Phthalocyaninoannulenes
3958±3967
phine oxide, concentrated and separated by column chromatography over
silica (eluent: CH2Cl2/petrol 1:2).The product was recrystallised from
cyclohexane to afford compound 7 as white crystals (2.75 g, 83.6%). M.p.
72 ± 738C; 1H NMR (270 MHz, CDCl3): d 4.24 (t, J 6.4 Hz, 4H), 1.92
(quint, J 7.0 Hz, 4H), 1.67 ± 1.53 (m, 4H), 1.04 (t, J 7.3 Hz, 6H); 13C
phine)palladium(ii) chloride (7 mg, 10 mmol), copper(I) iodide (2.2 mg,
11.6 mmol) and trimethylsilylamine (TMSA, 25 mg, 255 mmol) were added
in that order and at 10 min intervals to a stirred solution of 3 (40 mg,
23.3 mmol) in dry degassed triethylamine (3.5 mL) under Ar in a dry screw-
cap pressure tube.Under a fast stream of Ar the rubber septum was
removed and the screw-cap sealed; the reaction mixture was heated and
stirred in an oil bath at 1008C for 16 h.The tube was cooled, and further
bis(triphenylphosphine)palladium(ii) chloride (4.1 mg), copper(i) iodide
(1.7 mg) and TMSA (25 mg) were added under Ar. The reaction was
heated at 1008C for a further 12 h.The mixture was cooled, filtered and
concentrated under reduced pressure.The residue was dried at 05. mmHg
for 12 h to remove excess TMSA and triethylamine traces, and further
purified by column chromatography over silica (eluent: petrol/dichloro-
methane 97:3).The first fraction was unreacted starting material (34. mg).
The second fraction contained a mixture; subsequent green fractions
containing minor amounts of material were discarded.The second fraction
was further purified by column chromatography over silica (eluent: petrol/
dichloromethane 98.5:1.5 then 97:3) to afford compound 11 (8.0 mg, 22%)
À
À
(270 MHz, CDCl3): d 156.37 (ArC O), 129.61 (ArC Br), 112.33 (CN),
109.22 (ArC-CN), 76.43, 31.95, 18.92, 13.73; MS (70 eV, EI): m/z (%): 432
(3.1), 430 (5.2), 428 (3.5) [M] ; IR (nujol): nÄ 2230 cmÀ1 (m); elemental
analysis calcd (%) for C16H18N2O2Br2 (430.14): C 44.68, H 4.22, N 6.51, Br
37.15; found: C 44.51, H 4.28, N 6.47, Br 37.33.
4-Bromo-3,6-dibutoxyphthalonitrile (8): A mixture of compound 6 (3 g,
9.4 mmol), finely crushed potassium carbonate (3 g, excess) and N,N,N-
tributyl-1-butananinium bromide (TBAB, 0.26 g, 0.7 mmol) was heated
under reflux in MEK (80 mL) for 12 h.The reaction was cooled and
1-iodobutane (3.70 g, 20 mmol) was added. Heating under reflux was
continued for a further 72 h.Upon cooling, the reaction was filtered and
washed with ethyl acetate.The organics were removed under reduced
pressure, and the residue dissolved in ethyl acetate (100 mL).This was
washed with 5% HCl (25 mL), saturated K2CO3 (25 mL), water (25 mL)
and brine (25 mL), dried (MgSO4), filtered and concentrated under
reduced pressure.The crude product was purified by column chromatog-
raphy over silica (eluent: petrol/CH2Cl2 2:1) and recrystallised from
cyclohexane to afford compound 8 (1.43 g, 43%). M.p. 102.5 ± 1048C;
1H NMR (270 MHz, [D6]acetone): d 7.88 (s, 1H), 4.30 (t, J 6.4 Hz, 2H),
4.18 (t, J 6.4 Hz, 2H), 1.86 (m, 4H), 1.56 (m, 4H), 1.00 (t, J 7.3 Hz, 3H),
0.99 (t, J 7.3 Hz, 3H); 13C NMR (300 MHz, [D6]acetone): d 157.68
1
as the first eluted component; H NMR (270 MHz, CDCl3): d 7.76 (brs,
4H), 7.73 (brs, 2H), 4.63 (t, J 6.9 Hz, 2H), 4.50 ± 4.39 (m, 6H), 4.34 ± 4.25
(m, 8H), 2.13 ± 1.84 (m, 16H), 1.62 ± 1.03 (m, 88H), 0.96 ± 0.91 (2 Â t, 6H),
0.78 (brt, 18H), 0.42 (s, 9H).
