B. Boitrel et al.
FULL PAPER
Jm ϭ 1.5 Hz, 1 H), 7.98 (t, J ϭ 8.0 Hz, 1 H), 7.82 (s, 1 H), 7.67 (t, (1544.5): calcd. C 70.76, H 4.96, N 7.25; found C 70.68, H 5.06, N
J ϭ 7.5 Hz, 1 H), 7.57 (d, Jo ϭ 7.0 Hz, Jm ϭ 1.5 Hz, 1 H), 7.32 (d, 6.92. Ϫ UV/Vis (CH2Cl2): λ nm (10Ϫ3·ε, Ϫ1 cmϪ1) ϭ 419 (448.7),
Jo ϭ 7.5 Hz, Jm ϭ 1.5 Hz, 2 H), 7.29 (s, 1 H), 7.26 (t, Jo ϭ 8.0 Hz,
Jm ϭ 1.5 Hz, 2 H), 7.19 (m, 13 H), 7.10 (d, J ϭ 8.0 Hz, 6 H),
7.00Ϫ6.92 (m, 19 H), 6.88 (t, Jo ϭ 7.5 Hz, Jm ϭ 1.0 Hz, 2 H), 6.84
(d, J ϭ 7.0 Hz, 1 H), 6.80 (d, J ϭ 8.5 Hz, 2 H), 6.79Ϫ6.72 (m, 4
H), 6.61 (s, 1 H, H2Ј), 6.44 (d, J ϭ 5.0 Hz, 2 H), 6.36Ϫ6.33 (m, 2
H), 6.32 (d, J ϭ 1.5 Hz, 1 H), 5.84 (d, J ϭ 1.5 Hz, 1 H), 5.39 (s, 2
H), 5.16 (s, 1 H), 4.15 (s, 2 H), 1.70 (s, 3 H), Ϫ2.55 (s, 2 H). Ϫ MS
(FAB): m/z ϭ 1600.3 [M]ϩ.
[α-5,10,15-Tris(2-triphenylmethylaminophenyl)-β-20-(2-{[3-(imida-
zol-1-yl)methyl]benzoylamido}phenyl)porphyrin]zinc(II) (6Zn): In a
glove box, 6 was dissolved in methanol and an excess of Zn(OAc)2
and sodium acetate was added. The mixture was stirred and re-
fluxed for 10 hours. After evaporation to dryness, the residue was
suspended in CH2Cl2, filtered, and the solvent removed under va-
cuum. Chromatography on a silica gel column yielded the final
compound 6Zn eluted with CHCl3. Ϫ 1H NMR (500 MHz, CDCl3,
300 K): δ ϭ 9.24 (d, J ϭ 8.5 Hz, 1 H), 9.01 (d, J ϭ 4.0 Hz, 2 H),
8.99 (d, J ϭ 4.5 Hz, 2 H), 8.93 (d, J ϭ 4.5 Hz, 2 H), 8.78 (d, J ϭ
4.5 Hz, 2 H), 8.04 (d, Jo ϭ 7.5 Hz, Jm ϭ 1.5 Hz, 1 H), 7.98 (d, J ϭ
8.0 Hz, 1 H), 7.87 (t, Jo ϭ 8.0 Hz, Jm ϭ 1.5 Hz, 2 H), 7.57Ϫ7.46
(m, 4 H), 7.39Ϫ7.19 (m, 10 H), 7.18Ϫ7.01 (m, 16 H), 6.97Ϫ6.83
(m, 19 H), 6.82Ϫ6.67 (m, 14 H), 5.32 (t, J ϭ 1.5 Hz, 1 H, H2Ј),
5.05 (d, J ϭ 1.6 Hz, 1 H), 3.95 (s, 2 H), 1.51 (d, J ϭ 1.6 Hz, 1 H),
Ϫ1.50 (s, 3 H). Ϫ MS (FAB): m/z ϭ 1661.7 [M ϩ H]ϩ.
512 (24.6), 544 (4.9), 586 (7.6), 642 (1.9).
