Abstract
The mechanism of α-acetyl-γ-butyrolactone (ABL) synthesis from γ-butyrolactone (GBL) and ethyl acetate (EtOAc) was explored by detecting the material changes involved and the enthalpies of formation of the synthons, products, and possible intermediates were calculated using the density functional theory. GBL forms a carbanion of γ-butyrolactone by losing an α-H under strongly alkaline conditions. ABL is then obtained via two reaction mechanisms. One of the reaction mechanisms involves direct reaction of the carbanion of GBL with EtOAc to produce ABL. The other involves the formation of a carbanion of α-(2-hydroxy-tetrahydrofuran-2-yl)-γ-butyrolactone through the reaction of two molecules of GBL, and the subsequent combination of this anion with EtOAc to produce ABL. ABL is thus formed through the above two kinds of competitive ester condensation reactions. It is unnecessary to take into account synthons’ local thickness, and their self-condensation under these conditions. Both reactions of the carbanion of GBL with EtOAc and GBL are exothermic, so the control of their reaction rate is the key to their security. Considering the reasons above, this work applied synthon as the solvent, and avoided environmental pollution by alkylbenzene; also, accidents such as red material and fire were avoided by specific surface area of sodium metal control. Effective isolation of the organic and aqueous phases was performed using the salting out method. Thus, an environmentally friendly, safe, simple, and efficient new method for the synthesis of ABL with the yield higher than 90 % has been established.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Borges dos Santos, R. M., Muralha, V. S. F., Correia, C. F., Guedes, R. C., Costa Cabral, B. J., & Martinho Simöes, J. A. (2002). S-H bond dissociation enthalpies in thiophenols: A time-resolved photoacoustic calorimetry and quantum chemistry study. The Journal of Physical Chemistry A, 106, 9883–9889. DOI: 10.1021/jp025677i.
Elsasser, A. F., & Korte, T. J. (1993). U.S. Patent No. 5183908. Washington, DC, USA: U.S. Patent and Trademark Office.
Fascella, S., Cavallotti, C., Rota, R., & Carrà, S. (2004). Quantum chemistry investigation of key reactions involved in the formation of naphthalene and indene. The Journal of Physical Chemistry A, 108, 3829–3843. DOI: 10.1021/jp037518k.
Francisco-Márquez, M., Alvarez-Idaboy, J. R., Galano, A., & Vivier-Bunge, A. (2008). Quantum chemistry and TST study of the mechanism and kinetics of the butadiene and isoprene reactions with mercapto radicals. Chemical Physics, 344, 273–280. DOI: 10.1016/j.chemphys.2008.01.024.
Fu, X. C., Shen, W. X., & Yao, T. Y. (1990). Physical chemistry (4th ed.). Beijing, China: Highter Education Press.
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Montgomery, J. A., Jr., Vreven, T., Kudin, K. N., Burant, J. C., Millam, J. M., Iyengar, S. S., Tomasi, J., Barone, V., Mennucci, B., Cossi, M., Scalmani, G., Rega, N., Petersson, G. A., Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J. E., Hratchian, H. P., Cross, J. B., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E., Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J.W., Ayala, P. Y., Morokuma, K., Voth, G. A., Salvador, P., Dannenberg, J. J., Zakrzewski, V. G., Dapprich, S., Daniels, A. D., Strain, M. C., Farkas, O., Malick, D. K., Rabuck, A. D., Raghavachari, K., Foresman, J. B., Ortiz, J. V., Cui, Q., Baboul, A. G., Clifford, S., Cioslowski, J., Stefanov, B. B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Martin, R. L., Fox, D. J., Keith, T., Al-Laham, M. A., Peng, C. Y., Nanayakkara, A., Challacombe, M., Gill, P. M. W., Johnson, B., Chen, W., Wong, M. W., Gonzalez, C., & Pople, J. A. (2003). Gaussian 03, Revision A.1 [computer software]. Pittsburgh, PA, USA: Gaussian, Inc.
Ghule, V. D., Sarangapani, R., Jadhav, P. M., & Tewarri, S. P. (2011). Theoretical studies on polynitrobicyclo[1.1.1]pentanes in search of novel high energy density materials. Chemical Papers, 65, 380–388. DOI: 10.2478/s11696-011-0002-9.
