DE2906507A1 - Plant growth regulating compsn. - contg. alpha amino cyclo:alkanoic acid derivs., e.g. for dwarfing cereals - Google Patents

Abstract

(A) Plant-growth regulating compsn. contains >=1 cycloalkanoic acid deriv. of formula (I) (R = OH, alkoxy, aralkoxy, amino (opt. mono-or di-alkyl substd.) or O encircled negative M encircled positive; R1 = NH2, NHCOR2 or N encircled positive H3X encircled negative; n = 1-5; M+ = equiv. of an alkali or alkaline earth metal or NQ+4; each Q is H or alkyl; R2 = H, alkyl or aryl; and X is chloro, bromo or iodo). (B) Cpds. of formula (Ia) are new: (R3 is as R but not OH; R4 = NH2, NHCOR5 or N encircled positive H3X1 encircled negative; R5 = H (if R3 is not = ethoxy), alkyl (if R3 is not = methoxy) or aryl; X1 encircled negative is iodo, bromo, or, if R3 is not = ethoxy, chloro). (I) are more active than known regulators such as 2-chloroethyl-trimethylammonium chloride. Typical responses, depending on time and amt. of application, include inhibition of vegetative growth e.g. in cereals and grasses; increasing sugar content of beet or protein content of soya; induction of parthenocarpic fruiting; stimulation of latex in rubber trees; inhibition of side shoots in tobacco; as dessicants for vines or cotton; as fruit ripening or abscission agents, and to protect against frost and drought.

Description

Means for regulating plant growth

The present invention relates to the use of some known Cycloalkane-carboxylic acid derivatives as active ingredients for regulating plant growth.

It is already known that (2-chloroethyl) trimethylammonium chloride Has plant growth regulating properties (see US Pat. No. 3,156,554).

The effectiveness of this substance is, however, - especially at low levels Application rates - not always entirely satisfactory.

It has also become known that an under the name Off-Shoot-T " (R) commercially available product based on fatty alcohols with 6, 8, 10 and 12 Carbon atoms to regulate plant growth, especially to suppress of the scientific growth in tobacco can be used (cf. Farm. Chem. Handbook 1975, Masters Publishing Co., Willoughby, Ohio, 1975, Pesticide Dictionary D 147). In some cases, especially at low application rates, leaves However, the effectiveness of this product also leaves something to be desired.

It is also already known that 2-chloroethylphosphonic acid acts as a plant growth regulator can be used (cf. German Offenlegungsschrift 2 050 245). Their effect too however, it is not always entirely satisfactory at low application rates.

It has now been found that the partially known cyclcalkanecarboxylic acid derivatives of the formula in which R stands for hydroxy, alkoxy, aralkoxy, amino, alkylamino, dialkylamino or for the radical O0M, where M # stands for an alkali or alkaline earth metal ion equivalent or for an ammonium, alkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium ion, R¹ for amino, or for the rest where R is hydrogen, alkyl or aryl, and e R1 is also the radical -NH3 Xe, where X is chloride, bromide, or iodide, and n is 1 to 5, very good for regulating plant growth are suitable.

Surprisingly, the cycloalkanecarboxylic acid derivatives used according to the invention show of formula (I) a much higher plant growth regulating effect than that substances known from the prior art (2-chloroethyl) trimethylammonium chloride, Off-Shoot-T (R) and 2-chloratylphosphonic acid, which are highly active ingredients of the same Type of action are. The substances that can be used according to the invention are therefore valuable ones Enrichment of technology.

The cycloalkanecarboxylic acid derivatives which can be used according to the invention are generally defined by the formula (I).

In the formula (I), R is preferably hydroxy, alkoxy with 1 up to 20 carbon atoms, benzyloxy, amino, alkylamino with 1 to 4 carbon atoms, Dialkylamino with 1 to 4 carbon atoms per alkyl radical or for the radical ON whereby M # for a sodium or potassium ion, a magnesium or calcium ion equivalent, ammonium, Alkylammonium with 1 to 4 carbon atoms, dialkylammonium, trialkylammonium or Tetraalkylammonium each having 1 to 4 carbon atoms per alkyl radical, R1 for amino or the radical - NH - CO - R2, where R2 is hydrogen, alkyl with 1 to 4 carbon atoms or phenyl, e or for the radical -NH3 Cl and n for 1 or 2.

Those compounds of the formula (I) are very particularly preferred, in which R is hydroxy, alkoxy with 1 to 10 carbon atoms, benzyloxy, amino, Alkylamino with 1 or 2 carbon atoms, dialkylamino with 1 or 2 carbon atoms each alkyl radical or represents the radical, where M represents a sodium or potassium ion Magnesium or calcium ion equivalent, ammonium, alkylammonium with 1 or 2 carbon atoms, Dialkylammonium, trialkylammonium or tetraalkylammonium each with 1 or 2 carbon atoms each alkyl radical stands, R1 for amino, formylamino, acetylamino, propionylamino, Benzoylamino or NH3 # Cl # and n is 1 or 2.

Examples of the compounds of the formula (I) include: α-amino, α-formylamio, α-acetylamino-α-benzoylaminocyclopropanecarboxylic acid and cyclobutanecarboxylic acid, the sodium, potassium, magnesium, calcium, ammonium, Methylammonium, ethoxyammonium, dimethylammonium, diethylammonium, trimethylammonium, Triäthylammonium-, Tetramethylammonium- and Tetraöthylammonium- salt, also their Methyl, ethyl and benzyl esters and their amide, methyl amide, ethyl amide, dimethyl amide and diethyiamide; also cc -Arnino-cyclopropane- and <-amino-cyclobutanecarboxylic acid methyl ester-, -ethylester-, -propylester-, -butylester-, -pentylester-, hexylester-, -octylester -, - benzyl ester hydrochloride and ε-amino-cyclopropane and α-aminocyclobutane-carboxylic acid hydrochloride.

