meso-Aryl-Substituted Subporphyrins
FULL PAPER
1a (24.3 mg, 48.4 mmol) in deoxygenated CHCl3 (20 mL) in a 50-mL
round-bottomed flask, and the resulting solution was stirred at room tem-
perature for 2 h under N2 atmosphere. The reaction was quenched by the
addition of saturated Na2S2O3 solution (10 mL) and then the organic
layer was separated and washed with water twice and brine, dried over
anhydrous Na2SO4, and concentrated in vacuo. A mixture of CH2Cl2/
MeOH (1:1, 20 ml) was added to the residue, and heated at 508C for
10 min followed by concentration in vacuo. The crude material was puri-
fied by short path on silica with CH2Cl2/hexane/ether=1:4:1 as an eluent
and recrystallization from CH2Cl2/MeOH gave pure subporphyrin 2a
(46.4 mg, quant.) as a yellow solid. 1H NMR (600 MHz, CDCl3, À408C):
d=8.12 (d, J=7.80 Hz, 3H; meso-Ph-ortho), 7.74 (t, J=7.80 Hz, 3H;
meso-Ph-meta), 7.69 (t, J=7.80 Hz, 3H; meso-Ph-para), 7.49 (t, J=
7.80 Hz, 3H; meso-Ph-meta), 7.23 (d, J=7.80 Hz, 3H; meso-Ph-ortho),
0.84 ppm (s, 3H; axial-OMe); 11B NMR (193 MHz, CDCl3, À408C): d=
À16.2 ppm (s); 13C NMR (150 MHz, CDCl3, RT): d=135.1, 133.3, 132.6,
132.3, 129.4, 127.9, 120.1, 118.1, 47.4 ppm; UV/Vis (CH2Cl2): lmax (e)=
ration of 3a. Yield was 18.4 mg (73%). A single crystal suitable for X-ray
diffraction analysis was prepared by slow recrystallization from CH2Cl2/
1
methanol. H NMR (600 MHz, CDCl3, À508C): d=7.53 (s, 3H; meso-Ar-
ortho), 7.15 (d, J=7.32 Hz, 6H; b-Ph-ortho), 6.8–6.9 (m, 9H; meso-Ar-
para, b-Ph-para), 6.80 (t, J=7.32 Hz, 6H; b-Ph-meta), 6.63 (t, J=7.32 Hz,
6H; b-Ph-meta), 7.53 (d, J=7.32 Hz, 6H; b-Ph-ortho), 6.33 (s, 3H; meso-
Ar-ortho), 1.09 (s, 27H; meso-Ar-tert-butyl), 0.83 (s, 27H; meso-Ar-tert-
butyl), 0.81 ppm (s, 3H; axial-OMe); 11B NMR (193 MHz, CDCl3,
À508C): d=À15.5 ppm; 13C NMR (150 MHz, CDCl3, À508C): d=147.8,
147.3, 138.3, 136.6, 134.7, 133.6, 132.0, 130.3, 127.7, 126.7, 126.4, 126.3,
125.5, 122.3, 121.7, 47.5, 34.4, 34.1, 31.4, 31.1 ppm; UV/Vis (CH2Cl2): lmax
(e)=382 (199000), 464 nm (27000mÀ1 cmÀ1); fluorescence (CH2Cl2, lex
=
374 nm): lmax =497, 522 nm; FF =0.12; HR-ESI TOF-MS (positive
mode): m/z: calcd for C93H93N3B1: 1262.7471 [MÀOMe]+; found:
1262.7470.
Methoxo(2,3,7,8,12,13-hexa(trimethylsilylethynyl)-5,10,15-phenyl)-
A
ACHTUNGTERNN(UNG III) (4a): A sample test tube containing 2a
374 (189000), 460 nm (24000mÀ1 cmÀ1); fluorescence (CH2Cl2, lex
=
374 nm): lmax =522 nm; FF <0.01; HR-ESI TOF-MS (positive mode):
m/z: calcd for C33H15N3B1Br6: 943.6402 [MÀOMe]+; found: 943.6395.
