Multicomponent Synthesis of Iminocoumarins via Rhodium-Catalyzed C - H Bond Activation

Article abstract of DOI:10.1021/acs.joc.0c01303

We herein establish a multicomponent annulation method for the synthesis of valuable iminocoumarins using aryl thiocarbamates, internal alkynes, and sulfonamides as starting materials, which are safe and readily available. The key step is a Rh-catalyzed a

Full text of DOI:10.1021/acs.joc.0c01303

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Multicomponent Synthesis of Iminocoumarins
via Rhodium-Catalyzed C-H Bond Activation
Zhan Chen, Shengnan Jin, Wenyao Jiang, Feimin Zhu, Yuqi Chen, and Yingwei Zhao
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.0c01303 • Publication Date (Web): 16 Jul 2020
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The Journal of Organic Chemistry
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Multicomponent Synthesis of Iminocoumarins via Rhodium-
Catalyzed C−H Bond Activation
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Zhan Chen, Shengnan Jin, Wenyao Jiang, Feimin Zhu, Yuqi Chen, and Yingwei Zhao*
College of Chemical Engineering, Huaqiao University, 668 Jimei Boulevard, Xiamen 361021, P. R. China
[Cp*RhCl ] (2.5 mol%)
2
2
R2
R3
AgSbF (10 mol%)
6
O
NTs
R2
O
NMe2
Cu(OAc) (1 equiv)
R1
2
R1
+
+ TsNH2
DCE, 120 °C, 12 h
S
R3
ABSTRACT: We herein establish a multicomponent annulation method for the synthesis of valuable iminocoumarins using aryl
thiocarbamates, internal alkynes, and sulfonamides as starting materials which are safe and readily available. The key step is a Rh-
catalyzed and sulfur-directed C−H bond activation. Preliminary mechanistic investigations suggested that the nucleophilic attack of
sulfonamide onto an active iminium cation finally completes the imine segment.
Coumarins and their derivatives are known important
molecules with widespread applications in medicine,
perfumery, and material chemistry. The iminocoumarins have
a) Known cleavage style of Multicomponent Syntheses of Iminocoumarins
OR
OH
OH
1
3
O
or
or
O
NSO R
2
attracted considerable attentions own to their interesting
biomedical features including antagonistic, antitumor, anti-
R1
N
EWG
2
3
R2
R2
+
+
R1
4
5
R3 SO N
HIV and lipoxygenase inhibitory activities. In recent years,
iminocoumarins are also found to be efficient fluorescent
2
3
6
7
b) This work
dyes and fluorescence probes. Along with the increasing
studies spread out on various domains, the methods for the
construction of iminocoumarins are improving. Traditional
Knoevenagel condensation suffers from the drawbacks of
3
O
NSO R
O
NMe2
2
R1
R2
+
+
S
H
R3 SO2NH2
R2
R1
6a,
8
harsh condition and limited substrate scope.
Another

CH activation strategy
 Sulfamide instead of sulfonyl azide
strategy refers to the modification of coumarin framework
which requires the pre-activation of carbonyl group, usually
by transformation to more reactive thiocarbonyl by
Scheme 1. Synthetic strategies for iminocoumarins
In recent years, transition-metal-catalyzed C−H bond
activation has been regarded as an emerging weapon to
provide novel solutions for the problems in organic
5, 9
Lawesson’s reagent. Multicomponent reaction is a powerful
tool to construct complex functional molecules from simple
10
substrates in one pot. In 2006, Wang and co-workers
13
synthesis. It has also been successfully applied in annulation
pioneered a general and efficient copper-catalyzed three
component cyclization of a sulfonyl azide, a terminal alkyne,
and a salicylaldehyde or 2-hydroxylacetophenone to afford the
of multiple unreactive substrates via metallacyclic
14
intermediates to construct heterocycles. We and Satoh group
have independently developed a Rh-catalyzed oxidative
11
iminocoumarin skeleton. Following this strategy, a variety of
15
annulation protocol to construct coumarins
via
a
analogous reactions were developed for the preparation of
functionalized iminocoumarins by using other phenol
16
thiocarbamate group directed C−H activation. The final step
to finish coumarin’s lactone skeleton is the nucleophilic attack
of acetic anion on the highly reactive iminium cation in the
structure of rhodacycle intermediate. This reactivity of such
intermediates may allow the nucleophilic attack by amines to
afford iminocoumarin, while the direct attack and
condensation of an amine with the carbonyl group of coumarin
has rarely been seen. In this work, we proved that this strategy
derivatives
hydroxylacetophenone (Scheme 1a).
instead
of
salicylaldehyde
or
2-
2
, 12
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Page 2 of 9
could be used to disconnect iminocoumarin structure into an
aryl thiocarbamate which can be readily prepared from phenol,
an internal alkyne, and a sulfonamide instead of sulfonyl azide
as the nucleophile and imine source, which is safe and widely
available (Scheme 1b).
mmol), solvent (1 mL). All the reactions were performed in sealed
b
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
tubes under air atmosphere at 120 °C for 12 h.
1 mol% of
c
[
Cp*RhCl
2
]
2
and 4 mol% of AgSbF
6
were used. 130 °C.
With the optimal condition in hand, we then examined the
scope and limitations of the multicomponent annulation
reaction by changing the electronic and steric nature of the
aryl thiocarbamates (Scheme 2). The investigation of their
reactivity in annulation with diphenylacetylene (2a) and p-
toluenesulfonamide (3a) revealed that both electron donating
We began with this program by utilizing O-phenyl N,N-
dimethylthiocarbamate (1a), diphenylacetylene (2a) and p-
toluenesulfonamide (3a) as the model substrates (Table 1).
Exposure of them to the catalyst [Cp*RhCl
2 2
] , the additive
AgSbF and the oxidant Cu(OAc) in tert-amyl alcohol
6
2
(alkyl, alkoxy, methylthio, acetamido) and electron
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
afforded the desired iminocoumarin (4a) in a moderate 37%
yield (entry 1). Next, we screened various common solvents.
To our delight, the use of 1,2-dichloroethane (DCE) led to
84% yield of the product (entry 3). Other polar aprotic
solvents also resulted in good yields except for DMF. We then
studied the effect of different silver salts. It was found that
withdrawing (halogen, methoxycarbonyl, formyl,
trifluoromethyl) substituents at the para position of the
corresponding aryl thiocarbamate resulted in satisfactory
yields of the iminocoumarin products (4b – 4l). It is worth
noting that the existence of the known directing group
acetamido did not interfere with this reaction (4f), showing the
stronger coordination ability of thiocarbonyl. The
hydroquinone derived dithiocarbamate only led to mono-
cyclization product (4g), even when exposed to large excess of
AgNTf
unexpectedly inhibited the reaction completely (entries 7 and
). A moderate yield could also be obtained in the absence of a
silver salt (entry 9). Examination of the oxidants revealed that
stoichiometric amount of AgOAc and Cu(OAc) ·5H O were
also efficient oxidants compared to Cu(OAc) , albeit in
2
also exhibited comparative efficiency, while AgOTf
8
2
a and 3a. The structure of 4i was unambiguously confirmed
2
2
by X-ray single crystal diffraction analysis (See Supporting
2
1
7
Information).
