Klassen et al.
743
calcd. for C46H34O10: 746.21521, found: 746.21162; 746
(M+, 2), 670 (51), 604 3b, 462 (38), 439 (50), 297 (38), 231
(18), 105 (100). Analysis calcd. for C46H34O10: C, 73.99; H,
4.59. Found: C, 74.06; H, 4.66.
cipitated by the addition of methanol. Filtration gave 0.17 g
of 7a (78%): H NMR (250 MHz, CDCl3) d: 3.45 (6), 3.58
1
(6), 7.4–7.8 (m, 22H). 13C NMR (75 MHz, CDCl3) d: 52.5,
53.5, 127.4, 127.7, 128.0, 128.1, 128.3, 129.0, 129.3,
129.97, 130.01, 132.8, 133.0, 137.45, 137.53, 137.7, 138.7,
139.5, 168.8, 168.9. IR (KBr): 1741 and 1726, 1436, 1241,
1221, 1130, 773, 702 cm–1. MS (EI) m/e calcd. for
C46H34O8: 714.2253, found: 714.2267; 714 (M+, 100), 651
(18), 326 (10), 87 (5).
Dimethyl 1,3-phenylenebis(1,4-epoxy-1,4-dihydro-4-
phenyl-1-naphthalene-2,3-dicarboxylate), 6b
In a round-bottom flask, 3c (0.053 g, 0.115 mmol) and
DMAD (0.082 g, 0.573 mmol) were dissolved in toluene.
As the mixture was allowed to reflux (with stirring) for 2 h,
the solution turned from bright yellow to clear. The solvent
was removed by rotary evaporation to leave a pale yellow
oil. The oil was crystallized in ethyl acetate / petroleum
ether to give a 67% yield of 6b, a white solid: mp 162–170
Dimethyl 1,3-phenylenebis(4-phenyl-1-naphthalene-2,3-
dicarboxylate), 7b
Adduct 6b (0.43 g, 0.58 mmol) and NaI (0.43 g,
2.9 mmol) were dissolved in 50 mL of dry acetonitrile under
nitrogen. The solution was cooled to 0 8C and TMSCl
(0.37 mL, 2.9 mmol) added by syringe. The solution was
then stirred at room temperature for 24 h. Saturated NaHSO3
was added, and the solution was extracted twice with 50 mL
portions of chloroform. The organic phase was separated,
dried over MgSO4, and stripped of solvent. The residue sol-
idified and was recrystallized from methanol to give, in sev-
1
8C. H NMR (250 MHz, CDCl3) d: 3.65–3.68 (m, 12H),
7.14–7.18 (m, 4H), 7.44–7.61 (m, 11H), 7.72–7.84 (m, 6H),
8.11 (s, 1H). 13C NMR (62.5 MHz, CDCl3) d: 52.53, 52.56,
94.05, 94.08, 94.21, 94.24, 122.28, 122.36, 126.3, 127.7,
128.2, 128.8, 129.0, 129.1, 129.3, 133.3, 133.9. IR (KBr pel-
let): 702.08, 755.37, 793.51, 976.44, 1003.12, 1122.84,
1255.91, 1309.09, 1434.14, 1452.68, 1630.93, 1727.95,
2951.15 cm–1. MS (EI) m/e calcd. for C46H34O10: 746.2152,
found: 746.2173; 746 (M+, 0.3), 604 (27), 463 (14), 462
(38), 439 (41), 269 (18), 111 (12), 105 (100). Analysis
calcd. for C46H34O10: C, 73.99; H, 4.59. Found: C, 74.16;
H, 4.70.
1
eral crops, a total of 0.32 g (78%): mp 214–215 8C. H
NMR (250 MHz, CDCl3) d: 3.52 (3.67 and 3.68, J = 3s Hz,
12H), 7.33–7.78 (m, 22H). 13C NMR (62.5 MHz, CDCl3) d:
52.32, 52.35, 52.5, 52.6, 127.3, 127.5, 127.6, 127.7, 127.8,
127.95, 127.98, 128.90, 128.08, 128.13, 128.18, 128.24,
128.27, 128.33, 128.4, 128.8, 129.01, 129.07, 129.21, 129.5,
129.98, 130.13, 130.2, 130.3, 131.7, 132.2, 132.89, 132.95,
133.00, 137.72, 137.74, 137.80, 138.88, 139.4, 139.5,
168.86, 168.89, 168.97. IR (KBr): 1741 and 1726 (C=O),
1436, 1241, 1221, 1130, 773, 702 cm–1. Analysis calcd. for
C46H34O8: C, 77.30; H, 4.79. Found: C, 77.33; H, 5.00.
