DE3201190A1 - Tetracyclic nitrogen-containing norbornane compounds and compositions containing them for regulating the growth of plants - Google Patents

Abstract

Tetracyclic nitrogen-containing norbornane compounds of the formula <IMAGE> in which A represents the radical -N=N-, n represents 0 and 1, R<1> represents hydrogen, an acyclic or cyclic alkyl or alkylcarbonyl radical or a trimethylsilyl radical or trifluoroacetyl radical, R<2> represents hydrogen, or R<2> together with R<1> represents a bond, R<3> and R<4> represent hydrogen or an alkoxycarbonyl radical, or R<3> and R<4> together represent a bond and R<5> represents hydrogen, halogen or halogenoalkyl, and compositions for regulating the growth of plants.

Description

Tetracyclic nitrogen-containing norbornane compounds

and plant growth regulating agents containing them The present invention relates to new tetracyclic nitrogen-containing norbornane derivatives and plant growth regulating agents containing them.

It is known that polycyclic nitrogen-containing norbornane compounds, e.g. 5- (4-chloro (or 4-bromo) phenyl) - 3,4,5,9,10-pentaazatetracyclo- [5,4,1,02,6, 08,11] -dodeca-3,9-diene to regulate plant growth (2 ¢ -OS 26 15 878, DE-OS 27 42 034).

It has been found that the new compounds of formula I in which the spatial position of the substituents OR¹ and R² on the C1 bridge is not determined, A denotes the radical -N = Nn 0 and 1 R1 is hydrogen, an acyclic or acyclic alkyl or alkylcarbonyl radical (for example with 1 to 5 atoms in the alkyl radical ) or a trimethylsilyl radical or trifluoroacetyl radical, p2 denotes hydrogen or R² together with F1 denote a bond, R3 and R4 are identical or different and denote hydrogen or an alkoxycarbonyl radical (for example with 1 to 4 carbon atoms) or R3 and R together represent one Mean bond and mean hydrogen, halogen or haloalkyl (for example with 1 to 4 carbon atoms) are well suited for regulating plant growth.

The new compounds can be according to the DE-OS 26 15 878, 27 42 034 and 30 Ol 580 generally described processes.

1. Reaction of the compounds III, where R¹-R4 have the meanings given above, with arlazides (R5 as described above) to give the triazoline derivatives (nw 1).

2. Elimination of N2 from the triazolone ~ derivatives thus obtained in the presence of acids to give the corresponding aziridine derivatives.

3. Saponification and decarboxylation of the triazoline or

Aziridine derivatives (R³ and R4 = -COOAlkyl) with aqueous or alcoholic alkali to give the corresponding hydrazine derivatives (R³ and R4 = H) and oxidation of the hydrazine derivatives, if necessary without prior isolation, with aqueous NaOCl or H202 solution to the azo compounds (P3 and R4 form a bond).

With the appropriate implementation of ester compounds of the formula I (n = 0 or 1, R¹ = Alkylcarboxi, R² = R3 and R = -COOAlk) are formed corresponding hydrazine or azo derivatives with R¹ and R² = The implementation of the compounds III with arylazides to the triazoline derivatives I (n = 1) is for example with equimolar or non-equimolar amounts of the starting Products, with or without inert solvents, at temperatures from -20 to 1400 ° C., preferably 20 to 100 0C carried out. The choice of solvent depends on the solubility of the starting components. The reaction products fall either at Cooling or, when using polar solvents, by adding non-polar solvents from the reaction solution or can be obtained by concentrating the solution.

The N2 elimination from the triazoline derivatives to the aziridine derivatives can usually be sufficient, for example, in inert solvents by adding acids catalytic amounts, e.g. H2S04, acetic acid or trifluoroacetic acid, at temperatures from -20 to 120 ° C, preferably from 20 to 80 ° C.

Dio saponification and decarboxylation of the trlazoline or aziridine derivatives I (n 2 0 or 1, R3 and R 4 = -CCCAlk) is carried out, for example, in such a way that the starting compounds with aqueous or alcoholic (C1 -C4 alcohol, preferably Methanol) alkali (NaOH or KOH) at 20 to 1200C, preferably 40 to 8000, saponified and decarboxylated. The hydrazine derivatives I (n - O or 1, P.3 and R4 = H) can be removed by suction and washing with water or extraction from the reaction solution, optionally after adding water, or from the residue obtained after concentrating the reaction mixture.

