Facile One-Pot Synthesis of Flavanones Using Tetramethylguanidinum-Based
Ionic Liquids as Catalysts
Yan Zhou, Wei Huang, Xiang-Shu Chen*, Zhi-Bin Song*, Duan-Jian Tao
Key Laboratory of Functional Small Organic Molecules, Ministry of Education,
College of Chemistry and Chemical Engineering, Center of Analysis and Testing,
Jiangxi Normal University, Nanchang 330022, PR China
*Corresponding Author, E-mail: zbsong@jxnu.edu.cn (Z.-B. Song),
cxs66cn@jxnu.edu.cn (X.-S. Chen)
SUPPORTING INFORMATION
Five tetramethylguanidine-based ILs had been synthesized by the neutralization
reactions of tetramethylguanidine with different acids. 1H NMR, 13C NMR, and FT-IR
spectroscopy were used characterization for each ILs synthesized as follows:
[TMGH][Ac]. 1H NMR (400 MHz, D2O) δ: 1.75 (s, 3H), 2.79 (s, 12H); 13C NMR
(101 MHz, D2O) δ: 179.01 (s), 161.38 (s), 38.98 (s), 22.39 (s).
[TMGH][Gly]. 1H NMR (400 MHz, D2O) δ: 1.80 (s, 2H), 2.82 (s, 12H); 13C
NMR (101 MHz, D2O) δ: 179.41 (s), 160.88 (s), 38.49 (s), 22.46 (s).
[TMGH][PhO]. 1H NMR (400 MHz, D2O) δ: 2.69 (s, 12H), 6.46 (t, 1H), 6.52 (d,
2H), 7.01 (t, 2H);
13
C NMR (101 MHz, CDCl3) δ: 166.54(s) , 160.17(s), 129.25(s),
117.31(s), 116.58(s), 39.20(s).
[TMGH][4-F-PhO]. 1H NMR (400 MHz, D2O) δ: 2.45 (s, 12H), 6.26 (t, 2H),
6.49 (t, 2H);
13
C NMR (101 MHz, CDCl3) δ: 166.44(s), 156.47(s), 153.99(s),
116.81(s), 115.29(s), 39.10(s).
[TMGH][4-MeO-PhO]. 1H NMR (400 MHz, D2O) δ: 2.57 (s, 12H), 3.44 (s, 3H),
6.37 (d, 2H), 6.51 (d, 2H);
C NMR (101 MHz, CDCl3) δ: 166.82(s), 153.37(s),
13
151.70(s), 116.65(s), 114.62(s), 55.70(s), 39.11(s).
Figure S1.
FT-IR spectroscopy of [TMGH][Ac] (a), [TMGH][Gly]
(b),
[TMGH][PhO] (c), [TMGH][4-F-PhO] (d) and [TMGH][4-MeO-PhO] (e).
Products analysis were carried out using NMR (Bruker Avance 400 MHz
spectrometer), and GC–MS (Trace1300/ISQ, Thermo Fisher Scientific) analyzers.
The presence of the expected products were identified by GC-MS, 1H and 13C NMR.
2-Phenyl-2,3-dihydrochromen-4-one: 1H NMR (400 MHz, DMSO) δ=7.82 (d,
J=6.9, 1H), 7.38 (dd, J=11.0, 4.6, 3H), 7.28 (dt, J=17.3, 5.1, 3H), 6.91 (dd, J=17.1,
10.3, 2H), 5.34 (dd, J=13.3, 2.6, 1H), 2.95 (dd, J=16.8, 13.4, 1H), 2.76 (dd, J=16.9,
2.8, 1H);
13
C NMR (101 MHz, DMSO) δ: 192.38 (s), 161.99 (s), 139.82 (s), 137.13
(s), 129.42 (d, J = 5.1 Hz), 127.48 (s), 127.25 (s), 122.35 (s), 121.58 (s), 118.92 (s),
79.75 (s), 44.47 (s).
2-(4-Bromophenyl)-2,3-dihydrochromen-4-one:
1
H NMR(400 MHz, CDCl3):
δ=7.80-7.83 (m, 1H), 7.50-7.61 (m, 3H), 7.32-7.50 (m, 2H), 7.01-7.08 (m, 2H),
5.45-5.47 (m, 1H), 3.02-3.04 (m, 1H), 2.87-2.89(m, 1H). (C15H11BrO2, WM=303.15),
measured value: m/z=303.29
2-(2-Chlorophenyl)-2,3-dihydrochromen-4-one: 1H NMR (400 MHz, CDCl3):
δ=6.90-7.53(m, 8H), 5.44-5.45(m, 1H), 2.98-3.00(m, 1H), 2.83(m, 1H). (C15H11ClO2,
WM=258.70), measured value: m/z=258.31.
2-p-Tolyl-2,3-dihydrochromen-4-one: 1H NMR (400 MHz,CDCl3): δ=7.84-7.86
(m, 1H), 7.47-7.50 (m, 1H), 7.38-7.41(m, 2H), 7.33-7.36 (m, 2H), 6.94-76.98 (m, 2H),
5.34-5.36 (m, 1H), 2.98-3.01 (m, 1H), 2.75-2.76 (m, 1H), 2.30 (s, 3H). (C16H14O2,
WM=238.28), measured value: m/z=238.34.
2-(4-Methoxyphenyl)-2,3-dihydrochromen-4-one: 1H NMR(400 MHz, CDCl3):
δ=7.80-7.82 (m, 1 H), 7.46-7.50 (m,1H), 7.38-7.40(m, 2H), 7.01-7.05 (m, 2H),
6.95-6.98 (m, 2H), 5.40-5.42 (m, 1H), 3.81 (s, 3H), 3.09-3.12 (m, 1H), 2.84-2.86 (m,
1H). (C16H14O3, WM=254.28), measured value: m/z=254.35.
2-(3,4-Dimethoxyphenyl)-2,3-dihydrochromen-4-one:
1
H
NMR
(400
MHz,
CDCl3): δ=8.21-8.23 (m, 1H), 7.54-7.55 (m, 1H), 7.49-7.50 (m,1H), 7.38-7.40 (m,
1H), 7.33-7.34 (m, 1H), 6.94-6.96 (d, 1H), 6.70 (s, 1H), 5.40-7.43 (m, 1H), 3.97 (s,
3H), 3.92 (s, 3H), 3.08-3.10 (m, 1H), 2.83-3.85(m, 1H).
measured value: m/z=284.35.
(C17H16O4, WM=284.31),