1H and 13C NMR spectral assignments of twenty-six 1-aryl-5-(2-(styryl)phenyl)penta-1,4-dien-3-ones

Full text of DOI:10.1002/mrc.4993

Received: 19 September 2019
DOI: 10.1002/mrc.4993
Revised: 1 January 2020
Accepted: 3 January 2020
L E T T E R - S P E C T R A L A S S I G N M E N T
1H and 13C NMR spectral assignments of twenty-six 1-aryl-5-
(2-(styryl)phenyl)penta-1,4-dien-3-ones
Jihyun Park1 | Seunghyun Ahn1 | Youngshim Lee1 | Dongsoo Koh2
Yoongho Lim1
|
1Division of Bioscience and Biotechnology, BMIC, Konkuk University, Seoul, Korea
2Department of Applied Chemistry, Dongduk Women's University, Seoul, Korea
Correspondence
Yoongho Lim, Division of Bioscience and Biotechnology, BMIC, Konkuk University, 120 Neungdong-ro, Gwangjin-gu, Seoul 05029, Korea.
Email: yoongho@konkuk.ac.kr
1 | INTRODUCTION
compounds. According to recent literature,[16] angular
type compounds have shown different biological effects
compared with linear analogues. Linear curcumin deriv-
atives have been widely studied,[17] and hence, we
focused on angular type derivatives. Even there are mul-
tiple possibilities of combination, as described above, our
synthesis focused solely on monocarbonyl analogues
with various substituents where we tried to find other
types of biological activities. Nuclear magnetic resonance
(NMR) spectroscopy and high-resolution mass spectrom-
etry are utilized to identify these compounds. The spec-
tral data provided herein can be used for the
characterization of synthetic or natural compounds with
the monocarbonyl moiety of curcumin and stilbene moi-
ety of resveratrol.
Curcumin is a polyphenol produced from Curcuma longa
and is classified as a diarylheptanoid.[1] Curcumin report-
edly shows wound healing effects as well as antimicro-
bial, antifungal, and antiviral effects and modifies the
pathology of Alzheimer's by inhibiting β-amyloid disag-
gregation. Curcumin also exhibits anticancer effects and
acts as a protective agent against cardiac diseases.[2–6]
Therefore, the derivatization of curcumin has become the
center of interest. Curcumin has the 1,6-diene-3,5-dione
skeleton (Figure 1a) as the keto form and the 5-hydroxy-
1,4,6-triene-3-one skeleton as the enol form (Figure 1b).
One curcumin derivative is the monocarbonyl analogue,
1,4-dien-3-one (Figure 1c). Monocarbonyl analogues of
curcumin exhibit antibacterial activities against
Xanthomonas oryzae pv. Oryzae and antiviral activities
against tobacco mosaic virus[7] and act as activators of
the master gene transcription factor EB[8]; they also dis-
play neuroprotective effects[9] and antiparasitic activities
against Trypanosoma cruzi.[10] Another polyphenol pro-
duced from grapes, resveratrol (3,40,5-trihydroxy-trans-
stilbene; Figure 1d), is known to be a phytoalexin that
protects plants from bacteria and fungi.[11] Like cur-
cumin, resveratrol shows diverse biological activities
including anticancer, antidiabetes, and antioxidant
2 | EXPERIMENTAL
2.1 | Syntheses
Synthesis of the 1-aryl-5-(2-(styryl)phenyl)penta-1,4-dien-
3-one derivatives was accomplished using Compound III
(1 mmol), as shown in Scheme 1, which was obtained
through aldol condensation between Compound I[18] and
excess acetone (II) in alkali solution. An equivalent molar
amount of Compound III and the appropriate hetero/aro-
matic aldehyde were dissolved in ethanol. Excess 50% (w/
v) potassium hydroxide was added to the reaction mix-
ture and was stirred for 20–48 hr at room temperature.
The reaction mixture was poured into ice water and was
acidified with 3 N HCl (pH = 2−3) to induce
effects
and
targets
mitochondrial
metabolic
pathways.[12–15] To exploit the desirable features of both
compounds, we designed a combined structure con-
taining both the monocarbonyl moiety of curcumin and
stilbene moiety of resveratrol (Figure 1e) and synthesized
twenty-six 1-aryl-5-(2-(styryl)phenyl)penta-1,4-dien-3-one
Magn Reson Chem. 2020;1–13.
wileyonlinelibrary.com/journal/mrc
© 2020 John Wiley & Sons, Ltd.
1

