Synthesis and Reactivity of Allenylporphyrins
53 %) as purple crystals; m.p. Ͼ 300 °C. 1H NMR (400 MHz,
(130 mg, 0.52 mmol), and C6H5I(O2CCF3)2 (160 mg, 0.37 mmol) in
3
CDCl3, 25 °C): δ = 0.92 (t, JH,H = 7.4 Hz, 3 H, hexyl-CH3), 1.28– CHCl3 (200 mL) to yield 12a (0.32 mmol, 228 mg, 93%) as purple
1.40 (m, 6 H, hexyl-CH2), 2.22–2.28 (m, 2 H, hexyl-CH2), 2.64 (s, crystals; m.p. 265 °C. 1H NMR (400 MHz, CDCl3, 25 °C): δ =
4
3 H, tolyl-CH3), 4.49–4.54 (m, 2 H, hexyl-CH2), 5.25 (d, JH,H
=
7.65–7.71 (m, 9 H, Ph-o/p-CH), 7.95–7.97 (m, 6 H, Ph-o-CH), 8.66–
6.9 Hz, 2 H, allene-CH2), 7.46 (d, 3JH,H = 7.7 Hz, 4 H, tolyl-o-CH), 8.70 (m, 4 H, Hβ), 8.73 (d, 3JH,H = 5.0 Hz, 2 H, Hβ), 9.47 (d, 3JH,H
7.83 (d, JH,H = 7.7 Hz, 4 H, tolyl-m-CH), 8.21 (t, JH,H = 6.9 Hz,
3
4
= 5.0 Hz, 2 H, Hβ) ppm. 13C NMR (100 MHz, CDCl3, 25 °C): δ =
119.4, 119.7, 126.9, 127.8, 127.9, 132.2, 132.6, 133.6, 133.7, 137.9,
3
3
1 H, allene-CH), 8.71 (d, JH,H = 4.9 Hz, 2 H, Hβ), 8.73 (d, JH,H
= 4.9 Hz, 2 H, Hβ), 9.21 (d, 3JH,H = 4.9 Hz, 2 H, Hβ), 9.35 (d, 3JH,H 140.3, 140.5, 140.9, 142.7, 142.8, 142.9, 143.4, 144.5 ppm. UV/Vis
= 4.9 Hz, 2 H, Hβ) ppm. 13C NMR (100 MHz, CDCl3, 25 °C): δ
(CH2Cl2): λmax [log(ε/m–1 cm–1)] = 419 [5.54], 533 [4.40] nm. HRMS
= 14.1, 21.5, 22.6, 29.7, 30.0, 31.7, 37.3, 76.0, 92.4, 118.3, 125.3, (MALDI): calcd. for C38H23IN4Ni [M]+ 720.0331; found 720.0321.
128.2, 129.0, 130.4, 132.4, 132.6, 133.5, 137.3, 137.7, 141.3, 141.8,
[5-Iodo-10,20-bis(2-naphthalenyl)-15-phenylporphyrinato]nickel(II)
142.1, 215.9 ppm. UV/Vis (CH2Cl2): λmax [log(ε/m–1 cm–1)] = 424
(12b): Synthesized by using General Procedure D from 11c
[5.15], 541 [4.01], 587 [3.47] nm. IR (neat): ν = 2858.2, 2919.1,
˜
(300 mg, 0.43 mmol), I2 (150 mg, 0.60 mmol), and C6H5I(O2-
CCF3)2 (180 mg, 0.43 mmol) in CHCl3 (200 mL) to yield 12b
(0.41 mmol, 333 mg, 95 %) as purple crystals; m.p. 291 °C. 1H
NMR (400 MHz, CDCl3, 25 °C): δ = 7.68–7.73 (m, 7 H, Ar-CH),
8.00 (m, 2 H, naph-CH), 8.05 (m, 2 H, naph-CH), 8.15–8.20 (m, 6
H, Ar-CH), 8.44 (s, 2 H, naph-CH), 8.71 (s, 4 H, Hβ), 8.78 (d,
2850.4, 1939.6 cm–1. HRMS (MALDI): calcd. for C43H38N4Ni
[M]+ 668.2450; found 668.2465.
