№ 7 (97) июль, 2022 г. ab cd Figure 2. CEM microphotographs of (a) meyulose (b) sulfocationite containing COH (c) sodium metal ingested sulfocationite and (d) calcium metal ingested cellulose sulfocationite polumers Sulfocationite based on cellulose from walnut shell Conclusion has the property of sorption of metal ions from various solutions, and the CAS on NaOH was found to be Sulfocationite was obtained by the of sulfuric acid 3.36 mgeqv/g. aad allulose sulfuric and from walnut husks. Determine that the value of the obtained sulfocationite (SEC) in 3.36 mgeqv/g. The metals ca and Na were ingested into the samples obtained. Absorption of Ca and Na metal was determined using an IR spectrum and a scanning electron microscope. References: 1. Candido R.G., Godoy G.G., Goncalves A.R. Characterization and application of cellulose acetate synthesized from sugarcane bagasse. Carbohydrate Polymers, 2017 167, 280–289. 2. Naduparambath S., Jinitha T., Shaniba V., Sreejith M., Balan A.K., Purushothaman E. Isolation and characterisation of cellulose nanocrystals from sago seed shells. Carbohydrate Polymers, 2018 180, 13–20. 3. Collazo-Bigliardi S., Ortega-Toro R., Boix A.C. Isolation and characterization of microcrystalline cellulose and cel- lulose nanocrystals from coffee husk and com-parative study with rice husk. Carbohydrate Polymers. 2018 191, 205– 215. 4. Fujisawa S., Okita Y., Fukuzumi H., Saito T., Isogai A. Preparation andcharacterization of TEMPO-oxidized cellu- lose nanofibril films with free carboxyl groups. Carbohydrate Polymers, 2011 84(1), 579–583. 5. Osong S.H., Norgren S., & Engstrand P. (2016). Processing of wood-based micro-fibrillated cellulose and nanofibril- lated cellulose, and applications relating to papermaking: A review. Cellulose, 23(1), 93–123. 26
№ 7 (97) июль, 2022 г. COLLOID CHEMISTRY SEPARATION OF SUSTAINABLE EMULSIONS IN THE INSTALLATION OF PREPARATION OF OIL WITH USING DEMULGUATORS OF DIFFERENT NATURE AND MICROWAVE RADIATION Bobirzhon Adizov Doctor of Technical Sciences, Institute of General and Inorganic Chemistry of the Academy of Sciences of the Republic of Uzbekistan, Republic of Uzbekistan, Tashkent E-mail: bobirjon_adizov@mail Rasulbek Eshmetov Doctor of Technical Sciences, Institute of General and Inorganic Chemistry of the Academy of Sciences of the Republic of Uzbekistan, Republic of Uzbekistan, Tashkent E-mail: [email protected] Dilnoza Salikhanova Doctor of Technical Sciences, Professor, Prof., Institute of General and Inorganic Chemistry of the Academy of Sciences of Uzbekistan, Republic of Uzbekistan, Tashkent E-mail: [email protected] Rasul Usmanov PhD, Urgench State University, Republic of Uzbekistan, Urgench E-mail: [email protected] РАЗДЕЛЕНИЕ УСТОЙЧИВЫХ ЭМУЛЬСИЙ В УСТАНОВКЕ ПОДГОТОВКИ НЕФТИ С ИСПОЛЬЗОВАНИЕМ ДЕЭМУЛЬГАТОРОВ РАЗЛИЧНОЙ ПРИРОДЫ И МИКРОВОЛНОВОГО ИЗЛУЧЕНИЯ Адизов Бобиржон Замирович д-р техн. наук, Институт общей и неорганической химии АН РУз, Республика Узбекистан, г. Ташкент Эшметов Расулбек Жумязович д-р техн. наук, Институт общей и неорганической химии АН РУз, Республика Узбекистан, г. Ташкент Салиханова Дилноза Саидакбаровна д-р техн. наук, проф., Институт общей и неорганической химии АНРУз, Республика Узбекистан, г. Ташкент Усманов Расул Муратбоевич PhD, Ургенчский государственный университет, Республика Узбекистан, г. Ургенч _________________________ Библиографическое описание: SEPARATION OF SUSTAINABLE EMULSIONS IN THE INSTALLATION OF PREPARATION OF OIL WITH USING DEMULGUATORS OF DIFFERENT NATURE AND MICROWAVE RADI- ATION // Universum: химия и биология : электрон. научн. журн. Adizov B. [и др.]. 2022. 7(97). URL: https://7universum.com/ru/nature/archive/item/13895
№ 7 (97) июль, 2022 г. ABSTRACT In this article, the separation of stable emulsions in an oil treatment unit using demulsifies of various nature and microwave radiation is studied. It has been established that in the thermochemical method of oil demulsification with the combined use of microwave radiation, the nature, composition and properties of the emulsions to be separated should be taken into account. At the same time, a stepwise analysis of the process of oil demulsification by thermochemical and microwave methods makes it possible to scientifically substantiate the rational conditions and stages of their application. In the process of demulsifying oil with a high-strength armor shell of water globules, it is recommended to jointly use a composition of demulsifiers consisting of ionogenic and nonionic surfactants and microwave radiation of individual stages of this process. АННОТАЦИЯ В данной статье приводятся результаты разделения устойчивых эмульсий в установке подготовки нефти с использованием деэмульгаторов различной природы и микроволнового излучения. Установлено, что при термо- химическом способе деэмульгирования нефти с совместным использованием микроволнового излучения следует учитывать природу, состав и свойства разделяемых эмульсии. При этом по стадийный анализ процесса деэмуль- гирования нефти термохимическом и микроволновым способами позволяет научно-обоснованно определить рациональные условия и стадии их применения. В процессе деэмульгирования нефти с высокопрочной брони- рующей оболочкой глобул воды рекомендуется совместно использовать композицию деэмульгаторов, состоящих из ионогенного и неионогенного ПАВ и микроволновое излучение отдельных стадий данного процесса. Keywords: oil, water-oil emulsions, oil-water emulsions, thermochemical process, microwave radiation, ionic, nonionic, surfactant, demulsifier, demulsification. Ключевые слова: нефть, водонефтяная и нефтеводяная эмульсии, термохимический процесс, микроволновое излучения, ионогенность и неионогенность, поверхностно-активные вещества, деэмульгатор, деэмульсация. ________________________________________________________________________________________________ Introduction. Oil production in many countries of the considered their microwave radiation, which, in contrast world is complicated by the formation of stable water-oil to traditional convective heating, allows several tens of emulsions (WOE), the destruction of which requires times faster heating and changing the physicochemical the use of highly active emulsifiers or their compositions, properties of such emulsions [5]. external mechanical, electropgysical and other types of impact [1-2]. Consequently, the combined use of thermo chemical and microwave methods of destruction and separation In Uzbekistan, such stable WOEs are mainly formed of stable WOEs can significantly save the consumption in the fields of Jarkurganneft JSC dur to the high content of expensive imported demulsifierand other material of the produced oils, resins, asphaltenes, paraffins, mineral and energy resources. salts, etc. Therefore, the aim of the research was to establish For example, the use of imported highly active the effect of thermochemical and microwave destruction emulsifiers, even in excessive quantities, does not always methods and various demulsifiers on the separation allow reaching the values of oils in terms of the residual of stable water-oil emulsions. content of water and salts, which negatively affects the processes of their processing, corrosion of metal equip- Research methods and obtained results. For the ment, pipelines, etc. [3-4]. practical application of microwave radiation, it is necessary to determine the optimal stages of external influence in Therefore, an urgent task for scientists today is the an oil treatment unit (OTU), taking into account changes in development of effective methods for emulsifying such the composition and properties of emulsions. Therewith, heavy oils of complex composition using unconventional the analysis is based on the technologic flowchart of the methods of external electrophysical exposure. OTP, which in block form can be represented as following: Currently, one of the most perspective methods for intensifying chemical and technological processes, in- cluding destruction and separation of stable WOEs is А) B) C) Figure 1. Flowchart of the technology of oil preparation for industrial processing: A- block for dehydration and desalting of stable WOE; B- block for dehydration and desalting of oil-water emulsion; C- block for the removal of reservoir ter and salts from commercial oil 28
