1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

Experimental Section 6
6.2.6.10 N-(15 4 -Amino-5 4 ,10 4 ,20 4 -Tri-t-Butyl-[3,5 2 ]-Ethano-3 1 -Oxo-5 6 -Methyl-5,10,15,20-
O
Tetraphenylporphyrin)-Pyropheophorbide a amide, 94
In a 50 mL round bottom flask with N2
inlet, 10 mg (18.7 µmol) of pyropheo-
phorbide a 33 are dissolved in abs. DMF
(20 mL) and the solution is degassed by
utilization of a stream of N2 for 15 min.
Under inert gas atmosphere are added
further on: amino cycloketo-porphyrin 92
(17.5 mg, 20.6 µmol, 1.1 eq.), EDC
(5.4 mg, 28.1 µmol, 1.5 eq.), NHS (3.2 mg,
28.1 µmol, 1.5 eq.) and DMAP (catalytic
amount) and the mixture is stirred under N2 in the dark for 24 h. Then again, 17.5 mg
(20.6 µmol, 1.1 eq.) of amino cycloketo-porphyrin 92 and 5.4 mg (28.1 µmol, 1.5 eq.) of EDC
are added and stirring is continued for further 24 h. After that, the solvent is evaporated
completely and the residue is subjected to FC (silica, CH2Cl2 : ethyl acetate = 19 : 1) to give
19.5 mg (14.2 µmol) of pure 94 as dark green-violet powder equiv. to 68.9 % yield based on
33.
N
NH HN
N
HN
94
O
C 92 H 89 N 9 O 3
M = 1368.75 g·mol -1
N
O
N
H N
H
N
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -1.68 (s, 2 H, NH), -1.51 (s, 1 H, NH), 0.56 (s br, 1 H,
NH), 1.15 (s, 3 H, CH3), 1.42 (q, 3 J = 8.0 Hz, 3 H, 8 2 ), 1.50 (s, 9 H, t-BuH), 1.54 (s, 18 H, t-BuH),
1.84 (d, 3 J = 7.2 Hz, 3 H, 18 1 ), 2.33 (m, 1 H, 17 1/2 ), 2.48 (m, 1 H, 17 1/2 ), 2.74 (s, 3 H, CH3), 2.89
(m, 2 H, 17 1/2 ), 3.19 (s, 3 H, CH3), 3.29 (m, 1 H, 8 1 ), 3.38 (d, 3 J = 5.6 Hz, 3 H, CH3), 3.42 (m, 1 H,
8 1 ), 4.08 (d, 2 J = 11.6 Hz, 1 H, CH2), 4.49 (s br, 1 H, 17), 4.67 (m, 1 H, 18), 5.16 (d, 2 J = 19.6 Hz,
1 H, 13 2 ), 5.44 (d, 2 J = 20.0 Hz, 1 H, 13 2 ), 5.46 (d, 2 J = 10.8 Hz, 1 H, CH2), 6.11 (dd, 2 J = 9.0 Hz,
3 J = 10.8 Hz, 1 H, 3 2 ), 6.24 (dd, 2 J = 7.6 Hz, 3 J = 17.9 Hz, 3 2 ), 7.33 (s, 1 H, Ar’H), 7.40-8.35 (div.
m, 12 H, ArH), 7.66 (s, 1 H, Ar’H), 7.94 (m, 1 H, 3 1 ), 8.52 (m, 1 H, β-H), 8.58 (m, 2+1 H, β-
H/meso), 8.74 (m, 2+1 H, β-H/meso), 8.87 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.91 (s, 1 H, β-H), 9.35 (s,
1 H, meso). [Color coding: cycloketo-porphyrin moiety, pyropheophorbide a moiety]
13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 11.1, 12.0, 17.1, 19.0, 22.0, 22.4, 22.9, 23.8, 29.0,
31.4, 31.5, 33.2, 34.7, 34.8, 48.2, 50.1, 51.6, 53.7, 93.0, 97.2, 98.4, 103.9, 106.1, 107.9, 114.1,
117.9, 119.1, 121.1, 122.7, 123.9, 124.5, 125.7, 126.0, 128.3, 129.1, 131.8, 134.2-135.1 (four
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