Synthesis of 1,10-phenanthrolines fused with bicyclo[3.3.0]octane and bicyclo[3.3.1]nonane frameworks

Article abstract of DOI:10.1007/s10593-012-1081-4

Reactions of bicyclo[3.3.1]nonane-2,6-dione and bicyclo[3.3.0]octane-3,7- dione with 8-amino-7-quino-linecarbaldehyde under basic conditions led to fused nonplanar compounds with one or two 1,10-phenanthroline moieties. The novel heterocyclic systems bicy

Full text of DOI:10.1007/s10593-012-1081-4

Chemistry of Heterocyclic Compounds, Vol. 48, No. 6, September, 2012 (Russian Original Vol. 48, No. 6, June, 2012)
SYNTHESIS OF 1,10-PHENANTHROLINES FUSED WITH
BICYCLO[3.3.0]OCTANE AND BICYCLO[3.3.1]NONANE
FRAMEWORKS
S. Visniakova1, A. Zilinskas1, and S. Tumkevicius1*
Reactions of bicyclo[3.3.1]nonane-2,6-dione and bicyclo[3.3.0]octane-3,7-dione with 8-amino-7-quino-
linecarbaldehyde under basic conditions led to fused nonplanar compounds with one or two
1,10-phenanthroline moieties. The novel heterocyclic systems bicyclo[3.3.1]nonano[2,3-b]bis[1,10]-
phenanthroline, cis-bicyclo[3.3.0]octano[3,2-b:7,6-b']bis[1,10]phenanthroline, bicyclo[3.3.1]nona-
no[2,3-b:6,7-b']bis[1,10]phenanthroline, and 8H-9,16-methanoindolo[2',3':5,6]cycloocta[1,2-b]bis-
[1,10]-phenanthroline have been synthesized and characterized.
Keywords:. bicyclo[3.3.1]nonane, bicyclo[3.3.0]octane, 1,10-phenanthroline, cyclocondensation, Fischer
indole synthesis, Friedländer reaction.
1,10-Phenanthroline and its derivatives are known to have a multitude of practical uses. They possess
good chelation properties towards a wide range of metal ions [1, 2] and are considered as components for
constructing supramolecular assemblies [3, 4]. Also, because of their conjugated π-systems, they have been
applied as photosensitive materials [5-10]. Moreover, phenanthroline derivatives have been found to possess
valuable biological properties, such as anticancer, antibacterial, antimalarial, and HIV-1 protease inhibitory
activities [11-15]. On the other hand, compounds bearing bicyclic framework are used as ligands [16-19] and as
model compounds for interpreting reaction mechanisms [20]. Bicyclic fragments may also be transformed into
new polycyclic structures suitable for construction of chemosensors, biological probes, organic light-emitting
diodes, and dye-sensitized solar cells [21-23]. In this connection it seemed interesting to obtain molecules
consisting of both 1,10-phenanthroline and bicyclic moieties. We believe that compounds with
H
H
R
NH2
O
O
H
N
CHO
O
O
O
O
H
2
Me
Me
1
R
H
H
3a,b
4
3 a R = H; b R = CH3
_______
*To whom correspondence should be addressed, e-mail: sigitas.tumkevicius@chf.vu.lt.
1Vilnius University, 24 Naugarduko St., Vilnius LT-03225, Lithuania.
_________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 1013-1020, June, 2012. Original
article submitted September 2, 2011.
0009-3122/12/4806-0943©2012 Springer Science+Business Media New York
943

V-shaped geometry and phenanthroline motifs in periphery could be utilized as unusual metal complexing
agents, fluorescent materials, etc. Bicyclic fragments also possess the ability for further chemical
transformations. Thus, we present herein the synthesis of phenanthroline derivatives fused with a bicyclic
fragment and some of their transformations. The chosen synthetic strategy involved the construction of the
heterocyclic moiety onto the bicycloalkane framework.