Examination of steric effect was then
diminishment of the yield (entries 10 and 11). Control
experiments showed that both Rh catalyst and the oxidant are
indispensable for this reaction (entries 12 and 13). Still good
yield was obtained when the catalyst loading was lowered to 1
mol % (entry 14). Finally, the effect of reaction temperature
was studied and it was shown that further increasing to 130 °C
did not lead to an improvement on the product yield (entry 15).
performed through placing a substituent at the ortho position.
Desired nitro substituted iminocoumarin 4m and 1-naphthol
derivative 4o formed smoothly. The phenyl group at the ortho
position of phenyl thiocarbamate exhibited significant steric
effect for the reaction, resulting in a low yield for 4n. When
meta-methyl substituted thiocarbamate was submitted to this
reaction, iminocoumarin 4p was detected as the only product
in 57% yield. The same selectivity was obtained for the
benzodioxole derived product 4d.
Table 1 Optimization of the reaction conditions a
catalyst (2.5 mol%)
Ph
[Cp*RhCl2]2 (2.5 mol%)
AgSbF6 (10 mol%)
Ph
additive (10 mol%)
oxidant (1.2 equiv)
O
NTs
O
NTs
Ph
O
NMe2
O
NMe2
R
+
+
TsNH2
R
+
+
TsNH2
S
Cu(OAc)2 (1.2 equiv)
DCE, 120 °C, 12 h
solvent
Ph
S
Ph
2a
3a
120 °C, 12 h
Ph
1
Ph
4
Ph
4a
1
a
2a
3a
O
NTs
Ph
O
NTs
Ph
O
O
O
NTs
Ph
tBu
MeO
Yield
%)
Ph
Ph
Ph
Entry Catalyst
Additive Oxidant
Solvent
(
4b, 67%
4c, 81%
4d, 76%
1
[Cp*RhCl
2
]
2
AgSbF
6
Cu(OAc)
2
t-AmOH
37
O
NTs
Ph
O
NTs
Ph
O
NTs
Ph
S
2
[Cp*RhCl
[Cp*RhCl
[Cp*RhCl
[Cp*RhCl
[Cp*RhCl
[Cp*RhCl
[Cp*RhCl
[Cp*RhCl
[Cp*RhCl
[Cp*RhCl
[Cp*RhCl
-
2
2
2
2
2
2
2
2
2
2
2
]
]
]
]
]
]
]
]
]
]
]
2
2
2
2
2
2
2
2
2
2
2
AgSbF
AgSbF
AgSbF
AgSbF
AgSbF
6
6
6
6
6
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
2
2
2
2
2
2
2
2
THF
69
84
10
76
77
80
0
MeS
AcHN
Me2N
O
Ph
e, 88%
Ph
4f, 67%
3
DCE
Ph
4
4g, 48%
4
DMF
acetone
MeCN
DCE
O
NTs
Ph
O
NTs
Ph
O
NTs
Ph
5
MeO
Cl
Br
6
Ph
Ph
O
Ph
4j, 75%
7
AgNTf
2
4h, 50%
4i
,
73%
8
AgOTf Cu(OAc)
DCE
NO2
O
NTs
Ph
O
NTs
Ph
O
NTs
Ph
9
-
Cu(OAc)
AgOAc
Cu(OAc)
-
DCE
58
52
45
0
H
F3C
10
11
-
DCE
O
Ph
Ph
Ph
4m, 63%
AgSbF
AgSbF
AgSbF
AgSbF
AgSbF
6
6
6
6
6
2
2
·5H O DCE
4
k, 49%
4l, 75%
1
1
1
1
2
DCE
DCE
DCE
DCE
3
Cu(OAc)
Cu(OAc)
Cu(OAc)
2
2
2
0
Me
O
NTs
Ph
O
NTs
Ph
4 b [Cp*RhCl
O
NTs
Ph
2
]
]
2
2
79
77
5 c [Cp*RhCl
2
Ph
Ph
a
Ph
4n, 26%
Reaction conditions: 1a (0.25 mmol), 2a (0.3 mmol), 3a (0.25
mmol), catalyst (0.00625 mmol), additive (0.025 mmol), oxidant (0.3
4o, 80%
4p, 57%
Scheme 2 Scope of aryl thiocarbamates
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The Journal of Organic Chemistry
This result implied that the C=N double bond was not
1
2
3
4
5
6
7
8
9
Next, the effects of changing the substituent on the
diphenylacetylene (2) and sulfonamide (3) were surveyed
Scheme 3). It was found that electron-donating substituents
generated from the direct carbonyl-amine condensation. The
reactivity of thiocarbonyl is known to be much higher in
19
(
comparison with carbonyl. Thiocoumarins can readily react
5
7b
were well tolerated at the 3-position or 4-position to provide
iminocoumarins 4q and 4r in moderate to good yield
respectively. The electro-withdrawing Br and Cl group at 4-
position were also tolerated, albeit the yields were attenuated
(4s and 4t). The thienyl-substituted alkyne led to
corresponding product 4u in low yield probably because of the
instability of thiophene ring. The present reaction was also
successfully extended to aliphatic alkyne. The expected
iminocoumarin 4v was obtained from the reaction of 1a, 3a
and 4-octyne in 39% yield. The unsymmetric 1-phenyl-1-
butyne led to 4w (the structure was confirmed by the NOESY
spectrum, see Supporting Information) as the sole product,
with hydrazine or hydroxylamine to afford iminocoumarin
analogues. However, heating thiocoumarin with p-
6
toluenesulfonamide 3a in DCE led to no reaction (Scheme 4c).
It might be resulted from the low nucleophilicity of
sulfonamide. When the reaction was performed under the
standard Rh/Ag/Cu system, a S to O exchange product
coumarin 5b was isolated in 28% yield accompany with only
trace amount of corresponding iminocoumarin which was
detected by LC-MS (Scheme 4d). These results showed that
thiocoumarin could not be the intermediate of this reaction and
desulfurization might take place before the nucleophilic attack
by sulfonamide.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
8
O
O
which is attributed to the steric effect. The reaction using
terminal alkynes such as phenylacetylene did not proceed,
probably because of the formation of alkynyl copper species.
Benzensulfonamide and 4-methoxy benzensulfonamide led to
the corresponding products in comparative good yields (4x
and 4y), while 4-nitro benzensulfonamide gave low yield of 4z,
probably due to its low nucleophilicity. Finally, aliphatic-
substituted sulfonamide was also reactive in this
transformation (4za). However, the utilization of other kinds
of amine or amide compounds failed to afford corresponding
DCE, 120 °C, 12 h
+
TsNH2
No reaction
(a)
Ph
3a
Ph
5a
[
Cp*RhCl2]2 (2.5 mol%)
AgSbF6 (10 mol%)
Cu(OAc)2 (1 equiv)
O
O
S. M.
+
+
TsNH2
(b)
(c)
Ph
DCE, 120 °C, 12 h complex mixture
3a
Ph
5a
iminocoumarin products.
