D. A. Jose et al. / Tetrahedron 63 (2007) 12007–12014
12013
different wavelengths. For fluorescence decay measure-
ments, 10,000 peak counts were collected in 512 channels
with a time increment of 40 ps/channel and each measure-
ment was repeated three times. The measured fluorescence
decays were analyzed using the iterative reconvolution
method with the aid of the Marquardt algorithm as described
by Bevington.17 The criteria for a good fit were judged by
statistical parameters such as the reduced c2 being close to
unity and the random distribution of the weighted residuals.
121.2, 120.0, 118.6, 117.6, 117.2. FTIR (KBr; cmꢀ1):
3360 (NH), 3337 (NH), 1697 (–C]O). ESI MS [m/z (posi-
tive ion mode)]: 330.1 (M+Na+, 100%). Elemental analysis
for C17H13N3O3: calculated: C, 66.44; H, 4.26; N, 13.67.
Found: C, 66.40; H, 4.21; N, 13.61. L3 was also synthesized
by following another methodology (Supplementary data). In
both the methods, the yield was the same.
Acknowledgements
4.6. Synthesis
The Department of Science and Technology (DST) and the
Board of Research in Nuclear Science (BRNS), Government
of India, supported this work. Authors D.A.J. and D.K.K.
wish to acknowledge CSIR for Sr. Research Fellowship.
A.D., B.G., and H.N.G. wish to thank Dr. P. K. Ghosh
(CSMCRI, Bhavnagar) and Dr. T. Mukherjee (BARC,
Mumbai) for their keen interest in this work.
4.6.1. Synthesis of 1-naphthalen-1-yl-3-(2-nitro-phenyl)-
urea (L1). To a stirred dry THF solution (80 ml) of 1-amino
naphthalene (1.0 g, 6.99 mmol) and triethylamine (2 ml,
14 mmol), triphosgene (1.84 g, 6.2 mmol) dissolved in
20 ml of dry THF was added slowly to this solution under
nitrogen atmosphere at ice-cooled condition. The mixture
was allowed to stir at room temperature. After 30 min, 2-nitro
aniline (0.964 g, 6.99 mmol) dissolved in 40 ml of dry THF
was added to this reaction mixture. The reaction mixture
was stirred at room temperature for one day and filtered.
The solid obtained was washed with methanol and water.
The desired compound was isolated as a yellow solid (1.15 g,
Supplementary data
Crystal data for receptor L3 and L3$CH3COOL (CCDC
616327 and 616328), UV–vis, emission and 1H NMR titra-
tion spectra, job plots, and final co-ordinates of the opti-
mized structures are available free of charge via the
internet. Supplementary data associated with this article
1
60%). H NMR (200 MHz, DMSO-d6) d (ppm): 9.790 (s,
1H, –NH), 9.710 (s, 1H, –NH), 8.256 (d, 1H, HA, J¼8.4 Hz),
8.15 (d, 1H, J¼7.6 Hz), 8.096 (t, 1H, J¼8.2 Hz), 7.932 (d,
1H, J¼6 Hz), 7.818 (d, 1H, J¼7.6 Hz), 7.73–7.68 (m, 2H),
7.56 (m, 3H), 7.21 (t, 1H, J¼7.8 Hz). 13C NMR (DMSO-
d6) d (ppm): 153.1, 138.4, 135.0, 134.8, 133.9, 133.7,
128.5, 127.4, 126.3, 126.1, 125.9, 125.5, 124.7, 123.2,
124.6, 123.2, 122.7, 122.3, 120.3. FTIR (KBr; cmꢀ1):
3329 (NH), 3272 (NH), 1651 (–C]O). ESI MS [m/z (posi-
tive ion mode)]: 329.5 (M+Na+, 40%). Elemental analysis
for C17H13N3O3: calculated: C, 66.44; H, 4.26; N, 13.67.
Found: C, 66.21; H, 4.20; N, 13.61.
References and notes
1. (a) Ullman’s Encyclopedia of Industrial Chemistry, 6th ed.;
Wiley-VCH: New York, NY, Germany, 1998; (b) Krik, K. L.
Biochemistry of Halogens and Inorganic Halides; Plenum:
New York, NY, 1991; p 59l.