№ 7 (97) июль, 2022 г. In this technology, each block (A, B and C) has it's of individual stages of the process of dehydration and own composition, which determines its property, a suitable desalination of stable emulsions, as well as its intensifi- demulsifier (surfactant) and technological conditions for cation [6,7,8]. dehydration and desalting of oil Table 1 shows the stages, i.e. levels of research of Therefore, a systematic analysis of this technological individual stages of the process of separation of stable scheme is necessary for effective microwave radiation WOE. Table 1. Systematic analysis of the stages of the separation of stable WOE using microwave radiation Stage level Name of the stage of the separation process Aim and result of the stage of process First of stable WOE Mutual approach and collision of water globules. Coalescence of dispersed water droplets Microwave radiation reduces the viscosity of the (globules) dispersed medium, i.e. oil due towhich stage of coa- lescenesof formation water globules is intensified. Second Destruction of the multicomponent armor shell of Opening the shell of water globules by reducing water globules ts mechanical strength with ademulsifier and microwave radiation. Third Coagulation of dispersed water contained The volume enlargement of reservoir water droplets in globules by merging of numerous globules. Fourth Separation of residual water and dissolved salt Removal of reservoir waterand salts dissolved in it from oil from oil by sedimentation. Due to volumetric heat- ing of water and oil microwave radiation acceler- ates the stageof reservoir water sedimentation It is obvious from Table 1 that each stage of the sep- oil-water emulsion (OWE), which in its physicochemical aration process of stable WOE performs separate physi- cochemical tasks, which ultimately ensure the properties is very different from the first. achievement of the global goal, i.e. maximum removal Therefore, the types and conditions of the demulsifier of water and salts from commercial oil. At the same time, the quality of achieving local goals by stages shows the used or their compositions differ, as well as the modes ways of their improvement and intensification. For exam- ple, the combined use of thermochemical and microwave and stages of microwave radiation in the technological separation of stable WOE increases the intensity of par- ticular stages from Table 1of the process under consid- scheme of the primary oil treatment in the fields. eration. The analysis of the operation of the OTU at «Jarkur- It should be taken into account that in the course of ganneft» JSC showed that in the first block (A), 50-60% removing water from oil, the nature of the emulsion of the reservoir water is removed from the stable WOE us- changes dramatically, i.ewater-oil emulsion (WOE), after removing a part of the formation water, is converted into ing a nonionic surfactant, and in the second - 36-39.5%. It should be noted that a stable WOE is formed in the second block. Table 2 describes the conditions and main indicators of the separation of stable emulsions of various natures obtained from JSC «Jarkurganneft». Table 2. Indicators of separation of stable emulsions in blocks A and B Block Temperature, Demulsifier consumption, g/t Duration Amount of water Amount of salt № 0С of emulsion to be removed % to be removed, Non-ionic Ionic separation , h А 40 surfactants Surfactants ml/dm 60 80,0 - 4,5 51,5 400 Б 40 70,0 - 4,0 58,7 485 60 50,0 30 5 36,8 310 40,0 30 5,5 39,5 370 29
№ 7 (97) июль, 2022 г. It is obvious from Table 2 that a change in the nature reservoir water, which is a good electrical conductor, of the emulsion (WOE to OWE) strongly affects the du- and in block B this function is performed by oil, which is ration of reservoir water separation from them as well as considered a dielectric. Therefore, the magnetic radiation the amount of removed salts. Even an increase in the of the latter proceeds under conditions that are difficult temperature of the emulsion to be derived from 40 to 60° C to access to water globules. does not contribute to a significant reduction in the time of water separation. Replacing a part of a nonionic de- If to take into account that during microwave radia- mulsifier with an ionic one partially helps to reduce the tion the volumetric heating of the WOE proceeds much duration of reservoir water separation. faster than the WOE, then the reason for the intensive separation of the former becomes clear. This can be explained by the fact that initially the dis- persed medium (block A) in the emulsion is salt-dissolved In Pic.2 a diagram of the movement of water glob- ules in emulsions of various nature. Figure 2. Diagram of localization of dispersed medium and phase in stable WOE and OWE: I-stable WOE; II- stable OWE It is known that the smaller the size of the particles Affecting individual stages of the emulsion separation (globules), the greater the degree of phase dispersion. process, microwave radiation significantly intensifies Emulsions are usually considered coarse, with water them due to a decrease in viscosity and physicochemical globules up to 50 microns in size. Moreover, in WOE as well as colloidal-chemical properties of WOE and the size of the dispersed phase is 1.1-1.3 times greater OWE. than in OWE which is due to a change in the nature of the dispersed medium (water for oil) [9,10]. Conclusion. Thus, the systematic analysis of the operation of the oil preparation unit for industrial pro- In the OTU, residuum is the main method of ther- cessing showed that in the course of dehydration and de- mochemical dehydration and desalination of oil, where salination of oil, WOE is converted into OWE, I.e. there using the natural difference in the densities of oil and is a sharp change in the nature of the dispersed medium reservoir water, emulsion stratification is achieved. At and phase. the same time, sedimentation of mechanical impurities and the emergence of oil droplets on the surface of emul- Moreover, in the thermochemical method of oil de- sions is ensured. mulsification with the combined use of microwave radi- ation, the nature, composition and properties of the With microwave radiation of a stable WOE, the emulsion being separated should be considered. At the density of the dispersed medium changes in significantly, same time, the stage-by-stage analysis of the process of and vice versa, the OWE density of oil changes within demulsification of oil by thermochemical and microwave significant limits. Hence, the rate of separation of the methods makes it possible to scientifically substantiate emulsion is observed higher if the size of water globule the rational conditions and stages of their application. is larger and when the viscosity of the dispersed phase (oil) is the smallest [11,12]. It was revealed that the dehydration and desalination of the OWE is more complicated than the WOE which It is clear from the above mentioned that to intensify is due to the high viscosity of the dispersed medium of this process, you need to know: the difference in phase the former rather than the latter one. densities, oil viscosity and the size of emulsified water droplets. The smaller the size of the water globules, For the demulsification of oil with a high-strength the longer the phase separation time. Demulsifier used armor shell of water globules,it is recommended to use in practice increase the size of the globules, but this is a combination of demulsifiers consisting of ionic and not enough as residuum during thermochemical demul- non-ionic surfactants and microwave radiation of sepa- sification of oil takes more than 5 hours and even more. rate stages of this process. 30
№ 7 (97) июль, 2022 г. References: 1. Lutoshkin G.S. Sbor i podgotovka nefti, gaza i vody [Gathering of oil, gas and water treatment] // M.: PUBL Alliance. 2005.319 p. 2. Z.L. Ren, Y.H. Mou and F.Y. Cui, Mechanism and development trend of crude oil demulsifier, Oil-Gasfield Surface Engineering, 2005, 24, 16–17. 3. Shafiev R.U., Makhmudov N.N., Amirkulov N.S., Tursunov M.A., Bozorov Zh.T. Tekhnologiya sbora i podgotovki nefti, gaza i vody na promyslakh. [Gathering of oil, gas and water and treatment technology in the fields]. Textbook. - T.: Fan va technology, 2016 - 312 p. 4. Zhang, R.; Liang, C.; Wu, D.; Deng, S. Characterization and demulsification of produced liquid from weak base ASP flooding. Colloids Surf. A 2006, 290, 164–171. 5. Adizov B.Z., Razrusheniye vysoko mineralizovannykh emul'siy mestnykh neftey razrabotannymi deemul'gatorami v sochetanii s mikrovolnovym izlucheniyem [Destruction of highly saline emulsions of local oils by developed de- mulsifiers in combination with microwave radiation]. Diss. Cand. tech. sciences. - Tashkent, IONKh AN RUz, 2009.- 126 p. 6. Kafarov V.V., Metody kibernetiki v khimii i khimicheskoy tekhnologii [Methods of Cybernetics in Chemistry and Chemical Technology]. Moscow: Chemistry, 2004 - 478 p. 7. L.X. Liu, S.S. Hao, X.C. Wang, M.A. Jing and X.F. Zhao, Synthesis and demulsification of polyquaternium reverse demulsifier, Ind. Wastewater, 2010, 41, 70–73. 8. Nguyen, D.; Sadeghi, N. Stable emulsion and demulsification in chemical EOR flooding: Challenges and best prac- tices. In Proceedings of the SPE EOR Conference at Oil and Gas West Asia, Muscat, Oman, 16–18 April 2012 9. Voyutsky S.S. Kurs kolloidnoy khimii [Colloidal chemistry course]. - M.: Chemistry - 1976 - 511p. 10. Kuznetsov V.V. Fizicheskaya i kolloidnaya khimiya [Physical and colloidal chemistry]. M.: Higher school, 1964 - 385 p. 11. Usmanov R.M., Abdikamalova A.B., Eshmetov I.D., Kuldasheva Sh.A., Eshmetov R.J., Sharipova A.I. Obtaining coal adsorbents based on local wood waste, research of their physico-chemical and adsorption properties Journal of Critical Reviews Vol 7, Issue 12, 2020 – P. 138-135. 12. Yang, F.; Tchoukov, P.; Qiao, P.Q.; Ma, X.; Pensini, E.; Dabros, T.; Czarnecki, J.; Xu, Z. Studying demulsification mechanisms of water-in-crude oil emulsions using a modified thin liquid film technique. Colloids Surf. A 2018, 540, 215–223. 31
