SU900801A3 - Fertilizer containing microelements - Google Patents

Description

() FERTILIZER, CONTAINING ICON EMISSIONS

one

The invention relates to a fertilizer for supplying plants with iron, containing an active ingredient based on an organic iron-containing compound, as well as auxiliary components from the group of solid and liquid carriers.

It is known the use of iron-chelate complexes as a food {11.

However, iron-chelate complexes have a relatively short duration of action due to their cleavage by microorganisms.

Fertilizer is known for supplying plants with iron, containing deistants based on the iron-chelate complexes of synthetic ammonia polycarboxylic acids or their salts 2).

However, such a fertilizer, when introduced into the soil, partially decomposes with jo, the release of iron cations in the form of labor-soluble hydroxides or oxides. In addition, it forms very stable, highly toxic, and at the same time water soluble chelate 25

complexes with heavy metal ions cadmium, lead and mercury present in the soil, which adversely affects the dietary regime of plants.

The purpose of the invention is to increase the quality of iron supply to plants.

This is achieved by the fact that the proposed fertilizer as an active principle contains a ferrocene derivative of the general formula

where ft is the COOR group containing 0 ft-hydrogen, the equivalent of an alkali cation (potassium, sodium) or a heavy (iron) metal, and also an ammonium cation or the radical CHtNCCHj) HCJ; 39 in addition, a COR group, in which R is hydrogen or alkyl of the C (, C / j-Cg group; in addition, the group is C -NR in which hydrogen, R is the ureido radical or the radical of the formula - CUjCHfN C ferrocene in addition, hydroxyl or triazolin, in addition, the -SOjR radical, where R is hydrogen. The use of ferrocenes and their derivatives is known in the chemistry of organometallic compounds | 31. Ferrocene derivatives can be used as a fertilizer as such, in the form of pure preparations or solutions made from them, emulsions, foams, suspensions, powders, pastes, and granulates. common in agriculture and horticulture, for example, by direct soil application, watering, spraying, spraying, planting, dusting. Special types of application are roots, leaves, injection into the trunk and application of the .8 bark When applied to the roots, fertilizer can be mixed with the substrate for the culture or applied to the soil furrows. It is also possible to add fertilizer through the tube or through the holes in the deeper root zones. The application of the application on the leaves is carried out, as a rule, as follows: the plants are sprayed with a fertilizer solution or the plants or their masses are immersed in a solution of the fertilizer. During injection into the barrel, the fertilizer is directly introduced into the plants through holes drilled in the trunks or branches. The application to the bark is carried out in such a way: bare DREVESIMIM is sprayed with a solution of EFFICIENCY or nutrients impregnated with nutrients, for example, from fabric, paper or foam, is placed on the trunks or branches - if necessary after partial or complete removal of the cortex or cork layer in the treatment zone . It is also possible to use the bark with pastes containing nutrients. In addition, it is possible to apply the proposed ferrocene derivatives by the method of distributing the substance in an extremely low volume (ULV) or applying them to the ion exchanger and using it as a fertilizer. The amount of ferrocene derivatives proposed can be varied over a wider range, which mainly depends on the soil difference, and on the nutrient requirements of the respective plant. In general, the amounts of active principle used are between 0.1 and 100 kg / ha, preferably between 1 and 50 kg / ha. The proposed ferrocene derivatives are suitable for controlling and treating the disease due to iron deficiency in plants. Thus, for example, in fully chlorotic chrysanthemums (Chrysanthemum indicum, variety SePol Oelawage), by treating plants with ferrocene derivatives proposed, the iron deficiency is greatly reduced or disappears altogether. Example 1. Combating iron deficiency (experiment on absorption by roots). Chrysanthemum indrcum (cultivar Gellov / Delaware) is used as an experimental plant, and a mixture of flakes with polystyrene foam (Styromull) and potassium alginate in a volume ratio of 10: 1 is used as a culture substrate. To obtain an active