A Green Synthesis and a Chemical Study of the Coumarin, 1-(2-Hydroxy- 2-methyl-2H-chromen-3yl)ethanone

Author(s): Emerson Teixeira da Silva, Ligia Souza da Silveira Pinto, Solange Maria Silva Veloso Wardell, James Lewis Wardell, Marcus Vinícius Nora de Souza*.

Journal Name: Letters in Organic Chemistry

Volume 16 , Issue 2 , 2019

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Abstract:

Coumarins are a class of natural and synthetic products with a wide variety of applications in different fields. Due to the general importance of coumarins, the objective of this work is to further develop the chemistry of 1-(2-hydroxy-2-methyl-2H-chromen-3yl)ethanone, 1, a potentially useful and versatile coumarin but an under-reported compound in the literature. This work describes a green preparation of 1 in the absence of solvents and acids, thereby eliminating byproducts, normally obtained in classical procedures, and a mechanistic study of the reactions of 1 with nucleophiles. In addition, we report the characterisation of 1-(2-ethoxy-2-methyl-2H-chromen-3-yl)ethanone 2, via X-ray crystallography and 2D NMR spectra.

Keywords: Coumarin, green synthesis, X-ray crystallography, sonochemistry, free solvent, heterocycle.

[1]
Costa, M.; Dias, T.A.; Brito, A.; Proenca, F. Eur. J. Med. Chem., 2016, 123, 487-507.
[2]
(a) Kofinas, C.; Chinou, I.; Loukis, A.; Harvala, C.; Maillard, M.; Hostettmann, K. Phytochemistry, 1998, 48, 637-641.
(b) Cottiglia, F.; Loy, G.; Garau, D.; Floris, C.; Casu, M.; Pompei, R.; Bonsignore, L. Phytomedicine, 2001, 8, 302-305.
(c) Reyes-Chilpa, R.; Estrada-Muniz, E.; Ramirez Apan, T.; Amekraz, B.; Aumelas, A.; Jankowski, C.K.; Vazquez-Torres, M. Life Sci., 2004, 75, 1635-1647.
(d) Tada, Y.; Shikishima, Y.; Takaishi, Y.; Shibata, H.; Higuti, T.; Honda, G.; Ito, M.; Takeda, Y.; Kodzhimatov, O.K.; Ashurmetov, O.; Ohmoto, Y. Phytochemistry, 2002, 59, 649-654.
(e) Yasunaka, K.; Abe, F.; Nagayama, A.; Okabe, H.; Lozada-Perez, L.; Lopez-Villafranco, E.; Muniz, E.E.; Aguilar, A.; Reyes-Chilpa, R. J. Ethnopharmacol., 2005, 97, 293-299.
(f) Stein, A.C.; Alvarez, S.; Avancini, C.; Zacchino, S.; Von Poser, G. J. Ethnopharmacol., 2006, 107, 95-98.
(g) Zhang, W.; Brombosz, S.M.; Mendoza, J.L.; Moore, J.S. J. Org. Chem., 2005, 70, 10198-10201.
[3]
Venugopala, K.N.; Rashmi, V.; Odhav, B. BioMed Res. Int., 2013, 1-14.
[4]
Perkin, W.H. J. Chem. Soc., 1868, 21, 181-186.
[5]
Pechmann, H.; Duisberg, C. Ber. Dtsch. Chem. Ges., 1884, 17, 929-936.
[6]
Knoevenagel, E. Ber. Dtsch. Chem. Ges., 1904, 37, 4461-4463.
[7]
(a) Murray, R.D.H.; Mendez, J.; Brown, S.A. Chemistry and Biochemistry; Wiley & Sons: New York, 1982.
(b) Zahradnik, M. The Production and Application of Fluorescent Brightening Agents; Wiley & Sons: New York, 1992.
(c) O’Kennedy, R.; Thornes, R.D. Coumarins: Biology, Applications and Mode of Action; Wiley and Chichester: New York, 1997.
[8]
(a) Riveiro, M.E.; De Kimpe, N.; Moglioni, A.; Vazquez, R.; Monczor, F.; Shayo, C.; Davio, C. Curr. Med. Chem., 2010, 17, 1325-1338.
(b) Tekale, S.U. In: Ameta, K.L.; Chanthai, S. (Eds.) Natural Heterocycles. New Science Publishers: New York, , 2015.
[9]
(a) Pinto, L.S.S.; Couri, M.R.C.; de Souza, M.V.N. Curr. Org. Synth., 2017, 14, 1-17.
(b) Pinto, L.S.S.; de Souza, M.V.N. Synthesis, 2017, 49, 2677-2682.
[10]
Subbareddy, C.V.; Subashini, R.; Sumathi, S. Mol. Divers., 2017, 21, 841-848.
[11]
Data were collected at 100(2)K with Cu-Ka radiation using an Rigaku Saturn 724+ (2x2 bin mode) diffractometer of the UK National Crystallographic Service, based at the University of Southampton. Data collection, data reduction and unit cell refinement were achieved with Crystal Clear-SM Expert 3.1 b27 [12a]. Correction for absorption was achieved by an empirical absorption correction using a CrysAlisPro 1.171.39.30d [12b]. The program MERCURY [12c] were used in the preparation of the Figures. SHELXL97 [12d] and PLATON [12e] were used in the calculation of molecular geometry. The structures were solved by direct methods using SHELXS-97 [12d] and fully refined by means of the program SHELXL-97. All hydrogen atoms were placed in calculated positions.
[12]
(a) CrystalClear-SM Expert 3.1 b27: Rigaku Oxford Diffraction, 2012. (b) CrysAlisPro 1.171.39.30: Rigaku Oxford Diffraction, 2017. (c) Mercury, CCDC 2017 (d) Sheldrick, G.M. Acta Crystallogr., 2015, C71, 3-8. (e) Spek, A.L. J. Appl. Crystallogr., 2003, 36, 7.
[13]
Crystal data collected at 100(2)K; λ(CuKa) = 1.54184 Å; colourless needle: 0.3 × 0.1 × 0.05 mm; Formula: C14H16O3; M = 232.27; monoclinic, I 2/a; a = 19.1107(7) Å, α = 90°, b = 7.2653(2) Å, β = 115.962(5)°, c = 18.6673(7) Å, γ = 90°; Z = 8;V = 2230.30(17) Å3;, 2135 independent reflections [R(int) = 0.0509]; 2034 observed reflections [I > 2 σ(I)]; data / restrainsts / parameters 2135 / 0 / 157; R1 = 0.041; largest diff. Peak and hole 0.311 and -0.230 e. Å-3. Atomic coordinates, bond lengths, angles and thermal parameters have been deposited at the Cambridge Crystallographic Data Centre, deposition number 1825114
[14]
Cremer, D.; Pople, J.A. J. Am. Chem. Soc., 1975, 97, 1354-1358.
[15]
Yogavel, M.; Velmurugan, D.; Sekar, K.; Schenk, H.; Fraanje, J.; Peschar, R.; Srinivasan, S.; Athappand, P.R.; Rafie, Z.A. Acta E, 2003. E59, 0591-0593
[16]
Goodson, L.H.; Hope, C. J. Am. Chem. Soc., 1949, 71, 1117-1119.


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Article Details

VOLUME: 16
ISSUE: 2
Year: 2019
Page: [128 - 133]
Pages: 6
DOI: 10.2174/1570178615666180627103639
Price: $65

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