2,3ꢀDihydroꢀ1Hꢀcyclopenta[a]naphthalenes
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 12, December, 2008
2571
1,8ꢀDimethoxyꢀ5ꢀmethylꢀ2,3ꢀdihydroꢀ1Hꢀcyclopenta[a]ꢀ
naphthalene (17). Potassium hydroxide (10.8 g, 192.8 mmol) was
added in one portion to a solution of indanol 15 (10.99 g,
48.2 mmol) in DMSO (100 mL). Then MeI (6.84 g, 48.2 mmol)
was added dropwise for 5 min. After 70 min, an additional porꢀ
tion of MeI (6.84 g, 48.2 mmol) was added dropwise. The reacꢀ
tion mixture was stirred at room temperature for 2 h and poured
into water (400 mL). The product was extracted with CH2Cl2
(3×100 mL). The combined organic extracts were washed with
water (3×100 mL), dried over Na2SO4, and concentrated in waꢀ
ter aspirator vacuum. The yield of compound 17 was 11.08 g
(45.8 mmol, 95%). Found (%): C, 79.30; H, 7.50. C16H18O2.
Calculated (%): C, 79.31; H, 7.49. 1H NMR (CDCl3), δ: 7.91
(d, 1 H, H(6), J = 9.19 Hz); 7.47 (d, 1 H, H(9), J = 2.66 Hz);
7.15 (dd, 1 H, H(7), J1 = 9.19 Hz, J2 = 2.66 Hz); 7.10 (s, 1 H,
H(4)); 5.70 (m, 1 H, CHOMe); 3.95 (s, 3 H, OMe); 3.45 (s, 3 H,
CHOMe); 3.23 (m, 1 H, CHHCHOMe); 2.91 (m, 1 H,
CHHCHOMe); 2.67 (s, 3 H, Me); 2.57 (m, 1 H, CHH); 2.16
(m, 1 H, CHH). 13C NMR (CDCl3), δ: 158.34, 142.47, 136.87,
136.26, 127.79, 126.81, 126.63, 122.27, 117.58, 103.48, 76.46,
74.23, 55.78, 35.73, 31.28, 20.16.
82%). 1H NMR (DMSOꢀd6), δ: 9.48 (s, 1 H, 13ꢀOH); 9.21 (s, 1 H,
1ꢀOH); 7.77 (br.s, 1 H, H(14)); 7.75 (d, 1 H, H(3), J = 9.05 Hz);
7.60 (d, 1 H, H(11), J = 9.05 Hz); 7.04 (s, 1 H, H(9)); 7.01 (dd, 1 H,
H(12), J1 = 9.05 Hz, J2 = 2.50 Hz); 6.85 (d, 1 H, H(2),
J = 9.05 Hz); 6.84 (s, 1 H, H(5)); 4.83 (d, 1 H, J = 5.30 Hz); 3.60
(m, 1 H); 3.38 (s, 3 H, 10ꢀM); 3.12, 2.94 (both m, 1 H each); 2.52
(s, 3 H, 4ꢀMe); 2.50, 2.42, 1.87, 1.75 (all m, 1 H each). 13C NMR
(DMSOꢀd6), δ: 154.36, 154.20, 141.93, 141.00, 138.50, 135.80,
134.37, 133.09, 132.04, 131.07, 126.30, 125.91, 125.56, 124.28,
122.06, 121.12, 118.64, 117.13, 115.86, 111.15, 67.88, 49.11,
45.00, 42.82, 33.18, 31.74, 31.28, 20.18.
1. W. Vance, D. Levin, Environ. Mutagen, 1984, 6, 797.
2. N. G. Kundu, J. Med. Chem., 1980, 23, 512.
3. E. Aitola, A. Puranen, H. Setala, S. Lipponen, L. Sami,
J. Polym. Sci. (A), Polym. Chem., 2006, 44, 6569.
4. U. Stehling, J. Diebold, R. Kirsten, W. Roell, H. H. Brintꢀ
zinger, S. Juengling, R. Muelhaupt, F. Langhauser, Organoꢀ
metallics, 1994, 13, 964.
1,13ꢀDimethoxyꢀ4,10ꢀdimethylꢀ6,7,7a,7b,8,14cꢀhexahydroꢀ
benzo[6,7]indeno[1,2ꢀa]cyclopenta[cd]phenalene (19) and 8,8´ꢀ
dimethoxyꢀ5,5´ꢀdimethylꢀ2,3ꢀdihydroꢀ1H,3´Hꢀ1,2´ꢀbi(cycloꢀ
penta[a]naphthalene) (20). Concentrated HCl (0.5 mL) was addꢀ
ed to a boiling solution of indanol 15 (0.428 g, 2 mmol) in benꢀ
zene (50 mL). The reaction mixture was refluxed using a Dean—
Stark trap until the starting compound was completely consumed
(TLC, hexane—dichloromethane, 1 : 1). Then the mixture was
poured into saturated NaHCO3 (150 mL), the organic phase was
separated, and the solvent was removed in water aspirator vacuꢀ
um. The reaction products were separated by column chromaꢀ
tography with hexane—dichloromethane (1 : 1) as an eluent. The
yield of compound 19 was 0.209 g (0.497 mmol, 50%). The yield
of compound 20 was 0.114 g (0.271 mmol, 27%).
