Synthesis of lipophilic tetraphenylporphyrins to design lipid-porphyrin ensembles

Article abstract of DOI:10.1134/S106816200706009X

Synthesis of symmetrical meso-arylsubstituted porphyrins with long chain hydrophobic substituents in the phenyl rings was achieved. The lipoporphyrins can be used to design supramolecular lipid ensembles of nanometer size.

Full text of DOI:10.1134/S106816200706009X

ISSN 1068-1620, Russian Journal of Bioorganic Chemistry, 2007, Vol. 33, No. 6, pp. 589–593. © Pleiades Publishing, Inc., 2007.
Original Russian Text © I.N. Fedulova, N.A. Bragina, N.V. Novikov, O.A. Ugol’nikova, A.F. Mironov, 2007, published in Bioorganicheskaya Khimiya, 2007, Vol. 33, No. 6,
pp. 635–639.
Synthesis of Lipophilic Tetraphenylporphyrins
to Design Lipid–Porphyrin Ensembles
I. N. Fedulova1, N. A. Bragina, N. V. Novikov, O. A. Ugol’nikova, and A. F. Mironov
Lomonosov State Academy of Fine Chemical Technology, pr. Vernadskogo 86, Moscow, 119571 Russia
Received December 12, 2006; in final form, March 1, 2007
Abstract—Synthesis of symmetrical meso-arylsubstituted porphyrins with long chain hydrophobic substitu-
ents in the phenyl rings was achieved. The lipoporphyrins can be used to design supramolecular lipid ensembles
of nanometer size.
Key words: lipoporphyrins, meso-aryltetraphenylporphyrins, meso-aryldipyrromethanes
DOI: 10.1134/S106816200706009X
INTRODUCTION
be estimated according to fluorescence intensity and
changes in the absorption spectrum in solution.
Porphyrins play an important role in the processes
of energy transformation in nature. In biological sys-
tems, they usually function within the highly organized
membrane complexes [1].2 Such lipid–porphyrin
ensembles have been used for the modeling of electron
transfer processes and oxygen transport [2].
The necessary prerequisite for the obtaining of
supramolecular ensembles in aqueous media is the
amphiphility of the self-organizing molecules. Hence,
structural fragments of lipids should be introduced into
porphyrins, e.g., hydrocarbon residues with various
chain lengths. It was shown that such compounds pos-
sess liquid-crystalline properties [7]. The liquid crystals
on the basis of porphyrins are of interest for optoelec-
tronics and devices to display and store information [8].
A wide use of porphyrins in technology and medi-
cine is retarded by a low accessibility of the majority of
them. In this connection, the problems of chemistry of
synthetic porphyrins become important. The porphy-
rins containing aryl substituents in meso-positions are
especially attractive, because they can be subjected to
various chemical transformations [9].
Supramolecular ensembles on the basis of
amphiphilic porphyrin derivatives and lipids are pro-
spective subjects for nanotechnology. The introduction
of tetrapyrrol compounds in monolayer [3, 4], bilayer
[5], and micellar [6] lipid aggregates allows the obtain-
ing of supramolecular ensembles with unique physico-
chemical properties. These complexes can be widely
applied to the modeling of biological processes, trans-
port of medicinal preparations, diagnostics, and design
of sensors for the registration of intermolecular interac-
tions and devices for the transformation of energy and
the storage of information.
RESULTS AND DISCUSSION
The goal of this study was the development of effec-
tive synthetic methods for lipophilic meso-aryl substi-
tuted porphyrins with various hydrophobic substitu-
ents. A combination of the methods of synthesis of
meso-arylporphyrins with the modification of substitu-
ents in aromatic rings allows the obtaining of com-
pounds with the required physicochemical characteris-
tics.
