Macrocycles, derivatives of nitrogen-containing heterocycles Synthesis and electrochemical properties of diindolizinadiquinoxalinacyclooxaalkaphanes

Article abstract of DOI:10.1007/s11172-009-0200-6

Phenylindolizinylquinoxalinomonopodands, obtained by the reaction of 1-(phenylindolizin-2-yl)quinoxalin-2(15)-one with corresponding dibromotrioxa-and dibromopentaoxaalkanes, undergo oxidative dehydrocyclization assisted by molecular iodine to yield new r

Full text of DOI:10.1007/s11172-009-0200-6

Russian Chemical Bulletin, International Edition, Vol. 58, No. 7, pp. 1484—1492, July, 2009
1484
Macrocycles, derivatives of nitrogenꢀcontaining heterocycles
2.* Synthesis and electrochemical properties
of diindolizinadiquinoxalinacyclooxaalkaphanes
A. A. Kalinin, V. A. Mamedov, V. V. Yanilkin, N. V. Nastapova, I. Kh. Rizvanov, and V. I. Morozov
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843) 273 2253. Eꢀmail: mamedov@iopc.knc.ru
Phenylindolizinylquinoxalinomonopodands, obtained by the reaction of 1ꢀ(phenylindolizinꢀ
2ꢀyl)quinoxalinꢀ2(1H)ꢀone with corresponding dibromotrioxaꢀ and dibromopentaoxaalkanes,
undergo oxidative dehydrocyclization assisted by molecular iodine to yield new redoxꢀactive
diindolizinadiquinoxalinacyclooxaalkaphanes. Using CVA, the indolizine fragments of the
heterocyclophanes in acetonitrile are found to undergo threeꢀstep oxidation with transfer of
one electron in each step. The first and the third steps are reversible, whereas the second is
irreversible. The oxidation at potentials of the first peak leads to the stable radical cations
registered by ESR (g = 2.0024, a2N = 0.26 mT).
Key words: 1,nꢀdibromotrioxaꢀ and pentaoxaalkanes, 3ꢀ(indolizinꢀ2´ꢀyl)ꢀ2ꢀoxoquinꢀ
oxalinomonopodands, diquinoxalinadiindolizinacyclooxaalkaphanes, redoxꢀactive macroꢀ
cycles, NMR spectra, voltammetry, ESR, electron ionization and MALDI mass spectra.
Macrocyclic compounds capable of reversible response
to the external influence can serve as molecular switches,2,3
membrane transfer agents,4 as well as are of great interest
in development of molecular devices and new sensors for
modern technology based on molecular processes.5—7
Biindolizines were of little use as a redoxꢀactive fragꢀ
ment,8,9 which apparently is due to the difficulties in their
introduction into the composition of potential building
blocks for assemblage of macrocyclic systems of various size.
Earlier, we have shown that electrochemical10 or moꢀ
lecular iodine assisted1 oxidative dehydrocyclization of
3ꢀindolizinꢀ2´ꢀylquinoxalinꢀ2ꢀonomonopodand leads to the
new redoxꢀactive heterocyclophane, consisting of a redoxꢀ
switching biindolizine fragment in combination with
πꢀdeficient quinoxaline systems bound by the 3,6,9ꢀtriꢀ
oxaundecane bridge. This macrocycle exhibits electroꢀ
switching binding of Mg2+ ions. It is obvious that capacity
of the cavity depends on both the length of the spacer and
dihedral angle between the planes of indolizine fragments,
which directly depends on the redoxꢀstate of the molecule
as a whole.1 The easily performed sequence of transformaꢀ
tions (Scheme 1) from 3ꢀethylquinoxalinꢀ2(1H)ꢀone (1)
to the redoxꢀactive macrocycle 7 through 3ꢀacetylꢀ (2),
pyridiniumacetylꢀ (3a), indolizinꢀ2ꢀylquinoxalinꢀ2(1H)ꢀ
one (4a) and the corresponding monopodand 6a suggests
the use of this approach for the construction of other such
macrocycles with various spacer lengths, which characꢀ
ter can be changed to influence complexation and other
properties.
Results and Discussion
The present work is devoted to proliferation of this
approach on a wide number of 1,nꢀbisindolizinylquinꢀ
oxalinylalkanes with spacers differing in length, prospecꢀ
tive for the synthesis of redoxꢀactive diindolizinadiꢀ
quinoxalinacyclophanes with various cavity sizes.
Synthesis of heterocyclophanes
and their acyclic precursors
The synthesis of dibromooxaalkanes with a large length
of the polyethylene and/or polyoxyethylene chain was perꢀ
formed according to the modified Williamson reaction
between diethylene glycol and dibromoalkanes in DMSO
in the presence of КOH. These reactions irrespective of
conditions (in DMSO in the presence of КOH or in THF
in the presence of PriONa) give rise to (along with the
target products, dibromotrioxaalkanes 8) dibromopentaꢀ
oxaalkanes 9, resulting from the condensation of diethylꢀ
ene glycol to tetraethylene glycol under reaction condiꢀ
tions with subsequent alkylation with dibromoalkanes
(Scheme 2).
The reaction of compounds 8 and 9 with 3ꢀphenylꢀ
indolizinylquinoxalinꢀ2ꢀone11 (4a) leads to 1,nꢀbisindolꢀ
* For Part 1, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1441—1449, July, 2009.
1066ꢀ5285/09/5807ꢀ1484 © 2009 Springer Science+Business Media, Inc.

Diindolizinadiquinoxalinacycloalkaphanes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
1485
Scheme 1
R = Ph (a), H (b)
izinylquinoxalinyloxaalkanes 10 (Scheme 3 and 4). The
1H NMR spectra of compounds 10, in addition to the
signals for the aromatic protons of the phenylindolꢀ
izinylquinoxaline fragment11 in the region 6.5—8.5 ppm,
exhibit three group of signals for the spacer in the reꢀ
gions 4.1—4.5 ppm (NCH2), 3.5—3.8 ppm (OCH2), and
Scheme 2
n = 1 (8a, 9a), 3 (8b, 9b)

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
Kalinin et al.
