Oxidation of β-Ketoamides: The Synthesis of Vicinal Tricarbonyl Amides

Article abstract of DOI:10.1021/acs.joc.6b03062

A facile and direct oxidative reaction for the synthesis of vicinal tricarbonyl amides in moderate to excellent yields (53-88%) was developed starting from readily available β-ketoamides in the presence of phenyliodine(III) bis(trifluoroacetate). The resu

Full text of DOI:10.1021/acs.joc.6b03062

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Note
Oxidation of #-Ketoamides: The Synthesis of Vicinal Tricarbonyl Amides
Yueyang Liu, Zhiguo Zhang, Yameng Wan, Guisheng Zhang,
Zhonglian Li, Jingjing Bi, Nana Ma, Tong-Xin Liu, and Qingfeng Liu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b03062 • Publication Date (Web): 23 Feb 2017
Downloaded from http://pubs.acs.org on February 23, 2017
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Oxidation of β-Ketoamides: The Synthesis of Vicinal Tricarbonyl Amides
Yueyang Liu, Zhiguo Zhang,* Yameng Wan, Guisheng Zhang,* Zhonglian Li, Jingjing Bi, Nana Ma,
Tongxin Liu, Qingfeng Liu
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Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals,
Henna Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of
Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R.
China.
Fax: (+86)-373-332-5250; E-mail: zhangzg@htu.edu.cn or zgs6668@yahoo.com
Abstract: A facile and direct oxidative reaction for the synthesis of vicinal tricarbonyl amides
(VTAs) in moderate to excellent yields (53%−88%) was developed starting from readily available
β-ketoamides in the presence of phenyliodine(III) bis(trifluoroacetate) (PIFA). The resulting products
possess significant synthetic potential, making this approach a valuable addition to the traditional
methods already available for the preparation of these molecules.
Keywords: Vicinal tricarbonyl amides (VTAs); β-Dicarbonyl compounds; β-Ketoamides; PIFA;
Hypervalent iodine
Vicinal tricarbonyls are an important moiety that appears in biologically and pharmaceutically
significant compounds, such as the elastase inhibitors YM−47141 and YM−47142 (Figure 1).1 They
are also a key synthon2 that plays an important role in the construction of some natural products3 and
useful small molecules.4 Commonly, vicinal tricarbonyl compounds (VTCs) are usually obtained in a
mixture of the keto and dihydroxy forms,5 and the gem-diol can be easily dehydrated to provide the
original free vicinal tricarbonyls under certain conditions,6 which is indicative of the reversible
nature of this system (Figure 2, right box).7 Recent research has indicated that the reversible addition
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of alcohols, amines and thiols can also occur to the central carbonyl group of the VTCs to afford
hemiketal, hemiaminal, and hemithioketal formation, respectively.8 Generally, three strategies are
utilized for the synthesis of VTCs, in which β-ketoamides are always employed as a special case of
β-dicarbonyl compounds. First, starting with α-unfunctionalized β-dicarbonyl compounds has been
the most efficient way to obtain VTCs in the presence of various oxidation catalytic systems,
including DDQ/TEMPO,9 CAN,10 m-CPBA/Cu(OAc)2,11 Dess–Martin periodinane (DMP),12 SeO2,13
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and O2/Bu4NF14 over the past several decades (Scheme 1, path a). Second, the conversion of
α-mono- and disubstituted β-dicarbonyl derivatives to the desired VTCs constitutes another
important route (Figure 2, path b).13, 15 Third, oxidative cleavage of the C=C, C=N, C=S, C=P, and
C=I double bonds of some α-methylene functionalized β-dicarbonyl compounds such as
α-diazo-β-dicarbonyls, can also afford VTCs.2, 10, 16 This involves a two-step procedure consisting of
functionalizing the central carbon followed by oxidation with suitable reagents such as
tBuOCl/HCO2H,6 2-iodoxybenzoic acid (IBX),2 O2 or O3,17 Oxone,18 DMP,19 and NaIO4 (Figure 2,
path c).20 Although numerous, efficient approaches have been established to date, a literature review
showed a limited number of existing works addressing the systematic construction of vicinal
tricarbonyl amides (VTAs) directly using β-ketoamides through a one-step reaction,12 except for
several examples using the strategy of α-methylene-functionalized β-ketoamides by multi-step
reactions.17b, 19-21 At the time we prepared this manuscript, Zhang and co-workers22 reported a
complementary approach to VTCs by an iodosobenzene-mediated direct oxidation of β-dicarbonyls
C−H activation/annulation cascade using electrophilic α-halo and α-pseudohalo ketones assisted by
Fe(NO3)3·9H2O under mild and environmentally friendly conditions. In their work, only two types of
secondary amides were employed, and the desired VTAs were obtained in 67% and 68% yields,
respectively. Thus, as it can be seen, the synthesis of a VTA series using a simple catalytic system
with a high yield of the target products is largely unexplored. Here, we present our recent efforts
regarding the PIFA-mediated α-C–H bond oxidative reaction of β-ketoamide derivatives for the
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synthesis of VTAs.23
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Figure 1. Structure of YM−47141 and YM−47142.
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Figure 2. Representative routes to the VTCs and the equilibrium of the dihydroxyl and keto forms.
Hypervalent iodine reagents are advanced oxidants and advantageous because of their ready
availability, nontoxicity, ease of handling and environmentally benign characteristics; they have been
vastly utilized in many useful organic transformations.24 Previous works25 have demonstrated that, in
the presence of PIFA and water,26 the oxidization of amides bearing more active α-positions can
generate alcohols, which are easily oxidized to α-diketones.27 Very recently, we developed two
reliable, efficient, green oxidative C–N bond formation reactions in the presence of hypervalent
iodine reagents for the synthesis of 1H-indazoles28 and spirocyclopropane quinolinediones under
mild conditions.29 These metal-free reactions inspired us to synthesize other useful synthons, such as
VTAs, via α-C–H bond oxidative reactions starting from readily available β-ketoamides in the
presence of organoiodine reagents.
With this assumption in mind, N-(4-chlorophenyl)-3-oxo-3-phenylpropanamide (1g) was selected
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as the model substrate to explore the optimal conditions for the oxidative reaction. A portion of the
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key results are summarized in Table 1. At the beginning, we treated 1g with 1.5 equiv. of PIFA in
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MeCN (3 mL) at 60 °C. After 36 h, compound 2g, which was identified by H, C NMR, and MS,
could be obtained in 82% yield after work-up followed by column chromatography (Table 1, entry 1).
