A visible-light-induced “on-off” one-pot synthesis of 3-arylacetylene coumarins with AIE properties

Article abstract of DOI:10.1039/d0ob00479k

A mild and simple one-pot stepwise method to synthesize 3-arylacetylene coumarins from alkynoates was demonstrated. This catalytic system involves photosensitizer-free photocatalysis and thermocatalysis processes. A series of alkynoates and phenylacetylenes were well tolerated in the optimized multi-catalytic system. The corresponding 3-arylacetylene coumarins were obtained in moderate to excellent yields. The results of the studies of their optical properties showed that the aromatic ring at the C4-position of coumarins is unfavorable for improving the molecular fluorescence quantum yield in solution. Based on the spectral studies and X-ray single crystal diffraction analysis, it was found that AIE activities may exist in some of the 3-arylvinyl-4-aryl-coumarins in their solid state. We expect that these molecules may have potential optical applications.

Full text of DOI:10.1039/d0ob00479k

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DOI: 10.1039/D0OB00479K
ARTICLE
A visible-light-induced “on-off” one-pot synthesis of 3-
arylacetylene coumarins with AIE properties
Xinjie Wu,a,‡ Ming Jia,b,‡ Mengmeng Huang,a,‡ Jung Keun Kim,a Zheng Zhao,c Junkai Liu,c Jinhu Xi,a
Received 00th January 20xx,
Accepted 00th January 20xx
Yabo Lia,* and Yangjie Wua,*
DOI: 10.1039/x0xx00000x
A mild and simple one-pot stepwise method to synthesize 3-arylacetylene coumarins from alkynoates was demostrated.
This catalytic system involves photosensitizer-free photocatalysis and thermocatalysis processes. A series of alkynoates and
phenylacetylenes were well tolerated in the optimized multi-catalytic system. The corresponding 3-arylacetylene coumarins
were obtained in moderate to excellent yields. The results of their optical properties studies showed that the aromatic ring
at C4-position of coumarins is unfavorable for improving the molecular fluorescence quantum yield in solution. Based on
the spectral studies and X-ray single crystal diffraction analysis, it was found that the AIE-activity may exist in some of the 3-
arylvinyl-4-aryl-coumarins in their solid state. We expect that these molecules may have potential optical applications.
construct 3-arylacetylene (Fig.1): i) Pd-catalysed Sonogashira
coupling reaction of aryl halides with terminal alkynes;10 ii) C-H
bond activation of aryl thiocarbamates;11 iii) flash vacuum
thermolysis (FVT) of furan ketones.12 However, some
drawbacks still exist in most of catalytic systems, such as severe
reaction conditions, the pre-functionalization of the substrates
and limited sources of the skeleton materials used in the
preparation. Therefore, it is still a significant scientific challenge
to develop mild and efficient synthetic approaches to obtain 3-
arylacetylene coumarins.
Introduction
Coumarins as one of important heteroaryls have potential
applications in bioactive compounds,1 natural products,2
fluorescent probes/sensors3 and non-fullerene acceptors.4 To
achieve better optical properties, the coumarin structures are
often functionalized with alkyl, alkoxy, aryl, styryl, arylethynyl,
amido or heterocyclic groups on their C3 or/and C4 positions.5
Modifying these active positions, some of coumarin derivatives
could also exhibit aggregation-induced emission (AIE)
characteristics.6 3-Substituted coumarins containing D-π-A (D:
Donor, A: Acceptor) structure not only accelerate the
intramolecular charge transfer, but also adjust the absorption
as well as emission wavelength range to red shift, to enhance
the fluorescence properties.7 Especially, the functionalization of
coumarin C4 position can effectively enhance its fluorescence
emission property. Their fluorescence quantum yields are
significantly higher than that of coumarins without any
substituent at the C4 position in the solid state.8 The AIE
phenomenon may be caused by weakened intermolecular π-π
interactions.
One-pot synthesis method combined with multi-approaches
(such
as
thermocatalysis,
photocatalysis
or/and
electrocatalysis) is efficient in solving the environmental
pollution and low availability of atoms problems while avoiding
tedious separation steps and unnecessary side reactions.13 In
our previous works, the visible-light-induced on-off14 and the
electrochemical on-off15 one pot reactions were separately
realized to synthesize 3-styryl coumarins and pyrimidin-2(1H)-
one. Herein, we developed a mild one-pot method to synthesize
3-arylvinyl-4-aryl-coumarins from alkynotes, which involves
thermocatalysis and photocatalysis processes without any
photocatalyst. The optical properties of the obtained 3-
arylacetylene coumarins will be investigated.
Among of the coumarin compounds, the 3-arylacetylene
have been found to have the excellent fluorescent properties in
their solutions.9 Up to now, there are several efficient ways to
R2
i)
X
Sonogashira
R3
H
+
R1
[Pd], CuI, Et3
X = I, Br
N
O
O
aCollege of Chemistry, Henan Key Laboratory of Chemical Biology and Organic
Chemistry, Key Laboratory of Applied Chemistry of Henan Universities, Zhengzhou
University,
R1 = H, Me, OMe, F, CF3, et al;
R2 = H, Me, OMe, NH2, Aryl;
R3 = Alkyl, Aryl.
S
Zhengzhou,
450052,
P.R.
China.
R2
O
R3
O
N
ii)
C-H activation
E-mail: wyj@zzu.edu.cn, ybli@zzu.edu.cn
2
+
R
R3
H
R1
bSchool of Materials Science and Engineering, Zhengzhou University, Zhengzhou
450052, P.R. China.
[Rh], AgSbF6, Cu(OAc)2
R1 = Me, OMe, t-Bu, Et, F, et al;
R1
O
R2, R3 = Alkyl, Aryl.
cDepartment of Chemistry, The Hong Kong University of Science and Technology,
Hong Kong, P.R. China.
H
iii)
FVT
-HX
R1
‡
These authors contributed equally to this work.
O
O
X
Electronic Supplementary Information (ESI) available: Electronic experimental
procedures, characterization data, and copies of 1H and 13C NMR spectra. CCDC
1881743, 1966836, 1966837, 1966838 and 1966843. For ESI and crystallographic
data in CIF or other electronic format see DOI: 10.1039/x0xx00000x
R1 = Me, Ph;
X = Cl, Br.
Figure 1. Methods to construct 3-arylacetylene coumarins.
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Organic & Biomolecular Chemistry
Page 2 of 8
ARTICLE
Journal Name
in this reaction. All the test phenylacetylenes with para-
Results and discussion
View Article Online
DOI: 10.1039/D0OB00479K
3
substituents (R ) were well tolerated in this one-pot reaction to
afford the corresponding products (4m-q) in moderate to good
yields regardless of electron-donating (Me and OMe) or -
withdrawing (F, Cl and CF3) groups. The steric hindrance effect
of the substitutes did not prevent the reaction (4r-s). In
addition, several coumarins (4t-y) with D-π-A or D-π-D
constructions were also successfully prepared in medium to
excellent yields using this stepwise approach.