The general synthetic approach for the phenanthroline system is the Friedländer condensation reaction
[24]. We have applied this method for the synthesis of several phenanthroline derivatives starting from the readily
available 8-aminoquinoline-7-carbaldehyde (1) and bicyclic ketones – bicyclo[3.3.0]octane-3,7-dione (2),
bicyclo[3.3.1]nonane-2,6-diones 3a,b, and 4,6-dimethylbicyclo[3.3.1]nonane-2,8-dione (4).
When a diketone has several α-methylene groups, formation of different products could be expected.
Our initial objective was to monitor the double condensation reaction of 8-aminoquinoline-7-carbaldehyde (1)
and cis-bicyclo[3.3.0]octane-3,7-dione (2) at 2:1 molar ratio:
2
1
N
15
17
18
N
14
13a
16
3
H
15a
17a
18a
16a
16b
NaOH
MeOH
18b
4
13
12
9b
1
+
2
7b
4a
9a
7a
8a
N
6a
7
5
8
H
9
N10
6
H
11
5
N
N
N
N
H
6
We expected to get a mixture of products 5 and 6 with C2 and C1 symmetries, respectively. However,
1
only compound 5 was obtained in 24% yield. In the H NMR spectrum of the resulting product, protons H-7b
and H-16b appeared as one multiplet, which, consequently, confirmed the C2 symmetry of the derivative 5.
Protons H-2 and H-11 appeared in the most downfield region as a doublet of doublets with small coupling
constants at 9.15 ppm (J = 1.6, J = 4.4 Hz), whereas protons H-5, H-6 and H-14, H-15 showed doublets at 7.72
and 7.78 ppm, respectively. These values are characteristic for all phenanthroline derivatives. Calculations of
the equilibrium geometry of compounds 5 and 6 performed by the semi-empirical AM1 method using the
program SPARTAN 06 for Windows (Wavefunction Inc.) supports predominant formation of compound 5
instead of compound 6. The calculated values of molecular energies (185.2 and 189.3 kcal/mol) and dipole
moments (0.00 and 2.55 D) for compounds 5 and 6, respectively, also confirmed that formation of compound 5 is
more preferable.
Diketones 3 and 4 are bridged derivatives having a fixed nonplanar structure. The condensation reaction
using racemic bicyclo[3.3.1]nonane-2,6-dione (3a) and 2 equivalents of the aminoaldehyde 1 was accomplished
under basic conditions to give compound 7 in 62% yield.
2
1 N
H
3
20
18
16
17
20a
16a
10a
19a
4
17a
9a
19
21
N
20b
15
NaOH
MeOH
4a
1
+
3a
14a
10b
5
9
6a
7a
14
13
N
7
6
8
10
N
H
11
12
7
In the 1H NMR spectrum of compound 7, protons H-2 and H-12 appeared in the most downfield region at
9.28 ppm as a doublet of doublets with small coupling constants (J = 1.8, J = 4.5 Hz). The IR spectrum of
compound 7 does not contain the C=O absorption band, which is observed at 1705 cm–1 for the parent diketone 3a.
The 13C NMR spectroscopy and elemental analysis data are also consistent with the structure of compound 7.
944

However, the Friedländer reaction of diketone 3b with aminoaldehyde 1 in methanol failed to result in
the expected product 8. 4,8-Dimethylbicyclo[3.3.1]nonane-2,6-dione (3b) possesses a rigid bicyclic framework
with steric demands, therefore in order to force the reaction, we increased the temperature and time. By using
2-PrOH as a solvent, a complex mixture of products was formed, from which only 2-methyl-1,10-
phenanthroline (9) was isolated in relatively high 57% yield. Diketone 4 behaved in the same way:
H
Me
N
N
NaOH
3b
+
1
2-PrOH
Me
N
N
N
Me
H
N
N
8
N
N
H
N
NaOH
9
4
+
1
2-PrOH
Me
Me
H
10
Formation of phenanthroline 9 probably occurred by condensation of quinoline 1 with acetone which, in
turn, was formed by oxidation of 2-propanol in the presence of the bicyclic ketones and base according to the
Oppenauer mechanism. Similar problems in the construction of the phenanthroline moiety onto bridgehead
frameworks and the oxidation of solvent were observed in [25, 26].
