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Selective Catalytic Oxidation of Organic Sulfides to Sulfoxides without Forming Sulfones over Solid Molybdenum Blue: Kinetic and Thermodynamic Studies
Corresponding Author(s) : P.S. Raghavan
Asian Journal of Chemistry,
Vol. 32 No. 9 (2020): Vol 32 Issue 9, 2020
Abstract
The present investigation reports studies on the selective catalytic oxidation of organic sulfide substrates over molybdenum blue catalyst supported on boron phosphate. The catalyst was synthesized through partial precipitation method and characterized by XRD, FTIR and SEM techniques. The sulfoxidation was carried out in a batch reactor using benzyl phenyl sulfide as the substrate over the present catalyst and the reaction parameters were varied and optimized. The results were compared with the MoO3 impregnated boron phosphate. The catalyst was also studied for its performance over other sulfide substrates and the results were compared with available studies in literature. The reaction followed pseudo first-order kinetics and rate of the reaction under optimized condition was 10.1 × 10-3 min-1, with energy of activation of 29.3 kJ/mol. The Mo-O-Mo bridging and -Mo=O bonds present in molybdenum blue were participating in the reaction and possible mechanism has been proposed. The 100% selectivity of the product towards sulfoxide has been attributed to the big-wheel structure of molybdenum blue as it sterically hinders further reaction of sulfoxides formed to sulfones.
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- E.N. Prilezhaeva, Russ. Chem. Rev., 69, 367 (2000); https://doi.org/10.1070/RC2000v069n05ABEH000561
- D.C. Jocelyn, Biochemistry of the Thiol Group, Academic Press: New York (1992).
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- N. Iranpoor and B. Zeynizadeh, Synthesis, 49 (1999); https://doi.org/10.1055/s-1999-3693
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References
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D.C. Jocelyn, Biochemistry of the Thiol Group, Academic Press: New York (1992).
S. Oae, D. Fukushima and Y.H. Kim, J. Chem. Soc. Chem. Commun., 407 (1977); https://doi.org/10.1039/C3977000407B
J. Xan, E.A. Wilson, L.D. Roberts and N.H. Horton, J. Am. Chem. Soc., 63, 1139 (1941); https://doi.org/10.1021/ja01849a073
N. Iranpoor and B. Zeynizadeh, Synthesis, 49 (1999); https://doi.org/10.1055/s-1999-3693
M. Hirano, S. Yakabe, H. Chikamori, J.H. Clark and T. Morimoto, J. Chem. Res. (S), 308 (1998); https://doi.org/10.1039/A709079J
G. Lu and Y. Zhang, Synth. Commun., 28, 4479 (1998); https://doi.org/10.1080/00397919808004483
T. Aida, T. Akasaka, N. Furukawa and S. Oae, Bull. Chem. Soc. Jpn., 49, 1441 (1976); https://doi.org/10.1246/bcsj.49.1441
S. Caron, R.W. Dugger, S.G. Ruggeri, J.A. Ragan and D.H.B. Ripin,Chem. Rev., 106, 2943 (2006); https://doi.org/10.1021/cr040679f
N. Baig, V.K. Madduluri and A.K. Sah, RSC Adv., 6, 28015 (2016); https://doi.org/10.1039/C6RA01087C
A. Rostami, B. Tahmasbi, F. Abedi and Z. Shokri, J. Mol. Catal. Chem., 378, 200 (2013); https://doi.org/10.1016/j.molcata.2013.06.004
M. Madesclaire, Tetrahedron, 42, 5459 (1986); https://doi.org/10.1016/S0040-4020(01)88150-3
A.R. Supale and G.S. Gokavi, Catal. Lett., 124, 284 (2008); https://doi.org/10.1007/s10562-008-9447-z
F. Rajabi and R. Luque, Catal. Commun., 45, 129 (2014); https://doi.org/10.1016/j.catcom.2013.11.003
P. Kowalski, K. Mitka, K. Ossowska and Z. Kolarska, Tetrahedron, 61, 1933 (2005); https://doi.org/10.1016/j.tet.2004.11.041
M. Bagherzadeh and M. Zare, J. Sulfur Chem., 32, 335 (2011); https://doi.org/10.1080/17415993.2011.593634
K. Krishnasamy, V. Venkateswaran, M. Shanmugam and J. Dharmaraja, J. Sulfur Chem., 28, 365 (2007); https://doi.org/10.1080/17415990701420270
M. Rahimizadeh, M. Bakavoli, H. Hassani and M. Gholizadeh, J. Sulfur Chem., 28, 265 (2007); https://doi.org/10.1080/17415990701352499
M.M. Khodaei, K. Bahrami and M. Khedri, Can. J. Chem., 85, 7 (2007); https://doi.org/10.1139/v06-177
K. Jeyakumar and D.K. Chand, Tetrahedron Lett., 47, 4573 (2006); https://doi.org/10.1016/j.tetlet.2006.04.153
A. Carla Gamelas, Tiago Lourenço, A.P. da C.A.L. Simplício, B. Royo and C.C. Romão, Tetrahedron Lett., 49, 4708 (2008); https://doi.org/10.1016/j.tetlet.2008.05.126
H. Keypour, M. Balali, M.M. Haghdoost and M. Bagherzadeh, RSC Adv., 5, 53349 (2015); https://doi.org/10.1039/C5RA08653A
A. Bezaatpour, F. Payami and H. Eskandari, C.R. Chim., 20, 910 (2017); https://doi.org/10.1016/j.crci.2017.07.004
A. Müller, J. Meyer, E. Krickemeyer and E. Diemann, Angew. Chem.Int. Ed. Engl., 35, 1206 (1996); https://doi.org/10.1002/anie.199612061
P. Ratheshkumar, S. Induja, R. Ravishankar and P.S. Raghavan, Rasayan J. Chem., 13, 803 (2020); https://doi.org/10.31788/RJC.2020.1325631
S. Müller Roy, Coord. Chem. Rev., 245, 153 (2003); https://doi.org/10.1016/S0010-8545(03)00110-3
J.-W. Chu and B.L. Trout, J. Am. Chem. Soc., 126, 900 (2004); https://doi.org/10.1021/ja036762m
M.W. Tinsay, Eur. J. Sci. Res., 49, 49 (2011).
M. Kirihara, A. Itou, T. Noguchi and J. Yamamoto, Synlett, 1557 (2010); https://doi.org/10.1055/s-0029-1219947
L. Zhao, H. Zhang and Y. Wang, J. Org. Chem., 81, 129 (2016); https://doi.org/10.1021/acs.joc.5b02400
B. Karimi, M. Ghoreishi-Nezhad and J.H. Clark, Org. Lett., 7, 625 (2005); https://doi.org/10.1021/ol047635d