1798
V. Gandhi et al. / Tetrahedron 66 (2010) 1787–1799
(log10 3) 387 (4.57), 440 (5.10), 537 (4.29), 574 (4.41), 596 (4.16),
655 nm (4.15); UV–vis (1% TFA–CHCl3): lmax (log10 3) 449 (5.18), 589
(4.40), 637 nm (4.36); UV–vis (5% TFA–CHCl3): lmax (log10 3) 402
(sh, 4.59), 449 (5.12), 532 (4.43), 592 (4.40), 638 nm (4.33); 1H NMR
431 (4.89), 580 (4.29), 604 nm (4.25); UV–vis (1% TFA–CHCl3): lmax
(log10 3) 444 (5.05), 529 (4.02), 577 (4.03), 600 (4.08), 654 nm
(4.55); 1H NMR (400 MHz, TFA–CDCl3):
d
ꢁ2.00 (1H, br s), ꢁ0.77
(3H, br s), 1.00 (6H, t, J¼7.6 Hz), 1.53–1.62 (4H, m), 1.97–2.06 (4H,
m), 3.68 (6H, s), 4.13 (4H, t, J¼7.4 Hz), 8.45 (2H, s), 8.70–8.75 (6H,
m), 9.66 (2H, d, J¼4.8 Hz), 10.18 (2H, dd, J¼1.2, 6.4 Hz), 10.57 (2H, d,
(400 MHz, CDCl3):
d
ꢁ5.75 (2H, br s), 0.90 (12H, d, J¼6.8 Hz), 1.92
(2H, nonet, J¼6.7 Hz), 2.77 (6H, s), 2.94 (4H, t, J¼7.6 Hz), 3.76 (4H, t,
J¼8.0 Hz), 4.16 (4H, d, J¼6.8 Hz), 7.41 (2H, t, J¼7.6 Hz), 7.85 (2H, d,
J¼7.6 Hz), 7.94 (2H, d, J¼8.0 Hz), 8.01–8.06 (4H, m), 8.14–8.18 (4H,
m), 9.04 (1H, s), 9.12 (2H, d, J¼7.6 Hz), 9.25 (1H, br s), 9.45 (2H, s);
J¼8.4 Hz), 11.18 (2H, s), 11.48 (2H, s); 13C NMR (TFA–CDCl3):
d 12.4,
13.9, 23.1, 26.9, 34.3, 100.0, 100.4, 124.9, 125.0, 126.3, 126.9, 127.3,
127.8, 128.3, 128.8, 129.4, 131.3, 132.9, 135.6, 138.0, 139.9, 140.2,
141.3, 143.3, 144.0, 146.5, 147.9. HRMS (FAB), m/z calcd for
C54H44N6þH: 777.3706. Found: 777.3706.
1H NMR (400 MHz, TFA–CDCl3):
d
ꢁ2.18 (2H, br s), ꢁ1.74 (2H, br s),
0.91 (12H, d, J¼6.8 Hz), 1.94 (2H, nonet, J¼6.6 Hz), 3.15 (4H, t,
J¼8.0 Hz), 3.74 (6H, s), 3.96 (4H, d, J¼6.4 Hz), 4.46 (4H, t, J¼8.0 Hz),
8.45 (4H, s), 8.65 (2H, t, J¼7.6 Hz), 8.68–8.74 (6H, m), 10.09 (2H, d,
J¼7.0 Hz), 10.26 (2H, dd, J¼3.0, 6.0 Hz), 10.82 (1H, s), 11.58 (2H, s),
Acknowledgements
12.66 (1H, s); 13C NMR (CDCl3):
d 12.3, 19.0, 21.9, 27.8, 35.8, 72.2,
This material is based upon work supported by the National
Science Foundation under Grant Nos. CHE-0134472 and CHE-
0616555, and the Petroleum Research Fund, administered by the
American Chemical Society.
98.9, 100.5, 102.5, 125.0, 125.4, 126.7,126.8, 127.3,127.5,128.2, 128.3,
128.7, 128.9, 129.0, 130.2, 131.0, 133.0, 138.8, 139.4, 139.7, 140.3,
143.1, 143.4, 174.5. HRMS (FAB), m/z calcd for C64H54N4O4þH:
943.4225. Found: 943.4223.
Supplementary data
4.2.21. [13,17-Bis(2-isobutoxycarbonylethyl)-12,18-dimethyldipyr-
eno[4,5-b:4,5-g]porphyrinato]nickel(II) (40a). Dark green crystals,
Supplementary data associated with this article can be found, in
mp >300 ꢀC (chloroform–methanol); UV–vis (CHCl3): lmax (log10 3
)
436 (4.88), 556 (4.02), 599 nm (4.40); 1H NMR (CDCl3):
d 0.80 (12H,
d, J¼6.0 Hz), 1.77–1.85 (2H, br m), 2.46 (6H, s), 2.82 (4H, br t), 3.75
(4H, br t), 3.85 (4H, d, J¼6.0 Hz), 7.96–8.04 (2H, br), 8.10–8.25 (8H,
m), 8.30–8.40 (4H, m), 8.62–8.72 (2H, br), 8.78–8.86 (2H, br), 8.88
(1H, br s), 9.72 (1H, br s). HRMS (FAB), m/z calcd for C64H52N4NiO4:
998.3342. Found: 998.3341.
References and notes
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T. G.; Xie, L. Y. Acc. Chem. Res. 1997, 30, 251; (c) Meunier, B. Chem. Rev. 1992, 92,
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M., Guilard, R., Eds.; Academic: San Diego, CA, 2000; Vol. 6, pp 133–156.
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4.2.22. [13,17-Bis(2-isobutoxycarbonylethyl)-12,18-dimethyldipyr-
eno[4,5-b:4,5-g]porphyrinato]copper(II) (40b). Dark green crystals,
mp >300 ꢀC (chloroform–methanol); UV–vis (1% Et3N–CHCl3):
lmax (log10 3) 438 (4.93), 562 (4.08), 605 nm (4.38). HRMS (FAB), m/z
calcd for C64H52CuN4O4: 1003.3285. Found: 1003.3285.
4.2.23. [13,17-Bis(2-isobutoxycarbonylethyl)-12,18-dimethyldipyr-
eno[4,5-b:4,5-g]porphyrinato]zinc(II) (40c). Dark green crystals, mp
>300 ꢀC; UV–vis (CHCl3): lmax (log10 3) 446 (5.18), 572 (4.40),
613 nm (4.66); UV–vis (1% pyrrolidine–CHCl3): lmax (log10 3) 461
(5.12), 578 (4.27), 619 nm (4.49); 1H NMR (400 MHz, CDCl3):
d 0.91
(12H, d, J¼6.4 Hz), 1.88–1.96 (2H, m), 2.23 (6H, br s), 2.70 (4H, br t),
3.30 (4H, br t), 3.93 (4H, d, J¼6.8 Hz), 6.44–6.60 (2H, br), 6.96–7.05
(2H, br), 7.44–7.60 (6H, br), 7.62–7.68 (2H, br), 7.8–8.2 (5H, v br),
8.50–8.60 (2H, br), 8.64–8.72 (1H, br); 1H NMR (400 MHz, one drop
pyrrolidine–CDCl3):
d
0.90 (12H, t, J¼6.4 Hz), 1.79 (2H, nonet), 3.34
(4H, t, J¼7.8 Hz), 3.65 (6H, s), 3.99 (4H, d, J¼6.8 Hz), 4.38 (4H, t,
J¼7.8 Hz), 8.18–8.23 (6H, m), 8.25 (2H, t, J¼7.8 Hz), 8.34–8.42 (4H, 2
overlapping triplets), 9.85 (1H, s), 9.98 (2H, d, J¼7.2 Hz), 10.20 (2H,
d, J¼7.2 Hz), 10.90 (2H, s), 11.78 (1H, s). HRMS (FAB), m/z calcd for
C64H52N4O4Zn: 1004.3280. Found: 1004.3277.
13. Tsuda, A.; Osuka, A. Science 2001, 293, 79.
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4.2.24. 7,18-Dibutyl-8,17-dimethylphenanthrolino[9,10-b]pyr-
eno[4,5-l]porphyrin (35). Nitrogen gas was gently bubbled through
a pear shaped flask containing tripyrrane 34 (100 mg, 0.139 mmol)
and TFA (2 mL) for 10 min. Dichloromethane (38 mL) was added,
followed immediately by pyrenopyrrole dialdehyde 29 (42 mg,
0.14 mmol), and the reaction mixture stirred under nitrogen in dark
for 3 h. The mixture was neutralized by the dropwise addition of
Et3N, DDQ (33 mg) was added, and stirring was continued for an
additional 1 h. The solution was then diluted with chloroform,
washed with water and the solvent evaporated under reduced
pressure. The residue was chromatographed on grade 3 alumina
eluting with chloroform. Recrystallization from chloroform–
methanol gave the porphyrin (54 mg, 0.070 mmol, 50%) as a dark
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3152.
green powder, mp >300 ꢀC; UV–vis (1% Et3N–CHCl3): lmax (log10 3
)