Some of the compounds of the formula I are known (compare Liebigs Ann. Chem. 1973, 611-618; Chem.

Ber. 108: 1580-1592 (1975); J. Chem. Soc. 196o, 2119-2132 and 1962, 3977-3980).

Some of the compounds which can be used according to the invention are new. These new compounds are characterized by the formula in which R3 stands for alkoxy, aralkoxy, amino, alkylamino, dialkylamino or for the radical O # M #, where M # stands for an alkali or alkaline earth metal ion equivalent or for an ammonium, alkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium ion , R4 for amino or the rest where R5 is hydrogen if R3 is not ethoxy, it is also alkyl, if R3 is not methoxy, and also is aryl, or 4 ee R is the radical -NH3 X, where X # is iodide, Bromide and, if R3 does not stand for ethoxy, also stands for chloride, and n stands for 1 to 5.

The new fabrics can be manufactured using several processes. Thus, a) those cycloalkanecarboxylic acid derivatives of the formula (Ia) in which R4 stands for formylamino are obtained by adding o (-isocyanocycloalkanecarboxylic acid derivatives of the formula in which R6 stands for alkoxy, -except ethoxy-, aralkoxy, amino, alkylamino, dialkylamino or for the radical O # M #, in which stands for an alkali or Er, alkali metal ion equivalent or for an ammonium, alkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium ion, and n has the meaning given above, optionally hydrolyzed with water in the presence of a catalyst and optionally in the presence of an additional diluent, b) those cycloalkanecarboxylic acid derivatives of the formula (Ia) in which R4 is formylamino and R3 stands for OM, where M stands for an alkali metal ion by adding α-isocyano-cycloalkanecarboxylic acid derivatives of the formula in which R7 stands for alkyl and n has the meaning given above, under mild conditions, optionally in the presence of an additional diluent, with alkali metal hydroxides and the resulting CC-isocyano-carboxylic acid salts of the formula in which M 'stands for an alkali metal ion and n has the meaning given above, hydrolyzed by boiling with aqueous alcohol, c) those cycloalkanecarboxylic acid derivatives of the formula (Ia) in which R4 stands for formylamino and R³ stands for OM, in which M stands for the radicals indicated, but not an alkali metal ion, by adding α-formylamino-cycloalkanecarboxylic acid salts of the formula which can be prepared according to process (a) in which M 'and n have the meaning given above, optionally treated in the presence of a diluent with an equivalent amount of a strong acid and the resulting o (-formylaminocycloalkanecarboxylic acids of the formula) in which n has the meaning given above, with compounds of the formula M "OR8 (V) in which 'stands for one equivalent of an alkaline earth metal ion, = ammonium, mono-, di-, tri- or tetra-alkyl-ammonium and R8 stands for hydrogen, methyl or ethyl, optionally reacts in the presence of a diluent, d) those cycloalkanecarboxylic acid derivatives of the formula (Ia) in which R4 stands for formylamino and R3 stands for amino, alkylamino or dialkylamino, by according to process (b ) Preparable α-isocyano-carboxylic acid salts of the formula in which M 'and n have the meaning given above, with compounds of the formula in which R9 and R10 are identical or different and are hydrogen or alkyl, in the presence of hydrochloric acid and optionally in the presence of a diluent, e) those compounds of the formula (Ia) in which R3 is alkoxy or aralkoxy and R4 is the Radical -NH3X #, where X # stands for iodide, bromide and, if R³ does not stand for ethoxy, also stands for chloride by using C5-Form.ylaminocycloalkanecarboxylic acid derivatives of the formula, which can be prepared according to process (a) in which R11 stands for alkyl or araikyl and n has the meaning given above, with compounds of the formula H # X # (VII) in which has the meaning given above, optionally reacted in the presence of a diluent, f) those cycloalkanecarboxylic acid derivatives of the formula (Ia ), in which R4 stands for the radical -NH-CO-Rs, by using α-aminocycloalkanecarboxylic acid derivatives of the formula in which R3 and n have the meaning given above, with acylating agents of the formula in which R12 stands for hydrogen, alkyl or aryl and Y stands for chlorine or for the radical -O-CO-R12, in which R12 has the aforementioned meaning, reacts in the presence of an acid acceptor and optionally in the presence of a diluent, g) those cycloalkanecarboxylic acids - Derivatives of the formula (Ia) in which R4 stands for amino, by adding d-aminocycloalkanecarboxylic acid chlorides of the formula in which n has the meaning given above, is reacted with compounds of the formula R³H (X) in which R3 has the meaning given above, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.

Preferred new cycloalkanecarboxylic acid derivatives are those compounds of the formula (Ia) in which R3 represents alkoxy with 1 to 20, in particular 1 to 10 carbon atoms in the alkyl radical, benzyloxy, amino, alkylamino with 1 to 4, in particular 1 or 2 carbon atoms, dialkylamino with 1 to 4, especially 1 or 2 carbon atoms per alkyl radical or for the radical O # M # where M # stands for a sodium or potassium ion, a magnesium or calcium ion equivalent, ammonium, alkylammonium with 1 to 4, especially 1 or 2, piston material atoms, dialkylammonium , Trialkylammonium or tetraalkylammonium, each with 1 to 4, especially 1 or 2 carbon atoms per alkyl radical, R4 stands for amino or the radical where R5 is hydrogen when R3 is not ethoxy, furthermore it is alkyl having 1 to 4 carbon atoms, but not methyl when R3 is methoxy and R5 is also phenyl, and R4 furthermore is -NH3 Cl # if R³ does not stand for ethoxy.