The spectroscopic analysis showed product 2g was a mixture of the dihydroxy and keto forms; the
keto form was the major one. This spectral evidence corresponds with those available in the
literature.2, 10 It is worth noting that the ratio of compounds 2 and 3 could be determined based on 1H
NMR, but the ratio will vary with the amount of water. Further investigation of the solvent indicated
that a certain proportion of water can shorten the reaction time greatly (Table 1, entry 2 vs entry 1).
And after many attempts, the ratio of acetonitrile and water was finally identified as 10 to 1 (Table 1,
entry 2). The yield of 2g decreased slightly if 1.0 and 2.0 equiv. of PIFA was loaded or a lower or
higher reaction temperature was employed (Table 1, entries 3-6). Other organoiodine reagents
including diacetoxyiodobenzene (PIDA), PhIO, IBX, and DMP, were screened and they were found
to be not as efficient as PIFA (Table 1, entries 7-10). Several other solvents, such as PEG-400, EtOH,
dioxane, DCE, DMSO, DMF, and THF resulted in lower yields of 2g compared with those in the
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mixed-solvent of acetonitrile and water (VCH3CN/H2O = 10:1) (Table 1, entries 11–17).
Table 1. Survey of the Reaction Conditionsa
entry
oxidant (equiv)
PIFA (1.5)
PIFA (1.5)
PIFA (1.0)
PIFA (2.0)
solvent
MeCN
time/h
36
yield/%
82
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3
4
MeCN/H2O (10:1)
MeCN/H2O (10:1)
MeCN/H2O (10:1)
10
84
13
74
12
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PIFA (1.5)/40 oC
PIFA (1.5)/80 oC
PIDA (1.5)
PhIO (1.5)
IBX (1.5)
MeCN/H2O (10:1)
MeCN/H2O (10:1)
MeCN/H2O (10:1)
MeCN/H2O (10:1)
MeCN/H2O (10:1)
MeCN/H2O (10:1)
PEG-400
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DMP (1.5)
PIFA (1.5)
PIFA (1.5)
PIFA (1.5)
PIFA (1.5)
PIFA (1.5)
PIFA (1.5)
PIFA (1.5)
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72
EtOH
58
Dioxane
Traceb
20c
73
DCE
DMSO
DMF
74
THF
0d
a Unless otherwise indicated, all reactions were carried out with 1 (0.5 mmol) in 3 mL solvent at
60 °C. b 71% of 1g was recovered. c 61% of 1g was recovered. d 93% of 1g was recovered.
After having optimized the reaction conditions (Table 1, entry 2), the substrate scope of this
oxidative reaction was investigated (Table 2). Initially, various β-ketoamides were investigated (R2):
a number of functional aromatic amine groups bearing -CO2Et, -CF3, -F, -Cl, -Me, or -MeO at the
-ortho, -meta or -para positions were tolerated well (products 2a–q). The ester group, which can be
converted easily to other useful functional groups, was suitable for the oxidative reaction and gave
2a–c in good yields (70%−88%). Importantly, the chloro and fluoro substituents could be tolerated
well in this reaction, thereby facilitating additional modifications at these positions (2d–i).
Furthermore, the CF3 group also showed high reactivity leading to 2j in good yield (84%).
Gratifyingly, the starting materials 1k−q bearing electron-donating groups on the aromatic ring were
also viable for the construction of 2k−q in high yields (71%−86%). Subsequently, the aliphatic
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amine substituent cyclohexyl was employed inthe reaction and gave a satisfying yield of 2r (81%).
The investigation using β-keto ester (1s: R2 = OMe) resulted in an incomplete oxidative reaction.
Compound 2s was isolated in 72% yield along with the recovered starting material 1s (12%), and the
yield of 2s could not be increased further by prolonging the reaction times. It was found that the
dibenzoylmethane compound (1t: R2 = Ph) only gave product 2t in a yield of 53%. The reaction
toward the benzoyl group (R1) bearing a –Me at the -ortho, -meta or -para position on the phenyl
ring was also carried out with 1u−w under the optimized conditions, and they gave the
corresponding VTAs 2u−w in 77%–81% yields. However, fewer experiments were conducted
toward varying other arylcarbonyl groups because of the limited number of available substrates at
this position. To our delight, diamide 1x also afforded the desired compound 2x in 53% yield, along
with some unidentified complex mixture. This case suggested that the present method might be
utilized in oxidative reactions containing a plurality of amino groups.30 It should be emphasized that
all of the synthesized VTAs are stable enough for storage at room temperature.
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Table 2. Reaction Extensiona
O
O
O
O
PIFA (1.5 equiv)
O
O
R1
R2
R1
R2
H2O
R1
R2
VMeCN/VH O = 10:1
2
HO OH
O
60 oC
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2b: 13 h, 76% (4:1)
2c: 13 h, 70% (10:1)
2d: 10 h, 79% (3:1)
2h: 12 h, 84% (9:1)
2l: 13 h, 71% (3:1)
2a: 13 h, 88% (3:1)
2e: 15 h, 86% (2:1)
2i: 11 h, 85% (2:1)
2f: 11 h, 83% (2:1)
2j: 15 h, 84% (2:1)
2g: 12 h, 84% (14:1)
2k: 14 h, 72% (5:1)
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2o: 14 h, 86% (6:1)
2p: 15 h, 83% (10:1)
2t: 2 h, 88% (7:1)c
2m: 11 h, 71% (4:1)
2q: 20 h, 71% (2:1)
2n: 12 h, 80% (5:1)
2r: 12 h, 81% (2:1)
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2s: 6 h, 72% (6:1)b
2x: 10 h, 53%
2w: 20 h, 77% (20:1)
2v: 11 h, 77% (>95:5)
2u: 12 h, 81% (3:1)
(>95:5)
a Unless otherwise indicated, all reactions were carried out with 1 (0.5 mmol) and PIFA (1.5 equiv) in
3 mL mixed solvents of CH3CN and H2O (VCH3CN:VH2O = 10:1) at 60 °C, and the ratio of 2 and 3 in
parentheses is based on current 1H NMR. b 12% of 1s was recovered, and the yield of 2s could not be
increased by adding 2.5 equivalent of PIFA. c Reaction was performed at room temperature.
