Silver-catalyzed radical tandem cyclization: An approach to direct synthesis of 3-acyl-4-arylquinolin-2(1 H)-ones

Article abstract of DOI:10.1021/jo501301t

A silver-catalyzed efficient and practical synthesis of 3-acyl-4-arylquinolin-2(1H)-ones or 3-acyl-4-aryldihydroquinolin-2(1H)-ones through intermolecular radical addition/cyclization in aqueous solution is reported. This method provides a novel, highly e

Full text of DOI:10.1021/jo501301t

Article
pubs.acs.org/joc
Silver-Catalyzed Radical Tandem Cyclization: An Approach to Direct
Synthesis of 3‑Acyl-4-arylquinolin-2(1H)‑ones
Wen-Peng Mai,* Gang-Chun Sun,* Ji-Tao Wang, Ge Song, Pu Mao, Liang-Ru Yang, Jin-Wei Yuan,
Yong-Mei Xiao,* and Ling-Bo Qu
Chemistry and Chemical Engineering School, Henan University of Technology, Zhengzhou, Henan 450001, P. R. China
S
* Supporting Information
ABSTRACT: A silver-catalyzed efficient and practical syn-
thesis of 3-acyl-4-arylquinolin-2(1H)-ones or 3-acyl-4-aryldi-
hydroquinolin-2(1H)-ones through intermolecular radical
addition/cyclization in aqueous solution is reported. This
method provides a novel, highly efficient, and straightforward
route to substituted quinolin-2-ones or 3,4-dihydroquinolin-2-ones in one step. A possible mechanism for the formation of
quinolin-2-ones is proposed.
ones in one step via Pd-catalyzed carbonylative annulation of
internal alkyne in 2004.4a In 2010, Tsuji exploited Ir-catalyzed
annulation of N-arylcarbamoyl chlorides with internal alkynes
to afford 3,4-disubstituted 2-quinolones.4b Li’s group also
achieved the similar results through Pd-catalyzed intra- or
intermolecular carbocyclizations.4c−e In the previous elegant
studies, internal alkyne is necessary to generate the 3,4-
disubstituted quinolin-2(1H)-ones in one step. Other routes
toward 3,4-disubstituted quinolin-2(1H)-ones via the Fried-
INTRODUCTION
■
The skeletons of quinolin-2(1H)-one and dihydroquinolin-
2(1H)-one are outstanding structural motifs found in many
natural products and pharmaceutically active compounds
(Figure 1).1 Functionalized quinolin-2(1H)-ones have been
lander reaction have also been reported.5 To date, radical
̈
reactions have been extensively used in organic synthesis in
which radical tandem reactions for the synthesis of heterocycles
have received significant attention.6 Decarboxylative couplings
of carboxylic acids7 with another agent via radical processes
have been reported by Kochi,8a,b Minisci,8c,d Li,8e,g and other
groups.8h,i Recently, we just reported silver-catalyzed radical
tandem cyclization for the synthesis of 3,4-disubstituted
dihydroquinolin-2(1H)-ones using alkyl acids as the source of
the radicals.9 Here, as its extension, employing ketoacids as
radical source, we describe our development of a new strategy
for the synthesis of 3-acyl-4-arylquinolin-2(1H)-ones or 3-acyl-
4-aryldihydroquinolin-2(1H)-ones in one step through tandem
radical reactions (Scheme 1).
Figure 1. Some representative compounds containing the dihydro-
quinolin-2(1H)-one or quinolin-2(1H)-one structure.
synthesized as potential HIV-1 integrase inhibitors and
anticancer and antihypertensive agents in the past few
years.1,2 Many efforts have been made toward the synthesis
of quinolin-2(1H)-one derivatives; however, most of the
synthetic routes provide monosubstituted quinolin-2(1H)-
ones.3 A highly efficient and straightforward method to
construct 3,4-disubstituted quinolin-2(1H)-ones in one step is
still a challenging issue.
The previous strategy relies on constructing 3- or 4-
substituted quinolin-2(1H)-ones via intramolecular cyclization
in the first step and then introducing another group into the 4-
or 3-position of quinolin-2(1H)-ones by coupling reactions in
the second step.3a−d,g,h In comparison to this strategy, Larock et
al. developed the synthesis of 3,4-disubstituted quinolin-2(1H)-
RESULTS AND DISCUSSION
■
Our investigation started with treating N-methyl-N-phenyl-
cinnamamide (1a) and 2-oxo-2-phenylacetic acid (2a) under an
Ag−K2S2O8 system for screening the optimal reaction
conditions.10 To our delight, acyl radical induced by Ag(I) in
the system could attack the α-position of 1a, providing
dihydroquinolin-2(1H)-one 3a in 62% yield (Table 1, entry
1). However, when the loading of the oxidant was increased,
the yield of product 3a was decreased and other unexpected
product quinolin-2(1H)-one 4a was observed (Table 1, entry
Received: June 11, 2014
© XXXX American Chemical Society
A
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results indicated that K2S2O8 was the best choice (Table 1,
entries 12−14). Switching the catalyst from AgNO3 to AgBF4
or Ag2O did not show much difference (Table 1, entries 15 and
16). Note that the reaction failed to provide any of the products
in the absence of catalyst or oxidant (Table 1, entries 17 and
18).
Scheme 1. Radical Cyclization toward Substituted
Quinoline-2-one Derivatives
With this novel process in hand, our attention turned to the
full exploitation of the radical tandem cyclization. First, the
scope of α-oxocarboxylic acids was investigated under method
A (Table 2). As shown in Table 2, many 3,4-dihydroquinolin-
Table 2. Silver-Catalyzed Radical Cyclization toward 3-Acyl-
a
4-aryldihydroquinolin-2(1H)-ones
a
Table 1. Screening of Reaction Conditions
b
b
AgNO3
(x mol %)
K2S2O8
(y equiv)
yield of 3a
yield of 4a
entry
(%)
(%)
1
10
10
10
20
20
20
20
20
20
20
30
20
20
20
20
20
20
0
2.0
3.0
4.0
1.0
2.0
2.5
3.0
3.5
4.0
4.5
4.0
4.0
4.0
4.0
4.0
4.0
0
62
n.d.
40
2
13
3
trace
70
58
4
n.d.
n.d.
trace
62
5
79
6
68
7
18
8
trace
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d
79
9
83
10
11
78
81
c
12
75
d
13
n.d.
n.d.
74
e
14
f
15
g
16
70
h
17
n.d.
n.d
i
18
4.0
a
Reaction conditions: 1a (1.0 mmol), 2a (1.0 mmol), CH3CN/H2O
b
(3/3 mL), under air atmosphere, 12 h, 100 °C. Isolated yield.
c
d
e
(NH4)2S2O8 as oxidant. Oxone as oxidant. DTBP as oxidant.
f
g
h
i
AgBF4 as catalyst. Ag2O as catalyst. Without catalyst. Without
oxidant.
2). Then a series of reaction conditions were examined. As
shown in Table 1, product 3a was obtained in 70% yield with
20 mol % of AgNO3 as catalyst and 1.0 equiv of K2S2O8 as
oxidant (Table 1, entry 4). Compared with entry 4, the yield of
product 3a could be improved to 79% when 2.0 equiv of
K2S2O8 was used, but product 4a was not detected (Table 1,
entry 5). Products 3a and 4a were both obtained when the
amount of K2S2O8 was increased to 3.0 equiv (Table 1, entry
7). The reaction worked with 4.0 equiv of K2S2O8 to afford
product 4a in 83% yield without any product 3a (Table 1, entry
9). Notably, increasing the amount of K2S2O8 made the
product 3a reduced; meanwhile, product 4a was increased
(Table 1, entries 5−9). Moreover, when the K2S2O8 was loaded
less than 2.0 equiv or more than 4.0 equiv, the reaction lead to
the clean formation of product 3a or 4a, respectively (Table 1,
entries 1, 3, and 9−11). Subsequently, we investigated different
oxidants, such as (NH4)2S2O8, Oxone, and DTBP, and the
a
Reaction conditions: 1 (1.0 mmol), 2 (1.0 mmol), AgNO3 (20 mol
%), K2S2O8 (2.0 mmol), CH3CN (3 mL), H2O (3 mL), 100 °C, 12 h.
b
Using 4.0 mmol of K2S2O8 as oxidant.