The hydrazine derivatives can be in aqueous or alcoholic suspension or solution or without prior isolation by adding aqueous NaOCl or H2O2 solution to the reaction mixture at 20 to 10,000, preferably 40 to 90 ° C the azo compounds I (n = 0 or 1, R³ and R.4 form a bond) oxidize. The severing tion of the end products from the reaction mixture can be carried out in a corresponding manner as described for the hydrazine derivatives.

For the reaction of the compound I with the solution of alkali metal hydroxide for example, depending on the solubility of the alkali hydroxide, solutions of alkali hydroxide in water or methanol in concentrations of 1 to 600 g alkali hydroxide used in one liter of the solution, where per mole of the compound I 4 to 10 moles Alkali hydroxide can be used.

Aqueous solutions of sodium hypochlorite or Hydrogen peroxide is used, the tenth liter of solution 1 to 600 g of the oxidizing agent contain. For the oxidation, 1 to 10 moles, per mole of compound I, are preferred 1 to 2 moles, the oxidizing agent used.

The substituents on the Cl bridge can be in the syn or anti position stand by the Diazavierring. The invention therefore includes both the pure isomers or as well as the isomer mixtures.

The production of the starting products can take place, for example, according to the following regulations: Regulation 1 13 parts of dimethyl azodicarboxylate were added dropwise to 15 parts (parts by weight) of 7-t-butoxiquadricyclane and 50 parts of toluene with stirring at 80 ° C., and the mixture was stirred at 80 ° C. for 12 hours. After concentrating the reaction mixture in a rotary evaporator at 20 to 50 ° C. and 20 mbar, the residue was extracted for 10 hours with 200 parts of petroleum ether.

The petroleum ether phase is obtained by concentrating and drying the Residue at 20 mbar 26 parts (93 mol%) of 3,4-dimethoxlcarbonyl-9-t-butoxy-3,4-diaza-trlcyclo- [4.2.1.02.5] -nona-7-en, M.p. 860C (toluene / ligroin).

The following were produced accordingly: R1 (CH3) 3C-C2H5-CH3CO-CH3-CH3CO-C2H5-CH; C0-C4Hg-prescription 2 92 parts of 3.4-dimethoxicarbonyl-9-acetoxy-3.4-diazatricyclo- [4.2.1.02.5] -nona-7-ene - and 570 parts of 20 percent strength. aqueous NaOH was stirred for 3 hours at 700C and then 356 parts of 13 percent strength at 40 ° C. (% By weight) aqueous NaOCl was added dropwise and the mixture was stirred at 40 ° C. for 1 hour. The reaction mixture was extracted continuously for 12 hours with 300 parts of CH2C12, the organic phase was dried with MgSO4, treated with activated charcoal and concentrated, and the residue was digested with 200 parts of petroleum ether.

36.4 parts (86 mol%) of 9-hydroxy-3.4-diazatricyclo- [4.2.1.02.5] -nona-3.7-diene were obtained, Mp. 128 ° C (from cyclohexane).

Regulation 3 50 parts of 3,4-dimethoxicarbonyl-9-t-butoxy-3,4-diazatricyclo- [4.2.1.02.5] -nona-7-ene, 50 parts of KOH and 250 parts of methanol were refluxed for 7 hours. Then 36 parts of 30 percent were at 600C. Aqueous H 2 O 2 was added dropwise and the mixture was stirred at 60 ° C. for a further 1 hour. After cooling to 200 ° C., the solid product was filtered off with suction, washed with 50 parts of methanol and the combined filtrates were concentrated in a rotary evaporator at 20 to 4000 and 20 mbar. The residue was extracted with 300 parts of petroleum ether in a Soxhlet for 12 hours.

Concentration of the petroleum ether gave 28.5 parts (93 mol%) of 9-t-butoxy-3,4-diazatricyclo- [4.2.1.02.5] -nona-3.7-diene, m.p. 780C (from ligroin).

Regulation 4 5 parts of 9-hydroxy-3.4-diazatricyclo- [4.2.1.02.5] -nona-3.7-diene, 5 parts of acetic anhydride, 1 part of triethylamine and 100 parts of ether were refluxed for 24 hours. The reaction mixture was then extracted twice with 50 parts of water, and the organic phase was dried with MgSO4 and concentrated in a rotary evaporator.

