New phosphorusꢀcontaining phthalocyanines
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
1669
Found (%): C, 50.26, 50.72; H, 6.20, 5.99; N, 6.40, 6.19.
C18H26N2O6P2. Calculated (%): C, 50.47; H, 6.12; N, 6.54.
IR (KBr): 2233 (C≡N); 1240 (P=O); 1053, 1035 (P—O—C);
3031, 1603, 1506, 866 (arom.).
8 H, Ar); 2.98 (d, 16 H, Ar—CH2); 2.35 (m, 12 H, —СН3); 4.05
(q, 8 H, —СН2—СН3); 1.28 (m, 12 H, —СН2—СН3). 31P NMR:
26.94 ppm (s). MS, m/z: 1233 [M]+.
Cobalt 2,9,16,23ꢀtetrakis(diethoxyphosphorylmethyl)ꢀ
3,10,17,24ꢀtetramethylphthalocyanine (11) was synthesized by
method A. The yield was 0.21 g (72%).
Nickel 2,9,16,23ꢀtetrakis(diethoxyphosphorylmethyl)ꢀ
3,10,17,24ꢀtetramethylphthalocyanine (12) was synthesized by
method A. The yield was 0.21 g (72%).
2,3,9,10,16,17,23,24ꢀOctakis(diethoxyphosphorylmethyl)ꢀ
phthalocyanine (13). Metallic lithium (0.007 g, 0.1 mmol) was
dissolved on heating in 2 mL of isoamyl alcohol, then phthaloꢀ
nitrile 1 (0.214 g, 0.5 mmol) was added, and the mixture was
refluxed for 3 h. After completion of the reaction, isoamyl alcohol
was removed in vacuo, and the residue was dissolved in CHCl3
(40 mL), washed with dilute HCl, a solution of NaHCO3, and
distilled water. The solvent was evaporated in vacuo, and the
residue was washed with hexane and dried in air. The yield
was 0.086 g (40%). 1H NMR, δ: 7.71 (s, arom.); 4.08 (br.d,
Ar—CH2—); 3.61 (br.q, —СН2—СН3); 1.32 (br.t, —СН2—СН3).
31P NMR, δ: 23.35 ppm.
4ꢀDiethoxyphosphorylmethylꢀ5ꢀmethylphthalonitrile (2) was
isolated (~0.3 g) by chromatography of the reaction mixture.
MS, m/z: 292 [M]+; 155 [M—P(O)(OEt)2]+. 1Н NMR, δ: 7.68,
7.67 (both s, 2 H, Ar), 2.51 (s, 3 H, CH3); 3.26, 3.19 (d, 2 H,
Ar—CH2—P); 4.04 (q, 4 Н, CH2—CH3); 1.28 (t, 6 H,
—CH2—CH3). 13C NMR (CDCl3), δ: 17.2 (—CH2CH3);
62.7 (—CH2CH3); 115.3 (CN); 32.3 (Ar—CH2—P); 17.2
(CH3—Ar); 113.0, 133.9 (2 NC—CAr); 137.1 (CH3CAr); 138.6
(P—CH2CAr); 134.0, 136.3 (2 CHAr). 31P NMR: 23.47 ppm (s).
Found (%): C, 57.19, 57.45; H, 6.02, 6.20; N, 9.18, 9.25.
C14H17N2O3P. Calculated (%): C, 57.53; H, 5.82; N, 9.59.
Synthesis of metal phthalocyanine complexes 3—12 (general
procedure). Method A. A mixture of isoamyl alcohol (5 mL),
phthalonitrile 1 (1 mmol) or phthalonitrile 2 (0.5 mmol), DBU
(0.15 mL), and the corresponding metal acetate (0.25 mmol)
was refluxed until the phthalonitrile disappeared completely
(TLC monitoring). After completion of the reaction, isoamyl
alcohol was distilled off from the reaction mixture. The residue
was dissolved in CHCl3, and the solution was washed with dilute
HCl, a solution of NaHCO3, and distilled water. The solution
was dried with MgSO4, the solvent was evaporated, and the
resulting solid residue was washed with hexane and dried in air.
Method B. The reaction was carried out as in method A.
After removal of the solvent, the residue was washed with ethyl
acetate and hexane and dried in air.
Magnesium 2,3,9,10,16,17,23,24ꢀoctakis(diethoxyphosꢀ
phorylmethyl)phthalocyanine (3) was synthesized by method A.
The yield was 0.172 g (65%).
