measured into 2 mL glass test tubes, followed by 0.75 mL of the
acid stock solution. Final [glycerol] = 500 mmol L-1, [dimethyl
sulfone] = 100 mmol L-1, [catalyst] = 2.5 mmol L-1, [HOTf] =
10, 20, 30, 40 mmol L-1 in the sample test tubes. Dimethyl
sulfone stock solution (1.0 mL) was added to the four blank test
tubes. A 2 ¥ 2 mm stir bar was added to each test tube, but to
ensure complete homogeneity each tube was thoroughly mixed
using a vortex mixer. A 0.5 mL sample was taken for initial GC
analysis from all but the blank samples. The tubes were loaded
into the parallel reactor and the reactor sealed. The reactor
was evacuated for 2 min using a water aspirator, pressurized to
7.58 MPa with H2 gas, and allowed to equilibrate for 2 min.
The evacuation/pressurization cycle was repeated twice more.
The reactor was placed in a glass wool-lined aluminium heating
block on a hotplate, magnetic stirring was set to the maximum,
and the reactor was heated to the reaction temperature. Timing
started once the reactor reached the set operating temperature.
At the end of the reaction, heating was stopped and the reactor
placed in an ice bath for 30 min, followed by a dry ice/acetone
bath for 5 min to condense and freeze any volatile products. The
reactor was vented, warmed to room temperature, opened, and
the remainder of the solutions in the test tubes transferred to
GC vials for analysis.
19 C. W. Chin, M. A. Dasari, G. J. Suppes and W. R. Sutterlin, AlChE J.,
2006, 52, 3543–3548.
20 T. Miyazawa, Y. Kusunoki, K. Kunimori and K. Tomishige, J. Catal.,
2006, 240, 213–221.
21 T. Miyazawa, S. Koso, K. Kunimori and K. Tomishige, Appl. Catal.,
A, 2007, 318, 244–251.
22 T. Miyazawa, S. Koso, K. Kunimori and K. Tomishige, Appl. Catal.,
A, 2007, 329, 30–35.
23 S. Wang and H. C. Liu, Catal. Lett., 2007, 117, 62–67.
24 M. Balaraju, V. Rekha, P. S. S. Prasad, B. Devi, R. B. N. Prasad and
N. Lingaiah, Appl. Catal., A, 2009, 354, 82–87.
25 L. Huang, Y. L. Zhu, H. Y. Zheng, Y. W. Li and Z. Y. Zeng, J. Chem.
Technol. Biotechnol., 2008, 83, 1670–1675.
26 J. Feng, H. Fu, J. Wang, R. Li, H. Chen and X. Li, Catal. Commun.,
2008, 9, 1458–1464.
27 O. M. Daniel, A. DeLaRiva, E. L. Kunkes, A. K. Datye, J. A.
Dumesic and R. J. Davis, ChemCatChem, 2010, 2, 1107–1114.
28 S. Wang, Y. Zhang and H. Liu, Chem.–Asian J., 2010, 5, 1100–1111.
29 T. Kurosaka, H. Maruyama, I. Naribayashi and Y. Sasaki, Catal.
Commun., 2008, 9, 1360–1363.
30 L. F. Gong, Y. Lu, Y. J. Ding, R. H. Lin, J. W. Li, W. D. Dong, T.
Wang and W. M. Chen, Chin. J. Catal., 2009, 30, 1189–1191.
31 Y. Nakagawa, Y. Shinmi, S. Koso and K. Tomishige, J. Catal., 2010,
272, 191–194.
32 R. R. Dykeman, K. L. Luska, M. E. Thibault, M. D. Jones, M.
Schlaf, M. Khanfar, N. J. Taylor, J. F. Britten and L. Harrington,
J. Mol. Catal. A: Chem., 2007, 277, 233–251.
33 E. Arceo, P. Marsden, R. G. Bergman and J. A. Ellman, Chem.
Commun., 2009, 3357–3359.
34 Y. Liu, H. Tuysuz, C. J. Jia, M. Schwickardi, R. Rinaldi, A. H. Lu,
W. Schmidt and F. Schuth, Chem. Commun., 2010, 46, 1238–1240.
35 World Patent Pat. US 6,080,898 W 9,905,085, 2000.
36 G. Braca, A. M. R. Galletti and G. Sbrana, J. Organomet. Chem.,
1991, 417, 41–49.
Acknowledgements
This work was supported by the Natural Science and Engi-
neering Research Council of Canada (NSERC), the Canadian
Foundation for Innovation (CFI), Natural Resources Canada
(NRCAN), the Ontario Ministry of Agriculture, Food, and
Rural Affairs (OMAFRA), the BioCap Canada Foundation,
and DuPont. M. E. T. thanks NSERC and the Ontario Graduate
Scholarship program for graduate fellowships. M.N.E. and
P.V.A. thank the Brazilian Science Foundations FAPESP, CNPq
and FINEP for financial assistance.
