Brassinosteroid derivatives and regulating plant growth tool

 

(57) Abstract:

Brassinosteroid derivative represented by the formula (I) and formula (II)

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and the plant growth regulator containing at least one of them as the active ingredient, thus the invention is new brassinosteroids compounds expressed by the formula (I) and formula (II) and plant growth regulators containing these compounds exhibiting sustainable regulatory effects on plant growth. 3 S. p. f-crystals, 8 PL.

The invention relates to new brassinosteroids derived and plant growth regulator in which they are used as active ingredients.

Brassinosteroid was detected in the pollen of cabbage as growth regulating substance M. D. Jrove and the other in 1979, Nature, v. 281, p. 216 - 217, 1979), were subsequently disclosed stimulating plant growth steps brassinolide and brassinosteroid-like compounds (Brassinosteroids. Chemistry, Bioactivity & Applications. ACS Symposium Series 474, American Chemical Society, Washington, DC, 1981).

This dedicated application laid Japan N 1-125396.

However, so far studied brassinolide have the highest physiological activity, and brassinosteroid-like connection used.

The purpose of the invention is to obtain new brassinosteroid derivatives, perfectly suitable for practical use on the efficacy and duration of exposure accelerating the growth of plants by solving the above problems.

The invention provides brassinosteroid derivative expressed by the formula (I)

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The invention also provides brassinosteroid derivative of the formula (II)

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In addition, the invention is a plant growth regulator containing one type or two types brassinosteroid derivatives expressed by the formula (I)

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and formula (II)

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as the active ingredient.

The invention presents new brassinosteroid-like, with growth regulating activity in relation to plants, expressed by the compound (I) and compound (II), and a plant growth regulator containing them as active ingredients are useful because they possess growth regulating effects on various plants in combination with excellent exposure duration.

The best variant of the invention (particularly, the invention is described below).

The compound of formula (I) of the invention (called the large output through dihydrexidine education in the 2-position and 3-position, by throttling the reaction agent, in the exercise of the catalytic formation of hydroxyl-containing compounds (22E, 24S) -24-ethyl-5-cholesta-2,22-Dien-6-she (hereinafter referred to as compound (III) (K. Mori, Agric. Biol. Chem., 44 (5), 1211, 1980) using catalytic amounts of camerahouse osmium, in the presence of t-butylhydroperoxide or N-methylmorpholine N-oxide in an inert gas, such as nitrogen or argon. Thus obtained dihydroxy-form (IV), in position 2 and 3-position, is dissolved in pyridine containing 4-dimethylaminopyridine for the reaction with propionic anhydride or butyric acid anhydride, and thus receive (V) in the case of propionic anhydride, or (VI) in the case of butyric acid anhydride. This compound (V) or (VI) is dissolved in a chlorinated organic solvent, which is resistant to oxidation, and oxidized organic peroxide, such as adventurou acid, m-monochlorobenzene acid, m-monobromoacetic acid, monongalia acid, cryptanalyses acid and its sodium salt or calcium salt thus that of the compound (V) obtained compound (I) or compound (VI) to the compound (II) (see end of text).

The compound (I) and sohimicheskim drugs seeds or plants in the growth stage can be achieved the effect of growth acceleration, the effect of resistance to diseases, the effect of reducing chemical damage under the influence of bactericide, herbicide or insecticide, the effect of reducing chemical damage under the influence of salts, the effect of reducing damage due to exposure to low temperatures and high temperatures, the effect of reducing the impact of the lack of moisture and the like effects. When handling chemicals plants in the area of the flowering period is achieved by increasing yield and improving the quality of rice, wheat, maize and other cereals, soybeans, kidney beans and other legumes, potatoes, sugar cane and other tuberous, cabbage and other crops of the genus brassica (cabbage crops). When melon, watermelon, cucumbers and other cucurbit-containing culture kind of Cucurbit (pumpkin) or tomatoes, eggplants and other Solana-containing culture of the genus Solanum (Solanaceae) are processed with chemicals, can be increased harvest and can be improved taste, shape and other characteristics of quality. A feature of these compounds is that they do not harm plants.

When using these compounds as plant growth regulators selskohozyaistvennaia as growth regulators of plants, they can be mixed with other plant hormones or agricultural chemical auxiliary means, for example contributing to the expansion of the tool, emulsifier, wetting, dispersing agent, binder, disintegrator, and can be used in a unit dosage form of powder, granules, pellets, solids, wettable powder, emulsion or liquid.

Different shapes, which are compounds of the invention are not unchanged depending on the crop plants, cultivated area, processing method, processing time or season and can consequently be determined. Although there are no restrictions, usually an effective way is by immersion, such as pre-treatment of seed before sowing or planting, method of spraying on leaves, stems, flowers, fruits, and land for growing plants in processing plants during the growth period, or method of coating or spraying.