[α-5,10,α-15,20-Bis(2,2Ј-{3,3Ј-[2,2-(diethoxycarbonyl)propane-1,3-
diyl]dibenzoylamido}diphenyl)porphyrin]zinc(II) (8Zn): Porphyrin 8
(20 mg) was dissolved in CHCl3 containing 2,6 lutidine (0.2 mL).
The mixture was stirred and refluxed for 1 hour. After evaporation,
the crude product was chromatographed on a silica gel column with
1
CH2Cl2 to give 8Zn in 85% yield (23 mg). Ϫ H NMR (500 MHz,
CDCl3, 323 K): δ ϭ 9.07 (s, 4 H), 8.84 (s, 4 H), 8.65 (d, J ϭ 8.3 Hz,
4 H), 7.85 (t, Jo ϭ 7.8 Hz, Jm ϭ 1.3 Hz, 4 H), 7.78 (d, J ϭ 7.7 Hz,
4 H), 7.72 (s, 4 H), 7.48 (t, Jo ϭ 7.7 Hz, Jm ϭ 1.0 Hz, 4 H), 7.35
(d, J ϭ 7.8 Hz, 4 H), 6.78 (t, J ϭ 7.7 Hz, 4 H), 6.38 (d, J ϭ 7.4 Hz,
4 H), 5.63 (large s, 4 H, H2Ј), 3.29 [q, J ϭ 7.1 Hz, 4 H, -
(CH2)oCH3], 3.14 [q, J ϭ 6.1 Hz, 4 H, -(CH2)iCH3], 1.84 (d, J ϭ
13.0 Hz, 4 H), 1.10 (d, J ϭ 13.0 Hz, 4 H), 0.72 [t, J ϭ 7.1 Hz, 6
H, -CH2(CH3)o], 0.52 [t, J ϭ 6.8 Hz, 6 H, -CH2(CH3)i]. Ϫ MS
(MALDI-TOF): m/z ϭ 1520.3 [M]ϩ. Ϫ C90H72N8O12Zn·2H2O
(1559.0): calcd. C 69.34, H 4.91, N 7.19; found C 69.01, H 5.09, N
6.78. Ϫ UV/Vis (CH2Cl2): λ nm (10Ϫ3·ε, Ϫ1 cmϪ1) ϭ 425 (549.7),
516 (5.8), 554 (27.8), 590 (3.8).
α-5,15-(2,2Ј-{3,3Ј-[2,2Ј-(Diethoxycarbonyl)propane-1,3-diyl]di-
benzoylamido}diphenyl)-α-10,20-bis(2,2Ј-{3,3Ј-[1,1Ј-(diethoxy-
carbonyl)ethane-2-yl]benzoylamido}phenyl)porphyrin (9): The pro-
cedure described above for 8 was used. Sodium (0.89 g, 40 mmol)
and diethyl malonate (5.9 mL, 40 mmol) were dissolved in 30 mL
of EtOH and the porphyrin 2 (50 mg, 0.04 mmol), dissolved in
10 mL of THF, was added. After 24 hours, the solvent was removed
and the residue was chromatographed on a silica gel column, elut-
ing with 5% pentane/CH2Cl2. Compound 9 was obtained in 74%
yield (46 mg). Ϫ 1H NMR (500 MHz, CDCl3, 320 K): δ ϭ 9.08 (d,
