(m, 2H, bH), 6.29 (m, 2H, bH), 6.05 (d, J = 4.4, 2H, bH); 13C NMR
(100 MHz, CD2Cl2) d = 183.02, 163.12, 162.38, 151.55, 143.38,
138.86, 138.57, 136.80, 136.09, 135.94, 134.87, 134.73, 134.16,
134.07, 132.71, 131.53, 131.11, 128.86, 128.57, 127.72, 127.03,
126.09, 124.47, 117.68, 114.82, 83.03; m/z found 1248.1, calc. 1247.9
for C60H32Cl10N8O2 (M+).
y Crystal data for 3: C26H9F10N3Oꢀ1/2CH2Cl2, m = 611.83, mono-
clinic, a = 29.240(1) A, b = 23.151(9) A, c = 7.016(2) A, b =
93.06(1)1, V = 4743(3) A3, T = 173 K, space group C2/c (no. 15), z =
8, l(Mo-Ka) = 2.69 cmꢂ1, 16 039 reflections measured, 8018 unique
which were used in all calculations. The data were corrected for
Lorentz and polarization effects and absorption (multi-scan including
decay and scaling relative correction factors 0.681–0.987). The struc-
ture was solved by direct methods (SIR92). The final refinement
converged at R1 [F, 7238 reflections having I 4 2.00s(I)] = 0.084
and wR2(F2, all 13 171 unique reflections) = 0.246. All refinements
were performed using the SHELXTL crystallographic software pack-
age of Bruker-AXS. This particular structure was twinned, and the
data set used to refine the structure had reflections from both
components. This makes it look as though there are more reflections
than are necessary.
Fig. 7 Observed (a) and calculated (b) optical spectra of compound 7
in CH2Cl2.
than the tripyrrin; the calculated optical spectrum also
supports this extended conjugation. Both the observed and
calculated electronic spectra are congruent (Fig. 7).w
An understanding of the mechanism for the formation of
these compounds remains an important issue and further
research is continuing.
1 (a) The Porphyrins, ed. D. Dolphin, Academic Press, New York,
1978, vol. III–V; (b) Porphyrins and Metalloporphyrins, ed.
K. M. Smith, Elsevier, New York, 1976; (c) Expanded, Contracted
& Isomeric Porphyrins, ed. J. L. Sessler and S. J. Weghorn,
Pergamon, Oxford, 1997; (d) A. Jasat and D. Dolphin, Expanded
Porphyrins and their Heterologs, Chem. Rev., 1997, 97, 2267–2340.
2 (a) D. A. Lee and K. M. Smith, J. Chem. Soc., Perkin Trans. 1, 1997,
1215–1227; (b) D. K. Dogutan, S. H. H. Zaidai, P. Thamyongkit
and J. S. Lindsey, J. Org. Chem., 2007, 72, 7701–7714; (c) W. Jiao
and T. D. Lash, J. Org. Chem., 2003, 68, 3896–3901;
(d) D. T. Richter and T. D. Lash, J. Org. Chem., 2004, 68,
8842–8850.
This work was supported by the Natural Sciences and
Engineering Research Council (NSERC) of Canada.
Notes and references
z Selected data for 3: 23% yield, lmax (CH2Cl2)/nm 339.0, 541.1; 1H
NMR (600 MHz, CD2Cl2) d = 11.58 (br s, 1H, NH), 10.01 (br s, 1H,
NH), 7.51 (s, 1H, aH), 6.85 (d, J = 5.7, 1H, bH), 6.75 (d, J = 4.7, 1H,
aH), 6.43 (s, 1H, bH), 6.42 (d, J = 3.8, 1H, bH), 6.35 (d, J = 5.7, 1H,
bH), 6.28 (d, J = 4.8, 1H, bH); 19F NMR (282.4 MHz, CD2Cl2) d =
3 (a) M. G. P. M. S. Neves, R. M. Martins, A. C. Tome, A. J.
D. Silvestre, A. M. S. Silva, V. Felix, M. G. B. Drew and J. A.
S. Cavaleiro, Chem. Commun., 1999, 385–386; (b) Z. Gross,
N. Galili, L. Simkhovich, I. Saltsman, M. Botoshansky,
ꢂ139.13 (dd, J = 8.6, ddJ = 23.6, 2F, o-F), ꢂ139.61 (dd, J = 6.5, dd
J
= 19.3, 2F, o-F), ꢂ153.07 (t, J = 21.5, 1F, p-F), ꢂ153.25 (t, J = 21.5,
1F, p-F), ꢂ161.88 (m, 4F, m-F); 13C NMR (150.96 MHz, CD2Cl2) d =
171.77, 167.13, 151.14, 144.53, 147–137, 136.76, 135.23, 132.15,
131.95, 129.13, 127.73, 126.62, 124.41, 122.96, 113.98, 112.5–110.5
(the peaks are broadened by the multiple 13C–19F couplings of the
perfluorophenyl rings), 101.71; m/z EIMS found 570.0674, calc.
