Functionalization of cinnamaldehyde to arylidene barbituric acid, catalyzed by Samarium(III) Chloride

Article abstract of DOI:10.13005/ojc/340565

Benzaldehyde and cinnamaldehyde were successfully condensed with barbituric acid using samarium(III) chloride in water for 2 h at room temperature. The products were confirmed through FTIR, UV-Vis and GC-MS analysis.

Full text of DOI:10.13005/ojc/340565

ISSN: 0970-020 X
CODEN: OJCHEG
2018, Vol. 34, No.(5):
Pg. 2685-2688
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
Brief Communication
Functionalization of Cinnamaldehyde to Arylidene
barbituric acid, Catalyzed by Samarium(III) Chloride
ANTONIUS HERRY CAHYANA*, BAYU ARDIANSAH and AISYAH NADILA
Department of Chemistry, FMIPA, Universitas Indonesia, Depok, 16424 Indonesia.
*Corresponding author E-mail: herrykim@ui.ac.id
http://dx.doi.org/10.13005/ojc/340565
(Received: August 16, 2018; Accepted: August 22, 2018)
ABSTRACT
Benzaldehyde and cinnamaldehyde were successfully condensed with barbituric acid using
samarium(III) chloride in water for 2 h at room temperature. The products were confirmed through
FTIR, UV-Vis and GC-MS analysis.
Keywords: Arylidene barbituric acid, Cinnamaldehyde, Functionalization,
Samarium(III) chloride, Condensation.
INTRODUCTION
used to modify aryl aldehydes is Knoevenagel
condensation. It is valuable reaction to form new
C-C bond in the production of larger fine chemicals12.
This reaction involves the abstraction of proton
from active methylene compound to give enolate
ion then undergo nucleophilic attack to carbonyl
group12. In 2006, Li et al., synthesized 5-arylidenes
barbituric acid via Knoevenagel condensation
using grinding method13.Various yields of desirable
product were found from 35-96% with 1 to 15 min.
grinding time and 120 min. laying time13. Khurana
andVij (2010) performed Knoevenagel condensation
of aromatic aldehydes with barbituric acids and
2-thiobarbituric acids using nickel nanoparticles with
medium to good yield of isolated products14. Other
investigation in Knoevenagel condensation using
both of homogeneous and heterogeneous catalysts
were found in the literature, but some of them were
accompanied with limitations, such as in catalyst
Cinnamaldehyde (C9H8O) is an aryl
aldehyde and appears as yellow oily liquid1.Naturally,
it is the main constituent (60-65%) of leaf and bark
extract of cinnamon, particularly in Indonesian
(Cinnamomum burmannii) and Indian (Cinnamomum
zeylanicum) cinnamon2,3. This compound provides
wide range of biological action, like anticancer4,
anti-inflammatory5, antibacterial6 and antifungal7
properties.Effort to modify cinnamaldehyde into more
useful products with attractive bioactivities has been
shown in the last decade8-10. The presence of α,β-
unsaturated carbonyl group makes cinnamaldehyde
as prominent precursor for synthesis of organic
molecules with high complexity via various types of
organic transformation8-11
.
One of the key reactions which can be
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CAHYANA et al., Orient. J. Chem., Vol. 34(5), 2685-2688 (2018)
preparation or the use of harmful solvent8,12,15-17
.
(lit.270oC [8]);68% yield;Rf 0.58(ethylacetate:ethanol
7:3) IR (KBr, cm-1): 3629 (N-H), 3088 (C-H sp2), 1701
(C=O), 1559 (C=C stretch), 1221 (C-N), 669 (mono-
substituted benzene). UV-Vis (nm): 372. GC (min.):
15.61. MS (m/z): 242 (M+), 171, 155, 128, 127.
Therefore, the search for efficient method or catalyst
for Knoevenagel condensation is still become a
major challenge.
RESULTS AND DISCUSSION
The FTIR, UV-Vis, and GC-MS spectra
of compound 3a are presented in the Fig. 2. In
FTIR spectrum, the peaks at 3629, 3025, and
1693 cm-1 are corresponding to the secondary N-H
stretching, C-H sp2 stretching, and C=O stretching,
respectively. Additional peak appeared at 1386
cm-1 due to C-N stretching and peak at 697 cm-1
indicated the compound 3a as mono-substituted
benzene.Compound 3a has maximum absorption at
258 nm.The structure confirmation was determined
by GC-MS. From GC-MS analysis, compound 3a is
the most abundant with retention time at 13.51 min.
and M+ value of 216.
Fig. 1. Reaction scheme of arylidenes barbituric acid synthesis
Inthisresearch, wesynthesizethearylidene
derivatives of barbituric acid using samarium (III)
catalyst and characterize the products using some
analytical instruments such as FTIR, UV-Vis, and
GCMS.
MATERIALS AND METHODS
General
All chemicals were analytical grade and
obtained from commercial suppliers. FTIR spectra
were recorded on Shimadzu Prestige-21 FTIR
Spectrophotometer. Ultraviolet-visible absorptions
were screened using Shimadzu 2450 UV-Vis
Spectrophotometer.GC-MS analyses were done by
Agilent 7890A-5975C.
Synthesis of Arylidenes Barbituric Acid
Aldehyde (1 mmol), barbituric acid
(2 mmol), samarium(III) chloride (10 wt.%) in water
(2 mL) were stirred for 2 h at room temperature in
an Erlenmeyer flask. The reaction was monitored
using thin layer chromatography.The product formed
will precipitate. After completion, solid product was
filtered and recrystallized from hot ethanol.
Compound 3a, 5-benzylidenepyrimidine-
2,4,6(1H,3H,5H)-trione has physical and spectral
data as follows: pale yellow solid, m.p. 261-262oC
(lit. 271oC [18]); 61% yield; Rf 0.75 (ethyl acetate :
ethanol 7:3) IR (KBr, cm-1): 3629 (N-H), 3025 (C-H
sp2), 1693 (C=O), 1386 (C-N), 697 (mono-substituted
benzene). UV-Vis (nm): 230, 258. GC (min.): 13.51.
MS (m/z): 216 (M+), 215, 172, 129, 102.
Compound 3b, (E)-5-(3-phenylallylidene)
pyrimidine-2,4,6(1H,3H,5H)-trione has physical and
spectral data as follows: yellow solid, m.p. 260-261oC

