Peri-Amino ketones of the acenaphthene and acenaphthylene series

Article abstract of DOI:10.1134/S1070428010060114

peri-Amino-substituted methyl and aryl ketones of the acenaphthene and acenaphthylene series were subjected to protonation and acylation at the nitrogen atom, dehydrogenation, and reactions with aldehydes. Conformations of substituents in the peri positio

Full text of DOI:10.1134/S1070428010060114

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 6, pp. 844–854. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © V.V. Mezheritskii, A.N. Antonov, A.A. Milov, K.A. Lysenko, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 6,
pp. 850–859.
peri-Amino Ketones of the Acenaphthene
and Acenaphthylene Series
V. V. Mezheritskiia, A. N. Antonova, A. A. Milova, and K. A. Lysenkob
a Institute of Physical and Organic Chemistry, Southern Federal University,
pr. Stachki 194/2, Rostov-on-Don, 344090 Russia
e-mail: mezher@ipoc.rsu.ru
b Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, Moscow, Russia
Received February 18, 2008
Abstract—peri-Amino-substituted methyl and aryl ketones of the acenaphthene and acenaphthylene series
were subjected to protonation and acylation at the nitrogen atom, dehydrogenation, and reactions with
aldehydes. Conformations of substituents in the peri positions and probability for their participation in intra-
and intermolecular transformations were determined on the basis of spectral data and quantum-chemical
calculations.
DOI: 10.1134/S1070428010060114
peri-Amino-substituted alkyl and aryl naphthyl
ketones with a free amino group were not isolated, for
they readily undergo heterocyclization in statu nascendi
with formation of benzo[cd]indole derivatives [1–3].
By contrast, peri-amino ketones of the acenaphthene
series are relatively stable compounds due to “con-
tracting” effect of the ethylene bridge, which makes
the opposite peri positions in the naphthalene core
more distant from each other and thus increases the
distance between the substituents constituting the peri-
amino carbonyl fragment. First representatives of ace-
naphthene peri-amino ketones were synthesized ac-
cording to Scheme 1 as early as 1966 [4, 5]; however,
their properties and transformations have not been
studied so far.
group in intra- and intermolecular transformations,
and performed dehydrogenation of the ethylene bridge
(Scheme 2). As substrates we used previously synthe-
sized methyl and phenyl acenaphthenyl ketones IVa
and IVb [4, 5] and 5-amino-6-(p-methoxybenzoyl)-
naphthalene (IVc) obtained in the present work.
We traced variations of some spectral parameters of
intermediate compounds during the transformation of
acenaphthene (I) into previously unknown peri-amino
p-methoxyphenyl ketone IVc. In going from acenaph-
thene (I) to 5-(p-methoxybenzoyl)acenaphthene (IIc)
the 6-H signal in the 1H NMR spectrum shifts down-
field from δ 7.58 to 7.98 ppm due to magnetically
anisotropic effect of the carbonyl group in the peri
position. The position of the carbonyl stretching vibra-
tion band in the IR spectrum of ketone IIc (1635 cm–1;
mineral oil) suggests strong conjugation of the carbon-
yl group with the aromatic fragments in the crystalline
In the present work we examined the IR and
1H NMR spectra of methyl and aryl ketones IVa–IVc,
estimated the probability for participation of the amino
Scheme 1.
O
R
O
R
O2N
NH2 COR
6
5
7
8
4
3
1
2
I
IIa–IIc
IIIa–IIIc
IVa–IVc
R = Me (a), Ph (b), 4-MeOC6H4 (c).
844

peri-AMINO KETONES OF THE ACENAPHTHENE AND ACENAPHTHYLENE SERIES
845
Scheme 2.
HO
OH
H
R
R
NH3 COR
H2N
N
HN
N
R
H
R
ClO4
ClO4
ClO4
ClO4
Va–Vc
A
B
VIa–VIc
VIIb, VIIc
O
O
R
O
Me
O
Me
NH2 COR
Me
NH
VIII
O
Me
NH
N
IVa–IVc
IX
C
O
OH
Me
Me
Me
Me
NH
N
ClO4
ClO4
X
D
R = Me (a), Ph (b), 4-MeOC6H4 (c).
state. The carbonyl stretching vibration band in the IR
spectrum of peri-nitro ketone IIIc is located at a higher
frequency (1650 cm–1).
to the acenaphthene core and (2) partial conjugation
between the naphthalene π-electron system, on the one
hand, and the carbonyl group or p electrons of the
amino group, on the other, is conserved.
The geometric parameters of compounds IVa–IVc
were calculated in terms of the density functional
theory with B3LYP/6-31G** basis set using Gaussian
03 software; some results are presented in Table 1. It is
seen that the plane of the carbonyl group in molecules
IVa–IVc is turned through an angle of 26–43° relative
to the acenaphthene core: the torsion angles H1NC6C12
and H2NC6C7 are 37–41 and 12–14°, respectively
(Table 1). The configuration of bonds at the nitrogen
atom indicates that the lone electron pair on the nitro-
gen does not lie in the naphthalene ring plane. The
N–H1 ···O angle in molecules IVa–IVc ranges from
147 to 149°. These data show that (1) the seven-
membered H-chelate ring in isolated molecule of each
amino ketone IVa–IVc is neither planar nor coplanar
The conclusions drawn on the basis of the calcula-
tion results were confirmed experimentally. The
1H NMR spectra contained an upfield broadened two-
proton singlet at δ 4.25–4.51 ppm from the NH2 group,
indicating the absence of intramolecular hydrogen
bond, while conjugation of the peri-substituents with
the naphthalene ring induced downfield (δ 7.41–
7.78 ppm) and upfield (δ 6.83–6.86 ppm) displacement
of signals from protons in the ortho positions with
respect to the above substituents relative to the signals
from protons in positions 3 and 8.
The chemical shifts of the ortho protons in the
1H NMR spectra do not correlate with the calculated
electron densities (Table 1). A probable reason is sol-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

MEZHERITSKII et al.
