1048 K.-I. YAmAShItA et al.
general procedure of alkylation reactions on 8 (n = 0,
for C140H222O4N4: C, 83.03; H, 11.05; N, 2.77; found: C,
82.95; H, 10.96; N, 2.77.
M = 2H) for 8 (n = 6, 12, and 18, M = 2H). A mixture of
0.2 g of 8(0, 2H) (0.2 mmol), 0.44 g of K2CO3 (3.2 mmol,
8 eq.,), 8 eq. of the corresponding 1-bromoalkane (Kanto
Chemical Co., Inc.), and 30 mL of freshly distilled DMF
(Wako Pure Chemical Industries, Ltd.) was purged with
nitrogen carefully and the mixture was heated at 110 °C
with vigorous string for 2 h. After the reaction, hexane
and water were added to the mixture and the organic
phase was separated. Water phase was further extracted
with another three portions of hexane and the combined
extracts were dried under reduced pressure. The crude
products were chromatographed on silica gel eluted with
hexane, then, hexane: CH2Cl2 = 1:1 to give purple solids.
All analytical samples were obtained by recrystallization
from AcOEt. 8 (6, 2H). Using 225 μl (ca. 0.264 g) of
1-bromohexane (Tokyo Chemical Industry Co., Ltd.),
285 mg of 8(6, 2H) was obtained, 84%. Single crystal
suitable for diffraction study was also obtained from hot
AcOEt. Rf (hexane/AcOEt = 9/1) 0.62; mp 278–281 °C.
1H NMR (500 MHz, chloroform-d, rt, TMS): δ, ppm 8.91
(s, 8H), 7.95 (s, 8H), 4.06 (t, J = 6.7 Hz, 8H), 3.63 (sep-
tet, J = 6.7 Hz, 8H), 2.02 (quintet, J = 6.7 Hz, 8H), 1.67
(quintet, J = 6.7 Hz, 8H), 1.50–1.40 (m, 16H), 1.39 (d,
J = 6.7 Hz, 48H), 1.00 (t, J = 6.7 Hz, 12H), -2.71 (bs,
2H). 13C NMR (100 MHz, chloroform-d, rt, solvent): δ,
ppm 152.9, 139.8, 138.0, 131.0, 120.7, 75.4, 32.0, 30.7,
26.8, 26.0, 24.5, 22.9, 14.3. IR (KBr): ν, cm-1 3315(w),
2961(s), 2931(s), 2867(s), 1559(w), 1458(s), 1367(w),
1326(m), 1295(m), 1209(s), 1196(s), 1172(m), 1124(m),
1069(w), 979(w), 922(m), 892(w), 801(s). UV-vis (tolu-
ene): λmax, nm (ε) 651 (5800), 594 (5700), 554 (12600),
518 (19700), 487 (4500), 423 (538200), 400 nm (sh,
67000 M-1.cm-1). MS (MALDI): m/z (%) 1351 (100) [M]+;
elemental analysis calcd. (%) for C92H126O4N4: C, 81.73;
H, 9.39; N, 4.14; found: C, 81.76 ; H, 9.43; N, 4.13. 8(12,
2H). Using 0.415 g of 1-bromododecane (Kanto), 227 mg
of 8(12, 2H) was obtained. All spectroscopic date were
identical to those obtained by Route-A descried above.
8 (18, 2H): Using 0.536 g of 1-bromooctadecane (Kanto
Chemical Co., Inc.), 358 mg of 8(18, 2H) was obtained,
88%. Rf (hexane/AcOEt = 9/1) 0.66; mp 120–122 °C. 1H
NMR (500 MHz, chloroform-d, rt, TMS): δ, ppm 8.91
(s, 8H), 7.95 (s, 8H), 4.06 (t, J = 6.7 Hz, 8H), 3.63 (sep-
tet, J = 6.7 Hz, 8H), 2.01 (quintet, J = 6.7 Hz, 8H), 1.66
(quintet, J = 6.7 Hz, 8H), 1.50–1.20 (m, 112H), 1.39 (d,
J = 6.7 Hz, 48H), 0.87 (t, J = 6.7 Hz, 12H), -2.71 (bs,
2H). 13C NMR (100 MHz, chloroform-d, rt, solvent): δ,
ppm 152.9, 139.7, 138.0, 130.9, 120.7, 75.4, 32.0, 30.8,
29.9, 29.83, 29.80, 29.5, 26.7, 26.4, 24.5, 22.8, 14.3.
