DE2448057A1 - Plant growth regulant 5-hydroxy-dibenzo(a,d)cycloheptene derivs. - for example 10,11-dihydro-5-methyl-5-hydroxy-dibenzo(a,d)cycloheptene - Google Patents

Abstract

Agents for regulating plant growth contain >=1 5-hydroxy -dibenzo a,d -cycloheptene deriv of formula (I) (when X is -CH=CH- or -CH2-CH2- and R is alkyl alkoxycarbonyl or opt. substd. aryl). Effects which can be achieved include inhibition of vegetative growth inhibition of axial growth of cereals, improvement of crop yields by diverting nutrients from vegetative growth to fruit or seed production or by permitting denser planting, and improvement of the quality of crops.

Description

Agent for regulating plant growth The present invention relates to the use of some known 5-hydroxy Ea, fld -dibenzocycloheptene derivatives as active ingredients to regulate plant growth.

It is already known that certain 5-hydroxy-Ca -dibenzocycloheptene derivatives as starting materials for the preparation of compounds with antifungal respectively Let fungicidal effectiveness be used (see German Offenlegungsschriften 1 811 654, 2,009,020 and 2,053,080 and U.S. Patent 3,406,186).

Furthermore, it has already become known that certain 2-Halogenäthyltrialkylammonium-halide have plant growth-regulating properties (cf. US Pat. No. 3,156,544).

For example, with the help of (2-chloroethyl) = trimethylammonium chloride influencing plant growth in cereals and other crops achieve (cf.

U.S. Patents 3,318,910, 3,280,136, 3,264,317 and 3,270,027). The effect of this substance is, however, especially at low application rates and -concentrations, not always entirely satisfactory.

It has been found that the partially known 5-hydroxy-Ea, d3 -dibenzocycloheptene derivatives of the formula in which X stands for the -CH = CH- or -CH2-CH2- group and R stands for alkyl, alkoxycarbonyl or optionally substituted aryl, have strong plant growth-regulating properties.

Surprisingly, the 5-hydroxy-Ea, d -dibenzocycloheptene derivatives according to the invention show a higher plant growth regulating effect than that from the prior art known (2-chloroethyl) trimethyl ammonium chloride, which is recognized as being effective Substance of the same type of effect.

The substances that can be used according to the invention are therefore valuable ones Enrichment of technology.

The 5-hydroxy-Ca, d] -dibenzocycloheptene derivatives to be used according to the invention are clearly defined by the formula (I).

In the formula (I), R is preferably straight-chain or branched Alkyl with 1 to 4 carbon atoms, for alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, and also for optionally substituted aryl with 6 to 10, in particular with 6 carbon atoms. The aryl radical can be one or more, preferably 1 to 3, in particular 1 or 2, carry identical or different substituents. As a substituent The following are preferred: straight-chain or branched alkyl having 1 to 4 carbon atoms; Halogen, especially chlorine and bromine; Haloalkyl with 1 or 2 Carbon atoms and 2 to 5 halogen atoms, the halogen atoms being in particular Fluorine and / or chlorine, trifluoromethyl may be mentioned specifically.

Examples of the active ingredients which can be used according to the invention are specifically mentioned: 5-ethyl-5-hydroxy- [a, d] -dibenzocycloheptene, 5-t-butyloxycarbonyl-5-hydroxy- [a, d] -dibenzocycloheptene, 5-phenyl-5-hydroxy-Ca, dS-dibenzocycloheptene, 5- (2-chlorophenyl) -5-hydroxy-Ca, -dibenzocycloheptene, 5- (4-bromophenyl) -5-hydroxy- [a, d] -dibenzocycloheptene, 5- (3-ethylphenyl) -5-hydroxy- [a, d] -dibenzocycloheptene, 5- (2,4-dimethylphenyl) -5-hydroxy- [a, d] -dibenzocycloheptene, 5- (2-chloro-3-methylphenyl) -5-hydroxy- [a, d] -dibenzocycloheptene, 5- (4-trifluoromethylphenyl) -5-hydroxy- [a, d] -dibenzocycloheptene, 10,11-dihydro-5-ethyl-5-hydroxy- [a, d] -dibenzocycloheptene, lO, ll-dihydro-5-t. -butyloxycarbonyl-5-hydroxy- Ca, d -dibenzocyclohepten, 10, ll-dihydro-5-phenyl-5-hydroxy- Ca, d3 -dibenzocyclohepten, 10, ll-dihydro-5- (2-chlorophenyl) -5-hydroxy- Ca, d7 -dibenzocyclohepten, 10,11-dihydro-5- (4-bromophenyl) -5-hydroxy- [a, d] -dibenzocycloheptene, 10,11-dihydro-5- (3-ethylphenyl) -5-hydroxy- [a, d] - dibenzocyclohepten, 10,11-dihydro-5- (2,4-dimethylphenyl) -5-hydroxy- [a, d] -dibenzocycloheptene, 10, ll-dihydro-5- (2-chloro-3-methylphenyl) -5-hydroxy- i dibenzocycloheptene, 10,11-dihydro-5- (4-trifluoromethylphenyl) -5-hydroxy- [a, d] -dibenzocycloheptene.

