PRODUCTION OF VINYL ETHERS OF FURFURYL ALCOHOL

ABSTRACT

The article presents the synthesis of vinylfurfuryl ethers, the results of the study of factors affecting synthesis. Solvents for extractive separation of the resulting ether were studied. With the participation of the catalytic system, the reaction yield reached 80% and the acrylic acid copolymerization of the obtained vinyl ether was studied.

АННОТАЦИЯ

В статье представлены синтез винилфурфуриловых эфиров, результаты изучения факторов, влияющих на синтез. Исследованы растворители для экстракционного разделения образующегося эфира. С участием каталитической системы выход реакции достиг 80% и исследована сополимеризация акриловой кислоты с полученным виниловым эфиром.

Keywords: furfuryl, tetrahydrofurfuryl alcohol, DMSO, extraction, vinylacetylene, KOH, morpholine, acrylic acid

Ключевые слова: фурфурил, тетрагидрофурфуриловый спирт, ДМСО, экстракция, винилацетилен, КОН, морфолин, акриловая кислота.

Introduction

Currently, the scope of industrial organic synthesis is so large that the problem of limited natural resources of oil and gas necessary to meet its needs remains urgent. In this regard, the perspective of obtaining basic compounds based on natural renewable raw materials. The processing of plant carbohydrates, which make up 2/3 of the annual renewable biomass, opens a direct way to obtain furan compounds, which are genetically closely related to the simplest sugars. In recent years, furan derivatives have become increasingly important in the creation of materials and compositions with the desired properties. Furan rings are part of natural compounds and drugs widely used in medicine (fubromigan, ranitidine, didanosine, zidovudine, fluorofur, etc.). The traditional way of processing furfural is to hydrogenate it to furfuryl alcohol and obtain various heat-resistant resins from it. Tetrahydrofurfuryl alcohol is generally recognized as a "green" solvent for industrial use in the production of acrylates and epoxy resins, and is also included in environmentally friendly diesel fuel and technical cleaning compounds. Due to its low toxicity, ability to destroy microorganisms and high solubility in organic and aqueous media, 2 hydroxymethyltetrahydrofuran and its derivatives are successfully used in the pharmaceutical industry and cosmetology, in particular, as synthetic fragrances [1-4]. Numerous studies on the synthesis and chemistry of heteroatom derivatives of vinylacetylene, particularly vinyl ethers, have been summarized in recent reviews [4-5]. However, neither these publications nor systematic reviews of the literature on the chemistry of heterocyclic compounds contain information on vinyl esters of furan alcohols. Taking into account the goals and objectives of this work, in the review of this literature, we considered the synthesis of vinylfurfuryl ethers and reactions involving them[6-9].

Methods and results

Information on the direct vinylation of furfuryl alcohols with vinylacetylene is very limited. Furfuryl alcohol was chosen, taking into account the Canizzaro reaction of furfurol in an alkaline environment. For the first time, divinylfurfuryl ether was obtained from furfuryl alcohol and vinylacetylene in a highly basic system at room temperature and atmospheric pressure [9-11].

In a strongly basic system, DMSO forms an intermediate dimsyl complex and ensures the yield of the reaction. Also, the choice of vinylacetylene as a vinylizing agent was based on its reactivity and physical properties compared to acetylene. Dimacyl ion attacks the carbon atom of the hydroxyl group of the polar moiety in furfuryl by S_N1 and a coupling reaction occurs[12-14].

In the presence of a highly basic system, the duration of the reaction, depending on the temperature, the yield of the reaction reaches 80% (table-1).

Table 1.

