A. Ryan et al. / Tetrahedron 67 (2011) 8248e8254
8251
carbazoleeH) ppm; 13C NMR (100 MHz, CDCl3): dC¼13.6, 22.1, 24.5,
to column chromatography (CH2Cl2/hexane 1:1) to yield purple
26.5, 28.6, 31.2, 42.5, 83.3, 108.4, 114.6, 118.2, 119.2, 120.1, 124.5,
product 10 (54 mg, 86%, 0.07 mmol). Mp¼184 ꢀC; 1H NMR (400 MHz,
3
125.7, 139.5, 140.5 ppm; FT-IR (ATR):
n
¼2961, 2928, 2859, 1624,
CDCl3): dH¼ꢁ2.66 (s, 2H, NH), 0.76 (t, JHeH¼12.9 Hz, 3H, CH3),
1560, 1497, 1477, 1436, 1363, 1334, 1270, 1255, 1236, 1141, 1081, 966,
927, 854, 748, 732, 687 cmꢁ1; HRMS (ESIþ) [C24H32NO2þH]: calcd
378.2604, found 378.2606.
0.87e0.92 (m, 2H, CH2), 1.23e1.27 (m, 2H, CH2), 1.39e1.43 (m, 2H,
CH2), 1.92e1.99 (m, 2H, CH2), 2.73 (s, 6H, tolyleCH3), 2.75 (s, 3H,
tolyleCH3), 4.44 (t, 3JHeH¼14.0 Hz, 2H, CH2), 7.43 (t, 3JHeH¼14.0 Hz,
1H, carbazoleeH), 7.57e7.61 (m, 6H, tolyleH), 7.60e7.62 (m, 2H,
3
4.2.2. 3-(50,100,150-Triphenylporphyrin-200-yl)-9-hexyl-carbazole
(8). Porphyrin 4 (50 mg, 0.08 mmol), borylated carbazole 3 (61 mg,
0.16 mmol), and K3PO4 (210 mg, 0.97 mmol) were charged to a 50 mL
Schlenk tube and dried under high vacuum for 20 min. THF (10 mL)
was added and the solution was degassed via three freeze-pump-
thaw cycles. Pd(PPh3)4 (9 mg, 0.01 mmol) was added, the reaction
heated to 80 ꢀC under argon and left to stir at this temperature for
18 h. Solvents removed in vacuo, the residue dissolved in CH2Cl2 and
washed with saturated NaHCO3, brine and H2O. Organic layers dried
over MgSO4 and solvents removed in vacuo. Residue subjected to
column chromatography (CH2Cl2/hexane 1:1) to yield purple
product 8 (49 mg, 75%, 0.06 mmol). Mp¼201 ꢀC; 1H NMR (400 MHz,
carbazoleeH), 8.14 (d, JHeH¼7.0 Hz, 6H, tolyleH), 8.29 (s, 1H,
3
carbazoleeH), 8.38 (d, JHeH¼7.6 Hz, 1H, carbazoleeH), 8.44 (d,
3JHeH¼7.6 Hz, 1H, carbazoleeH), 8.88e8.92 (m, 8H,
b
-H) ppm; 13C
NMR (150 MHz, CDCl3): dC¼11.0, 13.9, 14.1, 21.6, 22.6, 29.1, 30.4, 38.7,
43.3, 68.2, 109.1, 115.8, 117.9, 119.2, 125.9, 127.4, 128.8, 130.9, 134.5,
137.3,139.3,139.4 ppm; FT-IR (ATR):
n
¼3319, 2924, 2856,1723,1458,
1325, 1271, 1121, 1071, 971, 793, 725 cmꢁ1; UVevis (CH2Cl2): lmax
(log
3
)¼423 (5.50), 518 (4.61), 554 (4.50), 591 (4.41), 650 nm (4.39);
HRMS (MALDI LDþ) [C59H51N5]: calcd 828.4144, found 829.4121.
