Synthesis of new methyl derivatives of aza-and diazaphenanthrene

Article abstract of DOI:10.1134/S1070428008070178

By condensation of acetone with 2-naphthylamine and 3-(4-fluorophenyl)-1H- pyrazole-4-, pyridine-3-, quinoline-2-, quinoline-6-carbaldehyde and 4-(2-fluorobenzyloxy)benzaldehyde new 3-aryl(heteryl)-1-methylbenzo[f]quinolines were synthesized. Reactions of

Full text of DOI:10.1134/S1070428008070178

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 7, pp. 1049−1053. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © N.G. Kozlov, K.N. Gusak, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 7, pp. 1059−1063.
Synthesis of New Methyl Derivatives
of Aza- and Diazaphenanthrene
N. G. Kozlov and K. N. Gusak
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, Minsk, 220072 Belarus
e-mail: loc@ifoch.bas-net.by
Received November 16, 2007
Abstract—By condensation of acetone with 2-naphthylamine and 3-(4-fluorophenyl)-1H-pyrazole-4-, pyridine-
3-, quinoline-2-, quinoline-6-carbaldehyde and 4-(2-fluorobenzyloxy)benzaldehyde new 3-aryl(heteryl)-1-
methylbenzo[f]quinolines were synthesized. Reactions of acetone with 6-quinolylamine and aromatic aldehydes
provided 3-aryl-1-methyl-4,7-phenanthrolines. Intermediate reaction products were isolated: 4-phenyl- or
(3-pyridyl)-4-(2-naphthylamino or 6-quinolylamino)butan-2-ones.
DOI: 10.1134/S1070428008070178
active compounds and key intermediates in the synthesis
of new heterocycles with practically useful properties.
The interest to methyl derivatives of aza- and
diazaphenanthrene is due to the high and versatile bio-
logical activity inherent to a number of members of this
class compounds [1, 2], and also the opportunity of their
application to the synthesis of difficultly available and
therefore poorly understood aldehydes, styryls, and dyes
of the aza- and diazaphenanthrene series [3–6].
In this study we for the first time brought into the
condensation with acetone (I) and 2-naphthylamine (II)
aldehydes of the heterocyclic series, 3-(4-fluorophenyl)-
1H-pyrazole-4-carbaldehyde (IIIa), pyridine-3- (IIIb),
quinoline-2- (IIIc), quinoline-6-carbaldehyde (IIId), and
also 4-(2-fluorobenzyloxy)benzaldehyde (IIIe). Besides
in the condensation of acetone (I) and substituted
benzaldehydes IIIf–IIIj we for the first time investigated
a heterocyclic amine, 6-aminoquinoline (IV).
The known method of the preparation of methyl-
substituted nitrogen heterocycles consisting in a reaction
of an aromatic amine with α,β-unsaturated carbonyl
compounds (methyl vinyl ketone,crotonaldehyde) or their
precursors (acetone, formaldehyde, paraformaldehyde)
(Doebner−Miller procedure) did not find extensive
application in the synthesis of azaphenanthrenes
proceeding from naphthyl- or quinolylamines due to the
low yield of the target products caused by the low activity
of the initial amines in this reaction and by prevalence
of condensations and polymerization of the initial
carbonyl compounds.
The condensation of acetone (I), 2-naphthylamine
(II), and aldehydes IIIa–IIIe was carried out by boiling
the reagents in ethanol solution in the presence of concn.
