8
A. GolAN eT Al.
ABq, JAB = 16.16 Hz, ArCH2Ar), 4.19 (4H, d, J = 13.08 Hz,
ArCH2Ar), 6.66 (10H, bs, 4 ArH + ArH of benzoate), 6.94
(6H, d, J = 1.92 Hz, ArH + ArH of benzoate), 7.09 (6H, bs,
2ArH of benzoate + 4oH), 7.39 (4H, s, ArH), 7.37 (4H, s, ArH),
9.16 (2H, s, oH); MS (eSI): m/z = 1392, 1415 (Na+), 1431 (K+).
Synthesis of 10: 0.632 g (1 eq, 0.45 mmol) of com-
pound 6 were dissolved in 60 ml of DCM and 0.485 g
(5 eq, 2.3 mmol) of 1,8-bis(dimethylamino)naphthalene
(proton sponge) was added and the content was stirred
under nitrogen for 30 min at room temperature. To the
flask, 0.31 ml of trifluoromethanesulfonic anhydride (4 eq,
18 mmol) was added gradually and the content was
stirred overnight. Then, 50 ml of 3 N HCl were added and
the mixture was stirred for 15 min. The organic layer was
separated, washed twice with 3 N HCl, dried over MgSo4,
filtered, and the solvent was evaporated to dryness. The
residue was subjected to column chromatography (dry
loading, 10% ethyl acetate/hexane) to give 0.30 g (40%)
of 10 as off-white foam (r.f. = 0.67 in 20% ethyl acetate/
hexane).
1H NMR (CDCl3): 1.08 (18H, s, C(CH3)3), 1.19 (36H, s,
C(CH3)3), 3.51 (4H, d, J = 14.48 Hz, ArCH2Ar), 3.58 (4H, d,
J = 15.04 Hz, ArCH2Ar), 3.81 (4H, d, J = 14.92 Hz, ArCH2Ar),
4.20 (4H, d, J = 14.4 Hz, ArCH2Ar), 4.63 (4H,bs, oH), 6.78
(4H, s, ArH), 6.94 (4H, d, J = 2.28 Hz ArH), 7.03 (4H, s, ArH),
7.20 (4H, d, J = 2.28 Hz ArH) 7.47 (4H, t, J = 7.84 Hz, ArH of
benzoate), 7.65 (2H, tt, J1 = 7.48, J2 = 1.24 Hz, ArH of benzo-
ate), 7.95 (4H, dd, J1 = 8.44, J2 = 1.24 Hz, ArH of benzoate);
19F NMR(CDCl3): −72.42; MS (eSI): m/z = 1656, 1679 (Na+),
1695 (K+).
Synthesis of 12: 0.2 g (1 eq, 0.12 mmol) of com-
pound 10 were dissolved in 7 ml of THF and stirred
over an ice bath at 0 °C under nitrogen. 0.3 ml (2.5 eq,
0.03 mmol) of 1 M solution of liAlH4 was added over
5 min. Upon the addition, the content of the flask
became dark brown and gradually turned deep
yellow. The reaction mixture was stirred at 0 °C for
3 h, and then 25 ml of ethyl acetate and 25 ml of
ammonium chloride were added. The organic layer
was separated and the aqueous phase was extracted
twice with 15 ml of ethyl acetate. The combined
organic phase was dried over MgSo4, filtered, and
the solvent evaporated. The residue was subjected
to column chromatography (dry loading, a gradient
of 0–20% ethyl acetate-hexane) to give 0.107 g (61%)
of 12 as bright yellow solid (r.f. = 0.23 in 20% ethyl
acetate/hexane, the spot becomes pale yellow with-
out staining).
7.23 (4H, s, ArH), 8.23 (2H, bs, oH); 19F NMR (CDCl3): -72.05
(s); MS (eSI): m/z = 1448, 1471(Na+), 1487(K+).
Synthesis of 13: 0.408 g (1 eq, 0.28 mmol) of com-
pound 12 were dissolved in 20 ml of acetonitrile and
0.093 g (2.4 eq, 0.67 mmol) of K2Co3 were added. The
reaction mixture was brought to reflux and then 0.22 ml
(8 eq, 2.25 mmol) of propyl iodide were added and upon
addition the reaction mixture turned yellow/orange. The
reaction was stirred under reflux for 1 h. The solvent was
evaporated, dissolved in DCM and washed with 3 N HCl.
