H-13 and H-17), 8.74 (d, 2 H, J 5.1, H-12 and H-18), 9.12 (s,
2 H, 2 × CHO), 9.29 (s, 2 H, H-3 and H-7). 13C NMR δ 118.7,
119.3, 124.7, 125.1; 127.25 and 127.28 (Cmeta-Ph-5,15), 127.7
(Cmeta-Ph-10,20); 128.2, 128.6 and 129.2 (Cpara-Ph); 133.3 (C-13
and C-17), 133.7 (Cortho-Ph-5,15), 133.8 (Cortho-Ph-10,20), 134.1
(C-12 and C-18), 136.9 (C-3 and C-7); 139.0, 139.1, 139.6,
140.4, 141.8, 142.1, 144.3, 145.1; 187.8 (2 × CHO); m/z
(LSIMS) 727 (M ϩ H)ϩ.
H-β), 8.71 (d, 1 H, J 5.2, H-β), 8.73 (d, 1 H, J 5.1, H-β), 9.10
(s, 1 H, 7-CHO), 9.14 (s, 1 H, 2-CHO), 9.24 (s, 1 H, H-8), 9.32
(s, 1 H, H-3). 13C NMR δ 118.5, 119.7, 121.2, 122.9; 127.3 and
127.7 (Cmeta-Ph); 128.2, 128.4, 129.2 and 129.4 (Cpara-Ph); 133.2,
133.6, 133.8 and 134.0 (C-β); 133.7 and 133.9 (Cortho-Ph); 136.2
(C-8), 136.9 (C-3); 139.3, 139.6, 140.05, 140.08, 140.3, 140.4,
140.7, 141.6, 142.2, 142.5, 143.3, 144.6, 144.7, 145.2; 187.7
(7-CHO), 187.8 (2-CHO); m/z (LSIMS) 727 (M ϩ H)ϩ.
2,7-Diformyl-meso-tetraphenylporphyrin 6b. 1H NMR
δ Ϫ2.24 (s, 2 H, 2 × NH ), 7.74–7.88 (m, 12 H, Hmeta,para-Ph),
8.17 (dd, 2 H, J 1.6 and 6.4, Hortho-Ph-10), 8.19 (dd, 2 H, J 2.0
and 7.9, Hortho-Ph-20), 8.22 (dd, 2 H, J 1.7 and 7.1, Hortho-Ph-5),
8.24 (dd, 2 H, J 1.4 and 6.1, Hortho-Ph-10), 8.78 (d, 2 H, J 3.8,
H-β), 8.82 (d, 1 H, J 3.8, H-β), 8.84 (d, 1 H, J 3.8, H-β), 9.18
(s, 1 H, 7-CHO), 9.23 (s, 1 H, 2-CHO), 9.37 (s, 1 H, H-8), 9.42
2,8-Diformyl-meso-tetraphenylporphyrin 3b. 1H NMR
δ Ϫ2.15 (s, 2 H, 2 × NH ), 7.74–7.85 (m, 12 H, Hmeta,para-Ph),
8.15 (dd, 2 H, J 1.5 and 8.0, Hortho-Ph-5), 8.19 (dd, 2 H, J 1.9 and
6.0, Hortho-Ph-15), 8.22 (dd, 4 H, J 1.7 and 6.5, Hortho-Ph-10,20),
8.77 (d, 2 H, J 4.9, H-13 and H-17), 8.83 (d, 2 H, J 4.9, H-12
and H-18), 9.24 (s, 2 H, 2 × CHO), 9.40 (s, 2 H, H-3 and H-7);
13C NMR (75 MHz, CDCl3) δ 120.2, 120.5, 125.3, 126.97 and
126.99 (Cmeta-Ph-5, 15), 127.6 (Cmeta-Ph-10, 20), 128.1, 128.6
and 129.2 (Cpara-Ph), 132.2 (C-13, 17), 132.9 (C-12, 18), 134.6
(Cortho-Ph-5), 134.7 (Cortho-Ph-15), 135.8 (Cortho-Ph-10, 20),
136.2 (C-3, 7), 140.4 (C-2, 8), 141.0, 141.3, 141.9, 188.8 (2 ×
(s, 1 H, H-3); m/z (LSIMS) 671 (M ϩ H)ϩ, 670 (Mϩ ); HRMS
ؒ
(FAB) m/z for C46H31N4O2 (M ϩ H)ϩ: calculated 671.2447,
found 671.2424; λmax (CH2Cl2)/nm (log ε): 674 (3.75), 613 (3.85),
577 (4.08), 537 (4.27), 444 (5.50).
