Porphyrins and their derivatives: XXVI. Synthesis and properties of 2-(3-butenyl)-5,10,15,20-tetraphenylporphyrin

Article abstract of DOI:10.1134/S1070428010090241

2-[2-(1,3-Dioxolan-2-yl)vinyl]-5,10,15,20-tetraphenylporphyrin and its copper complex were reduced into the corresponding ethyldioxolanes by diimide generated in the system hydrazine hydrate - air oxygen - pyridine. The hydrolysis of the obtained ethyldio

Full text of DOI:10.1134/S1070428010090241

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 9, pp. 1409−1413. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © V.V. Berezovskii, Yu.V. Ishkov, A.V. Mazepa, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 9, pp. 1405−1409.
Porphyrins and Their Derivatives: XXVI.*
Synthesis and Properties
of 2-(3-Butenyl)-5,10,15,20-tetraphenylporphyrin
V. V. Berezovskii, Yu. V. Ishkov, and A. V. Mazepa
Mechnikov Odessa National University, Odessa, 65026 Ukraine
е-mail: jvi@eurocom.od.ua
Received October 14, 2009
Abstract—2-[2-(1,3-Dioxolan-2-yl)vinyl]-5,10,15,20-tetraphenylporphyrin and its copper complex were reduced
into the corresponding ethyldioxolanes by diimide generated in the system hydrazine hydrate – air oxygen –
pyridine. The hydrolysis of the obtained ethyldioxolanes results in the formylethyl derivatives that react with the
methylenetriphenylphosphorane to form 2-(3-butenyl)-5,10,15,20-tetraphenylporphyrin and its copper complex.
DOI: 10.1134/S1070428010090241
Porphyrin-containing complexes are widely used
as catalysts of various reactions and as new specialty
materials [2, 3]. We formerly demonstrated that the
homopolymerization was impossible for 2-vinyl-
5,10,15,20-tetraphenylporphyrin, 5-(4-vinylphenyl)-
10,15,20-triphenylporphyrin, and their copper, zinc, and
nickel complexes whereas the copolymerization of these
porphyrin monomers with styrene, methyl methacrylate,
and acrylonitrile afforded polymers with low content of
macrocyclic fragments [4–6].
vinyl group in the above mentioned porphyrins and by the
specific inhibiting effect of the porphyrin macrocycle [4].
Inasmuch as the degree of copolymerization of 5-(4-vinyl-
phenyl)-10,15,20-triphenylporphyrin and its metal com-
plexes is higher that that of 2-vinyltetraphenylporphyrin
and its chelates the possible way to increase the content
of the porphyrin fragments in copolymers may consist
in removing the vinyl group to a larger distance from the
macrocycle in the porphyrin monomers.
We report here on the synthesis of derivatives of
meso-tetraphenylporphyrin containing in the β-position
of the pyrrole ring a butenyl substituent with a terminal
double bond.
R
Ph
As initial compounds we used vinyldioxolanes Ia
and Ib that had been obtained in [7] by Wittig reaction
of 2-formyltetraphenylporphyrin and its copper complex
with 1,3-dioxolan-2-ylmethylenetriphenylphosphorane
but had not been isolated in the individual state. The
purification of the crude dioxolanes Ia and Ib we first
carried out by chromatography on aluminum oxide us-
ing for elution a mixture benzene – tetrachloromethane,
1 : 1.5 (for free base) and 1 : 2 (for copper complex). The
best yield of porphyrin Ia was 71%, of its copper complex
Ib, 68%. It was further found that the free aldehydes
IIa and IIb obtained by hydrolysis of crude dioxolanes
Ia and Ib in a two-phase system benzene – water in the
presence of iodic acid in contrast to dioxolanes were
readily purified by chromatography on silica gel. The
acetalization of aldehydes IIa and IIb with ethylene
N
N
N
Ph
M
Ph
N
Ph
Ia, Ib_VIa, VIb
CH2CH2CHO (IV), CH2CH2CH3 (V), CH2CH2CH=CH2;
(VI); M = 2H (а), Сu (b).
It apparently originates from the steric screening of the
* For Communication XXV, see [1].
1409

BEREZOVSKII et al.
