M.-J. Lin, J.-D. Wang / Journal of Molecular Structure 837 (2007) 284–289
285
5
00 MHzandUV–visspectrawererecordedonPE-Lambda9
(s, Ph-H, 4H), 8.047 (s, Ph-H, 4H), 7.716 (s, Ph-H, 4H),
UV–vis spectrophotometer using 1 cm path length cuvettes
at room temperature.
4.762 (m, ACHA, 8H), 2.589 (m, ACH , 60H), ꢀ0.046
3
(br, NAH, 8H); UV–vis (nm, CHCl ): 223.34, 319.14,
3
635.56, 667.38, 702.02, 731.95.
2
3
.3. The synthesis of 5-(2,2,4-trimethyl-3-pentoxy)-1,
-diiminoisoindole [6]
2.7. Octakisbutyloxyphthalocyanine (3)
In a dried 100-mL round-bottom flask equipped with a
Yield 16.1%; Anal. Calcd (%) for C H N O : C, 70.43;
6
4
82
8
8
magnetic stirrer, a reflux condenser, and an ammonia gas
inlet, a solution of 3-(2,2,4-trimethyl-3-pentoxy)phthalonit-
rile (3 g, 11.7 mmol) and sodium (0.2 g, 8.7 mmol) in 30 mL
dry methanol was placed. Ammonia was blowed through,
and the solution was stirred at room temperature for 1 h.
The solution was then heated to reflux for 5 h with contin-
ued addition of ammonia. After cooling to room tempera-
ture, the solvent was distilled. The residue was dissolved
with toluene, washed three times with water to remove
any remaining NaCl, and dried. The product was recrystal-
lized several times with the mixing solvent of acetic ether/n-
hexane. Yield 2.0 g, 63.0%; mp 186.0–187.8 ꢁC; IR(KBr):
H, 7.574; N, 10.27; found C, 70.81; H, 7.21; N, 10.26;
ꢀ
1
ꢀ1
ꢀ1
IR(KBr): 1597.46, 1498.67 cm
(mC@N), 3298.29 cm
(mArAOAC), 1464.17 cm
ꢀ
1
(mNAH), 1267.93, 1037.76 cm
ꢀ
1
1
(mC@C), 2954.64 cm
ðmCH3 Þ; H NMR (ppm, CDCl3):
d = 7.587 (s, Ph-H, 8H), 4.845 (m, ACH A, 16H), 2.223–
2
2.260(m, ACH A, 16H), 1.61–1.681 (m, ACH A, 16H),
2
2
1.070–1.098 (m, ACH , 24H), ꢀ0.80 (br, NAH, 8H);
3
UV–vis (nm, CHCl ): 330.1, 751.26, 774.68
3
2.8. The synthesis of dikis(2,2,4-trimethyl-
3-pentoxy)phthalocyanine (4) [6]
ꢀ1
ꢀ1
1
1
1
651, 1614.7 cm
(mC@N), 3303.3, 3321.3 cm
(mNAH),
(mArAH),
A solution of 5-(2,2,4-trimethyl-3-pentoxy)-1,3-diimi-
ꢀ1
ꢀ1
ꢀ1
272.7, 1095.5 cm
(mArAOAC), 3488.6 cm
noisoindole
(0.6214 g,
2.27 mmol),
triethylamine
ꢀ
1
614.7, 1651 cm (mC@C), 2966.1, 2873.0 cm ðmCH3 Þ.
(0.64 mL) in dry THF (60 mL) was cooled to 0 ꢁC, then
another solution of 1,3,3-trichloroisoindolenine (0.5 g,
2.27 mmol) in dry THF (50 mL) was gradually added
under a slow stream of nitrogen. The reaction was carried
out with stirring for 1 h at approximately 0 ꢁC then slowly
warmed to room temperature over a 5-h period. After the
insoluble triethylamine hydrochloride was removed, hydro-
quinone (0.25 g, 2.27 mmol) and sodium methoxide (0.2 g
Na in 5 mL menthol) was added to the reaction vessel.