If, for example, in process (a) i -isccyanocyclopropanecarboxylic acid methyl ester and aqueous-alcoholic hydrochloric acid are used, in process (b) c (-isocyano-cyclopropanecarboxylic acid methyl ester and sodium hydroxide in ethanol, in process (c) in the first stage O (-formylamino) -cyclopropanecarboxylic acid sodium salt and concentrated hydrochloric acid and in the second stage an aqueous alcoholic calcium hydroxide solution, in process (d) C (-isocyano-cyclopropanecarboxylic acid sodium salt and concentrated ammonia in combination with concentrated hydrochloric acid, in process (e) α- Formyl amino-cyclopropanecarboxylic acid methyl ester and dilute hydrochloric acid, in process (f) ot-amino-cyclopropanecarbo-acid and benzoyl chloride and in process (g) α-aminocyclopropanecarboxylic acid chloride and diethylamine as reactants, the reactions according to process (a ) to (g) are represented by the following equations: The α-isocyano-cycloalkanecarboxylic acid derivatives to be used as starting materials in processes (a) and (b) according to the invention are generally defined by formulas (II) and (III). In the formula (II), R6 preferably represents alkoxy with 1 or with 3 to 20, in particular 3-10, carbon atoms, benzyloxy, amino, alkylamino with 1 to 4, in particular 1 or 2 carbon atoms, diaikylamino with 1 to 4, in particular 1 or 2 carbon atoms per alkyl radical, or for the radical O # M #, where M # stands for a sodium or potassium ion, a magnesium or calcium ion equivalent, ammonium, alkylammonium with 1 to 4, in particular 1 cler 2 carbon atoms, dialkylammonium, trialkylammonium or tetraalkylammonium with in each case 1 to 4, in particular 1 or 2, carbon atoms per alkyl radical. R7 in formula (III) preferably represents alkyl having 1 to 13 carbon atoms, in particular methyl or ethyl. In the formulas (II) and (III), n is in each case preferably 1 or 2.

The au -isocyano-cycloalkanecarboxylic acid derivatives of the formula (II) and (III) are already known or can be prepared by processes that are known in principle (cf. DT-OS 2 063 502; Angew. Chem. 83, (1971), 357-358; Chem. Ber.

108: 1580-1592 (1975) and Liebigs Ann. Chem. 1973, 611-618).

Those in processes (c) to (g) according to the invention as reaction components Compounds to be used are represented by the formulas (V), (VI), (VII), (VIII) and (X) generally defined. In the formula (V), M "preferably stands for those radicals those already in connection with the description of the α-isocycano-cycloalkanecarboxylic acid derivatives of the formula (II) were mentioned preferably for M, but not for sodium and Potassium. In the formula (VI), R9 and R10, independently of one another, are preferably for hydrogen and alkyl having 1 to 4, in particular 1 or 2, carbon atoms. In of the formula (VII), X preferably represents chlorine. In formula (VIII), R12 is preferably for hydrogen, alkyl having 1 to 4 carbon atoms or for phenyl.

In the formula (X), R3 preferably represents those radicals which already together hang with the description of the Compounds of the formula (Ia) have been mentioned as preferred for R3. - The connections of the formulas (V), (VI), (VII), (VIII) and (X) are already known in the case of the invention Process (f) α-amino-cycloalkanecarboxylic acid derivatives to be used as starting materials are generally defined by the formula (le).

In this formula, R3 preferably represents those radicals which already in connection with the description of the compounds of the formula according to the invention (Ia) are preferred for R3. The compounds of formula (Ie) leave can be produced by the process (g) according to the invention.

In the process (g) according to the invention as starting materials α-Amino-cycloalkanecarboxylic acid chlorides used are represented by the formula (IX) Are defined. The compounds of the formula (IX) are not yet known, they can, however, be prepared by using the corresponding acids according to the usual Methods, e.g. with thionyl chloride, converted into the acid chlorides. The necessities α-Amino-cycloalkanecarboxylic acid on which the compounds of the formula (IX) are based are known or can be produced by known methods (cf.

J. Org. Chem. 29: 2764-2766 (1964); Synthesis 1978, 46; J. Chem, Soc 1960, 2119-2132 and 1962, 3977-3980).

In the case of production process (a), one generally works in aqueous media Solution, or in a diluent, which is water and an organic solvent such as alcohol, dioxane or tetrahydrofuran.

The reaction can be carried out with acid catalysis, for example with hydrochloric acid can be carried out as a catalytic converter. The reaction temperature can be within a greater Range can be varied. In general, one works at temperatures between 0 and 100 ° C, when using a catalyst preferably at lo to 40 ° C, otherwise preferably at 60 to 90 ° C.

The reaction products are isolated in process (a) according to Usual methods: Extraction with a water-immiscible solvent, e.g. with methylene chloride, the organic phase is dried, filtered and distilled the solvent from in vacuo. The remaining crude products can be removed by distillation or optionally purified by recrystallization.

Method (b) is generally carried out using one or more organic solvent carried out. The following are particularly suitable: Ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane, ketones such as acetone, Methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile and alcohols such as methanol, ethanol and propanol. The implementation is generally at temperatures between Q and 100 ° C, in the first reac tion step preferably carried out at 5 to 250.degree. C., in the second stage preferably at 25 to 90.degree.

