Synthesis of Novel Molecular Clips Based on Diethoxycarbonyl Glycoluril

Abstract

A novel class of molecular clips was synthesized, which are soluble in most non-polar organic solvents. Aromatic amines and diethoxycarbonyl glycoluril were used for the first time in this type of reaction. All reaction products gave satisfying ¹H NMR, ¹³C NMR, MS, and IR spectra. In addition, the structure and conformation of 4d were confirmed by single crystal X-ray diffraction.

Key words

molecular clips - diethoxycarbonyl glycoluril - aromatic amines - synthetic receptors - conformers

References and Notes

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• 23 Crystal data for compound 4d: C₂₈H₃₂N₆O₈, M = 580.60, triclinic, a = 7.5266 (18), b = 13.438 (3), c = 14.167 (3) Å, a = 87.547 (4)°, β = 83.627 (4)°, γ = 81.942 (4)°, U = 1409.4 (6) ų, T = 292 (2) K, space group P-1, Z = 2, µ (Mo-K_α) = 0.102 mm^-1, 7110 reflections measured, 4870 unique (R _int = 0.0216) which were used in all calculations. The final wR ₂ (F ₂) was 0.1816 (all data). CCDC-281947 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: [phone]; email: [e-mail]]

22

Compound 4a: IR (KBr): 3457 (m), 2850 (m), 1762 (s), 1731 (s), 1464 (m), 1419 (m), 1389 (m), 1251 (s), 1173 (m), 1054 (m), 950 (m), 761 (m), 699 (m) cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.12 (t, 4 H), 6.94-6.88 (m, 6 H), 5.49 (d, 4 H, J = 13.2 Hz), 4.56 (d, 4 H, J = 13.2 Hz), 4.33 (q, 4 H, J = 6.8 Hz), 1.35 (t, 6 H, J = 6.8 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 165.13, 157.32, 145.86, 129.24, 121.71, 117.73, 76.13, 63.33, 58.31, 13.84. MS: m/z (%) = 521 (100) [M⁺], 416 (68), 387 (95), 343 (61), 240 (31), 105 (93).
Compound 4b: IR (KBr): 3456 (m), 2861 (m), 1763 (s), 1731 (s), 1522 (m), 1465 (m), 1418 (m), 1392 (m), 1247 (s), 1176 (m), 1052 (m), 944 (m), 809 (m) cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 6.92 (d, 4 H), 6.83 (d, 4 H), 5.43 (d, 4 H, J = 13.2 Hz), 4.53 (d, 4 H, J = 13.2 Hz), 4.32 (q, 4 H, J = 6.8 Hz), 2.24 (s, 6 H), 1.34 (t, 6 H, J = 6.8 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 165.18, 157.30, 143.58, 130.92, 129.73, 117.92, 76.09, 63.26, 58.51, 20.44, 13.81. MS: m/z (%) = 549 (100) [M⁺], 400(91), 356 (41), 118 (88).
Compound 4c: IR (KBr): 3453 (m), 2919 (m), 2847 (m), 1765 (s), 1727 (s), 1465 (m), 1412 (m), 1384 (m), 1248 (s), 1158 (m), 1057 (m), 936 (m), 782 (m), 701 (m) cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.04 (2 H), 6.80-6.72 (m, 6 H), 5.46 (d, 4 H, J = 13.2 Hz), 4.51 (d, 4 H, J = 13.2 Hz), 4.33 (q, 4 H, J = 7.2 Hz), 2.20 (s, 6 H), 1.35 (t, 6 H, J = 7.2 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 165.22, 157.44, 145.98, 139.00, 128.98, 122.84, 118.81, 115.03, 76.09, 63.34, 58.68, 21.44, 13.87. MS: m/z (%) = 549 (100) [M⁺], 400(97), 356 (49), 118 (60).