2(1H)-ones could be cleanly obtained using method A
(Scheme 1). Me, Cl, Br, Bz, thiophene, and pyridine
substituents in substrates 1 or 2 were compatible under the
conditions of method A. Electron-withdrawing and -donating
substituted groups, such as o-Cl, p-Br, p-OMe, and 3,4-diOMe
on the phenyl ring (2) of cinnamic acid, do not influence the
reactivity remarkably, and products could be obtained in
moderate yields (Table 2, 3n−o,x,y). Furthermore, 2-
B
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oxopropanoic acid could also undergo the transformation
successfully and gave the final product 3z in 72% yield. For the
product 3m, the reaction is sluggish under method A, and a
small amount of product was observed, but the 67% product
yield was obtained when the K2S2O8 was increased to 4.0 equiv.
The reason may be that the electron deficiency of the pyridine
ring makes it trap the radical with difficulty. Likewise, the 2-
(methyl(phenyl)amino)-2-oxoacetic acid was also an exception
and transferred into the final product 3a′ needing 4.0 equiv of
oxidant (Table 2, 3a′). The reason for this may be the low
efficiency of its decarboxylation in comparison with other 2-
oxoacetic acids.
(4d,e). Unfortunately, the t-Bu group was not compatible,
which did not lead to the product 4k, and the N-methyl-N-
phenylcinnamamide was recovered in 73% yield.
Subsequently, we investigated the scope and limitations of N-
arylcinnamamides in this transformation under the conditions
of method B, and the results are presented in Table 4. As
Table 4. Silver-Catalyzed Radical Cyclization of 2a with
a,b
Different N-Arylcinnamamides
We next sought to establish the formation of the
corresponding quinolin-2(1H)-ones using method B. As
shown in Table 3, N-methyl-N-phenylcinnamamide could
Table 3. Silver-Catalyzed Radical Cyclization toward 3-Acyl-
a
4-arylquinolin-2(1H)-ones
a
Reaction conditions: 1 (1.0 mmol), 2a (1.0 mmol), AgNO3 (20 mol
%), K2S2O8 (4.0 mmol), CH3CN (3 mL), H2O (3 mL), 100 °C, 12 h.
Isolated yield. K2S2O8 (8.0 mmol), other conditions are the same as
a
b
c
Reaction conditions: 1 (1.0 mmol), 2 (1.0 mmol), AgNO3 (20 mol
%), K2S2O8 (4.0 mmol), CH3CN (3 mL), H2O (3 mL), 100 °C, 12 h.
for method B.
react with different α-oxocarboxylic acids, and the products
4a−j were obtained in good to high yields (Table 3). For
example, 2-oxo-2-phenylacetic acid with p-methyl, o-methyl,
and 2,4-dimethyl groups could be converted to the desired
products in good yields (4f−h). Regardless of the electron-
withdrawing group (p-Cl) or electron-donating group (p-MeO)
on the 2-oxo-2-phenylacetic acid, the reaction still proceeded
smoothly, producing the corresponding products (4b,c,i) in
good yields (75−81%). The strong electron-withdrawing
group, for example, NO2, influenced the efficiency of the
reaction, and no product was obtained. We were pleased to find
that 2-oxo-2-(thiophene-2-yl) acetic acid was still tolerated
under the oxidative conditions, and product 4j was obtained in
83% yield. It is noteworthy that aliphatic α-oxocarboxylic acids,
such as 2-oxopropanoic acid and 2-oxobutanoic acid, were
likewise converted to the expected products in excellent yields
expected, the radical cyclization toward 3-acyl-4-arylquinolin-
2(1H)-ones proceeded well for various N-arylcinnamamides,
such as halogenated, methyl- or methoxy-substituted N-methyl-
N-phenylacrylamide (4n,l,q−s). Substituents like F or Cl on
aniline at the para position did not influence the trans-
formation, and the desired products were obtained in 80%
yields (4r,s). To our satisfaction, when the N-protected group
of the substrate 1 was changed from methyl to ethyl, benzyl,
and cyanoethyl, the corresponding quinolin-2(1H)-one de-
rivatives were obtained with little difference in yields (4t−v).
Notably, N-pyridylcinnamamide could also undergo the
tandem radical cyclization with phenylglyoxylic acid, leading
to product 4m in 66% yield. Interestingly, when N-methyl-N-p-
tolylcinnamamide was explored as substrate, the methyl on
aniline was oxidized to aldehyde group and the double bond
was not formed (3b′).
C
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Scheme 2. Investigation into the Chemoselectivity of 1m
When N-(3-chlorophenyl)-N-methylcinnamamide was trea-
ted with 2a under the conditions of method B, two
chemoselective products 3c′ and 4w were obtained, respec-
tively (Scheme 2). Interestingly, the reaction of 1m with 2a
showed little difference in chemoselectivity when the amount of
oxidant was increased to 6.0 equiv. Compound 3c′ could not be
transferred into quinolin-2(1H)-one even when using 8.0 equiv
of K2S2O8 was used as oxidant. The reason for this is not clear
at present.
acyl group was very important in the dehydrogenated process
toward the final product.
On the basis of the above results, a plausible catalytic cycle is
presented in Scheme 4. First, Ag2+, which was generated from
Scheme 4. Proposed Catalytic Cycle
The structures of products 4l and 4o were confirmed by
single-crystal X-ray crystallographic analysis (see the Support-
ing Information).11
To gain insight into the mechanism of this novel reaction,
some control experiments were performed (Scheme 3). The
Scheme 3. Investigation into the Reaction Mechanism
Ag+, abstracted a single electron from carboxylate to produce
the carboxyl radical, and the latter was quickly decarboxylated
to produce acyl radical A.8,12 The radical A was trapped by the
α-position of the N-methyl-N-phenylcinnamamide to generate
intermediate B. Then B underwent intramolecular cyclization
to afford intermediate C. Finally, sulfate radical anion
abstracted a hydrogen from C, delivering the product 3. The
redundant persulfate anion disproportionated into sulfate
dianion and sulfate radical anion with the help of Ag+.12
Sulfate radical anion abstracted the hydrogen on the 3-position
of product 3 to trigger the process of dehydrogenation, leading
to the final product 4.
CONCLUSION
■
In summary, we have developed an interesting new approach to
the synthesis of 3-acyl-4-aryldihydroquinolin-2(1H)-one or 3-
acyl-4-arylquinolin-2(1H)-ones, which may be of great
importance as biologically attractive molecules through radical
tandem cyclization. Two types of products could be controlled
and obtained only by adjusting the amount of oxidant. This
reaction catalyzed by silver in aqueous solution includes
decarboxylation, cyclization, and dehydrogention processes in
one step, which make the method green and atom-economic. In
view of the broad interest in quinolin-2(1H)-one derivatives,
this novel one-pot procedure could prove useful in synthetic
and medicinal chemistry. Further studies on this transformation
are ongoing in our laboratory.
reaction was completely shut off when 1.0 equiv of TEMPO
was added, indicating that a radical intermediate was involved
in this transformation (Scheme 3a). Notably, product 3a could
not be transformed into product 4a in the absence of catalyst or
oxidant (Scheme 3b,c). Gratifyingly, with 20 mol % of AgNO3
as catalyst and 2.0 equiv of K2S2O8 as oxidant, 3a could be
converted to 4a completely, which showed that both the
catalyst and oxidant played important roles in this trans-
formation (Scheme 3d). The reaction of Scheme 3e clearly
demonstrated the dehydrogenated process of 3a to 4a was also
initiated by a radical. The result of Scheme 3f indicated that the
D
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127.35, 123.5, 114.9, 55.8, 44.9, 30.0, 21.7; FT-IR ν/cm−1 (KBr) 1689,
1658, 1597, 1373, 752; HRMS (ESI) calcd for C24H22NO2 [M + H]+
356.1651, found 356.1658.