846
(a)
(b)
O
C14
H1
H2
N
C13
C5
C6
C12
H1
O
C7
C8
H2
C14
C13
C4
C3
OA
N
C6
C10
C5
C12
C7
C8
C9
C4
C3
C11
C10
C9
C1
C11
C2
C2
C1
Fig. 1. (a) Intra- and (b) intermolecular hydrogen bonds in the crystalline structure of compound IVa.
vent effect which changes configuration of the sub-
stituents. This assumption is indirectly supported by
considerable difference between the experimental and
calculated torsion angles H1NC6C12 and H2NC6C7
(Table 1).
considerably differ from the corresponding calculated
values, which may be due to specificity of crystal
packing. Figure 1 shows a fragment of crystal packing
of compound IVa. It is seen that both hydrogen
atoms in the amino group are involved in intra- and
intermolecular interactions with the carbonyl oxygen
atom. Judging by the NH···O distances (2.076 and
2.247 Å, respectively), these interactions may be
regarded as weak intra- and intermolecular hydrogen
bonds.
Comparison of the calculation results and experi-
mental NMR data allowed us to draw one more im-
portant conclusion: the formation of strong intramolec-
ular hydrogen bond requires that the seven-membered
H-chelate ring be planar and coplanar to the naphtha-
lene core and that the angle N–H1 ···O be close to
straight. Contracting effect of the ethylene bridge leads
to in-plane distortion of the naphthalene skeleton, so
that the distance between the peri-carbon atoms in
positions 5 and 6 increases to 2.620–2.657 Å (Table 1),
which is considerably longer than the corresponding
interatomic distance in naphthalene (2.450 Å). In addi-
tion, the bonds between C5 and C6 and the correspond-
ing substituents in compounds IVa–IVc deviate in
opposite directions. As a result, the nitrogen atom
becomes remote from the sp2-hybridized carbonyl
carbon atom by a considerable distance (>3 Å), which
(in combination with noncoplanar conformations of the
peri substituent) provides the possibility for rotation or
at least rocking oscillation of the amino group. Pre-
sumably, such rotation is responsible for averaging of
signals from two magnetically nonequivalent protons
in the amino group, observed in the 1H NMR spectrum
as signal broadening.
Treatment of peri-amino ketones IVa–IVc with per-
chloric acid in acetic acid or methanol at room tem-
perature resulted in the formation of ammonium per-
chlorates Va–Vc which did not undergo heterocycliza-
tion (Scheme 2). Optimization of the geometric par-
ameters of cation Va at the B3LYP/6-31G** level of
theory with no account taken of counterion and solvent
effects showed that one hydrogen atom in the protonat-
ed amino group participates in the formation of planar
seven-membered H-chelate ring which is coplanar to
the acenaphthene core (the torsion angles OC13C5C12
and H1NC6C12 are equal to zero (Table 2).
Replacement of the methyl group by aryl (com-
pounds Vb and Vc) leads to appreciable change in the
conformations of the ammonium and carbonyl substit-
uents in the peri positions. The above torsion angles in
cations Vb and Vc are 21–23 and 19–20°, respectively,
indicating some deviation of the seven-membered
H-chelate ring from planar structure (Table 2). The
NH1O angle (162–165°) is much closer to the straight
angle (as compared to amino precursors IV; Table 1),
Table 1 also contains the X-ray diffraction data for
methyl ketone IVa; some experimental parameters
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

peri-AMINO KETONES OF THE ACENAPHTHENE AND ACENAPHTHYLENE SERIES
847
and fairly similar distances N–H1 and H1···O suggest
that the proton involved in intramolecular hydrogen
bond is located almost in the middle between two
electronegative atoms. According to the calculations,
the barrier to proton transfer to the carbonyl oxygen
atom in system Vc is equal to zero (cf. the distances
O–H and N–H in Va and Vb and Vc; Table 2).
and IX is that the peri substituents in the latter could
be conjugated with each other through the aromatic
bond system.
According to the calculations, both acenaphthene
and acenaphthylene ketones VIII and IX are charac-
terized by slightly distorted (from planar structure)
seven-membered H-chelate ring where the NH hydro-
gen atom and the carbonyl oxygen atom deviate in-
significantly toward the same side of the naphthalene
ring plane and toward each other (see the correspond-
ing torsion angles in Table 2).
The calculated parameters correspond to a strong
intramolecular hydrogen bond. The formation of
bridging hydrogen bonds is also confirmed by the AIM
and NBO analyses. On the other hand, if the calculated
conformation of Va–Vc were present in solution, the
1H NMR spectra would contain a very downfield
signal from H1 (at about δ 15–16 ppm) and less down-
field signal from H2 and H3 (at δ ~10 ppm). In the real
1H NMR spectra of Va and Vc in deuterated nitro-
benzene we observed only a very diffuse three-proton
signal from the H3N+ group at δ 10.0–10.3 ppm, i.e.,
these protons are degenerate. The observed pattern
may be rationalized in terms of reversible exchange
interaction of a proton in the H3N+ group with the
solvent and rotation of the NH2 group thus released.
Protonation of the amino group induces more than
1-ppm downfield shift of signal from proton in the
ortho position with respect to the ammonium substit-
uent, as compared to analogous signal of peri-amino
ketones IVa–IVc, which correlates with the calculated
charge on the corresponding carbon atom in Va and Vc
(Table 2).
The calculated conformations of the peri substit-
uents and the H···O distances that are shorter than the
Table 1. Angles (deg) and interatomic distances (Å) in struc-
tures IVa–IVc, calculated at the DFT B3LYP/6-31G** level
of theory
H1
O
H2
13
N
R
6
5
12
10
7
8
4
3
9
11
1
2
Angle or
bond
NC6C12
C6C12C5
C12C5C13
C9C10C11
OC13C5C12 026.1 (54.07)
H1NC6C12 037.7 (47.35)
R = Ph R = p-MeOC6H4
R = Me (IVa)a
(IVb)
122.0
129.1
124.8
111.0
040.3
040.6
012.2
146.9
1.859
3.544
3.037
2.607
2.332
2.767
(IVc)
121.9
129.0
124.7
111.1
042.6
040.4
012.3
147.1
1.863
3.548
3.027
2.606
2.332
2.772
122.6 (121.63)
129.7 (128.94)
125.9 (123.94)
110.6 (111.61)
The position of the carbonyl stretching vibration
band (~1630 cm–1) in the IR spectrum of acetylace-
naphthenylammonium salt Va (mineral oil) suggests
formation of fairly strong intramolecular hydrogen
bond in the condensed phase. Stretching vibrations of
the H3N+ group give rise to two broad bands centered
at 3550 and 3180 cm–1 and a “plateau” at ~2700 cm–1.
The latter is typical of peri-substituted ketones with
strong intramolecular hydrogen bond [6].