ingredient preparation, the desired amount of active ingredient is dissolved in water. With active beginnings with low water solubility, the preparation of the active ingredient is obtained due to the fact that 1 g of the active agent is dissolved in 10 g of a mixture containing 7 parts by volume. diethylformamide, kj ob.ch. acetone and 6 ob.ch. alkylaryl polyglycol ether (emulsifier), thus obtained concentrate "," ". , nr, "a:, rat is then diluted with water to the desired concentration. Experimental plants are grown in the substrate for the culture of this composition. Fertilizer and irrigation are carried out in the following way: a mineral nutrient solution with an iron deficiency in Hoagland and Agpop is supplied twice a week. Divorced thus fully chlorotic experimental plants p. developmental stages with five leaves are transplanted into another substrate for the culture of the indicated composition, which was preliminarily added with the desired amount of iron-containing fertilizer. Fertilization and irrigation are carried out during the further growth of the hook as in the time of cultivation. The effectiveness of the fertilizer is estimated by the intestine color of the leaves. In each case, the average number of leaves formed in all experimental plants (an average of five leaves) is determined. The intensity of the green color of the newly formed leaves is indicated by numbers. Accept the following notation (points): 1 point - the plant is non-chlorotic (dark green); 2 points - the plant is chlorotic 5 points - the plant is chlorotic 75%; 9 points - plant is chlorotic per 100 (corresponding to untreated control plants). Active principle, their concentration and the results of the experiments are given in table. I and 2. Example 2. Combating iron deficiency (experiment on absorption by roots). Grapes (cultivar IIPEg Thurgau) are used as the experimental plant, and a mixture of styromull flakes and potassium alginate in a volume ratio of 10: 1 is used as a substrate for the culture. Experimental plants are grown in the substrate for the culture of this composition. Fertilizer and irrigation are carried out as follows: mineral nutrient diluent with iron deficiency is added twice a week according to Hoagland and Agpop (Circular, College of Agriculture, University of California Berkeley 1350). The fully chlorine-grown experimental plants are transplanted in stages development of five leaves in another substrate for the culture of the indicated composition, to which the desired amount of iron-containing fertilizer is preliminarily mixed Fertilizer and irrigation is carried out during further growth as well as during cultivation . Fertilizer efficacy is assessed by leaf color intensity. In each case, the average number of newly formed leaves in all experimental plants is determined (on average, one leaf). The intensity of the green color of the newly formed leaves is indicated by numbers. Accept the following notation (points): 1 point - the plant is non-chlorotic (dark green); 3 points - the plant is chlorotic 5 points - the plant is chlorotic 75%; 9 points - the plant is chlorotic 100% (compared to the untreated control). Example 3. Combating iron deficiency (experiment on leaf absorption). Chrysanthemum fndicum (cultivar Gel low Delaware) is used as an experimental plant, and a mixture of polystyrene foam flakes (StyroffluH) and potassium alginate in a volume ratio of 10: 1 is used as a culture substrate. Making current start. In order to obtain a drug, the desired amount in each case is dissolved in water. With active principles having a lower water solubility, the preparation is obtained in that 1 g of the active principle is dissolved in 10 ml of a mixture consisting of k7 vol. dimethylfluormamide, 7 ob.ch. acetone and 6 ob.ch. alkyl aryl polyglycol ether (emulsifier) and the concentrate thus obtained is then diluted with water to the desired concentration. 6, the culture substrate of the composition is grown, and fertilization and irrigation are carried out as follows: HoagJand and Agpop mineral nutrient solution is added twice a week (Circular, College of Agriculture, University of California, Berkeley 1950). Grown thus, completely chlorotic experimental 8th stage of development of five leaves before the formation of droplets is sprayed with the preparation of the active principle. Fertilizer efficacy is assessed by leaf color intensity. In each case, the average number of newly formed is determined.

