Dihydroferulic Acid Alkyl Ester Analogues
Journal of Natural Products, 2007, Vol. 70, No. 5 781
Table 3. Comparison of Growth Inhibition: Saccharomyces cereVisiae Wild Type and Mutant Strains to DFA Propyl Ester (4c)
wild type slt2∆ bck1∆
%
growth
% growth
inhibition
% growth
inhibition
cell numbera
inhibition
b
cell number
cell number
conc
no treatment
4.63 (0.33)
2.30 (0.13)
1.59 (0.11)
5.05 (0.30)
1.13 (0.13)
0.43 (0.03)
+9.0
75.5
90.7
4.88 (0.60)
1.07 (0.18)
0.32 (0.06)
+5.3
76.8
93.0
1
3
.6 mM
.2 mM
50.4
65.7
a
7
b
Cell number: × 10 cells/mL, determined at OD 600 nm. Number in parentheses: std. dev. Percent growth inhibition compared to the “no
treatment” control of the wild type.
Table 4. Growth Inhibition of Aspergillus fumigatus and A.
flaVus for the DFA Propyl Ester Analogue (4c)a
Dihydroferulic acid decyl ester (4f): silica gel column (CH
to provide a colorless oil (97%); UV (CH Cl ), λmax 292 nm; IR
), νmax 1734 cm ; H NMR δ 0.87 (3H, t, J ) 6.8 Hz), 1.25
14H, m), 1.59 (2H, sext, J ) 6.8 Hz), 2.58 (2H, t, J ) 7.2 Hz),
.87 (2H, t, J ) 7.2 Hz), 3.86 (3H, s), 4.05 (2H, t, J ) 6.8 Hz), 6.68
1H, dd, J ) 1.6 and 7.6 Hz), 6.70 (1H, d, J ) 1.6 Hz), 6.82 (1H, d,
2 2
Cl )
2
2
-
1
1
(
(
2
(
CCl
4
A. fumigatus (AF293)
A. flaVus 3357
radial
growth
% growth
inhibition
radial
growth
% growth
b
c
b
inhibitionc
conc (mM)
13
no treatment
4.7
4.7
4.6
4.2
3.9
2.7
1.0
0.0
0.0
0.0
2.2
10.7
17.1
42.6
78.8
100.0
3.2
3.2
3.1
3.0
2.8
2.3
1.5
0.0
0.0
0.0
3.2
J ) 7.6 Hz); C NMR δ 14.2 (CH
CH ′), 26.0 (CH , chain CH ′), 28.7 (CH
chain CH ′), 29.4 (CH , chain CH ′), 29.61 (CH
(CH , chain CH ′), 30.8 (CH , C-7), 32.0 (CH , chain C-2′), 36.4 (CH
C-8), 55.9 (CH , ArOCH ), 64.8 (CH , chain C-1′), 111.0 (CH, C-2),
114.4 (CH, C-5), 120.9 (CH, C-6), 132.6 (C, C-1), 144.1 (C, C-4),
3
, chain C-10′), 22.8 (CH
, chain CH ′), 29.3 (CH
, chain CH ′), 29.62
2
, chain
0
0
0
0
1
3
6
.1
.2
.4
.8
.6
.2
.4
2
2
2
2
2
2
,
2
2
2
2
2
6.3
2
2
2
2
2
,
12.5
28.2
53.2
100.0
3
3
2
+
1
46.5 (C, C-3), 173.2 (C, C-9); EIMS m/z 336 [M] (76), 196
(
17), 195 (17), 179 (3), 150 (57), 137 (100), 122 (5), 91 (7);
a
33 4 f
HRESIMS m/z 337.2239 (calcd for C20H O 337.2373); R 0.47
(hexanes/EtOAc, 4:1).
Reported values are means of triplicate testing. Std. dev. for
b
all were <3%. Radial growth of fungi on potato dextrose agar plate
cm). Percent growth inhibition compared to the “no treatment”
c
(
control.
Acknowledgment. This research was conducted under USDA-ARS
CRIS projects 5325-42000-035-00D and 6435-41420-004-00D. HRES-
IMS were provided by L. Harden, USDA-ARS WRRC. S.-C.C.
expresses gratitude to the Commonwealth Health Research Board (Grant
#17-04) for support with preliminary results.
(
R
10), 91 (15); HRESIMS m/z 225.1027 (calcd for C12
0.25 (hexanes/EtOAc, 4:1).