HCl. Thus we obtained in 35–50% yield previously
unknown 3-heteryl-1-methylbenzo[f]quinolines Va–Vd
and 1-methyl-3-[4-(2-fluorobenzyloxy)phenyl]benzo[f]-
quinoline (Ve). In keeping with previous studies [8, 9]
the reaction proceeds via the stage of azomethine VIa–
VIe formation that further reacts with methyl ketone by
the known mechanism [9] with the addition of the CH-
acid to the C=N bond of the azomethine, the cyclization
of the adduct VII obtained involving the C1 atom of the
naphthalene skeleton, the subsequent dehydration of
cyclic alcohol A, and the dehydrogenation of dihydro
derivative B into tolally aromatic benzo[f]quinoline Va–
Ve. In the presence of the catalyst (HCl) benzo[f]-
quinoline hydrochlorides were obtained that were
We showed in [7] that the three-component con-
densation of acetone, aromatic aldehydes, and 2-naphth-
ylamine led to the formation of 3-aryl-1-methylbenzo-
[f]quinolines, and therewith the acetone molecule
provided the methyl group to the structure of the
azaheterocycle. The variation of two other components
of the reaction mixture, aldehyde and amine, provides
an opportunity to obtain previously unknown methyl-
substituted azaphenanthrenes, potential biologically
1049

KOZLOV, GUSAK
1050
The reaction carried out under mild conditions
NH2
R
(without heating) by maintaining the reaction mixture at
room temperature for 24 h or at heating for 10–15 min at
40–60°C in the presence of a minimal quantity of the
catalyst (2–3 drops of concn. HCl per 10 mmol of
reagent) 3-pyridinecarbaldehyde (IIIb), and also its
azomethine VIb was converted into an intermediate
reaction product, aminoketone VIIb that at boiling in
ethanol in the presence of concn. HCl gave 1-methyl-3-
(3-pyridyl)-benzo[f]quinoline (Vb). Quinolinecarb-
aldehydes, substituted pyrazole and benzaldehyde IIIa,
IIIc–IIIe, and also the corresponding azomethines VIa,
VIc–VIe in the temperature range 20–60°C do not react
with acetone apparently because of the larger volume of
substituent R and sterical hindrances to the ketone
interaction with the Schiff base. This components were
involved into the reaction only at the boiling point of the
solvent (80°C), but we failed to isolate intermediate
products in this case since they were fast converted into
final reaction products Va, Vc–Ve.
X
N
O
II, IV
I
X
R
O
_
_
VIa VIe, VIIIf VIIIj
_
IIIa IIIj
O
R
R
HO
NH
NH
X
X
A
VIIb, IXf
R
R
The condensation of acetone (I) with arylaldehydes
IIIf–IIIj and 6-quinolylamine (IV) proceeding by
analogous scheme required more stringent conditions.
At heating for 1–2 h to 60°C in ethanol in the presence
of concn. HCl acetone reacted only with benzaldehyde
IIIf and 6-quinolylamine (IV) or with benzylidene-6-
quinolylamine (VIIIf), and the reaction stopped here at
the stage of aminoketone IXf formation. The cyclization
of the aminoketone into a derivative of diaza-
phenanthrene series, 1-methyl-3-phenyl-4,7-phenanthro-
line (Xf), occurred at boiling in ethanol for 6 h in the
presence of enhanced amount of the catalyst. Under these
conditions the substituted benzaldehydes IIIg–IIIj
reacted with amine IV and acetone forming the
corresponding 3-aryl-1-methyl-4,7-phenanthrolines Xg–
Xj in 22–28% yield. The prolonged heating required for
this condensation and the lower yield of the reaction
products Xg–Xj compared with Va–Ve indicated the
worse reactivity of 6-quinolylamine than that of
2-naphthylamine caused evidently by decreased
nucleophilic activity of the amino group due to the
electronegativity of the nitrogen in the quinoline ring of
amine IV. Bringing into the condensation with acetone
preliminary prepared arylmethylene-6-quinolylamines
VIIIg–VIIIj increased the yield of 4,7-phenanthrolines
Xg–Xj to 32–38%, but it is still lower than that of the
mononitrogen analogs (40–74%) [7] obtained proceeding
from 2-naphthylamine also due to the presence of the
heterocyclic nitrogen in the molecule of the Schiff bases
NH
N
X
X
_
_
Va Ve, Xf Xj
B
F
R =
(a),
(b),
N
NH
N
(c),
(d),
N
N
4-C6H4CH2O(2-FC6H4) (e), Ph (f), 4-FC6H4 (g), 4-
ClC6H4 (h), 4-BrC6H4 (i), 4-HOC6H4 (j); X = CH (II,
V–VII), N (IV, VIII–X).
converted into free bases Va–Ve by treating with
ammonium hydroxide.
To prove the involvement of azomethines in the
process of building benzoquinoline structure we
performed the condensation of amine II with aldehydes
IIIa–IIIe, and brought the obtained Schiff bases VIa–
VIe into the condensation with acetone under the above
described conditions. As a result of the reaction the
methylbenzoquinolines Va–Ve cleanly formed in 42–
56% yields.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

SYNTHESIS OF NEW METHYL DERIVATIVES OF AZA- AND DIAZAPHENANTHRENE
1051
VIIIg–VIIIj reducing the polarization and chemical
in the range 6.60–8.85 ppm. In the spectrum of benzo-
activity of the azomethine bond.
quinoline Va the proton of the NH group and the methine
proton of the pyrazoline ring gave rise respectively to
a broadened singlet at 13.30 ppm and a singlet at
8.35 ppm. In the spectrum of compound Ve the methylene
protons of the 2-fluorobenzyloxy group appear as
a singlet at 5.22 ppm.
