Synthesis of ε-Caprolactone by Oxidation of Cyclohexanone with Monoperoxysuccinic Acid

doi:10.1016/S1004-9541(13)60643-6

摘要/Abstract

摘要： In the absence of catalyst, 70% hydrogen peroxide was used to oxidize succinic anhydride to solid monoperoxysuccinic acid (PSA). Then PSA was applied to synthesis of ε-caprolactone (ε-CL) by oxidation of cyclohexanone in the heterogeneous system. In order to achieve material recycle, solid precipitated in the process of synthesizing ε-CL was dehydrated via reactive distillation followed by recrystallization to prepare succinic anhydride, which was characterized by IR (infrared spectra) and ¹HNMR (¹H nuclear magnetic resonance). Effects of molar ratio of PSA to cyclohexanone, acetic acid dosage, reaction temperature, reaction time on conversion of cyclohexanone, yield and selectivity of ε-CL were investigated respectively. The results indicated that conversion of cyclohexanone, yield and selectivity of ε-CL were upto 98.1%, 97.5% and 99.4% respectively under the optimal conditions. In addition, in the process of synthesizing succinic anhydride, the optimal yield of succinic anhydride reached 67.4%.

关键词: monoperoxysuccinic acid, cyclohexanone, &, epsilon, -caprolactone, reactive distillation, recrystallization

Abstract: In the absence of catalyst, 70% hydrogen peroxide was used to oxidize succinic anhydride to solid monoperoxysuccinic acid (PSA). Then PSA was applied to synthesis of ε-caprolactone (ε-CL) by oxidation of cyclohexanone in the heterogeneous system. In order to achieve material recycle, solid precipitated in the process of synthesizing ε-CL was dehydrated via reactive distillation followed by recrystallization to prepare succinic anhydride, which was characterized by IR (infrared spectra) and ¹HNMR (¹H nuclear magnetic resonance). Effects of molar ratio of PSA to cyclohexanone, acetic acid dosage, reaction temperature, reaction time on conversion of cyclohexanone, yield and selectivity of ε-CL were investigated respectively. The results indicated that conversion of cyclohexanone, yield and selectivity of ε-CL were upto 98.1%, 97.5% and 99.4% respectively under the optimal conditions. In addition, in the process of synthesizing succinic anhydride, the optimal yield of succinic anhydride reached 67.4%.

Key words: monoperoxysuccinic acid, cyclohexanone, &, epsilon, -caprolactone, reactive distillation, recrystallization

陈建, 赵小双, 张光旭, 陈波, 蔡卫权. Synthesis of ε-Caprolactone by Oxidation of Cyclohexanone with Monoperoxysuccinic Acid[J]. Chinese Journal of Chemical Engineering, 2013, 21(12): 1404-1409.

CHEN Jian, ZHAO Xiaoshuang, ZHANG Guangxu, CHEN Bo, CAI Weiquan. Synthesis of ε-Caprolactone by Oxidation of Cyclohexanone with Monoperoxysuccinic Acid[J]. Chin.J.Chem.Eng., 2013, 21(12): 1404-1409.

参考文献

1 Yu, Z.J., Liu, L.J., “Effect of microwave energy on chain propagation of poly(ε-caprolactone) in benzoic acid-initiated ring opening polymerization of ε-caprolactone”, Eur. Polym. J., 40, 71-80 (2004).

2 Christian, P., Jones, I.A., “Polymerisation and stabilisation of polycaprolactone using a borontrifluoride-glycerol catalyst system”, Polym. J., 42, 3989-3994 (2001).

3 Jiang, G., Evans, M.E., Jones, I.A., Rudd, C.D., Scotchford, C.A., Walker, G.S., “Preparation of poly(ε-caprolactone)/continuous bioglass fibre composite using monomer transfer moulding for bone implant”, Biomaterials, 26, 2281-2288 (2005).

4 Elomaa, L., Teixeira, S., Hakala, R., Korhonen, H., Grijpma, D.W., “Preparation of poly(ε-caprolactone)-based tissue engineering scaffolds by stereolithography”, Acta Biomater., 7, 3850-3856 (2011).

5 Kiskan, B., Yagci, Y., “Synthesis and characterization of naphthoxazine functional poly(ε-caprolactone)”, Polym. J., 46, 11690-11697 (2005).

6 Chang, K.Y., Lee, Y.D., “Ring-opening polymerization of ε-caprolactone initiated by the antitumor agent doxifluridine”, Acta Biomater, 5, 1075-1081 (2009).

7 Bikiaris, D.N., Papageorgiou, G.Z., Achilias, D.S., Pavlidou, E., Stergiou, A., “Miscibility and enzymatic degradation studies of poly(ε-caprolactone)/poly(propylene succinate) blends”, Eur. Polym. J., 43, 2491-2503 (2007).

8 Sivalingam, G., Karthik, R., Madras, G., “Blends of poly(ε-caprolactone) and poly(vinyl acetate): Mechanical properties and thermal degradation”, Polym. Degrad. Stab., 84, 345-351 (2004).

9 Gao, C.K., Xu, Z.F., Qin, X., “Empirical study of degradation performance of silk-fiber-reinforced polycaprolactone composite in vivo”, J. Trauma Surg., 6, 541-543 (2009).

10 Wang, N., Yu, J.G., Ma, X.F., “Progress on research of biodegradable thermoplastic materials”, Petrochem. Technol., 36, 1-6 (2007). (in Chinese)

11 Zhang, Y.Q., Tang, L.N., Sun, L.L., Bao, J.B., Song, C.X., Huang, L.Q., Liu, K.X., Tian, Y., Tian, G., Li, Z., Sun, H.F., Mei, L., “A novel paclitaxel-loaded poly(ε-caprolactone)/Poloxamer 188 blend nanoparticle overcoming multidrug resistance for cancer treatment”, Acta Biomater, 6, 2045-2052 (2010).