Jedliński, Z., Kowalczuk, M., Kurcok, P., Grzegorzek, M., & Ermel, J. (1987). A novel route to α-substituted Γ-lactones via lactone enolates. The Journal of Organic Chemistry, 52, 4601–4602. DOI: 10.1021/jo00229a030.
Koehler, G., & Uhlenbrock, W. (1998). U.S. Patent No. 5789603. Washington, DC, USA: U.S. Patent and Trademark Office.
Kiselev, V. G., & Gritsan, N. P. (2008). Theoretical study of the nitroalkane thermolysis. 1. Computation of the formation enthalpy of the nitroalkanes, their isomers and radical products. The Journal of Physical Chemistry A, 112, 4458–4464. DOI: 10.1021/jp077391p.
Khrapkovskii, G. M., Tsyshevsky, R. V., Chachkov, D. V., Egorov, D. L., & Shamov, A. G. (2010). Formation enthalpies and bond dissociation enthalpies for C1–C4 mononitroalkanes by composite and DFT/B3LYP methods. Journal of Molecular Structure: THEOCHEM, 958, 1–6. DOI: 10.1016/j.theochem.2010.07.012.
Lipkin, M. A., Markevich, V. S., Kirsanov, A. T., & Yurkevich, A.M. (1988). The condensation of γ-butyrolactone with ethyl acetate. Pharmaceutical Chemistry Journal, 22, 911–915.
Li, X., Zheng, Q. C., Zhang, J. L., & Zhang, H. X. (2011). Theoretical study on the mechanism of rearrangement reaction catalyzed by N 5-carboxyaminoimidazole ribonucleotide mutase. Computational and Theoretical Chemistry, 964, 77–82. DOI: 10.1016/j.comptc.2010.12.001.
Ochterski, J. W., Petersson, G. A., & Wiberg, K. B. (1995). A comparison of model chemistries. Journal of the American Chemical Society, 117, 11299–11308. DOI: 10.1021/ja00150a030.
Przybyłek, M., & Gaca, J. (2012). Reaction of aniline with ammonium persulphate and concentrated hydrochloric acid: Experimental and DFT studies. Chemical Papers, 66, 699–708. DOI: 10.2478/s11696-012-0163-1.
Qian, Q. Q. (2008). China Patent No. 200810018421. Beijing, P.R. China: State Intellectual Property Office of the P.R.C.
Shafagh, I., Hughes, K. J., & Pourkashanian, M. (2011). Modified enthalpies of formation for hydrocarbons from DFT and ab initio thermal energies. Computational and Theoretical Chemistry, 964, 100–107. DOI: 10.1016/j.comptc.2010.12.005.
Vessecchi, R., & Galembeck, S. E. (2008). Evaluation of the enthalpy of formation, proton affinty, and gas-phase basicity of γ-butyrolactone and 2-pyrrolidinone by isodesmic reactions. The Journal of Physical Chemistry A, 112, 4060–4066. DOI: 10.1021/jp800427q.
Waterlot, C., Couturier, D., Rigo, B., Ghinet, A., & De Backer, M. (2011). DFT calculations on the Friedel-Crafts benzylation of 1,4-dimethoxybenzene using ZnCl2 impregnated montmorillontie K10 — inversion of relative selectivites and reactivities of aryl halides. Chemical Papers, 65, 873–882. DOI: 10.2478/s11696-011-0073-7.
Zhang, S. W., Wang, W., Wu, J. H., Qi, C. F., Fu, J. P., Li, M. P., Hu, Y. G., & Feng, Y. L. (2010a). China Patent No. 201010033349. Beijing, P.R. China: State Intellectual Property Office of the P.R.C.
Zhang, S. W., Wang, W., Qi, C. F., Fu, J. P., Li, M. P., Zhao, Z. H., Chen, X. M., Hu, Y. G., & Feng, Y. L. (2010b). China Patent No. 2010105344248. Beijing, P.R. China: State Intellectual Property Office of the P.R.C.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Wang, W., Zhang, SW., Li, MP. et al. Mechanism of α-acetyl-γ-butyrolactone synthesis. Chem. Pap. 67, 624–630 (2013). https://doi.org/10.2478/s11696-013-0337-5
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.2478/s11696-013-0337-5