In the IR spectra of aza- and diazaphenanthrenes Va–
Ve and Xf–Xj absorption bands are observed in the region
3070–3030 cm–1 [H(C–H)] and 875–865, 840–835, 770–
755 cm–1 [δ(C–H)]. The secondary amino group present
in the pyrazole ring of compound Va appeared as a strong
band [H(NH)] at 3200 cm–1. In the spectrum of
benzoquinoline Ve a strong band is observed in the region
1235–1230 cm–1 corresponding to the stretching
vibrations of the ether bond in the benzoxyphenyl
substituent. In the IR spectra of open-chain precursors
VIIb and IXf characteristic bands of the stretching
vibrations of carbonyl and amino group are observed
respectively at 1695–1650 and 3365–3360 cm–1
disappearing after dehydrocyclization the aminoketones
into the corresponding azaheterocycles Vb and Xf.
1
In the H NMR spectra of aminoketones VIIb and
IXf alongside the signals of methyl group protons at
3.00–3.01 ppm and of aromatic (heteroaromatic) protons
in the range 6.72–8.59 ppm signal is present of methylene
protons at 3.44–3.51 ppm and a broadened singlet from
the proton of the amino group at 4.84–4.93 ppm. The
signal of methine proton at the central carbon atom linked
to amine, aryl (heteryl), and acetyl fragments is observed
as a multiplet at 5.11–5.14 ppm.
1
The H NMR spectra of compounds Xf–Xj were
In the mass spectra of azaphenanthrenes Va–Ve and
Xf–Xj the molecular ion peaks [M]+ are the most
abundant (100%), the peaks of fragment ions [M – H]+
and [M – 2H]+ (Irel 23–44%) and peaks of low intensity
(Irel 10–14%) [M – HCN]+, [M – H – HCN]+ are
characteristic of the nitrogen heteroaromatic compounds.
interpreted considering the spectral studies on 1,3-diaryl-
4,7-phenanthrolines published in [11]. Owing to the poor
solubility of methyl derivatives Xf–Xj in organic solvents
the spectra of the compounds were registered in
CF3COOD. Therefore compared to the spectra of
benzoquinolines Va–Ve registered in DMSO-d6 in the
spectra ofmethyl-substituted 4,7-phenanthrolines Xf–Xj
all the signals suffered a downfield shift caused by the
appearance of a positive charge on the nitrogen atoms of
the phenanthroline ring due to D+ addition. The
considerable downfield shift of signals from protons H9
and H10 observed in the spectra of methylphenanthrolines
Xf–Xj as compared to the spectra of 1,3-diaryl-4,7-
phenanthrolines [11] where these protons are located
under the phenyl ring plane is evidently caused by the
anisotropic deshielding resulting from replacement of
the arylsubstituent by the methyl group.
In the mass spectra of aminoketones VIIb and IXf
the intensity of the molecular ion peak (m/z 290) is
relatively low (20–22%). The most abundant (100%) are
peaks of m/z 232 and 56 corresponding to compounds
IVb, VIIIf, and I resulting from the rupture of C–C bond
and recombination of the fragment ions with a
simultaneous disproportionation.
Electron absorption spectra of compounds Va–Ve and
Xf–Xj in the UV region (220–365 nm) have a structure
characteristic of benzo[f]quinolines and 4,7-phenanthro-
lines [8, 10]. The long-wave band (331–365 nm) is
interpreted as the Clar α-band (‘Lb according to Platt).
In the spectra of benzoquinolines Va, Vc, and Vd this
band suffered a red shift compared to the previously
investigated spectra of azaphenanthrenes [8, 10] evident-
ly because of the increased conjugation chain resulting
from the introduction of fluorophenylpyrazoline or
quinoline substituent. More short-wave bands in the
region 281–293 and 220–263 nm are p- and β-bands (‘La
and ‘Bb) respectively, and the p-band is stronger than
the β-band, which is characteristic of compounds of
angular structure: phenanthrene and its heterocyclic
analogs.
EXPERIMENTAL
IR spectra were recorded on a Fourier spectro-
'
'
photometer Nicolet Protege-460 from pellets with KBr.