The organic layer was separated, dried over MgSo4, fil-
tered, and the solvent was evaporated to dryness to give
0.364 g (85%) of 13 as pale orange solid which was used
in the next step without further purification.
1H NMR (CDCl3): 0.88 (6H, t, J = 6.64 Hz, CH3 of propyl),
1.09 (18H, s, C(CH3)3), 1.34 (36H, s, C(CH3)3), 2.15 (4H, m,
CH2 of propyl), 3.31 (4H, d, J = 13.24 Hz, ArCH2Ar), 3.50
(4H, d, J = 13.88 Hz, ArCH2Ar), 3.96 (4H, d, J = 13.84 Hz,
ArCH2Ar), 4.09 (4H, t, J = 6.6 Hz, CH2 of propyl), 4.46 (4H,
d, J = 13.16 Hz, ArCH2Ar), 6.99 (4H, s, ArH), 7.01 (4H, d,
J = 2.28 Hz, ArH), 7.07 (4H, s, ArH), 7.15 (4H, d, J = 2.12 Hz,
ArH), 7.25 (4H, bs, oH); 19F NMR (CDCl3): -73.12 (s); MS (eSI):
m/z = 1532, 1555(Na+), 1571(K+).
Synthesis of 14: to a mixture of 0.0037 g of P(t-
-
Bu)3H+BF4 (0.2 eq, 0.013 mmol) and 0.003 g of
Pd2dba3 (0.05 eq, 0.003 mmol) dissolved in 10 ml
of DMF, 0.031 g of CuI (2.5 eq, 0.163 mmol), 0.039 ml
of DBU (4 eq, 0.26 mmol) and 0.072 ml of pheny-
lacetylene (10 eq, 0.65 mmol) were added and
stirred for a couple of minutes. Then, 0.1 g (1 eq,
0.065 mmol) of compound 13 was added and the
mixture was heated at ~85 °C over night. The sol-
vent was co-evaporated with toluene, dissolved
in DCM and washed with 3 N HCl and brine. The
organic layer was separated, dried over MgSo4, fil-
tered, and the solvent was evaporated to dryness.
The dark brown residue was subjected to column
chromatography (wet loading, a gradient of 0–40%
DCM/hexane) to give 0.025 g (~26%) of 14 as a pale
off-white/yellow solid, fluorescent under UV irradi-
ation which was used in the complexation studies.
1H NMR (CDCl3): 0.80 (6H, t, J = 6.64 Hz, CH3 of propyl),
1.11 (18H, s, C(CH3)3), 1.33 (36H, s, C(CH3)3), 1.72 (4H, m, CH2
of propyl), 3.43 (4H, d, J = 13.64 Hz, ArCH2Ar), 3.51 (4H, d,
J = 12.88 Hz, ArCH2Ar), 3.89 (4H, t, J = 6.8 Hz, CH2 of propyl),
4.02 (4H, d, J = 13.52 Hz, ArCH2Ar), 4.85 (4H, d, J = 12.72 Hz,
ArCH2Ar), 6.97 (4H, s, ArH), 6.99 (4H, d, J = 2.36 Hz, ArH), 7.12
(4H, s, ArH), 7.20 (4H, d, J = 2.32 Hz, ArH), 7.24 (4H, bs, oH),
7.29–7.36 (8H, m, ArH of phenyl), 7.69 (4H, dd, J1 = 8.2 Hz,
J2 = 1.6 Hz, ArH of phenyl); 13C NMR(CDCl3): 10.27, 22.91
(Pr), 31.09, 31.74 (t-Bu), 32.54 (CH2), 33.93, 32.10 (t-Bu),
36.86 (CH2), 78.86 (Pr), 89.73, 96.47 (C≡C), all aromatic
(s): 121.82, 124.06, 124.91, 125.75, 126.04, 126.20, 126.38,
1H NMR (CDCl3): 1.17 (18H, s, C(CH3)3), 1.29 (36H, s,
C(CH3)3), 3.57 (4H, d, J = 14.16 Hz, ArCH2Ar), 3.62 (4H, d,
J = 14.36 Hz, ArCH2Ar), 4.08 (4H, d, J = 13.44 Hz, ArCH2Ar),
4.37 (4H, d, J = 14.24 Hz, ArCH2Ar), 7.00 (8H,bs, ArH + oH),
7.09 (4H, d, J = 2.24 Hz, ArH), 7.14 (4H, d, J = 2.2 Hz ArH),