MRC Letters
Received: 31 May 2012
Revised: 19 August 2012
Accepted: 20 August 2012
Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI 10.1002/mrc.3873
1H and C NMR spectral assignments of novel
13
chromenylchalcones
Hyuk Yoon,a Seunghyun Ahn,b Doseok Hwang,a Geunhyeong Jo,a
Dong Woon Kim,c Sang Ho Kim,c Dongsoo Kohb and Yoongho Lima*
Several types of chalcones containing 2H-chromen group were synthesized. Claisen–Schmidt condensation of 2H-chromen-3-
carbaldehydes (I) with methoxy substituted acetophenones afforded (E)-3-(2H-chromen-3-yl)-1-(methoxyphenyl)prop-2-en-1-
ones (chromenylchalcones, 1–7). Other types of chromenylchalcone, (E)-1-(6-methoxy-2H-chromen-3-yl)-3-(methoxyphenyl)
prop-2-en-1-ones (8–13) were also obtained between reaction of methoxy substituted benzaldehydes and 1-(6-methoxy-2H-
chromen-3-yl)ethanone (II). Dichromenylchalcones (14–16) were also synthesized through the same reaction between
1
aldehydes (I) and ketone (II). Their complete H-NMR and 13C-NMR assignments are reported here and more polysubstituted
chromenylchalcones synthesized or isolated from the natural sources in the future can be identified on the basis of the NMR
data reported here. Copyright © 2012 John Wiley & Sons, Ltd.
Keywords: NMR; 1 H NMR; 13C NMR; 2D NMR; flavonoid; chalcone
methylvinylketone followed by intramolecular aldol condensa-
tion accounts for the formation of chromene aldehydes (I) or
Introduction
Chalcones are one of the secondary metabolites in plants and
belong to a flavonoid class with C6-C3-C6 skeletone, which are
named A, C, and B-ring [Fig. 1{A)]. Instead of a closed C-ring of
flavonoid, however, C3 skeleton of chalcone is a,b-unsaturated
carbonyl group [Fig. 1(B)]. Because of their diverse biological
activities, various chalcones have been isolated from natural
sources and synthesized, and their NMR data have been
reported.[1–3] Benzoflavones are one of the flavonoids, too, and
contain one more benzene ring attached to A-ring [Fig. 1(C)].
It has been known that they act as potent inhibitors of breast
cancer resistance protein.[4,5] Because of diverse biological activities
of chalcones and benzoflavones, we designed three types of novel
chromenylchalcones combined with chalcone and chromenes,
which are analogs of benzoflavone, and synthesized them: seven
(E)-3-(2H-chromen-3-yl)-1-phenylprop-2-en-1-ones [Fig. 1(D)], six
(E)-1-(6-methoxy-2H-chromen-3-yl)-3-phenylprop-2-en-1-ones [Fig. 1
(E)], and three (E)-3-(2H-chromen-3-yl)-1-(6-methoxy-2H-chromen-3-yl)
prop-2-en-1-ones [Fig. 1(F)]. Because their NMR data can help us
identify newly isolated or synthesized chromenylchalcone deriva-
chromene methyl ketone (II). Claisen–Schmidt condensation of
chromene aldehydes (I) with methoxy substituted acetophenone
under basic conditions afforded (E)-3-(2H-chromen-3-yl)prop-2-en-1-
ones (chromenylchalcones, 1–7) as we described in the previous
report.[6] When chromene methyl ketone (II) was treated with
methoxy substituted benzaldehydes under the same conditions,
other types of chromenylchalcone 8–13 were also obtained.
Dichromenylchalcones (14–16) were synthesized through the
same reaction between chromene aldehydes (I) and chromene
methyl ketone (II). To confirm the structures of the synthetic
compounds, mass spectrometry was performed on a high-resolution
electron impact ionization mass spectrometer (HREIMS, JMS700, Jeol
Ltd., Tokyo, Japan).
NMR spectra
The synthetic chromenylchalcones were dissolved in DMSO-d6.
1
The H and 13C chemical shifts of the deuterated solvent were
2.50 and 39.5 ppm referenced to TMS, respectively. The NMR
samples were prepared at approximately 50 mM, and they
were transferred to a 2.5-mm NMR tube. All NMR experiments
were carried out on a Bruker Avance 400 spectrometer system
1
tives, we report here the complete H and 13C NMR data of 16
chromenylchalcones (Fig. 2).
Experimental
*
Correspondence to: Yoongho Lim, Division of Bioscience and Biotechnology, BMIC,
Konkuk University, Hwayang-Dong 1, Kwangjin-Ku, Seoul 143-701, South Korea.
Email: yoongho@konkuk.ac.kr
Synthesis
All of the chromenylchalcone derivatives (1–16) were synthe-
sized as shown in Scheme 1. Methoxy or bromo substituted
salicylaldehydes were treated with acrolein in the presence
of K2CO3 in dioxane to give corresponding 2H-chromen-3-
carbaldehydes (I). When the same conditions were applied in
reaction between 5-methoxy salicylaldehyde and methylvinylketone,
1-(6-methoxy-2H-chromen-3-yl)ethanone (II) was obtained in
good yield. Michaels addition of salicylaldehydes to acrolein or
a Division of Bioscience and Biotechnology, BMIC, Konkuk University, Seoul 143-701,
South Korea
b Department of Applied Chemistry, Dongduk Women’s University, Seoul 136-714,
South Korea
c
Swine science division, National Institute of Animal Science, RDA, Cheonan
330-801, South Korea
Magn. Reson. Chem. (2012)
Copyright © 2012 John Wiley & Sons, Ltd.