Mass spectra were measured on a Finnigan MAT INCOS
50 instrument with the energy of ionizing electrons 70eV,
and on a GC-MS device HP 5890/5972 in the electron
impact mode at the energy 70eV; column HP-5MS (30
m...0.25 mm, stationary phase film 5% PLMe Silicone,
0.25 μm); vaporizer temperature 250°C. UV spectra of
compounds solutions in ethanol (c 10–4 mol l−1) were
taken on a spectrophotometer Specord UV-Vis. NMR
spectra were registered on spectrometers BrukerAC-500
(500 MHz) and Tesla BS-567 (100 MHz) in DMSO-d6
1
In the H NMR spectra of compounds Va–Ve the
protons of the methyl group appear as a singlet at 3.00–
3.13 ppm, signals of the aromatic protons are observed
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

KOZLOV, GUSAK
1052
and CF3COOD, internal reference TMS. Melting points
of compounds were measured on a Koeffler heating
block.
1-Methyl-3-[4-(2-fluorobenzyloxy)phenyl]benzo-
[f]quinoline (Ve). Yield 45% (a), 46% (b), mp 135–
136°C. UV spectrum, λmax, nm (log ε): 222 (4.60), 261
1
(4.58), 290 (4.83), 339 (4.02), 360 (3.91). H NMR
Aryl(heteryl)methylene-2-naphthylamines VIa–VIe
and arylmethylene-6-quinolylamines VIIIf–VIIIj were
prepared by procedure [12].
spectrum, δ, ppm: 3.13 s (3H, Me), 5.22 s (2H, ΟCH2),
7.10 d, 7.20 m, 7.60 m, 7.70 s, 7.96 m, 8.15 d, 8.78 m
3
(15Harom, J 7.4 Hz). Found, %: N 3.28. C27H20FNΟ.
3-Aryl(heteryl)-1-methylbenzo[f]quinolines Va–
Ve. a. A mixture of 10 mmol of acetone (I), 5 mmol of
2-naphthylamine (II), 5 mmol of an appropriate aldehyde
IIIa–IIIe, 20 ml of ethanol, and 0.5 ml of concn. HCl
was boiled for 2 h. On cooling the separated precipitate
was filtered off, neutralized with 25% aqueous NH4OH,
washed with water, and recrystallized from a mixture
ethanol–benzene, 3:1.
Calculated, %: N 3.56.
4-(3-Pyridyl)-4-(2-naphthylamino)butan-2-one
(VIIb). A solution of 10 mmol of acetone (I), 5 mmol of
2-naphthylamine (II), and 5 mmol of 3-pyridinecarb-
aldehyde (IIIb) (a) or 10 mmol of ketone I and 5 mmol
of N-(pyridin-3-ylmethylene)-2-naphthalenamine (VIb)
(b) in 20 ml of ethanol with 2 drops of concn. HCl was
maintained for 24 h at room temperature or was heated
on a water bath at 40–60°C for 15 min. The separated
precipitate was filtered off, treated with 25% water
solution of NH4OH, washed with water, and recrystal-
lized from ethanol. Yield 44% (a) and 51% (b), mp 164–
b. A solution of 10 mmol of acetone (I), 5 mmol of
azomethine VIa–VIe, 20 ml of ethanol, and 0.5 ml of
concn. HCl was boiled for 1.5 h. Reaction products Va–
Ve were isolated as described above.
1
165°C. H NMR spectrum, δ, ppm: 3.01 s (3H, Me),
1-Methyl-3-[3-(4-fluorophenyl)-1H-pyrazol-4-yl]-
benzo[f]quinoline (Va). Yield 50% (a), 56% (b), mp
245–246°C. UV spectrum, λmax, nm (log ε): 225 (4.61),
263 (4.59), 282 (4.74), 336 (3.70), 365 (3.80). 1H NMR
spectrum, δ, ppm: 3.05 s (3H, Me), 6.60–7.98 m, 8.80 m
(11Harom), 8.35 s (1H, =CH–NH), 13.30 br.s (1H, =CH–
NH). Found, %: N 11.73. C23H16FN3. Calculated, %:
N 11.90.
3.44 m (2H, CH2), 4.93 br.s (1H, NH), 5.14 m (1H, CH),
6.72–7.98 m, 8.65 s (11Harom, heteroarom). Found, %: C 78.54;
H 5.93; N 9.48. C19H18N2Ο. Calculated, %: C 78.62;
H 6.21; N 9.66.
