22
D. RA ET AL.
6H), 4.67 (s, 2H), 7.66 (d, J = 7.8 Hz, 2H), 7.63–7.68
(three overlapped doublets, 6H), 7.71 (d, J = 8.3 Hz, 2H),
7.84 (d, J = 8.2 Hz, 2H), 7.95 (d, J = 8.2 Hz, 2H), 8.03 (d,
J = 7.8 Hz, 2H), 8.05 (d, J = 8.3 Hz, 2H), 8.07 (d, J = 8.3
Hz, 2H), 8.64 (d, J = 4.4 Hz, 1H), 8.81 (s, 1H), 8.94 (s,
1H), 8.98 (d, J = 4.4 Hz, 1H), 9.02 (s, 1H), 9.27 (s, 1H),
9.99 (s, 1H). LD-MS: m/z obsd. 947.5, calcd. 947.4 ([M +
H]+, M = C65H46N4O4).
13C NMR spectrum showed a low signal-to-noise ratio, in
which case identification of several low-intensity signals
in the aromatic region was ambiguous). LD-MS: m/z
obsd. 686.4, calcd. 686.3 ([M]+, M = C47H34N4O2).
17,18-Dihydro-18,18-dimethyl-10-(4-methylphenyl)-
3,13-bis[2-(4-(N,N-dimethylamino)phenyl)ethynyl]
porphyrin (C-36). Following Procedure B, a mixture
of C-29 (20.0 mg, 34.0 mmol), 4-(N,N-dimethylamino)
phenylethyne (14.8 mg, 102 mmol), Pd2(dba)3 (6.2 mg,
6.7 mmol), and P(o-tol)3 (13.4 mg, 44.1 mmol) in toluene/
TEA (6.8 mL) was allowed to react overnight. Final workup
entailed column chromatography (silica, CH2Cl2) to provide
a semi-pure product, which was washed with MeOH (with
sonication, twice) to afford a purple solid (15.0 mg, 61%):
1H NMR (400 MHz, CDCl3): d, ppm -1.87 (bs, 1H), -1.44
(bs, 1H), 2.05 (s, 6H), 2.86 (s, 3H), 3.08 (s, 6H), 3.11 (s,
6H), 4.64 (s, 2H), 6.81 (d, J = 8.9 Hz, 2H), 6.85 (d, J = 8.8
Hz, 2H), 7.53 (d, J = 7.8 Hz, 2H), 7.74 (d, J = 8.8 Hz, 2H),
7.85 (d, J = 8.9 Hz, 2H), 8.02 (d, J = 7.8 Hz, 2H), 8.62 (d,
J = 4.3 Hz, 1H), 8.76 (s, 1H), 8.85 (s, 1H), 8.93 (s, 1H), 8.96
(d, J = 4.3 Hz, 1H), 9.28 (s, 1H), 10.02 (s, 1H). ESI-MS: m/z
obsd. 717.3692, calcd. 717.3700 ([M + H]+, M = C49H44N6).
1 7 , 1 8 - D i h y d r o - 1 8 , 1 8 - d i m e t h y l - 1 0 - ( 4 -
methylphenyl)-3,13-bis[2-(phenanthren-9-yl)
ethynyl]porphyrin (C-37). Following Procedure A,
a mixture of C-29 (19.7 mg, 33.5 mmol), 9-ethynyl-
phenanthrene (16.2 mg, 80.2 mmol), and Pd(PPh3)2Cl2
(4.7 mg, 6.7 mmol) in DMF/TEA (2.3 mL) was allowed
to react overnight. Final workup entailed column
chromatography [silica, hexanes/CH2Cl2 (3:2)] to afford
a violet-brown solid (7.4 mg, 27%): 1H NMR (400 MHz,
CDCl3): d, ppm -1.77 (bs, 1H), -1.35 (bs, 1H), 2.10 (s,
6H), 2.72 (s, 3H), 4.71 (s, 2H), 7.60 (d, J = 7.8 Hz, 2H),
7.66–7.79 (m, 4H), 7.81–7.94 (m, 4H), 7.99–8.02 (m,
1H), 8.04–8.06 (m, 1H), 8.09 (d, J = 7.8 Hz, 2H), 8.41
(s, 1H), 8.52 (s, 1H), 8.68 (d, J = 4.3 Hz, 1H), 8.74–8.75
(m, 2H), 8.77–8.79 (m, 1H), 8.81–8.83 (m, 1H), 8.85 (s,
1H), 8.96–8.98 (m, 1H), 9.02 (d, J = 4.3 Hz, 1H), 9.05 (s,
1H), 9.05–9.07 (m, 1H), 9.14 (s, 1H), 9.45 (s, 1H), 10.16
(s, 1H). 13C NMR (100 MHz, CDCl3): d, ppm 21.7, 31.3,
45.6, 52.2, 88.8, 89.1, 95.0, 95.2, 95.7, 96.4, 105.5 117.9,
119.9, 120.0, 122.5, 122.8, 122.9, 123.1, 123.2, 125.2,
127.2, 127.3, 127.4, 127.48, 127.54, 127.8, 127.9, 128.9,
129.0, 130.3, 130.4, 130.5, 130.6, 130.7, 131.4, 131.5,
132.4, 132.8, 133.0, 133.2, 134.2, 135.0, 135.5, 137.7,
138.3, 140.3, 140.4, 151.9, 153.8, 163.9, 176.1. LD-MS:
m/z obsd. 830.6, calcd. 830.3 ([M]+, M = C61H42N4).