O
S
1
NR3
R2
R
[Cp*RhCl2]2 (2.5 mol%)
AgSbF6 (10 mol%)
O
DCE, 120 °C, 12 h
No reaction
O
NMe2
+ TsNH2
3
Ph
+
+
R NH
2
S
Cu(OAc)2 (1.2 equiv)
DCE, 120 °C, 12 h
3a
Me
R2
2
R1
4
6
1a
3
O
NTs
O
NTs
[Cp*RhCl2]2 (2.5 mol%)
AgSbF6 (10 mol%)
Cu(OAc)2 (1 equiv)
O
NTs
O
S
O
O
+
TsNH2
(d)
Ph
DCE, 120 °C, 12 h
Ph
Br
3a
OMe
Me
6
Me
5b, 28%
Me
Me
OMe
r, 67%
Br
4s, 31%
Scheme 4 The reaction of coumarin or thiocoumarin with p-
toluenesulfonamide
4q, 47%
4
O
NTs
O
NTs
O
NTs
O
NTs
Based on the above results as well as the previous
mechanistic studies, we proposed the following catalytic cycle
S
Cl
Me
Me
III
S
as illustrated in Scheme 5. Initially, the reactive cationic Rh
complex is generated in the presence of AgSbF and/or
Cu(OAc) . Directed by polarized thiocarbamate group, the
Me
6
Cl
t, 33%
4w
, 56%
4u, 22%
4v, 39%
4
2
ortho C−H bond activation is realized to form a six-membered
rhodacyclic complex A. Next, alkyne insertion and
desulfurization take place to give the seven-membered
rhodacycle B containing an iminium cation. It is unclear which
step occurs prior. The nucleophilic attack by sulfonamide
affords the more thermodynamically stable imine intermediate
C, followed by reductive elimination to release the
OMe
NO2
O
O
O
O
O
S
N
O
S
N
O
NSO Ph
2
O
NSO2Me
Ph
Ph
Ph
Ph
Ph
Ph
Ph
4z, 21%
Ph
4za, 36%
4x, 66%
4y, 63%
I
iminocoumarin 4a and a Rh species which is then oxidized by
II
Scheme 3 Scope of alkynes and amines
Cu to complete the catalytic cycle. Alternatively, the
reductive elimination of B releases the reactive iminium
intermediate D which is attacked by sulfonamide to afford the
iminocoumarin product (shown in dashed arrows).
To gain insights into the sequence of the multiple step
reactions, 3,4-diphenyl coumarin (5a) and p-
toluenesulfonamide (3a) were heated together or exposed to
the standard reaction conditions. The corresponding
iminocoumarin (4a) was not detected (Scheme 4a and 4b).
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The Journal of Organic Chemistry
Page 4 of 9
4H), 2.38 (s, 3H); 13C { H} NMR (126 MHz, CDCl ) δ 158.5,
1
[
Cp*RhCl2]2
3
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
152.2, 151.1, 142.7, 139.6, 134.1, 133.4, 131.9, 130.7, 129.3,
129.1, 128.5, 128.3, 127.9, 127.7, 127.6, 127.1, 125.3, 120.7,
116.8, 21.5. IR (KBr, cm ): 3448, 3058, 2923, 1619, 1547, 1450,
Cu(OAc)2 AgSbF6
Cp*RhIII](X)2
(X= OAc or SbF6)
-1
[
O
NMe2
CuII
Cp*RhI]
S
1317, 1162, 1152, 871, 769, 758, 743, 694, 665, 570, 544; HRMS
1a
+
(ESI, m/z) calcd for C28
H
22NO
3
S (M+H ): 452.1315, found
[
4
52.1318.
O
NTs
Ph
TsNH2
O
NMe2
(Z)-N-(6-(tert-butyl)-3,4-diphenyl-2H-chromen-2-ylidene)-4-
Ph
4a
O
NMe2
Ph
S
methylbenzenesulfonamide (4b) was obtained as a white powder
Rh
Cp*
A
1
(
72.1 mg, 67%). M. P. 204 – 209 °C; H NMR (500 MHz, CDCl
3
)
NTs
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
O
δ 7.87 (d, J = 8.3 Hz, 2H), 7.61 (dd, J = 8.8, 2.3 Hz, 1H), 7.46 (d,
J = 8.8 Hz, 1H), 7.28 – 7.18 (m, 5H), 7.14 (d, J = 1.2 Hz, 1H),
7.14 – 7.13 (m, 3H), 7.07 – 7.04 (m, 4H), 2.38 (s, 3H), 1.20 (s,
Ph
D
Rh Cp*
Ph
Ph
2a
Ph
C
1
3
1
NMe2
Rh Cp*
Ph
Ph
3
9H); C { H} NMR (126 MHz, CDCl ) δ 158.8, 151.5, 150.3,
O
TsNH2
148.5, 142.6, 139.7, 134.2, 133.6, 130.7, 129.5, 129.3, 129.0,
128.5, 128.2, 128.2, 127.5, 127.1, 124.0, 120.0, 116.3, 34.7, 31.2,
21.5; IR (KBr, cm-1): 3439, 3055, 2967, 1618, 1537, 1323, 1086,
3a
Ph
B
157, 1086, 764, 682, 665, 603, 569, 556, 549; HRMS (ESI, m/z)
+
Scheme 5 Proposed mechanism
calcd for C32
H
30NO
3
S(M+H ): 508.1941, found 508.1941.
In conclusion, we have developed a novel synthetic method
to access iminocoumarin via multicomponent reaction of an
aryl thiocarbamate, an internal alkyne, and a sulfonamide. All
these starting materials are safe and readily available. This
process exploits a Rh-catalyzed and thiocarbamate-directed
C−H bond activation as the key step. Currently, we are
working toward utilizing this method to prepare potentially
bioactive and fluorescent molecules containing iminocoumarin
skeleton.
(Z)-N-(6-methoxy-3,4-diphenyl-2H-chromen-2-ylidene)-4-
methylbenzenesulfonamide (4c) was obtained as a white powder
1
(
58.0 mg, 81%). M. P. 203 – 208 °C; H NMR (500 MHz, CDCl
3
)
δ 7.85 (dd, J = 6.7, 1.6 Hz, 2H), 7.48 (d, J = 9.1 Hz, 1H), 7.28 –
7
–
.26 (m, 4H), 7.23 (d, J = 8.0 Hz, 1H), 7.15 – 7.13 (m, 4H), 7.07
7.04 (m, 4H), 6.63 (d, J = 2.9 Hz, 1H), 3.68 (s, 3H), 2.38 (s,
1
3
1
3
3H); C { H} NMR (126 MHz, CDCl ) δ 158.7, 156.6, 146.8,
142.6, 139.7, 134.1, 133.5, 130.6, 129.2, 129.1, 128.5, 128.3,
127.6, 127.6, 127.0, 121.4, 118.9, 117.8, 110.7, 55.7, 21.5; IR
-1
(
KBr, cm ): 3436, 2923, 2851, 1621, 1548, 1445, 1310, 1290,
Experimental Section
1269, 1153, 1088, 775, 699, 681, 599, 552; HRMS (ESI, m/z)
+
calcd for C29
H
24NO
4
S (M+H ): 482.1421, found 482.1422.
NMR spectra were recorded on BRUKER Avence III 500MHz
spectrometers. Chemical shifts were reported in parts per million
ppm) down field from TMS with the solvent resonance as the
internal standard. Coupling constants (J) were reported in Hz and
referred to apparent peak multiplications. High resolution mass
spectra (HRMS) were recorded on Bruker Micro TOF-QII mass
instrument (ESI).
(Z)-N-(7,8-diphenyl-6H-[1,3]dioxolo[4,5-g]chromen-6-
(
ylidene)-4-methylbenzenesulfonamide (4d) was obtained as a
1
white powder (94.0 mg, 76%). M. P. 232 – 235 °C; H NMR (500
MHz, CDCl
3
) δ 7.81 (d, J = 8.3 Hz, 2H), 7.22 (d, J = 8.1 Hz, 2H),
7
5
.19 – 7.15 (m, 3H), 7.12 – 7.10 (m, 3H), 7.05 – 7.00 (m, 6H),
.75 (s, 2H), 2.37 (s, 3H); C { H} NMR (126 MHz, CDCl ) δ
3
13
1
All the aryl thiocarbamates are known products which were
synthesized according to reported methods. The internal alkynes
were also prepared following the method described in known
literature. Other reagents used were purchased from Alfa Aesar
or J&K.
