Establishing optimal conditions for catalytic obtaining of allyl-1,3,4-trimethylcyclohex-3-encarboxylate

Authors

DOI:

https://doi.org/10.15587/1729-4061.2017.119491

Keywords:

2, 3-dimethylbuta-1, 3-diene, allyl methacrylate, allyl-1, 3, 4-trimethylcyclohex-3-enecarboxylate, Diels-Alder reaction

Abstract

Kinetics of the reaction of the catalytic cyclic addition of 2,3-dimethylbuta-1,3-diene and allyl methacrylate by the Diels-Alder reaction was studied. Reaction rate constants k=0.9·10-3 l/(mol·s) at T=303 K; k=1.6·10-3 l/(mol·s) at T=313 K; k=2.3·1-3 l/(mol·s) at T=323 K; k=2.9·10-3 l/(mole·s at T=333 K and the activation parameters of the reaction Eakt=32.6 kJ/mol, ΔS=−203.7 J/(mol·K), ΔH=30.0 kJ/mol were determined. Influence of temperature, molar ratio of reagents and catalyst on the yield of the target product was investigated. At temperature increase from 303 to 333 K, ATMCGC yield increases from 58 % to 76 %. With further increase in temperature, DMB boils and AMA remains in a liquid state, accordingly it is not expected that the target product yield will materially increase. An increase in the excess of DMB:AMA=from 1.5:1 to 4:1 makes it possible to increase yield of ATMCGC from 54 % to 76 %. According to decreasing of the catalytic activity in the reactions of [4+2]-cyclic addition of DMB and esters of acrylic acids, the catalysts are placed in an order: Agn.p.>Cu2Cl2>Pdn.p.>Aun.p..

At the established optimal conditions of catalytic production of allyl-1,3,4-trimethylcyclohex-3-enecarboxylate are: temperature of 323−333 K and molar ratio of reagents DMB:AMA=4:1 in the presence of Agn.p. catalyst (0.25 % mol), the yield of ATMCGC reaches 72−76 % at productivity of 111−117 g/(l/h). Based on the obtained reaction rate constants and the activation parameters of the catalytic [4+2]-cyclic addition of 2,3-dimethylbuta-1,3-diene and allyl methacrylate, it was found that the reaction under study is subject to the kinetic law of the second order.

It was established that in the presence of Agn.p. catalyst, the reaction of [4+2]-cyclic addition of 2,3-dimethylbuta-1,3-diene and esters of acrylic acids proceeds through a two-stage mechanism with the initial stage of formation of a catalytic complex which activates the reaction by reducing its energy barrier by 44 kJ/mol.

The synthesized alkyl esters of alkylcyclohexenecarbonic acids have the ability of polymerization and can be used as a raw material for preparation of polymeric materials, compositions and hyper plasticizers for concrete mixtures. Polymer compositions made with allyl-1,3,4-trimethylcyclohex-3-enecarboxylate are recommended for manufacture of contact lenses and artificial crystalline lenses

Author Biographies

Iryna Kostiv, Lviv Polytechnic National University S. Bandery str., 12, Lviv, Ukraine, 79013

PhD, Assistant

Department of chemical Engineering

Oleksandra Dzeryn, Lviv Polytechnic National University S. Bandery str., 12, Lviv, Ukraine, 79013

PhD, Assistant

Department of heat and gas supply and ventilation

Yuriy Malynovskyi, Lviv Polytechnic National University S. Bandery str., 12, Lviv, Ukraine, 79013