4-Phenyl-4-(6-quinolylamino)butan-2-one (IXa).
A solution of 10 mmol of acetone (I), 5 mmol of
benzaldehyde (IIIf), and 5 mmol of 6-quinolylamine (IV)
(a) or 10 mmol of ketone I and 5 mmol of N-(benzylid-
ene)-6-quinolinamine (VIIIf) (b) in 20 ml of ethanol with
5 drops of concn. HCl was heated on a water bath at
60°C for 2 h. The reaction product was isolated in the
same way as described for aminoketone VIIb. Yield 40%
(a) and 43% (b), mp 177–178°C. 1H NMR spectrum, δ,
ppm: 3.00 s (3H, Me), 3.51 m (2H, CH2), 4.84 br.s
(1H, NH), 5.11 m (1H, CH), 6.76–7.80 m, 8.59 d.d
(11Harom, heteroarom, 3J 4.8, 4J 2.4 Hz). Found, %:C 78.43;
H 5.88; N 9.51. C19H18N2Ο. Calculated, %: C 78.62;
H 6.21; N 9.66.
1-Methyl-3-(3-pyridyl)benzo[f]quinoline (Vb).
Yield 43% (a), 49% (b), mp 183–184°C. UV spectrum,
λ
max, nm (log ε): 220 (4.58), 259 (4.53), 281 (4.80),
1
331 (3.98), 358 (3.86). H NMR spectrum, δ, ppm:
3.00 s (3H, Me), 7.01–8.19 m, 8.24 s, 8.74 s, 8.81 m
(11Harom, heteroarom). Found, %: C 84.19; H 5.03; N 10.40.
C19H14N2. Calculated, %: C 84.44; H 5.19; N 10.37.
1-Methyl-3-(2-quinolyl)benzo[f]quinoline (Vc).
Yield 38% (a), 44% (b), mp 187–188°C. UV spectrum,
λ
max, nm (log ε): 226 (4.51), 259 (4.49), 291 (4.78), 340
3-Aryl-1-methyl-4,7-phenanthrolines Xf–Xj. a.
A mixture of 10 mmol of acetone (I), 5 mmol of an
appropriate aldehyde IIIf–IIIj, 5 mmol of 6-quinolyl-
amine (IV), 20 ml of ethanol, and 1 ml of concn. HCl
was boiled for 7 h. On cooling the separated precipitate
was filtered off, neutralized with 25% aqueous NH4OH,
washed with water, and recrystallized from a mixture
ethanol–benzene, 2:1.
1
(3.88), 359 (3.81). H NMR spectrum, δ, ppm: 3.04 s
(3H, Me), 7.11–8.63 m, 8.85 m (13Harom, heteroarom).
Found, %: C 86.02; H 4.81; N 8.64. C23H16N2.
Calculated, %: C 86.25; H 5.00; N 8.75.
1-Methyl-3-(6-quinolyl)benzo[f]quinoline (Vd).
Yield 35% (a), 40% (b), mp 170–171°C. UV spectrum,
λ
max, nm (log ε): 223 (4.52), 255 (4.41), 286 (4.73),
1
339 (3.91), 357 (3.68). H NMR spectrum, δ, ppm:
3.02 s (3H, Me), 7.00–8.22 m, 8.64 m, 8.80 m
(13Harom, heteroarom). Found, %: C 86.11; H 4.76; N 8.59.
C23H16N2. Calculated, %: C 86.25; H 5.00; N 8.75.
b. A solution of 10 mmol of acetone (I), 5 mmol of
azomethine VIIIf–VIIIj, 20 ml of ethanol, and 1 ml of
concn. HCl was boiled for 7 h. Reaction products Xf–Xj
were isolated as described above.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

SYNTHESIS OF NEW METHYL DERIVATIVES OF AZA- AND DIAZAPHENANTHRENE
1053
3
1-Methyl-3-phenyl-4,7-phenanthroline (Xf). Yield
28% (a), 38% (b), mp 170–171°C. UV spectrum, λmax
3.66 s (3H, Me), 7.38 d, 8.18 d (4Harom, J 7.6 Hz),
8.60 m (2H, H2, H9), 8.92 d, 9.02 d (2H, H5,6, 3J 9.1 Hz),
9.44 d (1H, H8, 3J 4.4 Hz), 10.40 d (1H, H10, 3J 8.1 Hz).
Found, %: C 79.57; H 4.81; N 9.63. C19H14N2Ο.
Calculated, %: C 79.72; H 4.90; N 9.79.
