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13
al Kimiya: Jurnal Ilmu Kimia dan Terapan
p-ISSN: 2407-1897, e-ISSN: 2407-1927
Vol. 10, No. 1 (13-19), Juni 2023/Dzulhijah 1444
the synthesis of chalcone analogues. The use of this phase was dried over sodium sulfate. After the
material is justified by the fact that 2- removal of the solvent, the desired product was
acetylnaphthalene and different substituted obtained in good purity.
acetophenones were the aromatic ketones
employed in earlier investigations, which claimed RESULT AND DISCUSSION
to have already synthesized chalcone analogues
from cinnamaldehyde [14] [15]. To the best of our Synthesis of Chalcone Compound
knowledge, there have been no reports suggesting
that an aromatic ketone variant in the form of 1- Compound 1-(1-naphthyl)-5-phenyl-2,4-
acetylnaphthalene has ever been used as an pentadiene-1-one (3) can be obtained by reacting 1-
aromatic ketone variant for cinnamaldehyde. So, acetonaphthone (1) with trans-cinnamaldehyde (2)
the proposed structural model is a new structural using sodium hydroxide as a catalyst, as shown in
model. To determine whether the synthesized Scheme 1.
substance matched the required target molecule,
FTIR, MS, and NMR spectroscopic studies were
used to characterize the compound [21]-[25] [26].
EKSPERIMENT
Scheme 1. Synthesis of the target compound.
Material
The synthesis of chalcone analogues can be
The chemicals used were analytical grades, catalyzed by a base, generally, the base used is a
such as trans-cinnamaldehyde (Merck), 1- homogeneous base catalyst, namely NaOH [14]
acetonaphthone (Sigma Aldrich), filter paper, pH [15] [27] and KOH [27]. The initial stage of this
paper, TLC plates F254 (Merck), and sodium research was to find out how much yield was
hydroxide pellet (Merck). The solvents used were produced by the chalcone analog compound. The
ethyl acetate (Merck), n-hexane (Merck), methanol reaction conditions were carried out using 1-
(Merck), ethanol (Merck), and deionized water. acetylnaphthalene (5 mmol) and cinnamaldehyde
(5 mmol), at room temperature, with absolute
Instrumentation ethanol solvent, the catalyst used was 10 mmol (2
equivalents) for 24 hours. To find out whether the
FTIR analysis was performed using a product has been formed, namely using the TLC
Thermo Scientific-Nicolet iS50 FT-IR test [28], [29]. The eluent ratio is hexane: ethyl
Spectrometer at the ILRC Laboratory, Universitas (9:1).
Indonesia. The Qtof LCMSMS analysis was Figure 1 is the result of TLC of the starting
carried out at the Indonesian National Police's compound with the product, where A is an
Criminal Investigation Agency, Center for Forensic acetylnaphthalene compound, B is a
Laboratory, Sentul, Bogor. 1H-NMR and 13C-NMR cinnamaldehyde compound and P is a product
analysis was carried out using the Bruker Avance sample produced. The results of the TLC showed
Neo 500 MHz and 126 MHz Nuclear Magnetic that the compound had been formed where the Rf
Resonance Spectrometer at the ILRC Laboratory, of the synthesized compound was different from
Universitas Indonesia. the initial compound.
Procedure
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al Kimiya: Jurnal Ilmu Kimia dan Terapan
p-ISSN: 2407-1897, e-ISSN: 2407-1927
Vol. 10, No. 1 (13-19), Juni 2023/Dzulhijah 1444
The 1-(1-naphthyl)-5-phenyl-2,4-pentadien- Figure 2 is the result of the product TLC. The TLC
1-one compound was obtained after the test used hexane: ethyl acetate and chloroform:
evaporation process using a rotary evaporator ethyl acetate eluent each 9:1. The TLC test results
because the product formed has a gel texture so it showed that the compound formed had one spot
cannot be separated by ordinary filtering. To with an Rf value of 0.7 (hexane: ethyl acetate) and
separate the product from the filtrate before being 0.75 (chloroform: ethyl acetate) indicating that the
evaporated with a rotary evaporator, an extraction compound was pure.
technique was used using a separating funnel by The ethyl acetate fraction was then
adding ethyl acetate to the synthesis product which evaporated using a rotary evaporator. From the
had previously been added with distilled water. weighing results obtained a product weight of 0.88
g with a yield of 61.97%.