158.2, 147.9, 146.5, 145.1, 144.3, 142.7, 139.6, 135.3, 133.0,
130.7, 129.1, 128.7, 128.2, 127.5, 127.4, 127.0, 111.1, 108.9,
2
0
-1
106.7, 102.3, 21.5; IR (KBr, cm ): 3439, 3063, 2902, 1642, 1558,
2
1
1451, 1306, 1232, 1146, 1071, 908, 815, 777, 695, 659, 548;
+
HRMS (ESI, m/z) calcd for C29
96.1213.
H
22NO
5
S(M+H ): 496.1213, found
In a typical reaction of Rh catalyzed oxidative annulation to
access iminocoumarin, aryl thiocarbamate 1 (0.25 mmol), internal
4
alkyne
Cp*RhCl
mg), Cu(OAc)
2
(0.3 mmol), the sulfonamide
(0.00625 mmol, 3.8 mg), AgSbF
(0.3 mmol, 54.5 mg), and 1,2-dichloroethane (1
3
(0.25 mmol),
(0.025 mmol, 6.4
(Z)-4-methyl-N-(6-(methylthio)-3,4-diphenyl-2H-chromen-2-
ylidene)benzenesulfonamide (4e) was obtained as a white
[
2
]
2
6
1
2
powder (109.2 mg, 88%). M. P. 201 – 207 °C; H NMR (500
mL) were added to a 25 mL dried Young-type tube under air
atmosphere. Then it was sealed and heated with stirring at 120 °C
in oil bath for 12 h. After cooling to room temperature, the
reaction mixture was concentrated under reduced pressure and the
residue was purified by chromatography on silica gel with ethyl
acetate/petroleum ether (1:10 to 1:5 for each case) to give the
corresponding product 4.
MHz, CDCl ) δ 7.84 (d, J = 8.3 Hz, 2H), 7.49 – 7.44 (m, 2H),
3
7.29 – 7.26 (m, 3H), 7.23 (d, J = 8.1 Hz, 2H), 7.14 – 7.12 (m,
3H), 7.07 – 7.02 (m, 5H), 2.38 (s, 3H), 2.36 (s, 3H); 13C {
1
H}
NMR (126 MHz, CDCl ) δ 158.3, 150.5, 150.2, 142.8, 139.6,
3
135.9, 133.8, 133.3, 130.6, 130.4, 129.2, 129.1, 128.7, 128.3,
-
127.7, 127.6, 127.0, 125.2, 121.2, 117.3, 21.5, 16.4; IR (KBr, cm
): 3429, 2919, 1608, 1560, 1443, 1309, 1275, 1207, 1146, 1089,
1
9
C
60, 780, 698, 672, 592, 547; HRMS (ESI, m/z) calcd for
(Z)-N-(3,4-diphenyl-2H-chromen-2-ylidene)-4-
methylbenzenesulfonamide (4a) was obtained as a white powder
94.0 mg, 84%). M. P. 228 – 230 °C; IR (KBr, cm-1): H NMR
3
) δ 7.86 (d, J = 8.3 Hz, 2H), 7.60 – 7.52 (m,
H), 7.28 – 7.22 (m, 7H), 7.14 – 7.13 (m, 3H), 7.08 – 7.04 (m,
+
29
H
24NO
3
S
2
(M+H ): 498.1192, found 498.1193.
1
(
(
2
(Z)-N-(3,4-diphenyl-2-(tosylimino)-2H-chromen-6-
500 MHz, CDCl
yl)acetamide (4f) was obtained as a white powder (85.0 mg,
ACS Paragon Plus Environment

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The Journal of Organic Chemistry
1
6
7%). M. P. 143 – 146 °C; H NMR (500 MHz, CDCl
3
) δ 8.09 (s,
129.3, 129.3, 129.2, 128.9, 128.5, 127.8, 127.6, 127.4, 127.0,
120.6, 117.1, 52.5, 21.5; IR (KBr, cm ): 3424, 3052, 2950, 1720,
-1
1
2
3
4
5
6
7
8
9
1H), 7.80 (d, J = 8.3 Hz, 2H), 7.70 (dd, J = 9.0, 2.5 Hz, 1H), 7.52
(d, J = 2.5 Hz, 1H), 7.27 – 7.22 (m, 6H), 7.13 – 7.11 (m, 3H),
7.02 – 6.98 (m, 4H), 2.39 (s, 3H), 2.01 (s, 3H); C { H} NMR
1552, 1412, 1371, 1312, 1256, 1206, 1165, 1090, 909, 775, 702,
1
3
1
+
671, 593, 545; HRMS (ESI, m/z) calcd for C30
H
24NO
5
S (M+H ):
(
1
1
1
126 MHz, CDCl
35.9, 133.7, 133.3, 130.6, 129.2, 128.8, 128.5, 128.3, 127.7,
27.6, 126.9, 123.8, 120.8, 118.0, 116.9, 24.3, 21.5; IR (KBr, cm
3
) δ 168.9, 158.7, 151.4, 148.1, 143.0, 139.3,
510.1370, found 510.1370.
-
(Z)-N-(6-formyl-3,4-diphenyl-2H-chromen-2-ylidene)-4-
methylbenzenesulfonamide (4k) was obtained as a white powder
(58.2 mg, 49%). M. P. 223 – 227 °C; H NMR (500 MHz, CDCl
): 3346, 3062, 2924, 1695, 1554, 1414, 1278, 1150, 1088, 937,
1
8
14, 779, 699, 539; HRMS (ESI, m/z) calcd for C30
H
25
N
2
O
4
S
3
)
+
(M+H ): 509.1530, found 509.1530.
δ 9.90 (s, 1H), 8.09 (dd, J = 5.6, 1.9 Hz, 1H), 7.82 (d, J = 8.3 Hz,
H), 7.73 (d, J = 1.9 Hz, 1H), 7.69 (d, J = 8.5 Hz, 1H), 7.33 –
7.32 (m, 3H), 7.26 – 7.24 (m, 2H), 7.16 – 7.14 (m, 3H), 7.08 –
2
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(Z)-O-(3,4-diphenyl-2-(tosylimino)-2H-chromen-6-yl)
13
1
dimethylcarbamothioate (4g) as a white powder (66.1 mg,
4
J = 8.3 Hz, 2H), 7.50 (d, J = 9.0 Hz, 1H), 7.32 (dd, J = 9.0, 2.7
Hz, 1H), 7.28 – 7.23 (m, 5H), 7.14 – 7.13 (m, 3H), 7.07 – 7.04
(m, 4H), 6.93 (d, J = 2.7 Hz, 1H), 3.03 (s, 3H), 2.95 (s, 3H), 2.39
3
7.06 (m, 4H), 2.39 (s, 3H); C { H} NMR (126 MHz, CDCl ) δ
190.0, 157.5, 155.4, 150.2, 143.1, 139.2, 133.4, 133.3, 132.9,
131.9, 130.5, 130.4, 129.7, 129.2, 129.2, 129.0, 128.6, 128.0,
127.7, 126.9, 121.3, 118.0, 21.5; IR (KBr, cm ): 3437, 3059,
2841, 1705, 1552, 1445, 1315, 1157, 1087, 934, 819, 771, 741,
1
8%). M. P. 204 – 213 °C; H NMR (500 MHz, CDCl
3
) δ 7.86 (d,
-
1
1
3
1
+
(s, 3H); C { H} NMR (126 MHz, CDCl
3
) δ 158.3, 154.4, 150.6,
49.3, 148.3, 142.9, 139.4, 133.8, 133.3, 130.6, 129.3, 129.1,
29.0, 128.6, 128.4, 127.7, 127.6, 127.1, 126.1, 121.2, 120.3,
701, 671, 545; HRMS (ESI, m/z) calcd for C29
480.1264, found 480.1264.
