Oxidative transformatons of 2-aryl-1,2,3,4,7,8-hexahydroacenaphtho[5,6-bc] azepin-4-ones

Article abstract of DOI:10.1134/S1070428008070208

Reactions of partial (elimination of H₂ from the bimethylene unit) and exhaustive (elimination of 2H₂ from the bimethylene unit and the seven-membered heterocycle) dehydrogenation of 2-aryl-1,2,3,4,7,8- hexahydroacenaphtho[5,6-bc]aze

Full text of DOI:10.1134/S1070428008070208

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 7, pp. 1064−1071. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © A.N. Antonov, R.V. Tyurin, K.A. Lysenko, A.F. Smol’yakov, V.V. Mezheritskii, 2008, published in Zhurnal Organicheskoi Khimii,
2008, Vol. 44, No. 7, pp. 1074−1080.
Oxidative Transformatons of 2-Aryl-1,2,3,4,7,8-hexahydro-
acenaphtho[5,6-bc]azepin-4-ones
A. N. Antonova, R. V. Tyurina, K. A. Lysenkob, A. F. Smol’yakovb, and V. V. Mezheritskiia
aResearch Institute of Physical and Organic Chemistry at the South Federal University,
Rostov-on-Don, 344090 Russia
e-mail: mezher@ipoc.rsu.ru
bNesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow, 119991 Russia
e-mail: kostya@xrlab.ineos.ac.ru
Received Novemner 19, 2007
Abstract—Reactions of partial (elimination of H2 from the bimethylene unit) and exhaustive (elimination of 2H2
from the bimethylene unit and the seven-membered heterocycle) dehydrogenation of 2-aryl-1,2,3,4,7,8-
hexahydroacenaphtho[5,6-bc]azepin-4-ones were performed. The effect of the electronic structure of initial and
dehydrogenated compounds on their spectral characteristics was discussed. New peri-fused heterocyclic systems
were obtained.
DOI: 10.1134/S1070428008070208
The key stage in the formation of the new heterocyclic
system IXa was evidently the [4+2]-cycloaddition of
partially dehydrogenated molecules IIIa (dienophile) to
azomethine VIIIa (as diene operated the fragment: abcd),
the product of a prototropic opening of the azepine
heterocycle; subsequently adduct B underwent aromatiz-
ation.
In the preceding publication [1] we described a prep-
aration method of 2-aryl-1,2,3,4,7,8-hexahydro-
acenaphtho[5,6-bc]-azepin-4-ones II bazed on a reaction
of acenaphthene peri-aminoketone I with aromatic
aldehydes. These compounds are possible synthons for
the preparation of qualitatively new heteroaromatic
systems by means of exhaustive dehydrogenation of the
saturated carbon-carbon units of the heterocycle and the
bimethylene fragment.
After the reaction with chloranil of N-methyl-
substited azepines Va and Vb (obtained from compounds
IIa and IIb and methyl iodide) products of partial VIa
and VIb and exhaustive dehydrogenation VIIa and VIIb
were isolated; hence a conclusion was possible that the
primary act was the dehydrogenation of the bimethylene
fragment. The same should be valid for the sequence of
azepines dehydrogenation stages in compounds lacking
a substituent at the nitrogen atom (II J III J IV).
The structure of compounds synthesized was
confirmed by the spectral data. The final proof of the
structure of compounds IIIa and Va was obtained by
XRD analysis (Figs. 1 and 2).
Dehydrogenation of NH-derivatives IIa and IIb of
the said heterocyclic system with chloranil (2,3,5,6-
tetrachloro-1,4-benzoquinone) in ether or THF resulted
in a multicomponent mixture that was subjected to
column chromatography to yield several individual
compounds. It was observed that the readiness and degree
of dehydrogenation depend on the character of the aryl
substituent in the position 2 of the heterocycle. For
instance, from compound IIa with a 2-anisyl substituent
only the product of bimethylene unit dehydrogenation
IIIa was obtained, whereas from 2-veratryl-substituted
compound IIb formed both products of the partial, IIIb,
and exhaustive, IVb, dehydrogenation. From the reaction
products of 2-anisyl derivative IIa with chloranil along-
side compound IIIa trace amount (yield 3%) was isolated
of one more compound that based on IR, 1H NMR, and
mass spectra was identified as a substance of structure
IXa.
The principal geometric parameters of the molecules
are close to the values expected for this class compounds.
