P. Suresh et al. / Tetrahedron: Asymmetry 24 (2013) 669–676
675
7.40 (m, 14H), 7.97–8.04 (m, 6H), 8.27 (s, 2H), 10.13 (s, 2H), 10.49
(s, 2H); 13C NMR [400 MHz, CDCl3] d 27.9, 115.9, 121.2, 121.2,
122.3, 123.8, 124.6, 125.0, 125.2, 126.2, 126.6, 127.7, 129.1,
129.1, 129.9, 131.2, 132.5, 136.6, 137.7, 146.1, 152.8, 169.3,
196.0; ESI-MS: m/z 711 ([M+H]+).
32.7, 60.4, 72.7, 113.5, 114.3, 117.7, 120.6, 123.3, 123.9, 124.5,
124.7, 126.5, 127.7, 128.2, 129.0, 129.2, 129.2, 130.0, 133.5,
134.7, 135.2, 151.5, 155.4, 164.9, 171.2. MALDI-TOF-MS: m/z
788.5 ([M+H]+).
4.3.2. Spectroscopic data for 13
4.2.2. Spectroscopic data for 6
(Yield 89%); ½a 2D5
ꢃ
¼ ꢁ20:6 (c 0.2, CHCl3); IR (KBr): 732, 811,
(Yield 97%); ½a 2D0
ꢃ
¼ ꢁ221 (c 1.4, CH2Cl3); IR (KBr): 754, 777, 790,
1115, 1203, 1348, 1508, 1628, 1753, 2852, 2922, 3055 cmꢁ1 1H
;
1119, 1147, 1254, 1295, 1442, 1505, 1630, 1655, 1754, 2853, 3060,
NMR [400 MHz, CDCl3] d 1.8–1.94 (m, 2H), 2.79–2.99 (m, 4H),
3.55 (s, 2H), 4.00 (s, 2H), 7.03–7.34 (m, 20H), 7.79–7.88 (m, 8H),
8.84 (s, 2H), 13.07 (s, 2H); 13C NMR [400 MHz, CDCl3] d 23.4,
58.3, 58.5, 73.8, 113.1, 116.3, 119.3, 122.8, 123.4, 123.4, 125.3,
126.4, 127.0, 127.4, 127.5, 127.8, 128.0, 128.9, 132.2, 133.7,
134.1, 150.1, 154.1, 164. MALDI-TOF-MS: m/z 866 ([M+H]+).
3193 cmꢁ1 1H NMR [400 MHz, CDCl3] d 0.95–0.99 (m, 2H), 1.49–
;
1.60 (m, 4H), 7.11–7.39 (m, 14H), 7.78–7.94 (m, 6H), 8.14 (s, 2H),
10.02 (s, 2H), 10.41(s, 2H); 13C NMR [400 MHz, CDCl3] d 19.2,
32.4, 116.6, 121.8, 123.1, 124.5, 125.3, 125.6, 125.8, 126.8, 127.2,
128.3, 129.7, 129.8, 131.1, 133.1, 137.2, 138.3, 146.8, 153.4,
170.5, 196.7; ESI-MS: m/z 747 ([M+Na]+).
4.3.3. Spectroscopic data for 14
4.2.3. Spectroscopic data for 7
(Yield 78%); ½a 2D5
ꢃ
¼ ꢁ312:5 (c 1.0, CHCl3); IR (KBr)
m
698, 733,
(Yield 95%); ½a 2D0
ꢃ
¼ ꢁ40:1 (c 0.4, CHCl3); IR (KBr): 750, 773, 794,
890, 1115, 1204, 1345, 1443, 1631, 1751, 2859, 3058 cmꢁ1 1H
;
1119, 1146, 1250, 1298, 1444, 1507, 1638, 1659, 1742, 2855, 3020,
NMR [400 MHz, CDCl3] d 0.69–0.76 (m, 2H), 1.00–1.40 (m, 2H),
3.45 (s, 2H), 3.54–3.61 (m, 4H), 4.24–4.27 (d, J = 12.2 Hz, 2H),
4.29–4.32 (d, J = 12.2 Hz, 2H), 6.82–7.44 (m, 22H), 7.60–7.83 (m,
8H), 8.35 (s, 2H), 12.75 (s, 2H);13C NMR [400 MHz, CDCl3] d 32.9,
70.8, 71.0, 73.4, 115.2, 120.1, 121.9, 123.5, 124.9, 125.6, 126.3,
126.9, 127.5, 127.7, 127.8, 128.2, 128.3, 129.0, 129.4, 132.1,
133.6, 134.9, 137.7, 137.8, 146.9, 154.6, 167.0, 170.3. ESI-MS: m/z
947 ([M+H]+).