EXPERIMENTAL SECTION
■
General Methods. All experiments were carried out using a
common flask in air. Cinnamic acids, thionyl chloride, aromatic
secondary amines, and benzoylformic acids were purchased from
commercial suppliers and used as received unless otherwise noted. All
solvents and other commercially available reagents were purchased
from suppliers and used directly. Reactions were monitored by thin-
layer chromatography (TLC). Products were detected using a UV/vis
3-(3-Bromobenzoyl)-1-methyl-4-phenyl-3,4-dihydroquinolin-
2(1H)-one (3d): white solid (336 mg, 80%); mp 158−160 °C; Rf =
0.65 (petroleum ether/ethyl acetate = 2:1); 1H NMR (400 MHz,
CDCl3) (main product) δ 8.01 (t, J = 1.6 Hz, 1H), 7.82−7.86 (m,
1H), 7.68 (dt, J = 8.0, 0.8 Hz, 1H), 7.21−7.41 (m, 5H), 7.21 (d, J = 7.2
Hz, 2H), 7.13 (d, J = 7.6 Hz, 1H), 7.03 (td, J = 7.6, 0.8 Hz, 1H), 6.85
(d, J = 7.6 Hz, 1H), 4.90 (dd, J = 9.2, 2.8 Hz, 1H), 4.74 (d, J = 8.4 Hz,
1H), 3.47 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 194.5, 166.5,
139.6, 139.3, 138.7, 136.1, 133.2, 131.6, 130.2, 129.9, 128.7, 128.6,
128.3, 128.2, 127.6, 127.2, 126.8, 123.6, 123.0, 115.0, 55.6, 44.6, 30.0;
FT-IR ν/cm−1 (KBr) 1685, 1651, 1593, 1454, 1365, 760, 702; HRMS
(ESI) calcd for C23H19BrNO2 [M + H]+ 420.0599, found 420.0605.
1-Methyl-4-phenyl-3-(thiophene-2-carbonyl)-3,4-dihydroquino-
lin-2(1H)-one (3j): pale yellow solid (250 mg, 72%); mp 166−169 °C;
Rf = 0.13 (petroleum ether/ethyl acetate = 5:1); 1H NMR (400 MHz,
CDCl3) δ 7.87 (dd, J = 3.6, 1.2 Hz, 1H), 7.65 (dd, J = 4.8, 1.2 Hz, 1H),
7.29−7.36 (m, 3H), 7.21−7.27 (m, 1H), 7.19−7.21 (m, 2H), 7.11−
7.14 (m, 2H), 7.04 (td, J = 7.6, 0.8 Hz, 1H), 6.94 (d, J = 7.2 Hz, 1H),
4.73−4.78 (m, 2H), 3.47 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
187.7, 166.0, 143.7, 140.0, 139.4, 134.7, 133.5, 129.1, 128.7, 128.3,
128.2, 128.14 127.5, 127.4, 123.6, 115.0, 57.5, 45.0, 30.1; FT-IR ν/
cm−1 (KBr) 1651, 1597, 1458, 1412, 1365, 1308, 752, 741, 702;
HRMS (ESI) calcd for C21H18NO2S [M + H]+ 348.1058, found
348.1064.
1
lamp. Column chromatography was performed on silica gel. The H
and 13C NMR spectra were obtained on 400 MHz NMR. H NMR
1
data are reported as chemical shift (δ ppm), multiplicity, coupling
constant (Hz), and integration. 13C NMR data are reported in terms of
chemical shift (δ ppm), multiplicity, and coupling constant (Hz). The
spectra are referenced against the internal solvent (CDCl3, δ 1H = 7.26
ppm, 13C = 77.0 ppm; DMSO-d6, δ 1H = 2.50 ppm, 13C = 40.0 ppm).
Data are reported as follows: s = singlet, d = doublet, t = triplet, q =
quartet and m = multiplet. High-resolution mass spectra (HR-MS)
were obtained on Q-TOF using the ESI technique.
General Procedure for the Synthesis of Substrate 1. A 50 mL
anhydrous flask was charged with a magnetic stir bar, cinnamic acid (5
mmol, 0.74g), and SOCl2 (5 mL). After the mixture was stirred at 60
°C for 3 h, the redundant SOCl2 was evaporated under reduced
pressure and then the liquid was dropwise added into another flask
containing N-methylaniline (10 mmol, 1.07g) dissolved in anhydrous
CH2Cl2 (20 mL). The mixture was stirred for 1 h at room
temperature. The organic phase was then washed with HCl aqueous
solution and K2CO3 aqueous solution and then dried with anhydrous
Na2SO4. After evaporation of the CH2Cl2, the N-methyl-N-phenyl-
cinnamamide was obtained in 97% yield and used in the next step
directly.
Typical Experimental Procedure for Products 3. Compounds
1(1.0 mmol) and 2 (1.0 mmol), AgNO3 (34 mg, 0.2 mmol), K2S2O8
(540 mg, 2.0 mmol), and a stir bar were added to 50 mL tube, and
then CH3CN (3 mL) and H2O (3 mL) were added. The mixture was
allowed to stir at 100 °C for 12 h (monitored by TLC). The solution
was then diluted with ethyl acetate (20 mL), washed with a solution of
K2CO3 and water, and then dried with anhydrous Na2SO4. The crude
mixture was purified by colum chromatography on silica gel
(petroleum ether/ethyl acetate = 15:1−6:1) to give the products
3a−d,j,m−o,u−z,a′.
3-Benzoyl-1-benzyl-4-phenyl-3,4-dihydro-1,8-naphthyridin-
2(1H)-one (3m): pale yellow solid (280 mg, 67%): mp 155−158 °C; Rf
1
= 0.54 (petroleum ether/ethyl acetate = 4:1); H NMR (400 MHz,
CDCl3) δ 8.32 (dd, J = 4.8 Hz, 1.2 Hz, 1H), 7.96 (d, J = 8.0 Hz, 2H),
7.60 (t, J = 7.2 Hz, 1H), 7.48 (q, J = 6.8 Hz, 4H), 7.27−7.29 (m,
overlapping CDCl3, 4H), 7.23−7.25 (m, 5H), 7.07−7.10 (m, 2H),
6.95 (dd, J = 7.2 Hz, J = 4.8 Hz, 1H), 5.53 (dd, J = 19.2 Hz, 14.4 Hz,
2H), 5.02 (d, J = 7.6 Hz, 1H), 4.70 (d, J = 7.6 Hz, 1H); 13C NMR
(100 MHz, CDCl3) δ 195.0, 166.7, 150.6, 146.7, 139.5, 137.7, 136.8,
136.3, 133.6, 129.2, 128.9, 128.7, 128.6, 128.2, 128.0, 127.7, 127.1,
122.6, 119.1, 55.9, 44.1, 43.6; FT-IR ν/cm−1 (KBr) 1689, 1666, 1585,
1442, 1377, 1319, 1211, 733, 690; HRMS (ESI) calcd for C28H23N2O2
[M + H]+ 419.1760, found 419.1762.
3-Benzoyl-4-(2-chlorophenyl)-1-methyl-3,4-dihydroquinolin-
3-Benzoyl-1-methyl-4-phenyl-3,4-dihydroquinolin-2(1H)-one
(3a): white solid (270 mg, 79%); mp 154−156 °C; Rf = 0.45
(petroleum ether/ethyl acetate = 3:1); 1H NMR (400 MHz, CDCl3) δ
7.92 (d, J = 7.2 Hz, 2H), 7.57 (t, J = 7.6 Hz, 1H), 7.46 (t, J = 7.6 Hz,
2H), 7.29−7.36 (m, 3H), 7.17−7.26 (m, 3H), 7.13 (d, J = 8.0 Hz,
1H), 7.03 (td, J = 7.6, 0.8 Hz, 1H), 6.88 (d, J = 7.6 Hz, 1H), 4.97 (d, J
= 7.6 Hz, 1H), 4.74 (d, J = 7.6 Hz, 1H), 3.48 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 195.7, 166.7, 140.0, 139.5, 136.6, 133.3, 129.0, 128.71,
128.67, 128.65, 128.2, 128.1, 127.43, 127.36, 123.5, 114.9, 55.8, 44.9,
30.0; FT-IR ν/cm−1 (KBr) 1697, 1662, 1597, 1373, 756; HRMS (ESI)
calcd for C23H20NO2 [M + H]+ 342.1494, found 342.1491.
1
2(1H)-one (3n): white solid (244 mg, 65%); mp 130−132 °C; H
NMR (400 MHz, CDCl3) δ 8.032 (dt, J = 7.2 Hz, 1.6 Hz, 2H), 7.60−
7.56 (m, 1H), 7.48−7.43 (m, 3H), 7.39 (td, J = 8.4 Hz, 1.2 Hz, 1H),
7.23(td, J = 7.6 Hz, 2.0 Hz, 1H), 7.16−7.12 (m, 2H), 7.09 (td, J = 7.6
Hz, 1.2 Hz, 1H),6.94−6.89 (m, 2H), 5.21 (d, J = 6.8 Hz, 1H), 5.06 (d,
J = 6.8 Hz, 1H), 3.47 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 195.3,
166.1, 139.8, 137.3, 136.6, 134.0, 133.5, 130.3, 129.4, 129.1, 128.8,
128.6, 128.4, 128.4, 127.5, 126.4, 123.9, 115.1, 54.5, 41.6, 30.1; FT-IR
ν/cm−1 (KBr) 1689, 1670, 1601, 1458, 1354, 760; HRMS (ESI) calcd
for C23H18ClNO2[M + H]+ 376.1104, found 376.1100.