1410
glycol in the mixture benzene–dioxane, 1 : 1, in the
presence of p-toluenesulfonic acid with the azeotropic
removal of the formed water gave dioxolanes Ia and Ib
in the yields 75 and 78% respectively. The addition to the
reaction mixture at the end of the azeotropic acetalization
of triethyl orthoformate and the subsequent distillation
of the formed ethanol resulted in the increase in the yield
of vinyldioxolane Ia to 89%, and of copper complex Ib,
ing the reaction temperature from ambient to the boiling
point of the mixture. We also investigated the system
tosylhydrazine – potassium carbonate in boiling pyridine,
hydrazine hydrate – 30% hydrogen peroxide in pyridine.
At the use of the system hydrazine hydrate – air oxygen
the heating, aeration, introducing catalytic quantities of
copper (at the reduction of copper complex Ib) resulted
in shortening of the reaction time and in decrease of the
yield of the target products IIIa and IIIb. It is evidently
due to the decrease in the regioselectivity of the diimide
hydrogenation and the increase in the degradation of the
porphyrin macrocycle.
1
to 91%. Vinyldioxolane Ia according to its Н NMR
spectrum was a mixture of cis- and trans-isomers which
we failed to separate by chromatography.
The exocyclic double bond of vinyldioxolanes Ia and
Ib was not hydrogenated by the system NaBH4–Pd/С,
and in the copper complex Ib also by systems NaBH4–
PdCl2, NaBH4–NiCl2· 6H2O in various solvent mixtures
(THF–methanol, THF–ethanol, dioxane–2-propanol)
both at room temperature and at boiling.
It was found that the reduction of vinyldioxolane Ib
with the system hydrazine hydrate (50-fold molar ex-
cess) – air oxygen in pyridine at room temperature within
10 days resulted in a complete consumption of the initial
porphyrin and in the formation of ethyldioxolane IIIb in
70% yield and its chlorin derivative in 9–11% yield. The
oxidation of the latter with p-chloranil in boiling toluene
raised the yield of ethyldioxolane IIIb to 81%.
The hydrogenation of the α,β-unsaturated aldehydes
IIa and IIb by the system formic acid–Рd/C at 50°С
proceeded very slow giving trace amounts of aldehydes
IVa and IVb and propylporphyrins Va and Vb, reduction
product of both the double bond and the aldehyde group.
The boiling resulted in fast conversion of aldehydes IIa
and IIb into propylporphyrins Va and Vb, after 3 h of
boiling their yield attained 78 and 77% respectively.
Unlike the copper complex of vinyldioxolane Ib free
base Ia was slowly (14 days) reduced by the system hy-
drazine hydrate (50-fold molar excess) – air oxygen in
pyridine, and the process was unselective: even at room
temperature alongside the exocyclic double bond actively
occurred the reduction of the cryptoolefin bonds of the
macrocycle providing a mixture of chlorin and bacterio-
chlorin derivatives of porphyrin IIIa. The dehydroge-
nation of the mixture with p-chloranil in boiling toluene
resulted in porphyrin ІІІа in 76% yield.
On boiling the solutions of vinyldioxolanes Ia and Ib
and hydrazine hydrate in THF or dioxane in the presence
of Pd/С ethyldioxolanes IIIa and IIIb formed in trace
amounts and also their derivatives with hydrogenated
cryptoolefin bonds, the corresponding chlorins and bac-
teriochlorins. The hydrogenation did not occur in the
inert atmosphere, and in the presence of air oxygen the
yields of ethyldioxolanes IIIa and IIIb grew with lower-
ing temperature and at room temperature were close to
the yields obtained in the absence of Pd/С. Evidently in
the latter case the reduction occurred under the action of
diimide formed by the oxidation of hydrazine.
The diimide reduction of vinyldioxolanes Ia and Ib in
THF or dioxane proceeded with lower yields (45–53%
after the treatment with p-chloranil in toluene) and slower
(14–17 days) than in pyridine. The boiling in toluene with
p-chloranil is the optimum method of conversion of the
mentioned chlorin and bacteriochlorin derivatives into
porphyrins IIIa and IIIb. This reaction did not occur in
benzene, was very slow in the boiling dioxane, and in
o-xylene the duration of dehydrogenation was three times
shorter, the yield of ethyldioxolane ІІІа was 63%, of its
copper complex IIIb, 56%.
