Oxybenziporphyrins, Oxypyriporphyrins, and Benzocarbaporphyrins
1H NMR (400 MHz, 1 drop TFA-CDCl3) δ -6.91 (1H, s), -4.37
(2H, br s), 1.80 (6H, t, J ) 7.2 Hz), 3.65 (6H, s), 4.10 (4H, q, J
) 7.2 Hz), 7.72-7.76 (2H, m), 8.66-8.70 (2H, m), 9.98 (2H, s),
10.29 (2H, s), 10.42 (2H, s); 13C NMR (TFA-CDCl3) δ 11.8,
17.1, 19.9, 94.9, 105.1, 122.0, 128.8, 129.1, 129.6, 135.5, 137.0,
140.1, 140.6, 140.9, 142.6, 153.2; HRMS (EI) calcd for C31H28N2O
m/z 444.2202, found 444.2206.
d, J ) 9 Hz), 8.27 (1H, s), 8.31 (1H, s), 8.35-8.40 (2H, AB
quartet, J ) 5.2 Hz), 8.66 (1H, d, J ) 9 Hz), 8.93 (1H, s), 9.54
(1H, s); 13C NMR (3 drops TFA-CDCl3) δ 11.3, 11.4, 15.4, 15.5,
19.0, 96.9, 98.5, 115.5, 118.4, 121.4, 123.5, 123.8, 126.0, 133.0,
133.8, 140.5, 141.5, 145.2, 146.5, 146.8, 148.3, 150.2, 151.8,
153.8, 176.4; HRMS (EI) calcd for C28H27N3O m/z 421.2154,
found 421.2150. Anal. Calcd for C28H27N3O‚H2O: C, 76.51; H,
6.42; N, 9.56. Found: C, 76.41; H, 6.53; N, 9.17.
8,17-Diet h yl-7,18-d im et h ylb en zo[b]-21-ca r b a -23-t h ia -
p or p h yr in (15). 2,5-Bis(5-ethoxycarbonyl-3-ethyl-4-methyl-
2-pyrrolylmethyl)thiophene (8, 100 mg) was dissolved in TFA
(20 mL) and the solution heated under nitrogen at 60 °C for 4
h. The solution was diluted with chloroform (50 mL) and
washed with water (50 mL) and saturated sodium bicarbonate
solution (50 mL). The organic phase was concentrated on a
rotary evaporator to give 9 as a viscous red oil. TFA (2 mL),
dichloromethane (200 mL), and 1,3-diformylindene48 (13, 38
mg) were added, and the resulting solution was stirred under
nitrogen at room temperature for 2 h. The solution was
neutralized by the dropwise addition of triethylamine, DDQ
(51 mg) was added, and the mixture was stirred for a further
1 h at room temperature. The solution was washed with water
and evaporated under reduced pressure and the residue
chromatographed on grade 3 alumina eluting with dichlo-
romethane. The product fraction was collected and washed
with a saturated sodium carbonate solution. Recrystallization
from chloroform-hexanes gave the thiacarbaporphyrin (30 mg,
31%) as dark brown crystals: mp >300 °C; UV-vis (CHCl3)
λmax (log ꢀ) 387 (4.60), 431 (4.89), 527 (4.14), 623 (3.80), 683
nm (3.22); UV-vis (0.01% TFA-CHCl3) λmax (log ꢀ) 428 (4.86),
617 (4.09), 667 nm (3.50); 1H NMR (400 MHz, CDCl3) δ -5.49
(1H, s), -4.30 (1H, br s), 1.81 (6H, t, J ) 7.6 Hz), 3.48 (6H, s),
3.89 (4H, q, J ) 7.6 Hz), 7.74-7.77 (2H, m), 8.85-8.88 (2H,
m), 9.89 (2H, s), 10.20 (2H, s), 10.41 (2H, s); 1H NMR (400
MHz, 1 drop TFA-CDCl3) δ -7.45 (1H, s), -5.86 (2H, br s),
1.81 (6H, t, J ) 7.6 Hz), 3.55 (6H, s), 4.02 (4H, q, J ) 7.6 Hz),
7.81-7.84 (2H, m), 8.66-8.70 (2H, m), 10.10 (2H, s), 10.21 (2H,
