connected to a 996 photodiode array detector with HPLC-grade
methanol, or acetonitrile as carrier solvents. Accurate molecular
weights were determined by a peak-matching method, using
leucine enkephaline (H-Tyr-Gly-Gly-Phe-Leu-OH) as the stan-
dard internal reference (m/z = 556.2771); all accurate mass were
calculated to ≤ 5 ppm. Melting points were determined using an
Electrothermal IA9000 digital melting point apparatus. Infrared
spectra were recorded on a Mattson Genesis II FTIR spectrometer
equipped with a Gateway 2000 4DX2–66 workstation and on
a Perkin Elmer Spectrum One FT-IR Spectrometer equipped
with Universal ATR sampling accessory. Elemental analysis was
carried out at the Microanalysis Laboratory, School of Chemistry
and Chemical Biology, University College Dublin.
125.55, 124.55, 123.93, 123.64, 122.72, 122.00, 120.23, 108.19,
104.55, 45.48, 34.27, 13.30; IR (cm-1): 3451.78, 3333.18, 3243.50,
2978.34, 1678.93, 1638.82, 1587.71, 1536.03, 1513.08, 1373.65,
1322.93, 1250.81, 1181.00, 1156.70, 1103.66, 1063.36, 878.42,
847.56, 823.46, 772.93, 499.47; MS (ES) Calcd for (M + H+) m/z
549.16, Found 549.38
Synthesis of 3
To a solution of 7 (0.12 g, 0.33 mmol) in dry chloroform (30 ml)
was added 4-(trifluoromethyl)phenyl isothiocyanate (0.09 g,
0.43 mmol) and the reaction stirred for 18 h. The resulting
solution was then washed with 0.5 M HCl and water and the
organic layer was dried over MgSO4, filtered and evaporated
to dryness. Purification by flash column chromatography on
neutral silica (chloroform) yielded 3 as a bright yellow solid
(0.09 g, 49%), mp 182–184 ◦C. Found: C 62.34, H 4.23, N
9.81%. C30H25F3N4O2S·H2O requires: C 62.06, H 4.69, N 9.65%.
dH (400 MHz, CDCl3): 1.33 (3H, t, J = 7.0 Hz, CH3), 3.15 (2H,
t, J = 6.5 Hz, NHCH2CH2), 3.74 (2H, br m, NHCH2), 4.24 (2H,
q, J = 7.0 Hz, CH2CH3), 5.26 (1H, br, NHCH2), 6.79 (1H, d, J =
8.0 Hz, Ar-H), 7.37 (4H, m, Ar-H), 7.58–7.67 (5H, m, Ar-H), 7.85
(1H, 7.85 (1H, br, NH), 7.93 (1H, br, NH), 7.96 (1H, d, J = 8.5 Hz,
Ar-H), 8.49 (1H, d, J = 8.5 Hz, Ar-H), 8.59 (1H, d, J = 7.5 Hz,
Ar-H); dC (100 MHz, CDCl3): 12.9, 34.0, 34.7, 43.9, 104.0, 110.7,
119.9, 122.0, 122.9, 123.7, 124.5, 125.0, 125.3, 126.0, 129.1, 129.3,
129.7, 130.6, 133.7, 135.0, 137.4, 140.3, 148.3, 163.4, 163.9, 179.5;
m/z 563 (M + H)+; umax/cm-1 3467, 3382, 3341, 3231, 2978, 2931,
1691, 1637, 1575, 1545, 1515, 1432, 1395, 1369, 1345, 1329, 1247,
1165, 1103, 1065, 1014, 840, 770, 756.
Synthesis of 1
To a solution of 6 (0.250 g, 0.723mmol) in dry chloroform (30 ml)
was added phenyl isothiocyanate (0.108 g, 0.796 mmol) under an
argon atmosphere. The resulting solution was stirred overnight
at room temperature then concentrated in vacuum. The residue
was extracted with chloroform and the organic phase was washed
with 1M HCl, water and brine, dried over sodium sulfate, and
evaporated to dryness. The product was purified by flash column
chromatography on silica gel, eluting with chloroform to afford 1
(0.191 g, 58%) as light yellow solid, mp 204–206 ◦C. Anal. calcd for
C28H24N4O2S·CH2Cl2.CHCl3: C, 55.40; H, 4.34; N, 8.61. Found:
C, 53.89; H, 3.83; N, 8.40. 1H-NMR (400 MHz, DMSO-d6): 1.17
(t, 3H, J = 7.0Hz), 4.05 (q, 2H, J = 7.0Hz), 4.64 (d, 2H, J =5.2Hz),
6.71 (d, 2H, J = 8.5Hz), 7.11 (t, 1H, J= 7.5), 7.29–7.38 (m, 4H),
7.44–7.48 (m, 4H), 7.72 (t, 1H, J = 7.5), 8.20 (d, 1H, J = 8.5),
8.43 (bs, -NH), 8.47 (d, 1H, J = 8.5Hz), 8.78 (d, 1H, J = 8.5Hz),
9.72 (bs, -NH). 13C-NMR (400 MHz, DMSO-d6): 179.62, 163.53,
162.70, 150.38, 143.41, 138.08, 134.90, 133.92, 130.67, 129.38,
128.49, 127.14, 125.56, 125.52, 124.51, 123.93, 122.75, 122.06,
120.33, 113.02, 108.28, 104.58, 45.57, 34.25, 13.30; IR (cm-1):
3358.25, 2974.67, 2930.51, 2108.40, 1679.89, 1639.20, 1579.42,
1536.61, 1390.62, 1346.46, 1248.30, 1181.13, 1100.96, 1065.87,
910.04, 876.30, 773.32, 757.12, 694.44, 581.43; MS (ES) Calcd
for (M + H+) m/z 481.1698, Found 481.2174.