It should be noted that, similar to Deng’s9 work in 2014, we also failed to purify the aliphatic VTC
product 2y by flash chromatography on silica gel, although a high yield was observed on the
thin-layer chromatography (TLC) plate. Accordingly, after producing 2y in situ at 40 °C under the
optimal conditions, further derivatization was carried out with benzene-1,2-diamine in the presence
of 4-methylbenzenesulfonic acid at 60 °C in one-pot. As expected, the quinoxaline derivative 4y was
isolated in 70% yield after 1 h, which proved the formation of 2y (Table 3, entry 1). To our delight,
four types of other aliphatic β-ketoamides, including 1z−c’ and aliphatic β-keto ester 1d’, could also
afford the derivatives 4z−d’ in 41%−87% total yields (Table 3, entries 2-5).
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Table 3. One-pot Synthesis of Quinoxaline Derivative 4.
Entry R1
R2
Time/h Yield of 4/%
Temperature/°C
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Me NHPh
Me NH2
40
r.t.
40
60
60
60
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4y: 70
4z: 41
15 min
Me N(Me)2
tBu NHPh
nBu NHPh
nBu OMe
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4a’: 83
4b’: 85
4c’: 87
4d’: 75
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In summary, we have demonstrated a facile method for the direct synthesis of VTAs from readily
available β-ketoamides in moderate to excellent yields through PIFA-mediated oxidative activation
of the sp3 C−H bond. The advantage of this protocol is associated with readily available starting
materials, excellent yields, dense and flexible substituted patterns, and important synthetic potential
of the products. It is noted that different from previous literature reports on the synthesis of VTCs
from 1,3-dicarbonyls, the present method focused on the preparation of VTA series. Moreover, as an
alternative and valuable route, it may be more practical for the construction of VTA
analogue-containing biomolecules.1, 3a, 3e, 31
Experimental Section
General Remarks. All reactions were carried out under air atmosphere, unless otherwise indicated.
Other all reagents were purchased from commercial sources and used without further treatment,
unless otherwise indicated. Petroleum ether (PE) used refers to the 60-90 °C boiling point fraction of
petroleum. Ethyl acetate is abbreviated as EA. 1H NMR and 13C{1H} NMR spectra were recorded on
Bruker Avance/600 (1H: 600 MHz, 13C{1H}: 150 MHz at 25 °C) or Bruker Avance/400 (1H: 400
MHz, C{1H}: 100 MHz at 25 °C) and TMS as internal standard. Data are represented as follows:
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chemical shift, integration, multiplicity (br = broad, s = singlet, d = doublet, dd = double doublet, t =
triplet, q = quartet, m = multiplet), coupling constants in Hertz (Hz). All high-resolution mass spectra
(HRMS) were measured on a mass spectrometer by using electrospray ionization (ESI-oa-TOF), and
the purity of all samples used for HRMS (>95%) were confirmed by H NMR and C{1H} NMR
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spectroscopic analysis. Melting points were measured on a melting point apparatus equipped with a
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thermometer and were uncorrected. All reactions were monitored by TLC with GF254 silica gel
coated plates. Flash chromatography was carried out on SiO2 (silica gel 200−300 mesh).
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Typical Experimental Procedure For 2 (2g as an example): To a round-bottom flask (25 mL)
1g (137 mg, 0.5 mmol) and PIFA (323 mg, 0.75 mmol) were added, and the mixture was well stirred
in CH3CN/H2O (3 mL) at 60 °C (the whole process was closely monitored by TLC). After 12 h, the
residue was purified by a short flash silica gel column chromatography (eluent: EA/PE = 3/10) to
give N-(4-chlorophenyl)-2,3-dioxo-3-phenylpropanamide 2g as white solid (128 mg, 84%).
Ethyl 4-(2,3-dioxo-3-phenylpropanamido)benzoate (2a). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (151 mg, 88%) with the ratio of 2a and 3a
was 3:1; 1H NMR (400 MHz, CDCl3) δ 8.76 (s, 1H), 8.09 (d, J = 8.4 Hz, 2H), 7.93 (d, J = 7.6 Hz,
2H), 7.76 (d, J = 8.8 Hz, 2H), 7.56 (t, J = 7.6 Hz, 2H), 4.37 (t, J = 7.0 Hz, 2H), 1.40 (t, J = 7.2 Hz,
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3H); C NMR (151 MHz, CDCl3) δ 193.6, 193.1, 188.5, 167.4, 166.0, 165.9, 156.8, 140.6, 139.7,
135.7, 134.9, 132.0, 131.3, 131.0, 130.84, 130.8, 130.77, 130.6, 129.6, 129.2, 128.8, 127.6, 127.0,
119.4, 119.3, 61.2, 61.1, 14.3; IR (KBr, neat): ν = 3503, 3408, 3343, 1713, 1688, 1597, 1525, 1411,
1288, 1182, 1115, 1008, 856, 769 cm-1; HRMS (ESI), m/z calcd. for C18H15NO5 ([M+Na]+) 348.0842,
found: 348.0845.
Ethyl 3-(2,3-dioxo-3-phenylpropanamido)benzoate (2b). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (130 mg, 76%) with the ratio of 2b and 3b
was 4:1; 1H NMR (400 MHz, CDCl3) δ 8.90 (s, 1H), 8.24 (s, 1H), 8.06-7.99 (m, 1H), 7.90 (t, J = 9.0
Hz, 2H), 7.69 (t, J = 7.6 Hz, 1H), 7.53 (t, J = 7.8 Hz, 2H), 7.34-7.47 (m, 2H), 4.41-4.32 (m, 2H),
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1.38 (t, J = 7.2 Hz, 3H); C NMR (151 MHz, CDCl3) δ 193.2, 188.7, 165.8, 156.7, 136.0, 135.59,
134.9, 132.0, 131.8, 130.8, 129.6, 129.5, 129.3, 129.2, 128.8, 126.9, 126.4, 124.3, 124.1, 120.9, 61.4,
14.3; IR (KBr, neat): ν = 3265, 3195, 3126, 1733, 1684, 1597, 1533, 1493, 1403, 1092, 827 cm-1;
HRMS (ESI), m/z calcd. for C18H15NO5 ([M+H]+)326.1023, found: 326.1023.
