A mixture of the latter compound (2.98 g, 9.6 mmol) with
15 ml of trifluoroacetic acid was stirred at room temperature
and then 1.54 g (11 mmol) hexamethylenetetraamine (HMTA)
was added. The resulting mixture was stirred overnight at
90 °C. After evaporation of trifluoroacetic acid the residue was
dissolved in water and stirred for 1 h. A solution of Na CO
Synthesis of the phthalocyanines 4a,b
1,2-Bis(1,8,11,14,17-pentaoxaoctadecyl)-4,5-
dibromobenzene.
A
mixture of 1,2-dibromocatechol (5 g,
18 mmol), 1-bromo-7,10,13,16-tetraoxaheptadecane, (13.1 g,
40 mmol) and K CO (16 g, 116 mmol) in 200 ml of DMF
2
3
2
3
was stirred and heated to 100 °C for 24 h and then poured
was added until pH=8. The solution was extracted with
into water and extracted with CHCl (3×150 ml). The organic
dichloromethane. The organic fractions were washed with
3
layers were washed with water (3×100 ml), dried with MgSO
4
NaCl solution, dried over MgSO and the solvent was evapor-
4
and the solvent was evaporated to give a brownish oil. The
ated under reduced pressure. The crude product was puri-
crude product was purified on silica gel (0.04–0.063 mm; eluent
ethyl acetate) yielding the title compound as a yellow oil (8.2 g,
60%). d (200 MHz, CDCl ), 1.40 (m, 8H), 1.55 (q, 4H), 1.75
fied on silica gel (eluent ethyl acetate–dichloromethane 151)
yielding 1.53 g (47%) of 4-(6,9,12,15-tetraoxahexadecyl)-
benzaldehyde.
H
3
(q, 4H), 3.34 (s, 6H), 3.4 (t, 4H), 3.6 (m, 24H), 3.89 (t, 4H),
The title compound was then synthesized by refluxing a
mixture of 1 equiv. of benzaldehyde together with 1 equiv.
pyrrole in propionic acid for 0.5 h. After evaporation of the
propionic acid, the crude mixture was purified on silica gel
(eluent dichloromethane with gradual addition of methanol)
and finally on Al O (act.II), eluent dichloromethane with
7.02 (s, 2H). n/cm−1 (CHCl ) 650 Ar–Br.
3
1,2-Bis(1,8,11,14,17-pentaoxaoctadecyl)-4,5-dicyanobenzene.
A mixture of the preceding compound (3.9 g, 5 mmol) and
CuICN (1.25 g, 15 mmol) in 50 ml of DMF was refluxed for
24 h under a nitrogen atmosphere. The cooled mixture was
poured in 150 ml of aqueous ammonia (25%) and air was
bubbled through the solution for 24 h. The desired dinitrile
was extracted with dichloromethane–methanol (4/1). The green
2
3
gradual addition of methanol, yielding of the desired TPP 2
in a yield of 10%. Elemental analysis, Found: C, 71.43; H, 8.42;
N, 3.55%. C H N O requires C, 71.56; H, 8.23; N, 3.63%.
92 126
4
16
d
(200 MHz, CDCl ): −2.76 (s, 2H), 1.5–2.0 (m, 24H), 2.96
H
3
organic phase was washed with water and dried over MgSO .
(t, 8H), 3.37 (s, 12H), 3.5–3.7 (m, 68H), 7.55 (d, 8H), 8.11 (d,
4
Chromatography (silica gel, eluent ethyl acetate–methanol,
8H), 8.86 (s, 8H). UV–VIS, l /nm (log e/dm3 mol−1 cm−1),
max
gradient 1–3%) afforded 1.8 g (55%) of the title compound.
CHCl : 421(5.68), 522 (4.25), 554 (4.01), 593 (3.75), 649 (3.76).
3
d
(200 MHz, CDCl ), 1.50 (m, 8H), 1.58 (q, 4H), 1.90 (q, 4H),
H
3
3.38 (s, 6H), 3.50 (t, 4H), 3.6 (m, 24 H), 4.05 (t, 4H), 7.11 (s,
2H). n/cm−1 (CHCl ): 2210 (CN).
Tetrakis(1,4,7,11-tetraoxahexadecyl)phenylporphyrin
(3).
3
A residual green fraction was isolated by elution with ethyl
Sodium (14 g, 0.61 mol) was dissolved in 364 g of triethylene
glycol (2.43 mol) at 100 °C and cooled to room temp. 100 g
(0.61 mol) of 1-bromohexane was added and the mixture was
stirred for 5 h at 200 °C. The mixture was poured into water
(500 ml) and light petroleum bp 100–120°C (400 ml) and
heated to 70 °C. After separation of the water layer, the
organic fraction was washed with hot water (3×100 ml)
and the solvent was evaporated. Vacuum distillation yielded
62.4 g (44%) triethylene glycol monohexyl ether (bp
125–130 °C/0.1 mmHg).
acetate–methanol (1/1) and identified as the copper–phthalocy-
anine 4b (70 mg). Elemental analysis, Found: C, 61.03; H, 8.52;
N, 4.06%. C
H
N O Cu requires C, 61.07; H, 8.44; N,
136 224 8 40
4.19%. UV–VIS, l /nm (log e/dm3 mol−1 cm−1), CHCl :
max
3
613(4.55), 680 (5.30).
