A general process for the cyclization of aminoalcohols to the corresponding amines over Cu–Cr–La/γ-Al2O3 is established in a continuous fixed-bed reactor. The catalyst was characterized by XRD, XPS and NH3-TPD. The doped Cr is found to improve the copper particle dispersion. The addition of La neutralized the strong acid sites and decreased the amount of the acid sites, which facilitated the desorption of amino compounds on the surface of catalysts and inhibited the carbon deposition. Under the optimum conditions, the yields of pyrrolidine, piperidine and piperazine were 99.5, 99.5 and 98.6 %, in order, while the yields of hexahydro-1H-azepine and homopiperazine were 46.5 and 32.7 % due to the unstable seven-membered ring by the cyclization of the corresponding aminoalcohols over Cu–Cr–La/γ-Al2O3.
1. Rudolf Z , Paul N, Gerhard F, Herbert D (1997) US Patent 5639886.
2. Baiker, A, Kijeriski, J 1985 Catal Rev Sci Eng 27:653–697 .
3. Hammerschmidt, W, Baiker, A, Wokaun, A, Fluhr, W 1986 Appl Catal 20:305–312 .
4. Kijeński, J, Niedzielski, PJ, Baiker, A 1989 Appl Catal 53:107–115 .
5. Poppelsdorf, F, Myerly, RC 1961 J Org Chem 26:131–134 .
6. Bai, GY, Li, Y, Yan, XL, He, F, Chen, LG 2004 React Kinet Catal Lett 82:33–39 .
7. Bai, GY, Chen, LG, Li, Y, Yan, XL, He, F, Xing, P, Zeng, T 2004 Appl Catal A 277:253–258 .
8. Wang, HF, Chen, LG, Luan, DZ, Li, Y, Yan, XL, Zhang, YC, Xing, JD 2006 Kinet Catal Lett 89:201–208 .
9. Zhang, YC, Bai, GY, Yan, XL, Li, Y, Zeng, T, Wang, J, Wang, HF, Xing, JD, Luan, DZ, Tang, XY, Chen, LG 2007 Catal Commun 8:1102–1106 .
10. Wu, ZW, Wang, HB, Sun, M, Du, XB, Chen, LG, Li, Y 2012 Res Chem Intermed 38:1149–1157 .
11. Yang, F, Wu, ZW, Ma, JC, Wang, HB, Li, Y, Chen, LG 2011 Catal Lett 141:1142–1148 .
12. Venot, A, Glacet, C 1971 C. R. Acad Sci Ser C 273:1266–1269.
13. Karpeiskaya, EI, Kukushkin, YN, Trofimov, VA, Ratner, ID, Shashkin, DP 1974 Russ Chem Bull 23:307–312 .
14. Yu, CL, Ge, QJ, Xu, HY, Li, WZ 2006 Appl Catal A 315:58–67 .
15. Ma, D, Zhang, WP, Shu, YY, Liu, XM, Xu, YD, Bao, XH 2000 Catal Lett 66:155–160 .
16. Ertl, G, Knozinger, H, Schuth, F, Weitkamp, J 1997 Handbook of heterogeneous catalysis 2 Wiley–VCH New York 1170–1181 .