M. Dukh et al. / Tetrahedron 59 (2003) 4069–4076
4075
3
%), 586.8 (Mþ1, 30%), 236.2 (32%), 250.2 (30%), 22.2
of the Ministry of education of the CR project No. COST
OCD12.20 (VP) and projects No. MSM 223400008 (VK),
QLK2-CT-2001-02360 (VK) and 223300006 (PD); as well
as from Spechem Ltd. Prague is greatly acknowledged. The
authors are indebted to Professor V a´ clav Hul ´ı nsk y´ (ICT
Prague) for taking the SEM images, Dr Old rˇ ich Lap cˇ ´ı k (ICT
Prague) for taking the Tyndall effect photos, and Dr K. Ubik
(IOCB) for MS measurements and Dr L. Holasov a´ , (IOCB),
for elemental analyses and optical rotation measurements.
1
(
(
3
24%), 196.2 (100%), 181.2 (50%). H NMR spectrum
CD ODþCDCl 4:3 v/v): 0.73 (s, 3H, 3H-18); 0.90 (s, 3H,
3
3
3
H-19); 1.12 (d, J¼6.5 Hz, 3H, 3H-21); 1.02–2.28 (m,
2
2H, Ster-H); 2.51 (m, 1H, H-23); 2.58 (m, 1H, H-23); 3.38
3
3
(
tt, J¼4.4 Hz, 11.2, 1H, H-3); 3.81 (bq, J¼3.3 Hz, 1H,
3
H-7); 3.98 (bs, 1H, H-12); 7.67 (dd, J¼4.2 Hz, 8.1, 1H,
0
3
0
H-8 ); 7.72 (dd, J¼4.3 Hz, 8.4, 1H, H-3 ); 8.05 (bs, 1H,
0
3
0
H-6 ); 8.29 (dd, J¼1.7 Hz, 8.1, 1H, H-7 ); 8.50 (dd,
3
0
3
J¼1.6 Hz, 8.4, 1H, H-4 ); 9.02 (dd, J¼1.6 Hz, 4.3, 1H,
0
:1 v/v, 858C): 0.67 (s, 3H, 3H-18); 0.84 (s, 3H, 3H-19);
.07 (d, J¼5.9 Hz, 3H, 3H-21); 0.98–2.12 (m, 22H,
3
0
H-9 ); 9.09 (dd, J¼1.7 Hz, 4.2, 1H, H-2 ); (CD ODþD O
3
2
1
3
1
Ster-H); 2.53 (m, 1H, H-23); 2.62 (m, 1H, H-23); 3.39 (tt,
References
3
3
J¼4.4 Hz, 11.1, 1H, H-3); 3.78 (bq, J¼3.1 Hz, 1H, H-7);
1. Dukh, M.; Kroul ´ı k, J.; Sˇ aman, D.; Cˇ ern y´ , I.; Pouzar, V.; Kr a´ l,
3
0
3
7
8
.95 (bs, 1H, H-12); 7.72 (dd, J¼4.2 Hz, 8.3, 1H, H-8 );
V.; Dra sˇ ar, P. Presented in part as preliminary communication.
ISBOMC ’02, First International Symposium on Bioorgano-
metallic Chemistry, ENSCP Paris, 18–20 July, 2002; Book of
Abstracts, p 120.
3
0
0
.76 (dd, J¼4.3 Hz, 8.3, 1H, H-3 ); 7.90 (bs, 1H, H-6 );
3
0
3
.33 (bd, J¼8.3 Hz, 1H, H-7 ); 8.43 (bd, J¼8.3 Hz, 1H,
0
0
0
H-4 ); 9.02 (bs, 1H, H-9 ); 9.08 (bs, 1H, H-2 ). For
C H N O , (585.78) cald: C, 73.81; H, 8.09; N, 7.17; O,
3
6
47
3
4
2. Sol–Gel Technology For Thin Films, Fibers, Preforms,
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1
0.93; found C, 74.02; H, 8.19; N, 7.02.
4
.2.3. Preparation of (3a,7a,12a)-trihydroxy-N-[1,10-
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phenanthrolin-5-yl]-5b-cholan-24-amide-zinc (II) sul-
phate heptahydrate complex (5). The complex 5 was
obtained by combined dissolving of 4 (8.2 mg, 14 mmol)
and ZnSO ·7H O (2 mg, 7 mmol) in the mixture of
methanol (0.4 ml) and chloroform (0.3 ml). After mixing
the components, the solvents were allowed at room
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4
2
9
.9 mg (97%). (Then the compound was taken up in
methanol–water (1:1), where it formed immediately the
translucent gel, which scatters the beam of laser light [see
above].) UV spectrum (MeOH–water 1:1): 237 (log 1 4.80),
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Sudh o¨ lter, E. J. R. Eur. J. Org. Chem. 2001, 2329–2335.