3-Benzoyl-4-(4-bromophenyl)-1-methyl-3,4-dihydroquinolin-
3-(4-Chlorobenzoyl)-1-methyl-4-phenyl-3,4-dihydroquinolin-
1
2(1H)-one (3o): yellow solid (315 mg, 75%); mp 208−210 °C; H
2(1H)-one (3b): pale yellow solid (278 mg, 74%); mp 133−136 °C; Rf
1
NMR (400 MHz, CDCl3) δ 7.92 (dt, J = 5.2 Hz, 1.2 Hz, 2H), 7.60−
7.56 (m, 1H), 7.48−7.42 (m, 4H), 7.37 (t, J = 7.6 Hz, 0.8 Hz, 1H),
7.13−7.01(m, 4H), 6.86 (d, J = 7.6 Hz, 1H), 4.92 (d, J = 8.8 Hz, 1H),
4.74 (d, J = 8.8 Hz, 1H), 3.47 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
195.3, 166.5, 139.4, 139.0, 136.7, 133.5, 132.2, 129.9, 128.7, 128.5,
128.4, 127.0, 123.6, 121.4, 115.0, 55.4, 44.2, 30.0; FT-IR ν/cm−1
(KBr) 1693,1666, 1597, 1373; HRMS (ESI) calcd for C23H18BrNO2
[M + H]+ 420.0599, found 420.0591.
= 0.50 (petroleum ether/ethyl acetate = 3:1); H NMR (400 MHz,
CDCl3) δ 7.87 (d, J = 8.4 Hz, 2H), 7.43 (d, J = 8.4 Hz, 2H), 7.23−7.36
(m, 4H), 7.19 (d, J = 8.4 Hz, 2H), 7.13 (d, J = 8.0 Hz, 1H), 7.03 (td, J
= 7.6, 0.8 Hz, 1H), 6.88 (d, J = 7.2 Hz, 1H), 4.90 (d, J = 8.4 Hz, 1H),
4.75 (d, J = 8.4 Hz, 1H), 3.47 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
194.5, 166.5, 139.9, 139.8, 139.3, 135.2, 130.1, 129.1, 129.0, 128.6,
128.2, 127.5, 123.6, 114.9, 55.7, 44.7, 30.0; FT-IR ν/cm−1 (KBr) 1685,
1662, 1597, 1466, 1377, 760; HRMS (ESI) calcd for C23H19ClNO2 [M
+ H]+ 376.1104, found 376.1109.
1-Methyl-3-(4-methylbenzoyl)-4-phenyl-3,4-dihydroquinolin-
2(1H)-one (3c): white solid (274 mg, 77%); mp 136−139 °C; Rf =
0.50 (petroleum ether/ethyl acetate = 3:1); 1H NMR (400 MHz,
CDCl3) δ 7.85 (d, J = 8.4 Hz, 2H), 7.18−7.35 (m, overlapping CDCl3,
8H), 7.13 (d, J = 8.0 Hz, 1H), 6.99−7.11 (m, 1H), 6.92 (d, J = 7.2 Hz,
1H), 4.94 (d, J = 7.2 Hz, 1H), 4.73 (d, J = 7.2 Hz, 1H), 3.47 (s, 3H),
2.41 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 195.1, 166.8, 144.3,
140.2, 139.6, 134.0, 129.4, 129.0, 128.9, 128.7, 128.1, 128.0, 127.39,
3-(3-Benzoyl-2-oxo-4-phenyl-3,4-dihydroquinolin-1(2H)-yl)-
propanenitrile (3v): white solid (320 mg, 84%); mp 158−160 °C; 1H
NMR (400 MHz, CDCl3) δ 7.93 (d, J = 8.0 Hz, 2H), 7.63 (t, J = 7.2
Hz, 1H), 7.51 (t, J = 8.0 Hz, 2H), 7.41−7.27 (m, 4H), 7.19(t, J = 8.8
Hz, 3H), 7.09 (t, J = 8.0 Hz, 0.8 Hz, 1H), 6.98 (d, J = 7.2 Hz, 1H),
4.97 (d, J = 6.0 Hz, 1H), 4.70 (d, J = 6.4 Hz, 1H), 4.40−4.27 (m, 2H),
2.85−2.75 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 195.1, 166.9,
139.7, 137.8, 135.9, 133.7, 129.7, 129.2, 128.9, 128.70, 128.65, 127.8,
127.7, 126.9, 124.3, 117.4, 114.4, 56.2, 45.0, 39.0, 15.9; FT-IR ν/cm−1
E
dx.doi.org/10.1021/jo501301t | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
(KBr) 1689, 1670, 1597, 1458, 1385, 760, 702; HRMS (ESI) calcd for
C25H21N2O2 [M + H]+ 381.1603, found 381.1608.
2:1); 1H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 6.8 Hz, 2H), 7.65−
7.69 (td, J = 8.4, 1.6 Hz, 1H), 7.46−7.52 (m, 2H), 7.35−7.39 (m, 3H),
7.31−7.33 (m, 3H), 7.24−7.28 (m, overlapping CDCl3, 2H), 7.19−
7.23 (m, 1H), 3.84 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 194.4,
159.9, 148.1, 140.0, 137.0, 133.9, 133.3, 131.5, 131.0, 130.1, 129.3,
129.2, 128.64, 128.60, 128.4, 128.3, 122.4, 120.8, 114.4, 29.6; FT-IR ν/
cm−1 (KBr) 1676, 1635, 1581, 1458, 1369, 1246, 1086, 815, 751;
HRMS (ESI) calcd for C23H18NO2 [M + H]+ 340.1338, found
340.1336.
3-(4-Chlorobenzoyl)-1-methyl-4-phenylquinolin-2(1H)-one (4b):
pale yellow solid (303 mg, 81%); mp 113−117 °C; Rf = 0.20
(petroleum ether/ethyl acetate = 3:1); 1H NMR (400 MHz, CDCl3) δ
7.75 (dt, J = 8.8 Hz, 2.4 Hz, 2H), 7.70 (t, J = 8.0 Hz, 1H), 7.50 (d, J =
8.4 Hz, 1H), 7.31−7.39 (m, 6H), 7.20−7.25 (m, 3H), 3.83 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 193.2, 159.8, 148.4, 140.1, 139.7,
135.4, 133.8, 131.6, 130.5, 129.2, 128.8, 128.7, 128.4, 122.5, 120.7,
114.5, 29.6; FT-IR ν/cm−1 (KBr) 1678, 1635, 1585, 1242, 1092, 868,
748; HRMS (ESI) calcd for C23H17ClNO2 [M + H]+ 374.0948, found
374.0950.
3-Benzoyl-1-benzyl-4-phenyl-3,4-dihydroquinolin-2(1H)-one
1
(3u): white solid (342 mg, 82%); mp 116−118 °C; H NMR (400
MHz, CDCl3) δ 8.01 (d, J = 0.8 Hz, 2H), 7.99 (t, J = 2.0 Hz, 1H),
7.63−7.50 (m, 3H), 7.49−7.27 (m, 6H), 7.26−7.20(m, 2H), 7.19 (d, J
= 5.6 Hz, 3H), 7.04−6.97 (m, 3H), 5.44 (d, J = 16.0 Hz, 1H), 5.15 (d,
J = 16.4 Hz, 1H), 5.08 (d, J = 16.4 Hz, 1H), 4.73(d, J = 5.6 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 195.5, 166.7, 140.4, 139.0, 136.6,
136.1, 133.6, 129.1, 129.1, 128.84, 128.80, 128.7, 128.6, 128.5, 128.3,
127.8, 127.5, 127.2, 126.79, 126.75, 126.7, 126.6, 123.7, 116.0, 56.8,
46.7, 45.2; FT-IR ν/cm−1 (KBr) 1685, 1666, 1597, 1493, 1458, 1381,
1323, 752, 729, 698; HRMS (ESI) calcd for C29H23NO2 [M + H]+
418.1807, found 418.1798.