Lipoporphyrins with four to eight residues of higher
fatty alcohols, acids, steroids, or natural lipids had pre-
viously been synthesized on the basis of tetraphe-
nylporphyrin [1, 9, 10]. The covalent binding of the res-
idues of higher fatty acids and alcohols was achieved by
acylation with higher fatty acid chlorides [8] or by alky-
lation with alkyl bromides of di-, tetra-, and
The presence of a lipid constituent provides for the
ability of such ensembles to self organization. At the
same time, the porphyrin component permits the use of
optical spectroscopy for the study of various processes
of intermolecular recognition. The conjugated 20π-
electron system of the porphyrin macrocycle serves as
a convenient probe for the detection of weak intermo-
lecular interactions with the host molecule by the main
spectral methods. The aggregation–deaggregation pro-
cesses of porphyrins at the interaction with ligands may
1
Corresponding author; phone: +7 (495) 936-8903, fax: +7 (495)
936-8901; e-mail: in_fedulova@mail.ru.
2
Abbreviations: DDQ, 2,3-dichloro-5,6-dicyanobenzoquinone;
DMAP, 4-(dimethylamino)pyridine; and LPPC, L-O-palmitoyl-
sn-glycero-3-phosphocholine.
589

590
FEDULOVA et al.
octa(hydroxyphenyl) derivatives of tetraphenylporphy- the use of two different aldehydes at the condensation
rins [10, 11]. Hydroxyphenylporphyrins, which have a enables the preparation of asymmetric porphyrins of
low solubility in organic solvents, were obtained by the ÄÇ3 type [16].
hydrolysis of tetraphenylporphyrin methoxy deriva-
tives. In turn, these were synthesized by pyrrol conden-
sation with methoxybenzaldehydes [12].
We have obtained for the first time meso-aryldipyr-
rolylmetanes with long hydrophobic substituents [17].
The meso-aryl substituted dipyrrolylmetanes (IIa) and
We suggest a more convenient scheme for the syn- (IIb) were synthesized in 75 and 55% yields by the
thesis of lipoporphyrins according to which the resi- condensation of substituted benzaldehydes (Ia) and
dues of higher fatty acids and alcohols are introduced (Ib) with a large excess of pyrrol, which was also a sol-
into the molecules of benzaldehydes at initial stages of vent. The substituted benzaldehydes (Ia) and (Ib) were
synthesis. This allows the purposeful obtaining of the obtained by acylation or alkylation of p-hydroxyben-
desired lipoporphyrins in high yields. The lengths of zaldehyde with tetradecyl bromide and myristic acid
hydrophobic substituents in porphyrins were chosen in chloride.
accordance with the size of hydrophobic area of natural
phospholipids that form biological membranes.
Porphyrins (Va) and (Vb) were obtained by the con-
densation of the corresponding meso-aryl substituted
The porphyrins were synthesized by two pathways: dipyrrolylmetanes (IIa) and (IIb) with benzaldehydes
with the use of dipyrrometanes [13] and on the basis of in the presence of trifluoroboron etherate, followed by
monopyrrol condensation [14]. The synthesis via dipyr- oxidation of the resulting porphyrinogen to porphyrin
rolylmetanes has a number of advantages, which under the action of DDQ (scheme). The yield of 5,15-
explains an elevated interest in it and its wide use [15]. bis(4-tetradecyloxyphenyl)-10,20-diphenylporphyrin
The building up of the porphyrin molecule from meso- was 54% and that of 5,15-bis(4-tetradecanoyloxyphe-
substituted dipyrrolylmetanes and substituted benzal- nyl)-10,20-diphenylporphyrin 38%. The substitution of
dehydes allows the preparation of symmetrical struc- trifluoroacetic acid for trifluoroboron etherate leads to a
tures with the required set of substituents. Moreover, decrease in the yield of the target product to 5–15%.
(IVa, b)
R
CHO
R = R' = OCH2(CH2)12CH3 (a)
R = R' = OCOCH2(CH2)12CH3 (b)
4
+ 4
i, ii
N
H
R
NH
N
N
(Ia, b)
R'
R'
HN
R
CHO
i, ii
(Va, b)
+
R = OCH2(CH2)12CH3 (a)
R' = H
R = OCO(CH2)12CH3 (b)
R' = H
R
HN
NH
(IIa, b)
R = OCH2(CH2)12CH3 (a)
R = OCO(CH2)12CH3 (b)
(IVb) and (Va), (Vb). Reagents: i, CHCl , BF · OEt , EtOH; ii, DDQ.
