Selectivity in photolysis of benzyl acetate and benzyl hexanoate upon cyclodextrin complexation

Journal of Photochemistry and Photobiology A: Chemistry

Volumn 184, Issue 1-2, 2006, Pages 34-43

  Annalakshmi, Subramanian ^a   Pitchumani, Kasi ^a  

^a MADURAI KAMARAJ UNIVERSITY   (India)

Author keywords

Benzyl esters; Cyclodextrin; Homolytic and heterolytic mechanisms; Photolysis

Indexed keywords

EID: 33749510627     PISSN: 10106030     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.jphotochem.2006.03.017     Document Type: Article

References (33)

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25. 1H NMR data δH (300 MHz; CDCl3) and GC-Mass data for benzyl hexanoate (2): 0.89 (3H, t), 1.34 (4H, m), 1.52 (2H, m), 2.34 (2H, t), 5.01 (2H,s), 7.35-7.45 (5H m); m/z (EI): 206, 188, 176, 114, 107, 91 (base peak). (b) GC-Mass data (m/z (EI)) for the photoproducts: benzyl methyl ether (3): 121, 120, 91 (base peak); 2-phenylethanol (4): 122, 91, 65; benzyl alcohol (5): 108, 79, 51; bibenzyl (6): 182, 91; 2-methylbenzyl alcohol (9): 122, 107, 104, 91, 77; hexanoic acid (10): 116, 96, 86, 72; hexylbenzene (11): 162, 132, 104, 92, 77. All the photoproducts reported also identified by coinjection with authentic samples
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27. Tee O.S., Mazza C., and Du X.-X. J. Org. Chem. 55 (1990) 3603. To calculate the binding constant values, a non-linear curve fitting method (using prism software) is adopted. The formation constant values for benzyl acetate calculated by this approach in α-, β- and γ-CDs are 1251 ± 20.9, 1329 ± 28.3 and 1771 ± 39.5, respectively; for benzyl hexanoate in α-, β- and γ-CDs are 1018 ± 27.7, 1962 ± 11.3 and 2826 ± 39.5, respectively. Binding isotherm curves for 1 and 2 with α-, β- and γ-CDs are given below (Fig. 1, Plots 1 and 2)
28. Fernandez M.A., and de Rossi R.H. J. Org. Chem. 68 (2003) 6887. To calculate the binding constant values, a non-linear curve fitting method (using prism software) is adopted. The formation constant values for benzyl acetate calculated by this approach in α-, β- and γ-CDs are 1251 ± 20.9, 1329 ± 28.3 and 1771 ± 39.5, respectively; for benzyl hexanoate in α-, β- and γ-CDs are 1018 ± 27.7, 1962 ± 11.3 and 2826 ± 39.5, respectively. Binding isotherm curves for 1 and 2 with α-, β- and γ-CDs are given below (Fig. 1, Plots 1 and 2)
29. Andres G.O., and de Rossi R.H. J. Org. Chem. 70 (2005) 1445. To calculate the binding constant values, a non-linear curve fitting method (using prism software) is adopted. The formation constant values for benzyl acetate calculated by this approach in α-, β- and γ-CDs are 1251 ± 20.9, 1329 ± 28.3 and 1771 ± 39.5, respectively; for benzyl hexanoate in α-, β- and γ-CDs are 1018 ± 27.7, 1962 ± 11.3 and 2826 ± 39.5, respectively. Binding isotherm curves for 1 and 2 with α-, β- and γ-CDs are given below (Fig. 1, Plots 1 and 2)
30. 1H NMR chemical shifts exhibit an upfield shift for H-3 and H-5 protons of CD in all CD-ester complexes. Chemical shifts for cyclodextrin protons were assigned based on the software [Advanced Chemistry, Development: Toronto; http://ww2.acdlabs.com/ilab/]. For example, the chemical shifts (in Hz) for uncomplexed α-CD are H1-1392, H2-1167, H3-1071, H4-1104, H5-1191, H6-1254 and for α-CD-benzyl acetate (1) complex the corresponding values are H1-1386, H2-1155, H3-1116, H4-1101, H5-1176, H6-1296, for α-CD-benzyl hexanoate (2) complex the corresponding values are H1-1404, H2-1176, H3-1086, H4-1107, H5-1203, H6-1236, Such change in chemical shift values are known to be strong the consequence of diamagnetic anisotropic effect of the aromatic ring residing inside the cavity and are considered to be evidence for the formation of inclusion complex in aqueous CD solution
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