Then a reflux condenser was equipped and the reaction
solution was refluxed under nitrogen for 6 h. After being
cooled to room temperature, the dark blue-black residue
was filtered out. The residue was washed by boiling water
and extracted in SOXHLET extractor with menthol and
acetone until the extraction was clear. Then, it was
further purified by recrystallization several times with chlo-
roform. Yield 0.1949 g, 22.3%; IR(KBr):1583.1,
2.4. General process of the synthesis of the symmetry metal-
free phthalocyanines
A solution of substituted phthalonitriles (4 mmol) in
1
-pentanol (6 mL) was heated to 120 ꢁC, and then lithium
(
28 mg, 4 mmol) was added to this solution and the reac-
tion was continued at the same temperature for 4 h. After
the reaction mixture was cooled to room temperature,
methanol (100 mL) and HCl (3 mL) were added to precip-
itate the rude product which was then purified on a silicon
column with dichloromethane/acetic ether as eluent and
recrystallized several times with the mixing solvent of
dichloromethane/ethanol.
2
.5. Tetrakis(i-propoxy)phthalocyanine (1)
ꢀ
ꢀ
ꢀ
1
1
1
ꢀ1
1
490.9 cm
(mC@N), 3274.9 cm
(mNAH), 1266.5,
(mC@C), 2955.6,
ꢀ1
Yield 8.4%; Anal. Calcd (%) for C H N O : C, 70.76;
1108.3 cm
(m
), 1583.1 cm
ArAOAC
6
4
82
8
4
1
H, 5.67; N, 15.00; found C, 71.15; H, 5.68; N, 13.78;
2866.4 cm ðm Þ; H-NMR (ppm, CDCl ): d = 9.213;
CH3
3
ꢀ
1
ꢀ1
ꢀ1
IR(KBr): 1585.6, 1491.5 cm (mC@N), 3296.4 cm (mNAH),
7.993; 7.676 (m, m, m, 14H, Pc-H), 4.759 (m, 2H,
OACHA), 2.608 (m, 2H, ACHA), 1.346–1.318 (t, 12H,
AC(CH ) ), 1.507–1.496 (s, 18H, AC(CH ) ), ꢀ1.423 (m,
ꢀ1
1
2
8
7
269.8, 1104.05 cm
(mArAOAC), 1450.77 cm
(mC@C),
ꢀ1
1
971.34 cm ðmCH3 Þ; H NMR (ppm, CDCl ): d = 8.887–
3
3 2
3 3
.969 (t, Ph-H, 4H), 7.924–8.067 (m, Ph-H, 4H), 7.261–
2H, HAN); MS: m/z (M+) 771.8, 1541.8; UV–vis (nm,
.532 (m, Ph-H, 4H), 5.1–5.5 (m, ACHA, 4H), 1.8–2.0
CHCl ): 333.97, 618.21, 650.96, 680.89, 714.87.
3
(
m, ACH , 24H), ꢀ1.423 (br, NAH, 8H); UV–vis (nm,
3
CHCl ): 316.92, 695.37, 728.21.
2.9. Crystal structure determination of compounds 2
3
2
.6. Tetrakis(2,2,4-trimethyl-3-pentoxy)phthalocyanine (2)
A suitable single crystal of 2 with dimensional
.25 · 0.25 · 0.12 mm was carefully selected under a polar-
izing microscope and glued to the tip of a glass fiber. Collec-
tion of diffraction data for compound 2 was performed on
Rigaku Raxis-Rapid Imaging Plate Diffractometer with
graphite-monochromated MoAKa (k = 0.071069 nm) in
the range of 1.80–27.48ꢁ at room temperature. The data
3
0
Yield 9.1%; Anal. Calcd (%) for C H N O : C, 74.82;
6
4
82
8
4
H, 8.04; N, 10.91; found C, 74.82; H, 8.07; N, 10.78;
IR(KBr), 1586.9, 1491.0 cm (mC@N), 3298.8 cm (mNAH),
1
2
ꢀ
1
ꢀ1
ꢀ
1
ꢀ1
241.5, 1109.9 cm
(mArAOAC), 1481.3 cm
(mC@C),
ꢀ1
1
956.8 cm ðmCH3 Þ; H NMR (ppm, CDCl ): d = 9.146
3