The diimide reduction of the cryptoolefin bonds of
the porphyrin macroring, in particular, of the tetra-
phenylporphyrin and a number of its metal complexes
was well known [8–10], but the hydrogenation by diimide
of exocyclic multiple bonds of porphyrins was described
in some early publications on conversion of the vinyl
groups in the natural porphyrins and chlorines into ethyl
groups [11–13].
The reduction of vinyldioxolanes Ia and Ib with the
system tosylhydrazine–K2CO3 in boiling pyridine under
inert atmosphere after treatment of the reduction products
with p-chloranil in boiling toluene gave ethyldioxolane
ІІІа in up to 70% yield and copper complex IIIb in up to
73% yield. The use of the system hydrazine hydrate–30%
solution of hydrogen peroxide resulted in the decrease in
We investigated the reduction of vinyldioxolanes Ia
and Ib by diimide generated in the systems hydrazine
hydrate – air oxygen in THF, dioxane, and pyridine vary-
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PORPHYRINS AND THEIR DERIVATIVES: XXVI.
1411
the yield of ethyldioxolanes IIIa and IIIb to 7–29% (after
p-chloranil treatment).
due was dissolved in toluene and applied to a column
(4 × 50 cm) packed with silica gel, eluent toluene. The
fraction containing formylporphyrin ІІа was evaporated
to dryness, the residue was recrystallized from the mixture
chloroform–methanol, 1 : 5. Yield 0.652 g (69%), Rf 0.25
(Silufol, eluent benzene). Electronic spectrum, λmax
(log ε): 433 (5.36), 524 (4.24), 565 (3.81), 605 (3.72), 662
Ethyldioxolanes IIIa and IIIb proved to be consid-
erably stable against hydrolysis, and the aldehydes IVa
and IVb were readily oxidized by air oxygen. Dioxolane
ІІІа was hydrolyzed in the mixture of trifluoroacetic acid
with 20% sulfuric acid, 3 : 1, aldehyde IVa was obtained
in 83% yield. Aldehyde IVb was obtained in 85% yield
by hydrolysis of dioxolane IIIb in the mixture benzene–
water in the presence of trifluoroacetic and iodic acids.
1
(3.56). Н NMR spectrum, δ, ppm: –2.73 br.s, –2.59 br.s
(2Н, NН), 6.07 d.d (J 8.25, 10.45 Hz), 6.85 d.d (J 7.50,
15.5 Hz), 6.99 d (J 15.5 Hz), 7.35 d.d (2H, СН=CH,
J 1.8, 10.45 Hz), 7.76 m (12Н, m-, p-phenyl), 8.023 d.t,
8.11 d.t (J 1.5, 6.5 Hz), 8.19 m (8Н, о-phenyl), 8.83 m,
8.99 s (7Н, β-pyrrole), 10.24 d, 9.20 d (1Н, СНО). Mass
spectrum: m/z 669.791 [M + 1]+.
The reaction of aldehydes IVa and IVb with the
methylenetriphenylphosphorane generated in situ from
the corresponding iodide by the action of potassium
carbonate complex with 18-crown-6 in boiling benzene
furnished the target butenylporphyrins VIa and VIb in
80% and 87% yield respectively.
2-(2-Formylvinyl)-5,10,15,20-tetraphenyl-porphy-
rinatocopper (ІІb) was similarly obtained from 1.005 g
(1.30 mmol) of crude vinyldioxolane Ib in 100 ml of
benzene, 1.766 g (7.75 mmol) of iodic acid in 50 ml of
water. Yield 0.711 g (75%), Rf 0.32 (Silufol, eluent ben-
zene). Electronic spectrum, λmax (log ε): 433 (5.34), 549
(4.23), 592 (3.99). Mass spectrum: m/z 730.313 [M]+.
The copper complexes IIIb and VIb cleanly underwent
demetallation with the system NaBH4–Cu(CH3COO)2 in
the mixture THF–methanol giving free bases IIIa and
VIa in 87 и 88% yield respectively.