CHO); m/z (LSIMS) 671 (M ϩ H)ϩ, 670 (Mϩ ); calc. for
ؒ
(2,18-Diformyl-meso-tetraphenylporphyrinato)nickel(II) 7a.
1H NMR δ 7.66–7.85 (m, 12 H, Hmeta,para-Ph), 7.96 (dd, 6 H,
J 1.6 and 7.4, Hortho-Ph-5,10,15), 8.07 (dd, 2 H, J 1.4 and 7.6,
Hortho-Ph-20), 8.66 (d, 2 H, J 5.1, H-7,13 or H-8,12), 8.74 (d, 2
H, J 5.1, H-8,12 or H-7,13), 8.99 (s, 2 H, 2 × CHO), 9.25 (s, 2 H,
H-3 and H-17). 13C NMR δ 117.6, 120.0, 121.7; 127.2 and 127.3
(Cmeta-Ph); 128.2, 128.3 and 128.4 (Cpara-Ph); 130.4; 133.3 and
133.7 (C-7,13 and C-8,12); 133.6 (Cortho-Ph-15), 133.8 (Cortho-Ph-
10,20), 134.7 (Cortho-Ph-15); 136.2 (C-3 and C-17); 139.4, 139.7,
140.5, 141.2, 141.3, 143.0, 143.8, 145.0; 187.5 (2 × CHO); m/z
(LSIMS) 727 (M ϩ H)ϩ.
C46H30N4O2ؒH2O: C, 80.21; N, 8.13; H, 4.68; found: C, 80.07;
N, 8.11; H, 4.54%; λmax (CH2Cl2)/nm (log ε): 671 (3.76), 612
(3.79), 575 (4.05), 535 (4.22), 436 (5.47).
(2,12-Diformyl-meso-tetraphenylporphyrinato)nickel(II)
4a
and (2,13-diformyl-meso-tetraphenylporphyrinato)nickel(II) 5a
(1 : 1 mixture). 1H NMR δ 7.65–7.76 (m, 2 × 12 H, Hmeta
Ph), 7.92–7.96 (m, 8 H, Hortho-Ph), 7.98–8.02 (m, 2 × 8 H, Hortho
-
-
ϩ
para
Ph), 8.68, 8.70, 8.72 (3 s, 2 × 4 H, H-β), 9.12 (s, 2 H, CHO), 9.14
(s, 2 H, CHO), 9.28 (s, 2 H, H-β), 9.29 (s, 2 H, H-β). 13C NMR
δ 118.6, 118.9, 121.8, 122.2; 127.2, 127.68 and 127.71 (Cmeta-Ph);
128.4 and 129.2 (Cpara-Ph); 133.5, 133.57, 133.62 and 133.66
(C-β); 133.66, 133.7, 133.83 and 133.9 (Cortho-Ph); 136.6 and
136.9 (C-β); 139.4, 140.0, 140.3, 140.4, 141.1, 141.4, 142.3,
142.5, 143.7, 143.9, 144.8, 144.9; 187.78 and 187.82 (2 × CHO);
m/z (LSIMS) 727 (M ϩ H)ϩ.
