A new approach to the synthesis of chromene derivatives

Article abstract of DOI:10.1081/SCC-100104009

3-Acetyl-5,6-benzopyran and 3-benzoyl-5,6-benzopyran have been simply prepared by condensation of methylvinyl ketone and phenylvinyl ketone with salicylaldehyde in an aqueous DABCO medium at room temperature.

Full text of DOI:10.1081/SCC-100104009

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A NEW APPROACH TO THE
SYNTHESIS OF CHROMENE
DERIVATIVES
Subramanian Ravichandran a
a School of Chemistry, University of Hyderabad ,
Hyderabad, 500 046, India
Published online: 09 Nov 2006.
To cite this article: Subramanian Ravichandran (2001) A NEW APPROACH TO THE
SYNTHESIS OF CHROMENE DERIVATIVES, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 31:8, 1233-1235,
DOI: 10.1081/SCC-100104009
To link to this article: http://dx.doi.org/10.1081/SCC-100104009
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SYNTHETIC COMMUNICATIONS, 31(8), 1233–1235 (2001)
A NEW APPROACH TO THE SYNTHESIS
OF CHROMENE DERIVATIVES
Subramanian Ravichandran
School of Chemistry, University of Hyderabad,
Hyderabad – 500 046, India
ABSTRACT
3-Acetyl-5,6-benzopyran and 3-benzoyl-5,6-benzopyran
have been simply prepared by condensation of methylvinyl
ketone and phenylvinyl ketone with salicylaldehyde in an
aqueous DABCO medium at room temperature.
Some chromene derivatives1–4 might prove useful synthetic intermedi-
ates for the synhesis of certain naturally occurring substances, such as
Miroestrol.5 Also, in a study of the photochemistry of some structurally
related unsaturated ketones, the chromenes were needed. Many works
describing chromene derivatives preparation have been reported. Attempts
to prepare 3-acetyl-5,6-benzopyran, 3-benzoyl-5,6-benzopyran, and 1:2-
benzopyran-3-carboxaldehyde by the method of Taylor and Tamlinson6
gave only polymeric mixtures. Attempts to convert 1:2-benzopyran-
3-carboxylic acid to 1:2-benzopyran-3-carboxaldehyde, 1:2-benzopyran-
3-methylcarboxylate, or 3-benzoyl-5,6-benzopyran by conventional
reactions (Friedal-Crafts, Grignard, reduction, etc.) also failed, or at best
gave poor yields with many side-products. Later, DeBoer reported7 vapor-
1233
Copyright & 2001 by Marcel Dekker, Inc.
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1234
RAVICHANDRAN
phase introduction of vinyl ketones in Michael addition, which apparently
prevents polymerization and gives desired products in reasonable yields. In
recent years, Kaye and Robinson8 attempted to prepare chromene deriva-
tives, but the isolated yields were very low.
Recently, it has been reported that polyfunctional vinylic compounds
can be prepared by using 1,4-diazabicyclo[2.2.2]octane (DABCO) as a
catalyst by coupling various aldehydes with monofunctional vinylic sub-
strates9–13 Accidently, I undertook an investigation to prepare chromene
derivatives (1a–1f). It seems desirable to publish some of my results at
this stage. During my study in this direction, I first carried out the reaction
of salicylaldehyde(0.6106 g, 5 mM) in water (5 mL) and 20 mol% of 1,4-
diazabicyclo[2.2.2]octane (DABCO), followed by 10 mM (0.83 mL) of
methyl vinyl ketone (mvk), and the stirring continued at room temperature
for 2 h. Then the reaction mixture was acidified with 2 mL of concentrated
HCl and the lower layer was separated, washing the water layer with
dichloromethane (DCM). The organic layer was dried and, after vacuum
distillation, provided the desired 3-acetyl-5,6-benzopyran (2a) in 73% yield
Scheme 1.
Table 1. Synthesis of Chromene Derivativesa,b
Compound
R
Yieldc(%)
M.p.(ꢀC)
1a
1b
1c
1d
1e
1fd
COOMe
COCH3
COC6H5
CN
CHO
COOH
74
73
71
79
73
77
171
51–54
63
52
69–71
187
aAll reactions were carried out in 5 mM scale of salicylaldehyde in water (5 mL) and
20 mol% DABCO, followed by 10 mM of the corresponding substrates at room
temperature for 2 h.
bSatisfactory spectral data IR, 1H (200 MHz), and 13C NMR (50 MHz) and elemen-
tal analysis14 were obtained.
cIsolated yields after column chromatography (silica gel, 1% ethyl acetate in hexane).

CHROMENE DERIVATIVES
1235
(1.273 g). This interesting result encourages me to continue my investiga-
tions with other substrates, like 1b–1e under similar reaction conditions to
provide a simple and convenient synthesis of chromene derivatives (2a–2e)
in reasonable yields Table 1, Scheme 1.
In conclusion, this condensation method offers an alternative route for
the simple synthesis of chromene and takes advantage over the vapor-phase
introduction.7
ACKNOWLEDGMENTS
SR thanks his brothers SS and Dr. SP for financial support and con-
stant encouragement in research. SR also thanks COSIST programme in
organic synthesis in the School of Chemistry, University of Hyderabad.
REFERENCES AND NOTES
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2. Heathcock, C.H.; Pirrung, M.C. J. Org. Chem. 1974, 39, 2426.
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4. Bachman, L. J. Am. Chem. Soc. 1948, 70, 599.
5. Corey, E.J.; Lawrence, I. J. Am. Chem. Soc. 1993, 115, 9327.
6. Taylor, H.V.; Tomlinson, M.L. J. Chem. Soc. Chem. Commun. 1950,
50, 272.
7. DeBoer, J. Org. Chem. 1974, 39, 2426.
8. Kaye, P.T.; Robinson, R.S. Synth. Commun. 1996, 26, 2085–2097.
9. Basavaiah, D.; Bharathi, T.K.; Gowriswari, V.V.L. Synth. Commun.
1987, 17, 1893.
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13. Fikentcher, R.; Hahn, E.; Kud, A.; Oftring, A. Chem. Abstr. 1986,
105, 115538k.
14. Elemental analysis calculated for (1d) C10H7ON: C, 76.4; H, 4.5; N
8.9% and found C, 76.3; H, 4.7; N, 8.7. Elemental analysis calculated
for (1f) C10H8O3: C, 68.2; H, 4.5% and found C, 68.4; H, 4.6.
Accepted June 16, 2000