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32 AZERBAIJAN CHEMICAL JOURNAL № 4 2019 ISSN 2522-1841 (Online)
ISSN 0005-2531 (Print)
UDC: 547.314.316.784.546.847.862
HOMOGENEOUS VINYLATION OF 2-HYDROXY-2-PHENYLETHANICAL ACID
112 2 1 A.B.Parmanov , S.E.Nurmanov , Beata Kolesinsko , Tomash Maniecki , O.E.Ziyadullayev
National university of Uzbekistan, t. Tashkent
asqar.parmanov@mail.ru
2Lodz University of Technology, Lodz, Poland
Received 29.06.2018
Homogeneous-catalytic vinylation of 2-hydroxy-2-phenylethanical acid was carried out. The influence of the nature of the catalysts, the temperature and the duration of the reaction on the yield of the synthesized vinyl ether was studied.
Keywords: almondsal acid, acetylene, heterogeneous catalysis, influencing factors on product yield, catalysts: AlCl3 6H2O and (C6H5CH(OH)COO)2Zn).
doi.org/10.32737/0005-2531-2019-4-32-34
Introduction
Vinyl ethers are important compounds, since due to the presence of a double bond and an ether group in their molecules, various chemical transformations can be carried out on their basis. Such compounds are widely used in the preparation of dyes and in the production of monomers for the synthesis of various polymers. Known methods for producing compounds by various chemical transformations of the double bonds of vinyl esters of carbonic acids, their polymers and copolymers were used to create effective emulsifiers and dyes. Similarly, materials that improve the viscosity of lubricants and crosslinking agents for the rubber industry have also been obtained. Currently, high demands on polymeric materials are associated with the expediency of improving the quality of products and their cost. From this point of view, the use of natural compounds for similar purposes is also very important [1, 2].
Part of the almond-2-hydroxy-2-phenyl-ethanical acid (almondsal acid) is a natural compound. On its basis, antiseptics have been
obtained, which are used in medicine as starting compounds for the production of antibiotics. Currently, ammonium and calcium salts of al-mondsal acid are used as urogenic substances in urology. It is also used as an analytical reagent for the determination of ions Ti, Fe, Al, Cr, V and for the separation of Zn from Mo [3-5]. The acidic properties of the acid under study are higher compared to acetic acid, which affects its biological activity and the limited scope of its use. For this reason, a decrease in its acidic properties allowed us to increase the biological activity of almondsal acid.
Experimental part
Homogeneous catalytic vinylation of al-mondsal acid was carried out in a solution of dimethyl sulfoxide (DMSO) in the presence of catalyst composition, containing zinc salt of almondsal acid and AlCl36H2O at a temperature of 80-1400C. Acetylene was passed through a mixture of almondsal acid and catalyst in DMSO with a speed of 0.1 mol/h. The almond acid vinyl ester was formed as the main product according to the following reaction scheme:
/-v 0 /-^ O
// \ II (C6H5CH(0H)C00)2Zn // \ ||
// \V_CH-C-0H + HC^CH -► ^ ^_CH-C-0-CH=CH2.
OH 0H
HOMOGENEOUS VINYLATION OF 2-HYDROXY-2-PHENYLETHANICAL ACID
33
The resulting ester is a new organic compound, unknown in the literature.
Vinyl of 2-hydroxy-2-phenylethanical
acid
Yield - 84.4%. IR (KBr): 3430, 3003, 2917, 1712, 1663, 1407,1210, 1025, 901. 1H-NMR, 5, ppm (400 MHz, CDCl3): 7.33-7.53 (6H, 7.47 (dd, 7=14.8, 7.8 Hz), 7.45 (dtd, 7=8.4, 1.2, 0.5 Hz), 7.38 ( dddd, 7=8.4, 7.4, 1.6, 0.5 Hz), 7.36 (tt, 7=7.4, 1.3 Hz), 6.00 (1H, s), 5.14 (1H, dd, 7=14.8, 2.3 Hz), 5.06 (1H, dd, 7=7.8, 2.3 Hz).
13C NMR (100 MHz, CDCls): 171.5, 141.3, 138.6, 128.9, 126.6, 128.5, 98.2, 73.0
Results
Temperature significantly influenced the catalytic reaction under investigation. For this reason, the effect of temperature on the vinyla-tion of almondsal acid by acetylene was investigated. The results are presented in Table 1.
Table 1. Influence of temperature on vinylation of almondsal acid in the presence of zinc salt of almondsal acid (10%) (Rate of acetylene - 0.1 mole/h)_
Temperature of reaction, t Yield of vinyl ester, %
80 45.8
90 49.4
100 56.6
110 63.2
120 65.9
130 61.5
140 53.4
As the results obtained showed, temperature had a great influence on the vinylation of almondsal acid by acetylene. In the investigated temperature range of 80-1400C, vinyl ether is formed, the output of which varies with temperature. An increase in temperature from 80 to 1200C leds to an increase in the yield of the product from 45.8 to 65.9%, and a subsequent increase in temperature to 1300C leds to a decrease in it, while also decomposing DMSO with formation of sulfur-containing compounds with following formation cross-linking oligo-meric products.
For vinylation of almondsal acid with acetylene, the optimum temperature was 1200C,
and the yield of the vinyl ester formed was 65.9%, and accordingly the following studies were carried out at this temperature.
Table 2 presents the results on the effect of temperature on the vinylation of almond acid in the presence of its zinc salt and AlCl36H2O (10%) as a catalyst.
