2208
D. T. Gryko, B. Koszarna
PAPER
HRMS (EI): m/z calcd for C13H14O7: 282.0740; found: 282.0738.
Anal. Calcd for C38H18F10N4O: C, 61.96; H, 2.46; N, 7.61. Found:
C, 61.67; H, 2.11; N, 7.37.
Anal. Calcd for C13H14O7: C, 55.32; H, 5.00. Found: C, 55.36; H,
5.17.
5,15-Bis(pentafluorophenyl)-10-ethylcorrole (15)
The reaction mixture was evaporated with silica and put on the top
of a chromatography column (silica; CH2Cl2–hexanes, 1:3). All
fractions containing contaminated corrole were combined and evap-
orated. Subsequent dry column vacuum chromatography (silica;
CH2Cl2–cyclohexane, 1:9) afforded pure corrole (4.7 mg, 3.2%).
trans-A2B-Corrole Starting Dipyrromethanes Bearing Electron
Withdrawing Groups and Aldehydes; General Procedure
Samples of a dipyrromethane (0.40 mmol) and an aldehyde (0.20
mmol) were dissolved in a pre-prepared solution (3 mL) of TFA (10
mL, 0.13 mmol) in CH2Cl2 (10 mL). After 20 min at r.t., the reaction
mixture was dissolved in CH2Cl2 (300 mL) and a solution of DDQ
(118 mg, 0.52 mmol) in toluene (2 mL) was added, and the reaction
mixture was stirred at r.t. for a further 5 min. Alternatively, the re-
action mixture was diluted to 10 mL with CH2Cl2 and added to vig-
orously stirred CH2Cl2 (40 mL) simultaneously with the solution of
DDQ (118 mg, 0.52 mmol) in THF (10 mL) over 10 min, and the
reaction was stirred at r.t. for a further 5 min. Then the reaction mix-
ture was purified as described below.
Rf = 0.54 (silica; CH2Cl2–hexanes, 2:3)
1H NMR (500 MHz, CDCl3): d = –2.71 (br s, 3 H, NH), 2.08 (t,
J = 7.6 Hz, 3 H, CH3), 4.88 (q, J = 7.6 Hz, 2 H, CH2), 8.52 (d,
J = 3.5 Hz, 2 H, b-H), 8.78 (d, J = 4.7 Hz, 2 H, b-H), 9.06 (d, J = 4.2
Hz, 2 H, b-H), 9.29 (d, J = 4.8 Hz, 2 H, b-H).
HRMS (ESI): calcd for C33H17F10N4 [M + H+]: 659.1288; found:
659.1305.
UV-Vis (toluene): lmax (e × 10–3) = 418 (94), 523 (5.8), 562 (15),
621 (10), 638 nm (7.4).
5,15-Bis(pentafluorophenyl)-10-(4-cyanophenyl)corrole (3)
The reaction mixture was evaporated and chromatographed (silica;
acetone–hexanes, 1:9, then 1:4). All fractions containing contami-
nated corrole were combined and evaporated. Subsequent dry col-
umn vacuum chromatography (silica; toluene–hexanes, 1:9, then
2:3 and 1:1) afforded pure corrole (32 mg, 21%). Spectral and phys-
ical properties concur with published data.7d
5,15-Bis(4-nitrophenyl)-10-(4-methoxyphenyl)corrole (16)
The reaction mixture was evaporated to half of the volume and
passed over a chromatography column (silica; CH2Cl2–hexanes,
3:2) to give corrole contaminated with a few unidentified com-
pounds. After evaporation, hexanes–acetone (4:1) was added to the
dark crystals, and the suspension was filtered. Then the compound
was recrystallized from THF–CH2Cl2–hexanes to afford pure cor-
role (51 mg, 19%). Spectral and physical properties concur with
published data.7d
5,15-Bis(pentafluorophenyl)-10-(4-methylphenyl)corrole (13)
After evaporation to dryness, the reaction mixture was redissolved
(toluene–hexanes, 1:3) and passed over a chromatography column
(silica; toluene–hexanes, 1:3) to give corrole contaminated with
porphyrin. Subsequent chromatography (silica; CH2Cl2–hexanes,
1:3) afforded pure corrole (27 mg, 19%), which was crystallized
(CH2Cl2–hexanes) to give dark crystals.
5,15-Bis(4-cyanophenyl)-10-(3,4-dimethoxycarbonylphe-
nyl)corrole (17)
The reaction mixture was concentrated to half of the volume and
passed over a chromatography column (silica; CH2Cl2 then
CH2Cl2–EtOAc, 95:5). All fractions containing corrole were com-
bined and evaporated. Subsequent crystallization (CH2Cl2–hex-
anes) gave dark crystals (26 mg, 9%).