Acknowledgements
The authors would like to thank Deakin University for financial
support to FMP in the form of an overseas study programme to
visit Trinity College Dublin to finalise this work, and travelling
support for TG. We also thank IRCSET for a BASIC research
grant awarded to PEK and TG for this project. PEK is also
thankful for generous support from the Department of Chemistry,
University of Canterbury.
Synthesis of 2
Notes and references
To a solution of 6 (0.250 g, 0.723mmol) in dry chloroform (30 ml)
was added 4-(trifluoromethyl)phenyl isothiocyanate (0.161 g,
0.796 mmol) under an argon atmosphere. The resulting solution
was stirred overnight at room temperature then concentrated
in vacuum. The residue was extracted with chloroform and the
organic phase was washed with 1M HCl, water and brine, dried
over sodium sulfate, and evaporated to dryness. The residue was
purified by flash column chromatography on silica gel, eluting with
chloroform to afford 2 (0.245 g, 60%) as light yellow solid, mp 157–
159 ◦C. Anal. calcd for C29H25F3N4O3S·CHCl3:C, 53.94; H, 3.62;
N, 8.39. Found: C, 53.89; H, 3.83; N, 8.40.1H-NMR(400 MHz,
DMSO-d6): 1.18 (t, 3H, J = 7.0Hz), 4.05 (q, 2H, J = 7.0Hz),
4.66 (d, 2H, J =5.2Hz), 6.72 (d, 1H, J = 8.5Hz), 7.38–7.47 (m,
4H), 7.65–7.76 (m, 4H), 8.29 (d, 1H, J = 8.5), 8.45 (bs, NH), 8.47
(d, 2H, J = 7.5Hz), 8.74 (d, 1H, J = 8.5Hz), 10.02 (bd, -NH).
13C-NMR (400 MHz, DMSO-d6): 179.54, 163.51, 162.67, 150.35,
143.38, 138.04, 134.88, 133.94, 129.35, 128.46, 127.11, 125.58,
1 J. L. Sessler, P. A. Gale, and W. S. Cho, Anion Receptor Chemistry, Royal
Society of Chemistry, Cambridge UK. 2006; P. A. Gale, S. E. Garcia-
Garrido and J. Garric, Chem. Soc. Rev., 2008, 37, 151; P. Padros and R.
Quesada, Supramol. Chem., 2008, 20, 201; P. A. Gale and R. Quesada,
Coord. Chem. Rev., 2006, 250, 3219; M. H. Filby and J. W. Steed, Coord.
Chem. Rev., 2006, 250, 3200; E. A. Katayev, Y. A. Ustynyuk and J. L.
Sessler, Coord. Chem. Rev., 2006, 250, 2952; A. Gale, Acc. Chem. Res.,
2006, 39, 465; J. W. Steed, Chem. Commun., 2006, 2637; J. P. Leonard
and T. Gunnlaugsson, J. Fluoresc., 2005, 15, 585; R. Mart´ınez-Ma´n˜ez
and F. Sanceno´n, Chem. Rev., 2003, 103, 4419.
2 T. Gunnlaugsson, M. Glynn, G. M. Tocci (ne´e Hussey), P. E. Kruger
and F. M. Pfeffer, Coord. Chem. Rev., 2006, 250, 3094; T. Gunnlaugsson,
H. D. P. Ali, M. Glynn, P. E. Kruger, G. M. Hussey, F. M. Pfeffer,
C. M. G. dos Santos and J. Tierney, J. Fluoresc., 2005, 15, 287.
3 C. M. G. dos Santos, T. McCabe, G. W. Watson, P. E. Kruger and
Thorfinnur Gunnlaugsson, J. Org. Chem., 2008, 73, 9235; M. Duke,
J. E. O’Brien, T. McCabe and T. Gunnlaugsson, Org. Biomol. Chem.,
2008, 6, 4089; E. Quinlan, S. E. Matthews and T. Gunnlaugsson, J. Org.
Chem., 2007, 72, 7497; F. M. Pfeffer, P. E. Kruger and T. Gunnlaugsson,
Org. Biomol. Chem., 2007, 5, 1894; E. Quinlan, S. E. Matthews and T.
Gunnlaugsson, Tetrahedron Lett., 2006, 47, 9333; F. Y. Wu, Z. Li, L.
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The Royal Society of Chemistry 2009
Org. Biomol. Chem., 2009, 7, 3447–3454 | 3453
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