CS264313B2 - Cytokinin membrane active agent for increasing of plant productivity, albumin nitrogen content and aniont reception - Google Patents

Abstract

The composition contains as effective 0.5 to 90% by weight of the derivative of imidazole of formula I wherein R 1 is hydrogen, chloro optionally with chlorine or hydroxyl a group-substituted alkyl group C 1 -C 4 or alkenyl (C 2 -C 4) amino group methylamino, hydroxyl, mercapto, methylmercapto or an alkoxy group having 1 to 4 C atoms, R2 is optionally substituted by bromine alkyl having 1 to 4 atoms carbon and X is inorganic or organic an anion, preferably chloride, bromide or a sulfate anion, and in an amount 10 to 95% by weight liquid and / or solid support and from 1% to 15% by weight active ingredient.

Description

The invention relates to cytokinin, a membrane-active agent to increase plant productivity, protein nitrogen content and receiving anion which is suitable as a replacement kinethinu and which contains as active ingredient 0.5 to 90% of the imidazole derivative of formula ^I-1 --In CH

. Í í / ^{r r r} ,,,,

Ι ^ .Λν> ^Η · ^ΗΧ 'NI r ₂

Wherein X is hydrogen, chlorine, C1-C4alkyl optionally substituted by chlorine or hydroxyl, C2-C4alkenyl, mercapto, hydroxy, methylmercapto, C1-C4alkoxy, amino , methylamino or dimethylamino, R @ ₂ further represents an alkyl group having 1 to 4 carbon atoms optionally substituted by bromine, and

X an inorganic or organic anion, preferably a chloride anion, a bromide anion or a sulphate anion, and in an amount of 10 to 95% by weight of a liquid and / or solid carrier and 1 to 15% by weight of a surfactant.

Chemicals have long been used in plant cultivation: in addition, fertilizers and pest control products have been increasingly used in recent decades to influence the growth and yield of crops: collectively these are referred to as regulators.

These regulators are mostly natural or affect and control various plant growth processes (Lapja 34, 3, 122-126, 1979).

synthetic hormones that can be used (M. Kólcei, M. Nádasy: Kagyar Kémíkusok

Natural and artificial auxins (indolootic acid derivatives) affect plant life processes in many ways. There are four main types of synthetic auxins: indole derivatives, naphthyl derivatives, phenoxy derivatives and benzoic acid derivatives. In practice, naphthylacetic acid methyl ester is used as a dusting agent to prevent the germination of potatoes, potassium salt of naphthylacetic acid for rooting of seedlings and to prevent premature fruit dropping.

The second large group of regulators are the gibberellins, which stimulate growth, induce flowering and interrupt the resting state. They are also used in practice.

and

The third group consists of cytokinins, whose action is very multifaceted. They stimulate cell division, delay aging processes, maintain application dominance, and interrupt the resting state. Of the natural cytochinones, seatin and lupine are known, but are not used in practice.

The fourth group includes abszisins, which affect endogenous regulation of aging and, in addition, inhibit growth and promote organ separation. Although more than 70 compounds with xanthonine structure and ebscisin action have been synthesized so far, these compounds have not been used in practice.

The only gaseous hormone is ethylene, which is produced to a large extent by fruit ripening and which speeds up fruit ripening. In practice, 2-chloroethylphosphonic acid is used for this purpose.

In addition to plant hormones (auxins, gibberellins, cytokinins, growth of brake substances, abszisins, ethylene, etc.), many other biologically active substances are used in agriculture. The widespread use of 2-chloroethyltrimethylammonium chloride (CCC) for wheat and barley is recalled (U.S. Pat. No. 3,156,544).

Endogenous cytokinins (seatin, lupine) and synthetic cytochinins (kinethin, benzyladenine, etc.) increase protein yield and content, but are barely used in agrotechnics for their high production costs (F. Skoog, FM Strong, 0. 0. friller: Science 148, 532-533, 1965).

Hungarian Patent No. 162,937 discloses germinating, development of budding promoting and maturation-accelerating amide derivatives of 2-chloroethane / thiono / phosphonic beast. Hungarian Patent No. 163,510 discloses thiocarbamide derivatives which affect the separation of fruits. Hungarian Patent No. 164,190 discloses a maturation-accelerating, aging-retarding, growth-inhibiting halenethansulfinic acid, for example ihlorothynylfinic acid. According to Hungarian Patent No. 164,512, civiva is treated by sieving with tois / dimethylammonium (? -Chlorobenzylphosphonate derivatives), thereby increasing grain yield and nitrogen uptake.

Hungarian Patent Nos. 164,567 and 164,866 describe maturation accelerating the action of beta-haloethylsilanes.

Individual pyrimidine derivatives (e.g. 2-methylthio-4-ethylamino-5-nitro-5-methylaminopyrimidine) and their salts inhibit germination and inhibit growth to length (Hungarian Patent Specification 164 885),

Suitable symtriazinedione derivatives for influencing the flowering and sexual reproduction of plants are described in Hungarian Patent Specification 167 576. Hungarian Patent Specification 168 916 also discloses flowers and a generative reproduction-affecting composition comprising allophanimidates.

