1-Azaacepleiadylene-A novel peri-fused heterocyclic system

Article abstract of DOI:10.1134/S1070428009060219

Treatment of 2-aryl-1H,4H-2,3,7,8-tetrahydroacenaphtho[5,6-bc]azepin-4-one with hydrazine hydrate on heating in ethylene glycol in the presence of alkali resulted in the reduction of the oxo group to CH2. Dehydrogenation of the reduction product with 2,3,

Full text of DOI:10.1134/S1070428009060219

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 6, pp. 928–933. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © V.V. Mezheritskii, A.N. Antonov, R.V. Tyurin, L.G. Minyaeva, K.A. Lysenko, M.S. Korobov, 2009, published in Zhurnal
Organicheskoi Khimii, 2009, Vol. 45, No. 6, pp. 940–945.
1-Azaacepleiadylene—A Novel peri-Fused Heterocyclic System
V. V. Mezheritskiia, A. N. Antonova, R. V. Tyurina, L. G. Minyaevaa, K. A. Lysenkob,
and M. S. Korobova
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,
ul. Vavilova 28, Moscow, 119991 Russia
Received May 13, 2008
Abstract—Treatment of 2-aryl-1H,4H-2,3,7,8-tetrahydroacenaphtho[5,6-bc]azepin-4-one with hydrazine
hydrate on heating in ethylene glycol in the presence of alkali resulted in the reduction of the oxo group to CH2.
Dehydrogenation of the reduction product with 2,3,5,6-tetrachloro-1,4-benzoquinone gave 2-aryl-1-azaace-
pleiadylene which is the first representative of a novel peri-fused heterocyclic system.
DOI: 10.1134/S1070428009060219
In the previous communication [1] we reported on
the synthesis of 2-aryl-1H,4H-2,3,7,8-tetrahydroace-
naphtho[5,6-bc]azepin-4-ones (I) which may be conve-
nient starting compounds in the transformation of car-
bonyl group into methylene according to Wolff–Kish-
ner (reaction sequence I → II → III in Scheme 1) [2].
2-aryl-1-azaacepleiadylenes IV by heating their poten-
tial precursors IIIa and IIIb in p-xylene or mesitylene
over Pd/C were also unsuccessful: only contaminated
initial compounds were recovered from the reaction
mixtures.
The structure of the newly synthesized compounds
was confirmed by spectral methods, and the structure
of IV was proved by X-ray analysis.
For this purpose, ketones Ia and Ib were heated for
a short time with hydrazine hydrate in alcohol. We thus
obtained the corresponding hydrazones IIa and IIb in
good yield. However, our attempt to reduce hydra-
zones IIa and IIb with potassium tert-butoxide in di-
methyl sulfoxide at room temperature according to the
procedure described in [3] was unsuccessful: only the
initial compounds were isolated.
Protons on C2 and C3 in the molecules of hydra-
zones IIa and IIb form a strongly coupled spin system.
Owing to nonequivalence of the geminal C3H2 protons
in the seven-membered ring, the Ha and Hc (2-H)
signals appear as doublets of doublets at δ 2.70 and
4.70 ppm (IIa) and 2.73 and 4.70 ppm (IIb), respec-
tively. The other methylene proton signal (Hb) is
obscured by the wide multiplet in the region δ 3.2–
3.4 ppm, which belongs to C7H2 and C8H2. The
1H NMR spectra of reduction products IIIa and IIIb in
the region δ 2.2–4.5 ppm are even more complex.
Although some signals were identified on the basis of
chemical shifts of the corresponding protons, it was
difficult to determine spin–spin coupling constants for
methylene protons, for their signals were complex
multiplets. We were able to identify only the Hc signal
as a doublet of doublets. Broadened signal from the
NH proton was overlapped by one (IIIa) or two (IIIb)
singlets from the methoxy protons. In the aromatic
region, the 5-H and 6-H protons resonated as one two-
proton singlet.
As applied to ketones Ia and Ib, a successful ver-
sion of the Kishner reaction turned out to be Huang–
Minlon modification [4], i.e., heating of ketone I with
hydrazine hydrate and sodium hydroxide in ethylene
glycol. This procedure ensured preparation of naphtho-
[5,6-bc]azepines IIIa and IIIb in high yield.