Some of the substances that can be used according to the invention are known (cf. German Offenlegungsschrift 1,811,654, 2,009,020 and 2,053,080, U.S. Patent 3 406 186 and Chem. Ber.

83, 367-371 (1950) and Chem Ber. 84, 671-679 (1951))).

However, their use as plant growth regulators is new.

Some of the substances that can be used according to the invention are new; however, they can be produced in a simple manner by known processes. They are obtained if Ea, di -dibenzocyclohepten-5-ones of the formula in which X has the meaning given above, with organometallic compounds of the formula Me-R (III) in which R has the meaning given above and Me is an alkali metal or the radical Y-Mg- in which Y is chlorine, bromine or Iodine is reacted in the presence of an inert solvent (see preparation examples).

The compounds of the formula (II) to be used as starting materials, the Ea, d-dibenzocyclohepten-5-one (dibenztropon, dibenzosuberenone) and the 10,11-dihydro- [1, d] -dibenzocyclohepten-5-one (Dibenzosuberone) are known (see US patent specification 3 406 186 also Chem. Ber. 84, 671-679 (1951) and J. Med. Chem 8 = 886 (1965)).

In the formula (III), Me preferably represents lithium, sodium and the so-called "Grignard group" Y-Mg, where Y stands for chlorine, bromine and iodine. The organometallic compounds of the formula (III) are generally known (a A summary and overview of numerous publications can be found e.g. beige. Coates, "Organo-Metallic Compounds", 2nd Edition, Methuen and Co., London (1960)).

Preferred solvents are used when carrying out the reaction anhydrous ethers such as diethyl ether, dibutyl ether and glycol dimethyl ether as well cyclic ethers such as tetrahydrofuran.

The reaction temperatures can be varied within a relatively wide range will. In general, the temperature is between -20.degree. C. and 100.degree. C., and the procedure is preferred one at the boiling point of the solvent.

When carrying out the process, 1 mole of a compound is used of the formula (II) about 1 to 2 mol of an organometallic compound of the formula (III) a. The compounds which can be used according to the invention are isolated in accordance with customary methods Methods. For example, you can carry out the work-up in such a way that you first the organometallic compounds present in the reaction mixture in known Hydrolyzed manner, then after optionally adding one with water beforehand The immiscible solvent separates the organic phase, shakes off with water and after drying it constricts. Those which can be used according to the invention are obtained Compounds of the formula (I) in the form of crystalline substances.

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 depend essentially on them from the time of application, based on the development stage of the seed or the plant as well as by those applied to the plants or their surroundings Amount of active ingredient and the type of application. In any case, you want growth regulators positively influence the crop plants in the desired manner.

Plant growth regulating substances can for example. for inhibition of vegetative plant growth can be used.

Such an inhibition of growth is economical in the case of grasses, among other things Interest, because by dampening grass growth, e.g. the frequency of Reduced grass cuttings in ornamental gardens, parks and sports facilities or at roadsides will. The inhibition of the growth of herbaceous and woody ones is also important Plants on roadsides and near overhead lines or in general in areas where heavy 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 kinking (storage) of the plants before harvest is reduced or completely eliminated.

In addition, growth regulators can strengthen the stalk in cereals cause, which also counteracts the storage.

Inhibition of vegetative growth is possible in many cultivated plants a denser planting of the culture, so that an increased yield based on the soil area can be achieved.

Another mechanism of increasing yield is based on growth inhibitors on the fact that the nutrients benefit to a greater extent the formation of flowers and fruits come 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. A promotion of vegetative growth can, however 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 Make growth noticeable.

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.

Under the influence of growth regulators it can lead to training parthenocarpic fruits come. The sex of the flowers can also be influenced will.

With growth regulators the production or the outflow can also be controlled positive influence of secondary plant substances.

An example is the stimulation of the latex flow in rubber trees called.

During the growth of the plant can through the use of growth regulators 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 Tobacco plants after capping to prevent the formation of side shoots and thus to 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.