2,18-Diformyl-meso-tetraphenylporphyrin 7b. 1H NMR
δ Ϫ2.28 (s, 2 H, 2 × NH ), 7.68–7.92 (m, 12 H, Hmeta,para-Ph), 8.18
(dd, 6 H, J 1.5 and 7.5, Hortho-Ph-5,10,15), 8.28 (d, 2 H, J 7.5,
Hortho-Ph-20), 8.80 (d, 2 H, J 4.8, H-7,13 or H-8,12), 8.82 (d,
2 H, J 4.8, H-8,12 or H-7,13), 9.10 (s, 2 H, 2 × CHO), 9.36 (s, 2
H, H-3 and H-17); m/z (LSIMS) 671 (M ϩ H)ϩ, 670 (Mϩ );
ؒ
2,12-Diformyl-meso-tetraphenylporphyrin 4b. 1H NMR
δ Ϫ2.53 (s, 2 H, NH ), 7.76–7.87 (m, 12 H, Hmeta,para-Ph), 8.21 (d,
4 H, J 6.6, Hortho-Ph-5,15), 8.24 (d, 4 H, J 6.6, Hortho-Ph-10,20),
8.93 (d, 2 H, J 4.8, H-7 and H-17), 8.96 (d, 2 H, J 4.8, H-8 and
calc. for C46H30N4O2ؒ½ H2O: C, 81.28; N, 8.24; H, 4.60; found:
C, 81.10; N, 8.67; H, 4.51%; λmax(CH2Cl2)/nm (log ε): 670 (3.94),
613 (3.82), 578 (4.11), 537 (4.19), 442 (5.44).
H-18), 9.18 (s, 2 H, 2 × CHO), 9.38 (s, 2 H, H-3 and H-13). 13
C
Acknowledgements
NMR δ 120.4, 122.9; 127.0 and 127.6 (Cmeta-Ph); 128.4 and
129.2 (Cpara-Ph); 134.8 and 135.1 (Cortho-Ph); 139.5 (C-3 and
C-13); 141.2, 141.9; 189.0 (2 × CHO) (because of the small
amount of sample available these are the only observable
13C signals). HRMS (FAB) m/z for C46H31N4O2 (M ϩ H)ϩ:
calculated 671.2447, found 671.2419; λmax (CH2Cl2)/nm (log ε):
679 (4.02), 619 (3.64), 575 (3.74), 532 (4.17), 432 (5.42).
Thanks are due to “Fundação para a Ciência e Tecnologia –
FCT” for funding the Organic Chemistry Unit and Project
Praxis/2/2.1/QUI/145. One of us (A. M. G. Silva) also thanks
FCT for a PhD grant.
References
2,13-Diformyl-meso-tetraphenylporphyrin 5b. 1H NMR
δ Ϫ2.54 (s, 2 H, NH ), 7.75–7.87 (m, 12 H, Hmeta,para-Ph), 8.19 (d,
4 H, J 6.9, Hortho-Ph-5,10), 8.26 (d, 4 H, J 7.0, Hortho-Ph-15,20),
8.93 (s, 2 H, H-7 and H-8), 8.97 (s, 2 H, H-17 and H-18), 9.17 (s,
2 H, 2 × CHO), 9.38 (s, 2 H, H-3 and H-12). 13C NMR δ 120.4,
122.9; 127.0 and 127.6 (Cmeta-Ph); 128.4 and 129.3 (Cpara-Ph);
130.9 (C-7,8 and C-17,18); 134.7 and 135.3 (Cortho-Ph); 140.2
(C-3 and C-12); 141.0, 142.1; 188.9 (2 × CHO) (because of the
small amount of sample available these are the only observable
13C signals). HRMS (FAB) m/z for C46H31N4O2 (M ϩ H)ϩ:
calculated 671.2447, found 671.2427; λmax (CH2Cl2)/nm (log ε):
679 (4.01), 619 (3.66), 574 (3.71), 532 (4.19), 436 (5.50).
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6a.
-
Ph-20), 7.99 (d, 2 H, J 6.8, Hortho-Ph-5), 8.01 (dd, 2 H, J 1.1 and
6.9, Hortho-Ph-15), 8.65 (d, 1 H, J 5.1, H-β), 8.68 (d, 1 H, J 5.2,
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1777