CS214799B2 - Means for regulation of the plant growth and method of making the active substances - Google Patents

Description

BACKGROUND OF THE INVENTION The present invention relates to a plant growth regulating composition comprising, as an active ingredient, partially known cycloalkanecarboxylic acid derivatives. The invention further relates to a process for the preparation of these active substances.

It is already known that (2-chloroethyl) trimethylammonium chloride has the ability to control plant growth (cf. U.S. Pat. No. 3,156,554 J. However, the efficacy of this substance is not always sufficient, especially at low application rates.

Furthermore, it is known that a product based on fatty alcohols having 6, 8, 10 and 12 carbon atoms, marketed under the designation "Off-Shoot-T" ^(R) , can be used to control plant growth, in particular to inhibit growth side shoots in tobacco (cf. Farm. Chem, Handbook 1975, Meister Publishing Co., Willoughby, Ohio, 1975, Pesticide Dictionary D 147). In many cases, especially at low rates of application, the efficacy of this product is also insufficient.

It is also known that 2-chloroethylphosphonic acid can be used as a plant growth regulator (cf. DOS 2,050,245). However, its effect is not entirely sufficient at low application rates.

It has now been found that the partially known cycloalkanecarboxylic acid derivatives of formula I,

in which it means

R is hydroxy, C 1 -C 8 alkoxy, benzyloxy, amino, methylamino, C 1 -C 3 dialkylamino in each of the alkyl groups, or a radical of formula (0-6), wherein:

M6 is an alkali metal ion or calcium ion equivalent, an ammonium group or a trialkylammonium group having 1 to 2 carbon atoms in each of the alkyl groups,

R @ ^{1 is} amino or the radical —NH — C — R @ ² ,

AND!

where

R ² is hydrogen, methyl or phenyl, and R ^{1 is} —N HH3X ©, wherein:

Znamenáθ stands for chloride, bromide or iodide ion, and n number 1 or 2 is very well suited for regulating plant growth.

The present invention relates to a plant growth regulating agent, characterized in that it contains at least one cycloalkanecarboxylic acid derivative of the formula I as active ingredient.

Surprisingly, the cycloalkanecarboxylic acid derivatives of formula (I) used according to the invention exhibit a significantly higher potency in controlling the growth of plants than the known substances, ie (2-chloroethyl) trimethylammonium chloride, Off-Shoot-T ^{, R)} and 2-chloroethylphosphonic acid, which are highly active substances of the same type of action. Thus, the active compounds useful according to the invention represent a valuable enrichment of the prior art.

The cycloalkanecarboxylic acid derivatives useful herein are generally defined by Formula I. In this formula, the general symbols have the following preferred meanings:

R is hydroxy, C 1 -C 8 alkoxy, benzyloxy, amino, methylamino, C 1 -C 2 dialkylamino in each of the alkyl radicals or a radical

PřičemžθΜ ©, where

M © represents a sodium or potassium ion, a calcium ion equivalent, an ammonium group or a trialkylammonium group having in each case 1 or 2 carbon atoms in the alkyl radical,

R ¹ is amino, formylamino, acetylamino, benzoylamino or NH 3 C 1-6 is 1 or 2.

Examples of compounds of formula I include:

α-aminocyclopropanecarboxylic acid, α-formylaminocyclopropanecarboxylic acid, α-acetylaminocyclopropanecarboxylic acid, α-acetylaminocyclopropanecarboxylic acid, α-acetylaminocyclopropanecarboxylic acid, α-acetylaminocyclopropanecarboxylic acid, α-formylaminocyclobutanecarboxylic acid, α-acetylaminocarboxylic acid , trimethylammonium, triethylammonium salts, their methyl, ethyl and benzyl esters as well as their amide, methylamide, dimethylamide and diethylamide;

methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, octyl ester, benzyl ester of α-aminocyclopropanecarboxylic acid and α-aminocyclobutanecarboxylic acid, and α-aminocyclopropanecarboxylic acid hydrochloride and α-aminocarboxylic acid hydrochloride.

Compounds of formula I are partially known compounds (cf. Liebigs Ann. Chem., 1973, 611-618; Chem. Ber. 108 [1975], 1580-1922; J. Chem. Soc. 1960, 2119-2132 and 1962, 3977-7). 3980],

The individual compounds useful herein are novel. These novel compounds are characterized by the general formula Ia,

in which

R ³ is C 1 -C 8 alkoxy, benzyloxy, amino, methylamino, C 1 -C 3 dialkylamino, carbon in each alkyl group or a radical of formula

ΟθΜ © in which

M6 is an alkali metal ion or calcium ion equivalent, an ammonium group or a trialkylammonium group having 1 to 2 carbon atoms in each of the alkyl groups,

R ⁴ represents an amino group or a radical of formula -NH-C-R ⁵ ,

About where

R ⁵ is hydrogen when R ^{3 is} not ethoxy, furthermore is methyl, if R ^{3 is} not methoxy, and in addition is phenyl, or

R ⁴ represents a radical -N © © H3x wherein

ΧΘ denotes an iodide ion, a bromide ion, and if R ^{3 is} not an ethoxy group, it also means a chloride ion, and n is 1 or 2.