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2
(
74 (log 1 4.67), CD spectra see Figure 5. IR spectrum
2
KBr) 1114, 981, 611 (SO4 ), 3265, 1078, 1043 (O–H),
2
1
1
1
679, 1532 (amide), 733 (phenanthroline C–H), 1625,
607, 1589, 1508, 1423 (phenanthroline ring), 1525 and
431 (phenanthroline ring complexed), 1463, 2926, 2863
1
(CH ), and 1380 (CH ). H NMR spectrum (CD ODþ
CDCl 4:3 v/v): 0.73 (s, 3H, 3H-18); 0.90 (s, 3H, 3H-19);
1
Ster-H); 2.55 (m, 1H, H-23); 2.64 (m, 1H, H-23); 3.38 (tt,
2
3
3
3
3
.13 (d, J¼6.3 Hz, 3H, 3H-21); 1.02–2.13 (m, 22H,
3
3
J¼4.3 Hz, 11.1, 1H, H-3); 3.80 (bq, J¼3.2 Hz, 1H, H-7);
8. Gladiali, S.; Chelucci, G.; Mudadu, M. S.; Gastaut, M.-A.;
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3
0
3
7
8
.98 (bs, 1H, H-12); 7.83 (dd, J¼4.2 Hz, 8.1, 1H, H-8 );
3
0
0
.91 (dd, J¼4.4 Hz, 8.4, 1H, H-3 ); 8.31 (bs, 1H, H-6 );
3
0
3
.54 (dd, J¼1.7 Hz, 8.1, 1H, H-7 ); 8.83 (dd, J¼1.6 Hz,
1997, 97, 1567–1608.
10. (a) Dukh, M.; Pouzar, V.; Cˇ ern y´ , I.; Urbansk y´ , M.; Kr a´ l, V. M.;
0
3
0
8
.4, 1H, H-4 ); 8.67 (dd, J¼1.6 Hz, 4.3, 1H, H-9 ); 8.92 (dd,
3
0
mass: 1234,64, mol. wt.: 1236,94, experimental MS (m/z,
2þ
J¼1.7 Hz, 4.2, 1H, H-2 ). For C H N O Zn , exact
Dra sˇ ar, P. Chem. Listy 2000, 94, 797. (b) Dra sˇ ar, P.; Dukh, M.;
Urbansk y´ , M.; Cˇ ern y´ , I.; Pouzar, V.; Kr a´ l, V. M. Chem. Listy
7
2 94 6 8
FAB): 587 (18%), 600 (8), 614 (19) 630 (100), 634 (66), 648
1999, 93, 747. (c) Dukh, M.; Pouzar, V.; Cˇ ern y´ , I.; Urbansk y´ ,
M.; Kr a´ l, V. M.; Dra sˇ ar, P. Chem. Listy 2000, 94, 1045.
(d) Dukh, M.; Cˇ ern y´ , I.; Pouzar, V.; Kr a´ l, V. M.; Dra sˇ ar, P.
(
27), 652 (12), 666 (6), 686 (45), 1238 (6). For the range of
the molecular ion (1230–1244, enlarged) 1232.5 (25),
233.6 (38), 1234.5 (62), 1235.5 (91), 1236.4 (88), 1237.5
85), 1238.4 (100), 1239.6 (65), 1240.5 (42), 1241.4 (38),
242.5 (8).
1
(
1
Chem. Listy 2001, 95, 749–750. (e) Dukh, M.; Cˇ ern y´ , I.;
Urbansk y´ , M.; Pouzar, V.; Kr a´ l, V.; Dra sˇ ar, P. Czech 290491,
June 5, 2002; Czech Pat. Appl. PV3098-99, August 31, 1999.
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1
ˇ
B.; Zini c´ , M. Chem. Eur. J. 2001, 15, 3328–3341.
Acknowledgements
The support from the research project Z4 055 905 (IC, DS)
12. Shaul, M.; Cohen, Y. J. Org. Chem. 1999, 64, 9358–9364.
1
3. Cortese, F.; Bauman, L. J. Am. Chem. Soc. 1935, 57,
1393–1395.