3197 cmꢁ1 1H NMR [400 MHz, CDCl3] d 0.70–0.71 (m, 4H), 1.62–
;
1.67 (m, 4H), 7.17–7.52 (m, 14H), 7.90–8.06 (m, 6H), 8.27 (s, 2H),
10.15 (s, 2H), 10.50 (s, 2H); 13C NMR [400 MHz, CDCl3] d 25.6,
35.5, 118.9, 123.9, 124.0, 125.2, 126.6, 127.5, 127.8, 127.9, 128.9,
129.4, 130.5, 131.7, 131.8, 132.7, 134.0, 135.3, 139.4, 140.3,
149.0, 155.6, 173.1, 198.8; ESI-MS: m/z 739 ([M+H]+).
4.2.4. Spectroscopic data for 8
(Yield 50%); ½a 2D0
ꢃ
¼ ꢁ123:8 (c 0.82 CHCl3); IR (KBr): 756, 779,
4.3.4. Spectroscopic data for 15
802, 1122, 1148, 1259, 1304, 1451, 1515, 1641, 1662, 1747,
(Yield 94%); ½a 2D5
ꢃ
¼ ꢁ123:8 (c 0.3, CHCl3); IR (KBr)
m
;
739, 1133,
2859, 3028, 3112 cmꢁ1
;
1H NMR [400 MHz, CDCl3] d 1.72 (s, 3H),
1435, 1582, 1630, 1751, 2859, 2919, 3380 cmꢁ1 1H NMR
7.17–7.38 (m, 7H), 7.85–7.95 (m, 3H), 8.23 (s, 1H), 10.10 (s, 1H),
10.40 (s, 1H); 13C NMR [400 MHz, CDCl3] d 20.6, 116.8, 121.8,
121.9, 123.1, 124.5, 125.7, 125.7, 126.8, 127.3, 128.3, 129.6,
129.7, 130.6, 131.8, 133.2, 137.3, 138.3, 147.0, 153.4, 169.1,
196.6; ESI-MS: m/z 357 ([M+H]+).
[400 MHz, CDCl3] d 0.24–0.27 (m, 2H), 0.98–1.06 (m, 2H), 1.12–
1.33 (m, 2H), 1.66–1.76 (m, 4H), 1.92–2.02 (m, 4H), 3.40–3.43
(dd, J = 4 Hz, J = 8 Hz, 2H), 7.08–7.10 (d, J = 8.4 Hz, 2H), 7.28–
7.56(m, 12H), 7.88–7.90 (d, J = 8.4 Hz, 2H), 8.00 (s, 2H), 8.02–8.04
(d, J = 8.4 Hz, 2H), 8.07–8.10 (d, J = 8.8 Hz, 2H), 8.66 (s, 2H), 13.12
(s, 2H); 13C NMR [400 MHz, CDCl3] d 18.8, 24.2, 32.8, 60.4, 73.6,
76.7, 115.2, 120.1, 121.7, 123.3, 124.8, 125.0, 125.6, 126.0, 126.7,
127.1, 128.2, 128.3, 128.6, 129.4, 132.0, 133.4, 134.3, 134.7,
146.7, 154.5, 164.9, 170.1. MALDI-TOF-MS: m/z 802 ([M+H]+).
4.3. General experimental procedure for the synthesis of [n+n]
macrocycles under microwave irradiation
The chiral diamine salt (1.2 equiv) and K2CO3 (2.4 equiv) were
weighed in a boiling tube. Next, 3 mL of water was added to form
a clear solution. The dialdehyde (1 equiv) was then weighed in a
separate boiling tube and dissolved in 3 mL of ethanol to form a
clear solution. The aldehyde solution was added in one portion to
the boiling tube containing a diamine salt and potassium carbonate
to form a pale yellow solution. The reverse addition however did
not produce any macrocycle and resulted in polymeric materials.
