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5,15-Diphenyl-10-(trimethylsilyl)methylporphyrin (3ab). Brown-
purple solid; 87.5 mg, 86% yield; Rf = 0.69 (1:2 THF/hexane); H
d, J = 4.9 Hz), 8.26−8.18 (4H, m), 7.82−7.72 (6H, m), 4.71 (2H, s),
4.10−4.01 (1H, m), 1.15 (6H, d, J = 5.9 Hz), 0.05 (6H, s), −2.62 (2H,
br s); 13C NMR (CDCl3, 100 MHz) δ 146.2 (8C, br), 142.3, 134.6,
131.7, 130.7, 130.4, 128.9, 127.6, 126.7, 120.3, 119.1, 103.0, 65.7, 28.2,
25.9, −0.8; IR (KBr) 3313, 3113, 3028, 2962, 1593, 1477, 1246, 1115,
1026, 802,740 cm−1; UV/vis (CHCl3) λmax (log ε) 416.5 (5.7), 516.5
(4.3), 551.5 (4.0), 591.5 (3.7), 646.5 (3.8) nm; HRMS-FAB+ ([M +
H]+) calcd for C38H37N4OSi 593.2737, found 593.2742.
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NMR (CDCl3, 400 MHz) δ 9.94 (1H, s), 9.39 (2H, d, J = 4.9 Hz),
9.18 (2H, d, J = 4.9 Hz), 8.92 (2H, d, J = 4.9 Hz), 8.90 (2H, d, J = 4.9
Hz), 8.27−8.23 (4H, m), 7.83−7.75 (6H, m), 4.64 (2H, s), 0.08 (9H,
s), −2.55 (2H, br s); 13C NMR (CDCl3, 100 MHz) δ 146.2 (8C, br),
142.3, 134.6, 131.7, 130.7, 130.4, 128.6, 127.6, 126.7, 121.6, 119.1,
103.0, 27.3, −0.8; IR (KBr) 3309, 3104, 3024, 2947, 1593, 1477, 1246,
1134, 968, 849, 791, 733 cm−1; UV/vis (CHCl3) λmax (log ε) 416.5
(5.6), 516.0 (4.2), 551.0 (4.0), 591.5 (3.7), 648.0 (3.8) nm; HRMS-
FAB+ ([M + H]+) calcd for C36H33N4Si 549.2474, found 549.2479;
Anal. calcd for C36H32N4Si: C, 78.79; H, 5.88; N, 10.21, found: C,
78.57; H, 5.79; N, 10.00.
5,15-Diphenyl-10-(triethylsilyl)methylporphyrin (3ac). Brown-pur-
ple solid; 90.6 mg, 83% yield; Rf = 0.68 (1:2 THF/hexane); 1H NMR
(CDCl3, 400 MHz) δ 9.94 (1H, s), 9.40 (2H, d, J = 4.9 Hz), 9.17 (2H,
d, J = 4.9 Hz), 8.89 (2H, d, J = 4.9 Hz), 8.86 (2H, d, J = 4.9 Hz),
8.25−8.18 (4H, m), 7.82−7.72 (6H, m), 4.63 (2H, s), 0.75 (9H, t, J =
7.8 Hz), 0.57 (6H, q, J = 7.8 Hz), −2.64 (2H, br s); 13C NMR
(CDCl3, 100 MHz) δ 146.5 (8C, br), 142.2, 134.6, 131.7, 130.7 (4C),
128.5, 127.6, 126.7, 122.1, 119.1, 102.9, 23.0, 7.3, 3.9; IR (KBr) 3313,
3055, 2951, 2924, 2873, 1477, 1404, 968, 791, 729 cm−1; UV/vis
(CHCl3) λmax (log ε) 415.0 (5.6), 512.5 (4.2), 551.0 (3.8), 589.5 (3.6),
646.5 (3.5) nm; HRMS-FAB+ ([M + H]+) calcd for C39H39N4Si
591.2944, found 591.2938.