Based on the literatures16 and our previous work13,14,15,17, a
stepwise one-pot reaction involving light-driven radical
cyclization and Pd-catalyzed Sonogashira cross-coupling
processes was designed (Table 1). To realize the one-pot
synthesis, the simple and efficient photocatalytic reaction of p-
tolyl 3-phenylpropiolate (1a) with N-iodosuccinimide (NIS, 2)
was chosen to construct the main intermediate 3-iodocoumarin
(5a). Our main focus was on optimization of Sonogashira
reaction conditions for the multistep one-pot synthesis. After
the photosynthetic step, the desired product 4a could be
Scheme 1 Scope of the one-pot reactiona,b
R2
O
R2
R3
o
I
Light - ON
1)
isolated in excellent yield (80%) at 80 C under Ar atmosphere
N
MeCN, air, 24 h, blue LED
O
O
+
R1
by adding the following substances: phenylacetylene 3a (3
equiv.), Pd(PPh3)2Cl2 (10 mol %), CuI (10 mol %) and Et3N (0.5
mL) (entry 1). No improvement of the one-pot transformation
was observed when Pd(PPh3)2Cl2 was changed into Pd(PPh3)4,
Pd(OAc)2, Cat-Py1 or Cat-Q1 (entries 2-5).17 A more suitable
reaction temperature was 60 oC (entries 6-8). The desired
product 4a was obtained in 74% yield, even if the Sonogashira
reaction was carried out at room temperature. A lower yield of
product 4a was followed by shortening the reaction time to 8
hours (entry 9). To our delight, the one-pot reaction could
proceed under air atmosphere with a satisfied yield (entry 10).
In addition, there was no desired product without Et3N (entry
11).
2) Light - OFF
R1
3
O
Compound , Pd(PPh3
)2Cl2 (10 mol %),
O
O
CuI (10 mol %), Et3N (0.5 mL), Ar, 60 oC, 12 h
2
4
1
R2
4a
4b
4c
4d
4e
4f
R
1 = Me, 83%;
1
R
=
tBu, 83%;
Ph
Ph
R
1 = OMe, 58%;
Ph
O
Ph
Me
Ph
R
1 = OPh, 56%;
1 = H, 71 %;
R
2 = OMe, 43%;
2 = F, 74%;
2 = Cl, 79%.
4j
R
R
O
O
R
1 = F, 75%;
R1
O
Me
Me
O
O
4k
4l
R
1 = Cl, 71%;
1 = CF3, 65%.
4g
4h
R
4i
, 78%
R
R3
Ph
O
Ph
Ph
4m
4n
4o
4p
4q
R
3 = Me, 74%;
OMe
F
R
R
R
R
3 = OMe, 79%;
3 = F, 75%;
3 = Cl, 70%;
3 = CF3, 53%.
Me
O
Me
O
O
Me
O
O
4r
4s
, 79%
, 70%
F
F
CF3
Ph
Ph
O
Ph
t-Bu
O
O
MeO
OMe
O
c
MeO
O
O
Table 1 Optimization of the one-pot reaction conditionsa
4t
4u
4v
, 82%
, 46%
, 35%
OMe
OMe
Ph
I
Ph
O
Ph
Ph
O
O
Ph
Ph
I
N
Light - ON
Light - OFF
3a
[Pd], CuI, temp.,
Et3N, Ar, time
O
O
+
,
Me
MeCN, r.t., air
blue LED, 24 h
Me
O
O
Me
O
F
O
O
MeO
O
O
F3
C
O
O
Ph
1a
2
5a
4a
4w
4x
4y
, 76%
, 45%
, 72%
aReaction conditions: 1 (0.2 mmol), 2 (2 equiv.), MeCN (1.5 mL), 3 W blue
LED (λmax = 450-465 nm), room temperature, under air atmosphere for 24 h;
then add 3 (3 equiv.), Pd(PPh3)2Cl2 (10 mol %), CuI (10 mol %), Et3N (0.5 mL)
under Ar at 60 oC for 12 h. bIsolated yield. cTime 2: 24 h.
Entry
1
2
3
4
5
6
7
8
[Pd]
Pd(PPh3)2Cl2
Pd(PPh3)4
Pd(OAc)2
Cat-Py1
T/ oC
Time / h
12
12
12
12
12
12
12
12
Yieldb (%)
80
80
80
80
80
60
40
r.t.
60
60
60
80
75
70
54
64
83
76
74
73
65
0
Ph
I
O
O
I
N
Cat-Q1
O
O
step 1
step 2
exp 1: standard condtions of
exp 2: standard condtions of
+
Me
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Me
O
O
Ph
1a
2
5a
, 93% for exp 1
0% for exp 2
Ph
Ph
Ph
O
9
10c
11d
8
12
12
I
step 2
exp 3: standard condtions of
Ph
+
Me
O
O
Me
O
5a
3a
4a
, 95% for exp 3
Scheme 2 Mechanistic studies.
Me
N
N
Ph
Ph
Ph
Ph
O
O
2AcOH
2AcOH
Pd
N
Pd
N
O
O
Ph
Ph
Ph
Ph
To get insight into the reaction mechanism, several control
experiments were carried out under the standard conditions
(Scheme 2). 3-Iodocoumarin (5a) could be obtained in 93% yield
under 3 W blue LED irradiation (exp 1), but it could not be
afforded from the Pd-catalyzed reaction of p-tolyl 3-
phenylpropiolate (1a) with NIS (exp 2). On the other hand, 3-
iodocoumarin (5a) reacted well with phenylacetylene (3a)
under Pd-catalyzed Sonogashira reaction to give 3-
arylacetylene coumarin (4a) in 95% (exp 3). These experimental
results indicate that 3-iodocoumarin (5a) is the crucial
intermediate for this stepwise one-pot reaction.
Me
Cat-Py1
Cat-Q1
aReaction conditions: 1) 1a (0.2 mmol), 2 (2 equiv.), MeCN (1.5 mL), 3 W blue LED
(λmax = 450-465 nm), room temperature, under air atmosphere for 24 h; 2) 3a (3
equiv.), [Pd] (10 mol %), CuI (10 mol %), Et3N (0.5 mL) under Ar atmosphere.
bIsolated yield. cUnder air atmosphere. dWithout Et3N.
With the optimized conditions in hand, the scope of the
substrates was examined (Scheme 1). Initially, various
alkynoates could be transformed into the corresponding 3-
arylacetylene coumarins (4a-l) in moderate to excellent yields.