When 2-(4-methoxyphenyl)-1H,4H-2,3,7,8-tetra-
hydroacenaphtho[5,6-bc]azepine (IIIa) was heated
with 2,3,5,6-tetrachloro-1,4-benzoquinone in tetrahy-
drofuran, we isolated 2-(4-methoxyphenyl)-1-azaace-
pleiadylene IV with a small yield, whereas 2-(3,4-di-
methoxyphenyl) derivative IIIb under analogous con-
ditions gave rise to a mixture of products which we
failed to separate and identify. Our attempts to obtain
928

1-AZAACEPLEIADYLENE—A NOVEL peri-FUSED HETEROCYCLIC SYSTEM
929
Scheme 1.
Hc Hb
Hc Hb
Ar
Ha
Ar
Ha
NNH2
N
HN
HN
CHAr
N
N2H4, EtOH
Hc Hb
Ar
Ha
IIa, IIb
V
O
HN
t-BuOK, DMSO
Hc Hb
Ar
Ar
Ha
2
3
Hd
Ia, Ib
1N
4
N2H4, NaOH
HOCH2CH2OH
HN
He
C6Cl4O2, THF
10
9
5
6
8
7
IIIa, IIIb
IV
I–III, Ar = 4-MeOC6H4 (a), 3,4-(MeO)2C6H3 (b); IV, V, Ar = 4-MeOC6H4.
Apart from sufficiently informative spectral data,
the presence of a reactive amino group in the molecule
of hydrazone IIa was confirmed by its reaction with
4-methoxybenzaldehyde which resulted in the forma-
tion of azine V (Scheme 1).
However, it seems inappropriate to presume en-
hanced aromaticity of the 1-azapleiadylene system
(IV) compared to compounds I–III on the basis of
“boundary” chemical shifts of protons in the naphtha-
lene ring (most downfield 5-H and most upfield 10-H),
for the position of their signals strongly depends on the
electron-withdrawing or electron-donating effect of the
neighboring functional groups. In other words, the
chemical shifts of 5-H and 10-H are determined not so
much by the ring current as by the electron density on
C5 and C10, which depends on the above effects and
disturbs the ring current. It would be more appropriate
to compare molecular systems differing by the pres-
ence or absence of the double bond at the peri posi-
tions opposite to the heteroring, e.g., structures A and
B, C and D, or E and F. In these cases, structural
variations induced by the double bond are minimal,
while differences in the electronic structures are quite
significant. Isolated heteroring in structures A, C, and
E becomes involved in aromatic conjugation in going
to 14π-electron peripheral contour in structures B, D,
and F.** Taking into account the above stated, the
downfield shift of naphthalene proton signals, as well
as of signals from protons in the heteroring and substit-
Signals from protons in the naphthalene fragment
of compounds IIa, IIb, IIIa, and IIIb were located in
their 1H NMR spectra in the regions δ 6.6–7.6 (II) and
6.6–7.1 ppm (III), whereas naphthalene protons in
1-azapleiadylene IV resonated at δ 7.33–8.25 ppm.
The observed downfield shift may be interpreted in
terms of increased diamagnetic constituent of the ring
current in IV, i.e., in terms of higher aromaticity of
the latter compound. In fact, 1-azapleiadylene can be
regarded as an aromatic ring system: its 16π-electron
structure can be represented as a superposition of
14π-electron peripheral contour and 10π-electron
naphthalene fragment. Taking into account that each
skeletal carbon atom in molecule IV is included into
14π- or 10π-electron cyclic system, each conforming
to the 4n + 2 constraint, such molecular entities may
be considered to constitute a specific “supplement to
Hückel’s rule.”* Formalistically, structure IV contains
16π (4n) electrons, so that it should be classed with
antiaromatic systems according to Hückel.
** Divinyl (isolated) character of the seven-membered ring in the
molecule of acepleiadiene and aromaticity of acepleiadylene
were discussed in [5, 6].
* The term “supplement to Hückel’s rule” is introduced by us for
the first time.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 6 2009

MEZHERITSKII et al.
930
R
X
R
X
O
O
:
:
Y
N
N
N
N
Y
A
B
C
D
E
F
Y = O, RN; X = CH, N.
uents therein, observed by us previously in going from
structure C to D [7] or from E to F [8] may be inter-
preted as unambiguous evidence in favor of increased
aromaticity of the whole peri-fused heteroaromatic
system. Unfortunately, analogous comparison of struc-
tures A and B cannot be performed in the framework
of the present study because of the lack of compounds
having structure A.