2
PARK ET AL.
reaction. Compound III (1 mmol, 338 mg) and 2-fur-
analdehyde (1 mmol, 96 mg) were dissolved in 10 ml of
ethanol. Sodium ethoxide (2 mmol, 136 mg) was added to
the reaction mixture and stirred at room temperature for
20 hr. After completion of the reaction, the mixture was
poured into ice water and acidified with 3 N HCl (pH =
3) to give a crude solid. The resulting solid was vacuum
filtered and purified by recrystallization in ethanol (yield:
25%, mp: 120–122 ꢀC).
2.2 | NMR spectra
Derivatives
1
and
11
were
dissolved
in
dimethylformamide-d7, and 6, 13, 17, 19, 20, 24, and
25 were dissolved in chloroform-d; all other compounds
were dissolved in dimethylsulfoxide-d6. The concentra-
tion was adjusted to approximately 50 mM, and the
solutions were transferred to 2.5-mm NMR tubes. All
NMR data were collected on an Avance 400 spectrometer
system (9.4 T; Bruker, Karlsruhe, Germany) at room
temperature, and the chemical shifts were referenced to
tetramethylsilane. The relaxation delay, 90ꢀ pulse, spec-
tral width, number of data points, and digital resolution
FIGURE 1 Structures of (a) 1,6-diene-3,5-dione, (b) 5-
hydroxy-1,4,6-triene-3-one, (c) 1,4-dien-3-one, (d) resveratrol
(3,5,40-trihydroxy-trans-stilbene), where ellipse denotes stilbene
moiety, and (e) combined structure containing both monocarbonyl
moiety of curcumin and stilbene moiety of resveratrol, where
rectangles denote two moieties
1
for the H NMR experiments were 1 s, 11.6 μs, 5,500
Hz, 32 K, and 0.34 Hz/point, respectively. The
corresponding parameters for the 13C NMR experiments
were 3 s, 15.0 μs, 21,000 Hz, 64 K, and 0.64 Hz/point,
respectively. Two-dimensional experiments including
COSY, HMQC, and HMBC were performed with 2 K ×
256 (t2 × t1) data points.[19] The long-range coupling
time for HMBC was 70 ms. The NMR data were
processed using the NMR Pipe program[20] and analyzed
using the SPARKY 3 program developed by T. D. God-
dard and D. G. Kneller in the University of California at
San Francisco.
precipitation. The precipitate was filtered under vacuum
and washed with cold ethanol. Recrystallization in an
appropriate solvent gave the pure product. The typical
procedure for synthesis of derivative 23 is as follows:
Compound I (2.5 mmol, 745 mg) was dissolved in 11 ml
of acetone (II, excess) and was combined with 5 ml of
2 M NaOH solution. The reaction mixture was stirred at
room temperature for 20 hr. The reaction mixture was
poured into 150 ml of ice water for precipitation. The pre-
cipitate was vacuum filtered and used for further
SCHEME 1 Procedure for synthesis of 1-aryl-5-(2-
(styryl)phenyl)penta-1,4-dien-3-one derivatives

PARK ET AL.
3
TABLE 1 Structures and names of 1-aryl-5-(2-(styryl)phenyl)penta-1,4-dien-3-one derivatives and corresponding high-resolution mass
spectroscopic data, theoretical surface area, volume, and log p values
Mass
(calcd/found)
Area
(Å2)
Volume
(Å3)
log
P
Derivative
R
Name
1
472.1760/472.1757
440.99 393.94
6.61 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(4-nitrophenyl)
penta-1,4-dien-3-one
2
487.2121/487.2109
469.67 424.99
5.58 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(2,3-dimethoxyphenyl)
penta-1,4-dien-3-one
3
4
487.2121/487.2074
457.2015/457.2009
472.12 426.01
445.18 401.33
5.58 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(3,4-dimethoxyphenyl)
penta-1,4-dien-3-one
5.71 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(2-methoxyphenyl)
penta-1,4-dien-3-one
5
6
7
457.2015/457.1985
457.2015/457.2006
487.2121/487.2079
446.89 401.10
447.26 398.49
469.67 421.73
5.71 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(3-methoxyphenyl)
penta-1,4-dien-3-one
5.71 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(4-methoxyphenyl)
penta-1,4-dien-3-one
5.58 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(2,4-dimethoxyphenyl)
penta-1,4-dien-3-one
(Continues)