№ 7 (97) июль, 2022 г. INORGANIC CHEMISTRY PHYSICO-CHEMICAL ANALYSIS OF FURFUROLIDENDIUREA BASED ON FURFURAL AND UREA Saidmurod Mukhammedov Doctoral student, Fergana Polytechnic Institute, Republic of Uzbekistan, Fergana E-mail: [email protected] Ibrokhim Askarov DSc, professor, Department of chemistry Andijan State University, Republic of Uzbekistan, Andijan Khayatulla Isakov DSc, professor, Department of Chemistry Andijan State University, Republic of Uzbekistan, Andijan ФИЗИКО-ХИМИЧЕСКИЙ АНАЛИЗ ФУРФУРОЛИДЕНДИКАРБАМИДА НА ОСНОВЕ ФУРФУРОЛА И МОЧЕВИНЫ Мухаммедов Саидмурод Боходиржон угли докторант, Ферганский политехнический институт, Республика Узбекистан, г. Фергана Аскаров Иброхим Рахманович д-р. хим. наук, профессор, Андижанский государственный университет, Республика Узбекистан, г. Андижан Исаков Хаётулла д-р. тех. наук, профессор, кафедра химии Андижанский Государственный Университет, Республика Узбекистан, г. Андижан ABSTRACT Today it is important to optimize agricultural production and provide it with biologically active, inexpensive, low- toxic fertilizers and stimulants. Compounds of furfural with urea have biological activity, they exhibit bactericidal and fungicidal properties. The individuality of the synthesized compound was determined using IR spectroscopy, scanned electron microscopic analysis methods. АННОТАЦИЯ Сегодня важно оптимизировать сельскохозяйственное производство и обеспечить его биологически активными, недорогими, малотоксичными удобрениями и стимуляторами. Соединения фурфурола с мочевиной обладают биологической активностью, проявляют бактерицидные и фунгицидные свойства. Индивидуальность синтезированного соединения определяли с помощью ИК-спектроскопии, методов сканирующего электронного микроскопа. Keywords: furfural, urea, IR spectroscopic, electron microscopic, content, analysis. Ключевые слова: фурфурол, мочевина, ИК-спектроскопия, электронная микроскопия, содержание, анализ. ________________________________________________________________________________________________ Today, a lot of research is being done to provide time, the complex recycling of agricultural, industrial agriculture with high-efficiency, inexpensive organic and wastes and domestic wastes is very important today. inorganic fertilizers and stimulants, as well as to further Extraction of furfural, which has high fungicidal and improve their physiological properties [1]. At the same bactericidal properties from pentose-containing wastes, _________________________ Библиографическое описание: Mukhammedov S., Askarov I., Isakov K. PHYSICO-CHEMICAL ANALYSIS OF FURFUROLIDENDIUREA BASED ON FURFURAL AND UREA // Universum: химия и биология : электрон. научн. журн. 2022. 7(97). URL: https://7universum.com/ru/nature/archive/item/14009
№ 7 (97) июль, 2022 г. serves to provide agriculture with biologically active, CORP., Japan, 2017) full internal reflective (ATR) inexpensive and effective drugs. Furfural products from binder MIRAcle-10 diamond / ZnSe prism (spectral agricultural wastes such as cotton stalks, rice husks, oscillations on the scale of wave count - 4000 ÷ 400 cm- sunflower baskets, corn kernels, and wheat straw have 1; resolution - 4 cm-1, sensitivity signal-to-noise ratio - been identified [2]. Compounds were obtained as a 60,000: 1; scanning speed - 20 spectra per second) using result of the reaction of the obtained furfural with urea Infrared Fure spectrometry. The results obtained using in different mole ratios. One of these is furfuralidendic the device were analyzed [5,6,7]. morphological study urea compound [3]. Initially, quantum chemical of the furfuralidendiurea surface in the crystalline state calculations of furfural and urea molecules were was performed and analyzed using SEM-EVOMA 10 performed in the theoretical evaluation of this (Zeiss, Germany) scanning electron microscopy [8,9]. compound [4]. Furfuralidendiurea was analyzed using physicochemical methods. Results and discussion. The results obtained by infrared spectroscopy analysis for structural analysis of Methods and materials. IR-spectral analysis of the compound formed by the reaction of furfural and furfuralidendiurea \"IRTracer-100\" (SHIMADZU urea in a 1: 2 mole ratio are given in Table 1. Absorption points (sм–1) Absorption frequencies in the IR spectrum Table 1. 3446,79 3292,77 Connection Intensity 2877,44 νasNH2 strong middle 1647,21 νsNH2 1525,69 νC–H Middle 1367,53 νC=O Strong 1010,70 ������NH2 verystrong 945,12 ������C–N weaknees 738,74 Middle 653,87 ������Furan ring Middle ������C–C Middle ������C–H weaknees Middle ������N–C–N As can be seen from this table, νasNH2 ва νsNH - a diameter of 1 cm and a thickness of 1-3 mm using bonds at the absorption points 3446.79 - 3292.77 sm – 1; special molds. [10] Using a SmartSEM device, the sample The νC–H bond is also present in this compound at a surface was magnified 100 times and the morphological frequency of 2877.44 sm – 1, while νC=О at 1647.21 sm – structure of the substance was determined. The resulting 1, the deformation state of ������NH2 is 1525.69 sm – 1, images are shown in Figure 1. At the same time, the C – N, furan ring, C-C, C-H, deformation bonds such as composition of the element was determined using the N-C-N were found to be 1367.53 sm – 1, 1010.70 sm – 1, graphical spectrum of the substance under investigation. 945.12 sm – 1, 738.74 sm – 1, 653.87 sm – 1, respectively. In this case, the mass fractions of the elements in the substance were calculated. The results are shown in The crystalline compound was also analyzed using Figure 2. a scanned electron microscope. To perform the inspection process, the sample is brought to the tablet state with Figure 1. Electron microscopic imaging of furfuralidendiurea 33
№ 7 (97) июль, 2022 г. Figure 2. Element graphic representation In the graphical representation of this component, compounds were confirmed by chemical and the mass of the substance in terms of carbon is 47.8%; physicochemical methods. IR spectroscopic analysis of oxygen - 26.8% and nitrogen - 25.3%. furfuralidenic urea proved that the functional groups formed individually based on the characteristic absorption Conclusion. Furfural, which has fungicidal and frequencies. As a result of analytical research on the bactericidal properties, was synthesized from agricultural appearance of the compound and the proportions of its wastes and compounds based on it were obtained. These constituent elements, we obtained accurate data. References: 1. Исаков Х. “Формальдегид ва фурфурол асосида кўп функционал таъсирга эга бўлган биологик фаол моддалар синтези, синфланиши ва олиш технологиясини ишлаб чиқиш” мавзусидаги техника фанлари доктори (DSc)диссертацияси автореферати Тошкент 2019. 58 б. 2. Асқаров И.Р., Исақов Х., Мухаммедов С.Б., Тўрахонов Ш.О. Получение фурфурола и его производных из отходов селскохозяйственных культур таких как хлопчатник, подсолнух, кукуруз //Life Sciences and Agriculture. 2020. №4. 17-20 б. 3. Асқаров И.Р., Исақов Х., Мухаммедов С.Б., Абдурахимова Н.Х. Махаллий ўсимлик чиқиндиларидан олинган фурфурол ва карбамид асосида биологик фаол моддалар олиш. ТОВАРЛАР КИМЁСИ ҲАМДА ХАЛҚ ТАБОБАТИ МУАММОЛАРИ ВА ИСТИҚБОЛЛАРИ Мавзусидаги VIII- республика илмий-амалий конфе- ренция материаллари. Андижон 2021.86-87б. 4. QUANTUM-CHEMICAL STUDY OF FURFURAL MOLECULE// Universum: химия и биология : электрон. научн. журн. Askarov I. [и др.]. 2022. 5(95). URL: https://7universum.com/ru/nature/archive/item/13417 5. Беллами Л. Инфракрасные спектры сложных молекул. – М.: ИЛ, 1963. 508-511 б. 6. Наканиси К. Инфракрасные спектры и строение органических соединений / К. Наканиси. – М.: Мир, 1965. 7. Беккер Ю. Спектроскопия / Ю. Беккер. – М.: Техносфера, 2009. 8. Сканирующая электронная микроскопия и рентгеноспектральный микроанализ в примерах практического применения / М.М. Криштал, И.С. Ясников, В.И. Полунин, А.М. Филатов, А.Г. Ульяненков (Серия «Мир физики и техники» II-15). – М.: Изд-во Техносфера, 2009. 205– 208 б. 9. Сергеева Н.Е. Введение в электронную микроскопию минералов — М.: Изд-во Моск. ун-та, 1977. – 144 с. 10. Эдельман В.С. Сканирующая туннельная микроскопия. // Приборы и техника эксперимента, М. 1989. № 5, с. 25 – 49. 34
