G. J. Bodwell et al. / Tetrahedron 57 )2001) 3577±3585
3583
23.3 mmol). After stirring for 4 h, the solvent was removed
and to the residue was added ether /100 mL) and saturated
aqueous NH4Cl solution /50 mL). The layers were separated
and the organic layer was washed with water /50 mL), satu-
rated aqueous NaCl solution /50 mL) and dried over
MgSO4. Chromatography /1:9 ethyl acetate/hexanes) of
the residue afforded 26 /0.805 g, 73% from 25, 53% from
24) as a pale yellow solid. A small portion was recrystal-
lized from heptane for characterization. Mp99±1028C
¯ask via a needle through a septum. The mixture was stirred
at rt for 20 h, ®ltered though a plug of MgSO4 and the
solvent was removed under reduced pressure to afford
1
analytically pure 29 as a white solid. Mp138±1418C. H
NMR /CDCl3, 300 MHz): d8.53 /t, J1.6 Hz, 2H), 8.09
/t, J1.6 Hz, 4H), 3.94 /s, 12H), 3.42 /t, J6.4 Hz, 4H),
2.86±2.81 /m, 4H), 1.98±1.92 /m, 4H). 13C NMR /CDCl3,
75 MHz): d166.4, 142.9, 133.9, 130.6, 130.6, 128.3, 69.6,
52.3, 32.0, 31.0. MS m/z /%)486 /9, M1), 454 /29), 236
/16), 235 /25), 234 /100), 221 /34), 207 /53), 203 /53), 189
/36) 177 /39), 175 /37), 149 /62). Anal. Calcd for C26H30O9:
C, 64.19; H, 6.22. Found: C, 63.98; H, 6.16.
1
/heptane). H NMR /CDCl3, 300 MHz): d7.12 /s, 4H),
6.77 /s, 2H), 6.13 /d, J1.2 Hz, 4H), 4.20±4.17 /m, 4H),
3.61±3.56 /m, 4H). 13C NMR /CDCl3, 75 MHz): d155.4,
136.5, 135.0, 114.3, 69.6, 67.4 /one aromatic signal over-
lapped). MS m/z /%)306 /37, M1), 206 /24), 205 /16), 190
/22), 189 /100), 178 /47). Anal. Calcd for C20H18O3: C,
77.40; H, 6.14. Found: C, 77.41; H, 5.92.
4.1.8. Bisꢀ3-ꢀ3,5-bisꢀbromomethyl)phenyl)propyl) ether
30. This reaction was performed under a nitrogen atmos-
phere. To a 08C, magnetically stirred slurry of LiAlH4
/4.75 g, 125 mmol) in THF /200 mL) a solution of tetraester
29 /4.96 g, 10.2 mmol) in THF /200 mL) was added drop-
wise from a dropping funnel over 1 h. The mixture was
stirred at rt for 20 h, cooled to 08C and quenched by the
careful addition of ethyl acetate /40 mL). After stirring for
2 h, the solvent was removed and the resulting grey residue
was dried under high vacuum for 5 h. To this was added
with vigourous stirring 125 mL of a 4:1 mixture of 48%
aqueous HBr solution and concentrated H2SO4, followed
by a further portion of H2SO4 /65 mL). Caution: a powerful
exotherm occurs upon mixture of the two acids and upon
addition of the mixture to the residue. The resulting orange
solution was stirred for 3 h, water /200 mL) and dichloro-
methane /200 mL) were added and stirring was continued
until all solids had dissolved. The layers were separated and
the aqueous layer was extracted with dichloromethane
/100 mL). The combined organic layers were washed with
water /200 mL), saturated aqueous NaHCO3 solution
/200 mL), saturated aqueous NaCl solution /200 mL) and
dried over MgSO4. The solvent was evaporated under
reduced pressure and the residue was chromatographed
/1:4 ethyl acetate/hexanes) to afford 30 /5.02 g, 77%) as a
4.1.5. 1,4,7-Trioxa[7]ꢀ2,7)pyrenophane 3. This reaction
was performed under a nitrogen atmosphere. To a stirred
ca. 758C solution of cyclophanediene 26 /0.175 g,
0.567 mmol) in benzene /50 mL) was added DDQ
/0.130 g, 0.573 mmol) in ca. 10 mg portions over 24 h.
After a further 12 h, the mixture was cooled to rt and the
solvent was removed. The residue was dissolved in
dichloromethane /50 mL) and washed with 1 M aqueous
NaOH solution /50 mL), saturated aqueous NaCl solution
/50 mL), dried over MgSO4 and concentrated under reduced
pressure. Chromatography /1:19 ethyl acetate/hexanes) of
the residue afforded starting material /ca. 50% recovery)
1
that contained, by H NMR, a small amount /ca. 5%) of 3.