Ethyl 2-(2,3-dioxo-3-phenylpropanamido)benzoate (2c). The product was isolated by flash
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chromatography (eluent: EA/PE = 3/10) as a white solid (120 mg, 70%) with the ratio of 2c and 3c
was 10:1; 1H NMR (400 MHz, CDCl3) δ 12.58 (s, 1H), 8.72 (d, J = 8.4 Hz, 1H), 8.14 (dd, J = 8.0 Hz,
1.6 Hz, 1H), 7.94 (dd, J = 8.4 Hz, 2H), 7.69 (t, J = 7.4 Hz, 1H), 7.57 (m, 3H), 7.27-7.18 (m, 1H),
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4.47 (dd, J = 14.4 Hz, 7.2 Hz, 2H), 1.45 (t, J = 7.2 Hz, 3H); C NMR (101 MHz, CDCl3) δ 193.8,
188.7, 167.8, 157.5, 139.2, 135.4, 134.7, 132.2, 131.3, 129.6, 129.1, 124.4, 120.7, 116.9, 62.0, 14.2;
IR (KBr, neat): ν = 3234, 3185, 3119, 1697, 1666, 1589, 1529, 1451, 1303, 1281, 1222, 1102, 866,
767, 752 cm-1; HRMS (ESI), m/z calcd. for C18H15NO5 ([M+Na]+) 348.0842, found: 348.0843.
N-(4-fluorophenyl)-2,3-dioxo-3-phenylpropanamide (2d). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (114 mg, 79%) with the ratio of 2d and 3d
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was 3:1; H NMR (600 MHz, CDCl3) δ 8.64 (s, 1H), 7.92 (dd, J = 8.4 Hz, 2H), 7.71 (t, J = 7.5 Hz,
1H), 7.67-7.64 (m, 2H), 7.55 (t, J = 7.8 Hz, 2H), 7.11-7.07 (m, 2H); 13C NMR (151 MHz, CDCl3) δ
193.3, 189.0, 161.0, 159.4, 156.4, 135.6, 135.0, 132.1, 130.8, 129.6, 129.2, 128.8, 122.0, 121.9,
121.7, 121.68, 116.3, 116.1, 116.0, 115.9; IR (KBr, neat): ν = 3419, 3352, 3067, 1680, 1658, 1595,
1558, 1509, 1209, 1110, 1090, 834 cm-1; HRMS (ESI), m/z calcd. for C15H10FNO3 ([M+Na]+)
294.0537, found: 294.0541.
N-(3-fluorophenyl)-2,3-dioxo-3-phenylpropanamide (2e). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (124 mg, 86%) with the ratio of 2e and 3e
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was 2:1; H NMR (600 MHz, CDCl3) δ 8.66 (s, 1H), 7.82 (d, J = 7.8 Hz, 2H), 7.62 (t, J = 7.5 Hz,
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1H), 7.52 (d, J = 10.2 Hz, 1H), 7.46 (t, J = 7.8 Hz, 2H), 7.25 (s, 2H), 6.86-6.81 (m, 1H); C NMR
(151 MHz, CDCl3) δ 193.1, 188.6, 163.8, 162.2, 156.6, 137.2, 137.16, 135.6, 132.0, 130.8, 130.6,
130.55, 129.6, 129.2, 128.8, 115.5, 115.4, 112.9, 112.7, 107.7, 107.5; IR (KBr, neat): ν = 3454, 3305,
3210, 1737, 1686, 1671, 1614, 1551, 1493, 1449, 1147, 1095, 967, 775 cm-1; HRMS (ESI), m/z calcd.
for C15H10FNO3 ([M+Na]+) 294.0537, found: 294.0538.
N-(2-fluorophenyl)-2,3-dioxo-3-phenylpropanamide (2f). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (120 mg, 83%) with the ratio of 2f and 3f
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was 2:1; H NMR (600 MHz, CDCl3) δ 8.93 (s, 1H), 7.93 (d, J = 7.2 Hz, 2H), 7.56 (t, J = 7.8 Hz,
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2H), 7.47 (m, 2H), 7.18 (dd, J = 7.8 Hz, 4.2 Hz, 3H); C NMR (101 MHz, CDCl3) δ 193.0, 188.2,
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167.2, 156.5, 154.0, 135.6, 134.8, 132.0, 130.8, 129.6, 129.2, 128.7, 126.3, 126.2, 125.7, 124.9,
124.6, 121.8, 121.5, 115.4, 115.2, 115.1; IR (KBr, neat): ν = 3386, 3350, 3074, 1696, 1680, 1598,
1530, 1487, 1456, 1412, 1263, 1196, 1116, 992, 925, 846, 780, 754 cm-1; HRMS (ESI), m/z calcd.
for C15H10FNO3 ([M+Na]+) 294.0537, found: 294.0539.
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N-(4-chlorophenyl)-2,3-dioxo-3-phenylpropanamide (2g). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (128 mg, 84%) with the ratio of 2g and 3g
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was 14:1; H NMR (400 MHz, CDCl3) δ 8.73 (s, 1H), 7.89 (dd, J = 8.4 Hz, 1.6 Hz, 2H), 7.72-7.67
(m, 1H), 7.65-7.60 (m, 2H), 7.53 (t, J = 7.8 Hz, 2H), 7.36-7.32 (m, 2H); 13C NMR (101 MHz, CDCl3)
δ 193.1, 188.6, 156.4, 135.6, 134.3, 131.9, 131.0, 129.5, 129.4, 129.2, 121.2; IR (KBr, neat): ν =
3315, 3115, 3061, 1728, 1694, 1666, 1596, 1539, 1493, 1449, 1403, 1220, 1011, 870, 827, 758 cm-1;
HRMS (ESI), m/z calcd. for C15H10ClNO3 ([M+Na]+) 310.0241, found: 310.0246.
N-(3-chlorophenyl)-2,3-dioxo-3-phenylpropanamide (2h). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (128 mg, 84%) with the ratio of 2h and 3h
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was 9:1; H NMR (400 MHz, CDCl3) δ 8.63 (s, 1H), 7.94-7.89 (m, 2H), 7.80 (t, J = 2.0 Hz, 1H),
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7.72 (t, J = 7.6 Hz, 1H), 7.59-7.49 (m, 3H), 7.33 (t, J = 8.2 Hz, 1H), 7.23-7.18 (m, 1H); C NMR
(101 MHz, CDCl3) δ 193.1, 188.5, 156.5, 136.8, 135.6, 135.0, 131.9, 130.3, 129.5, 129.2, 126.0,
120.1, 117.9; IR (KBr, neat): ν = 3300, 3133, 3063, 1734, 1686, 1670, 1597, 1549, 1485, 1449, 1430,
1417, 1225, 1092, 909, 876, 781 cm-1; HRMS (ESI), m/z calcd. for C15H10ClNO3 ([M+Na]+)
310.0241, found: 310.0240.
