STUDY OF POLYTHERMAL SOLUBILITY OF NH2C2H4OH – C6H4(OH)COOH – H2O SYSTEM

ABSTRACT

In this work, the polythermal solubility of a three-component system containing NH₂C₂H₄OH – C₆H₄(OH)COOH - H₂O is studied and its diagram is constructed based on binary systems and internal sections by the visual polythermal method in the temperature range from -49 °C to 5.0 °C.

In the solubility diagram, the phase-separating secondary and tertiary points were identified and the projection is drawn.

In the diagram, the crystallization areas of ice, salicylic acid, monoethanolamine dihydrate, monoethanolamine monohydrate, monoethanolamine, and a new chemical compound monoethanolammonium salicylate formed in the system were delimitted.

The new compound formed in the system was seperated. The compound was analyzed using chemical, and NMR spectroscopy (spectrum ¹ H and ¹³C), and the presence of C₆H₄(OH)COOH∙NH₂C₂H₄OH was confirmed.

АННОТАЦИЯ

В данной работе на основе бинарных систем и внутренних разрезов изучена политермическая растворимость трехкомпонентной системы NH₂C₂H₄OH – C₆H₄(OH)COOH – H₂O визуальным политермическим методом в интервале температур от -49 °С до 5,0 °С на основе бинарных систем и внутренних разрезов визуальным политермическим методом, и была построена ее диаграмма. На диаграмме растворимости определены двойная и тройная точки разделения фаз, сформированы таблица и проекция. 

На схеме разграничены области кристаллизации льда, салициловой кислоты, дигидрата моноэтаноламина, моногидрата моноэтаноламина, моноэтаноламинов и нового химического соединения, образующегося в системе моноэтаноламмонийсалицилата. Новое соединение, образовавшееся в системе, было выделено и проанализировано химическим, физико-химическим методом на ЯМР-спектроскопии (спектр ¹Н и ¹³С) и подтверждено наличие C₆H₄(OH)COOH∙NH₂C₂H₄OH.

Keywords: solubility diagram, crystallization temperature, physiologically active substance, salicylic acid, monoethanolamine, monoethanolammonium salicylate, NMR spectroscopy.

Ключевые слова: диаграмма растворимости, температура кристаллизации, физиологически активное вещество, салициловая кислота, моноэтаноламин, салицилат моноэтаноламмония, ЯМР-спектроскопия.

Today, the demand for high yields from agricultural crops is increasing day by day. Accordingly, the demand for physiologically active substances is increasing. Physiologically active substances ensure the transfer of nutrients from the leaves and branches of plants to the harvest. Such events make it possible to increase productivity and widely use mechanization in harvesting agricultural products. [1].

Many studies involving salicylic acid have been of great interest for several years and in almost all fields. Also, many physiologically active compounds have been obtained on the basis of salicylic acid and their biological and pharmacological activity has been studied. [2]. In particular, salicylic acid itself, as an internal regulatory hormone of the plant, carries out various physiological processes in the plant, the mechanism of its protection from biotic and abiotic influences has been studied in a number of literature [3]. The synthesis of complex salts based on salicylic acid, monoethanolamine and d-elements, their physico-chemical analysis, laboratory and field experiments on the example of cotton were studied. Experimental tests of these compounds have shown that they really exhibit properties that increase plant growth and productivity. It can also be used as a promising stimulator of plant development in agriculture [4-7].

At the same time, monoethanolamine, which is found in radishes, cumin, grapes, and a number of other similar foods, has significant plant growth and antimicrobial activity [8-9]. Also, monoethanolamine and its derivatives help plants survive and even enhance growth under abiotic and biotic stresses such as salinity [10-11]. Monoethanolamine – takes an active part in redox processes in plants, enhances the synthesis of organic phosphorus compounds, increases protein metabolism and the activity of enzymatic processes [12-13].

M. Crisan and his colleagues synthesized a salt based on benzoic acid and monoethanolamine in order to increase the physiological activity of monoethanolamine and conducted biological activity tests. These studies confirmed that the plant growth promoting effect of salt was dramatically improved [14-16]. Also experiments on plant growth and antimicrobial properties of salt between 4-nitrobenzoic acid and monoethanolamine show that both types of acid components have enhanced bioactivity properties despite losing their fungicidal effect [17].

Ethanolamines and their compounds with acetic [18], citric [19], nitric [20] and orthophosphate [21-22] acids have physiological activity. The presence of the ethylene (-CH₂-CH₂-) group in these compounds leads to an increase in the amount of ethylene in the leaf band of the plant, the shedding of leaves and the acceleration of the defoliation process [23].