Scheme 3
i. Δ, KOH, dioxane.
1.7—1.8 ppm (other CH2). The ratio of integral intensities
of the signals for the NCH2 and OCH2 groups is 1 : 3 for
compounds 10a,b and 1 : 5 for compounds 10c,d. These
data, as well as the presence of absorption bands ν(C=O)
in the IR spectra confirm the Nꢀalkylation at both ends of
the molecule and formation of compounds 10.
The indolizine derivatives having one unsubstituted
position in the fiveꢀmembered ring rapidly undergo deꢀ
hydrocyclization to biindolizines upon the action of variꢀ
ous oxidants under mild conditions (FeIII salts in the
flow of oxygen,12 Pt/C, 10% Pt,13 Pd/C, 10% Pd,14
K3Fe(CN)68,9,15—17) in high yields. However, only the
presence of weakly electronꢀreleasing or weakly electronꢀ
withdrawing substituents (Me, Et, Ph, MeC6H4) in two
other positions of the fiveꢀmembered ring of the indolizine
system provides almost quantitative yields in the transꢀ
formation of indolizines to biindolizines. Introduction of
12
electronꢀwithdrawing groups, such as C6H4NO2 or
pyridyl,9 onto the pyrrole ring reduces the yields to
18—20%, whereas introduction of the CO2Et group12 gives
no oxidative dimerization at all. The low yield is also
observed in the oxidation of hetarylindolizines.9 The
use of molecular iodine in the oxidation of compound 6a
to cyclophane 7 was successful (see Ref. 1). Therefore, we
used iodine also for the oxidation of bisindolizinylquinꢀ
oxalines 10.
Treatment of compounds 10 with iodine in dichloroꢀ
methane is accompanied by oxidative cyclocondensation

Diindolizinadiquinoxalinacycloalkaphanes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
1487
Scheme 4
ii. Δ, KOH, dioxane.
to form cyclophanes 11. The yields of compounds 11 were
60—80%, and the residue contains unreacted compound
10, easily separated from macrocycle 11 by column chroꢀ
matography; the fraction of 10 is ~10% on the taken
amount in the transformation of compounds 10a,b to 11a,b
and ~30% in the transformation of compounds 10c,d to
11c,d. The reaction performed in a polar solvent, for exꢀ
ample, in CH3CN, as well as in the presence of equimolar
amount of triethylamine, requires shorter time of 1—2 h
and, in the case of transformation of compounds 10a,b to
11a,b, the starting compound 10 completely disappears
from the reaction mixture, whereas in the transformation
of compounds 10c,d to 11c,d, amount of unreacted comꢀ
pounds 10c,d decreases to 10%. However, the yields of
cyclophanes 11 not only were not increased, but were deꢀ
creased to 30—40% apparently due to the increase in
amount of oligomeric products.
The absence of the singlet signal for the H(3) of the
indolizine fragment in the region 8.4—8.5 ppm in the
1H NMR spectra of compounds 11 confirms the oxidative
dehydrocyclization, whereas the presence of the molecuꢀ
lar ion peaks in the mass spectra of macrocycles 11 conꢀ
firms the formation of intramolecular dehydrocyclization
products. The methylene protons of the spacer become

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Kalinin et al.
nonequivalent in the 1H NMR spectra of compounds 11.
The largest effect is observed for the NCH2 group, which
signals are as well displaced upfield from 4.3 ppm in the
starting compounds 10 to 4.0—3.8 ppm in products 11.
The aromatic region of the 1H NMR spectra of macroꢀ
cycles 11 exhibit virtually identical position of the signals
for the indolizine system and phenyl group for all four
compounds. The signals for the quinoxaline system are
close in pairs for compounds 11a and 11b, from the one
hand, and 11c and 11d from the other hand, and differ in
the chemical shift values for all four protons of the
quinoxaline system, the three of which (H(6), H(7), and
H(8)) in compounds 11a and 11b are downfield shifted by
0.15—0.25 ppm and one (H(5)) is shifted upfield by
0.15 ppm as compared to compounds 11c and 11d. The
aromatic part of the spectra of macrocycles 11c,d is alꢀ
most identical to that in bisindolizine 5 obtained by oxidaꢀ
tion of Nꢀethyl derivative of indolizinylquinoxalinone 4a
(see Ref. 1). This confirms almost identical conformation
of the biindolizinylquinoxaline fragment of macrocycles
11c,d and biindolizine 5, which is explained by the presꢀ
ence of longer spacers in them as compared to the spacers
in macrocycles 11a and 11b.
(cyclic) and 7 (acyclic) studied earlier,1 which differ from
compounds 10 and 11 only in the spacer length (3,6,9ꢀtriꢀ
oxaundecane fragment).
The reduction processes exhibit no any noticeable difꢀ
ferences between macrocycles 11a—d and their acyclic
analogs 10a—d. All the compounds in their cyclic voltꢀ
amograms obtained on a glassꢀfilled carbon electrode
in MeCN/0.1 M Bu4NBF4 exhibit two reduction peaks
–
–
of the quinoxaline fragments ( 2.07— 2.18 and
+
–
–
2.37— 2.40 V rel.Fc/Fc ), the first of which is partially
reversible, whereas the second is weakly pronounced and
irreversible (Fig. 1).
In the process of oxidation, heterocyclophanes 11a—d
are indistinguishable from each other, as are indistinguishꢀ
а
I
2.5 μA
In the 1H NMR spectra of 3ꢀindolizinylquinoxalinꢀ2ꢀ
one derivatives (compounds 4a, 5, 6a, 7, 10, and 11c,d)
containing a phenyl substituent at position 1 of the
indolizine system, the proton H(5) resonates by 0.8 ppm
more upfield as compared to the proton H(5) of the
indolizinylquinoxalinone 4b containing no phenyl group.
Apparently, this is explained by the shielding influence of
the diamagnetic ring current of the phenyl group. In more
"strained" macrocycles 11a,b, the shielding effect of the
phenyl group, probably, is somewhat weaker, which leads
to the downfield shift of the proton H(5) by 0.15 ppm.
