DE3143720A1 - Acetylene compounds, their preparation, and their use as plant growth regulators - Google Patents

Abstract

The present invention relates to acetylene compounds of the formula <IMAGE> in which R<1> to R<10> have the meanings given in the description, to processes for their preparation, and to their use as plant growth regulators.

Description

Acetylene compounds, processes for their preparation and

their use for regulating plant growth The present The invention relates to acetylene compounds, processes for their preparation, these compounds containing plant growth regulating agents and their use for regulating of plant growth.

It is known that the phytohormone which occurs naturally in plants Abscissic acid (ABA) regulates various physiological processes in plants intervenes (Die Pharmazie 27, 619 (1972); B.V. Milborrow "Abscisic Acid" in "Phytohormones and Related Compounds -A Comprehensive Treatise Vol. I, pp. 295 ff, Editor: Letham Goodwin and Higgins, Elsevier 1978).

For example, ABA influences the dormancy of the seeds and buds and the ripening of the fruit and the abscission process of fruits and leaves. Is of particular importance the abscissic acid in the regulation of the plant water balance. So will E.g. in dry conditions due to increased biosynthesis the endogenous concentration of ABA increases in the leaves, this then leads to a closure of the gap opening of the leaves (stomata) and thus to a reduced water release of the plants via the stomata (decreased stomatal perspiration). In this way, the Counteract an inadequate water supply. However, enough the effect of the endogenous ABA at high stress does not always affect the plant to protect from damage by heat or drought.

Exogenously supplied ABA - e.g. by spraying the plants with solutions from ABA - leads to an increased closure of the stomata and thus to a considerable decreased perspiration. The treated plants are thereby much more resistant to heat and drought stress than untreated.

Treatment of crops with transpiration inhibitors would therefore be of great use in agricultural practice, since with such a treatment damage to the cultivated plants due to heat and drought stress, which lead to internal water shortage, to. Wilt, yield loss or even complete Can lead to death, let avoid. Such damage occurs in some agricultural growing areas, especially in arid areas, on a regular basis threatened by heat or drought is a major problem. There is an urgent need for means to reduce transpiration of crops.

Although ABA was applied exogenously due to its biological effect is suitable as a perspiration inhibitor for crop plants, it has not yet had any Found use in agricultural practice. The reason for this is in this to seek that adequate amounts of ABA are not with one in view of the desired agricultural objective provided reasonable technical effort can be. ABA occurs in plants only in very small amounts and is only to isolate from it with very considerable effort. On the other hand, the well-known Total syntheses of abscissic acid [s. e.g .: J.W. Vornforth et al., J. Chem. Soc. C, 1968, 1565; D.L. Roberts et al., J. Org. Chem. 33, 3566 (1968); T.

Oritani et al., Agric. Biol. (Chem. (Tokyo) 34, 108 (1970); J. A. Findlay et al., Can. J. Chem. 49, 2369 (1971); H.J. Mayer et al., Helv. Chim. Acta 59, 1424 (1976); F. Kienzle et al., Helv. Chim. Acta 61, 2616 (1978)] so difficult and require such a high technical and economic effort that they are used to Manufacture of agents for regulating plant growth, in particular for Manufacture of means for regulating the transpiration of crops, no be considered.

It has now been found that acetylene compounds of the formula in which R1 stands for hydrogen or the radical -0R2 and R2 stands for alkyl with 1 to 6 carbon atoms or in which stands for the radical -0R11 and R11 together with R2 is a methylene chain of the formula - (CH2) n-, which is replaced by one or two Alkyl groups with 1 to 4 carbon atoms can be substituted, where n is 2, 3 or 4, and in which R3 is hydrogen, methyl, ethyl, isopropyl or tert-butyl, R5 is hydrogen, straight-chain or optionally branched alkyl or alkenyl with up to 4 carbon atoms and R4, R6, R7, R8, R9 and R10 each stand for hydrogen or methyl, the stereochemical arrangement of the substituents R3 to R10 relative to one another and relative to the acetylenic side chain and in each case one of the dashed lines in the acetylenic side chain means a double bond and the endocyclic dashed line can mean a further double bond, very good plant growth-regulating, in particular perspiration inhibition rende, have an effect and can be produced in a relatively simple manner without undue technical effort.