From the analysis of the literature, it can be seen that salicylic acid and monoethanolamine play an important role in the growth and development of plants. However, the interaction of these two components in aqueous solution has not been studied. Therefore, the solubility of the ternary system consisting of salicylic acid, monoethanolamine and water was studied by visual polythermal method [24].

Binary systems and four internal sections are used to construct a diagram of the polythermal solubility of system NH₂C₂H₄OH – C₆H₄(OH)COOH - H₂O. The studies were carried out by transferring internal incisions from the NH₂C₂H₄OH- H₂O side to the C₆H₄(OH)COOH site. A polythermal solubility diagram of the NH₂C₂H₄OH – C₆H₄(OH)COOH - H₂O system was constructed over the temperature range of −49.0 °C to 5.0 °C using binary systems and internal cuts (Fig.1.). In this polythermal solubility diagram, isotherms were studied at every 10°C temperature interval.

Figure 1. A Polythermal solubility diagram of the NH₂C₂H4OH – C₆H₄(OH)COOH - H₂O system

Table 1.

Binary and ternary points of the NH₂C₂H₄OH – C₆H₄(OH)COOH - H₂O system

Crystallization areas of ice, salicylic acid, monoethanolamine dihydrate, monoethanolamine monohydrate, monoethanolamine and monoethanolammonium salicylate were separated in the phase diagram of this studied system. These crystallization areas are connected at four triple points (Fig. 2).

Figure 2. A Polythermal projections of the NH₂C₂H₄OH – C₆H₄(OH)COOH - H₂O system

The initial triple point crystallizes at -40.2°C temperature and corresponding to 26.0% monoethanolamine, 45.6% salicylic acid, 28.4% water. The composition of the second triple point corresponds to 50.4% monoethanolamine, 4.0% salicylic acid, 45.6% water, and the crystallization temperature corresponds to -49.0°C. The next triple point composition is 62.0% monoethanolamine, 5.2% salicylic acid, 32.8% water, which exhibits a crystallization temperature of -47.5°C, and the last triple point is 72.4% monoethanolamine, 7.2% salicylic acid, corresponds to 20.4% water and crystallizes at -28.0 °C (Table 1).  

It can be seen from the constructed diagram that ice is bounded by salicylic acid in the temperature range from -0 °C to -40.2 °C, and by monoethanolamine dihydrate in the temperature range from -40.2 °C to -48.5 °C. Ice crystallizes with salicylic acid and monoethanolammonium salicylate at a temperature of -40.2 °С, with monoethanolamine dihydrate and monoethanolammonium salicylate at a temperature of -49.0 °С. In the diagram, the phase boundary of salicylic acid and monoethanolammonium salicylate separated in the temperature range from -40.2 °C to 1.0 °C and the phase boundary of monoethanolamine dihydrate and monoethanolammonium salicylate is separated in the temperature range from -49.0 °C to -47.5 °C. The phases of monoethanolamine dihydrate and monoethanolamine monohydrate are limited in the temperature range from -47.5 °C to -46.1 °C. Monoethanolamine monohydrate and monoethanolammonium salicylate has a phase boundary between -47.5 °C and -28.0 °C, monoethanolamine monohydrate and monoethanolamine phase separated in the temperature range from -28.0 °C to -25.2 °C. Monoethanolamine is limited to monoethanolammonium salicylate at temperatures from -28.0 ° C to 5.0 ° C.

The compound isolated from the new phase formed in the polythermal solubility diagram was analyzed using chemical and physicochemical (NMR. ¹H and ¹³C.) methods of analysis (Fig.3 and Fig.4.).

Chemical analysis gave the following results:

found mass. % С – 54.23; Н – 6.52; N – 7.03;

Calculated for C₆H₄(OH)COOH∙NH₂C₂H₄OH ,

wt.% C – 54.27; H – 6.53; H - 7.04

It can be seen from the ¹H NMR spectrum of the sample that salicylic acid and monoethanolamine satisfy a 1:1 stoichiometric ratio and together form a salt-like compound.

Figure 3. ¹H NMR spectrum of matter

Figure 4. ¹³C NMR spectrum of matter

Thus, new information was obtained about the solubility of components in the NH₂C₂H₄OH – C₆H₄(OH)COOH - H₂O system.

The system belongs to the complex eutonic type, the formation of a new phase was observed in it, the extracted compound (monoethanolammonium salicylate) was analyzed using NMR spectroscopy (¹H and ¹³C spectrum).

The results obtained are serve as a scientific basis for the development of technology for the production of physiologically active substances based on salicylic acid and monoethanolamine.

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