J ϭ 8.4 Hz, 2 H), 9.06 (d, J ϭ 4.7 Hz, 4 H), 8.95 (d, J ϭ 4.7 Hz,
4 H), 8.71 (d, J ϭ 8.4 Hz, 2 H), 8.56 (s, 2 H), 8.04 (d, Jo ϭ 6.9 Hz,
Ethyl 3-[(2-Methylimidazol-1-yl)methyl]benzoate (7): 3-(Chlorome-
thyl)benzoyl chloride (100 µL, 0.7 mmol) was injected into 10 mL
of degassed ethanol over the space of one hour. After evaporation
1
of the solvent to dryness, a brown oil was obtained. Ϫ H NMR
(500 MHz, CDCl3, 300 K): δ ϭ 8.04 (t, Jm ϭ 1.5 Hz, 1 H), 7.97 (d,
Jo ϭ 8.0 Hz, Jm ϭ 1.5 Hz, 1 H), 7.54 (d, Jo ϭ 8.0 Hz, Jm ϭ 1.5 Hz,
1 H), 7.39 (t, J ϭ 7.5 Hz, 1 H), 4.58 (s, 2 H), 4.36 (q, J ϭ 7.0 Hz,
2 H), 1.37 (t, J ϭ 7.0 Hz, 3 H). This ester was then added to 2-
MeIm (57.4 mg, 0.7 mmol) in 5 mL of DMF under reflux and
stirred for 4 hours. The solvent was removed under vacuum and
the resulting mixture was chromatographed on a silica gel column
with CHCl3 as eluent to give 7 as an yellow oil. Ϫ 1H NMR
(500 MHz, CDCl3, 300 K): δ ϭ 7.98 (d, J ϭ 8.0 Hz, 1 H), 7.83 (s,
Jm ϭ 1.1 Hz, 2 H), 7.94 (large t, J ϭ 6.6 Hz, 4 H), 7.85 (t, Jo
ϭ
8.2 Hz, Jm ϭ 1.3 Hz, 2 H), 7.69 (d, J ϭ 7.7 Hz, 2 H), 7.65 (d, Jo ϭ
7.7 Hz, Jm ϭ 1.3 Hz, 2 H), 7.59 (t, J ϭ 7.2 Hz, 2 H), 7.55 (s, 2 H,
H2Ј), 7.47 (t, J ϭ 7.5 Hz, 2 H), 6.97 (t, J ϭ 7.7 Hz, 2 H), 6.50 (d,
J ϭ 7.8 Hz, 4 H), 6.44 (d, J ϭ 5.7 Hz, 2 H), 5.88 (t, J ϭ 7.4 Hz, 2
H), 4.84 (s, 2 H, H2Ј*), 4.09 [m, 8 H, -(CH2)p-CH3], 3.38 (t, J ϭ
7.6 Hz, 2 H, -CH2CH-), 2.81 (d, J ϭ 7.6 Hz, 4 H, -CH2CH-), 1.63
(s, 4 H, -CH2-), 1.17 [t, J ϭ 7.2 Hz, 12 H, -CH2(CH3)p], 0.95 [large
s, 4 H, -(CH2)s-CH3], Ϫ0.60 [large s, 6 H, -CH2-(CH3)s], Ϫ2.25 (s,
2 H). Ϫ MS (MALDI-TOF): m/z ϭ 1619.3 [M]ϩ. Ϫ C97H86N8O16·
H2O (1637.8): calcd. C 71.14, H 4.42, N 6.84; found C 69.92, H
4.25, N 6.63. Ϫ UV/Vis (CH2Cl2): λ nm (10Ϫ3·ε, Ϫ1 cmϪ1) ϭ 422
(283.5), 516 (19.8), 550 (5.4), 590 (5.9), 647 (2.2).