The difference between two groups of macrocycles
+
–2.5 –2.0 –1.5 –1.0 –0.5
0
υ/V rel. Fc/Fc
b
I
1
11a,b and 11c,d are observed not only in the H NMR
2.5 μA
spectra. Melting points for these two groups also strongly
change from 293—297 °C for 11a,b to 122—132 °C for 11c,d.
Apparently, this is due to the fact that compounds 11c,d exist
as monohydrates, this agrees with the elemental analysis
data. The MALDI mass spectra of compounds 11c,d exꢀ
hibit peaks [M + H3O]+ 993 and 1049, which confirms
a high enough stability of the monohydrate. Similar picture
is characteristic of acyclic precursors of macrocycles 11c,d,
compounds 10c,d. The elemental analysis data demonꢀ
strate that compounds 10c,d also exist as monohydrates
and in the MALDI mass spectra of compounds 10c,d,
there are present peaks [M + H3O]+ 995 and 1051.
Electrochemical properties of heterocyclophanes
and their acyclic precursors
+
–2.5 –2.0 –1.5 –1.0 –0.5
0
υ/V rel. Fc/Fc
Electrochemical behavior of heterocyclophanes 11 and
their acyclic precursors 10 in entire available region of
potentials is completely identical to that of compounds 6a
Fig. 1. CVAꢀcurves of heterocyclophane 11c (a) and bisindolizine
10c (b) (C = 5•10–4 mol L–1) in MeCN/0.1 M Bu4NBF4 on
a glassꢀfilled carbon electrode; υ = 100 mV s–1
.

Diindolizinadiquinoxalinacycloalkaphanes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
1489
able properties of their precursors 10a—d. However, conꢀ
siderable differences exist between these two groups of
compounds. The cyclophanes exhibit three oneꢀelectron
oxidation peaks for the indolizine moieties, the first and
third of which are reversible, whereas the second is irreꢀ
versible (see Fig. 1, a). For higher concentrations, due to
some expansion of the anode region of potentials, the forth
irreversible oxidation peak emerges at more positive poꢀ
tentials. Electrolysis at potentials of the first peak leads to
stable enough indolizine radical cations, which were regꢀ
istered by ESR (see Fig. 2). The ESR spectra of radical
cations 10a—d are identical and consist of five lines with the
ratio of line intensities being approximately 1 : 2 : 3 : 2 : 1
due to the superfine interactions with the nuclei of two
equivalent nitrogen atoms of the conjugated indolizine
fragments and have the following characteristics: gꢀfactor
2.0024, a2N = 0.26 mT.
For acyclic biindolizines 10a—d in the anode region of
potentials, there are observed three (four for high concenꢀ
trations) irreversible oxidation peaks for the same potenꢀ
tials (see Fig. 1, Table 1). The height of the first peak
corresponds to the transfer 0.8—1.7 e per molecule, the
intensities of other peaks are considerably lower. Potential
of the first peak corresponds to the oxidation potential of
indolizines to radical cations. Therefore, irreversibility of
the peak is due to the involvement of the radical cations
(RC) of bisindolizinylquinoxalines 10a—d into the subseꢀ
quent rapid chemical reactions. Earlier,1 it has been shown
that preparative electrooxidation of bisindolizine 6a leads
to macrocycle 7. For compounds 10a—d, during multiple
cycling of potential in the range –0.60 → +0.40 → –0.60 V,
–0.60 → +0.40 → –1.60 → –0.60 V, i.e. with oxidation of
biindolizines 10a—d at potentials of the first peak and
with variation of maximum cathode potential, no change
of the CVAꢀcurve was observed. This means that no interꢀ
molecular coupling of radical cations to form polymeric
film on the surface of electrode occurs in any noticeable
extent. The same conclusion follows from the ESR specꢀ
tra, according to which even prolonged electrolysis leads
to emergence of only weak signal of radical cations of
indolizine moieties of the polymeric surface film. All these
data confirm the formation of macrocyclic compounds
11a—d by the oxidation of 10a—d, respectively, resulting
from intramolecular homocoupling of two radical cations
with elimination of two protons.1 According to this scheme
of the process, the first oxidation peak of 10a—d should be
threeꢀelectron, whereas subsequent peaks should coincide
with oxidation peaks of the macrocycles. But actually we
observed another picture. The height of the first peak was
even lower than the twoꢀelectron level, whereas potenꢀ
tials of the second and subsequent peaks of biindolizines
10a—d do not coincide with potentials of the correspondꢀ
ing peaks of macrocycles 11a—d. The reason for these
differences can be protonation of the starting compounds
and macrocycles with protons generated during coupling
of radical cations. To smooth the influence of protons, we
used the base, i.e., tris(hydroxymethyl)aminoethane, in
twoꢀfold amount in the solution of biindolizine 10c, which
is electrochemically inactive in the region of potentials
under study. The intensity of the first oxidation peak inꢀ
creases to the level of 2.3 e, the intensity of the second
peak decreases, whereas the third peak virtually disapꢀ
pears (Fig. 3, see Table 1). In addition, the second peak
becomes reversible and its potential, shifting toward less
positive values, approximates to the potential of the
second oxidation peak of macrocycle 11c. The picture
of oxidation observed in the absence and in the presꢀ
ence of the base as a whole agrees with the oxidation
scheme of compounds 10a—d to the corresponding macroꢀ
cycles 11a—d.
Experimental
Melting points of compounds obtained were measured on
a Boetius heating stage. IR spectra were recorded on a Bruker
Vectorꢀ22 Fourier spectrometer in KBr pellets. 1H NMR spectra
were recorded on a Bruker Avanceꢀ400 spectrometer (400.00 MHz)
for compounds 8, 9, 10b,d, and 11b,d in CDCl3. 1H NMR specꢀ
tra for compounds 10a,c, 11a,c and 13C NMR spectra were reꢀ
I
5 μA
+
–0.3
0
0.3
0.6 υ/B rel. Fc/Fc
0.3 mT
H
Fig. 3. CVAꢀcurves of biindolizine 10c (C = 5•10–4 mol L–1
in the presence of tris(hydroxyethyl)aminoethane
(C = 1•10–3 mol L–1) in MeCN/0.1 M Bu4NBF4 on a glassꢀ
filled carbon electrode; υ = 100 mV s–1
)
Fig. 2. ESRꢀspectrum for the radical cation of heterocyclophane
10c generated electrochemically at potential E = + 0.4 V in
MeCN/0.1 M Bu4NBF4 on a Ptꢀelectrode (C = 5•10–4 mol L–1).