The electronic effect of the substituents (R1 or R2) is not obvious
2 | J. Name., 2012, 00, 1-3
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ARTICLE
Based on the above experimental results and the previous S1). The shapes of absorption spectra of all compounds were
View Article Online
reports,16,18 a possible mechanism of the one-pot method was similar, and the absorption maxima (λabs) were observed in the
proposed involving the photocatalytic and thermocatalytic range from 352 to 375 nm (see ESI, Figures S1-S4). The emission
processes (Scheme 3). Initially, alkynoate 1 reacts with NIS via maxima (λem) were mainly distributed in the spectral region
iodination/spirocyclization/ring expansion to afford the between 445 and 506 nm (see ESI, Figures S5-S8). In comparison
intermediate product 5. Subsequently, the intermediate with other compounds, the absorption maxima of molecules
product 5 participates in a classical palladium-catalyzed (4v-y) with D-π-A configuration showed obvious red-shift,
Sonogashira coupling reaction to afford 3-arylacetylene meanwhile, the trend observed in fluorescence emission
DOI: 10.1039/D0OB00479K
coumarins 4.
maxima was the same for absorption maxima. Subsequently,
the influence of various solvents (THF, MeCN, DMF, DMSO and
EtOH) was analyzed on several synthesized compounds (4a, 4e,
4h, 4n and 4x) (see ESI, Figures S9-S13). The spectral properties
of compounds 4a (λabs = 357-363 nm, λem = 447-454 nm), 4e (λabs
= 352-359 nm, λem = 445-451 nm) and 4h (λabs = 356-360 nm, λem
= 446-455 nm) were almost independent of the polarity of
Ar2
R1
I
O
B
O
Ar2
O
Ar2
I
R1
I
Step1: Light-ON
O
R1
NIS
Visible-Light Photocatalysis
O
O
C
PdIIL2
base
A
hv
Pd0L2
Ar2
O
solvent. The emission maxima of 4n (λabs = 368-374 nm, λem
=
Ar2
I
R1
466-489 nm) and 4x (λabs = 365-370 nm, λem = 470-495 nm) have
certain red-shift with the increase of the polarity of solvent
(Table 2a). Comparing to other solvents, the high fluorescence
quantum yields of compounds 4a, 4e, 4h, 4n and 4x was
detected in THF (ФF = 0.047-0.209) except compound 4n (ФF =
0.160 in DMSO, Table 2b). More surprising, all studied
compounds (4a, 4e, 4h, 4n and 4x) could emitted different
intensities of yellow or yellow-green fluorescence under 365 nm
UV light in solid-state (Table 2d,e). The fluorescence quantum
yields of 4a (0.486), 4e (0.168) and 4x (0.439) in solid state are
higher than that in solution (Table 2b). These phenomenons
suggested the following: 1) the electronic effect of substituents
(R1, R2 or R3) has obvious effect on the spectral properties; 2)
the synthesized 3-arylacetylene coumarins might exist AIE-
activity.19
R1
Step2: Light-OFF
O
O
O
5
Pd-Catalysed Sonogashira
1
Ar2
L
PdII
I
R1
L
O
O
Ar2
Ar3
D
Et3
N
I(Et3N)Cu
Ar3
R1
Ar3
H
F
Ar2
L
O
4
O
PdII
Ar3
CuI
R1
L
O
O
E
Scheme 3 Possible mechanism for this reaction.
Considering the outstanding photoluminescence properties
of 3-arylacetylene coumarins,2-4 the spectral properties of all
synthesized coumarins were investigated. The absorption and
emission properties as well as fluorescence quantum yields (ΦF)
of all compounds (4a-y) were measured in MeCN (see ESI, Table
Table 2 Absorption, emission and fluorescence quantum yields (ΦF) of the compounds 4a, 4e, 4h, 4n and 4x in different solventsa,b
4a
4e
4h
4n
4x
λabs
(nm)
λem
(nm)
λabs
(nm)
λem
(nm)
λabs
(nm)
λem
(nm)
λabs
(nm)
λem
(nm)
λabs
(nm)
λem
(nm)
Solvent
ФF
ФF
ФF
ФF
ФF
THF
361
357
447
451
0.047
0.014
357
352
446
445
0.061
0.011
359
356
446
450
0.136
0.066
372
368
466
475
0.143
0.080
370
365
470
484
0.209
0.115
MeCN
DMF
DMSO
EtOH
Solid
362
363
362
441
452
454
454
490
0.047
0.034
0.022
0.486
358
359
358
446
450
451
451
476
0.033
0.106
0.020
0.168
360
360
359
435
453
454
455
486
0.136
0.055
0.061
-
372
374
373
458
479
488
489
514
0.155
0.160
0.121
-
368
370
370
472
489
494
495
512
0.172
0.137
0.128
0.439
X-ray
Analysisc
(b)
(e)
(d)
aUV and FL spectra were recorded at a concentration of 5 x 10-2 mM in different solvents. bFluorescence quantum yield was calculated by using quinine sulfate as an
external standard. cX-ray crystal structures of compounds 4a, 4e, 4h, 4n and 4x. Photos of the THF solutions (10 mM) and solid powders of compounds 4a, 4e, 4h, 4n and
4x under natural lightd and 365 nm UV lighte.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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To further explore the AIE characteristic of the synthesized was recorded on a C13534 UV-NIR absolute PL Quantum Yield
View Article Online
DOI: 10.1039/D0OB00479K
coumarin compounds, the single crystals of compounds 4a, 4e, Spectrometer.
4h, 4n and 4x have been obtained by the slow diffusion of their General procedure for the synthesis of 3-arylacetylene
alcohol/dichloromethane (V/V = 1/1) solution for several days coumarins 4
at room temperature (Table 2c). The X-ray single crystal To a reaction tube equipped with a magnetic stirring bar were
diffraction analysis results of the five compounds showed that added phenyl 3-phenylpropiolate (0.2 mmol), NIS (2 equiv.),
the coumarin fragment and phenylacetylene unit exhibit good MeCN (1.5 mL) stirred under 3 W blue LED (λmax = 450-465 nm)
coplanarity with small dihedral angles (4a: 10.44o, 4e: 11.81o, under air atmosphere and at room temperature for 24 hours.
