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.

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

References and Notes

1 Diederich F. Cyclophanes   The Royal Society of Chemistry; Cambridge: 1991. 

2 Lehn JM. Supramolecular Chemistry, Concepts and Perspectives   VCH; Weinheim: 1995. 

3 Purse BW. Rebek J. Proc. Natl. Acad. Sci. U.S.A.  2005,  102:  10777 

4a Rebek J. Science  1987,  235:  1478 

4b Shimizu KD. Dewey TM. Rebek J. J. Am. Chem. Soc.  1994,  116:  5145 

4c Warrener RN. Margetic D. Amarasekara AS. Butler DN. Mahadevan IB. Russell RA. Org. Lett.  1999,  1:  199 

5 Adrian JC. Wilcox CS. J. Am. Chem. Soc.  1989,  111:  8055 

6 Sanderson PEJ. Kilburn JD. Still WC. J. Am. Chem. Soc.  1989,  111:  8314 

7 Chen CW. Whitlock HW. J. Am. Chem. Soc.  1978,  100:  4921 

8 Zimmerman SC. VanZyl CM. J. Am. Chem. Soc.  1987,  109:  7894 

9 Zimmerman SC. Wu W. J. Am. Chem. Soc.  1989,  111:  8054 

10 Klärner FG. Kahlert B. Acc. Chem. Res.  2003,  36:  919 

11 Harmata M. Acc. Chem. Res.  2004,  37:  862 

12a Klärner FG. Lobert M. Naatz U. Bandmann H. Boese R. Chem.-Eur. J.  2003,  9:  5036 

12b Wu A. Chakraborty A. Fettinger JC. Flowers RA. Isaacs L. Angew. Chem. Int. Ed.  2002,  41:  4028 

13 Dixon RP. Geib SJ. Hamilton AD. J. Am. Chem. Soc.  1992,  114:  365 

14a Paliwal S. Geib S. Wilcox CS. J. Am. Chem. Soc.  1994,  116:  4497 

14b Lagona J. Fettinger JC. Isaacs L. Org. Lett.  2003,  5:  3745 

15a Sijbesma RP. Nolte RJM. J. Org. Chem.  1991,  56:  3122 

15b Sijbesma RP. Wijmenga SS. Nolte RJM. J. Am. Chem. Soc.  1992,  114:  9807 

15c Sijbesma RP. Kentgens APM. Lutz ETG. van der Maas JH. Nolte RJM. J. Am. Chem. Soc.  1993,  115:  8999 

15d Reek JNH. Priem AH. Engelkamp H. Rowan AE. Elemans JAAW. Nolte RJM. J. Am. Chem. Soc.  1997,  119:  9956 

15e Rowan AE. Elemans JAAW. Nolte RJM. Acc. Chem. Res.  1999,  32:  995 

15f Jansen RJ. de Gelder R. Rowan AE. Scheeren HW. Nolte RJM. J. Org. Chem.  2001,  66:  2643 

16 Savostianoff DFr. inventors; Patent Appl.  2 291 203.  ; Chem. Abstr. 1977, 86, 121377n

17 Mock WL. Manimaran T. Freeman WA. Kuksuk RM. Maggio JE. Williams DH. J. Org. Chem.  1985,  50:  60 

18 Liu S. Wu X. Zhang S. Yao J. Liang F. Wu C. New J. Chem.  2004,  28:  562 

19 Burnett CA. Logona J. Wu A. Shaw JA. Coady D. Fettinger JC. Day AI. Isaacs L. Tetrahedron  2003,  59:  1961 

20 Smeets JWH. Sijbesma RP. Niele FGM. Spek AL. Smeets WJJ. Nolte RJM. J. Am. Chem. Soc.  1987,  109:  928 

21 Nunen JLM. Nolte RJM. J. Chem. Soc., Perkin Trans. 2  1997,  1473 

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).

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]]