In both structures the acenaphthene and acenaphthylene
fragments are planar. The appearance of a double bond
in the molecule results in insignificant shortening of the
bond distances in the five-membered ring of compound
1064

OXIDATIVE TRANSFORMATINS OF 2-ARYL-1,2,3,4,7,8-HEXAHYDRO-...
1065
Ar
Ar
Me
H2N
2
3
O
N 1
4
O
O
Me
HN
10
5
MeI/K2CO3
ArCHO
9
6
8Va, V7b
IIa, IIb
I
Chloranil
Chloranil
Ar
Ar
Ar
Ar
2
3
2
3
4
2
3
2
3
1
N
O
O
O
O
1
1
4
Me
1
8
4
7
Me
4
HN
HN
N
10
10
5
5
6
10
10
5
5
9
6
9
9
9
6
6
8
8
7
7
8
7
IIIa, IIIb
VIa, VIb
VIIa, VIIb
IVb
O
Ar
Ar
6
Ar
7
5
2
3
H
O
Me
a
4
O
4
3
Me
OH
N b
c
1
N
N
8
9
2
5
6
10
9
d
1
10
11
Ar
N
H
H
15
16
14
8
7
13
12
B
A
VIIIa
O
6
Ar
5
7
O
4
3
2
Me
N
8
9
1
10
11
Ar
N
H
15
16
14
13
12
IXa
Ar = 4-MeOC6H4 (a), 3,4-(MeO)2C6H3 (b).
these compounds is apparently due to the appearance of
a conjugation between the nitrogen heteroatom and the
carbonyl group through a system of the multiple bonds
of the acenaphthylene framework in molecule IIIa and
the absence of this conjugation in molecule Va.
IIIa compared with compound Va. The conformations
of the azepine ring in compounds IIIa and Va are slightly
different. For instance, the conformation of the azepine
ring in compound IIIa may be described as a distorted
envelope with the deviation of atom C14 from the plane
formed by atoms C10, C11, C1, N1, C15, and C13, and that
of compound Va, as distorted sofa with the deviation of
atoms C14 and C15 from the plane formed by atoms C1,
C11, C10, N1, and C13. The observed difference in the
conformation of the seven-membered heterocycle in
The bond surrounding of nitrogen atoms in
compounds IIIa and Va is pyramidal: the sum of the
bond angles equals 355.5 and 350.9° respectively. The
analysis of crystal packing showed that beside the
...
...
intermolecular hydrogen bond N–H O [N1–H O1 (–x
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

ANTONOV et al.
1066
Fig. 1. General view of a molecule of compound IIIa. Carbon
Fig. 2. General view of a molecule of compound Va. Main
bond distances: C4–C5 1.510(3), C5–C6 1.538(3), C6–C7
1.515(3), O1–C13 1.218(2), C1–N1 1.417(2), N1–C15 1.470(2),
atoms of the minor component are shown (see
EXPERIMENTAL). Main bond distances: C4–C5 1.464(2),
C5–C6 1.355(2), C6–C7 1.465(2), O1–C13 1.221(2), N1–C1
°
N1–C23 1.458(2) A.
°
1.377(2), N1–C15 1.450(2) A.
°
...
+ 2, y + 1/2, –z + 1/2), N1 O1 2.986(2) A] in compound
IIIa (Fig. 3) all other contacts in the crystals under study
corresponded to the common van der Waals interactions.
The mentioned hydrogen bond joined the molecules of
compound IIIa into chains directed along the
crystallographic axis b.
In the H NMR spectra the signals of protons H10
1
(upfield) and H5 (downfield) are the boarder signals of
naphthalene framework protons. It is readily observed
that in going from hydrogenated to partially and then to
completely dehydrogenated compounds these signals
gradually shifted downfield. The latter compounds are
aromatic despite the presence of 16 π-electrons for they
consist of two aromatic fragments: 10π-electron fragment
of the naphthalene ring and 14π-electron contour situated
on the perimeter of the peri-fused heterocyclic system.
Some spectral characteristics of hydrogenated,
partially and completely dehydrogenated peri-fused
heterocyclic systems make it possible to follow clearly
the changes in their electronic structure.
To ensure the validity of conclusions the spectra of
compounds IIa and IIb described in [1] were again
registered on the same instruments and in the same
conditions as the spectra of compounds III–VII
described in this publication.