H2NC6C7
N–H1···O 149.3 (144.4)
014.1 0(8.32)
H1···O
H2···O
N···C13
C6 ···C5
C9 ···C11
N···O
1.786 (2.076)
3.477 (3.625)
3.119 (2.975)
2.623 (2.588)
2.327 (2.325)
2.710 (2.867)
The effect of an electron-withdrawing substituent
on the nitrogen atom on the conformation of the peri-
amino carbonyl fragment was studied by analyzing
spectral parameters and calculated data for peri-acetyl-
amino-substituted methyl ketone VIII. This compound
was synthesized by treatment of a suspension of peri-
amino ketone IVa in water with acetic anhydride. Ana-
logous analysis was performed with acenaphthylene
methyl ketone IX which was prepared by dehydro-
genation of the ethylene bridge in VIII by the action of
tetrachloro-1,4-benzoquinone (chloranil). The differ-
ence in the electronic structures of compounds VIII
Calculated charges on the naphthalene carbon
atoms
Atom no.
3
4
7
8
–0.16
–0.12
–0.11
–0.16
–0.16
–0.11
–0.11
–0.16
–0.16
–0.11
–0.11
–0.16
a
Selected experimental X-ray diffraction data are given in paren-
theses.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

MEZHERITSKII et al.
848
Table 2. Angles (deg), distances (Å), and charges on atoms in cations Va–Vc and N-acetyl-substituted acenaphthene and
acenaphthylene derivatives VIII and IX, calculated at the B3LYP/6-31G** level of theory
Me
Me
H2
H···O
H···O
H···O
14
14
R
Me
Me
N
N
N
13
5
13
5
13
H1
O
O
6
6
6
5
12
10
12
10
12
10
7
4
3
7
8
4
3
7
8
4
3
8
9
11
9
11
9
11
1
2
1
2
2
1
Va–Vc
VIII
IX
Angle or bond
Va (R = Me) Vb (R = Ph) Vc (R = p-MeOC6H4)
VIIIa
IX, [IX]·H2Oa
NC6C12
C6C12C5
C12C5C13
C9C10C11
NH1O
OC13C5C12
H1NC6C12
H2NC6C7
C14NC6C7
H3NC6C7
N–H1
121.6
132.5
126.5
110.2
171.7
000.0
000.0
060.0
120.7
131.9
125.5
110.6
164.8
021.5
019.4
082.2
120.5
131.2
126.4
110.5
161.9
022.8
020.4
087.3
120.3 (120.9)
132.2 (130.2)
127.9 (124.5)
107.7 (111.1)
164.1 (147.4)
15.2 (31.1)
120.4 (124.5)
131.1 (130.9)
127.4 (123.8)
110.3 (109.4)
159.4 (58.7)
023.1 (40.8)
0022.0 (138.4)
09.1 (41.5)
07.3 (45.8)
018.6 (130.2)
060.0
1.151
1.327
2.472
3.003
3.003
3.173
2.648
2.324
038.2
1.148
1.337
2.463
2.877
3.095
3.099
2.634
2.328
032.0
1.409
1.091
2.469
2.824
3.138
3.092
2.631
2.326
1.025 (0.913)
1.624 (1.895)
2.625 (2.709)
1.021 (0.826)
1.675 (3.185)
2.655 (2.845)
H1···O
N···O
H2···O
H3···O
N···C13
C6 ···C5
C9 ···C11
3.200 (3.062)
2.681 (2.614)
2.300 (2.329)
3.139 (3.130)
2.646 (2.614)
2.323 (2.308)
Atom no.
Calculated charges on the naphthalene carbon atomsb
3
4
7
8
–0.14
–0.12
–0.08
–0.15
–0.15
–0.12
–0.08
–0.15
–0.15
–0.12
–0.08
–0.15
–0.16
–0.12
–0.09
–0.17
–0.15
–0.13
–0.11
–0.16
a
X-Ray diffraction data are given in parentheses.
The charge on the H1 atom is +0.43 for all cations.
b
sum of the corresponding van der Waals radii (Table 2)
indicate formation of fairly strong intramolecular hy-
drogen bond, which does not contradict the experimen-
tal spectral parameters. In the 1H NMR spectra of VIII
and IX in DMSO-d6, the proton involved in intra-
molecular hydrogen bond resonates at δ 9.68 and
10.10 ppm, respectively. The corresponding signal of
acenaphthylene derivative IX in chloroform-d appears
in a weaker field, at δ 10.70 ppm. In the IR spectra of
VIII and IX (mineral oil) stretching vibrations of the
N–H bond give rise to absorption band at 3275 cm–1.
Some structural parameters of N-acylamino ketones
VIII and IX, determined by X-ray analysis, differ con-
siderably from those calculated by quantum-chemical
method (Table 2; Figs. 2, 3). Insofar as the calculations
were performed for isolated molecule in the gas phase,
the observed differences may be assigned to specificity
of crystal packing, the more so as compound IX crys-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

peri-AMINO KETONES OF THE ACENAPHTHENE AND ACENAPHTHYLENE SERIES
849
H2W
O1W
H15B
H15B
H15A
C15
H15C
H1N
H1W
H15C
H1N
C15
O2
H16A
C16
H15A
C14
H16A
C16
C14
H16C
H16C
O2
O1
H7
N
C13
C13
N
O1
C6
H7
H16B
H4
H16B
C12
C6
C5
C7
C8
C12
C5
C4
C7
C8
H8
C4
C3
H4
H8
C10
C10
C3
C9
C9
C11
H2B
H2A
H3
C1
H1A
H1B
C11
C2
H3
H1
C2
C1
H2
Fig. 2. Structure of the molecule of N-(6-acetylacenaphthen-5-
yl)acetamide (VIII) according to the X-ray diffraction data.
Fig. 3. Structure of the molecule of N-(6-acetylacenaphthylen-
5-yl)acetamide (IX) according to the X-ray diffraction data.
tallizes as monohydrate. According to the X-ray dif-
fraction data (unlike the calculation results), no planar
seven-membered H-chelate ring is formed in the crys-
talline structure of peri-acetylamino-substituted ace-
naphthenyl methyl ketone VIII (cf. the corresponding
torsion angles in Table 2). Although the carbonyl
oxygen atom and NH hydrogen atom are located at the
same side of the naphthalene ring plane, the distances
between these atoms and between the nitrogen and
oxygen atoms are considerably longer than the cal-
culated ones, and these distances rule out formation of
a strong intramolecular hydrogen bond in crystal. On
the other hand, fairly strong intramolecular hydrogen
bond exists in solution (see above). Comparison of the
calculated and experimental (X-ray diffraction) data
for compound IX seems to be inappropriate, for ketone
IX crystallizes together with a water molecule. In this
case, one hydrogen atom in water molecule is involved
Scheme 3.