6.2 parts (95 mol, O) of 9-acetoxy-3.4-diazatricyclo- [4.2.1.02.5] -nona-3.7-diene were obtained, M.p. 58 ° C.

The following were produced accordingly: R CF3CO-C2H5CO-C3H7CO-i-C3H7CO-C4H9CO- (CH3) 3Si- Regulation 5 To 5 parts of 9-hydroxy-3.4-diazatricyclo- [4.2.1.02.5] -nona-3.7-diene and 100 parts of acetonitrile, 1 part of NaH was added in portions at 200 ° C. with stirring. Then 20 parts of methyl iodide were added and the mixture was stirred at 200 ° C. for 12 hours. The reaction mixture was concentrated in a rotary evaporator (20 to 50 ° C., 20 mbar) and the residue was extracted with 200 parts of petroleum ether.

Concentration of the petroleum ether gave 5 parts (90 mol%) of 9-methoxy-3.4-diazatricyclo- [4.2.1.02.5] -nona-3.7-diene as O1, H-NMR (in ppm): 6.2 (bs, 2H), 4.1 (bs, 2H), 3.1-3.3 (m, 6H).

The following were produced accordingly: R C2H5-C3H7-i-C3H7-O'4H9 Regulation 6 1.3 parts of orthophosphoric acid were added in portions to a mixture of 18.5 parts of I, 78 parts of dicyclohexylcarbodiimide and 140 parts of anhydrous DMSO, while stirring and cooling at 20 to 30 ° C., and the mixture was stirred at about 250 ° C. for 5 hours. After adding 460 parts of OH Cl2, the mixture was filtered and the filtrate was stirred for 3 hours at 25 ° C. with 400 parts of saturated aqueous NaHOO3 solution and 10 parts of soda. The organic phase was separated off, the aqueous phase was extracted 5 × with 200 parts of CH2C12 and the combined organic phases were washed 2 × with 300 parts of water. After drying with MgSO4 and treatment with activated charcoal, the CH2C12 phase was concentrated and the residue was extracted continuously for 12 hours with 200 parts of petroleum ether.

Concentration of the petroleum ether phase gave 14.5 parts (79 Mol%) II, m.p. 90 ° C.

The new compounds of the formula I can be prepared, for example, in accordance with the following examples: Example 1 30 parts of 9-hydroxy-3.4-diazatricyclo- [4.2.1.02.5] -nona-3.7-diene and 34 parts of p-chlorophenylazide were heated in 100 parts of toluene to 80 ° C. for 3 hours with stirring. After concentration in a rotary evaporator at 20 to 40 ° C. and 20 mbar, the residue was digested successively with 100 parts of diethyl ether and 100 parts of petroleum ether and dried at 200 ° C. and 1 mbar.

59 parts (92 mol%) of 8- (4-chlorophenyl) -12-hydroxi-3.4.8.9.10-pentazatetracyclo- [5.4.1.02.5.07.11] -dodeca-3.9-diene, melting point 178 ° C (decomp.) (Compound No. 1).

00 parts of 3,4-dimethoxicarbonyl-8- (4-chlorophenyl) -12-t-butoxy-3.4.8.9.10-pentazatetracyclo- [5.4.1.02.5.07.11] - dodeca-9-en (Compound no. 9) were 25 percent in 1000 parts. suspended aqueous sodium hydroxide solution and stirred at 85 ° C for 6 hours. Then at 600C 1150 points 13 percent. Aqueous NaOCl was added over the course of 2 hours and the mixture was subsequently stirred at 60 ° C. for 4 hours, after cooling to 20 ° C, the solid product was filtered off, washed with 3000 parts of water and at 300C and 1 mbar dried.

270 parts (96 mol of 8- (4-chlorophenyl) -12-t-butoxy-3.4.8.9.10-pentazatetracyclo- [5.4.1.02.5.07.11] -dodeca-3.9-dlene, melting point 17800 ( Decomposition) (compound no. 2).

To 50 parts of 8- (4-bromophenyl) -12-hydroxy-3.4.8.9.10-penta azatetracyclo- [5.4.1.0. 0.11] -dodeca-9-en (compound no. 69) in 400 parts of methanol and 5 parts of 25 percent by weight.