Inasmuch as the IR spectra were recorded from mulls
in mineral oil the position of the “carbonyl” band νCO
depended on many factors (the presence or absence of
hydrogen bonds, type of the crystal lattice etc.) and
therefore could not underlie a rigorous conclusion.
Nonetheless, the considerable shift of this band from the
values 1650–1687 cm–1 in hydrogenated (II, V) and
partially dehydrogenated (III, VI) compounds into the
low-frequency region (~1600 cm–1) in systems subjected
to exhaustive dehydrogenation (IV, VII) indicated the
aromatization of the latter and the significant contribution
of the betaine form D into their structure.
Fig. 3. Intermolecular hydrogen bonds in the crystal of
...
compound IIIa. Parameters of the H-bond: N1 O1A 2.986(3),
°
...
...
N1H O1A 2.12 A, angle N1–H O1A 163°.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

OXIDATIVE TRANSFORMATINS OF 2-ARYL-1,2,3,4,7,8-HEXAHYDRO-...
1067
The electronic structure of the new heteroaromatic
systems is sufficiently completely and clearly described
by presented below resonance structures C and D whose
protons (R = H) or methyl groups (R = Me) at the nitrogen
atom also suffer a downfield shift. The signals of protons
H7 and H8 belonging to the vinyl group appear in the
region characteristic of aromatic protons evidencing their
involvement into the aromatic conjugation in the 14π-
electron peripheral contour. The most upfield signal
belonged to atom H3 of the heteroaromatic system due
to the “pumping” of the electron density into this position
at the sacrifice of the lone electron pair of nitrogen
heteroatom.
center are magnetically nonequivalent and therefore
appear in the 1H NMR spectra as one-proton doublets of
doublets of dissimilar appearance. The methine proton
(ArCH) at the asymmetrical center in the heterocycle of
these compounds gives rise in the 1H NMR spectrum to
one-proton doublet or doublet of doublets at ~4.8 ppm
In the mass spectrum of compound IIIa a molecular
ion [M]+ was detected; it underwent fragmentation with
ejection of a p-vinylanisole molecule giving a fragment
ion Φ1.
Ar
.
+
.
O
HN
HN
O
+
Ar
Ar
_n
p
-MeOC6H4CH=CH2 (_134)
O_
+
RN
O
RN
.
IIIa, m/z 327 [M]+
Φ1 (m/z 193)
A choice between two tautomeric structures IVb and
A in favor of the former was done based on the
comparison of the electronic spectra of compounds IVb
and VIIb (Fig. 4). However the essential difference in
the extinction coefficients at the coincidence of the
position of the absorption bands in the electronic spectra
of the compared compounds and the presence of two
singlets of equal intensity (1:1) from the proton in the
C
D
The protons of vinyl group of compounds III, IV,
VI, and VII are distinguished from the protons of naph-
thalene framework by low coupling constant (~5 Hz) in
conformity to the characteristic data of the previously
obtained [2–5] peri-fused heterocyclic systems,
acenaphthylene derivatives.
1
position 3 in the H NMR spectrum of compound IVb
suggests that both tautomers can exist in solutions.
The methylene group protons of azepine heterocycle
in compounds II, III, V, and VI involved into a strongly
coupled spin system and located near the asymmetrical
In the IR spectrum of compound IXa appear two
carbonyl bands and a band of the NH group. The 1H NMR
.
.
.
.
.
.
.
.
Fig. 4. Electron absorption spectra of compounds IVb (1) and VIIb (2) in acetonitrile.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

ANTONOV et al.
1068
Main crystallographic data and parameters of refinement of
compounds IIIa and Va
heterocycle of the molecular ion with the closure of
a five-membered heterocycle similarly to the process
observed in the fragmentation of compound IIIa.
The analysis of the mass spectra of compounds IIIa
and IXa leads to a conclusion that this kind molecules
are prone to elimination of a neutral vinylaromatic
fragment, and therefore this fact may serve as a proof of
the presence in their structure of a seven-membered
heterocycle. This process resembles the elimination of
arylacetylenes that we have observed in the mass spectra
of 2-aryl-1,4-dihydroacenaphtho[5,6-bc]oxepin-4-ones
[6] and 2-aryl-1,4,7,8-tetrahydroacenaphtho[5,6-bc]-
oxepin-4-ones [7].
