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

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

Iryna Kostiv, Oleksandra Dzeryn, Yuriy Malynovskyi

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

Keywords


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

References


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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

Moskva, V. V. (1996). Ponyatie kisloty i osnovaniya v organicheskoy himii. Sorosovskiy obrazovatel'nyy zhurnal, 12, 33–40.

Lindström, B., Petterson, L. J. (2003). A brief history of catalysis. Cattech, 7 (4), 130–138. doi: 10.1023/a:1025001809516

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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.

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.

Shmid, R., Sapunov, V. N. (1985). Neformal'naya kinetika. V poiskah putey himicheskih reaktsiy. Moscow: Mir, 264.

Vascerman, A. (1986). Reaktsiya Dil'sa-Al'dera. Moscow: Mir, 133.

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.

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.


GOST Style Citations


Anisimova, N. A. Synthesis and structure of nitrocyclohexenylcarboxylates [Text] / N. A. Anisimova, A. A. Kuzhaeva, G. A. Berkova, V. M. Berestovitskaya // Russian Journal of General Chemistry. – 2011. – Vol. 81, Issue 9. – P. 1845–1852. doi: 10.1134/s1070363211090180 

Monnier-Benoit, P. Synthesis of 2,4-dimethyl-cyclohex-3-ene carboxaldehyde derivatives with olfactory properties [Text] / P. Monnier-Benoit, I. Jabin, J.-N. Jaubert, P. Netchitaïlo, B. Goyau // Comptes Rendus Chimie. – 2007. – Vol. 10, Issue 3. – P. 259–267. doi: 10.1016/j.crci.2006.10.006 

Moskva, V. V. Ponyatie kisloty i osnovaniya v organicheskoy himii [Text] / V. V. Moskva // Sorosovskiy obrazovatel'nyy zhurnal. – 1996. – Issue 12. – P. 33–40.

Lindström, B. A brief history of catalysis [Text] / B. Lindström, L. J. Petterson // Cattech. – 2003. – Vol. 7, Issue 4. – P. 130–138. doi: 10.1023/a:1025001809516 

Hawkins, J. M. Asymmetric Catalysis in the Pharmaceutical Industry [Text] / J. M. Hawkins, T. J. N. Watson // Angewandte Chemie International Edition. – 2004. – Vol. 43, Issue 25. – P. 3224–3228. doi: 10.1002/anie.200330072 

Farina, V. Asymmetric Synthesis of Active Pharmaceutical Ingredients [Text] / V. Farina, J. T. Reeves, C. H. Senanayake, J. J. Song // Chemical Reviews. – 2006. – Vol. 106, Issue 7. – P. 2734–2793. doi: 10.1021/cr040700c 

Grubbs, R. H. Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials (Nobel Lecture) [Text] / R. H. Grubbs // Angewandte Chemie International Edition. – 2006. – Vol. 45, Issue 23. – P. 3760–3765. doi: 10.1002/anie.200600680 

Gradillas, A. Macrocyclization by Ring-Closing Metathesis in the Total Synthesis of Natural Products: Reaction Conditions and Limitations [Text] / A. Gradillas, J. Pérez-Castells // Angewandte Chemie International Edition. – 2006. – Vol. 45, Issue 27. – P. 6086–6101. doi: 10.1002/anie.200600641 

Chen, H.-T. Urea and Thiourea-Functionalized Mesoporous Silica Nanoparticle Catalysts with Enhanced Catalytic Activity for Diels-Alder Reaction [Text] / H.-T. Chen, B. G. Trewyn, J. W. Wiench, M. Pruski, V. S.-Y. Lin // Topics in Catalysis. – 2009. – Vol. 53, Issue 3-4. – P. 187–191. doi: 10.1007/s11244-009-9423-x 

Cong, H. Silver Nanoparticle-Catalyzed Diels−Alder Cycloadditions of 2′-Hydroxychalcones [Text] / H. Cong, C. F. Becker, S. J. Elliott, M. W. Grinstaff, J. A. Porco // Journal of the American Chemical Society. – 2010. – Vol. 132, Issue 21. – P. 7514–1518. doi: 10.1021/ja102482b 

Meuzelaar, G. J. Diels-Alder reactions of carbonyl-containing dienophiles catalyzed by tungstophosphoric acid supported on silica gel [Text] / G. J. Meuzelaar, L. Maat, R. A. Sheldon // Catalysis Letters. – 1998. – Vol. 56, Issue 1. – P. 49–51. doi: 10.1023/a:1019020004168 

Mamedov, E. G. Asymmetrical [4+2]-Cycloadditionof (3)-Menthyl Acrylateand (3)-Menthyl Methacrylate to Cyclopentadiene in the Presence of BBr3 [Text] / E. G. Mamedov // Russian Journal of Organic Chemistry. – 2001. – Vol. 37, Issue 2. – P. 217–222. doi: 10.1023/a:1012374828303 