Preferred acetylene compounds of the formula I are those in which R1 is a radical OR2, where R2 is alkyl with 1 to 4 carbon atoms, also those in which R1 stands for the remainder -0R11 and R11 together with R2 forms a methylene chain of the formula (CH2) n which is substituted by methyl or ethyl may be, with n = 2 being particularly preferred.

Preferred meanings of the substituents in formula I are also: R³ = CH3 R4 = H, CH3 R5 = H, CH3 R6 = H 7 8 9 R7, R8, R9 = H R10 = CH3 The acetylene compounds of the formula I are obtained by reacting ketones the formula in which R3 to R10 and the endocyclic dashed line have the meanings given above, with compounds of the formula in which R1, R2 and the dashed lines have the meanings given above, in the presence of an inert solvent or diluent and in the presence of a base as a condensing agent.

The bases are alkali hydroxides, such as KOH, alkali alcohols, such as NaOCH3, KOC2H5, K-tert.-butylate, alkali metal organyls such as n-butyllithium, alkaline earth metal organyls, such as CH3MgCl, CH3MgBr, alkali hydrides such as KH and NaH, and alkali amides such as NaNH2 and KNH2. The preferred basic condensation agents are CH3MgCl, KOH and potassium isobutylate used.

Suitable inert solvents or diluents are ethers, such as diethyl ether, Diisopropyl ether, diethylene glycol dimethyl ether, tetrahydrofuran; aliphatic hydrocarbons, such as hexane, heptane, cyclohexane; aromatic hydrocarbons such as benzene, toluene, Xylene; Amides such as dimethylformamide, N-methylpyrrolidone, hexamethylene phosphoric acid triamide; Amines, such as ammonia.

To carry out the process one proceeds in such a way that the connection of formula III is added to the suspension or solution of the condensing agent. The ketone of the formula II is then added and allowed to react to completion.

9 The reaction temperature can be in the range between -50 and + 1000C, are preferably between -20 and +65 0C.

The reaction time is sufficient, depending on the reactant, condensation agent or temperature, from a few hours to several days. The processing of the The reaction mixture is carried out in the usual way, e.g. by washing out the inorganic Proportions, if necessary after neutralization with acids.

The ketones of the formula II required as starting compounds are partly known (US-PS 4,126,641) or

can be prepared by known methods.

The starting compounds of the formula III in which R1 is not hydrogen are known (Bull. Chem.

Soc. Yep 50, 1584 (1977)) and according to known acetalization methods Easily accessible from 3-methyl-2-penten-4-yinal (Bull. Chem. Soc. Jap. 49, 292 (1976)).

Compounds of the formula III in which R1 is hydrogen are also known or according to known etherification methods from 3-methyl-2-pentene-4-ynol accessible (J. Organomet. Chem. 117, 201 (1976).

In addition, all compounds of the formula III can also be prepared by dehydrating the corresponding carbinols of the formula in which R1 and R2 have the same meanings as in formula III, are prepared by methods known per se.

In turn, the carbinols of the formula IV are easy to use prepare in a known manner by ethynylation of the corresponding methyl ketones (Houben-Weyl, Methods of Organic Chemistry, Volume IV / 2, p. 413 ff, Georg Thieme-Verlag, Stuttgart, 1955).

The compounds of the formula III fall depending on the manufacturing process usually as a mixture of isomeric compounds, which in the usual way, e.g. by Chromatography, can be separated. Before using the compounds of the formula III for the preparation of the acetylene compounds of the formula I is a separation of the Isomers are generally not required.

The isomeric components of the formula III are hereinafter referred to as Gem.-III according to the formula as Z-III according to the formula as E-III according to the formula designated.

The acetalization of 3-methyl-2-penten-4-ynal and the etherification of 3-methyl-2-penten-4-ynol generally lead to mixtures of the forms Z-III / E-III, without that Gem.-III arises in noteworthy proportions. In contrast, arise with the dehydration of compounds of the formula V is generally also larger Shares of geminally substituted ethylene of the form Gem.-III.

Depending on the nature of the substituents R1 and R², the isomers mentioned Gem.-III, Z-III and E-III in turn each consist of several isomers, e.g. when R1 and / or R2 contain chiral carbon atoms. The separation of this Isomer is also possible by customary methods for the use of the compounds for the preparation of the acetylene compounds of the formula I, however, as a rule not necessary.

Accordingly, the acetylene compounds of the formula I can also occur as a mixture of several isomers. The isomer ratios in the side chain generally correspond to those of the compounds of the formula III used as starting compounds, ie, depending on the relative proportions of the isomers Gem.-III, Z-III and E-III used for the preparation, corresponding proportions of the corresponding are obtained isomeric compounds of the formulas Gem.- ZI and EI.