Dihydroferulic acid propyl ester (4c): pale brown oil (92%); UV
17 4
H O 225.1121);
f
-
1 1
(
CH
2
Cl
2
), λmax 292 nm; IR (CCl
4
), νmax 1735 cm ; H NMR δ 0.90
(
3H, t, J ) 7.2 Hz), 1.61 (2H, sext, J ) 7.2 Hz), 2.58 (2H, t, J ) 7.6
Supporting Information Available: 1H and 13C NMR spectra and
experimental data for compounds 1 and 4a-f. This material is available
free of charge via the Internet at http://pubs.acs.org.
Hz), 2.86 (2H, t, J ) 7.6 Hz), 3.82 (3H, s), 4.01 (2H, t, J ) 7.2 Hz),
6
.67 (1H, dd, J ) 2.0 and 8.4 Hz), 6.69 (1H, d, J ) 2.0 Hz), 6.81 (1H,
1
3
d, J ) 8.4 Hz); C NMR δ 10.4 (CH
C-2′), 30.8 (CH , C-7), 36.4 (CH , C-8), 55.9 (CH
CH
32.6 (C, C-1), 144.1 (C, C-4), 146.6 (C, C-3), 173.3 (C, C-9); EIMS
3
2
, chain C-3′), 22.0 (CH , chain
2
2
3
, ArOCH
3
), 66.2
References and Notes
(
2
, chain C-1′), 111.1 (CH, C-2), 114.5 (CH, C-5), 120.9 (CH, C-6),
1
(1) Mendez, J. Food Chem. 2005, 93, 251-252.
(2) Saha, S.; Smith, R. M.; Lenz, E.; Wilson, I. D. J. Chromatogr. A
+
m/z 238 [M] (42), 195 (5), 179 (6), 150 (45), 137 (100), 122 (5), 91
2
003, 991, 143-150.
19 4 f
(7); HRESIMS m/z 239.1211 (calcd for C13H O 239.1277); R 0.33
(
(
(
3) Leong, Y.-W.; Harrison, L. J.; Powell, A. D. Phytochemistry 1999,
(hexanes/EtOAc, 4:1).
50, 1237-1241.
Dihydroferulic acid hexyl ester (4d): silica gel column (hexanes/
EtOAc, 4:1) and Sephadex LH-20 (CH OH/CH Cl , 3:2) to provide a
colorless oil (89%); UV (CH Cl ), λmax 292 nm; IR (CCl ), νmax 1736
4) Ordoudi, S. A.; Tsimidou, M. Z.; Vafiadis, A. P.; Bakalbassis, E. G.
J. Agric. Food Chem. 2006, 54, 5763-5768.
3
2
2
2
2
4
5) Shimoji, Y.; Tamura, Y.; Nakamura, Y.; Nanda, K.; Nishidai, S.;
Nishikawa, Y.; Ishihara, N.; Uenakai, K.; Ohigashi, H. J. Agric. Food
Chem. 2002, 50, 6501-6503.
-
1 1
cm ; H NMR δ 0.88 (3H, t, J ) 6.8 Hz), 1.27 (6H, m), 1.58 (2H,
sext, J ) 6.8 Hz), 2.58 (2H, t, J ) 7.6 Hz), 2.87 (2H, t, J ) 7.6 Hz),
3
.84 (3H, s), 4.05 (2H, t, J ) 6.8 Hz), 6.67 (1H, dd, J ) 2.2 and 8.0
(6) Chou, S.-C.; Everngam, M. C.; Sturtz, G.; Beck, J. J. Phytother. Res.
2006, 20, 153-156.
13
Hz), 6.70 (1H, d, J ) 2.0 Hz), 6.81 (1H, d, J ) 8.0 Hz); C NMR δ
4.1 (CH , chain C-6′), 22.6 (CH , chain CH ′), 25.7 (CH , chain
CH ′), 28.7 (CH , chain CH ′), 30.8 (CH , C-7), 31.5 (CH , chain C-2′),
6.4 (CH , C-8), 55.9 (CH , ArOCH ), 64.8 (CH , chain C-1′),
(
7) Kwon, Y.-S.; Kobayashi, A.; Kajiyama, S.-I.; Kawazu, K.; Kanzaki,
H.; Kim, C.-M. Phytochemistry 1997, 44, 887-889.