.

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Kalinin et al.
Table 1. The CVA data for the oxidation of heterocyclophanes
11 and biindolizines 10 on a glassꢀfilled carbon electrode in
MeCN/0.1 M Et4NClO4
were degassed by three cycles of freezing—evacuation—defrostꢀ
ing. The temperature was 295 К.
The phane IUPAC nomenclature was used for naming
macrocycles.18,19
a
b
2
3
4
1,nꢀDibromooxaalkanes. Potassium hydroxide (7.0 g, 125 mmol)
was added to a solution of diethylene glycol (5.0 g, 47 mmol) in
DMSO (25 mL) and the mixture was stirred for 5 min, then
a solution of corresponding dibromoalkane (120 mmol) in DMSO
(5 mL) was added. The reaction mixture was stirred 5 days
and poured into water, then extracted with dichloromethane
(3×30 mL). The solvent was evaporated in vacuo together with
excess of starting dibromoalkane. The residue distilled in vacuo.
1,15ꢀDibromoꢀ5,8,11ꢀtrioxapentadecane (8a). The yield was
1.77 g (10%), b.p. 159—162 °C (0.22 Torr). Found (%): C, 38.45;
H, 6.37; Br, 42.58. C12H24Br2O3. Calculated (%): C, 38.32;
H, 6.43; Br, 42.49. 1H NMR, δ: 1.69—1.77 (m, 4 H); 1.92—1.98
(m, 4 H); 3.44 (t, 4 H, BrCH2, J = 6.8 Hz); 3.49 (t, 4 H,
OCH2, J = 6.2 Hz); 3.57—3.60 (m, 4 H, OCH2); 3.62—3.65
(m, 4 H, OCH2).
Comꢀ
pound
Ep,ox1/V
n1
Ep,ox
Ep,ox
Ep,ox
V
6ac
7c
0.30
0.26
0.30
0.29
0.29
0.28
0.32
0.26
0.26
0.26
0.26
1.7
1.0
0.8
1.3
1.4
2.3
1.4
1.0
1.0
1.0
1.0
0.60
0.46
0.61
0.52
0.53
0.49
0.56
0.43
0.43
0.46
0.47
0.77
0.97
0.78
0.77
0.73
—
0.74
0.97
0.94
0.97
0.96
1.01
—
—
—
—
—
—
—
—
—
—
10a
10b
10c
10cd
10d
11a
11b
11c
11d
1,19ꢀDibromoꢀ7,10,13ꢀtrioxanonadecane (8b). The yield was
2.63 g (12%), b.p. 185—195 °C (0.18 Torr). Found (%): C, 44.57;
H, 7.33; Br, 36.92. C16H32Br2O3. Calculated (%): C, 44.46;
H, 7.46; Br, 36.97. 1H NMR, δ: 1.32—1.40 (m, 4 H); 1.40—1.50
(m, 4 H); 1.55—1.65 (m, 4 H); 1.83—1.91 (m, 4 H); 3.40 (t, 4 H,
BrCH2, J = 6.8 Hz); 3.46 (t, 4 H, OCH2, J = 6.7 Hz); 3.56—3.60
(m, 4 H, OCH2); 3.63—3.66 (m, 4 H, OCH2).
a Potentials were measured relative to the standard potential of
the redoxꢀsystem Fc0/+ (internal standard) using comparison
electrode Ag/0.01 M AgNO3 in MeCN; the rate of potential
scanning was 100 mV s–1; C6a,10a,c,11a,c = 5•10–4 mol L–1
,
C7,10b,d,11b,d = 1•10–4 mol L–1
.
b The number of electrons were determined by comparison
method with reversible oneꢀelectron peak of ferrocene oxidaꢀ
1,21ꢀDibromoꢀ5,8,11,14,17ꢀpentaoxaheneicosane monohyꢀ
drate (9a). The yield was 4.00 g (20%), b.p. 95—97 °C (0.25 Torr).
Found (%): C, 39.92; H, 7.03; Br, 33.02. C16H34Br2O6. Calcuꢀ
lated (%): C, 39.85; H, 7.11; Br, 33.14. 1H NMR, δ: 1.69—1.77
(m, 4 H); 1.92—1.98 (m, 4 H); 3.42 (t, 4 H, BrCH2, J = 6.8 Hz);
3.50 (t, 4 H, OCH2, J = 6.2 Hz); 3.56—3.62 (m, 8 H, OCH2);
3.63—3.67 (m, 4 H, OCH2); 3.70—3.74 (m, 4 H, OCH2).
1,25ꢀDibromoꢀ7,10,13,16,19ꢀpentaoxapentacosane monohyꢀ
drate (9b). The yield was 3.90 g (16%), b.p. 125—130 °C
(0.18 Torr). Found (%): C, 44.71; H, 7.80; Br, 29.55. C20H42Br2O6.
Calculated (%): C, 44.62; H, 7.86; Br, 29.68. 1H NMR, δ: 1.30—1.40
(m, 4 H); 1.40—1.50 (m, 4 H); 1.55—1.65 (m, 4 H); 1.80—1.90
(m, 4 H); 3.39 (t, 4 H, BrCH2, J = 6.8 Hz); 3.46 (t, 4 H,
OCH2, J = 6.6 Hz); 3.55—3.59 (m, 4 H, OCH2); 3.59—3.63
(m, 4 H, OCH2); 3.65—3.68 (m, 4 H, OCH2); 3.70—3.74
(m, 4 H, OCH2).
1,nꢀBisꢀ{3ꢀ(1ꢀphenylindolizinꢀ2ꢀyl)quinoxalinꢀ2ꢀonꢀ1ꢀyl}ꢀ
oxaalkanes 10. A mixture of compound 4a (1.50 g, 4.5 mmol),
КOH (0.50 g, 8.9 mmol), dibromide 8 or 9 (2.1 mmol), and
dioxane (60 mL) was refluxed for 24 h. Dioxane was partially
evaporated, the residue was poured into water (40 mL), neutralꢀ
ized with AcOH, extracted with CH2Cl2, and dried with CaCl2.