EXPERIMENTAL
1H NMR spectra were registered on a spectrometer
Varian Unity-300 (300 MHz). As internal reference
served residual signals of CHCl3 (δ 7.25 ppm) and
(CH3)2SO (δ 2.50 ppm). Electron absorption spectra were
recorded in acetonitrile on a spectrophotometer Specord
M-40. Vibrational spectra were measured on a Specord
75IR instrument from mulls in mineral oil. XRD investig-
ation of single crystals of compounds IIIa and Va was
carried out on three-circle diffractometers using MoKα-
radiation, graphite monochromator, and ω-scanning. The
structures were solved by the direct method and refined
by least-squares procedure in full-matrix anisotropic
approximation by F2hkl. The position of hydrogen atoms
in IIIa molecule were calculated geometrically, and in
Va molecule the hydrogen atoms were localized from
the difference Fourier syntheses of the electron density
and refined isotropically. Analysis of the difference
Fourier charts showed that atoms C14 and C15 in com-
pound IIIa are disordered by two positions with
occupancy of the positions 0.9 and 0.1. The refinement
of the minor component was performed in the isotropic
approximation. The main crystallographic data and
parameters of the refinement of compounds IIIa and Va
are presented in the table.All calculations were perform-
ed by the software complex SHELXTL PLUS [8].
2-(4-Methoxyphenyl)-1,2,3,4,7,8-hexahydro-
spectrum corresponds to a structure containing an acetyl
group (CH3C=O), two methoxy groups (two three-proton
singlets), a fragment ArCHCH2, a bimethylene “bridge”
(CH2CH2), a single NH group, and 15 aromatic protons.
The mass spectrum contains a peak with a mass 653
[M + H]+ and two fragment ions: Φ2 arising from ejec-
tion of a CO molecule, and Φ3 formed by elimination of
p-methoxyphenylethylene from the seven-membered
acenaphtho[5,6-bc]azepin-4-one (IIa) [1]. IR spectrum,
1
ν, cm–1: 1650 (C=O). H NMR spectrum (CDCl3), δ,
ppm: 6.80 (H10), 8.15 (H5), 4.36 (NH).
2-(3,4-Dimethoxyphenyl)-1,2,3,4,7,8-hexahydro-
acenaphtho[5,6-bc]azepin-4-one (IIb) [1]. IR spectrum,
1
ν, cm–1: 1650 (C=O). H NMR spectrum (CDCl3), δ,
ppm: 6.82 (H10), 8.14 (H5), 4.36 (NH).
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OXIDATIVE TRANSFORMATINS OF 2-ARYL-1,2,3,4,7,8-HEXAHYDRO-...
1069
2-(4-Methoxyphenyl)-1,2,3,4-tetrahydroacenaph-
tho[5,6-bc]azepin-4-one (IIIa). To a solution of 100 mg
(0.3 mmol) of compound IIa [1] in 3 ml of THF was
added a solution of 75 mg (0.3 mmol) of chloranil in 5 ml
of THF, and the mixture was stirred at room temperature
for 1 h. The solution was evaporated, the dry residue
was dissolved in chloroform and subjected to column
chromatography on aluminum oxide collecting the
fraction of the highest chromatographic mobility,
whereas the other products were retained “at the start”.
Yield 52 mg (53%), violet powder, mp 138–139°C.
IR spectrum, ν, cm–1: 3407 (NH), 1660 (C=O), 1607.
1H NMR spectrum (CDCl3), δ, ppm: 3.20 d.t (1H,
40 mg (17%), dark-red powder, mp 208–209°C. UV
spectrum, λmax, nm (ε 10–4): 550 (0.063), 468 (0.25), 418
(0.27), 395 (0.35), 360 (0.44), 311 (1.39), 288 (1.28),
253 (1.07). IR spectrum, ν, cm–1: 3350, 3320 (NH), 1620
(C=O), 1590. 1H NMR spectrum (CDCl3), δ, ppm:
3.92 s (3H, CH3O), 3.97 s (3H, CH3O), 6.28 d (1H, H3,
J 1.91 Hz), 6.95 d (1H, H10, J10,9 8.41 Hz), 7.19–7.32 m
(3HAr, H6, H7, H9), 7.45 d (1H, H8, J8,7 5.35 Hz), 7.90 d
(1HAr, J 7.65 Hz), 8.10 d (1HAr, J 7.65 Hz), 8.20 br.s
(1H, NH), 8.89 d (1H, H5, J5,6 7.27 Hz). Found, %:
C 77.64; H 5.00; N 4.23. C23H17NO3. Calculated, %:
C 77.75; H 4.79; N 3.94.
