72 2.130 C _{(CH3) 2} w CH ₂ C (CH ₃ ) * CH ₂ m.p. 55 to 57 2.131 ^{M (CH3} > 2 ea ₃ CH ₂ CH = CHCl wax

° C ° c

Example 5

Examples illustrating the composition and preparation of compositions for the active compounds of the formula I (% by weight)

(a) Wettable substance Active substance Lignin sulphate sodium Sodium lauryl sulphate Sodium di-butylbutylnaphthalenesulphonate octylphenolpolyethylene glycol (7 to 8 moles of ethylene oxide) High-dispersive acid Silica kaolin Sodium chloride

and) (b) C) 20 May % 60 % 0.5 % 5 % 5 % 5 % 3 % - - » 6 % 6 % 2 % 2 % 5 % 27 Mar: % 27 Mar: % 67 % - - - - 59.5 %

The active ingredient is well mixed with the ingredients and the mixture is ground well in a suitable mill. A wettable powder is obtained which can be diluted with water to a suspension of each desired concentration.

(b) Emulsion concentrate: E) (b) active substance _k 10% 1% octylphenolpolyethylene glycol ether (4 to 5 moles of ethylene oxide) 3% 3% calcium dodacylbenzenesulfonic acid acid 3% 3% castor oil polyglycol ether (36 moles of ethylene oxide) 4% 4% cyclohexenone 30% 10% mixture of xylenes 50% 79%

From this concentrate, ce.

they can produce emulsions of any desired concentration by diluting with water)

and)

(b) the active substance talc kaolin

0.1%

99.9%

Effective ^la Units is mixed with the carrier obtained directly applicable l.átkou premixed and ground in a suitable mill. dust.

Thus

(d) Extruded grannuate: active substance ligpiinsuioonic acid sodium salt of carboimylcellulose kaolin

and) (b) 10% 1% 2% 2% 1% 1% 87% 96%

The active ingredient is mixed with the ingredients, ground and moistened with water. This mixture is processed into an extruder and then the product is dried in an air stream.

(e) Coated granulate:

Active ingredient polyethylene glycol (molecular rank 200) kaolin%

%%

The finely divided active substance is uniformly applied to a kaolin moistened with polyethylene glycol in a mixer. In this way a dust-free coated granulate is obtained.

i) Suspension concentrate; and) (b) active substance 40% 5 % ethylene glycol 10% 10 % moiophenyl polylyl glycol ether (15 mol of nyllxide) 6% 1 % Sodium salt of the acid 10% 5 % karbox ^ ymeylc sky 1% 1 % 37% aqueous fumaldehyde solution 0.2% 0, 2% silioon oil in the form of a 75% aqueous emulsion 0.8% 0, 8% water 32% 77 %

The finely divided active ingredient is intimately mixed with the ingredients. This gives a suspension conenenate from which suspensions of any desired concentration can be prepared by dilution with water.

g) Salt solution active substance isopropylamine octylienolpolyethylene glycol ether (78 moles ethylene oxide) water%

%

%.

Herbicidal effect in pre-emergence treatment

He attaches

Seeds of different plants are planted in 11 cm diameter pots in the greenhouse. Immediately, the soil surface is treated with an aqueous emulsion of the active ingredient. The active substance is applied in mls, which corresponds to a concentration of 4 kg of active substance per ha. The pots are then kept in an acclimat at a temperature of ^{d 22 d} at ²⁵ ° C and at 50 to 70% relative air humidity. »After 3 weeks, the experiment is discarded, the effect on the test plants being evaluated according to the following scale:

the plant does not say neio is completely dead

2-3: very strong effect

4-6: medium effect

7-8: weak effect

9: no effect (as in the case of untreated control rossiin).

The test results are summarized in the following table:

Table experimental plant

Active Substance Avena sativa Setaria italica Sinepis alia Stellaria media

2.371

2.471

2.61,1

2.63 .3

2.641

99

99

99

99

88

Example 7

Herbicidal effect in the application of active substances after plant emergence

In the greenhouse, different pot plants and weeds are seeded in pots until they reach the 4-6 leaf stage. Thereafter, the plants are treated with aqueous active substance emulsions (which were obtained from a 25% emulsion broth) at a rate of 4 kg of active substance per ha. The treated plants are then kept under optimum conditions of light, regular irrigated te ^ ^p ^ s oto ²² to 25 ° C and ^p s ⁵⁰ to ^70% y ^ ^e latl HV ^and vlhtosti chu ^ vz. The experiment was performed 15 days after the treatment according to the above scale.

