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Synthesis of New Porphyrin Trimers via Buchwald-Hartwig Amination Reaction
Vladimir S. Tyurin, Elena A. Mikhalitsyna, Alexandr S. Semeikin, and Irina P. Beletskaya
Supporting Information
Figure 1. Synthesis of aminophenylporphyrins ZnPMes3PhNH2 и ZnPMes2(PhNH2)2.
+
NH
CH3H3C
OHC
MeOH, HBrN HN
NNH
H3C
H3C
H3C
C5H11 C5H11
CH3
CH3
CH3
Br
H+
NH+ HN
+HNNH
H3C
H3C
H3C
C5H11 C5H11
CH3
CH3
CH3
2Br-ArCHO
Ar = -C6H4Br-4
57%
NH
NH
H3C
C5H11
C5H11
H3C
H2PPhBr
HN
CH3H3C
OHC
Figure 2. Synthesis of 5-(4-bromophenyl)-β-octaalkylporphyrin.
Figure 3. The structure of the porphyrin trimer ZnPMes2(PhNH)2-(ZnPPh)2 . Table 1. 1Н NMR data of the b-unsubstituted porphyrin substrates and coupling productsa.
β-Н,
δ(Δδ), ppm
meso-H δ(Δδ), ppm
HAr δ(Δδ), ppm Compound
1 2 Ha Hb a b c d
HArmes CH3
mes CH’3mes
ZnPPhBr - 9.90 9.52 7.90 - - - - - ZnPMes2(PhNH2)2 8.85 8.65 - - - - 7.98 7.05 7.41 2.61 1.86 ZnPMes3PhNH2 8.79 8.71 - - - - 7.69 6.03 7.28 2.69 1.84
ZnPMes2(PhNH)2-(ZnPPh)2
9.15 (0.3)
8.89 (0.24)
10.04 (0.14)
9.76 (0.24)
8.05 (0.15)
7.78 (-0.12)
8.30 (0.32)
7.74 (0.69)
7.34 (-0.07)
1.93 (-0.68)
1.54 (-0.32)
(ZnPMes3Ph)2 8.72 (-0.07)
8.55 (-0.16)
8.49 (-0.22) - - - - 8.12
(0.43) 7.58
(1.55)
7.27 (-0.01)
7.26 (-0.02)
2.54 (-0.15)
1,76 (-0,08)
(ZnPMes3Ph)2NH 8.85 (0.06)
8.78 (0.07) - - - - 8.22
(0.24) 7.49
(0.44) 7.27
(-0.01) 2.63
(-0.06) 1.84 (0)
aIn CDCl3 Table 2. 1Н NMR data of the b-substituted porphyrin substrates and coupling productsa.
aIn CDCl3, bIn DMSO-d6
meso-H δ(Δδ), ppm
HAr δ(Δδ), ppm
CH2 of diaza-18-Cr-6 δ, ppm Compound
Ha Hb a b
NCH2 N’CH2
1, 1’ 2, 2’ 3, 3’ 4, 4’ ZnP(PhPip)2
b 10.00 8.11 7.28 3.55 3.31 - - - -
ZnP(PhDiaza18C6)2 10.03 7.81 7.07 3.78 3.68 3.64 3.57 3.52 3.45
ZnP(PhPip)2-(ZnPPh)2 10.19 10.11 7.95 7.28 3.04 2.84 - - - - ZnP(PhDiaza18C6)2-(ZnPPh)2
10.13-9.91 7.79 6.91 3.86 3.86 3.86 3.73 3.73 3.73
ZnP(PhDiaza18C6)2-ZnPPh 10.16-10.05 7.63 7.47 3.98 3.98 3.98 3.98 3.98 3.98
Figure 4. UV-Vis spectra of the porphyrin trimer ZnPMes2(PhNH)2-(ZnPPh)2 .
10.1 10.0 9.9 9.8 9.7 9.6 9.5 9.4 9.3 9.2 9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3Chemical Shift (ppm)
7.29
7.34
7.73
7.747.77
7.78
8.04
8.05
8.29
8.30
8.88
8.899.14
9.15
9.76
10.0
4
3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0Chemical Shift (ppm)
3.93
3.92
3.90
3.57
3.56
2.71
2.67
1.93
1.79
1.78
1.77
1.75
1.74
1.60
1.59 1.58
1.57
1.03
1.02
1.01
H-meso
H'-mesoH'
b Hb Hb
Hd Hc Ha
Hames
CDCl3
H4
H1
H2
H3
N
N N
N
CH2
HN
H2C
HNZn
N
N N
N
C5H11
H3C
C5H11
Zn
N
NN
N
C5H11
H2C
H2C
CH2
CH
Zn
HCCH
HC
H2C
H'b
HaHb
Hb
H-meso
Hc
12
3
45
69
10
1112
13
14
23
2425
2627
28
2930
3133
34
35
Hbmes
Hames
H'-meso
H1
H2
H4
H3
H5
H6
H7
H8
Hd
Hemes
36
38
4
3
8 7
14
15
15
16
17
1618 20
21
22
2425
3237
35
Hames
H5
Hbmes
H6
H7
H8
Figure 5. NMR spectra of the porphyrin trimer ZnPMes2(PhNH)2-(ZnPPh)2 .