[5-(n-Butyl)-10,20-bis(1-ethylpropyl)-15-propadienylporphyrinato]-
nickel(II) (5h): Synthesized by using General Procedure C from 4h
(180 mg, 0.28 mmol), PdCl2(PPh3)2 (20 mg, 28 μmol), CuI (16 mg,
84 μmol), and 15 (234 mg, 1.68 mmol) in THF/TEA (40 mL, 4:1
v/v). The title compound was obtained from crude 16h with
Pd2(dba)3 (26 mg, 28 μmol) and P(C6F5)3 (60 mg, 0.11 mmol) in
CHCl3 (5 mL). The product was purified by column chromatog-
raphy (n-hexane/CH2Cl2, 8:1, v/v) to yield 5h (74 mg, 0.12 mmol,
44%) as purple crystals; m.p. 164 °C. 1H NMR (400 MHz, CDCl3,
25 °C): δ = 0.88 (t, 3JH,H = 7.4 Hz, 12 H, alkyl-CH3), 0.99 (t, 3JH,H
= 7.4 Hz, 3 H, butyl-CH3), 1.51 (m, 2 H, butyl-CH2), 2.17 (m, 2
H, butyl-CH2), 2.53–2.68 (m, 8 H, alkyl-CH2), 4.23 (m, 2 H, alkyl-
3
3JH,H = 5.0 Hz, 2 H, Hβ), 9.53 (d, JH,H = 5.0 Hz, 2 H, Hβ) ppm.
13C NMR (100 MHz, CDCl3, 25 °C): δ = 119.4, 119.8, 126.2, 126.7,
126.9, 127.9, 128.2, 128.4, 129.0, 130.2, 131.7, 132.2, 132.3, 132.7,
132.8, 133.6, 133.7, 137.5, 137.9, 140.4, 142.8, 142.9, 143.0, 143.6,
144.6 ppm. UV/Vis (CH2Cl2): λmax [log(ε/m–1 cm–1)] = 422 [5.37],
535 [4.25] nm. HRMS (MALDI): calcd. for C46H27IN4Ni [M]+
820.0634; found 820.0618.
5-Iodo-10,20-bis(4-methylphenyl)-15-phenylporphyrin (12c): Synthe-
sized by using General Procedure D from 9b (260 mg, 0.47 mmol),
I2 (165 mg, 0.65 mmol), and C6H5I(O2CCF3)2 (205 mg, 0.48 mmol)
in CHCl3 (300 mL) to yield 12c (0.39 mmol, 270 mg, 83%) as pur-
3
4
CH), 4.40 (t, JH,H = 8.0 Hz, 2 H, butyl-CH2), 5.22 (d, JH,H
=
4
6.9 Hz, 2 H, allene-CH2), 8.11 (t, JH,H = 6.9 Hz, 1 H, allene-CH),
9.14 (d, 3JH,H = 4.9 Hz, 2 H, Hβ), 9.26 (m, 4 H, Hβ), 9.30 (d, 3JH,H
= 4.9 Hz, 2 H, Hβ) ppm. 13C NMR (100 MHz, CDCl3, 25 °C): δ =
14.0, 23.3, 33.4, 39.1, 49.3, 76.1, 92.4, 107.2, 117.7, 120.7, 129.6,
130.6, 130.8, 131.1, 215.8 ppm. UV/Vis (CH2Cl2): λmax [log (ε/
ple crystals; m.p. Ͼ 300 °C. 1H NMR (400 MHz, CDCl3, 25 °C): δ
3
= –2.72 (s, 2 H, NH), 2.70 (s, 6 H, tolyl-CH3), 7.55 (d, JH,H
=
7.7 Hz, 4 H, tolyl-o-CH), 7.72–7.74 (m, 3 H, Ph-o/p-CH), 8.05 (d,
3JH,H = 7.7 Hz, 4 H, tolyl-m-CH), 8.15–8.17 (m, 2 H, Ph-m-CH),
8.78 (m, 4 H, Hβ), 8.87 (d, 3JH,H = 4.8 Hz, 2 H, Hβ), 9.65 (d, 3JH,H
= 4.8 Hz, 2 H, Hβ) ppm. 13C NMR (100 MHz, CDCl3, 25 °C): δ =
21.5, 78.4, 121.0, 126.8, 127.5, 127.8, 134.4, 134.5, 137.6, 138.9,
141.8 ppm. UV/Vis (CH2Cl2): λmax [log(ε/m–1 cm–1)] = 423 [5.48],
522 [4.07], 558 [3.85], 598 [3.51], 655 [3.64] nm. HRMS (MALDI):
calcd. for C40H29IN4 [M]+ 692.1437; found 692.1431.
m
–1 cm–1)] = 429 [5.24], 552 [4.17], 594 [3.82] nm. IR (neat): ν =
˜
2956.6, 2924.2, 2866.9, 1938.3, 1641.3 cm–1. HRMS (MALDI):
calcd. for C37H42N4Ni [M]+ 600.2763; found 600.2755. LRMS
(ESI+, 200 V): m/z (%) = 600.35 (12) [M]+, 440.13 (100) [M –
C11H28], 253.16 (10) [M – C21H23NNi].