H
22NO
4
S (M+H ):
1
1
1
1
-1
17.5, 36.8, 36.5, 21.5; IR (KBr, cm ): 3435, 2956, 2922, 1727,
625, 1557, 1444, 1390, 1263, 1154, 1090, 825, 779, 698, 547;
(Z)-N-(3,4-diphenyl-6-(trifluoromethyl)-2H-chromen-2-
ylidene)-4-methylbenzenesulfonamide (4l) was obtained as a
white powder (97.0 mg, 75%). M. P. 214 – 219 °C; H NMR (500
+
1
HRMS (ESI, m/z) calcd for C31
found 555.1410.
H
27
N
2
O
4
S
2
(M+H ): 555.1407,
MHz, CDCl
3
) δ 7.82 – 7.80 (m, 3H), 7.66 (d, J = 8.6 Hz, 1H),
7
.48 (d, J = 1.5 Hz, 1H), 7.32 – 7.31 (m, 3H), 7.26 – 7.23 (m,
13
(
Z)-N-(6-chloro-3,4-diphenyl-2H-chromen-2-ylidene)-4-
2H), 7.15 – 7.14 (m, 3H), 7.07 – 7.04 (m, 4H), 2.38 (s, 3H). C
1
methylbenzenesulfonamide (4h) was obtained as a white powder
(60.3 mg, 50%). M. P. 231 – 239 °C; H NMR (500 MHz, CDCl
δ 7.82 (d, J = 8.3 Hz, 2H), 7.53 – 7.48 (m, 2H), 7.30 – 7.29 (m,
3H), 7.23 (d, J = 8.1 Hz, 2H), 7.17 (d, J = 1.9 Hz, 1H), 7.14 –
3
{ H} NMR (126 MHz, CDCl ) δ 157.5, 153.7, 149.9, 143.0,
1
3
)
139.3, 133.2, 132.9, 130.5, 130.0, 129.2 (d, JCF = 6.8 Hz), 129.0,
128.6, 128.4 (d, JCF = 12.9 Hz), 128.1 (q, JCF = 200.5 Hz), 128.0,
127.7, 126.9, 125.2, 125.2, 124.4, 121.0, 117.7, 21.5; F NMR
1
9
1
3
1
-1
7
(
1
1
3
7
.13 (m, 3H), 7.05 – 7.04 (m, 4H), 2.38 (s, 2H); C { H} NMR
126 MHz, CDCl ) δ 157.9, 150.5, 149.8, 142.8, 139.4, 133.5,
33.1, 131.8, 130.9, 130.5, 129.6, 129.2, 129.1, 128.8, 128.5,
(282 MHz, CDCl
3
) δ –62.1; IR (KBr, cm ): 3425, 3058, 2917,
3
1710, 1590, 1358, 1262, 1147, 1089, 960, 814, 766, 688, 673, 595,
545; HRMS (ESI, m/z) calcd for C29
520.1189, found 520.1189.
+
H
21
F
3
NO
3
S (M+H ):
-1
27.9, 127.6, 127.1, 126.9, 122.0, 118.3, 21.5; IR (KBr, cm ):
437, 3058, 2921, 1618, 1568, 1312, 1262, 1147, 1089, 960, 814,
66, 699, 673, 595, 545; HRMS (ESI, m/z) calcd for
(Z)-4-methyl-N-(8-nitro-3,4-diphenyl-2H-chromen-2-
ylidene)benzenesulfonamide (4m) was obtained as a white
powder (78.0 mg, 63%). M. P. 205 – 208 °C; H NMR (500 MHz,
3
CDCl ) δ 8.06 (dd, J = 8.1, 1.6 Hz, 1H), 7.77 (d, J = 8.3 Hz, 2H),
+
C
28
H
21ClNO
3
S (M+H ): 486.0925, found 486.0926.
1
(Z)-N-(6-bromo-3,4-diphenyl-2H-chromen-2-ylidene)-4-
methylbenzenesulfonamide (4i) was obtained as a white powder
(96.0 mg, 73%). The single crystal was prepared by
recrystallization of the crude product in ethyl acetate/petroleum
ether at –20 °C. M. P. 238 – 243 °C; H NMR (500 MHz, CDCl
7.45 (dd, J = 8.1, 1.6 Hz, 1H), 7.33 – 7.31 (m, 4H), 7.21 (d, J =
8.0 Hz, 2H), 7.16 – 7.14 (m, 3H), 7.06 – 7.03 (m, 4H), 2.37 (s,
1
3
1
3
3H); C { H} NMR (126 MHz, CDCl ) δ 155.5, 149.3, 144.3,
1
3
)
143.0, 139.0, 138.2, 133.4, 132.3, 132.2, 130.4, 130.3, 129.2,
129.2, 129.0, 128.6, 128.1, 127.7, 126.8, 126.8, 124.5, 122.9,
δ 7.81 (dd, J = 6.7, 1.7 Hz, 2H), 7.66 (dd, J = 8.8, 2.3 Hz, 1H),
-1
7
2
{
1
1
.43 (d, J = 8.8 Hz, 1H), 7.32 – 7.29 (m, 4H), 7.23 (d, J = 8.0 Hz,
21.5; IR (KBr, cm ): 3437, 3064, 1625, 1584, 1455, 1454, 1317,
1
3
H); 7.14 – 7.12 (m, 3H); 7.06 – 7.02 (m, 4H), 2.38 (s, 3H);
C
1244, 1170, 1089, 864, 779, 692, 568; HRMS (ESI, m/z) calcd for
1
+
H} NMR (126 MHz , CDCl
3
) δ 157.8, 151.0, 149.7, 142.9,
C
28
H
21
N
2
O
5
S (M+H ): 497.1166, found 497.1168.
39.4, 134.6, 133.4, 133.0, 130.5, 130.1, 129.6, 129.2, 129.1,
28.8, 128.5, 127.9, 127.6, 126.9, 122.4, 118.5, 118.3, 21.3; IR
(Z)-4-methyl-N-(3,4,8-triphenyl-2H-chromen-2-
ylidene)benzenesulfonamide(4n) was obtained as
powder (34.1 mg, 26%). M. P. 233 – 238 °C; H NMR (500 MHz,
3
CDCl ) δ 7.81 – 7.80 (m, 2H), 7.65 (t, J = 7.7 Hz, 2H), 7.60 (dd, J
= 7.5, 1.6 Hz, 1H), 7.55 (t, J = 7.4 Hz, 1H), 7.31 – 7.28 (m, 6H),
7.20 (dd, J = 8.0, 1.5 Hz, 1H), 7.14 – 7.13 (m, 3H), 7.09 – 7.05 (m,
4H), 6.98 (d, J = 8.1 Hz, 2H), 2.30 (s, 3H); C { H} NMR (126
-1
(KBr, cm ): 3435, 3060, 1615, 1564, 1443, 1399, 1312, 1263,
a
white
1
1
203, 1146, 1089, 957, 891, 814, 777, 699, 670, 588, 544; HRMS
+
(ESI, m/z) calcd for C28
H
21BrNO
3
S (M+H ): 530.0420, found
5
30.0420.