Defoliation of this kind is of interest in order to avoid 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 fruit fall can be prevented by using growth regulators impede. However, it is also possible to prevent the fruit falling - for example in the case of fruit - in the sense of 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 delay the ripening 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 egg market. Furthermore, growth regulators can be used in 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 z. B. with tobacco, tomatoes or coffee, a complete mechanical or manual harvesting can be carried out in just one operation.

By using growth regulators, the seeds or Bud rest of the plants, so the endogenous annual rhythm can be influenced, see above that the plants, such as pineapples or ornamental plants in nurseries, at a time germinate, sprout or bloom when they are normally unwilling to do so demonstrate.

With growth regulators can also be achieved that the budding of buds or the germination of seeds is delayed, e.g. in frost-prone Areas of damage from late frosts. 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.

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

The active compounds according to the invention can be used in the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granulates. These are produced in a known manner, e.g. by mixing the active ingredients liquefied pressurized liquids with extenders, i.e. liquid solvents Gases and / or solid carriers, optionally using surface-active substances Means, that is, emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents, for example, can also be used can be used as co-solvents. The liquid solvents used are essentially in question: aromatics such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated Aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes and chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol as well as their ethers and esters, Ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, are strong polar solution medium, such as dimethylformamide and dimethyl sulfoxide, and water; with Liquefied gaseous extenders or carriers are such liquids meant which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane; as fixed Carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, Attapulgite, montmorillonite or diatomaceous earth, and powdered synthetic rocks such as highly disperse silica, aluminum oxide and silicates; as emulsifier: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol Ethers, e.g., alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, and aryl sulfonates; as dispersants: e.g. lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be mixed in the formulations with other known active ingredients, such as fungicides, insecticides, acaricides and herbicides, as well as mixed with fertilizers.

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

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, 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. It can also treat the seeds of the plants will.

The active ingredient concentrations can be varied over a wide range will. In general, concentrations of from 0.00005 to 2% are used, preferably from 0.0001 to 0.5 5 '.

In addition, 0.01 to 50 is generally used per hectare of soil area kg, preferably 0.05 to 10 kg of active ingredient.

For the application time, the use of the growth regulators applies is carried out in a preferred period of time, the exact definition of which is based on the climatic and vegetative conditions.

The substances according to the invention not only have very good growth-regulating properties Properties, but also have microbicidal, insecticidal, herbicidal, bactericidal and fungicidal effectiveness. Here is the fungicidal effectiveness especially against powdery mildew and, when used as a stain, against Helminthosporium directed.

In the following examples, the activity of the invention Substances presented as growth regulators without the possibility of further application to exclude as growth regulators.

Example A Influencing the growth of grass (Festuca pratensis) Solvent: 10 parts by weight of methanol emulsifier: 2 parts by weight of polyethylene 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.

3 to 4 cm high grass plants (Festuca pratensis) are mixed with the active compound preparations sprayed dripping wet. After 14 days, the increment is measured and the influence on the growth calculated in% of the growth of the control plants. 0 5 'means growth, which corresponds to that of the control plants. Positive values indicate one Promotion of growth compared to the control plants while negative values correspond accordingly indicate an inhibition of growth.

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

Table A Influencing the growth of grass (Festuca pratensis) Active ingredient active ingredient concentration growth effect tration in, 'in 96 of increment of the control plants (Control) O 0.02 + egg @ 3 0.02 + 5 0.05 + 10 HO (X) COOCH3 Example B Growth inhibition in cress seedlings Solvent: 10 parts by weight of methanol Emulsifier: 2 parts by weight of polyethylene sorbitan monolaurate To produce an active preparation, 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.

50 cress seeds are cut to a stiff, rectangular one Filter paper placed with a 0.02 show solution of the respective active ingredient preparation is soaked. The seeds adhere so tightly to the damp filter paper that they too do not fall while straightening the paper. The moist one laden with seeds Filter paper is placed vertically in a beaker (content: 250 ml), the 20 ml of the respective 0.02% active ingredient solution. The beaker comes with a Covered glass pane. After 4 days, the length of the seedlings is measured and the growth inhibition compared to the control plants is expressed in 96. It mean 100 96 indicate a standstill in growth and 0% a growth that corresponds to that of the control plants is equivalent to. The control plants are treated with distilled water that an amount of solvent and emulsifier corresponding to the active compound preparations contains.

Active ingredients, active ingredient concentrations and results are shown in Table B below: Table B Growth inhibition in cress seedlings Active ingredient Active ingredient growth remark concentration inhibition in in 96 5 'of the trolls - (control) O Cl-CH2-CH2-N (CH3) 3 C 5 (known) 0.02 0.02 21 none Geotro HO COOCH3 pism - (3) 0.02 0.02 11 HO Example C Growth inhibition in wheat Solvent: 10 parts by weight of methanol Emulsifier: 2 parts by weight of polyethylene sorbitan 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.

