can be regarded as another example of ‘green photochemistry’17
and a further contribution to Giacomo Ciamician’s vision of
‘the photochemistry of the future’ (presented at the International
Congress of Applied Chemistry in New York in 1912).18,19
References
‡ This phenomenon is currently being further investigated. The synthesis
of Juglone starting from 1b has previously been reported.7b,10g
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Experimental
Compound 4a was synthesized as described by Jindal and co-
workers.13a All other 5-amido-1-naphthols 4b–h were prepared
following a modified procedure reported by Neidlein and
Moller.13b General procedure: 7.0 g (44 mmol) of 5-amino-1-
naphthol 3 were dissolved in 75 ml of pyridine. 60 mmol of the
corresponding acid chloride were added dropwise to the solution
at -10 ◦C. After stirring for 3 h, the reaction mixture was poured
onto ice-water. The precipitate was filtered off and washed twice
with cold water. The crude product was recrystallized from
ethanol–water or ethyl acetate–cyclohexane. Exemplary details
for 5-pivaloylamino-1-naphthol (5d). Purple solid; m.p.: 258 ◦C;
1H NMR (400 MHz, DMSO-d6): d = 1.31 (s, 9H), 6.86 (dd,
3J = 6.4, 4J = 2.4 Hz, 1H), 7.30 (dd, 3J = 6.4 Hz, 1H), 7.34-7.43
(m, 3H), 8.02 (d, 3J = 8.0 Hz, 1H), 9.37 (br. s, 1H), 10.17 ppm
(br. s, 1H). 13C NMR (100 MHz, DMSO-d6): d = 27.5, 38.9,
108.0, 113.7, 120.2, 124.0, 124.5, 126.3, 125.4, 131.1, 133.8,
153.4, 177.1 ppm; IR (KBr): n = 3284, 2970, 1655, 1599, 1577,
1493, 1408, 1274, 1209, 1141, 960, 779, 736, 555 cm-1.
General Procedure for photooxygenation
1 mmol of 5-amido-1-naphthol 4 and 50 mg of rose bengal were
dissolved in 100 ml of tert-amyl alcohol. The clear solution was
irradiated (500 W halogen lamp) or exposed to direct sunlight
in a Pyrex Schlenk-flask equipped with a cold finger and a reflux
condenser for 4, 6 or 24 h at ambient temperature while purging
with a gentle stream of air. Evaporated solvent should be refilled
whenever necessary. The progress of the reaction was monitored
by TLC analysis (SiO2, cyclohexane:ethyl acetate 3:1). The
solvent was removed under vacuum, and the residue was purified
by column chromatography (SiO2, cyclohexane:ethyl acetate
3:1). Experimental details and results are given in Table 1.
Exemplary details for 5-◦pivaloylamino-1,4-naphthoquinone (5d).
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4331; (c) D. Murtinho, M. Pineiro, M. M. Pereira, A. M. d’A.
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Burrows, J. Chem. Soc., Perkin Trans. 2, 2000, 2441–2447; (d) A. S.
Amarasekara, Synth. Commun., 1999, 29, 3063–3066; (e) H. M.
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733–737; (f) S. Croux, M.-T. Maurette, M. Hocquaux, A. Ananides,
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1
Yellow solid; m.p.: 186 C; H NMR (400 MHz, acetone-d6):
2
2
d = 1.36 (s, 9H), 7.04 (d, J = 14.4 Hz, 1H), 7.06 (d, J =
3
4
14.4 Hz, 1H), 7.78 (dd, J = 7.6, J = 1.2 Hz, 1H), 8.85 (dd,
3J = 7.6, 8.4 Hz, 1H), 9.14 (dd, J = 8.4, J = 1.2 Hz, 1H),
12.13 ppm (br. s, 1H). 13C NMR (100 MHz, CDCl3): d = 27.7,
40.8, 116.4, 121.9, 126.3, 132.3, 135.9, 138.1, 140.1, 141.9, 179.1,
184.7, 189.3 ppm; IR (KBr): n = 3249, 2965, 1687, 1646, 1604,
1577, 1491, 1408, 1304, 1254, 1152, 1100, 944, 836, 740, 550,
448 cm-1.
3
4
Acknowledgements
This research project was financially supported by Dublin City
University (Research Alliance Funds 2005 and 2008), the Irish
Research Council for Science, Engineering and Technology
(IRCSET) and the Environmental Protection Agency (EPA,
2007-PhD-ET-7). Elodie Haggiage thanks ERASMUS for a
Visiting Fellowship. The authors thank Dr Peter J. Dunn (Pfizer)
for the generous donation of tert-amyl alcohol.
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H. P. Kleine, C. Knight, M. A. Nagy, D. A. Perry and M. Stefaniak,
Green Chem., 2008, 10, 31–36.
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Yakugaku Zasshi - J. Pharm. Soc. Jpn., 1968, 88, 1602–1609.
320 | Green Chem., 2009, 11, 318–321
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