17,18-Dihydro-18,18-dimethyl-3,13-bis(3-N,N-
dimethylamino-1-propyn-1-yl)-10-(4-methylphenyl)-
porphyrin (C-38). Following Procedure A, a mixture of
C-29(24.0mg,40.8mmol),N,N-dimethylpropargylamine
(21 mL, 0.20 mmol), and Pd(PPh3)2Cl2 (5.6 mg, 8.0 mmol)
in DMF/TEA (4 mL) was allowed to react overnight.
Final workup entailed column chromatography [silica,
CH2Cl2/MeOH (25:1)] to afford a violet-brown solid
17,18-Dihydro-3,13-bis[2-(4-methoxycarbonylphenyl)
ethynyl]-18,18-dimethyl-10-(4-methylphenyl)-porphyrin
(C-34). Following Procedure A, a mixture of C-29
(45.5 mg, 77.3 mmol), 4-methoxycarbonylphenylethyne
(37.1 mg, 232 mmol), and Pd(PPh3)2Cl2 (10.7 mg,
15.2 mmol) in DMF/TEA (4.9 mL) was allowed to react
overnight. Final workup entailed column chromatography
[silica, hexanes CH2Cl2 (1:1)] to afford a purple-brown
1
solid (25.1 mg, 43%): H NMR (400 MHz, CDCl3): d,
ppm -1.83 (bs, 1H), -1.40 (bs, 1H), 2.07 (s, 6H), 2.70 (s,
3H), 3.99 (s, 6H), 4.67 (s, 2H), 7.56 (d, J = 7.8 Hz, 2H),
7.90 (d, J = 8.3 Hz, 2H), 8.00 (d, J = 8.3 Hz, 2H), 8.03
(d, J = 7.8 Hz, 2H), 8.17 (d, J = 8.3 Hz, 2H), 8.20 (d, J =
8.3 Hz, 2H), 8.64 (d, J = 4.3 Hz, 1H), 8.81 (s, 1H), 8.95
(s, 1H), 8.98 (d, J = 4.3 Hz, 1H), 9.03 (s, 1H), 9.26 (s,
1H), 9.98 (s, 1H). ESI-MS: m/z obsd. 747.2963, calcd.
747.2965 ([M + H]+, M = C49H38N4O4).
17,18-Dihydro-3,13-bis[2-(4-formylphenyl)
ethynyl]-18,18-dimethyl-10-(4-methylphenyl)
porphyrin (C-35). Following Procedure B, a mixture
of C-29 (22.3 mg, 39.8 mmol), 4-formylphenylethyne
(12.7 mg, 99.5 mmol), Pd2(dba)3 (7.1 mg, 7.7 mmol),
and P(o-tol)3 (15.4 mg, 50.6 mmol) in toluene/TEA
(3.9 mL) was allowed to react overnight. TLC analysis
showed complete consumption of starting material, and
formation of one major product accompanied by a smaller
amount of byproducts. Final workup entailed column
chromatography (silica, CH2Cl2) to provide a semi-pure
product, for which 1H NMR spectroscopy showed a small
amount of impurities in the aromatic region (probably
dba remnants, and/or a product of homocoupling of
4-formylphenylethyne). Further purification by column
chromatography [silica, hexanes/CH2Cl2 (1:2), twice]
afforded a pure product as a purple-brown solid, but with
a significant loss in yield (4.4 mg, 16%; no effort was
made to optimize the reaction conditions to improve the
1
yield): H NMR (400 MHz, CDCl3): d, ppm -1.79 (bs,
1H), -1.36 (bs, 1H), 2.08 (s, 6H), 2.70 (s, 3H), 4.68 (s,
2H), 7.56 (d, J = 7.7 Hz, 2H), 7.98-8.12 (m, 10H), 8.64
(d, J = 4.3 Hz, 1H), 8.82 (s, 1H), 8.97 (s, 1H), 8.98 (d,
overlapped with a singlet, 1H), 9.06 (s, 1H), 9.27 (s, 1H),
9.99 (s, 1H), 10.11 (s, 1H), 10.17 (s, 1H). 13C NMR (100
MHz, CDCl3): d, ppm 21.7, 31.2, 46.6, 52.2, 88.2, 88.8,
95.2, 95.6, 96.0, 97.0, 105.3, 116.9, 121.8, 122.9, 125.4,
125.7, 127.9, 128.4, 129.2, 129.6, 129.8, 129.98, 129.99,
130.00, 130.91, 132.4, 132.6, 133.3, 134.1, 134.9, 135.5,
135.7, 136.0, 137.9, 138.0, 140.2, 148.0, 152.1, 153.9,
163.9, 176.2, 191.6 (only one signal from the formyl
carbon was visible; due to the low quantity of sample, the
1
(21.4 mg, 88%): H NMR (400 MHz, CDCl3): d, ppm
-1.99 (bs, 1H), -1.58 (bs, 2H), 2.04 (s, 6H), 2.64 (s, 6H),
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 22–26