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(80 mL) for 30 min to completely monodeprotonate the 2,2´-dihydroxydiphenyl sulfide. A solution of
1-(bromoacetyl)pyrene (1.00 g, 3.10 mmol) in acetonitrile (300 mL) was then added to the reaction
mixture, followed by stirring at the reflux temperature for 6 h. The reaction mixture was neutralized
with a few drops of acetic acid, and the solvent was removed. The residue was purified by
recrystallization from chloroform to afford 9. Yield 70% (0.80 g) of yellow powder; mp 154–155 °C
1
dec; H-NMR (CDCl3) δ 5.85 (s, 2H), 6.79 (td, J = 7.8 Hz, 1.4, 1H), 6.80 (dd, J = 7.8 Hz, 1.7, 1H),
6.87 (td, J = 7.7 Hz, 1.1, 1H), 6.96 (dd, J = 8.0 Hz, 1.1, 1H), 7.07–7.24 (m, 4H), 8.18 (t, J = 7.7 Hz,
1H), 8.29 (d, J = 9.0 Hz, 1H), 8.32–8.45 (m, 5H), 8.74 (d, J = 8.3 Hz, 1H), 8.86 (d, J = 9.3 Hz, 1H),
9.89 (s, 1H); 13C-NMR (DMSO-d6) δ; 72.2, 79.2, 112.3, 115.7, 117.8, 119.9, 121.4, 123.4, 123.9,
124.0, 124.3, 126.3, 126.7, 126.9, 127.0, 127.2, 128.8 128.9, 129.0, 129.6, 129.8, 129.9, 130.6, 133.7,
134.1, 155.0, 157.2, 198.5; HRMS (FAB): calcd for (M+H)/z: 461.1212. found (M+H): 461.1206.
Anal. calcd for C30H20O3S: C, 78.20; H, 4.38%. found: C, 77.90; H, 4.29%.
2-(1-Pyrenylacetyloxy)-2´-hydroxydiphenyl sulfoxide (10): This compound was prepared by the same
procedure given for the synthesis of compound 9 except that 2,2´-dihydroxydiphenyl sulfoxide (0.59 g) [15]
was used instead of 2,2´-dihydroxydiphenyl sulfide. Yield 25% (0.29 g) of yellow powder; mp
1
168–169 °C dec; H-NMR (CDCl3) δ 5.76 (d, J = 17.3 Hz, 1H), 5.87 (d, J = 17.3 Hz, 1H), 6.89 (td,
J = 8.0 Hz, 0.84, 1H), 6.89 (dd, J = 7.4 Hz, 0.84, 1H), 7.16 (td, J = 7.4 Hz, 0.84, 1H), 7.20 (d,
J = 7.7 Hz, 1H), 7.32 (td, J = 8.0 Hz, 1.7, 1H), 7.38 (dd, J = 7.7 Hz, 1.7, 1H), 7.48 (td, J = 7.4 Hz, 1.7,
1H), 7.55 (dd, J = 7.7 Hz, 1.7, 1H), 8.18 (t, J = 7.7 Hz, 1H), 8.29 (d, J = 9.1 Hz, 1H), 8.36–8.45 (m,
13
5H), 8.68 (d, J = 8.0 Hz, 1H), 8.84 (d, J = 9.4 Hz, 1H), 10.38 (s, 1H); C-NMR (DMSO-d6) δ; 72.3,
113.1, 116.2, 119.5, 121.6, 123.3, 124.0, 124.1, 124.3, 126.1, 126.3, 126.5, 126.8, 126.9, 127.0, 127.2,
128.5 128.9, 129.4, 129.8, 129.9, 130.5, 132.0, 132.3, 132.4, 133.8, 155.2, 155.4, 197.8; HRMS
(FAB): calcd for (M+H)/z: 477.1161. found (M+H)/z: 477.1161. Anal. calcd for C30H20O4S: C, 75.61;
H, 4.23%. Found: C, 75.31; H, 4.12%.
2-(1-Pyrenylacetyloxy)-2´-hydroxydiphenyl sulfone (11): This compound was prepared by the same
procedure given for the synthesis of compound 9 except that 2,2´-dihydroxydiphenyl sulfone [15]
(0.63 g) was used instead of 2,2´-dihydroxydiphenyl sulfide. Yield 27% (0.34 g) of yellow powder; mp
178–179 °C dec; 1H-NMR (300 MHz CDCl3) δ 5.62 (s, 2H), 6.71 (td, J = 8.0 Hz, 0.84, 1H), 6.84 (dd,
J = 8.3 Hz, 0.84, 1H), 7.20 (t, J = 7.7 Hz, 1H), 7.21 (d, J = 8.5 Hz, 1H), 7.38 (td, J = 8.5 Hz, 1.7, 1H),
7.61 (td, J = 8.3 Hz, 1.7, 1H), 7.78 (dd, J = 8.0 Hz, 1.7, 1H), 8.06 (dd, J = 7.7 Hz, 1.7, 1H), 8.18 (t,
J = 7.7 Hz, 1H), 8.30 (d, J = 9.0 Hz, 1H), 8.32–8.45 (m, 5H), 8.55 (d, J = 8.0 Hz, 1H), 8.71 (d,
J = 9.4 Hz, 1H), 10.39 (s, 1H); 13C-NMR (DMSO-d6) δ; 72.3, 79.5, 114.0, 116.9, 118.0, 120.4, 123.3,
124.0, 124.1, 124.3, 126.1, 126.3, 126.8, 126.9, 127.1, 127.2, 128.5, 128.9, 129.7, 129.8, 129.9, 130.4,
130.5, 130.6, 133.7, 134.8, 135.0, 155.5, 155.7, 197.0; HRMS (FAB): calcd for (M+H)/z: 493.1110.
found (M+H)/z: 493.1105. Anal. calcd for C30H20O5S: C, 73.16; H, 4.09%. found: C, 72.86; H, 4.08%.
4. Conclusions
We have synthesized new podand-type fluoroionophores by connecting two pyrene units with
2,2´-dihydroxydiphenyl sulfide, sulfoxide, and sulfone. The fluorescent change upon addition of alkali