Applied concentrations vary from culture plants, processing method, processing time and period and dosage forms, but usually when using an aqueous solution the concentration of the active ingredientsyou of the invention can be used either by themselves or mixed with insecticide, fungicide, herbicide or fertilizer.

The invention presented below using the following embodiments, it should, however, be noted that the technical implementation is not limited to the given examples.

The following PMR-spectra: s - singlet; t - triplet, m = multiplet; dd = double doublet.

The method of embodiment 1. Synthesis of 2,3- -dipropionate-24S-ethyl-5-cholesterol-22-EN-6-it (V)

To 20.5 g (49,92 mol) (22E, 24S)-24S-ethyl - 5-cholesta-2, 22-Dien-6-ONU (III) (K. Mori, Agric. Biol. Chem./ 44, 1211, 1980) is added to 7.3 g (54,42 mmol) N-methylmorpholine-N-oxide and 1000 ml of acetone and stirred. After purification of the reaction container with nitrogen gas to the reaction mixture overnight at room temperature, a mixed solution of 22 ml of water and 32 ml of t-butyl alcohol containing 390 mg (1.5 mmol) of camerahouse OS. Landed in the reaction solution crystals (15.6 g) is filtered off, the filtrate is stirred for 1 h, adding an aqueous solution of sodium bisulfite and extracted with chloroform, washed with water and dried over anhydrous magnesium sulfate, the solvent is distilled off in vacuum and get the crude product. This crude product is clean column chromatography on si is e filtered crystals (19, 37 g), add 150 ml of pyridine, 76 ml of propionic anhydride and 500 mg of 4-dimethylaminopyridine, leaving to react overnight at room temperature. Extragere chloroform, washing with water and drying over anhydrous magnesium sulfate and driving the solvent in vacuo, get the crude product.

This crude product is clean column chromatography on silica gel (benzene, ethyl acetate 30 : 1 to 15 : 1) and get 21,06 g (75.7 percent) of 2,3- -dipropionate-24S-ethyl - 5-cholesterol-22-EN-6-it (V).

The crystal type: needle. So pl.: 128 - 129oC (acetone)

The Rf value : 0,48 TLC plate (Merck 1.5 cm x 6.7 cm, Kieselgel 60F254, 0.25 mm layer thickness of film Art. 5715), hexane-ethyl acetate, 4 : 1 V/V.

PMR (CDCl3) (M. D.): 0,72 (3H, s), 1,10 (3H, t), of 1.16 (3H, t), 2,58 (1H, m), equal to 4.97 (1H, m), 5,09 (2H, m), of 5.40 (1H,m).

The method of embodiment 2. Synthesis of (22R, 23R, 24S)- 2,3-dipropionate-22, 23-epoxy-B-Homo-7-oxa-5-stigmasta-6-she (compound (I)).

Dissolving of 2.06 g (3,70 mmol) of 2,3- -dipropionate-24S-ethyl - 5-cholesterol-22-EN-6-it (V) obtained in the method of embodiment 1 in 100 ml of dichloromethane, add 8,0, (31,08 mol) m-chlormadinone acid and the mixture is stirred for 15 days at room temperature. Then, by adding 8.0 g of powdered calcium hydroxide, stirring Noi chromatography on silica gel (benzene : ethyl acetate 30:1 to 15:1) and gain of 0.85 g (39,0%) of (22R, 23R, 24S)- 2,3- -dipropionate-22,23 - epoxy-B-Homo-7-oxa - 5-stigmasta-6-it [the compound (I)].

The crystal type: needle. So pl.: 147 - 148oC (methanol). Rf value: 0,23 TLC plate (Merck - 1.5 cm x 6.7 cm, Kieselgel 60F254, 0.25 mm film thickness, Art. 5715), benzene-ethyl acetate, 10 : 1 V/V.

FD - MS: m/z 589 (M++1).

PMR (CDCl3) (M. D.): 0,72 (3H, s), 1,10 (3H, t), of 1.18 (3H, t), by 2.73 (1H, dd), of 3.00 (1H, dd), 4,10 (2H, m), 4,89 (1H, m), 5,38 (1H, m).

The method of embodiment 3. Synthesis of (22R, 23R, 24S)- 2,3-dibutyrate-22, 23-epoxy-B-Homo-7-oxa - 5-stigmasta-6-she (the compound (II)).