1
3
1
Methyl-(Z)-3,4-diphenyl-2-(tosylimino)-2H-chromene-6-
carboxylate (4j) was obtained as a white powder (50.4 mg, 75%).
M. P. 204 – 209 °C; H NMR (500 MHz, CDCl
8
2
MHz, CDCl ) δ 158.0, 151.3, 149.4, 142.3, 139.0, 135.2, 134.5,
3
1
3
) δ 8.23 (dd, J =
133.7, 133.5, 131.0, 130.6, 130.5, 129.3, 128.9, 128.8, 128.6,
.7, 2.0 Hz, 1H), 7.93 (d, J = 2.0 Hz, 1H), 7.83 (d, J = 8.3 Hz,
H), 7.59 (d, J = 8.7 Hz, 1H), 7.31 – 7.29 (m, 3H), 7.26 – 7.23
128.6, 128.5, 128.3, 127.6, 127.2, 126.9, 125.1, 121.3, 21.5; IR
-1
(KBr, cm ): 3434, 2919, 1619, 1540, 1444, 1324, 1158, 1087,
(m, 2H), 7.15 – 7.13 (m, 3H), 7.07 – 7.04 (m, 4H), 3.86 (s, 3H),
1013, 881, 857, 814, 771, 696, 554; HRMS (ESI, m/z) calcd for
1
3
1
+
2
1
.38 (s, 3H). C { H} NMR (126 MHz, CDCl
3
) δ 165.5, 157.7,
C H NO S (M+H ): 528.1628, found 528.1624.
3
4
26
3
54.6, 150.5, 142.9, 139.4, 133.5, 133.1, 132.7, 130.6, 129.8,
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 9
(
Z)-N-(3,4-diphenyl-2H-benzo[h]chromen-2-ylidene)-4-
131.2, 129.9, 128.1, 128.0, 127.3, 126.6, 122.6, 121.7, 120.7,
116.6, 21.5; IR (KBr, cm ): 3445, 3077, 2918, 1632, 1541, 1289,
-1
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
methylbenzenesulfonamide (4o) was obtained as a white powder
(100.3 mg, 80%). M. P. 212 – 217 °C; H NMR (500 MHz,
CDCl
1
1150, 1091, 1002, 831, 787, 754, 698, 664, 545; HRMS (ESI,
+
3
) δ 8.93 (d, J = 8.3 Hz, 1H), 7.89 – 7.83 (m, 3H), 7.78 –
.75 (m, 1H), 7.70 (t, J = 7.2 Hz, 1H), 7.63 (d, J = 8.8 Hz, 1H),
.32 – 7.31 (m, 3H), 7.21 (d, J = 8.5 Hz, 3H), 7.16 – 7.11 (m, 7H),
m/z) calcd for C28
H
19Br
2
NO
3
SNa (M+Na ): 629.9324, found
7
7
2
1
1
1
2
6
5
629.9345.
1
3
1
3
.36 (s, 3H); C { H} NMR (126 MHz, CDCl ) δ 158.9, 152.2,
49.7, 142.5, 140.0, 134.7, 134.5, 133.5, 130.7, 129.4, 129.1,
28.5, 128.3, 128.0, 127.9, 127.6, 127.6, 127.5, 126.4, 125.2,
(Z)-N-(3,4-bis(4-chlorophenyl)-2H-chromen-2-ylidene)-4-
methylbenzenesulfonamide (4t) was obtained as a white powder
-1
1
23.3, 122.9, 122.7, 116.2, 21.49; IR (KBr, cm ): 3360, 3064,
(58.0 mg, 45%). M. P. 228 – 230 °C; H NMR (500 MHz,
925, 1604, 1562, 1541, 1441, 1290, 1166, 1090, 964, 816, 768,
6
DMSO-d ) δ 7.92 (d, J = 8.2 Hz, 1H), 7.73 (t, J = 7.7 Hz, 1H),
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
+
95, 565; HRMS (ESI, m/z) calcd for C32
H
23NO
3
SNa (M+Na ):
7.64 (d, J = 8.3 Hz, 1H), 7.43 – 7.37 (m, 6H), 7.31 (d, J = 8.4 Hz,
2H), 7.24 – 7.19 (m, 4H), 7.08 (d, J = 7.9 Hz, 1H), 2.37 (s, 3H);
24.1291, found 524.1290.
13
1
6
C { H} NMR (126 MHz, DMSO-d ) δ 158.4, 151.8, 151.0,
(
Z)-4-methyl-N-(7-methyl-3,4-diphenyl-2H-chromen-2-
143.7, 139.0, 133.8, 133.2, 133.2, 133.1, 132.9, 132.8, 131.5,
129.9, 128.8, 128.2, 128.1, 127.9, 127.4, 126.6, 120.7, 116.6, 21.5;
IR (KBr, cm ): 3435, 3036, 2916, 1619, 1548, 1322, 1152, 1089,
ylidene)benzenesulfonamide (4p) was obtained as a white
powder (66 mg, 57%). M. P. 226 – 233 °C; H NMR (500 MHz,
CDCl
1
-1
) δ 7.85 (d, J = 8.1 Hz, 2H), 7.36 (d, J = 18.1 Hz, 1H), 7.34
1011, 878, 817, 764, 714, 661, 551; HRMS (ESI, m/z) calcd for
3
+
– 7.20 (m, 6H), 7.16 – 7.11 (m, 3H), 7.09 (d, J = 8.2 Hz, 1H),
C
28
H
19Cl
2
NO
3
SNa (M+Na ): 542.0355, found 542.0355.
1
3
1
7
(
.08 – 7.01 (m, 4H), 2.48 (s, 3H), 2.38 (s, 3H); C { H} NMR
126 MHz, CDCl ) δ 158.9, 152.2, 151.3, 143.4, 142.6, 134.3,
33.5, 130.8, 129.3, 129.1, 128.4, 128.2, 127.5, 127.0, 126.6,
18.3, 117.0, 77.3, 77.1, 76.8, 21.7, 21.5; IR (KBr, cm ): 3433,
055, 2918, 1628, 1537, 1311, 1289, 1154, 1087, 906, 816, 767,
(Z)-N-(3,4-di(thiophen-2-yl)-2H-chromen-2-ylidene)-4-
3
methylbenzenesulfonamide (4u) was obtained as a white powder
1
1
3
7
4
1
-1
(25.0 mg, 22%). M. P. 214 – 218 °C; H NMR (500 MHz, CDCl )
3
δ 7.94 (d, J = 8.2 Hz, 2H), 7.60 – 7.54 (m, 1H), 7.53 – 7.48 (m,
2H), 7.45 (dd, J = 5.0, 0.9 Hz, 1H), 7.31 – 7.26 (m, 4H), 7.10 –
+
00, 670, 558; HRMS (ESI, m/z) calcd for C29
66.1471, found 466.1474.