The solvent was evaporated, the reaction mixture was dried and
purified by column chromatography on silica gel (Silicagel L
100/160μ, eluent: CH2Cl2 (compound 10a), CH2Cl2 : hexane =
= 9 : 1 (compound 10b), CH2Cl2 : EtOH = 150 : 1 (comꢀ
pounds 10c,d)).
tion.
c The data from Ref. 1.
d
In the presence of tris(hydroxymethyl)aminoethane
(C = 1•10–3 mol L–1).
corded on a Bruker Avanceꢀ600 spectrometer (600.00 MHz (1H)
and 150.864 MHz (13C)) in CDCl3. Residual signal of chloroꢀ
form (δH 7.26 ppm) was used as an internal standard. The MALDI
spectra were obtained on a Finnigan Dynamo timeꢀofꢀflight mass
spectrometer using 1,8,9ꢀtrihydroxyanthracene matrix for comꢀ
pounds 10c, 11c and on a Bruker Ultraflex III mass spectroꢀ
meter using 2,5ꢀdihydroxybenzoic acid as a matrix for compounds
10d, 11a, and 11d. Mass spectra of electron ionization (EI) were
obtained on a TRACE MS quadrupole mass spectrometer
(ThermoQuest). The inlet of the sample was performed by direct
injection with water cooling (DIP).
Cyclic voltamograms were recorded in a typical threeꢀelecꢀ
trode glass cell using a PIꢀ50ꢀ1 potentiostat on a H 307/2 xꢀyꢀ
recorder. A glassꢀfilled carbon disk electrode (∂ = 2 mm)
pressed in the Teflon served as a working electrode, platinum
wire served as an auxiliary electrode. Before each measurement,
the working electrode was mechanically polished. The potential
scanning rate υ = 100 mV/s. Potentials were measured relative
to the standard potential of the redoxꢀsystem Fc0/+ (internal
standard) using the Ag/0.01 M AgNO3 in MeCN silver compariꢀ
son electrode. Dissolved oxygen was removed by bubbling nitroꢀ
gen gas through the solution, the temperature was 295 К.
The ESR study together with the in situ electrolysis was perꢀ
formed on a device combining a Radiopan SE/Xꢀ2544 ESR specꢀ
trometer, a PIꢀ50ꢀ1 potentiostat, and an electrochemical cell.
The device allowed us to perform electrochemical process diꢀ
rectly in the resonator of the ESR spectrometer. A platinum
plate was a working electrode, platinum wire served as an auxilꢀ
iary electrode, silver wire was a comparison electrode. Solutions
1,15ꢀBis(3ꢀindolizinꢀ2ꢀylꢀ2ꢀoxoquinoxalinꢀ1ꢀyl)ꢀ5,8,11ꢀtriꢀ
oxapentadecane (10a). The yield of compound 10a was 0.09 g
(18%) from quinoxaline 4a (0.57 g), m.p. 73—75 °C. Found (%):
C, 75.52; H, 5.87; N, 9.50. C56H52N6O5. Calculated (%):
C, 75.65; H, 5.90; N, 9.45. IR, ν/cm–1: 433, 461, 500, 616, 665,
700, 760, 1038, 1085, 1122, 1176, 1223, 1285, 1311, 1372,
1
1457, 1492, 1544, 1581, 1600, 1648, 2860, 2923. H NMR, δ:
1.70—1.75 (m, 4 H, OCH2CH2CH2CH2N); 1.82—1.88 (m, 4 H,

Diindolizinadiquinoxalinacycloalkaphanes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
1491
OCH2CH2CH2CH2N); 3.52 (t, 4 H, OCH2, J = 6.2 Hz); 3.59
(t, 4 H, OCH2, J = 4.8 Hz); 3.65 (t, 4 H, OCH2, J = 5.0 Hz);
(28), 393 (19), 392 (18), 379 (17), 378 (35), 365 (16), 364 (25),
352 (11), 351 (30), 350 (11), 339 (21), 338 (58), 337 (58), 336
(39), 323 (18), 322 (37), 321 (16), 320 (31), 310 (15), 309 (34),
308 (100), 307 (49), 306 (22). No peaks for masses of fragment
ions with relative intensities less than 10% are given.
1,25ꢀBis(3ꢀindolizinꢀ2ꢀylꢀ2ꢀoxoquinoxalinꢀ1ꢀyl)ꢀ7,10,13,
16,19ꢀpentaoxapentacosane monohydrate (10d). The yield of
compound 10d was 0.30 g (37%) from quinoxaline 4 (0.57 g),
m.p. 72—75 °C. Found (%): C, 72.97; H, 6.71; N, 7.90.
C64H70N6O8. Calculated (%): C, 73.12; H, 6.71; N, 7.99. IR,
ν/cm–1: 428, 464, 516, 580, 582, 642, 670, 699, 728, 747, 1119,
1188, 1281, 1311, 1459, 1526, 1579, 1599, 1648, 2857, 2929.
1H NMR, δ: 1.40—1.53 (m, 8 H, O(CH2)2CH2CH2(CH2)2N);
1.58—1.66 (m, 4 H, OCH2CH2(CH2)4N); 1.74—1.83 (m, 4 H,
O(CH2)4CH2CH2N); 3.48 (t, 4 H, OCH2, J = 6.6 Hz); 3.55—3.65
(m, 8 H, OCH2); 3.65—3.70 (m, 4 H, OCH2); 3.73 (t, 4 H,
OCH2, J = 4.6 Hz); 4.28 (t, 4 H, NCH2, J = 7.7 Hz); 6.50 (dd, 2 H,
4.41 (t, 4 H, NCH2 J = 8.1 Hz); 6.50 (dd, 2 H, H(6)indolizine
,
J = 7.1 Hz, J = 6.7 Hz); 6.64 (dd, 2 H, H(7)indolizine, J = 9.2 Hz,
J = 6.9 Hz); 7.21 (dd, 2 H, H(6)quinoxaline, J = 7.7 Hz, J = 7.1 Hz);
7.20—7.30 (m, 4 H, H(7)quinoxaline or pꢀHPh); 7.31 (d, 2 H, Ar,
J = 8.0 Hz); 7.36 (dd, 4 H, mꢀHPh, J = 7.6 Hz, J = 7.6 Hz); 7.42
(d, 2 H, Ar, J = 9.0 Hz); 7.43—7.47 (m, 8 H, Ar); 7.90 (d, 2 H,
H(5)indolizine, J = 7.1 Hz); 8.45 (s, 2 H, H(3)indolizine). MS (EI),
m/z (Irel): 889 (2), 888 [M]+ (3), 337 (33), 308 (16), 204 (18),
169 (18), 168 (100), 167 (39). No peaks for masses of fragment
ions with relative intensities less than 10% are given.