№ 7 (97) июль, 2022 г. ORGANIC CHEMISTRY SYNTHESIS AND PROPERTIES OF HALOGEN DERIVATIVES BASED ON Β-CYANO ETHYL ESTERS OF ACETYLENIC AMINO ALCOHOLS Mansur Sodikov PhD, senior teacher Department of Food Technology, Shakhrisabz branch of the Tashkent Institute of Chemical Technology, Republic of Uzbekistan, Shakhrisabz E-mail: [email protected] Erkhan Turgunov Doctor of Chemical Sciences, professor of the Department of Chemistry, Tashkent Pedagogical University, Republic of Uzbekistan, Tashkent E-mail: [email protected] Sarvigul Khuzhanazarova Teacher Department of Food Technology, Shakhrisabz branch of the Tashkent Institute of Chemical Technology, Republic of Uzbekistan, Shakhrisabz E-mail: [email protected] Davron Tursunov Teacher Department of Food Technology, Shakhrisabz branch of the Tashkent Institute of Chemical Technology, Republic of Uzbekistan, Shakhrisabz E-mail: [email protected] СИНТЕЗ И СВОЙСТВА ГАЛОГЕНПРОИЗВОДНЫХ НА ОСНОВЕ Β-ЦИАНОЭТИЛОВЫХ ЭФИРОВ АЦЕТИЛЕНОВЫХ АМИНОСПИРТОВ Содиков Мансур Каххарови PhD, ст. преподаватель кафедры Технология пищевых продуктов, Шахрисабзский филиал Ташкентского химико-технологического института, Республика Узбекистан, г. Шахриса́ бз Тургунов Эрхан д-р хим. наук, профессор кафедры Химия Ташкентского педагогического университета Республика Узбекистан, г. Ташкент Хужаназарова Сарвигул Рустам кизи- преподаватель кафедры Технология пищевых продуктов, Шахрисабзский филиал Ташкентского химико-технологического института, Республика Узбекистан, г. Шахриса́ бз Турсунов Даврон преподаватель кафедры Технология пищевых продуктов, Шахрисабзский филиал Ташкентского химико-технологического института, Республика Узбекистан, г. Шахриса́ бз _________________________ Библиографическое описание: SYNTHESIS AND PROPERTIES OF HALOGEN DERIVATIVES BASED ON Β-CYANO ETHYL ESTERS OF ACETYLENIC AMINO ALCOHOLS // Universum: химия и биология : электрон. научн. журн. Sodikov M. [и др.]. 2022. 7(97). URL: https://7universum.com/ru/nature/archive/item/13958
№ 7 (97) июль, 2022 г. ABSTRACT This article is devoted to the synthesis of acetylenic amino alcohols, their β-cyanoethyl esters and halogen-containing com- pounds based on them. At the same time, we studied the properties of these compounds. The halogenation of β-cyanoethyl esters proceeds with the formation of their trans-dihalogen derivatives in high yields. Temperature has been found to affect the rate of halogenation. The average reaction rate is of great importance in the presence of a copper monochloride catalyst. It is shown that the synthesized halogen derivatives have an increased inhibitory activity against corrosion of steel and metal struc- tures. The inhibitory properties were determined gravimetrically. The structure of the synthesized compounds was established by infrared (IR) and proton magnetic resonance (PMR) spectroscopy. АННОТАЦИЯ Данная статья посвящена синтезу ацетиленовых аминоспиртов, их β-цианоэтиловых эфиров и галогенсодержа- щих соединений на их основе. При этом нами изучены свойства этих соединений. Галогенирование β-цианоэтиловых эфиров протекает с образованием их транс-дигалогенпроизводных с высокими выходами. Было обнаружено, что на скорость галогенирования влияет температура. Средняя скорость реакции имеет большое значение в случае присут- ствия катализатора монохлорида меди. Показано, что синтезированные галогенпроизводные обладают повышенной ингибирующей активностью в отношении коррозии стали и металлоконструкций. Ингибирующие свойства опреде- ляли гравиметрическим методом. Строение синтезированных соединений установлено методами инфракрасной (ИК) и протонной магнитно-резонансной (ПМР) спектроскопии. Keywords: acetylene, acetylene alcohol, acrylonitrile, cyano ethylation, acetylene ester, β-cyanoethyl ester, chlorine, bro- mine. Ключевые слова: ацетилен, ацетиленовый спирт, акрилонитрил, цианоэтилирование, ацетиленовый эфир, β-ци- аноэтиловый эфир, хлор, бром. ________________________________________________________________________________________________ The chemistry of acetylene and its derivatives is an im- trans-dihalogenated allyl amines, and the resulting com- portant branch of organic chemistry. It was the industrial pounds are non-flammable. At the same time, the addition production of acetylene and the possibility of obtaining var- of halogens to the C≡C bond of acetylenic amines has not ious compounds on its basis that increased the theoretical been sufficiently studied [6, 7]. We have previously inves- and practical significance of research in this area. Com- tigated the chlorination and bromination of acetylenic ami- pounds containing a modeling atom N, Cl, Br, O have val- noalcohols synthesized by the Mannich reaction [7,8]. It uable performance properties: they can be used as was found that when these reactions are carried out in a sol- biologically active compounds in medicine, agriculture; in vent such as diethyl ether, acetone, CC14, benzene, the cor- the production of quality fragrances. At the same time, spe- responding ammonium halide salts are formed [9]. cial attention is drawn to the synthesis of halogen deriva- tives on their basis, as well as to the study of their Catalysts are an important and essential component of properties. chemical production. Non-precious catalysts available; they have attracted increased attention due to their activity In this direction, work has been carried out on the syn- in the reduction of oxygen-containing compounds [10]. thesis of acetylenic alcohols and the study on this basis of The reactions of halogenation of acetylenic aminoesters the reactions of esterification, halogenation at the triple (Fig. 1A) in a CHCl3 solution were carried out in the pres- bond, as well as the study of various physicochemical or ence of Cu2Cl2 as a catalyst with the formation of trans-di- biological properties of the obtained compounds [1-3]. halogenated β-cyano ethyl esters compounds in high yields Conducted research, reflect the legitimacy of the tasks. [11]. These reactions proceeded according to the following scheme: As is known [4,5], acetylenic amines in the form of their hydrochlorides easily interact with halogens, forming CH3 X R C C C CH2 N(R)2 + X2 Cu2Cl2 CH3 C CH2 N(R)2 OR' RCCX (I - VIII) A OCH2CH2CN' R= -CH3 , -C2H5; - N(R)2= -N( C2H5)2, - N ; X= -Cl,-Br. Figure 1. Halogenation reaction of acetylenic aminoesters Various substituents in the amino group did not affect 70% in 4 hours at a temperature of 18-20 ° C. An increase the results of the reaction. The production of the process in temperature leads to an increase in the reaction products depended on such factors as the duration of the reactions, up to 83% in 2 hours. and it should be noted that halogenation in a solvent Structure of synthesized trans-dihalogen ethylenic (CHCl3) at a temperature of 20-40 ° C occurred with the amino esters was determined on the base of IR- and PMP- accumulation of halogen derivatives in 10 hours; at 50- spectrums. Deformational of nitrile group in IR-spectrum 60оC, the reaction time was halved. The use of Cu2Cl2 as a of 5-(diethylamino-3,4-dichlorine-2-methylpent-3-en-2- catalyst made it possible to increase the product yield to 68- iloxi)-propannitrile were observed in range 2895-2870 sm- 36
№ 7 (97) июль, 2022 г. 1; valent vibrations of middle intensively typical for ternary organic (bottom) portion is separated through a separate amino-group were observed in range 2965-2820 sm-1, wheat absorption at 2160 sm-1 has been characteristical for funnel and the upper aqueous portion is extracted three bond –C≡C- and absorption corresponding to group CCl=CCl has been observed in range 560-635 sm-1. times with chloroform. Peculiar absorption bands in the proton magnetic reso- The combined chloroform extracts were dried over nance (PMR) spectrum of 6-(diethylamino-4,5-dichlorine- 3-methylhex-4-en-3-yloxy) propanenitrile: the protons of CaCl2, then chloroform was distilled off and the rest was the δ (3H) methyl group appear at 1.33 ppm as singlet, the protons for the methyl group in the β position δ (2H) are distilled under vacuum. The resulting dibrom derivative shifted to 0.69 ppm in the form of a triplet, the protons of the methylene group at 1.5 ppm and the protons of the me- has boiled at 195-1970C/10 mm Hg. And its result was thyl group δ (6H) in the β state are 1.0 ppm. in the form of a triplet, a quartet relative to tertiary nitrogen. The protons fixed as (35.16 g) 81.0%, its n2D0 was 1.5285, and d 20 was of the methylene groups δ (6Н) near the nitrogen atom and 4 the cyanide group in the field are 2.58–2.64, and the pro- tons of the methylene group δ (2H) near the halogen and at the point 1.2295 g/cm3. double bond are 3.0 ppm. Individual protons of the meth- ylene group δ (2H) next to the ester group - at 3.74 ppm. The hydroxyl group of acetylenic amino alcohols has The determination of the inhibitory properties of the a different effect on the addition of the halogen to the triple synthesized substances was carried out by gravimetric method [12]. bond, slowing down as the mass of the radical increases, Results and experimental part that is, H> CH3> C2H5. Moreover, the