N1=C2–C3=C4 fragment is slightly forced out from
conjugation with the other part of the molecule. In
addition, steric repulsion between hydrogen atoms on
C4 and C5, which should hamper flattening of the
molecule, cannot be ruled out.
Distribution of bond lengths in the C3C4C13C12
fragment (Table 1) is almost the same as in the molec-
ular complex of acepleiadylene with trinitrobenzene,
studied previously [9]. An exception is the C2–C3 bond
which is longer [1.451(4) Å] than in the above com-
plex (1.425 Å). The N1–C2 bond [1.302(4) Å] in
molecule IV is considerably shorter than the N1–C11
bond [1.395(3) Å]; on the other hand, the latter is ap-
preciably shorter than the corresponding bond distance
in, e.g., N-benzylidenenaphthalen-1-amine (1.422 Å)
[10]. The bond angles at the bridgehead carbon atoms
in the naphthalene ring (Table 2) are distorted to a con-
siderable extent: the C11C12C13 angle (seven-membered
ring) is 128.3(3)°, while the C14C15C16 angle in the
five-membered ring is much smaller, 109.0(2)°. Thus,
mutual approach of carbon atoms in the peri positions
at the side of the five-membered ring is accompanied
by extension of the distance between the opposite peri-
carbon atoms belonging to the seven-membered het-
eroring. In other words, we observed consistent con-
tributions of the five-membered carbocycle and seven-
membered heteroring to the in-plane distortion of the
naphthalene ring.
The structure of 2-(4-methoxyphenyl)-1-azaaceplei-
adylene (IV) was determined by X-ray analysis. This
compound forms non-centrosymmetric crystals be-
longing to space group P1 with two independent mole-
cules in a unit cell. The main geometric parameters of
both molecules were similar within the experimental
error, so that the parameters of only one of them will
be considered here. Molecule IV is essentially planar,
except for the 4-methoxyphenyl substituent which is
turned through a dihedral angle of 23.6° about the
C2–C1′ bond. However, the N1C2C3C4 fragment slightly
deviates from the acenaphthene plane, the minimal
deviation being 0.05 Å for C2, while the other atoms in
that fragment deviate from the acenaphthene plane to
a considerably stronger extent (0.11–0.13 Å). The ob-
served bend of the seven-membered ring cannot be
induced only by the effect of crystal packing. In fact,
deviations of the corresponding atoms from the ace-
naphthene plane in the second independent molecule,
which appears in a different crystal environment, range
from 0.06 to 0.11 Å. Therefore, we presume that the
Unlike electron-rich compounds like F (X = N)
described previously, we now report on the synthesis
of the first representative of 16π-electron π-deficient
peri-fused heteroaromatic compounds having a 1-aza-
acepleiadylene skeleton and pyridine type nitrogen
atom. 1-Azaacepleiadylene IV and 1-azapleiadylen-4-
one derivatives D (Y = NR) synthesized previously
should display some similarity in chemical properties
to pyridine (quinoline) and pyridin-4-one (quinolin-4-
one), respectively. 1- and 2-Azapyrenes [11, 12] may
also be regarded as compounds that are structurally
related and isoelectronic to 16π-electron π-deficient
peri-fused heteroaromatic system. 1-Azaacepleia-
dylene and 1-azapyrene differ from each other as
MeO
1'
2
3
1N
4
11
13
12
15
10
9
5
6
16
14
8
7
Atom numbering in the molecule of 2-(4-methoxyphenyl)-
acenaphtho[5,6-bc]azepine (IV).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 6 2009

1-AZAACEPLEIADYLENE—A NOVEL peri-FUSED HETEROCYCLIC SYSTEM
931
Table 1. Principal bond lengths d in one independent mole-
cule of 2-(4-methoxyphenyl)acenaphtho[5,6-bc]azepine (IV)
aromatic hydrocarbons acepleiadylene [6] and azulene
differ from pyrene and naphthalene, respectively.
Analysis of the spectral parameters and crystallo-
graphic data of compound IV, as well as comparison
with other carbo- and heteroaromatic structures, led us
to presume essential delocalization of π-electron den-
sity in the molecule of 2-(4-methoxyphenyl)-1-azaace-
pleiadylene and hence aromatic character of this novel
heterocyclic system.