The process can be in two isolated reaction steps or as a "one-pot process" can be carried out.

In general, the α-isocyano-cycloalkanecarboxylic acid derivative to be used as the starting material is used dispersed in one of the specified solvents and mixed with alcoholic alkali metal hydroxide solution, which contains 1 to 1.2 Y.cl hydroxide per mole of carboxylic acid derivative, added.

The ε-isocyano-cycloalkanecarcic acid salts initially formed crystallize generally with prolonged stirring and can be isolated by suction.

The further conversion of these intermediates is generally carried out by Cooking with aqueous alcohol containing 1 to 1.2 moles of water per mole per mole of α-isocyano-cycloalkanecarboxylic acid salt contains. The work-up is carried out, for example, by adding the cooled Reaction mixture with ether and suction of the crystallized α-formylamino-cycloalkanecarboxylic acid salt.

To carry out process (c), the to be used are generally used (-Formylamino-cycloalkanecarboxylic acid salts dissolved in water and with the equimolar Quantities of concentrated hydrochloric acid are added. The reaction is carried out at temperatures between 0 and 30 ° C. The products which after prolonged standing of the reaction mixture crystallize can be isolated by suction. -During execution the second stage of procedure (c) are generally my alcohols, in particular methanol and ethanol are used as solvents. To 1 mole of i-Forraylarnino-cycloalkanecarboxylic acid 1 mol of a base of the formula (V) is used. The reaction takes place at temperatures between 10 and 400C. After briefly stirring the reaction mixture, the solvent becomes distilled off in vacuo, the residue triturated with ether, filtered off with suction and dried.

In general, up to 3 Mole of ammonia or amine of the formula (VI) and 1 mole of hydrochloric acid per mole of α-isocyano-cycloalkanecarboxylic acid derivative used. The reaction is generally carried out using water as the solvent carried out at temperatures between 0 and 400C. After stirring the In the reaction mixture, volatile components and solvents are distilled off in vacuo.

The remaining crude product is worked according to customary methods e.g. by extraction with methylene chloride, drying, filtration and concentration of the filtrate.

Method (e) is usually carried out using aqueous hydrochloric acid carried out as a reaction medium. In general, they are used as starting materials o (-Formylamino-cycloalkanecarboxylic acid derivatives to be used for a few days at room temperature stirred or heated to boiling under reflux for several hours. Then it is in a vacuum evaporated to dryness and the remaining crystalline products are over Phosphorus pentoxide dried in a desiccator.

In method (f), water is generally used as a solvent. 1 to 1.2 moles of acylating agent are added to 1 mole of α-amino-cycloalkanecarboxylic acid derivative and 2 to 2.5 moles of acid acceptor are used.

The following acylating agents are preferably used: acetic anhydride, Acetyl chloride, propionic anhydride, propionyl chloride and benzoyl chloride.

The following are preferably used as acid acceptors: alkali hydroxide wic sodium and potassium hydroxide or alkali carbonates and bicarbonates such as Sodium carbonate and sodium hydrogen carbonate.

The reaction according to process (f) is carried out at temperatures between 10 and 400C performed. After briefly stirring the reaction mixture, a strong Acid, such as hydrochloric acid, adjusted to pH 1. The resulting crystalline products can be isolated by suction and purified by recrystallization.

In process (g) according to the invention, diluents are used Water and inert organic solvents are suitable. However, in many cases Component (X) used in excess also act as a diluent.

The acid binders used in process (g) according to the invention are all common acid acceptors are considered. Appropriately, it functions in excess used reaction component of the formula (x), however, as an acid binder.

The reaction temperatures can in the process according to the invention can be varied within a larger range.

In general, temperatures between 0 ° C. and 40 ° C. are used ° C, preferably between 10 ° C and 25 OC.

When carrying out the process according to the invention (one uses about 1 to 1 mol of α-amino-cycloalkanecarboxylic acid chloride of the formula (IX) up to 2 moles of a compound of the formula (X) and optionally 1 mole of acidic agents a. Working up is carried out by customary methods.

The active ingredients which can be used according to the invention intervene in the metabolism of the plants and can therefore be used as growth regulators.

The following applies to the mode of action of plant growth regulators previous experience that an active ingredient is one or more different types Can have effects on plants.

The effects of the substances essentially depend on the point in time the application, based on the development stage of the seed or the plant as well as of the amounts of active ingredient applied to the plants caer their environment and of the type of application. In any case, the crop plants should be growth regulators have a positive influence in the desired manner.

Substances regulating plant growth can be used, for example, to inhibit the vegetative plant growth can be used. Such inhibition of growth is Among other things, in the case of grasses of economic interest, because through damping of grass growth can e.g. the frequency of grass cuttings in ornamental gardens, parks and Sports facilities or roadsides are reduced. That is also important Inhibition of the growth of herbaceous and woody plants on roadsides and in near vcn 't, Weland lines or more generally in areas where a strong Vegetation is undesirable.

The use of growth regulators for inhibition is also important the increase in length in cereals, because shortening the stalk increases the risk the twisting ("storage") of the Po zen reduced or completely eliminated before harvest. In addition, growth regulators can cause stalks to be strengthened in cereals, which also counteracts the storage.

Inhibition of vegetative growth is possible in many cultivated plants a denser planting of the culture, so that additional yield based on the soil area can be achieved Another mechanism for increasing earnings mit Wuchsae. = r.ern is based on the fact that the nutrients in greater measure of the flower and Fruit formation benefit while vegetative growth is restricted.

