Catalytic Modulation on the Regioselectivity of the Photosensitized Oxidation of α-Pinene with Molecular Oxygen under Sodium Lamp Irradiation

doi:10.1016/S1872-2067(10)60271-9

Abstract

Abstract: A simple and efficient photosensitized catalytic oxidation approach for α-pinene with molecular oxygen in a temperature-controlled reactor with sparged dioxygen as oxidant and an immersed high-pressure sodium lamp as a green irradiation light source was developed. The effects of various catalysts and reaction parameters on reaction performance were studied. The results indicated that 98% conversion with 84% total selectivity for verbenone and verbenol was obtained when N,N′-dimethylformamide (DMF) was used as a solvent. The product distributions were remarkably affected by the reaction media and DMF was found to especially modulate the regioselectivity of the products. Moreover, a possible photosensitized catalytic oxidation reaction mechanism in DMF is proposed and a clear acid-base synergetic catalysis effect was evident. The relationship between chemical reactivity and selectivity was modeled using density functional theory at the B3LYP/6-311+G(d) level from optimized molecular configurations.

Key words: photosensitized oxidation, α-pinene, catalytic modulation, molecular oxygen, N,N′-dimethylformamide, density functional theory

YOU Kui-Yi, YIN Du-Lin, MAO Li-Qiu, LIU Ping-Le, LUO He-An. Catalytic Modulation on the Regioselectivity of the Photosensitized Oxidation of α-Pinene with Molecular Oxygen under Sodium Lamp Irradiation[J]. Chinese Journal of Catalysis, 2011, 32(10): 1610-1616.

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References

1Erman W F. Chemistry of the Monoterpenes: An Encyclopedic Handbook. New York: Dekker, 1985. 28
2Bauer K, Garbe D, Surburg H. Common Fragrance and Flavor Materials. New York: Wiley-VCH, 1997. 35
3Wender P A, Mucciaro T P. J Am Chem Soc, 1992, 114: 5878
4Geier III G R, Sasaki T. Tetrahedron, 1999, 55: 1859
5Laslo P, Levart M, Singh G P. Tetrahedron Lett, 1991, 32: 3167
6Reddy M M, Punniyamurthy T, Iqbal J. Tetrahedron Lett, 1995, 36: 159
7Salvador J A R, Melo M L S, Neves A S C. Tetrahedron Lett, 1997, 38: 119
8Blatter F, Frei H. J Am Chem Soc, 1994, 116: 1812
9Mori H, Ikoma K, Isoee S, Kitaura K, Katsumura S. J Org Chem, 1998, 63: 8704
10DeRosa M C, Crutchley R J. Coord Chem Rev, 2002, 233-234: 351
11Prein M, Adam W. Angew Chem, Int Ed, 1996, 35: 477
12Joy A, Robbins R J, Pitchumani K, Ramamurthy V. Tetrahe-dron Lett, 1997, 38: 8825
13Li X, Ramamurthy V. J Am Chem Soc, 1996, 118: 10666
14Robbins R J, Ramamurthy V. Chem Commun, 1997: 1071
15Murphy E F, Mallat T, Baiker A. Catal Today, 2000, 57: 115
16Guo C C, Yang W J, Mao Y L. J Mol Catal A, 2005, 226: 279
17Li H R, Wu L Z, Tung C H. Tetrahedron, 2000, 56: 7437
18Allal B A, Firdoussi L E, Allaoud S, Karim A, Castanet Y. J Mol Catal A, 2003, 200: 177
19阳卫军, 李子阳, 陶能烨, 郭灿城. 催化学报 (Yang W J, Li Z Y, Tao N Y, Guo C Ch. Chin J Catal), 2006, 27: 454
20You K, Yin D, Mao L, Liu P, Luo H. J Photochem Photobiol A, 2011, 217: 321
21Geerlings P, De Proft F, Langenaeker W. Chem Rev, 2003, 103: 1793
22Yang W, Parr R G. Proc Natl Acad Sci USA, 1985, 82: 6723
23Yang W, Mortier W J. J Am Chem Soc, 1986, 108: 5708
24Ayers P W, Morrison R C, Roy R K. J Chem Phys, 2002, 116: 8731
25Becke A D. Phys Rev A, 1988, 38: 3098
26Becke A D. J Chem Phys, 1993, 98: 1372
27Becke A D. J Chem Phys, 1993, 98: 5648
28Lee C, Yang W, Parr R G. Phys Rev B, 1988, 37: 785
29Marakchi K, Kabbaj O, Komiha N, Jalal R, Esseffar M. J Mol Struct: THEOCHEM, 2003, 620: 71
30Bonnett R. Chem Soc Rev, 1995, 24: 19

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