Rareꢀearth diphthalocyanines
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 3, March, 2004
559
132.77 (C(3), C(6)); 148.12 (C(4), C(5)). IR (Nujol mulls),
ν/cm–1: 2930 s, 2860 s, 2235 s, 1598 m, 1467 s, 1380 m, 1245 m,
1070 m, 930 m, 900 m, 882 m, 795 m, 730 m. MS (EI, 70 eV),
m/z: 184 [M]+.
denser. The reaction mixture was heated with a gradual increase
in the temperature from 100 to 290 °C and then kept at 290 °C
for 2—8 h until the mixture was solidified. After completion of
the synthesis, the reaction mixture was dissolved in CHCl3 and
filtered off from insoluble impurities on a sinter funnel. The
solvent was distilled off. Subsequent purification was carried out
as described above.
Synthesis of bis(2,3,9,10,16,17,23,24ꢀoctabutylphthaloꢀ
cyanine)lanthanides 7d and 7f under microwave irradiation (genꢀ
eral procedure). Phthalonitrile 2 (0.2 g, 0.820 mmol) and
Ln(OAc)3•nH2O or Ln(acac)3•3H2O (Ln = Lu, Dy, or Eu)
(0.089 mmol) were placed in a roundꢀbottom flask and the flask
was placed in a microwave oven. The microwave power was
300—450 W. The reaction time was 5—8 min. After completion
of the synthesis, the reaction mixture was dissolved in CHCl3
and filtered off from insoluble impurities on a sinter funnel. The
solvent was distilled off. Subsequent purification was carried out
as described above.
4,5ꢀDibutylphthalodinitrile (2). Compound 6 (6.53 g,
0.019 mol), CuCN (8.44 g, 0.094 mol), and DMF (110 mL)
were placed in a roundꢀbottom flask equipped with a reflux
condenser. The reaction mixture was refluxed for 4 h and poured
into a 7.5% aqueous FeCl3•6H2O solution (80 mL). After the
formation of a precipitate, H2O (200 mL) was added to the
reaction mixture. After 30 min, the precipitate that formed was
filtered off from the solution on a sinter funnel and dried in a
vacuum desiccator. The dry residue was rinsed off the filter with
CHCl3, washed with water (3×100 mL), and dried with calcined
MgSO4. Subsequent purification was carried out by column
chromatography (Merck silica gel, C6H6 as the eluent), and the
target compound containing impurities of 2ꢀbromoꢀ4,5ꢀdibutylꢀ
benzonitrile and octabutylꢀsubstituted copper phthalocyanine
was isolated. The crude product was purified by repeated extracꢀ
tion from a hot hexane solution with 80% aqueous EtOH. After
evaporation of the aqueousꢀalcoholic extract, the dry residue
was recrystallized from nꢀhexane. Compound 2 was obtained in
a yield of 2.86 g (63.5%) as colorless needleꢀlike crystals,
m.p. 51 °C (cf. lit. data16: 51—52 °C), Rf 0.55 (SiO2 F254, C6H6).
Found (%): C, 80.20, 80.50; H, 8.25, 8.30; N, 11.86. 11.76.
C16H20N2. Calculated (%): C, 80.00; H, 8.33; N, 11.67.
13C NMR ((CD3)2SO), δ: 13.66 (CH3); 22.01
(CH3CH2CH2CH2); 31.35 (CH3CH2CH2CH2); 32.05
(CH3CH2CH2CH2); 111.65 (C(1), C(2)); 116.08 (CN); 134.33
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 00ꢀ03ꢀ32658)
and the International Science and Technology Center
(Grant 1526).
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Synthesis of bis(2,3,9,10,16,17,23,24ꢀoctaalkylphthaloꢀ
cyanine)lanthanides 7a—f in solution (general procedure).
Phthalonitrile 1 (2) (0.820 mmol), Ln(OAc)3•nH2O or
Ln(acac)3•3H2O (Ln = Lu, Dy, or Eu) (0.089 mmol), and
isoamyl alcohol (2 mL) were placed in a roundꢀbottom flask and
the reaction mixture was heated until a transparent solution was
obtained. Then DBU (70 mg, 0.460 mmol) was added and the
reaction mixture was refluxed under a stream of Ar until the
starting nitrile was completely disappeared (15—20 h). The
course of the reaction was monitored by TLC (Merck Aluꢀ
minium Oxide F254 neutral, C6H6 as the eluent). After compleꢀ
tion of the reaction, the mixture was diluted with CHCl3 (25 mL)
and filtered off from insoluble impurities on a sinter funnel. The
solvent was distilled off and the dry residue was refluxed in 80%
aqueous MeOH (3×50 mL) followed by filtration and drying in a
vacuum desiccator to prepare a powder, which was dissolved in
C6H6 and chromatographed on a column (Merck Silica Gel 40
(0.063—0.200 mm), C6H6 as the eluent). Preparative purificaꢀ
tion of diphthalocyanines was carried out by TLC (Merck Aluꢀ
minium Oxide F254 neutral, C6H6 as the eluent). The yields and
spectroscopic data for the compounds synthesized are given in
Tables 1—3.
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cyanine)lanthanides 7d and 7f by fusing reagents (general proceꢀ
dure). Phthalonitrile 2 0.2 г (0.820 mmol) and Ln(OAc)3•nH2O
or Ln(acac)3•3H2O (Ln = Lu, Dy, or Eu) (0.089 mmol) were
placed in a roundꢀbottom flask equipped with a reflux conꢀ
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