Growth regulators can often also be used to promote the achieve vegetative growth. This is of great use when the vegetative Plant parts are harvested. However, vegetative growth can be suppressed also at the same time lead to a promotion of generative growth, so that e.g.

more or larger fruits come to the training.

In some cases, increases in yield can also be achieved through an intervention in the vegetable metabolism can be achieved without any changes in the vegetative Noticeable growth.

Growth regulators can also change the composition of the plants in order to bring about a better quality of the harvested products. For example, it is possible to determine the sugar content in sugar beet, sugar cane, Pineapples as well as citrus fruits increase or the protein content in soy or cereals to increase.

Parthenocarpus can develop under the influence of growth regulators Fruits come. The sex of the flowers can also be influenced.

With growth regulators the production or the outflow can also be controlled positive influence of secondary plant substances. An example is stimulation called the latex flow in rubber trees.

During the growth of the plant, growth regulators can be used also the lateral branching through a chemical breaking of the apical dominance be increased. There is interest in this, for example, when propagating plants from cuttings. However, it is also possible to inhibit the growth of the side shoots, e.g. in order to increase the development of side shoots in tobacco plants after decapitation prevent and thus promote leaf growth.

Under the influence of growth regulators, the leaf population of Plants are controlled so that a defoliation of the plants to a desired one Time is reached. Such defoliation is of interest to mechanical To facilitate harvesting, e.g. for wine or cotton, or to facilitate transpiration at a time when the plant is to be transplanted.

The premature fall of fruit can be prevented by using growth regulators impede. However, it is also possible to drop the fruit, for example in the case of fruit - to promote chemical thinning to a certain extent. Growth regulators can also be used to control crops at the time the harvest to reduce the force required to detach the fruit, so that mechanical or manual harvesting of the plants is possible Harvesting is facilitated ..

Growth regulators can also be used to accelerate or also achieve a delay in the ripeness of the crop before or after the harvest. This is of particular advantage because it allows for an optimal adaptation bring about the needs of the market. Furthermore, growth regulators can be used in some cases improve the color of the fruit.

In addition, with the help of growth regulators, a temporal Concentration of maturity can be achieved. This creates the prerequisites for this created that e.g. with tobacco, tomatoes or coffee, a complete mechanical or manual harvesting can be carried out in just one operation, By Application of growth regulators can also stop the S & men or the buds Plants, i.e. the endogenous annual rhythm, are influenced so that the plants, e.g. pineapples or ornamental plants in nurseries, germinate at a time, sprout or bloom on which they normally show no willingness to do so.

With growth regulators can also be achieved that the budding of buds or the germination of sera is delayed, e.g.

in order to avoid damage from late frosts in areas at risk of frost avoid.

Growth regulators can also cause halophilia in crops produce. This creates the conditions for cultivation can be carried out by plants on salty soils.

With growth regulators, frost and drought resistance can also be achieved induced in plants.

The active ingredients can be transferred into the usual formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, Pastes, molten powders, granulates, aerosols, suspension-emulsion-centers, Seed powder, active ingredient-impregnated natural and synthetic substances and ultra-fine encapsulation in torymerer materials and in coating compounds for seeds, as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for example by Mixing the active ingredients with extenders, i.e. liquid solvents, under Liquefied gases under pressure and / or solid carriers, if applicable using surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents. In the case of using water as an extender For example, organic solvents can also be used as auxiliary solvents. The following liquid solvents are essentially: aromatics, such as xylene, Toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic Hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers are meant liquids which are at normal temperature and under normal pressure are gaseous, e.g. aerosol propellants, they are halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers are possible: e.g. 13. natural rock flour, such as kaolins, clays, TalXtum, Chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flour, such as finely divided silica, aluminum oxide and silicates; as solid carriers for granulates are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours as well as granules made of organic material such as sawdust, coconut shells, Corn on the cob and tobacco stalks; come as emulsifying and / or foam-producing agents in question: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latex are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azole-metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be mixed in the formulations with other known active ingredients. present such as fungicides, insecticides; Acaricides and herbicides, as well as in mixtures with fertilizers and other growth regulators.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable Concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, Dusts and granules. The application happens in the usual way Way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, Gassing, etc. It is also possible to use the active ingredients using the ultra-low-volume method to apply plants or parts of plants with the active compound preparation or the To coat the active ingredient itself or the active ingredient preparation or the active ingredient inject yourself into the ground.

The seeds of the plant can also be treated.

The active ingredient concentrations can be varied over a wide range will. In general, from 0.01 to 50 kg, preferably used, per hectare of soil area 0.05 to 10 kg of active ingredient.

For the period of use, the following applies: the use of the growth regulators is carried out in a preferred period, the exact delimitation of which is based on takes into account the climatic and vegetative conditions.

In the following examples, the activity of the invention Substances presented as growth regulators without the possibility of further Exclude applications as growth regulators.

Example A ilemmuny of side shoot growth in tobacco solvents: 30 parts by weight of dimethylformamide 1 part by weight of polyoxyethylene sorbitan monolaurate To produce an appropriate preparation of active ingredient, 1 part by weight is mixed Active ingredient with the specified amounts of solvent and emulsifier and fill with water on the desired concentration.

Tobacco plants are grown in the greenhouse until the 7th leaf has unfolded dressed. At this stage, the apical top of the vegetation of the plants is removed and the plants are sprayed with the active compound preparations until they drip off. After 3 weeks, the side shoots of the plants are broken out and weighed.

The weight of the side shoots of the treated plants is compared with the of control plants compared. 100% inhibition means the absence of side shoots and 0 96 a growth of the side shoots corresponding to that of the control plants.

Active ingredients, active ingredient concentrations and results are based on the following Table.