Depending on the nature of the substituents R1> R2, R3 and R4, these can be used Isomers Gem.-I, Z-I and E-I in turn each consist of several isomers. It also gives the chirality of the carbon atom to which the hydroxy group is attached is, cause for the occurrence of enantiomers and optionally of diastereomers. All of the isomers mentioned of the compounds of the formula I can be 9 suitable methods are separated; for the application of the invention Compounds used as agents for regulating plant growth are the acetylene compounds of the formula Z-I preferred; however, isomer separation prior to use is common not mandatory.

The following examples illustrate the preparation of the acetylene compounds of the formula I and the precursors of the formula III necessary for their preparation.

Example 1 a) Production of 153 g (2, 0 moles) 1,2-propanediol. The mixture is then heated for a further 5 hours until the separation of water has ended, with approx. 50 ml of a water / propanediol mixture being separated out by distillation. After the reaction mixture had cooled, an oil (approx. 150 ml, mainly 1,2-propanediol) has settled on the bottom of the reaction flask and is discarded. The supernatant hexane solution is separated off, washed twice with 150 ml each of 5% aqueous sodium carbonate solution and then twice with 150 ml of water each time. After the organic phase has been dried over sodium sulfate, the hexane is removed by distillation under reduced pressure and the remaining residue L (126 g) is distilled under reduced pressure. After a forerun (6 g, bp 0.4 mbar = 51 to 56 ° C.), 107 g of the desired acetal la with a bp 0.4 mbar = 560 ° C. are obtained. According to 1H- and 13C-NMR, the product contains approx. 85% of the Z-form and approx. 15% of the E-form. B) Production of To a solution of 9 g of methyl magnesium chloride in 80 ml of dry tetrahydrofuran is added dropwise under a nitrogen atmosphere at 0 ° to 50 ° C., while stirring, 18.3 g of the acetal Ia over 30 minutes. The reaction mixture is then left at 200 ° C. for 3 hours. Then, while cooling at 0 ° to 50 ° C., 13.8 g of 2,5,6-trimethyl-cyclohex-2-en-1-one are added dropwise over 30 minutes; the mixture is then stirred at 2000 for 15 hours. It is then hydrolyzed with ice-cooling by adding dropwise 12 ml of water, the precipitate is filtered off and the filtrate is freed from tetrahydrofuran by distillation under reduced pressure. The residue taken up in 200 ml of diethyl ether is washed twice with 100 ml of water each time, the ethereal solution is dried over sodium sulfate, filtered and the ether is distilled off under reduced pressure. The remaining oil (28 g) is then subjected to a bulb tube distillation, with unreacted starting products being distilled off at 0.005 mbar between 50 and 1600C.

At 0.005 mbar and 205 to 21,000 then 16.0 g of the compound distill 1 over.

J IR (film): 2965, 2925, 2915, 2875> 1445, 1375, 1150, 1080, 1055, 1045, 1025, 960, cm 1 According to 1H-NMR spectra, are in the isomer mixture again about 85% Z-isomers and 15% E-isomers.

Example 2 a) Production of A suspension of 50 g of anhydrous copper (II) sulfate in 250 ml of paraffin oil is heated to 160 ° C. while stirring.

After setting a pressure of 135 mbar, for 4 hours slowly 300 g of 3-hydroxy-3-methyl-5-methoxy - pentine was added dropwise to the suspension, whereby gradually a mixture in the template of a connected distillation bridge collected from water, starting material and dehydration product 2a. When the addition is complete, 180 g of distillate have accumulated, which is contained in 400 ml of diethyl ether taken up, washed with aqueous sodium hydrogen carbonate solution, then with water and dried over sodium sulfate. After distilling off the ether, the Fractionated residue under reduced pressure after adding 0.5 g of hydroquinone distilled. 97 g of compound 2a are obtained at 67 mbar and 52 to 60 ° C. from the isomers of the form Gem.-III, Z-III and E-III in a ratio of 60: 30: 10 accordingly 1 H-NMR and 130-NMR spectrum.

