Maya Chatterjee et al.
COMMUNICATIONS
Fierro, J. Chem. Soc. Faraday Trans. 1993, 89, 3981–
3986; e) X. Yu, H. Li, J. F. Deng, Appl. Catal. A: Gen-
eral 2000, 199, 191–198; f) X. Yu, H. Li, J. F. Deng,
Appl. Catal. A: General 2001, 216, 51–58; g) X. Yu, H.
Li, J. F. Deng, New J. Chem. 1999, 23, 1059–1061.
[5] M. Serra, P. Salagre, Y. Cesteros, F. Madina, J. E. Suei-
ras, Appl. Catal. A: General 2004, 272, 353–362.
[6] L. Zhao, C. Y. Wang, J. X. Chen, J. Y. Zhang, Chinese
Chem. Lett. 2007, 18, 685–688.
process could be highly relevant to develop clean and
green methodology for aminonitrile formation leading
to the synthesis of caprolactam, which is a future
target.
Experimental Section
Materials
[7] D. Tichit, R. Durand, A. Rolland, B. Coq, J. Lopez, P.
Marion, J. Catal. 2002, 211, 511–520.
Adiponitrile, terephthalonitrile, isophthalonitrile and phtha-
lonitrile (Aldrich) were used as received. Carbon dioxide
(>99.99%) was supplied by Nippon Sanso Co. Ltd. All cata-
lysts were reduced in H2 at 3008C for 2 h prior to the reac-
tion.
[8] a) S. Alini, A. Bottino, G. Capannelli, R. Carbone, A.
Comite, G. Vitulli, J. Mol. Catal. A: Chemical 2003,
206, 363–370; b) R. Di Felice, A. Bottino, G. Capannel-
li, A. Comite, T. Di Felice, Int. J. Chem. React. Eng.
2005, 3, A34; c) S. Alini, A. Bottino, G. Capannelli, A.
Comite, S. Paganelli, Appl. Catal. A: General 2005, 292,
105–112.
Catalytic Activity
The hydrogenation of adiponitrile was studied at 808C over
5% Rh/Al2O3 catalyst. All reactions were carried out in a
50-mL stainless steel batch reactor placed in a hot-air circu-
lating oven and the details are given elsewhere.[12] Briefly,
0.1 g of catalyst and 1.2 g of the reactant were introduced in
the reactor. After the required temperature had been at-
tained, H2, followed by CO2, were charged into the reactor
using a high-pressure liquid pump and then compressed to
the desired pressure. The crude liquid product was separated
from the catalyst simply by filtration using Minisart RC 15
single-use syringe filters. After that the product was subject-
ed to structural characterization using NMR and FT-IR
(Please see Supporting Information for details). Finally, the
selectivity of the product was analyzed by GC/MS and GC.
It has to be mentioned that for NMR analysis, after the re-
action CDCl3 was added to the product catalyst mixture and
separated from the solid catalyst as described above.
[9] a) J. L. Pellegatta, C. Blandy, V. Colliꢂre, R. Chouk-
roun, B. Chaudret, P. Cheng, K. Philippot, J. Mol.
Catal. A Chemical 2002, 178, 55–61; b) R. Di Felice, A.
Bottino, G. Capannelli, A. Comite, T. Di Felice, Int. J.
Chem. React. Eng. 2005, 3, A34; c) S. Alini, A. Bottino,
G. Capannelli, A. Comite, S. Paganelli, Appl. Catal. A:
General 2005, 292, 105–112; d) ref.[4g]
[10] F. Mares, J. E. Galle, S. E. Diamond, F. J. Regina, J.
Catal. 1988, 112, 145–156.
[11] a) P. G. Jessop, T. Ikariya, R. Noyori, Chem. Rev. 1999,
99, 475–493; b) A. Baiker, Chem. Rev. 1999, 99, 453–
473; c) J. Grunwaldt, R. Wandeler, A. Baiker, Catal.
Rev. Sci. Eng. 2003, 45, 1–96.
[12] a) M. Chatterjee, A. Chatterjee, Y. Ikushima, Green
Chem. 2004, 6, 114–118; b) M. Chatterjee, Y. Ikushima,
T. Yokoyama, M. Sato, Adv. Synth. Catal. 2008, 350,
624–632; c) M. G. Hitzler, M. Poliakoff, Chem.
Commun. 1997, 1667–1668; d) U. R. Pillai, E. Sahle-
Demessie, Chem. Commun. 2002, 422–423.
[13] a) X. Xie, C. L. Liotta, C. A. Eckert, Ind. Eng. Chem.
Res. 2004, 43, 7907–7911; b) A. Fuerstner, L. Acker-
mann, K. Beck, H. Hori, D. Koch, K. Langermann, M.
Liebl, C. Six, W. Leitner, J. Am. Chem. Soc. 2001, 123,
9000–9006; c) J. R. Hyde, P. Licence, D. Carter, M. Po-
liakoff, Appl. Catal. 2001, 222, 119–131.
[14] a) W. Leitner, Acc. Chem. Res. 2002, 35, 746–756;
b) K. Wittmann, W. Wsiniewski, R. Mynott, W. Leitner,
L. Kranemann, T. Rische, P. Eilbracht, S. Kluwer, J.
Ernsting, C. J. Elsevier, Chem. Eur. J. 2001, 7, 4584–
4589.
References
[1] K. Weissermel, H. J. Arpe, in: Industrial Organic
Chemistry, 4th edn., Wiley-VCH, Weinheim, 2003,
pp 239–240.
[2] a) S. M. Aharoni, in: n-Nylons: Their Synthesis Struc-
ture and Properties, Wiley-VCH, Weinheim, 1997,
pp 170–204; b) G. Dahlhoff, J. P. M. Niederer, W. F.
Hoelderich, Catal. Rev. Sci. Eng. 2001, 43, 381–441.
[3] P. Bassler, D. Baumann, R. H. Fischer, (BASF, AG
(DE), US Patent 2003125546, 2003.
[4] a) F. Medina, P. Salagre, J. E. Sueiras, J. L. G. Fierro, J.
Catal. 1993, 142, 392–405; b) F. Medina, P. Salagre,
J. E. Sueiras, J. L. G. Fierro, J. Mol. Catal. 1993, 81,
363–371; c) F. Medina, P. Salagre, J. E. Sueiras, J. L. G.
Fierro, J. Chem. Soc. Faraday Trans. 1993, 89, 3507–
3512; d) F. Medina, P. Salagre, J. E. Sueiras, J. L. G.
[15] B. W. Hoffer, J. A. Moulijn, Appl. Catal. A: General
2009, 352, 193–201.
[16] NIST Chem. web book; Standard Reference Database.
[17] A. Stanislaus, B. H. Cooper, Catal. Rev. Sci. Eng. 1994,
36, 75–123.
2398
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 2394 – 2398