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
Methoxo(2,3,7,8,12,13-hexabromo-5,10,15-tri(3,5-di-tert-butylphenyl)-
to the mixture and the resulting solution was stirred at 708C for 24 h
under N2 atmosphere. The resulting mixture was cooled to room room
temperature, washed with water twice, dried over anhydrous Na2SO4, and
then concentrated in vacuo. A mixture of CH2Cl2/MeOH (1:1) was added
to the residue and heated at 508C for 10 min followed by concentration
in vacuo. The crude material was purified by a short silica-gel column
using a mixture of CH2Cl2/hexane/diethyl ether=1:4:1 as an eluent. Re-
crystallization from CH2Cl2/MeOH gave pure subporphyrin 4a (46.1 mg,
85%) as a red solid. 1H NMR (600 MHz, CDCl3, RT): d=7.72 (br, 6H;
meso-Ph-ortho), 7.59 (t, 3H; J=7.80 Hz, meso-Ph-para), 7.49 (t, J=
7.32 Hz, 6H; meso-Ph-meta), 0.90 (s, 3H; axial-OMe), 0.11 ppm (s, 54H;
b-TMS); 11B NMR (193 MHz, CDCl3, RT): d=À15.4 ppm; 13C NMR
(150 MHz, CDCl3, RT): d=138.6, 133.8, 133.2, 129.0, 127.3, 123.9, 120.2,
108.2, 97.3, 47.2, 0.23 ppm; UV/Vis (CH2Cl2): lmax (e)=424 (216000), 506
(34000), 533 nm (20000mÀ1 cmÀ1); fluorescence (CH2Cl2, lex =424 nm):
lmax =540, 583 nm; FF =0.05; HR-ESI TOF-MS (positive mode): m/z:
calcd for C63H69N3B1Si6: 1046.4206 [MÀOMe]+; found: 1046.4206.
ACHTUNGTRENNUNGsubporphyrinate)boronACHTUNGTRENNUNG(III) (2b): The subporphyrin 2b was prepared
from 1b (18.6 mg, 22.2 mmol) by the same procedure used for the prepa-
ration of 2a. Yield was 24.9 mg (88%). A single crystal suitable for X-ray
diffraction analysis was prepared by slow recrystallization from CH2Cl2/
MeOH. 1H NMR (600 MHz, CDCl3, RT): d=7.83 (s, 3H; meso-Ar-
ortho), 7.62 (s, 3H; meso-Ar-para), 7.14 (s, 3H; meso-Ar-ortho), 1.47 (s,
27H; meso-Ar-tert-butyl), 1.29 (s, 27H; meso-Ar-tert-butyl), 0.86 ppm (s,
3H; axial-methoxy); 11B NMR (193 MHz, CDCl3, RT): d=À16.1 ppm;
13C NMR (151 MHz, CDCl3, RT): d=150.4, 149.5, 134.5, 131.1, 128.3,
127.4, 122.3, 121.1, 118.0, 47.5, 35.3, 35.2, 31.8, 31.6 ppm; UV/Vis
(CH2Cl2): lmax (e)=377 (198000), 434 (7000), 461 nm (25000mÀ1 cmÀ1);
fluorescence (CH2Cl2, lex =374 nm): lmax =524 nm; FF <0.01; HR-ESI
TOF-MS (positive mode): m/z: calcd. for C57H63N3B1Br6: 1280.0179
[MÀOMe]+; found: 1280.0181.
Methoxo(2,3,5,7,8,10,12,13,15-nonaphenylsubporphyrinate)boronACTHNUTRGNE(UNG III)
(3a): A sample test tube containing 2a (28.3 mg, 30.2 mmol), dihydroxy-
phenylboron (110.0 mg, 898 mmol), and CsCO3 (675.4 mg, 2.07 mmol) was
purged with N2, and then charged with dehydrated toluene (6 mL). [Pd-
Methoxo(2,3,7,8,12,13-hexa(trimethylsilylethynyl)-5,10,15-tri(3,5-di-tert-
butylphenyl)subporphyrinate)boronACTHNUGRTNEUNG(III) (4b): The subporphyrin 4b was
A
prepared from 2b (37.5 mg, 29.3 mmol) by the same procedure used for
the preparation of 4a except the reaction temperature was 1108C. Yield
was 18.5 mg (63%). A single crystal suitable for X-ray diffraction analy-
sis was prepared by slow recrystallization from CH2Cl2/methanol.