As a higher-boiling action, at 67 mbar and 61 to 890C again 58 g of a mixture of starting compound and compound 2a collected, which again can be subjected to dehydration.

b) Manufacture of According to the process according to Example 1b), 13.5 g of methyl magnesium chloride, 19.8 g of compound 2a and 20.7 g of 2,6,6-trimethyl-cyclohex-2-en-1-one are obtained after the distillation of volatile constituents at 0.001 mbar and 50 to 120 ° C as the second fraction at the same pressure and 125 to 150 ° C an oil (25 g) which, according to the 1H-NMR spectrum, consists of different isomers of compound 2 (60% Gem.-2, 30% Z-2, 10% E-2). IR (film): 2960, 2940, 2915, 2870, 1445, 1375, 1360, 1115, 1090, 1075, 1055, 1030, 1000, 975, 965 cml.

Further examples of acetylene compounds of the formula I may be the following are mentioned in detail: At- R² R1 R³ R4 R5 R6 R7 R8 R9 R10 endocycl. Interplay of isomers, double ratio no. Bond Gem / Z / E 3 CH3 -OCH3 CH3 CH3 H H H H H CH3 yes 0/90/10 IR (film): 2965, 2920, 2825, 1440, 1375, 1360, 1185, 1130, 1065, 1050, 1000, 950 cm-1 4 -CH2-C (CH3) 2-CH2-O-CH3 CH3 H H H H H CH3 no 0/90/10 IR (film): 2950, 2930, 2860, 2845, 1455, 1390, 1195, 1090, 1025, 1010, 980, 955, 925 cm-1 5 -CH2-CHCH3-O- CH3 H H H H H H CH3 no 0/85/15 IR (film): 2955, 2920, 2865, 2850, 1455, 1440, 1370, 1310, 1145, 1035, 955, 935 cm-1 6 -CH2-CHCH3-O- CH3 H CH3 H H H H H no 0/85/15 IR (film): 2965, 2920, 2870, 1450, 1375, 1145, 1055, 1050, 1030, 1005, 990, 960, 935 cm-1 7 -CH2-CH2-O- CH3 CH3 H H H H H CH3 no 0/80/20 IR (film): 2960, 2930, 2880, 1455, 1445, 1375, 1355, 1335, 1325, 1145, 1125, 1060, 1030, 950 cm-1 8 -CH2-CHCH3-O- H H CH3 CH3 H H CH3 H yes 0/85/20 IR (film): 2945, 2920, 2885, 2860, 1445, 1370, 1360, 1145, 1070, 1040, 990, 960, 930 cm-1 # CH2 9 -CH2-CHCH3-O- H H -C H H H H CH3 yes 0/85/15 # CH3 IR (film): 2970, 2920, 2880, 1450, 1375, 1150, 1035, 955, 890 cm-1 At- R² R1 R³ R4 R5 R6 R7 R8 R9 R10 endocycl. Isomer play double ratio no. Bond Gem / Z / E 10 -CH2-CHCH3-O- H H H H H H H H yes 0/85/15 IR (film): 2965, 2920, 1435, 1370, 1310, 1195, 1140, 1040, 950, 925 cm-1 11 -CH2-CHCH3-O- H H H H CH3 CH3 H CH3 yes 0/85/15 IR (film): 2950, 2860, 2860, 1440, 1370, 1350, 1305, 1140, 1040, 1015, 1000, 955, 925 cm-1 12 -CH2CHCH3-O- -CH (CH3) 2 H H H H H H H no 0/85/15 IR (film): 2930, 2865, 1435, 1370, 1355, 1310, 1140, 1115, 1085, 1040, 995, 960, 930 cm-1 13 -CH2-CHCH3-O- -C (CH3) 2 H H H H H H H no 0/85/15 IR (film): 2930, 2865, 1435, 1385, 1370, 1355, 1135, 1075, 1040, 960, 935 cm-1 14 -CH2-CH2-O- H H H H H H H H no 0/80/15 IR (film): 2965, 2930, 2850, 1435, 1365, 1330, 1320, 1305, 1140, 1120, 1045, 990, 955, 930 cm-1 15 -CH2-CHCH3-O- H CH3 H H H H H CH3 yes 0/85/15 IR (film): 2980, 2935, 2890, 1455, 1385, 1330, 1155, 1050, 1010, 970 cm-1 16 CH3 H H H H H H H H H yes 60/30/10 IR (film): 3414, 2932, 2866, 2838, 1376, 1358, 1108, 1060, 960 cm-1 At- R² R1 R³ R4 R5 R6 R7 R8 R9 R10 endocycl. Isomer play double ratio no. Bond Gem / Z / E 17 CH3 H CH3 CH3 CH3 H H H H CH3 yes 60/30/10 IR (film): 3455, 2974, 2957, 1453, 1387, 1376, 1102, 1061, 1014 cm-1 18 CH3 H H H H H H H H CH3 yes 60/30/10 IR (Film): 3433, 2973, 2929, 2875, 1452, 1376, 1110, 1076, 1004 cm-1 19 CH3 H CH3 CH3 H H H H H CH3 yes 60/30/10 IR (film): 2960, 2920, 1440, 1370, 1350, 1110, 1070, 1050, 995, 975, 960 cm-1 20 CH3 H CH3 H CH3 H H H H CH3 yes 60/30/10 IR (film): 2980, 2960, 2930, 2890, 2835, 1455, 1285, 1120, 1015, 1005, 915, 905 cm-1 21 CH3 H CH3 CH3 H H H H H CH3 no 60/30/10 IR (film): 2950, 2920, 2860, 1450, 1370, 1110, 1070, 1050, 1025, 965, 945 cm-1 22 n-C6H13 H CH3 CH3 H H H H H CH3 yes 23 n-C4H9 H CH3 CH3 H H H H H CH3 yes 24 n-C4H9 n-C4H9O CH3 CH3 H H H H H CH3 yes The acetylene compounds of formula I intervene in the metabolism of plants and can therefore be used as Growth regulators are used.