Table A Inhibition of side shoot growth in tobacco active ingredient Active ingredient concentration Growth inhibition in% in% 0 (control) "Off-Shoot-T" (R) 0.2 20 (known) 0.2 64 Example B Inhibition of growth in barley Solvent: 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitam monolaurate To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier and made up to the desired concentration with water.

Barley plants are grown in the greenhouse to the 2-leaf stage. At this stage, the plants are sprayed with the active compound preparations until they are dripping wet. After 3 weeks, the increment and the inhibition of growth are measured on all plants Calculated as a% of the growth of the control plants. 100% mean a standstill of the growth and 0% a growth corresponding to that of the control plants.

Active ingredients, active ingredient concentrations and results are based on the following Table.

Table B Inhibition of growth in barley Active ingredient Active ingredient concentration Inhibition of growth in% in% 0 (control) 0.05 25 0.05 30 Example C Wuchshenunung in wheat Solvent: 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate desired focus on.

Wheat plants are grown in the greenhouse to the 2-leaf stage. At this stage, the plants are sprayed with the active compound preparations until they are dripping wet. After 3 weeks, the increment and the inhibition of growth are measured on all plants calculated in% of the growth of the control plants. 100% mean a standstill of the growth and 0% a growth corresponding to that of the control plants.

Active ingredients, active ingredient concentrations and results are based on the following Table.

Table C Inhibition of growth in wheat Active ingredient Active ingredient concentration Inhibition of growth in 8 in% 0 (control) 0.05 45 0.05 30 Example D growth in soybeans Solvent: 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate desired concentration on.

Soybean plants are grown in the greenhouse to full development of the first following sheet tightened. At this stage the plants will become dripping wet sprayed with the active ingredient preparations. After 3 weeks all plants the growth measured and the growth inhibition in% of the growth of the control plants calculated. 10% means a standstill in growth and 0% means growth accordingly that of the control plants.

Active ingredients, active ingredient concentrations and results are based on the following Table.

Table D Growth inhibition in soybeans Active ingredient Active ingredient concentration Growth inhibition in% in% O (control) Cl-CH2-CH2-N (CH3) 3 Cl 0.05 0 (known) 0.05 85 0.05 75 + 0.05 25 +) plants show a dark green color Quantities of solvent and emulsifier and fill up with water to the desired concentration.

Tomatoes are grown in the greenhouse in the usual way until about 30 96 of the fruits are ripe. At this stage the plants are ready to drain sprayed with the active ingredient preparations. After different time intervals the number of ripe fruits in the individual test members is determined and in Percentage of the total number of fruits of the respective test member calculated. Consequently 100% means that all fruits are ripe.

The results of this experiment are shown in the table below emerged.

Table E Accelerated ripening of tomatoes active ingredient active ingredient concentration Ripe fruits in% after centration in 2 days 4 days 7 days 37 40 44 (control) 0.1 46 57 79 (known) 0.1 53 65 86 Example E Stimulation of ethylene biosynthesis Solvent: 30 parts by weight of dimethylforman, id emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate desired focus on.

Pieces of leaf of the same size are punched out of soybean leaves. In Petri dishes containing 10 ml of the active ingredient preparations or the corresponding Xontroll solutions are filled without active ingredients, a constant number of leaf fragments is given for 1 hour long incubated. Then the leaf pieces together with 1 ml of the respective Put the active ingredient preparation or control solution in airtight containers. After 24 hours, the ethylene that has accumulated in the vessels is reduced to normal Detection methods determined. The ethylene development of the treated with active ingredient preparation Leaf pieces are compared with the ethylene evolution of the controls.

In the table below: 0 no effect + weak Stimulation of ethylene biosynthesis ++ medium stimulation of ethylene biosynthesis + strong stimulation of ethylene biosynthesis This test is in particularly suitable, the growth-regulating properties of the invention To clarify connections.

The plant hormone ethylene intervenes in numerous development processes of plants a. An increase in ethylene biosynthesis, as is the case with the invention Substances can be obtained, it allows these processes to be controlled. As examples, for which there is a particular commercial interest, are mentioned here: fruit detachment, Accelerated ripening of fruits and leaves, induction of heat, seed germination, fruit thinning, Stimulation of the latex flow e.g. in Hevea, sexual influence and growth inhibition e.g. also to prevent grain from being stored.

The active ingredients and the results are shown in the table below emerged.

Table F Stimulation of ethylene biosynthesis Active ingredient Active ingredient concentration in% 0 (control) e Cl-CH2-CH2-N (CH3) 3 Cl 0.001 0 (known) 0.001 ++ 0.001 +++ 0.001 + 0.001 + Table F (continued) Active ingredient Active ingredient concentration Effect in% 0.001 ++ 0.001 0.001 +++ 0.001 +++ 0.001 +++ Table F (continued) Active ingredient Active ingredient concentration Effect in% 0.001 +++ 0.001 +++ 0.001 ++ 0.001 +++ Table F (continued) Active ingredient Active ingredient concentration Effect concentration in% 0.001 +++ 0.001 +++ 0.001 ++ 0.001 +++ 0.001 Table F (continued) Active substance Active substance concentration Effect in% 0.001 +++ 0.001 +++ Production examples Example 1: 0.3 ml of concentrated hydrochloric acid and a solution of 5 g (0.04; ol) methyl α-isocyano-cyclopropanecarboxylate in lo ml of methanol are added successively to 40 ml of water at 20.degree. The reaction mixture is stirred for 6 hours. It is then extracted twice with 50 ml of methylene chloride each time, the organic phase is dried over magnesium sulfate, filtered and the solvent is distilled off in vacuo. 4 g (70 of theory) of methyl α-formylamino-cyclopropanecarboxylate remain as a residue in the form of a colorless liquid.