4
PARK ET AL.
TABLE 1 (Continued)
Mass
(calcd/found)
Area
(Å2)
Volume
(Å3)
log
P
Derivative
R
Name
8
517.2226/517.2209
496.62 451.15
5.45 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(2,3,4-trimethoxyphenyl)
penta-1,4-dien-3-one
9
517.2226/517.2220
498.40 449.31
5.45 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(2,4,5-trimethoxyphenyl)
penta-1,4-dien-3-one
10
11
517.2226/517.2211
488.1709/488.1718
500.86 454.32
5.45 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(2,4,6-trimethoxyphenyl)
penta-1,4-dien-3-one
448.50 401.71
6.22 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(2-hydroxy-5-nitrophenyl)
penta-1,4-dien-3-one
12
13
521.0964/521.0980
472.1760/472.1774
446.18 398.97
6.27 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(5-bromo-2-hydroxyphenyl)
penta-1,4-dien-3-one
441.55 393.94
6.61 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(3-nitrophenyl)penta-1,4-
dien-3-one
(Continues)

PARK ET AL.
5
TABLE 1 (Continued)
Mass
(calcd/found)
Area
(Å2)
Volume
(Å3)
log
P
Derivative
R
Name
14
445.1815/445.1806
423.97 377.59
5.99 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(2-fluorophenyl)
penta-1,4-dien-3-one
15
16
445.1815/445.1815
445.1815/445.1786
425.15 377.92
424.09 379.74
5.99 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(3-fluorophenyl)
penta-1,4-dien-3-one
5.99 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(4-fluorophenyl)
penta-1,4-dien-3-one
17
18
19
20
21
495.1783/495.1771
443.1858/443.1833
505.1014/505.1013
461.1520/461.1537
487.2121/487.2079
449.81 404.47
428.57 384.23
439.45 395.11
434.95 389.96
473.92 426.39
6.75 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(3-(trifluoromethyl)phenyl)
penta-1,4-dien-3-one
5.44 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(3-hydroxyphenyl)
penta-1,4-dien-3-one
6.49 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(4-bromophenyl)
penta-1,4-dien-3-one
6.39 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(4-chlorophenyl)
penta-1,4-dien-3-one
5.58 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(3,5-dimethoxyphenyl)
penta-1,4-dien-3-one
(Continues)

6
PARK ET AL.
TABLE 1 (Continued)
Mass
(calcd/found)
Area
(Å2)
Volume
(Å3)
log
P
Derivative
R
Name
22
517.2226/517.2186
495.378 451.90
5.45 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(3,4,5-trimethoxyphenyl)
penta-1,4-dien-3-one
23
24
417.1702/417.1685
483.1630/483.1643
403.36 355.66
452.27 408.54
4.45 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(furan-2-yl)
penta-1,4-dien-3-one
6.87 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(benzo[b]thiophen-2-yl)
penta-1,4-dien-3-one
25
26
428.1862/428.1863
433.1474/433.1477
416.44 369.95
412.25 366.70
4.92 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(pyridin-2-yl)
penta-1,4-dien-3-one
5.76 (1E,4E)-1-(2-((E)-4-methoxystyryl)-4,6-
dimethoxyphenyl)-5-(thiophen-3-yl)
penta-1,4-dien-3-one
2.3 | General experimental procedures
3 | RESULTS AND DISCUSSION
To confirm the structures of the 1-aryl-5-(2-(styryl)phe-
nyl)penta-1,4-dien-3-one derivatives determined based
on the NMR assignments, ultraperformance liquid chro-
matography-hybrid quadrupole-time-of-flight mass spec-
trometry was carried out on a Waters Acquity UPLC
system (Waters Corp., Milford, MA).[21] The theoretical
log P, volume, and area of the synthetic derivatives were
calculated using the Sybyl software (Tripos, St. Louis,
MO, USA) built on an Intel Core 2 Quad Q6600 (2.4
GHz) Linux personal computer.[22]
Twenty-six
1-aryl-5-(2-(styryl)phenyl)penta-1,4-dien-3-
one derivatives were prepared to explain the substituent
effects of electron withdrawing, electron donating, and
steric. The NMR assignments for all derivatives listed in
Table 1 were performed in a similar manner because all
of the derivatives have the 1-aryl-5-(2-(styryl)phenyl)
penta-1,4-dien-3-one structure in common. As a repre-
sentative, the NMR assignment for derivative 2, (1E,4E)-
1-(2-((E)-4-methoxystyryl)-4,6-dimethoxyphenyl)-5-(2,3-
dimethoxyphenyl)penta-1,4-dien-3-one, was as follows:

PARK ET AL.
7
There were 28 peaks in the 13C NMR spectrum. These
peaks were classified as five methoxy, one carbonyl,
13 methines (including six aromatics), and nine quater-
nary carbons based on the chemical shifts and HMQC
with the carbonyl carbon (188.7 ppm) in the HMBC spec-
trum, meaning that they were placed near the ketone
group. The adjacent protons were determined from the
COSY connections, and the positions were determined
1
spectrum. The H spectrum showed five methoxy and
13 methines. The 13 methines were divided into two
groups, seven aromatics and six alkenes, based on the
coupling constants. Among the aromatics, the two 1H sig-
nals at 6.95 ppm (2H, d, J = 8.7 Hz) and 7.56 ppm (2H, d,
J = 8.7 Hz) were assigned as H-300/500 and H-200/600, respec-
tively, because of their double intensities. The quaternary
13C peak at 159.3 ppm was assigned as C-400 because it
1
was correlated with the H signals of the methoxy (3.77
ppm) and H-200/600 (7.56 ppm) groups in the HMBC spec-
1
trum. The H peaks at 6.60 ppm (1H, d, J = 2.3 Hz) and
6.83 ppm (1H, d, J = 2.3 Hz) were assigned to H-50 and
H-30 based on the coupling constants. Further, H-30 was
correlated to the quaternary 13C signal at 114.6 ppm (C-
10) and the alkenyl 13C signal at 124.4 ppm (C-100β) in the
HMBC spectrum. The two methoxy peaks at 3.88 ppm
(3H, s) and 3.91 ppm (3H, s) were assigned as 40-OCH3
and 60-OCH3, respectively. C-40 (161.6 ppm) was corre-
lated to the H-30, H-50, and 40-OCH3 signals in the HMBC
spectrum. The other aromatic peaks at 7.13 ppm (1H, dd,
J = 8.1, 2.4 Hz), 7.12 ppm (1H, dd, J = 8.1, 6.4 Hz), and
7.39 ppm (1H, dd, J = 6.4, 2.4 Hz) were assigned to H-4,
H-5, and H-6, respectively. The other two methoxy pro-
tons (3.72 and 3.82 ppm) were also assigned based on the
HMBC correlations. The six protons in the alkene group
all had coupling constants of approximately 16 Hz
because they were all trans isomers. The signals of the
alkene group were assigned using the COSY and HMBC
spectra. In the COSY spectrum, the correlation between
the signals at 7.08 ppm (1H, d, J = 15.9 Hz) and 7.35 ppm
(1H, d, J = 15.9 Hz) indicated adjacent protons. In the
1
HMBC spectrum, the H signal at 7.08 ppm was corre-
lated to C-600, whereas the 1H signal at 7.35 ppm was cor-
related to C-30. Thus, these signals were assigned as H-
100α and H-100β, respectively. The last four proton signals
of the alkenes at 7.08 ppm (1H, d, J = 15.9 Hz), 7.27 ppm
(1H, d, J = 16.1 Hz), 7.82 ppm (1H, d, J = 16.1 Hz), and
7.98 ppm (1H, d, J = 15.9 Hz) were long-ranged coupled
FIGURE 2 Important correlations obtained from the COSY
FIGURE 3 Partial HMBC spectrum of derivative 2 showing
(dotted lines) and HMBC (solid lines) spectra of derivative 2
important long-ranged couplings for the assignment of alkenes