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carbonyl group, which activate the carbon atom.In the
second step, the activated carbonyl group is attacked
by an enol to produce compound that contains new
carbon-carbon bond. The last step is dehydration
process to give final product. The product obtained
in medium yield probably due to competition between
acid base interaction of the catalyst with lone pair
electrons in oxygen or nitrogen atom.
Fig. 2. FTIR, UV-Vis, and GC-MS spectra of compound 3a
Figure 3 showed the FTIR, UV-Vis, and GC-
MS spectra of compound 3b. The major absorption
peaks in FTIR spectrum are observed at 3629, 3088,
and 1701 cm-1 which attributed to the secondary N-H
stretching, C-H sp2 stretching, and C=O stretching
vibration, respectively. The peaks at 1559 and 1221
cm-1 are correspond to the C=C and C-N stretching
vibration, respectively. It is indicated the successful
adduct between cinnamaldehyde with barbituric acid
to give compound 3b. The maximum absorption of
3b is occurred at 372 nm. Analysis using GC-MS
revealed that compound 3b is formed with molecular
cation value of 242. It is in good agreement with our
previous work, when the formation of cinnamaldehyde-
barbituric acid adduct was conducted using citric acid
supported on Fe3O4 as catalys11.
The possible mechanism of Knoevenagel
condensation between aryl aldehyde and barbituric
acid is depicted in Fig. 4. The first step is keto-enol
tautomerism of barbituric acid to give structure in enol
form. Then a physical interaction occurs between
SmCl3 as Lewis acid catalyst with oxygen atom in

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CAHYANA et al., Orient. J. Chem., Vol. 34(5), 2685-2688 (2018)
Fig. 4. Proposed mechanism of the condensation reaction
Fig. 3. FTIR, UV-Vis, and GC-MS spectra of compound 3b
CONCLUSION
synthesis of organic compound promoted by simple
catalyst.
The synthesis arylidenes barbituric acid
using samarium(III) chloride as Lewis acid catalyst
has been done in mild condition. Compound 3a
and 3b are formed in medium yield, 61 and 68%,
respectively. The successive formation of these
compounds was confirmed by some analytical
instruments including FTIR, UV-Vis, and GC-MS.
This research highlights an environment-friendly
ACKNOWLEDGEMENT
This work was financially supported by The
Directorate General of Higher Education (DIKTI),
Ministry of Research,Technology and Higher Education,
Republic of Indonesia through Penelitian Unggulan
Perguruan Tinggi (PUPT) 2017 Research Grant.
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