10108
A. Wiehe et al. / Tetrahedron 57 42001) 10089±10110
418 .5.65), 485 .3.53), 517 .4.24), 552 .3.97), 593 .3.69),
648 .3.71); HRMS [C67H54N4O4 [M14H]]: calcd
978.414510, found 978.414440; HRMS .FAB1)
[C67H50N4O4]: calcd 974.383207, found 974.385666,
[C67H51N4O4 [M1H]]: calcd 975.391032, found
975.388626.
3H, OMe), 4.50 .d, 2H, J7.2 Hz, CH2CHMe2), 4.57 .m,
4H, CH2CHMe2), 6.41 .s, 1H, triptycene), 6.50 .s, 1H, trip-
tycene), 6.62 .s, 2H, arom. H), 7.04 .s, 1H, triptycene 3-H),
7.12 .m, 2H, arom. H), 7.59 .m, 2H, arom. H), 7.88 .d, 2H,
J8.3 Hz, arom. H), 8.35 .AB system, 2H, arom. H), 8.93
.d, 1H, J5.0 Hz, b-pyrrole H), 9.09 .d, 2H, J4.6 Hz,
b-pyrrole H), 9.14 .d, 2H, J4.6 Hz, b-pyrrole H), 9.16
.d, 1H, J5.0 Hz, b-pyrrole H), 9.41 .m, 4H, b-pyrrole
H), 9.38 .s, 2H, b-pyrrole H), 9.45 .d, 2H, J4.6 Hz,
b-pyrrole H), 9.94 .s, 1H, b-pyrrole H), 10.38 .s, 2H,
meso-H); 13C NMR .125 MHz, CDCl3, TMS): d21.76,
23.40, 29.51, 35.44, 36.05, 36.68, 36.88, 42.36, 42.79,
43.69, 44.23, 57.15, 58.02, 95.04, 105.85, 117.21, 117.46,
117.87, 118.20, 125.64, 126.09, 128.04, 130.83, 131.05,
131.50, 131.55, 131.84, 131.93, 131.97, 132.02, 134.92,
135.52, 142.51, 143.56, 145.29, 145.43, 145.47, 145.72,
146.91, 148.39, 151.34, 151.79, 151.90, 182.36, 182.43;
MS .FAB1, DMSO/m-NO2-Bzl-OH/Xe); m/z .%): 1319
.100) [[M12H]1], 1318 .62) [[M1H]1], 1317 .43) [M1],
1261 .49) [M12C4H8]; UV/vis .CH2Cl2): lmax .log 1)
409 nm .5.19) 435 .5.32), 505 .4.37), 549 .4.42), 582
.4.13), 635 .3.68).
3.4.20. 4R,S)-{5-[44e)-42-41,4,5,8,9,10-Hexahydro-1,4,5,8-
tetraoxo-9,10-4o-benzeno)anthracenyl)-cyclohex-4e)-yl)]-
10,15,20-tri-p-tolylporphyrinato}zinc4II) 445). Mp.3008C
.decomp.); 1H NMR .500 MHz, CDCl3, TMS): d1.93 .qd,
2H, 2Jae<Jaa<13 Hz, Jae3 Hz, cyclohexylene 3a-H, 5a-H),
2.23±2.34 .m, 2H, cyclohexylene 3e-H, 5e-H), 2.69 .s, 3H,
tolyl CH3), 2.72 .s, 6H, tolyl CH3), 2.87 .d, 2H, 2Jea13 Hz,
cyclohexylene 2e-H, 6e-H), 3.34±3.49 .m, 3H, 2a-H, cyclo-
hexylene 6a-H, 4a-H), 5.40 .tt, 1H, Jaa13 Hz, Jae3 Hz,
cyclohexylene 1a-H), 6.22, 6.32 .each s, 1H, triptycene 9-H,
10-H), 6.63 .s .br.), 2H, triptycene 6-H, 7-H), 6.66 .s .br.),
1H, triptycene 3-H), 7.10±7.15 .m, 2H, triptycene H), 7.51±
7.59 .m, 8H, 2 triptycene H, 6 tolyl H), 8.05±8.10 .m, 6H,
tolyl H), 8.91 .m, 4H, b-pyrrole 12-H, 13-H, 17-H, 18-H,
AB), 9.05 .d, 2H, J5 Hz, b-pyrrole 2-H, 8-H), 9.79 .s .br.),
2H, b-pyrrole 3-H, 7-H); 13C NMR .125 MHz, CDCl3,
TMS): d21.52, 34.19, 34.35, 36.63, 38.17, 42.16 and
42.53 .C-9, C-10, triptycene bridgehead C), 46.59, 120.66,
120.72 124.66, 125.50, 125.90, 127.24, 128.77, 129.85,
131.90, 134.31, 135.41, 137.05, 139.77, 140.02, 142.34,
142.44, 150.02, 150.40, 151.22, 151.73, 151.82, 151.92,
153.06, 182.26 and 182.35, 182.75 .C-1, C-4, C-5, C-8,
CvO); MS .EI, 80 eV); m/z .%): 1040 .1) [M14H]1,
1038 .1) [M12H]1, 1036 .1) [M1], 642 .100) [M12
C26H18O4], 400 .84) [C26H24O41]; UV/vis .CH2Cl2): lmax
.log 1)300 nm .4.26), 345 .4.10), 400 .4.63), 420 .5.71),
512 .3.72), 550 .4.34), 587 .3.91); HRMS [C67H52N4O4Zn
[M14H]]: calcd 1040.3280, found 1040.3282; HRMS
.FAB1) [C67H49N4O4Zn [M1H]]: calcd 1037.304527,
found 1037.304291.