4h: 4.25o, 4n: 0.61o and 4x: 2.31o), while the aromatic rings at Then Pd(PPh3)2Cl2 (0.0144 g, 10 mol %), CuI (0.0039 g, 10 mol
4-position lie out of the plane of the conjugated backbones with %), phenylacetylene (3 equiv.) and Et3N (0.5 mL) were added.
large dihedral angles (4a: 60.60o, 4e: 63.26o, 4h:60.45o, 4n: The obtained reaction mixture was heated at 60 oC for 12 hours
61.66o and 4x: 60.85o), which indicate that their AIE under Ar atmosphere. The solvent was removed under vacuum,
characteristic is not caused by intramolecular planarization.20a and the residue was purified by flash chromatography on silica
It was found that though the crystal stacking models of the five gel (eluent: petroleum ether/dichloromethane = 6:1/1:1, V/V)
compounds are different in their crystal packing diagrams. They to give the desired compound 4.
all arrange in a loose accumulation due to the steric hindrance
Characterization data for intermediate 5a and products 4
imposed by the 4-subsituted aromatic rings. There are multiple
3-iodo-7-methyl-4-phenyl-2H-chromen-2-one (5a). White solid
intermolecular forces (such as C-H···π and C-H···O or C-H···F
(67.1 mg, 93%). mp. 157.6-159.0 °C. IR (KBr) 1716, 1614, 1582,
short-range forces) between the adjacent molecules of each
1531, 1340, 1250, 1132, 981, 958, 729, 692 cm-1. 1H NMR (400
compounds (see ESI, Tables S3-S7). The experimental results
MHz, CDCl3): δ =7.58-7.54 (m, 3H), 7.24-7.20 (m, 3H), 6.97-6.91
confirm that the aromatic ring at 4-position of coumarins not
only destroys the coplanarity of the whole molecule, but also
hinders the strong π-π intermolecular interaction and the close
π-π stacking between adjacent molecules. The collective force
of these multiple electrostatic interactions can restrict
intramolecular rotation (RIR) in the solid, thus resulting in the
fluorescence enhancement in aggregation state.20 The detailed
(m, 2H), 2.43 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 160.8,
158.4, 153.2, 143.9, 139.2, 129.3, 128.9, 127.8, 127.6, 125.9,
117.9, 116.8, 90.7, 21.8. HRMS (ESI) calcd. for C16H11IO2 [M+H]+:
362.9876, found: 362.9877.
7-methyl-4-phenyl-3-(phenylethynyl)-2H-chromen-2-one (4a).
Light yellow solid (56.1 mg, 83%). mp. 171.7-172.9 oC. IR (KBr) 3053,
1
2918, 1719, 1615, 1533, 1485, 1436, 1064, 748, 687 cm-1. H NMR
AIE mechanism of the synthesized 3-arylvinyl-4-aryl-coumarins
is under way in our laboratory.
(400 MHz, CDCl3): δ = 7.57-7.55 (m, 3H), 7.50-7.48 (m, 2H), 7.26-7.23
(m, 5H), 7.21 (s, 1H), 7.16 (d, J = 8.1 Hz, 1H), 7.02 (d, J = 8.1 Hz, 1H),
2.46 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 160.0, 156.4, 153.0, 143.6,
134.6, 131.7, 129.3, 129.1, 128.7, 128.4, 128.2, 127.3, 125.8, 122.6,
Experimental section
General information
117.3, 117.2, 110.0, 98.2, 83.9, 21.8. HRMS (ESI) calcd. for C24H17O2
[M+H]+: 337.1223, found: 337.1224.
All reactions were performed using quartz tube. Solvents were dried
7-(tert-butyl)-4-phenyl-3-(phenylethynyl)-2H-chromen-2-one
by standard methods before they were used. Aryl alkynoates were
synthesized according to the literature.21 Commercial grade reagents
o
(4b). Light yellow solid (62.8 mg, 83%). mp. 180.5-182.4 C. IR (KBr)
1
3053, 2963, 1720, 1613, 1578, 1533, 1483, 1067, 710, 689 cm-1. H
were used without further purification. Silica gel was purchased from
NMR (400 MHz, CDCl3): δ = 7.56-7.53 (m, 3H), 7.51-7.49 (m, 2H), 7.41
Qing Dao Hai Yang Chemical Industry Co. All reactions were carried
(d, J = 1.3 Hz, 1H), 7.23-7.20 (m, 7H), 1.34 (s, 9H). 13C NMR (100 MHz,
out with photoreactor (Serial No: PEA12) which was purchased from
CDCl3): δ = 160.0, 156.8, 156.2, 153.0, 134.6, 131.7, 129.3, 129.1,
LUOYANG JINFENG ELECTROMECHANICAL EQUIPMENT CO., LTD. The
128.7, 128.4, 128.2, 127.2, 122.6, 122.1, 117.2, 113.9, 110.1, 98.2,
LCD Digital Hotplate Magnetic Stirrer MS-H-Pro+ and Digital Single
84.0, 35.3, 31.0. HRMS (ESI) calcd. for C27H23O2 [M+H]+: 379.1693,
Channel Adjustable Automatic Electronic Pipette Micropipette
found: 379.1695.
dPettee+ were purchased from Dragon Laboratory Instruments
7-methoxy-4-phenyl-3-(phenylethynyl)-2H-chromen-2-one (4c).
Limited. 1H NMR and 13C NMR spectra were recorded on 400 and 100
Light yellow solid (40.5 mg, 58%). mp. 145.9-147.7 oC. IR (KBr) 3056,
MHz NMR instruments using CDCl3 as the solvent and TMS as the
1
2933, 2839, 1727, 1610, 1534, 1486, 1435, 1045, 751, 694 cm-1. H
internal standard. 19F NMR spectra was recorded at 376.5 MHz on
NMR (400 MHz, CDCl3): δ = 7.56-7.53 (m, 3H), 7.49-7.47 (m, 2H),
Bruker DPX-400, the chemical shifts δ are reported relative to CFCl3
7.26-7.17 (m, 6H), 6.89 (d, J = 2.5 Hz, 1H), 6.72 (dd, J = 8.9 Hz, J = 2.5
(δ = 0 ppm) as internal standard. The multiplicity of signals is
Hz, 1H), 3.89 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 163.1, 160.0,
designated by the following abbreviations: s (singlet), d (doublet), t
156.6, 154.8, 134.7, 131.6, 129.3, 129.1, 128.7, 128.5, 128.4, 128.2,
(triplet), q (quartet), m (multiplet), dd = doublet of doublet. High
122.8, 113.3, 112.8, 107.8, 100.9, 97.6, 84.0, 55.9. HRMS (ESI) calcd.
resolution mass spectra (HRMS) was obtained on an Agilent LC-MSD-
for C24H17O3 [M+H]+: 353.1172, found: 353.1174.
