O.A. Kholdeeva et al. / Journal of Catalysis 236 (2005) 62–68
67
[2] L.F. Fieser, J. Biol. Chem. 133 (1940) 391.
[3] R.A. Sheldon, Top. Curr. Chem. 164 (1993) 21.
[4] R.A. Sheldon, J. Dakka, Catal. Today 19 (1994) 215.
[5] W. Bonrath, T. Netscher, Appl. Catal. A: Gen. 280 (2005) 55.
[6] W. Adam, W.A. Herrmann, W. Lin, Ch.R. Saha-Moller, R.W. Fischer,
J.D.G. Correia, Angew. Chem. Int. Ed. 33 (1994) 2475.
[7] W.A. Herrmann, J.J. Haider, R.W. Fischer, J. Mol. Catal. A: Chem. 138
(1999) 115.
[8] J. Kowalski, J. Ploszynska, A. Sobkowiak, Catal. Commun. 4 (2003) 603.
[9] A. Sorokin, A. Tuel, Catal. Today 57 (2000) 45.
[10] A.B. Sorokin, S. Mangematin, C. Pergrale, J. Mol. Catal. A: Chem. 182–
183 (2002) 267.
[11] S. Yamaguchi, M. Inone, S. Enomoto, Chem. Lett. (1985) 827.
[12] O.S. Anunziata, L.B. Pierella, A.R. Beltramone, J. Mol. Catal. A: Chem.
149 (1999) 255.
[13] O.S. Anunziata, A.R. Beltramone, J. Cussa, Appl. Catal. A: Gen. 270
(2004) 77.
[14] L.H. Klemm, J. Shabtai, D.R. Taylor, J. Org. Chem. 33 (1968) 1480.
[15] B.E. Leach, C.M. Starks, US Patent 3 993 701 (1976).
[16] H. Grabowska, W. Mista, L. Syper, J. Wrzyszcz, M. Zawadski, J. Catal.
160 (1996) 134.
Fig. 5. Catalyst recycling. Reaction conditions: MNL, 0.025 M; H O ,
2
2
◦
0.125 M; Ti-MMM-2 (sample 2) 3.8 mg, MeCN 1 ml, 80 C, 30 min, MNL
solution in 250 µl of MeCN was added to the reaction mixture by portions
50 µl/2 min.
[17] S. Shimizu, T. Ishitoku, H. Nanbu, Japanese Patent 58 065 235 (1983).
[18] I. Calinescu, R. Avram, Rev. Chim. 45 (1994) 865.
[19] M.V. Kheifets, D.A. Sibarov, V.V. Sobolev, N.A. Petrova, J. Appl. Chem.
USSR 59 (1986) 990.
[20] I. Yuranov, L. Kiwi-Minsker, A. Renken, Appl. Catal. A: Gen. 226 (2002)
193.
[21] F. Monteleone, F. Cavani, C. Felloni, R. Trabace, European Patent 014 832
(2004).
[22] M. Frostin-Rio, D. Pujol, C. Bied-Charreton, M. Perree-Fauvet, A. Gaude-
mer, J. Chem. Soc., Perkin Trans. 1 (1984) 1971.
[23] K.I. Matveev, A.P. Krysin, T.F. Titova, B.M. Khlebnikov, V.F. Odjakov,
T.G. Egorova, E.G. Zhizhina, V.N. Parmon, Russian Patent 2 022 958
(1994).
[24] K.I. Matveev, E.G. Zhizhina, V.F. Odjakov, V.N. Parmon, Russian Patent
2 061 669 (1996).
using sample 3. No loss in either catalytic activity or selectiv-
ity was observed during at least three catalytic cycles (Fig. 5).
The MNQ yields were 73, 77, and 76% in three consecutive
oxidations. These results strongly support the absence of cata-
lyst deactivation during the catalytic runs. If some amount of
the catalyst were in fact deactivated, this would correspond to
a diminishing effective catalyst/substrate molar ratio. In turn,
this would lead to decreasing MNQ selectivity (at 100% con-
version), as had been established in the experiments with de-
creasing catalyst amount (Fig. 4B).