3-Acetyl-1-benzyl-4-phenyl-3,4-dihydroquinolin-2(1H)-one (3z):
1
white solid (256 mg, 72%); mp 150−152 °C; H NMR (400 MHz,
CDCl3) δ 7.35−7.25 (m, overlapping CDCl3, 7H), 7.23−7.17 (m,
2H), 7.13 (dd, J = 7.6 Hz, 1.6 Hz, 2H), 7.04−6.99 (m, 3H), 5.23 (td, J
= 18.0 Hz, 4.0 Hz, 2H), 4.74 (d, J = 6.0 Hz, 1H), 4.13 (d, J = 6.4 Hz,
1H), 2.28 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 202.3, 166.5,
139.8, 138.5, 136.5, 129.2, 129.0, 128.8, 128.2, 127.9, 127.43, 127.35,
127.2, 126.82, 126.75, 126.4, 123.9, 115.9, 62.1, 46.5, 43.6, 29.5; FT-IR
ν/cm−1 (KBr) 1720, 1666, 1597, 1493, 1458, 1381, 756, 694; HRMS
(ESI) calcd for C24H21NO2 [M + H]+ 356.1651, found 356.1657.
3-Benzoyl-4-(4-methoxyphenyl)-1-methyl-3,4-dihydroquinolin-
3-(4-Chlorobenzoyl)-1-methyl-4-(p-tolyl)quinolin-2(1H)-one (4c):
white solid (303 mg, 78%); mp 194−198 °C; Rf = 0.23 (petroleum
ether/ethyl acetate = 3:1); 1H NMR (400 MHz, CDCl3) δ 7.70 (dt, J
= 8.8 Hz, 2.0 Hz, 2H), 7.69 (t, J = 7.6 Hz, 1H), 7.51 (d, J = 8.4 Hz,
1H), 7.42 (dd, J = 8.0 Hz, 1.6 Hz, 1H), 7.35 (dt, J = 9.2 Hz, 2.4 Hz,
2H), 7.23 (t, J = 7.6 Hz, 1H), 7.16 (d, J = 8.4 Hz, 4H), 3.82 (s, 3H),
2.34 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 193.3, 159.8, 148.6,
140.0, 139.6, 138.7, 135.5, 131.6, 130.8, 130.5, 130.4, 129.1, 128.8,
128.7, 122.5, 120.8, 114.4, 29.6, 21.3; FT-IR ν/cm−1 (KBr) 1678,
1635, 1581, 1458, 1369, 1315, 1246, 1088, 810, 748; HRMS (ESI)
calcd for C24H19ClNO2 [M + H]+ 388.1104, found 388.1106.
3-Acetyl-1-methyl-4-phenylquinolin-2(1H)-one (4d): white solid
(250 mg, 90%); mp 169−172 °C, Rf = 0.19 (petroleum ether/ethyl
1
2(1H)-one (3x): white solid (264 mg, 71%); mp 132−133 °C; H
NMR (400 MHz, CDCl3) δ 8.01 (dt, J = 5.6 Hz, 1.6 Hz, 2H), 7.59−
7.54 (m, 1H), 7.47−7.43 (td, J = 7.2 Hz, 1.6 Hz, 2H), 7.35 (t, J = 1.2
Hz, 1H), 7.13(dd, J = 7.6 Hz, 2.0 Hz, 3H), 7.04 (td, J = 7.6 Hz, 0.8 Hz,
1H), 6.90 (d, J = 7.6 Hz, 1H), 6.85 (dd, J = 6.4 Hz, 2.0 Hz, 2H), 4.93
(d, J = 8.4 Hz, 1H), 4.71 (d, J = 8.0 Hz, 1H), 3.78 (s, 3H), 3.47 (s,
3H); 13C NMR (100 MHz, CDCl3) δ 195.8, 166.9, 158.8, 139.5,
136.8, 133.3, 131.9, 129.2, 128.7, 128.7, 128.6, 128.1, 127.9, 123.5,
114.9, 114.4, 55.9, 55.2, 44.1, 29.9; FT-IR ν/cm−1 (KBr) 1693,1658,
1597, 1512, 1462, 1373, 1246, 1034, 752; HRMS (ESI) calcd for
C24H21NO3 [M + H]+ 372.1600, found 372.1609
1
acetate = 3:1); H NMR (400 MHz, CDCl3) δ 7.65 (t, J = 8.0 Hz,
1H), 7.51 (td, J = 5.6 Hz, 4.0 Hz, 4H), 7.33 (dt, J = 7.6 Hz, 2.0 Hz,
3H), 7.20 (t, J = 7.6 Hz, 1H), 3.82 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 201.7, 159.4, 146.4, 139.7, 134.2, 133.1, 131.4, 129.2, 128.9,
128.7, 128.6, 122.4, 120.7, 114.3, 31.4, 29.5; FT-IR ν/cm−1 (KBr)
1709, 1628, 1458, 1369, 1076, 764, 706; HRMS (ESI) calcd for
C18H16NO2 [M + H]+ 278.1181, found 278.1182.
3-Benzoyl-4-(3,4-dimethoxyphenyl)-1-methyl-3,4-dihydroquino-
1
lin-2(1H)-one (3y): white solid (253 mg, 63%); mp 166−167 °C; H
NMR (400 MHz, CDCl3) δ 7.93 (dd, J = 7.2 Hz, 1.2 Hz, 2H), 7.58−
7.54 (m, 1H), 7.47 (td, J = 7.2 Hz, 1.6 Hz, 2H), 7.36−7.32 (m, 1H),
7.13(d, J = 4.0 Hz, 1H), 7.05 (td, J = 7.2 Hz, 0.8 Hz, 1H), 6.90 (d, J =
7.6 Hz, 1H),6.81−6.69 (m, 3H), 4.96 (d, J = 9.2 Hz, 1H), 4.72 (d, J =
8.8 Hz, 1H), 3.85(s, 3H), 3.77(s, 3H), 3.47 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 195.9, 167.1, 149.2, 148.3, 139.4, 137.0, 133.3, 132.1,
128.6, 128.5, 128.1, 123.5, 120.6, 114.9, 111.6, 111.3, 55.8, 55.5, 44.4,
29.9, 29.7; FT-IR ν/cm−1 (KBr) 1689, 1662, 1597, 1516, 1458, 1365,
1265, 1142, 1026, 764; HRMS (ESI) calcd for C25H23NO4 [M + H]+
402.1705, found 402.1712.
1-Methyl-4-phenyl-3-propionylquinolin-2(1H)-one (4e): yellow
solid (253 mg, 87%); mp 148−150 °C; Rf = 0.20 (petroleum ether/
1
ethyl acetate = 3:1); H NMR (400 MHz, CDCl3) δ 7.65 (td, J = 8.8
Hz, 1.6 Hz, 1H), 7.45−7.50 (m, 4H), 7.32 (t, J = 1.6 Hz, 3H), 7.20 (t,
J = 8.0 Hz, 1H), 3.81 (s, 3H), 2.53 (q, J = 7.2 Hz, 2H), 0.94 (t, J = 7.2
Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 204.9, 159.5, 146.2, 139.7,
134.2, 1332, 131.3, 129.3, 128.8, 128.54, 128.48, 122.4, 120.6, 114.3,
37.1, 29.5, 7.4; FT-IR ν/cm−1 (KBr) 1712, 1635, 1585, 1454, 1373,
1315, 756, 706; HRMS (ESI) calcd for C19H18NO2 [M + H]+
292.1338, found 292.1336.
1-Methyl-3-(4-methylbenzoyl)-4-phenylquinolin-2(1H)-one (4f):
pale yellow solid (251 mg, 71%); mp 217−220 °C; Rf = 0.16
(petroleum ether/ethyl acetate = 3:1); 1H NMR (400 MHz, CDCl3) δ
7.71 (d, J = 8.0 Hz, 2H), 7.68 (t, J = 8.8 Hz, 1H), 7.52 (d, J = 8.4 Hz,
1H), 7.38 (dd, J = 8.4 Hz, 1.6 Hz, 1H), 7.33 (t, J = 3.2 Hz, 3H), 7.26−
7.28 (m, overlapping CDCl3, 3H), 7.20 (t, J = 7.6 Hz, 1H), 7.16 (d, J =
8.0 Hz, 2H), 3.83 (s, 3H), 2.36 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ 194.0, 159.9, 147.8, 144.2, 140.0, 134.6, 134.0, 131.4, 131.2, 129.3,
129.2, 128.6, 128.3, 122.4, 120.8, 114.4, 29.6, 21.7; FT-IR ν/cm−1
(KBr) 1670, 1639, 1597, 1458, 1365, 1319, 1250, 752; HRMS (ESI)
calcd for C24H20NO2 [M + H]+ 354.1494, found 354.1493.