Due to its V-shaped bicyclic framework, bicyclo[3.3.1]nonano[2,3-b:6,7-b']bis[1,10]phenanthroline (7)
seems to be interesting for further modifications. To study the introduction of various fuctional groups into this
molecule, we attempted a bromination reaction of the derivative 7. Performing the reaction of compound 7 with
bromine in chloroform without additives gave a yellow precipitate of variable composition. Therefore its
reactivity was modified by forming dihydrochloride 11.
H
N
N
NBS, (PhCOO)2
Br–Br
N
CHCl3, 89%
N
H
Br
H
N
N
7
H
HCl
CHCl3
N
Br2
N
Br
H
HCl
N
C6H5NO2
17%
12
N
N
N
HCl
H
11
However, treatment of the latter with bromine in nitrobenzene furnished dibromide 12 only in 17%
yield. Compound 12 was synthesized in reasonable yield (89%) also by Wohl–Ziegler bromination using
N-bromosuccinimide and benzoyl peroxide.
945

1
In the H NMR spectrum of compound 12, a doublet of H-8 and H-18 protons was observed at 5.93
ppm with J = 2.2 Hz. The 13C NMR spectrum consists of 15 peaks, which are consistent with the symmetric
structure of dibromide 12. Elemental analysis showed that the structure contains one molecule of bromine.
Compound 12 appeared to be stable and showed no indication of change in color, melting point, or infrared
spectrum after 4 months of storage in the air.
It was also interesting to study the possibility to synthesize derivatives bearing different heterocyclic
moieties fused with a bicyclic core scaffold. The synthesis of such compounds was started from monoprotected
diketone – 6,6-ethylenedioxybicyclo[3.3.1]nonan-2-one (13):
H
9
H
8
O
O
7
6
6a
7a
5
13% HCl
10
1, NaOH
15
O
O
4a
14b
Me2CO
77%
11
MeOH
34%
4
3
13a
14a
O
N
12
13
14
N1
H
13
H
14
2
H
H
9
8
6
7
H
N10
9a
6a
7a
O
5
10a
PhNHNH2
11
17b
18
4a
14b
14a
AcOH, HCl
48%
4
3
16a
17a
N
N
12
15
17
16
14
N
N1
13
H
H
15
16
2
The reaction of compound 13 with aminoaldehyde 1 under basic conditions gave product 14 in 34% yield.
Deprotection of compound 14 with hydrochloric acid furnished ketone 15. The presence of carbonyl group in
13
compound 15 was proved by IR (absorption band at 1703 cm–1) and C NMR spectra (signal at 213.9 ppm).
Compound 15 further reacted with phenylhydrazine under the conditions of Fischer indole synthesis to give
compound 16 in 48% yield. The structure of compound 16 was assigned according to spectral and elemental analysis
data. Thus, in the 1H NMR spectrum the signal of NH group was observed as a singlet at 7.95 ppm.
In conclusion, the present investigation has demonstrated a simple methodology for the construction of
a variety of novel mono- and bisphenanthroline derivatives fused with a bicycloalkane scaffold, which were
otherwise hardly obtainable until now. Studies of the photophysical and charge-transporting properties of the
synthesized representatives of novel heterocyclic systems are currently in progress, and the results will be
reported in due course.
EXPERIMENTAL
1
13
IR spectra were obtained on a Perkin-Elmer Spectrum BX II FT-IR spectrometer in KBr. H and C
NMR spectra were recorded on a Varian Unity Inova spectrometer at 300 and 75 MHz, respectively, using
residual signals of solvents as internal standard. Elemental analyses were performed with a Flash 2000 CHNS-O
analyzer (Thermo Fisher Scientific). Melting points were determined in open capillaries with a Gallenkamp
apparatus and are uncorrected. Column chromatography was performed using Silica gel 60 (0.040–0.063 mm,
Merck). All reactions and purity of the synthesized compounds were monitored by TLC using Silica gel 60
F254 aluminum plates (Merck). Visualization was accomplished by UV light or with p-anisaldehyde and basic
KMnO4 solutions. 8-Aminoquinoline-7-carbaldehyde [26], bicyclo[3.3.1]nonane-2,6-dione [27], 6,6-ethylene-
dioxybicyclo[3.3.1]nonan-2-one [28], 4,8-dimethylbicyclo[3.3.1]nonane-2,6-dione and 4,6-dimethylbicyclo-
[3.3.1]nonane-2,8-dione [29, 30] were obtained according to the reported procedures. cis-Bicyclo[3.3.0]octane-
3,7-dione is commercially available.