Preparation of meso-aryl-substituted porphyrins (IVa),
3
3
2
We used a modified method of monopyrrol conden- maximal yields of porphyrins are achieved at the con-
sation for the obtaining of 5,10,15,20-tetraphenylpor- centrations of benzaldehyde and pyrrol equal to 10–2 M
phyrins. It was shown under the conditions that the [10]. The symmetrical porphyrins (IVa) and (IVb)
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SYNTHESIS OF LIPOPHILIC TETRAPHENYLPORPHYRINS
591
were obtained from the substituted benzaldehydes (Ia)
and (Ib) in 30–35% yields.
I, rel. units
30000
OCH CH 12CH3
(
)
2
2
1
The homogeneity and structure of the compounds
25000
20000
15000
10000
5000
1
were confirmed by TLC and electronic and H NMR
spectroscopies.
N H
N
N
Literature data [18] indicate that lipoporphyrins
(Va) and (Vb) should possess liquid crystalline proper-
ties, which opens an opportunity of their use as materi-
als for nanotechnology, e.g., in the high density devices
for information storage [8].
We carried out preliminary experiments on the por-
phyrin (Va) solubilization in micelles at the porphyrin–
detergent ratios of 1 : 100, 1 : 200, and 1 : 400, LPPC
being used as a detergent. An analysis of fluorescence
spectra of (Va) at its various concentrations within the
LPPC micelles showed that an increase in the porphy-
rin content in micelle lead to self quenching of fluores-
cence (figure). The tendency to the decrease of fluores-
cence at an increase in porphyrin concentration points
out to the inclusion of several (more than one) porphy-
rin molecules at the porphyrin–detergent ratios.
H N
2
OCH2(CH2)12CH3
3
0
–5000
600
650
700
750
800
850
λ, nm
Fluorescence spectra of porphyrin (Va) at various porphyrin
concentrations within the LPPC micelles in water at por-
phyrin–detergent molar ratios: 1, 400; 2, 200; and 3, 100.
λ
513 nm; temperature 20°C.
ex
Rf 0.5 (1 : 1 petroleum ether–diethyl ether); mp 37°C;
IR (ν, cm–1): 2914, 2851, 1468, 734 ((ëç2)13ëç3),
1676 (C=O), 1601, 824 (Ar), 1275, 1033 (C–O). Calc.,
%: C 79.19, H 10.76; Found, %: 79.16, H 10.81.
EXPERIMENTAL
We used in this work: triethylamine, calcium
hydride, phosphorus pentoxide, trifluoroboron etherate,
and organic solvents of domestic production; pyrrol
and TFA (Fluka); tetradecyl bromide (Merck); DDQ,
4-hydroxybenzaldehyde, benzaldehyde, and DMAP
(Aldrich); and potassium carbonate (Sigma). Myristic
acid chloride was obtained by a standard procedure
[19]. Chloroform and dichloromethane were distilled
over phosphorus pentoxide; triethylamine and pyrrol,
over calcium hydride. IR spectra were recorded on a
Fourier Bruker EQUINOX 55 spectrometer (Ger-
many). NMR spectra were obtained on a pulse Fourier
Bruker MSL-500 spectrometer (Germany) with the
working frequency 500 MHz; chemical shifts are given
in δ scale; internal standard was Me4Si; and solvent,
CDCl3. Electron spectra were registered on a Jasko UV-
7800 spectrometer in dichloromethane. Silufol UV-254
(Kavalier, Czech Republic) was used for TLC. Chro-
matographic purification of compounds was carried out
on open columns with silica gel G 60 (Sigma). Elution
systems were (A) 15 : 1 petroleum ether–diethyl ether,
(B) 4 : 1 : 0.1 chloroform–hexane–triethylamine, and
(C) 4 : 1 chloroform–hexane.