Bond
d, Ǻ
Bond
d, Ǻ
N1–C2
N1–C11
C2–C3
C2–C1″
C3–C4
C4–C13
C5–C13
C5–C6
C6–C14
C7–C8
1.302(4)
1.395(3)
1.451(4)
1.492(4)
1.348(4)
1.436(4)
1.401(4)
1.409(4)
1.372(4)
1.371(5)
C7–C14
C8–C16
C9–C16
C9–C10
C10–C11
C11–C12
C12–C15
C12–C13
C14–C15
C15–C16
1.453(5)
1.451(4)
1.378(4)
1.401(4)
1.406(4)
1.448(4)
1.385(4)
1.445(4)
1.430(4)
1.428(4)
EXPERIMENTAL
1
The H NMR spectra were recorded on Bruker
DPX-250 and Varian Unity-300 spectrometers at 250
and 300 MHz, respectively, using hexamethyldisilox-
ane as internal reference. The IR spectra were obtained
on a Specord 75IR instrument from samples dispersed
in mineral oil. Chromatographic purification was per-
formed using aluminum oxide as sorbent and chloro-
form as eluent.
Table 2. Selected bond angles ω in one independent mole-
cule of 2-(4-methoxyphenyl)acenaphtho[5,6-bc]azepine (IV)
Angle
φ, deg
Angle
φ, deg
N1C11C12
N1C11C10
C11C12C13
C12C13C4
C4C13C5
129.2(2)
112.94()
128.3(3)
123.7(3)
117.4(3)
C8C16C9
C8C16C15
C14C15C16
C6C14C7
C7C14C15
136.2(3)
106.4(3)
109.0(3)
135.8(3)
106.1(3)
X-Ray diffraction study on 2-(4-methoxyphenyl)-
acenaphtho[5,6-bc]azepine (IVa). C22H15NO.
M 309.35. Single crystals suitable for X-ray analysis
were obtained by isothermal evaporation of a solution
of IVa in toluene. Triclinic crystals with the following
unit cell parameters (120 K): a = 5.1780(4), b =
12.2346(10), c = 12.4865(10) Å; α = 105.2135(15),
β = 99.6982(16), γ = 90.5036(17)°; V = 751.23(10) Å3;
the remaining solution was diluted with water, the
precipitate was filtered off, dried, and dissolved in
chloroform, and the solution was subjected to chroma-
tography on aluminum oxide, a fraction with Rf 0.3
being collected. Yield 0.668 g (89%), light yellow
powder, mp 135–136°C (from ethanol). IR spectrum,
ν, cm–1: 3287, 3180, 3154 (NH, NH2); 1630 (C=N).
1H NMR spectrum (CDCl3), δ, ppm: 2.70 d.d (1H, Ha,
J = 2.83, 3.14, 16.33 Hz), 3.24–3.43 m (5H, CH2CH2,
Hb), 3.80 s (3H, CH3O), 4.10 br.s (1H, NH), 4.70 d.d
(1H, Hc, J = 3.14, 10.68 Hz), 5.30 br.s (2H, NH2),
6.64 d (1H, 10-H, J10,9 = 7.22 Hz), 6.92 d (2H, 3′-H,
d
calc = 1.368 g/cm3; μ = 0.84 cm–1; Z = 2 (Z′ = 2); space
group P1. Intensities of 7364 reflections were meas-
ured at 120 K on a Smart 1000 CCD automatic dif-
fractometer (MoKα irradiation, graphite monochro-
mator, ω-scannibg, 2θmax = 59°); 4055 independent
reflection intensities (Rint = 0.0189) were used in sub-
sequent calculations. The structure was solved by the
direct method and was refined by the full-matrix aniso-
tropic–isotropic approximation with respect to F2. Hy-
drogen atoms were localized by difference syntheses
of electron density, and their positions were refined
according to the riding model. The final divergence
factors were wR2 = 0.1105 for all reflections and R1 =
0.0480 for 3272 reflections with I > 2σ(I); goodness
of fit 0.967. Calculations were performed using
SHELXTL PLUS 5.0 software package [13].
3
5′-H, J = 8.48 Hz), 7.03 d (1H, 9-H, J9,10 = 7.22 Hz),
7.23 d (1H, 6-H, J6,5 = 7.22 Hz), 7.37 d.d (2H, 2′-H,
3
6′-H, J = 8.48 Hz), 7.67 d (1H, 5-H, J5,6 = 7.22 Hz).
