108
V. A. BURMISTROV ET AL.
in column to provide the infinitely diluted solutions and
the rectilinear part of dissolution isotherm.
The autosampler “Shimadzu AOC-20i” with syringe
10 mL was used. Dead retention time was determined
using propane. Deference between retention times of
replicate observations did not exceed 0.5 s.
heating. Then under cooling methanol (5 mL) was
added, solution was stirred for 1 h, then the mixture of
conc. ammonia solution (5 mL) in water (50 mL) was
added. The mixture was stirred for 30 min acetic acid
was added to slight acidic reaction, organic solvents were
distilled off. The residue was isolated, washed with water
and dried at 70°C. Yield 0.85 g (98%). MS: m/z 743.51
(calcd. for [M + H]+ 742.74).
Specific retention volumes of test sorbates were
calculated according to equation:
5,10,15,20-Tetrakis[3′,5′-di(2′′-methylbutyloxy)
phenyl]porphine. The grinded K2CO3 (2.0 g) was added
to solution of 0.4 g (0.545 mmol) 5,10,15,20-tetrakis(3,5,-
dihydroxyphenyl)porphine and 1.0 mL (8.3 mmol)
1-bromo-2-methylbutane in 20 mL DMFA. The mixture
was stirred without heating for 48 h (control with thin-
layer chromatography), then poured in 100 mL water,
refluxed, cooled. The residue was filtered off, washed
with water, dried, dissolved in dichloromethane and
chromatographed on Al2O3 (II Brockman degree) with
dichloromethane. The first fraction of porphyrin was
collected. The eluate was evaporated and product was
precipitated by methanol. Yield 0.58 g (83.0 %), mp
83–97°C. Rf: 0.77 (benzene-hexane; 2:1) (silufol). UV-
vis (CHCl3): lmax, nm (log e) 646 (3.79), 590 (3.95),
τR − τo
(1)
.
.
F j
Vg =
m
where tR — retention time of sorbate, s; t0 — retention
time of propane, s; F — helium flow, mL.min-1; m — mass
of stationary phase, g; j — factor of gas compressibility
which depends on pressure at the inlet to column (Pin)
and Patm
:
(P / Patm )2 −1
3
2
in
.
(2)
j =
(P / Patm )3 −1
in
Synthesis
5,10,15,20-Tetrakis(3,5,-dimethoxyphenyl)
porphine.Methoda.Solutionof5mL(0.072mol)pyrrole
and 12.0 g (0.072 mol) 3,5-dimethoxybenzaldehyde in
50 mL p-xylene was smoothly added to a boiling solution
of 5.0 mL trifluoroacetic acid in 300 mL p-xylene. The
mixture was refluxed for 1 h, the solvent was distilled off
with water vapor, the residue was filtered off, washed with
water and dried. The mixture was dissolved in benzene
andchromatographedonAl2O3 (IIBrockmandegree).The
porphyrin fraction was collected, evaporated, dissolved
in benzene and repeatedly chromatographed on silica by
benzene, then precipitated by the mixture with methanol.
Yield 2.78 g (18.1%). Method b. 0.4 mL (3.2 mmol)
BF3 etherate was added to solution of 1.7 g (10 mmol)
3,5-dimethoxybenzaldehyde and 0.7 mL (10 mmol)
pyrrole in 1000 mL dichloromethane (containing 0.4%
ethanol) under argon. The mixture was stirred for 2 h,
1.7 g (7.32 mmol) p-chloranil was added, then the mixture
was stirred 2.5 h and 1.0 mL (10.4 mmol) diethanolamine
was added. Dichloromethane was distilled off, residue
was washed with solution of KOH, filtered off, washed
1
555 (3.95), 516 (4.38), 422 (5.73). H NMR (500 MHz;
CDCl3; Me4Si): dH, ppm 9.01s (8H, b-H); 7.42s (8H,
2′,6′-H); 6.94t (4H, J = 2.1 Hz, 4′-H); 4.02m (8H, OCH);
3.95m (8H, OCH′); 1.99m (8H, CH); 1.66m (8H, CH2);
1.34m (8H CH2′); 1.10d (24H, J2 = 6.8 Hz, CH3); 1.00t
(24H, J2 = 6.8 Hz, CH3); -2.78bs (2H, NH). MS: m/z
1304.67 (calcd. for [M + H]+ 1303.82).
Ni(II) complex of 5,10,15,20-tetrakis[3′,5′-di(2′′-
methylbutyloxy)-phenyl]porphine. The solution of
0.5 g (0.38 mmol) 5,10,15,20-tetrakis[3′,5′-di(2′′-methyl-
butyloxy)-phenyl]porphine and 1.0 g (3.9 mmol) Ni(II)
acetylacetonate in 30 mL DMFA was refluxed for 3.0 h,
then poured in water. The residue was filtered off, washed
with water and dried at 70°C. The precipitate obtained
was dissolved in dichloromethane and chromatographed
on Al2O3 (II Brockman degree). The porphyrins zone was
evaporated and precipitated with methanol. Yield 0.47 g
(91%), mp 73–80°C. Rf: 0.80 (benzene-hexane; 1:1)
(silufol). UV-vis (CHCl3): lmax, nm (log e) 529 (4.35);
418 (5.48). 1H NMR (500 MHz; CDCl3; Me4Si): dH, ppm
8.88s (8H, b-H); 7.20d (8H, J = 2.0 Hz 2′,6′-H); 6.84t
(4H, J = 2.0 Hz, 4′-H); 3.95m (8H, OCH); 3.86m (8H,
OCH′); 1.94m (8H, CH); 1.59m (8H, CH2); 1.28m (8H,
CH2′); 1.06d (24H, J2 = 6.8 Hz, CH3); 0.97t (24H, J2 =
6.8 Hz, Et-CH3). MS: m/z 1361.44 (calcd. for [M + H]+
1360.498).
1
with water and dried at 70°C. Yield 0.6 g (28.1%). H
NMR (500 MHz; CDCl3; Me4Si): dH, ppm 8.97s (8H,
b-H); 7.43d (8H, J = 2.3 Hz, 2′,6′-H); 6.93t (4H, J = 2,3
Hz, 4′-H); 3.99s (24H, OCH3); -2.79bs (2H, NH). UV-vis
(CHCl3): lmax, nm (log e) 644 (3.6), 589 (3.9), 550 (3.9),
515 (4.4), 421 (5.7). Rf: 0.83 (benzene–methanol 30:1);
0.93 (CHCl3); 0.24 (benzene) (silufol). MS: m/z 855.61
(calcd. for [M + H]+ 854.97).
COMPUTATIONAL
5,10,15,20-Tetrakis(3,5,-dihydroxyphenyl)
porphine. 5,10,15,20-tetrakis(3,5,-dimethoxyphenyl)
porphine (1.0 g, 1.17 mmol) was dissolved in 30 mL
dried dichloromethane, then under stirring and cooling
(0°C) the solution of 1.5 mL (15.9 mmol) BBr3 in 15 mL
dichloromethane added and stirred for a night without
TheNi(II)complexesof5,10,15,20-tetrakis[3′,5′-di(2′′-
methylbutyloxy)-phenyl]porphine, 5,10,15,20-Tetraphen-
ylporphine and their axial complexes with picoline and
lutidine isomers were studied by density functional
theory (DFT) computations utilizing the B3LYP hybrid
Copyright © 2017 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2017; 21: 108–109