main effect arises In the halogenation reaction, Cu2Cl2 was used as a cat- from the action of the hydroxyl group on the triple bond in alyst in an amount of 0.005 mol based on the total mass of the reacting components. the state in which these substituents are retained, since the 3.1. Synthesis of 5-diethylamino-3-(3,4-dichlorine-2- interaction of the intermolecular hydroxyl group with the methylpent-3-en-2-yloxy) propannitrile. triple bonds leads to an association. Based on these theoret- In flash will relax refrigerator gas-paining tube and mechanical mixer 22.2 g (0.1 mol) of 5-diethylamino-3-(2- ical concepts, the interaction of acetylenic aminoesters with methylpent-3-yn-2-yloxy) propane nitrile has been intro- duced which was dissolved in 50 ml of chloroform and then chlorine or bromine was studied in order to study the addi- aright obtained reaction mixture at stirring during 2h at 350C 7.1 g (0.1 mol) purified gaseous chlorine has been tion of a halogen at the triple bond [13-15]. Various substit- added. Then reaction mixture has been kieped at room tem- perature during 10h. and after this it was treatment by solu- uents in the amino group practically do not affect the result tion of K2CO3 and washed by solution Na2SO4. The organic portion was separated, and the aqueous portion is of the reaction. Productivity depends on factors such as re- extracted three times with chloroform. The organic portion and extract are combined and dried over MgSO4 for 24 h. action time, and it should be noted that the halogenation Then the solvent was distilled off and the residue was dis- tilled under vacuum. The resulting dichlor derivative was process takes place in chloroform solution at room temper- isolated at 1900C at 10 mm Hg. with a result (23.15 g) 79.0%, its refractive index was 1.5301 and density detected ature (20-400C) by 60-70% for 10 h, and at 50-600C the in 1.2105 g/cm3. reaction time is halved respectively. Thus, the use of a cop- The rest of the dichlor derivatives of the other ami- noesters were synthesized in a similar way and some of per chloride catalyst increases the product yield to 68-70% their physico-chemical constants (Table 1, I, III, V, VII compounds) of the obtained substances were determined. within 4 hours at room temperature, while an increase in 3.2. Synthesis of 5-diethylamino-3-(3,4-dibromo-2- temperature leads to an increase in the product yield to 83% methylpent-3-en-2-yloxy) propannitrile. within 2 hours. It can be seen that the formation of trihalide In a three-necked flask with a reflux condenser, a drop- ping funnel and a mechanical stirrer, the catalyst mono- ions by solvation of the halogen during the reaction without chloride (I) copper and 22.2 g (0.1 mol) of 5-diethylamino- a catalyst increases the tendency to form a π-bond interme- 3-(2-methylpent-3-yn-2-yloxy) propannitrile are intro- duced dissolved in 50 ml of chloroform, under cooling the diate complex, while the solvation of the trihalide ions reaction mixture with ice water, and 16.0 g (0.1 mol) of liq- uid bromine are added to the reaction mixture within 2 h. readily increases with increasing temperature. In turn, the Then the reaction mixture was left for 10 h at the tempera- ture 18-21˚C. Then, it was neutralized with saturated solu- use of a catalyst facilitates the decomposition of a halogen tion of K2CO3 and washed with a solution of Na2SO4. The molecule into ions, and the formation of a carbocation due to a π-complex with a carbon atom at a triple bond allows ionized halogens to combine from opposite sides. Conse- quently, the product yield is relatively high in the presence of a catalyst. It is known that the halogenation of acetylene compounds with different structures depends largely on the nature of the solvents [16-18]. As noted in the literature, mainly in the halogenation of acetylene compounds in polar solvents, new compounds can be obtained, that is, the products of conjugated addition of halogens. In this regard, it should be mentioned that the reaction of acetylenic amino alcohol esters with halogens in the presence of a copper (I) chloride catalyst in an acetic acid solution resulted in the isolation of the corresponding acetoxy derivatives of monohalogenated amino esters in 18-30% yield. In this case, with an increase in the molar ratio of acetylenic amino ester (AAE) and halogen: AAE = 2: 1, a trans-dihalogenated ester compound of amino ke- toalcohols is formed in the reaction medium, and their yield increases to 68-70% at 40°C for 1.5 h. However, not all electrophiles possess such activity, and, as noted above, the electrophilic of halogens manifests itself only under certain conditions, and in this case, their interaction with the С≡С bond can take place. Thus, the halogen molecule must be polarized to the state Xδ + ─Xδ− for the formation of a car- 37
№ 7 (97) июль, 2022 г. bocation. The formation of a nucleophile and an electro- phile occurs when the solvent chloroform interacts with a halogen (Fig. 2). Figure 2. The scheme of the nucleophile formation and an electrophile These cases can be expressed as follows: the addition X-) accumulate in a \"trans state\" with a double bond. It of a halogen begins with the interaction of chloroform with should be noted that dihalogenated compounds are formed it, in which a partially positively charged halogen binds to at the initial stage of the reaction [16, 18, 19]. an unbound electron pair of the nitrogen atom, then a π- Boiling temperature, density and d420 of halogen deriv- bonded halogen molecule is formed as a result. electro- atives of β-cianoethylenic esters (I-VIII) were determined philic halogen attack. A halogen atom, which is a sextet of and are presented in table 1. The halogenated derivatives of electrons (i.e. positively charged), electrophilically attacks amino ethers synthesized by us are readily mobile, slightly one of the carbon atoms bound to the π-bond and pulls out a pair of π-electrons, forming a bond with the carbon atom, yellow oil-like liquids with a peculiar amine odor. and the second carbon loses the π-electron pair and be- The effect of the temperature and reaction time on the comes positive, turning into a charged carbocation. productivity of 5-(diethylamino-3,4-dichlor-2-methylpent- The second carbon atom is nucleophilically attacked 3-en-2-yloxy) propanenitrile (I) was studied (Fig. 3) and it by the second halogen atom (electron-octet anion). In this was found that when chlorination in in the temperature range 30-50˚C, the best result is achieved at 45oC. With in- case, a mainly trans compound is formed. This situation is creasing temperature, the productivity decreases with par- explained by the fact that the attacking electrophilic particle first binds to two carbon atoms in the C≡C bond, forming tial formation of unknown compounds. When the temperature rises to 50-55 ° C, the initial rate of the process a three-membered onium ring, and the second opens due to is high and after 8 hours the product yield is about 30-35%. Waldenian reversion of the anion during the next nucleo- philic attack. As a result, the attacking particles (X+ and Table 1. Bromine and chlorine derivatives on the base of β-cianoethyl esters of acetylene aminoalcohols № Structure of molecule Name and brutto-formula Yield, Т.b./0С n2D0 d 20 % mm.m.st. 4 H3C CH3 Cl CH2 N(CH3)2 5-(dimethylamino-3,4- CCC dichlorine-2-methylpent-3-en- I 2-iloxy)-propannitril 79.0 190/10 1.5301 1.2105 Cl OCH2CH2CN C13H22N2OCl2 H3C CH3 Br CH2 N(CH3)2 5-(dimethylamino-3,4- CCC dibromine-2-methylpenten-3- II en-2-iloxy)-propannitril 81.0 195-197/10 1.5285 1.2295 Br OCH2CH2CN C13H22N2OBr2 38
№ 7 (97) июль, 2022 г. № Structure of molecule Name and brutto-formula Yield, Т.b./0С n2D0 d 20 % mm.m.st. 4 H3CH2C CH3 Cl CH2 N(C2H5)2 6-(diethylamino-4,5-dichlo- CCC rine-3-methylhex-4-en-3- III 80.0 193/10 1.5525 1.2210 Cl iloxy)-propannitril OCH2CH2CN C14H24N2OCl2 H3CH2C CH3 Br CH2 N(C2H5)2 6-(diethylamino-4,5-dibro- CCC mine-3- methylhex-4-en-3- IV 83.0 198-199/10 1.5895 1.2945 Br iloxy)-propannitril OCH2CH2CN C14H24N2OBr2 Cl CH3 5-(pyperidino-3,4- dichlorine - V N CH2 C C C CH3 2-methylpent-3-en-2-iloxy) 77.0 196/10 1.5685 1.4215 propannitril Cl OCH2CH2CN C14H22N2OCl2 H3C CH3 Br CH2 N 5-(pyperidino-3,4-dibromine- CCC 2-methylpent-3-en-2-iloxy)- VI propannitril 82.0 201-202/10 1.5975 1.3125 Br C14H22N2OBr2 OCH2CH2CN H3CH2C CH3 Cl CH2 N 6-(pyperidino -4,5-dichlorine- CCC 3-methylhex-4-en-3-iloxy)- VII propannitril 78.0 197-198/10 1.5785 1.3045 Cl C15H24N2OCl2 OCH2CH2CN H3CH2C CH3 Br CH2 N 6-(pyperidino-4,5-dibromine- CCC 3-methylhex-4-en-3-iloxy)- VIII propannitril 77.0 203-204/10 1.7985 1.3550 Br C15H24N2OBr2 OCH2CH2CN Figure 3. Influence of temperature and duration of reaction on productivity of 5-(diethylamine-3,4-dichlorine-2-methylpent-3-en-2-iloxi)-propannitril Therefore, all kinetic measurements of the rate were temperature has a straight line (Fig. 4). According to this carried out at a given temperature, and the dependence graph, the values of the activation energy for chlorina- of the income of 5-(diethylamino-3,4-dichloro-2- tion of acetylenic aminoesters were found. methylpent-3-en-2-yloxy) propanenitrile on the reverse 39