The results of this test are summarized in the following table:

Table

Experimental plants Active substance Avena sativa Setaria itaicca loUm perenne Solanum lycopersicum S. apis alia Stellaria media Phaaetlua vulgaris 2.37 1 2 2 9 8 8 7 2.47 2 4 2 4 6 8 9 2.61 1 2 2 7 7 8 9 2.63 1 1 2 8 5 8 5 2.64 1 1 2 4 7 8 9

Example

Growth retarding legumes used in tropical areas as an interculture to protect soil against erosion (cover crops)

The test plants (Centrosema plumieri and Centrosoma pubescens) are grown until they are grown and then cut to a height of 60 cm. After 7 days, the plants are sprayed with the active ingredient in the form of an aqueous emulsion. The test plants are then maintained at 70% relative humidity and artificial light at 6000 lux per day for 14 hours, at 27 ° C overnight and at 21 ° C at night · 4 weeks After the application, the experiment is evaluated. In doing so, a new growth in comparison with control plants shall be estimated and considered and phytotoxicity shall be assessed.

In this experiment, plants treated with the active formulas I appear to have a smaller new growth (less than 20% of the new growth of untreated control plants) without damaging the test plants.

Example 9

Regulation of soybean growth

Hark soybean seeds are sown in plastic containers filled with a mixture of soil, peat and sand in a 6: 3: 1 ratio and left in an air-conditioned room. By optimum choice of temperatures, lighting, fertilizer addition, the plants develop after about 5 weeks up to the 5-6 leaf stage (Trifolia). At this stage, the plants are sprayed with an aqueous suspension of the active compound of the formula I until the leaves are well dewed. The active substance concentration is up to 100 g of active substance per ha. Evaluation of the experiment is carried out about 5 weeks after application of the active compound. In comparison with untreated control plants, the active compounds of the formula I according to the invention cause a remarkable increase in the number and weight of pods on the main shoot.

Example 10

Growth inhibition of cereals

Seeds of two different types of cereals, ie spring barley (Hordeum vulgare) and spring rye (Secale) are sown in the greenhouse of plastic pots filled with sterilized soil and the soil is watered if necessary · Plant shoots are sprayed with water about 21 days after sowing The amount of active ingredient applied is up to 100 g of active ingredient per ha. Cereal growth is assessed 21 days after application. The new increment of the treated plants is lower compared to the untreated control plants (about 60 to 90% of the increment of the untreated control plants). In addition, harsh plants have a partially thicker stem diameter.

Example 11

Growth inhibition of various grasses

Seeds of various grass species, ie perennial ryegrass (Lolium poronne), meadowgrass (Poe pratensis), fescue (Festuce ovina), fritillary (Dactylis), are sown in plastic bowls filled with a 6: 3: 1 mixture of soil, peat and sand. glomerata) and marigold (Cynodon dactylon) and watered if necessary. The weekly grasses are re-trimmed to a height of 4 cm each week and sprayed with an aqueous suspension of the active ingredient of the formula I about 50 days after sowing and one day after the last trimming. The growth of the individual grass species is evaluated 21 days after the application of the active ingredients.

The test compounds of the formula I according to the invention cause a reduction in the new increase of 10 to 30% compared to the untreated control plants.

Claims (16)

