m.p. 55 °C. Yield 47%. 1H NMR (CCl , TMS) d 0.88 (m,
NMR (CCl , TMS) d 0.88 (m, 12H, CH ), 1.27 (m, 48H,
4
4
3
12H, CH ), 1.27 (m, 80H, CH ), 3.42, 3.83 (t+t, 8H, OCH ),
CH ), 3.17–4.00 (m, 8H, OCH ), 6.27–7.80 (m, 9H, Ph), 9.83
3
2
2
max
2
2
3.83 (s, 3H, COOCH ), 6.40–7.97 (m, 9H, Ph). IR (neat) n
(s, 1H, CHO). IR (neat) n
1695 cm−1 (CO).
3
max
1720 cm−1 (CO).
17c: Purified by column chromatography (silica gel, benzene;
15b: Purified by column chromatography (silica gel, benzene;
R =0.55). Yellowish white solid. m.p. 58 °C. Yield 93%. 1H
f
R =0.60). Yellowish brown syrup. Yield 44%. 1H NMR
NMR (CCl , TMS) d 0.88 (m, 12H, CH ), 1.25 (m, 112H,
f
4
3
(CCl , TMS) d 0.87 (m, 12H, CH ), 1.30 (m, 48H, CH ),
CH ), 3.40–4.07 (m, 8H, OCH ), 6.37–7.80 (m, 9H, Ph), 9.87
(s, 1H, CHO). IR (KBr) n
4
3
2
2
2
3.27–4.00 (t+t, 8H, OCH ), 3.83 (s, 3H, COOCH ), 6.33–8.00
(m, 9H, Ph). IR (neat) n
1695 cm−1 (CO).
2
3
max
1725 cm−1 (CO).
17d: Purified by column chromatography (silica gel, benzene;
R =0.60). Yellow syrup. Yield 95%. 1H NMR (CCl , TMS)
max
15c: Purified by column chromatography (silica gel,
f
4
benzene–carbon tetrachloride 251; R =0.56). Light brown
d 0.90 (m, 6H, CH ), 1.30 (m, 40H, CH ), 3.83 (t, J=6.0 Hz,
f
solid. m.p. 50 °C. Yield 49%. 1H NMR (CCl , TMS) d 0.87
4
3
2
4H, OCH ), 6.40–7.77 (m, 11H, Ph), 9.87 (s, 1H, CHO). IR
(neat) n
2
max
(m, 12H, CH ), 1.30 (m, 112H, CH ), 3.40–4.00 (m, 8H,
1700 cm−1 (CO).
3
2
OCH ), 3.83 (s, 3H, COOCH ), 6.33–7.90 (m, 9H, Ph). IR
2
3
(KBr) n
1720 cm−1 (CO).
5,10,15,20-Tetrakis(3,4,3◊,4◊-tetradodecyloxy-o-terphenyl)-
porphyrin [1; (C O) -TTPH ]. A mixture of aldehyde 17a
max
15d: Purified by column chromatography (silica gel,
12 16
2
benzene–carbon tetrachloride 151; R =0.45). Yellowish brown
(1.48 g, 1.49 mmol) and pyrrole (0.23 g, 3.43 mmol) in propi-
onic acid (10 ml, 0.13 mol) was refluxed for 30 min. After the
reaction mixture was cooled to room temperature, sodium
hydroxide (5.20 g, 0.13 mol) was added. The mixture was
extracted with diethyl ether, and the organic layer was washed
with water. After being dried and concentrated, the residue
was purified by column chromatography (alumina, benzene;
f
syrup. Raw yield 71% (this product contained some impurit-
ies.). 1H NMR (CCl , TMS) d 0.90 (m, 6H, CH ), 1.27 (m,
4
3
40H, CH ), 3.80 (m, 7H, OCH , COOCH ), 6.47–7.87 (m,
2
2
3
11H, Ph). IR (neat) n
1725 cm−1 (CO).
max
3,4,3◊,4◊-Tetradodecyloxy-4∞-hydroxymethyl-o-terphenyl
(16a). Under a nitrogen atmosphere, a solution of carboxylate
15a (2.11 g, 2.06 mmol) in 20 ml of dry diethyl ether was
added dropwise to a suspension of lithium aluminium hydride
R =1.00) to yield 0.38 g of the crude (chlorin-contained)
f
porphyrin derivative. The crude product was dissolved in the
minimum amount of chloroform and a small amount of
benzene. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ;
0.14 g, 0.62 mmol) was added, and the mixture was refluxed
for 3 h. The mixture was concentrated and the residue was
(LiAlH ; 0.31 g, 8.17 mmol) in 15 ml of dry diethyl ether. The
4
mixture was gently refluxed for 1 h. After the reaction mixture
was cooled by ice water, water was added slowly till no LiAlH
remained. Then, a small amount of 20% sulfuric acid was
4
purified by column chromatography (silica gel, benzene; R =
f
added to dissolve the precipitate, and extracted with diethyl
ether. The organic layer was washed with water, dried over
sodium sulfate, and concentrated. The residue was purified by
1.00, and alumina, hexane; R =0.00, chloroform; R =1.00)
f
f
to give 0.22 g of 1 as a red-purple liquid crystal. Yield 14%.
1H NMR (CDCl , TMS) d −2.63 (s. 2H, NH), 0.80 (m, 48H,
3
column chromatography (silica gel, chloroform; R =0.44) to
CH ), 1.26 (m, 320H, CH ), 3.44–4.10 (m, 32H, OCH ),
f
3
2
2
give 1.58 g of 16a as a faintly-brown syrup. Yield 93%. 1H
6.52–8.24 (m, 36H, Ph), 8.90 (s, 8H, porphyrin). IR (neat)
3320 (NH), 2930, 2860 (CH ), 1600, 1580 (Ph),
1260 cm−1 (ROPh).
