636
M. DellaGreca et al. / Chemosphere 54 (2004) 629–637
(
C-10), 77.9 (C-11), 32.8 (C-12), 48.2 (C-13), 49.1 (C-14),
2.9 (C-15), 34.2 (C-16), 89.3 (C-17), 17.5 (C-18), 25.0
C-19), 213.0 (C-20), 67.5 (C-21).
Compound 6 had EIMS m=z 360 [M] , H-NMR: d
CDCl
) 5.90 (1H, d, J ¼ 1:3 Hz, H-4), 4.69 (1H, brs, H-
1), 4.64 (1H, d, J ¼ 19:2 Hz, H-21), 4.27 (1H, d,
J ¼ 19:2 Hz, H-21), 0.90 (3H, s, H-19), 1.15 (3H, s, H-
8). C-NMR: d (CD OD) 58.3 (C-1), 37.3 (C-2), 212.8
C-3), 131.5 (C-4), 188.3 (C-5), 32.1 (C-6), 30.9 (C-7),
30.0 (C-7), 36.2 (C-8), 99.7 (C-9), 143.8 (C-10), 98.1 (C-
11), 31.2 (C-12), 49.6 (C-13), 42.5 (C-14), 21.2 (C-15),
34.3 (C-16), 90.1 (C-17), 17.0 (C-18), 20.5 (C-19), 212.1
2
(
þ
1
(C-20), 67.8 (C-21), 14.9 (C-22).
1
(
3
Compound 12 had H-NMR: d (CD
3
OD) 5.98 (1H,
1
s, H-4), 4.62 (1H, d, J ¼ 19:1 Hz, H-21), 4.52 (1H, m, H-
11), 4.29 (1H, d, J ¼ 19:1 Hz, H-21), 3.09 (1H, m, H-
16b), 3.01 (1H, m, H-2), 2.65 (1H, m, H-2), 2.51 (2H, m,
1
3
1
3
0
(
H-6 e H-6 ), 2.51 (1H, m, H-7), 2.38 (1H, m, H-12), 2.21
4
1
9
0.4 (C-8), 62.7 (C-9), 76.8 (C-10), 70.3 (C-11), 40.3 (C-
2), 40.3 (C-13), 53.7 (C-14), 26.0 (C-15), 34.7 (C-16),
0.8 (C-17), 18.7 (C-18), 20.4 (C-19), 213.8 (C-20), 68.1
(1H, m, H-14), 1.77 (2H, m, H-1, H-7), 1.68 (1H, m, H-
15), 1.46 (1H, m, H-12), 1.3 (1H, m, H-15), 1.25 (1H, m,
H-8), 1.22 (3H, s, H-19), 1.00 (3H, s, H-18), 0.89 (3H, d,
1
3
(
C-21).
Compound 7 had H-NMR: d (CD
3
J ¼ 17:2 Hz, H-22). C-NMR: d (CD OD) 50.3 (C-1),
1
3
OD) 7.45 (1H, d,
37.2 (C-2), 212.5 (C-3), 131.8 (C-4), 187.9 (C-5), 32.7 (C-
6), 35.2 (C-7), 41.6 (C-8), 103.8 (C-9), 79.1 (C-10), 72.4
(C-11), 40.4 (C-12), 49.9 (C-13), 45.8 (C-14), 25.3 (C-15),
37.2 (C-16), 92.6 (C-17), 18.3 (C-18), 20.6 (C-19), 213.2
(C-20), 68.5 (C-21), 15.9 (C-22).
J ¼ 5:9 Hz, H-1), 6.24 (1H, d, J ¼ 5:9 Hz, H-2), 6.01
(
1H, brs, H-4), 4.39 (1H, brs, H-11), 1.18 (3H, s, H-18),
3
1
1
.52 (3H, s, H-19). C-NMR: d (CD
28.0 (C-2), 189.5 (C-3), 123.0 (C-4), 174.9 (C-5), 35.0
3
OD) 161.0 (C-1),
1
(
(
C-6), 33.1 (C-7), 32.5 (C-8), 57.5 (C-9), 46.8 (C-10), 71.1
C-11), 42.0 (C-12), 46.8 (C-13), 53.2 (C-14), 23.7 (C-15),
3
7.0 (C-16), 214.4 (C-17), 17.5 (C-18), 22.5 (C-19).
1
References
3
Compound 8 had H-NMR: d (CDCl ) 7.70 (1H, d,
J ¼ 5:9 Hz, H-1), 6.18 (1H, d, J ¼ 5:9 Hz, H-2), 4.46
Aherne, G.W., Briggs, R., 1989. The relevance of the presence
of certain synthetic steroids in the aquatic environment.
J. Pharm. Pharmacol. 41, 735–736.
(
1H, brs, H-11), 2.84 (1H, d, J ¼ 19:5 Hz, H-4), 1.92
1H, d, J ¼ 19:5 Hz, H-4), 1.15 (3H, s, H-19), 1.09 (3H,
(
1
3
s, H-18). C-NMR: d (CDCl
3
) 167.1 (C-1), 134.8 (C-2),
09.9 (C-3), 45.9 (C-4), 74.8 (C-5), 33.9 (C-6), 26.8 (C-7),
American Society for Testing and Materials, 1991. Standard
guide for acute toxicity with the rotifer Brachionus. E 1440–
2
3
1
2
9
1 (reapproved 1998). Philadelphia, PA, USA.
