S. Kumar et al. / Tetrahedron 63 (2007) 11724–11732
11731
20%, yellow solid, mp 121–123 ꢂC; FAB mass m/z 542 (M+);
1H NMR (CDCl3): d 3.58 (s, 2H, CH2S), 3.75 (s, 2H, CH2S),
4.13 (s, 2H, NH2, exchanges with D2O), 5.17 (br s, 2H,
CH2N), 5.21 (br s, 1H, NH, exchanges with D2O), 6.60 (t,
J¼7.5 Hz, 1H, ArH), 6.63–6.67 (m, 2H, ArH), 6.69 (d,
J¼7.5 Hz, 2H, ArH), 6.80 (d, J¼7.5 Hz, 2H, ArH), 7.04–
7.11 (m, 2H, ArH), 7.14 (d, J¼7.5 Hz, 1H, ArH), 7.21 (d,
J¼7.5 Hz, 1H, ArH), 7.39 (t, J¼7.5 Hz, 1H, ArH), 7.46–
7.54 (m, 4H, ArH), 8.06 (d, J¼9.0 Hz, 2H, ArH), 8.25 (d,
J¼9.0 Hz, 2H, ArH), 8.50 (s, 1H, ArH); 13C NMR (normal/
DEPT-135) (CDCl3): d 38.8 (ꢅve, CH2), 39.4 (ꢅve, CH2),
40.8 (ꢅve, CH2), 110.0 (+ve, ArCH), 114.8 (+ve, ArCH),
117.0 (+ve, ArCH), 117.2 (ab, ArC), 117.3 (ab, ArC),
118.4 (+ve, ArCH), 124.1 (+ve, ArCH), 125.2 (+ve,
ArCH), 126.5 (+ve, ArCH), 128.0 (+ve, ArCH), 128.6
(+ve, ArCH), 128.7 (+ve, ArCH), 129.2 (+ve, ArCH),
130.0 (+ve, ArCH), 130.5 (ab, ArC), 130.6 (+ve, ArCH),
131.5 (ab, ArC), 136.5 (+ve, ArCH), 136.6 (ab, ArC),
136.7 (+ve, ArCH), 136.9 (ab, ArC), 148.6 (ab, ArC),
149.1 (ab, ArC); IR lmax (cmꢅ1): 3463, 3363 (NH2). Found
C, 77.23; H, 5.38; N, 4.98; S, 11.61%. C35H30N2S2 requires
C, 77.45; H, 5.57; N, 5.16; S, 11.82%.
(+ve, ArCH), 125.6 (+ve, ArCH), 126.5 (+ve, ArCH),
125.7 (+ve, ArCH), 126.6 (+ve, ArCH), 126.7 (+ve,
ArCH), 128.1 (+ve, ArCH), 129.2 (+ve, ArCH), 130.1
(+ve, ArCH), 130.5 (ab, ArC), 130.8 (+ve, ArCH), 131.4
(ab, ArC), 131.6 (ab, ArC), 133.4 (ab, ArC), 136.6 (+ve,
ArCH), 137.0 (+ve, ArCH), 148.7 (ab, ArC), 149.3 (ab,
ArC). Found C, 78.93; H, 5.33; N, 4.56; S, 10.67%.
C39H32N2S2 requires C, 79.02; H, 5.44; N, 4.73; S, 10.82%.
4.4. UV–vis and fluorescence experiments
UV–vis absorption and fluorescence spectra were recorded
on Shimadzu UV-1601-PC spectrophotometer and Shi-
madzu RF1501 spectrofluorophotometer with a 1 cm quartz
cell at 25ꢃ0.1 ꢂC. The solutions of fluoroionophores 3, 8, 9,
and 12 and metal nitrates were prepared in double distilled
acetonitrile. A number of solutions containing 3/8/9/12
(5 mM) and different concentrations of metal nitrates were
prepared and kept at 25ꢃ1 ꢂC for 2 h before recording their
absorption or fluorescence spectra. The spectra obtained
were analyzed through curve fitting procedures by using
SPECFIT 3.0.36 to determine the stability constants and
the distribution of various species.