New substances can be produced by several processes.

According to the invention, cycloalkanecarboxylic acid derivatives of formula (Ia) in which R ^{@ 4} is a formylamino group are obtained by obtaining the .alpha.-isocyanocycloalkanecarboxylic acid derivatives of formula (II);

un in which

R ⁶ is C 1 -C 8 alkoxy except ethoxy, benzyloxy, amino, methylamino, C 1 -C 3 dialkylamino or the remainder of the formula

0 © M © where

M 2 is an alkali metal ion or calcium ion equivalent, an ammonium group, or a C 1 -C 2 trialkylammonium group, and n is as defined above, hydrolyzed with water optionally in the presence of a catalyst and optionally in the presence of an additional diluent.

The process according to the invention will hereinafter be referred to as process a).

In addition to this process, the compounds of formula (Ia) can be prepared by the production of:

(b) those cycloalkanecarboxylic acid derivatives of formula (Ia) in which R ^{@ 4 is} formylamino and R @ ³ is OM, where M is an alkali metal ion by obtaining the .alpha.-isocyanocycloalkanecarboxylic acid derivatives of the general formula:

^of 9 * in which

R ⁷ is an alkyl group and n is as defined above, and under gentle conditions, optionally in the presence of an additional diluent, reacts with alkali metal hydroxides and the resulting α-isocyanocarboxylic acid salts of formula IV,

(IV) in which:

M 'is an alkali metal ion, as defined above, hydrolyzed by boiling with an aqueous alcohol, including those cycloalkanecarboxylic acid derivatives of formula (Ia) wherein R ^{4 is} formylamino and R ³ is OM, where M is the abovementioned radicals, but is not an alkali metal ion, obtained by the process according to process b) of obtainable salts of α-formylaminocycloalkanecarboxylic acid of the general formula Ib, ¹ NH-CHO c-qm 'in which:

M ‘and n are as defined above, optionally reacting in the presence of a diluent with an equivalent amount of a strong acid and the resulting α-formylaminocycloalkanecarboxylic acids of the formula Ic,

wherein n is as defined above, are reacted with compounds of formula V,

M 'OR ⁸ , (V) wherein

M 'calcium ion equivalent, ammonium, C1-C2 trialkylammonium,

R ^{8 is} hydrogen, methyl or ethyl, optionally in the presence of a diluent;

(d) those cycloalkanecarboxylic acid derivatives of formula (Ia) in which R ^{@ 4 is} formylamino and R ^{@ 3 is} amino, methylamino or C1 -C3 dialkylamino, obtained by obtaining, according to process b), the α-isocyanocarboxylic acid salts obtainable by the formula IV, u

\ ' ^r 0' = (IV) in which

M ‘and n are as defined above, reacted with compounds of formula VI,

R ⁹

Η — N,

R10 (VI) wherein _{R9 and R10 are SO2 the} same or different from each other and are hydrogen or an alkyl group, in the presence of hydrochloric acid and optionally in the presence of a diluent, or

e) those compounds of formula Ia wherein R ³ is alkoxy having 1 to 8 carbon atoms or benzyloxy, and R ⁴ the radical -Ν © Η3ΧΘ wherein X © represents iodide, bromide, and when R ³ is not an ethoxy group, also a chloride ion, in that, according to process a), the α-formylaminocycloalkanecarboxylic acid derivatives of the formula Id, (CH 1 NH-CHO) obtainable

O (Id) in which

R ¹¹ represents an alkyl group or an aralkyl group, as defined above, reacted with compounds of formula VII,

H © X ©, (I know in which

X © is as defined above, optionally in the presence of a diluent, or is present

(f) those cycloalkanecarboxylic acid derivatives of formula (Ia) in which R ^{@ 4} is —NH — CO — R ^{@ 5} are obtained by obtaining the .alpha.-aminocycloalkanecarboxylic acid derivatives of formula (Ie);

O f / c) in which

R ^{3 and} n have the abovementioned meaning, are reacted with acylating agents of general formula VIII

O

II

R12-C-Y, (VIII) wherein is

R ^{12 is} hydrogen, alkyl or aryl, and

Y is chlorine or a residue of -O-CO-R ¹² in which R ¹² is as defined above in the presence of an acid binding agent and optionally in the presence of a diluent;

g) those cycloalkanecarboxylic acid derivatives of general formula Ia, wherein R ⁴ represents an amino group obtained by chlorides and acid-aminocykloalkankarboxylové Formula IX ic _{HI) n}

NHi> Cl

II o (IX) wherein n is as defined above, is reacted with compounds of formula X,

R ³ H, (X) wherein

R ³ has the meaning given above, optionally in the presence of an acid acceptor and optionally in the presence of a diluent.