2,3,9,10,16,17,23,24-Octa(1,8,11,14,17-pentaoxaoctadecyl)
phthalocyanine (4a). The dinitrile (1.6 g, 2.5 mmol) and DBN
(0.37 g, 2.5 mmol) were dissolved in 8 ml of absolute ethanol
and refluxed for 48 h. The reaction mixture turned dark green.
After evaparation of ethanol, the crude oil was chromato-
graphed on silica gel (eluent ethyl acetate–methanol 2–10%),
alumina (act.II/III, eluent 2% MeOH in CH Cl ). The last
A mixture of 58.5 g (0.25 mol) triethylene glycol monohexyl
ether and 19.75 g of pyridine (0.25 mol) was stirred and cooled
in ice. 44.6 g (0.38 mol) Thionyl chloride was slowly added
and the solution was refluxed for 1.5 h. After cooling to room
temp., the mixture was poured into ice–water. A 10% (m/m)
NaCl solution was then added and the resulting mixture was
extracted with diethyl ether. The organic layers were washed
with 10% (m/m) NaCl solution, dried and evaporated to
dryness. Vacuum distillation yielded 52.7 g (84%) of 1-chloro-
(3,6,9-trioxa)pentadecane (bp 125–130 °C/0.1 mmHg).
2
2
impurities were removed by soxhlet extraction with light
petroleum (60–80) yielding the green sticky phthalocyanine 4a
(200 mg, 10%). Elemental analysis, Found: C, 62.67; H, 8.85;
N, 3.93%. C
H
N O requires C, 62.50; H, 8.72; N, 4.29%.
136 226
8 40
d (200 MHz, CDCl ): 1.5–1.8 (m, 8H), (q, 16H), 3.34 (s, 24H),
H
3
3.5–3.7 (m, 108H), 4.63 (t, 16H), 8.95 (s, 8H). UV–VIS: l /nm
max
(log e/dm3 mol−1 cm−1) CHCl : 602 (4.41), 646 (sh, 4.67), 665
1-Chloro-(3,6,9-trioxa)pentadecane (38.3 g, 0.15 mol), 4-
hydroxybenzaldehyde (12.2 g, 0.1 mol), K CO (27.6 g,
3
(5.11), 702 (5.21).
2
3
0.2 mol) and 5.0 g of potassium iodide were stirred in 200 ml
butanone and refluxed for 3 d. The precipitate was filtered off
and washed with dichloromethane. The filtrate was concen-
This work is supported financially by the Dutch Agency for
Energy and Environment (Novem). We are indebted to A. van
Veldhuizen for performing the NMR measurements.
trated and a solution of 30 g NaHSO in 63 ml of water and
3
38 ml of ethanol was added and the resulting mixture stirred
for 2 h. Extraction was then carried out with diethyl ether and
References
the organic fractions were washed with water, dried over
1
(a) B. A. Gregg, M. A. Fox and A. J. Bard, J. Am. Chem. Soc., 1989,
111, 3024; (b) B. A. Gregg, M. A. Fox and A. J. Bard, J. Phys.
Chem., 1989, 93, 4227.
MgSO and evaporated under reduced pressure.
4
Yield 7.6 g (23%) of 4-(1,4,7,10-tetraoxahexadecyl)-
benzaldehyde.
2
3
Y. Shimizu, M. Miya, A. Nagata, K. Ohta, I. Yamamoto and
S. Kusabayashi, L iq. Cryst., 1993, 14, 795.
The title compound 3 was then synthesized in ca. 10% yield
using the same procedure as described above. Elemental analy-
(a) M. J. Cook, J. Mater. Sci.: Mater. Electron., 1994, 5, 117; (b)
M. J. Cook, Adv. Mater., 1995, 7, 877; (c) G. C. Bryant, M. J. Cook,
T. G. Ryan and A. J. Thorne, Tetrahedron, 1996, 52, 809.
C. F. van Nostrum, S. J. Picken, A. J. Schouten and R. J. M. Nolte,
J. Am. Chem. Soc., 1995, 117, 9957.
sis, Found: C, 71.66; H, 8.53; N, 3.51%. C
H
N O requires
92 126
4 16
C, 71.56; H, 8.23; N, 3.63%. d (200 MHz, CDCl ), −2.70 (s,
H
3
4
5
2H), 0.9 (t, 12H), 1.3 (m, 24H), 1.62 (q, 8H), 3.50 (t, 8H),
3.7–3.9 (m, 32H), 4.0 (t, 8H), 4.36 (t, 8H), 7.25 (d, 8H), 8.10
(a) C. Piechowski, J. Simon, A. Skoulios, D. Guillon and P. Weber,
J. Am. Chem. Soc., 1982, 104, 5245; (b) C. Piechowski and J. Simon,
Nouv. J. Chim., 1985, 3, 159; (c) P. Weber, D. Guillon and
A. Skoulios, L iq. Cryst., 1991, 9, 369.
(d, 8H), 8.89 (s, 8H). UV–VIS,
l
/nm (log e/dm3
max
mol−1 cm−1), CHCl : 422(5.66), 519 (4.19), 556 (4.01), 593
3
(3.67), 650 (3.74).
J. Mater. Chem., 1997, 7(4), 615–624
623