2810
T. Hayashi et al. / Tetrahedron 58 12002) 2803±2811
reduced pressure, the residue was chromatographed on
alumina *CHCl3). The crude zinc porphyrin was recrystal-
lized from CHCl3/MeOH to yield 0.0269 g *88%,
8.94 *m, 18H), 8.91 *t, J2Hz, 2H), 8.08 *t, J2Hz, 2H),
8.05 *t, J2Hz, 4H), 8.04 *t, J2Hz, 2H), 7.99 *t, J2Hz,
4H), 7.82*t, J2Hz, 2H), 7.79 *t, J2Hz, 4H), 3.94 *s,
6H), 1.52*s, 18H), 1.51 *s, 18H), 1.50 *s, 36H), 1.42*s,
38H); 13C NMR *CD2Cl2) d 167.4, 150.9, 150.8, 150.8,
150.1, 149.1, 149.1, 144.6, 142.1, 142.0, 139.0, 137.2,
134.3, 132.9, 132.5, 131.7, 130.0, 128.0, 123.1, 122.9,
121.4, 119.1, 52.64, 35.29, 35.23, 31.81, 31.76; HRFAB
MS calcd for C140H154N8O4ZN2 2139.0676 *M1), found
2139.0811.
1
0.0192mmol) of pure 3: H NMR *C5D5N) d 10.47 *s,
4H), 10.41 *s, 2H), 9.01 *s, 2H), 8.41 *d, J8 Hz, 2H),
8.16 *d, J7 Hz, 2H), 7.88 *t, J8 Hz, 2H), 4.17 *t,
J8 Hz, 8H), 3.66 *s, 12H), 3.56 *s, 12H), 2.72 *s, 12H),
2.40 *m, 8H), 1.79 *m, 8H), 1.49 *m, 8H), 1.35 *m, 8H), 0.88
*t, J7 Hz, 12H); HRFAB MS calcd for C88H102N8ZN2
1398.6819 *M1), found 1398.6846.
4.3.5. Dimethyl 3,30-diformyl-5,50-biphenylcarboxylate
214). Zinc powder *0.223 g, 3.41 mmol) puri®ed with 2%
HCl, NiBr2*PPh3)2 *0.236 g, 0.318 mmol), Et4NI *0.605 g,
2.35 mmol) and methyl 3-formyl-5-bromobenzoate
*0.388 g, 1.22 mmol) were dried in vacuo. Anhydrous
THF *4.0 mL) was then added and stirred at 508C under
N2 for 22 h. After removal of the solvent, CHCl3 was
added to the residue and the mixture was ®ltered through
Celite. The ®ltrate was washed with H2O and the crude
product was chromatographed on silica gel *CHCl3/
4.4. Binding studies
Initially, a porphyrin solution *2.0 mL, [zinc porphyrin
dimer]1026 M) was poured into a 1 cm quartz cell. The
UV±Vis spectrum of the pure host solution was recorded,
and some of the stock guest solution *e.g. 10 mL) was trans-
ferred into the cell with a syringe. The spectrum was
recorded and the process was repeated until the desired
guest-to-host ratio was obtained. The parameters from the
changes in the monitored absorbance were calculated using
a nonlinear curve-®tting procedure based on the damped
Gauss±Newton method.
1
AcOEt) to yield 0.0986 g *50%, 0.302mmol) of 14: H
NMR *CDCl3) d 10.16 *s, 2H), 8.58 *t, J2Hz, 2H), 8.57
*t, J2Hz, 2H), 8.37 *t, J2Hz, 2H), 4.06 *s, 6H); HRFAB
MS calcd for C19H14O6 326.0790 *M1), found 326.0780.
Acknowledgements
4.3.6. 3,30-Bis[10,15,20-tris23,5-di-tert-butylphenyl)-por-
phyrin-5-yl]-5,50-dimethoxycarbonyl-1,10-biphenyl 216).
Pyrrole *3.5 mL, 50.4 mmol), 14 *1.09 g, 3.34 mmol), 15
*8.84 g, 35.9 mmol) and Zn*OAc)2´2H2O *2.43 g,
11.1 mmol) were dissolved in 270 mL of propionic acid.