Ar
N
R
O
Me
O
Me
R
O
NH
Ar
N
ArCHO, OH–
OH–
ArCHO
IVa
IVa, VIII
XIIa, XIIb
XI
Ar
N
Ac
O
Me
Ac
O
Ar
Ac
O
NH
NH
ArCHO, OH–
OH–
ArCHO
E
IX
XIII
E
R = H (a), Ac (b), Ar = 4-MeOC6H4.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

MEZHERITSKII et al.
850
Table 3. Crystallographic and structure refinement parameters for compounds IVa, VIII, and IX
Parameter
IVa
VIII
IX
Formula
C14H13NO
211.25
120
C16H15NO2
253.29
120
C16H14NO2.5
260.28
120
Molecular weight
Temperature, K
Crystal system
Space group
Z(Z′)
Orthorhombic
Pbca
Triclinic
P-1
Orthorhombic
Pbca
8(1)
2(1)
8(1)
a, Å
13.5853(12)
8.7637(8)
18.1318(16)
90
6.3447(5)
8.8113(7)
12.0186(10)
100.462(2)
104.987(2)
103.306(2)
610.49(9)
1.378
12.5798(11)
9.6502(9)
21.3532(19)
90
b, Å
c, Å
α, deg
β, deg
90
90
γ, deg
V, Å3
90
90
2158.7(3)
1.300
2592.2(4)
1.334
d
calc, g cm–3
μ, cm–1
0.82
0.91
0.91
F(000)
896
268
1096
θ
max, deg
28.00
26.00
28.99
Total number of reflections
17049
0.0841
2573
5095
25202
Rint
0.0516
2358
0.0674
3436
Number of independent reflections
Number of reflections with I>2σ(I)
Number of refined parameters
R1
1898
2385
0154
0.0418
0178
0188
0.0406
0.1204
1.0120
0.202/–0.269
0.0530
0.1060
1.0110
0.777/–0.254
wR2
0.0976
Goodness of fit
Residual electron density dmax/dmin, e A–3
1.0130
0.216/–0.159
in weak (dHO–H···O=C = 2.057 Å) hydrogen bond with
the carbonyl oxygen atom, as if it is wedged between
the peri-substituents thus making the latter more dis-
tant from each other and considerably changing the
conformation of the entire peri-acylamino ketone frag-
ment. The result is that the distance between the NH
hydrogen atom and carbonyl oxygen atom reaches
3.185 Å, which excludes formation of hydrogen bond
although these atoms appear at the same side of the
naphthalene ring plane.
we failed to isolate 2-methyl-substituted analog VIIa
because of fast tarring. By treatment of N-acetylamino
ketone VIII with perchloric acid we obtained O-pro-
tonated perchlorate X which, unlike protonated peri-
amino ketones V, did not undergo heterocyclization to
structure D on heating (Scheme 2). Our attempts to
effect dehydrogenation of free bases VII with tetra-
chloro-1,4-benzoquinone or acid-catalyzed hetero-
cyclization of acenaphthylene derivative IX with a view
to obtain a new 14π-electron heterocyclic system C
were unsuccessful. In all cases, unchanged initial com-
pounds were recovered from the reaction mixtures.
Heating of amino ketones IV with perchloric acid
or of ammonium perchlorates V in acetic acid lead to
their heterocyclization with formation of acenaphtho-
[5,6-bc]pyrrolium salts VI. A probable heterocycliza-
tion path is shown in Scheme 2: IV→V→A→B→
VI. Deprotonation of 2-aryl-substituted salts VI gave
the corresponding free bases VIIb and VIIc, whereas
By heating peri-amino methyl ketone IVa with
p-methoxybenzaldehyde in ethanol we obtained the
corresponding Schiff base XI which underwent base-
catalyzed intramolecular ring closure with formation of
acenaphthoazepinone XIIa (Scheme 3). Compound
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

peri-AMINO KETONES OF THE ACENAPHTHENE AND ACENAPHTHYLENE SERIES
851
3
4
XIIa, as well as its N-acetyl derivative XIIb, can be
synthesized in one step by reaction of peri-amino
ketones IVa and VIII with p-methoxybenzaldehyde in
the presence of alkali. Under analogous conditions,
acenaphthylene peri-acetylamino ketone IX gave rise
to trans-chalcone XIII instead of expected hetero-
cyclization product E, and no heterocyclization of XIII
occurred even on prolonged heating.
OCH3), 6.96 d.d (2H, 3′-H, 5′-H, J = 9.11, J =
2.19 Hz), 7.31 br.d (1H, 3-H, J3,4 = 7.70 Hz), 7.37 br.d
(1H, 8-H, J8,7 = 6.91 Hz), 7.51 t (1H, 7-H, J7,8 = 6.91,
J7,6 = 6.90 Hz), 7.66 d (1H, 6-H, J6,7 = 6.91 Hz),
7.87 d.d (2H, 2′-H, 6′-H, J = 9.11, J = 2.19 Hz),
7.98 d (1H, 4-H, J4,3 = 7.70 Hz).
3
4
4-Methoxyphenyl(6-nitroacenaphthen-5-yl)-
methanone (IIIc). Compound IIc, 4.5 g (15.6 mmol),
was dissolved in 6 ml of tetrachloroethane, 2.3 ml of
nitric acid (d = 1.45 g/cm3) was slowly added dropwise
under stirring, and the mixture was stirred for 40 min,
washed with water to remove excess nitric acid, and
subjected to steam distillation to remove tetrachloro-
ethane. The product was recrystallized from acetic
acid. Yield 4.15 g (80%), mp 226–227°C. IR spectrum,
EXPERIMENTAL
The IR spectra were recorded on a Specord 75IR
spectrometer from samples dispersed in mineral oil.