2-[2-(1,3-Dioxolan-2-yl)vinyl]-5,10,15,20-tetrap-
henylporphyrin (Іа). Asolution of 0.693 g (1.04 mmol)
of aldehyde IIa, 1.15 ml (1.28 g, 20.7 mmol) of ethylene
glycol, 0.404 g (2.12 mmol) of p-toluenesulfonic acid
monohydrate in a mixture of 150 ml of benzene and
150 ml of dioxane was boiled in a device equipped with
a Dean-Stark trap for 7 h. Then to the solution was added
0.43 ml (0.384 g, 2.59 mmol) of triethyl orthoformate,
the mixture was boiled for 2 h, and the solution was dis-
tilled off till bp 90°С. On cooling 1.005 g (7.27 mmol)
of potassium carbonate was added, and the mixture was
stirred at room temperature for 24 h. The dispersion was
filtered, the precipitate was washed with benzene on the
filter, the combined filtrates were evaporated to dryness,
the residue was dissolved in benzene, filtered through
a bed (5 cm) of aluminum oxide, the filtrate was evapo-
rated to the minimum volume and crystallized from the
mixture benzene–methanol, 1:3. Yield 0.657 g (89%),
Rf 0.36 (Alufol, eluent benzene–tetrachloromethane,
1 : 2). Electronic spectrum, λmax (log ε): 425 (5.56),
520 (4.35), 555 (3,93), 597 (3.82), 653 (3.52). 1Н NMR
spectrum, δ, ppm: –2.68 br.s, –2.72 br.s (2Н, NH), 3.95 m
(4Н, СН2–СН2-dioxolane), 5.08 d (1Н, СН-dioxolane),
6.42 d, 6.31 d.d, 5.72 d, 5.58 d.d (2Н, СН=СН-trans,
J 15.6, 6 Hz, СН=СН-cis, J 7.2, 6 Hz), 7.76 m (12Н, m-,
p-phenyl), 8.20 m, 8.10 m, (8Н, о-phenyl), 8.93 s, 8.79 m
(7Н, β-pyrrole). Mass spectrum: m/z 713.844 [M + 1]+.
EXPERIMENTAL
1Н NMR spectra were registered on spectrometers
Bruker DPX-300 and DPX-400 at operating frequen-
cies 300.13 and 400.447 MHz, internal reference TMS,
solvent CDCl3. Mass spectra FAB were recorded on an
instrument VC 7070 EQ. The ion desorption was per-
formed with a beam of xenone atoms with the energy 8 kV
from the matrix of a solution of the studied compound in
3-nitrobenzyl alcohol. The precise mass of molecular ions
was evaluated at the resolution of the mass spectrometer
equal 10000. Electron absorption spectra were mea-
sured on a spectrophotometer Specord M-40 in benzene
(с 10–6–10–4 mol l–1). TLC was carried out on Silufol and
Alufol plates, the column chromatography was performed
using silica gel L 40/100 and aluminum oxide of the III
grade of activity. The crude vinyldioxolanes Ia and Ib
were prepared by scaled procedures [4].
2-(2-Formylvinyl)-5,10,15,20-tetraphenylporphy-
rin (ІІа). To a solution of 1.007 g (1.41 mmol) of crude
vinyldioxolane Ia in 100 ml of benzene was added a so-
lution of 1.919 g (8.42 mmol) of iodic acid in 50 ml of
water, and the mixture was boiled for 1.5 h in an argon
atmosphere under vigorous stirring. Then the reaction
mixture was cooled, neutralized with 5% water solution
of sodium carbonate, the organic layer was separated,
washed with water, and evaporated to dryness. The resi-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 9 2010

BEREZOVSKII et al.
1412
2-[2-(1,3-Dioxolan-2-yl)vinyl]-5,10,15,20-tetra-
droxide in 100 ml of water for 8 h at room temperature.
The product was subjected to chromatography on silica
gel, eluent benzene–tetrachloromethane, 1 : 1. Yield
0.440 g (81%), Rf 0.28 (Silufol, eluent benzene). Elec-
tronic spectrum, λmax (log ε): 418 (5.75), 540 (4.18). Mass
spectrum: m/z 776.382 [M]+.
phenylporphyrinatocopper (Іb) was similarly pre-
pared from 0.710 g (0.97 mmol) of aldehyde IIb,
1.08 ml (1.207 g, 19.4 mmol) of ethylene glycol, 0.01 g
(0.05 mmol) of p-toluenesulfonic acid monohydrate,
0.40 ml (0.36 g, 2.43 mmol) triethyl orthoformate in
a mixture of 150 ml of benzene and 150 ml of dioxane.