Further elution gave a second fraction and compound 1a (13.2 mg, 35%)
was isolated after recrystallisation from THF/methanol.Mp.69
8C;
1H NMR (270 MHz, CDCl3): d 7.78 (brs, 4H), 7.75 (s, 2H), 4.60 (t, J
7.2 Hz, 4H), 4.47 (t, J 6.9 Hz, 4H), 4.35 ± 4.26 (m, 8H), 2.10 ± 1.90 (m,
16H), 1.60 ± 1.08 (m, 88H), 0.95 (t, J 7.4 Hz, 6H), 0.80 (t, J 6.6 Hz,
12H), 0.79 (t, J 6.6 Hz, 6H), 0.43 (s, 18H); 13C NMR (67.5 MHz, CDCl3):
d 154.18 (ArCO), 147.99, 139.19, 138.13, 137.77, 134.75, 134.66, 134.43,
À
À
À
(ArC O), 152.80 (ArC O), 124.94, 123.33 (ArC H), 112.81 (CN), 112.69
À
À
(CN), 111.39 (ArC CN), 103.83 (ArC CN), 75.75, 70.40, 31.81, 30.57, 18.70,
18.66, 13.07, 12.98; MS (70 eV, EI): m/z (%): 350.1 (4.8), 352.1 (4.5) [M] ;
IR (nujol): nÄ 2230 cmÀ1 (m); elemental analysis calcd (%) for
C16H19N2O2Br1 (351.24): C 54.85, H 5.47, N 8.00, Br 22.54; found C 54.71,
H 5.43, N 7.89, Br 22.67.
130.83, 130.47, 130.29, 130.19, 129.16, 128.17, 127.81, 127.47, 104.74 (C CSi),
À
À
100.97 (C CSi), 75.43 (OCH2), 32.66, 32.56, 32.18, 31.88, 31.50, 30.53, 29.90,
29.85, 29.72, 29.67, 29.61, 29.45, 29.31, 22.64, 22.55, 19.37, 14.20, 14.07, 0.20;
UV/Vis (2.80 Â 10À6 m in toluene): lmax (loge) 732 (4.99), 702 nm (4.95);
1,4-Dibutoxy-2,3-dibromo-8,11,15,18,22,25-hexakis(decyl)phthalocyanin-
ato nickel(ii) (3): Freshly cleaned lithium (ca.50 mg, 75. mmol) was added
to 3,6-didecylphthalonitrile[21] (2.56 g, 6.27 mmol) and 7 (0.30 g, 0.70 mmol)
in refluxing butanol (20 mL) under argon.The reaction was heated under
reflux in the dark for 16 h, cooled, nickel acetate tetrahydrate (0.53 g,
2.1 mmol) was added and heating under reflux was continued for 2 h. After
cooling, the solvents were removed under reduced pressure, and the
residue triturated with methanol to afford a green solid.Purification by
column chromatography over silica (eluent: petrol) afforded 1,4,8,11,15,18,
22,25-octakis(decyl)phthalocyaninato nickel(ii) (0.71 g, 24%) as the first
fraction; changing the eluent to petrol/dichloromethane (1:1) afforded a
second fraction.The latter was further purified by column chromatography
over silica (eluent: petrol/dichloromethane 19:1) to afford 3 (45.7 mg,
3.8%) after recrystallisation from THF/methanol. M.p. 728C (K ! I), 678C
(I ! D), 578C (D ! K); 1H NMR (300 MHz, [D6]benzene): d 7.82 (s,
4H), 7.81 (s, 2H), 4.75 (t, J 7.5 Hz, 4H), 4.66 ± 4.57 (3 overlapping t, 12H),
2.34 ± 2.17 (m, 16H), 1.92 ± 1.11 (m, 88H), 0.95 (t, 6H, J 7.4 Hz), 0.87 ±
0.80 (m, 18H); UV/Vis (3.68 Â 10À6 m in toluene): lmax (loge) 716 (5.10),
MS (FAB): m/z: isotopic cluster at 1747 [MH] ; IR (KBr): nÄ 2929 (s),
2861 (m), 2155 (w), 1598 (w), 1457 (w), 1200 (w), 1092 cmÀ1 (m).
1,4-Dibutoxy-2,3-di(ethynyl)-8,11,15,18,22,25-hexakis(decyl)phthalocyani-
nato nickel(ii) (1b): Tetrakis(triphenylphosphine)palladium(0) (10.5 mg,
9.0 mmol) was added to a solution of 3 (48.6 mg, 28.3 mmol), anhydrous
lithium chloride (10 mg, 233 mmol) and triphenylphosphine (9.5 mg,
36 mmol) in dry degassed toluene (6 mL) under argon.After stirring for
10 min, tributyl(ethynyl)tin (60 mg, 190 mmol) was added, and the reaction
heated at 1008C for 16 h.The reaction was cooled, and the toluene
removed under reduced pressure.The residue was triturated with acetone
to remove excess tributyl(ethynyl)tin and washed from the filter paper with
THF.The THF was removed under reduced pressure, and the residue was
purified by column chromatography (eluent: petrol/dichloromethane 19:1)
and recrystallised from THF-methanol to afford compound 1b (27.2 mg,
60%).Mp..83 8C (K ! D), 918C (D ! I); 1H NMR (270 MHz, [D6]ben-
zene): d 7.81 ± 7.78 (m, 6H), 4.83 ± 4.76 (m, 8H), 4.61 ± 4.56 (m, 8H), 3.53
(s, 2H), 2.33 ± 2.21 (m, 16H), 1.93 ± 1.11 (m, 88H), 0.96 (t, J 7.4 Hz, 6H),
0.92 ± 0.81 (m, 18H); 13C NMR (67.5 MHz, [D6]benzene): d 154.86,
148.47, 148.40, 142.86, 139.57, 138.37, 138.01, 135.40, 135.31, 131.45, 130.93,
130.89, 130.00, 121.68, 87.63, 80.13, 75.87, 33.23, 32.93, 32.20, 31.16, 31.09,
30.57 ± 29.6, 23.04, 23.01, 19.70, 14.33, 14.26; UV/Vis (2.51 Â 10À6 m in
toluene): lmax (loge) 729 (4.99), 698 (4.88), 666 (4.44), 628 (4.23) nm; MS
698 (5.03), 636 nm (4.39); MS (FAB): m/z: isotopic cluster at 1716 [MH] ;
elemental analysis calcd (%) for C100H150N8O2Br2Ni1 (1715.84): C 70.04, H
8.82, N 6.53; found C 70.40, H 8.90, N 6.30.