1H NMR (600 MHz, CDCl3, À508C): d=7.93 (s, 3H; meso-Ar-ortho),
7.54 (s, 3H; meso-Ar-para), 6.96 (s, 3H; meso-Ar-ortho), 1.46 (s, 27H;
meso-Ar-tert-butyl), 1.27 (s, 27H; meso-Ar-tert-butyl), 0.92 ppm (s, 3H;
axial-OMe); 11B NMR (193 MHz, CDCl3, RT): d=À15.6 ppm (s);
13C NMR (150 MHz, C2D2Cl4, 1008C): d=148.8, 137.2, 133.5, 127.7,
125.7, 121.8, 120.6, 108.3, 98.3, 47.6, 35.0, 32.0, 0.9 ppm; UV/Vis
(CH2Cl2): lmax (e)=426 (242000), 471 (12000), 507 (38000), 534 nm
(18000mÀ1 cmÀ1); fluorescence (CH2Cl2, lex =426 nm): lmax =543 (sh),
584 nm; FF =0.05; HR-ESI TOF-MS (positive mode): m/z: calcd for
C87H117N3B1Si6: 1383.7982 [MÀOMe]+; found: 1383.7987.
1108C for four days under N2 conditions. The resulting solution was
cooled to room temperature, diluted with 10 mL of CH2Cl2, washed with
water twice, dried over anhydrous Na2SO4, and then concentrated in
vacuo. A mixture of CH2Cl2/MeOH (1:1, 20 mL) was added to the resi-
due and heated at 508C for 10 min followed by concentration in vacuo.
The resulting mixture was concentrated in vacuo and then purified by
column chromatography on silica with CH2Cl2/hexane/diethyl ether=
1:4:1 as an eluent. The 1H NMR spectrum of the mixture indicated the
presence of b-pentaphenylated product. Repeated silica-gel column chro-
matography and recrystallization from CH2Cl2/MeOH gave pure 3a as a
yellow solid. As a more convenient method, one more cycle of bromina-
tion with bromine and subsequent Suzuki–Miyaura coupling reaction of
the mixture of b-pentaphenylated product and 3a gave pure 3a in 55%
yield without difficult separation. 1H NMR (600 MHz, CDCl3, À508C):
d=7.29 (d, J=7.32 Hz, 3H; meso-Ph-ortho), 6.89 (d, J=7.32 Hz, 6H; b-
Ph-ortho), 6.80 (t, J=7.74 Hz, 3H; meso-Ph-para), 6.78 (t, J=6.90 Hz,
6H; b-Ph-para), 6.72 (t, J=7.32 Hz, 6H; b-Ph-meta), 6.59 (t, J=8.22 Hz,
3H; meso-Ph-meta), 6.27 (br, 6H; b-Ph-meta), 6.24 (t, 8.22 Hz, 3H;
meso-Ph-meta), 6.09 (d, J=6.90 Hz, 3H; meso-Ph-ortho), 6.05 (d, J=
6.00 Hz, 6H; b-Ph-ortho), 0.70 ppm (s, 3H; axial-OMe); 11B- and
13C NMR spectra were not recorded because of poor solubility. UV/Vis
(CH2Cl2): lmax (e)=380 (200000), 464 nm (26000mÀ1 cmÀ1); fluorescence
(CH2Cl2, lex =374 nm): lmax =499, 528 nm; FF =0.12; HR-ESI TOF-MS
(positive mode): m/z: calcd for C69H45N3B1: 926.3712 [MÀOMe]+; found:
926.3710.
Methoxo(2,3,7,8,12,13-hexa(phenylethynyl)-5,10,15-phenyl)subpor-
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
solution was stirred at 708C for 24 h under N2 atmosphere. The resulting
mixture was cooled to RT, washed with water twice, dried over anhy-
drous Na2SO4, and then concentrated in vacuo. A mixture of CH2Cl2/
MeOH (1:1) was added to the residue and heated at 508C for 10 min fol-
lowed by concentration in vacuo. The crude material was purified with a
short silica-gel column using a mixture of CH2Cl2/hexane/diethyl ether=
1:4:1 as an eluent. Recrystallization from CH2Cl2/MeOH gave pure sub-
porphyrin 5a (26.4 mg, 89% yield) as a red solid. A single crystal suitable
for X-ray diffraction analysis was prepared by slow recrystallization from
CH2Cl2/methanol. 1H NMR (600 MHz, CDCl3, À608C): d=8.43 (br, 3H;
Methoxo(2,3,7,8,12,13-hexaphenyl-5,10,15-tri(3,5-di-tert-butylphenyl)-
A
Chem. Eur. J. 2009, 15, 237 – 247
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
245