Trap-XCT spectrometer with micromass MS software using
7-phenoxy-4-phenyl-3-(phenylethynyl)-2H-chromen-2-one (4d).
electrospray ionisation (ESI). The UV/Vis absorption spectra was
Yellow solid (46.6 mg, 56%). mp. 185.3-186.9 oC. IR (KBr) 3054, 2921,
recorded on a Perkin Elmer Lambda 35 Spectrometer, and the
fluorescence emission was recorded using
spectrophotometer, the solid fluorescence quantum yield spectra
1
2853, 1727, 1614, 1585, 1484, 1367, 1047, 756, 694 cm-1. H NMR
a
F-4500 FL
(400 MHz, CDCl3): δ =7.59-7.54 (m, 3H), 7.50-7.48 (m, 2H), 7.43-7.40
(m, 2H), 7.27-7.20 (m, 7H), 7.10 (dd, J = 8.7 Hz, J = 1.1 Hz, 2H), 6.90
4 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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Journal Name
ARTICLE
(d, J = 2.5 Hz, 1H), 6.85 (dd, J = 16.6Hz, J = 2.5 Hz, 1H). 13C NMR (100 131.7, 130.9, 128.6, 128.2, 127.4, 126.6, 125.7, 122.8, 117.5, 117.2,
View Article Online
MHz, CDCl3): δ = 161.6, 159.7, 156.2, 154.9, 154.4, 134.6, 131.7, 113.8, 97.8, 84.2, 55.5, 21.7. HRMS (ESI) calDcdO.I:f1o0r.1C02359H/1D9O0O3 B[M00+4H79]+K:
130.2, 129.4, 129.1, 129.0, 128.7, 128.5, 128.2, 125.3, 122.6, 120.5, 367.1329, found: 367.1330.
114.7, 114.6, 108.7, 105.0, 98.0, 83.9. HRMS (ESI) calcd. for C29H19O3
[M+H]+: 415.1329, found: 415.1326.
4-(4-fluorophenyl)-7-methyl-3-(phenylethynyl)-2H-chromen-2-
o
one (4k). Yellow solid (52.6 mg, 74%). mp. 187.7-188.8 C. IR (KBr)
1
4-phenyl-3-(phenylethynyl)-2H-chromen-2-one (4e).10e Light 3066, 1717, 1611, 1535, 1488, 1224, 1065, 751, 684 cm-1. H NMR
yellow solid (45.9 mg, 71%). mp. 169.3-170.4 oC. IR (KBr) 3054, 2922, (400 MHz, CDCl3): δ = 7.52-7.48 (m, 2H), 7.29-7.25 (m, 7H), 7.68-7.55
1
1719, 1601, 1538, 1484, 1445, 1059, 748, 696 cm-1. H NMR (400 (m, 5H), 7.21 (s, 1H), 7.14 (d, J = 8.2 Hz, 1H), 7.04 (d, J = 8.2 Hz, 1H),
MHz, CDCl3): δ = 7.60-7.55 (m, 3H), 7.51-7.47 (m, 3H), 7.40 (d, J = 8.1 2.46 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 163.2 (d, J = 250.2 Hz),
Hz, 1H), 7.30-7.19 (m, 7H). 13C NMR (100 MHz, CDCl3): δ = 159.5, 159.7, 155.1, 152.9, 143.8, 131.7, 131.2 (d, J = 8.1 Hz), 130.5, 128.9,
156.3, 152.9, 134.4, 132.1, 131.8, 129.4, 129.1, 128.8, 128.5, 128.2, 128.3, 127.1, 125.9, 122.4, 117.3, 115.7, 115.5, 110.2, 98.4, 83.7,
127.6, 124.5, 122.5, 119.7, 117.0, 111.2, 98.7, 83.8. HRMS (ESI) calcd. 21.7. 19F NMR (376.5 MHz, CDCl3): δ = -111.1. HRMS (ESI) calcd. for
for C23H15O2 [M+H]+: 323.1067, found: 323.1068.
C24H16FO2 [M+H]+: 355.1129, found: 355.1130.
7-fluoro-4-phenyl-3-(phenylethynyl)-2H-chromen-2-one
(4f).
4-(4-chlorophenyl)-7-methyl-3-(phenylethynyl)-2H-chromen-2-
Light yellow solid (50.9 mg, 75%). mp. 204.1-205.2 oC. IR (KBr) 3059, one (4l). Light yellow solid (58.4 mg, 79%). mp. 185.2-186.7 C. IR
1737, 1603, 1546, 1495, 1431, 1050, 853, 748, 695 cm-1. 1H NMR (400 (KBr) 2362, 2333, 1717, 1617, 1534, 1483, 1065, 752, 728, 686 cm-1.
MHz, CDCl3): δ = 7.60-7.54 (m, 3H), 7.49-7.48 (m, 2H), 7.29-7.20 (m, 1H NMR (400 MHz, CDCl3): δ = 7.56-7.54 (m, 2H), 7.46-7.44 (m, 2H),
6H), 7.11 (dd, J = 8.8 Hz, J = 2.3 Hz, 1H), 6.95 (td, J = 8.3 Hz, J = 2.3 Hz, 7.29-7.26 (m, 5H), 7.21 (s, 1H), 7.12 (d, J = 8.2 Hz, 1H), 7.03 (dd, J =
1H). 13C NMR (100 MHz, CDCl3): δ = 164.5 (d, J = 256.0 Hz), 159.2, 33.4 Hz, J = 1.0 Hz, 1H), 2.46 (s, 3H), 2.43 (s, 3H). 13C NMR (100 MHz,
155.7, 153.9 (d, J = 13.2 Hz), 134.2, 131.7, 130.0, 129.4 (d, J = 9.5 Hz), CDCl3): δ = 159.6, 154.8, 152.9, 143.8, 135.5, 133.0, 131.7, 130.6,
129.0, 128.9, 128.6, 128.2, 122.4, 116.5, 112.6 (d, J = 22.7 Hz), 110.1, 128.9, 128.8, 128.3, 127.0, 125.9, 122.4, 117.3, 117.0, 110.2, 98.7,
104.5 (d, J = 25.7 Hz), 98.7, 83.5. 19F NMR (376.5 MHz, CDCl3): δ = - 83.6, 21.7. HRMS (ESI) calcd. for C24H16ClO2 [M+H]+: 371.0833, found:
104.5. HRMS (ESI) calcd. for C23H14FO2 [M+H]+: 341.0972, found: 371.0834.
o
341.0971.
7-methyl-4-phenyl-3-(p-tolylethynyl)-2H-chromen-2-one (4m).
7-chloro-4-phenyl-3-(phenylethynyl)-2H-chromen-2-one
(4g). Light yellow solid (52.1 mg, 74%). mp. 191.5-192.8 oC. IR (KBr) 2363,
Light yellow solid (50.4 mg, 71%). mp. 177.8-178.4 oC. IR (KBr) 3058, 2333, 1717, 1617, 1535, 1509, 1368, 1063, 811, 763, 712 cm-1. H
1
2923, 1735, 1596, 1518, 1484, 1413, 1054, 755, 693 cm-1. H NMR NMR (400 MHz, CDCl3): δ = 7.58-7.53 (m, 3H), 7.51-7.47 (m, 2H), 7.20
1
(400 MHz, CDCl3): δ = 7.58-7.57 (m, 3H), 7.49-7.47 (m, 2H), 7.41 (d, J (s, 1H), 7.16-7.10 (m, 3H), 7.05-7.00 (m, 3H), 2.45 (s, 3H), 2.30 (s, 3H).
