3252
X.-L. Ni et al. / Tetrahedron 67 (2011) 3248e3253
and evaporated to give the solid crude product. The residue eluted
from a column chromatography of silica gel with hexane/ethyl ac-
etate (v/v¼4:1) to give the desired product 1,3-alternate-1 (194 mg,
73%) as colorless prisms. Mp 154e156 ꢂC. 1H NMR (300 Hz, CDCl3)
solid crude product. The residue eluted from a column chroma-
tography of silica gel with hexane/ethyl acetate (6:1, v/v) to give the
desired product 3 (134 mg, 60%) as pale yellow prisms. Mp
147e149 ꢂC. 1H NMR (300 MHz, CDCl3) 1.24 (9H, s, tBu), 5.07 (2H,
d
d
0.88 (18H, s, tBu), 1.08 (18H, s, tBu), 1.22 (6H, t, J¼7.1 Hz, CH2CH3),
s, CH2), 6.25 (2H, s, CH2), 6.82 (2H, d, J¼5.4 Hz, ArH), 7.22 (2H, d,
4.15 (4H, q, J¼7.1 Hz, CH2CH3), 4.45 (4H, s, CH2), 4.84 (4H, s, CH2),
6.28 (4H, s, CH2), 7.24 (4H, s, ArH), 7.28 (2H, s, Triazole-H), 7.33 (4H,
s, ArH), 7.88 (2H, d, J¼9.0 Hz, Pyrene-H), 7.99e8.23 (14H, m, Pyrene-
H), 8.34 (2H, d, J¼9.0 Hz, Pyrene-H). 13C NMR (75 MHz, CDCl3):
14.07, 22.59, 31.01, 33.82, 52.08, 60.43, 64.85, 67.60, 122.18, 123.22,
124.45, 124.85, 124.94, 125.62, 125.71, 126.21, 127.18, 127.25, 128.04,
128.23, 128.79, 129.07, 130.54, 131.13, 131.84, 131.96, 133.15, 144.59,
145.97, 146.00, 156.51, 157.20, 167.91. IR: nmax (KBr)/cmꢀ1 2960,
2360, 1768, 1442, 1380, 1265, 1190, 1045. FABMS: m/z 1483.42 (Mþ).
Anal. Calcd for C88H86N6O8S4 (1483.92): C, 71.23; H, 5.84; N, 5.66.
Found: C, 71.09; H, 5.70; N, 5.64.
J¼5.4 Hz, ArH), 7.37 (1H, s, Triazole-H), 7.94e8.25 (9H, m, Pyrene-
H). 13C NMR (75 MHz, CDCl3)
d 31.41, 33.98, 52.42, 62.10, 114.19,
121.85, 124.42, 124.88, 125.02, 125.79, 125.90, 126.15, 126.35, 126.61,
127.15, 127.62, 128.27, 129.03, 129.26, 130.51, 131.12, 132.10, 143.84,
155.88. IR: nmax (KBr)/cmꢀ1 2954, 2360, 1768, 1442, 1380, 1265,
1190, 1045. FABMS: m/z 445.26 (Mþ). Anal. calcd for C30H27N3O
(445.57): C, 80.87; H, 6.11; N, 9.43. Found: C, 80.62; H, 6.03; N, 9.36.
Acknowledgements
We would like to thank the OTEC at Saga University and the
International Collaborative Project Fund of Guizhou province at
Guizhou University for financial support. We also would like to
thank the EPSRC (for a travel grant to C.R.).
4.2.3. 5,11,17,23-Tetra-tert-butyl-25,27-dibenzyloxy-26,28-[bis-
(propargyloxy)]-tetrathiacalix[4]arene (7). A suspension of com-
pound 6 (300 mg, 0.333 mmol) and Cs2CO3 (1.085 g, 3.33 mmol)
was refluxed for 1 h in dry acetone (15 ml). A solution of 3-bromo-
1-propyne [propargyl bromide (396 mg, 3.33 mmol)] in dry acetone
(10 ml) was added and the mixture refluxed for 20 h. The solvents
were evaporated and the residue partitioned between 10% HCl and
CH2Cl2. The organic layer was dried (MgSO4) and evaporated. The
residue was recrystallized from CHCl3/hexane (1:3, v/v) to afford
the desired product 7 as colorless prisms with a yield of 81%
Supplementary data
Experimental procedures, 1H and 13C NMR spectral data, fluo-
rescence and 1H NMR titration spectra data are available. Supple-
mentary data related to this article can be found online at
(263.5 mg). Mp 180e182 ꢂC. 1H NMR (300 MHz, CDCl3)
d
0.60, 0.85,
t
0.98, 1.11, 1.31 (each s, 36H, Bu), 2.20e2.51, 4.41e5.08 (m, 10H,
acetylene-H, ArOeCH2eacetylene and ArOeCH2ePh) and 7.0e8.8
(18H, m, ArH). IR: nmax (KBr)/cmꢀ1 3307, 2960, 1575, 1432, 1367,
1265, 1085, 1008. FABMS: m/z 977.4 (Mþ). Anal. Calcd for
C60H64O4S4 (977.42): C, 73.74; H, 6.61. Found: C, 74.10; H, 6.67. The
splitting pattern in 1H NMR shows that the isolated compound is
a mixture of cone- and partial-cone-7.
References and notes
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(18H, s, Bu), 4.64 (4H, s, CH2eTriazole), 5.08 (4H, s, CH2Ph), 6.24
(4H, CH2ePyrene), 6.74 (4H, s, ArH), 7.11e6.9 (14H, m, PheH), 7.45
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d 30.38, 31.25, 33.41, 34.15, 52.26, 63.93, 72.69,
122.29, 123.29, 124.52, 124.84, 125.01, 125.75, 125.79, 126.29,
126.83, 126.97, 127.23, 127.29, 127.34, 127.41, 127.85, 127.99, 128.16,
128.98, 129.24, 129.69, 129.76, 130.62, 131.22, 131.98, 132.98, 137.86,
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4.2.5. 4-tert-Butyl-[1H-(1-pyrenylmethyl-(1,2,3-triazolyl)-4-me-
thoxy)] benzene (3). A mixture of 4-tert-butyl-1-(propargyloxy)
benzene (95 mg, 0.5 mmol) and 8 (140 mg, 1.1 mmol) in 20 mL THF/
H2O (4:1) and the mixture was heated at 65 ꢂC for 24 h at the
presence of CuI as catalyst. The resulting solution was cooled and
diluted with water and extracted thrice with CH2Cl2. The organic
layer was separated and dried (MgSO4) and evaporated to give the
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