NMR(CCl , TMS) d 0.90 (m, 12H, CH ), 1.30 (m, 80H,
n
4
3
max
2
CH ), 1.70 (s, 1H, OH), 3.43–4.00 (m, 8H, OCH ), 4.60 (s,
2
2
2H, PhCH O), 6.40–7.23 (m, 9H, Ph). IR (neat)
n
2
max
3330 cm−1 (OH).
5,10,15,20-Tetrakis(3,4,3◊,4◊-tetraoctyloxy-o-terphenyl)-
16b: Purified by column chromatography (silica gel,
porphyrin [2; (C O) -TTPH ]. The title compound was synthe-
8
16
2
chloroform; R =0.21). Pale brown syrup. Yield 90%. 1H
sized from aldehyde 17b according to the method described
above, and purified by column chromatography (alumina,
benzene and chloroform; R =1.00, and silica gel, hexane; R =
f
NMR (CCl , TMS) d 0.87 (m, 12H, CH ), 1.30 (m, 48H,
4
3
CH ), 2.26 (s, 1H, OH), 3.30–4.00 (t+t, 8H, OCH ), 4.58 (s,
2H, PhCH O), 6.33–7.26 (m, 9H, Ph). IR (neat) n
2
2
f
f
0.00 and benzene; R =1.00). Red-purple solid. Yield 17%. 1H
2
max
f
3200 cm−1 (OH).
NMR(CDCl , TMS) d −2.63 (s. 2H, NH), 0.57–1.00 (m,
48H, CH ), 1.00–2.33 (m, 192H, CH ), 3.44–4.17 (m, 32H,
OCH ), 6.47–8.27 (m, 36H, Ph), 8.90 (s, 8H, porphyrin). IR
3
16c: Purified by column chromatography (silica gel,
3
2
chloroform; R =0.38). White solid. m.p. 52 °C. Yield 67%. 1H
f
2
NMR (CCl , TMS) d 0.88 (m, 12H, CH ), 1.27 (m, 112H,
(neat) n
3320 (NH), 2930, 2860 (CH ), 1605, 1580, 1510
4
3
max
2
CH ), 1.63 (s, 1H, OH), 3.33–4.00 (m, 8H, OCH ), 4.55 (s,
2H, PhCH O), 6.27–7.20 (m, 9H, Ph). IR (KBr) n
(Ph), 1250 cm−1 (ROPh).
2
2
2
max
3300 cm−1 (OH).
5,10,15,20-Tetrakis(4,4◊-didodecyloxy-o-terphenyl)-
porphyrin [3; (C O) -TTPH ]. The title compound was synthe-
16d: Purified by column chromatography (silica gel,
12
8
2
chloroform; R =0.40). Pale orange solid. m.p. 47.5 °C. Yield
sized from aldehyde 17d according to the method described
above, and purified by column chromatography (silica gel,
chloroform; R =1.00, alumina, carbon tetrachloride; R =0.00,
f
42%. 1H NMR (CCl , TMS) d 0.90 (m, 6H, CH ), 1.27 (m,
4
3
40H, CH ), 1.93 (s, 1H, OH), 3.80 (t, J=6.0 Hz, 4H, OCH ),
4.53 (s, 2H, PhCH O), 6.47–7.13 (m, 11H, Ph). IR (neat) n
3330 cm−1 (OH).
2
2
max
f
f
and benzene; R =1.00) and recrystallization (hexane, ethyl
2
f
acetate). Purple solid. Yield 15%. 1H NMR (CCl , TMS) d
4
−2.53 (s, 2H, NH), 0.90 (m, 24H, CH ), 1.67 (m, 160H,
3
3,4,3◊,4◊-Tetradodecyloxy-o-terphenyl-4∞-carbaldehyde (17a).
A mixture of hydroxymethyl 16a (1.54 g, 1.54 mmol) and
pyridinium dichromate (PDC; 0.87 g, 2.31 mmol) in 3 ml of
dichloromethane was stirred for 10 h. The reaction mixture
was concentrated and the residue was purified by column
CH ), 3.77 (m, 12H, OCH ), 6.40–8.30 (m, 44H, Ph), 8.90 (s,
2
2
max
8H, porphyrin). IR (film) n
1610, 1510 (Ph), 1250 cm−1 (ROPh).
3320 (NH), 2930, 2860 (CH ),
2
5,10,15,20-Tetrakis(3,4,3◊,4◊-tetradodecyloxy-o-terphenyl)-
chromatography (silica gel, benzene; R =0.70) to give 1.46 g
of 17a as a yellowish white solid. m.p. 64–65 °C. Yield 95%.
porphyrinatocopper(II) [1-Cu; (C O) -TTPCu]. Porphyrin 1
f
12 16
(0.12 g, 2.88×10−2 mmol) and anhydrous cupric chloride
1H NMR (CCl , TMS) d 0.88 (m, 12H, CH ), 1.30 (m, 80H,
(0.04 g, 0.30 mmol) were dissolved in 30 ml of dry N,N-
dimethylformamide (DMF) and refluxed for 5 h. The reaction
mixture was cooled and separated by filtration. The remaining
precipitate was washed by methanol, and purified by column
4
3
CH ), 3.40–4.13 (m, 8H, OCH ), 6.40–7.85 (m, 9H, Ph), 9.92
2
2
(s, 1H, CHO). IR (neat) n
17b: Purified by column chromatography (silica gel,
1700 cm−1 (CO).
max
chloroform; R =0.65). Brownish yellow syrup. Yield 98%. 1H
chromatography (alumina, benzene; R =1.00) to give 0.11 g
f
f
2648
J. Mater. Chem., 1998, 8, 2637–2650