1
The H NMR spectra were measured on Bruker DPX-
250 (250 MHz) and Varian Unity-300 (300 MHz)
spectrometers using hexamethyldisiloxane as internal
reference (for atom numbering, see Scheme 1). The
products were purified by chromatography on alumi-
num oxide using chloroform as eluent. The X-ray dif-
fraction data for compounds IVa, VIII, and IX were
acquired on a Smart Apex II CCD diffractometer
(MoKα irradiation, graphite monochromator, ω-scan-
ning) at the X-Ray Analysis Center, Chemistry and
Materials Science Department, Russian Academy of
Sciences (Nesmeyanov Institute of Organometallic
Compounds, Russian Academy of Sciences). The
structures were solved by the direct method and were
refined by the least-squares procedure with respect to
F2hkl in full-matrix anisotropic approximation. Hydro-
gen atoms in all structures were localized by the
Fourier difference syntheses of electron density. The
principal crystallographic and refinement parameters
are listed in Table 3. All calculations were performed
using SHELXTL PLUS software package [7]. Quan-
tum-chemical calculations in terms of the density func-
tional theory (B3LYP/6-31G** and B3LYP/6-311-G**)
with account taken of zero point vibration energy were
performed using Gaussian 03 software [8].
ν, cm–1: 1650 (C=O), 1607, 1560. H NMR spectrum
1
(CDCl3), δ, ppm: 3.53 br.s (4H, CH2CH2), 3.90 s (3H,
3
4
OCH3), 6.98 d.d (2H, 3′-H, 5′-H, J = 8.79, J =
2.19 Hz), 7.42 br.d (1H, 3-H, J3,4 = 7.71 Hz), 7.46 br.d
(1H, 8-H, J8,7 = 7.22 Hz), 7.75 d (1H, 7-H, J7,8
=
4
4
7.22 Hz), 7.97 d.d (2H, 2′-H, 6′-H, J = 8.79, J =
2.19 Hz), 8.14 d (1H, 4-H, J4,3 = 7.71 Hz).
6-Aminoacenaphthen-5-yl(4-methoxyphenyl)-
methanone (IVc). A suspension of 1.46 g of Raney
nickel in 10 ml of methanol was added to a suspension
of 3.038 g (9.12 mmol) of compound IIIc in 50 ml of
methanol, and 5 ml of hydrazine hydrate was added in
portions under stirring (each next portion was added
when hydrogen no longer evolved after addition of
the preceding portion). The reaction was performed
until initial nitro ketone IIIc dissolved completely
(~90 min). The mixture was filtered from the catalyst
through a small layer of aluminum oxide on a Schott
filter, the filtrate was poured into water, and the yellow
precipitate was filtered off. Yield 1.5 g (54%),
mp 166–167°C (from ethanol). IR spectrum, ν, cm–1:
1
3447, 3354 (NH2), 1620 (C=O), 1600, 1560. H NMR
spectrum (CDCl3), δ, ppm: 3.38 centrosymmetric m
(4H, CH2CH2, J = 8.00, 7.03, 2.05 Hz), 3.87 s (3H,
Acenaphthen-5-yl(4-methoxyphenyl)methanone
(IIc). Aluminum chloride, 3.7 g (27.7 mmol), was
added in small portions under stirring at room tem-
perature to a suspension of 2.85 g (18.5 mmol) of ace-
naphthene (I) and 3 ml (27.7 mmol) of p-methoxyben-
zoyl chloride in 5 ml of tetrachloroethane. The mixture
was stirred for 2 h, poured into water, and left over-
night. Tetrachloroethane was removed by steam distil-
lation, and the light brown material was recrystallized
from alcohol. Yield 4.62 g (87%), slightly colored
powder, mp 105°C (from ethanol). IR spectrum, ν,
OCH3), 4.25 br.s (2H, NH2), 6.83 d (1H, 7-H, J7,8
7.40 Hz), 6.94 d.d (2H, 3′-H, 5′-H, J = 8.93, J =
2.05 Hz), 7.20 br.d (1H, 8-H, J8,7 = 7.40 Hz), 7.21 br.d
=
3
4
(1H, 3-H, J3,4 = 7.02 Hz), 7.41 d (1H, 4-H, J4,3
7.02 Hz), 7.91 d.d (2H, 2′-H, 6′-H, J = 8.93, J =
=
3
4
2.05 Hz).
6-Aminoacenaphthen-5-yl(phenyl)methanone
(IVb). 5-Benzoyl-6-nitroacenaphthene, 5 g (17 mmol),
was dispersed in 70 ml of methanol, 2.1 g (36 mmol)
of Raney nickel in 15 ml of methanol was added, and
8.3 ml (166 mmol) of hydrazine hydrate was then add-
1
cm–1: 1635 (C=O), 1600, 1560. H NMR spectrum
(CDCl3), δ, ppm: 3.47 br.s (4H, CH2CH2), 3.90 s (3H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

MEZHERITSKII et al.
852
ed in portions under stirring (each next portion was
added when hydrogen no longer evolved after addition
of the preceding portion). The progress of the reaction
was monitored by thin-layer chromatography. When
the reaction was complete, the mixture was poured into
water, the precipitate was filtered off, dried in air,
dissolved in chloroform, and subjected to column chro-
matography on aluminum oxide (8×4 cm), a fraction
with Rf 0.8 (TLC, development with iodine vapor)
being collected. Yield 3.5 g (78%), yellow powder,
mp 148–149°C [6]. IR spectrum, ν, cm–1: 3420, 3340
(NH2), 1640 (C=O), 1615, 1600, 1580. 1H NMR spec-
trum (CDCl3), δ, ppm: 3.38 centrosymmetric m (4H,
CH2CH2, J = 7.91, 6.52, 1.90 Hz), 4.30 br.s (2H, NH2),
6.86 d (1H, 7-H, J7,8 = 7.40 Hz), 7.21 br.d (1H, 3-H,
J3,4 = 6.96 Hz), 7.23 br.d (1H, 8-H, J8,7 = 7.40 Hz),
7.44 d (1H, 4-H, J4,3 = 6.96 Hz), 7.48 d (2H, 3′-H,
3-H, J3,4 = 7.55 Hz), 7.50 d (1H, 8-H, J8,7 = 7.54 Hz),
8.20 d (1H, 7-H, J7, 8 = 7.48 Hz), 8.51 d (1H, 4-H,
J4,3 = 7.55 Hz), 10.30 br.s (3H, NH3+).
6-Benzoylacenaphthen-5-ylammonium perchlo-
rate (Vb). Yield 73%, mp 212–213°C. IR spectrum, ν,
cm–1: 3090, 2700 (NH3+), 1625 (C=O), 1600, 1100
(ClO4−). 1H NMR spectrum (CF3COOH), δ, ppm: 3.35 s
(4H, CH2CH2), 7.20–7.91 m (9H, Harom).