According to Hungarian patent specification 170 761, emergence and growth are accelerated by numerous phthalimide derivatives, for example 3-trichloromethylphthalimidera, 1- (3-chlorophthalimido) cyclohexylcarboxamide. Sugar-enhancing compounds are known from Hungarian Patent Specification 162,520 L2- (aminoalkoxy) -4-phenylthiazole derivatives] and Hungarian Patent Specification 165,576-2,4-bis- (N'-methyl-4'-pyridinium-sym). -triazinediodide /].

According to Hungarian Patent No. 165,576, it is used to stimulate the vegetative growth of sugar beet in addition to gibberellin, imidazoles and also to the fungicides of some herbicides in very low amounts. However, these funds have not survived in practice.

Both endogenous cytochinins (seatin, lupine) and synthetic cytokinins (quinathine, benzyladenine) (F.M. Strong: Topics in Microbial Chemistry, Wiley, New York 1958, F. Sttog,

F.M. Strong, F.M. Miller: Science 148, 532-533, 1965) are exclusively 6-aminopurine derivatives whose main biological activity is manifested by stimulating the frequency of mitoses. In addition to this, numerous side effects have also been useful, in agro-technical and microbiological applications, for example:

(a) when growing kallus and mericlon, increases both fresh and dry weight?

bj the enrichment of organic substances in the vegetative and genetic organs is more favorable?

(c) is the storage of chlorophyll stimulated, thereby increasing its phytochemical efficacy?

(d) is the rejuvenation of the leaves encouraged, thereby suppressing aging?

e) carbon dioxide is more strongly fixed in phytosynthesis?

f) Does measurable photolytic efficiency increase by degradation of RTO?

(g) the intensity of synthesis of amino acids and proteins increases, in particular there is a significant absolute and relative increase in the amount of protein nitrogen fractions soluble in 0,5% sodium chloride solution;

h) synthesis of the nuclinic acid is intensified.

Adenine and special derivatives have so far been prepared only in small quantities in the laboratory. Despite many promising experimental results, cytokinins have not been used in practice because of their high production costs. Among the many known growth retardants there are none with cytochinin activity. The known formulations do not have a cytoohinin action, so they are not expected to have a cytoohinin action either.

In an investigation of increasing plant growth, productivity and protein levels, as well as attempts to increase yield, it has been found that a composition according to the invention which contains imidazole derivatives of the formula I in an amount of 0.5 to 90% by weight, liquid and / or solid carriers. an amount of 10 to 95% by weight and 1 to 10% by weight of surfactants is suitable for influencing physiological processes in plants.

Some imidazole derivatives of the formula I are known from the literature (Auwers, Mausa; Chem. Ber. 61, 2 414, 1928; Davies Mamalis, Petrow, Sturgeon: J. Pharm. Pharmacoi, 3, 420, 1951; Weidenhagen, Train, Wegner Nordstrom, Chem., Ber., 1936, 1942, Pozharsky, Simonow, Zur, Obshchej, Chlm., 33, 179 (1963); however, the effect of these compounds on plant productivity has not been known.

The compositions according to the invention contain, in addition to the carrier and the surfactants, the compounds of the formula I and influence the physiological processes in plants even at relatively low concentrations (1 to 200 ppm or 0.5 kg of active substance per hectare).

It has been shown experimentally that the controlling effect of the composition of the invention on plant productivity, protein synthesis and photosynthesis is stronger than that of chemically proximate plant growth regulators according to Maar. .

The imidazole derivatives of the formula (I) do not only have a biological cytokinin activity exerted on cells, but, unlike cytochinines, their production and use in agriculture are also economical. Furthermore, the compounds of formula I possess membrane activity (i.e., stimulate anion uptake) which is completely lacking in endogenous and synthetic cytokinins

Research into biological action has revealed that the regulatory action on nitrogen exchange occurs in almost all of the plants tested, while the degree of influence on protein synthesis and photosynthesis depends on the type of plant being treated.

Well-reproducible methods have been developed for the biological testing of the novel composition with respect to its action. Effect on protein synthesis was assayed isotope technique using labeled amino acids (glycine-l- ¹⁴ C glycine-2- ¹⁴ C methionine [S-methyl- ¹⁴ C]). Stimulation of photosynthesis is also tested using the isotope technique by incorporating labeled carbon dioxide ( ¹⁴ CO ₂ ).

The effect on nutrient uptake is measured by determining the incorporation of labeled phosphate ion, while the chlorophyll decay inhibition is measured by extinction using methanol prepared samples at 665 microns.

There is a perfect match between the results of laboratory tests and field trials. The composition according to the invention acts on plant life processes in this way.

(a) the development of the intermodium (for wine, for example) is shortened, the number of leaves and the dry weight of the leaves are increased, the nitrogen-carbon ratio gains a favorable lower value;

b) stimulation of root growth (root factor) also intensifies the growth of above-ground shoots.