¨
D. Blaser, R. Boese and I. Goldberg, Org. Lett., 1999, 1, 599–602;
(c) J.-Y. Shin, H. Furuta, K. Yoza, S. Igarashi and A. Osuka, J. Am.
Chem. Soc., 2001, 123, 7190–7191; (d) R. Taniguchi, S. Shimizu,
J.-Y. Shin, H. Furuta and A. Osuka, Tetrahedron Lett., 2003, 44,
2505–2507; (e) Y. Tanaka, J.-Y. Shin and A. Osuka, Eur. J. Org.
Chem., 2008, 1341.
570.0664 for C26H10N3OF10 ([M + H+ +
] ). Selected data for 4: 5%
yield, 1H NMR (400 MHz, CD2Cl2) d = 11.43 (br s, 1H, NH), 9.91
(br, 1H, NH), 7.45 (m, 5H, aryl-H and aH), 7.39 (dt, J = 7.0, dtJ =
9.0, aryl-H), 6.71 (d, J = 5.5, 1H, bH), 6.57 (d, J = 4.3, 1H, bH), 6.37
(dd, J = 3.9, ddJ = 1.6, bH), 6.28 (dd, J = 4.5, ddJ = 1.0, bH), 6.26
(d, J = 5.9, bH), 6.08 (d, J = 4.7, bH); m/z ESIMS found 526.0045,
calc. 526.0047 for C26H16N3OCl4 ([M + H]+). Spectral data for 5:
4 S. Shimizu, R. Taniguchi and A. Osuka, Angew. Chem., Int. Ed.,
2005, 44, 2225–2229.
5 Unpublished results, J.-Y. Shin, B. O. Patrick and D. Dolphin, Org.
Biomol. Chem., submitted.
6 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr, T. Vreven,
K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi,
V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega,
G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota,
R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,
O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox,
H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo,
R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi,
C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma,
G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski,
S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick,
A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz,
Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov,
G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin,
D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara,
M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen,
M. W. Wong, C. Gonzalez and J. A. Pople, GAUSSIAN 03.
(Revision E.01), Gaussian, Inc, Wallingford, CT, 2007.
1
10% yield, H NMR (300 MHz, CD2Cl2) d = 12.03 (br s, 1H, NH),
8.06 (dd, J = 5.8, ddJ = 1.4, 1H, aH), 8.00 (br s, 1H, NH), 7.35 (s, 1H,
aH), 6.74 (d, J = 4.7, 1H, bH), 6.50 (d, J = 4.7, 1H, bH), 6.39 (dd, J
= 6.0, ddJ = 1.7, 1H, bH), 6.37 (m, 1H, bH), 6.36 (s, 1H, bH); 19F
NMR (282.4 MHz, CD2Cl2) d = ꢂ138.40 (d, J = 17.2, 2F, o-F),
ꢂ139.67 (dd, J = 4.1, ddJ = 8.9, 2F, o-F), ꢂ153.24 (t, J = 20.6, 1F, p-
F), ꢂ153.25 (t, J = 21.5, 1F, p-F), ꢂ161.51 (m, 2F, m-F), ꢂ161.98 (m,
2F, m-F); 13C NMR (75.48 MHz, CD2Cl2) d = 171.64, 164.64, 150.01,
144.02, 147–137 (the peaks are broadened by the multiple 13C–19
F
couplings of the perfluorophenyl rings), 137.27, 134.54, 132.88, 132.27,
127.96, 126.14, 122.68, 119.57, 113.96; m/z ESIMS (+ev) found 570.0,
calc. 570.1 for C26H10N3OF10 ([M + H+ +
]
), (ꢂev) found 567.9, calcd.
568.1 for C26H8N3OF10 ([M ꢂ H+]ꢂ). Selected data for 6: o0.5%
yield, m/z ESIMS found 526.0052, calc. 526.0047 for C26H16N3OCl4
([M + H+ +). Selected data for 7: 30% yield, 1H NMR (300 MHz,
]
CD2Cl2) d = 12.84 (br s, 2H, NH), 12.35 (br s, 2H, NH), 7.88 (s, 2H,
aH), 749–7.36 (m, 12H, aryl-H), 6.95 (dd, J = 5.5, ddJ = 1.7, 2H, bH),
6.60 (d, J = 5.5, ddJ = 1.7, 2H, bH), 6.47 (d, J = 4.4, 2H, bH), 6.33
ꢁc
This journal is The Royal Society of Chemistry 2009
Chem. Commun., 2009, 2323–2325 | 2325