946

Phenanthroline derivatives 5, 7 (General Method). Methanolic 2 M NaOH solution (0.5 ml) was
added to a solution of ketone 2 or 3a (1.02 mmol) and 8-aminoquinoline-7-carbaldehyde (1) (0.35 g,
2.04 mmol) in MeOH (25 ml). The mixture was heated to reflux until the complete conversion of starting
materials (TLC). After cooling, the reaction mixture was evaporated to dryness and the residue recrystallized
from the appropriate solvent.
cis-Bicyclo[3.3.0]octano[3,2-b:7,6-b']bis[1,10]phenanthroline (5). Reaction time 3 h. Yield 0.10 g (24%);
1
mp >300C (2-PrOH). IR spectrum, ν, cm-1: 1398-1491 (C=C), 1622 (C=N), 2921 (C–H). H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 3.93-4.05 (4H, m, 2CH2); 4.47-4.49 (2H, m, H-7b,16b); 7.58 (2H, dd, J = 8.0, J = 4.4,
H-3,12); 7.72 (2H, d, J = 8.8, H-5,14); 7.78 (2H, d, J = 8.8, H-6,15); 8.21-8.23 (4H, m, H-4,7,13,16); 9.15 (2H,
dd, J = 4.4, J = 1.6, H-2,11). 13C NMR spectrum (CDCl3), δ, ppm: 41.3 (C-8,17); 45.9 (C-7b,16b); 122.9
(C-3,12); 125.9 (C-6,15); 126.9 (C-5,14); 128.1 (C-7,16); 128.6 (C-4a,13a); 132.5 (C-6a,15a); 136.2 (C-4,13);
139.5 (C-9a,18a); 146.2 (C-9b,18b); 146.3 (C-7a,16a); 150.4 (C-2,11); 166.0 (C-8a,17a). Found, %: C 82.01;
H 4.65; N 13.87. C28H18N4. Calculated, %: C 81.93; H 4.42; N 13.65.
Bicyclo[3.3.1]nonano[2,3-b:6,7-b']bis[1,10]phenanthroline (7). Reaction time 2 h. Yield 0.27 g
(62%); mp > 300°C (EtOAc–MeOH, 3:1). IR spectrum, ν, cm–1: 1410-1491 (C=C), 1618 (C=N), 2923 (C–H).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.66 (2H, t, J = 2.9, 21-CH2); 3.72-3.86 (4H, m, 8,18-CH2); 4.26 (2H, t,
J = 2.9, H-9,19); 7.58–7.62 (6H, m, H-3,5,6,13,15,16); 7.82 (2H, s, H-7,17); 8.21 (2H, dd, J = 8.3, J = 1.8,
H-4,14); 9.28 (2H, dd, J = 4.5, J = 1.8, H-2,12). 13C NMR spectrum (CDCl3), δ, ppm: 29.2 (C-21); 36.4
(C-8,18); 38.8 (C-9,19); 122.8 (C-3,13); 125.9 (C-6,16); 126.5 (C-5,15); 127.9 (C-4a,14a); 128.8 (C-7,17);
131.0 (C-6a,16a); 136.3 (C-7a,17a); 136.8 (C-4,14); 145.1 (C-10a,20a); 146.5 (C-10b,20b); 150.5 (C-2,12);
161.8 (C-9a,19a). Found, %: C 82.12; H 5.09; N 12.82. C29H20N4. Calculated, %: C 82.05; H 4.75; N 13.20.