Preferred novel cycloalkanecarboxylic acid derivatives are those compounds of formula (Ia) wherein

R ³ is C 1 -C 8 alkoxy, benzyloxy, amino, methylamino, C 1 -C 3 dialkylamino, in particular 1 or 2 carbon atoms in each of the alkyl radicals, or is a radical of formula

0 © M ©, where

M © represents sodium or potassium ion, calcium ion equivalent, ammonium, trialkylammonium having 1 or 2 carbon atoms in each alkyl radical,

R ⁴ represents an amino group or a radical of formula -NH-C-R ⁵ ,

II o

in which

R ⁵ is hydrogen if R ^{3 is} not ethoxy, hereinafter. is methyl, but is not methyl when R ³ is methoxy, and R ⁵ is additionally phenyl,

R < ^{4 &gt}; is furthermore a group -NNH3Cl, unless R < ³ > is ethoxy.

If, for example, the process according to the invention uses [process α] α-iso214799 methyl ester of cyanocyclopropanecarboxylic acid and aqueous-alcoholic hydrochloric acid, process process b) α-isocyanocyclopropanecarboxylic acid methyl ester and sodium hydroxide in ethanol, process c) in the first step sodium salt α-formylaminocyclopropanecarboxylic acid and concentrated hydrochloric acid and, in the second step, an aqueous alcoholic calcium hydroxide solution, in process d) sodium isocyanocyclopropanecarboxylic acid and concentrated ammonia in combination with concentrated hydrochloric acid, process e) α-formylaminocyclopropanecarboxylic acid methyl ester, hydrochloride, in process f) α-aminocyclopropanecarboxylic acid and benzyloxy chloride and in process g) .alpha.-aminocyclopropanecarboxylic acid chloride and diethylamine as reactants, then the reactions according to processes a) to g) may be illustrated. The following reaction schemes are used:

and)

>

.NH-CHO

CO 'CH ^ li ^J

O

(b)

NH-CHO

HCl

NH-CHO

<3, © '

C-O N- ^H 1 °

II o

C 6 - (OH) ₈

C _Z H _S OH

(d)

NC

NH 3 HCl 3

Θ ® H, 0

C-0 Na.

II

NHCHO

C-NH, n ^&

O

θ)

NH-CHO

COCHx n ³ O ©

The α-isocyanocycloalkacarboxylic acid derivatives used as starting materials in processes a) and b) according to the invention are generally defined by formulas II and III. In formula II, R @ ⁶ preferably denotes alkoxy having 1 or 3 to 8 carbon atoms, benzyloxy, amino, methylamino, dialkylamino having 1 to 3, in particular 1 or 2, carbon atoms in each of the alkyl radicals, or is O? M®, wherein M M is a sodium or potassium cation or a calcium ion equivalent, an ammonium group, a trialkylammonium group having 1 or 2 carbon atoms in each of the alkyl radicals. R ⁷ in formula III is preferably an alkyl group having 1 to 13 carbon atoms, in particular a methyl or ethyl group. In formulas II and III, n is preferably 1 or 2.

The .alpha.-isocyanocycloalkanecarboxylic acid derivatives of formulas II and III are already known or can be prepared in principle by known methods (cf. DOS 2,063,502; Angew. Chem. 83, [1971], 357-358; Chem. Ber. 108 [1975] , 1580-1592, and Liebigs Ann. Chem. 1973, 611-618).

The compounds used as reactants in processes c) to g) according to the invention are generally defined by formulas V, VI, VII, VIII and X. In formula V, M 'is preferably those already mentioned in the description of α-isocyanocycloalkanecarboxylic acid derivatives The acids of formula II are preferred for the symbol M, but are not sodium and potassium. In formula VI, R ⁹ and R ^{10 are} independently hydrogen and C 1 -C 4 alkyl, especially C 1 or C 2. In formula VII, X is preferably chlorine. In formula VIII, R ^{12 is} preferably hydrogen, C 1 -C 4 alkyl or phenyl. In Formula X, R @ ³ preferably represents those radicals which have already been in connection with the description of compounds of the formula I mentioned as preferred for the symbol R ³ Compounds of formulas V, VI, VII, VIII and X are known.

The α-aminocycloalkanecarboxylic acid derivatives used as starting materials in process f) of the invention are generally defined by the formula Ie. In this formula, R @ ^{3 is} preferably those already mentioned in the description of the compounds of the formula Ia according to the invention as being preferred for R @ ³ . The compounds of formula (Ie) can be prepared by the process g1 according to the invention.

The α-aminocycloalkanecarboxylic acid chlorides used as starting materials in process (g) of the invention are defined by formula IX. The compounds of formula IX have not been known so far, but can be prepared by converting the corresponding acids into acid chlorides according to conventional methods, for example by treatment with thionyl chloride. The necessary α-aminocycloalkanecarboxylic acids underlying the compounds of formula IX are known or can be prepared according to known me214799 tod (cf. J. Org. Chem. 29 [1964], 2764-2766; Synthesis 1978, 46; J. Chem. Soc., 1960, 2119-2132 and 1962, 3977-3980).