Compound 4d: IR (KBr): 3451 (s), 2987 (m), 2939 (m), 1768 (s), 1729 (s), 1515 (s), 1463 (m), 1416 (m), 1284 (m), 1242 (s), 1179 (m), 1032 (m), 824 (m) cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 6.93 (d, 4 H, J = 8.8 Hz), 6.71 (d, 4 H, J = 8.8 Hz), 5.34 (d, 4 H, J = 12.8 Hz), 4.53 (d, 4 H, J = 12.8 Hz), 4.33 (q, 4 H, J = 7.2 Hz), 3.73 (s, 6 H), 1.34 (t, 6 H, J = 7.2 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 165.21, 157.48, 154.91, 139.73, 120.12, 114.40, 76.05, 63.27, 59.32, 55.20, 13.83. MS: m/z (%) = 581 (100)[M⁺], 416 (41), 372 (26), 191 (27), 176 (30), 134 (99), 120 (71).
Compound 4e: IR (KBr): 3457 (m), 2962 (m), 1753 (s), 1737 (s), 1261 (s), 1093 (s), 1050 (s), 802 (s) cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.05 (d, 4 H, J = 8.8 Hz), 6.90 (d, 4 H, J = 8.8 Hz), 5.41 (d, 4 H, J = 12.8 Hz), 4.49 (d, 4 H, J = 12.8 Hz), 4.33 (q, 4 H, J = 7.2 Hz), 2.78-2.82 (m, 2 H), 1.34 (d, 6 H, J = 7.2 Hz), 1.18 (d, 12 H, J = 2.4 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 165.32, 157.63, 144.01, 142.63, 127.13, 118.49, 76.14, 63.33, 59.20, 33.21, 23.95, 13.92. MS: m/z (%) = 605 (100) [M⁺], 428 (74), 385 (45), 287 (28), 202 (28), 146 (40), 132 (83).
Compound 4f: IR (KBr): 3411 (s), 1765 (s), 1722 (s), 1498 (m), 1468 (m), 1415 (s), 1238 (s), 1048 (m), 903 (m), 833 (m), 717 (m) cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.02 (d, 4 H, J = 8.8 Hz), 6.82 (d, 4 H, J = 8.8 Hz), 5.48 (d, 4 H, J = 14.0 Hz), 4.62 (d, 4 H, J = 14.0 Hz), 4.33 (q, 4 H, J = 7.2 Hz), 1.35 (t, 6 H, J = 7.2 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 164.93, 157.10, 144.22, 129.21, 126.47, 118.46, 76.20, 63.53, 57.61, 13.87. MS: m/z (%) = 590 (100) [M⁺], 538 (21), 420 (70), 376 (27), 202 (25), 191 (9), 189 (21), 145 (65).
Compound 4g: IR (KBr): 3448 (m), 2981 (w), 2936 (w), 1746 (s), 1726 (s), 1496 (m), 1467 (m), 1417 (m), 1280 (m), 1239 (s), 1094 (m), 1047 (m), 975 (m), 908 (m), 818 (m) cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.18 (d, 4 H, J = 8.8 Hz), 6.77 (d, 4 H, J = 8.8 Hz), 5.48 (d, 4 H, J = 14.0 Hz), 4.62 (d, 4 H, J = 14.0 Hz), 4.34 (q, 4 H, J = 7.2 Hz), 1.35 (t, 6 H, J = 7.2 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 164.87, 157.04, 144.77, 132.15, 118.88, 113.93, 76.16, 63.51, 57.53, 13.86. MS: m/z (%) = 679 (73) [M⁺], 467 (58), 466 (10), 464 (66), 423 (30), 420 (26), 409 (4), 243 (10), 241 (24), 240 (63), 182 (100).
Compound 4h: IR (KBr): 3426 (m), 1749 (s), 1727 (s), 1493 (m), 1466 (m), 1417 (m), 1279 (m), 1245 (s), 1174 (m), 1093 (m), 909 (m), 812 (m), 694 (m) cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.37 (d, 4 H, J = 7.6 Hz), 6.66 (d, 4 H, J = 7.6 Hz), 5.47 (d, 4 H, J = 14.0 Hz), 4.61 (d, 4 H, J = 14.0 Hz), 4.33 (q, 4 H, J = 7.2 Hz), 1.34 (t, 6 H, J = 7.2 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 164.95, 157.11, 145.62, 138.20, 119.46, 84.29, 76.24, 63.56, 57.62, 13.94. MS: m/z (%) = 723 (93) [M⁺], 647 (13), 513 (70), 387 (18), 231 (100), 208 (48).