4.2.5. 3-(5,10,15-Tris(4-methylphenyl)porphyrinato(zinc)(II)-20-yl)-
9-hexyl-carbazole (11). Porphyrin 10 (50 mg, 0.06 mmol) was dis-
solved in CHCl3 (10 mL) and heated to 70 ꢀC. Zn(OAc)2 (54 mg,
0.30 mmol) in MeOH (0.5 mL) was added and the reaction stirred for
30 min. Solvents removed and the residue redissolved in CH2Cl2 and
filtered through a plug of silica. Solvents removed in vacuo to yield
a bright purple solid 11 (43 mg, 81%, 0.05 mmol). Mp¼144 ꢀC; 1H
3
CDCl3): dH ¼ꢁ2.68 (s, 2H, NH), 0.78 (t, JHeH¼14.0 Hz, 3H, CH3),
0.88e0.93 (m, 2H, CH2), 1.24e1.29 (m, 2H, CH2), 1.41e1.46 (m, 2H,
CH2),1.96e2.00 (m, 2H, CH2), 4.45 (t, 3JHeH¼14.0 Hz, 2H, CH2), 7.42 (t,
3JHeH¼14.6 Hz, 1H, carbazoleeH), 7.59e7.63 (m, 2H, carbazoleeH),
3
7.77e7.82 (m, 9H, PheH), 8.16 (d, JHeH¼9.4 Hz, 1H, carbazoleeH),
3
3
8.26 (d, 3J
¼15.2 Hz, 6H, PheH), 8.38 (d, JHeH¼7.6 Hz, 1H,
NMR (400 MHz, CDCl3): dH¼0.78 (t, JHeH¼9.3 Hz, 3H, CH3),
HeeH
3
carbazoleeH), 8.44 (d, JHeH¼7.6 Hz, 1H, carbazoleeH), 8.86e8.88
0.87e0.92 (m, 4H, CH2), 1.29e1.33 (m, 2H, CH2), 1.96e1.99 (m, 2H,
CH2), 2.74 (s, 6H, tolyleCH3), 2.75 (s, 3H, tolyleCH3), 4.44 (t,
3
(m, 6H,
b-H), 8.93 (d, JHeH¼4.7 Hz, 2H,
b
-H) ppm; 13C NMR
3
(150 MHz, CDCl3): dC¼13.9, 22.5, 26.9, 29.1, 31.5, 43.3, 109.1, 115.7,
3JHeH¼6.0 Hz, 2H, CH2), 7.41 (t, JHeH¼9.3 Hz, 1H, carbazoleeH),
117.9, 119.2, 120.1, 127.7, 131.2, 134.5, 139.3, 139.7, 141.2, 142.2 ppm;
7.57e7.62 (m, 6H, PheH), 7.60 (m, 2H, carbazoleeH), 8.14e8.17 (m,
3
FT-IR (ATR):
n
¼3314, 3055, 2910, 2873, 1590, 1487, 1440, 1354, 1176,
6H, PheH), 8.29 (s, 2H, carbazoleeH), 8.38 (d, JHeH¼4.9 Hz, 1H,
1070, 1005, 776, 747, 700, 669 cmꢁ1; UVevis (CH2Cl2): lmax (log
3 )¼
carbazoleeH), 8.44 (d, JHeH¼4.9 Hz, 1H, carbazoleeH), 8.98e9.01
3
422 (5,40), 517 (4.43), 522 (4.31) 591 (4.28), 646 nm (4.23); HRMS
(MALDI LDþ) [C56H45N5]: calcd 787.3675, found 787.3652.
(m, 8H,
b
-H) ppm; 13C NMR (150 MHz, CDCl3): dC¼13.9, 21.5, 21.9,
22.7, 27.1, 31.6, 53.4, 77.2, 109.0, 115.6, 117.8, 119.2, 120.6, 125.9, 127.3,
127.4,131.9,132.1,134.3,134.4,134.5,147.9 ppm; FT-IR (ATR):
1598, 1492, 1437, 1324, 1180, 1068, 998, 850, 794, 743, 720 cmꢁ1
UVevis (CH2Cl2): lmax (log
)¼422 (5.52), 547 (4.63), 588 nm (4.40);
HRMS (MALDI LDþ) [C59H49N5Zn]: calcd 891.3279, found 891.3237.
n
¼2921,
4.2.3. 3-(50,100,150-Triphenylporphyrinato(zinc)(II)-200-yl)-9-hexyl-
carbazole (9). Porphyrin 8 (27 mg, 0.03 mmol) was dissolved in
CHCl3 (10 mL) and heated to 70 ꢀC. Zn(OAc)2 (26 mg, 0.34 mmol) in
MeOH (0.5 mL) was added and the reaction stirred for 30 min. Sol-
vents removed and the residue redissolved in CH2Cl2 and filtered
through a plug of silica. Solvents removed in vacuo to yield a bright
purple solid 10 (24 mg, 74%, 0.03 mmol). Mp¼182 ꢀC; 1H NMR
(400 MHz, CDCl3): dH¼0.80 (t, 3JHeH¼14.0 Hz, 3H, CH3),1.25e1.30 (m,
4H, CH2), 1.40e1.47 (m, 2H, CH2), 1.94e2.00 (m, 2H, CH2), 4.44 (t,
;
3
4.2.6. 3-(5,10,15-Tris(4-methylphenyl)porphyrinato(palladium)(II)-
20-yl)-9-hexyl-carbazole (12). Porphyrin 10 (30 mg, 0.04 mmol),