1H NMR /CDCl3, 300 MHz): d7.71 /s, 4H), 7.20 /s, 4H),
3.31±3.28 /m, 4H), 1.99±1.96 /m, 4H).
4.1.6. Bisꢀ3-ꢀ3,5-bisꢀmethoxycarbonyl)phenyl)prop-2-ynyl)
ether 28. This reaction was performed under a nitrogen
atmosphere. A mixture of dipropargyl ether /2.50 g,
26.6 mmol), Pd/PPh3)2Cl2 /0.50 g, 0.71 mmol), CuI
/0.62 g, 3.3 mmol), DBU /9.80 g, 64.4 mmol) and tri¯ate
27 /18.47 g, 54.0 mmol) in benzene /175 mL) was stirred
at rt for 40 h. The resulting mixture was washed with water
/2£100 mL), 1 M aqueous HCl solution /2£100 mL), satu-
rated aqueous NaHCO3 solution /2£100 mL), and saturated
aqueous NaCl solution /100 mL). The organic layer was
then dried over MgSO4 and the solvent was removed
under reduced pressure. Chromatography /2:3:5 dichloro-
methane/ethyl acetate/hexanes) of the residue afforded
some pure /by tlc analysis) 28 and some impure fractions,
from which pure 28 was isolated by recrystallization /ethyl
acetate/heptane). Diyne 28 was obtained in a total yield
of 10.43 g /82%) as a white solid. Mp153±1548C /ethyl
1
white solid. Mp65±678C. H NMR /CDCl3, 300 MHz):
d7.25 /s, 2H), 7.16 /d, J1.7 Hz, 4H), 4.45 /s, 8H), 3.42
/t, J 6.3 Hz, 4H), 2.73±2.68 /m, 4H), 1.93±1.88 /m, 4H).
13C NMR /CDCl3, 75 MHz): d143.4, 138.3, 129.3, 127.1,
69.7, 33.1, 32.0, 31.0. MS m/z /%)M1 not observed, 467
/4), 465/8), 463 /4), 385 /4), 383 /4), 306 /27), 304 /54), 302
/27), 279 /10), 277 /18), 275 /9), 225 /100), 223 /93), 199
/34), 197 /37). Anal. Calcd for C22H26Br4O: C, 43.29; H,
4.11. Found: C, 43.18; H, 4.12.
4.1.9. 4-Oxa-15,24-dithia[7.3.3]ꢀ1,3,5)cyclophane 31. To
a vigourously stirred solution of tetrabromide 30 /4.75 g,
7.44 mmol) in 9:1 dichloromethane/absolute ethanol
/3000 mL) was added freshly prepared Na2S/Al2O3 /6.24 g,
ca. 2.5 mmol g21, <15.6 mmol) in several approximately
equal portions over 4 h and stirring was continued for 20 h.
Tlc analysis indicated incomplete reaction, so a further
1
acetate/heptane). H NMR /CDCl3, 300 MHz): d8.64 /t,
J1.6 Hz, 2H), 8.31 /t, J1.7 Hz, 4H), 4.58 /s, 4H), 3.96 /s,
12H). 13C NMR /CDCl3, 75 MHz): d165.5, 136.7, 131.0,
130.4, 123.4, 86.2, 85.0, 57.4, 52.6. MS m/z /%)478 /5,
M1), 447 /14), 414 /32), 214 /10), 43 /100). Anal. Calcd for
C26H22O9: C, 65.27; H, 4.63. Found: C, 65.06; H, 4.52.
portion of Na2S/Al2O3 /2.68 g @ ca. 2.5 mmol g21
,
<6.7 mmol) was added and stirring was continued for 4 h.
The mixture was suction ®ltered, the solvent was removed
under reduced pressure and the residue was chromatographed
/2:3:15 ethyl acetate/dichloromethane/hexanes) to afford 31
/1.95 g, 71%) as a white solid. Mp.2308C. 1H NMR
/CDCl3, 300 MHz): d7.11 /s, 2H), 6.67 /d, J0.7 Hz,
4H), 3.81 /s, 8H), 3.22±3.18 /m, 4H), 2.48±2.44 /m, 4H),
4.1.7.
Bisꢀ3-ꢀ3,5-bisꢀmethoxycarbonyl)phenyl)propyl)
ether 29. A solution of diyne 28 /5.18 g, 10.8 mmol) in
ethyl acetate /400 mL) was purged with nitrogen and
Pd/OH)/C /Pearlman's catalyst, 250 mg) was added. Hydro-
gen /ca. 1 L) was bubbled through the well-stirred solution
and then a balloon containing hydrogen was attached to the