s), 10.71 (2H, s); 1H NMR (400 MHz, 50% TFA-CDCl3) δ -6.69
(1H, s), -5.34 (2H, s), 1.94 (6H, t, J ) 7.2 Hz), 3.76 (6H, s),
4.23 (4H, q, J ) 7.6 Hz), 7.88-7.92 (2H, m), 8.86-8.90 (2H,
m), 10.40 (2H, s), 10.67 (2H, s), 11.10 (2H, s); 13C NMR (3 drops
TFA-CDCl3) δ 11.6, 17.0, 20.1, 105.0, 108.1, 122.1, 129.7,
135.8, 137.2, 138.5, 141.1, 141.4, 141.5, 144.8; HRMS (EI) calcd
for C31H28N2S m/z 460.1973, found 460.1967. Anal. Calcd for
9,18-Dieth yl-8,19-d im eth yl-24-oxa -2-oxyben zip or p h y-
r in Hyd r och lor id e (17). The title compound was prepared
from 10b (100 mg) and 5-formylsalicylaldehyde (22, 38 mg)
by the procedure described for 14. The crude product was
chromatographed on
a grade 3 alumina column eluting
initially with dichloromethane and then with chloroform. A
green fraction was collected, and this was washed first with
saturated sodium carbonate solution and then 10% hydrochlo-
ric acid. Recrystallization from chloroform-hexanes gave the
oxaoxybenziporphyrin (60 mg, 52%) as dark green crystals:
mp >300 °C; IR (KBr) νCdO 1625 cm-1; UV-vis (5% Et3N-
CHCl3) λmax (log ꢀ) 416 (4.95), 466 (4.70), 597 (4.23), 724 nm
(3.96); UV-vis (CHCl3) λmax (log ꢀ) 424 (5.19), 478 (4.83), 592
(3.99), 639 (4.24), 680 nm (3.85); UV-vis (5% TFA-CHCl3)
λmax (log ꢀ) 348 (4.72), 423 (4.87), 556 (3.79), 600 (4.11), 653
(3.80), 719 nm (3.79); 1H NMR (400 MHz, CDCl3) δ -5.23 (1H,
s), 0.40 (1H, br s), 0.52 (1H, br s), 1.64-1.69 (6H, 2 overlapping
triplets), 3.38 (3H, s), 3.47 (3H, s), 3.79-3.88 (4H, 2 overlap-
ping quartets), 7.32 (1H, d, J ) 9.2 Hz), 8.63 (1H, d, J ) 9.2
Hz), 9.51 (1H, d, J ) 3.6 Hz), 9.59 (1H, d, J ) 3.6 Hz), 9.71
(1H, s), 9.76 (1H, s), 9.82 (1H, s), 10.84 (1H, s); 1H NMR (400
MHz, pyridine-d5) δ -4.5 (1H, br s), 1.30-1.39 (6H, 2 overlap-
ping triplets), 2.99 (3H, s), 3.06 (3H, s), 3.44 (2H, q, J ) 7.6
Hz), 3.52 (2H, q, J ) 7.6 Hz),7.35 (1H, d, obscured by pyridine
peak), 8.74 (1H, d, J ) 9.6 Hz), 9.54-9.61 (2H, poorly resolved
AB quartet), 9.77 (1H, s), 9.82 (1H, s), 9.97 (1H, s), 10.86 (1H,
1
s); H NMR (400 MHz, CDCl3) δ 1.33 (1H, s), 1.45-1.50 (6H,
2 overlapping triplets), 3.03 (3H, s), 3.04 (3H, s), 3.35 (4H, q,
J ) 7.3 Hz), 5.46 (1H, s), 5.58 (1H, s), 7.67 (1H, d, J ) 8.8
Hz), 8.33 (1H, s), 8.36 (1H, s), 8.69 (1H, d, J ) 8.8 Hz), 8.72-
8.77 (2H, AB quartet, J ) 5 Hz), 9.06 (1H, s), 9.68 (1H, s); 13
C
NMR (3 drops TFA-CDCl3) δ 11.3, 11.5, 15.5, 15.6, 18.8 (2),
95.2, 96.5, 120.0, 120.8, 121.6, 123.6, 124.0, 128.3, 133.9, 135.0,
139.5, 140.3, 140.8, 140.9, 145.2, 146.1, 149.1, 150.7, 151.1,
156.9, 161.0, 177.2; HRMS (EI) calcd for C28H26N2O2 m/z
422.1994, found 422.1992.
C
31H28N2S‚1/4H2O: C, 80.05; H, 6.17; N, 6.02. Found: C, 79.92;
H, 6.01; N, 6.07.