2-(4-Methoxyphenyl)-5,6-dihydroindeno-
[6,7,1-cde]indolium perchlorate (VIc). One drop of
72% perchloric acid was added to a suspension of
0.21 g (0.52 mmol) of perchlorate Vc in 1.5 ml of
acetic acid, the mixture was heated for 1 h under
reflux, 0.3 ml of acetic anhydride was added, and the
mixture was heated under reflux for 40 min more. The
mixture was cooled, and the precipitate was filtered off
and washed with diethyl ether. Yield 0.17 g (85%),
mp 247°C (decomp.). IR spectrum, ν, cm–1: 1600,
1580, 1100 (ClO4−).
3
5′-H, J = 7.69 Hz), 7.60 t (1H, 4′-H, J = 7.47,
3
7.32 Hz), 7.92 d (2H, 2′-H, 6′-H, J = 7.10 Hz).
1-(6-Aminoacenaphthen-5-yl)ethanone (IVa).
Yield 93%, mp 121–122°C [5]. IR spectrum, ν, cm–1:
Perchlorates VIa and VIb were synthesized in
a similar way.
1
3410, 3320 (NH2), 1660 (C=O) 1600, 1580. H NMR
spectrum (CDCl3), δ, ppm: 2.80 s (3H, CH3), 3.34 cen-
trosymmetric m (4H, CH2CH2, J = 8.02, 6.37,
2-Methyl-5,6-dihydroindeno[6,7,1-cde]indolium
perchlorate (VIa). Yield 82%, mp 226–227°C. IR
spectrum, ν, cm–1: 3170 (NH+), 1630 (C=N), 1480,
3.74 Hz), 4.51 br.s (2H, NH2), 6.84 d (1H, 7-H, J7,8
=
1100 (ClO4−). H NMR spectrum (C6D5NO2), δ, ppm:
1
7.40 Hz), 7.18 br.d (1H, 8-H, J8,7 = 7.40 Hz), 7.22 br.d
(1H, 3-H, J3, 4 = 7.22 Hz), 7.78 d (1H, 4-H, J4, 3
=
3.42 s (3H, CH3), 3.62 m (4H, CH2CH2), 7.67 d (1H,
3-H, J3,4 = 7.54 Hz), 7.90 d (1H, 8-H, J8,7 = 7.40 Hz),
8.31 d (1H, 7-H, J7,8 = 7.40 Hz), 8.74 d (1H, 4-H,
7.22 Hz).
6-(4-Methoxybenzoyl)acenaphthen-5-ylammo-
nium perchlorate (Vc). Compound IVc, 0.303 g
(1 mmol), was dispersed in 0.7 ml of acetic acid, and
0.1 ml of 72% perchloric acid was added dropwise
under stirring. After 1–2 min, abundant solid separated,
the mixture was diluted with diethyl ether, and the
precipitate was filtered off and washed with diethyl
ether. Yield 0.395 g (98%), mp 176–178°C. IR spec-
trum, ν, cm–1: 3052, 2620 (NH3+), 1625 (C=O), 1600,
J
4,3 = 7.54 Hz), 13.22 br.s (1H, NH+).
2-Phenyl-5,6-dihydroindeno[6,7,1-cde]indolium
perchlorate (VIb). Yield 88%, mp 232–234°C. IR
spectrum, ν, cm–1: 1600, 1580, 1100 (ClO4−).
2-(4-Methoxyphenyl)-5,6-dihydroindeno-
[6,7,1-cde]indole (VIIc). Perchlorate VIc, 0.3 g
(0.78 mmol), was dispersed in 5 ml of diethyl ether,
0.12 ml (1.2 mmol) of triethylamine was added, and
the mixture was stirred for 5 min at room temperature.
The mixture was evaporated to dryness, and the
residue was dissolved in chloroform and subjected to
chromatography on aluminum oxide, the first fraction
with Rf 0.8 being collected. Yield 0.21 g (95%), yellow
powder, mp 167–168°C. IR spectrum, ν, cm–1: 1625
1090 (ClO4−). H NMR spectrum (C6D5NO2), δ, ppm:
1
3.40 s (4H, CH2CH2), 3.80 s (3H, CH3), 6.87 d (2H,
3
3′-H, 5′-H, J = 8.79 Hz), 7.46 d (1H, 3-H, J3,4
=
7.47 Hz), 7.56 d (1H, 8-H, J8,7 = 7.76 Hz), 8.00 d (2H,
2′-H, 6′-H = 8.79 Hz), 8.03 d (1H, 7-H, J7,8 = 7.76 Hz),
8.24 d (1H, 4-H, J4,3 = 7.47 Hz), 10.00 br.s (3H, NH3+).
1
Perchlorates Va and Vb were synthesized in a simi-
lar way.
(C=N), 1600, 1560. H NMR spectrum (CDCl3), δ,
ppm: 3.55 centrosymmetric m (4H, CH2CH2), 3.90 s
3
4
(3H, OCH3), 7.08 d.d (2H, 3′-H, 5′-H, J = 8.93, J =
2.05 Hz), 7.42 br.d (1H, 7-H, J7,8 = 7.03 Hz), 7.53 br.d
6-Acetylacenaphthen-5-ylammonium perchlo-
rate (Va). Yield 84%, mp 207–208°C. IR spectrum, ν,
cm–1: 3550, 3180, 2690 (NH3+), 1640 (C=O), 1600,
(1H, 4-H, J4,3 = 7.03 Hz), 7.88 d (1H, 8-H, J8,7
=
1100 (ClO4−). H NMR spectrum (C6D5NO2), δ, ppm:
1
7.03 Hz), 8.26 d (1H, 3-H, J3,4 = 7.03 Hz), 8.36 d.d
(2H, 2′-H, 6′-H, 3J = 8.93, 4J = 2.05 Hz).
3.05 s (3H, CH3), 3.30 s (4H, CH2CH2), 7.41 d (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

peri-AMINO KETONES OF THE ACENAPHTHENE AND ACENAPHTHYLENE SERIES
853
2-Phenyl-5,6-dihydroindeno[6,7,1-cde]indole
(VIIb) was synthesized in a similar way. Yield 91%,
mp 157–158°C. IR spectrum, ν, cm–1: 1625 (C=N),
reflux and cooled, and the precipitate was filtered off.