1.0 (C-8), 51.8 (C-9), 54.3 (C-10), 69.6 (C-11), 40.2 (C-
2), 47.0 (C-13), 51.5 (C-14), 23.2 (C-15), 35.5 (C-16),
19.3 (C-17), 16.1 (C-18), 21.7 (C-19).
Daughton, C.G., Ternes, T.A., 1999. Special report: pharma-
ceuticals and personal care products in the environment:
agents of subtle change? Environ. Health Perspect. 107,
1
Compound 9 had H-NMR: d (CDCl
3
) 5.44 (1H, dt,
9
07–938.
J ¼ 2:1 and 7.2 Hz, H-1), 4.45 (1H, brs, H-11), 4.18 (1H,
s, H-4), 1.08 (3H, s, H-18), 1.40 (3H, s, H-19). C-
NMR: d (CDCl ) 116.4 (C-1), 37.9 (C-2), 204.1 (C-3),
6.4 (C-4), 53.9 (C-5), 25.7 (C-6), 25.2 (C-7), 30.5 (C-8),
4.7 (C-9), 144.8 (C-10), 76.7 (C-11), 33.0 (C-12), 47.4
DellaGreca, M., Fiorentino, A., Iesce, M.R., Isidori, M.,
Nardelli, A., Previtera, L., Temussi, A., 2003. Identification
of phototransformation products of prednisone by sun-
light. Toxicity of the drug and its derivatives on aquatic
organisms. Environ. Toxicol. Chem. 22, 534–539.
1
3
3
8
5
(
C-13), 48.9 (C-14), 25.2 (C-15), 35.3 (C-16), 219.7 (C-
7), 15.6 (C-18), 21.0 (C-19).
Halling-Sorensen, B., Nors Nielsen, S., Lanzky, P.F., Ingerslev,
F., Holten L u€ tzhoft, H.C., Jorgensen, S.E., 1998. Occur-
rence, fate and effects of pharmaceutical substances in the
environment––a review. Chemosphere 36, 357–393.
International Organization for Standardization, 1987. Water
quality––algal growth inhibition test. ISO/DIS 8692. Ge-
neva, Switzerland.
1
1
Compound 10 had H-NMR: d (CD
3
OD) 5.94 (1H,
s, H-4), 4.68 (1H, m, H-11), 1.17 (6H, s, H-18, H-19).
1
3
C-NMR: d (CD
), 131.7 (C-4), 187.9 (C-5), 32.0 (C-6), 29.4 (C-7), 40.4
C-8), 63.4 (C-9), 76.8 (C-10), 69.7 (C-11), 41.1 (C-12),
1.1 (C-13), 53.9 (C-14), 23.9 (C-15), 36.7 (C-16), 215.0
3
OD) 58.2 (C-1), 36.7 (C-2), 212.6 (C-
3
(
International Organization for Standardization, 1996. Water
quality––determination of the inhibition of the mobility of
Daphnia magna Straus (Cladocera, Crustacea) Acute toxi-
city test. ISO/6341. Geneva, Switzerland.
4
(
C-17), 17.1 (C-18), 20.5 (C-19).
1
Compound 11 had H-NMR: d (CD
3
OD) 5.45 (1H,
dt, J ¼ 2:0 and 7.0 Hz, H-1), 4.63 (1H, d, J ¼ 19:5 Hz,
International Organization for Standardization, 2001. Water
quality––determination of chronic toxicity to Ceriodaphnia
dubia in 7 days-Population growth inhibition test. ISO/CD
H-21), 4.27 (1H, d, J ¼ 19:5 Hz, H-21), 4.21 (1H, s, H-
4
), 4.19 (1H, m, H-11), 3.18 (1H, m, H-6), 3.02 (1H, m,
2
0665. Geneva, Switzerland.
H-16b), 3.00 (1H, m, H-2), 2.75 (1H, dd, J ¼ 7:0 and
Jones, O.A.H., Voulvoulis, N., Lester, J.N., 2002. Aquatic
environmental assessment of the top 25 English prescription
pharmaceuticals. Water Res. 36, 5013–5022.
1
1
1
1
0
3
5.6 Hz, H-2), 2.38 (1H, brs, H-6), 2.25 (3H, m, H-7, H-
2 and H-14), 1.80 (1H, m, H-12), 1.65 (1H, m, H-15),
.53 (1H, m, H-7), 1.37 (3H, s, H-19), 1.17 (1H, m, H-
5), 0.92 (4H; 1H, m, H-8; 3H, d, J ¼ 5:6 Hz, H-22),
Maayan, R., Segal, R., Feuerman, E.J., Sandbank, M.,
Kaufman, H., 1988. Simple methods for estimation of
prednisone intake and metabolism. Biomed. Pharmacother.
42, 409–414.
1
3
3
.90 (3H, s, H-18). C-NMR: d (CD OD) 116.8 (C-1),
8.0 (C-2), 203.5 (C-3), 85.7 (C-4), 53.0 (C-5), 25.1 (C-6),