G. R. Martinez et al. / Tetrahedron 62 (2006) 10762–10770
10769
´
ꢀ
Desenvolvimento Cientıfico e Tecnologico)—Instituto do
until pH w1 and the solid was separated by filtration. MS
(ESIꢂ): m/z¼409 [MꢂH]ꢂ, 365 [MꢂCO2ꢂH]ꢂ, 321
[Mꢂ2CO2ꢂH]ꢂ, and 277 [Mꢂ3CO2–H]ꢂ. The decarboxyl-
ation was done by keeping the solid at 120 ꢀC for 5 days to
get ADPA. MS (ESIꢂ): m/z¼321 [MꢂH]ꢂ and 277
[MꢂCO2–H]ꢂ.
^
Milenio Redoxoma, FAPESP (Fundac¸ao de Amparo a Pes-
quisa do Estado de Sao Paulo) and the John Simon Memorial
~
ꢁ
~
Guggenheim Foundation (P.D.M. Fellowship). G.R.M. was
post-doctorate recipients of FAPESP fellowship. G.E.R.
and M.C.B.O. are Ph.D. and post-doctorate recipients of
FAPESP fellowship, respectively.
4.4. Synthesis of diethyl 9,10-anthracenedipropionate
(DEADP)
References and notes
The ADPA was subsequently used for the synthesis of
DEADP by acid-catalyzed esterification.35 In this way,
150 mg of ADPA (0.47 mmol) was refluxed in 23 mL of
ethanol and 0.1 mL of H2SO4 (95%) during 2 h. Dean–Stark
trap was settled in the presence of 6 mL of toluene and the
reflux was left for 4 h. The organic phase was washed with
5% aqueousNaHCO3, dried, and evaporated to yield DEADP
as a oil. MS (ESI+): m/z¼379 [M+H]+ and 396 [M+Na]+.
1. Kanofsky, J. R. Chem. Biol. Interact. 1989, 70, 1.
2. Steinbeck, M.; Khan, A.; Karnovsky, M. J. Biol. Chem. 1992,
267, 13425.
3. Babior, B. M.; Takeuchi, C.; Ruedi, J.; Gutierrez, A.;
Wentworth, P. Proc. Natl. Acad. Sci. U.S.A. 2003, 100,
3031.
4. Wentworth, P.; Jones, L. H.; Wentworth, A. D.; Zhu, X. Y.;
Larsen, N. A.; Wilson, I. A.; Xu, X.; Goddard, W. A.; Janda,
K. D.; Eschenmoser, A.; Lerner, R. A. Science 2001, 293,
1806.
4.5. Synthesis of N,N0-di(2,3-dihydroxypropyl)-9,10-
anthracenedipropanamide (DHPA)
5. Foote, C. S.; Peterson, E. R.; Lee, K. W. J. Am. Chem. Soc.
1972, 94, 1032.
6. McCall, D. B. Ph.D. Thesis, Wayne State University, 1984.
7. Kreitner, M.; Ebermann, R.; Alth, G. J. Photochem. Photobiol.,
B 1996, 36, 109.
8. Foote, C. S.; Clennan, E. L. Active oxygen in chemistry; Foote,
C. S., Valentine, J. S., Greenberg, A., Liebman, J. F., Eds.;
Chapman and Hall: London, 1995; Vol. 2, p 105.
9. MacManus-Spencer, L. A.; Latch, D. E.; Kroncke, K. M.;
McNeill, K. Anal. Chem. 2005, 77, 1200.
10. Moureu, C.; Dufraisse, C.; Dean, P. M. C.R. Acad. Sci. 1926,
182, 1584.
11. Dufraisse, C.; Velluz, L. Bull. Soc. Chim. Fr. 1942, 9, 171.
12. Wasserman, H.; Scheffer, J. R. J. Am. Chem. Soc. 1967, 89,
3073.