Yield 0.608 g (82%), yellow powder, mp 109–110°C
(from ethanol). IR spectrum, ν, cm–1: 1680 (C=O),
1
1
1560. H NMR spectrum, (CDCl3), δ, ppm: 3.60 cen-
1620 (C=N), 1607. H NMR spectrum (CDCl3), δ,
trosymmetric m (4H, CH2CH2), 7.46 br.d (1H, 7-H,
J7,8 = 7.07 Hz), 7.50–7.62 m (4H, 4-H, Harom), 7.96 d
ppm: 2.50 s (3H, COMe), 3.40 m (4H, CH2CH2),
3.90 s (3H, OMe), 7.02 d (2H, 3′-H, 5′-H, J =
3
(1H, 8-H, J8,7 = 7.07 Hz), 8.31 d (1H, 3-H, J3,4
7.14 Hz), 8.40 d (2H, Harom, J = 8.13 Hz).
=
8.75 Hz), 7.20 d (1H, 7-H, J7,8 = 7.40 Hz), 7.28 br.s
(2H, 3-H, 4-H), 7.33 d (1H, 8-H, J8,7 = 7.40 Hz),
7.86 d (2H, 2′-H, 6′-H, J = 8.75 Hz), 8.53 s (1H,
N=CH). Found, %: C 80.00; H 5.89; N 4.47.
C22H19NO2. Calculated, %: C 80.24; H 5.76; N 4.26.
3
N-(6-Acetylacenaphthen-5-yl)acetamide (VIII).
Amino ketone IVa, 0.568 g (2.7 mmol), was dispersed
in 5 ml of water on heating to 40–50°C, 1 ml of acetic
anhydride was added, the mixture turned homogene-
ous, and a solid separated in 3–5 min and was filtered
off. Yield 0.554 g (81%), light yellow powder,
mp 161–162°C (from ethanol); published data [1]:
mp 160.2–161°C. IR spectrum, ν, cm–1: 3280 (NH),
2-(4-Methoxyphenyl)-2,3-dihydroacenaphtho-
[5,6-bc]azepin-4(1H)-one (XIIa). Amino ketone IVa,
0.162 g (0.77 mmol), was dispersed in 1 ml of ethanol,
0.104 ml (0.77 mmol) of p-methoxybenzaldehyde and
0.4 ml of 30% aqueous sodium hydroxide were added,
and the mixture was heated to 50–60°C and kept for
2 h at room temperature. The solution was cooled, and
the precipitate was filtered off. Yield 76%, orange–red
powder, mp 109–110°C. IR spectrum, ν, cm–1: 3420
1
1673 (C=O, amide), 1647 (C=O, ketone). H NMR
spectrum (DMSO-d6), δ, ppm: 1.97 s (3H, NCOCH3),
2.6 s (3H, COCH3), 3.36 m (4H, CH2CH2), 7.34 d (1H,
7-H, J7,8 = 7.17 Hz), 7.39 s (2H, 3-H, 4-H), 7.5 d (1H,
8-H, J8,7 = 7.18 Hz), 9.68 br.s (1H, NH). Found, %:
C 75.51; H 6.12; N 5.75. C16H15NO2. Calculated, %:
C 75.89; H 5.93; N 5.53.
1
(NH), 1700 (C=O). H NMR spectrum (CDCl3), δ,
ppm: 3.1–3.2 d.d (1H, 3-H, J = 16.7 Hz), 3.34–3.44 m
(4H, CH2CH2), 3.5–3.6 d.d (1H, 3-H, J = 16.7 Hz),
3.84 s (3H, OMe), 4.36 br.s (1H, NH), 4.70–4.76 d
(1H, 2-H, J = 11.1 Hz), 6.75–6.85 d (1H, 10-H, J =
7.4 Hz), 6.90–6.95 d (2H, C6H4, J = 8.6 Hz), 7.10–
7.15 d (1H, 9-H, J = 7.4 Hz), 7.30–7.35 d (1H, 6-H,
J = 7.4 Hz), 7.34–7.38 (2H, C6H4, J = 8.6 Hz), 8.13–
8.17 d (1H, 5-H, J = 7.4 Hz). Found, %: C 80.42;
H 5.68; N 4.45. C22H19NO2. Calculated, %: C 80.24;
H 5.78; N 4.26.
N-(6-Acetylacenaphthylen-5-yl)acetamide (IX).
N-Acetylamino ketone VIII, 0.3 g (1.2 mmol), was
dissolved in 2 ml of o-dichlorobenzene, 0.438 g
(1.8 mmol) of tetrachloro-1,4-benzoquinone was
added, and the mixture was heated for 2 h under reflux.
The mixture was evaporated to dryness, and the resi-
due was dissolved in chloroform and subjected to
chromatography on aluminum oxide. Yield 0.04 g
(13%), yellow powder, mp 107–108°C. IR spectrum, ν,
cm–1: 3270 (NH), 1670 (C=O, amide), 1650 (C=O,
1-Acetyl-2-(4-methoxyphenyl)-2,3-dihydroace-
naphth[5,6-bc]azepin-4(1H)-one (XIIb). A mixture
of 0.3 g (1.2 mmol) of 6-acetylamino-5-acetylace-
naphthene VIII, 0.16 ml (1.2 mmol) of p-methoxy-
benzaldehyde, 0.6 ml of 30% aqueous sodium hydrox-
ide, and 2 ml of ethanol was stirred for 3 h at room
temperature. The precipitate was filtered off and dried
in air. Yield 0.25 g (62%), light yellow powder,
mp 172–173°C. IR spectrum, ν, cm–1: 1687 (1-C=O),
1
ketone). H NMR spectrum, δ, ppm: in CDCl3: 2.23 s
(3H, NCOMe), 2.84 s (3H, COMe), 6.88 d (1H, 2-H,
J2,1 = 5.3 Hz), 7.11 d (1H, 1-H, J1,2 = 5.3 Hz), 7.62 d
(1H, 3-H, J3, 4 = 7.6 Hz), 7.66 d (1H, 7-H, J7, 8
=
7.2 Hz), 8.10 d (1H, 8-H, J8,7 = 7.3 Hz), 8.30 d (1H,
4-H, J4, 3 = Hz), 10.7 br.s (1H, NH); in DMSO-d6:
2.00 s (3H, COMe), 2.60 s (3H, NCOMe), 7.05 d (1H,
2-H, J2,1 = 5.3 Hz), 7.15 d (1H, 1-H, J1,2 = 5.3 Hz),
7.47 d (1H, 7-H, J7,8 = 7.3 Hz), 7.70–7.83 m (3H, 3-H,
4-H, 8-H), 10.1 s (1H, CONH). Found, %: C 76.15;
H 5.41; N 5.77. C16H13NO2. Calculated, %: C 76.49;
H 5.18; N 5.58.