The results of the analysis of the mass LCMSMS data confirm that the compound
spectrum of the compound 1-(1-naphthyl)-5- synthesized matches the molecular formula
phenyl-2,4-pentadiene-1-one showed a molecular C21H16O or matches the target compound (Figure
ion peak at m/z 285.1289 (M+H). The results of the 4).
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al Kimiya: Jurnal Ilmu Kimia dan Terapan
p-ISSN: 2407-1897, e-ISSN: 2407-1927
Vol. 10, No. 1 (13-19), Juni 2023/Dzulhijah 1444
The H NMR spectrophotometer is used to C-3, C-4, and C-5, the biggest chemical shift is at
detect the position of the proton nucleus. In position C-3 (Hβ). This can be explained because a
addition, it can also be used to determine the resonance occurs in unsaturated α,β-ketones so that
number of protons bonded to carbon, nitrogen, or the carbon in Hβ (proton on C-3) is relatively more
oxygen atoms. Proton positions are expressed in positive than the carbon in Hα (proton on C-2). As
chemical shifts (δ) expressed in ppm, usually a result, the electron density of Hβ is smaller than
between 0 to 10 ppm. The greater the electron
the electron density of Hα. In addition, there is a
density (σ), the smaller the frequency, and the
geometric or spatial effect of the carbonyl on C-1,
smaller the chemical shift of the proton (δ) [25]. 1H-
NMR analysis using chloroform solvent. The so that C-3 is more deshielded than C-2, C-4, and
number of H atoms in the chalcone analog C-5. The chemical shift at δ 8.3058 ppm shows the
compound is 16, according to the data from the proton at the position of the C-9' atom with a
analysis. doublet peak, which is the highest peak. This is
In addition to measurements using 1H-NMR, because, besides the anisotropic effect, there is also
measurements were made using 13C-NMR analysis an aromatic effect so that the H in the C-9' position
for analysis of carbon shift values to serve as is deshielded. In the aromatic naphthalene ring, the
confirmatory data on the molecular structure of aromatic compound is bonded to the C carbonyl
products produced using chloroform solvent. The group (ketone), because the C carbonyl group
number of C atoms in the chalcone analog bonded to an aromatic compound attracts electrons,
compound is 21, but from the data synthesized it is so three types of protons are obtained, namely H
known that there are 18 C atoms. This indicates the
ortho, H meta, and H para with a chemical shift (δ)
presence of equivalent C atoms. From the analysis
data, confirmation of the proposed structure is Ho > Hp > Hm. This can be explained because
shown in Table 1. resonance occurs in aromatic compounds, the
The 1H-NMR spectrum of the chalcone carbonyl group attracts electrons so that the ortho
analog showed a chemical shift at δ 7.03 (d, 1H); carbon is relatively more positive than the para
7.56 ppm (m, 1H); 6.85 ppm (t, 1H); and 6.94 ppm carbon and the para carbon is more positive than
(d, 1H), each compound exhibiting protons at the meta carbon. As a result, the electron density of
positions C-2, C-3, C-4, and C-5. In unsaturated H ortho is smaller than the electron density of H
α,β- ketones, the proton adjacent to the carbonyl para, as well as the electron density of H para is
(Hα) will have a small δ (shielded) and Hβ will smaller than the electron density of H meta [24].