4.6.2. Synthesis of 1-naphthalen-1-yl-3-(3-nitro-phenyl)-
urea (L2). The methodology adopted for the synthesis of
receptor L2 was the same as that mentioned for L1. Instead
of 2-nitro aniline, here 3-nitroaniline was used. Yield
2. (a) Rurack, K.; Resch-Genger, U. Chem. Soc. Rev. 2002, 31,
116–127; (b) Tajc, S. G.; Miller, B. L. J. Am. Chem. Soc.
2006, 128, 2532–2533.
3. For an overview on anion sensors please see following articles:
(a) Supramolecular Chemistry of Anions; Bianchi, E.,
Bowman-James, K., Garcia-Espana, E., Eds.; Wiley-VCH:
New York, NY, 1997; (b) Gale, P. A. Amide and Urea Based
Anion Receptors. In Encyclopedia of Supramolecular
Chemistry; Marcel Dekker: New York, NY, 2004; p 31; (c)
Sukasai, C.; Tuntulani, T. Chem. Soc. Rev. 2003, 32, 192–
202; (d) Gale, P. A. Acc. Chem. Res. 2006, 39, 465–475; (e)
Martinez-Manez, R.; Sancenon, F. Chem. Rev. 2003, 103,
4419–4476; (f) De Silva, A. P.; Gunaratne, H. Q. N.;
Gunnlaugsson, T.; Hauxley, A. J. M.; McCoy, C. P.;
Rademacher, J. T.; Rice, T. E. Chem. Rev. 1997, 97, 1515–
1566; (g) Beer, P. D.; Gale, P. A. Angew. Chem., Int. Ed.
2001, 40, 486–516; (h) Yoon, J.; Kim, S. K.; Singh, J.; Kim,
K. S. Chem. Soc. Rev. 2006, 35, 355–360; (i) Gunnlaugsson,
T.; Glynn, M.; Tocci, G. M.; Kruger, P. E.; Pfeffer, F. M.
Coord. Chem. Rev. 2006, 250, 3094–3117.
1
(1.15 g, w62%). H NMR (200 MHz, DMSO-d6) d (ppm):
9.799 (s, 1H, –NH), 9.002 (s, 1H, –NH), 8.248 (d, 2H,
J¼9.2 Hz), 8.148 (d, 1H), 7.987 (d, 2H), 7.774 (d, 2H,
J¼9.2 Hz), 7.627–7.469 (m, 4H). 13C NMR (DMSO-d6)
d (ppm): 152.9, 148.2, 141.1, 133.8, 130.1, 128.4, 125.9,
125.8, 125.8, 124.2, 123.2, 126.4, 121.4, 118.4, 116.3,
112.0. FTIR (KBr; cmꢀ1): 3295 (NH), 1644 (–C]O).
ESI MS [m/z (positive ion mode)]: 330.3 (M+Na+,
20%). Elemental analysis for C17H13N3O3: calculated:
C, 66.44; H, 4.26; N, 13.67. Found: C, 66.31; H, 4.34;
N, 13.73.
4.6.3. Synthesis of 1-naphthalen-1-yl-3-(4-nitro-phenyl)-
urea (L3). Receptor L3 was also synthesized by the same
procedure explained above by using 4-nitroaniline. Yield
1
(61%). H NMR (200 MHz, DMSO-d6) d (ppm): 9.762 (s,
1H, –NH), 8.981 (s, 1H, –NH), 8.19 (d, 2H, J¼9.0 Hz),
8.072 (d, 1H, J¼8.2 Hz), 7.93 (d, 2H, J¼7.0 Hz), 7.92 (d,
1H, J¼7.2 Hz), 7.71 (d, 2H, J¼9.0 Hz), 7.70–7.67 (m,
1H), 7.59–7.44 (m, 2H). 13C NMR (DMSO-d6) d (ppm):
152.5, 146.51, 140.1, 133.6, 133.4, 133.0, 126.3, 126.2,
126.0, 125.9, 125.6, 125.7, 125.1, 124.9, 123.9, 121.6,
4. (a) Gunnlaugsson, T.; Davis, A. P.; Hussey, G. M.; Tierney, J.;
Glynn, M. Org. Biomol. Chem. 2004, 2, 1856–1863; (b) Pfeffer,
F. M.; Seter, M.; Lewcenko, N.; Barnett, N. W. Tetrahedron
Lett. 2006, 47, 5241–5244; (c) Lee, J. Y.; Cho, E. J.;
Mukamel, S.; Nam, K. C. J. Org. Chem. 2004, 69, 943–950;
(d) Xu, G.; Tarr, M. A. Chem. Commun. 2004, 1050–1052;