PhD, Associate Professor

Department of Theoretical and Applied Economics

References

  1. Anisimova, N. A., Kuzhaeva, A. A., Berkova, G. A., Berestovitskaya, V. M. (2011). Synthesis and structure of nitrocyclohexenylcarboxylates. Russian Journal of General Chemistry, 81 (9), 1845–1852. doi: 10.1134/s1070363211090180
  2. Monnier-Benoit, P., Jabin, I., Jaubert, J.-N., Netchitaïlo, P., Goyau, B. (2007). Synthesis of 2,4-dimethyl-cyclohex-3-ene carboxaldehyde derivatives with olfactory properties. Comptes Rendus Chimie, 10 (3), 259–267. doi: 10.1016/j.crci.2006.10.006
  3. Moskva, V. V. (1996). Ponyatie kisloty i osnovaniya v organicheskoy himii. Sorosovskiy obrazovatel'nyy zhurnal, 12, 33–40.
  4. Lindström, B., Petterson, L. J. (2003). A brief history of catalysis. Cattech, 7 (4), 130–138. doi: 10.1023/a:1025001809516
  5. Hawkins, J. M., Watson, T. J. N. (2004). Asymmetric Catalysis in the Pharmaceutical Industry. Angewandte Chemie International Edition, 43 (25), 3224–3228. doi: 10.1002/anie.200330072
  6. Farina, V., Reeves, J. T., Senanayake, C. H., Song, J. J. (2006). Asymmetric Synthesis of Active Pharmaceutical Ingredients. Chemical Reviews, 106 (7), 2734–2793. doi: 10.1021/cr040700c
  7. Grubbs, R. H. (2006). Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials (Nobel Lecture). Angewandte Chemie International Edition, 45 (23), 3760–3765. doi: 10.1002/anie.200600680
  8. Gradillas, A., Pérez-Castells, J. (2006). Macrocyclization by Ring-Closing Metathesis in the Total Synthesis of Natural Products: Reaction Conditions and Limitations. Angewandte Chemie International Edition, 45 (37), 6086–6101. doi: 10.1002/anie.200600641
  9. Chen, H.-T., Trewyn, B. G., Wiench, J. W., Pruski, M., Lin, V. S.-Y. (2009). Urea and Thiourea-Functionalized Mesoporous Silica Nanoparticle Catalysts with Enhanced Catalytic Activity for Diels-Alder Reaction. Topics in Catalysis, 53 (3-4), 187–191. doi: 10.1007/s11244-009-9423-x
  10. Cong, H., Becker, C. F., Elliott, S. J., Grinstaff, M. W., Porco, J. A. (2010). Silver Nanoparticle-Catalyzed Diels−Alder Cycloadditions of 2′-Hydroxychalcones. Journal of the American Chemical Society, 132 (21), 7514–7518. doi: 10.1021/ja102482b
  11. Meuzelaar, G. J., Maat, L., Sheldon, R. A. (1998). Diels-Alder reactions of carbonyl-containing dienophiles catalyzed by tungstophosphoric acid supported on silica gel. Catalysis Letters, 56 (1), 49–51. doi: 10.1023/a:1019020004168
  12. Mamedov, E. G. (2001). Asymmetrical [4+2]-Cycloadditionof (3)-Menthyl Acrylateand (3)-Menthyl Methacrylate to Cyclopentadiene in the Presence of BBr3. Russian Journal of Organic Chemistry, 37 (2), 217–222. doi: 10.1023/a:1012374828303
  13. Mamedov, E. G. (2007). Asymmetric Diels-Alder reaction of 1,3-butadienes with (−)-dimenthyl fumarate in the presence of BBr3 and BBr3·OEt2. Russian Journal of Organic Chemistry, 43 (2), 184–187. doi: 10.1134/s1070428007020054
  14. Mamedov, E. G. (2006). Asymmetric Diels-Alder reaction between acrylates and cyclopentadiene in the presence of chiral catalysts. Russian Journal of Applied Chemistry, 79 (10), 1621–1625. doi: 10.1134/s1070427206100120
  15. Gast, L. E., Bell, E. W., Teeter, H. M. (1956). Reactions of conjugated fatty acids. III. Kinetics of the Diels-Alder reaction. Journal of the American Oil Chemists Society, 33 (6), 278–281. doi: 10.1007/bf02630861