8
PARK ET AL.

PARK ET AL.
9

10
PARK ET AL.

PARK ET AL.
11
TABLE 3 13C NMR chemical shifts of 1-aryl-5-(2-(styryl)phenyl)penta-1,4-dien-3-one derivatives 1–26
Position
C-100
1
2
3
4
5
6
7
8
9
10
11
12
13
130.9
129.2
115.2
160.8
115.2
129.2
56.0
133.4
125.6
115.9
142.9
105.2
163.3
98.7
162.2
56.3
56.6
138.8
129.1
189.8
131.3
140.0
142.8
130.4
125.0
149.3
125.0
130.4
-
129.5
128.1
114.3
159.3
114.3
128.1
55.2
129.6
128.1
114.3
159.3
114.3
128.1
55.2
129.5
128.1
114.3
159.3
114.3
128.1
55.2
132.0
124.6
114.7
141.2
104.1
161.5
97.8
160.6
55.5
55.9
136.6
128.3
188.8
126.3
136.6
123.0
158.1
111.8
132.0
120.7
128.4
55.6
-
129.5
128.1
114.3
159.3
114.3
128.1
55.2
132.0
124.6
114.7
141.2
104.0
161.5
97.8
160.6
55.5
55.9
136.9
128.1
188.8
126.7
141.8
136.1
113.1
159.6
121.2
129.9
116.4
-
130.1
128.2
114.4
159.8
114.4
128.2
55.5
129.5
128.1
114.3
159.3
114.3
128.1
55.2
129.5
128.1
114.2
159.3
114.2
128.1
55.1
129.5
128.1
114.2
159.3
114.2
128.1
55.2
129.6
128.0
114.3
159.3
114.3
128.0
55.2
131.0
129.2
115.2
160.8
115.2
129.2
56.0
133.1
125.6
116.1
142.6
105.1
163.0
98.7
162.1
56.3
56.6
137.9
129.9
190.1
128.6
137.0
123.6
166.2
118.2
127.7
140.2
125.8
-
129.5
128.1
114.3
159.3
114.3
128.1
55.2
132.0
124.4
114.7
141.1
103.9
161.5
97.8
160.6
55.5
55.9
136.7
128.7
188.8
126.4
135.7
123.8
156.3
118.4
133.8
110.7
130.3
-
129.9
128.2
114.4
159.9
114.4
128.2
55.5
C-200
C-300
C-400
C-500
C-600
400-OCH3
C-100α
C-100β
C-10
132.0
124.4
114.6
141.3
104.1
161.6
97.8
131.8
124.6
114.8
141.0
104.0
161.4
97.8
131.7
125.8
116.3
141.5
103.8
161.5
97.8
131.8
124.6
114.8
141.0
104.0
161.4
97.8
131.9
124.5
114.6
141.1
104.0
161.4
97.8
131.8
124.5
114.8
141.0
104.0
161.3
97.8
131.7
125.1
114.8
140.9
104.1
161.3
97.8
132.2
125.4
115.7
142.1
104.1
162.0
97.8
C-20
C-30
C-40
C-50
C-60
160.6
55.5
160.5
55.5
160.8
55.6
160.4
55.5
160.5
55.4
160.5
55.5
160.4
55.5
161.1
55.6
40-OCH3
60-OCH3
C-10β
C-10α
C=O
C-1α
55.9
55.9
55.8
55.9
55.8
55.9
55.9
55.9
136.9
128.1
188.7
127.2
135.9
128.2
148.1
152.8
114.8
124.3
118.9
60.8
136.3
128.4
188.6
124.3
142.4
127.5
110.5
149.0
151.1
111.6
123.4
-
137.2
128.9
189.8
124.5
142.5
127.8
130.1
114.4
161.6
114.4
130.1
-
135.9
128.6
188.6
123.9
136.9
115.9
159.8
98.3
136.3
128.2
188.5
125.0
136.4
121.0
152.8
141.8
155.5
108.4
123.2
61.3
135.9
128.8
188.6
123.5
136.5
114.3
154.0
97.6
135.3
129.0
189.4
124.8
133.3
105.0
161.2
91.0
138.7
128.1
189.0
129.0
139.4
137.0
122.5
148.8
124.4
130.0
134.1
-
C-1β
C-1
C-2
C-3
C-4
162.8
106.3
130.0
55.7
152.6
143.1
110.8
56.3
163.2
91.0
C-5
C-6
161.2
55.9
2-OCH3
3-OCH3
4-OCH3
5-OCH3
6-OCH3
Position
C-100
-
55.8
55.6
55.2
-
-
-
60.4
-
-
-
-
-
-
-
55.6
-
55.5
55.7
56.0
55.8
55.5
-
-
-
-
-
-
-
-
-
-
-
56.2
-
-
-
-
-
-
-
-
-
-
-
-
-
55.9
-
-
-
14
15
16
17
18
19
20
21
22
23
24
25
26
129.5
128.2
114.3
159.3
114.3
128.2
55.2
132.1
129.5
128.1
114.2
159.3
114.2
128.1
55.1
129.5
128.1
114.3
159.3
114.3
128.1
55.2
130.0
128.2
114.4
159.9
114.4
128.2
55.5
129.5
128.1
114.3
159.3
114.3
128.1
55.1
130.0
128.2
114.4
159.8
114.4
128.2
55.5
130.0
128.2
114.4
159.8
114.4
128.2
55.5
129.5
128.1
114.3
159.3
114.3
128.1
55.1
129.5
128.1
114.2
159.3
114.2
128.1
55.2
129.5
128.1
114.3
159.3
114.3
128.13
55.2
130.0
128.2
114.4
159.8
114.4
128.2
55.5
132.0
130.0
128.2
114.3
159.7
114.3
128.2
55.4
132.0
129.5
128.1
114.3
159.3
114.3
128.1
55.2
C-200
C-300
C-400
C-500
C-600
400-OCH3
C-100α
132.0
131.9
132.1
131.9
131.9
131.9
131.9
131.9
132.0
131.9
(Continues)

