RU2766699C1 - Ethylenebis(thioacetate)-dimonoethanolamine aqueous solution as microfertilizer for crops - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to chemistry of organic sulfur-containing ligands of the complexon class and use thereof as microfertilizers. An ethylenebis(thioacetate)-dimonoethanolamine compound of structural formula: HOOC-H₂C-S-CH₂-CH₂-S-CH₂COOH × 2 (H₂N-CH₂-CH₂-OH), in the form of an aqueous solution is used as a microfertilizer for crops, in particular for potatoes and sour grape varieties.

EFFECT: disclosed ethylenebis(thioacetate)-dimonoethanolamine compound in form of an aqueous solution increases yield and quality of potatoes and grapes.

1 cl, 1 ex, 3 dwg

Description

The present invention relates to the chemistry of organic sulfur-containing ligands of the class of complexons and directly relates to a new compound - ethylenebis(thioacetate)-dimonoethanolamine, which in the form of an aqueous solution can be used as a microfertilizer for crops, in particular for potatoes and sour grapes.

It is known that sulfur and nitrogen are the most important elements of plant nutrition and are required for metabolic processes to occur in them [M., In L.J. De Kok et al. Sulfur metabolism in plants: Mechanisms and applications to food security, and responses to climate change. Proc. Int Plant S Workshop, Springer Netherlands, 2012, p. 11-24]. In this regard, in order to ensure the vital activity of agricultural crops, increase their yield and quality, nitrogen and sulfur-containing fertilizers are introduced into the soil. The range of nitrogen-containing macrofertilizers includes amide, ammonia and nitrate fertilizers. Sulphates are the only form from which a plant can absorb sulfur from the soil or through its leaves. In this regard, sulfur-containing fertilizers include sulfates, or such sulfur compounds, which are subsequently converted into them. More often than others, sulfates of ammonium, magnesium, potassium, phosphogypsum are used [R. Norton, R. Mikkelsen, T. Jensen. The value of sulfur in plant nutrition // Plant nutrition. 2014. №3. S. 2-5].

Of particular importance in the metabolism of plants is the mutual influence of sulfur and nitrogen. It is known that the lack of sulfur limits the absorption of nitrogen by plants. In this regard, the successful vital activity of plants must be simultaneously provided with sulfur- and nitrogen-containing fertilizers.

As a fertilizer for vegetables, including potatoes, the domestic preparation Aquarin-12 is currently used, which is a water-soluble complex mineral fertilizer that contains (wt%): nitrogen - 12, P ₂ O ₅ - 12, K ₂ O - 13, MgO - 1, S - 0.7, Fe - 0.054, B - 0.02, Mo - 0.004, Mn - 0.042, as well as Cu - 0.01 and Zn - 0.014 in the form of chelates. This fertilizer is considered as an analogue for use as a microfertilizer for potatoes, since it contains sulfur and trace elements.

However, Aquarin-12 does not provide sufficiently high biometric parameters of potatoes, which include the content of starch and solids, which limits its suitability for processing.

In order to increase the efficiency and expand the range of microfertilizers that have the ability to simultaneously provide nutrition to agricultural plants with sulfur and additional nitrogen, as well as supply plants with microelements from the soil, ethylenebis(thioacetate)-dimonoethanolamine is proposed with the structural formula:

HOOC-H ₂ CS-CH ₂ -CH ₂ -S-CH ₂ COOH × 2 (H ₂ N-CH ₂ -CH ₂ -OH),

used in the form of an aqueous solution as a microfertilizer for crops.

An aqueous solution of ethylenebis(thioacetate)-dimonoethanolamine is used as a microfertilizer for potatoes and sour grape varieties.

The starting material for the synthesis of ethylenebis(thioacetate)-dimonoethanolamine is ethylenebis(thioacetic acid) (EBTA). This acid is obtained according to the method described in the well-known publication "D.G. Danielyan, N.V. Tsirulnikova, V.Ya. Temkin. Synthesis of sulfur-containing organic ligands such as complexones // Reagents and especially pure substances. Tr.IREA. 1984. Issue. 46. S. 3-6. According to this method, ethylenebis(thioacetic acid) (EBTA) is obtained by the interaction of thioglycolic acid formed during the reaction from aminodiacetic acid, taken as a raw material, with dichloroethane, followed by acidification of the reaction solution with hydrochloric acid and the isolation of EBTA from it in solid form.

As is known, EBTA is practically insoluble in water and alkalis, and therefore it cannot be used as a fertilizer. To solve this problem, it is proposed to convert solid EBTA into its water-soluble form, which is the salt of EBTA with monoethanolamine (ethylenebis(thioacetate)-dimonoethanolamine). This EBTA derivative is a water-soluble compound not previously described.

The process of obtaining ethylenebis(thioacetate)-dimonoethanolamine is carried out by the interaction of EBTA with monoethanolamine in an aqueous solution at a molar ratio of reagents 1:2, at room temperature. The final product, ethylenebis(thioacetate)-dimonoethanolamine, is isolated from the obtained aqueous solution by evaporation, cooling and filtration in the form of a white crystalline substance.

The process for obtaining this compound is illustrated in detail in Example 1 below.

Example 1

In a glass with a capacity of 200 ml, equipped with a stirrer, pour 70-80 ml of distilled water and with stirring load 14.7-15.0 g (0.070-0.071 mol) of EBTA. The resulting suspension is stirred until a homogeneous mass is formed for 10-15 minutes and 8.5-8.7 g (0.140-0.142 mol) of monoethanolamine are added dropwise. Stirring is continued until complete dissolution of the acid. The resulting solution is then filtered on a Buchner funnel through filter paper and analyzed for its sulfur content. The amount of sulfur (4.5-4.6%) corresponds to the amount of loaded EBTA.