Effect of temperature on (E)-1-(tetrahydrofuranyl-2)penta-2,4-dienol (the amount of catalyst KOH in relation to the mass of morpholine - 15%) duration of reaction, 4 hours

Conventional conditions for synthesizing vinyl ethers are too harsh for furfuryl alcohol, and DMSO was used as a solvent to eliminate tar formation during this process. Vinylacetylene was added to the reaction mixture at 30-120 ºC for 2-5 hours[15-17]. A more detailed study of the vinylization of furfuryl alcohol showed that furfuryl alcohol undergoes a nucleophilic addition reaction to vinylacetylene much more easily than its other homologues: when heating alcohol with acetylene in a jacketed reactor, vinyl ether has a 68% complete conversion of the initial alcohol. it is formed with fertility [18-20]. Raising the temperature and increasing the duration of heating leads to a decrease in the yield of vinylfurfuryl and more tarnishing. At given temperatures and conditions, furfuryl compounds tend to form tars, and this problem has been solved in DMSO.

When choosing a solvent for the extraction method, we took into account the solubility of reactants and reaction products under the influence of solvents. For example, when reactants and products are dissolved in acetone, the following are soluble: morpholine, DMSO, DMSO + KOH, and (E)-1-(tetrahydrofuranyl-2)penta-2,4-dienol-1 mixture. From this we can conclude that acetone cannot be used as a solvent in extraction, because all reagents, including the necessary products resulting from the reaction, are dissolved in it, which must be separated and analyzed [19-21]. The effect of other solvents was tested in the same way. The results of the analysis are presented in Table 2. From these data, we can conclude that the insolubility of some substances in diethyl ether allows it to be used in the extraction process to extract the necessary synthesized substance. Here it is important to pay attention to the purity of diethyl ether.

Table 2.

Solubility of reactants and products in solvents

Based on the data of the experiments on the determination of the solubility of the substance in solvents (Table 2) and its use in our experiments, it can be said with confidence that diethyl ether is used as a solvent after extraction.

In one layer of the extraction mixture, unreacted and ether-soluble substances (KOH+DMSO+furfuryl alcohol), in the second layer, ether-insoluble, synthesized product (E)-1-(tetrahydrofuranyl-2)penta-2,4 -dienol-1 was determined [22-24].

Discussion

Based on the data from the research results, a temperature dependence graph of the product yield was created (Fig. 1). This pattern is explained by the decrease in the solubility of vinylacetylene at high temperatures, as a result of which its amount in the reaction system decreases, the rate of reaction and the yield of (E)-1-(tetrahydrofuranyl-2)penta-2,4-dienol-1. (E)-1-(tetragidrofuranil-2)penta-2,4-dienol-Copolymerization of 1 with acrylic acid in the presence of reciprocal DAK was carried out. Copolymerization of acrylic acid system of (E)-1-(tetrahydrofuranyl-2)penta-2,4-dienol-1 was carried out in the presence of acrylic acid (DAK) in divinylfurfuryl ether at a temperature of 75 - 95 °C for 2-5 hours.

Figure 1. (E)-1-(tetrahydrofuranyl-2)penta-2,4-dienol-1 temperature dependence of the yield (reaction duration 4 hours)

A white powdery product soluble in alcohol, DMFA, DMSO, tetrahydrofuran (THF) was obtained. Radical copolymerization proceeds along the vinyl group.

The effect of the amount of initial reacting components on the yield, viscosity and molecular mass of the obtained product was studied. In this case, the amount of reactants was changed in the range from 1:9 to 9:1. As mentioned above, DAA was used as an initiator and the reaction was carrie out at a temperature of 75-95 ºС. The change of the reaction parameters (yield, viscosity, molecular mass) according to the initial ratio of reactants in the reaction was studied and confirms the obtained results. Compared to acrylic acid, the reaction with methyl methacrylate is somewhat more difficult due to the steric effect. Therefore, further studies were conducted in the presence of acrylic acid[25-26]. Molecular masses of copolymers were determined by cryoscopic method, and their sizes ranged from 110,000 to 300,000 (Table 3).

Table 3.