4.3.2. 1-[2-(Anthracenyl-9-methylamino)phenylthio-
methyl]-4-(2-aminophenylthiomethyl)-2,5-dimethoxy-
benzene (9). Yield 28%, yellow solid, mp 124–125 ꢂC
(CH2Cl2–MeOH); FAB mass m/z 602 (M+); 1H NMR
(CDCl3): d 3.11 (s, 3H, OCH3), 3.40 (s, 3H, OCH3), 3.65
(s, 2H, CH2S), 3.79 (s, 2H, CH2S), 5.19 (br s, 2H, NH2, ex-
changes with D2O), 5.21 (s, 2H, CH2N), 6.14 (s, 1H, ArH),
6.18 (s, 1H, ArH), 6.59–6.70 (m, 3H, ArH), 7.06–7.19 (m,
3H, ArH), 7.31 (d, J¼1.6 Hz, 1H, ArH), 7.48–7.54 (m, 5H,
ArH), 8.06 (d, J¼9.4 Hz, 2H, ArH), 8.27 (d, J¼9.4 Hz, 2H,
ArH), 8.51 (s, 1H, ArH); 13C NMR (normal/DEPT-135)
(CDCl3): d 33.5 (ꢅve, CH2), 34.0 (ꢅve, CH2), 41.0 (ꢅve,
CH2), 55.5 (+ve, OCH3), 55.8 (+ve, OCH3), 109.9 (+ve,
ArCH), 113.2 (+ve, ArCH), 114.7 (+ve, ArCH), 116.9
(+ve, ArCH), 117.5 (ab, ArC), 117.6 (ab, ArC), 118.2 (+ve,
ArCH), 124.1 (+ve, ArCH), 125.2 (+ve, ArCH), 125.3 (ab,
ArC), 125.8 (ab, ArC), 126.5 (+ve, ArCH), 127.9 (+ve,
ArCH), 129.1 (+ve, ArCH), 129.2 (ab, ArC), 129.9 (+ve,
ArCH), 130.5 (+ve, ArCH), 130.6 (ab, ArC), 131.5 (ab,
ArC), 136.9 (+ve, ArCH), 137.0 (+ve, ArCH), 148.8 (ab,
ArC), 149.4 (ab, ArC), 150.3 (ab, ArC), 150.5 (ab, ArC);
IR lmax (cmꢅ1): 3429, 3380, 3334 (NH2). Found C, 73.57;
H, 5.52; N, 4.52; S, 10.47%. C37H34N2O2S2 requires C,
73.72; H, 5.69; N, 4.65; S, 10.64%.
4.5. pH titration experiments
The pH titrations of 3 (5 mM), 8, 9, and 12 (1 mM) in
CH3CN–H2O (4:1 v/v) were performed with acid (HCl) to
investigate the <7 pH range and in a separate experiment
with base (NaOH) to investigate the >7 pH range and at reg-
ular intervals pH fluorescence spectra were recorded.
4.6. Experimental procedure for AND gate
Solution containing 9 (5 mM) was treated with HCl and pH
of the solution was adjusted to 2.5 and fluorescence spec-
trum was recorded. In a separate experiment, a solution con-
taining 9 (5 mM) and copper nitrate (100 mM) was prepared
in CH3CN–H2O (4:1 v/v) at pH 6.0 separately in a 50 ml
measuring flask and recorded its fluorescence spectrum.
Then the pH of the solution was changed with acid (HCl)
and at regular intervals pH fluorescence spectra were re-
corded.
Acknowledgements
We thank DST, New Delhi for the financial assistance.
4.3.3. 1-[2-(Anthracenyl-9-methylamino)phenylthio-
methyl]-4-(2-aminophenylthiomethyl)naphthalene (12).
Yield: 27%, yellow solid, mp 135–137 ꢂC; FAB mass 592
References and notes
1
(M+); H NMR (CDCl3): d 4.05 (s, 2H, CH2S), 4.19 (s,
2H, CH2S), 5.21 (br s, 2H, NH2, exchanges with D2O),
5.23 (br s, 2H, CH2N), 6.56–6.69 (m, 5H, ArH), 6.97 (t,
J¼7.5 Hz, 1H, ArH), 7.05–7.15 (m, 3H, ArH), 7.24 (d,
J¼7.5 Hz, 1H, ArH), 7.32–7.44 (m, 2H, ArH), 7.46–7.53
(m, 4H, ArH), 7.75 (d, J¼8.4 Hz, 1H, ArH), 7.99 (d,
J¼8.4 Hz, 1H, ArH), 8.08 (d, J¼7.5 Hz, 2H, ArH), 8.27
(d, J¼7.5 Hz, 2H, ArH), 8.54 (s, 1H, ArH); 13C NMR (nor-
mal/DEPT-135) (CDCl3): d 37.2 (ꢅve, CH2), 37.7 (ꢅve,
CH2), 40.8 (ꢅve, CH2), 110.1 (+ve, ArCH), 114.8 (+ve,
ArCH), 117.1 (+ve, ArCH), 117.7 (ab, ArC), 118.4 (+ve,
ArCH), 124.1 (+ve, ArCH), 124.3 (+ve, ArCH), 125.2
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