№ 7 (97) июль, 2022 г. .lgW+2 .1,6 1,5 . .1,4 1,3 1 10-3 К Т 3,14 3,19 3,24 3,30 Figure 4. Dependence of ratio of 5-(diethylamine-3,4-dichlorine-2-methylpent-3-en-2-iloxi)-propannitril formation on reverse temperature An additional π-bond is formed in the halogen mol- the free 3- and 4d-orbitals of the other, and they are iso- ecule due to the unbound electron pair of one atom and lated as crystalline products (a) [11, 16]: RR'C(OR'')C CCH2N(C2H5)2 + X2 .[ RR'C(OR\")C CCH2N(C2H5)2 ] X- aX During the halogenation of esters of acetylenic amino it was found that the C≡C bond forms with halogens alcohols in carbon tetrachloride, diethyl ether or acetone, π-connected complex (b) of the type [16]: R' C2H5 R C C C CH2 N X OR\" X X C2H5 Xb After neutralization of the aqueous solution of the obtained products with sodium carbonate, the first ami- noesters containing the π-halogen complex at the С≡С bond were isolated (c) [9, 11]: In these substances, after a day, halogen molecules Accordingly, the use of a catalyst based on copper migrate to the nitrogen atom, that is, with the formation of halogen compounds Comparison of the results ob- monochloride significantly accelerates the exothermic tained shows that, under the studied conditions, the for- addition of halogens with a C≡C bond and leads to the mation of a π-complex between the C≡C bond and halogens and the breaking of these bonds often requires formation of trans-dihalogenated products in high yield. high temperatures or the use of catalysts. At the same time, isolated π-complexes were identified for the first time, which indicates an electrophilic reac- tion (d) [8-9]: 40
№ 7 (97) июль, 2022 г. [(R)2NCH2C CC(OR\")RR'] X- X2 [ (R)2NCH2C+ CC(OR\")RR'] CuCl - CuCl X - X X2 [ (R)2NCH2C CC(OR\")RR' ] X3- X d Additional chlorination and bromination to obtain Action of different factors including reaction time tetra halogenated derivatives does not give the desired and temperature in synthesize of acetylenic amino result due to the steric barrier. This is confirmed by the esthers and their halogen derivatives (Table 2). At com- data of IR spectroscopy, elemental analysis and dipole paratively higher temperatures (50-550C), product moments. Halogenated derivatives of all synthesized yields turned out to be relatively low (Fig. 3). aminoesters are readily soluble in water, alcohol, ace- tone, and carbon tetrachloride [17-26]. Table 2. Results of synthesis of 5-(dimethylamino-3,4-dichlorine-2-methylpent-3-en-2- iloxy)-propannitril (solvent–chlorophorm) Duration of reaction. h. Yield of product, % Average rate of reaction (W) %/h mol/l h. 1 Temperature 300С 2 4.5 4.50 0.20 3 10.8 5.40 0.24 4 22.3 7.43 0.33 43.5 10.87 0.48 1 2 Temperature 350С 6.40 0.28 3 6.4 6.50 0.29 4 13.0 8.46 0.37 25.4 10.97 0.52 1 47.9 2 8.60 0.38 4 Temperature 400С 9.45 0.42 6 8.6 9.20 0.41 8 18.9 8.33 0.37 36.8 7.25 0.32 1 50.0 2 58.1 10.80 0.48 3 10.50 0.47 4 Temperature 450С 10.05 0.44 10.8 13.05 0.58 21.0 40.2 54.2 Elemental analysis of the synthesized compounds At the initial stage, the rate of halogenation was high showed that the composition corresponded to its gross formula, and the obtained values are presented in table 3. and there is a rapid change in the concentration of halogen over time (table 4). The maximum speed was observed at 35°C after 2 hours. 41
№ 7 (97) июль, 2022 г. Table 3. Indexes of trans-dihalogen derivatives of oxyaminonitriles (I-VIII) № compounds C Found,% X Brutto-formulas Calculated, % 52.90 N 24.13 CNX I 40.10 42.14 C13H22N2OCl2 53.25 9.55 24.18 II 54.18 9.11 23.13 C13H22N2OBr2 40.86 7.33 41.82 III 42.68 7.61 39.86 C14H24N2OCl2 54.73 9.12 23.08 IV 54.66 9.30 22.58 C14H24N2OBr2 42.45 7.07 40.34 V 42.66 7.10 40.07 C14H22N2OCl2 55.09 9.18 23.23 VI 55.88 8.80 21.77 C14H22N2OBr2 42.66 7.11 40.55 VII 43.61 7.11 38.88 C15H24N2OCl2 56.43 8.77 22.21 VIII 8.68 C15H24N2OBr2 44.14 6.86 39.15 6.86 The data obtained once again confirm the electro- philic mechanism of the addition of halogens to the tri- ple bond of the studied aminoesters as a whole. Table 4. Rate of halogenation of 5-(diethylamino)-3-(2-methylpent-3-in-2-iloxy)-propannitril in dependence of chlorine concentration (35°С) Duration of reaction, h. Concentration of chlorine, mol k; M-1, s-1 0 0.0241 0 18 0.0238 22 0.0221 0.0290 24 0.0213 0.1706 51 0.0178 0.2272 68 0.0153 0.2879 116 0.0119 0.3405 131 0.0081 0.3665 172 0.0062 0.6256 184 0.0043 0.6954 226 0.0036 1.0380 1.0455 Obtained results have proved the fact that halogen Along with the above, the effect of some of the atoms are in trans-position at double correction in obtained halogenated derivatives of enyloxyamines on molecules of synthesized compounds. the corrosion of metals was also studied and the results obtained are presented in tables 5-7. Table 5. Action of some inhibitors on the base of halogen derivatives of amino oxynitriles on steel-20 corrosion Inhibitor Concentration С0 Ск Z% Y of inhibitor, g/m2, h g/m2, h. g/l I. 5-(diethylamino-3,4-dichlorine-2- 0.5 37.6231 0.2310 99.3 128.5 methylpent-3-en-2-iloxi)-propannitril + urotropin =1:0,001 III. 5-(diethylamino-3,4-dichlorine-2- 1.0 37.6231 0.2460 99.4 131.8 methylpent-3-en-2-iloxi)-propannitril + urotropin =1:0,001 1.0 37.6231 0.3271 99.1 115.0 I-1-А (known inhibitor) 42
№ 7 (97) июль, 2022 г. Table 6. Indexes 5-(diethylamino-3,4-dichlorine-2-methylpent-3-en-2-iloxy)-propannitrile against corrosion of steel in two-phase water-hydrocarbon medium Concentration, g/l Middle lost Middle rate of Degree rate of mass, corrosion, of protec- Compo-unds Time, h. Water amount of % g/m2,h Note I 24 H2S inhibitor tion, 24 0.0058 0.13 % On water 0.8 0.5 0.0026 0.06 75.9 30 g/l NaCl was 72 1.0 1.0 0.0027 0.06 88.9 III 24 0.8 2.6 0.0239 0.54 88.9 added 0.0041 0.09 - - 0.0053 0.04 83.2 1.1 1.0 0.0340 0.26 84.6 1.1 -2.0 0.0175 0.39 - 0.0155 0.35 27.8 - 0.0239 0.54 35.2 0.9 0.5 0.0230 0.52 - 0.0344 0.78 33.0 1.0 - 1.1 - 1.0 Table 7. Protection action of 5-(diethylamino-3,4-dichlorine-2-methylpent-3-en-2-iloxy)-propannitrile on steel in water-oil medium Reaction time, The amount of urotropine Average loss, g Corrosion rate, Degree of h injected, g / l g / m2 hour protection, % 30 0.1 0.0016 0.036 0.4 0.0013 0.030 61.3 78 0.6 0.0012 0.027 67.8 1.6 0.0010 0.022 71.0 _ 0.0041 0.093 76.3 0.1 0.0018 0.013 0.4 0.0018 0.013 _ 0.8 0.0021 0.010 65.8 1.6 0.0019 0.014 65.8 - 0.0050 0.008 73.7 72.6 - Conclusions At the same time, if the ratio of the reacting compo- nents halogen: ether is equal to 2:1 it is possible to achieve Have been found, acetylenic aminoesters containing encouraging results. oxypropanenitrile fragments easily enter into reactions of electrophilic addition of halogens with the formation Along this, high inhibitory properties of halogenated of trans-structure products. aminoesters have been established, that, in synergy with urotropin, give positive results. References: 1. Turgunov E., Acetylene alcohols. Part I. Text book. LAP LAMBERT, 260 (2018). ISBN: 978-613-9-86984-8. 2. Selina А.А., Karlov S.S. and Zaytseva G.S., Bromination and iodochlorination of acetylenes. Bull. Moscow Univ. Series 2. Chemistry, 45(3), 147-171(2004). 3. Zokirov S., Zokirov S.S., Juraboev F.M. and Turgunov E., Research of synthesis of acetylene amino alcohols and study of their properties. Intern. J. Disaster Recov. and Bus. Continuity, 11(3), 2850-2857(2020). 4. Turgunov E., Sadikov M.K., Sirliboev T., Nuriakhmedova T. Synthesis of halogen-containing compounds based on propargylamines. // J.Org.chem. -1999. -35. –V. 8. -pp.1161-1164. 5. Sirlibaev T.S., Kurbanov A.I., Turgunov E. Halogenation of heterocyclic mono- and diamines. // Chem. Heterocycle. Comp.-1988.-№. 10, -pp. 1369-1371. 6. Kurbanov AI, Sirlibaev TS, Turgunov E. Synthesis of halogenated acetylenic amino alcohols. // Uzbek. chem. j. - 1984. -№. 6. -pp. 58-61. 7. Kurbanov A.I., Sirlibaev T.S., Kultaev K.K. Halogenation and hydrohalogenation of some acetylenic amino alco- hols. // J. of Applied Chemistry (Rus). —1985. -№. 11. - pp. 2583-2586. 43