[5,15-Bis(2-naphthalenyl)-10-phenyl-20-propadienylporphyrinato]-
copper(II) (5j): Synthesized by using General Procedure C from 4i
(233 mg, 0.3 mmol), PdCl2(PPh3)2 (21 mg, 30 μmol), CuI (17 mg,
90 μmol), and 15 (208 mg, 1.5 mmol) in THF/TEA (40 mL, 4:1,
v/v). The title compound was obtained from crude 16i with
Pd2(dba)3 (27 mg, 30 μmol) and P(C6F5)3 (64 mg, 0.12 mmol) in
CHCl3 (5 mL). The product was purified by column chromatog-
raphy (n-hexane/CH2Cl2, 6:1, v/v) to yield 5j (104 mg, 0.14 mmol,
47%) as red-purple crystals; m.p. Ͼ 300 °C. UV/Vis (CH2Cl2): λmax
[log(ε/m–1 cm–1)] = 427 [5.95], 549 [4.76], 585 [4.31] nm. HRMS
(MALDI): calcd. for C49H30N4Cu [M]+ 737.1766; found 737.1743.
LRMS (ESI+, 150 V): m/z (%) = 737.17 (16) [M]+, 601.47 (20) [M –
C6HCu], 462.04 (37) [M – C17H8Cu], 387.85 (65) [M – C23H11Cu],
253.61 (100) [M – C33H11CuN].
General Procedure E. Suzuki Reaction with (4-Bromophenyl)boronic
Acid: In an oven-dried Schlenk flask, the appropriate bromopor-
phyrin was dissolved in dry THF, and the solution was subjected
to freeze-pump-thaw cycles (3ϫ), before being released to argon.
(4-Bromophenyl)boronic acid (5 equiv.), PdCl2(PPh3)2 (20 mol-%),
triphenylarsane (40 mol-%), and K3PO4 (5 equiv.) were added, and
the solution was heated to 60 °C for 18 h. The product was filtered
through silica gel (CH2Cl2) and then purified by column
chromatography.
[5-(4-Bromophenyl)-10,15,20-triphenylporphyrinato]nickel(II) (19a):
Synthesized by using General Procedure E from 4a (200 mg,
0.33 mmol), (4-bromophenyl)boronic acid (330 mg, 1.62 mmol),
PdCl2(PPh3)2 (46 mg, 66 μmol), AsPh3 (40 mg, 0.13 mmol), and
K3PO4 (346 mg, 1.62 mmol) in THF (50 mL). The product was
purified by column chromatography on silica gel (n-hexane/
CH2Cl2, 6:1, v/v) and then crystallized (CHCl3/MeOH) to yield 19a
(0.28 mmol, 208 mg, 84%) as purple crystals; m.p. Ͼ 300 °C. 1H
NMR (400 MHz, CDCl3, 25 °C): δ = 7.66–7.73 (m, 9 H, Ph-o/p-
General Procedure D. Iodination of Porphyrins: By following the
procedure of Boyle and co-workers,[17,41] the porphyrin was dis-
solved in CHCl3, and the reaction vessel was purged with argon.
Iodine (1.5 equiv.) and bis(trifluroacetoxy)iodobenzene (1.1 equiv.)
were added, and the flask was shielded from light. The reaction was
left to stir at room temp., until there was complete consumption of
the starting material (approximately 48 h). The solution was then
filtered through silica gel (CH2Cl2), and the solvents were removed.
The product was recrystallized from CHCl3/MeOH.
3
3
CH), 7.81 (d, JH,H = 8.3 Hz, 2 H, o-C6H4Br), 7.89 (d, JH,H
=
8.3 Hz, 2 H, m-C6H4Br), 8.01–8.03 (m, 6 H, Ph-o-CH), 8.73 (d,
3JH,H = 5.0 Hz, 2 H, Hβ), 8.77–8.78 (m, 6 H, Hβ) ppm. 13C NMR
(100 MHz, CDCl3, 25 °C): δ = 117.3, 119.1, 119.2, 122.4, 126.9,
127.3, 127.7, 127.8, 128.5, 130.1, 131.8, 131.9, 132.2, 132.3, 132.4,
(5-Iodo-10,15,20-triphenylporphyrinato)nickel(II) (12a): Synthesized
by using General Procedure D from 11a (200 mg, 0.34 mmol), I2
Eur. J. Org. Chem. 2013, 1566–1579
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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