This shortens the vegetative growth time (for example in brewing barley by 6 weeks) and increases the development of generative organs and harvest;

(c) the intake of nitrogen and phosphate from the soil is increased in crops of perennial, butterfly-like plants (such as alfalfa) and in green fodder crops (silage maize, grassland), the protein content rises substantially in the leaves and the ratio is reduced nitrogen-carbon;

(d) in the treatment of maize, soybean, barley, wheat and similar crops, the grain yield increases, the total nitrogen content increases by about 20%, but the protein content increases to a greater extent;

(e) in the treatment of sugar beet, the yield of the eyeballs is increased and their sugar content, measurable by polarometry, increases, so that more sugar can be produced per unit area. Genetically determined sugar content in beets is more quickly achieved and thus may begin harvesting earlier;

(f) if the vines are treated twice before flowering and then before ripening, the mean weight of the grapes, the weight of 1 000 grapes and the refractometrically detectable sugar content shall be increased;

(g) the rooting of wine and fruit trees shall be encouraged and the treatment shall also stimulate the differentiation of the central axis and sprouts and the sprouting and ripening, while also affecting the ripening (woody) of the shoots and thereby their resistance to frost;

h) the compositions can also be used for growing plant tissue, for differentiating the tissue of kallus organs; their action is based on increasing the frequency of mitosis;

i) The composition according to the invention, when applied to crop plants by spraying, acts as an antidote which compensates for the phytotoxic action of numerous herbicides.

Treatment with the composition according to the invention is possible before sowing or before planting, however, the composition can be used after sowing by spraying on the soil or on the plants themselves in their different stages of development; the way of use depends on which development stage and which properties are to be influenced. In most cases, a single treatment is sufficient, but there are also cases, for example in the case of vines, when the treatment is repeated.

In general, minimal doses are required for the treatment (depending on the composition of 0.5 to 20 kg / ha, even 0.5 to 2 kg / ha), but the composition according to the invention even when used in extremely large doses (20 to 30 kg / ha). ha) has no phytotoxic effect on plants. It is preferred that the composition of the invention does not irritate the skin, do not lead to allergies or damage the eyes and is practically non-toxic (ΙΌ, θ 2,500 mg / kg).

. The imidazyl derivatives of formula (I) may be prepared by methods described in the literature. The correspondingly substituted imidazole is reacted in a solvent such as acetone, benzene or toluene at 50 to 160 ° C with alkyl halides or alkyl chloroformates. The imidazolium salt formed is filtered off, washed and dried. The compound may contain, as an impurity, a slightly dialkylated product. Its amount is so small that it does not affect the action of the composition according to the invention. If the end product is to be devoid of dialkylated product, it is prepared in two steps: first, N-alkylimidazole is prepared and from it is prepared in a separate process an imidazolium salt, for example a halide or sulfate.

The plant growth regulators of the invention may be in solid form (dusting agent, granulate). In this case, kaolin, bentonite, active silicic acid, gypsum, calcium carbonate, talc and the like are used as solid carriers and fillers.

Liquid formulations may also be prepared. Of these, the most preferred formulations are oils. The dosage forms prepared therefrom can be applied to the plants at any stage of development. Suitable diluents for oily compositions are vaseline oil, wood oil, other vegetable oils, as well as non-phytotoxic mineral oil fractions.

Both solid and liquid formulations contain surfactants. Surfactants which may be used are cationic, anionic and nonionic surfactants.

Suitable cationic surfactants are quaternary ammonium compounds (cetyltrimethylammonium chloride), as anionic surfactants of the salt of dodecylbenzenesulfonic acid, as anionic surfactants of polyoxyethylene alkylphenols, polyoxyethylene sorbitates, polyoxyethylene triglycerides and similar mixtures of the surfactants, but also of the surfactants.

The preparation of the compounds of formula I is illustrated in Example 1, the preparation of the compositions of the invention is illustrated in Examples 2-5, and the other examples describe the physiological action of the composition of the invention.

He did

To a 2,000 ml flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel was charged 118.2 g (1 mol) of benzimidazole and 800 ml of toluene. 200 ml of isopropyl chloroformate is added with stirring, while maintaining the temperature at 20 ° C. After the addition was complete, the mixture was heated to 60 ° C and stirred at this temperature for two hours. The mixture was stirred at 90-100 ° C for two additional hours and then cooled to 15-20 ° C. The off-white crystals were filtered off, washed and dried at 80 ° C.

125.5 g (81.7%) of N-isopropylbenzimidazolium chloride having a melting point of 134-136 ° C are obtained.

Other compounds of formula I may be prepared by analogous methods.

Example 2

48 g of technical (94%) N-isopropylbenzimidazolium chloride as filler 4 g of Ultrasil VN-3 as emulsifier are 20 g of Emulsogen M and 128 g of technical vaseline oil are fed into a laboratory bead mill. The mixture is milled after adding 400 g of glass beads of diameter 1.5 mm for one hour at a rate of 775 r.p.m. ^first The mixture is then separated from the glass beads by means of a 1 mm sieve. The oily preparation, containing 20% of N-isopropylbenzimidazolium chloride, diluted to 1% with water, still remains after 12 hours a stable emulsion without deposit. .

Example 3

11 g of technical (96%) N-isopropylbenzimidazolium chloride, 4 g of Ultrasil VN 3 as filler and 16 g of Emulsogen M as emulsifier and 170 g of vaseline oil are charged into a laboratory bead mill. After the addition of 400 g of 1.5 mm diameter glass beads, the mixture is milled for 1 hour at 775 rpm. The glass beads are separated on a 1 .mu.m sieve.

The composition diluted with water 20 times forms a stable emulsion.