  16. Onaka, M., Hashimoto, N., Kitabata, Y., Yamasaki, R. (2003). Aluminum-rich mesoporous aluminosilicate (Al-HMS) as a solid acid catalyst for the Diels–Alder reaction of acrylates with 1,3-dienes. Applied Catalysis A: General, 241 (1-2), 307–317. doi: 10.1016/s0926-860x(02)00495-7
  17. Bomholdt, K., Lechert, H. (1995). Catalysis of a liquid-phase Diels-Alder-reaction by zeoutes Y, EMT and BETA. Studies in Surface Science and Catalysis, 167–168. doi: 10.1016/s0167-2991(06)81137-7
  18. Bittner, B., Janus, E., Milchert, E. (2011). N-hexylpyridinium bis(trifluoromethylsulfonyl)imide and Lewis acids – catalytic systems for Diels-Alder reaction. Open Chemistry, 9 (1). doi: 10.2478/s11532-010-0138-4
  19. Dintzner, M. R., Little, A. J., Pacilli, M., Pileggi, D. J., Osner, Z. R., Lyons, T. W. (2007). Montmorillonite clay-catalyzed hetero-Diels–Alder reaction of 2,3-dimethyl-1,3-butadiene with benzaldehydes. Tetrahedron Letters, 48 (9), 1577–1579. doi: 10.1016/j.tetlet.2007.01.010
  20. Polevaya, I. S., Fedevich, M. D., Polyuzhin, I. P., Marshalok, O. I. (2011). Optimization of synthesis conditions of 2,3-dimethylbutadiene. Russian Journal of Applied Chemistry, 84 (2), 261–265. doi: 10.1134/s1070427211020169
  21. Polova, I. S., Karpiak, N. M., Marshalok, H. O., Yatchyshyn, Y. Y. (2011). Osoblyvosti oderzhannia (R) alil-1,3,4 trymetyltsykloheks-3-enkarboksylatu. XIII vseukrainska konferentsiya studentiv ta aspirantiv «Suchasni problemy khimiy». Kyiv, 102.
  22. Polova, I. S., Poliuzhyn, I. P., Marshalok, H. O., Hladiy, A. I. (2011). Analitychnyi kontrol protsesu oderzhannia alil 1,3,4-trymetyltsykloheks-3-en-karboksylatu metodom hazoridynnoi khromatohrafiy. III vseukrainska naukova konferentsiya studentiv ta aspirantiv «Khimichni Karazinski chytannia – 2011». Kharkiv, 41–42.
  23. Shmid, R., Sapunov, V. N. (1985). Neformal'naya kinetika. V poiskah putey himicheskih reaktsiy. Moscow: Mir, 264.
  24. Vascerman, A. (1986). Reaktsiya Dil'sa-Al'dera. Moscow: Mir, 133.
  25. Yatchyshyn, Y. Y., Polova, I. S., Tsiupko, I. I., Ilnytskyi, Z. M., Marshalok, H. O., Fedevych, M. D. et. al. (2013). Pat. No. 80876 UA. Sposib oderzhannia polikarboksylatnoho plastyfikatora dlia tsementnykh sumishei. MPK S 04 V 24/26, S 08F 220/00. No. 201300061; declareted: 02.01.2013; published: 10.06.2013, Bul. No. 11.
  26. Polyova, I., Marshalok, G., Yatchyshyn, J., Polyuzhin, I. (2012). Kinetics of allyl-1,3,4-trimethylcyclohex-3-encarboxylate obtaining. Сhemistry & Сhemical Тechnology, 6 (2), 119–122.

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Published

2017-12-25

How to Cite

Kostiv, I., Dzeryn, O., & Malynovskyi, Y. (2017). Establishing optimal conditions for catalytic obtaining of allyl-1,3,4-trimethylcyclohex-3-encarboxylate. Eastern-European Journal of Enterprise Technologies, 6(6 (90), 17–25. https://doi.org/10.15587/1729-4061.2017.119491

Issue

Vol. 6 No. 6 (90) (2017): Technology organic and inorganic substances

Section

Technology organic and inorganic substances

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Copyright (c) 2017 Iryna Kostiv, Oleksandra Dzeryn, Yuriy Malynovskyi

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