290 JOURNAL OF CHEMICAL RESEARCH 2007
7.5
7.3
7.1
6.9
6.7
6.5
6.3
6.1
5.9
5.7
5.5
Rosette
Rosette
Porphyrin
Dimer
Fig. 6 Artists sketch of the predicted dimeric aggregate
formed from rosette 11 and zinc porphyrin dimer 4.
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Received 6 March 2007 ; accepted 10 May 2007
Paper 07/4518 doi: 10.3184/030823407X215636
[Porphyrin]/[Porphyrin]+[Rosette]
Fig. 5 Plot of the chemical shift of the pyridyl Hb atoms versus
the mole fraction of porphyrin.
References
1
G.M. Whitesides, E.E. Simanek, J.P. Mathias, C.T. Seto, D.N. Chin, M.
Mammen and D.M. Gordon, Acc. Chem. Res., 1995, 28, 37.
G.M. Whitesides, J.P. Mathias and C.T. Seto, Science, 1991, 254, 1312.
A. Ranganathan, V.R. Pedireddi and C.N.R. Rao, J. Am. Chem. Soc.,
1999, 121, 1752; Y. Wang, B. Wei and Q. Wang, J. Crystallogr. Spectrosc.
Res., 1990, 20, 79.
J.P. Mathias, E.E. Simanek, C.T. Seto and G.M. Whitesides, Angew.
Chem. Int. Ed. Engl., 1993, 32, 1766.
C.T. Seto and G.M. Whitesides, J. Am. Chem. Soc., 1993, 115, 905.
J. Mathias, C.T. Seto, E.E. Simanek and G.M. Whitesides, J. Am. Chem.
Soc., 1994, 116, 1725.
R.H. Vreekamp, J.P.M. van Duynhoven, M. Hubert, W. Verboom and
D.N. Reinhoudt, Angew. Chem. Int. Ed. Engl., 1996, 35, 1215.
K.A. Jolliffe, P. Timmerman and D.N. Reinhoudt, Angew. Chem. Int. Ed.
Engl., 1999, 38, 933.
K.C. Russell, E. Leize, A. van Dorsselaer and J.-M. Lehn, Angew. Chem.
Int. Ed. Engl., 1995, 34, 209.
with H2O, and dried in a vacuum oven to yield the title compound
(0.82 g, 98%) as a grey powder, m.p. 209–211°C (from methanol)
2
3
l
max(DMSO)/nm 280 (log e 4.3); nmax(KBr)/cm-1 3406 m, 3299 m,
3190br, 2962 m, 1620 m, 1571 s, 1500 s, 1410 s, 831 m, 809 m, 801 m,
552 m and 536 m; dH(250 MHz; DMSO-d6) 1.26 (9H, s, C(CH3)3),
4.05 (1H, s, acetylenic H), 6.70 (2H, br s, NH2), 7.30 (4H, m, Ph),
7.60 (2H, br d, Ph), 7.80 (2H, br d, Ph), 9.05 (1H, s, NH) and 9.30
(1H, s, NH); dc(62.9 MHz; DMSO-d6) 31.3, 38.5, 79.5, 84.1, 113.9,
119.2, 120.2, 125.1, 132.0, 137.4, 141.3, 144.2, 163.3, 164.5 and
166.8; m/z (ES+) 359.1976 ([M+ + H], C21H22N6 requires 359.1979);
m/z (EI+) 358.2 (M+, 71%) and 342.2 (100).