10-Bis(trimethylsilyl)methyl-5,15-diphenylporphyrin (3ah). The
general procedure with 5 equiv, instead of 2 equiv, of the Grignard
reagent 2h gave the title compound as a brown-purple solid (84.1 mg,
1
71%); Rf = 0.68 (1:2 THF/hexane); H NMR (CDCl3, 400 MHz) δ
9.89 (1H, s), 9.42 (1H, d, J = 4.9 Hz), 9.40 (1H, d, J = 4.9 Hz), 9.16
(1H, d, J = 4.9 Hz), 9.15 (1H, d, J = 4.9 Hz), 8.89 (1H, d, J = 4.9 Hz),
8.88 (1H, d, J = 4.9 Hz), 8.87 (1H, d, J = 4.9 Hz), 8.85 (1H, d, J = 4.9
Hz), 8.27−8.21 (4H, m), 7.82−7.74 (6H, m), 4.52 (1H, s), 0.23 (18H,
s), −2.42 (2H, br s); 13C NMR (CDCl3, 100 MHz) δ 146.5 (8C, br),
142.5, 142.5, 134.6, 132.0, 131.7, 130.9, 130.7 (2C), 130.5 (2C), 129.6,
127.6, 127.6, 127.5, 127.0, 126.68, 126.65, 119.2, 119.0, 102.6, 31.0,
1.6; IR (KBr) 3317, 3093, 3051, 2954, 2900, 1593, 1469, 1246, 1065,
978, 852, 791, 741, 694 cm−1; UV/vis (CHCl3) λmax (log ε) 419.0
(5.6), 519.5 (4.2), 555.5 (4.1), 595.5 (3.6), 651.0 (3.8) nm; HRMS-
FAB+ ([M + H]+) calcd for C39H41N4Si2 621.2870, found 621.2866;
Anal. calcd for C39H40N4Si2: C, 75.44; H, 6.49: N, 9.02, found: C,
75.62; H, 6.51; N, 9.16.
5,15-Diphenyl-10-(triphenylsilyl)methylporphyrin (3ad). Brown-
purple solid; 102.3 mg, 75% yield; Rf = 0.70 (1:2 THF/hexane); H
5,15-Di(p-tolyl)-10-(trimethylsilyl)methylporphyrin (3bb). Brown-
purple solid; 88.5 mg, 83% yield; Rf = 0.68 (1:2 THF/hexane); H
1
1
NMR (CD2Cl2, 300 MHz) δ 10.00 (1H, s), 9.23 (2H, d, J = 4.8 Hz),
8.96 (2H, d, J = 4.8 Hz), 8.90 (2H, d, J = 4.8 Hz), 8.46 (2H, d, J = 4.8
Hz), 8.19−8.11 (4H, m), 7.84−7.72 (6H, m), 7.26 (3H, t, J = 7.4 Hz),
7.18 (6H, d, J = 7.3 Hz), 7.02 (6H, dd, J = 7.4, 7.3 Hz), 5.24 (2H, s),
−2.83 (2H, br s); 13C NMR (CD2Cl2, 75 MHz) δ 146.7 (8C, br),
142.5, 136.4, 135.0, 134.1, 131.9, 131.1, 130.3, 129.9, 129.1, 128.1,
128.0, 127.1, 119.5, 119.1, 103.6, 25.4; IR (KBr) 3294, 3062, 2924,
2854, 1431, 1103, 791, 710 cm−1; UV/vis (CHCl3) λmax (log ε) 419.0
(5.6), 517.5 (4.2), 551.5 (3.9), 591.5 (3.7), 648.5 (3.6) nm; HRMS-
FAB+ ([M + H]+) calcd for C51H39N4Si 735.2944, found 735.2952.
10-(Dimethylphenylsilyl)methyl-5,15-diphenylporphyrin (3ae).