1 H, H2Ј), 7.41 (t, J ϭ 8.0 Hz, 1 H), 7.18 (d, Jo ϭ 8.0 Hz, Jm
ϭ
0.5 Hz, 1 H), 6.96 (s, 1 H), 6.85 (s, 1 H), 5.10 (s, 2 H), 4.36 (q, J ϭ
7.5 Hz, 2 H), 2.33 (s, 3 H), 1.39 (t, J ϭ 7.5 Hz, 3 H).
α-5,10,α-15,20-Bis(2,2Ј-{3,3Ј-[2,2-(diethoxycarbonyl)propane-1,3-
diyl]dibenzoylamido}diphenyl)porphyrin (8): A 50 mL three neck
round bottom flask equipped with a stir bar was charged with so-
dium (0.8 mmol, 18 mg) in 3 mL of EtOH. After 30 min., diethyl
malonate (0.8 mmol, 118 µL) was added and the mixture was
stirred for 1 hour. The porphyrin 2 (0.04 mmol, 50 mg) was dis-
solved in 10 mL of dry THF and slowly added to the reaction mix-
α-5,10,β-15,20-Bis(2,2Ј-{3,3Ј-[2,2-(diethoxycarbonyl)propane-1,3-
diyl]dibenzoylamido}diphenyl)porphyrin (10): The procedure de-
scribed for 8 was used. Sodium (190 mg, 40 mmol) and diethyl ma-
ture. After 24 hours, the solvent was removed and the residue was lonate (1.3 mL, 40 mmol) were dissolved in 20 mL of EtOH and
chromatographed on a silica gel column eluting with 0.5% CH3OH/
the porphyrin 3 (35 mg, 0.04 mmol), dissolved in 10 mL of CH2Cl2,
was added. After 2 hours, the solvent was removed and the residue
CH2Cl2. Compound 8 was obtained in 80% yield (45 mg). Ϫ 1H
NMR (500 MHz, CDCl3, 300 K): δ ϭ 8.92 (s, 4 H), 8.86 (s, 4 H), was chromatographed on a silica gel column, eluting with CH2Cl2.
8.69 (d, J ϭ 8.4 Hz, 4 H), 7.91 (t, Jo ϭ 7.8 Hz, Jm ϭ 1.3 Hz, 4 H),
Compound 10 was obtained in 75% yield (44 mg). Ϫ 1H NMR
7.80 (d, Jo ϭ 7.5 Hz, Jm ϭ 1.2 Hz, 4 H), 7.48 (t, J ϭ 7.5 Hz, 4 H), (500 MHz, CDCl3, 323 K): δ ϭ 8.98 (s, 4 H), 8.70 (d, Jo ϭ 8.4 Hz,
7.40 (s, 4 H), 7.07 (d, J ϭ 7.9 Hz, 4 H), 6.65 (d, J ϭ 7.5 Hz, 4 H), m ϭ 1.0 Hz, 4 H), 8.69 (s, 4 H), 7.89 (d, Jo ϭ 8.4 Hz, Jm ϭ 1.6 Hz,
6.59 (s, 4 H, H2Ј), 6.39 (t, J ϭ 7.7 Hz, 4 H), 3.98 [q, J ϭ 7.0 Hz, 4 4 H), 7.87 (t, Jo ϭ 7.3 Hz, Jm ϭ 1.0 Hz, 4 H), 7.55 (t, Jo ϭ 7.3 Hz
H, -(CH2)oCH3], 3.53 [q, J ϭ 7.1 H, 4 H, -(CH2)iCH3], 2.38 (d, Jm ϭ 1.6 Hz, 4 H), 7.51 (t, Jo ϭ 7.6 Hz, Jm ϭ 1.2 Hz, 4 H), 7.42
J
J ϭ 13.8 Hz, 4 H), 2.18 (d, J ϭ 13.8 Hz, 4 H), 1.09 [t, J ϭ 6.9 Hz, (s, 4 H), 6.93 (t, J ϭ 7.6 Hz, 4 H), 6.61 (d, J ϭ 7.6 Hz, 4 H), 4.84
6 H, -CH2(CH3)o], 0.64 [t, J ϭ 7.1 Hz, 6 H, -CH2(CH3)i], Ϫ2.95 (s, (s, 4 H, H2Ј), 3.29 [q, J ϭ 7.0 Hz, 4 H, -(CH2)oCH3], 2.53 [q, J ϭ
2 H). Ϫ HR-MS (LSI-MS): m/z (C90H74N8NaO12 [M ϩ Na]ϩ):
7.0 Hz, 4 H, -(CH2)iCH3], 1.44 (d, J ϭ 13.5 Hz, 4 H), 0.63 [t, J ϭ
7.0 Hz, 6 H, -CH2(CH3)o], 0.57 (d, J ϭ 13.5 Hz, 4 H), 0.01 [t, J ϭ
calcd. 1481.5335; found 1481.5324.
1924
Ϫ C90H74N8O12·CH2Cl2
Eur. J. Org. Chem. 2001, 1917Ϫ1926