4
8.5 Hz), 3.87 (2H, s), 2.76 (4H, m). 13C NMR (CD3OD, 100 MHz):
156.9, 149.8, 143.2, 135.8, 131.6, 130.60, 130.59, 124.1, 123.0,
116.3, 53.4, 51.7, 35.8. IR (cm-1): 3278, 3200-2400, 3088, 2920,
2847, 2676, 2601, 1611, 1530, 1513, 1459, 1345, 1255, 1168, 1085,
843, 809, 738, 688. ESI-HRMS: m/z 273.1211 ([M+H]+, calc.
273.1234).
3. Borounov, A.V.; Lukyanenko, N.G.; Pastushok, V.N.;
Krakowiak, K.E.; Bradshaw, J.S.; Dalley N.K.; Kou, X. J. Org.
Chem
4. Rajakumar, P.; Rasheed, A.M.A. Tetrahedron
5. Gloe, K. Macrocyclic Chemistry; Springer, Netherlands, 2005
6. Sato, M.; Uehara, F.; Sato, K.; Yamaguchi, M.; Kabuto, C. J. Am.
Chem. Soc 1999, 121, 8270.
. 1995, 60, 4912.
,
2005, 61, 5351.
.
General Procedure for the synthesis of 4a
-
4c
:
To
a saturated
.
solution of corresponding N-benzyltyramine 3a
-
c (150 mg) in
7. Arunachalam, M.; Ravicumar, I.; Ghosh, P. J. Org. Chem
.
2008
,
ethanol (aprox. 5 mL) was added excess formaldehyde 37% (2.5-3
mL). The reaction mixture was allowed to stir for 72 h at room
temperature before removing the solvent under reduced pressure.
The resulting yellow oil was suspended in water (10 mL) and
extracted with CHCl3 (3 x 10 mL). The combined organic fractions
were dried over anhydrous sodium sulfate and concentrated under
reduced pressure. The resulting oil was purified by column
chromatography [gradient from CHCl3 to CHCl3/MeOH 90:10] to
give the desired product.
N-benzylazacyclophane (4a): Light brown solid (66%). Melting
point: 84-86°C. 1H NMR (CDCl3, 400 MHz): 7.32-7.18 (10H, m),
6.82 (2H, m), 6.66 (4H, m), 3.68 (4H, s), 3.60 (4H, s), 2.72 (8H, m).
13C NMR (CDCl3, 100 MHz): 156.0, 136.8, 129.6, 129.4, 128.9,
128.7, 128.5, 127.5, 121.8, 116.0, 58.1, 57.6, 54.8, 31.9. IR (cm-1):
3500-2500, 3025, 2923, 2826, 1599, 1498, 1452, 1363, 1254, 1111,
939, 822, 743, 698. EI-MS: m/z 478.3 (M+, 5.8%), 91.1 (100%).
N-benzylazacyclophane (4b): Light yellow solid (96%). Melting
point: 76-80°C. 1H NMR (CDCl3, 400 MHz): 7.12 (4H, d, J = 8.6
Hz), 6.81 (6H, m), 6.66 (4H, m), 3.75 (6H, s), 3.69 (4H, s), 3.53
(4H, s), 2.69 (8H, m). 13C NMR (CDCl3, 100 MHz): 159.0, 156.1,
130.7, 129.6, 128.9, 128.8, 128.7, 121.9, 116.1, 113.9, 57.4, 57.3,
55.2, 54.6, 31.9. IR (cm-1): 3500-2300, 3003, 2929, 2834, 1612,
1513, 1498, 1462, 1364, 1252, 1176, 1106, 1032, 817, 757. EI-MS:
m/z 538.7 (M+).
73, 9144.
8. Kanamathareddy, S.; Gutsche, C.D. J. Org. Chem
. 1992, 57,
3160.
9. Rivera, A.; Quevedo, R. Tetrahedron Lett
. 2004, 45, 8335.
10. Akdas, H.; Bringel, L.; Graf, E.; Hosseini, M.W.; Mislin, G.;
Pansanel, J.; De Cian, A.; Fischer, J. Tetrahedron Lett
2311.
11. Quevedo R.; Moreno-Murillo, B. Tetrahedron Lett
.
.
1998, 39,
2009, 50,
936.
12. Nuñez-Dallos, N.; Reyes, A.; Quevedo, R. Tetrahedron Lett
2012, 53, 530.
.
13. Quevedo, R.; Sierra, C.A. Heterocycles, 2011, 83, 2769.
14. Quevedo, R.; Ortiz, I.; Reyes, A. Tetrahedron Lett. 2010, 51,
1216.
15. Quevedo, R.; González, M.; Díaz-Oviedo, C. Tetrahedron Lett
2012, 53, 1595.
.
16. Bulman, P.; Heaney, H.; McGrath, M.; Sampler, E.; Wilkins, R.
Tetrahedron Lett 2003, 44, 2965.
.
17. MOPAC2009, Stewart, J.J.P. Stewart Computational Chemistry,
Version 11.366W web. <http://OpenMOPAC.net>.