Found, %: C 76.73; H 5.98; N 12.43. C22H21N3O. Cal-
culated, %: C 76.94; H 6.16; N 12.24.
2-(3,4-Dimethoxyphenyl)-1,2,3,4,7,8-hexahydro-
acenaphtho[5,6-bc]azepin-4-one hydrazone (IIb)
was synthesized in a similar way. Yield 87%, light
yellow powder, mp 198–199°C (from ethanol). IR
spectrum, ν, cm–1: 3327, 3170, 3150 (NH, NH2); 1630
2-(4-Methoxyphenyl)-1,2,3,4,7,8-hexahydroace-
naphtho[5,6-bc]azepin-4-one hydrazone (IIa). A mix-
ture of 0.718 g (2.2 mmol) of compound Ia, 0.12 ml
(2.4 mmol) of hydrazine hydrate, and 5 drops of acetic
acid in 10 ml of ethanol was heated for 2 h under
reflux. A part of the solvent (5–6 ml) was distilled off,
1
(C=N). H NMR spectrum (CDCl3), δ, ppm: 2.73 d.d
(1H, Ha, Jab = 16.17, Jac = 3.14 Hz), 3.21–3.44 m (5H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 6 2009

MEZHERITSKII et al.
932
CH2CH2, Hb), 3.85 s (6H, CH3O), 4.10 br.s (1H, NH),
4.70 d.d (1H, Hc, Jcb = 10.70, Jca = 3.14 Hz), 5.25 br.s
(2H, NH2), 6.66 d (1H, 10-H, J10,9 = 7.22 Hz), 6.87 d
The mixture was evaporated to dryness, the residue
was dissolved in chloroform, and the solution was
subjected to chromatography on aluminum oxide, the
first fraction with Rf 0.8 being collected. Yield 6 mg
(6%), red powder, mp 131–132°C (from toluene). IR
3
(1H, 5′-H, J = 7.85 Hz), 6.94–7.05 m (3H, 9-H, 2′-H,
6′-H), 7.23 d (1H, 6-H, J6,5 = 7.22 Hz), 7.67 d (1H,
5-H, J5,6 = 7.22 Hz). Found, %: C 73.73; H 6.08;
N 11.43. C23H23N3O2. Calculated%: C 73.97; H 6.21;
N 11.25.
1
spectrum, ν, cm–1: 1600, 1590. H NMR spectrum
(CDCl3), δ, ppm: 3.88 s (3H, CH3O), 7.02 d.d (2H,
3
4
3′-H, 5′-H, J = 9.11, J = 2.20 Hz), 7.33 d (1H, 3-H,
J3,4 = 11.93 Hz), 7.76 d (1H, 7-H, J7,8 = 5.02 Hz),
7.81 d (1H, 4-H, J4,3 = 11.93 Hz), 7.84 d (1H, 8-H,
J8,7 = 5.02 Hz), 7.86 d (1H, 6-H, J6,5 = 7.22 Hz),
2-(4-Methoxyphenyl)-1,2,3,4,7,8-hexahydroace-
naphtho[5,6-bc]azepine (IIIa). Hydrazine hydrate,
0.1 ml (2 mmol), was added to a suspension of 0.2 g
(0.6 mmol) of compound Ia and 0.11 g (2.75 mmol) of
sodium hydroxide in 3 ml of ethylene glycol, and the
mixture was heated for 2 h under reflux. The mixture
was cooled, diluted with water, acidified with dilute
(1:1) hydrochloric acid to pH 1–2, and extracted with
three portions of chloroform. The extracts were com-
bined and evaporated to dryness, and the residue was
dissolved in chloroform and subjected to chromatog-
raphy on aluminum oxide, the first fraction with Rf 0.9
being collected. Yield 134 mg (70%), light pink
powder, mp 107–108°C (from methanol). IR spectrum,
ν, cm–1: 3380 (NH), 1580. 1H NMR spectrum (CDCl3),
δ, ppm: 2.29 m (2H, Ha, Hb), 3.05 m (1H, Hc), 3.30 m
(4H, 7-H, 8-H), 3.60 m (1H, Hd), 3.80 (4H, CH3O,
NH), 4.50 d.d (1H, He, J = 6.74, 9.44 Hz), 6.56 d (1H,
3
4
8.12 d.d (2H, 2′-H, 6′-H, J = 9.11, J = 2.20 Hz),
8.25 d (1H, 5-H, J5,6 = 7.22 Hz), 8.32 d (1H, 9-H,
J9,10 = 7.54 Hz), 8.39 d (1H, 10-H, J10,9 = 7.54 Hz).