1
3
2
2
2
2
2
2
2
2
(
8) Rechner, A. R.; Kuhnle, G.; Bremner, P.; Hubbard, G. P.; Moore,
K. P.; Rice-Evans, C. A. Free Radical Biol. Med. 2002, 33, 220-
3
1
1
2
3
3
2
11.0 (CH, C-2), 114.4 (CH, C-5), 120.9 (CH, C-6), 132.6 (C, C-1),
44.1 (C, C-4), 146.5 (C, C-3), 173.3 (C, C-9); EIMS m/z 280 [M]
235.
+
(
9) D’Abrosca, B.; Dellagreca, M.; Fiorentino, A.; Isidori, M.; Monaco,
(
50), 195 (13), 179 (4), 150 (55), 137 (100), 122 (5), 91 (8); HRESIMS
m/z 281.1644 (calcd for C16 281.1747); R 0.38 (hexanes/EtOAc,
:1).
Dihydroferulic acid octyl ester (4e): silica gel column (hexanes/
EtOAc, 4:1) to provide a colorless oil (67%); UV (CH Cl ), λmax 290
), νmax 1735 cm ; H NMR δ 0.88 (3H, t, J ) 6.8 Hz),
.27 (10H, m), 1.59 (2H, sext, J ) 6.8 Hz), 2.58 (2H, t, J ) 7.6 Hz),
.87 (2H, t, J ) 7.6 Hz), 3.86 (3H, s), 4.05 (2H, t, J ) 6.8 Hz), 6.68
P.; Pacifico, S. J. Chem. Ecol. 2006, 32, 81-96.
H
25
O
4
f
(10) Chou, S.-C.; Beck, J. J. Unpublished results, 2006.
(11) Kim, J. H.; Campbell, B. C.; Mahoney, N. E.; Chan, K. L.; Molyneux,
R. J. J. Agric. Food Chem. 2004, 52, 7814-7821.
4
(
12) Campbell, B. C.; Molyneux, R. J.; Schatzki, T. F. J. Toxicol. 2003,
2
2
2
2, 225-266.
-
1 1
nm; IR (CCl
1
2
4
(
13) Bartlett, D. W.; Clough, J. M.; Godwin, J. R.; Hall, A. A.; Hamer,
M.; Parr-Dobrzanski, B. Pest Manag. Sci. 2002, 58, 649-662.
(14) Cuppen, J. G. M.; Van den Brink, P. J.; Camps, E.; Uil, K. F.; Brock,
T. C. M. Aquat. Toxicol. 2000, 48, 233-250.
(
1H, dd, J ) 2.0 and 7.6 Hz), 6.70 (1H, d, J ) 2.0 Hz), 6.82 (1H, d,
13
J ) 7.6 Hz); C NMR δ 14.2 (CH
CH ′), 26.0 (CH , chain CH ′), 28.7 (CH
chain CH ′), 29.30 (CH , chain CH ′), 30.8 (CH
chain C-2′), 36.4 (CH , C-8), 55.9 (CH , ArOCH
3
, chain C-8′), 22.7 (CH
, chain CH ′), 29.26 (CH
, C-7), 31.9 (CH
), 64.8 (CH
2
, chain
(15) Arterburn, J. B.; Pannala, M.; Gonzalez, A. M.; Chamberlin, R. M.
Tetrahedron Lett. 2000, 41, 7847-7849.
2
2
2
2
2
2
,
,
(
16) Solladie, G.; Ziani-Cherif, C. J. Org. Chem. 1993, 58, 2181-2185.
2
2
2
2
2
(17) Soni, M. G.; Carabin, I. G.; Burdock, G. A. Food Chem. Toxicol.
2
3
3
2
, chain
2
005, 43, 985-1015.
C-1′), 111.0 (CH, C-2), 114.4 (CH, C-5), 120.9 (CH, C-6), 132.6 (C,
(
(
18) Maddox, D. N. Cosmet. Toiletries 1982, 97, 85-88.
C-1), 144.1 (C, C-4), 146.5 (C, C-3), 173.2 (C, C-9); EIMS m/z 308
19) Rosen, W. E.; Berke, P. A. J. Soc. Cosmet. Chem. 1973, 24, 663-
+
[
M] (61), 196 (14), 195 (17), 150 (58), 137 (100), 122 (5), 91 (7);
675.
HRESIMS m/z 309.1931 (calcd for C18
H
29
O
4
309.2060); R
f
0.40
(20) Winzeler, E. A.; Shoemaker, D. D.; Astromoff, A.; Liang, H.;
Anderson, K.; Andre, B.; Bangham, R.; Benito, R.; Boeke, J. D.;
(hexanes/EtOAc, 4:1).