1,19ꢀBis(3ꢀindolizinꢀ2ꢀylꢀ2ꢀoxoquinoxalinꢀ1ꢀyl)ꢀ7,10,13ꢀ
trioxanonadecane (10b). The yield of compound 10b was
0.75 g (33%) from quinoxaline 4a (1.73 g), m.p. 102—105 °C.
Found (%): C, 76.08; H, 6.33; N, 8.82. C60H60N6O5. Calcuꢀ
lated (%): C, 76.25; H, 6.40; N, 8.89. IR, ν/cm–1: 429, 464,
515, 561, 583, 646, 669, 700, 749, 1038, 1086, 1122, 1187,
1221, 1247, 1283, 1311, 1369, 1457, 1494, 1528, 1552,
H(6)indolizine, J = 6.6 Hz, J = 6.6 Hz); 6.65 (dd, 2 H, H(7)indolizine
J = 9.0 Hz, J = 6.6 Hz); 7.22 (dd, 2 H, H(6)quinoxaline, J = 8.1 Hz,
J = 7.3 Hz); 7.25—7.32 (m, 4 H, Ar); 7.36 (dd, 4 H, mꢀHPh
,
1
1579, 1600, 1649, 2857, 2930, 3048. H NMR, δ: 1.40—1.53
,
(m, 8 H, O(CH2)2CH2CH2(CH2)2N); 1.58—1.66 (m, 4 H,
OCH2CH2(CH2)4N); 1.74—1.83 (m, 4 H, O(CH2)4CH2CH2N);
3.48 (t, 4 H, OCH2, J = 6.6 Hz); 3.58—3.63 (m, 4 H, OCH2);
3.65—3.69 (m, 4 H, OCH2); 4.29 (t, 4 H, NCH2, J = 7.9 Hz);
6.51 (ddd, 2 H, H(6)indolizine, J = 6.8 Hz, J = 6.6 Hz, J = 1.3 Hz);
6.65 (ddd, 2 H, H(7)indolizine, J = 9.2 Hz, J = 6.6 Hz, J = 0.7 Hz);
7.21 (ddd, 2 H, H(6)quinoxaline, J = 7.7 Hz, J = 7.5 Hz, J = 0.9 Hz);
7.25—7.32 (m, 4 H, Ar); 7.37 (dd, 4 H, mꢀHPh, J = 7.7 Hz,
J = 7.7 Hz, J = 7.3 Hz); 7.40—7.47 (m, 10 H, Ar); 7.90 (d, 2 H,
H(5)indolizine, J = 7.0 Hz); 8.46 (s, 2 H, H(3)indolizine). MS
(MALDI): 1051 [M + H3O]+, 1050 [M + H2O]+.
12,42ꢀDioxoꢀ21,31ꢀdiphenylꢀ1,4(3,1)ꢀdiquinoxalinaꢀ2(2,3),
3(3,2)ꢀdiindolizinacyclooxaphanes 11. A solution of I2 (100 mg,
0.47 mmol) in CH2Cl2 (100 mL) was added to a solution of
compound 10 (0.20 mmol) in CH2Cl2 (200 mL), the mixture
was stirred for 6 h and kept for 16 h. Then the reaction mixture
was refluxed for 6 h, cooled, washed with aqueous soda, sodium
thiosulfate, and water, CH2Cl2 was evaporated. The brown tarꢀ
like residue was separated by column chromatography on silica
gel (Silicagel L 100/160μ, eluent: CH2Cl2 : EtOH = 200 : 1 (comꢀ
pounds 11a,b) and 100 : 1 (compounds 11c,d).
J = 7.0 Hz); 7.40—7.47 (m, 10 H, Ar); 7.91 (d, 2 H, H(5)indolizine
,
J = 7.0 Hz); 8.47 (s, 2 H, H(3)indolizine). MS (EI), m/z (Irel): 945
(3) 944 [M]+ (5), 525 (19), 464 (22), 437 (25), 436 (48), 421 (20),
420 (17), 407 (18), 378 (15), 365 (11), 364 (26), 352 (10), 351
(30), 350 (11), 339 (17), 338 (62), 337 (70), 336 (34), 323 (13),
322 (30), 321 (12), 320 (22), 310 (12), 309 (28), 308 (100), 307
(39), 306 (15). No peaks for masses of fragment ions with relaꢀ
tive intensities less than 10% are given.
1,21ꢀBis(3ꢀindolizinꢀ2ꢀylꢀ2ꢀoxoquinoxalinꢀ1ꢀyl)ꢀ5,8,11,14,17ꢀ
pentaoxaheneicosane monohydrate (10c). The yield of comꢀ
pound 10c was 1.10 g (48%) from quinoxaline 4a (1.70 g),
m.p. 132—134 °C. Found (%): C, 71.28; H, 6.38; N, 8.33.
C60H62N6O8. Calculated (%): C, 72.41; H, 6.28; N, 8.44.