Ethylenebis(thioacetate)-dimonoethanolamine is isolated from the obtained filtered solution. To do this, the resulting aqueous solution is evaporated on a boiling water bath until crystals appear, then the resulting mass is cooled to 10-15°C, the precipitated white crystals are filtered off, which are ethylenebis(thioacetate)-dimonoethanolamine.

The solubility of the compound in water is 56%.

The structure of the isolated crystalline salt of ethylenebis(thioacetate)-dimonoethanolamine was confirmed by the NMR spectra shown below (FIGS. 1-3). 1H and 13C NMR spectra were recorded ^on a Bruker Avance Nanobay spectrometer ¹ ( ¹ Analytical studies were performed using the scientific equipment of the Central Collective Use Center ^of the National Research Center "Kurchatov Institute" - IREA), with an operating frequency of 300 MHz for protons and 100.6 MHz for carbon atoms . The residual signals of the solvent D ₂ O - 4.70 ppm were used as an internal standard. (in 1H ^NMR spectra).

An aqueous solution of ethylenebis(thioacetate)-dimonoethanolamine amine was used as a microfertilizer for potatoes and grapes. The effectiveness of using an aqueous solution of ethylenebis(thioacetate)-dimonoethanolamine as a microfertilizer for potatoes and grapes is confirmed by the studies described below and their results.

Research on the effectiveness of an aqueous solution of ethylenebis(thioacetate)-dimonoethanolamine as a microfertilizer for potatoes.

These studies were carried out under conditions of a two-field crop rotation by the method of systematic placement of plots. The repetition of the experiment is fourfold. Grain grasses were used as a precursor of potatoes.

Before planting, the tubers were treated with water (control), an aqueous solution of ethylenebis(thioacetate)-dimonoethanolamine, and, for comparison, with the industrial preparation Aquarin-12. The consumption of the working solution was 10 liters per ton of tubers, when diluted at the rate of 30 ml of the drug per 10 liters of water.

During the growing season, potato plants were sprayed with water, an aqueous solution of ethylenebis(thioacetate)-dimonoethanolamine, and the industrial drug Aquarin-12. The flow rate of the working solution was 300 l/ha, dilution of 15 ml of the drug per 10 l of water.

The studies were carried out on potato varieties "Kolobok" for 3 years. At the same time, we studied changes in the content of trace elements in the soil before planting and after harvesting potatoes, as well as in planting material and crops.

At the same time, biometric indicators of potato plants of the Kolobok variety (flowering phase) were taken into account. The average values of biometric indicators for 2016-2018 were calculated. (m ² /bush).

Among the main indicators of the quality of potato tubers is the content of starch and dry substances in them, which determine the yield of products during processing, which is a significant indicator of the suitability of potatoes for this purpose.

In potato tubers of the Kolobok variety (in 2018), when grown using ethylenebis(thioacetate)-dimonoethanolamine, the starch content was 15.95% (14.55% - when using Aquarin-12), dry matter 21.68% (20.3% - when using Aquarin-12).

Higher values of starch and dry matter content were also achieved when growing potatoes of the Udacha variety.

Potato yield was studied during the growing season 2016-2018. for potato variety "Kolobok".

The obtained results indicate the assimilation of microelements by potatoes from the soil when treated with a solution of ethylenebis(thioacetate)-dimonoethanolaine and confirm that the use of this drug when growing potatoes of the "Kolobok" variety during the growing season leads to an increase in the number of stems and, accordingly, the number of tubers formed under the bush.

In addition, compared with Aquarin-12, the height of the stem increases by 23.6%; haulm weight by 2.6 times; leaf area by 3.4 times, which allows us to draw conclusions about the benefits of using the proposed drug to improve the biometric parameters of potatoes.

Higher values of starch and dry matter content were also achieved when growing potatoes of the Udacha variety.

The use of a solution of ethylenebis(thioacetate)-dimonoethanolamine provided an increase in yield by an average of 6.4 t/ha compared to Aquarin-12.

Study of the effectiveness of the proposed drug as a microfertilizer for acidic grape varieties.

These studies were carried out on the example of Cabernet Sauvignon grapes) in the conditions of the South Coast viticulture zone of Crimea. The studies were carried out in a field production experiment with the placement of plants by the method of elongated plots and the use of a two-time tractor spraying. The consumption rate of the working fluid is 800 l/ha.

As a result of studies with a double application of ethylenebis(thioacetate)-dimonoethanolamine, a conditioned harvest of technical grapes was obtained with a significant increase of 12.9% or 8 c/ha compared to the standard due to an increase in the weight of a bunch of grapes by an average of 12.2 g. sugar content was on the same level with the standard and amounted to 216-221 g/DM ³ .

The advantage of the new water-soluble compound as a microfertilizer is the fact that it contains both sulfur and nitrogen in the structure at the same time, and is able to supply plants with microelements from the soil, creating the necessary conditions for the successful use of the drug in growing high-quality agricultural products, in particular potatoes and grapes.

In addition, the use of this solution as a microfertilizer is economically feasible, since the process of obtaining it is technologically simple and not energy-consuming.

Claims (4)

1. Ethylenebis(thioacetate)-dimonoethanolamine, structural formula: HOOC-H ₂ CS-CH ₂ -CH ₂ -S-CH ₂ COOH × 2 (H ₂ N-CH ₂ -CH ₂ -OH), used in the form of an aqueous solution as a microfertilizer for crops. 2. An aqueous solution according to claim 1, used as a microfertilizer for potatoes and sour grapes.

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