,
nm (log ε): 223 (4.21), 253 (4.42), 283 (4.60), 337 (3.82),
350 (3.77). 1H NMR spectrum, δ, ppm: 3.63 s (3H, Me),
7.56 m, 7.89 m (5H, Ph), 8.62 m (2H, H2, H9) 8.94 d,
9.03 d (2H, H5,6, 3J 8.9 Hz), 9.45 d (1H, H8, 3J 4.9 Hz),
10.40 d (1H, H10, 3J 8.0 Hz). Found, %: C 84.32; H 4.97;
N 10.21. C19H14N2. Calculated, %: C 84.44; H 5.19;
N 10.37.
Cyclization of aminoketones VIIb and IXf.
Amixture of 2.5 mmol of aminoketone VIIb or IXf, 0.5–
1.0 ml of concn. HCl, and 20 ml of ethanol was boiled
for 2 h for compound VIIb or 6 h for aminoketone IXf.
The precipitate was worked up as described for
compounds Vb and Xf. Yield of benzo-[f]quinoline Vb
52%, 4,7-phenanthroline Xf 34%.
1-Methyl-3-(4-fluorophenyl)-4,7-phenanthroline
(Xg). Yield 24% (a), (34%) (b), mp 181–182°C. UV
spectrum, λmax, nm (log ε): 225 (4.33), 253 (4.56), 286
(4.68), 338 (3.46), 355 (3.37). 1H NMR spectrum, δ, ppm:
3.65 s (3H, Me), 7.52 m, 8.24 m (4Harom), 8.63 m (2H,
H2, H9) 8.98 d, 9.10 d (2H, H5,6, 3J 9.0 Hz), 9.50 d (1H,
H8, 3J 4.8 Hz), 10.44 d (1H, H10, 3J 8.1 Hz). Found, %:
N 9.54. C19H13FN2. Calculated, %: N 9.72.
The study was carried out under a financial support
of Belorus’ Republic Foundation for Fundamental
Research (grant X07-007).
REFERENCES
1-Methyl-3-(4-chlorophenyl)-4,7-phenanthroline
(Xh). Yield 27% (a), 37% (b), mp 216–217°C. UV
spectrum, λmax, nm (log ε): 227 (4.24), 255 (4.47), 288
(4.62), 339 (3.45), 356 (3.29). 1H NMR spectrum, δ, ppm:
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Akad. Nauk BSSR, Ser. Khim. Nauk, 1969, p. 796.
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3
3.65 s (3H, Me), 7.83 d, 8.11 d (4Harom, J 7.9 Hz),
3
4
8.62 d.d (1H, H9, J 7.8, J 4.3 Hz), 8.65 s (1H, H2),
8.98 d, 9.09 d (2H, H5,6, J 8.8 Hz), 9.48 d (1H, H8,
3J 4.3 Hz), 10.43 d (1H, H10, J 7.8 Hz). Found, %:
3
3
C 74.61; H 4.12; Cl 11.41; N 9.04. C19H13ClN2.
Calculated, %: C 74.88; H 4.27; Cl 11.66; N 9.20.
3-(4-Bromophenyl)-1-methyl-4,7-phenanthroline
(Xi). Yield 22% (a), 33% (b), mp 183–184°C. UV spec-
trum, λmax, nm (log ε): 230 (4.28), 256 (4.45), 290 (4.64),
1
339 (3.95), 362 (3.89). H NMR spectrum, δ, ppm:
3
3.63 s (3H, Me), 7.79 d, 8.14 d (4Harom, J 7.8 Hz),
3
4
8.61 d.d (1H, H9, J 8.0, J 4.1 Hz), 8.64 s (1H, H2),
8.94 d, 9.05 d (2H, H5,6, J 8.9 Hz), 9.49 d (1H, H8,
3J 4.1 Hz), 10.42 d (1H, H10, J 8.0 Hz). Found, %:
3
3
C 65.19; H 3.76; Br 22.63; N 7.79. C19H13BrN2.
Calculated, %: C 65.33; H 3.82; Br 22.92; N 8.02.
3-(4-Hydroxyphenyl)-1-methyl-4,7-phenanthro-
line (Xj). Yield 23% (a), 32% (b), mp 312–313°C. UV
spectrum, λmax, nm (log ε): 236 (4.55), 255 (4.563), 290
(4.69), 320 (4.39), 360 (3.76). 1H NMR spectrum, δ, ppm:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008