12
PARK ET AL.
TABLE 3 (Continued)
Position
C-100β
C-10
14
15
16
17
18
19
20
21
22
23
24
25
26
124.4
114.5
141.4
104.1
161.7
97.8
160.7
55.5
55.9
137.3
128.1
188.5
128.4
133.3
122.4
160.8
116.1
132.3
125.0
129.1
-
124.5
114.6
141.3
104.0
161.6
97.8
160.6
55.5
55.9
137.2
128.1
188.7
127.7
140.3
137.3
114.4
162.5
117.0
130.8
125.0
-
124.6
114.7
141.2
104.0
161.5
97.8
160.6
55.5
55.9
136.8
128.1
188.6
126.3
140.6
131.4
130.8
115.9
163.2
115.9
130.8
-
125.5
115.9
142.0
104.0
162.0
97.8
161.0
55.6
55.9
138.4
128.3
189.3
128.1
140.6
136.1
124.8
131.4
126.6
129.5
131.5
-
124.6
114.67
141.1
104.0
161.5
97.8
160.5
55.5
55.9
136.7
128.1
188.6
126.3
142.1
136.0
119.5
157.7
117.6
129.9
114.73
-
125.7
116.0
141.8
104.0
161.8
97.8
160.9
55.6
55.8
138.1
128.4
189.5
127.0
141.1
134.1
129.8
132.2
124.5
132.2
129.8
-
125.7
116.0
141.8
104.0
161.8
97.7
160.9
55.6
55.8
138.0
128.4
189.5
126.9
141.0
133.7
129.5
129.2
136.1
129.2
129.5
-
124.6
114.7
141.2
104.1
161.6
97.8
160.6
55.5
55.9
136.7
128.07
188.8
126.9
142.0
136.9
106.3
160.7
102.6
160.7
106.3
-
124.5
114.7
141.1
104.0
161.5
97.8
160.6
55.5
55.9
136.6
128.2
188.7
125.8
142.3
130.3
106.1
153.1
139.6
153.1
106.1
-
124.5
114.6
141.2
104.1
161.6
97.8
160.6
55.5
55.9
136.5
128.1
188.0
123.4
128.6
-
125.0
116.0
141.9
103.9
161.9
97.8
161.0
55.8
55.6
138.0
128.6
189.1
127.7
135.5
-
125.3
115.8
141.9
103.8
161.8
97.7
161.0
55.7
55.5
138.2
128.7
189.9
129.8
140.8
-
124.6
114.7
141.1
104.0
161.5
97.8
160.5
55.5
55.9
136.5
128.1
188.9
125.8
135.8
-
C-20
C-30
C-40
C-50
C-60
40-OCH3
60-OCH3
C-10β
C-10α
C=O
C-1α
C-1β
C-1
C-2
151.0
116.5
113.0
146.0
-
140.7
129.3
124.5
125.0
126.3
122.6
140.3
139.9
-
153.7
124.9
136.8
124.1
150.1
-
129.8
138.1
126.1
127.7
-
C-3
C-4
C-5
C-6
C-7
-
-
C-8
-
-
-
-
-
-
-
-
-
-
-
-
C-9
-
-
-
-
-
-
-
-
-
-
-
-
3-OCH3
4-OCH3
5-OCH3
3-CF3
-
-
-
-
-
-
-
55.4
-
56.0
60.1
56.0
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
55.4
-
-
-
-
-
-
-
-
122.6
-
-
-
-
-
-
-
from the HMBC correlations (Figure 2). In the HMBC
spectrum (Figure 3), the proton signal at 7.98 ppm was
correlated to C-20 and C-60, as was thus assigned to H-10β,
whereas the other proton signal at 7.82 ppm was corre-
lated to the 13C signals of C-6 (118.9 ppm) and C-2 (148.1
ppm), and the proton was thus assigned as H-1β. The
structure of the other derivatives is identical except for