4
5
6
7
8
9
2-Amino-4-(4-tert-butylphenylamino)-6-{4-[(4-pyridyl)ethynyl]
phenylamino}-1,3,5-triazine 10: A degassed solution of compound
9 (0.5 g, 1.4 mmol), 4-bromopyridine hydrochloride (0.28 g,
1.5 mmol), (PPh3)2PdCl2 and copper(I)iodide in catalytic amounts; in
freshly distilled Et3N (40 ml) was refluxed for 1 day under anhydrous
conditions. The reaction mixture was then concentrated and dry-loaded
onto a column with THF. The column was eluted with dichloromethane
then with tetrahydrofuran to give the crude product. Repeated extraction
into ethyl acetate and concentration followed by drying in a vacuum
oven at 50°C gave the title compound (100 mg, 17%) as a yellow/
orange crystalline solid, m.p. 140–144°C (from tetrahydrofuran)
10 C.M. Drain, K.C. Russell and J.-M. Lehn, Chem. Commun., 1996, 337.
11 J.A. Zerkowski, C.T. Seto and G.M. Whitesides, J. Am. Chem. Soc., 1992,
114, 5473.
12 M.J. Plater, J.P. Sinclair, S. Aiken, T. Gelbrich and M.B. Hursthouse,
Tetrahedron, 2004, 60, 6385.
13 P. Timmerman, R.H. Vreekamp, R. Hulst, W. Verboom, D.N. Reinhoudt,
K. Rissanen, K.A. Udachin and J. Ripmeester, Chem. Eur. J., 1997, 3, 1823.
14 X.-B. Shao, X.-K. Jiang, S.-Z. Zhu and Z.-T. Li, Tetrahedron, 2004, 60,
9155.
15 M.J. Plater, S. Aiken and G. Bourhill, Tetrahedron, 2002, 58, 2405.
16 M.J. Plater, S. Aiken and G. Bourhill, Tetrahedron Lett., 2001, 42, 2225.
17 X.-B. Shao, X.-K. Jiang, S.-Z. Zhu and Z.-T. Li, Tetrahedron, 2004, 60,
9155.
18 P.N. Taylor and H.L. Anderson, J. Am. Chem. Soc., 1999, 121, 11538.
19 A. Diaz-Ortiz, J. Elguero, C. Foces-Foces, A. de la Hoz, A. Moreno, S.
Moreno, A. Sanchez-Migallon and G. Valiente, Org. Biomol. Chem.,
2003, 1, 4451.
20 T.E.O. Screen, J.R.G. Thorne, R.G. Denning, D.G. Bucknall and H.L.
Anderson, J. Am. Chem. Soc., 2002, 124, 9712.
l
max(DMSO)/nm 272 (log e 4.4), 333 (4.1); nmax(KBr)/cm-1 2412 m,
3335 m, 3956 m, 2214 m, 1565 s, 1490vs, 1412 s, 1238 m and 825 m;
dH(250 MHz; DMSO-d6) 1.30 (18 d, C(CH3)3), 6.66 (2H, br s, NH2),
7.28 (2H, d, J = 8.9, Ph), 7.48 (4H, m, Ph), 7.63 (2H, br d, Ph), 8.6
(2H, br d, Ph), 9.06 (1H, s, NH) and 9.36 (1H, s, NH); dc(62.9 MHz;
DMSO-d6) (30.4, 31.3), (33.9, 34.4), 85.8, 94.8, 113.2, 120.2, 120.3,
124.9, 128.1, 132.2, 137.4, 139.2, 142.1, 144.2, 151.5, 164.3, 164.5
and 166.8; m/z (ES) 436.2242 ([M ]+, C26H26N7 requires 436.2244),
m/z (EI) 435.3 (M+, 75%) and 420.3 (100).
21 M.J. Plater, J.P. Sinclair, S. Aiken, V.E. Ronaldson, H.M. Ng, T. Gelbrich
and M.B. Hursthouse, Recent Res. Devel. Organic Chem., 2005, 9, 1.
22 M.J. Plater, J.P. Sinclair, S. Kemp, T. Gelbrich, M.B. Hursthouse and
C.J. Gómez-García, J. Chem. Res., 2006, 515.
Mass spectra were obtained by the EPSRC National Mass
Spectrometry Service Centre. Funding was from the
University of Aberdeen.
PAPER: 07/4518