18. Quevedo, R.; Nuñez-Dallos, N.; Wurst, K.; Duarte-Ruiz, A. J.
3-(((4-hydroxyphenethyl)(3-nitrobenzyl)amino)methyl)-N-methyl-
N-(3-nitrobenzyl)tyramine (5a): Light yellow solid (22%). Melting
point: 102-105°C. 1H NMR (CDCl3, 400 MHz): 8.14-8.00 (4H, m),
7.57-7.40 (4H, m), 6.94-6.67 (7H, m), 3.82 (2H, s), 3.71 (2H, s),
3.63 (2H, s), 2.85-2.67 (8H, m), 2.29 (3H, s). 13C NMR (CDCl3, 100
MHz): 155.4, 154.4, 148.3, 148.2, 141.4, 139.0, 135.5, 135.0,
131.1, 130.7, 129.7, 129.2, 129.1, 128.9, 124.3, 123.6, 122.7, 122.1,
121.3, 116.1, 115.6, 61.3, 59.4, 57.7, 57.3, 55.1, 42.1, 32.9, 32.0. IR
(cm-1): 3500-2500, 3343, 2924, 2851, 1614, 1528, 1498, 1459,
Mol. Struct
19. General Procedure for the synthesis of 3a
tyramine in ethanol was added corresponding aldehyde (1 equiv.).
. 2012, 1029, 175.
-
3c: To a solution of
1
The reaction mixture was heated to reflux for 24 h before removing
the solvent under reduced pressure. The resulting orange solid was
dissolved in methanol and sodium borohydride (1.25 equiv) was
added in small portions over the course of 15 min. The reaction was
allowed to stir for 24 h at room temperature before removing the
solvent under reduced pressure. The resulting light-brown solid was
treated with water (20 mL) and filtrated. The resulting solid was
dried in oven at 60°C overnight to give the desired product.
N-benzyltyramine (3a): Light brown solid (68%). Melting point:
139-142°C. 1H NMR (DMSO-d6, 400 MHz): 7.22 (5H, m), 6.95
(2H, d, J = 8.4 Hz), 6.64 (2H, d, J = 8.4 Hz), 3.67 (2H, s), 2.60 (4H,
m). 13C NMR (DMSO-d6, 100 MHz): 155.7, 141.0, 130.5, 129.6,
128.3, 128.1, 126.7, 115.2, 53.0, 51.0, 35.1. IR (cm-1): 3500-2500,
3277, 3036, 2949, 2815, 2585, 1613, 1515, 1448, 1269, 1230, 834,
740, 698, 547. ESI-HRMS: m/z 228.1326 ([M+H]+, calc.
228.1383).
1347, 1252, 1112, 806, 732. ESI-HRMS: m/z 286.1268 ([M+2H]2+
,
calc. 286.1312).
N-methyl-N-(3-nitrobenzyl)tyramine
(5b): Light yellow solid
(13%). Melting point: 68-70 °C. 1H NMR (CDCl3, 400 MHz): 8.15
(1H, br t, J ≈ 2 Hz), 8.09 (1H, ddd, J = 8.1 Hz, 2.2 Hz, 0.8 Hz), 7.61
(1H, d, J = 7.5 Hz), 7.45 (1H, t, J = 7.9 Hz), 7.02 (2H, d, J = 8.4
Hz), 6.74 (2H, d, J = 8.5 Hz), 3.64 (2H, s), 2.75 (2H, t, J = 7.6 Hz),
2.63 (2H, t, J = 7.5 Hz), 2.30 (3H, s). 13C NMR (CDCl3, 100 MHz):
154.2, 148.4, 141.4, 135.1, 132.1, 129.9, 129.3, 123.9, 122.3, 115.4,
61.4, 59.4, 42.2, 33.0. IR (cm-1): 3385, 2923, 2852, 1614, 1528,
1460, 1347, 1249, 1117, 805, 732. ESI-HRMS: m/z 287.1345
([M+H]+, calc. 287.1390).
N-(4-methoxybenzyl)tyramine
(3b): White solid (53%). Melting
point: 99-100°C. 1H NMR (CDCl3, 400 MHz): 7.17 (2H, d, J = 8.6
Hz), 6.97 (2H, d, J = 8.4 Hz), 6.82 (2H, d, J = 8.7 Hz), 6.65 (2H, d,
J = 8.4 Hz), 4.44 (2H, br s), 3.77 (3H, s), 3.74 (2H, s), 2.87 (2H, t, J
= 6.9 Hz), 2.75 (2H, t, J = 6.9 Hz). 13C NMR (CDCl3, 100 MHz):
158.8, 155.2, 131.2, 130.4, 129.7, 129.6, 115.8, 113.9, 55.3, 52.9,
50.0, 34.7. IR (cm-1): 3297, 3282, 3200-2200, 3012, 2946, 2834,
2674, 2598, 1614, 1517, 1462, 1255, 1173, 1090, 1032, 826, 812,
576. ESI-HRMS: m/z 258.1448 ([M+H]+, calc. 258.1489).
msu.su/gran/firefly/index.html
21. Schmidt, M.; Baldridge, K.; Boatz, J.; Elbert, S.; Gordon, M.;
Jensen, J.; Koseki, S.; Matsunaga, N.; Nguyen, K.; Su, S.; Windus,
T.; Dupuis, M.; Montgomery Jr., J. J. Comput. Chem
.
1993, 14,
1347.
22. Harding, J.; Jones, J.; Lu, S.; Wood, R. Tetrahedron Lett
.
2002,
N-(3-nitrobenzyl)tyramine (3c): White solid (92%). Melting point:
114-117°C. 1H NMR (CD3OD, 400 MHz): 8.22 (1H, t, J = 1.7 Hz),
8.12 (1H, ddd, J = 8.2 Hz, 2.1 Hz, 0.9 Hz), 7.70 (1H, d, J = 7.7 Hz),
7.55 (1H, t, J = 7.9 Hz), 7.01 (2H, d, J = 8.5 Hz), 6.70 (2H, d, J =
43, 9487.