In the same way as in the method of embodiment 1, and 8.3 g of 2 ,3- -dihydroxy-24S-ethyl - 5-cholesterol-22-EN-6-she (IV) obtained by the processing of 10.0 g (23,45 mmol) (22E, 24S)-24S-ethyl-5-cholesta-2,22-Dien-6-she (III) as in the method of embodiment 1, add 100 ml of pyridine, 40 ml of butyric acid anhydride and 300 mg of 4-dimethylaminopyridine and allow to react overnight at room temperature. After extraction with chloroform, washing with water, drying over benzoic hydroxide of magnesium and removal of solvent in vacuo get the crude product. This crude product is purified column chromatography on silica gel (benzene : ethyl acetate 30 : 1 to 15 : 1), and obtain 10.0 g (72,9%) of 2,3- -dibutyrate-24S-ethyl-5- -cholesterol-22-EN-6-she (VI).

The crystal type: needle.

Rf value: 0,51 TLC plate (Merck - 1.5 cm x 6.7 cm, Kieselgel 60F254, 0.25 mm film thickness, Art. 5715), benzene-ethyl acetate, 4 : 1 V/V.

Processing 2,0 2,3-dibutyrate-24S-ethyl-5-cholesterol-22-EN-6-it (VI) as well as in the method of embodiment 2, get 640 mg (30,3%) of (22R, 23R, 24S)- 2,3-dibutyrate-22,23-epoxy-B-Homo-7-oxa - 5-stigmasta-6-it [the compound (II)].

The crystal type: amorphous substance.

Rf value: 0,49 TLC plate (Merck-made, 1.5 cm x 6.7 cm, Kieselgel 60F254, 0.25 mm film thickness, Art. 5715), benzene-ethyl acetate, 5 : 1 about/about.

FD - MS : m/z 617 (M++1).

PMR (CDCl3) (M. D.): to 0.67 (3H, s), 0,99 (3H, s), 2,70 (1H, dd), of 3.00 (1H, dd), 4,10 (2H, m), a 4.86 (1H, m), are 5.36 (1H, m).

The method of embodiment 4. The effect of stimulation of the growth of radish.

Prepare a solution concentration of 100 ppm, separately dissolving the compound (I) and (II) in ethanol. Prepare chemical solutions, bringing the concentration of compounds (I) and (II) to 1/100 h/million each, adding 2 ml of each ethanol solution to 20 ml of water containing 4 ml of a commercial spreader Guramin (Sankyo). Compound a (Japanese patent application laid N 1-125396, N 11) and brassinolide prepared in a similar manner, receiving a concentration of 1/100 h/million

Radish exp the period of the initial thickening of the roots. On the 12th and 24th day after treatment 30 hives best development taken from each plot, the weight of the plants was measured by the deciduous part and a root part, and calculate an average individual weight. The percentage of the treated plot compared to the untreated calculated and presented in table. 1.

As a result, as shown in the table. 1, on the 12th day after treatment brassinolide was the most effective. On the 24th day after the treatment, however, was excellent compounds (I) and (II) of the invention and further behind them, the compound A (Japanese patent application laid N 1-125396, N 11) and brassinolide, which suggests that the compounds (I) and (II) of the invention have excellent duration effect.

The method of embodiment 5. Effect of germination and growth when imensional (by immersion) treatment of rice grains

Of the compounds (I) and (II) the same way as described in the method of embodiment 3, prepare chemical solutions with a concentration of 1/100 h/million Compound B (Japanese patent application laid N 1-125396, N 6) and brassinolide similarly reduced to a concentration of 1/100 h/million

100 seeds of each seed (variety: Nipponbare) immersed in 20 ml of each solution (20 ml of water for some half of the seedling grows to stage 4 of the sheet, determine the degree of growth (the results are shown in table. 2).

In the compounds (I) and (II) of the invention have an excellent effect on the germination and the effect of growth acceleration in respect of rice, better than action B (Japanese patent application laid N 1-125396, N 6).

The method of embodiment 6. The effect of stimulation of tying seeds on the rice.

In each area of the rice field area 1 ar carried out the following test, using planting rice (cultivar Nipponbare), then prepare solutions of the compounds (I), (II), A and brassinolide) concentration of 1/1000 h/million and sprinkle on 15 l/ar, each using a small hand sprayer at the stage of troublevania (3 August, one week before earing) and at the end of the flowering phase (August 22). At harvest was taken 70 - 80 new grains with a single stem with treated plots and the control plot, average weight for each ear stem, and the calculated ratio to the control area. The result is shown in table. 3.

As can be seen from the table. 3, the weight of the spike to the original grain, it follows that the output (yield) increased, the compound (I) shows the greatest effect, the compound (II) is in second place and both outperform the impact .