Refractive index: nD20 = 1.4730.

Example 2: A solution of 7 g (0.05 mol) of ethyl α-isocyano-cyclopropanecarboxylate in 100 ml of ether is treated dropwise at 5 ° C. with a solution of 3.1 g (0.55 mol) of potassium hydroxide in 50 ml of ethanol. The mixture is stirred at 20 ° C. for 12 hours. After filtering off with suction and washing with ether, 6.4 g (86% of theory) of α-isocyano-cyclopropanecarboxylic acid potassium salt are obtained as a white powder.

Melting point: 225 ° C.

A suspension of 9 g (0.06 mol) of α-isocyano-cyclopropane-carboxylic acid potassium salt in 50 ml of ethanol is mixed with 1.18 g (0.066 mol) of water. The mixture is heated to boiling under reflux for 12 hours and, after cooling at 20 ° C., 50 ml of ether are added. After filtering off with suction, 7 g (70% of theory) of α-formylaminocyclopropanecarboxylic acid potassium salt are obtained in the form of white crystals. Melting point: 1860C Example 3: 8.36 g (0.05 mol) of α-formylamino-cyclopropanecarboxylic acid potassium salt are dissolved in 20 ml of water and 5 g (0.05 mol) of concentrated hydrochloric acid are added at OOC.

The mixture is left to stand at 5 ° C. overnight.

After filtering off with suction and drying, colorless crystals are obtained 5.2 g (80% of theory) of α-formylamino-cyclopropanecarboxylic acid.

Melting point: 189 ° C.

Example 4: 7.46 g (0.05 mol) of a-isocyano-cyclopropanecarboxylic acid potassium salt are added at 20 ° C. to a solution of 6.7 g (0.15 mol) of dimethylamine in 50 ml of water. After cooling to 50 ° C., 5 g (0.05 mol) of concentrated hydrochloric acid are added to the reaction mixture and the mixture is left to stand in the closed reaction vessel at 20 ° C. for 12 hours. At a bath temperature of 60 ° C., the volatile components are drawn off in a water jet vacuum. The product is extracted from the residue with methylene chloride; the solution is dried with magnesium sulfate and after filtration the solvent is distilled off in vacuo. 5.5 g (70% of theory) of oC-formylamino-cyclopropanecarboxylic acid-N, N-dimethylemide remain in the form of a pale yellow liquid.

20 refractive index: n20 = 1.4350.

Example 5: A mixture of 2.5 g (0.02 mol) of α-formylaminocyclopropanecarboxylic acid and 4 ml of ethanol is admixed with o.74 g (o, ol mol) of calcium hydroxide while stirring at 25 ° C. and then left for 12 hours at room temperature stir. The solution is then evaporated in vacuo and the residue is triturated with ether. After filtering off with suction and drying, 2.6 g (97% theoretical) of calcium α-formylamino-cyclopropanecarboxylic acid salt are obtained in the form of a white powder.

Melting point: 2900C.

Example 6: A mixture of 19.4 g (0.15 mol) of α-formylaminocyclopropane-carboxylic acid and 200 ml of 18% hydrochloric acid is refluxed for 3 hours.

It is then evaporated to dryness in vacuo and the remaining Solid dried over phosphorus pentoxide in a vacuum desiccator.

Yield: 18 g (92% of theory) of α-amino-cyclopropanecarboxylic acid hydrochloride.

Melting point: 232 ° C.

Example 7: A mixture of 2 g (0.02 mol) α-amino-cyclopropanecarboxylic acid, 25 ml water and 2.55 g (0.044 mol) potassium hydroxide is mixed with 3.1 g (0.022 mol) at 20 ° C. Benzoyl chloride added. After stirring for 30 minutes, the mixture is acidified to pH 1 with concentrated hydrochloric acid and filtered off with suction. For cleaning, the product is boiled with 30 ml of water.

Yield: 2.1 g (51% of theory) [C-Benzoylaminocyclopropanecarboxylic acid.

Melting point 209 ° C.

Analogously to one of Examples 1 to 7, the compounds of the formula I listed in the table below getting produced: Refractive At- | Yield index n6 °; spi eX 1 (% of the melting point No n theory melting point Theory) (OC); tzw. boiling point . C / mbar) 8 1 OCH2 NHCHO 74 1.5079 9 2 OK. NHCHO 31 loo (Z) lo 1 QHN (C2H5) 3 NHCHO 85 1.4461 Refractive index, 20; Bite yield SShlslet point game 1 (96 der-. {CC); respectively. Nli. n RR lheorle) boiling point (0C / bar) 1l 1 OC2H NHCHO 71 llo / o, l 12 1 NH2 NHCHO 70 145 13 2 OC2E NHCHO 24 65/4 14 1 OCH NH3Cl 81 15o :) 15 l NOCH3 NH 77 1, arc491 16 3 wx30cl 51 92 17 l H2 NH2 86 1.4849 18 1 QQNaQ NH2 t 97 216 19 1 OH NK2 75 220 2 1 23K5 NH3C1 83 108 2 1 2H5 NHi 75 1.4440 22 1 OgK NHCOCHa 82 246 23 AL 0C2H5 NHCOCH3 9 ° 76 24 1 O (CH2) 7CH3 NHCHO 95 1.4321 25 l 2) 7CH3 O (CH2) 7CH3 NH3C1 91 1.4429 26 1 Q8aZ, B, NHCHO 90 221 27 1 OC4H9-tert NH C10 73 1Ö8 3

