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DOI: 10.1055/s-0028-1088212
meso-Oxidation of Porphyrins: Convenient Iron(III)-Mediated Synthesis of Dioxoporphyrins
Publication History
Publication Date:
16 March 2009 (online)
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Abstract
Iron(III)-mediated meso-oxidation reactions of 5,15-diarylporphyrins resulted in a variety of dioxoporphyrins in high yields. In the case of meso-amino-substituted diarylporphyrins, a variety of products was produced.
Key words
FeCl3˙6H2O - oxidation - dioxoporphyrin
- Supporting Information for this article is available online:
- Supporting Information
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References and Notes
Typical Procedure
for the Fe(III)-Mediated Synthesis of Dioxoporphyrins Zn2
A
mixture of Zn1a (100 mg, 0.19 mmol, 1.0
equiv) and FeCl3˙6H2O (513 mg, 10
equiv) was stirred in DMF (20 mL) in air at 130 ˚C for
5 h. After cooling to r.t., the reaction mixture was diluted with
CH2Cl2 (20 mL) and washed with H2O
three times. The organic layer was passed through dry SiO2 and
evaporated to dryness. The resulting solid was crystallized from
CH2Cl2-MeOH or purified by flash column
chromatography (SiO2, 300-400 mesh, PE-EtOAC 4:1)
to produce the desired dioxoporphyrin Zn2a (90
mg, 85% yield).
Characterization
Data for Selected Representative CompoundsDioxoporphyrin
Zn2a
¹H NMR (300 MHz, acetone-d
6
): δ = 6.28-6.31
(m, 4 H,
β-H), 6.87-6.90 (m, 4 H, β-H),
7.33 (d, J = 3.6
Hz, 4 H, PhH), 7.40-7.42 (m, 6 H, PhH). MS (MALDI): m/z = 555.1 [M + H+].
UV/vis (CH2Cl2): λmax (%) = 403
(13.0), 450 (6.7), 509 (2.6), 546 (5.6), 708 (1.0) nm. Anal. Calcd
for C32H18N4O2Zn˙2MeOH:
C, 65.86; H, 4.23; N, 9.04. Found: C, 65.14; H, 4.07; N, 8.86.
Dioxoporphyrin H
2
2a
¹H NMR
(300 MHz, CDCl3): δ = 6.51
(br s, 4 H, β-H), 7.17 (d, J = 4.2
Hz, 4 H, β-H), 7.42-7.53 (m, 10 H, PhH), 14.02 (s,
2 H, NH). MS (MALDI): m/z = 493.2 [M + H+].
UV/vis (CH2Cl2): λmax (%) = 408
(3.1), 472 (1.0), 499 (1.2) nm. Anal. Calcd for C32H20N4O2˙0.5EtOH:
C, 76.88; H, 4.50; N, 10.87. Found: C, 76.37; H, 4.31; N, 10.45.
Dioxoporphyrin Ni2a
¹H
NMR (300 MHz, CDCl3): δ = 6.20
(d, J = 4.2
Hz, 4 H,
β-H), 6.45 (d, J = 4.5
Hz, 4 H, β-H), 7.45 (s, 10 H, PhH).
MS (MALDI): m/z = 549.1 [M + H+].
UV/vis (CH2Cl2):
λmax (%) = 358
(14.4), 445 (35.4), 524 (8.1), 660 (1.0) nm. Anal. Calcd for C32H18N4O2Ni:
C, 68.85; H, 3.43; N, 10.04. Found: C, 68.63; H, 3.49; N, 9.67.
Crystal data: C34H26NiO4, M = 613.30,
triclinic, space group P-1, a = 7.6032
(11), b = 8.6684
(12), c = 11.3434
(16) Å, α = 94.136
(2), β = 100.890
(2), γ = 108.289
(2)˚, V = 690.11
(17) ų, T = 293
(2) K, Z = 1, D
c = 1.476
g/cm-³, 4091 reflections measured,
2937 unique which were used in all calculations. R(int) = 0.0734; R
1 = 0.0465.
The final wR(F
²)
was 0.0465 (all data). CCDC 711638 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.