1-Methyl-3-(2-methylbenzoyl)-4-phenylquinolin-2(1H)-one (4g):
yellow solid (230 mg, 65%); mp 123−127 °C; Rf = 0.33 (petroleum
ether/ethyl acetate = 3:1); 1H NMR (400 MHz, CDCl3) δ 7.67 (t, J =
8.0 Hz, 1H), 7.58 (d, J = 7.2 Hz, 1H), 7.51 (d, J = 8.4 Hz, 1H), 7.31−
7.34 (m, 4H), 7.27−7.29 (m, overlapping CDCl3, 3H), 7.17−7.22 (m,
3H), 7.11−7.14 (m, 2H), 3.84 (s, 3H), 2.39 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 196.1, 160.0, 147.4, 140.0, 139.8, 136.9, 134.0, 132.6,
131.9, 131.7, 131.3, 131.0, 129.2, 128.6, 128.5, 128.2, 125.4, 122.3,
120.9, 114.3, 29.6, 21.1; FT-IR ν/cm−1 (KBr) 1678, 1639, 1601, 1558,
N,1-Dimethyl-2-oxo-N,4-diphenyl-1,2,3,4-tetrahydroquinoline-3-
carboxamide (3a′): sticky pale yellow oil (263 mg, 71%); Rf = 0.27
(petroleum ether/ethyl acetate = 2:1); 1H NMR (400 MHz, CDCl3) δ
7.34−7.38 (m, 3H), 7.26−7.33 (m, overlapping CDCl3, 4H), 7.24 (t, J
= 8.0 Hz, 1H), 7.07−7.09 (m, 2H), 6.98 (d, J = 8.0 Hz, 2H), 6.90 (t, J
= 7.6 Hz, 1H), 6.66 (d, J = 7.6 Hz, 1H), 4.82 (d, J = 13.2 Hz, 1H), 3.85
(d, J = 13.2 Hz, 1H), 3.43 (s, 3H), 3.13 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 168.3, 167.2, 143.4, 139.6, 139.1, 129.6, 129.5, 128.6, 128.2,
128.1, 127.9, 127.7, 127.5, 127.5, 123.0, 114.5, 52.2, 45.4, 37.3, 30.0;
FT-IR ν/cm−1 (KBr) 1677, 1658, 1595, 1519, 1455, 1376, 752; HRMS
(ESI) calcd for C24H23N2O2 [M + H]+ 371.1760, found 371.1764.
Typical Experimental Procedure for Products 4. Compounds
1 (1.0 mmol) and 2 (1.0 mmol), AgNO3 (68 mg, 0.2 mmol), K2S2O8
(1.08 g, 4.0 mmol), and a stir bar were added to 50 mL tube, and then
CH3CN (3 mL) and H2O (3 mL) were added. The mixture was
allowed to stir at 100 °C for 12 h (monitored by TLC). The solution
was then diluted with ethyl acetate (20 mL), washed with a solution of
K2CO3 and water, and then dried with anhydrous Na2SO4. The crude
mixture was purified by colum chromatography on silica gel
(petroleum ether/ethyl acetate = 15:1−5:1) to give the product 4a−v.
3-Benzoyl-1-methyl-4-phenylquinolin-2(1H)-one (4a): sticky col-
orless oil (265 mg, 78%); Rf = 0.21 (petroleum ether/ethyl acetate =
F
dx.doi.org/10.1021/jo501301t | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
1458, 1369, 1315, 1242, 756, 706; HRMS (ESI) calcd for C24H20NO2
[M + H]+ 354.1494, found 354.1491.
3-Benzoyl-4-(4-bromophenyl)-1-methylquinolin-2(1H)-one (4o):
yellow solid (351 mg, 84%); mp 216−220 °C; Rf = 0.14 (petroleum
ether/ethyl acetate = 3:1); 1H NMR (400 MHz, CDCl3) δ 7.81 (d, J =
7.6 Hz, 2H), 7.70 (t, J = 7.6 Hz, 1H), 7.50−7.54 (m, 2H), 7.48 (d, J =
8.4 Hz, 2H), 7.40 (t, J = 7.6 Hz, 2H), 7.33 (dd, J = 8.0 Hz, 1.2 Hz,
1H), 7.24 (t, J = 7.6 Hz, 1H), 7.15 (d, J = 8.0 Hz, 2H), 3.83 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 194.1, 159.7, 146.8, 140.0, 136.9,
133.5, 132.9, 131.7, 131.6, 131.2, 130.9, 129.2, 128.6, 128.3, 123.1,
122.6, 120.4, 114.6, 29.7; FT-IR ν/cm−1 (KBr) 1674, 1643, 1593,
1361, 1311, 1238, 1011, 756; HRMS (ESI) calcd for C23H17BrNO2 [M
+ H]+ 418.0443, found 418.0447.
3-(2,4-Dimethylbenzoyl)-1-methyl-4-phenylquinolin-2(1H)-one
(4h): sticky colorless oil (294 mg, 80%); Rf = 0.22 (petroleum ether/
1
ethyl acetate = 3:1); H NMR (400 MHz, CDCl3) δ 7.66 (t, J = 8.0
Hz, 1H), 7.50 (dd, J = 8.4 Hz, 4.4 Hz, 2H), 7.33 (m, 4H), 7.25 (td, J =
4.4 Hz, 2.4 Hz, 2H), 7.20 (t, J = 8.0 Hz, 1H), 6.94 (d, J = 10.4 Hz,
2H), 3.83 (s, 3H), 2.39 (s, 3H), 2.30 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 195.7, 160.0, 147.2, 142.5, 140.1, 139.9, 134.2, 134.1, 132.7,
132.7, 131.6, 131.2, 129.2, 128.5, 128.4, 128.2, 126.1, 122.3, 120.9,
114.3, 29.6, 21.5, 21.3; FT-IR ν/cm−1 (KBr) 1658, 1639, 1597, 1562,
1454, 1369, 1319, 1230, 752, 706; HRMS (ESI) calcd for C25H22NO2
[M + H]+ 368.1651, found 368.1650.
3-(4-Methoxybenzoyl)-1-methyl-4-phenylquinolin-2(1H)-one (4i):
white solid (277 mg, 75%); mp 192−196 °C; Rf = 0.22 (petroleum
ether/ethyl acetate =2:1); 1H NMR (400 MHz, CDCl3) δ 7.80 (dt, J =
9.6 Hz, 2.8 Hz, 2H), 7.68 (t, J = 8.0 Hz, 1H), 7.51 (d, J = 8.0 Hz, 1H),
7.38 (dd, J = 8.0 Hz, 1.6 Hz, 1H), 7.32 (d, J = 2.4 Hz, 3H), 7.28 (m,
overlapping CDCl3, 3H), 7.22 (t, J = 7.6 Hz, 1H), 6.85 (dt, J = 9.6 Hz,
2.8 Hz, 2H), 3.83 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 192.8,
163.7, 159.9, 147.6, 140.0, 134.1, 131.6, 131.3, 131.2, 130.2, 129.3,
128.6, 128.5, 128.2, 122.4, 120.8, 114.4, 113.7, 55.4, 29.6; FT-IR ν/
cm−1 (KBr) 1658, 1635, 1597, 1570, 1315, 1254, 1165, 864, 748;
HRMS (ESI) calcd for C24H20NO3 [M + H]+ 370.1443, found
370.1446.
1-Methyl-4-phenyl-3-(thiophene-2-carbonyl)quinolin-2(1H)-one
(4j): yellow solid (287 mg, 83%); mp 209−212 °C; Rf = 0.25
(petroleum ether/ethyl acetate = 2:1); 1H NMR (400 MHz, CDCl3) δ
7.69 (t, J = 8.0 Hz, 1H), 7.58 (dd, J = 4.8 Hz, 0.8 Hz, 1H), 7.52 (m,
2H), 7.40 (dd, J = 8.4 Hz, 1.6 Hz, 1H), 7.34−7.36 (m, 3H), 7.31 (m,
2H), 7.23 (t, J = 7.6 Hz, 1H), 7.01 (dd, J = 4.8 Hz, 4.0 Hz, 1H), 3.84
(s, 3H); 13C NMR (100 MHz, CDCl3) δ 186.2, 159.7, 148.0, 144.2,
140.1, 134.5, 134.2, 133.8, 131.6, 130.8, 129.4, 128.8, 128.7, 128.3,
128.0, 122.5, 120.6, 114.5, 29.7; FT-IR ν/cm−1 (KBr) 1655, 1628,
1408, 1049, 744; HRMS (ESI) calcd for C21H16NO2S [M + H]+
346.0902, found 346.0903.
