M.S. Ag˘ırtaßs, M.S. Izgi / Journal of Molecular Structure 927 (2009) 126–128
127
poured into 400 ml ice–water, and precipitate was filtered off,
washed with water and dried. The residue was recrystallized from
ethanol.
The yield was 2.40 g (86, 6%). mp 236 °C. Calcd. for C16H11N3O2:
C, 69,31; H, 4.00; N, 15.15%. Found: C, 69.35; H, 3.97; N, 15.13%. IR
spectrum (cmÀ1): 3296, 3068, 2227, 1666, 1611, 1592, 1557, 1493,
1309, 1247, 1197, 855, 846, 524. 1H NMR (DMSO-d6) d, ppm: 8.04
(NH), 7.71–7.11 (Ar–H), 2.33 (CH3).
N-(4-(3,4-dicyanophenoxy)phenyl)acetamide
3
was based on
the reaction of 4-acetamidophenol with 4-nitrophthalonitrile
(DMF in the presence of K2CO3 as base, at room temperature
for 26 h) [23,25]. The phthalocyanine 4 was obtained by the
reaction compound 3 with ZnCl2 in DMF. The phthalocyanine
5, 6 were obtained by the reaction compound 3 with metal salts
(MgCl2 Á6H2O, NiCl2) under nitrogen at 300 °C (Scheme 1). While
compound 4 was obtained by high yield in DMF, 5, 6 compounds
were not obtained by the reaction 3 with MgCl2 Á6H2O, NiCl2 in
DMF. However, compounds 5, 6 were obtained directly from
the reaction of phthalonitrile derivative with the appropriate
metal salts. The effect of different metal ions differed in solvent
under the same conditions. Thus, optimum reaction conditions of
each metallophthalocyanine could be changed by solvent and the
template effect. So, high yield of compound 4 can be attributed
to the template effect of zinc. In this study, we tried the synthe-
sis of phthalocyanines both with solvent and without solvent.
We cited the best yielded results in the paper. For compound
4 the best results were obtained with solvent, whereas for
compounds 5, 6 the best results were obtained without solvent.
Spectral data of the newly synthesized compounds are consistent
with the proposed structures. Comparison of the IR spectral data
2.2. Tetrakis [(phenoxyacetamide)-phthalocyaninato] zinc (4)
Compound1 (0.138 g, 0.498 mmol) and ZnCl2 (0.017 g) were
dissolved in 1.5 mL of DMF. The reaction mixture was refluxed
under nitrogen for 22 h. The product was precipitated by adding
water. The precipitate was filtered and washed with water. The
product was washed with CHCl3, toluene, diethyl ether and dried.
Compound 4 is soluble in THF, DMF, DMSO and DMF/water.
The yield of 4: 0.085 g (58.6%). Calcd. for C64H44N12O8Zn: C,
65.45; H, 3.78; N, 14.31%. Found C, 65.40; H, 3.85; N, 14.28%. IR
spectrum (cmÀ1):3275, 1653, 1607, 1540, 1506, 1474, 1223,
1090, 1044, 945, 837, 746. UV–vis (DMF) kmax nm (loge):
355(3.86), 612(3.53), 679(4.24). 1H NMR (DMSO-d6) d, ppm: 8.58
(NH), 7.80–7.02 (Ar–H), 2.83–2.12 (CH3 protons).
CH3
2.3. Tetrakis [(phenoxyacetamide)-phthalocyaninato] magnesium (5)
O2N
CN
O
+
NH
Compound 1 (0.138 g, 0.498 mmol) and MgCl2 Á6H2O (0.020 g)
were powdered in a quartz crucible and heated in a sealed glass
tube for 7 min under nitrogen at 300 °C. After cooling to room tem-
perature, a green-colored reaction product was obtained. The prod-
uct was washed with EtOH, CHCl3, and ethyl acetate. DMF (2 mL)
was added to the residue in order to dissolve the product. The reac-
tion mixture was precipitated by adding EtOH. The precipitate was
filtered and washed with EtOH. Compound 5 is soluble in THF,
DMF, DMSO and DMF/water.
CN
OH
i
1
2
CH3
NH
O
The yield of 5: 0.020 g (14.3%). Calcd. for C64H44N12O8Mg: C,
67.82; H, 3.91; N, 14.83%. Found C, 67.86; H, 3.95; N, 14.79%. IR
spectrum (cmÀ1):3393, 1654, 1506, 1314, 1233, 1084, 1043,
O
CN
CN
946,834,751. UV–vis (DMF) kmax nm (loge): 353(4.28), 614(3.76),
3
679(4.33). 1H NMR (DMSO-d6) d, ppm: 7.79(NH), 7.67–7.13(Ar–
H), 2.49–2.04(CH3 protons).
ii
O
2.4. Tetrakis [(phenoxyacetamide)-phthalocyaninato] nickel (6)
CH3
NH
CH3
NH
Compound 1 (0.138 g, 0.498 mmol) and NiCl2 (0.017 g) were
powdered in a quartz crucible and heated in a sealed glass tube
for 5 min under nitrogen at 300 °C. After cooling to room temper-
ature, a green-colored reaction product was obtained. The product
was washed with EtOH, hot EtOH, and THF. DMF (2 mL) was added
to the residue in order to dissolve the product. The reaction mix-
ture was precipitated by adding ethyl acetate. The precipitate
was filtered and washed with ethyl acetate. Compound 6 is soluble
in THF, DMF, DMSO and DMF/water.
O
O
O
N
N
N
N
N
N
M
N
The yield of 6: 0.021 g (14.5%). Calcd. for C64H44N12O8Ni: C,
65.82; H, 3.80; N, 14.39%. Found C, 65.83; H, 3.84; N, 14.35%. IR
spectrum (cmÀ1): 3421, 1607, 1506, 1473, 1406, 1317, 1238,
N
O
O
1121, 1093, 1060, 958, 839, 518. UV–vis (DMF) kmax nm (loge):
331(4.07), 629 (4.00), 672 (4.07).
NH
H3C
O
HN
H3C
3. Results and discussion
4
5
6
O
M : Zn Mg Ni
We reported on the preparation of a new phthalonitrile deriv-
ative (3) and conversion to metallophthalocyanines (4–6) that
are soluble in solvents such as THF, DMSO, DMF (dimethyl
formamide) and DMF/water (1/1). For this, the synthesis of
Scheme 1. Synthesis of compounds 3–6. Reagents and conditions: (i) K2CO3, N2,
DMF, rt, 26 h; (ii) ZnCl2, N2, DMF, reflux temperature, 22 h; MgCl2 Á6H2O, N2
300 °C,7 min; NiCl2, N2, 300 °C, 5 min.