4-Tetradecanoyloxybenzaldehyde (Ib). A solution
of myristoyl chloride (0.62 g, 2.46 mmol) was added
dropwise for 30 min to a solution of p-hydroxybenzal-
dehyde (0.25 g, 2.05 mmol) and DMAP (0.19 g, 1.54
mmol) in dichloromethane (10 ml). The solution was
stirred at room temperature for 20 h, evaporated in a
vacuum, and the residue was chromatographed on sil-
ica gel eluting with system C. Yield of (Ib) 0.59 g
(82%); Rf 0.65 (C), mp 43°ë; IR (ν,–1): 2925, 2853
((ëç2)12ëç3), 1757, 1744 (C=O), 1463 (Ar), 1025,
1200 (C–O). Calc., %: C 75.97, H 9.64. Found, %: C
75.93, H 9.75.
meso-Tetradecyloxyphenyl)dipyrromethane
(IIa). An inert gas was passed through a mixture of tet-
radecyloxybenzaldehyde (0.4 g, 1.25 mmol) and pyrrol
(3.5 ml, 50.2 mmol) for 5 min. TFA (9.3 µl,
0.013 mmol) was added, and the mixture was stirred for
30 min at room temperature. The reaction mixture was
diluted with dichloromethane (60 ml), washed with
0.1 N NaOH and water to neutral reaction, and dried
4-Tetradecyloxybenzaldehyde (Ia). Potassium with sodium sulfate. (IIa) was isolated by flash chro-
carbonate (1.39 g, 10.02 mmol) in acetone (30 ml) was matography eluting with system B. Solvent and unre-
added to a solution of p–hydroxybenzaldehyde (0.7 g, acted pyrrol were removed in a vacuum at 40°ë. The
5.73 mmol) and tetradecyl bromide (1.59 g, residue was dissolved in dichloromethane (1 ml) and
5.73 mmol). The mixture was refluxed for 15 h, diluted ethanol (7 ml) was added. The precipitated solid was
with water (60 ml), and extracted with ether (2 × filtered and dried in a vacuum; yield 0.41 g (75%); Rf
50 ml). The combined extract was shaken with 10% 0.6 (4 : 1 : 0.1 chloroform–hexane–triethylamine); mp
NaOH (2 × 50 ml), washed with water (100 ml), dried 41°ë; IR (ν, cm–1): 3420 (NH, pyrrol), 3124 (CH, pyr-
with anhydrous sodium sulfate, and evaporated in a rol), 2920, 2857, 1468, 734 ((ëç2)13ëç3), 1595, 824
vacuum. The residue was chromatographed on a silica (Ar), 1513, 1324 (C–C, pyrrol), 1262, 1031 (C–C);
gel column eluted with system A; yield 0.41 g (71%); 1H NMR: 0.89 (3 H, t, ëç3), 1.24 [20 H, m, (ëç2)10),
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 33 No. 6 2007

592
FEDULOVA et al.
1
1.85 [2 H, q, J 7, éëç2ëç2ëç2(ëç2)10ëç3), 1.45 [2 589.20 (14.4), 644.80 (7.18); H NMR: –2.8 (2 H, s,
H, q, J 7, éëç2ëç2ëç2(ëç2)10ëç3), 3.97 [2 H, t, J
7, éëç2ëç2ëç2(ëç2)10ëç3), 5.4 (1 H, s, meso-ëH),
5.89–5.94(2 H, m, βëH), 6.17 (2 H, m, βëH), 6.68–
6.72 (2 H, m, αëH), 6.75–6.82 (4 H, m, ArH), 7.9 (2 H,
s, NH).