Compound 19. 1H NMR (CDCl3), δ: 7.86 (d, 1 H, H(3),
J = 9.37 Hz); 7.80 (d, 1 H, H(14), J = 2.63 Hz); 7.75 (d, 1 H, H(11),
J = 9.38 Hz); 7.15 (s, 1 H, H(9)); 7.13 (dd, 1 H, H(12), J1 = 9.38
Hz, J2 = 2.64 Hz); 7.02 (d, 1 H, H(2), J = 9.38 Hz); 6.95 (s, 1 H,
H(5)); 5.03 (d, 1 H, J = 5.56 Hz); 4.03 (s, 3 H, 13ꢀOMe); 3.73,
3.29 (both m, 1 H each); 3.12 (s, 3 H, 1ꢀOMe); 3.01 (m, 1 H);
2.63 (s, 3 H, 10ꢀMe); 2.63 (m, 1 H); 2.59 (s, 3 H, 4ꢀMe); 2.42,
2.00 (both m, 1 H each).
Compound 20. 1H NMR (CDCl3), δ: 7.92 (d, 1 H, H(6),
J = 9.38 Hz); 7.91 (d, 1 H, H(6´), J = 9.38 Hz); 7.30 (d, 1 H,
H(9), J = 2.64 Hz); 7.20 (s, 2 H, H(4), H(4´)); 7.19 (d, 1 H,
H(9´), J = 2.64 Hz); 7.14 (dd, 1 H, H(7), J1 = 9.38 Hz, J2 = 2.64 Hz);
7.08 (dd, 1 H, H(7´), J1 = 9.38 Hz, J2 = 2.64 Hz); 7.06 (br.s, 1 H,
H(1´)); 4.86 (m, 1 H, CHCH2); 3.94 (s, 3 H, 8ꢀOMe); 3.65 (s, 3 H,
8´ꢀOMe); 3.45 (m, 1 H); 3.27 (m, 2 H); 3.05 (m, 1 H); 2.70 (s, 3 H,
5ꢀMe); 2.64 (s, 3 H, 5´ꢀMe); 2.63, 2.26 (both m, 1 H each).
4,10ꢀDimethylꢀ6,7,7a,7b,8,14cꢀhexahydrobenzo[6,7]indenoꢀ
[1,2ꢀa]cyclopenta[cd]phenaleneꢀ1,13ꢀdiol (23). pꢀTolueneꢀ
sulfonic acid monohydrate (0.59 g, 2.68 mmol) was added in one
portion to a boiling solution of indanol 16 (0.5745 g, 2.6815 mmol)
in toluene (50 mL). After 60 s, the solution was filtered through
a short column (10 cm) with silica gel. The silica gel was washed
with CH2Cl2 (200 mL). The combined solutions were concenꢀ
trated in water aspirator vacuum. The product was additionally
purified by column chromatography with THF—hexane (2 : 5) as
an eluent. The yield of compound 23 was 0.432 g (1.102 mmol,
5. V. V. Izmer, A. Y. Lebedev, M. V. Nikulin, A. N. Ryabov,
A. F. Asachenko, A. V. Lygin, D. A. Sorokin, A. Z. Voskꢀ
oboynikov, Organometallics, 2006, 25, 1217.
6. T. Seraidaris, B. Lofgren, J. Polym. Sci. (A), Polym. Chem.,
2005, 43, 6455.
7. J. S. Moffatt, J. Chem. Soc. (C), 1966, 734.
8. G. M. Badger, W. Carruthers, J. W. Cook, J. Chem. Soc. (C),
1952, 4996.
9. J. R. Merchant, R. B. Upasani, Chem. Ind. (London), 1980,
11, 466.
10. G. A. R. Kon, F. C. J. Ruþièka, J. Chem. Soc. (C), 1935, 187.
11. B. P. Taduri, Y. Ran, C. Huang, R. Liu, Org. Lett., 2006,
8, 883.
12. A. Odedra, C. Wu, B. P. Taduri, Y. Ran, C. Huang, R. Liu,
J. Am. Chem. Soc., 2005, 127, 3406.
13. J. Svoboda, Z. Kocfeldova, J. Paleèek, Coll. Czech. Chem.
Commun., 1988, 53, 822.
14. L. F. Tietze, T. Eicher, Reaktionen und Synthesen im orgaꢀ
nischꢀchemischen Praktikum und Forschungslaboratorium,
Georg Thieme Verlag, Stuttgart—New York, 1991.
15. C. F. H. Allen, J. VanAllan, Org. Synth., 1955, 3, 733.
16. P. Di Raddo, R. G. Harvey, Tetrahedron Lett., 1988, 29, 3885.
17. E. A. A. Wallen, A. M. C. Christiaans, S. M. Saario, M. M.
Forsberg, J. I. Venalainen, P. M. Hanna, M. T. Pekka,
J. Gynther, Bioorg. Med. Chem., 2002, 10, 2199.
18. J. Wang, Q. Ji, J. Xu, X. Wu, Y. Xie, Synth. Commun., 2005,
35, 581.
19. G. Majetich, R. Hicks, S. Reister, J. Org. Chem., 1997,
62, 4321.
20. E. A. Braude, L. M. Jackman, R. P. Linstead, G. Lowe,
J. Chem. Soc., 1960, 3123.
21. J. F. W. McOmie, M. L. Watts, D. E. West, Tetrahedron,
1968, 24, 2289.
22. I. V. Taidakov, I. E. Nifant´ev, M. Yu. Talanova, K. A. Lysꢀ
senko, Izv. Akad. Nauk, Ser. Khim., 2004, 860 [Russ. Chem.
Bull., Int. Ed., 2004, 53, 897].
Received August 29, 2008;
in revised form October 20, 2008