1
24
F. Cavani et al. / Applied Catalysis A: General 391 (2011) 118–124
Scheme 2. A possible mechanism for the formation of adipic acid from activated cyclohexanone without intermediate formation of partially oxidized products.
4
. Conclusions
The reactivity of homogeneous Keggin-type P/Mo/V poly-
[6] E. Crezee, F. Kapteijn, J.A. Moulijn, Catal. Today 69 (2001) 283–290.
[
[
[
7] A. Shimizu, K. Tanaka, H. Ogawa, Y. Matsuoka, M. Fujimori, Y. Nagamori, H.
Hamachi, K. Kimura, Bull. Chem. Soc. Jpn. 76 (2003) 1993–2001.
8] M. Constantini, L. Krumenacker, FR Patent 2,541,993 (1983) (assigned to Rhone
Poulenc).
9] C. Fumagalli, F. Minisci, R. Pirola, WO Patent 01/87,815 (2001) (assigned to
Lonza SpA).
oxometalates as catalysts for the liquid-phase oxidation of
cyclohexanone with oxygen was investigated under various con-
ditions. The use of acetic acid as a co-solvent led to a strongly
enhanced cyclohexanone conversion with respect to the reaction
carried out with water-only solvent. The conditions used for cat-
alytic experiments also affected the reaction mechanism: either
with a water-only solvent, or in the presence of acetic acid/water
solvent but with high catalyst-to-cyclohexanone molar ratio, the
prevailing mechanism was redox-type, with direct involvement
of the POM in the reaction. Conversely, when the catalyst-to-
cyclohexanone ratio used was low, in the presence of acetic
acid co-solvent, the prevailing mechanism was a radicalic chain-
reaction autoxidation. The latter was more selective to AA than the
redox mechanism, due to the lower contribution of parallel reac-
tions of cyclohexanone oxidative degradation leading to lighter
[
10] A. Atlamsani, J.-M. Brégeault, M. Ziyad, J. Org. Chem. 58 (1993) 5663–5665.
[11] J.M. Brégeault, E.A. Bassam, J. Martin, US Patent 4,983,767 (1991) (assigned to
Rhone Poulenc Chimie).
12] S.A. Chavan, D. Srinivas, P. Ratnasamy, J. Catal. 212 (2002) 39–45.
13] L. Aakel, F. Launay, A. Atlamsani, J.-M. Brégeault, Chem. Commun. (2001)
2218–2219.
[
[
[14] M. Vennat, P. Herson, J.-M. Brégeault, G.B. Shul’pin, Eur. J. Inorg. Chem. (2003)
08–917.
15] L. Aakel, F. Launay, J.-M. Brégeault, A. Atlamsani, J. Mol. Catal. A 212 (2004)
71–182.
[16] I.V. Kozhevnikov, Chem. Rev. 98 (1998) 171–198.
9
[
1
[
[
[
17] N. Mizuno, M. Misono, Chem. Rev. 98 (1998) 199–217.
18] R. Neumann, A.M. Khenkin, Chem. Commun. (2006) 2529–2538.
19] J.-M. Brégeault, M. Vennat, L. Salles, J.-Y. Piquemal, Y. Mahha, E. Briot, P.C.
Bakala, A. Atlamsani, R. Thouvenot, J. Mol. Catal. A 250 (2006) 177–189.
20] N. Ballarini, F. Cavani, L. Casagrandi, T. D’Alessandro, A. Frattini, P. Accorinti, S.
Alini, P Babini, in: S. Ernts, A. Jess, F. Nees, U. Peters, M. Ricci, E. Santacesaria
(Eds.), Preprints of the DGMK Conference on Future Feddstocks for Fuels and
Chemicals, DGMK Tagungsbericht, 2008, pp. 225–232.
[
acids and CO . On the other hand, consecutive oxidation reac-
2
tions led to the formation of significant amounts of the mentioned
by-products, which instead gave a minor contribution under con-
ditions of prevailing redox mechanism. Tests carried out in the
presence of a radical scavenger confirmed the hypothesis formu-
lated on the presence of two different reaction mechanisms.
[
[
21] A.M. Khenkin, R. Neumann, Angew. Chem. Int. Ed. 39 (2000) 4088–4090.
22] A.M. Khenkin, L. Weiner, Y. Wang, R. Neumann, J. Am. Chem. Soc. 123 (2001)
8531–8542.
[23] J.-M. Brégeault, F. Launay, A. Atlamsani, C.R. Acad. Sci. Ser. IIc: Chim. 4 (2001)
11–26.
24] J.M. Brégeault, J. Chem. Soc. Dalton Trans. (2003) 3289–3302.
25] J.G.D. Schulz, A. Onopchenko, J. Org. Chem. 38 (1973) 3729–3733.
[
[
Acknowledgements
[26] V.F. Odyakov, E.G. Zhizhina, R.I. Maksimovskaya, K.I. Matveev, Kinet. Catal. 36
1995) 733–738.
(
[
[
27] K. Tanaka, Chemische Technik (1974) 555–559.
28] T. Iwahama, K. Syojyo, S. Sakaguchi, Y. Ishii, Org. Process Res. Dev. 2 (1998)
255–260.
The ISA (Institute of Advances Studies), The University of
Bologna, is acknowledged for their financial support to K.R.
[29] D.G. Rao, R.S. Tirukkoyllur, Ind. Eng. Chem. Prod. Res. Dev. 25 (1986) 299–304.
[30] H.-C. Shen, H.-S. Weng, Ind. Eng. Chem. Res. 27 (1988) 2254–2260.
[31] I. Belkhir, A. Germain, F. Fajula, E. Fache, J. Chem. Soc., Faraday Trans. 94 (1998)
References
1
761–1764.
[
1] U. Schuchardt, D. Cardoso, R. Sercheli, R. Pereira, R.S. da Cruz, M.C. Guerreiro,
D. Mandelli, E.V. Spinace, E.L. Pires, Appl. Catal. A 211 (2001) 1–17.
2] F. Cavani, J.H. Teles, ChemSusChem 2 (2009) 508–534.
[
[
[
[
[
[
32] D. Bonnet, T. Ireland, E. Fache, J.-P. Simonato, Green Chem. 8 (2006) 556–559.
33] K.I. Matveev, V.F. Odyakov, E.G. Zhizhina, J. Mol. Catal. A 114 (1996) 151–160.
34] I. Hermans, P. Jacobs, J. Peeters, Chem. Eur. J. 13 (2007) 754–761.
35] I. Hermans, P. Jacobs, J. Peeters, Chem. Eur. J. 12 (2006) 4229–4240.
36] I. Hermans, P. Jacobs, J. Peeters, J. Mol. Catal. A 251 (2006) 221–228.
37] I. Hermans, J. Peeters, P. Jacobs, Top. Catal. 50 (2008) 124–132.
[
[
3] F. Cavani, S. Alini, in: F. Cavani, G. Centi, S. Perathoner, F. Trifirò (Eds.), Sustain-
able Industrial Chemistry, Wiley-VCH, Weinheim, 2009, pp. 367–425.
4] F. Cavani, J. Chem. Techol. Biotechnol. (2010), doi:10.1002/jctb.2389.
5] M. Besson, F. Gauthard, B. Horvath, P. Gallezot, J. Phys. Chem. B 109 (2005)
[
[
2
461–2467.