Yield 0.685 g (91%), Rf 0.44 (Alufol, eluent benzene–tet-
rachloromethane, 1 : 2). Electronic spectrum, λmax (log ε):
423 (5.65), 548 (4.60). Mass spectrum: m/z 774.366 [M]+.
2-(2-Formylethyl)-5,10,15,20-tetraphenylporphy-
rin (IVа). A solution of 0.401 g (0.56 mmol) dioxolane
IIIa in a mixture of 60 ml of trifluoroacetic acid and
20 ml of 20% water solution of sulfuric acid was stirred
for 3 h at room temperature under an argon atmosphere,
then it was poured into a solution of 2.464 g (23.2 mmol)
of sodium carbonate in 800 ml of water. The separated
precipitate was filtered off, washed with water, dried for
4 h at 110°С, then it was dissolved in a minimum volume
of the mixture benzene– tetrachloromethane, 1 : 1, and
applied to a column (3.5 × 40 cm) packed with silica
gel. Elution with the same solvent mixture, the fraction
containing aldehyde IVа was evaporated to dryness, the
residue was recrystallized from the mixture chloroform–
methanol, 1 : 5. Yield 0.312 g (83%), Rf 0.30 (Silufol,
eluent benzene). Electronic spectrum, λmax (log ε): 418
(5.67), 514 (4.31), 550 (3.83), 588 (3.78), 647 (3.51).
1Н NMR spectrum, δ, ppm: –2.77 br.s (2Н, NH), 2.90 m
(2Н, β-СН2), 3.22 t (2Н, α-СН2), 7.74 m (12Н, m-, p-
phenyl), 8.20 m, 8.12 m, (8Н, о-phenyl), 8.84 s, 8.81 d,
8.76 d, 8.63 d, 8.58 s (7Н, β-pyrrole), 9.69 t (1Н, СНО).
Mass spectrum: m/z 671.807 [M + 1]+.
2-[2-(1,3-Dioxolan-2-yl)ethyl]-5,10,15,20-tet-
raphenylporphyrin (ІІІа). A solution of 0.502 g
(0.70 mmol) of vinyldioxolane Іа and 1.71 ml (1.763 g,
35.2 mmol) of hydrazine hydrate in 40 ml of pyridine was
maintained for 14 days in the dark in contact with air at
20°С. Then the reaction mixture was poured in a solu-
tion of 5 g of ammonim chloride in 800 ml of water, the
separated precipitate was filtered off, washed with water,
dried for 4 h at 120°С, dissolved in 150 ml of toluene,
2.592 g (10.5 mmol) of p-chloranil was added, and the
mixture was boiled for 50 h. On cooling to the reaction
mixture was added a solution of 25.127 g (0.45 mol)
of potassium hydroxide in 100 ml of water, and the
mixture was vigorously stirred at room temperature for
8 ч, then the organic layer was separated, washed with
water (3 × 100 ml), passed through a bed of aluminum
oxide (3 cm), evaporated to dryness, the residue was
dissolved in a minimum volume of the mixture ben-
zene– tetrachloromethane, 1 : 2, and applied to a column
(3.5 × 50 cm) packed with silica gel. Elution with the
same solvent mixture, the fraction containing dioxolane
ІІІа was evaporated to dryness, the residue was recrys-
tallized from the mixture chloroform–methanol, 1 : 5.
Yield 0.383 g (76%), Rf 0.20 (Silufol, eluent benzene).
Electronic spectrum, λmax (log ε): 420 (5.66), 515 (4.36),
2-(2-Formylethyl)-5,10,15,20-tetraphenyl-porphy-
rinatocopper (IVb.Asolution of 0.405 g (0.52 mmol) of
dioxolane ІІІb in 40 ml of benzene was boiled for 12 h
with a solution of 1.919 g (8.42 mmol) of iodic acid and
5 ml (7.445 g, 65.3 mmol) of trifluoroacetic acid in 20 ml
of water at viorous stirring under an argon atmosphere.