Example 4

The powder mixer for laboratory use is charged with 53 g of N-isopropylbenzimidazolium chloride, 37 g of Zeolex 444, 5 g of powdered sulphite lye, 3.5 g of Supermittel 1494,

1.5 g Netzer IS and 0.3 g Tensia defoamer antifoam. The substances are mixed and homogenized. Then the mixture is ground in an Ultraplex Alpine mill

100 LU.

If 50% of the composition is diluted to 0.5% with water, 86-90% of the particles are still in the floating state after half an hour. The wet residue on the screen (DIN 100 screen) is 0.5 to 1.5%.

and

Example 5

In a powder mixer for laboratory use, 84.2 g of N-isopropylbenzimidazolium chloride, 9.5 g of talc, 5 g of powdered sulfite lye are charged. 1 g Netzer IS and 0.3 g methylene blue. The substances are mixed and homogenized. The mixture is ground in a laboratory mill according to the preceding examples. The wet sieve residue (DIN 100 sieve) is 2 to 4 w.

He does

Effect on tobacco kallus growth

The composition of the invention is diluted with water to a concentration of 10 ppm and mixed into the broth prior to incubation. The treated broth as well as the untreated control broth is incubated for three weeks with the tobacco kallus. Daily gain, cell growth, and mitosis frequency were determined by the Skoog method. The results are shown in Table I

and b u 1 k and I Treatment Daily Number of cells Frequency of mitosis growth mg g.10 ⁴ % 1. untreated control 16.0 227.7 100 ALIGN! 2. N- (n-propyl) benzimidazolium bromide 22.8 327.5 143

It can be seen from the table that treatment with the compositions of the invention increases the daily increment and cell number and mitosis rate by 43%.

Example7

Effect on tobacco kallus growth

The procedure is analogous to Example 6, except that 1 ppm quinathine is used for comparison. The composition of the invention is used at a concentration of 2 ppm. The results are shown in Table IX.

Table II

Number Treatment Dry weight of kallus mg Speed index growth % 1 quinethine 174.11 97.17 100 ALIGN! 2 N- / n-propyl- benzimidazolium- chloride 194.09 116.89 119.0 Example 1 ad 8. '

Influence on growth from Datura innoxia roots of isolated isolated kallus

The procedure is the same as in the previous examples, and the nutrient is used as a control

264-313 soil containing 2 ppm quinethine. The results are shown in Table III. The substance according to the invention, N- (n-propyl) benzimidazolium bromide, is listed in the table under letter A.

) for 1 k a III Treatment Mass kallusu Dry matter Value growth Growth rate fresh dry fresh dry G mg % mg / day quinethine 4,969 4 175.06 3.52 15.56 15.56 95.28 quinethine + A 6,577 2 209.13 3.17 20.92 18.78 128.10 untreated 0,396 8 28.08 7.07 0.32 1.65 1.97 AND 0,612 0 43.29 7.07 1.04 3.09 6.36

Table IV shows the effect of the composition of the invention on the growth rate in percent.

Table IV

Treatment Control AND Chinethin 100 ALIGN! 134 Without quinethine 100 ALIGN! 322 : k 1 and d 9

Braking of chlorophyll decomposition in barley, salsa, bean, alfalfa and corn

The composition of the invention is diluted with water to a concentration of 200 ppm. A 200 mg leaf segment of the test plant is allowed to float on the surface of the solution obtained for 4 days with the exclusion of light. The chlorophyll is then extracted from the leaf segments with methanol.

At the same time leaf samples are extracted at the initial stage and after 4 days of residence time on the surface of distilled water. The concentration of chlorophyll in the methanolic extract is determined by measuring the texturing at 665 microns. The results are shown in Table V.

Table V

Effect of various N-alkylbenzimidazolium bromides on chlorophyll content in alfalfa and maize

Compound of Formula I Alfalfa Corn increase chlorophyll content

mg % mg % N-methyl derivative 0.83 6.4 0.80 23.0 N-ethyl derivative 0.85 8.9 0.79 21.5 N-bromoethyl derivative 0.64 - 0.71 9.2 N-n-propyl / derivative 0.96 23.0 0.82 26.1 N- (n-butyl) derivative 0.81 3.8 0.76 16.9 untreated 0.79 - 0.65 -

Examined chlorophyll content in 100 mg of alfalfa and corn in green. The results show that the compositions of the invention inhibit the breakdown of chlorophyll.

Example 10

Effect on chlorophyll preservation

The chlorophyll preservation effect of the composition of the invention is compared to that of endogenous and synthetic cytochinines. The bean plants of the Pinto species are used as experimental plants. The action is determined two weeks after treatment by measuring extinction at 665 nm.

The following table shows that at a concentration of 200 ppm the compound of the invention has a stimulating effect on chlorophyll. The action is somewhat weaker than that of endogenous and synthetic cytokinin. Even at concentrations above 10,000 ppm, the compositions of the invention are not phytotoxic.

Table VI Treatment Concentration Ppm Extinction Stimula · % untreated control - 0,671 seatin 20 May 1,283 91.3 kinethin 30 1,120 67.0 benzyladenin 30 1,229 83.1 AND 200 1,081 61.2

Example 11 Stimulation of protein formation in sc / ji

The composition of the invention is diluted with water to a concentration of 200 ppm. 200 mg of soya leaf segments are allowed to float on the surface of the solution for 24 hours. Equally heavy segments are used as controls and allowed to float on the surface of distilled water. Then the segments are rinsed with distilled water and stored in a radiolabeled amino acid (glycine-l- ¹⁴ C 2fíCí) solution (20 ml) for three hours. The leaf segments are then rinsed with plenty of water to isolate the protein in the usual manner. A stock solution is prepared from the isolated protein and its specific radioactivity is measured by a liquid scintillator. The values obtained are shown in Table VII.

