D. Patil et al. / Journal of Molecular Catalysis B: Enzymatic 73 (2011) 5–8
7
1
00
0
0
.6
.4
Cinnamic acid
8
6
4
2
0
0
0
0
0
4
MCA
0.2
0
.0
2
00
250
300
350
5
0
60
70
80
Wavelength (nm)
Temperature (°C)
Fig. 4. UV spectra of cinnamic acid and 4-methoxy cinnamic acid in methanol.
Fig. 3. Effect of reaction temperature on conversion of 4MCA to 4-methoxy cin-
namoyl glycerol after 24 h in iso-octane.
nature of 4MCG [22], it turns to potential for use in personal care
products as UV filters.
excess using lipase (Chirazyme L-2) from C. antarctica. In the
present study, the isolated product was found to optically active
with enantiomeric excess of 12% which was determined by Chi-
radex (4.6 mm × 250 mm) HPLC column (4.6 mm × 250 mm, 95%
acetonitrile in water, flow rate 0.8 ml/min).
4. Conclusion
To observe the typical difference in acid and ester carbonyl
stretching frequency, infrared spectra of 4MCA and 4MCG were
Enzymatic esterification of 4MCA with glycerol was success-
fully carried out using C. antarctica lipase. Maximum conversion
−
1
recorded. A strong absorption was observed in 3200–3600 cm
region for hydroxyl groups and a pair of bands at 1172 and
of 34% as a monoester was achieved after 24 h in isooctane at
◦
◦
7
0 C. Almost same conversions were obtained at 70 and 80 C.
−
1
1
116 cm consistent with the C–O stretching mode. In addition,
Prolonged reaction time (>30–36 h) leads to the formation diester
along with monoester. Since present method is superior to chem-
ical method in terms of conversion yield and priority for the
monoester formation, it can be applied for the production of
−
1
carbonyl frequency of ester was observed at 1700 cm which was
typically shifted from 1686 cm (4MCA).
−1
The synthesized product was also characterized by NMR spec-
troscopy in deuterated chloroform (CDCl ) solvent and spectra
3
4
MCG.
were recorded using Bruker AC NMR spectrometer.
1
H NMR (CDCl , 400 MHz): ␦ (ppm) 7.68 (d, 1H, J = 16.0), 7.48
3
(
d, 2H, J = 8.8), 6.91 (d, 2H, J = 8.8), 6.33 (d, 1H, J = 16), 4.31 (ddd, 2H,
Appendix A. Supplementary data
J = 11.6, 4.4), 4.00 (t, 1H, J = 4.4), 3.84 (s, 3H), 3.73 (dd, 1H, J = 11.6,
.0), 3.65 (dd, 1H, J = 11.6, 5.6).
4
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.molcatb.2011.07.002.
13
C NMR (CDCl , 100 MHz): 167.8 C1, 161.6 C7, 145.6 C3, 129.9
3
C5, 129.9 C9, 126.8 C4, 116.1 C2, 114.4 C6, 114.3 C8, 70.4 C12, 65.2
C11, 63.2 C13, 55.3 C10.
The UV spectra (Fig. 4) of cinnamic acid and 4MCA were recorded
on UV–vis double beam spectrophotometer (UV-1601, Shimadzu,
Japan). The UV absorption of cinnamic acid shows up to 315 nm
whereas in case of 4MCA it is extended up to 350 nm. An ideal
sunscreen is one which can absorb a wide spectrum of UV radi-
ation [25], 4MCA absorbed at longer wavelength than cinnamic
acid. The synthesized monoesters have shown the same absorption
characteristic as they are having the same UV absorptive moiety.
Considering the UV absorbance capacity and increased hydrophilic
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◦
7
0
C.
nd = Not detected.