12 Hernán Pérez de la Ossa, D., Ligresti, A., Aberturas, M.R., Molpeceres, J., Di Marzo, V., Torres Suárez A.I., “Poly-ε-caprolactone microspheres as a drug delivery system for cannabinoid administration: Development, characterization and in vitro evaluation of their antitumoral efficacy”, J. Control. Release, 1-6 (2012).

13 Ciapetti, G., Ambrosio, L., Savarino, L., Granchi, D., Cenn, E., Baldini, N., Pagani, S., Guizzard, S., Causa, F., Giunti, A., “Osteoblast growth and function in porous poly ε-caprolactone matrices for bone repair: A preliminary study”, Biomaterials, 24, 3815-3824 (2003).

14 Kaneda, K., Yamashita, T., “Heterogeneous Baeyer-Villiger oxidation of ketones using m-chloroperbenzoic acid catalyzed by hydrotalcites”, Tetrahedron Lett., 37, 4555-4558 (1996).

15 Anoune, N., Hannachi, H., Lantéri, P., Longeray, R., Arnaud, C., “Use of theoretical chemistry to explain Baeyer-Villiger oxidations of methoxy aromatic aldehydes”, J. Chem. Educ., 75, 1920-1923 (1998).

16 Lambert, A., Elings, J.A., Macquarrie, D.J., Carr, G., Clark, J.H., “The Baeyer-Villiger oxidation of ketones using HMS-supported peroxycarboxylic acids”, Synlett., 7, 1052-1054 (2000).

17 Steffen, R.A., Teixeira, S., Rinaldi, R., Sepulveda, J., Rinaldi, R., Schuchardt, U., “Alumina-catalyzed Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide”, J. Mol. Catal. A Chem., 287, 41-44 (2008).

18 Ruiz, J.R., Jimenez-Sanchidrian, C., Llamas, R., “Hydrotalcites as catalysts for the Baeyer-Villiger oxidation of cyclic ketones with hydrogen peroxide/benzonitrile”, Tetrahedron Lett., 62, 11697-11703 (2006).

19 Llamas, R., Jimenez-Sanchidrian, C., Ruiz, J.R., “Heterogeneous Baeyer-Villiger oxidation of ketones with H₂O₂/nitrile, using Mg/Al hydrotalcite as catalyst”, Tetrahedron Lett., 63, 1435-1439 (2007).

20 Llamas, R., Jimenez-Sanchidrian, C., Ruiz, J.R., “Environmentally friendly Baeyer-Villiger oxidation with H₂O₂/nitrile over Mg(OH)₂ and MgO”, Appl. Catal., B, 72, 18-25 (2007).

21 Subramanian, H., Nettleton, E.G., Budhi, S., Koodali, R.T., “Baeyer-Villiger oxidation of cyclic ketones using Fe containing MCM-48 cubic mesoporous materials”, J. Mol. Catal. A Chem., 330, 66-72 (2010).

22 Pillai, U.R., Sahle-Demessie, E., “Sn-exchanged hydrotalcites as catalysts for clean and selective Baeyer-Villiger oxidation of ketones using hydrogen peroxide”, J. Mol. Catal. A Chem., 191, 93-100 (2003).

23 Kawabata, T., Fujisaki, N., Shishido, T., Nomura, K., Sano, T., Takehira, K., “Improved Fe/Mg-Al hydrotalcite catalyst for Baeyer-Villiger oxidation of ketones with molecular oxygen and benzaldehyde”, J. Mol. Catal. A Chem., 253, 279-289 (2006).

24 Dutta, B., Jana, S., Bhunia, S., Honda, H., Koner, S., “Heterogeneous Baeyer-Villiger oxidation of cyclic ketones using tert-BuOOH as oxidant”, Appl. Catal. A, 382, 90-98 (2010).

25 Jiménez-Sanchidrian, C., Hidalgo, J.M., Llamas, R., “Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide/benzonitrile over hydrotalcites as catalysts”, Appl. Catal., A, 312, 86-94 (2006).

26 Corma, A., Navarro, M.T., Nemeth, L., Renz, M., “Sn-MCM-41 a heterogeneous selective catalyst for the Baeyer-Villiger oxidation with hydrogen peroxide”, Chem. Commun., 21, 2190-2191 (2001).

27 Yao, C.S., Weng, H.S., “Liquid-phase oxidation of cyclohexane and cyclohexanone over supported cerium oxide catalysts”, Ind. Eng. Chem. Res., 37, 2647-2653 (1998).

28 Stamicarbon, N.V., “Caprolactone from cyclohexanone”, NL Pat., 6703001 (1968).

29 Asahi Chemical Industry Co., Ltd., “Method for producing lactones and carboxylicacids”, GB Pat., 1103885 (1968).

30 Mandal, D., Ahamad, A., Khan, M.I., Kumar, R., “Process for preparation of a lactone from a cyclic ketone”, US Pat., 6559322 (2003).

31 Mandal, D., Ahamad, A., Khan, M.I., “Biocatalytic transformation of cyclohex anone by Fusarium SP”, J. Mol. Catal. A Chem., 181, 237-241 (2002).

32 Baeyer, A., Villiger, V., “Einwirkung des Caróschen Reagens auf Keton”, Ber. Dtsch. Chem. Ges., 32, 3625-3633 (1998).

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