3.4.22. 4R,S)-5-{4-[1,4,5,8,9,10-Hexahydro-1,4,5,8-tetra-
oxo-9,10-4o-benzeno)anthracen-2-yl]-phenyl}-10-[5,10,15,
20-tetrakis42-methylpropyl)-porphyrin-2-yl]-porphyrin
455). 30 mg .0.023 mmol) of the porphyrin quinone triad 54
were converted to the corresponding nickel-free tetrad by
reduction with sodium dithionite, reaction with 1 M boron
tribromide solution .3.4 ml, 0.340 mmol), and oxidation
with 15 mg .0.060 mmol) p-chloranil, followed by chroma-
tography on silica gel .eluent dichloromethane/acetone,
10:1, v/v), as described for 40. Reddish brown crystals,
yield: 22 mg .0.018 mmol, 80%), mp.2508C .decomp.);
1H NMR .500 MHz, CDCl3, TMS): d22.75 .s, 1H,
NH), 22.52 .s, 1H, NH), 22.08 .s .br.), 2H, NH), 20.52
.s .br.), 6H, CH2CHMe2), 1.26 .m, 18H, CH2CHMe2), 1.87
.m, 1H, CH2CHMe2), 2.81 .m, 2H, CH2CHMe2), 2.94 .m,
1H, CH2CHMe2), 3.60 .d, 2H, J7.1 Hz, CH2CHMe2), 4.86
.d, 2H, J7.1 Hz, CH2CHMe2), 4.90 .d, 2H, J7.1 Hz,
CH2CHMe2), 4.97 .d, 2H, J7.1 Hz, CH2CHMe2), 6.40
.s, 1H, triptycene), 6.47 .s, 1H, triptycene), 6.64 .s, 2H,
triptycene 6-H, 7-H), 7.10 .s, 1H, triptycene 3-H), 7.18
.m, 2H, arom. H), 7.64 .m, 2H, arom. H), 7.87 .m, 2H,
arom. H), 8.35 .m, 2H, arom. H), 9.01 .s .br.), 1H, b-pyrrole
H), 9.12 .d, 3H, J4.5 Hz, b-pyrrole H), 9.19 .d, 1H,
J4.7 Hz, b-pyrrole H), 9.28 .s .br.), 2H, b-pyrrole H),
9.41 .d, 1H, J4.7 Hz, b-pyrrole H), 9.43 .d, 2H, J
4.6 Hz, b-pyrrole H), 9.52 .s, 2H, b-pyrrole H), 9.57 .d,
1H, J4.7 Hz, b-pyrrole H), 9.61 .d, 1H, J4.7 Hz,
b-pyrrole H), 10.15 .s, 1H, b-pyrrole H), 10.35 .s, 2H,
meso-H); 13C NMR .125 MHz, CDCl3, TMS): d21.78,
23.39, 23.42, 23.45, 36.11, 36.67, 36.72, 36.92, 42.21,
42.24, 42.27, 42.69, 43.65, 43.81, 44.19, 44.21, 105.86,
117.20, 117.44, 118.19, 119.75, 125.64, 125.68, 126.05,
126.06, 128.03, 130.85, 131.87, 131.89, 131.95, 131.96,
131.98, 134.89, 135.02, 135.47, 142.30, 142.44, 143.48,
145.22, 145.81, 151.70, 151.72, 151.84, 151.97, 182.15,
182.36, 182.39, 182.41. MS .FAB1, DMSO/m-NO2-Bzl-
OH/Xe); m/z .%): 1233 .8) [[M13H]1], 1232 .5) [[M1
2H]1], 1177 .5) [[M13H]12C4H8]; UV/vis .CH2Cl2):
lmax .log 1)420 nm .5.32), 435 .5.41), 510 .4.44), 549
.4.34), 638 .3.95), 664 .3.91).
3.4.21. 4R,S)-42-{10-[4-41,4,9,10-Tetrahydro-5,8-dimeth-
oxy-1,4-dioxo-9,10-4o-benzeno)anthracen-2-yl)-phenyl]-
porphyrinyl}-5,10,15,20-tetrakis42-methylpropyl)-por-
phyrinato)nickel4II) 454). The porphyrin aldehyde 52
.50 mg, 0.08 mmol), 38 mg .0.084 mmol) of the triptycene
hydroquinone aldehyde 30, and 25 mg .0.17 mmol) of
dipyrromethane 53 were dissolved in 30 ml of dry dichloro-
methane under an argon atmosphere. Tri¯uoroacetic acid
.12 ml, 0.16 mmol) was added and the reaction mixture
was stirred for 18 h in the dark. Subsequently, 77 mg
.0.34 mmol) of DDQ dissolved in dry dichloromethane
.30 ml) were added and the reaction mixture was stirred
for 1 h followed by addition of 1 g of wet sodium bicarbo-
nate. The mixture was ®ltered through silica gel and washed
with dichloromethane. All high Rf-value fractions were
collected, evaporated to dryness and then chromatographed
on silica using dichloromethane as eluent. The ®rst fraction
was a porphyrin trimer, the second fraction is the porphyrin
quinone 54. Reddish brown crystals, yield: 32 mg
.0.024 mmol, 30%). Mp.3008C .decomp.); 1H NMR
.500 MHz, CDCl3, TMS): d22.84 .s, 1H, NH), 22.65
.s, 1H, NH), 20.90 .d, 6H, J5.6 Hz, CH2CHMe2), 0.82
.d, 6H, J6.7 Hz, CH2CHMe2), 0.91 .m, 12H, CH2CHMe2),
1.08 .m, 1H, CH2CHMe2), 2.28 .m, 3H, CH2CHMe2), 2.97
.d, 2H, J7.2 Hz, CH2CHMe2), 3.88 .s, 3H, OMe), 3.89 .s,