Growing normally in field corn (grade Honey Bandam), put 1/100 ppm, solutions of the compounds (I), (II), A and brassinolide) 20 l/ar for 5 days before the formation of stamens and in the period of full bloom. The usual collection of female panicles selected an average of 50 panicles from each plot to measure the length of the section responsible for tying seeds and calculate the average length. The results are shown in table. 4.

Part responsible for tying seeds in plots treated with compounds (I) and (II) longer than the corresponding part in the plots treated with compound A and brassinolide, and noted the effect of the stimulation setting seed.

The method of embodiment 8. The effect of the stimulation thickening and fruit set of grapes.

Using Mature vines grown on plantations (sort Delaware), 1/100 ppm of each of the compounds (I), (II), A and brassinolide - sprayed on each brush 7 days prior to flowering. Collecting harvest ripening period, calculate the average weight of bunches from each plot. The result is given in table. 5.

The average weight of bunches from the plots treated with compounds (I) and (II) more than plots treated with compound A and brassinolide, and is celebrated with great yields in the processing of wheat seeds.

The compound (I), (II), A and brassinolide dissolved in a solution of ethanol and water 50 (about) : 50 (about), obtaining a concentration of 0.01 h/million In each solution are immersed for 2 with wheat seeds (cultivar Norin N 61) and air-dried. For the control plot seeds similarly treated with a mixture of ethanol and water, 50 (vol.) : 50 (vol.).

Treated seeds are sown in the usual way in November and grown in the field. Two months after planting is randomly selected to sample an average of 50 seedlings from each plot and determine the average weight of plants and the number of sprouts/seedlings (stem) and at harvest to determine the average weight of the ear/seedlings (stem). The results are shown in table. 6.

The method of embodiment 10. The effect of preventing damage to the plants from the cold.

Prepare aqueous solutions of 0.01 ppm of the compounds (I), (II), A and brassinolide) and put on benjamin tree with 150 to 200 leaves, grown in pot vessel in the greenhouse, and the vessel carrying the next day in the open air in late November.

After a 30-day trial count the number of leaves, fallen because of the cold weather, and calculate the intensity of leaves falling relative to the number originally estimated leaf.connections (I) and (II), lower than that treated with compound A and brassinolide, and there is a high effect of preventing damage to the plants from the cold.

The method of embodiment 11. The effect of reducing chemical damage by the herbicide (growth inhibition).

Three days before transplanting seedling of rice (cultivar Nipponbare) sprinkle of 0.01 ppm aqueous solutions of compounds (I), (II) and brassinolide) in the amount of 100 l / 10, ar. Then transplanted treated and untreated seedlings of five each in vessel area of 1/5000 ar and grown in the greenhouse. On the 5th day after transplantation into the vessel to make a commercial herbicides Simetryn and Butachlor equivalent to 5 kg of ingredient/10 ar. On the 20th day after herbicide treatment of the transplanted seedling vypilivayut, dried and calculated relative to untreated herbicide plot (%) and compared the degree of growth at each site. The result is shown in table. 8.

As shown in the table. 8, all connections reduce chemical damage (growth inhibition) herbicides, in particular the compounds (I) and (II) are largely the effect of reducing chemical damage compared to brassinolide.

The method of embodiment 12. The effect of the stimulation infructescence by reducing cloneconnection is to artificial pollination spray of 0.01 ppm aqueous solution of the compounds (I), (II) and brassinolide) equivalent to 300 l/10 ar.

Artificial pollination was performed using pollen taken from normal pollinator and using self-pollination.

2 months after pollination on the studied branches of each test plot to determine the number of fruits on pollen for pollination and calculate the rate of fruit set. The results are shown in table. 9.

Compared with the number of fruits to the usual way the rate of fruit set on the processed connection parts is increased and the compound (I) and (II) more effective than brassinolide. When using compounds (I) and (II) fruit set when self-pollination is equally comparable to the rate of fruit set when using pollen from pollinators and compound (I) and (II) of the invention have the effect of reducing the failure of fruit set in self-incompatibility and increase the rate of fruit set.

The technical applicability of the invention is that new brassinosteroid-like compounds exhibiting activity on the regulation of plant growth, expressed by the compound (I) and compound (II) represented by the invention, and the plant growth regulator containing them as AK the agricultural and horticultural fields and have postregulatory effects on plants and therefore, it is very useful industrially.

1. Brassinosteroid derivative of the formula (I)

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2. Brassinosteroid derivative of the formula (II)

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3. Regulating the growth of plants, the tool comprising as an active ingredient derived brassinosteroid in an effective amount and the target additives, characterized in that the quality of the derived brassinosteroid contains a compound of formula I under item 1 or the compound of formula II under item 2.

 

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