= 1.2 Hz, 1H), 7.30-7.16 (m, 7H). 13C NMR (100 MHz, CDCl3): δ = 158.9, 13C NMR (100 MHz, CDCl3): δ = 159.9, 156.0, 152.9, 143.4, 139.0,
155.4, 153.0, 138.0, 134.0, 131.8, 129.6, 129.0, 128.9, 128.6, 128.5, 134.6, 131.6, 129.3, 129.2, 129.0, 128.4, 127.3, 125.7, 119.6, 117.4,
128.3, 125.1, 122.3, 118.4, 117.3, 111.1, 99.2, 83.6. HRMS (ESI) calcd. 117.2, 110.2, 98.6, 83.4, 21.7, 21.6. HRMS (ESI) calcd. for C25H19O2
for C23H14ClO2 [M+H]+: 357.0677, found: 357.0676.
[M+H]+: 351.1380, found: 351.1384.
4-phenyl-3-(phenylethynyl)-7-(trifluoromethyl)-2H-chromen-2-
3-((4-methoxyphenyl)ethynyl)-7-methyl-4-phenyl-2H-chromen-
o
one (4h). Yellow solid (50.6 mg, 65%). mp. 169.3-170.8 C. IR (KBr) 2-one (4n). Light yellow solid (58.0 mg, 79%). mp. 180.9-182.4 oC. IR
1
3056, 2924, 1739, 1613, 1546, 1497, 1425, 1058, 748, 682 cm-1. H (KBr) 3056, 3018, 2970, 2926, 1732, 1612, 1503, 1449, 1058, 1023,
NMR (400 MHz, CDCl3): δ = 7.65 (s, 1H), 7.62-7.58 (m, 3H), 7.51-7.49 821, 756, 694 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.53-7.53 (m, 3H),
(m, 2H), 7.46-7.40 (m, 2H), 7.32-7.22 (m, 5H). 13C NMR (100 MHz, 7.49-7.47 (m, 2H), 7.19 (s, 1H), 7.16-7.13 (m, 3H), 7.01 (d, J = 8.1 Hz,
CDCl3): δ = 158.5, 153.5 (d, J = 230.4 Hz), 133.8, 133.3 (d, J = 33.0 Hz), 1H), 6.76 (d, J = 8.8 Hz, 2H) 3.77 (s, 3H), 2.44 (s, 3H). 13C NMR (100
131.9, 129.8, 129.2, 129.0, 128.7, 128.3, 128.2, 124.5, 122.4, 122.1, MHz, CDCl3): δ = 160.0 159.9, 155.5, 152.8, 143.3, 134.7, 133.2, 129.2,
121.8, 120.9 (q, J = 7.3 Hz, J = 3.7 Hz), 114.4 (q, J = 8.1 Hz, J = 3.7 Hz), 129.1, 128.4, 127.2, 125.7, 117.4, 117.1, 114.7, 113.9, 110.3, 98.5,
113.3, 100.3, 83.4. 19F NMR (376.5 MHz, CDCl3): δ = -62.9. HRMS (ESI) 82.9, 55.3, 21.7. HRMS (ESI) calcd. for C25H19O3 [M+H]+: 367.1329,
calcd. for C24H14F3O2 [M+H]+: 391.0940, found: 391.0936.
found: 367.1328.
6,8-dimethyl-4-phenyl-3-(phenylethynyl)-2H-chromen-2-one (4i).
3-((4-fluorophenyl)ethynyl)-7-methyl-4-phenyl-2H-chromen-2-
o
Yellow solid (54.9 mg, 78%). mp. 189.4-190.7 oC. IR (KBr) 3054, 3017, one (4o). Yellow solid (52.9 mg, 75%). mp. 208.7-210.2 C. IR (KBr)
1
2916, 1721, 1600, 1541, 1480, 1077, 1051, 752, 690 cm-1. H NMR 3064, 3030, 2922, 2332, 1721, 1611, 1499, 1366, 1323, 1221, 1057,
(400 MHz, CDCl3): δ = 7.57-7.55 (m, 3H), 7.48-7.46 (m, 2H), 7.25-7.21 761, 700, 643 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.57-7.55 (m, 3H),
(m, 6H), 6.85 (s, 1H), 2.47 (s, 3H), 2.26 (s, 3H). 13C NMR (100 MHz, 7.49-7.47 (m, 2H), 7.21-7.14 (m, 4H), 7.02 (d, J = 8.1 Hz, 1H), 6.93 (t,
CDCl3): δ = 159.8, 156.8, 149.5, 135.0, 134.7, 133.6, 131.7, 129.2, J = 8.7 Hz, 2H), 2.46 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 162.7 (d,
129.1, 128.7, 128.4, 128.2, 126.1, 125.0, 122.6, 119.2, 110.8, 98.4, J = 250.9 Hz), 159.8, 156.4, 153.0, 143.7, 134.6, 133.6 (d, J = 8.8 Hz),
84.2, 20.9, 15.6. HRMS (ESI) calcd. for C25H19O2 [M+H]+: 351.1380, 129.4, 129.1, 128.4, 127.3, 125.8, 118.7 (d, J = 3.7 Hz), 117.3, 117.2,
found: 351.1382.
115.5 (d, J = 22.0 Hz), 109.8, 97.1, 83.7, 21.7. 19F NMR (376.5 MHz,
CDCl3): δ = -109.9. HRMS (ESI) calcd. for C24H16FO2 [M+H]+: 355.1129,
4-(4-methoxyphenyl)-7-methyl-3-(phenylethynyl)-2H-chromen-
2-one (4j). Yellow solid (31.7 mg, 43%). mp. 169.1-170.2 oC. IR (KBr) found: 355.1126.