Process (a) is generally carried out in an aqueous solution or in a diluent containing water and an organic solvent such as an alcohol, dioxane or tetrahydrofuran. The reaction can be carried out under acid catalysis, for example with hydrochloric acid as catalyst. The reaction temperature can be varied within a wide range. In general, the reaction is carried out at temperatures between 0 and 100 [deg.] C., using a catalyst preferably at 10 to 40 [deg.] C., otherwise preferably at 60 to 90 [deg.].

The isolation of the reaction products in process a) is carried out according to the usual methods:

Extraction is carried out with a solvent which is not miscible with water, for example methylene chloride, the organic phase is dried, filtered and the solvent is distilled off in vacuo. The remaining crude products can be purified by distillation or optionally by recrystallization.

Process b) is generally carried out using one or more organic solvents. Suitable such as in particular: ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methylisopropyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, and alcohols such as methanol, ethanol and propanol. The reaction is generally carried out at temperatures between 0 and 100 ° C, in the first reaction step preferably at 5 to 25 ° C, in the second step preferably at 25 to 90 ° C.

The process can be carried out in 2 isolated reaction steps or in a single step. Generally, the N -isocyanoeylloalkanecarboxylic acid derivative used as the starting material is dispersed in one of the solvents mentioned and an alcoholic alkali metal hydroxide solution containing 1 to 1.2 moles of hydroxide per mole of carboxylic acid derivative is added. Initially formed α-isocyanocycloalkanecarboxylic acid salts crystallize generally with prolonged stirring and can be isolated by filtration. Further conversion of these intermediate products is generally carried out by boiling with an aqueous alcohol containing 1 to 1.2 moles of water per 1 mol of α-isocyanocycloalkanecarboxylic acid salt. The work-up is carried out, for example, by adding ether to the cooled reaction mixture and filtering out the salt of N -ormylaminocycloalkanecarboxylic acid, which crystallizes therein.

To carry out process c), the commonly used α-formylaminocycloalkanecarboxylic acid salts are dissolved in water and an equimolar amount of concentrated hydrochloric acid is added. The reaction is carried out at temperatures between 0 and 30 ° C. Products which crystallize after prolonged standing of the reaction mixtures can be isolated by filtration. In carrying out the second step of process (c), it abolishes generally alcohol, in particular methanol or ethanol, as a solvent. For 1 mole of α-formylaminocycloalkanecarboxylic acid, 1 mole of base V is used. The reaction is carried out at temperatures between 10 and 40 ° C. After briefly stirring the reaction mixture, the solvent was distilled off in vacuo, the residue was triturated with ether, filtered off and dried.

In general, up to 3 moles of ammonia or an amine of the formula VI and 1 mol of hydrochloric acid per mole of the N -isocyanocycloalkanecarboxylic acid derivative are used for carrying out process d). This reaction is generally carried out using water as solvent at temperatures between 0 and 40 ° C. After stirring the reaction mixture for several hours, the volatiles and solvent were distilled off in vacuo. The remaining crude product is worked up by conventional methods, for example extraction with methylene chloride, drying by filtration and concentration of the filtrate.

Process e) is usually carried out using aqueous hydrochloric acid as the reaction medium. In general, α-formyl-aminocycloalkanecarboxylic acid derivatives used as starting materials are stirred for several days at room temperature or heated to reflux for several hours. The reaction mixture is then evaporated to dryness in vacuo and the remaining crystalline products are dried over phosphorus pentoxide in a desiccator.

In process f1, generally water is used as the solvent. 1 to 1.2 moles of acylating agent and 2 to 2.5 moles of acid binding agent are used per mole of α-aminocycloalkane carboxylic acid derivative. Preferred acylating agents are: acetic anhydride, acetyl chloride, propionic anhydride, propionyl chloride and benzoyl chloride.

Preferred acid binding agents are: alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or alkali metal carbonates and acidic carbonates such as sodium carbonate and sodium bicarbonate.

The reaction in process f) is carried out at temperatures between 10 and 40 ° C. After briefly stirring the reaction mixture, the pH is adjusted to 1 by addition of a strong acid such as hydrochloric acid. The crystalline precipitated reaction products can be isolated by filtration and purified by recrystallization.

Water and inert organic solvents are suitable as process diluents according to the invention. In many cases, however, an excess of the reactant X used may also serve as a diluent.

Suitable acid binding agents in process g) according to the invention are all customary acid-binding agents. Suitably, however, the excess reactant X used serves as an acid-binding agent.

The reaction temperatures can be varied within a wide range in the process according to the invention. Generally, the operation is carried out at temperatures between 0 and 40 ° C, preferably between 10 and 25 ° C.

In carrying out process (g) according to the invention, about 1 to 2 moles of the compound of the formula (X) and optionally 1 mol of the acid-binding agent are used per mole of α-aminocycloalkanecarboxylic acid chloride of the formula IX. The work-up is carried out by conventional methods.