H
24NO
3
S (M+H ):
7
.07 (m, 1H), 7.04 (dd, J = 3.5, 1.0 Hz, 1H), 6.94 (dd, J = 3.6, 1.0
13
1
Hz, 1H), 6.87 – 6.83 (m, 1H), 2.40 (s, 3H); C { H} NMR (126
MHz, CDCl ) δ 157.2, 151.6, 144.5, 143.0, 139.3, 134.4, 133.5,
(Z)-N-(3,4-di-m-tolyl-2H-chromen-2-ylidene)-4-
3
methylbenzenesulfonamide (4q) was obtained as a white powder
(55.9 mg, 47%). M. P. 178 – 181 °C; H NMR (500 MHz, CDCl
δ 7.87 (d, J = 8.3 Hz, 2H), 7.55 – 7.53 (m, 2H), 7.26 – 7.22 (m,
4H), 7.15 (t, J = 7.6 Hz, 1H), 7.07 (d, J = 7.7 Hz, 1H), 7.01 (t, J =
132.2, 131.0, 130.3, 129.2, 128.8, 128.1, 127.8, 127.2, 126.1,
1
-1
3
)
125.5, 120.6, 116.7, 77.5, 77.3, 77.0, 76.8, 21.6; IR (KBr, cm ):
3434, 3098, 2918, 1618, 1547, 1451, 1326, 1288, 1161, 1085, 858,
832, 728, 663, 577, 541; HRMS (ESI, m/z) calcd for C24
(M+H ): 464.0443, found 464.0427.
H
18NO
3
S
3
+
7
3
.6 Hz, 1H), 6.94 – 6.91 (m, 2H), 6.85 – 6.82 (m, 3H), 2.38 (s,
1
3
1
H), 2.25 (s, 3H), 2.18 (s, 3H); C { H} NMR (126 MHz,
) δ 158.7, 152.1, 151.2, 142.7, 139.7, 137.9, 136.9, 134.1,
33.3, 131.7, 131.3, 129.8, 129.2, 129.1, 128.4, 128.4, 128.1,
28.0, 127.7, 127.4, 127.0, 126.4, 125.3, 122.8, 120.8, 116.7,
(Z)-N-(3,4-dipropyl-2H-chromen-2-ylidene)-4-
CDCl
1
1
3
methylbenzenesulfonamide (4v) was obtained as a white powder
1
(
37.2 mg, 39%). M. P. 149 – 152 °C; H NMR (500 MHz, CDCl
3
)
-1
δ 8.01 (d, J = 8.0 Hz, 2H), 7.62 (d, J = 8.0 Hz, 1H), 7.52 – 7.49
m, 1H), 7.39 (d, J = 8.2 Hz, 1H), 7.35 – 7.29 (m, 3H), 2.81 (t, J =
8.0 Hz, 2H), 2.64 (t, J = 8.0 Hz, 2H), 2.42 (s, 3H), 1.62 – 1.58 (m,
2
1
1.5, 21.3, 21.3; IR (KBr, cm ): 3434, 2918, 1621, 1541, 1296,
150, 1091, 831, 787, 753, 737, 698, 664, 578, 540; HRMS (ESI,
(
+
3
m/z) calcd for C30H26NO S (M+H ): 480.1628, found 480.1630.
13
1
4
H), 1.10 (t, J = 7.4 Hz, 3H), 1.01 (t, J = 7.4 Hz, 3H); C { H}
(Z)-N-(3,4-bis(4-methoxyphenyl)-2H-chromen-2-ylidene)-4-
NMR (126 MHz , CDCl ) δ 14.4, 14.5, 21.5, 22.0, 23.0, 29.5,
3
methylbenzenesulfonamide (4r) was obtained as a white powder
(85.6 mg, 67%). M. P. 195 – 203 °C; H NMR (500 MHz, CDCl
30.7, 116.9, 119.9, 124.6, 125.3, 127.2, 127.4, 129.1, 130.8,
1
-1
3
)
139.7, 142.8, 150.1, 151.4, 158.7; IR (KBr, cm ): 3445, 3012,
δ 7.91 (d, J = 8.2 Hz, 2H), 7.58 – 7.51 (m, 2H), 7.30 – 7.24 (m,
H), 7.02 (d, J = 8.8 Hz, 2H), 6.98 (d, J = 8.8 Hz, 2H), 6.83 (d, J
8.7 Hz, 2H), 6.68 (d, J = 8.7 Hz, 2H), 3.78 (s, 3H), 3.73 (s, 3H),
2901, 1619, 1545, 1450, 1317, 1159, 994, 871, 760, 743, 694,
+
4
=
665, 570, 545; HRMS (ESI, m/z) calcd for C22
H
26NO
3
S (M+H ):
384.1628, found 384.1629.
1
3
1
2
3
.38 (s, 2H); C { H} NMR (126 MHz, CDCl ) δ 159.5, 158.9,
(Z)-N-(3-ethyl-4-phenyl-2H-chromen-2-ylidene)-4-
1
1
58.8, 152.0, 150.7, 142.7, 139.6, 132.1, 131.6, 130.8, 129.1,
28.0, 127.9, 127.2, 126.4, 125.8, 125.2, 121.0, 116.7, 113.8,
methylbenzenesulfonamide (4w) was obtained as a white
1
-1
powder (56.1 mg, 56%). M. P. 197 – 203 °C; H NMR (500 MHz,
1
1
13.1, 55.2, 55.1, 21.5; IR (KBr, cm ): 3438, 2966, 2839, 1618,
541, 1302, 1248, 1155, 1088, 1024, 828, 746, 561; HRMS (ESI,
CDCl
7.55 (m, 1H), 7.49 (d, J = 7.8 Hz, 1H), 7.44 – 7.36 (m, 4H), 7.22
7.20 (m, 4H), 2.64 (q, J = 7.6 Hz, 2H), 2.36 (s, 3H), 1.13 (t, J =
3
) δ 7.79 (d, J = 8.2 Hz, 2H), 7.71 – 7.70 (m, 1H), 7.59 –
+
5
m/z) calcd for C30H26NO S (M+H ): 512.1526, found 512.1527.
–
1
3
1
(Z)-N-(3,4-bis(4-bromophenyl)-2H-chromen-2-ylidene)-4-
3
7.6 Hz, 3H); C { H} NMR (126 MHz, CDCl ) δ 158.7, 153.2,
methylbenzenesulfonamide (4s) was obtained as a white powder
(47.2 mg, 31%). M. P. 228 – 230 °C; H NMR (500 MHz,
152.1, 143.4, 142.7, 139.5, 139.3, 134.0, 131.7, 129.7, 129.5,
129.1, 128.5, 128.2, 128.1, 127.0, 126.5, 125.6, 125.2, 119.4,
1
-1
DMSO-d
6
) δ 7.92 (d, J = 8.3 Hz, 2H), 7.74 – 7.71 (m, 1H), 7.65 –
.63 (m, 1H), 7.57 – 7.54 (m, 2H), 7.46 – 7.41 (m, 4H), 7.39 –
.36 (m, 1H), 7.18 – 7.13 (m, 4H), 7.06 (dd, J = 8.0, 1.4 Hz, 1H),
.37 (s, 3H); C { H} NMR (126 MHz, DMSO-d
51.8, 150.9, 143.7, 139.0, 133.5, 133.5, 133.1, 131.8, 131.7,
117.2, 23.1, 21.5, 14.1; IR (KBr, cm ): 3434, 3091, 2908, 1641,
7
7
2
1
1529, 1266, 1155, 1091, 831, 779, 732, 698, 660, 578, 541;
+
HRMS (ESI, m/z) calcd for C24
H
22NO
3
S (M+H ): 404.1315,
1
3
1
) δ 158.4,
found 404.1315.