Mamedov, E. G. Asymmetric Diels-Alder reaction of 1,3-butadienes with (−)-dimenthyl fumarate in the presence of BBr3 and BBr3·OEt2 [Text] / E. G. Mamedov // Russian Journal of Organic Chemistry. – 2007. – Vol. 43, Issue 2. – P. 184–187. doi: 10.1134/s1070428007020054 

Mamedov, E. G. Asymmetric Diels-Alder reaction between acrylates and cyclopentadiene in the presence of chiral catalysts [Text] / E. G. Mamedov // Russian Journal of Applied Chemistry. – 2006. – Vol. 79, Issue 10. – P. 1621–1625. doi: 10.1134/s1070427206100120 

Gast, L. E. Reactions of conjugated fatty acids. III. Kinetics of the Diels-Alder reaction [Text] / L. E. Gast, E. W. Bell, H. M. Teeter // Journal of the American Oil Chemists Society. – 1956. – Vol. 33, Issue 6. – P. 278–281. doi: 10.1007/bf02630861 

Onaka, M. Aluminum-rich mesoporous aluminosilicate (Al-HMS) as a solid acid catalyst for the Diels–Alder reaction of acrylates with 1,3-dienes [Text] / M. Onaka, N. Hashimoto, Y. Kitabata, R. Yamasaki // Applied Catalysis A: General. – 2003. – Vol. 241, Issue 1-2. – P. 307–317. doi: 10.1016/s0926-860x(02)00495-7 

Bomholdt, K. Catalysis of a liquid-phase Diels-Alder-reaction by zeoutes Y, EMT and BETA [Text] / K. Bomholdt, H. Lechert // Studies in Surface Science and Catalysis. – 1995. – P. 167–168. doi: 10.1016/s0167-2991(06)81137-7 

Bittner, B. N-hexylpyridinium bis(trifluoromethylsulfonyl)imide and Lewis acids – catalytic systems for Diels-Alder reaction [Text] / B. Bittner, E. Janus, E. Milchert // Open Chemistry. – 2011. – Vol. 9, Issue 1. doi: 10.2478/s11532-010-0138-4 

Dintzner, M. R. Montmorillonite clay-catalyzed hetero-Diels–Alder reaction of 2,3-dimethyl-1,3-butadiene with benzaldehydes [Text] / M. R. Dintzner, A. J. Little, M. Pacilli, D. J. Pileggi, Z. R. Osner, T. W. Lyons // Tetrahedron Letters. – 2007. – Vol. 48, Issue 9. – P. 1577–1579. doi: 10.1016/j.tetlet.2007.01.010 

Polevaya, I. S. Optimization of synthesis conditions of 2,3-dimethylbutadiene [Text] / I. S. Polevaya, M. D. Fedevich, I. P. Polyuzhin, O. I. Marshalok // Russian Journal of Applied Chemistry. – 2011. – Vol. 84, Issue 2. – P. 261–265. doi: 10.1134/s1070427211020169 

Polova, I. S. Osoblyvosti oderzhannia (R) alil-1,3,4 trymetyltsykloheks-3-enkarboksylatu [Text] / I. S. Polova, N. M. Karpiak, H. O. Marshalok, Y. Y. Yatchyshyn // XIII vseukrainska konferentsiya studentiv ta aspirantiv «Suchasni problemy khimiy». – Kyiv, 2011. – P. 102.

Polova, I. S. Analitychnyi kontrol protsesu oderzhannia alil 1,3,4-trymetyltsykloheks-3-en-karboksylatu metodom hazoridynnoi khromatohrafiy [Text] / I. S. Polova, I. P. Poliuzhyn, H. O. Marshalok, A. I. Hladiy // III vseukrainska naukova konferentsiya studentiv ta aspirantiv «Khimichni Karazinski chytannia – 2011». – Kharkiv, 2011. – S. 41–42.

Shmid, R. Neformal'naya kinetika. V poiskah putey himicheskih reaktsiy [Text] / R. Shmid, V. N. Sapunov. – Moscow: Mir, 1985. – 264 p.

Vascerman, A. Reaktsiya Dil'sa-Al'dera [Text] / A. Vascerman. – Moscow: Mir, 1968. – 133 p.

Pat. No. 80876 UA. Sposib oderzhannia polikarboksylatnoho plastyfikatora dlia tsementnykh sumishei. MPK S 04 V 24/26, S 08F 220/00 [Text] / Yatchyshyn Y. Y., Polova I. S., Tsiupko I. I., Ilnytskyi Z. M., Marshalok H. O., Fedevych M. D. et. al.; zaiavnyk i patentovlasnyk NU «Lvivska politekhnika». – No. 201300061; declareted: 02.01.2013; published: 10.06.2013, Bul. No. 11.

Polyova, I. Kinetics of allyl-1,3,4-trimethylcyclohex-3-encarboxylate obtaining [Text] / I. Polyova, G. Marshalok, J. Yatchyshyn, I. Polyuzhin // Сhemistry & Сhemical Тechnology. – 2012. – Vol. 6, Issue 2. – P. 119–122.







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ISSN (print) 1729-3774, ISSN (on-line) 1729-4061