The active compounds useful according to the invention interfere with the metabolism of plants and can therefore be used as growth regulators.

For the type of effect of the plant growth regulators, it has been known to date that the active ingredient can have one or several different effects on plants. The effects of the substances depend essentially on the time of application, based on the developmental stage of the seed or plant, as well as on the amount of active substance applied to or in the vicinity of the plant and on the method of application. In any case, plant growth regulators are expected to positively influence the culture plants in the desired manner.

Plant growth regulators can be used, for example, to suppress vegetative plant growth. Such growth suppression is of economic importance, inter alia, in grassland, since the suppression of grass growth can, for example, reduce the frequency of mowing in ornamental gardens, parks and sports facilities or on the roadside. It is also important to suppress the growth of herbaceous and woody plants at roadside and close to overhead lines or, in general, where strong growth is undesirable.

It is also important to use plant growth regulators to suppress crop growth in cereals, as this will reduce or eliminate the risk of plants lying down before harvest due to crop shortening. In addition, plant growth regulators can cause the stalks to strengthen, which also counteracts lodging.

Suppression of vegetative growth allows for more dense sowing or planting of many crops, so that yields per area can be increased.

Another mechanism for increasing yield by growth inhibitors is that nutrients are used more intensively for the formation of flowers and fruits while reducing vegetative growth.

Stimulators of vegetative growth can also often be achieved with growth regulators. This is of great importance when vegetative parts of plants are harvested. However, stimulation of vegetative growth can also simultaneously lead to stimulation of generative growth so that, for example, more fruits can be formed or larger fruits can be produced.

In many cases, an increase in yield can also be achieved by interfering with the metabolism of the plants without observing vegetative changes _; growth. Growth regulators can also act on changes in the composition of plants to achieve better quality harvested products. For example, it is possible to increase the sugar content of sugar beet, cane, pineapple as well as citrus fruits or to increase the protein content of soybeans or cereals.

Under the influence of growth regulators, the development of parthenocarpic fruits (fruits without seeds) can occur, and the sex of the flowers can be influenced by these regulators.

The growth regulators can also positively influence the production or efflux of secondary plant substances. An example is the stimulation of latex outflow in rubber trees.

During plant growth, the number of side shoots can be increased by the use of growth regulators due to chemical violation of apical dominance. This is important, for example, for the propagation of plants by rootstocks. However, it is also possible to suppress the growth of the side shoots, for example in tobacco, where, after decapitation, the development of the side shoots is prevented and thus the growth of the leaves is promoted.

The influence of plant growth regulators on plant foliage can be controlled so that plants can be completely de-leafed at the desired point in time. Such defoliation is important for facilitating mechanical harvesting, for example in wine or cotton, or for reducing transpiration during the period when plants are to be transplanted.

Due to growth regulators, premature fruit loss can be prevented. However, it is also possible to encourage fruit dropping, for example in the case of fruit, in the sense of a kind of "chemical thinning" to some extent. Growth regulators can also be used to reduce the force required at harvest time to tear off fruits in crop plants, so that mechanical harvesting or manual harvesting is facilitated.

By means of growth regulators, it is furthermore possible to accelerate or slow down the ripening of the harvested products before or after harvesting. This is particularly advantageous since it can be optimally adapted to market requirements. Furthermore, growth regulators can in many cases serve to improve the coloring of the fruit. In addition, growth regulators can achieve a concentration of fruit ripening within a certain period of time. This creates the prerequisites for, for example, tobacco, tomatoes or coffee plants to be able to carry out fully mechanical or manual harvesting in only one working stage.

The use of growth regulators can also affect seed or bud rest periods, i.e. endogenous annual rhythm, so that plants, such as pineapple or ornamental plants in horticulture, germinate, sprout or bloom when they would not germinate, sprout or sprout under normal conditions. . nekvetly.

Growth regulators can also be used to delay bud sprouting or delayed seed germination, for example to reduce late frost damage in colder climates.

Halophilia can also be achieved in crop plants with growth regulators. This creates the preconditions for growing plants on soils containing salts.

Growth regulators can also provide higher resistance to frost and drought in plants.

The active substances can be converted into the customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, concentrates based on suspensions and emulsions, seed dressing powders, natural and active-impregnated synthetic substances, small particles coated with polymeric substances and seed coatings, as well as formulations of active substance diffusers for cold or hot mist dispersion.

These compositions are prepared in a known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. . If water is used as a filler, it is also possible to use, for example, organic solvents as co-solvents. Basically suitable liquid solvents are: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane, or paraffins, for example 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 dimethylsulfoxide; and water. By liquefied gaseous fillers or carriers is meant those liquids which are gaseous at normal temperature and pressure, for example aerosol propellants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Suitable solid carriers for the preparation of granulates are crushed and fractionated natural stone materials such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells , corn sticks and tobacco stalks. Suitable emulsifiers and / or foaming agents are non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, fatty alcohol polyoxyethylene ethers, e.g.