3020, 1724, 1608, 1539, 1490, 1441, 1060, 1027, 757, 690 cm-1. H
3-((4-chlorophenyl)ethynyl)-7-methyl-4-phenyl-2H-chromen-2-
1
o
NMR (400 MHz, CDCl3): δ = 7.47 (d, J = 8.7 Hz, 2H), 7.32-7.20 (m, 7H), one (4p). Yellow solid (51.7 mg, 70%). mp. 234.3-236.4 C. IR (KBr)
7.08 (d, J = 8.7 Hz, 2H), 7.03 (d, J = 21.4 Hz, 1H), 3.92 (s, 3H), 2.46 (s, 3055, 3042, 2909, 1716, 1614, 1582, 1531, 729, 692, 630 cm-1. H
1
3H). 13C NMR (100 MHz, CDCl3): δ = 160.5, 160.0, 156.0, 153.0, 143.5, NMR (400 MHz, CDCl3): δ = 7.59-7.54 (m, 3H), 7.49-7.47 (m, 2H),
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ARTICLE
Journal Name
7.21-7.19 (m, 3H), 7.17-7.11 (m, 3H), 7.02 (dd, J = 8.2 Hz, J = 0.9 Hz, (376.5 MHz, CDCl3): δ = -110.2. HRMS (ESI) calcd. Vfioewr ACrt2ic4lHe 1O6nFlOine3
1H), 2.46 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 159.7, 156.7, 153.0, [M+H]+: 371.1078, found: 371.1081.
DOI: 10.1039/D0OB00479K
143.8, 134.7, 134.5, 132.8, 129.4, 129.1, 128.6, 128.4, 127.4, 125.8,
7-methoxy-4-phenyl-3-((4-(trifluoromethyl)phenyl)ethynyl)-2H-
121.1, 117.2, 109.7, 96.9, 84.9, 21.8. HRMS (ESI) calcd. for C24H16ClO2 chromen-2-one (4v). Light yellow solid (29.4 mg, 35%). mp. 209.6-
o
[M+H]+: 371.0833, found: 371.0837.
7-methyl-4-phenyl-3-((4-(trifluoromethyl)phenyl)ethynyl)-2H-
210.5 C. IR (KBr) 3057, 2927, 2851, 1726, 1613, 1537, 1511, 1462,
1322, 1284, 1124, 837, 701, 630 cm-1. 1H NMR (400 MHz, CDCl3): δ =
chromen-2-one (4q). Light yellow solid (42.9 mg, 53%). mp. 221.9- 7.59-7.56 (m, 3H), 7.50-7.47 (m, 4H), 7.29 (d, J = 8.1 Hz, 2H), 7.20 (d,
o
223.8 C. IR (KBr) 3060, 2924, 1739, 1613, 1540, 1486, 1322, 1256, J = 8.9 Hz, 1H), 6.91 (d, J = 2.5 Hz, 1H), 6.80 (dd, J = 9.1 Hz, J = 2.6 Hz,
1166, 1125, 1048, 775, 730, 694, 655 cm-1. 1H NMR (400 MHz, CDCl3): 1H), 3.90 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 163.4, 159.9, 157.8,
δ = 7.59-7.56 (m, 3H), 7.50-7.48 (m, 4H), 7.30 (d, J = 8.0 Hz, 2H), 7.22 155.0, 134.5, 131.7, 130.0 (d, J = 33.0 Hz), 129.5, 129.0, 128.9, 128.5,
(s, 1H), 7.17 (d, J = 8.2 Hz, 1H), 7.04 (dd, J = 8.2 Hz, J = 1.1 Hz, 1H), 126.5, 125.1 (q, J = 7.3 Hz, J = 3.7 Hz), 122.5, 113.2, 113.1, 107.1,
2.47 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 159.6, 157.6, 153.1, 144.2, 100.9, 95.8, 86.3, 55.9. 19F NMR (376.5 MHz, CDCl3): δ = -62.9. HRMS
134.4, 131.8, 130.7, 130.2 (d, J = 32.3 Hz), 129.5, 128.7 (d, J = 55.8 (ESI) calcd. for C25H16F3O3 [M+H]+: 421.1046, found: 421.1047.
Hz), 127.5, 126.4 (d, J = 1.5 Hz), 125.9, 125.1 (q, J = 8.1 Hz, J = 3.7 Hz),
7-methoxy-3-((4-methoxyphenyl)ethynyl)-4-phenyl-2H-
122.5, 117.3, 117.2, 109.4, 96.3, 86.2, 21.8. 19F NMR (376.5 MHz, chromen-2-one (4w). Yellow solid (34.0 mg, 45%). mp. 231.4-232.1
CDCl3): δ = -62.9. HRMS (ESI) calcd. for C25H16F3O2 [M+H]+: 405.1097, oC. IR (KBr) 3059, 3009, 2199, 1723, 1609, 1503, 1460, 1376, 1277,
found: 405.1100.
3-((2-methoxyphenyl)ethynyl)-7-methyl-4-phenyl-2H-chromen-
1055, 1020, 828, 761, 706, 633 cm-1. 1H NMR (400 MHz, CDCl3): δ =
7.57-7.54 (m, 3H), 7.49-7.47 (m, 2H), 7.17 (t, J = 9.2 Hz, 3H), 6.89 (d,
2-one (4r). Yellow solid (51.3 mg, 70%). mp. 162.1-163.4 oC. IR (KBr) J = 2.5 Hz, 1H), 6.79-6.75 (m, 3H), 3.89 (s, 3H), 3.78 (s, 3H). 13C NMR
3057, 2984, 1726, 1615, 1582, 1487, 1454, 1246, 1054, 1017, 699, (100 MHz, CDCl3): δ = 162.9, 160.2, 159.9, 155.7, 154.6, 134.8, 133.1,
647 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.55-7.49 (m, 5H), 7.26-7.14 129.2, 129.1, 128.6, 128.4, 114.9, 113.9, 113.4, 112.8, 108.1, 100.8,
(m, 4H), 7.01 (d, J = 8.2 Hz, 1H) 6.84-6.77 (m, 2H), 3.76 (s, 3H), 2.45 97.9, 82.8, 55.9, 55.3. HRMS (ESI) calcd. for C25H19O4 [M+H]+:
(s, 3H). 13C NMR (100 MHz, CDCl3): δ = 160.2, 159.8, 155.5, 152.9, 383.1278, found: 383.1279.
143.3, 134.6, 133.7, 130.3, 129.2, 129.1, 128.3, 127.3, 125.7, 120.3,
117.4, 117.2, 112.0, 110.7, 110.3, 94.9, 87.7, 55.8, 21.7. HRMS (ESI) one (4x). Light yellow solid (52.9 mg, 72%). mp. 197.3-198.1 C. IR
calcd. for C25H19O3 [M+H]+: 367.1329, found: 367.1327.