The mixture was heated to 1108C for 100 min and then
allowed to cool to ambient temperature. The solvents were
removed under high vacuum with successive portions of
toluene. To the residue, 0.993 g of DDQ in 200 mL of
CHCl3 was added and the mixture was stirred at room
temperature with air-bubbling. After the oxidation was
completed, the reaction mixture was ®ltered through Celite
and washed with saturated NaHCO3. After removal of the
solvent, the residue was separated on Silica Gel column
chromatography *hexane/CHCl3) to collect the zinc
porphyrin dimer. To remove the zinc atom, 6N HCl was
poured into the CHCl3 solution and the mixture was vigor-
ously stirred for 5 min. The organic layer was collected and
then washed with saturated NaHCO3. The crude free base
porphyrin was then puri®ed by column chromatography on
silica gel *hexane/CHCl3) and recrystallized from CH2Cl2/
MeOH to yield 0.192g *2.9%, 0.0952mmol) of pure 16: 1H
NMR *CD2Cl2) d 8.98 *t, J2Hz, 2H), 8.95 *t, J2Hz,
2H), 8.92 *t, J2Hz, 2H), 8.87 *br, 16H), 8.08 *t, J2Hz,
2H), 8.06 *t, J2Hz, 4H), 8.05 *t, J2Hz, 2H), 8.00 *t,
J2Hz, 2H), 7.84 *t, J2Hz, 2H), 7.80 *t, J2Hz, 4H),
3.94 *s, 6H), 1.52*s, 36H), 1.51 *s, 18H), 1.50 *s, 18H), 1.42
*s, 38H), 22.79 *s, 4H); HRFAB MS calcd for
C140H158N8O4 2015.2406 *M1), found 2015.2864.
This work was supported by a Grant-in-Aid for Scienti®c
Research from the Ministry of Education, Science and
Culture, Japan.
References
1. Lehn, J.-M. Supramolecular Chemistry; VCH: Weinheim,
1995.
2. *a) Hayashi, T.; Ogoshi, H. Chem. Soc. Rev. 1997, 26, 355±
364. *b) Ogoshi, H.; Mizutani, T. Acc. Chem. Res. 1998, 31,
81±89. *c) Ogoshi, H.; Mizutani, T.; Hayashi, T.; Kuroda, Y.
The Porphyrin Handbook; Kadish, K. M., Smith, K. M.,
Guilard, R., Eds.; Academic Press *San Diego) 2000; Vol. 6
Chapter 6.
3. Hsu, M.-C.; Woody, R. W. J. Am. Chem. Soc. 1971, 93, 3515±
3525.
4. *a) Ogoshi, H.; Saita, K.; Sakurai, K.; Watanabe, T.; Toi, H.;
Aoyama, Y.; Okamoto, Y. Tetrahedron Lett. 1986, 27, 6365±
6368. *b) Aoyama, Y.; Saita, K.; Toi, H.; Ogoshi, H.;
Okamoto, Y. Tetrahedron Lett. 1987, 28, 4853±4856.
5. Groves, J. T.; Myers, R. S. J. Am. Chem. Soc. 1983, 105,
5791±5796.
6. *a) Aoyama, Y.; Uzawa, T.; Saita, K.; Tanaka, Y.; Toi, H.;
Ogoshi, H.; Okamoto, Y. Tetrahedron Lett. 1988, 29, 5271±
5274. *b) Boitrel, B.; Lecas, A.; Rose, E. Tetrahedron Lett.
1988, 29, 5653±5655. *c) Konishi, K.; Yahara, K.; Toshishige,
H.; Aisa, T.; Inoue, S. J. Am. Chem. Soc. 1994, 116, 1337±
1344. *d) Mizutani, T.; Ema, T.; Tomita, T.; Kuroda, Y.;
Ogoshi, H. J. Am. Chem. Soc. 1994, 116, 4240±4250.
4.3.7. Zinc porphyrin dimer 24). To a solution of CH2Cl2
containing 16 *0.059 g, 0.0292 mmol) was added 20 drops
of saturated Zn*OAc)2 solution in MeOH. The mixture was
stirred at room temperature for 2h and passed through basic
alumina to yield 0.0623 g *quant.) of 4. The zinc porphyrin
dimer was further puri®ed by recrystallization from CH2Cl2/
Â
*e) Mizutani, T.; Ema, T.; Yoshida, T.; Renne, T.; Ogoshi,
H. Inorg. Chem. 1994, 33, 3558±3566. *f) Kuroda, Y.; Kato,
Y.; Higashioji, T.; Hasegawa, J.; Kawanami, S.; Takahashi,
M.; Shiraishi, N.; Tanabe, K.; Ogoshi, H. J. Am. Chem. Soc.
1995, 117, 10950±10958. *g) Bonar-Law, R. P. J. Am. Chem.
Soc. 1995, 117, 12397±12407. *h) Konishi, K.; Kimata, S.;
1
MeOH: H NMR *CD2Cl2) d 8.99 *t, J2Hz, 2H), 8.97±