N-(2-chlorophenyl)-2,3-dioxo-3-phenylpropanamide (2i). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (130 mg, 85%) with the ratio of 2i and 3i
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was 2:1; H NMR (600 MHz, CDCl3) δ 9.11 (s, 1H), 8.21 (d, J = 8.4 Hz, 1H), 7.93 (d, J = 7.8 Hz,
1H), 7.71 (t, J = 9.0 Hz, 1H), 7.61 (t, J = 6.6 Hz, 2H), 7.55 (dd, J = 16.5 Hz, 8.7 Hz, 2H), 7.46 (t, J =
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7.8 Hz, 1H), 7.27 (t, J = 6.6 Hz, 1H); C NMR (151 MHz, CDCl3) δ 193.4, 192.7, 188.1, 167.5,
156.6, 135.6, 134.9, 133.3, 133.0, 132.0, 131.2, 130.7, 129.6, 129.2, 128.8, 126.6, 126.5, 126.3,
125.8, 125.5, 124.2, 123.2; IR (KBr, neat): ν = 3384, 1743, 1700, 1594, 1537, 1462, 1321, 1289,
1190, 1130, 1098, 1037, 765 cm-1; HRMS (ESI), m/z calcd. for C15H10ClNO3 ([M+Na]+) 310.0241,
found: 310.0241.
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N-(2-trifluoromethyl)- 2,3-dioxo-3-phenylpropanamide (2j). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (142 mg, 84%) with the ratio of 2j and 3j
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was 2:1; H NMR (600 MHz, CDCl3) δ 9.12 (s, 1H), 8.21 (d, J = 7.8 Hz, 1H), 7.93 (d, J = 7.8 Hz,
1H), 7.71 (t, J = 10.2 Hz, 1H), 7.61 (t, J = 8.1 Hz, 2H), 7.58-7.52 (m, 2H), 7.45 (t, J = 7.8 Hz, 1H),
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7.27 (t, J = 7.5 Hz, 1H); C NMR (151 MHz, CDCl3) δ 193.4, 192.7, 188.1, 167.5, 156.6, 135.6,
134.9, 133.3, 133.0, 132.0, 131.2, 130.7, 129.6, 129.2, 128.8, 126.6, 126.5, 126.3, 125.8, 125.5,
124.2, 123.2; IR (KBr, neat): ν = 3396, 1709, 1594, 1537, 1456, 1321, 1293, 1174, 1120, 1035, 937,
866, 766 cm-1; HRMS (ESI), m/z calcd. for C16H10F3NO3 ([M+Na]+) 344.0505, found: 344.0521.
N-2,3-dioxo-3-diphenylpropanamide (2k). The product was isolated by flash chromatography
(eluent: EA/PE = 3/10) as a white solid (98 mg, 72%) with the ratio of 2k and 3k was 5:1; 1H NMR
(400 MHz, CDCl3) δ 8.82 (s, 1H), 7.96 (d, J = 7.2 Hz, 2H), 7.73 (d, J = 7.6 Hz, 3H), 7.57 (t, J = 7.4
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Hz, 2H), 7.42 (t, J = 7.6 Hz, 2H), 7.26 (t, J = 7.2 Hz, 1H); C NMR (101 MHz, CDCl3) δ 193.5,
189.0, 156.5, 135.7, 135.4, 132.0, 130.7, 129.5, 129.3, 129.1, 129.0, 128.6, 125.8, 125.3, 120.0,
119.9; IR (KBr, neat): ν = 3345, 3284, 3194, 1689, 1648, 1596, 1532, 1492, 1395, 1325, 1315, 1244,
1164, 1006, 935, 828, 816 cm-1; HRMS (ESI), m/z calcd. for C15H11NO3 ([M+H]+) 254.0812, found:
254.0810.
2,3-dioxo-3-phenyl-N-(p-tolyl)propanamide (2l). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (101 mg, 71%) with the ratio of 2l and 3l
was 3:1; 1H NMR (600 MHz, CDCl3) δ 8.63 (s, 1H), 7.91 (d, J = 7.8 Hz, 2H), 7.54 (dd, J = 15.3 Hz,
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7.5 Hz, 4H), 7.44 (t, J = 7.2 Hz, 1H), 7.18 (d, J = 7.8 Hz, 2H), 2.34 (s, 3H); C NMR (151 MHz,
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CDCl3) δ 193.9, 193.6, 189.3, 166.9, 156.4, 135.8, 135.5, 134.8, 133.9, 133.3, 132.2, 131.4, 130.8,
129.9, 129.6, 129.5, 129.2, 128.8, 120.2, 119.9, 21.0; IR (KBr, neat): ν = 3343, 3033, 2921, 1679,
1598, 1530, 1453, 1403, 1242, 1113, 996, 925, 811, 763 cm-1; HRMS (ESI), m/z calcd. for
C16H13NO3 ([M+Na]+) 290.0788, found: 290.0788.
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2,3-dioxo-3-phenyl-N-(m-tolyl)propanamide (2m). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (101 mg, 71%) with the ratio of 2m and 3m
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was 4:1; H NMR (600 MHz, CDCl3) δ 8.59 (s, 1H), 7.91 (d, J = 8.4 Hz, 2H), 7.70 (t, J = 7.5 Hz,
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1H), 7.54 (t, J = 7.8 Hz, 3H), 7.28 (d, J = 7.8 Hz, 1H), 7.03 (d, J = 7.8 Hz, 1H), 2.36 (s, 3H); C
NMR (151 MHz, CDCl3) δ 193.6, 189.3, 156.4, 139.5, 135.7, 135.5, 134.9, 132.2, 130.8, 129.5,
129.2, 129.18, 129.0, 128.8, 126.8, 126.2, 120.5, 117.0, 21.5; IR (KBr, neat): ν = 3357, 3066, 2923,
1680, 1614, 1546, 1538, 1491, 1451, 1257, 1113, 1003, 988, 932, 849, 777 cm-1; HRMS (ESI), m/z
calcd. for C16H13NO3 ([M+H]+) 268.0968, found: 268.0968.