Further elution (petrol/dichloromethane 1:1) afforded a second fraction,
and compound 10 (38.2 mg, 3.2%) was isolated after recrystallisation from
THF/methanol.Mp..65 8C (K ! D), 878C (D ! I); 1H NMR (270 MHz,
CDCl3): d 7.78 (s, 4H), 7.72 (s, 2H), 4.59 ± 4.43 (m, 10H), 4.30 (brt, 8H),
2.13 ± 1.89 (m, 18H), 1.75 ± 1.08 (m, 90H), 0.95 (t, 3H), 0.91 (t, 3H), 0.85 ±
0.76 (brt, 21H); 13C NMR (67.5 MHz, CDCl3): d 151.73, 149.58, 147.39,
147.35, 147.26, 147.12, 146.81, 145.57, 143.49, 143.06, 139.05, 137.88, 137.70,
134.59, 134.41, 134.36, 130.66, 130.60, 130.21, 130.21, 129.69, 125.52, 117.00,
75.31 (OCH2), 75.04 (OCH2), 74.54 (OCH2), 32.69, 62.62, 32.38, 32.33,
32.19, 32.11, 32.01, 31.84, 31.75, 31.45, 30.59, 30.44, 30.23, 30.17, 30.03, 29.89,
29.72, 29.64, 29.60, 29.44, 29.33, 29.29, 22.63, 19.52 (OCH2CH2CH2), 19.34
(OCH2CH2CH2), 19.19 (OCH2CH2CH2), 14.10, 14.04; UV/Vis (1.92 Â
10À6 m in toluene): lmax (loge) 714 (5.21), 694 (sh), 636 nm (4.57); MS
(FAB): m/z: isotopic cluster at 1606 [MH] ; elemental analysis calcd (%)
for C104H152N8O2Ni1 ´ CH3OH (1637.14): C 77.03, H 9.60, N, 6.84; found C
76.99, H 9.56, N 6.98.
1,4-Dibutoxy-2,3-di(ethynyl)-8,11,15,18,22,25-hexakis(decyl)phthalocyani-
nato nickel(ii) (1b) from 1a: Potassium hydroxide solution (0.1 mL of a
solution containing 1 flake in 0.5 mL of H2O) was added to a solution of 1a
(9.2 mg, 5.3 mmol) in THF (5 mL) and methanol (1 mL), and the reaction
was stirred under Ar in the dark for 12 h.One drop of 5% HCl was added,
and the solvents were removed under reduced pressure.The residue was
triturated with methanol and further purified by column chromatography
over silica (eluent: petrol/dichloromethane 10:1) to afford 1b as a green
solid (6.7 mg, 79%) identical to the sample obtained above.
(FAB): m/z: isotopic cluster at 1635 [M À OC4H9] ; MS (MALDI): m/z:
1707 [M À H] ; elemental analysis calcd (%) for C104H159N8O3Br1Ni1 ´
1,4-Dibutoxy-2-bromo-8,11,15,18,22,25-hexakis(decyl)phthalocyaninato
nickel(ii) (4): Compound 4 was prepared from a mixed cyclotetramerisation
of 8 and 9 (R decyl) by using the method which afforded 3 above.Yield
4%.Mp..30 8C (K ! D), 1068C (D ! I); 1H NMR (300 MHz, [D6]ben-
CH3OH (1740.09): C 72.48, H 9.44, N 6.44; found C 72.04, H 9.12, N 6.49.
1,4-Dibutoxy-2,3-(2'-trimethylsilylethynyl)-8,11,15,18,22,25-hexakis(de-
cyl)phthalocyaninato nickel(ii) (1a) and compound 11: Bis(triphenylphos-
Chem. Eur. J. 2000, 6, No. 21
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
0947-6539/00/0621-3965 $ 17.50+.50/0
3965