79

/ Leaves in all experimental plants (on average, two leaves). The intensity of the green color of the newly formed leaves is indicated by numbers. Accept the following (s) (points):

I point - the plant is non-chlorotic (dark green);

3 points plant chlorotic 25%;

5 points - the plant is chlorotic 502;

7points - plant is chlorotic on

9 points - the plant is chlorotic 1001 (compared to the untreated control).

Active principle, their concentration and the results of the experiments are given in table. 3

An example. Combating iron deficiency (leaf absorption).

8 grapes (variety MiJller Thurgau) are used in the experimental plant, and a mixture of x opier-polystyrene foam (Styromul) is used as a substrate for crops.

and potassium alginate in a volume ratio of 10: 1.

Production of the active principle In order to obtain the preparation of the active principle, the desired amount in each case is its solution in water. With active principles having a lower water solubility, the preparation is made as follows: g of the active principle is dissolved in tO ml of the mixture consisting of 7 parts by volume. dimetiformamide, 7 ob.ch. acetone and 6 vol. alkyl aryl polyglycol ether (emulsifier), and the concentrate thus obtained is dissolved in the desired concentration with water.

Experimental plants are grown in the substrate for the culture of this composition. Fertilizer and irrigation are carried out as follows: a mineral nutrient solution with insufficient iron content is added twice a week according to Hoagland and Agpop (Circuit College of Agriculture, University of California, Berkeley 1950). Thus grown, fully chlorotic experimental plants in the stage of development of five leaves are sprayed with a preparation of the active principle to form droplets.

18

After douh days repeat

spraying.

Fertilizer efficacy is assessed by leaf color intensity. In each case, the average number of newly formed leaves in all experimental plants is determined (on average, one leaf). The intensity of the green color of the newly formed leaves is indicated by numbers. Accept the following designations (points):

1 point - the plant is non-chlorotic (dark green);

3 points - the plant is chlorotic 25%;

5 points - the plant is chlorotic 501;

7 points - the plant is chlorotic 75%;

9 points - the plant is chlorotic by} 00% (compared to the untreated control).

Active principle, their concentration and the results of the experiments are given in table. four.

Ferrocene derivatives of the general formula can be obtained:

a) the ferrocencarboxylic or ferrocene sulphonic acid is converted by conventional methods into its salts, esters or amides, or

b) ferrocene is reacted with N-methyl-formanilyl and phosphoroxychloride at temperatures between and and

c) ferrocene is reacted with an acyl chloride of the formula

R - CO - C1,

in which R has the indicated meanings or with an acid anhydride of the formula

,

in which R is alkyl and, if necessary, in the presence of a solvent, such as methylene chloride, as well as in the presence of a Friedel-Crafts catalyst, such as aluminum chloride, zinc chloride, boron trifluoride, hydrogen fluoride or phosphoric acid, at temperatures between O C and, or

