Leznoff and Suchozak
885
(CDCl3) δ: 160.02, 133.62, 115.17, 114.60, 105.63, 92.39,
78.08, 32.08, 26.80, 0.32. Anal. calcd. for C16H24OSi: C
73.79, H 9.29; found: C 73.40, H 9.23.
[2,3,9,10,16,17,23,24-Octa(p-
neopentoxyphenylethynyl)phthalocyaninyl]dilithium (19)
To a suspension of 10 mg (0.72 mmol) of lithium metal in
2 mL of dry THF was added 2 mg (1.0 × 10–3 mmol) of Pc
18. The mixture was stirred at 50°C for 5 days, after which
time the excess lithium was removed by filtration and the
solvent was removed in vacuo at 40°C to give 19 (2 mg,
100% yield). FAB-MS: 2010 (M – Li), 2004 (M – 2Li).
UV–vis (THF) λmax (nm) (log ⑀): 720 (6.89), 686 (6.04), 648
p-Neopentoxyphenylacetylene (16)
The same procedure was used as for the synthesis of 8,
using 10 g (38 mmol) of 15, 23 mL (115 mmol) of 5 M
NaOH, and 600 mL of MeOH to afford 16. The crude prod-
uct was chromatographed using silica gel and hexane as
eluent giving the title compound as a clear, colourless oil
(6.5 g, 95% yield). EI-MS m/z (%): 188 (M+, 10), 118 (100).
UV–vis (THF) λmax (nm): 213, 252, 293, 318, 343. IR (neat)
(cm–1): 2107 (CϵC). 1H NMR (CDCl3) δ: 7.42 (d, J =
8.7 Hz, 2H), 6.84 (d, J = 8.6 Hz, 2H), 3.60 (s, 2H), 2.99 (s,
1H), 1.04 (s, 9H). 13C NMR (CDCl3) δ: 160.21, 133.73,
114.71, 114.03, 84.05, 78.11, 75.81, 32.08, 26.78. Anal.
calcd. for C13H16O: C 82.94, H 8.57; found: C 82.20, H
8.39.
1
(6.07), 398 (6.52), 316 (6.40), 282 (6.35), 212 (6.40). H
NMR (pyridine-d5, 4.0 × 10–4 M, 333 K) δ: 8.86 (br, 8H),
7.75 (br, 16H), 6.79 (d, J = 7.4 Hz), 3.53 (s, 16H), 1.12 (s,
72H).
1-Iodo-2-(p-neopentoxyphenyl)acetylene (20)
To 11.5 mL (35 mmol) of ethylmagnesium bromide
(3.0 M solution in ether) was slowly added a solution of
5.0 g (27 mmol) of p-neopentoxyphenylacetylene (16) in
15 mL of anhydrous ether. The reaction mixture was then
heated to reflux as 6.7 g (23 mmol) of powdered iodine was
slowly added through the top of the condenser. The solution
was refluxed for another hour, allowed to cool to room tem-
perature and then poured into 150 mL of H2O. The mixture
was acidified with glacial acetic acid, the ether layer was
separated, and the aqueous layer was extracted twice with
50 mL portions of ether. The combined organic extracts
were washed with sat. Na2S2O3, sat. NaHCO3, H2O, and
brine, then dried over MgSO4, filtered and evaporated under
reduced pressure. The title compound (20) was obtained as a
white solid after recrystallization from MeOH–H2O (2.2 g,
26% yield), mp 54 to 55°C. EI-MS m/z (%): 314 (M+, 35),
244 (100), 118 (65). UV–vis (THF) λmax (nm): 214, 262. IR
4,5-Di(p-neopentoxyphenylethynyl)phthalonitrile (17)
The same procedure was used as for the synthesis of 3,
using 760 mg (2.0 mmol) of 1, 791 mg (4.2 mmol) of 16,
147 mg (0.32 mmol) of Pd(PPh3)2Cl2, 40 mg (0.16 mmol) of
CuI, and 25 mL of TEA to give 700 mg of 17 in 70% yield,
mp 168–170°C. EI-MS m/z (%): 501 (M+, 18), 500 (55), 360
(100). UV–vis (THF) λmax (nm): 214, 252, 284, 325, 366. IR
1
(KBr) (cm–1): 2209 (CϵN). H NMR (CDCl3) δ: 7.87 (s,
2H), 7.51 (d, J = 8.6 Hz, 4H), 6.92 (d, J = 8.7 Hz, 4H), 3.64
(s, 4H), 1.06 (s, 18H). 13C NMR (acetone-d6) δ: 162.37,
137.24, 134.80, 131.70, 116.33, 116.03, 114.91, 114.66,
101.51, 86.12, 79.12, 32.69, 27.02. Anal. calcd. for
C34H32N2O2: C 81.57, H 6.44, N 5.60; found: C 81.00, H
6.45, N 5.44.