IR, ν/cm–1: 433, 466, 516, 563, 582, 645, 672, 702, 751, 763,
1005, 1039, 1066, 1086, 1121, 1180, 1220, 1249, 1282, 1449,
1460, 1526, 1579, 1559, 1650, 2865, 2937. 1H NMR, δ: 1.70—1.77
(m, 4 H, OCH2CH2CH2CH2N); 1.82—1.90 (m, 4 H,
OCH2CH2CH2CH2N); 3.55 (t, 4 H, OCH2, J = 6.2 Hz);
3.58—3.64 (m, 8 H, OCH2, J = 4.3 Hz); 3.67 (t, 4 H, OCH2,
J = 4.6 Hz); 3.71 (t, 4 H, OCH2, J = 4.3 Hz); 4.33 (t, 4 H,
NCH2, J = 7.6 Hz); 6.50 (ddd, 2 H, H(6)indolizine, J = 6.6 Hz,
J = 6.6 Hz, J = 0.9 Hz); 6.64 (ddd, 2 H, H(7)indolizine, J = 9.2 Hz,
J = 6.5 Hz, J = 0.9 Hz); 7.22 (dd, 2 H, H(6)quinoxaline, J = 7.8 Hz,
J = 7.3 Hz); 7.27 (dd, 2 H, H(7)quinoxaline or pꢀHPh, J = 7.6 Hz,
12,42ꢀDioxoꢀ21,31ꢀdiphenylꢀ9,12,15ꢀtrioxaꢀ1,4(3,1)ꢀdiquinꢀ
oxalinaꢀ2(2,3),3(3,2)ꢀdiindolizinacyclononadecaphane (11a). The
yield of compound 11a was 76 mg (66%) from quinoxaline 10a
(110 mg), m.p. 295—297 °C (DMSO). Found (%): C, 75.67; H,
5.77; N, 8.52. C56H50N6O5. Calculated (%): C, 75.83; H, 5.68;
N, 8.47. IR, ν/cm–1: 435, 465, 558, 606, 660, 704, 728, 762,
1042, 1097, 1125, 1236, 1279, 1306, 1348, 1364, 1454, 1486,
1
1524, 1584, 1601, 1648, 2858, 2922. H NMR, δ: 1.30—1.37,
1.38—1.42, 1.43—1.50, 1.52—1.60 (all m, 2 H each); 3.30—3.38,
3.45—3.54, 3.55—3.60 (all m, 4 H each); 3.60—3.65, 3.78—3.88
(both m, 2 H each); 6.64 (dd, 2 H, H(6)indolizine, J = 7.1 Hz,
J = 6.2 Hz); 6.86 (dd, 2 H, H(7)indolizine, J = 9.0 Hz, J = 6.4 Hz);
7.05—7.15 (m, 4 H, pꢀHPh, H(6)quinoxaline); 7.16 (d, 2 H, H(5) or
H(8)quinoxaline, J = 7.9 Hz); 7.21 (dd, 4 H, mꢀHPh, J = 7.6 Hz,
J = 7.6 Hz); 7.33—7.42 (m, 8 H, oꢀHPh, H(7)quinoxaline, H(5)
or H(8)quinoxaline); 7.65—7.70 (m, 4 H, H(5), H(8)indolizine).
MS (MALDI): 887 [MH]+, 886 [M]+.
12,42ꢀDioxoꢀ21,31ꢀdiphenylꢀ11,13,17ꢀtrioxaꢀ1,4(3,1)ꢀdiꢀ
quinoxalinaꢀ2(2,3),3(3,2)ꢀdiindolizinacyclotricosaphane (11b).
The yield of compound 11b was 200 mg (80%) from quinoxaline
10b (250 mg), m.p. 293—295 °C (MeOH). Found (%): C, 76.27;
H, 6.17; N, 8.90. C60H58N6O5. Calculated (%): C, 76.41;
H, 6.20; N, 8.91. IR, ν/cm–1: 431, 461, 553, 703, 760, 1040,
1097, 1261, 1278, 1307, 1348, 1365, 1454, 1526, 1601, 1647,
J = 7.6 Hz); 7.32 (d, 2 H, Ar, J = 8.4 Hz); 7.37 (dd, 4 H, mꢀHPh
,
J = 7.6 Hz, J = 7.3 Hz); 7.40—7.47 (m, 10 H, Ar); 7.90 (d, 2 H,
H(5)indolizine, J = 6.8 Hz); 8.45 (s, 2 H, H(3)indolizine). 13C NMR,
δ: 24.23, 26.94, 42.20, 61.80, 70.30, 70.48, 70.77, 72.49, 111.70,
113.40, 115.08, 116.92, 118.07, 118.64, 121.57, 123.29, 125.24,
125.62, 127.67, 129.38, 130.21, 130.61, 130.93, 131.76, 133.28,
136.01, 151.01, 154.35. MS (MALDI TOF): 995 [M + H3O]+.
MS (EI), m/z (Irel): 977 (0.2), 976 (0.3) [M]+, 499 (15), 498 (23),
497 (71), 453 (11), 452 (19), 436 (21), 423 (13), 409 (21), 408
1
2854, 2928. H NMR, δ: 1.12—1.62 (m, 16 H); 3.40 (dd, 4 H,
J = 6.6 Hz, J = 5.8 Hz); 3.52—3.59 (m, 6 H); 3.61—3.65 (m, 4
H); 3.70—3.80 (m, 2 H); 6.64 (dd, 2 H, H(6)indolizine, J = 7.0 Hz,
J = 6.6 Hz, J = 1.1 Hz); 6.86 (dd, 2 H, H(7)indolizine, J = 8.8 Hz,

1492
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
Kalinin et al.
J = 6.6 Hz); 7.10—7.15 (m, 6 H, pꢀHPh, H(6)quinoxaline, H(5) or
H(8)quinoxaline); 7.21 (dd, 4 H, mꢀHPh, J = 8.0 Hz, J = 7.4 Hz);
7.35 (d, 4 H, oꢀHPh, J = 7.4 Hz); 7.40—7.48 (m, 4 H,
and 07ꢀ03ꢀ00391) and Federal Purposed Program "Study
and Elaboration on Priority Directions in Development of
Russian Scientific and Technical Complex in 2007—2012
(State Contract No. 02.512.11.2237).