Aqueous NaOH was added dropwise while guiding at 6500 within 1 hour 35 parts 30 percent aqueous H2O2 and stirred at 6500 for 5 hours. Flat that AbElhlen to 20 ° C., 1500 parts of water were added, the product was filtered off with suction and the residue was washed with 300 parts of water and dried at 300 ° C. and 1 mbar.

44 parts (88 mol%) of 8- (4-bromophenyl) -12-hydroxi -3.4.8.9.10-pentaza-tetracyclo- [5.4.1.02.5.07.11] -dodeca-3.9-diene were obtained, M.p. 187 ° C (dec.) (Compound No. 3).

The following connections were established accordingly: In the event that R1 and R2 represent a bond, the following radical results in the 12-position of the molecule Ver R¹ R² R³ R4 R5 n Fp [° C] am- manure No. 4 H- H- one bond H- 1 148 (decomp.) 5 """" m-CF3-1 177 " 6 "nnn pF- 1 181 7 nn "o-Br- 1 166 8 nn "m-CF3- 0 135 lt 9 (CH3) 3C- "CH3OCO- CH3OCO- o-Cl- 1 186" 10 """" m-CF3-1 183 " 11 """" p-Br- 1 210 " 12 "" C2H5OCO- C2H5OCO H-1 184 " 13 "n lt n p-Br- 1 179" 14 n "a bond m-CF3-1 192 n Ver R¹ R² R³ R4 R5 n Fp [° C] am- manure No. 15 (CH3) 3C- H- one bond p-Br- 1 200 (dec.) 16 """" p-Br- 0 133 " 17 a bond "" m-CF3-1 168 18 nn "" p-Cl-1 186 19 """" m-Cl- 1 173 " 20 """" p-Br- 1 187 " 21 """" m-CF3- 0 138 " 22 """" p-Cl- 0 151 " 23 CF3CO-H- n "p-Cl- 1 180 24 """""m-CF3-1 177 25 CH3CO- n CH30C0- CH30CC- p-Cl 1 197 26 """""o-Cl- 1 174" 27 """""m-CF3-1175" 28 """" nn p-Br- 1 153 " 29 "" C4H9OCO-C4H9OCO-H-1,191 30 """" p-Cl-1 182 31 """" pF-1 180 32 e a bond p-Cl- 1 185 33 """" m-CF3-1 152 " 34 """" m-Br- 1 187 " 35 """" p-Br- 1 193 " 36 CH3- """p-Br- 0 139" 37 """" m-CF3-1 176 " 38 """" p-Br- 1 191 " 39 """" p-Cl- 1 183 " 40 """" p-Cl- 0 138 " 41 C2H5- """H- 1 178" 42 """" p-Cl- 1 179 " 43 """" pF- 1 174 " 44 """" p-Br- 0 133 " 45 C2H5CO- """p-Cl- 1 189" 46 """" m-CF3-1 185 " Ver R¹ R² R³ R4 R5 n Fp [° C] am- manure 47 CH3CH (CH3) CO- H- one bond p-Br- 1 149 (dec.) 77 (CH3) 3Si- nn lt p-Cl- 1 186 78 nnn lt m-CF3-1 189 79 nnn "lt p-Br- 1 178"

Example 2 10 parts of 8- (3-trifluoromethyl-phenyl) -12-acetoxi-3.4.8.9.10-pentaza-tetracyclo- [5.4.1.02.5.07.11] -dodeca-3.9-diene (compound no. 33) were in 50 parts of acetic acid and 150 parts of ether were stirred at 2500 for 5 hours. After concentration in a rotary evaporator at 20 ° C. and 1 to 20 mbar, the residue was digested successively with 50 parts of ether and petroleum ether.

After drying at 1 mbar, 9.1 parts (94 mol%) of 8- (3-trifluoromethyl-phenyl) -12-acetoxy-3.4.8-triazatetracyclo- [4.3.1.02.5.07.9] -deca-3- were obtained en, Fp.

154 ° C (dec.) [4.3.1.02.5.07.9] -deca-3-en, m.p.