Zinc 2,3,9,10,16,17,23,24ꢀoctakis(diethoxyphosphorylmethyl)ꢀ
phthalocyanine (4) was synthesized by method A. The yield was
0.19 g (34%). 1H NMR, δ: 7.72 (s, Ar); 4.06 (q, —СН2—СН3); 3.53
(d, Ar—СН2—P); 1.28 (t, —СН2—СН3). MS, m/z: 1779 [M]+.
Copper 2,3,9,10,16,17,23,24ꢀoctakis(diethoxyphosphorylꢀ
methyl)phthalocyanine (5) was synthesized by method A. The
yield was 0.172 g (95%).
Neodymium 2,3,9,10,16,17,23,24ꢀoctakis(diethoxyphosphorylꢀ
methyl)phthalocyanine (6) was synthesized by method A. The
yield was 0.248 g (60%). IR (KBr), ν/cm–1: 1047 (Р—О—С);
1240 (Р=О).
Europium 2,3,9,10,16,17,23,24ꢀoctakis(diethoxyphosphorylꢀ
methyl)phthalocyanine (7) was synthesized by method B. The
yield was 0.172 g (40%). IR (KBr), ν/cm–1: 1046 (P—O—C);
1240 (P=O).
2,9,16,23ꢀTetrakis(diethoxyphosphorylmethyl)ꢀ3,10,17,24ꢀ
tetramethylphthalocyanine (14) was synthesized similarly from
phthalonitrile 2 (0.10 g, 0.34 mmol). The yield was 0.04 g (40%).
Zinc 2,3,9,10,16,17,23,24ꢀoctakis(phosphonomethyl)phthaloꢀ
cyanine (15). Compound 4 (0.089 g, 0.5 mmol) was refluxed for
2 h in a 10% aqueous solution of NaOH (5 mL), the solution was
cooled, neutralized with concentrated HCl, and the precipitate
that formed was filtered off, washed with water, and dried in air.
The dark green powder was obtained in a yield of 0.052 g (78%).
Electrochemical measurements were carried out with an IPCꢀ
Pro potentiostat using a threeꢀelectrode scheme with a graphite
electrode (pyrolyzed polyacrylonitrile VMNꢀ4, Тtr = 2400 °С,
specific surface 12 m2 g–1, m ≈ 2 mg) at 20 °С vs 0.15 М
Bun4NBF4 in acetonitrile and vs 0.1 М BunOH in water. A Pt
plate was the auxiliary electrode, and a silver chloride electrode
was used as a reference electrode. Oxygen was removed from the
cell by purging dry argon. Voltammetric curves were detected by
cyclic voltammetry at a sweep rate of 200 mV s–1. The measured
peak potentials were recalculated with allowance for the resistance
of the electrolyte, which were calculated from the anodic and
cathodic peaks of ferrocene oxidation: (Ec – Ea) – 0.059 = I•R,
where Ec and Ea are the potentials of the cathodic and anodic
oxidation peaks of ferrocene, respectively; I is the sum of currents
of the cathodic and anodic processes; R is the resistance of the
electrolyte. The concentration in solutions of the complexes was
2•10–4 mol L–1
.
Terbium 2,3,9,10,16,17,23,24ꢀoctakis(diethoxyphosphorylꢀ
methyl)phthalocyanine (8) was synthesized by method B. The
yield was 0.267 g (60%). IR (KBr), ν/cm–1: 1047 (Р—О—С);
1240 (Р=О).
Lutetium 2,3,9,10,16,17,23,24ꢀoctakis(diethoxyphosphorylꢀ
methyl)phthalocyanine (9) was synthesized by method B. The
yield was 0.364 g (85%). 1H NMR, δ: 7.81 (s, 8 H, Ar); 3.85 (q,
16 H, —СН2—СН3); 1.17 (t, 24 H, —СН2—СН3); 3.45 (s, 16
Ar—CH2—); 2.56 (s, 3 H, —С(О)СН3). 31P NMR: 19.97 ppm
(s). IR (KBr), ν/cm–1: 1045 (P—O—C); 1240 (P=O).
Zinc 2,9,16,23ꢀtetrakis(diethoxyphosphorylmethyl)ꢀ
3,10,17,24ꢀtetramethylphthalocyanine (10) was synthesized by
method A. The yield was 0.063 g (31.8%). 1H NMR, δ: 7.45 (m,
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 05ꢀ03ꢀ33202)
and the Presidium of the Russian Academy of Sciences
(Program “Development of Methods for the Synthesis of
Chemical Substances and Design of New Materials”).
References
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J. E. van Lier, J. Med. Chem., 1997, 40, 3897.
2. R. W. Boyle, J. E. van Lier, Synthesis, 1995, 1079.