SUPRAMOLECULAR CHEMISTRY
3
−1 1
1H), 7.33–7.20 (m, 5H), 4.47 (d, J = 6.0 Hz, 2H). 13C NMR
1
709, 1643, 1603, 1504, 1451 cm . H NMR (CDCl , 400 MHz):
3
δ 8.60 (t, J = 2.0 Hz, 1H), 8.34 (ddd, J = 8.2, 2.2, 1.1 Hz, 1H),
.17 (ddd, J = 7.8, 1.7, 1.1 Hz, 1H), 7.63 (t, J = 8 Hz, 1H), 7.34
(DMSO-d , 100 MHz): δ 166.3, 152.1, 146.3, 145.7, 141.1,
6
8
139.7, 139.2, 135.3, 128.9, 128.4, 127.3, 125.2, 121.5, 121.2,
13
+
+
+
(m, 5H), 6.82 (t, J = 5.7 Hz, 1H), 4.65 (d, J = 5.7 Hz, 1H). C
118.1, 117.7, 42.7. MS (FAB ): 391 [M+H] . HRMS (FAB ):
calculated for C H N O 391.1406, found 391.1412.
NMR (CDCl , 100 MHz): δ 164.0, 137.7, 136.1, 133.5, 130.1,
3
21 19
4
4
1
29.1, 128.8, 128.2, 128.1, 126.3, 122.0, 44.6. MS (EI) m/z: 256
The same procedures were used to obtain products
3 and 4, respectively, but 2-amino-N-benzylbenzamide
(9) was used as precursor to give the products in ortho
position.
+
+
(M , 100), 150 (50), 134 (10), 104 (25), 91 (25). HRMS (FAB ):
calculated for C H N O 257.0926, found 257.0903.
14
13
2
3
3-Amino-N-benzylbenzamida (7). A mixture of 6 (0.192 g,
0
.749 mmol) and Pd/C 10% (40 mg) was stirred at room
N-Benzyl-2-(3-(naphthalen-1-yl)ureido)benzamide (3).
Pale yellow solid. 95% yield. Mp 196–198 °C. FTIR (ATR):
temperature and Ar atmosphere for 10 min. Then dry
CH OH (20 mL) was added, and the reaction mixture was
−1 1
3280, 1680, 1626, 1508 cm . H NMR (DMSO-d , 400 MHz):
3
6
stirred for 4 h under H atmosphere. The resulting mix-
δ 10.29 (s, 1H), 9.63 (s, 1H), 9.24 (t, J = 5.8 Hz, 1H), 8.22 (d,
J = 8.0 Hz, 1H), 8.16 (m, 1H), 7.93 (m, 1H), 7.72 (m, 3H),
7.56–7.24 (m, 9H), 7.1 (t, J = 7.3 Hz, 1H), 4.51 (d, J = 5.8 Hz,
2
ture was filtered and washed with CH OH. The solvent
3
was removed in vacuo and heat to obtain a pale yellow
1
13
solid. 75% yield. Mp 71–72 °C. H NMR (CDCl , 400 MHz):
2H). C NMR (DMSO-d , 100 MHz): δ 168.3, 153.5, 139.7,
3
6
δ 7.33 (m, 5H), 7.17 (t, J = 7.7 Hz, 1H), 7.14 (s, 1H), 7.06
139.4, 134.3, 133.8, 132.0, 131.3, 128.4, 128.2, 127.8, 127.7,
(
d, J = 7.7 Hz, 1H), 6.78 (dd, J = 7.7, 1.3 Hz, 1H), 6.49 (t,
127.2, 126.9, 125.9, 125.7, 125.6, 124.1, 122.7, 121.8, 121.2,
1
3
+
J = 5.7 Hz, 1H), 4.60 (d, J = 5.7 Hz, 2H), 3.26 (brs, 2H).
C
120.6. 42.6. MS (EI) m/z: 395 (M , 1), 252 (10), 226 (30), 142
+
+
+
NMR (CDCl , 100 MHz): δ 167.7, 146.9, 138.3, 135.5, 129.4,
(80), 91 (100). MS (FAB ): 396 [M+H] . HRMS (FAB ): calcu-
lated for C H N O 396.1712, found 396.1709.
3
1
28.7, 127.8, 127.5, 117.9, 116.4, 113.8, 44.0. MS (EI) m/z:
2
5
22
3
2
+
+
226 (M , 65), 120 (90), 92 (100), 91 (98). HRMS (FAB ): cal-
N-Benzyl-2-(3-(4-nitrophenyl)ureido)benzamide (4). Pale
culated for C H N O 257.0926, found 257.0903
yellow solid. 75% yield. Mp 218–220 °C. FTIR (ATR): 3277,
1
4
13
2
3
−1 1
N-Benzyl-3-(3-(naphthalen-1-yl)ureido)benzamide (1).