1
1647 (C4=O). H NMR spectrum (CDCl3), δ, ppm:
3.1–3.2 d.d (1H, 3-H, J = 13.7 Hz), 3.4–3.5 m (4H,
CH2CH2), 3.43–3.53 d.d (1H, 3-H, J = 13.7 Hz), 3.7 s
(3H, OMe), 6.44–6.50 d.d (1H, 2-H, J = 9.9 Hz), 6.72–
6.76 d (2H, C6H4, J = 8.75 Hz), 7.12–7.16 d (1H,
10-H, J = 7.25 Hz), 7.22–7.26 d (2H, C6H4, J =
8.75 Hz), 7.27–7.30 d (1H, 9-H, J = 7.25 Hz), 7.36–
7.40 d (1H, 6-H, J = 7.25 Hz), 7.96–8.00 d (1H, 5-H,
J = 7.25 Hz). 13C NMR spectrum (CDCl3), δC, ppm:
23.0, 30.0, 31.0, 48.0, 55.0, 56.5, 76.5, 77.0, 77.5,
1-[6-(4-Methoxybenzylideneamino)acenaphthen-
5-yl]ethanone (XI). Amino ketone IVa, 0.478 g
(2.27 mmol), was dissolved on heating in 1 ml of etha-
nol, 0.31 ml (2.27 mmol) of p-methoxybenzaldehyde
was added, the mixture was heated for 3–4 min under
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

MEZHERITSKII et al.
854
2. Mezheritskii, V.V., Pikus, A.L., Minyaeva, L.G., and
Dorofeenko, G.N., Zh. Org. Khim., 1980, vol. 16, p. 1958.
3. Mezheritskii, V.V., Pikus, A.L., Minyaeva, L.G., and
Dorofeenko, G.N., Zh. Org. Khim., 1981, vol. 17, p. 1998.
4. Dokunikhin, N.S. and Vorozhtsov, G.N., Zh. Org. Khim.,
113.6, 119.6, 119.8, 128.4, 130.2, 131.2, 131.6, 132.4,
132.8, 140.0, 146.0, 152.0, 158.5, 170.5, 200.0. Found,
%: C 77.86; H 5.62; N 3.87. C24H21NO3. Calculated,
%: C 77.63; H 5.66; N 3.77.
(2E)-1-(6-Acetylaminoacenaphthylen-5-yl)-3-(4-
methoxyphenyl)prop-2-en-1-one (XIII). N-(6-Ace-
tylacenaphthylen-5-yl)acetamide, 0.5 g (1.99 mmol),
was dissolved in 5 ml of ethanol on slight heating,
0.24 ml (1.99 mmol) of p-methoxybenzaldehyde and
1 ml of 30% aqueous sodium hydroxide were added,
and the mixture was heated for 5 min under reflux. The
mixture was cooled, the precipitate was filtered off,
dried in air, and dissolved in chloroform, and the solu-
tion was subjected to chromatography on aluminum
oxide to isolate a red fraction with Rf 0.7. Yield
0.507 g (69%), red–orange powder, mp 176–177°C.
IR spectrum, ν, cm–1: 3300 (NH), 1673 (C=O, amide),
1640 (COCH=CH), 1600. 1H NMR spectrum (CDCl3),
δ, ppm: 2.15 s (3H, NCOCH3), 3.85 s (3H, OCH3),
6.90 d (1H, 2-H, J2,1 = 5.26 Hz), 6.92 d (2H, 3′-H,
1966, vol. 2, p. 148.
5. Dokunikhin, N.S., Vorozhtsov, G.N., and Kichina, F.I.,
Zh. Org. Khim., 1968, vol. 4, p. 2000.
6. Tkachenko, V.V., Zhukovskaya, O.N., Mezheritskii, V.V.,
and Dorofeenko, G.N., Zh. Org. Khim., 1977, vol. 13,
p. 2009.
7. Sheldrick, G.M., SHELXTL-Plus Reference Manual.
Version 5.0, Madison, WI: Siemens Analytical X-ray
Instruments, 1996.
8. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E.,
Robb, M.A., Cheeseman, J.R., Montgomery, J.A., Jr.,
Vreven, T., Kudin, K.N., Burant, J.C., Millam, J.M.,
Iyengar, S.S., Tomasi, J., Barone, V., Mennucci, B.,
Cossi, M., Scalmani, G., Rega, N., Petersson, G.A., Na-
katsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R.,
Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y.,
Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J.E.,
Hratchian, H.P., Cross, J.B., Bakken, V., Adamo, C.,
Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O.,
Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W.,
Ayala, P.Y., Morokuma, K., Voth, G.A., Salvador, P.,
Dannenberg, J.J., Zakrzewski, V.G., Dapprich, S.,
Daniels, A.D., Strain, M.C., Farkas, O., Malick, D.K.,
Rabuck, A.D., Raghavachari, K., Foresman, J.B.,
Ortiz, J.V., Cui, Q., Baboul, A.G., Clifford, S., Cioslow-
ski, J., Stefanov, B.B., Liu, G., Liashenko, A., Pis-
korz, P., Komaromi, I., Martin, R.L., Fox, D.J., Keith, T.,
Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Challa-
combe, M., Gill, P.M.W., Johnson, B., Chen, W.,
Wong, M.W., Gonzalez, C., and Pople, J.A., Gaussian
03, Revision B.03, Wallingford CT: Gaussian, 2004.
3
5′-H, J = 8.77 Hz), 7.07 d (1H, 1-H, J1,2 = 5.27 Hz),
7.22 d [1H, C(O)CH=CH, J = 15.78 Hz], 7.55 d (2H,
3
2′-H, 6′-H, J = 8.77 Hz), 7.62 d [1H, C(O)CH=CH,
J = 15.78 Hz], 7.63 d (1H, 7-H, J7,8 = 7.01 Hz), 7.64 d
(1H, 3-H, J3,4 = 7.72 Hz), 7.82 d (1H, 8-H, J8,7
=
7.01 Hz), 8.18 d (1H, 4-H, J4,3 = 7.72 Hz), 9.80 br.s
(1H, NH). Found, %: C 77.65; H 5.31; N 3.51.
C24H19NO3. Calculated, %: C 77.95; H 5.14; N 3.79.
REFERENCES
1. Mezheritskii, V.V. and Tkachenko, V.V., Advances in
Heterocyclic Chemistry, Katritzky, A.R., Ed., New York:
Academic, 1990, vol. 51, p. 1.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010