have a larger δ (deshielded) [24]. At positions C-2, chemical shift at δ 7.98 (d, 1H); 7.39 ppm (m, 1H);
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al Kimiya: Jurnal Ilmu Kimia dan Terapan
p-ISSN: 2407-1897, e-ISSN: 2407-1927
Vol. 10, No. 1 (13-19), Juni 2023/Dzulhijah 1444
7.90 ppm (d, 1H), 7.73 ppm (d, 1H); 7.54 ppm (m, 160 ppm, while carbonyls from ketones have a
1H); 7.57 ppm (m, 1H) indicates protons at chemical shift between 190-230 ppm [24]. The 13C-
positions C-2', C-3', C-4', C-6', C-7', and C-8'. The NMR spectrum of the chalcone derivative showed
second aromatic ring is mono-substituted aromatic, a chemical shift at δ 137.2 ppm and 136.0 ppm
where the prevalence of proton signals is three respectively to carbon C-1' and C-1''. It is known
groups of signals originating from ortho, meta, and from the peak intensities during the chemical shift
δ 137.2 ppm and 136.0 ppm, which have low
para signals. The chemical shift at δ 7.49 ppm (d,
intensities which indicate that the C in the chemical
2H) shows the protons in the positions of the C-2''
shift is quaternary C because there is no H directly
and C-6'' atoms (two equivalent protons at the ortho bound to the C atom. The chemical shift at δ 195.9
position) with doublet peaks. The chemical shift at ppm is the C carbonyl of a ketone (C=O). The
δ 7.26 ppm (m, 1H) shows the proton at the position chemical shift at δ 146.1 and 142.1 ppm indicated
of the C-4'' atom (para proton signal) with multiplet the presence of carbon at C-3 and C-5. The
peaks. The chemical shift at δ 7.33 ppm (m,2H) chemical shift at δ 126.9 and 125.7 ppm indicated
shows the protons at the positions of the C-3'' and the presence of carbon in C-2 and C-4. The
C-5'' atoms (from two H protons at equivalent chemical shift at δ 124.5-133.9 ppm indicated the
positions meta) with multiplet peaks. presence of carbon in both aromatic rings. The
number of C atoms in the chalcone analogous
Table 1. Interpretation of 1H NMR data of the compound is 21, but from the analysis data, it is
compound 1-(1-naphthyl)-5-phenyl-2,4-pentadiene-1- known that there are 18 C atoms. This indicates the
one. presence of equivalent C atoms. The C atom is
equivalent to C-2'' with C-6'' and C-3'; C-3'' with C-
Atom Label ™H (ppm) ™C (ppm) 5''. The characterization results show that the
1 - 195.9 resulting product is following the target compound.
2 7.03 (d, 1H) 126.9 (Figure 5).
3 7.56 (m, 1H) 146.1
4 6.85 (t, 1H) 125.7
5 6.94 (d, 1H) 142.1
1’ - 137.2
2’ 7.98 (d, 1H) 131.4
3’ 7.39 (m, 1H) 127.4
4’ 7.90 (dd, 1H) 130.5
5’ - 129.3
6’ 7.73 (d, 1H) 128.4
7’ 7.54 (m, 1H) 126.8 Figure 5. Molecular structure of the target compound.
8’ 7.57 (m, 1H) 133.9
CONCLUSION
9’ 8.31 (d, 1H) 124.5
10’ - 127.4 The chalcone analogue compound has been
1’’ - 136.0 successfully synthesized using the starting
2’’ 7.49 (d, 1H) 127.4 materials in the form of cinnamaldehyde as an
3’’ 7.33 (m, 1H) 128.9 aromatic aldehyde and 1-acetylnaphthalene as an
4’’ 7.26 (m, 1H) 126.5 aromatic ketone with a yield of 61.97%. The results
5’’ 7.33 (m, 1H) 128.9 of the characterization of the compound using
6’’ 7.49 (d, 1H) 127.4
FTIR, LCMSMS, and NMR showed that the
product formed corresponds to the expected target
molecule, namely Compound 1-(1-naphthyl)-5-
The 13C-NMR spectrum has a much wider phenyl-2,4-pentadiene-1-one.
chemical shift, namely 0-230 ppm, compared to 1H-
NMR which ranges from 0-10 ppm, sometimes up ACKNOWLEDGEMENT
to 13-14 ppm (if there are hydrogen bonds) [24]. It
is known that the chalcone analogues formed This research was supported by the LPPM
consist of alkene, aromatic, and carbonyl groups UIN Sulthan Thaha Saifuddin Jambi through the
from ketones. Alkene and aromatic compounds Ministry of Religion's research grant 2022 with
generally have a chemical shift (δ) between 100- contract No. B-2311/Un.15/PPK/KU.01/06/2022.
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al Kimiya: Jurnal Ilmu Kimia dan Terapan
p-ISSN: 2407-1897, e-ISSN: 2407-1927
Vol. 10, No. 1 (13-19), Juni 2023/Dzulhijah 1444
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al Kimiya: Jurnal Ilmu Kimia dan Terapan
p-ISSN: 2407-1897, e-ISSN: 2407-1927
Vol. 10, No. 1 (13-19), Juni 2023/Dzulhijah 1444
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