g) a ferrocene derivative of the formula

O "-COR in which R has the indicated meanings, is reacted with an amine of formula IH N - R, in which k has the indicated meanings, in the presence of a solvent, such as ethanol, at temperatures between Ou and 150 ° C, preferably between 20 ° C and 100 ° C, or d) ferrocene with formaldehyde-amine of formula / R (R) In which R and R have the indicated meanings, in the presence of a solvent, such as acetic acid, and in the presence of a catalyst, such as phosphoric acid, t before the reaction and the compounds thus obtained are subjected to the interaction with hydrogen halide, alkyl halo genide or dimethyl sulfate, or e) the derivative of ferrocene obtained by method e is reacted with water or brought to reaction with potassium cyanide and, if necessary, then washed, or g) of the formula in which R has a specified ferrocene values are subjected to reduction by conventional methods. The ferrocene derivatives of the general formula used according to the invention are excellent for supplying plants with the iron trace element. They are particularly well absorbed by the leaves and are therefore very suitable for fertilizing leaves. Ferrocene derivatives of the general formula can be used to prevent and eliminate diseases on the soil (iron deficiency in plants). In many cases and in the progressive stage of the disease, success can be achieved. The ferrocene derivatives used according to the invention may be altered as such or in the form of preparations for supplying plants with iron. The ferrocene derivatives according to the invention can be converted into conventional preparations such as solutions, emulsions, suspensions, powders, pastes and granules. They are obtained in a known manner, for example, by mixing the active principles with diluents, i.e. liquid solvents, pressurized liquefied gases and / or solid carriers, if necessary with the use of surface active agents, i.e. emulsifiers and / or dispersants and / or blowing agents. If water is used as a diluent, for example, organic solvents can also be used as an auxiliary solvent. Suitable liquid solvents are mainly: aromatic hydrocarbons, such as xylene, toluene, benzene or alkyl naphthalenes, chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, x orthylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example, petroleum, or petroleum, for example, petroleum, alcohols, like butano or glycol, as well as their simple and complex, ketones, like acetone, methyl ethyl tone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents like dimethylformamide and dimethyl sulfoxide, as well as water; liquefied gaseous diluents or carriers should be understood to be liquids that are gaseous at normal temperature and under normal pressure, for example, aerosol-working gases such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural stone flours, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone flours, such as highly dispersed silicic acid, aluminum oxide and silicates; under emulsifiers: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example, alkylaryl polyglycol ether, alkyl sulfonyls, alkyl sulfates, and protein hydrolysates, under dispersants: for example, oginine, spent sulfite, and pulp sugar, as well as protein hydrolysates, under dispersants: methylcelt) obaz. Obtaining derivatives of ferrocene, are given in table. -k. To obtain a compound of the formula, to a solution of 1.7 g (0, mop) of sodium hydroxide in too ml of water, stir, 9.9 g (0.043 mO) of ferro | eu1 of arboxylic acid are added at room temperature and then a solution of g C0.01 + 3 mol) ferric chloride hexahydrate in 30 ml of water. A gray precipitate is precipitated, which, after stirring for 2 hours, is sucked off, washed and dried. Thus, 9.8 g (almost 100% of the theoretical) ferro-cenrocarboxylate with a higher point is obtained. Elementary analysis: Found,%: C 52.7; M 3.9. С «2гОв 4 () it is calculated,%: С 53.35; And 3.66. Similarly to the description for the derivative I method, the compounds listed in Table 2 are obtained. 5. To obtain a compound of the formula C0-Shz. A mixture of 93.0 g (0.5 mol) ferrocene 250 ml of acetic anhydride and 20 ml of phosphoric acid is heated for 10 minutes, sucked off the solid residue overnight and washed with water. For further purification, heating, the residue is dissolved in cyclohexanone, with animal carbon tonyl added. Then the filtrate is sucked off and the filtrate is evaporated under reduced pressure to dryness. Thus obtained is g (55 f from theoretical acetypferrocene with melting point b) To obtain a compound of the formula CO (CHj) g-CH3 to a suspension of 0.5 mol of aluminum chloride 8 500 ml of ethylene chloride with slight cooling, a solution of 0 is added dropwise 5 mol of caprianoic acid hporanhydride in t50 ml of ethylene chloride. This suspension is added dropwise to 0-5 ° C while cooling to a solution of 0.5 mol of ferrocene in 750 ml of ethylene chloride. The reaction solution is stirred overnight at room temperature, then over 20 min heats with reflux , cooled and poured: from into ice water. To prepare a compound of the formula S, co-ctCHj) a mixture of 0.5 mol of ferrocene, 250 ml of trimetyphosphonic anhydride and 20 ml of 851th phosphoric acid is heated for 10 minutes before cooled with ice. After settling the reaction mixture for "eyes, it is extracted with methylene chloride". The organic phase is washed with water, dried and distilled in vacuum. In this way, kg (33% of theoretical) of trimetylaceto-ferrocene with a boiling point mm is obtained. The organic phase is separated, washed with water and sufat. The solvent is then distilled off and the remaining residue is distilled under reduced pressure. In this way, 95 g (56% of the theoretical) of n-decanoyl-ferrocene are obtained, having it at a pressure of 1 Torr and a boiling point of 210 ° C. the desired amount is dispersed into the plants or their biotope, G. The preparation for the method of distribution of the substance in an extremely low volume. With the aim of obtaining an expedient preparation of the current beginning, to 116 90 weight.h. it is added 3 wt. including polyethylene oxide as an emulsifier and dissolve this mixture in 7 parts by weight. aromatic fraction of mineral oil. This mixture is used to distribute the substance in an extremely low volume (ULV).

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37 Derivatives 2 3 - --------- Note Derivative

 H

S5N "-N SVN" -N

C-, HB-H

CgH - and

900801

38 Table 5

55 116 59

5k kk Structural formula Point "melting, With Reg-COOMa Above 300 Fer-COO K Above 300 Fer-COONH Above 195 (decomposes) -------------------.-- --- ----- i. «« «---« st. Per means in each case the radical of the formula R The boiling point or the melting point, Yield,% of о ft (о Table 6, laziness, С theoretical

Claims (2)

Claim Application of the general formula I derivatives of ferrocene where R is the group R ' - thioureido radical or a radical of the formula - CH ₂ ~ CH _z -N = CH - ferrocene, in addition, hydroxyl or triazoline; R in addition, the radical is S0 ₃ R ⁵ , where R ⁵ is hydrogen, as a fertilizer containing trace elements. Priority by signs: 10/02/75 by all signs of the invention, except for R ² - alkyl C4-Sd. 01/22/07 at R ^r is alkyl C _y -C ₉ . COOR ', in which hydrogen, the equivalent of an alkali cation (potassium, sodium) or heavy (iron) metal, as well as an ammonium cation or radical CH ₂ N (CH ₃ ) ₂ - HC I; _? R is, in addition, a COR ^Z group, in which R ² is hydrogen or alkyl C,, C 4 ~ C g; R moreover, the group A $ C = N - R, in which R is hydrogen, b * ko