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

The variety of effects of the plant growth regulators depends on mainly a) the type and variety of the plant, b) the time of application on the developmental stage of the plant, and on the season, c) on the application site and methods (seed dressing, soil treatment or foliar application), d) geoclimatic Factors, e.g. duration of sunshine, average temperature, amount of precipitation, e) the nature of the soil (including fertilization), f) the formulation or Application form of the active ingredient and finally g) the concentrations used the active substance.

In any case, growth regulators should give the crop plants the desired Way to influence positively.

From the number of different possible uses of the invention Plant growth regulators in plant cultivation, agriculture and horticulture, some examples are explained: 9 A. With the invention Compounds can influence the transpiration of cultivated plants. The treatment using these connections leads to an increased closure of the stomata and thus to a significantly reduced perspiration. The treated plants are thereby much more resistant to drought stress than untreated. With that you can Damage to crops by this stress factor, which leads to yield losses or even lead to complete death, avoid and regulate the Achieve water balance.

B. With the compounds according to the invention, the vegetative Strongly inhibit the growth of the plants which results in a reduction of the Expresses growth in length. The treated plants accordingly have a stocky appearance Grew out; a darker leaf color can also be observed.

The reduction, for example, has proven to be advantageous in practice the grass growth on roadsides, canal embankments and on lawns such as parks, Sports and orchards, ornamental lawns and airfields, so that the labor-intensive and costly Grass clippings can be reduced.

The increase in stability is also of economic interest For crops that are susceptible to storage, choose cereals, maize, sunflowers and soya. The one with it The resulting shortening and strengthening of the stalk reduce or eliminate the risk the "storage" (twisting) of plants under unfavorable weather conditions before harvest.

The use of growth regulators for inhibition is also important the growth in length and the temporal change in the ripening process for cotton.

This enables fully mechanized harvesting of this important one Cultivated plant allows.

By using growth regulators, the lateral Branching of the plants can be increased or inhibited. There is interest in if e.g.

the formation of side shoots in tobacco plants (Geizt'r> ieben) should be inhibited in favor of leaf growth.

Another mechanism of increasing yield with growth inhibitors is based on the fact that the nutrients to a greater extent the flower and fruit formation benefit while vegetative growth is restricted. Furthermore, so can due to the relatively low leaf or plant mass, the infestation with various, especially fungal diseases are prevented.

The inhibition of vegetative growth also enables many Cultivated plants a denser planting, so that a higher yield, based on the Floor area, can be achieved. The compounds according to the invention are suitable especially for inhibiting vegetative growth in crops such as soy, sunflower, Peanuts, rapeseed, ornamental plants, cotton, rice, wheat, barley and grasses.

C. With the new active ingredients, increased yields can be achieved with both parts of the plant as well as plant ingredients. For example, it is possible to use the Growth of large amounts of buds, flowers, Leaves, fruits, Seeds, roots and tubers to induce the content of sugar in sugar beets, Sugar cane as well as citrus fruits increase the protein content in cereals or SoYes to increase or rubber trees to stimulate increased latex flow.