7-fluoro-3-((4-methoxyphenyl)ethynyl)-4-phenyl-2H-chromen-2-
o
(KBr) 2378, 2313, 2203, 1728, 1606, 1547, 1511, 1427, 1247, 1050,
1
3-((2-fluorophenyl)ethynyl)-7-methyl-4-phenyl-2H-chromen-2-
1025, 822, 762, 703 cm-1. H NMR (400 MHz, CDCl3): δ = 7.60-7.55
o
one (4s). Yellow solid (56.5 mg, 79%). mp. 179.6-181.3 C. IR (KBr) (m, 3H), 7.49-7.47 (m, 2H), 7.29-7.25 (m, 1H), 7.16 (d, J = 8.8 Hz, 2H),
3057, 2984, 2940, 2840, 1726, 1615, 1582, 1487, 1455, 1246, 1054, 7.11 (dd, J = 8.9 Hz, J = 2.5 Hz, 1H), 6.94 (td, J = 8.4 Hz, J = 2.5 Hz, 1H),
1017, 753, 699 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.57-7.48 (m, 5H), 6.77 (d, J = 8.7 Hz, 2H), 3.78 (s, 3H). 13C NMR (100 MHz, CDCl3): δ =
7.31-7.17 (m, 4H), 7.04-6.96 (m, 3H), 2.46 (s, 3H). 13C NMR (100 MHz, 164.3 (d, J = 255.3 Hz), 160.1, 159.3, 154.8, 153.8 (d, J = 13.2 Hz),
CDCl3): δ = 162.7 (d, J = 253.8 Hz), 159.7, 156.8, 153.1, 143.9, 134.2, 134.4, 133.3, 129.5, 129.2 (d, J = 9.5 Hz), 129.1, 128.5, 116.6 (d, J =
133.5, 130.5 (d, J = 7.3 Hz), 129.4, 129.0, 128.5, 127.5, 125.8, 123.8 2.9 Hz), 114.5, 113.9, 112.6 (d, J = 22.7 Hz), 110.4 (d, J = 2.9 Hz), 104.5
(d, J = 3.7 Hz), 117.2, 115.4 (d, J = 20.5 Hz), 111.4, 111.3, 109.6, 91.3, (d, J = 25.7 Hz), 99.1, 82.5, 55.3. 19F NMR (376.5 MHz, CDCl3): δ = -
88.5 (d, J = 3.7 Hz), 21.7. 19F NMR (376.5 MHz, CDCl3): δ = -108.5. 105.0. HRMS (ESI) calcd. for C25H16FO3 [M+H]+: 371.1078, found:
HRMS (ESI) calcd. for C24H16FO2 [M+H]+: 355.1129, found: 355.1126. 371.1076.
7-(tert-butyl)-3-((4-fluorophenyl)ethynyl)-4-phenyl-2H-
3-((4-methoxyphenyl)ethynyl)-4-phenyl-7-(trifluoromethyl)-2H-
chromen-2-one (4t). Light yellow solid (65.0 mg, 82%). mp. 185.9- chromen-2-one (4y). Light yellow solid (63.7 mg, 76%). mp. 200.8-
o
o
186.7 C. IR (KBr) 2961, 2905, 2869, 1738, 1614, 1500, 1415, 1367, 201.5 C. IR (KBr) 3067, 3024, 2924, 2378, 2198, 1742, 1598, 1546,
1330, 1218, 1049, 828, 763, 699 cm-1. 1H NMR (400 MHz, CDCl3): δ = 1508, 1425, 1327, 1170, 1133, 1049, 1021, 830, 758, 699 cm-1. H
1
7.57-7.55 (m, 3H), 7.50-7.48 (m, 2H), 7.42 (d, J = 1.7 Hz, 1H), 7.27- NMR (400 MHz, CDCl3): δ = 7.63-7.58 (m, 4H), 7.51-7.48 (m, 2H),
7.19 (m, 4H), 6.93 (t, J = 8.7 Hz, 2H), 1.35 (s, 9H). 13C NMR (100 MHz, 7.44-7.39 (m, 2H), 7.17 (d, J = 8.8 Hz, 2H), 6.78 (d, J = 8.8 Hz, 2H), 3.79
CDCl3): δ = 162.7 (d, J = 250.2 Hz), 159.9, 156.9, 156.3, 152.9, 134.5, (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 160.3, 152.3, 150.4, 142.3,
133.6 (d, J = 8.8 Hz), 129.4, 129.1, 128.4, 127.2, 122.2, 118.7 (d, J = 136.9, 136.6, 135.0, 133.3, 130.3, 128.9, 128.8, 127.8, 127.2, 126.0,
2.9 Hz), 117.2, 115.5 (d, J = 22.7 Hz), 113.9, 110.0, 97.1, 83.7, 35.3, 125.4, 125.1, 122.9, 120.7, 118.6, 116.6, 21.6, 19.9. 19F NMR (376.5
31.0. 19F NMR (376.5 MHz, CDCl3): δ = -109.9. HRMS (ESI) calcd. for MHz, CDCl3): δ = -62.9. HRMS (ESI) calcd. for C25H16F3O3 [M+H]+:
C27H22FO2 [M+H]+: 397.1598, found: 397.1596.
421.1046, found: 421.1048.
3-((4-fluorophenyl)ethynyl)-7-methoxy-4-phenyl-2H-chromen-2-
o
one (4u). Yellow solid (33.8 mg, 46%). mp. 178.8-179.6 C. IR (KBr)
3064, 2992, 2943, 2841, 1731, 1611, 1500, 1375, 1267, 1214, 1055,
829, 761, 700, 645 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.59-7.55 (m,
Conclusions
In summary, we have developed a mild and efficient one-pot
3H), 7.49-7.46 (m, 2H), 7.21-7.17 (m, 3H), 6.95-6.89 (m, 3H), 6.78 (dd, stepwise method to synthesize 3-arylacetylene coumarins from
J = 8.9 Hz, J = 2.5 Hz, 1H), 3.89 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = simple alkynoates via the thermocatalysis and photocatalysis
163.1, 162.6 (d, J = 250.2 Hz), 160.1, 156.6, 154.8, 134.7, 133.5 (d, J processes. This catalytic system exhibits the excellent functional
= 8.8 Hz), 129.3, 129.0, 128.7, 128.4, 118.8 (d, J = 3.7 Hz), 115.5 (d, J group tolerance and substrate suitability. Moreover, the optical
= 22.0 Hz), 113.3, 112.9, 107.6, 100.9, 96.5, 83.7, 55.9. 19F NMR properties of these synthesized coumarins were systematically
studied. Based on the spectral studies and X-ray single crystal
6 | J. Name., 2012, 00, 1-3
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Y. Moon, C. Lee, S. Choi, N. G. Almstead, N. A. VNieawrAyrstihclkeiOnn,liAne.
diffraction analysis, we found that some of the 3-arylvinyl-4-
aryl-coumarins may have AIE-activity. The AIE- and other
biological activity of 4-aryl substituted coumarins is under way
in our laboratory.
Dakka, J. Narasimhan, V. Gabbeta, E. Welch, X. Zhao, N.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We greatly acknowledge partial financial support from the
National Natural Science Foundation (NSF) of China (21172200
and 21302172) and Zhengzhou University.
7
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