3-Benzoyl-4-(2-bromophenyl)-1-methylquinolin-2(1H)-one (4p):
white solid (368 mg, 88%); mp 160−163 °C; Rf = 0.20 (petroleum
ether/ethyl acetate = 3:1); 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J =
7.2 Hz, 2H), 7.69 (td, J = 8.4 Hz, 1.2 Hz, 1H), 7.49−7.54 (m, 3H),
7.39 (t, J = 8.0 Hz, 2H), 7.29−7.34 (m, 2H), 7.19−7.24 (m, 2H), 7.17
(dd, J = 8.0 Hz, 1.6 Hz, 1H), 3.85 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 193.8, 160.0, 147.0, 139.8, 136.6, 134.7, 133.5, 132.8, 131.7,
131.6, 131.4, 130.4, 129.3, 128.3, 127.3, 123.4, 122.9, 122.6, 119.7,
114.6, 29.7; FT-IR ν/cm−1 (KBr) 1674, 1639, 1597, 1562, 1369, 1319,
1246, 771, 752; HRMS (ESI) calcd for C23H17BrNO2 [M + H]+
418.0443, found 418.0441.
3-Benzoyl-4-(3-methoxyphenyl)-1-methylquinolin-2(1H)-one
(4q): sticky colorless oil (288 mg, 78%); Rf = 0.28 (petroleum ether/
ethyl acetate = 2:1); 1H NMR (400 MHz, CDCl3) δ 7.83 (s, 1H), 7.82
(t, J = 1.6 Hz, 1H), 7.69 (t, J = 8.0 Hz, 1H), 7.52 (t, J = 8.0 Hz, 2H),
7.44 (dd, J = 8.0 Hz, 1.2 Hz, 1H), 7.39 (t, J = 7.2 Hz, 2H), 7.20−7.24
(m, 2H), 6.86 (td, J = 5.2 Hz, 2.8 Hz, 2H), 6.77 (s, 1H), 3.83 (s, 3H),
3.65 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 194.3, 159.9, 159.2,
147.9, 140.0, 137.1, 135.1, 133.3, 131.5, 130.9, 129.4, 129.2, 128.6,
128.4, 122.4, 121.7, 120.6, 114.7, 114.6, 114.4, 55.2, 29.7, 29.6; FT-IR
ν/cm−1 (KBr) 1678, 1628, 1589, 1454, 1365, 1250, 1169, 698; HRMS
(ESI) calcd for C24H20NO3 [M + H]+ 370.1443, found 370.1446.
3-Benzoyl-6-chloro-1-methyl-4-phenylquinolin-2(1H)-one (4r):
yellow oil (299 mg, 80%); Rf = 0.17 (petroleum ether/ethyl acetate
= 3:1); 1H NMR (400 MHz, CDCl3) δ 7.79 (d, J = 7.2 Hz, 2H), 7.62
(dd, J = 9.2 Hz, 2.4 Hz, 1H), 7.49−7.51 (m, 1H), 7.48 (t, J = 8.0 Hz,
1H), 7.31−7.38 (m, 6H), 7.25 (dd, J = 5.6 Hz, 2.0 Hz, 2H), 3.81 (s,
3H); 13C NMR (100 MHz, CDCl3) δ 193.9, 159.6, 147.0, 138.6,
136.7, 133.5, 133.2, 132.1, 131.5, 129.2, 129.1, 129.0, 128.5, 128.2,
127.6, 121.9, 116.0, 29.8; FT-IR ν/cm−1 (KBr) 1678, 1643, 1601,
1365, 1315, 768, 698; HRMS (ESI) calcd for C23H17ClNO2 [M + H]+
374.0948, found 374.0950.
3-Benzoyl-1-methyl-4-(p-tolyl)quinolin-2(1H)-one (4l): White
solid (307 mg, 87%): mp 168−170 °C, Rf = 0.20 (petroleum ether/
1
ethyl acetate =3:1); H NMR (400 MHz, CDCl3) δ 7.82 (d, J = 7.2
Hz, 2H), 7.68 (t, J = 8.0 Hz, 1H), 7.51 (t, J = 8.0 Hz, 2H), 7.34−7.42
(m, 3H), 7.22 (t, J = 7.6 Hz, 1H), 7.16 (dd, J = 13.6 Hz, 8.4 Hz, 4H),
3.82 (s, 3H), 2.32 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 194.5,
159.9, 148.3, 140.0, 138.5, 137.1, 133.3, 131.4, 130.9, 129.2, 129.0,
128.6, 128.4, 122.4, 120.9, 114.4, 29.7, 29.6, 21.3; FT-IR ν/cm−1
(KBr) 1678, 1631, 1580, 1450, 1365, 1319, 1242, 1109, 825, 760;
HRMS (ESI) calcd for C24H20NO2 [M + H]+ 354.1494, found
354.1495.
3-Benzoyl-1-benzyl-4-phenyl-1,8-naphthyridin-2(1H)-one (4m):
pale yellow solid (275 mg, 66%); mp 186−189 °C; Rf = 0.44
(petroleum ether/ethyl acetate = 3:1); 1H NMR (400 MHz, CDCl3) δ
8.70 (d, J = 4.0 Hz, 1H), 7.80 (d, J = 7.2 Hz, 2H), 7.68 (t, J = 8.4 Hz,
3H), 7.52 (t, J = 7.6 Hz, 1H), 7.25−7.38 (m, overlapping CDCl3,
11H), 7.17 (dd, J = 7.6 Hz, 4.4 Hz, 1H), 5.85 (s, 2H); 13C NMR (100
MHz, CDCl3) δ 193.7, 160.6, 150.6, 149.40, 146.8, 137.5, 136.7, 136.5,
133.5, 132.9, 132.1, 129.4, 129.2, 129.0, 128.5, 128.3, 127.4, 118.5,
116.2, 44.3; FT-IR ν/cm−1 (KBr) 1678, 1635, 1601, 1558, 1454, 1315,
1254, 756, 694; HRMS (ESI) calcd for C28H21N2O2 [M + H]+
417.1603, found 417.1604.
3-Benzoyl-6-fluoro-1-methyl-4-phenylquinolin-2(1H)-one (4s):
yellow oil (282 mg, 79%); Rf = 0.28 (petroleum ether/ethyl acetate
= 3:1); 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 7.2 Hz, 2H), 7.46−
7.51 (m, 2H), 7.42 (dd, JH−F = 7.6 Hz, 2.8 Hz, 1H), 7.32−7.38 (m,
5H), 7.25 (d, J = 3.6 Hz, 2H), 7.06 (dd, JH−F = 9.2 Hz, 2.8 Hz, 1H),
3.83 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 194.0, 159.6, 159.2 (d, J
= 41 Hz), 156.8, 147.1, 136.8, 136.6, 133.4, 133.4, 132.2, 129.1, 129.0,
128.5, 121.9, 121.8, 119.3, 119.1 (d, J = 24 Hz), 116.1, 116.0, 113.9,
113.6 (d, J = 24 Hz), 29.9, 29.7; 19F-NMR (376.5 Hz, CDCl3) δ
−119.71; FT-IR ν/cm-1 (KBr) 1678, 1639, 1500, 1442, 1242, 810,
752, 702; HRMS (ESI) calcd for C23H17FNO2 [M + H]+ 358.1243,
found 358.1244.