N-(4-methoxyphenyl)-2,3-dioxo-3-phenylpropanamide (2n). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (120 mg, 80%) with the ratio of 2n and 3n
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was 5:1; H NMR (600 MHz, CDCl3) δ 8.62 (s, 1H), 7.91 (d, J = 7.8 Hz, 2H), 7.69 (t, J = 7.2 Hz,
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1H), 7.60 (d, J = 7.8 Hz, 2H), 7.53 (t, J = 7.5 Hz, 2H), 6.90 (d, J = 7.8 Hz, 2H), 3.81 (s, 3H); C
NMR (151 MHz, CDCl3) δ 193.6, 189.4, 166.8, 157.4, 156.1, 149.5, 135.4, 129.5, 129.1, 121.4,
114.4, 55.5; IR (KBr, neat): ν = 3495, 3323, 3057, 1678, 1598, 1534, 1514, 1448, 1303, 1247, 1125,
1034, 931, 824 cm-1; HRMS (ESI), m/z calcd. for C16H13NO4 ([M+Na]+) 306.0737, found: 306.0731.
N-(3-methoxyphenyl)-2,3-dioxo-3-phenylpropanamide (2o). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (130 mg, 86%) with the ratio of 2o and 3o
was 6:1; 1H NMR (400 MHz, CDCl3) δ 8.65 (s, 1H), 7.95-7.84 (m, 2H), 7.71-7.65 (m, 1H), 7.52 (t, J
= 7.6 Hz, 2H), 7.42 (t, J = 2.2 Hz, 1H), 7.26 (m, 1H), 7.14-7.08 (m, 1H), 6.73-6.77 (m, 1H), 3.78 (s,
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3H); C NMR (101 MHz, CDCl3) δ 193.5, 189.0, 160.2, 156.4, 136.9, 135.5, 132.0, 130.7, 130.0,
129.5, 129.1, 128.7, 112.1, 112.0, 105.4, 55.3; IR (KBr, neat): ν = 3361, 3072, 2994, 1720, 1700,
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1672, 1609, 1552, 1498, 1448, 1420, 1294, 1265, 1202, 1176 ,1156, 1097, 1045, 960, 851, 839, 786
cm-1; HRMS (ESI), m/z calcd. for C16H13NO4 ([M+Na]+) 306.0737, found: 306.0738.
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N-(2-methoxyphenyl)-2,3-dioxo-3-phenylpropanamide (2p). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (125 mg, 83%) with the ratio of 2p and 3p
was 10:1; 1H NMR (400 MHz, CDCl3) δ 9.34 (s, 1H), 8.39 (dd, J = 8.0 Hz, 1H), 7.92 (dd, J = 8.4 Hz,
2H), 7.69 (t, J = 7.4 Hz, 1H), 7.54 (t, J = 7.8 Hz, 2H), 7.16 (m, 1H), 6.99 (t, J = 7.8 Hz, 1H), 6.95 (d,
J = 8.4 Hz, 1H), 3.96 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 193.8, 189.2, 156.4, 148.7, 135.4,
132.2, 129.5, 129.2, 125.8, 125.5, 121.2, 120.1, 110.3, 55.9; IR (KBr, neat): ν = 3382, 3025, 2970,
1721, 1688, 1669, 1596, 1535, 1488, 1465, 1450, 1318, 1292, 1254, 1217, 1120, 1082, 1025, 937,
865, 785, 757 cm-1; HRMS (ESI), m/z calcd. for C16H13NO4 ([M+Na]+) 306.0737, found: 306.0738.
2,3-dioxo-3-phenyl-N-mesitylpropanamide (2q). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (111 mg, 71%) with the ratio of 2q and 3q
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was 2:1; H NMR (400 MHz, CDCl3) δ 8.13 (s, 1H), 7.93 (d, J = 7.2 Hz, 2H), 7.70 (t, J = 7.6 Hz,
1H), 7.55 (t, J = 7.8 Hz, 2H), 6.93 (s, 2H), 2.29 (s, 3H), 2.24 (s, 6H); 13C NMR (151 MHz, CDCl3) δ
193.2, 189.1, 157.5, 137.9, 135.4, 134.9, 134.7, 132.1, 130.9, 129.6, 129.2, 129.1, 129.0, 128.7, 21.0,
20.9, 18.4, 17.7; IR (KBr, neat): ν = 3335, 3229, 3061, 1660, 1598, 1520, 1449, 1255, 1121, 1006,
927, 854 cm-1; HRMS (ESI), m/z calcd. for C18H17NO3 ([M+H]+) 296.1281, found: 296.1286.
2,3-dioxo-3-phenyl-N-cyclohexyl-propanamide (2r). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (112 mg, 81%) with the ratio of 2r and 3r
was 2:1; 1H NMR (400 MHz, CDCl3) δ 8.14 (d, J = 7.2 Hz, 1H), 7.87 (dd, J = 8.4 Hz, 1H), 7.67 (t, J
= 7.4 Hz, 1H), 7.51 (t, J = 7.8 Hz, 2H), 3.82 (m ,1H), 1.97 (d, J = 12.0 Hz, 2H), 1.83-1.58 (m, 5H),
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1.44-1.00 (m, 7H); C NMR (101 MHz, CDCl3) δ 193.8, 189.2, 168.2, 158.1, 135.2, 130.5, 129.5,
129.0, 128.6, 49.4, 48.7, 32.5, 32.3, 25.2, 24.6; IR (KBr, neat): ν = 3305, 3064, 2932, 2855, 1651,
1530, 1450, 1385, 1253, 1178, 1151, 1099, 1062, 1028, 892 cm-1; HRMS (ESI), m/z calcd. for
C15H17NO3 ([M+Na]+) 282.1101, found: 282.1100.
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2,3-dioxo-3-phenyl-ethylpropanoate (2s).10 The product was isolated by flash chromatography
(eluent: EA/PE = 3/10) as a yellow solid (81 mg, 72%) with the ratio of 2s and 3s was 6:1; 1H NMR
(400 MHz, CDCl3) δ 8.07 (d, J = 7.2 Hz, 2H), 7.62 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.8 Hz, 2H), 4.21
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(q, J = 7.2 Hz, 2H), 1.08 (t, J = 7.2 Hz, 3H); C NMR (101 MHz, CDCl3) δ 191.5, 169.9, 134.6,
131.4, 130.1, 130.0, 129.1, 128.8, 63.2, 13.6; HRMS (ESI), m/z calcd. for C11H10O4 ([M+Na]+)
229.0471, found: 229.0468.