The new substances can increase yield through intervention in the plant metabolism or

by promoting or inhibiting the vegetative and / or the generative Cause growth.

D. With plant growth regulators, finally, both a shortening or lengthening of the growth stages as well as an acceleration respectively.

Delayed maturity of the harvested plant parts before or after reach the harvest. With the compounds according to the invention can in particular achieve an acceleration of senescence.

For example, the easing of the harvest is of economic importance, those caused by the time-concentrated decrease or reduction in the adhesive strength on the tree with citrus fruits, olives or other types and varieties of pome, Stone and shell fruit is made possible. The same mechanism, i.e. the promotion the formation of dividing tissue between the fruit or leaf and sprout part of the plant, is also essential for a well-controllable defoliation of the trees. This mode of action is particularly pronounced in the compounds according to the invention.

The effect of the acetylene compounds can be seen in monocots, E.g. with cereals such as wheat, barley, rye, oats, sorghum and rice or maize or Grasses and dicots, e.g. sunflowers, tomatoes, peanuts, vines, cotton Oilseed rape, sugar beet and soy, and various cereal plants, such as chrysanthemums, Polish Settias and hibiscus.

The active compounds according to the invention can be applied to the crop plants from the seed (as a seed dressing agent) as well as from the soil, i.e. through the roots, and in particular fed by spraying over the sheet.

As a result of the high level of plant tolerance, the application rate can be high can be varied.

In the treatment of seeds, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are required.

For foliage and soil treatment, application rates are generally used from 0.001 to 12 kg of active ingredient, preferably 0.01 to 3 kg / ha, is sufficient.

The agents according to the invention can be in the form of customary formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The forms of application depend entirely on the intended use; In any case, they should ensure a fine and even distribution of the active substance guarantee. The formulations are prepared in a known manner, e.g. Extension of the active ingredient with solvents and / or carriers, if appropriate using emulsifiers and dispersants, with in the case of use Other organic solvents are also added to water as a diluent will can. The main additives used in the formulation are 9 in question: solvents such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g.

Chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, Butanol), amines (e.g.

Ethanolamine, ketones (e.g. cyclohexanone), dimethylformarnide and water; solid carriers such as natural rock flour (e.g. kaolins, clays, talc, Chalk) and synthetic rock powder (e.g. highly dispersed silica, silicates); Emulsifiers or other surface active agents such as nonionic and anionic Emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates) and dispersants such as lignin, sulphite waste liquors and methyl cellulose.

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

The formulations or the ready-to-use ones made from them Preparations such as solutions, emulsions, suspensions, powders, dusts, pastes or Granules are used in a known manner, for example in the pre-emergence process, post-emergence or as a pickling agent.

Examples of formulations are: I. 2Q parts by weight of the compound of Example 1 are in 3 parts by weight of the sodium salt of diisobutylnaphthalene sulfonic acid, 17 parts by weight of the sodium saliva of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel mixed well and placed in a hammer mill grind. By finely distributing the mixture in 20,000 parts by weight Water gives a spray mixture which contains 0.1% by weight of the active ingredient.

II. 3 parts by weight of the compound of Example 1 are 97 parts by weight finely divided kaolin intimately mixed. In this way you get a dusting device, which contains 3% by weight of the active ingredient.

III. 30 parts by weight of the compound of Example 2 are with a Mixture of 92 parts by weight of powdered silica gel and 8 parts by weight Paraffin oil that has been sprayed onto the surface of this silica gel, intimately mixed. In this way, the active ingredient is prepared with good results Adhesiveness.

IV. 40 parts by weight of the compound of Example 3 are mixed with 10 Parts of sodium salts of a phenolsulfonic acid-urea-formaldehyde condensate, 2 Parts of silica gel and 48 parts of water are intimately mixed. A stable aqueous solution is obtained Dispersion. An aqueous solution is obtained by dilution with 100,000 parts by weight of water Dispersion containing 0.04% by weight of active ingredient.

V. 20 parts of the compound of Example 3 are mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenol sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic Mineral oil intimately mixed. A stable oily dispersion is obtained.

VI. 90 parts by weight of the compound from Example 1 are mixed with 10 parts by weight of N-methyl-pyrrolidone and get a solution, which is suitable for use in the form of tiny drops.