The amidation of the diester DEADP with 3-amino-1,2-pro-
panediol was made by stirring, under reflux, a solution of
DEADP (80 mg, 0.21 mmol) and 3-amino-1,2-propanediol
(0.2 g, 2.2 mmol) in 7 mL methanol and 4 mL of isopropa-
nol for 24 h. After evaporation of the solvent, the residue
was triturated with 20 mL of acetone. The colorless precip-
itate was filtered by suction, rinsed with acetone, and recrys-
tallized in methanol (yield: 40.5 mg, 41%). MS (ESI+):
m/z¼491 [M+Na]+. 1H NMR (CD3OD): d 2.66 (4H, t,
J¼8.3 Hz), 3.17 (2H, dd, J¼13.8, 6.8 Hz), 3.31 (2H, dd),
3.38 (2H, dd, J¼11.5, 4.9 Hz), 3.59 (2H, m), 3.95 (4H, t,
J¼8.3 Hz), 7.54 (4H, dd, J¼6.9, 3.3 Hz), 8.41 (4H, dd,
J¼6.9, 3.2 Hz). 13C NMR (CD3OD): d 24.8 (CH2), 38.0
(CH2), 43.2 (CH2), 64.5 (CH2), 71.5 (CH), 125.8 (CH),
126.2 (CH), 130.4 (C), 133.2 (C), 175.4 (C]O). The solu-
bility in water is around 0.8 mM.
13. Aubry, J. M.; Pierlot, C.; Rigaudy, J.; Schmidt, R. Acc. Chem.
Res. 2003, 36, 668.
14. Miyamoto, S.; Martinez, G. R.; Rettori, D.; Augusto, O.;
Medeiros, M. H. G.; Di Mascio, P. Proc. Natl. Acad. Sci.
U.S.A. 2006, 103, 293.
4.6. Endoperoxide of N,N0-di(2,3-dihydroxypropyl)-
9,10-anthracenedipropanamide
15. Miyamoto, S.; Martinez, G.; Medeiros, M. H. G.; Di Mascio, P.
J. Am. Chem. Soc. 2003, 125, 6172.
16. Miyamoto, S.; Martinez, G.; Martins, A. P. B.; Medeiros,
M. H. G.; Di Mascio, P. J. Am. Chem. Soc. 2003, 125, 4510.
17. Aubry, J. M.; Rigaudy, J.; Cuong, N. K. Photochem. Photobiol.
1981, 33, 149.
18. Lindig, B. A.; Rodgers, M. A. J.; Schaap, A. P. J. Am. Chem.
Soc. 1980, 102, 5590.
19. Di Mascio, P.; Sies, H. J. Am. Chem. Soc. 1989, 111, 2909.
20. Botsivali, M.; Evans, D. F. J. Chem. Soc., Chem. Commun.
1979, 1114.
The chemical trap capacity of DHPA was evaluated by the
reaction with 1O2, generated by photooxidation or by naph-
thalene endoperoxide thermolysis. The photooxidation was
performed in methanol without sensitizer and it was fol-
lowed by the loss of UV–vis absorption in 372 nm and by
HPLC analysis. In order to further confirm the identity of
the product formed, the reaction was performed with
DHPA (0.8 mM) and DHPNO2 (0.5 mM) or 18O-labeled
naphthalene endoperoxide (DHPN18O2, 0.5 mM) under
argon atmosphere at 37 ꢀC for 2 h. The products were
submitted to HPLC separation and ESI+-MS analysis. The
DHPA UV–vis spectrum was followed along the time of
incubation. For comparison, a known chemical trap (EAS,
0.8 mM) was also submitted to the same conditions of
reaction and its spectrum was also recorded.
21. Nardello, V.; Aubry, J.-M.; Johnston, P.; Bulduk, I.; Vries,
A. H. M.; Alsters, P. L. Synlett 2005, 2667.
22. Tanaka, K.; Miura, T.; Umezawa, N.; Urano, Y.; Kikuchi, K.;
Higuchi, T.; Nagano, T. J. Am. Chem. Soc. 2001, 123, 2530.
23. Nardello, V.; Aubry, J. M. Tetrahedron Lett. 1997, 38, 7361.
24. Nardello, V.; Azaroual, N.; Cervoise, I.; Vermeersch, G.;
Aubry, J. M. Tetrahedron 1996, 52, 2031.
Acknowledgements
25. Nardello, V.; Brault, D.; Chavalle, P.; Aubry, J. M.
J. Photochem. Photobiol., B 1997, 39, 146.
This work was supported by the Brazilian research
funding institutions: CNPq (Conselho Nacional para o
26. Dewilde, A.; Pellieux, C.; Pierlot, C.; Wattre, P.; Aubry, J. M.
Biol. Chem. 1998, 379, 1377.