Dimethyl 4,4’-biphenylenebis(1,4-epoxy-1,4-dihydro-4-
phenyl-1-naphthalene-2,3-dicarboxylate), 6c
In a round-bottom flask, 47.5 mg (0.088 mmol) of 3c and
0.108 mL (0.882 mmol) of DMAD were dissolved in tol-
uene. The mixture was allowed to reflux with stirring for
0.5 h as the solution turned from orange to lime green to
clear. The solvent was removed, and the resulting yellow
oil was dissolved in methanol to crystallize. Adduct 6c, a
white solid was obtained in 75% yield: mp 224–228 8C
Dimethyl 4,4’-biphenylenebis(4-phenyl-1-naphthalene-2,3-
dicarboxylate), 7c
Difuran 3c (0.30 g, 0.56 mmol) and 240 mg DMAD
(1.7 mmol) were refluxed in 150 mL dioxane for 8 h. The
solvent was removed by rotary evaporation and evacuation
under high vacuum. Acetonitrile (30 mL) and sodium iodide
(0.54 g, 3.4 mmol) were added, the flask purged with nitro-
gen, and cooled to 0 8C. Chlorotrimethylsilane (0.50 mL,
3.9 mmol) was added by syringe and the reaction stirred for
6 h. The mixture was filtered and the solid material
recrystallized from CHCl3/MeOH to give 246 mg of 7c,
(57%): mp 368–370 8C. 1H NMR (250 MHz, CDCl3) d:
3.54 (s, 6H), 3.60 (s, 6H), 7.40–7.55 (m, 18H), 7.68–7.79
(m, 4H), 7.87 (d, J = 7 Hz, 4H). 13C NMR (62.5 MHz,
CDCl3) d: 52.4, 52.6, 126.9, 127.6, 127.7, 127.96, 127.98,
128.1, 128.3, 129.0, 130.2, 130.8, 133.0, 137.1, 137.8,
138.9, 139.4, 140.1, 169.0. IR (Nujol): 1742, 1227, 1163,
1130, 774, 721, 700 cm–1. MS (EI) m/e: 790 (M+, 22),
744 (5), 552 (21), 457 (44), 456 (100), 207 (20), 126 (9),
78 (11).
1
(melt/dec.). H NMR (250 MHz, CDCl3) d: 3.71 (s, 6H),
3.72 (s, 6H), 7.17–7.20 (m, 4H), 7.47–7.56 (m, 10H), 7.72–
7.75 (m, 8H), 7.82–7.85 (m, 4H). 13C NMR (250 MHz,
CDCl3) d: 52.58, 52.62, 94.1, 94.3, 122.43, 122.46, 126.3,
127.6, 128.2, 128.8, 129.3, 132.7, 133.3, 141.5, 149.27,
149.33, 153.6, 154.5, 164.3, 164.4. IR (Nujol): 752.3,
1255.7, 1311.7, 1454.4, 1722.5 cm–1. MS (FAB) m/e: 823
(MH+, 0.9), 791 (2.4), 680 (2.1), 538 (2.5), 515 (2.9), 309
(5.1), 155 (39.7), 135 (48.7), 119 (100), 105 (73.1). Analysis
calcd. for C52H38O10: C, 75.90; H, 4.65. Found: C, 75.89; H,
4.86.
Dimethyl 1,4-phenylenebis(4-phenyl-1-naphthalene-2,3-
dicarboxylate), 7a
Adduct 6a (0.23 g, 0.32 mmol) and NaI (0.29 g,
1.9 mmol) were dissolved in 30 mL of dry acetonitrile. Tri-
methylsilyl chloride (0.25 mL, 1.9 mmol) was added by sy-
ringe and the mixture refluxed for 2 days. An equal volume
of water was added and the mixture extracted twice with
50 mL of chloroform. The combined chloroform extracts
were washed with 10% NaHSO3 solution and dried over
MgSO4. The solvent was removed and the residue columned
on 4 inches of silica eluting with chloroform graded to 1%
ethyl acetate in chloroform. The fractions containing the
product were stripped of solvent, and the product was pre-
Acknowledgements
The authors wish to thank the Natural Sciences and
Engineering Research Council of Canada (NSERC) and the
University of Lethbridge for funding (RTB and PWD) and
the Centre for Molecular Architecture, Central Queensland,
Australia for analytical support.
Published by NRC Research Press