The mixture was neutralized with 20% water solution
of sodium carbonate, the benzene layer was separated,
washed with water, and evaporated to dryness. The
residue it was dissolved in a minimum volume of the
mixture benzene– tetrachloromethane, 1 : 1, and applied
to a column (3.5 × 50 cm) packed with silica gel. Elution
with the same solvent mixture, the fraction containing
aldehyde IVb was evaporated to dryness; the residue
was recrystallized from the mixture chloroform–metha-
nol, 1 : 5. Yield 0.325 g (85%), Rf 0.39 (Silufol, eluent
benzene). Electronic spectrum, λmax (log ε): 418 (5.76),
548 (4.45). Mass spectrum: m/z 732.329 [M]+.
1
549 (3.95), 592 (3.90), 648 (3.79). Н NMR spectrum,
δ, ppm: –2.78 br.s (2Н, NH), 2.20 m (2Н, β-СН2), 3.00 t
(2Н, α-СН2), 3.89 m (4Н, СН2–СН2-dioxolan), 4.80 t
(1Н, СН-dioxolane), 7.75 m (12Н, m-, p-phenyl), 8.20 m,
8.11 m (8Н, o-phenyl), 8.85 s, 8.79 d, 8.74 d, 8.66 s, 8.60 d
(7Н, β-pyrrole). Mass spectrum: m/z 715.860 [M + 1]+.
2-[2-(1,3-Dioxolan-2-yl)ethyl]-5,10,15,20-tetrap-
henylporphyrinatocopper (ІІІb) was obtained similarly
from 0.542 g (0.70 mmol) of copper complex Ib, 1.7 ml
(1.752 g, 35.0 mmol) of hydrazine hydrate in 40 ml of
pyridine within 10 days. The reduction products were
boiled for 26 h with 1.353 g (5.50 mmol) of p-chloranil
in 150 ml of toluene, on cooling the solution was stirred
with a solution of 17.815 g (0.32 mol) of potassium hy-
2-Propyl-5,10,15,20-tetraphenylporphyrin (Vа).
A mixture of 0.212 g (0.32 mmol) of porphyrin ІІа and
0.212 g of 5%-ного Pd/C in 50 ml of formic acid was
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PORPHYRINS AND THEIR DERIVATIVES: XXVI.
1413
boiled for 2 h, Pd/C was filtered off, washed on the filter
with formic acid, then with THF. The combined filtrates
were poured into 500 ml of water, neutralized with 10%
water solution of sodium carbonate. The separated pre-
cipitate was filtered off, washed with water, dried for
5 h at 120°С, dissolved in a minimum volume of the
mixture benzene–hexane, 1 : 1, and this solution was
applied to a column (2.5 × 30 cm) packed with silica
gel. Elution with the mixture benzene–hexane, 1 : 1, the
fraction containing propylporphyrin Vа was evaporated
to dryness, the residue was recrystallized from the mix-
ture chloroform–methanol, 1 : 5. Yield 0.162 g (78%),
Rf 0.81 (Silufol, eluent benzene). Electronic spectrum,
λmax (log ε): 420 (5.61), 516 (4.23), 550 (3.73), 592 (3.72),
J 7.8 Hz), 4.91 m (2Н, СН2-vinyl), 5.74 m (1Н, СН-
vinyl), 7.73 m (12Н, m-, p-phenyl), 8.20 m, 8.11 d (8Н,
о-phenyl), 8.82 s, 8.75 d, 8.70 m, 8.62 s, 8.57 d (7Н,
β-pyrrole). Mass spectrum: m/z 669.834 [M + 1]+.
2-(3-Butenyl)-5,10,15,20-tetraphenylporphyrinato-
copper (VІb) was similarly obtained from 0.546 g (0.75
mmol) of aldehyde IVb, 1.51 g (3.73 mmol) of methyl-
triphenylphosphonium iodide, 1.030 g (7.45 mmol)
of potassium carbonate, and 0.05 g (0.19 mmol) of
18-crawn-6 in 70 ml of benzene. Yield 0.474 g (87%),
Rf 0.92 (Silufol, eluent benzene– tetrachloromethane,
1:1). Electronic spectrum, λmax (log ε): 417 (5.72), 548
(4.37). Mass spectrum: m/z 730.357 [M]+.