4. Conclusions
[25] K.I. Matveev, E.G. Zhizhina, V.F. Odjakov, Russian Patent 2 162 837
(2001).
[26] K.I. Matveev, V.F. Odjakov, E.G. Zhizhina, J. Mol. Catal. A: Chem. 114
(1996) 151.
[27] B. Notari, Adv. Catal. 41 (1996) 253.
[28] A. Corma, M.T. Navarro, J. Perez Pariente, J. Chem. Soc., Chem. Com-
mun. (1994) 147.
[29] A. Corma, Chem. Rev. 97 (1997) 2373.
[30] M. Schneider, A. Baiker, Catal. Today 35 (1997) 339.
[31] W. Zhang, M. Froba, J. Wang, P.T. Tanev, J. Wong, T.J. Pinnavaia, J. Am.
Chem. Soc. 118 (1996) 9164.
[32] P.T. Tanev, M. Chibwe, T.J. Pinnavaia, Nature 368 (1994) 321.
[33] A. Sayari, Chem. Mater. 8 (1996) 1840.
[34] X. Gao, I.E. Wachs, Catal. Today 51 (1999) 233.
[35] N.N. Trukhan, V.N. Romannikov, E.A. Paukshtis, A.N. Shmakov, O.A.
Kholdeeva, J. Catal. 202 (2001) 110.
[36] O.A. Kholdeeva, N.N. Trukhan, M.P. Vanina, V.N. Romannikov, V.N. Par-
mon, J. Mrowiec-Białon´, A.B. Jarze˛bski, Catal. Today 75 (2002) 203.
[37] O.A. Kholdeeva, M.S. Melgunov, A.N. Shmakov, N.N. Trukhan, V.V.
Kriventsov, V.I. Zaikovskii, V.N. Romannikov, Catal. Today 91–92 (2004)
205.
[38] O.A. Kholdeeva, M.S. Melgunov, A.N. Shmakov, N.N. Trukhan, M.E.
Malyshev, V.B. Fenelonov, V.N. Parmon, V.N. Romannikov, Russian
Patent 2 229 930 (2004).
[39] V.B. Fenelonov, V.N. Romannikov, A.Yu. Derevyankin, Microporous
Mesoporous Mater. 28 (1999) 57.
[40] V.B. Fenelonov, A.Yu. Derevyankin, S.D. Kirik, L.A. Solovyov, A.N.
Shmakov, J.-L. Bonardet, A. Gédéon, V.N. Romannikov, Microporous
Mesoporous Mater. 44–45 (2001) 33.
[41] N.N. Trukhan, V.N. Romannikov, A.N. Shmakov, M.P. Vanina, E.A. Pauk-
shtis, V.I. Bukhtiyarov, V.V. Kriventsov, I.Yu. Danilov, O.A. Kholdeeva,
Microporous Mesoporous Mater. 59 (2003) 73.
The oxidation of MNL to MNQ by aqueous H2O2 effec-
tively proceeds over mesoporous titanium silicates of the Ti-
MMM-2 type. Crucial factors affecting MNQ yield are MNL
concentration, H2O2/MNL molar ratio, solvent nature, reac-
tion temperature, and the mode of MNL addition to the reaction
mixture. At optimal reaction conditions, MNQ yield attained
75–78% at 100% substrate conversion. The Ti-MMM-2 cata-
lyst can be used repeatedly with no loss of catalytic activity or
selectivity. The proposed method of MNQ production is envi-
ronmentally benign and avoids product contamination by traces
of transition metals. The catalytic material obtained with the
mixture of ionic and nonionic surfactant (a representative of
these materials is sample 5) is a novel type of mesoporous tita-
nium silicate that should be studied in more detail.
Acknowledgment
OVZ acknowledges financial support from the Embassy of
France in Moscow through a doctoral fellowship. Financial
support of RFBR-CNRS (Grant 05-03-34760) is highly appre-
ciated.
References
[1] P. Schudel, H. Mayer, O. Isler, in: W.H. Sebrell, R.S. Harris (Eds.), The
Vitamines, vol. 5, Academic Press, New York, 1972, p. 165.
[42] G.N. Vayssilov, Catal. Rev.-Sci. Eng. 39 (3) (1997) 209.