NH), 0.89 (6 H, t, ëç3), 1.27 [40 H, m, (ëç2)10), 1.91
(4 H, q, J 7, éëéëç2ëç2(ëç2)10), 2.75 (4 H, t, J 7,
éëéëç2), 7.48–7.75 [10 H, m, 10,20-(ArH)], 8.2 (8
H, m, 5,15-(ArH)), 8.85 (8 H, m, pyrrol); MS (m/z):
calc. for ë72N4O4H82: 1066, found: 1065.936 (å+).
meso-Tetradecanoyloxyphenyl)dipyrromethane
(IIb) was synthesized as described for (IIa) from 4-tet-
radecanoyloxybenzaldehyde (0.25 g, 0.753 mmol) and
pyrrol (3 ml, 43 mmol) in the presence of TFA (5.6 µl,
0.075 mmol). Ammonia was used for the treatment of
reaction mixture. Yield of (IIb) 0.23 g, 55%); Rf 0.62
(B); mp 52°ë; IR (ν, cm–1): 3344 (CH, pyrrol), 3320,
1600 (CH, pyrrol), 2925; 2853 ((ëç2)12ëç3), 1757
(C=O), 1555 (N–N, pyrrol); 1463 (Ar); 1200, 1025 (C–
5,10,15,20-Tetra(4-tetradecyloxyphenyl)porphy-
rin (IVa). Trifluoroboron etherate (13 µl, 0.1 mmol)
and absolute ethanol (30 µl) were added to a solution of
4-tetradecyloxybenzaldehyde (Ia) (0.319 g, 1 mmol)
and pyrrol (0.067 g, 1 mmol) in dichloromethane
(100 ml) in argon atmosphere at room temperature. The
reaction mixture was strirred for 1 h in an inert gas flow
at room temperature; DDQ (0.204 g, 0.09 mmol) was
added, and stirring was continued for additional 1 h.
Oligomeric products were separated by flash chroma-
tography in system C. The target product (IVa) was
purified by chromatography on a column eluted with
system C; yield 0.12 g (33%); Rf 0.9 (chloroform); elec-
1
O); H NMR: 0.89 (3 H, t, ëç3), 1.27 [2 H, m,
(ëç2)10), 1.91 (2 H, q, J 7, éëéëç2ëç2(ëç2)10),
2.51 (2 H, t, J 7, éëéëç2), 5.47 (1 H, s, meso-CH),
5.76–5.91 (2 H, m, βëç), 6.12–6.25 (2 H, m, βëç),
6.65–6.75 (2 H, m, αëç), 7.0–7.30 (4 H, m, ArH), 7.91
(2 H, s, NH).
tron spectrum, λmax, nm (ε × 10–3): 418.2 (300); 515.4
1
5,15-Bis(4-tetradecyloxyphenyl)-10,20-diphenyl- (26.3); 550.4 (10.8); 590.6 (7.1); 646 (6.3); H NMR
porphyrin (Va). Trifluoroboron etherate (16 µl,
spectrum: –3.36 (2 H, s, NH), 0.29 (12 H, t, ëç3), 0.91
(80 H, m, (ëç2)10), 1.02 (8 H, q, 7,
0.12 mmol) and absolute ethanol (20 µl) were added to
J
a
solution of meso-(4-tetradecyloxyphenyl)dipyr-
éëç2ëç2ëç2(ëç2)10ëç3), 1.4 (8 H, q, J 7,
éëç2ëç2ëç2(ëç2)10ëç3), 3.65 [8 H, t, J 7
éëç2ëç2ëç2(ëç2)10ëç3), 6.65–7.15 [16 H, m,
meso-(ArH)], 8.25 (8 H, m, pyrrol); MS (m/z): calc. for
ë100N4O4H142: 1462, found: 1461.682 (å+).