Pd(OAc)2 (24 mg, 0.11 mmol), and toluene (20 mL) were placed in
a two-necked round bottomed flask and heated to 110 ꢀC. Upon
reaction completion, the solvent was removed in vacuo and the
residue was redissolved in CH2Cl2. The crude product was filtered
through a plug of silica, solvents were removed in vacuo to yield
a red colored solid 12 (30 mg, 89%, 0.03 mmol). Mp¼130 ꢀC; 1H
3
3JHeH¼14.6 Hz, 2H, CH2), 7.40 (t, JHeH¼12.8 Hz, 1H, carbazoleeH),
7.57e7.63 (m, 2H, carbazoleeH), 7.76e7.83 (m, 9H, PheH), 8.18 (d,
3JHeH¼6.4 Hz, 1H, carbazoleeH), 8.27e8.31 (m, 6H, PheH), 8.37 (d,
3
3
3JHeH¼7.6 Hz, 1H, carbazoleeH), 8.45 (d, JHeH¼7.6 Hz, 1H,
NMR (400 MHz, CDCl3): dH¼0.79 (t, JHeH¼13.4 Hz, 3H, CH3),
carbazoleeH), 8.95e9.00 (m, 6H,
b
-H), 9.06 (d, 3JHeH¼4.7 Hz, 2H,
b-
1.25e1.31 (m, 2H, CH2), 1.59e1.64 (m, 2H, CH2), 1.93e1.99 (m, 2H,
CH2), 2.71(s, 6H, tolyleCH3), 2.73 (s, 3H, tolyleCH3), 4.42 (t,
3JHeH¼14.2 Hz, 2H, CH2), 7.39e7.42 (m, 1H, carbazoleeH), 7.48 (d,
3JHeH¼5.9 Hz, 1H, carbazoleeH), 7.56e7.61 (m, 6H, tolyleH), 8.08
H) ppm; 13C NMR (100 MHz, CDCl3): dC¼13.9, 22.6, 27.1, 29.2, 31.6,
43.3, 109.1, 115.6, 117.9, 119.2, 120.7, 121.1, 121.2, 122.1, 122.9, 125.9,
126.5,126.6,127.5,131.9,132.3,134.4,139.2,140.3,141.2,142.8,150.2,
3
(d, JHeH¼7.8 Hz, 6H, tolyleH), 8.24 (s, 1H, carbazoleeH), 8.37 (d,
150.6 ppm; FT-IR (ATR):
n
¼3052, 2926, 2870,1596,1486,1438,1326,
3
3JHeH¼7.8 Hz, 1H, carbazoleeH), 8.43 (d, JHeH¼7.8 Hz, 1H,
1239, 1174, 1067, 1001, 767, 727, 699, 665 cmꢁ1; UVevis (CH2Cl2):
carbazoleeH), 8.84e8.89 (m, 8H, b
-H) ppm; 13C NMR (100 MHz,
lmax (log
3
)¼423 (5.42), 549 (4.45), 587 nm (4.28); HRMS (MALDI
LDþ) [C56H43N5Zn ]: calcd 849.2810, found 849.2801.
CDCl3): dC¼13.9, 21.6, 22.6, 24.9, 27.1, 29.1, 29.6, 31.6, 34.2, 43.3,
66.7, 109.1, 115.3, 118.1, 119.2, 120.6, 121.8, 122.2, 122.5, 125.9, 126.1,
127.4, 128.2, 128.6, 129.7, 130.9, 131.1, 134.1, 137.4, 138.9, 139.3, 139.4,
4.2.4. 3-(5,10,15-Tris(4-methylphenyl)porphyrin-20-yl)-9-hexyl-car-
bazole (10). Porphyrin 5 (50 mg, 0.08 mmol), borylated carbazole 3
(60 mg, 0.16 mmol), and K3PO4 (194 mg, 0.91 mmol) were charged to
a 50 mL Schlenk tube and dried under high vacuum for 20 min. THF
(10 mL) was added and the solution was degassed via three freeze-
pump-thaw cycles. Pd(PPh3)4 (9 mg, 0.01 mmol) was added, the re-
action heated to 80 ꢀC under argon and left to stir at this temperature
for 18 h. Solvents removed in vacuo, the residue dissolved in CH2Cl2
and washed with saturated NaHCO3, brine and H2O. Organic layers
dried over MgSO4 and solvents removed in vacuo. Residue subjected
141.2, 141.7, 141.9 ppm;; FT-IR (ATR):
n
¼2933, 1580, 1490, 1422,
1313, 1188, 1072, 1001, 844, 774, 735 cmꢁ1; UVevis (CH2Cl2): lmax
(log
3
)¼421 (4.42), 526 nm (3.53); HRMS (MALDI LDþ)
[C59H49N5Pd]: calcd 933.3023, found 933.3058.
4.2.7. 3-[Chloro{5,10,15-tris(4-methylphenyl)porphyrinato}in-
dium(III)-20-yl]-9-hexyl-carbazole (13). Porphyrin 10 (33 mg,
0.04 mmol), InCl3 (88 mg, 0.40 mmol), CH3COONa (298 mg,
4.25 mmol), and glacial acetic acid (15 mL) were placed in a round