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ORGANIC CHEMISTRY
PRODUCTION OF VINYL ETHERS OF FURFURYL ALCOHOL
Nigina Jamilova
Doctoral student of the Department of Chemistry of the Bukhara Institute of Engineering-Technology, Republic of Uzbekistan, Bukhara E-mail: chemistry292 [email protected]
Mizrob Zaripov
Researcher
of the Bukhara Institute of Engineering-Technology, Republic of Uzbekistan, Bukhara
ПРОИЗВОДСТВО ВИНИЛОВЫХ ЭФИРОВ ФУРФУРИЛОВЫХ СПИРТОВ
Жамилова Нигина
докторант кафедры химии Бухарского инженерно-технологического института, Республика Узбекистан, г. Бухара
Зарипов Мизроб
соискатель
Бухарского инженерно-технологического института, Республика Узбекистан, г. Бухара
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
Библиографическое описание: Jamilova N., Zaripov M. PRODUCTION OF VINYL ETHERS OF FURFURYL ALCOHOL // Universum: химия и биология : электрон. научн. журн. 2023. 9(111). URL:
https://7universum. com/ru/nature/archive/item/15919
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].
C\ KOH/DMSO / \
/CH2ÜH +HC=C-CH=CH2-J
CH2OH-CH=CH-CH=CH2
Ü
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 Sn1 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
№ Reaction temperature, oC Yield of (E)-1-(tetrahydrofuranyl-2-penta-2,4-dienol-1 , %
1 30 9.6
2 35 13,8
3 40 19,6
4 45 25,4
5 50 35,2
6 55 45,6
7 60 58,2
8 65 65,2
9 70 75,3
10 75 80,1
11 80 78,2
12 85 72,2
13 90 67,8
14 100 57,6
15 110 52,7
16 120 48,8
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 °C 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
Solvents Solvent dipole moment, D Reagents and product
Furfuryl alcohol DMSO DMSO+KOH DMSO+KOH+ + morpholine (E)-1-(tetrahydro-furanyl-2) penta-2,4-dienol-1
Water 1,854 dissolves dissolves the mixture dissolves the mixture dissolves dissolves
Acetone 2,7 dissolves dissolves the mixture dissolves the mixture dissolves dissolves
Diethyl ether 1,3 dissolves dissolves the mixture dissolves the mixture dissolves does not dissolve
Dioxane-1,4 0,45 dissolves dissolves the mixture dissolves the mixture dissolves dissolves
Isopropyl alcohol 1,66 dissolves dissolves the mixture dissolves the mixture dissolves dissolves
Hexane 0,08 does not dissolve does not dissolve the mixture is insoluble the mixture is insoluble does not dissolve
Benzene 0 dissolves dissolves the mixture dissolves the mixture dissolves dissolves
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.
Temperature, oC
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 °C. 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)
Mole ratio of reagents Profit % Copolymer molecular mass (M)
M1
(E)-1-(tetrahydrofuranyl-2)penta-2,4-dienol-1-acrylic acid
0,15 1,35 42,8 115 000
0,25 1,25 48,6 125 000
0,35 1,15 53,4 135 000
0,45 1,05 56,2 150 000
0,55 0,95 60,5 162 000
0,65 0,85 66,5 173 000
0,75 0,75 72,3 210 000
0,85 0,65 79,4 278 000
0,95 0,55 80,6 310 000
1,05 0,45 82,7 330 000
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.
Molecular mass, g/mole
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.
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