2994
X. Qian, Y. Xiao / Tetrahedron Letters 43 (2002) 2991–2994
yield can be analyzed according to the following equa-
118.45, 121.16, 123.77, 129.00, 130.24, 137.98, 139.37,
151.19; ESI–MS [M+H]+ (m/z 194), [M+NH4]+ (m/z 211),
[M+Na]+ (m/z 216), [M+K]+ (m/z 232), [2M+NH4]+ (m/z
404), [2M+Na]+ (m/z 409), [2M+K]+ (m/z 452); IR (KBr)
3369, 3232, 2216, 1579, 1521.
tion:9 log[(Fmax−F)/(F−Fmin)]=pH−pK%, the pK%
a
a
values of the fluorescence switches H1 and H2 being 8.0
and 7.7, respectively.
Compound HHH1: Mp 128.2–128.4°C; 1H NMR (400
MHz, CDCl3) l 1.08–1.11 (t, J=7.1 Hz, 6H, CH3),
2.62–2.66 (q, J=7.8 Hz, 4H, CH2CH3), 2.88–2.90 (t,
J=5.8 Hz, 2H, NHCH2CH2NEt2), 3.29–3.32 (q, J=5.5
Hz, 2H, NHCH2CH2NEt2), 6.46 (s, –NH–, 1H), 6.54–
6.56 (d, J=8.9 Hz, 1H), 7.50–7.53 (t, J=7.6 Hz, 1H),
7.79–7.81 (d, J=8.3 Hz, 1H), 7.96–7.97 (d, J=7.21, 1H),
8.03–8.05 (d, J=8.55 Hz, 1H); 13C NMR (100 MHz,
CDCl3) 12.64, 40.63, 46.94, 50.89, 93.89 104.93, 109.253,
117.95, 119.43, 123.00, 125.07, 126.70, 131.00, 137.85,
140.41, 149.02; ESI–MS m/z 292 (M+); IR (KBr) 3361,
2219, 2206, 1581, 1531, 1342; C18H20N4 Requires: C,
73.94; H, 6.89; N, 19.16. Found: C, 74.18; H, 6.79; N,
19.57%.
In summary, we have designed a new fluorophore,
4-amino-1,8-dicyanonaphthalene (ADCN), and its
derivatives H1 and H2 which respond to transition
metal ions and protons sensitively. Further studies on
their application in chemical biology and the structure–
property relationships of the amino-dicyanonaph-
thalene derivatives are currently under investigation.
Acknowledgements
The National Natural Science Foundation of China,
The Ministry of Education of China and Shanghai
Foundation of Science and Technology financially sup-
ported this study.
Compound H2: Mp 140–141°C; 1H NMR (400 MHz,
CDCl3) l 2.25 (s, 6H, CH3), 2.66–2.69 (t, J=5.4 Hz, 2H,
CH2N(CH3)2), 3.22–3.26 (t, J=8 Hz, 2H, HNCH2), 6.42–
6.44 (d, J=8.4 Hz, 1H), 7.36–7.40 (t, J=8 Hz, 1H),
7.69–7.71 (d, J=8.8 Hz, 1H), 7.84–7.86 (d, J=7.6 Hz,
1H), 8.16–8.21 (d, J=8.4 Hz, 1H); 13C NMR (100 MHz,
CDCl3) 40.3, 44.82, 56.51, 92.89, 103.84, 108.10, 117.08,
118.52, 122.22, 124.12, 126.67, 130.17, 137.07, 139.51,
148.35; IR (KBr) 3384, 2948, 2821, 2219, 2206, 1581,
1540, 1340; ESI-MS [M+H]+ (m/z 265).
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