1. A herbicidal composition, you zinkující in that in addition to carrier substances or / and additives obaaliuj · longer as active ingredient at least one derivative of an acid of cyklohexandionkarboxylové - formula I (I) wherein ultaíku ▼ ^B 1 «2» »3" К * 3 * 8 * 4 is -ORg or -NB1Rp is hydroxyl, -NfflOR or its alkyl or C1-C4 alkyl ammonium salt, C1-C6 alkyl or cycloalkyl C 3 -C 6 optionally substituted by halogen, C 1 -C 4 alkoxy or C 1 -C 4 alkyl, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl (C,-C alk) alkenyl, (C až-C alk alk) alkenyl, (Cr-C hal hal) haloalkanyl or (C až-C alkiny) alkynyl group, independently of one another, are alkyl, group with 1 a 6 carbon atoms, C 1 -C 6 haloalkyl, C 2 -C 10 alkoxyalkyl, C 2 -C 10 alkylthroalkyl, C 3 -C 6 alkenyl, optionally substituted with halogen C 1 -C 4 alkoxy or C 1 -C 4 alkyltrifluorin, furthermore C 3 -C 6, phenyl or benzyl, wherein the phenyl core is optionally substituted with halogen, C 1-6 alkyl C 1-4 alkoxy, C 1-4 alkoxy, C 1-4 haloalkyl, together with the nitrogen atom on which the heterocyclic ring is in the ring or at least sulfur. carbon atoms, nitro or cyano, are also 5- to 6-membered or still contain oxygen 2. The composition according to item 1, characterized by: characterized in that, as an active ingredient, at least one cyclrhexanedione carboxylic acid derivative of the formula Ia contains (Ia) O in which A and R are not as defined in 1, or an anonium salt thereof or an alkylanonium salt thereof having from 1 to 4 carbon atoms in the alkyl moieties. 3. A composition according to claim 1, characterized in that it contains as active ingredient at least one cyclic hexadecahydrocarbosylic acid derivative of the formula Ia in which Λ is -OR2 and R and Rg have the meanings given in point 1, or an assembly hall thereof or having 1 to 4 carbon atoms in the alkyl moieties. 4. A composition according to claim 1, wherein the active ingredient comprises at least one cyclohexanedilaccarbololeic acid derivative of the formula Ie in which A is -NR2R4 and R, R and R2 are as defined in item 1. , or an anionic salt thereof or an γ-1 to 4-carbon atom of an alkylanonium salt in the cup portion. 5. The composition of claim 1, wherein the active ingredient comprises at least one cyclohexanedioacartolic acid derivative of formula (Ia) wherein A is as defined in (1) and R is (C 3 -C 6) cycloalkyl or a cationic salt thereof. or an alkyl group having 1 to 4 carbon atoms in the alkyl moieties. 6. A composition according to claim 1, wherein the active ingredient comprises a compound of formula (Ib) wherein: A, R and R 1 are as defined in 1, or a cationic salt or a C 1 -C 4 -alkylanonium salt thereof. 7. A composition according to claim 1 which comprises at least one compound of the general formula Ib as active ingredient, wherein A is ORg and A, E, R and Rg are as defined in point 1, or its cationic salt L or βίζ. C 1 -C 4 salt of alkyl moieties. 8. A composition according to claim 1, wherein the active ingredient comprises at least one cyclohexanedilacarbolic acid derivative of the formula Ib wherein A is -NRR4 and A, R, R, R and R5 are as defined in or a cationic salt thereof or an alkylanonium salt of 1 to 4 carbon atoms in the alkyl moieties. 9. A composition according to claim 1, wherein the active ingredient is 4-butyryl-3,5 &apos; -cyclohexaadione-carbolic acid ethyl ester. 10. A composition according to claim 1, wherein the active ingredient is 4-bulyryl-3,5-cyclohexanedioacsulfonic acid isobutyl ester. 11. A composition according to claim 1, wherein the active ingredient is 4- (cyclopentylhydroxyphenyl) -3,5-cyclodexilandecarboxylic acid. 12. The composition of claim 1, wherein the active ingredient is 4- (1-atoxlanine-4-ylidene) -3,5-cyclohexeadilane-benzylic acid as the active ingredient. 13. A composition according to claim 1, wherein the active ingredient is 4- (1-allyl-araninobutylidene) -3,5-cyclohexanedione carboxylic acid diethylamide. 14. A composition according to claim 1, wherein the active ingredient is 4- (1-etooyaminobutylbenzyl) -3,5-cyclohexanedione carboxylic acid benzylemide. 15. The composition of claim 1, wherein the active ingredient is 4- (1-aylamino-butyutyl) -, 4-C-cyano-oxo-di-carboxylic acid isobutyl ester. 16. A process for the preparation of an active ingredient according to claim 1, which process comprises the preparation of a 3,5-cyclohexenediocarboxylic acid derivative of the formula II in which: A is an ester or amide residue as defined in item 1, acting in an inert organic solvent in the presence of a base as an acid binding agent, an acid halide salt of the formula III Hal-COR (III) wherein R is as defined in 1 and, if B is not a hydroxyl group, the product obtained is treated with an hydroxylamine of formula IV in an inert organic solvent at boiling point under water cleavage conditions. HOWHR (IV) in which Rj 'is as defined above, and the product obtained is isolated.