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Two-step Synthesis of Tetraaromatic Tetraamide Macrocycles; General Procedure:
Step 1: One-Step Synthesis of Diamine 6 and 7
ortho-Phenylene diamine (1.85 mmol, 2.0 equiv), EDCI (1.94 mmol, 2.1 equiv) and HOAt (0.37 mmol, 0.4 equiv) were successively added to a solution of diacid derivative (isophthalic or dipicolinic acid; 0.92 mmol, 1.0 equiv) in DMF (50 mL) under an inert atmosphere. After the addition, the reaction mixture was allowed to stir at r.t. for 16 h. The mixture was concentrated under reduced pressure to a crude oil that was purified by flash column chromatography (silica gel, CH2Cl2-5% MeOH) to afford the expected diamine (6 or 7) as a pale yellow powder, with chemical yields given in the text. Compound 6: R
f
0.6 (CH2Cl2-10% MeOH); mp 198 °C. 1H NMR (300 MHz, DMSO-d
6): δ = 9.77 (s, 2 H), 8.59 (s, 1 H), 8.15 (br d, J = 7.8 Hz, 2 H), 7.66 (t, J = 7.7 Hz, 1 H), 7.20 (d, J = 7.8 Hz, 2 H), 6.99 (td, J = 8.2 Hz, J′ = 1.3 Hz, 2 H), 6.80 (dd, J = 8.1 Hz, J′ = 1.2 Hz, 2 H), 6.62 (td, J = 8.2 Hz, J′ = 1.3 Hz, 2 H), 4.94 (br s, 4 H). 13C NMR (75.3 MHz, DMSO-d
6): δ = 165.0, 143.6, 135.2, 131.0, 128.8, 127.7, 127.2, 127.1, 123.5, 116.7, 116.6. Compound 7: R
f
0.17 (CH2Cl2-5% MeOH); mp 240 °C. 1H NMR (300 MHz, DMSO-d
6): δ = 10.70 (s, 2 H), 8.18-8.35 (m, 3 H), 7.16 (dd, J = 7.8 Hz, J′ = 1.2 Hz, 2 H), 7.03 (td, J = 8.1 Hz, J′ = 1.5 Hz, 2 H), 6.81 (dd, J = 8.1 Hz, J′ = 1.2 Hz, 2 H), 6.63 (td, J = 7.5 Hz, J′ = 1.2 Hz, 2 H), 5.00 (br s, 4 H). 13C NMR (75.3 MHz, DMSO-d
6): δ = 162.5, 149.3, 144.5, 140.0, 128.0, 127.7, 125.2, 122.7, 116.7, 116.4.
Step 2: Macrobislactamization Reaction for the Synthesis of 1, 2 and 3
Mukaiyama salt (2-chloromethylpyridinium iodide; 0.75 mmol, 2.5 equiv), tri-n-butylamine (1.5 mmol, 5.0 equiv) and the diamine derivative (6 or 7, 0.3 mmol, 1.0 equiv) were successively added to a solution of diacid derivative (isophthalic or dipicolinic acid, 0.30 mmol, 1.0 equiv) in CH2Cl2 (100 mL) under an inert atmosphere. The reaction mixture was stirred at reflux temperature for 16 h. After cooling to r.t., Et2O (200 mL) was added providing a white precipitate that was collected by filtration. The corresponding tetraaromatic tetraamide macrocycles (1, 2 or 3) were obtained as a white powder, with chemical yields given in Table
[1]
. Compound 1: mp 310 °C. IR (KBr): 3240 (NH), 1648 (CO), 1603 (NH), 1303 (CN), 755 (CH) cm-1. 1H NMR (300 MHz, DMSO-d
6): δ = 10.18 (br s, 4 H), 9.16 (d, J = 5.4 Hz, 2 H), 8.50-8.63 (m, 3 H), 8.38 (d, J = 8.1 Hz, 2 H), 8.20 (d, J = 8.4 Hz, 1 H), 7.52-7.70 (m, 4 H), 7.22-7.40 (m, 4 H). EI-MS: m/z (%) = 477 (67) [M + H+]. Compound 2: mp 304 °C. IR (KBr): 3474 (NH), 3245 (CH), 1685 (CO), 1591 (NH), 1307 (CN), 749 (CH) cm-1. 1H NMR (300 MHz, DMSO-d
6): δ = 10.94 (s, 2 H), 10.17 (s, 2 H), 8.24 (br t, 3 H), 8.00-8.12 (m, 1 H), 7.68 (br d, 2 H), 7.52 (m, 4 H), 7.21 (m, 4 H), 6.75 (m, 1 H). EI-MS: m/z (%) = 479 (100) [M + H+], 496 (8) [M + NH4
+]. Compound 3: mp 196 °C. IR (KBr): 3423 (NH), 3247 (CH), 1677 (CO), 1600 (NH), 1308 (CN), 754 (CH) cm-1. 1H NMR (300 MHz, DMSO-d
6): δ = 11.00 (s, 4 H), 8.40 (d, J = 8.0 Hz, 4 H), 8.30 (t, J = 7.7 Hz, 2 H), 7.82-7.86 (m, 4 H), 7.37-7.41 (m, 4 H). EI-MS: m/z (%) = 479 (30) [M + H+], 496 (28) [M + NH4
+].
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