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

In addition, these compositions may contain coloring agents such as inorganic pigments such as iron oxide, titanium dioxide and ferrocyanide / blue, and organic dyes such as alizarin dyes and metallic azo-phthalocyanine dyes as well as trace elements such as iron, manganese, boron, copper salts. , cobalt, molybdenum and zinc.

The concentrates generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight of active ingredient. .

The active compounds according to the invention can be present in the active compounds in admixture with other known active substances, such as fungicides, insecticides, acarcides and herbicides, as well as in mixtures with fertilizers and other growth regulators. ?

The active compounds can be applied either as such, in the form of concentrates, or from their ready-to-use forms, as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules. The application is carried out in the usual way, for example by watering, spraying, spreading, dusting, application in the form of foam, application in the form of vapors etc.

In addition, the active compounds can be applied by the ULV method (Ultra-Low-Volume), the plants or parts of plants can be coated with the active agent or the active compound itself or injected into the soil. Plant seeds can also be treated.

The amounts of active compounds used can be varied within wide limits. In general, between 0.01 and 50 kg, preferably between 0.05 and 10 kg, of active substance are used per hectare of soil surface.

For the period of use, the application of the growth regulators is carried out within a convenient period of time, the exact boundaries of which are governed by climatic and vegetative conditions.

The following examples illustrate the efficacy of the compounds of the invention as growth regulators without excluding the possibility of further use of these compounds as growth regulators.

2147 »9

Example A

Retarding the growth of side shoots in tobacco

Solvent:

parts by weight of dimethylformamide. Emulsifier:

1 part by weight of polyoxyethylene sorbitan monolaurate.

¹ To produce a suitable preparation of active mixing 1 part by weight of active ingredient of indicated amounts of solvent and emulsifier and the mixture was made up with water to the desired concentration.

Tobacco plants are grown in the greenhouse until the 7th leaf development stage. At this stage, the apical vegetation peaks are removed ^: plants and plants are sprayed with active agents until dew. After 3 weeks, the side shoots of the plants are cut off and weighed. The weight of the side shoots of the treated plants is compared to the weight of the side shoots of the untreated control plants. A value of 100% means complete suppression of the side shoots formation and 0 percent represents the growth of the side shoots corresponding to the condition of the control plants.

The active substances, the active substance concentrations and the results obtained are given in the following Table A.

TABLE A

Retarding the growth of side shoots in tobacco

Active substance Concentration of the active substance in% Growth inhibition. -___ side shoots in ° / o (control) "Off-Shoot-T" ^(R) (known) - 0 0.2 20

0.2 64 (2)

Example B

Barley growth inhibition

Solvent:

parts by weight of dimethylformamide. Emulsifier:

part by weight of polyoxyethylene sorbitan monolaurate.

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the mixture is made up to the desired concentration with water.

Barley plants are grown in a greenhouse up to two leaf stage. At this stage, the plants are sprayed with active agents until they are dew-dried. After 3 weeks, the increment of treated plants is compared to that of untreated control plants. 100% means no growth and 0% means growth corresponding to control plants.

Active substances, active substance concentrations and results are shown in the following Table B.

TABLE B

Suppression of barley growth Active substance

Active substance concentration in%

% Growth inhibition

0.05 y

-OH

0.05

(2)

21'47! Ϊί)

Example C

The inhibition of wheat growth

Solvent:

parts by weight of dimethylformamide. Emulsifier:

part by weight of polyoxyethylene sorbitan monolaurate. ___

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and emulsifier, and the mixture is made up to the desired concentration with water.

Wheat plants are grown in a greenhouse up to two leaf stage. In this . In this stage, the plants are sprayed with active agents until dripping. After 3 weeks, the increment of treated plants is compared to that of untreated control plants. 100% means no growth and 0 o / o means growth corresponding to control plants.

The active substances, active substance concentrations and results are shown in Table C.

Suppression of wheat growth Active substance

TABLE C

Concentration of the active substance in%

(3)

0.05

0.05 '45 »Example D

Soy growth inhibition

Solvent:

parts by weight of dimethylformamide. Emulsifier:

part by weight of polyoxyethylene sorbitan monolaurate.

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the mixture is made up to the desired concentration with water.

Soybean plants are grown in a greenhouse until fully developed. .assimi fasting sheet. At this stage, the plants are sprayed with the active ingredients until wet. After 3 weeks, the increment of treated plants is compared with that of untreated plants with that of untreated control plants. 100% means no growth and 0% means growth corresponding to control plants.

The active substances, active substance concentrations and results are given in Table D below.

Suppression of soybean growth

Active substance

TABLE D

Active substance concentration in

% Growth inhibition (control)

Cl — CH2 — CH2 — N (CH3) 3Cl (known)

0.05

0.05 (2)

* plants show dark green color

Example E

Speeding ripening of tomatoes

Solvent:

parts by weight of dimethylformamide. Emulsifier:

part by weight of polyoxyethylene sorbitan monolaurate.