the R group, and the NMR assignments followed the
same approach as used for derivative 2. The full NMR
assignments for all derivatives are presented in Tables 2
and 3.
All derivatives possess identical structures except for
the R group. For derivatives 1–22, the R group was a ben-
zene ring with different substituents, and the R group
was heteroaromatics for derivatives 23–26, as shown in
Table 1. Therefore, the 1H and 13C chemical shifts related
to 1β, which is close to the R group, varied depending on
the substituents of the R group. The chemical shifts of C-
1β varied from 128.6 to 142.5 ppm. For the derivatives
containing a substituent at the ortho position of the ben-
zene ring in the R group, the chemical shifts of C-1β were
located at relatively low frequency. For example, the
chemical shifts of C-1β for derivatives 2, 4, 7, 8, 9, 10,
11, 12, and 14 containing methoxy, hydroxyl, or fluoride
at the ortho position were lower than 137 ppm. Derivative
23 and 24 with chemical shifts of 128.6 and 135.5 ppm for
C-1β contained furan and benzothiofuran as the R group,
respectively. For the other derivatives having hydrogen at
the ortho position, the chemical shifts of C-1β occurred at
frequencies higher than 139.4 ppm. On the other hand,
the chemical shifts of H-1β tended to be at higher fre-
quency when substituents were present at the ortho posi-
tion. The chemical shift of H-1β for derivative 4 having a
methoxy group at the ortho position was 7.87 ppm,

PARK ET AL.
13
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Some of the carbon chemical shifts also varied based
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ACKNOWLEDGEMENTS
This work was supported by Konkuk University in 2017.
J. Park, S Ahn, and Y. Lee contributed equally to this
work. Quadrupole-time-of-flight mass spectrometry was
carried out with the help of Prof. Choong Hwan Lee at
Konkuk University, Korea.
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ORCID
Yoongho Lim https://orcid.org/0000-0002-8945-3027
SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
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How to cite this article: Park J, Ahn S, Lee Y,
Koh D, Lim Y. 1H and 13C NMR spectral
assignments of twenty-six 1-aryl-5-(2-(styryl)
phenyl)penta-1,4-dien-3-ones. Magn Reson Chem.
2020;1–13. https://doi.org/10.1002/mrc.4993