№ 7 (97) июль, 2022 г. 8. Turgunov E. / Dissertation of the candidate of chemical sciences. Tashkent.-1990. -210 p. 9. Turgunov E., Yuldashev A., Sadikov M.K. /Quaternary ammonium salts of acetylenic amines. // Reports of the Acad- emy of Sciences of the Republic of Uzbekistan. -2010. -№2. -pp.64-67. 10. Nadirov R. and Sabirov Y. The New Approach to Enhance the Activity of Fe/N/C Catalyst for Oxygen Reduction Reaction by Electrochemical Treatment. J New Mater Electrochem Syst, 21(2), 91-95(2018). 11. Sodikov М.К., Xujanazarova S.R., Turgunov E., Synthesis of ethers and esters of acetylenic alcohols. UNIVERSUM: Chem. & Biol., 7(85), 85-90(2021). 12. Podobaev N.I. and Avdeev Ya.G., Acetylene compounds as inhibitors of acid corrosion of iron. Review. Metal Pro- tect, 40(1), 11-16(2004). 13. Liu Y., Zhang H., Li X., Wang L., Dong Y., Li W. and Zhang J., Solvent-assisted synthesis of N-doped activated carbon-based catalysts for acetylene hydrochlorination. Applied Catalysis A: General, 611, 117902(2021). 14. Matemb Ma Ntep T., Breitzke H., Schmolke L. et al., Facile in Situ Halogen Functionalization via Triple-Bond Hydrohalogenation: Enhancing Sorption Capacities through Halogenation to Halofumarate-Based Zr (IV)-Metal- Organic Frameworks. Chem Mater, 31(21), 8629-8638(2019). 15. Gliese J.P., Jungbauer S.H. and Huber S.M., A halogen-bonding-catalyzed Michael addition reaction. Chem Communic, 53(88), 12052-12055(2017). doi: 16. Sodikov М., Sharipov Ya., Haknazarova М. and Turgunov E., Synthesis and application of halogen derivatives based on benzoyl ethers of tertiary acetylenic alcohols. Bull NUU: Estestv Nauki, 3(1), 307-311(2021). 17. Kumar S., Shah T.A. and Punniyamurthy T. Recent advances in the application of tetrabromomethane in organic synthesis. Organic Chem Front, 8, 4288-4314(2021). 18. Alami M., Hamze A. and Provot O. Hydrostannation of alkynes. ACS Catalysis, 9(4), 3437-3466(2019). 19. Yu S. and Ma S. How easy are the syntheses of allenes? Chem Communic, 47(19), 5384-5418(2011). 20. Nagar P.R., Gajjar N.D. and Dhameliya T.M. In search of SARS CoV-2 replication inhibitors: Virtual screening, molecular dynamics simulations and ADMET analysis. J Molecul Struct 1246, 131190(2021). 21. Li S. Manufacture of fine chemicals from acetylene. De Gruyter, 2021. https://doi.org/10.1515/9783110714999 22. Ali F.I. Thermal Stability and Solid State Cyclization of Dipeptides (Doctoral dissertation), 2020. https://hdl.handle.net/10214/21341 23. Zabeti M., Daud W.M.A.W. and Aroua M.K. Activity of solid catalysts for biodiesel production: a review. Fuel Proces Tech, 90(6), 770-777(2009). 24. Rak Lee S., Schalk F., Schwitalla J.W. et al. Polyhalogenation of Isoflavonoids by the Termite-Associated Actinomadura sp. RB99. J Nat Prod, 83(10), 3102-3110(2020). 25. Tchizova N.V., Ivanova Yu.B. and Mamardashvili N.Zh. Halogenation of -Positions in Co(II)-Tetrapenylporphyrins. Macroheterocycles, 11(1), 85-88(2018) 26. Sodigov M.Қ., Turgunov E., Khuzhanazarova S.R. Halogenation of β-cyanoethyl ether 1-Diethylamino-4- methylpentin-2-ol-4. In Actual Probl Chem (pp. 280), Tashkent, 2021. 44
№ 7 (97) июль, 2022 г. CHEMICAL COMPOSITIONS OF BIODEGRADABLE DISPOSABLE TABLEWARE BASED ON CORN BRAN Madinabonu Dilmurod qizi Khamdamova Doctoral student specializing in chemistry of goods, Andijan State University, Uzbekistan, Andijan Ibrokhimjon R. Asqarov Doctor of Chemical Sciences, Professor, Department of Chemistry, Andijan State University, Uzbekistan, Andijan E-mail: [email protected] ХИМИЧЕСКИЙ СОСТАВ БИОРАЗЛАГАЕМЫХ ОДНОРАЗОВЫХ ПОСУД НА ОСНОВЕ КУКУРУЗНЫХ ОТРУБЕЙ Хамдамова Мадинабону Дилмурод кизи докторант по специальности химия товаров, Андижанский государственный университет, Республика Узбекистан, г. Андижан Аскаров Иброхимжон Рахмонович д-р хим. наук, профессор кафедры химии Андижанского государственного университета, Республика Узбекистан, г. Андижан E-mail: [email protected] ABSTRACT In the article, we studied biodegradable disposable tableware as an environmentally friendly product with a raw material composition and chemical component content that has a useful organoleptic complex. АННОТАЦИЯ В статье мы исследовали биоразлагаемую одноразовую посуду, как экологический чистый продукт для бытья и как товар с сырьевым составом по химическому компонентному содержанию имеющий полезный органо- лептический комплекс. Keywords: biodegradable tableware, starch, bran, corn, polyacid, chemical composition, scientific and economic review, fatty acids. Ключевые слова: биоразлагаемая посуда, крахмал, отруби, кукуруза, полиактид, химический состав, научный и экономический обзор, жирные кислоты. ________________________________________________________________________________________________ Introduction Literature analysis Since the pandemic period, the global market has Back in 2019, the CIS countries and Russia in par- been dominated by the demand for disposable tableware. ticular, created a completely biodegradable plastic from In turn, we would like to mention that disposable plastic ordinary potato or grain starch and began the mass pro- utensils were acceptable until the world ecology duction of it. Disposable innovative tableware made recognized the harmful facts in the use and disposal of from it is so harmless that it can even be eaten after use these petroleum products. To solve the above problems, if desired [1]. Analyzing the chemistry of biodegradable we studied the research of some scientists in the field of tableware according to the Scopus database and Web of production of biodegradable disposable tableware based Science publications, the query for the tag \"Biopolymer on a plant component (secondary raw materials of grain materials\" received a response to more than 121 thou- crops in our country). Based on such biopolymers, it is sand publications on a global scale, including China possible to obtain films for the manufacture of durable (about 25 thousand), leaders among countries, United bags (as packaging materials) and disposable tableware. States (about 25 thousand) and India (more than 10 thou- sand) [2]. _________________________ Библиографическое описание: Khamdamova M, Asqarov I.R. CHEMICAL COMPOSITIONS OF BIODEGRADABLE DISPOSABLE TABLEWARE BASED ON CORN BRAN // Universum: химия и биология : электрон. научн. журн. 2022. 7(97). URL: https://7universum.com/ru/nature/archive/item/14039
№ 7 (97) июль, 2022 г. Methods and mechanical characteristics of samples of rectangular plates from wheat bran and introduced the process of In this scientific article, we wish to use research molding prototypes (rectangular plates) hydraulically methods for the processing of secondary raw materials modernized by the P-500 press of laboratory composite of plant origin. We studied the chemical composition of materials, and a mold for the above samples was de- corn bran and offer optimal conditions for the produc- signed by laboratory specialists [2]. tion of biodegradable tableware. The production line can use starch, calcium car- The main areas of application of biodegradable pol- bonate (calcium carbonate), talc powder, polylactic acid, ymeric materials are wholesale and retail trade enter- polypropylene, polystyrene, vegetable fibers (corn cobs, prises using polystyrene foam substrates and film straw, bagasse) and other decomposing raw materials. materials for packaging of goods sold; public catering Depending on the raw materials used, biodegradable ta- enterprises (i.e. cafes, restaurants, food delivery, fast bleware of various qualities is formed and processed. food enterprises), catering (i.e. organization of off-site banquets, receptions). The proposed production line can produce knives, forks, spoons by injection molding, and can also pro- Results and discussion duce disposable cups, dishes, glasses by extrusion and vacuum forming. According to the different require- Nowadays, among the natural components, which ments of the buyer, a different configuration of the pro- are proposed for the technology of biodegradable mate- duction line is formed [4]. rials, secondary products of plant and animal origin, which, are waste products of processing industries, are One of the most promising modern bioplastics is of particular interest. A significant share of renewable polylactide (PLA), for the synthesis of which renewable raw materials mainly consists of waste from grain and natural resources are used, mainly sugar cane and corn. flour production, textile and wood processing industries In terms of its chemical properties, polylactide is close [3]. to PET and polystyrene, but decomposes within two months at an air humidity of 80% and a temperature of In a sunny country of ours, many varieties of agri- 55–70 °C. cultural crops are grown, in particular, cereal crops of plants occupy a predominant place. Most often, in the The volume of the Russian biodegradable tableware technologies of molded products, the use of grain bran, market in 2019 increased by 15% compared to 2018. collapsed seed coats of grain crops, sugar cane pro- More than half of this increase was provided by in- cessing waste, straw, etc. is suggested as a raw material creased imports, whose share in the total volume does basis in compositions. not yet exceed 30%. Domestic production also grew, but less significantly both in percentage and in absolute We have studied the research of many scientists terms. The export of biodegradable tableware from Rus- from developing countries on the production of biode- sia is insignificant and does not make any significant gradable tableware in recent years. For example, in the contribution to the market volume. In the following scientific works of Doctor of Technical Sciences, Pro- chart, we want to look at the size of the biodegradable fessor of the South Ural State University I.Yu. Potorok tableware market before the pandemic. and a number of her employees developed the physical Diagram 1. The market volume of biodegradable tableware in the period of 2018 and 2020 Pink colour is for production, blue colour is for market volume, yellow colour is for imports. In 2020, due to restrictions imposed during the first production after wheat and rice. Sweet corn (lat. Zea wave of COVID-19 virus, the consumption of biode- mays) is the only cultivated representative of the genus gradable tableware decreased. However, in 2022, these \"corn\" of the cereal family. Man began to grow it 7-12 figures increased significantly by 22% [5]. thousand years ago on the territory of modern Mexico. Corn is the oldest cereal grain in the world. One of the main raw materials for the production of biodegradable tableware is starch and corn bran. Cur- Up to 90% of the nutrients are in the shell, called rently, corn is the third largest in the world in terms of bran, which is obtained during the processing of corn 46