9,18-Dieth yl-8,19-d im eth yl-24-th ia -2-oxyben zip or p h y-
r in (18). The title compound was prepared from thiatripyrrane
diethyl ester 8 (100 mg) and 5-formylsalicylaldehyde (22, 32
mg) by the procedure described for 15. The crude product was
chromatographed on a grade 3 alumina column eluting with
dichloromethane. The product fraction was washed with
saturated sodium carbonate solution and recrystallized from
chloroform-hexanes to give the thiaoxybenziporphyrin (14 mg,
15%) as dark green crystals: mp >300 °C; IR (KBr) νCdO 1624
cm-1; UV-vis (CHCl3) λmax (log ꢀ) 353 (4.27), 427 (4.93), 471
(4.72), 605 (4.19), 733 nm (3.88); UV-vis (0.01% TFA-CHCl3)
λmax (log ꢀ) 319 (4.40), 330 (4.40), 440 (4.91), 492 (4.50), 606
(4.06), 726 nm (3.79); UV-vis (50% TFA-CHCl3) λmax (log ꢀ)
358 (4.54), 441 (4.86), 577 (3.64), 624 (3.91), 730 nm (3.74); 1H
NMR (400 MHz, CDCl3) δ -5.80 (1H, s), -4.24 (1H, br s),
1.67-1.74 (6H, 2 overlapping triplets), 3.25 (3H, s), 3.37 (3H,
s), 3.65-3.75 (4H, 2 overlapping quartets), 7.40 (1H, d, J )
9.2 Hz), 8.68 (1H, d, J ) 9.2 Hz), 9.25 (1H, s), 9.50 (1H, d, J
) 4 Hz), 9.55 (1H, d, J ) 4 Hz), 9.85 (1H, s), 9.93 (1H, s), 10.59
(1H, s); 1H NMR (400 MHz, 1 drop TFA-CDCl3) δ -4.63 (1H,
s), 1.69-1.75 (6H, 2 overlapping triplets), 3.45 (3H, s), 3.49
(3H, s), 3.85-3.93 (4H, 2 overlapping quartets), 7.68 (1H, d, J
) 8.8 Hz), 8.97 (1H, d, J ) 8.8 Hz), 9.80-9.87 (2H, AB quartet,
J ) 5 Hz), 9.92 (1H, s), 10.35 (1H, s), 10.46 (1H, s), 10.96 (1H,
s); 1H NMR (400 MHz, 50% TFA-CDCl3) δ 0.45 (1H, d, J ) 2
Hz), 1.54-1.59 (6H, 2 overlapping triplets), 3.14 (3H, s), 3.15
(3H, s), 3.43-3.49 (4H, 2 overlapping quartets), 3.6 (2H, v br),
9,18-Dieth yl-8,19-d im eth yl-2-oxyben zip or p h yr in (16).
Tripyrrane 10b (200 mg) was stirred with TFA (2 mL) under
nitrogen for 10 min. The solution was diluted with dichlo-
romethane (38 mL), and 5-formylsalicylaldehyde (22, 76 mg)
was added immediately. The resulting mixture was stirred
under nitrogen for 2 h. The solution was neutralized by the
dropwise addition of triethylamine, DDQ (116 mg) was added,
and the resulting mixture was stirred at room temperature
for 1 h. The solution was washed with water and evaporated
under reduced pressure, and the residue was chromatographed
on grade 3 alumina eluting initially with dichloromethane and
then with chloroform. Recrystallization from chloroform-
methanol gave the oxybenziporphyrin (80 mg, 38%) as purple
crystals: mp >300 °C; IR (KBr) νCdO 1627 cm-1; UV-vis
(CHCl3) λmax (log ꢀ) 426 (5.24), 450 (4.91), 546 (3.90), 587 (4.42),
638 (3.83), 701 nm (3.85); UV-vis (0.01% TFA-CHCl3) λmax
(log ꢀ) 425 (5.21), 451 (4.78), 588 (4.26), 633 (3.93), 695 nm
(3.81); UV-vis (5% TFA-CHCl3) λmax (log ꢀ) 317 (4.42), 348
(4.68), 430 (4.86), 558 (3.83), 604 (4.26), 710 (3.83), 775 nm
(3.98); 1H NMR (400 MHz, CDCl3) δ -7.11 (1H, s), -3.56 (2H,
br s), 1.72-1.79 (6H, 2 overlapping triplets), 3.41 (3H, s), 3.53
(3H, s), 3.84-3.92 (4H, 2 overlapping quartets), 7.41 (1H, d, J
) 9.6 Hz), 8.67 (1H, d, J ) 9.6 Hz), 8.92-8.94 (2H, AB quartet,
J ) 4.4 Hz), 9.20 (1H, s), 9.32 (1H, s), 9.37 (1H, s), 10.46 (1H,
1
s); H NMR (400 MHz, 50% TFA-CDCl3) δ 1.20 (1H, s), 1.46
(6H, t, J ) 7 Hz), 3.00 (3H, s), 3.01 (3H, s), 3.30-3.36 (4H, 2
overlapping quartets), 5.18 (1H, br s), 5.23 (1H, br s), 7.62 (1H,
4
3
7.84 (1H, d, J ) 8.8 Hz), 8.96 (1H, dd, J ) 2 Hz, J ) 2 Hz,
J . Org. Chem, Vol. 69, No. 18, 2004 6091