Found, %: C 85.50; H 4.59; N 4.92. C22H15NO. Calcu-
lated, %: C 85.41; H 4.89; N 4.53.
2-(4-Methoxyphenyl)-1,2,3,4,7,8-hexahydroace-
naphtho[5,6-bc]azepin-4-one N′-(4-methoxyben-
zylidene)hydrazone (V). Compound IIa, 0.98 g
(2.86 mmol), was dissolved on heating in 10 ml of
ethanol, 0.35 ml (2.86 mmol) of 4-methoxybenzalde-
hyde was added, and the mixture was heated for
5–7 min under reflux and evaporated to dryness in air.
The residue was dissolved in chloroform and subjected
to chromatography on aluminum oxide using chloro-
form as eluent. The first fraction with Rf 0.8 was
collected. Yield 1.05 g (80%), yellow powder, mp 67–
3
10-H, J10,9 = 7.07 Hz), 6.86 d (2H, 3′-H, 5′-H, J =
1
68°C. IR spectrum, ν, cm–1: 3340, 1610. H NMR
8.75 Hz), 6.98 br.d (1H, 9-H, J9,10 = 7.07 Hz), 7.07 br.s
3
spectrum (CDCl3), δ, ppm: 3.28–3.45 m (5H, CH2CH2,
Ha), 3.63–3.76 m (4H, 4-OCH3, Hb), 3.84 s (3H,
4′-OCH3), 4.10 br.s (1H, NH), 4.78 d.d (1H, 2-H, J =
(2H, 5-H, 6-H), 7.30 d (2H, 2′-H, 6′-H, J = 8.75 Hz).
Found, %: C 83.43; H 7.00; N 4.28. C22H21NO. Calcu-
lated, %: C 83.78; H 6.71; N 4.44.
4.08, 4.40, 10.21 Hz), 6.70 d (1H, 10-H, J10,9
=
2-(3,4-Dimethoxyphenyl)-1,2,3,4,7,8-hexahydro-
acenaphtho[5,6-bc]azepine (IIIb) was synthesized in
a similar way. Yield 68%, light pink powder, mp 138–
139°C (from methanol). IR spectrum, ν, cm–1: 3340
7.23 Hz), 6.83 d (2H, 3′-H, 5′-H, 3J = 8.79 Hz), 6.91 d
3
(2H, 3″-H, 5″-H, J = 8.79 Hz), 7.07 br.d (1H, 9-H,
J9,10 = 7.22 Hz), 7.28 br.d (1H, 6-H, J6,5 = 7.22 Hz),
3
1
7.35 d (2H, 2′-H, 6′-H, J = 8.79 Hz), 7.69 d (2H,
(NH), 1580. H NMR spectrum (CDCl3), δ, ppm:
3
2″-H, 6″-H, J = 8.79 Hz), 7.89 d (1H, 5-H, J5,6
=
2.27 m (2H, Ha, Hb), 3.08 m (1H, Hc), 3.30 m (4H,
7-H, 8-H), 3.62 m (1H, Hd), 3.83 br.s (1H, NH), 3.85 s
and 3.89 s (3H each, CH3O), 4.52 d.d (1H, He, J = 6.48,
9.53 Hz), 6.61 d (1H, 10-H, J10,9 = 7.22 Hz), 6.84 d
(1H, 5′-H, 3J = 8.13 Hz), 6.91–6.98 m (2H, 2′-H, 6′-H),
7.01 br.d (1H, 9-H, J9,10 = 7.22 Hz), 7.09 br.s (2H, 5-H,
6-H). Found, %: C 79.51; H 6.49; N 4.30. C23H23NO2.
Calculated, %: C 79.97; H 6.71; N 4.05.
7.22 Hz), 8.35 s (1H, N=CH). Found, %: C 78.40;
H 5.59; N 8.92. C30H27N3O2. Calculated, %: C 78.07;
H 5.90; N 9.10.
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