Brown-purple solid; 98.5 mg, 87% yield; Rf = 0.69 (1:2 THF/
hexane); 1H NMR (CDCl3, 300 MHz) δ 9.95 (1H, s), 9.25 (2H, d, J =
4.8 Hz), 9.19 (2H, d, J = 4.8 Hz), 8.92 (2H, d, J = 4.8 Hz), 8.81 (2H,
d, J = 4.8 Hz), 8.28−8.20 (4H, m), 7.84−7.74 (0H, m), 7.52 (2H, d, J
= 7.3 Hz), 7.43 (1H, t, J = 7.4 Hz), 7.32 (2H, dd, J = 7.4, 7.3 Hz), 4.81
(2H, s), 0.21 (6H, s), −2.58 (2H, br s); 13C NMR (CDCl3, 75 MHz)
δ 146.3 (8C, br), 142.3, 138.6, 134.6, 133.8, 131.7, 130.7, 130.3, 129.3,
128.6, 128.0, 127.6, 126.7, 120.5, 119.1, 103.1, 26.9, −2.6; IR (KBr)
3313, 3059, 2954, 1477, 1246, 980, 840, 787, 737 cm−1; UV/vis
(CHCl3) λmax (log ε) 417.0 (5.7), 515.0 (4.3), 551.5 (4.0), 591.5 (3.7),
646.5 (3.7) nm; HRMS-FAB+ ([M + H]+) calcd for C41H35N4Si
611.2631, found 611.2640; Anal. calcd for C41H34N4Si: C, 80.73; H,
5.81; N, 8.97, found: C, 80.77; H, 5.62; N, 9.09.
10-(Benzyldimethylsilyl)methyl-5,15-diphenylporphyrin (3af).
Brown-purple solid; 101.8 mg, 88%yield; Rf = 0.67 (1:2 THF/
hexane); 1H NMR (CDCl3, 500 MHz) δ 9.97 (1H, s), 9.21 (2H, d, J =
4.6 Hz), 9.20 (2H, d, J = 4.6 Hz), 8.93 (2H, d, J = 4.6 Hz), 8.87 (2H,
d, J = 4.6 Hz), 8.26−8.22 (4H, m), 7.85−7.75 (6H, m), 7.29 (2H, dd, J
= 7.9, 7.3 Hz), 7.17 (1H, t, J = 7.3 Hz), 7.08 (2H, d, J = 7.9 Hz), 4.64
(2H, s), 2.34 (2H, s), −0.08 (6H, s), −2.63 (2H, br s); 13C NMR
(CDCl3, 125 MHz) δ 146.1 (8C, br), 142.1, 139.6, 134.6, 131.7, 130.7
(6C), 128.4, 128.3, 127.6, 126.7, 124.4, 120.7, 119.1, 103.1, 26.2, 25.1,
−2.9; IR (KBr) 3317, 3055, 3028, 2951, 1593, 1481, 1404, 1246, 1153,
968, 837, 791, 737, 698 cm−1; UV/vis (CHCl3) λmax (log ε) 417.0
(5.7), 516.5 (4.3), 552.5 (4.1), 592.5 (3.8), 647.5 (3.8) nm; HRMS-
FAB+ ([M + H]+) calcd for C42H37N4Si 625.2787, found 625.2790;
Anal. calcd for C42H36N4Si: C, 80.73; H, 5.81; N, 8.97, found: C,
80.73; H, 5.91; N, 8.69.
NMR (CDCl3, 500 MHz) δ 9.95 (1H, s), 9.40 (2H, d, J = 4.9 Hz),
9.19 (2H, d, J = 4.9 Hz), 8.96 (2H, d, J = 4.9 Hz), 8.94 (2H, d, J = 4.9
Hz), 8.14 (4H, d, J = 7.6 Hz), 7.59 (4H, d, J = 7.6 Hz), 4.65 (2H, s),
2.74 (6H, s), 0.07 (9H, s), −2.60 (2H, br s); 13C NMR (CDCl3, 125
MHz) δ 146.1 (8C, br), 139.2, 137.2, 134.5, 131.7, 130.5 (4C), 128.5,
127.4, 121.4, 119.1, 102.8, 27.2, 21.5, −0.8; IR (KBr) 3313, 3020,
2951, 1477, 1404, 1246, 1153, 968, 845, 791, 737 cm−1; UV/vis
(CHCl3) λmax (log ε) 417.5 (5.7), 516.5 (4.2), 552.5 (4.1), 591.5 (3.7),
649.0 (3.8) nm; HRMS-FAB+ ([M + H]+) calcd for C38H37N4Si
577.2787, found 577.2783; Anal. calcd for C38H36N4Si: C, 79.13; H,
6.29; N, 9.71, found: C, 78.73; H, 6.28; N, 9.44.
5,15-Bis(3-vinylphenyl)-10-(trimethylsilyl)methylporphyrin (3cb).
