422
Q. Zhang et al. / Polyhedron 87 (2015) 417–423
c
(cmꢀ1) (3353, 1686, 1638, 1577, 1533, 1498, 1472). APCI-MS
127.8 (ArCH), 124.5 (ArCH), 123.4 (ArCH), 117.1 (ArC), 76.6
(CH2), 71.5 (CH2), 63.4 (CH2), 41.4 (CH2), 36.6 (CH2), 28.5 (CH2).
FTIR (KBr):
(cmꢀ1) (3387, 1749, 1732, 1656, 1575, 1531, 1454,
calculated for C28H32O5N+2 = 478; Found = 478.
c
4.6. N-(Aminoethyl)-2,3-bis(benzyloxy)benzamide, TFA Salt (8)
1026). UV–Vis (CH2Cl2): kmax (nm) (228, 294). APCI-MS calculated
for C51H51O10N+2 = 852; Found = 852.
A solution of 7 (0.48 g, 1.0 mmol) in CH2Cl2 (15 mL) was stirred
at 0 °C for 30 min. TFA/CH2Cl2 (20%, 15 mL) was added dropwise
over 1 h with vigorous stirring. The mixture was stirred at room
temperature for 3 h. After adding benzene (30 mL), the solution
was concentrated to half of the total volume. This process was
repeated thrice. Then, the solution was concentrated in vacuo.
The residue was dissolved in 5 mL of hot ethanol. A large amount
of ether was added, and then the white crystal was precipitated.
The solution was filtered to obtain the product 8 as white solid
(yield of 76%). 1H NMR (300 MHz, CDCl3, 297.6 K): d = 8.42 (br s,
1H, CO-NH), 7.56 (m, 1H, Ar-H), 7.52–7.00 (m, 12H, Ar-H), 5.14
(s, 2H, O-CH2-Ar), 5.11 (s, 2H, O-CH2-Ar), 3.34 (q, 2H, CH2), 2.93
4.9. Bis(2,3-bis(benzyloxy)-N-(4-hydroxybutyl)benzamide)malonate
(4c)
A solution of malonyl dichloride (1.0 mmol) in CH2Cl2 (20 mL)
was droped in the solution of 2,3-bis(benzyloxy)-N-(4-hydroxybu-
tyl) benzamide 3c (0.81 g, 2.0 mmol), Et3N (2 mL) in CH2Cl2
(20 mL) under ice bath and vigorous stirring conditions. The mix-
ture stirred at room temperature for 16 h. After evaporation of sol-
vent and the residue purified by flash column chromatography [1:1
toluene/ethyl acetate (v/v)] to give the product 4c as clear oil (yield
of 90%). Rf = 0.7 [1:1 toluene/ethyl acetate (v/v)]. 1H NMR
(400 MHz, CDCl3, 298.0 K): d (ppm) = 7.95 (br s, 2H, CO-NH), 7.72
(m, 2H, Ar-H), 7.50–7.10 (m, 24H, Ar-H), 5.15 (s, 4H, O-CH2-Ar),
5.08 (s, 4H, O-CH2-Ar), 4.03 (t, J = 6.4, 4H, CH2), 3.32 (s, 2H, CO-
CH2-CO), 3.26 (m, 4H, CH2), 1.54 (m, 4H, CH2), 1.37 (m, 4H, CH2).
13C NMR (150 MHz, CDCl3, 300.0 K): d = 166.7 (C@O), 165.4
(C@O), 151.8 (ArC), 146.9 (ArC), 136.6 (ArCH), 128.9 (ArCH),
128.8 (ArCH), 128.4 (ArCH), 127.8 (ArCH), 124.6 (ArCH), 123.4
(ArCH), 117.1 (ArC), 76.6 (CH2), 71.4 (CH2), 65.2 (CH2), 60.6
(t, 2H, CH2). 13C NMR (150 MHz, CD3OD, 298.0 K):
d
(ppm) = 168.26 (C@O), 152.03 (ArC), 146.20 (ArC), 136.72 (ArCH),
128.66 (ArCH), 128.26 (ArCH), 128.22 (ArCH), 128.18 (ArCH),
127.95 (ArCH), 127.88 (ArCH), 127.62 (ArCH), 124.17 (ArCH),
121.46 (ArCH), 117.20 (ArCH), 75.94 (CH2), 70.86 (CH2), 39.37
(CH2), 37.19 (CH2). FTIR (KBr):
1453, 1200). APCI-MS calculated for
c
(cmꢀ1) (3378, 1687, 1575, 1531,
C
23H24O3N+2 = 377;
Found = 377.