The yellow solution was irradiated in a domestic microwave oven
for a total time period of 5 min. The immediate appearance of a
yellow solid was observed and the mixture was cooled after every
1 min period of irradiation. The mixture was finally filtered, and
washed with ethanol and water. Ethyl acetate was then added to
the reaction mixture and the insoluble materials were filtered
again. The ethyl acetate layer was dried over anhydrous Na2SO4
and concentrated to yield the crude product, which was purified
by a short-path column chromatography over silica gel to give pure
[n+n] macrocycles.
4.3.5. Spectroscopic data for 16
(Yield 91%); ½a 2D5
ꢃ
¼ ꢁ195:3 (c 0.63, CHCl3); IR (KBr)
m
;
692, 737,
1125, 1209, 1335, 1445, 1634, 1753, 2869, 3061 cmꢁ1
1H NMR
[400 MHz, CDCl3] d 0.203–0.167 (m, 2H), 0.95–0.87 (m, 2H),
1.26–1.19 (m, 2H), 3.63–3.61 (m, 2H), 3.80–3.73 (m, 4H), 4.50–
4.42 (dd, J = 12 Hz, J = 12 Hz, 4H), 7.03–7.01 (d, J = 8 Hz, 2H),
7.48–7.20 (m, 20H), 7.81–7.79 (d, J = 7.6 Hz, 2H), 7.96–7.94 (d,
J = 8.4 Hz, 2H), 7.92 (s, 2H), 8.02–7.99 (d, J = 8.8 Hz, 2H), 12.94 (s,
2H), 8.54 (s, 2H); 13C NMR [400 MHz, CDCl3] d 18.9, 32.1, 70.6,
73.3, 115.1, 120.0, 121.8, 123.4, 124.8, 125.6, 126.0, 126.7, 127.2,
127.6, 127.7, 128.3, 128.4, 128.8, 129.4, 132.0, 134.7, 137.7,
146.8, 154.5, 166.9, 170.25. MALDI-TOF-MS: m/z 989 ([M+H]+).
4.3.6. Spectroscopic data for 17
(Yield 96%); ½a 2D5
ꢃ
¼ ꢁ185:4 (c 0.3 CHCl3); IR (KBr)
m
741, 1137,
1439, 1579, 1632, 1748, 2859, 2921, 3382 cmꢁ1
;
1H NMR
[400 MHz, CDCl3] d ꢁ0.557 (m, 2H), ꢁ0.24 (m, 2H), 0.80–0.76 (m,
2H), 1.18–0.98 (m, 2H), 1.41–1.36 (m, 2H), 1.76–1.66 (m, 2H),
1.86–1.77 (m, 4H), 3.43–3.40 (d, J = 9.2 Hz, 2H), 6.93–6.91 (d,
J = 7.6 Hz, 2H), 7.39–7.11 (m, 12H), 7.71–7.69 (d, J = 7.6 Hz, 2H),
7.88–7.86 (d, J = 7.6 Hz, 4H), 7.94–7.92 (d, J = 8.8 Hz, 2H), 8.53 (s,
2H), 13.03 (s, 2H); 13C NMR [400 MHz, CDCl3] d 18.8, 24.2, 32.8,
60.4, 73.6, 76.7, 115.2, 120.1, 121.7, 123.3, 124.8, 125.0, 125.6,
126.0, 126.7, 127.1, 128.2, 128.3, 128.6, 129.4, 132.0, 133.4,
134.3, 134.7, 146.7, 154.5, 164.9, 170.11. MALDI-TOF-MS: m/z
816.5 ([M+H]+).
4.3.1. Spectroscopic data for 12
(Yield 97%); ½a 2D5
ꢃ
¼ ꢁ642 (c 1.0, CHCl3); IR (KBr)
m
;
735, 1121,
1435, 1592, 1631, 1754, 2858, 2925, 3383 cmꢁ1
1H NMR
[400 MHz, CDCl3] d 1.13–1.16 (m, 2H), 1.18–1.22 (m, 4H), 1.38–
1.40 (m, 2H), 1.80–1.83 (m, 4H), 3.28–3.30 (d, J = 9.6 Hz, 2H),
6.88–6.90 (d, J = 8.4 Hz, 2H), 7.13–7.33 (m, 10H), 7.37–7.41 (t,
J = 7.6 Hz, 2H), 7.75–7.77 (d, J = 8.4 Hz, 2H), 7.86–7.92 (m, 6H),
8.54 (s, 2H), 12.92 (s, 2H); 13C NMR [400 MHz, CDCl3] d 24.0,