1,3-diphenylpropane-1,2,3-trione (2t).10 The product was isolated by flash chromatography
(eluent: EA/PE = 3/10) as a white solid (113 mg, 88%) with the ratio of 2t and 3t was 7:1; 1H NMR
(400 MHz, CDCl3) δ 8.07-8.02 (dd, J = 7.2 Hz, 4H), 7.52 (t, J = 7.4 Hz, 2H), 7.42 (d, J = 7.0 Hz,
1H), 7.38 (t, J = 7.8 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ 194.2, 192.5, 188.3, 172.3, 135.4,
134.6, 133.8, 132.1, 130.3, 130.2, 129.4, 129.1, 128.8, 128.5; HRMS (ESI), m/z calcd. for C15H10O3
([M+Na]+) 261.0522, found: 261.0517.
N-(4-chlorophenyl)-2,3-dioxo-3-(p-tolyl)propanamide (2u). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (129 mg, 81%) with the ratio of 2u and 3u
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was 3:1; H NMR (400 MHz, CDCl3) δ 8.67 (s, 1H), 7.81 (d, J = 8.4 Hz, 2H), 7.63 (d, J = 8.8 Hz,
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2H), 7.35 (dd, J = 8.8 Hz, 6.4 Hz, 4H), 2.46 (s, 3H); C NMR (101 MHz, CDCl3) δ 192.6, 188.8,
156.5, 147.1, 134.4, 131.0, 129.9, 129.7, 129.5, 129.2, 121.1, 22.1; IR (KBr, neat): ν = 3400, 3348,
3072, 1656, 1605, 1551, 1492, 1404, 1307, 1263, 1090, 1013, 830, 765 cm-1; HRMS (ESI), m/z calcd.
for C16H12ClNO3 ([M+H]+) 302.0578, found: 302.0576.
N-(4-chlorophenyl)-2,3-dioxo-3-(o-tolyl)propanamide (2v). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (123 mg, 77%) with the ratio of 2v and 3v
was >95:5; 1H NMR (400 MHz, CDCl3) δ 8.64 (s, 1H), 7.62 (dd, J = 14.0 Hz, 9.2 Hz, 3H), 7.55 (t, J
= 7.4 Hz, 1H), 7.39-7.31 (m, 4H), 2.69 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 195.2, 188.2, 156.5,
141.4, 134.5, 134.4, 132.7, 132.6, 131.0, 130.5, 129.4, 126.1, 121.1, 21.7; IR (KBr, neat): ν = 3316,
3189, 3127, 1733, 1683, 1668, 1600, 1545, 1494, 1403, 1290, 1237, 1176, 1084, 1012, 833, 767 cm-1;
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HRMS (ESI), m/z calcd. for C16H12ClNO3 ([M+H]+) 302.0578, found: 302.0573.
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N-(4-chlorophenyl)-2,3-dioxo-3-(m-tolyl)propanamide (2w). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (123 mg, 77%) with the ratio of 2w and 3w
was 20:1; 1H NMR (400 MHz, CDCl3) δ 8.80 (s, 1H), 7.68 (d, J = 12.4 Hz, 2H), 7.62 (d, J = 8.8 Hz,
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2H), 7.49 (d, J = 7.2 Hz, 1H), 7.40 (t, J = 7.6 Hz, 1H), 7.31 (d, J = 8.4 Hz, 2H), 2.40 (s, 3H); C
NMR (101 MHz, CDCl3) δ 193.4, 188.7, 156.5, 139.2, 136.4, 134.3, 131.9, 131.0, 129.8, 129.3,
129.0, 126.9, 121.2, 21.2; IR (KBr, neat): ν = 3308, 3195, 3060, 1734, 1685, 1666, 1602, 1545, 1494,
1404, 1222, 1078, 1014, 937, 870, 833, 748, 725 cm-1; HRMS (ESI), m/z calcd. for C16H12ClNO3
([M+H]+) 302.0578, found: 302.0574.
2-oxo-N1,N3-diphenylmalonamide (2x). The product was isolated by flash chromatography
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(eluent: EA/PE = 3/10) as a white solid (76 mg, 53%) with the ratio of 2x and 3x was >95:5; H
NMR (400 MHz, CDCl3) δ 9.08 (s, 2H), 7.57 (d, J = 7.6 Hz, 4H), 7.37 (t, J = 7.8 Hz, 4H), 7.17 (t, J
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= 7.4 Hz, 2H), 4.85 (d, J = 2.8 Hz, 1H), 4.75 (d, J = 2.8 Hz, 1H); C NMR (101 MHz, CDCl3) δ
166.4, 136.5, 129.2, 125.3, 120.0, 70.6; IR (KBr, neat): ν = 3355, 3307, 3055, 1694, 1599, 1536,
1443, 1312, 1196, 1123, 983, 930, 897 cm-1; HRMS (ESI), m/z calcd. for C15H12N2O3 ([M+Na]+)
291.0740, found: 291.0743.
3-methyl-N-phenylquinoxaline-2-carboxamide (4y).32 The product was isolated by the
precipitate filtered, washed with ethyl acetate and ether as a yellow solid (92 mg, 70%): mp 177-179
oC; 1H NMR (400 MHz, CDCl3) δ 10.02 (s, 1H), 8.16-8.08 (m, 2H), 7.86 (m, 1H), 7.82-7.78 (m, 3H),
7.42 (t, J = 8.0 Hz, 2H), 7.19 (t, J = 7.4 Hz, 1H), 3.22 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 162.2,
154.6, 143.1, 142.8, 138.9, 137.7, 131.9, 130.0, 129.2, 128.6, 124.7, 120.0, 25.1; IR (KBr, neat): ν =
3349, 3055, 2991, 1694, 1595, 1526, 1482, 1441, 1423, 1373, 1315, 1137, 1067, 1008, 912, 881, 779,
758 cm-1; HRMS (ESI), m/z calcd. for C16H13N3O ([M+Na]+) 286.0951, found: 286.0940.