Table VII

Treatment Number

N- (n-propyl) benzimidazolium bromide

Radioactivity γU Ci / 100 mg

13.7

Stimulation%

15.2

It is apparent that protein formation in the soybean leaves treated with the composition of the invention is greater than in the untreated control leaves.

Example

Effects on protein synthesis

The bean leaves of Pinto are left for 18 hours in a solution of natural or synthetic cytochinins and in the composition of the invention. The effect on protein synthesis is measured by detecting the incorporation of a radiolabeled amino acid (glycine-2-C). In Table VIII, the radioactivity is at 1000 dpm / 200 mg fresh weight.

Table VIII

Treatment

Concentration

PPm

Radioactivity

000 dpm / 200 mg in the TCA insoluble fraction

Stimulation untreated seatin

3.17

6.18

95.1

AND

) for 1 k and VIII continuation Treatment Concentration Radioactivity Stimulation ppm 1000 dpm / 200 mg in the TCA insoluble fraction % kinethin 30 5.36 69.4 benzyladenin 30 5.92 87.0 AND 200 4.52 42.7

As shown in the table, the action of the composition of the invention is somewhat weaker than cytochinine, but considering that these are not trace hormones but are readily available compounds, the action is severe.

Example 13

Slices of alfalfa, soybean, bean and maize leaves weighing 200 mg are allowed to float on the surface of the composition of the present invention diluted to 200 ppm with water.

The leaf pieces are then introduced into the assimilation chamber of a suitable apparatus. With careful control of the illumination by means of a metering valve, a known amount of radioactive carbon monoxide (CO ₂ ) is introduced from said chamber. After 30 minutes, the leaf samples are frozen in liquid nitrogen, triturated in a Potter 50% perchloric acid homogenizer and processed to a stock solution.

The specific radioactivity of the stock solutions is measured by a liquid scintillator.

Untreated leaf samples also exposed to labeled carbon dioxide in the same assimilation chamber were used as controls. Untreated sheets received amount

is considered 100%. In addition, the amount received is i b u 1 k and IX in Table IX states in percent. Treatment Lucerne , Soya Bean Maize in addition, the amount of CO ₂ received % % % % 1. N-methylbenzimidazolium- bromide 125 2. N-ethylbenzimidazolium- bromide 184 3. N- (bromoethyl) -benz- imidazolium bromide - 57 4. N- (n-propyl) benz- imidazolium bromide 12 236 - 84 5. N- (n-butyl) benzimidazolium- bromide 41 47

It can be seen from the table that the composition according to the invention influences the crop plants to various but mostly to a large extent.

Example 14

Strengthening of carbon dioxide fixation

The intensity of fixation of photosynthetically bound carbon dioxide was measured on Pinto species.

The leaf samples are allowed to float for 18 hours in a bioactive solution, fixation is performed for 14 half-hour exposure (at 100 µCi / 5000 ml CC> ₂ ).

The following table X shows that seatin ('root factor') has the greatest effect, while synthetic cytochinins are somewhat inferior and the composition of the invention has the same type of action, but not so strong. However, as in Example 12, it is recalled that according to the invention, these are not trace hormone plants but are readily available compounds.

bulka X Treatment Concentration Radioactivity Increase in the light, in the dark, total ppm dpm / 200 mg % untreated - 2.14 0.18 2.32 - seatin 20 May 5.12 0.46 5.58 140.8 kinethin 30 4.15 0.37 4.52 95.2 benzyladenin 30 4.87 0.41 5.28 128.0 AND 200 3.92 0.34 4.26 84.0

Example 15

Stimulation of plant photosynthesis

The composition of the invention is diluted to 500 ppm with water. Samples of 200 mg maize leaves were treated in this solution for two hours. The samples are then stored for one hour in a 10 .mu.l / 50 ml RTO, then frozen in liquid nitrogen, triturated, chromatographed and chromatographed to determine their radioactivity by appropriate glycerinaldehyde treatment. The results are shown in Table XI.

Table XI

Treatment Dry matter dpm / mg untreated control 4.64

A 8.76

Stimulation%

The measurement results show that the composition of the invention effectively stimulates photolysis.

Example 16

Stimulation of photolytic activity

The photolytic efficacy of endogenous cytochinins (seatin), synthetic cytochinins (quinethine, benzyladenine) and regulators according to the invention are compared. Tests of Pinto bean leaves are allowed to float in violative solutions for 18 hours, the exposure to RTO-photolysis lasting one hour (200 µCi / 100 ml). Radioactivity is reported in dpm / mg tartaric sugar.

Table XIX Treatment Concentration ppm Photolytic potency of grape sugar dpm / mg Stimulation % untreated - 7.64 - seatin 20 May 15.94 108 kinethin 30 13.96 82 benzyladenin 30 17.21 125 AND 200 14.08 84

Example 17

Stimulation of nutrient uptake

The composition of the invention is diluted with distilled water to a concentration of 200 ppm. The solution is treated with pieces of leaves weighing 200 mg of wheat, corn and peas.

