P. Kutschy et al. / Tetrahedron Letters 42 (2001) 9281–9283
9283
14b–14e by cyclization of thiocarbamates 12b–12e in
37–55% yield. The biological activity of the synthesized
compounds and experimental details for the synthesis
of further analogs will be published elsewhere.
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Experimental procedure for photocyclization: To a
stirred solution of thiocarbamate 12a–12e (1 mmol) in
methanol (200 ml) was added triethylamine (0.202 g,
0.28 ml, 2 mmol) and the mixture was irradiated (high
pressure mercury lamp, Tesla RVK-125) through a
Pyrex filter in a water-cooled immersed apparatus for
35 min (12a, 12c–12e) or 75 min (12b). Nitrogen gas
was bubbled through the solution for 15 min before
irradiation and during the reaction. After evaporation
of the methanol, the residue was dissolved in chloro-
form (5 ml) and chromatographed on 50 g of silica gel
(benzene/acetone 7:1). The eluate was evaporated and
thiazinoindoles 14a–14e were crystallized from an
appropriate solvent (14a, 14b–14c acetone/cyclohexane;
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Spectral data for 9-methylcyclobrassinon (14a): Yield
33%, mp 202–205°C. IR (CHCl3, cm−1): 1580 and 1650
(CꢁN-CꢁO). 1H NMR (500 MHz, CDCl3, l, ppm): 3.69
(s, 3H, NCH3); 4.17 (s, 3H, OCH3); 7.13–7.50 (m, 3H,
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H
arom.); 8.25–8.55 (m, 1H, Harom.). 13C NMR (125
13. Kutschy, P.; Dzurilla, M.; Takasugi, M.; To¨ro¨k, M.;
Achbergerova´, I.; Homzova´, R.; Ra´cova´, M. Tetrahedron
1998, 54, 3549–3566.
14. Suchy´, M.; Kutschy, P.; Monde, K.; Goto, H.; Harada,
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63, 681–690; (b) Andreani, A.; Rambaldi, M.; Bonazzi,
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16. In this case we could not use the direct transformation of
aldehyde 8a to acid bromide under the conditions
employed in the synthesis of cyclobrassinon,8 because of
the decomposition of the starting compound.
17. Kutschy, P.; Dzurilla, M.; Takasugi, M.; Sabova´, A. Coll.
Czech. Chem. Commun. 1999, 64, 348–362.
MHz, CDCl3, l, ppm): 30.72 (NCH3), 57.68 (OCH3),
102.70 (C), 108.58 (CH), 121.79 (CH), 122.50 (CH),
124.06 (CH), 125.07 (C), 138.27 (C), 139.49 (C), 164.54
and 166.42 (CꢁN-CꢁO). EIMS: [70 eV, m/z (%)]: 246
(M+, 61), 189 (100), 160 (15), 117 (25), 89 (10). Anal.
calcd for C12H10N2O2S: C, 58.52; H, 4.09; N, 11.37.
Found: C, 58.37; H, 3.88, N, 11.52.
Acknowledgements
We thank the Grant Agency for Science, Slovak
Republic (Grant No. 1/6080/99) for financial support of
this work.
18. Comber, M. F.; Moody, C. J. Synthesis 1992, 731–733.
19. Olesen, P. H.; Hansen, J. B.; Engelstoff, M. J. Hetero-
cycl. Chem. 1995, 32, 1641–1642.
20. Sun, L.; Rubin, J. R.; Kraker, A. J.; Showalter, H. D. J.
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