2-Methyl-1,10-phenanthroline (9). NaOH (0.100 g, 2.5 mmol) was added to a solution of
4,8-dimethylbicyclo[3.3.1]nonane-2,6-dione (3b) (0.126 g, 0.7 mmol) and 8-aminoquinoline-7-carbaldehyde (1)
(0.241 g, 1.4 mmol) in 2-PrOH (25 ml). The reaction mixture was refluxed for 12 h and concentrated under
reduced pressure. The residue was purified by column chromatography eluting with EtOAc–hexane, 1:1. Yield
0.18 g (57%); mp 83–84°C (mp 84–86°C [31]). The physicochemical and spectral characteristics of the obtained
compound 9 corresponds to those given in [31].
Bicyclo[3.3.1]nonano[2,3-b:6,7-b']bis[1,10]phenanthroline Dihydrochloride (11). Gaseous HCl was
bubbled through a solution of bicyclo[3.3.1]nonano[2,3-b:6,7-b']bis[1,10]phenanthroline (7) (0.71 g, 1.67 mmol)
in CHCl3 (30 ml). The precipitate formed was filtered off and washed several times with Et2O to provide 0.67 g
1
(81%) of compound 11, mp > 300°C. IR spectrum, ν, cm-1: 1415–1535 (C=C), 1618 (C=N), 2923 (C–H). H
NMR spectrum (D2O), δ, ppm (J, Hz): 2.40 (2H, s, 21-CH2); 3.23-3.28 (2H, m, 8,18-CH2); 3.47-3.55 (2H, m,
8,18-CH2); 3.81-3.82 (2H, m, H-9,19); 7.50 (2H, d, J = 9.0, H-5,15); 7.59 (2H, d, J = 9.0, H-6,16); 7.84 (2H, s,
H-7,17); 7.91 (2H, dd, J = 8.3, J = 5.3, H-3,13); 8.61 (2H, dd, J = 8.3, J = 1.2, H-4,14); 8.96 (2H, dd, J =5.3,
J = 1.2, H-2,12). Found, %: C 70.15; H 4.66; N 11.53. C29H22Cl2N4. Calculated, %: C 70.02; H 4.46, N 11.26.
8,18-Dibromobicyclo[3.3.1]nonano[2,3-b:6,7-b']bis[1,10]phenanthroline Dibromide (12). A. A solution
of bicyclo[3.3.1]nonano[2,3-b:6,7-b']bis[1,10]phenanthroline hydrochloride (11) (0.61 g, 1.22 mmol) in
nitrobenzene (10 ml) was heated to 130-145°C, and a solution of bromine (0.55 g, 3.44 mmol) in nitrobenzene
(10 ml) was added dropwise during 2 h. The reaction mixture was heated at the same temperature for 6 h. After
cooling, the reaction mixture was washed with aq. NH3 (30 ml) and extracted with CH2Cl2 (315 ml). The
organic layer was washed with water (220 ml), dried with Na2SO4, and concentrated under reduced pressure.
The residue was purified by column chromatography eluting with CH2Cl2 and then with CH2Cl2–MeOH, 9:1, to
afford compound 12. Yield 0.12 g (17%).