The leaf pieces are then transferred to a 30 µCi / 50 ml labeled phosphate solution and processed for half an hour. Then the pieces of leaves are processed in a conventional manner. The nucleic acid fractions were isolated and dissolved in 6N ammonia. From solution

A stock solution is prepared and its radioactive phosphate content is measured by a liquid scintillator. The results are shown in Table XIII. Table XIII Treatment Wheat Maize Pea control 1 000 cpm / g 17.4 31.2 25.3 AND 22.8 39.3 32.7 (+31.0 i) (+ 25.9%) (+29.2 The numbers in parentheses indicate In percent stimulating themselves with regard to untreated control.

Obviously, treatment with the composition of the present invention increases the incorporation of significant phosphate ion into the nucleic acid fraction by 26-30%, suggesting an increase in nutrient uptake.

Example 18

Stimulation of membrane activity

The composition of the invention also has a membrane active action. This effect was not found in endogenous or synthetic cytochinins. Table XIV shows the stimulation of nitrate uptake for cytochinines and for the compositions used according to the invention. Nitrate uptake results in an increase in total nitrogen and protein nitrogen content.

The experiments were carried out on leaves of a Pinto bean plant; evaluation is performed two weeks after treatment.

Table XIV

Treatment Concentration Dry substance contains nitrogen Protein total protein nitrogen in% of total ppm % % nitrogen untreated - 3.8 2.4 63 seatin 20 May 3.8 2.8 (+16.6 %) 73 kinethin 30 3.8 2.8 (+16.6 %) 73 benzyladenin 30 3.8 2.8 (+16.6 %) 73 AND 200 5.3 (+39.4 %) 4.4 (+83.3 %> 83

The numbers in parentheses indicate the percentage increase with respect to the untreated control.

Example 19

Stimulation of the effect on total nitrogen and protein nitrogen in alfalfa

The compositions of the invention are treated with alfalfa in a free field. The experiments are repeated four times on a plot of 1 hectare each. The composition of the invention formulated with oil is diluted with water and sprayed once or twice on the plot. The first treatment is carried out at a time when the resulting alfalfa covers the soil. For the plots to be treated again, a further dose of the composition according to the invention is applied two weeks after the first treatment. In both cases a quantity of 2 kg / ha is used.

After cutting the alfalfa, the total nitrogen and protein nitrogen are determined. The results are shown in Table XV, where the numbers in brackets indicate an increase in percent relative to the untreated control.

Table XV

Treatment untreated Compound A

1. treatment

2. treatment

Total nitrogen content in dry matter%

3.36

3.51 (+4 4)

3.91 (+ 13%)

Protein nitrogen content in dry matter%

2.25

2.48 (+22%) 2.75 (+22%)

As can be seen from the table, a single treatment increases the nitrogen content of the dry matter by 4% and the protein nitrogen content by 22%. The proportion of protein nitrogen in the total nitrogen content rises from 67% to 70%, that is, by 5%. In two repeated treatments, the nitrogen content of the dry substance increases by 13%, the protein nitrogen content by 22% and the protein nitrogen content in the total nitrogen content by 5%.

Table XVI

Treatment Yield of green matter Raw protein Ratio 100 kg / ha P ₂ Drawbar in dry substance C: N untreated 120 21,3 8,3 AND 142 ⁺ ( ⁺ 18.7%) 25.8 ⁺⁺⁺ 10.9 ⁺⁺ 4,30 ' (+21.5%) (+31.7%) (-21.1

Signature limits:

+ ++ +++ ^SD 5% ^SD 1% ^SD 0, 1% The numbers in parentheses indicate the difference from the untreated control in percent.

Example 20

Effect on total nitrogen content and protein nitrogen content in a mixed culture of sdji and sunflower

The soybean-sunflower mixed culture intended for green fodder is treated with a composition according to the invention in a field test. The tests are carried out with 4 repetitions on plots of 1 hectare. The composition according to the invention is diluted with water and the emulsion squeezing is applied at a rate of 2 kg / ha each. The first spraying is carried out when the emerging plants cover the soil. The second treatment is carried out two weeks after the first treatment and the treatment is carried out two weeks after the second treatment. The green vegetable matter is harvested on untreated and treated plots and its total nitrogen and protein nitrogen content is determined.

Table XVII

Treatment not treated

AND

Nitrogen content of dry matter total protein%%

2.56 2.27

2.80 (+ 9.7%) 2.75 (+ 21.1%)

Total nitrogen / protein ratio 100%

65.2

98.9

The numbers in parentheses indicate the percentage increase with respect to the untreated control.

The table shows that the treatment increases the total content by almost 10%, the protein nitrogen content by approximately 20%. The proportion of protein nitrogen in the total nitrogen content increases much more, by up to 52%. This makes the feed value of green feed better, which is very important for animal nutrition.

Example 21

Action of the composition according to the invention on the weight of the green substance, on the total nitrogen content and on the protein nitrogen content of silage maize

Experiments are carried out on a plot of 200 m. The composition of the invention is diluted with water and treated immediately before sowing. The weight of harvested maize for silage from treated and untreated parcels shall be determined. The composition of plant matter is also investigated. The results are shown in Table XVIII.