VII. 20 parts by weight of the compound of Example 1 are in a Dissolved mixture consisting of 80 parts by weight of xylene and 10 parts by weight of the adduct from 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight Calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring it out and distributing it finely the solution in 100,000 parts by weight of water gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

VIII. 20 parts by weight of the compound of Example 3 are in a Dissolved mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil consists. By pouring the solution into 100,000 parts by weight and finely distributing it Water gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

The agents according to the invention can also be used in these forms present together with other active ingredients, such as herbicides, insecticides, growth regulators and fungicides or fertilizers are mixed and applied. Iim Mixing with growth regulators results in an enlargement in many cases of the spectrum of activity. With a number of such growth regulator mixtures, step also synergistic effects, i.e. the effectiveness of the combination product is greater than the added effectiveness of the individual components.

Fungicides which are combined with the compounds according to the invention are, for example, dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate, Zinc dimethyldithiocarbamate, manganese ethylene bisthiocarbamate, manganese zinc ethylenediamine-bis-dithiocarbamate, Zinc ethylene bisthiocarbamate, tetramethylthiuramide sulfide, ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate) and N, N'-polyethylene-bis- (thiocarbamoyl) -disulfide, zinc- (N, N'-propylene-bis-dithiocarbamate), Ammonia complex of zinc (N, N'-propylene-bis-dithio carbamate) and N, N'-propylene-bis- (thiocarbamoyl) -disulfide; Nitrophenyl derivatives, such as dinitro (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate, 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate; heterocyclic structures such as N-trichloromethylthio-tetrahydrophthalamide, N-trichloromethylthio-phthalimide, 2-heptadecyl-2-imidazole acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl phthalimidophosphonthionate, 5-Amino-1- (bis- (dimethylamino) -phosphinyl) -3-phenyl-1,2,4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, 2,3-dicyano-1,4-dithiaanthraquinone, 2-thio-1,3-dithio- (4,5-b) -quinoxaline, 1-butylcarbamoyl-2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2-rhodanmethylthio-benzthiazole, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, Pyridine-2-thio-1-oxide, 8-hydroquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide, 2,3-Dihydro-5-carboxanilido-6-methyl-1,4-oxathiin, 2- (furyl-2)) benzimidazole, piperazine-1,4-diyl-bis (2,2,2-trichloro- ethyl) formamide, 2-thiazolyl- (4)) - benzimidazole, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, Bis- (p-chlorophenyl) -3-pyridinemethanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) benzene, 1,2-bis- (3-methoxycarbonyl-2-thioureido) -benzene, and various fungicides, such as dodecylguanidine acetate, 3- (2- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl) - glutarimide, Hexachlorobenzene, N-dichlorofluoromethylthio-N, N'-dimethyl-N-phenyl-n-sulfuric acid diamide, D, L-methyl-N- (2,6-dimethyl-phenyl) -N-furyl (2) -alaninate, D, LN- (2,6-dimethyl-phenyl) -N- (2'-methoxyacetyl) - alanine methyl ester, 5-nitro-isophthalic acid-di-isopropyl ester, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid-cyclohexylamide, 2-methyl-benzoic acid-anilide, 1- (3,4-dichloroanilino9-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, 2,3-dichloro-1,4-naphthoquinone, 1,4-dichloro-2,5-dimethoxybenzene, p-dimethylaminobenzene-diazine sodium sulfonate 1-chloro-2-nitro-propane, polychloronitrobenzenes, such as pentachloronitrobenzene, methyl isocyanate, fungicidal antibiotics such as griseofulvin or kasugamycin, tetrafluorodichloroacetone, 1-phenylthiosemicarbazide, Bordeaux mixture, compounds containing nickel and sulfur.

In the following examples, the effect is that which can be used according to the invention Acetylene compounds of the formula I as plant growth regulators, for example shown without excluding the possibility of further applications as growth regulators.

The antiperspirant effect of the acetylene compounds Formula I can, for example, by wilt rating in the case of drought stress, by determination water consumption and by measuring the diffusion resistance.

1.Wilt behavior in drought stress (greenhouse test) plants, e.g. barley, are supplied with sufficient nutrients in the usual procedure Torr culture substrate in plastic containers with a diameter of approx. 12.5 cm up to the leaf spray attracted when the substrate is fully saturated. The application rates are 0.2 and 0.1 mg, respectively Active ingredient per vessel. After the application of the aqueous With the prepared substances, the vessels are placed in dry pallets without any additional water supply set. The wilting of the plants that occurs is rated (rating grade O means no wilt, 9 means total wilt).