IR (KBr): ν, cm-1 3315(w), 2961(s), 2923(s), 2853(s),
1559(w), 1457(s), 1363(w), 1326(m), 1295(m), 1207(s),
1195(s), 1172(m), 1124(m), 979(w), 922(m), 891(w),
799(s). UV-vis (toluene): λmax, nm (ε) 651 (6700), 594
(5800), 554 (12800), 518 (19800), 487 (4500), 423
(537400), 400 nm (sh, 65200 M-1.cm-1). MS (MALDI):
m/z (%) 2024 (100) [M]+; elemental analysis calcd. (%)
general procedure of metalation reactions. A
mixture of free-base 8(n, 2H), excess amount of metal
acetate, and chloroform (Kanto Chemical Co., Ltd.) were
heated to reflux for 1h. The cooled reaction mixture was
poured on top of the silica gel column and eluted with
chloroform. The solvent was removed under reduced
directly pressure and the residues were recrystallized
from the appropriate solvents. [Zinc complexes] 8(6,
Zn). Using 135 mg of 8(6, 2H) (0.1 mmol), 216 mg of
Zn(OAc)2·2H2O (1 mmol, 10 eq., Kanto Chemical Co.,
Inc.), and 50 mL of chloroform, 139 mg of the complex
was obtained, 98% (from ethanol). Rf (hexane/AcOEt =
9/1) 0.54; mp 291–295 °C. 1H NMR (500 MHz, chloro-
form-d, rt, TMS): δ, ppm 9.02 (s, 8H), 7.95 (s, 8H), 4.07
(t, J = 6.7 Hz, 8H), 3.63 (septet, J = 6.7 Hz, 8H), 2.02
(quintet, J = 6.7 Hz, 8H), 1.68 (quintet, J = 6.7 Hz, 8H),
1.50–1.40 (m, 16H), 1.39 (d, J = 6.7 Hz, 48H), 1.00 (t,
J = 6.7 Hz, 12H). 13C NMR (100 MHz, chloroform-d, rt,
solvent): δ, ppm 152.8, 150.2, 139.6, 138.5, 132.0, 130.8,
121.8, 75.4, 32.0, 30.7, 26.7, 26.0, 24.5, 22.9, 14.3. IR
(KBr): ν, cm-1 2961(s), 2933(s), 2867(m), 1458(s),
1363(w), 1321(s), 1302(m), 1205(s), 1174(s), 1126(w),
1064(w), 1004(s), 940(w), 893(w), 818(w), 799(m). UV-
vis (toluene): λmax, nm (ε) 593 (6600), 551 (23900), 513
(3600), 480 (sh, 1800), 426 (575800), 410 nm (sh, 47600
M-1.cm-1). MS (MALDI): m/z (%) 1413 (100) [M]+; ele-
mental analysis calcd. (%) for C92H124O4N4Zn: C, 78.07;
H, 8.83; N, 3.96; found: C, 77.82; H, 8.87; N, 3.94. 8(12,
Zn). Using 169 mg of 8(12, 2H) (0.1 mmol), 220 mg of
Zn(OAc)2·2H2O (1 mmol, 10 eq.), and CHCl3 (50 mL),
175 mg of the complex was obtained quantitatively (from
acetone). Rf (hexane/AcOEt = 9/1) 0.58; mp 180-183 °C.
1H NMR (500 MHz, chloroform-d, rt, TMS): δ, ppm 9.02
(s, 8H), 7.95 (s, 8H), 4.06 (t, J = 6.7 Hz, 8H), 3.63 (sep-
tet, J = 6.7 Hz, 8H), 2.02 (quintet, J = 6.7 Hz, 8H), 1.67
(quintet, J = 6.7 Hz, 8H), 1.50–1.40 (m, 64H), 1.39 (d,
J = 6.7 Hz, 48H), 0.90 (t, J = 6.7 Hz, 12H). 13C NMR (100
MHz, chloroform-d, rt, solvent): δ, ppm 152.7, 150.2,
139.6, 138.5, 132.0, 130.8, 121.8, 75.3, 32.1, 30.7, 29.82,
29.80, 29.5, 26.7, 26.3, 24.5, 22.8, 14.3. IR (KBr): ν, cm-1
2961(s), 2925(s), 2853(m), 1459(s), 1363(w), 1321(s),
1302(m), 1205(s), 1174(s), 1127(w), 1067(w), 1004(s),
940(w), 894(w), 818(w), 799(m). UV-vis (toluene): λmax
,
nm (ε) 591 (7000), 551 (24400), 514 (3600), 480 (sh,
1600), 426 (584300), 410 nm (sh, 51600 M-1.cm-1). MS
(MALDI): m/z (%) 1750 (100) [M]+; elemental analysis
calcd. (%) for C116H172O4N4Zn: C, 79.52; H, 9.90; N,
3.20; found: C, 79.27; H, 10.10; N, 2.97. 8(18, Zn). Using
202 mg of 8(18, 2H) (0.1 mmol), 220 mg of Zn(OAc)2·2H2O
(1 mmol, 10 eq.), and 50 mL of CHCl3 (50 mL), 208 mg of
the complex was obtained quantitatively (from acetone).
Rf (hexane/AcOEt = 9/1) 0.66; mp 131–147 °C. 1H NMR
(500 MHz, chloroform-d, rt, TMS): δ, ppm 9.02 (s, 8H),
7.95 (s, 8H), 4.06 (t, J = 6.7 Hz, 8H), 3.63 (septet, J =
6.7 Hz, 8H), 2.02 (quintet, J = 6.7 Hz, 8H), 1.67 (quintet,
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 1048–1051