Table XVIII

Parameter Control Compound A Green matter yield (kg) 365 389 dry matter content (%) (dried to air) 20.57 23.48 (+14.1%) Crude protein (%) 1.85 2.25 ⁺ ( ⁺ 21.7%) true protein (%) 1.35 1.4 (+4.4%) total carbon content (%) 8.99 10.27 ⁺⁺⁺ total nitrogen content 0.30 0.86 ⁺ ratio C: N 30.86 28.67

Signature limits are the same as in Table XVI. The numbers in parentheses indicate the percentage increase with respect to control. It can be seen from the table that the weight of green matter is greater by 10%, the dry matter content of silage maize by 14% and the crude protein content by 36%. The true protein content shows an increase of 4.4%.

The C / N ratio has a numerically lower value, which means favorably influencing and displacing the nitrogen fraction. The results are summarized in Table XIX. The values in brackets indicate the percentage difference from the untreated control.

Table XIX Treatment Weight of green matter Crude protein ^P 2 ° 5 C / N in dry matter 100 kg / ha % % untreated 310.2 13.2 7.5 31.4 compound A 398.2 ⁺⁺⁺ 17.1 ⁺⁺ . 9.8 ⁺⁺⁺ 23,5 ⁺⁺⁺ (+28.4%) (+29.7%) (30.8%) (-25.4% Compound A is in this case N- (i-propyl) benzimidazolium chloride

Signature boundaries are the same as Table XVI.

Example 22

The hybrid corn seed is treated with the composition of the invention; The composition according to the invention is used as a moistened powdered mordant in an amount of 0.5 kg / ha. After unfolding the fresh leaf, spraying is carried out at a rate of 3 kg / ha. The second field treatment is carried out on the appearance of flowers (1 kg / ha, the third field treatment is carried out at the time of ripening of the ears (2 kg / ha). Table XX shows the weights mass.

Table XX Treatment Grain yield maize 100 kg / ha Rise in% untreated 132.8 - compound AND 149.3 12.4 compound (B) 208.5 57.1

Compound B is N- (i-propyl) benzimidazolium chloride

The data show that the composition according to the invention significantly increases the corn grain yield (by 12 to 57%).

Example 23

Effect on soybean yield

The soybean culture is sprayed three times at a rate of 2 kg / ha during the growing season. The first treatment is carried out at the beginning of flowering, the second at the flowering tip of the flower bunch and the third two weeks after the second spraying. The grain yield is measured. The results are shown in Table XXI.

Table XXI

Treatment Grain yield (100 kg / ha) Rise (%) untreated 29.33 Compound A 38.67 30.0

The results show that the composition according to the invention greatly increases soybean grain yield (by 30%).

Example 24

Effect on wheat grain yield and total nitrogen content and protein nitrogen content of the grains

On large plots, tests on wheat Libelulla and Mexikói 226 K are carried out. Immediately before sowing, the soil is treated with 2 kg / ha of active ingredient. After harvest, the yield, total nitrogen content and protein nitrogen content of treated wheat and untreated wheat are compared. The results are shown in Tables XXII and XXIII. Table XXII refers to Libelulla wheat, Table XXIII to Mexikói 226 K.

Table XXII

Treatment Weight of grains from 100 ears G Stimulation % untreated 215.79 - Compound A 357.73 65

It can be seen from the table that the grain yield of wheat of the Libelulla species increases by 65% after use of the composition according to the invention.

Table XXIII

Treatment Total nitrogen content Protein nitrogen in dry matter untreated Compound A%

2.12

2.13 (+1.0 »)%

1.61

1.74 (+8.0 »)

Tests with Mexikói 226 K wheat show that in addition to a minor increase in total content, there is a substantial increase in protein nitrogen content.

Example 25

Effect on yield and sugar content in beet

Sugar beet seeds are treated with the composition according to the invention, using 1 kg of the composition according to the invention per hectare. Spent plants are sprayed twice with 2 kg / ha each. The treated sugar content is higher (16.1% vs. 15%). After harvest, the yield of the eyeballs and the yield of sugar are determined. The results are shown in Table XXIV.

Table XIV

Treatment Yield 200 kg / ha Content Yield Rise versus sugar control % 100 kg / ha % untreated 541 16.00 87.56 - Compound A 877 17.05 149.49 70

It will be appreciated that the composition of the invention substantially increases the sugar yield.

Example 26

Effects on the yield of grapes and on the sugar content of the grapes

The vine plants are treated with the composition according to the invention before flowering, then three weeks or six weeks after the first treatment. The water-diluted composition is sprayed using 2 kg / ha.

Tests are carried out in parallel with commercial plant growth regulators; CCC (OH) is used, Ethrel (Etaphone: 2-chloroethylphosphonic acid) and Nevirol (N-phenylphthalimic acid). The results given in Table XXV relate to the species of vine Pannonia,

Table XXVI shows the results with the Egru bunch of grapes.

Table XXV

Treatment Grape yield 100 kg / ha Sugar content % Sugar yield 100 kg / ha untreated 216 13.0 28.08 Compound A 226 15.8 (+21.5 ») 35.7 (+27%) CCC 175 16.0 (+23.0 %) 28.0 Ethrel 194 14.0 (+7.5 «) 27.2 Nevirol 238 15.4 (+18.4 %)  36.52 (+30%)

Values in brackets represent increments in percent with respect to the untreated control.