№ 7 (97) июль, 2022 г. kernels into flour. They are made from the skin, which Table 1 presents data on the rich chemical is removed from the main product. The shell is crushed composition and analysis of the nutritional value of the or pressed and sold as a separate commodity unit. This main raw materials in the production of biodegradable production method causes many people to associate bran corn bran dishes. The table shows the content of with waste. However, the rich chemical composition nutrients (calories, proteins, fats, carbohydrates, does not allow to treat the product with disdain [6]. vitamins and minerals) per 100 grams of the edible part of the product [7]. Chemical composition of corn bran Table 1. Composite Components Quantity Norm % of the norm % relative to in 100 gr 100 kcal Сalories 224 kcal 1684 kcal 13,3% 5,9% Squirrels 8.36 g 76 g 11% 4,9 % Fats 0.92 g 56 g 1,6% 0,7% Carbohydrates 6.64 g 219 g 3% 1,3% Alimentary fiber 79 g 20 g 395% 176,3% Water 4.71 g 2273 0,2% 0,1% Ash 0.36 g - - - Vitamins Vitamin A, P, E 4 mcg 900 mcg 0,4% 0,2% Alpha carotene 21 mcg - - - Betta carotene 0.006 mg Lutein-Zeaxanthin 1355 mcg 5 mg 0,1% 0,1% Vitamin B1, thiamine 0.01 mg - - - Vitamin B2, riboflavin 0.1 mg Vitamin B4, choline 18.1 mg 1.5 mg 0,7% 0.3% Vitamin B5, pantothene to-ta 0.636 mg 1.8 mg 5,6% 2,5% Vitamin B6, pyridoxine 0.152 mg 500 mg 3,6% 1,6% Vitamin B9, folate 4 mcg 5 mg 12,7% 5,7% Vitamin E, alpha tocopherol 0.42 mg 2 mg 7,6% 3,4% Vitamin K, phylloquinone 0.3 µg 400 mcg 1% 0,4% Vitamin PP, picric acid 2.735 mg 15 mg 2,8% 1,3% Betaine 4.6 mg 120 mcg 0,3% 0,1% Macronutrients 20 mg 13,7% 6,1% Potassium, K Calcium Ca - - - Magnesium Sodium, Na 44 mg 2500 mg 1,8% 0,8% Sulfur, S 42 mg 1000 mg 4,2% 1,9% Phosphorus, P 64 mg 400 mg 16% 7,1% trace elements 7 mg 1300 mg 0,5% 0,2% Iron, Fe 83.6 mg 1000 mg 8,4% 3,8% Manganese, Mn 72 mg 800 mg 9% 4% Copper, Cu Selenium, Se 2.79 mg 18 mg 15,5% 6,9% Zinc, Zn 0.14 mg 2 mg 7% 3,1% Saturated fatty acids 248 mcg 1000 mcg 11,1% Saturated fatty acids 16.5 mcg 55 mcg 24,8% 13,4% 16:0 Palmitic 1.56 mg 12 mg 30% 5,8% 18:0 Stearic 13% 0.13 g Max 18.7 g 0.111 g - 0.015 g - 47
№ 7 (97) июль, 2022 г. Composite Components Quantity Norm % of the norm % relative to in 100 gr 100 kcal Monounsaturated fatty acids 0.243 g Min 16.8g 1,4 % 0,6% 16:2 palmitol 0.001 g - 18:3 Oleic Omega-9 0.243 - 3,8% 1,7% Polyunsaturated fatty acids 0.421 g 18:2 Linoleic 0.408 g From 11.2 to 20.6g 1,4% 0,6% 18:3 Linolenic 0.013 g - 8,7% 3,9% Omega-3 fatty acids 0.013 g - Omega-6 fatty acids 0.408 g 0.9- 3.7 g 4.7-16.8 g Amino acids in the composition of corn bran are body is especially important during pregnancy; 2) Fiber both a source of nitrogen and carbon, the latter being ab- is good for the intestines - it prevents the absorption of sorbed from the keto acids formed as a result of the elim- glucose, normalizing blood sugar levels. It also increases ination of amino groups. Direct assimilation of amino intestinal patency, helping to get rid of constipation, acids from a nutrient medium containing their complete which often bothers women during pregnancy and fans set and any fermentable sugar is also possible. of strict diets; 3) Unsaturated fats reduce the amount of bad cholesterol and strengthen the heart and blood vessels. As a nutrient medium, up to 4% nitrogen can be ob- Monounsaturated fatty acids reduce the risk of cancer tained from corn extract in relation to 100 g product [10]. and normalize glucose levels. Polyunsaturated fats sup- port the beauty of hair, nails and skin [8]. Conclusion The raw materials are first compressed under a press We mentioned that biodegradable tableware can be with hot air and turned into plates, cups, forks and consumed after use. And corn bran dishes, have the fol- knives. From one ton of bran comes 10 thousand plates. lowing beneficial properties for the human body: Moreover, the dishes turn out to be quite solid, you can 1) B vitamins contribute to the proper absorption of also heat food in it, use it for hot or cold, liquid or solid nutrients and support the immune system. Thiamine (B1) food. It is proved that biodegradable tableware based on increases human performance, improves appetite, is re- corn bran at a temperature of 55-70 C and a humidity sponsible for the normal activity of the cardiovascular of 45-60%, the disintegration of dishes occurs within and nervous systems. Pantothenic acid (B5) prevents the 30-31 days. This disposable plastic plate will take development of malignant tumors and is involved in the 500 years to decompose. (1-pic.) [9]. synthesis of adrenal hormones. Folic acid (B9) regulates hormonal processes in the female body and is involved in the formation of red blood cells. Its presence in the Figure 1. Disposable biodegradable tableware Given the diversity and three-time sowing of corn with a low cost, with an organoleptic chemical compo- varieties in our irrigated fields only to obtain corn flour sition useful for the human body. That is why we would (as well as starch) and silage, we want to offer the pro- like to offer the production of absolutely harmless, envi- cessing of secondary raw materials of corn bran for the ronmentally friendly, biodegradable tableware based on production of biodegradable tableware, as raw materials corn bran and corn starch as a substitute for disposable plastics from oil refining. 48
№ 7 (97) июль, 2022 г. References: 1. Макушин А.Н., Кудрякова Е.П., Макушина Т.Н., Пашкова Е.Ю. Перспектива производства биоразлагаемой одноразовой посуды и упаковки из отходов мукомольного производства// АПК России: образование, наука, производство: сборник статей Всероссийской (национальной) научно-практической конференции. – 2020. – С. 144–149. 2. И.Ю. Потороко, Н.В. Науменко, А.В. Малинин, А.В. Цатуров, А.М. Кади, А.В. Никонов. Разработка технологии формованной биоразлагаемой экопосуды на основе вторичных ресурсов зерномучного производства. Южно-Уральский государственный университет, г. Челябинск, Россия. Bulletin of the South Ural State University. Ser. Food and Biotechnology. 2021, vol. 9, no. 3, pp. 62–71 3. Gurunathan T., Mohanty S., Nayak S.K. A review of the recent developments in biocomposites based on natural fibres and their application perspectives // Composites Part A: Applied Science and Manufacturing. – 2015. – Vol. 77. – Р. 1–25. 4. А. Цатуров, магистрант кафедры «Пищевые и биотехнологии» Южно-Уральского государственного университета. Электронный ресурс. https://www.sostav.ru/publication/sest-vsyu-tarelku-v-rossii-sozdali-polnostyu- razlagaemuyu-posudu-iz-krakhmala-40019.html 5. Электронный ресурс. https://www.megaresearch.ru/news_in/analiz-rynka-biorazlagaemoj-posudy-i-perspektivy- razvitiya-do-2025-goda 6. Электронный ресурс. https://sad24.ru/konservaciya/lekarstvennye/kukuruznye-otrubi.html 7. Электронный ресурс. USDA National Nutrient Database for Standard Reference. https://health- diet.ru/base_of_food/sostav/19921.php 8. Электронный ресурс. https://nadietu.net/dietary-products/cereals-flour/kukuruznye-otrubi.html 9. Электронный ресурс. https://b-mag.ru/4-shaga-dlja-proizvodstva-biorazlagaemoj-odnorazovoj-posudy/ 10. Справочник химика 21. Химия и химическая технология. Электронный ресурс. https://www.chem21.info/info/923608/ 49
ДЛЯ ЗАМЕТОК
ДЛЯ ЗАМЕТОК
Научный журнал UNIVERSUM: ХИМИЯ И БИОЛОГИЯ № 7(97) Июль 2022 Часть 3 Свидетельство о регистрации СМИ: ЭЛ № ФС 77 – 55878 от 07.11.2013 Издательство «МЦНО» 123098, г. Москва, улица Маршала Василевского, дом 5, корпус 1, к. 74 E-mail: [email protected] www.7universum.com Отпечатано в полном соответствии с качеством предоставленного оригинал-ма- кета в типографии «Allprint» 630004, г. Новосибирск, Вокзальная магистраль, 3 16+