Claims (6)

Claims 1. Agent for regulating plant growth, characterized by a content of at least one cycloalkanecarboxylic acid derivative of the formula in which R stands for hydroxy, alkoxy, aralkoxy, amino, alkylamino, dialkylamino or for the radical O # M #, where M # stands for an alkali or alkaline earth metal ion equivalent or for an ammonium, alkyl ammonium, dialkylammonium, trialkylammonium or Tetraalklylammonium ion, R¹ for amino, or for the remainder where R is hydrogen, alkyl or aryl and R¹ is also the radical -NH3 X # is chloride, bromide or iodide, and n is 1 to 5 2. Process for regulating plant growth, characterized in that one cycloalkanecarboxylic acid -Derivate according to claim 1 can act on the plants or their habitat. 3. Use of cycloalkanecarboxylic acid derivatives according to claim 1 to regulate plant growth. 4. Process for the production of plant growth regulators, characterized in that cycloalkanecarboxylic acid derivatives according to Claim 1 mixed with extenders and / or surface-active agents, 5. Cycalkanecarboxylic acid derivatives of the formula in which R3 stands for alkoxy, aralkoxy, amino, alkylamino, dialkylamino or for the radical O # M #, where M # stands for an alkali or alkaline earth metal ion equivalent or for an ammonium, alkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium ion R4 stands for amino or the remainder is, in which R5 is hydrogen, if R3 is not ethoxy, also stands for alkyl, if R3 is not methoxy, and also stands for aryl, or for the radical -NH3X #, in which stands for iodide, bromide and, - if R3 does not stand for ethoxy -, also stands for chloride, and n stands for 1 to 5. 6. A process for the preparation of cycloalkanecarboxylic acid derivatives according to claim 5, characterized in that a) for the preparation of those cycloalkanecarboxylic acid derivatives of the formula (Ia) in which R4 is formylamino, α-isocyano-cycloalkanecarboxylic acid derivatives of the formula in which R6 stands for alkoxy, - except ethoxy -, aralkoxy 'amino, alkylamino, dialkylamino or for the radical O # M #, in which stands for an alkali or alkaline earth metal ion equivalent or for an ammonium, alkylarmonium, dialkylammonium, trialkylammonium or tetralkylammonium -ion, and n has the meaning given above, optionally hydrolyzed with water in the presence of a catalyst and optionally in the presence of an additional diluent, bg for the preparation of those cycloalkanecarboxylic acid derivatives of the formula (Ia) in which R4 is amino and R3 stands for OM, where Mg stands for an alkali metal ion, α-isocyano-cycloalkanecaronic acid derivatives of the formula in which R7 stands for alkyl and n has the meaning given above, under mild conditions, optionally in Gc <the presence of an additional diluent, with alkali metal hydroxides and the resulting -isocyano-carboxylic acid salts of the formula in which M 'stands for an alkali metal ion and n has the meaning given above, hydrolyzed by boiling with aqueous alcohol, c) for the preparation of those cycloalkanecarboxylic acid derivatives of the formula (Ia) in which R4 stands for formula amino and R3 stands for OM, where M fip stands for the given radicals, but not for an alkali metal, α-formylamino cycloalkanecarboxylic acid salts of the formula which can be prepared according to process (b) in which M 'and n have the meaning given above, optionally treated in the presence of a diluent with an equivalent amount of a strong acid and the resulting α-formylaminocycloalkanecarboxylic acids of the formula in which n has the meaning given above, with compounds of the formula MOR8 (V) in which M ?? stands for one equivalent of an alkaline earth metal ion, for ammonium, mono-, di-, tri- or tera-alkyl-ammonium and R8 stands for hydrogen, methyl or ethyl, optionally reacted in the presence of a diluent, d) for the preparation of those cycloalkanecarboxylic acid Derivatives of the formula (Ia) in which R4 stands for yormylamino and R3 stands for amino, alkylamino or dialkylamino, oC-isocyanocarboxylic acid salts of the formula which can be prepared according to process (b) in which M 'and n have the meaning given above, with compounds of the formula in which R9 and R10 are identical or different and represent hydrogen or alkyl, reacts in the presence of hydrochloric acid and optionally in the presence of a diluent, e) for the preparation of those compounds of the formula (Ia) in which R # ³ is alkoxy or aralkoxy and R4 stands for the radical -NH3X #, where X # stands for iodide, bromide and - if R3 does not stand for ethoxy - also stands for chloride, α-formylaminocycloalkanecarboxylic acid derivatives of the formula which can be prepared according to process (a) in which R11 stands for alkyl or aralkyl and n has the meaning given above, reacts with compounds of the formula HX (VII) in which has the meaning given above, optionally in the presence of a diluent, f) for the preparation of those cycloalkanecarboxylic acid derivatives of the formula ( Ia), in which R4 represents the radical -NH-CO-R5, α-aminocycloalkanecarboxylic acid derivatives of the formula in which R3 and n have the meaning given above, with acylating agents of the formula in which R12 stands for hydrogen, alkyl or aryl and 12 Y stands for chlorine or for the radical -O-CO-R-, in which R¹² has the aforementioned meaning, reacts in the presence of an acid acceptor and optionally in the presence of a diluent, g) for the preparation of those cycloalkanecarboxylic acid derivatives of the formula (Ia) in which R4 represents amino, α-amino-cycloalkanecarboxylic acid chlorides of the formula in which n has the meaning given above, with compounds of the formula R3H (x) in which R3 has the meaning given above, optionally in the presence of an acid binder and optionally in the presence of a diluent.