B. A solution of bicyclo[3.3.1]nonano[2,3-b:6,7-b']bis[1,10]phenanthroline (7) (0.150 g, 0.35 mmol),
NBS (0.160 g, 0.89 mmol), and benzoyl peroxide (0.023 g, 0.09 mmol) in dry CHCl3 (10 ml) was stirred at
room temperature for 1 h, after which the solution became red-yellow. The insoluble solids were filtered off and
washed with dry CHCl3. The chloroform solution was dried with Na2SO4, the solvent was removed under
947

reduced pressure, and the residue was purified by column chromatography (gradient elution with Et2O–Me2CO)
to afford compound 12. Yield 0.18 g (89%); mp >300°C. IR spectrum, ν, cm-1: 686 (C–Br), 1416-1490 (C=C),
1617 (C=N), 2945 (C–H). 1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 3.29 (2H, t, J = 3.0, 21-CH2); 4.46-4.48
(2H, m, H-9,19); 5.93 (2H, d, J = 2.2, H-8,18); 7.66-7.73 (6H, m, H-3,5,6,13,15,16); 7.94 (2H, s, H-7,17); 8.24
(2H, dd, J = 8.2, J = 1.8, H-4,14); 9.31 (2H, dd, J = 4.5, J = 1.8, H-2,12). 13C NMR spectrum (CDCl3), δ, ppm:
20.9 (C-21); 44.2 (C-9,19); 52.8 (C-8,18); 123.7 (C-3,13); 126.5 (C-6,16); 127.2 (C-5,15); 128.6 (C-4a,14a);
129.5 (C-7,17); 131.8 (C-7a,17a); 136.7 (C-6a,16a); 139.2 (C-4,14); 145.9 (C-10a,20a); 146.5 (C-10b,20b);
150.9 (C-2,12); 155.8 (C-9a,19a). Found, %: C 47.13; H 2.65; N 7.75. C29H18Br4N4. Calculated, %: 46.94; H
2.44, N 7.55.
10,10-Ethylenedioxybicyclo[3.3.1]nonano[2,3-b][1,10]phenanthroline (14). Methanolic 2 M NaOH
solution (0.5 ml) was added to a solution of ketone 13 (0.20 g, 1.02 mmol) and 8-aminoquinoline-7-
carbaldehyde (1) (0.18 g, 1.02 mmol) in MeOH (25 ml). The mixture was heated to reflux for 2 h until the
complete conversion of the starting materials (TLC). After cooling, the reaction mixture was evaporated to
dryness and the residue recrystallized from EtOH. Yield 0.12 g (34%); mp 219-220°C. IR spectrum, ν, cm-1:
1
1108 (C–O–C), 1414-1489 (C=C, C=N); 2888 (C–H). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.55 (1H, d,
J = 12.1, H-9); 2.08-2.46 (6H, m, 11,12,15-CH2); 3.17-3.39 (2H, m, 8-CH2); 3.72 (1H, t, J = 3.1, H-13);
3.99-4.02 (4H, m, OCH2CH2O); 7.61 (1H, dd, J = 8.0, J = 4.4, H-3); 7.72 (1H, d, J = 8.8, H-5), 7.75 (1H, d,
13
J = 8.8, H-6); 7.92 (1H, s, H-7); 8.24 (1H, dd, J = 8.0, J = 1.6, H-4); 9.23 (1H, dd, J = 4.4, J = 1.6, H-2). C
NMR spectrum (CDCl3), δ, ppm: 28.6 (C-12); 29.1 (C-11); 30.2 (C-15); 31.6 (C-8); 36.6 (C-13); 36.9 (C-9);
64.6–64.8 (OCH2CH2O); 111.2 (C-10); 122.6 (C-3); 125.8 (C-6); 126.6 (C-5); 127.9 (C-4a); 128.6 (C-7a);
132.4 (C-6a); 135.2 (C-7); 136.2 (C-4); 144.6 (C-18a); 146.5 (C-18b); 150.4 (C-2); 162.1 (C-17a). Found, %:
C 76.08; H 6.11; N 8.08. C21H20N2O2. Calculated, %: C 75.88; H 6.06; N 8.43
Bicyclo[3.3.1]nonano[2,3-b][1,10]phenanthrolin-10-one (15). 10,10-Ethylenedioxybicyclo[3.3.1]no-
nano[2,3-b][1,10]phenanthroline (14) (0.11 g, 0.33 mmol) was dissolved in a mixture of acetone (15 ml) and