H(7)quinoxaline, H(5) or H(8)quinoxaline); 7.67 (d, 2 H, H(8)indolizine
,
J = 9.2 Hz); 7.72 (d, 2 H, H(5)indolizine, J = 7.0 Hz). MS (EI),
m/z (Irel): 943 (41), 942 [M]+ (100), 472 (11), 471 (16), 377 (12),
336 (14), 335 (21). No peaks for masses of fragment ions with
relative intensities less than 10% are given.
References
12,42ꢀDioxoꢀ21,31ꢀdiphenylꢀ9,12,15,18,21ꢀpentaoxaꢀ1,4(3,1)ꢀ
diquinoxalinaꢀ2(2,3),3(3,2)ꢀdiindolizinacyclopentacosaphane moꢀ
nohydrate (11c). The yield of compound 11c was 120 mg (60%)
from quinoxaline 10c (200 mg), m.p. 130—132 °C. Found (%):
C, 72.38; H, 5.95; N, 8.36. C60H60N6O8. Calculated (%):
C, 72.56; H, 6.09; N, 8.46. IR, ν/cm–1: 430, 463, 446, 559, 704,
761, 1068, 1093, 1221, 1278, 1307, 1348, 1365, 1455, 1519, 1582,
1600, 1644, 2855, 2924. 1H NMR, δ: 1.38—1.48 (m, 4 H);
1.50—1.56, 1.58—1.66, 3.26—3.31, 3.32—3.38 (all m, 2 H each);
3.48 (dd, 4 H, J = 4.8 Hz, J = 4.4 Hz); 3.57 (dd, 4 H, J = 4.4 Hz,
J = 4.4 Hz); 3.60 (dd, 4 H, J = 5.2 Hz, J = 4.4 Hz); 3.68 (dd, 4 H,
J = 4.8 Hz, J = 4.4 Hz); 3.69—3.75, 4.01—4.09 (both m, 2 H
each); 6.66 (dd, 2 H, H(6)indolizine, J = 7.0 Hz, J = 6.5 Hz); 6.86
(dd, 2 H, H(7)indolizine, J = 8.8 Hz, J = 6.6 Hz); 6.94 (dd,
2 H, H(6)quinoxaline, J = 7.9 Hz, J = 7.0 Hz); 6.97 (d, 2 H,
H(5)quinoxaline, J = 7.4 Hz); 7.11 (dd, 2 H, pꢀHPh, J = 7.4 Hz,
J = 7.4 Hz); 7.13 (d, 2 H, H(8)quinoxaline, J = 7.9 Hz); 7.22 (dd,
4 H, mꢀHPh, J = 7.9 Hz, J = 7.4 Hz); 7.33 (ddd, 2 H,
H(7)quinoxaline, J = 7.7 Hz, J = 7.7 Hz, J = 1.3 Hz); 7.39 (d, 4 H,
oꢀH(o)Ph, J = 7.0 Hz); 7.64 (d, 2 H, H(5)indolizine, J = 7.0 Hz);
7.68 (d, 2 H, H(8)indolizine, J = 9.2 Hz). 13C NMR, δ: 23.79,
26.37, 41.33, 61.77, 70.13, 70.43, 70.57, 72.50, 111.83, 113.13,
114.81, 115.19, 118.43, 118.80, 122.59, 124.47, 125.40, 125.73,
127.94, 129.31, 129.89, 130.06, 131.14, 132.40, 133.30, 135.30,
153.41, 153.89. MS (MALDI): 993 [M + H3O]+.
12,42ꢀDioxoꢀ21,31ꢀdiphenylꢀ11,13,17,20,23ꢀpentaoxaꢀ
1,4(3,1)ꢀdiquinoxalinaꢀ2(2,3),3(3,2)ꢀdiindolizinacyclononacosaꢀ
phane monohydrate (11d). The yield of compound 11d was 63 mg
(63%) from quinoxaline 10d (100 mg), m.p. 122—124 °C.
Found (%): C, 73.07; H, 6.50; N, 8.07. C64H68N6O8. Calcuꢀ
lated (%): C, 73.26; H, 6.53; N, 8.01. IR, ν/cm–1: 433, 466, 501,
558, 703, 726, 760, 1070, 1095, 1222, 1276, 1306, 1347, 1364,
1455, 1523, 1583, 1600, 1646, 2856, 2927. 1H NMR, δ: 1.20—1.70
(m, 16 H); 3.43 (dd, 4 H, J = 6.6 Hz, J = 6.6 Hz); 3.45—3.55
(m, 2 H); 3.59 (dd, 4 H, J = 5.1 Hz, J = 4.0 Hz); 3.64 (dd, 4 H,
J = 5.1 Hz, J = 4.0 Hz); 3.70 (dd, 4 H, J = 4.8 Hz, J = 4.4 Hz);
3.75 (dd, 4 H, J = 5.1 Hz, J = 4.0 Hz); 3.95—4.05 (dd, 2 H);
6.65 (dd, 2 H, H(6)indolizine, J = 7.3 Hz, J = 6.2 Hz); 6.86 (dd,
2 H, H(7)indolizine, J = 8.8 Hz, J = 6.6 Hz); 6.94 (dd, 2 H,
H(6)quinoxaline, J = 7.7 Hz, J = 7.3 Hz); 6.98 (d, 2 H,
H(5)quinoxaline, J = 7.3 Hz); 7.07 (dd, 2 H, H(8)quinoxaline, J = 8.4 Hz);
7.13 (dd, 2 H, pꢀHPh, J = 7.7 Hz, J = 7.4 Hz); 7.22 (dd, 4 H,
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mꢀHPh, J = 7.7 Hz, J = 7.4 Hz); 7.30 (d, 2 H, H(7)quinoxaline
,
J = 7.9 Hz, J = 7.3 Hz, J = 1.5 Hz); 7.39 (d, 4 H, oꢀHPh, J = 7.4 Hz);
7.66 (d, 2 H, H(5)indolizine, J = 5.8 Hz); 7.68 (d, 2 H, H(8)indolizine
,
J = 8.1 Hz). MS (MALDI): 1049 [M + H3O]+, 1048 [M + H2O]+.
This work was financially supported by the Russian
Foundation for Basic Research (Projects Nos 07ꢀ03ꢀ00613ꢀa
Received July 31, 2008;
in revised form May 14, 2009