Young wheat plants 5-8 cm high are treated with the preparation of the active compound Sprayed dripping wet. After 14 days, the growth is measured and the inhibition of growth calculated in% of the growth of the control plants. 100% mean a standstill of growth and 0 96 a growth corresponding to that of the control plants.

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

Table C Inhibition of growth in wheat I. Active ingredient active ingredient growth inhibition centering I in 5 'of the control in% in - (control) 0.05 15 HO f) CH3 Preparation examples Example 1 In a solution of 104 g (0.5 mol) of dibenzosuberone in 250 ml of ether, a Grignard solution consisting of 14.4 g (0.6 mol) of magnesium in 250 ml of absolute ether and 85.2 g (0.6 Mole) methyl iodide, added dropwise. The mixture is stirred overnight and then a solution of 200 g of ammonium chloride in 800 ml of water is added.

The ethereal phase is separated off, washed with water and after concentrated before drying over sodium sulfate. The remaining one The residue is recrystallized from ligroin / ethyl acetate (1: 1), 66 g are obtained (60 96 of theory) on 10,11 -dihydro-5-methyl-5-hydroxy- Fa, -dibenzocyclohepten with a melting point of 140 ° C.

Example 2 In a mixture of 9.6 g (0.4 mol) of magnesium turnings in 250 ml of absolute ether, 90 g (0.4 mol) of m-trifluoromethylbromobenzene are added dropwise with stirring. After the magnesium has dissolved, the Grignard solution obtained in this way is added dropwise at -10 ° C. to a solution of 51.6 g (0.25 mol) of dibenztropone in 250 ml of ether. After the end of the dropwise addition, the reaction mixture is heated to boiling for 1 hour and then kept at room temperature overnight, with stirring. The reaction mixture is then poured onto ice and brought to a pH of 1 with dilute hydrochloric acid. The ethereal phase is separated off, washed with water and dried over sodium sulfate. After the solvent has been distilled off, 47 g (53% of theory) of 5-m-trifluoromethyl-5-hydroxyla, d-dibenzocyclohepten with a melting point of 134-136 ° C. are obtained.

Example 3 20.8 g (0.1 mol) of dibenzosuberone are added to a suspension of 4.6 g (0.2 mol) of finely cut sodium in 200 ml of glycol dimethyl ether. The suspension is then heated to the boil under a nitrogen atmosphere and with stirring until the sodium has dissolved. The reaction mixture is then allowed to cool and a solution of 10 g (0.1 mol) of dimethyl carbonate in 75 ml of ether is then added dropwise. To complete the reaction, stirring is continued overnight at room temperature. The reaction mixture is then carefully mixed with water. The organic phase is then separated off, washed with water and, after drying over sodium sulfate, concentrated. The remaining residue is recrystallized from ligroin / carbon tetrachloride. 17.5 g (64% of theory) of 10,11-dihydro-5-methoxycarbonyl-5-hydroxy- [a, d] -dibenzocycloheptene with a melting point of 136 ° C. are obtained of the compounds listed below in Table 1 obtained.

Table 1 At- Melting clearance XR point (° C) No.

4 -CH2-CH2 3-Cl-C6H4 134-136 5 -CH2-CH2 2-Cl-C6H4 136-137 6 -CH2 -CH2 4-Cl-C6H4 105-106 7 -CH = CH- 2-Cl-C6 H4 154-155 8 -CH = CH- 3-Cl-C6H4 155-157 9 -CH = CH- -C6H5 152-154

Claims (5)

Means for regulating plant growth, characterized by a content of at least one 5-hydroxy- [a, d] -dibenzocycloheptene derivative of the formula in which X stands for the -CH = CH- or -CH2-CH2 - group and R stands for alkyl, alkoxycarbonyl or optionally substituted aryl. 2) agents for inhibiting growth and influencing the habitus of higher plants, characterized in that there is at least one 5-hydroxy-C, di-dibenzo-cycloheptene derivative according to claim 1 contains. 3) method for regulating plant growth, characterized in that that 5-hydroxy- [a, d] -dibenzo-cycloheptene derivatives according to claim 1 on the plants or let their living space act. 4) Use of 5-hydroxy- [a, d] -dibenzo-cycloheptene derivatives according to Claim 1 for regulating plant growth. 5) process for the production of plant growth regulators, characterized in that 5-hydroxy- [a,] -dibenzo-cycloheptene derivatives according to Claim 1 mixed with extenders and / or surface-active agents.