13% aq. HCl (1 ml). The reaction mixture was refluxed for 6 h. After cooling, the mixture was neutralized with
NaHCO3 and extracted with CH2Cl2 (315 ml). The organic layer was dried with Na2SO4 and evaporated under
reduced pressure. The residue was recrystallized to provide compound 15. Yield 0.07 g (77%); mp 215°C
(PhMe). IR spectrum, ν, cm-1: 1411–1491 (C=C, C=N), 1703 (C=O), 2861 (C–H). 1H NMR spectrum (CDCl3), δ,
ppm (J, Hz): 1.85-2.13 (2H, m, 12-CH2); 2.18-2.58 (4H, m, 11,15-CH2); 3.08-3.14 (2H, m, 8-CH2); 3.41-3.52
(1H, m, H-9); 3.93-3.97 (1H, m, H-13); 7.66 (1H, dd, J = 8.0, J = 4.5, H-3); 7.78 (2H, s, H-5,6); 8.03 (1H, s,
13
H-7); 8.27 (1H, dd, J = 8.0, J =1.8, H-4); 9.25 (1H, dd, J = 4.5, J = 1.8, H-2). C NMR spectrum (CDCl3), δ,
ppm: 31.6 (C-12); 32.1 (C-15); 34.2 (C-8); 36.6 (C-11); 36.9 (C-13); 44.8 (C-9); 123.1 (C-3); 126.4 (2C, C-
5,6); 128.1 (C-4a); 128.9 (C-7a); 130.5 (C-7); 135.8 (C-6a); 136.4 (C-4); 145.2 (C-14a); 146.4 (C-14b); 150.7
(C-2); 160.4 (C-13a); 213.9 (C(10)=O). Found, %: C 79.59; H 5.61; N 10.16. C19H16N2O. Calculated, %:
C 79.14; H 5.59; N 9.71.
9,10,15,16-Tetrahydro-8H-9,16-methanoindolo[2',3':5,6]cycloocta[1,2-b][1,10]phenanthroline (16).
A solution of phenylhydrazine (37.5 µl, 0.381 mmol) in concentrated HCl (2 ml) was added dropwise to a
solution of bicyclo[3.3.1]nonano[2,3-b][1,10]phenanthrolin-10-one (15) (0.1 g, 0.346 mmol) in AcOH (10 ml).
The resulted mixture was refluxed for 3 h, cooled, and poured into 10 ml of H2O with 2.5 g ice. The formed
solids were collected and recrystallized to provide compound 16. Yield 0.06 g (48%); mp >300°C (EtOH). IR
spectrum, ν, cm-1: 1138 (C–NH–C), 1411-1489 (C=C, C=N), 2914 (C–H). 1H NMR spectrum (CDCl3), δ, ppm
(J, Hz): 2.39-2.51 (2H, m, 18-CH2); 3.21-3.50 (5H, m, 8,15-CH2, H-9); 4.16-4.23 (1H, m, 16-CH); 6.98 (1H, t,
J = 7.3, H-13); 7.07 (1H, t, J = 7.3, H-12); 7.29-7.37 (2H, m, H-11,14); 7.57-7.65 (3H, m, H-3,5,6); 7.75 (1H, s,
13
H-7); 7.95 (1H, s, NH); 8.19 (1H, d, J = 8.0, H-4); 9.25 (1H, d, J = 3.3, H-2). C NMR spectrum (CDCl3), δ,
ppm: 27.6 (C-18); 30.0 (C-15); 30.8 (C-16); 36.6 (C-9); 36.8 (C-8); 106.5 (C-11); 111.5 (C-14b); 118.0 (C-14);
118.8 (C-13); 121.1 (C-12); 123.6 (C-3); 126.3 (C-6); 126.9 (C-5); 127.6 (C-14a); 127.9 (C-4a); 128.8 (C-7a);
131.8 (C-7); 136.6 (C-6a); 136.9 (C-9a); 137.1 (C-4); 137.9 (C-10a); 144.0 (C-17a); 145.7 (C-17b); 150.1
(C-2); 162.6 (C-16a). Found, %: C 83.42; H 5.74; N 11.84. C25H19N3. Calculated, %: C 83.08; H 5.30; N 11.63.
948

The Research Council of Lithuania is greatefully acknowledged for financial support (project No. MIP-
65/2010). The authors also wish to express their gratitude to Prof. E. Butkus for the possibility to use the
SPARTAN 06 PC for Windows version 1.02 program package and to Dr. E. Orentas for useful discussions.
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