6
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Page 7 of 9
The Journal of Organic Chemistry
(
Z)-N-(3,4-diphenyl-2H-chromen-2-ylidene)-4-
(m, 1H), 7.46 (t, J = 7.4 Hz, 2H), 7.42 – 7.38 (m, 2H), 7.35 – 7.31
(m, 3H), 2.33 (s, 3H); C { H} NMR (126 MHz, CDCl ) δ 161.0,
3
152.7, 147.6, 134.5, 131.3, 130.0, 128.5, 128.2, 127.4, 125.1,
124.3, 120.6, 116.9, 16.6.
1
3
1
1
2
3
4
5
6
7
8
9
methoxybenzenesulfonamide (4x) was obtained as a white
powder (77.1 mg, 66%). M. P. 200 – 209 °C; H NMR (500 MHz,
CDCl
1
3
) δ 7.93 – 7.91 (m, 2H), 7.54 – 7.51 (m, 2H), 7.27 – 7.26
(
4
m, 3H), 7.22 – 7.21 (m, 2H), 7.13 – 7.12 (m, 3H), 7.07 – 7.03 (m,
H), 6.92 – 6.90 (m, 2H), 3.81 (s, 3H); 13C { H} NMR (126 MHz,
) δ 162.6, 158.3, 152.2, 151.1, 134.3, 134.1, 133.4, 131.9,
30.7, 129.3, 129.2, 128.5, 128.5, 128.3, 127.9, 127.7, 127.6,
1
The thiocoumarin 6 was synthesized according to previous
literature:22
A mixture of coumarin 5b (0.5 mmol) and
CDCl
3
1
1
2
6
4
Lawesson’s reagent (1 mmol) in anhydrous toluene, was refluxed
for about 24 h. After cooling, solvent was removed under reduced
pressure and the residue was then separated by flash column
chromatography with petroleum ether-EtOAc mixtures (9:1) to
-1
25.4, 120.7, 116.7, 113.7, 55.6; IR (KBr, cm ): 3434, 3080,
919, 1622, 1545, 1491, 1444, 1322, 1148, 1090, 869, 805, 773,
+
96, 565; HRMS (ESI, m/z) calcd for C28
H
22NO
4
S (M+H ):
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
68.1264, found 468.1264.
afford thiocoumarin 6 as a yellow solid (0.108 g, 86%). H NMR
(
3
500 MHz, CDCl ) δ 7.72 (d, J = 7.3 Hz, 1H), 7.61 (t, J = 7.7 Hz,
(Z)-N-(3,4-diphenyl-2H-chromen-2-
1H), 7.53 (d, J = 8.0 Hz, 1H), 7.47 (t, J = 7.3 Hz, 2H), 7.43 – 7.37
1
3
1
ylidene)benzenesulfonamide (4y) was obtained as a white
powder (68.4 mg, 63%). M. P. 188 – 199 °C; H NMR (500 MHz,
(m, 1H), 7.22 (d, J = 7.0 Hz, 2H), 2.19 (s, 3H); C { H} NMR
(126 MHz, CDCl ) δ 197.3, 155.5, 141.3, 138.8, 138.0, 131.7,
1
3
CDCl
m, 5H), 7.25 – 7.20 (m, 3H), 7.14 – 7.04 (m, 4H); C { H}
NMR (126 MHz, CDCl ) δ 158.8, 152.1, 151.4, 142.5, 134.0,
33.4, 132.1, 132.0, 130.7, 129.3, 128.6, 128.5, 128.4, 128.3,
3
) δ 7.98 – 7.96 (m, 2H), 7.57 – 7.42 (m, 5H), 7.28 – 7.23
129.5, 128.6, 128.0, 125.3, 125.2, 122.0, 116.8, 17.0.
1
3
1
(
3
ASSOCIATED CONTENT
1
1
3
7
Supporting Information
The Supporting Information is available free of charge on
the ACS Publications website.
NMR data and X-ray crystallography data and CIF files.
Accession Codes
-1
27.9, 127.7, 127.6, 127.0, 125.4, 120.7, 116.8; IR (KBr, cm ):
436, 3060, 1618, 1552, 1447, 1304, 1204, 1145, 1088, 956, 873,
85, 745, 701, 588, 545; HRMS (ESI, m/z) calcd for C27
H
20NO
3
S
+
(M+H ): 438.1158, found 438.1158.
CCDC
crystallographic data for this paper. These data can be
obtained free of charge via
1949758
contains
the
supplementary
(Z)-N-(3,4-diphenyl-2H-chromen-2-ylidene)-4-
nitrobenzenesulfonamide (4z) was obtained as a white powder
(25.3 mg, 21%). M. P. 205 – 211 °C; H NMR (500 MHz, CDCl
δ 8.26 – 8.24 (m, 2H), 8.06 – 8.04 (m, 2H), 7.64 – 7.63 (m, 2H),
7.32 – 7.29 (m, 5H), 7.17 – 7.16 (m, 3H), 7.09 – 7.07 (m, 4H);
{
1
1
cm ): 3422, 2924, 1716, 1668, 1602, 1449, 1380, 1351, 1242,
1
C
1
3
)
www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
1
3
C
1
3
H} NMR (126 MHz, CDCl ) δ 159.7, 152.4, 152.1, 149.6,
48.3, 133.8, 133.2, 132.4, 130.5, 129.2, 128.8, 128.4, 128.2,
28.1, 128.0, 127.9, 127.7, 125.8, 123.8, 120.7, 117.0; IR (KBr,
-1
AUTHOR INFORMATION
Corresponding Author
Email: zhaoyingwei@hqu.edu.cn
078, 921, 755, 709, 541, 446; HRMS (ESI, m/z) calcd for
+
27
H
19
N
2
O
5
S (M+H ): 483.1009, found 483.1010.
*
(Z)-N-(3,4-diphenyl-2H-chromen-2-
ORCID
ylidene)methanesulfonamide (4za) was obtained as a white
Yingwei Zhao: 0000-0001-8688-2363
1
powder (33 mg, 36%). M. P. 228 – 239 °C; H NMR (500 MHz,
CDCl ) δ 7.65 – 7.62 (m, 1H), 7.57 (ddd, J = 8.5, 6.6, 2.1 Hz,
1H), 7.32 – 7.27 (m, 3H), 7.22 (ddd, J = 7.9, 7.0, 2.7 Hz, 2H),
3
ACKNOWLEDGMENT
We appreciate the financial support from the Natural
Science Foundation of Fujian Province (2017J01019). We
thank the Instrumental Analysis Center of Huaqiao University
for analysis support.
1
3
1
7.18 – 7.12 (m, 3H), 7.11 – 7.03 (m, 4H), 3.00 (s, 3H); C { H}
NMR (126 MHz, CDCl ) δ 158.8, 152.1, 151.2, 134.1, 133.5,
31.9, 130.6, 130.5, 129.4, 129.3, 128.5, 128.2, 128.1, 127.8,
27.6, 127.6, 125.3, 120.6, 117.1, 77.3, 77.1, 76.8, 43.0; IR (KBr,
3
1
1
-1
cm ): 3061, 3027, 2939, 1712, 1624, 1574, 1454, 1301, 1206,
1
for C22
REFERENCES
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+
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3
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3
) δ 7.12
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3
1
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3
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3
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ACS Paragon Plus Environment

The Journal of Organic Chemistry
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