Table XXVI

Treatment Grape yield Sugar content Sugar yield 100 kg / ha % 100 1 kg / ha untreated 151.15 16.7 18.93 Compound A 176.92 (+17.0%) 16.7 22.16 (+17.0%) CCC 144.61 17.0 18.44 - Ethrel 164.61 (+8.9 «) 15.7 19 ', 38 (+2.3 ») Nevirol 169.22 (+11.9%) 16.4 20.81 (+9.9%)

The results show the effect of the vine species on the effect of the composition according to the invention. The composition according to the invention stimulates the yield of grapes and the sugar content of the Pannonia species, while in the case of the girl's grape the sugar content does not increase, but the yield of the grapes is 17% higher.

Example 27

Effect on protein nitrogen yield in pastures

In a meadow covered with grass, plots of 4 m are delineated and sprayed three times with the composition according to the invention, which is diluted with water. The treatment is carried out at intervals of two weeks and 2 kg / ha are used for each treatment. Then the grass is mown, the green matter, the total nitrogen content and the protein nitrogen content of the mown grass are determined.

The results are shown in Table XXVII, with the numbers in brackets indicating an increase in percent compared to the untreated control.

Table XXVII

Treatment Yield kg / 4 m ² untreated 5.10 Compound A 5.27

Total nitrogen%

4.22

5.36 (+ 27.0%)

Protein nitrogen%

2.80

3.54 (+26.4%)

Example 28

The bean (Superalit) is sprayed once or twice with the composition according to the invention.

Table

XXVIII

Yield increase%

Treatment

Yield 100 kg / ha

untreated 15.00 compound AND, one treatment 20 May 6. 1979 17.77 18.4 compound AND, one treatment 6. 7. 1979 17.03 13.5 compound AND/ treatment 20 May 6. 1979 treatment 6. 7. 1979 19.52 30.1

Example 29

Some compounds of formula I are compared with respect to their biological activity. The cytoohin-like activity of the compounds can be characterized by the intensity of photosynthetic fixation of carbon dioxide and the incorporation of radiolabeled amino acids into the TCA insoluble protein fraction.

Table XXIX shows the values for photosynthetic CO ₂ fixation in maize leaves and the incorporation of glycine-β-C into the protein synthesis of beans, for benzimidazolium salts with various substituents on nitrogen. Radioactivity is reported in yiCi / g fresh green and the mean error of the mean is not greater than + 7%. The test samples were left in the drug solution for 18 hours and exposed to radiobiology for one hour.

Table XXIX

Treatment not treated

C0 ₂ fixation / uCi / g +%

5.72

The incorporation of glycine-2- @ ¹ C Juci / g +%

3.52

Table XXIX continued

Treatment Fixation m / z ¹⁴ co ₂ +% Built-in glycine-2- / iCi / g +% · N- (methyl) benzimidazolium chloride (m.p. 248-250 ° C) 8.12 42 4.75 35 N- (ethyl) benzimidazolium chloride (m.p. 270 ° C) 6.72 18 4.25 21 N- (n-propyl) benzimidazolium bromide (m.p. 160-162 ° C) 10.52 84 4.96 41 N- (n-butyl) benzimidazolium chloride (mp 227-229 ° C) Substituent. R ₂ 7.49 31 4.57 30 bromethyl- 6.46 13 4.36 24 i-propyl- (chloride) 10.92 92 4.85 35

Example 30

The intensity of photosynthetic fixation of carbon dioxide for various N- / n-propyl / benzimidazolium bromides (with different substituents R @ 1) is determined. As Pinto test plants, the solutions are used at a concentration of 200 ppm and the radioactivity is given in Table XXX at dpm / 200 g fresh weight. The results are shown in Table XXX.

XXX

Sutstituent Fixation intensity carbon dioxide (in position 5/8 or in position 4/7) dpm % increase control 2.32 - methyl 4.26 84.0 ethyl 4.13 78.0 n-propyl 4.22 81.8 isopropyl 4.30 85.3 n-butyl 4.20 81.0 hydroxyethyl 4.10 76.7 chloroethyl 4.00 72.4 allyl 4.15 78.8 chlorine 4.20 81.0 bromine 4.10 76.7 merkapto 4.32 86.2 hydroxy 4.16 79.3 methylmerkapto 4.00 72.4 methoxy 4.09 76.2 amino 3.37 45.2 methylamino 3.84 65.0 dimethylamino 3.76 62.0

Claims (1)

SUBJECT OF THE INVENTION Cytokinin, a membrane-active agent for increasing plant productivity, protein nitrogen content and anion uptake, characterized in that it contains, in an amount of 0.5 to 90% by weight, as active substance, an imidazole derivative of the formula I X® '2 where it is hydrogen, chlorine, C1-C4alkyl optionally substituted by chlorine or hydroxyl, C2-C4alkenyl, mercapto, hydroxy, methylmercapto, C1-C4alkoxy , amino, methylamino or dimethylamino, furthermore R1 represents a C1 -C4 alkyl group optionally substituted by bromine, and X represents an inorganic or organic anion, preferably a chloride, bromide or sulphate anion, in an amount of 10 to 95% by weight, and and / or a solid carrier and in an amount of from 1 to 15% by weight of surfactants.