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the mixture is made up to the desired concentration with water.

Tomatoes are grown in the greenhouse in the usual way until about 30% of the fruits are ripe. At this stage, the plants are sprayed until dripping with the active ingredients. After various time intervals, the number of ripe fruits per unit of experiment is determined and expressed as a percentage of the total number of units involved in the experiment. 100 o / _o means that all fruits are ripe.

The results of this test are shown in Table E below.

TABLE E

Active substance

Concentration of the active substance in% Fruit ripening in% after 4 days 7 days

(control) O OH 11 37 40 44 Cl — CH2 — CH2 — P \ OH (known) 0.1 46 57 79 _to NH-CHO 0.1 53 65 86

TO

C-OK o

(2)

Example F

Stimulation of ethylene biosynthesis

Solvent:

parts by weight of dimethylformamide. Emulsifier:

part by weight of polyoxyethylene sorbitan monolaurate.

To obtain a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the concentrate obtained is made up to the desired concentration with water.

Leaf segments of the same size are cut from the soybean leaves. A constant number of leaf segments is incubated for 1 hour in Petri dishes, which are filled with 10 ml of active ingredient or appropriate control solutions without active ingredients. The pieces of leaf are then placed in airtight containers together with 1 ml of the respective active agent or control solution. After hours, the ethylene that has accumulated in the containers is determined by conventional methods. The development of ethylene of the leaf segments treated with the active agent is compared to that of the ethylene of leaf pieces that have been treated with control solutions only.

The following table means:

no effect, + weak stimulation of ethylene biosynthesis, ++ moderate stimulation of ethylene biosynthesis, +++ strong stimulation of ethylene biosynthesis.

This assay is particularly useful to elucidate the ability of the compounds of the invention to control plant growth.

The plant hormone ethylene interferes with numerous processes in plant development. Increased ethylene biosynthesis as can be achieved with the compounds of the invention allows these processes to be controlled. Examples of particular commercial interest include: harvesting fruits, accelerating the ripening of fruits and leaves, inducing inflorescence, germination of seeds, thinning fruits, stimulating latex outflow, for example in a Hevea rubber tree, affecting sex and inhibiting growth, for example to prevent cereal lodging.

The substances and results are shown in Table F below.

TABLE F

Stimulation of ethylene biosynthesis active substance concentration of active substance in ° / o effect - (control)

Cl — CH2 — CH2 — N (CH3) 5 Cl (known)

NH-CHO

0.001

0,001 ++

(3J (5) (8) (9)

0.001

0.001

0.001

0.001 +++ ++ (12)

0.001

213 7 9> 9

(16)

0.001 + -h + CO-CH ² II ⁴

O and NH ₂ in \>

(17)

0.001 + -F + 'C ^_ OC ₅ H ^ u "(21)

0.001 +++ o

nh-cho

C ~ O N &.

II

O (26)

0.001 ++ ® Θ

NH 4 CP

C-OC.bis

0.001

(6) (6)

0.001

0.001 ++ +

2%

2 íW7’S! Gi

Ή active- substance.

the active ingredient in% effect

(18) (19) (22)

0.001

0.001

0.001

0.001 ++ +++ +++

O

NH-CC-CH

0,001 +++

C-OC, H

O

Examples illustrating a process for the preparation of active substances

JL fc

To 40 ml of water was gradually added at 20 ° C. 0.3 ml of concentrated hydrochloric acid and a solution of 5 g (0.04 mol) of α-isocyanocyclopropanecarboxylic acid methyl ester in 10 ml of methanol. The reaction mixture was stirred for 6 hours. It is then extracted twice with 50 ml of methylene chloride each time, the organic phase is dried over magnesium sulphate, filtered and the solvent is distilled off in vacuo. A colorless liquid remains, representing 4 g (70% of theory) of the .alpha.-formylaminocyclopropanecarboxylic acid methyl ester. Refractive index n _D ²⁰ = 1.4730.

Example 2

NH-CHO

ll σ

A solution of 3.1 g (0.55 mol) of potassium hydroxide in 50 ml of ethanol is added dropwise at 5 DEG C. to a solution of 7 g (0.05 mol) of ethyl .alpha.-isocyanocyclopropanecarboxylic acid ethyl ester in 100 ml of ether. The mixture was stirred at 20 ° C for 12 hours. After filtration and washing with ether, it is obtained in the form of a white powder

6.4 g (86% of theory) of potassium isocyanocyclopropaucarboxylic acid salt. Melting point 225 ° C.

To a suspension of 9 g (0.06 mol) of the potassium salt of α-isocyanocyclopropanecarboxylic acid in 50 ml of ethanol is added 1.18 g (0.066 mol) of water. After cooling, 50 ml of ether are added at 20 DEG C. After filtration, 7 g are obtained; (70%: theory) .alpha.-formylaniinoeyl-lopropanecarboxylic acid, potassium, white crystals. Melting point. 186 ° C ·

of white powder, 2.6 g (97% of theory) of or-formylaminocyclopropanecarboxylic acid calcium salt. Melting point 290 ° C.