Rf = 0.64 (silica, CH2Cl2–hexanes, 2:3)
1H NMR (500 MHz, CDCl3): d = –2.70 (br s, 3 H, NH), 2.69 (s, 3
H, CH3), 7.57, 8.06 (AA¢BB¢, J = 7.7 Hz, 4 H, MeC6H4), 8.56 (d,
J = 3.6 Hz, 2 H, b-H), 8.69 (d, J = 4.7 Hz, 2 H, b-H), 8.72 (d, J = 4.7
Hz, 2H, b-H), 9.09 (d, J = 4.2 Hz, 2 H, b-H).
Rf = 0.64 (silica; CH2Cl2–EtOAc, 9:1).
1H NMR (200 MHz, THF): d = 3.73 (s, 3 H, CH3), 3.84 (s, 3 H,
CH3), 4.95 (s, 2 H, CH2), 5.02 (s, 2 H, CH2), 7.38 (d, J = 8.4 Hz, 1
H, ArH), 7.72 (d, J = 8.0 Hz, 1 H, ArH), 7.83 (s, 1 H, ArH), 8.18
(AA¢BB¢, J = 8.0 Hz, 4 H, Ar), 8.53–8.63 (m, 8 H, b-H + AA¢BB¢),
8.83 (d, J = 4.2 Hz, 2 H, b-H), 9.01 (d, J = 2.8 Hz, 2 H, b-H).
HRMS(ESI): calcd for C45H33N6O6: [M + H+] 753.2456; found:
753.2480.
HRMS (ESI): calcd for C38H19F10N4 [M + H+]: 721.1445; found:
721.1474.
Anal. Calcd for C38H18F10N4 + H2O: C, 62.56; H, 2.62; N, 7.68.
Found: C, 62.86; H, 2.02; N, 7.42.
UV-Vis (toluene): lmax (e × 10-3) = 419 (95), 524 (6.8), 563 (15),
617 (9.0), 638 (7.2) nm.
UV-Vis (toluene): lmax (e × 10–3) = 432 (108), 576 (17), 632 (13),
5,15-Bis(pentafluorophenyl)-10-(4-methoxyphenyl)corrole (14)
After evaporation to dryness, the reaction mixture was redissolved
in CH2Cl2–hexanes (1:3) and passed over a chromatography col-
umn (silica; CH2Cl2–hexanes, 1:3). All fractions containing corrole
were combined and evaporated. The dark green residue was dis-
solved in hot hexanes, and cooled in the freezer. After filtration sol-
id was recrystallized from cyclohexane afforded pure corrole (31
mg, 21%).
656 nm (13).
Anal. Calcd for C45H32N6O6 + H2O: C, 70.12; H, 4.45; N, 10.90.
Found: C, 70.44; H, 4.49; N, 10.65.
5,15-Bis(pentafluorophenyl)-10-(4-pyridylphenyl)corrole (18)
5-(Pentafluorophenyl)dipyrromethane (125 mg, 0.40 mmol) and the
pyridine-4-carboxaldehyde (19 mL, 0.20 mmol) were dissolved in
CH2Cl2 (12 mL) and then TFA (46 mL, 0.6 mmol) was added. After
1 h at r.t., the reaction mixture was dissolved in CH2Cl2 (300 mL),
neutralized with Et3N (84 mL, 0.6 mmol) and then a solution of
DDQ (118 mg, 0.52 mmol) in toluene (2 mL) was added. The reac-
tion mixture was stirred at r.t. for an additional 5 min. Then the re-
action mixture was evaporated to half of the volume and passed
over a chromatography column (silica; CH2Cl2) to give corrole con-
taminated with a few unidentified compounds. After evaporation,
subsequent dry column vacuum chromatography (silica; CH2Cl2
then CH2Cl2–EtOAc, 95:5) afforded pure corrole (26 mg, 18%)
which was crystallized (CHCl3–cyclohexane) to give dark crystals.
Rf = 0.47 (silica; CH2Cl2–hexanes, 2:3)
1H NMR (500 MHz, CDCl3): d = –2.66 (br s, 3 H, NH), 4.08 (s, 3
H, CH3), 7.29, 8.09 (AA¢BB¢, J = 8.5 Hz, 4 H, MeOC6H4), 8.56 (d,
J = 3.9 Hz, 2 H, b-H), 8.69 (d, J = 4.7 Hz, 2 H, b-H), 8.72 (d, J = 4.8
Hz, 2 H, b-H), 9.10 (d, J = 4.2 Hz, 2 H, b-H).
HRMS (ESI): calcd for C38H19F10N4O [M + H+]: 737.1394; found:
737.1412.
UV-Vis (toluene): lmax (e × 10–3) = 418 (114), 523 (7.8), 564 (17),
617 (10), 638 nm (8.5).
Synthesis 2004, No. 13, 2205–2209 © Thieme Stuttgart · New York