In this test, the active ingredients No. 1 to 21 show good transiration-inhibiting properties Effect.

2. Determination of water consumption (short-term laboratory test) Young sunflowers are at a height of approx.

25 cm sprayed with aqueous preparations of the test substances, immediately then cut off approx. 10 cm below the center of the vegetation and put in with Graduated (centrifugal) tubes filled with water. The application rates are 0.2 or 0.1 mg active ingredient per vessel. At room temperature, diffuse light and draft-free is the water decrease in tedding intervals by reading on the oraduation detected. At the end of the experiment (after 24 hours) the leaf area becomes the test limbs measured with the leaf area measuring device from LJ-COR Inc., the Water consumption is shown in / ul / cm2.

This test shows that the water consumption of the plants that with the active ingredients No. 1 and 3 were treated, is much lower than that of the untreated plants.

3. Measurement of the diffusion resistance (greenhouse experiment) of test plants (Sunflowers, SoYes) are sprayed with aqueous preparations of the substances and at normal Water supply> continued in the greenhouse. The application rates are 0.2 or 0.1 mg of active ingredient per vessel. The diffusion resistance of the leaves - as a parameter for the state of opening of the stomata - is measured by means of an autoporometer certainly.

This test shows that the diffusion resistance of the leaves of plants treated with active ingredients No. 1 and 3 is higher than that of the leaves of untreated plants.

4. Determination of the growth-regulating properties For determination the growth-regulating properties of the acetylene compounds of the formula I are Test plants on a growing medium sufficiently supplied with nutrients in plastic containers about 12.5 cm in diameter.

In the pre-emergence process, the test substances are processed in water poured onto the seedbed on the day of sowing.

In the post-emergence process, the substances to be tested are aqueous Preparation sprayed on the plants. The observed growth regulating effect is documented by measurement of the height of the growth at the end of the test. The measured values obtained in this way are related to the height of the untreated plants.

At the same time as the reduction in length growth, the color intensity increases of the leaves. The increased chlorophyll content also increases the rate of photosynthesis and thus expect increased earnings.

In this test, the active ingredients No. 1, 2, 3, 5, 7, 12, 13, 15, 17, 18, 19, 20 and 21 both post-emergence and pre-emergence pronounced growth-regulating effect.

Claims (9)

Claims 1. Acetylene compounds of the formula in which R1 stands for hydrogen or the radical -0R2 and R2 stands for alkyl with 1 to 6 carbon atoms or in which R1 stands for the radical -OR11 and R11 together with R2 is a methylene chain of the formula - (CH2) n-, which is replaced by a or two alkyl groups can be substituted with 1 to 4 carbon atoms, where n is 2, 3 or 4, and in which R3 is hydrogen, methyl, ethyl, isopropyl or tert-butyl, R5 is hydrogen, straight-chain or optionally branched alkyl or alkenyl with up to 4 carbon atoms and R4, R, R7, R8, R9 and R10 each represent hydrogen or methyl, the stereochemical arrangement of the substituents R3 to R10 relative to one another and relative to the acetylenic side chain and in each of which one of the The dashed lines in the acetylenic side chain mean a double bond and the endocyclic dashed line can mean another double bond. 2. Process for the preparation of acetylene compounds of the formula I according to Claim 1, characterized in that ketones of the formula in R3 to R10 and the endocyclic dashed line have the meanings given in claim 1 with compounds of the formula in which R1, R2 and the dashed lines have the meanings given in claim 1, in the presence of an inert solvent or diluent and a base as the condensing agent. 3. Agent for regulating plant growth, containing an acetylene compound of formula I according to claim 1. 4. Agents for regulating plant growth, containing inert Additives and an acetylene compound of the formula I according to Claim 1. 5. Means for reducing perspiration and preventing Impairment of plants by heat and drought stress, containing a Acetylene compound of the formula I according to Claim 1. 6. Means for reducing perspiration and preventing it Impairment of plants through heat and drought stress, containing inert Additives and an acetylene compound of the formula I according to Claim 1. 7. A method for regulating plant growth, characterized in that that an effective amount of an acetylene compound of the formula I according to claim 1 can act on the plants or their seeds. 8. - Method of reducing the transpiration of plants, thereby characterized in that there is an effective amount of an acetylene compound of the formula I according to claim 1 can act on the plants or their seeds. 9. Use of acetylene compounds of formula 1 according to claim 1 to reduce the transpiration of plants.