1
(KBr) (cm–1): 2166 (CϵC). H NMR (CDCl3) δ: 7.36 (d, J =
8.7 Hz, 2H), 6.83 (d, J = 8.7 Hz, 2H), 3.59 (s, 2H), 1.03 (s,
9H). 13C NMR (CDCl3) δ: 160.26, 133.94, 115.45, 114.62,
94.38, 78.13, 32.08, 26.79, 3.56. Anal. calcd. for C13H15IO:
C 49.70, H 4.81; found: C 50.06, H 4.78.
2,3,9,10,16,17,23,24-Octa(p-
neopentoxyphenylethynyl)phthalocyanine (18)
The
by-product,
1,4-di-(p-neopentoxyphenyl)-1,3-
butadiyne (21), was obtained in 59% yield (2.9 g) as a white
solid, mp 189–191°C. UV–vis (THF) λmax (nm): 214, 269,
282, 300, 320, 343. IR (KBr) (cm–1): 2388, 2139, 1601,
To 2.5 mL of dimethylaminoethanol (DMAE) was added
30 mg (4.3 mmol) of lithium metal. After the metal had
completely dissolved, 200 mg (0.4 mmol) of 17 was added
to the well-stirred alkoxide solution, and the reaction mix-
ture was heated to 100°C for 15 h. After this time, the reac-
tion mixture was cooled to room temperature and diluted
with 10 mL of 20% MeOH–H2O. After being allowed to
stand for 90 min, the reaction mixture was centrifuged and
the crude Pc was collected, dissolved in THF and precipi-
tated from hexane. This crude pigment was
chromatographed using silica gel and CH2Cl2 as eluent, fol-
lowed by gel permeation chromatography using SX-2
Biobeads® and THF as eluent. This material was further pu-
rified by reprecipitation from benzene–ethanol and then by
chromatography using silica gel and CH2Cl2 as eluent to
give 18 as a dark green solid (64 mg, 8% yield). FAB-MS:
2004. MALDI-MS m/z: 2003.9 (M+). UV–vis (THF) λmax
(nm) (log ⑀): 716 (6.08), 678 (6.19), 390 (6.18), 330 (6.41),
1
1503, 1291, 1247, 1166, 1016, 831. H NMR (CDCl3) δ:
7.44 (d, J = 8.7 Hz, 2H), 6.85 (d, J = 8.7 Hz, 2H), 3.60 (s,
2H), 1.04 (s, 9H). 13C NMR (CDCl3) δ: 160.50, 134.19,
114.89, 113.85, 81.59, 78.16, 73.10, 32.09, 26.78. EI-MS
m/z (%): 374 (M+, 50), 234 (100). Anal. calcd. for
C26H30O2: C 83.38, H 8.07; found: C 82.90, H 8.40.
1-(Trimethylsilyl)-4-(p-neopentoxyphenyl)-1,3-butadiyne
(22)
To a solution containing 200 mg (0.64 mmol) of 20 dis-
solved in 5 mL of THF were added 22 mg (0.032 mmol) of
Pd(PPh3)3Cl2, 3.0 mg (0.016 mmol) of CuI, 0.16 mL
(116 mg, 1.15 mmol) of diisopropylamine (DIPA), and then
0.36 mL (250 mg, 2.55 mmol) of trimethylsilylacetylene (6).
The reaction mixture was allowed to stir overnight at room
temperature, after which time the solvent was evaporated in
vacuo, the residue was suspended in hexane and then filtered
through a bed of celite. The filtrate was concentrated under
reduced pressure, chromatographed using silica gel and hex-
ane as eluent, and then recrystallized from EtOH–H2O to
1
258 (6.14), 216 (6.23). H NMR (toluene-d8, 1.0 × 10–3 M,
363 K) δ: 8.71 (br, 8H), 7.71 (d, J = 7.8 Hz), 6.81 (d, J =
8.1 Hz), 3.58 (s, 16H), 1.14 (s, 72H), –4.81 (br, 2H). Anal.
calcd. for C136H130N8O8: C 81.49, H 6.54, N 5.59; found: C
80.06, H 5.80, N 5.27.
© 2001 NRC Canada