1
651 (3.52). Н NMR spectrum, δ, ppm: –2.78 br.s (2Н,
REFERENCES
NH), 0.85 t (3Н, СН3), 1.80 m (2Н, β-СН2), 2.79 t (2Н,
α-СН2), 7.73 m (12Н, m-, p-phenyl), 8.20 m, 8.10 m (8Н,
о-phenyl), 8.86 s, 8.79 m, 8.73 d, 8.63 m (7Н, β-pyrrole).
Mass spectrum: m/z 657.824 [M + 1]+.
1. Ishkov, Yu.V., Vodzinskii, S.V., Kirichenko, A.M., and
Mazepa, A.V., Zh. Org. Khim., 2008, vol. 44, 1081.
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2-Propyl-5,10,15,20-tetraphenylporphyrinato-
copper (Vb) was obtained similarly from 0.210 g
(0.29 mmol) of aldehyde IIb, 0.210 g of 5% Pd/C in
a mixture of 50 ml of formic acid and 50 ml of dioxane.
The reaction products were subjected to chromatography
on a column (2.5×50 cm) packed with silica gel, eluent
benzene–hexane, 1.5:1. Yield 0.159 g (77%), Rf 0.93
(Silufol, eluent benzene–tetrachloromethane, 1 : 1).
Electronic spectrum, λmax (log ε): 416 (5.71), 540 (4.23).
Mass spectrum: m/z 718.346 [M]+.
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Pomogailo, S.I., Glagolev, N.N., Zhilina, Z.I.,
Voloshanovskii, I.S., Roshchupkin, V.P., and
Pomogailo,A.D., Izv. Akad. Nauk, Ser. Khim., 2007, p. 152.
2-(3-Butenyl)-5,10,15,20-tetraphenylporphyrin
(VIа). A mixture of 0.503 g (0.75 mmol) of porphy-
rin IVа, 1.516 g (3.75 mmol) g of methyltriphenyl-
phosphonium iodide, 1.036 g (7.50 mmol) of potassium
carbonate, and 0.05 g (0.19 mmol) of 18-crawn-6 in 70 ml
of benzene was boiled under an urgon atmosphere for
10 h, then the mixture was cooled, filtered through a bed
of aluminum oxide (3 cm), concentrated to the volume
of 40 ml, 40 ml of tetrachloromethane was added, and
the solution was applied to a column (3.5×40 cm) packed
with silica gel, eluent benzene–tetrachloromethane, 1 : 1.
The fraction containing butenylporphyrin VІа was evapo-
rated to dryness, the residue was recrystallized from the
mixture chloroform–methanol, 1 : 5. Yield 0.401 g (80%),
Rf 0.81 (Silufol, eluent benzene). Electronic spectrum,
λmax (log ε): 419 (5.63), 515 (4.19), 550 (3.76), 591 (3.72),
7. Ishkov, Yu.V., Zhilina, Z.I., and Grushevaya, Zh.V., Zh.
Org. Khim., 1993, vol. 29, p. 2270.
8. Whitlock, H.W.Jr., Oester, H.M.J., and Brower, B.K.,
J. Am. Chem. Soc., 1969, vol. 91, p. 7485.
9. Sidorov, A.N., Biofizika, 1965, vol. 10, p. 226.
10. Savel’ev, D.A., Sidorov, A.N., Evstigneeva, R.P., and
Ponomarev, G.V., Dokl. Akad. Nauk SSSR, 1966, vol. 167,
p. 135.
11. Fischer, H. and Gibian, H., Lieb. Ann., 1941, vol. 548,
p. 183.
12. Fischer, H. and Gibian, H., Lieb. Ann., 1942, vol. 550,
p. 208.
1
13. Baker, E.W., Corwin, A.H., Klesper, E., and Wei, P. E.,
648 (3.51). Н NMR spectrum, δ, ppm: –2.78 br.s (2Н,
NH), 2.55 q (2Н, β-СН2, J 7.2 Hz), 2.93 t (2Н, α-СН2,
J. Org. Chem., 1968, vol. 33, p. 3144.
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