romethane (0.33 g, 0.76 mmol) (IIa) and benzaldehyde
(0.12 g, 1.14 mmol) in chloroform (50 ml) in argon
atmosphere. The reaction mixture was stirred for 1 h,
DDQ (0.16 g, 0.68 mmol) was added, and stirring was
continued for 1 h at room temperature. Oligomeric
products were separated by flash chromatography at
system C elution. The target product (IVa) was purified
by chromatography on a column eluted with system C;
yield 0.2 g (54%); Rf 0.68 (chloroform); electron spec-
trum, (λmax, nm (ε × 10–3): 418.0 (616), 515.2 (28.3),
550.6 (15.8), 590.4 (9.1), 646.2 (7.47); 1H NMR: –2.72
(2 H, s, NH), 0.91 (6 H, t, ëç3), 1.31 [40 H, m, (ëç2)10),
1.60 [4 H, q, J 7, éëç2ëç2ëç2(ëç2)10ëç3), 2.01 [4
H, m, J 7, éëç2ëç2ëç2(ëç2)10ëç3), 4.27 [4 H, t, J
7, éëç2ëç2ëç2(ëç2)10ëç3), 7.78 [10 H, m, J 7,
10,20-(ArH)], 8.23 [8 I, m, J 7, 5,15-(ArH)], 8.85 (8 H,
m, β-ç, pyrrol); MS, m/z: calc. for ë72N4O2H86: 1039,
found: 1038.781 (å+).
5,10,15,20-Tetra(4-tetradecanoyloxyphenyl)por-
phyrin (IVb) was synthesized as described for (IVa)
from 4-tetradecanoyloxybenzaldehyde (0.332 g,
1 mmol) and pyrrol (0.067 g, 1 mmol) in dichlo-
romethane (100 ml) in the presence of trifluoroboron
etherate (13 µl, 0.1 mmol) and absolute ethanol (30 µl);
yield 0.162 g (35%); electron spectrum, λmax, nm (ε ×
10–3): 418.0 (380), 516.0 (23.6), 551.6 (11.2), 590.0
1
(7.4), 646.80 (6.42); H NMR spectrum: –2.8 (2 H, s,
NH), 0.89 (12 H, t, ëç3), 1.27 [80 H, m, (ëç2)10), 1.91
(8 H, q, J 7, éëéëç2ëç2(ëç2)10), 2.75 (8 HI, t, J 7,
éëéëç2), 7.48–8.25 (16 H, m, meso-(ArH)], 8.85
(8 H, m, pyrrol); MS (m/z): calc. for ë72N4O4H82: 1518,
found: 1517.675 (å+).
5,15-Bis(4-tetradecyloxyphenyl)-10,20-diphenyl-
porphyrin (Vb) was synthesized like (Va) from meso-
(4-tetradecanoyloxyphenyl)dipyrromethane
(IIb)
Inclusion of porphyrins in micelles. An aliquot of
porphyrin dissolved in chloroform was added to LPPC
(10 mg) in a 4 : 1 chloroform–methanol mixture. The
solvents were removed in a vacuum, and the residue
was thoroughly dried. The resulting thin film was inten-
sively shaken with warm water (55°ë) for 10 min. The
samples contained 5 mg/ml (0.01 M) LPPC; porphyrin
concentrations varied from 2 × 10–4 to –2.5 × 10–5 M.
The fluorescence spectra were measured for the freshly
prepared micellar dispersions. The samples remained
transparent for a month after the preparation; no por-
(0.225 g, 0.50 mmol), and benzaldehyde (0.08 g,
0.75 mmol) in chloroform (50 ml) in the presence of tri-
fluoroboron etherate (11 µl, 0.08 mmol) and absolute
ethanol (20 µl). The reaction mixture was stirred for 2 h
in argon flow at room temperature; DDQ (0.103 g,
0.45 mmol) was added; and stirred at room temperature
for 1 h. Oligomeric products were separated by flash
chromatography at elution with dichloromethane. The
target product was purified by chromatography on a
column eluted with system C; yield 0.101 g (38%); Rf
0.6 (chloroform); electron spectrum, λmax, nm (ε ×
10−3): 418.00 (530), 514.00 (24.8), 548.80 (16.1), phyrin precipitation was observed.
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SYNTHESIS OF LIPOPHILIC TETRAPHENYLPORPHYRINS
593
9. Semeikin, A.S., Syrbu, S.A., and Koifman, O.I., Izv.
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ACKNOWLEDGMENT
This work was supported by the Russian Foundation
for Basic Research, project no. 04-03-33064.
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pp. 1599–1603.
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