37 US Pat., 4 642 394, 1987.
38 M. Schlaf, J. Chem. Soc. Dalton Trans., 2006, 4645–4653.
39 D. Pressman and H. J. Lucas, J. Am. Chem. Soc., 1942, 64, 1953–1957.
40 R. H. Hall and E. S. Stern, J. Chem. Soc., 1950, 490–498.
41 Nimlos et al. have provided a detailed theoretical study of the
dehydration of glycerol in the gas phase: M. R. Nimlos, S. J. Blanksby,
X. Qian, M. E. Himmel and D. K. Johnson, J. Phys. Chem. A, 2006¢,
110¢, 6145.
42 M. Schlaf, P. Ghosh, P. J. Fagan, E. Hauptman and R. M. Bullock,
Adv. Synth. Catal., 2009, 351, 789–800.
43 M. Schlaf, P. Gosh, P. J. Fagan, E. Hauptman and R. M. Bullock,
Angew. Chem., Int. Ed., 2001, 40, 3887–3890.
44 Z. Xie and M. Schlaf, J. Mol. Catal. A: Chem., 2005, 229, 151–158.
45 D. Taher, M. E. Thibault, D. D. Mondo, M. Jennings and M. Schlaf,
Chem.–Eur. J., 2009, 10132–10143.
References
46 N. Oshima, H. Suzuki and Y. Moro-Oka, Chem. Lett., 1984, 1161–
1 M. McCoy, Chem. Eng. News, 2005, 83, 19–20.
2 R. R. Soares, D. A. Simonetti and J. A. Dumesic, Angew. Chem., Int.
Ed., 2006, 45, 3982–3985.
3 M. Pagliaro, R. Ciriminna, H. Kimura, M. Rossi and C. Della Pina,
Angew. Chem., Int. Ed., 2007, 46, 4434–4440.
4 Y. H. Shen, S. Wang, C. Luo and H. C. Liu, Progress in Chemistry,
2007, 19, 431–436.
1164.
47 T. D. Tilley, R. H. Grubbs and J. E. Bercaw, Organometallics, 1984,
3, 274–278.
48 U. Koelle and J. Kossakowski, Inorg. Synth., 1992, 29, 225–228.
49 U. Koelle and J. Kossakowski, J. Organomet. Chem., 1989, 362, 383–
398.
50 J. Osuna, M. Canestrari, H. Krentzien, J. Cadenas and L. D’Ornelas,
Quimica Acta Cientifica Venezolana, 1992, 43, 213–217.
51 As rationalized in our previous studies, sulfolane was chosen as the
reaction medium due to its ability to dissolve both sugar alcohols and
metal complex salts, high boiling point of 285 ◦C, chemical inertness,
low toxicity and complete miscibility with water.
5 C. H. C. Zhou, J. N. Beltramini, Y. X. Fan and G. Q. M. Lu, Chem.
Soc. Rev., 2008, 37, 527–549.
6 A. Westfechtel, J. Pe´rez Gomes and A. Behr, Chem. Eng. Technol.,
2008, 31, 700–714.
7 Y. Zheng, X. Chen and Y. Shen, Chem. Rev., 2008, 108, 5253–5277.
8 M. McCoy, Chem. Eng. News, 2006, 84, 7.
9 M. McCoy, Chem. Eng. News, 2007, 85, 7.
52 S. Constant, S. Tortoioli, J. Muller, D. Linder, F. Buron and J. Lacour,
Angew. Chem., Int. Ed., 2007, 46, 8979–8982.
10 US Pat., 6 903 044 and more than 30 preceeding patents, 2005.
11 US Pat., 6 342 646 and previous patents, 2002.
12 T. Haas, B. Jaeger, R. Weber, S. F. Mitchell and C. F. King, Appl.
Catal., A, 2005, 280, 83–88.
-
53 The PF6 counter ion is not hydrolytically stable and therefore
unsuitable for catalysis in aqueous acidic medium.
54 E. P. Kundig and F. R. Monnier, Adv. Synth. Catal., 2004, 346, 901–
904.
13 WO 9821339 A1 19980522, 1998.
55 See ESI† for a digital photo of the glass apparatus used.
56 P. J. Fagan, M. H. Voges and R. M. Bullock, Organometallics, 2010,
29, 1045–1048.
14 WO 9958686 A2 19991118, 1999.
15 WO 2001012833 A2 20010222, 2001.
16 M. A. Dasari, P. P. Kiatsimkul, W. R. Sutterlin and G. J. Suppes,
Appl. Catal., A, 2005, 281, 225–231.
17 Y. Kusunoki, T. Miyazawa, K. Kunimori and K. Tomishige, Catal.
Commun., 2005, 6, 645–649.
18 A. Perosa and P. Tundo, Ind. Eng. Chem. Res., 2005, 44, 8535–8537.
57 D. DiMondo, M. Schlaf, unpublished results to be reported else-
where.
58 Reaction conditions: [glycerol] = 500 mmol L-1, ~4.83 MPa H2 (cold),
0.5 mol % catalyst, [dimethyl sulfone] = 100 mmol L-1 (internal
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