Table 2. Influence of temperature on vinylation of al-mondsal acid in the presence of [Zinc salt+AlQ3-6H2O (10%)] catalyst (time-2 h, rate of acetylene past through 0.1 mole/h)_
Temperature of reaction, t Yield of synthesised vinyl ester, %
80 65.3
90 68.7
100 69.6
110 73.9
120 79.8
130 67.5
140 63.4
From obtained results show that in presence of elaborated catalyst in temperature range 80-1200C yield of forming vinyl ester of almondsal acid has increased from 65.3 to 79.8 and presence of AlCl3-6H2O in composition of catalyst has increased the catalytic activity.
It is known, that in the steady state the duration of the reaction (time) plays a very important role. For this reason, the influence of this factor on the formation of the main product - almondsal vinyl ester was investigated and the results obtained are presented in Table 3.
Table 3. Influence of process duration on vinylation of almondsal acid in the presence of Zink salt catalyst (rate of feeding of acetylene 0.1 mole/h, temperature 1200C)
Duration of reaction, h Yield of vinyl ester of almondsal acid, %
1 48.7
2 65.9
3 69.7
4 71,1
5 69.8
6 67.2
It is shown, that the yield of the obtained vinyl ether increased accordingly from 48.7 to 71.1% with an increase in reaction time from 1.0 to 4.0 hours, but with a further increase in the duration of the reaction, the yield of the
34
A.B.PARMANOV et al.
product decreased by 1.3-2.6%. Thus, 4 h is the optimal duration of the test reaction. According to the chromatographic analysis at the time of the 3-hour reaction, no initial almondsal acid was detected in the reaction products. During the reaction for more than 4 hours, the formation of rubber-like compounds was also observed due to oligomerization and polymerization of the obtained vinyl ether and its cross-linking with H2S as a result of decomposition of the DMSO. Influence of process duration on vinylation of almondsal acid in the presence of catalyst at 1200C and rate feeding of acetylene 0.1 mol/h are presented in Table 4.
Table 4. Influence of duration of vinylation almondsal acid in the presence of [Zinc salt+AlCls^^O (10%)] catalyst at temperature 1200C and rate feeding of acetylene 0.1 mol/h
Duration of reaction, h Yield of vinyl ester of almondsal acid, %
1 56.5
2 79.8
3 83.2
4 84.4
5 82.9
6 81.1
From the data of table 4 it can be seen, that the introduction of the ingredient AlCV6H2O into the composition of the catalyst increased its activity due to the fact that it acts as a promoter. In the presence of this catalyst, the yield of vinyl ether for 1 -4 hours increased from 56.5 to 84.4%.
Conclusions
It was shown that when almond acid was vinyllated with acetylene in the presence of a catalyst (C6H5CH (OH)COO)2Zn, its vinyl ether was formed.
It has been established that the introduction of the catalyst AlCl3'6H2O (10%) as a promoter into the catalyst composition led to an increase in the yield of the vinyl ether formed.
It was found that the temperature, the duration of the reaction and the nature of the catalyst used have a great influence on the yield of almond acid vinyl ester.
References
1. Parmanov A.B., Nurmanov S.E., Phayzullaeva M.Ph., Abdullaev J.U., Soliev M.I. Synthesis of vinyl esters of some carbonic acids. Aust. J. Tech. Nat. Sci. 2017. No 1-2. P. 129-132.
2. Ioan-Teodor Trotus, Tobias Zimmerman, Ferdi Schuth. Catalytic reactions of acetylene. A Feedstock for the Chemical industry revisited. Chem. Rev. 2014. V. 114. P. 1761-1782.
3. Stanley R., Sandler. Atmospheric vinylation of several haloacetic acids and benzoic acid by acetylene. J. Chem. Eng. Data. 1973. V. 18. No 4. P. 445-448.
4. Suming Ye, Weng Kee Leong. Synthesis and structure of some ruthenium-rhenium heterodinuclear complexes and their catalytic activity in the addition of carboxylic acids to phenylacetylene. J. Or-ganomet. Chem. 2006. V. 691. No 6. P. 1216-1222.
5. Francisco Alonso, Irina P. Beletskaya, Miguel Yus. Transition-metal-catalyzed addition of het-eroatom-hydrogen bonds to alkynes. Chem. Rev. 2004. V. 104. No 6. P. 3079-3160.
2-HÍDROKSÍ-2-FENÍLETÍL TUR§UNUN HOMOGEN VÍNÍLLa§DÍRlLMOSÍ
A.B.Parmanov, S.E.Nurmanov, Beata Kolesinsko, Tomash Maniecki, O.E.Ziyadullayev
2-Hidroksi-2-feniletil tur§unun homogen vinillaíjdirilmasi apanlmi§dir. Karalizatorun tabiatinin, temperaturun va reaksiya müddatinin sintez olunmu§ vinil efirinin giximina tasiri öyranilmi§dir.
Agar sözlar: badam tur§usu, asetilen, heterogens kataliz, mahsulun giximina tasir elan amillar, katalizatorlar: AlCl36H2O va (C6H5CH(OH)COO)2Zn).
ГОМОГЕННОЕ ВИНИЛИРОВАНИЕ -2-ГИДРОКСИ-2-ФЕНИЛЭТИЛОВАЯ КИСЛОТА
A^.napMaHOB, С.Е.Нурманов, Беата Колесинско, Томаш Маниески, О.Е.Зиядуллаев
Проведено гомогенно-каталитическое винилирование 2-гидрокси-2-фенилэтиловой кислоты. Изучено влияние природы катализаторов, температура и продолжительности реакции на выход синтезированного винилового эфира.
Ключевые слова: миндальная кислота, ацетилен, гетерогенный катализ, влияющие факторы на выход продукта, катализаторы: AlCl36H2O и (C6H5CH(OH)COO)2Zn.