3-methylquinoxaline-2-carboxamide (4z).33 The product was isolated by the precipitate filtered,
washed with ethyl acetate and ether as a yellow solid (38 mg, 41%): mp 192-194 oC; 1H NMR (400
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MHz, CDCl3) δ 8.09-8.05 (m, 2H), 7.89 (d, J = 6.8 Hz, 1H), 7.86-7.81 (m, 1H), 7.74-7.78 (m, 1H),
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5.70 (s, 1H), 3.14 (s, 3H); C NMR (101 MHz, CDCl3) δ 167.2, 154.3, 143.1, 142.7, 139.2, 131.8,
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129.7, 129.3, 128.5, 24.8; IR (KBr, neat): ν = 3449, 3264, 3180, 1703, 1583, 1566, 1467, 1412, 1369,
1342, 1211, 1139, 1030, 956, 821 ,787, 754 cm-1; HRMS (ESI), m/z calcd. for C10H9N3O ([M+H]+)
188.0818, found: 188.0817.
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N,N,3-trimethylquinoxaline-2-carboxamide (4a’).34 The product was isolated by flash
chromatography (eluent: EA/PE = 1/2)as a yellow liquid (89 mg, 83%); 1H NMR (400 MHz, CDCl3)
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δ 8.04 (m, 2H), 7.80-7.70 (m, 2H), 3.22 (s, 3H), 2.94 (s, 3H), 2.76 (s, 3H); C NMR (101 MHz,
CDCl3) δ 167.5, 151.3, 149.7, 141.6, 139.7, 130.8, 129.7, 129.0, 128.4, 38.2, 34.9, 21.9; IR (KBr,
neat): ν = 3449, 3068, 2995, 1642, 1502, 1485, 1410, 1321, 1260, 1184, 1123, 1061, 1007, 886, 765
cm-1; HRMS (ESI), m/z calcd. for C12H13N3O ([M+H]+) 216.1131, found: 216.1127.
3-(tert-butyl)-N-phenylquinoxaline-2-carboxamide (4b’). The product was isolated by the
o
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precipitate filtered, washed with ether as a yellow solid (78 mg, 85%): mp 217-219 C; H NMR
(600 MHz, DMSO) δ 10.82 (s, 1H), 8.14 (d, J = 7.8 Hz, 1H), 8.10 (d, J = 7.8 Hz, 1H), 7.94-7.86 (m,
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2H), 7.73 (d, J = 7.8 Hz, 2H), 7.40 (t, J = 7.8 Hz, 2H), 7.16 (t, J = 7.5 Hz, 1H), 1.52 (s, 9H); C
NMR (151 MHz, DMSO) δ 167.1, 160.4, 149.7, 140.8, 139.2, 138.8, 131.5, 130.8, 129.5, 129.2,
128.8, 124.6, 120.0, 39.2, 30.0; IR (KBr, neat): ν = 3283, 3254, 1655, 1607, 1561, 1445, 1330, 1166,
1113, 1057, 767, 756 cm-1; HRMS (ESI), m/z calcd. for C19H19N3O ([M+H]+) 306.1601, found:
306.1600.
3-butyl-N-phenylquinoxaline-2-carboxamide (4c’). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a white solid (133 mg, 87%) : mp 119-121 oC; 1H NMR
(600 MHz, CDCl3) δ 10.00 (s, 1H), 8.12 (t, J = 7.5 Hz, 2H), 7.85 (t, J = 7.5 Hz, 1H), 7.79 (t, J = 8.7
Hz, 3H), 7.42 (t, J = 7.8 Hz, 2H), 7.19 (t, J = 7.5 Hz, 1H), 3.62 (t, J = 7.8 Hz, 2H), 1.91-1.83 (m, 2H),
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1.54 (m, 2H), 0.99 (t, J = 7.2 Hz, 3H); C NMR (151 MHz, CDCl3) δ 162.2, 158.5, 143.2, 142.8,
138.7, 137.7, 131.7, 129.9, 129.2, 129.1, 128.8, 124.6, 120.0, 36.8, 31.8, 23.0, 14.1; IR (KBr, neat): ν
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= 3349, 2956, 1689, 1599, 1531, 1446, 1361, 1315, 1131, 1070, 913, 777, 755 cm-1; HRMS (ESI),
m/z calcd. for C19H19N3O ([M+H]+) 306.1601, found: 306.1588.
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Methyl 3-butylquinoxaline-2-carboxylate (4d’). The product was isolated by flash
chromatography (eluent: EA/PE = 3/10) as a colorless oil (92 mg, 75%); 1H NMR (600 MHz, CDCl3)
δ 8.17 (d, J = 8.4 Hz, 1H), 8.07 (d, J = 8.4 Hz, 1H), 7.83 (t, J = 7.5 Hz, 1H), 7.76 (t, J = 7.5 Hz, 1H),
4.08 (s, 3H), 3.25 (t, J = 7.8 Hz, 2H), 1.85-1.77 (m, 2H), 1.48 (m, 2H), 0.98 (t, J = 7.2 Hz, 3H); 13C
NMR (151 MHz, CDCl3) δ 166.2, 156.6, 144.2, 142.7, 139.7, 131.7, 129.8, 129.7, 128.7, 53.3, 35.8,
31.5, 22.8, 13.9; IR (KBr, neat): ν = 3443, 2957, 2872, 1732, 1560, 1483, 1465, 1438, 1324, 1263,
1235, 1193, 1125, 1080, 850, 762 cm-1; HRMS (ESI), m/z calcd. for C14H16N2O2 ([M+H]+) 245.1285,
found: 245.1274.
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Author Information
Corresponding Author
*E-mail: zhangzg@htu.edu.cn or zgs6668@yahoo.com.
Acknowledgements
We thank the NSFC (21272057, 21372065 and U1604285), Young Backbone Teachers Fund of
Henan (2014GGJS-049), Key Project of Henan Educational Committee (14A150019, 14B150042,
15B610005 and 15A150015), Science & Technology Innovation Talents in Universities of Henan
Province (17HASTIT002), the Program of Foundation and Frontier Technology Research of Henan
Province (122300410296), Outstanding Young Talent Cultivation Project Funding of Henan Normal
University (14YR002).
Supporting Information
Experimental procedure, 1H and 13C NMR spectra of all compounds. Crystallographic data in CIF or
other electronic format. This material is available free of charge via the internet at http://pubs.acs.org.
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