Brown-purple solid; 85.3 mg, 77% yield; Rf = 0.67 (1:2 THF/hexane);
1H NMR (CDCl3, 500 MHz) δ 9.95 (1H, s), 9.40 (2H, d, J = 4.6 Hz),
9.19 (2H, d, J = 4.6 Hz), 8.97 (2H, d, J = 4.6 Hz), 8.95 (2H, d, J = 4.6
Hz), 8.32 (2H, s), 8.15 (2H, d, J = 7.3 Hz), 7.88 (2H, d, J = 7.9 Hz),
7.74 (2H, dd, J = 7.9, 7.3 Hz), 7.04 (2H, dd, J = 17.7, 11.0 Hz), 6.02
(2H, d, J = 17.7 Hz), 5.45 (2H, d, J = 11.0 Hz), 4.64 (2H, s), 0.09 (9H,
s), −2.56 (2H, br s); 13C NMR (CDCl3, 125 MHz) δ 146.0 (8C, br),
142.4, 136.9, 135.9, 134.1, 132.4, 131.6, 130.5 (4C), 128.6, 126.8,
125.4, 121.7, 118.8, 114.7, 103.0, 27.2, −0.8; IR (KBr) 3313, 3093,
3051, 2954, 1589, 1473, 1396, 1335, 1250, 1157, 1065, 984, 906, 849,
787, 733 cm−1; UV/vis (CHCl3) λmax (log ε) 418.0 (5.6), 516.5 (4.2),
552.5 (4.0), 592.5 (3.7), 648.5 (3.8) nm; HRMS-FAB+ ([M + H]+)
calcd for C40H37N4Si: 601.2787, found 601.2792.
5,15-Bis[4-{2-(triisopropylsilyl)ethynyl}phenyl]-10-(trimethylsilyl)-
methylporphyrin (3db). Brown-purple solid; 160.2 mg, 95% yield; Rf
1
= 0.65 (1:2 THF/hexane); H NMR (CDCl3, 300 MHz) δ 9.92 (1H,
s), 9.36 (2H, d, J = 4.8 Hz), 9.16 (2H, d, J = 4.8 Hz), 8.89 (2H, d, J =
4.8 Hz), 8.87 (2H, d, J = 4.8 Hz), 8.17 (4H, d, J = 7.9 Hz), 7.92 (4H,
d, J = 7.9 Hz), 4.60 (2H, s), 1.57−1.10 (42H, m), 0.07 (9H, s), −2.59
(2H, br s); 13C NMR (CDCl3, 75 MHz) δ 147.1 (br), 145.8 (6C, br),
142.4, 134.5, 131.5, 130.9, 130.5, 130.2, 128.7, 123.1, 122.0, 118.4,
107.4, 103.2, 91.9, 27.3, 18.9, 11.6, −0.8; IR (KBr) 3313, 3116, 3035,
2947, 2866, 1466, 1400, 1246, 987, 845, 795, 671 cm−1; UV/vis
(CHCl3) λmax (log ε): 420.0 (5.6), 517.0 (4.2), 554.0 (4.1), 592.0
(3.7), 649.5 (3.9) nm; HRMS-FAB+ ([M + H]+) calcd for
C58H73N4Si3: 909.5143, found 909.5158; Anal. calcd for
C58H72N4Si3: C, 76.60; H, 7.98; N, 6.16, found: C, 76.81; H, 7.97;
N, 5.78.
5,15-Diphenyl-10-(iso-propoxyldimethylsilyl)methylporphyrin
(3ag). Brown-purple solid; 89.1 mg, 81%yield; Rf = 0.61 (1:2 THF/
hexane); 1H NMR (CDCl3, 400 MHz) δ 9.94 (1H, s), 9.47 (2H, d, J =
4.9 Hz), 9.17 (2H, d, J = 4.9 Hz), 8.89 (2H, d, J = 4.9 Hz), 8.87 (2H,
5,15-Bis(2,4,6-trimethylphenyl)-10-(trimethylsilyl)-
methylporphyrin (3eb). Brown-purple solid; 101.8 mg, 87% yield; Rf
1
= 0.69 (1:2 THF/hexane); H NMR (CDCl3, 400 MHz) δ 9.94 (1H,
10493
dx.doi.org/10.1021/jo302122f | J. Org. Chem. 2012, 77, 10488−10497