3-Benzoyl-1-ethyl-4-phenylquinolin-2(1H)-one (4t): sticky pale
yellow oil (307 mg, 87%); Rf = 0.26 (petroleum ether/ethyl acetate
1
= 3:1); H NMR (400 MHz, CDCl3) δ 7.08 (s, 1H), 7.79 (t, J = 1,6
3-Benzoyl-4-(2-chlorophenyl)-1-methylquinolin-2(1H)-one (4n):
Hz, 1H), 7.68 (t, J = 8.0 Hz, 1H), 7.54 (d, J = 8.8 Hz, 1H), 7.50 (t, J =
7.6 Hz, 1H), 7.31−7.39 (m, 6H), 7.27 (q, J = 3.2 Hz, 2H), 7.21 (t, J =
7.6 Hz, 1H), 4.50 (q, J = 6.8 Hz, 2H), 1.48 (t, J = 7.2 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 194.5, 159.4, 148.0, 139.0, 137.1, 134.0,
133.3, 131.4, 131.1, 129.3, 129.1, 128.8, 128.6, 128.4, 128.3, 122.2,
121.0, 114.3, 37.5, 12.8; FT-IR ν/cm−1 (KBr) 1682, 1631, 1593, 1446,
1369, 1311, 1250, 764, 702; HRMS (ESI) calcd for C24H20NO2 [M +
H]+ 354.1494, found 354.1498.
white solid (333 mg, 89%); mp 198−202 °C; Rf = 0.14 (petroleum
1
ether/ethyl acetate = 3:1); H NMR (400 MHz, CDCl3) δ 7.84 (s,
1H), 7.83 (t, J = 2.0 Hz, 1H), 7.69 (t, J = 7.6 Hz, 1H), 7.48−7.53 (m,
2H), 7.33−7.39 (m, 3H), 7.26−7.31 (m, overlapping CDCl3, 4H),
7.24 (td, J = 8.0 Hz, 0.8 Hz, 1H), 7.17 (dd, J = 8.0 Hz, 1.6 Hz, 1H),
3.85 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 193.9, 160.0, 145.7,
139.8, 136.6, 133.5, 133.0, 132.7, 131.7, 131.59, 131.56, 130.3, 129.6,
129.2, 128.4, 128.1, 126.8, 122.7, 119.8, 114.6, 29.7, 29.7; FT-IR ν/
cm−1 (KBr) 1678, 1643, 1597, 1562, 1365, 1319, 1246, 775, 752;
HRMS (ESI) calcd for C23H17ClNO2 [M + H]+ 374.0948, found
374.0946.
3-Benzoyl-1-benzyl-4-phenylquinolin-2(1H)-one (4u): colorless oil
1
(353 mg, 85%); Rf = 0.20 (petroleum ether/ethyl acetate = 3:1); H
NMR (400 MHz, CDCl3) δ 7.84 (d, J = 6.8 Hz, 2H), 7.48−7.54 (m,
3H), 7.45 (d, J = 8.0 Hz, 1H), 7.35−7.40 (m, 7H), 7.29−7.34 (m,
G
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Article
5H), 7.17 (td, J = 7.2 Hz, 1.2 Hz, 1H), 5.65 (s, 2H); 13C NMR (100
MHz, CDCl3) δ 194.3, 160.1, 148.6, 139.5, 137.1, 136.2, 133.9, 133.3,
131.4, 130.9, 129.3, 129.2, 128.9, 128.7, 128.5, 128.3, 127.5, 127.0,
122.5, 121.0, 115.3, 46.1; FT-IR ν/cm−1 (KBr) 1678, 1635, 1601,
1566, 1454, 1373, 1315, 1250, 756, 694; HRMS (ESI) calcd for
C29H22NO2 [M + H]+ 416.1651, found 416.1654.
(131PCXTD605), and the Plan for Scientific Innovation
Talent of Henan University of Technology (171147).
REFERENCES
■
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3-(3-Benzoyl-2-oxo-4-phenylquinolin-1(2H)-yl)propanenitrile
(4v): yellow solid (291 mg, 77%); mp 168−173 °C; Rf = 0.17
(petroleum ether/ethyl acetate = 2:1); 1H NMR (400 MHz, CDCl3) δ
7.79 (s, 1H), 7.78 (t, J = 1.6 Hz, 1H), 7.73 (t, J = 8.0 Hz, 1H), 7.58 (d,
J = 8.8 Hz, 1H), 7.52 (t, J = 7.6 Hz, 1H), 7.43 (dd, J = 8.4 Hz, 1.6 Hz,
1H), 7.31−7.38 (m, 5H), 7.23−7.27 (m, 3H), 4.72 (t, J = 6.8 Hz, 2H),
2.98 (t, J = 6.8 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 193.9, 159.6,
149.1, 138.6 136.8, 133.6, 133.5, 131.9, 130.7, 129.4, 129.1, 128.9,
128.5, 128.4, 123.1, 121.1, 117.2, 113.7, 38.4, 16.0; FT-IR ν/cm−1
(KBr) 1678, 1635, 1597, 1454, 1373, 1315, 1250, 764, 702; HRMS
(ESI) calcd for C25H19N2O2 [M + H]+ 379.1447, found 379.1451.
3-Benzoyl-5-chloro-1-methyl-4-phenylquinolin-2(1H)-one (4w):
white solid (161 mg, 43%); mp 236−240 °C; Rf = 0.36 (petroleum
ether/ethyl acetate = 3:1); 1H NMR (400 MHz, CDCl3) δ 7.79 (d, J =
7.2 Hz, 2H), 7.50 (t, J = 6.8 Hz, 2H), 7.30−7.38 (m, 6H), 7.23−7.24
(m, 2H), 7.18 (dd, J = 8.4 Hz, 1.6 Hz, 1H), 3.80 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 194.0, 159.8, 147.5, 140.8, 137.7, 136.8, 133.5,
133.4, 131.1, 129.8, 129.2, 129.1, 128.9, 128.5, 128.4, 122.8, 119.3,
114.4, 29.7; FT-IR ν/cm−1 (KBr) 1674, 1635, 1597, 1585, 1550, 1439,
1369, 1315, 968, 764; HRMS (ESI) calcd for C23H17ClNO2 [M + H]+
374.0948, found 374.0945.
3-Benzoyl-1-methyl-2-oxo-4-phenyl-1,2,3,4-tetrahydroquinoline-
6-carbaldehyde (3b′): white solid (270 mg, 73%); mp 133−136 °C;
Rf = 0.20 (petroleum ether/ethyl acetate = 3:1); 1H NMR (400 MHz,
CDCl3) δ 9.85 (s, 1H), 7.95 (d, J = 7.6 Hz, 2H), 7.89 (dd, J = 8.4 Hz,
1.6 Hz, 1H), 7.62 (t, J = 7.6 Hz, 1H), 7.50 (t, J = 7.2 Hz, 3H), 7.35 (t,
J = 7.2 Hz, 2H), 7.25−7.29 (m, overlapping CDCl3, 3H), 7.19 (d, J =
6.8 Hz, 2H), 5.02 (d, J = 6.8 Hz, 1H), 4.77 (d, J = 6.8 Hz, 1H), 3.53 (s,
3H); 13C NMR (100 MHz, CDCl3) δ 195.0, 190.7, 166.7, 144.6,
139.4, 136.0, 133.8, 131.8, 130.5, 130.1, 129.3, 128.82, 128.79, 127.9
127.7, 115.3, 55.7, 44.8, 30.3; FT-IR ν/cm−1 (KBr) 1689, 1674, 1597,
1365, 1296, 1207, 1111, 756, 690; HRMS (ESI) calcd for C24H20NO3
[M + H]+ 370.1443, found 370.1446.
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3-Benzoyl-7-chloro-1-methyl-4-phenyl-3,4-dihydroquinolin-
2(1H)-one (3c′): white solid (132 mg, 35%); mp 147−149 °C; Rf =
0.53 (petroleum ether/ethyl acetate = 3:1); 1H NMR (400 MHz,
CDCl3) δ 8.09 (d, J = 8.4 Hz, 2H), 7.66 (t, J = 7.2 Hz, 1H), 7.55 (t, J =
7.6 Hz, 2H), 7.26−7.35 (m, overlapping CDCl3, 5H), 7.15 (t, J = 7.2
Hz, 3H), 7.07 (d, J = 8.0 Hz, 1H), 4.97 (s, 1H), 4.90 (d, J = 1.2 Hz,
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C23H19ClNO2 [M + H]+ 376.1104, found 376.1105.
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ASSOCIATED CONTENT
* Supporting Information
Crystallographic data and NMR spectral data. This material is
available free of charge via the Internet at http://pubs.acs.org.
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AUTHOR INFORMATION
Corresponding Authors
*E-mail: maiwp@yahoo.com.
*E-mail: sungangchun@163.com.
*E-mail: xymxbr@aliyun.com.
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We gratefully acknowledge the National Natural Science
Foundation of China (Nos. 21302042 and 21172055), the
Program for Innovative Research Team from Zhengzhou
H
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