Copolymerization of (E)-1-(tetrahydrofuranyl-2)penta-2,4-dienol-1- (M1) with acrylic acid (M2) (DMFA, DAA - 1.5% by weight, 60 °C, 6 hours)

 Increasing the proportion of monomer (E)-1-(tetrahydrofuranyl-2)penta-2,4-dienol-1 in the initial mixture causes an increase in the molecular mass of the copolymers. This, in turn, is explained by the high tendency of the vinyl group to polymerize.

Figure 2. Dependence of the amount of monomers on the molecular mass in the copolymerization reaction of (E)-1-(tetrahydrofuranyl-2)penta-2,4-dienol-1 and acrylic acid 1-blue line: dependence of the amount of 1-(E)-1-(tetrahydrofuranyl-2)penta-2,4-dienol-1 on the molecular mass. 2-red line: dependence of the amount of acrylic acid on the molecular mass

In figure 2, the results of the dependence of the amount of monomer on the molecular mass are the same as the results of the mathematical processing and are carried out with the same regression equation, which confirms the correctness of the results. Also, mathematical processing for each monomer confirms the results with inverse proportionality. For the regression equation, R² = 0.9954 and R² = 0.9835 indicate the agreement between the mathematical report and the experimental results.

In the studied systems, the copolymers mainly consist of nitrogen-containing heterocyclic chains of various lengths and are separated by individual chains of carbonyl-containing vinyl monomers. In the acrylic acid system of (E)-1-(tetrahydrofuranyl-2)penta-2,4-dienol-1, products with a definite sequence of links or a 2 to 1 polymer chain structure are formed.

Conclusion

In a strongly basic system, DMSO forms an intermediate dimsyl complex and ensures the yield of the reaction. Also, the choice of vinylacetylene as a vinylizing agent was based on its reactivity and physical properties compared to acetylene. It was determined that the duration of the reaction in the presence of a highly basic system, the yield of the reaction, depending on the temperature, reaches 80%. When choosing a solvent for the extraction method, we took into account the solubility of reactants and reaction products under the influence of solvents.

References:

1. Сипкина Е.И. Гибридные композиты на основе азотсодержащих гетероциклических низко- и высокомолекулярных соединений и диоксида кремния. Авто. Дисс. Иркутск - 2017 г.
2. Ostonov Firuz, Akhmedov Vohid SYNTHESIS OF IONITES BASED ON CREMNISOLE // Universum: технические науки. 2022. №4-13 (97).
3. Ostonov Firuz, Akhmedov Vokhid SYNTHESIS AND PROPERTIES OF COMPLEX FORMING IONITES // Universum: технические науки. 2023. №2-6 (107).
4. Остонов Ф.И., Ахмедов В.Н. Гибридные композиты на основе морфолина. // Меж. Конф.-Руминия, Бухарест. 20.11.2020 г. С. 38-42.
5. Ахмедов В. Н., Назаров Ш. К. Электронная структура и квантово-химические расчёты виниловых эфиров фенолов.
6. Olimov B. B., Akhmedov V. N., Gafurova G. A. Application of derivatives of diatomic phenols as corrosion inhibitors //Euro Asian Conference on Analytical Research (Germany. – 2021. – Т. 15. – С. 136-138.
7. Olimov B., Akhmedov V., Gafurova G. Production and use of corrosion inhibitors on the basis of two-atomic phenols and local raw materials //environment. – Т. 7. – С. 11.
8. Олимов Б. Б., Ахмедов В. Н. Винилацетилен асосида фенолларнинг винил эфирлари синтези.“ //Замонавий ишлаб чикаришнинг мухандислик ва технологик муаммоларини инновацион ечимлари” Халкаро илмий анжуман материаллари Бухоро. – 2019. – С. 37-39.
9. Olimov B. B., Yoldosheva N. J. Gravimetric study of the mechanism of action of corrosion inhibitors used in the oil and gas industry //Международный научно-образовательный электронный журнал «Образование и наука в xxi веке». Выпуск. – №. 19.
10. Olimov B. B., Ahmedov V. N., Hayitov S. Ikki atomli fenollar asosida vinilli efirlarni olish usullari //Fan va texnologiyаlar taraqqiyoti ilmiy-texnikaviy jurnal. – 2020. – №. 1.
11. Олимов Б. Б., Гафурова Г. А., Кудратов О. Х. Production and properties of corrosion inhibitors in the oil and gas industry //Universum: химия и биология: электрон. научн. журн. – 2022. – Т. 2. – С. 92.
12. Olimov, B. B., M. I. Sadiqova, and I. A. Beshimov. "Technology of obtaining effective corrosion inhibitors in the oil and gas industry." Universum: технические науки: электрон. научн. журн 1 (2022): 94.
13. Ахмедов В., Олимов Б., Гафурова Г. Винилачетилен иштирокида винил эфирлар олиш //НамДУ илмий ахборотномаси-Научный вестник НамГУ. – 2021. – С. 37-43.
14. Shomurod N., Vokhid A., Bobir O. Preliminary quantum chemical analysis of synthesized monomers with the participation of vinylacetylene //International journal of progressive sciences and technologies. – 2020. – Т. 22. – №. 2. – С. 50-56.
15. Паноев Э. Р., Дустов Х. Б., Ахмедов В. Н. Проблемы коррозии в кислых компонентных системах и способы ее уменьшения //Universum: технические науки. – 2021. – №. 12-5 (93). – С. 47-50.
16. Olimov B., Akhmedov V. The effect of reaction duration and catalyst on the synthesis of arylvinyl esters //Збірник наукових праць ΛΌГOΣ. – 2020. – С. 33-37.
17. Bahodirovich O. B. et al. Synthesis of Resorcinol Vinyl Ether in the Mono-position, Influence of the Catalyst, Temperature and Solvent on the Reaction Yield // JournalNX. – 2020. – С. 44-51.
18. Ахмедов В. Н., Олимов Б. Б. Способ получения виниловых эфиров на основе винилацетилена //Gaydar Aliyevning. – 2020. – Т. 97.
19. Назаров Ш. и др. Синтез мономеров при участии винилацетилена из одноатомных фенолов содержащих ариловую группу //Universum: химия и биология. – 2020. – №. 11-2 (77). – С. 11-15.
20. Ганиев Б. Ш., Олимов Б. Б. Влияние температуры синтеза на абсорбционные свойства сополимерных композитов содержащих навбахорского бентонита // Химия и химическая технология: достижения и перспективы. – 2018. – С. 304.1-304.2.
21. Olimov B. B., Akhmedov V. N., Gafurova G. A. Application of derivatives of diatomic phenols as corrosion inhibitors. Euro Asian Conference on Analytical Research (Germany).
22. Sh, Ganiev B. "Olimov BB influence of the temperature of synthesis on the absorption properties of copolymer composites containing navbahor bentonite." chemistry and chemical technology: achievements and prospects.-2018.--S: 304-1.
23. Nazarov S. K., Olimov B. B., Akhmedov V. N. Electronic structure and quantum-chemical calculations of vinyl esters of phenols //Austrian Journal of Technical and Natural Sciences. – 2020. – №. 3-4. – С. 46-51.
24. Остонов Ф.И., Ахмедов В.Н. Винилморфолин иштирокида гибрид полимер композит олиш //Рес. Конф. Бухра. 4-5 декабр. 2020 г. С.406-406.
25. Ахмедов В.Н., Остонов Ф.И., Дўстов Ҳ.Б. Получение модифицированных акриловых соединений на основе соединений кремния // Развитие науки и технологий. 2021. №2. С. 24-30.
26. Остонов Ф.И., Ахмедов В.Н. Производство новых видов гибридных композитов // Научный вестник Наманганского государственного университета. 2021 №9. С. 44-49.