complete extraction of the product into the ®ltrate. The ®ltrate
was evaporated and chromatographed (initially CH2Cl2±
EtOAc 10 : 1 as eluent, gradually increasing polarity). Solvent
removal and vacuum drying, yielded the product 11 (7.63 g,
99%) as a yellow oil.
repeatedly with water to remove Cu2z salts. The red/brown
solution was evaporated and chromatographed (initially
chloroform±2% pyridine). The ®rst and major fraction from
this column was dissolved in chloroform±1% pyridine (20 ml)
and centrifuged (4500 rpm, 10 min), decanted and centrifuged
again to remove all insoluble material. The volume was then
reduced to ca. 1 ml, polymer precipitated with methanol
(20 ml) and centrifuged (4500 rpm, 10 min). The precipitate
was resuspended and centrifuged twice with methanol and then
three times with 30±40 petroleum ether. Vacuum drying yielded
polymer 4 (0.158 g, 71%). Found: C, 76.2: H, 8.7: N, 6.6.
[C108H150N8O4Zn]n requires C, 76.7: H, 8.9: N, 6.6%.
N,N,N',N'-Tetrakis(2-ethylhexyl)-5-trimethylsilylethynyl-
isophthalamide (12)
Trimethylsilylacetylene (430 ml, 3.05 mmol) was added to a
mixture of 11 (1.50 g, 2.03 mmol), Pd(OAc)2 (9.1 mg,
0.04 mmol), PPh3 (21 mg, 0.08 mmol) and CuI (1.9 mg,
0.01 mol) in Et3N (8 ml) and the reaction stirred at 50 ³C for
1 h. Within 20 min, the mixture had become brown and cloudy.
After cooling, the reaction mixture was ®ltered through silica
then chromatographed in chloroform. Solvent removal and
vacuum drying yielded the product 12 (1.28 g, 89%) as a yellow
oil.
lmax(CHCl3±1% pyridine)/nm 481 (log e 5.02), 532 (4.96),
698 (4.38), 815 (4.38); nmax(KBr)/cm±1 2177 and 2121 (CMC),
1634 (CLO); dH (500 MHz; CDCl3, d5-pyridine) 9.98 (4 H, s,
bH), 9.83 (4 H, s, bH), 8.13 (4 H, s, aryl H), 7.45 (2 H, s, aryl
H), 3.55 (8 H, br s, NCH2), 3.36 (8 C, br s, NCH2), 1.94±0.93
(120 H, m, alkyl H); dC(125.8 MHz; CDCl3, d5-pyridine)
171.06, 153.24, 152.21, 138.47, 132.18, 131.00 (8 C, bC), 125.58,
124.92, 103.20, 102.28, 95.58, 93.87, 87.70, 82.80, 52.80 z
47.02 (CH2), 37.65z36.74 (CH), 30.84z30.52 (CH2), 28.78
(CH2), 24.16z23.76 (CH2), 23.25z23.13 (CH2), 14.25z14.20
(CH3), 11.01z10.84 (CH3); m/z (MALDI) 5097 (trimer Mz,
calc. 5071), 6824 (tetramer Mz, calc. 6761), 8533 (pentamer
Mz, calc. 8451), 10236 (hexamer Mz, calc. 10141), 11940
(heptamer Mz, calc. 11831), 13600 (octamer Mz, calc. 13520),
15285 (nonamer Mz, calc. 15210), 17005 (decamer Mz, calc.
16900), 18732 (11-mer Mz, calc. 18590), 20375 (12-mer Mz,
calc. 20280), 22048 (13-mer Mz, calc. 21969); GPC (THF)
Mn~53 000; Mw~119 000.
N,N,N',N'-Tetrakis(2-ethylhexyl)-5-ethynylisophthalamide (13)
K2CO3 (1.24 g, 9.00 mmol) was added to a solution of 12
(1.28 g, 1.80 mmol) in THF (40 ml) and MeOH (40 ml). The
mixture was stirred at room temperature for 90 min. CH2Cl2
(100 ml) was added and the organic layer washed with water
(3640 ml). Chromatography in chloroform followed by
vacuum drying yielded 13 as a brown oil (1.082 g, 94%).
5,15-Bis{3,5-bis[N,N-bis(2-ethylhexyl)carbamoyl]-
phenylethynyl}-10,20-bis[(triisopropylsilyl)ethynyl]-
porphyrinato}Zn(II) (Zn14)
A
solution of Pd2(dba)3 (13.3 mg, 0.0145 mmol), PPh3
meso-meso'-5,15-Bis{3,5-bis[N,N-bis(2-ethylhexyl)carbamoyl]-
phenylethynyl}-10-[(triisopropylsilyl)ethynyl]porphyrinato}-
Zn(II) dimer (Zn217)
(31.8 mg, 0.121 mmol), and CuI (11.5 mg, 0.0606 mmol) in
Et3N (25 ml) was heated at 70 ³C for 30 min under argon. This
catalyst solution was then transferred by cannula into an
oxygen-free solution of Zn7 (0.216 g, 0.24 mmol) and aryl
acetylene 13 (0.617 g, 0.97 mmol) in toluene (25 ml) and
pyridine (500 ml), and the reaction mixture was heated at
80 ³C for 4±5 h, with monitoring was by TLC (CH2Cl2±4%
MeOH) and UV (red shift of Soret band for product). The
reaction mixture was then ®ltered through silica (CH2Cl2 as
eluent), evaporated and chromatographed in 60±80 petroleum
ether±EtOAc±pyridine (10 : 0.75 : 0.1) to separate two main
green bands. The trace of faster running product was identi®ed
as the mono-substituted compound derived from the mono-
bromo species and the major, slower running product as the
desired compound Zn14 (0.462 g, 95%).
To the mono-protected acetylene porphyrin Zn16 (0.128 g,
0.0694 mmol) stirring vigorously in a 1 litre ¯ask under dry air
at room temperature in CH2Cl2 (160 ml) and pyridine (1.6 ml),
CuCl (0.550 g, 5.55 mmol) and TMEDA (0.838 ml, 5.55 mmol)
were added. The green solution immediately reddened. The
reaction was monitored by TLC (chloroform±1% pyridine),
and after 15 min no more starting material was seen and the
reaction mixture was washed repeatedly with water to remove
Cu2z salts. The organic layer was separated and solvents
removed. Recrystallisation from CH2Cl2 and methanol yielded
dimer Zn217 (0.112 g, 87%) as a sticky green solid which
hardened on vacuum drying.
5,15-Bis{3,5-bis[N,N-bis(2-
ethylhexyl)carbamoyl]phenylethynyl}-10,20-
bis(ethynyl)porphyrinato}Zn(II) (Zn15)
Acknowledgements
We are grateful to the EPSRC for supporting this work, and to
the EPSRC mass spectrometry service (Swansea) for FAB mass
spectra.
TBAF (160 ml of a 1.0 M solution in THF, 0.160 mmol) was
added to Zn14 (0.160 g, 0.0798 mmol) stirring in CH2Cl2
(20 ml). The reaction was complete by TLC (60±80 petroleum
ether±EtOAc±pyridine 10 : 2 : 0.1) after 15 min, and acetic acid
(10 ml, 0.168 mmol) was added to quench the reaction. The
solvents were evaporated and the reaction mixture was
chromatographed in 60±80 petroleum ether±EtOAc±pyridine
(10 : 2 : 0.5). Removal of solvents and vacuum drying yielded
the product Zn15 (0.120 g, 89%) as a green solid.
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319