"The following connections were established accordingly: R1 R2 R3 R4 R5 Fp [° C] manure No. 49 H- H- one bond H- 132 (decomp.) 50 """" p-Cl- 124 " 51 """" p-Br- 141 " 52 (CH3) 3C- "CH3OCO-CH3OCO- m-CF3-98 53 """" p-Cl-74 54 "" C2H5OCO-C2H5OCO p-Br-60 55 "" a bond p-Cl- 149 (dec.) 56 """" m-CF3-121 57 a bond "" p-Br-129 58 CF3CO-H- "" p-Cl- 82 59 CH3CO- "CH3OCO CH3OCO p-Cl- 87 60 """" m-CF3-61 61 """" p-Br-64 62 """a bond p-Cl- 126 (dec.) 63 CH3- """m-CF3-131 64 """" p-Br-144 65 C2H5- """m-CF3-128 80 (CH3) 3 Si """p-Cl-150 81 """" m-CF3-128 Example 3 300 parts of 3,4-dimethoxicarbonyl-8- (4-chlorophenyl) -12-t-butoxy-3.4.8-triaza-tetracyclo- [4.3.1.02.5.07.9] -decane (compound no. 53), 150 parts of NaOH and 2000 parts of methanol were heated to 650 ° C. for 6 hours with stirring. It was then filtered off with suction, the residue was washed with 500 parts of methanol and the filtrates were concentrated in a rotary evaporator at 20 to 40 ° C. and 20 mbar. The residue was washed with 1000 parts of water and dried at 20 to 40 ° C. and 1 mbar.

185 parts (84 mol%) of 8- (4-chlorochenyl) -12-t-butoxy-3.4.8-triaza-tetracyclo- [4.3.1.02.5.07.9] -decane were obtained, M.p. 890c (compound no. 66).

The following connections were established accordingly: A: -N = N-R³: H R4: H Ver R¹ R² R5 n Fp [° C] am- manure No. 67 H- H- H- 1 123 (dec.) 68 H-H-p-Cl-1 142 69 H-H-p-Br-1 137 70 H-H-m-CF3-1 150 71 H- H- p-Cl- 0 83 72 H-H-m-CF3-0 41 73 (CH3) 3c- H- p-Cl- 1 139 (dec.) 74 "H-m-CF3-1 148 75 "H-p-Br-1 160 76 H-m-CF3-0 74 The new active ingredients intervene in the metabolism of plants and can therefore be used as growth regulators.

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

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 the stage of development of the plant and the time of year, c) the place of application 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 are mentioned below.

A. With the new compounds, the vegetative growth of the Strongly inhibit plants, which in particular results in a reduction in length growth expresses. The treated plants accordingly have a stocky growth; aside from that a darker leaf color can 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 Cuttings can be reduced, which is also of economic interest Increasing the stability of crops susceptible to storage such as grain, maize, sunflowers and soy. Reduce the shortening and strengthening of the stalk caused by this or eliminate the risk of "storage" (twisting) of plants under unfavorable conditions 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.

in tobacco plants the formation of side shoots (stinging shoots) 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 because of the relatively low sheet or. Plant mass to infestation with different, 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 to inhibit vegetative growth in crops such as soy, sunflowers, Peanuts, rapeseed, ornamental plants, cotton, rice and grasses.

B. With the new active ingredients, increased yields can be achieved on 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, boards, fruits, seeds, roots and tubers induce the level of sugar in sugar beet> sugar cane as well To increase citrus fruits, or to increase the protein content in cereals or soya To stimulate rubber trees to the increased flow of latex, the new substances can Yield increases through interventions in the plant metabolism or

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

C. 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.

Of economic interest is, for example, the easing of the harvest, 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 pithead and nuts is made possible. The same mechanism, that is, becoming the formation of separating tissue between fruit or. Leaf and shoot part of the plant is also essential for a well-controllable defoliation of the trees.

The effect of the new compounds is better than that of known growth regulators. The effect can be seen in monocots, e.g. cereals such as wheat, barley, Rye, oats and rice or maize or grasses as well as especially dicots (e.g. sunflowers, tomatoes, peanuts, vines, cotton, rape and especially soa) and various ornamental plants such as chrysanthemums, poinsettias and hibiscus.

The new active ingredients can be applied to the cultivated plants both from the seed (as seed dressing) as well as silver the soil, i.e. through the roots as well as - particularly preferred - fed by spraying over the sheet.