(CH2), 41.6 (CH2), 39.3 (CH2), 26.0 (CH2), 25.9 (CH2). FTIR (KBr):
c
4.7. Bis(2,3-bis(benzyloxy)-N-(hydroxyethyl)benzamide)malonate
(cmꢀ1) (3387, 1747, 1731, 1655, 1575, 1531, 1454, 1027). UV–Vis
(4a)
(CH2Cl2): kmax (nm) (228, 294). APCI-MS calculated for
C
53H55O10N+2 = 880; Found = 880.
A solution of malonyl dichloride (1.0 mmol) in CH2Cl2 (20 mL)
was dropped in the solution of 2,3-bis(benzyloxy)-N-(hydroxy-
ethyl)benzamide 3a (0.75 g, 2.0 mmol), Et3N (2 mL) in CH2Cl2
(20 mL) under ice bath and vigorous stirring conditions. The mix-
ture stirred at room temperature for 16 h. After evaporation of sol-
vent and the residue purified by flash column chromatography [1:1
toluene/ethyl acetate (v/v)] to give the product 4a as clear oil (yield
of 82%). Rf = 0.7 [1:1 toluene/ethyl acetate (v/v)]. 1H NMR
(300 MHz, CD3Cl3, 298.0 K): d (ppm) = 8.13 (br s, 2H, CO-NH),
7.69 (m, 2H, Ar-H), 7.50–7.10 (m, 24H, Ar-H), 5.14 (s, 4H, O-CH2-
Ar), 5.06 (s, 4H, O-CH2-Ar), 4.07 (t, 4H, CH2), 3.51 (m, 4H, CH2),
2.99 (s, 2H, CO-CH2-CO). 13C NMR (150 MHz, CDCl3, 298.0 K): d
(ppm) = 166.3 (C@O), 165.6 (C@O), 151.9 (ArC), 146.9 (ArC),
136.5 (ArC), 128.9 (ArCH), 128.8 (ArCH), 128.4 (ArCH), 127.8
(ArCH), 127.3 (ArCH), 124.7 (ArCH), 123.3 (ArCH), 117.2 (ArC),
76.5 (CH2), 71.4 (CH2), 64.3 (CH2), 40.9 (CH2), 38.4 (CH2). FTIR
4.10. N,N’-Bis(N-(aminoethyl)-2,3-bis(benzyloxy)benzamide)
malonamide (4d)
TFA salt 8 (0.49 g, 1.0 mmol) in 20 mL 1.25 N NaOH aqueous
solution, The mixture stirred 20 min. CH2Cl2 extraction
(20 mL ꢂ 3), the organic layer was dried over anhydrous Na2SO4
and filtered, the solvent removed in vacuo give the 3d. A solution
of malonyl dichloride (0.5 mmol) in CH2Cl2 (20 mL) was droped
in the solution of N-(aminoethyl)-2,3-bis(benzyloxy)benzamide
3d, Et3N (2 mL) in CH2Cl2 (20 mL) with ice bath and vigorous stir-
ring conditions. The mixture stirred room temperature for 16 h.