1696, 1618, 1596, 1560, 1495 cm . H NMR (DMSO-d ,
6
1
-Naphthyl isocyanate (30 μL, 0.212 mmol) was added to
400 MHz): δ 10.7 (s, 1H), 10.5 (s, 1H), 9.35 (t, J = 5.8 Hz, 1H),
8.26 (d, J = 8.4 Hz, 1H), 8.19 (d, J = 9.2 Hz, 2H), 7.78 (d,
J = 7.6 Hz, 1H), 7.75 (d, J = 9.2 Hz, 2H), 7.49 (td, J = 7.8,
a stirred mixture of 7 (0.048 g, 0.212 mmol) and dry THF
under Ar atmosphere, the reaction mixture was stirred
overnight at room temperature. Then, the solvent was
removed heating in vacuo. The product was suspended
in ethyl ether and then filtered to give a pale yellow solid.
1.0 Hz, 1H), 7.35–7.20 (m, 5H), 7.11 (t, J = 7.6 Hz, 1H). 13
C
NMR (DMSO-d , 100 MHz): δ 168.3, 151.9, 146.7, 141.1,
6
140.4, 139.4, 139.2, 131.8, 128.4, 128.0, 127.2, 126.9, 125.1,
+
9
1
1
1
7
1
1
1
2
6% yield. Mp 208–210 °C. FTIR (ATR): 3263, 1642, 1624,
580, 1548 cm . H NMR (DMSO-d , 400 MHz): δ 9.25 (s,
121.8, 120.8, 117.3, 42.6. MS (EI) m/z: 390 (M , 1), 252 (100),
−
1
1
+
+
+
91 (60). MS (FAB ): 391 [M+H] . HRMS (FAB ): calculated for
C H N O 391.1406, found 391.1412.
6
H), 9.06 (t, J = 6.2 Hz, 1H), 8.82 (s, 1H), 8.13 (d, J = 8.0 Hz,
2
1
19
4
4
H), 8.02 (d, J = 8.0 Hz, 1H), 7.98 (s, 1H), 7.95 (m, 1H), 7.73–
1
3
.23 (m, 15H), 4.49 (d, J = 6.2 Hz, 2H). C NMR (DMSO-d ,
6
Molecular modelling
00 MHz): δ 166.3, 153.0, 139.9, 139.8, 135.3, 134.2, 133.8,
28.9, 128.3, 127.2, 126.8, 126.0, 125.8, 123.2, 121.4, 120.8,
3D molecular modelling and optimisation of geometries
of the proposed sensor structures and its complexes were
base using Gaussian 09 computational programme (34).
+
20.5, 117.6, 117.5, 42.7. MS (EI) m/z: 395 (M , 1), 252 (10),
+
26 (20), 169 (50), 142 (100), 115 (55), 91 (35). MS (FAB ): 396
+
+
[
M+H] . HRMS (FAB ): calculated for C H N O 396.1712,
25 22 3 2
found 396.1693.
N-benzyl-3-(3-(4-nitrophenyl)ureido)benzamide
(2).
4-Nitrophenyl isocyanate (40 mg, 0.234 mmol) was dis-
Results and discussion
solved in dry THF (5 mL) and was added slowly to a stirred
mixture of 7 (0.055 g, 0.243 mmol) and THF (20 mL) under
Ar atmosphere. The reaction mixture was stirred overnight
at room temperature. Then the solvent was removed in
vacuo and temperature. The product was suspended in
light petroleum and the solvent was removed to give a
solid product. Mp 209–210 °C. FTIR (ATR): 3302, 1700, 1629,
Synthesis
The synthetic routes for compounds 1–4 are shown in
Scheme 1. First, m-nitrobenzoyl chloride was treated
with benzylamine obtaining the benzamide 6. Then, the
nitro-reduction of 6 under hydrogen atmosphere gave the
3-aminobenzamide 7, and finally the addition of the naph-
thyl or nitrophenyl isocyanate lead to the products 1 and
2. In the other route, isatoic anhydride was treated with
benzylamine to obtain the 2-aminobenzamide 9. Then, the
−1 1
1
553 cm . H NMR (DMSO-d , 400 MHz): δ 9.50 (s, 1H), 9.10
6
(
(
s, 1H), 9.04 (t, J = 6.0 Hz, 1H), 8.19 (d, J = 9.2 Hz, 1H), 7.95
t, J = 1.7 Hz, 1H), 7.70 (d, J = 9.2 Hz, 2H), 7.64 (d, J = 7.8 Hz,