Journal of Chemistry
5
e hydrogen of the methyl group correlated with C7 at ꢁ
135.3, and H5 correlated with C8a at ꢁ 152.8 and C7 at ꢁ
135.3. In EIMS spectrum, the molecular ion at m/z 204 was
observed, in addition to the base peak at m/z 160 assigned
to ion-fragment [M − 44]+∙; some other worthy of note
fragments are m/z 187 [M − 17]+, m/z 132 [M − 72]+∙, and m/z
103 [M − 101]+. Finally, the respective HRMS-DART+ results
were in agreement with the expected elemental composition,
C H O : calculated m/z 205.0501 and experimental m/z
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[8] H. von Pechmann, “Neue bildungsweise der cumarine. Syn-
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11
9
4
205.0509 (3.80 ppm error) [M + H]+.
[9] J. R. Johnson, “e Perkin and related reactions,” Organic
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4. Conclusions
[10] G. Brufola, F. Fringuelli, O. Piermatti, and F. Pizzo, “Simple
and efficient one-pot preparation of 3-substituted coumarins in
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In conclusion, coumarin-3-carboxylic acids 3a–e have been
prepared using a one-pot procedure, where the best syn-
thetic strategy was obtained in solution conditions. Different
activating energy sources were employed, providing several
environmental benefits: less energy consumption, product
isolation by simple filtration, and use of ethanol as a green
solvent, without catalyst and very good atom economy. In
other words, the overall process occurs with a good incidence
in the Green Chemistry Protocol (the twelve principles). e
NIR irradiation is proposed as a new alternative and as a clean
energy to produce this kind of molecules.
[11] R. L. Shriner, “e Reformatsky reaction,” Organic Reactions,
vol. 1, pp. 1–37, 1942.
[12] I. Yavari, R. Hekmat-Shoar, and A. Zonouzi, “A new and efficient
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Claisen-cope rearrangements of coumarate derivatives. Total
syntheses of the naturally occurring coumarins: suberosin,
demethylsuberosin, ostruthin, balsamiferone and gravellifer-
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21, pp. 3101–3107, 1994.
[14] K. Pihlaja, M. Seilo, U. Svanholm, A. M. Duffield, A. T.
Balaban, and J. C. Craig, “e acidity and general base-catalyzed
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Competing Interests
e authors declare no potential conflict of interests.
[15] M. O. Noguez, V. Marcelino, H. Rodr´ıguez et al., “Infrared
assisted production of 3,4-dihydro-2(1H)-pyridones in solvent-
free conditions,” International Journal of Molecular Sciences, vol.
12, no. 4, pp. 2641–2649, 2011.
[16] V. V. Lipson and N. Y. Gorobets, “One hundred years of
Meldrum’s acid: advances in the synthesis of pyridine and
pyrimidine derivatives,” Molecular Diversity, vol. 13, no. 4, pp.
399–419, 2009.
[17] A. S. Ivanov, “Meldrum’s acid and related compounds in the
synthesis of natural products and analogs,” Chemical Society
Reviews, vol. 37, no. 4, pp. 789–811, 2008.
[18] R. Maggi, F. Bigi, S. Carloni, A. Mazzacani, and G. Sartori,
“Uncatalysed reactions in water—part 2. Preparation of 3-
carboxycoumarins,” Green Chemistry, vol. 3, no. 4, pp. 173–174,
2001.
[19] B. P. Bandgar, L. S. Uppalla, and D. S. Kurule, “Solvent-free
one-pot rapid synthesis of 3-carboxycoumarins: using focused
microwaves,” Green Chemistry, vol. 1, no. 5, pp. 243–245, 1999.
[20] B. Bandgar, L. Uppalla, and V. Sadavarte, “Lithium perchlorate
and lithium bromide catalysed solvent free one pot rapid
synthesis of 3-carboxycoumarins under microwave irradiation,”
Journal of Chemical Research, vol. 2002, no. 1, pp. 40–41, 2002.
[21] A. Song, X. Wang, and K. S. Lam, “A convenient synthesis of
coumarin-3-carboxylic acids via Knoevenagel condensation of
Meldrum’s acid with ortho-hydroxyaryl aldehydes or ketones,”
Tetrahedron Letters, vol. 44, no. 9, pp. 1755–1758, 2003.
Acknowledgments
e authors appreciate the financial support to the
Ca´tedra Qu´ımica Verde-PIAPIC13, FESC-UNAM, and
also CONACyT-Me´xico 205289 for the postdoctoral
scholarship to Joel Mart´ınez.
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