After evaporation of solvents and the residue purified by flash col-
umn chromatography [1:20 ethanol/CH2Cl2 (v/v)] to give the prod-
uct 4d as slight yellow solid (yield of 93%). Rf = 0.8 [1:20 ethanol/
CH2Cl2 (v/v)]. 1H NMR (600 MHz, CDCl3, 298.0 K): d (ppm) = 8.12
(t, 2H, CO-NH), 7.65 (m, 2H, Ar-H), 7.50–7.23 (m, 22H, Ar-H),
7.13 (m, 2H, Ar-H), 5.14 (s, 4H, O-CH2-Ar), 5.08 (s, 4H, O-CH2-Ar),
3.33 (m, 4H, CH2), 3.22 (m, 4H, CH2), 2.97 (s, 2H, CO-CH2-CO). 13C
NMR (150 MHz, CDCl3, 300.0 K): d = 167.87 (C@O), 166.54 (C@O),
151.90 (ArC), 146.93 (ArC), 136.53 (ArCH), 129.89 (ArCH), 129.02
(ArCH), 128.98 (ArCH), 128.94 (ArCH), 128.88 (ArCH), 128.78
(ArCH), 128.47 (ArCH), 127.85 (ArCH), 127.24 (ArCH), 126.61
(ArCH), 124.64 (ArCH), 123.22 (ArCH), 117.37 (ArC), 76.63 (CH2),
(KBr):
c
(cmꢀ1) (3381, 1753, 1735, 1658, 1576, 1530, 1454,
1027). UV–Vis (CH2Cl2): kmax (nm) (228, 294). APCI-MS calculated
for C49H47O10N+2 = 824; Found = 824.
4.8. Bis(2,3-Bis(benzyloxy)-N-(3-hydroxypropyl)benzamide)malonate
(4b)
A solution of malonyl dichloride (1.0 mmol) in CH2Cl2 (20 mL)
was droped in the solution of 2,3-bis(benzyloxy)-N-(3-hydroxy-
propyl)benzamide 3b (0.78 g, 2.0 mmol), Et3N (2 mL) in CH2Cl2
(20 mL) under ice bath and vigorous stirring conditions. The mix-
ture stirred at room temperature for 16 h. After evaporation of sol-
vent and the residue purified by flash column chromatography [1:1
toluene/ethyl acetate (v/v)] to give the product 4b as a clear oil
(yield of 88%). Rf = 0.7 [1:1 toluene/ethyl acetate (v/v)]. 1H NMR
(300 MHz, CDCl3, 298.0 K): d (ppm) = 8.00 (br s, 2H, CO-NH), 7.69
(m, 2H, Ar-H), 7.50–7.10 (m, 24H, Ar-H), 5.15 (s, 4H, O-CH2-Ar),
5.08 (s, 4H, O-CH2-Ar), 4.06 (t, 4H, CH2), 3.33 (m, 4H, CH2), 3.28
(s, 2H, CO-CH2-CO), 1.68 (m, 4H, CH2). 13C NMR (150 MHz, CDCl3,
298.0 K): d (ppm) = 166.6 (C@O), 165.5 (C@O), 151.9 (ArC), 147.0
(ArC), 136.6 (ArC), 129.0 (ArCH), 128.9 (ArCH), 128.4 (ArCH),
71.46 (CH2), 42.98 (CH2), 40.18 (CH2), 39.19 (CH2). FTIR (KBr):
c
(cmꢀ1) (3296, 1666, 1637, 1576, 1533, 1497, 1449). UV–Vis
(CH2Cl2): kmax (nm) (228, 294). APCI-MS calculated for
C
49H48O8N+4 = 822; Found = 822.
4.11. Bis(2,3-bis(hydroxy)-N-(hydroxyethyl)benzamide)malonate (5a)
A mixture of 4a (0.99 g, 1.2 mmol) and Pd/C (10%) (200 mg) in
THF (50 mL) was stirred under H2 (130 mL/min) atmosphere for
5 h. The resulting mixture was filtered over Celite, evaporated to
dryness and dried under vacuum to give 5a as a clear oil (yield
of 99%). 1H NMR (600 MHz, (CD3)2CO, 298.0 K): d = 12.70 (br s,
2H, Ar-OH), 8.16 (br s, 2H, CO-NH), 7.68 (br s, 2H, Ar-OH), 7.11