As a result of the high plant tolerance, the amount of application 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 leaf and soil treatment, a dose of 0.001 is generally required up to 12 kg / ha, preferably 0.01 to 3 k6 / ha, should be considered 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 used in addition to water as a diluent can be. The following are essentially suitable auxiliaries for this: 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), Dimethyltormamld and water; solid carriers such as natural rock flour (e.g. Kaolins, clays, talc, chalk) and synthetic rock flour (e.g. highly dispersed Silicic acid, silicates); Emulsifiers 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 use of those according to the invention is preferred Compounds in aqueous solution or in a solution of water with the addition of water-miscible organic solvents such as methanol or other lower solvents Alcohols, acetone, dimethylformamide or N-methylpyrrolidine. the Formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90.

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

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 mixed with fertilizers and applied. At the Mixing with growth regulators results in an enlargement in many cases of the spectrum of activity. Step into a number of such growth regulator mixtures also have synergistic effects, i.e.

the effectiveness of the combination product is greater than the added ones Effectiveness of the individual components.

In the following experiments, the effect is that according to the invention usable substances shown as PPlance growth regulators without the possibility to exclude further applications as growth regulators.

The following experiments explain the biological effect of the new Links.

Comparative substances: Experiment Test for growth-regulating action To determine the growth-regulating property of the test substances, test plants were grown on a culture substrate sufficiently supplied with nutrients in plastic containers with a diameter of approximately 12.5 cm.

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

In the follow-up process, the substances to be tested were aqueous Preparation sprayed on the plants. the observed growth regulators At the end of the experiment, the effect was demonstrated by measuring the height of growth. The ones won in this way Measured values were related to the height of growth of the untreated plants.

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

In this experiment, the active ingredients 39 and 77 showed a significant greater reduction in length growth in spring barley in the pre-emergence method at Aufwanomengen of 3 and 12 mg of active ingredient per vessel than compounds A, B and C.

In a further experiment, the active ingredients 1, 3, 32 and 48 showed a Significantly greater reduction in length growth in post-emergence lawns at application rates of 1.5 and 6 mg of active ingredient per vessel than compounds A, B and C.

Example I 20 parts of the active ingredient 1 are mixed with 12 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 condensate, 68 parts of a paraffinic mineral oil intimately mixed. A stable oily dispersion is obtained.

Example II 3 parts by weight of active ingredient 3 are 97 parts by weight finely divided kaolin intimately mixed. In this way a dust is obtained which contains 3 percent by weight of the active ingredient.

Example III 30 percent by weight of the active ingredient 1 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, a preparation with good adhesion is obtained.

Example IV 40 parts by weight of active ingredient 3 are mixed with 10 parts Sodium salt of a phenolsulfonic acid-formaldehyde condensate, 2 parts of silica gel and 48 parts of water mixed intimately. A stable aqueous dispersion is obtained.

An aqueous dispersion is obtained by dilution with water.

Example V 20 parts by weight of the active ingredient 3 are in a mixture dissolved, the 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 and finely distributing it 100 000 parts by weight of water give an aqueous dispersion.

Example VI 20 parts by weight of the active ingredient 39 are in a mixture dissolved that of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from boiling point 210 to 2800C and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring it in and distributing it finely the solution in water gives an aqueous dispersion.

Example VII 80 parts by weight of active ingredient 1 are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulphonic acid from a sulphite waste liquor and 7 parts by weight powdered silica gel mixed well and ground in a hammer mill. A spray liquor is obtained by finely distributing the mixture in water.

The active ingredients can also be used with good success in the ultra-low-volume process (ULV) can be used whereby it is possible to use formulations with more than 95 wt. Apply the active ingredient or even the active ingredient without additives.

Claims (3)

Claims 1. Tetracyclic nitrogen-containing norbornane compound of the formula in which the spatial position of the substituents OR¹ and R² on the C1 bridge is not fixed, A is the radical -N = Nn 0 and 11 cyclic R is hydrogen, an acyclic or alkyl or alkylcarbonyl radical or a trimethylsilyl radical or trifluoroacetyl radical, R2 is hydrogen or R2 together with R1 denote a bond and R are identical or different and denote hydrogen or an alkoxicarbonyl radical or R3 and R together denote a bond and R5 denote hydrogen, halogen or haloalkyl. 2. Agent for regulating plant growth, containing a compound according to claim 1. 3. A method for regulating plant growth, characterized in that that one treats the plants or the soil or the seeds of the plants with a Compound according to claim 1.