Example 1 a d 6

8.36 g (0.05 mol) of the potassium salt of α-formylaminocyclopropanecarboxylic acid are dissolved in 20 ml of water and 5 g (0.05 mol) of concentrated hydrochloric acid are added at 0 ^° C. The mixture was left overnight at 5 ° C. After filtration and drying, 5.2 g (80% of theory) of t-formylaminocyclopropanecarboxylic acid are obtained in the form of colorless crystals. Melting point 189 ° C.

Example 4

IX,

OOH

NH-CHO

C-MICHjJj.

O

To a solution of 6.7 g (0.15 mol) of dimethylamine in 50 ml of water was added at 20 ° C with stirring 7.46 g (0.05 mol) of the potassium salt of isocyanocyclopropanecarboxylic acid. After cooling to 5 °, 5 g (0.05 mol) of concentrated hydrochloric acid are added to the reaction mixture and the reaction mixture is left at 20 ° C in a closed reaction vessel for 12 hours. At a bath temperature of 60 ° C, volatile components are distilled off in a water pump vacuum. The residue was extracted with methylene chloride. The resulting solution was dried over magnesium sulfate and, after filtration, the solvent was distilled off in vacuo. 5.5 g (70 o / o) of .alpha.,. Beta.-dimethylamide and .alpha.-formylaminocyclopropanecarboxylic acid remain as a pale yellow liquid. Refractive index n _D ²⁰ = 1.4350.

Example 5

A mixture consisting of 19.4 g (0.15 mol) of α-formylaminocyclopropanecarboxylic acid and 200 ml of 18% hydrochloric acid was heated under reflux for 3 hours. The reaction mixture is then evaporated to dryness in vacuo and the residual solid is dried over phosphorus pentoxide in a vacuum desiccator. Yield: 18 g (92% of theory) of .alpha.-aminocyclopropanecarboxylic acid hydrochloride. Mp 232 ° C. Example 7

NH-CHO

Θ

C-0 o J

Cl ·

Θ ©

To a mixture consisting of 2 g (0.02 mol) of α-aminocyclopropanecarboxylic acid, 25 ml of water and 2.55 g (0.044 mol) of potassium hydroxide was added with stirring at 20 ° C 3.1 g (0.022 mol) of benzoyl chloride. After stirring for 30 minutes, the reaction mixture was acidified to pH 1 with concentrated hydrochloric acid and filtered. For purification, the product is boiled with 30 ml of water. Yield: 2.1 g (51% of theory) of .alpha.-benzoylamino-cyclopropanecarboxylic acid. Mp 209 ° C.

In an analogous manner to that described in Examples 1 to 7, the compounds of formula I shown in the following table can be prepared:

To a mixture of 2.5 g (0.02 mol) of oro-my-lamino cyclopropanecarboxylic acid and 40 ml of ethanol is added 0.74 g (0.01 mol) of calcium hydroxide with stirring at 25 ° C and then the reaction mixture is stirred 12 hours at room temperature. The solution was then evaporated in vacuo and the residue triturated with ether. After filtration and drying, it is in the mold

LX 'tl

Claims (2)

Composition for controlling plant growth, characterized in that it contains at least one cycloalkanecarboxylic acid derivative of the formula I as an active ingredient, in which: R is hydroxy, C 1 -C 8 alkoxy, benzyloxy, amino, methylamino, C 1 -C 3 dialkylamino in each alkyl group, or is a radical of formula 0 © M © where M6 is an alkali metal ion or calcium ion equivalent, an ammonium group or a trialkylammonium group having 1 to 2 carbon atoms in each of the alkyl groups, R ¹ is amino or a group -NH-R ² C About where R ² is hydrogen, methyl or phenyl, and R ^{1 is} —N HH3X ©, wherein: X6 is a chloride, bromide or iodide ion, and n is 1 or 2. 2. A process for the preparation of the active compounds according to the general formula Ia, in which R ³ is C 1 -C 8 alkoxy, benzyloxy, amino, methylamino, C 1 -C 3 dialkylamino or the remainder of the formula 0 © M © in which M © means an alkali metal ion or calcium ion equivalent, an ammonium group, a trialkyl ammonium group having 1 to 2 carbon atoms in alkyls, R a is a formylamino group ^{and n} is 1 or 2, characterized by 214793, wherein the α-isocyanocycloalkanecarboxylic acid derivatives of formula (II) wherein: R ⁶ is C 1 -C 8 alkoxy except ethoxy, benzyloxy, amino, methylamino34, C 1 -C 3 dialkylamino, or a radical of formula 0®M® where M ® is an alkali metal ion or calcium ion equivalent, ammonium or C 1 -C 2 trialkylammonium, and n is as defined above, hydrolyzed with water, optionally in the presence of a catalyst and optionally in the presence of an additional diluent.