1-Methyl-2-(4-methoxyphenyl)-1,2,3,4,7,8-hexa-
hydroacenaphtho[5,6-bc]azepin-4-one (Va). To
a solution of 200 mg (0.61 mmol) of compound IIa [1]
in 4 ml of acetonitrile was added 200 mg (1.45 mmol) of
potassium carbonate, 0.2 ml (3.24 mmol) of methyl
iodide, and the mixture was heated at reflux for 10 h. On
removing the solvent in air the dry residue was dissolved
in chloroform and subjected to column chromatography
on aluminum oxide (eluent chloroform), collecting the
most mobile fraction (Rf 0.9). Yield 188 mg (90%),
yellow crystals, mp 144–145°C. IR spectrum, ν, cm–1:
HαCHβ, J 16.11, J 1.58 Hz), 3.60 d.d (1H, HαCHβ,
2J 11.06, 3J 2.50 Hz), 3.80 s (3H, CH3O), 4.77 br.d (1H,
ArCH, J 11.37 Hz), 5.00 br.s (1H, NH), 6.63 d (1H, H10,
J10,9 7.58 Hz), 6.83 d (1H, H7, J7,8 5.05 Hz), 6.92 d (2HAr,
J 8.85 Hz), 7.14 d (1H, H8, J8,7 5.05 Hz), 7.35 d (2HAr,
J 8.53 Hz), 7.45 d (1H, H9, J9,10 7.58 Hz), 7.78 d (1H,
H6, J6,5 7.27 Hz), 8.34 d (1H, H5, J5,6 7.59 Hz). Mass
spectrum, m/z (Irel, %): 327 [M]+ (50), 193 (100). Found,
%: C 80.50; H 5.36; N 4.45. C22H17NO2. Calculated, %:
C 80.73; H 5.20; N 4.28.
2
3
2-(3,4-Dimethoxyphenyl)-1,2,3,4-tetrahydroace-
naphtho[5,6-bc]azepin-4-one (IIIb) was obtained
similarly to compound IIIa from 108 mg (0.3 mmol) of
compound IIb [1], 75 mg (0.3 mmol) of chloranil in
10 ml of THF. Yield 64 mg (60%), violet powder, mp
184–185°C. IR spectrum, ν, cm–1: 3340 (NH), 1650
1
1680 (C=O), 1650, 1607. H NMR spectrum (CDCl3),
δ, ppm: 2.75 s (3H, CH3N), 2.94 q (1H, Hα CHβ, J1 5.66,
J2 6.65 Hz), 3.32–3.48 m (5H, HαCHβ, CH2CH2), 3.80 s
(3H, CH3O), 4.83 q (1H, ArCH, J1 5.34, J2 6.03 Hz),
6.82 d (2H, HAr, J 8.71 Hz), 6.89 d (1H, H10, J 7.27 Hz),
7.19 d (2HAr, J 8.71 Hz), 7.26–7.29 m (2H, H6, H9), 7.76
d (1H, H5, J 7.27 Hz). Found, %: C 80.54; H 5.92;
N 4.28. C23H21NO2. Calculated, %: C 80.47; H 6.12;
N 4.08.
1
(C=O), 1600. H NMR spectrum (CDCl3), δ, ppm:
3.22 d.t (1H, HαCHβ, 2J 16.01, 3J 1.57 Hz), 3.60 q (1H,
2
3
HαCHβ, J 11.30, J 2.50 Hz), 3.85 s (6H, 2CH3O),
4.75 br.d (1H, ArCH, J 10.99 Hz), 5.03 br.s (1H, NH),
6.65 d (1H, H10, J10,9 7.53 Hz), 6.83 d (1H, H7,
J7,8 5.03 Hz), 6.86 d (1HAr, J 8.17 Hz), 6.92 s (1HAr),
6.98 d (1HAr, J 8.16 Hz), 7.13 d (1H, H8, J8,7 5.34 Hz),
7.44 d (1H, H9, J9,10 7.54 Hz), 7.77 d (1H, H6,
J6,5 7.54 Hz), 8.34 d (1H, H5, J5,6 7.53 Hz). Found, %:
C 77.59; H 5.06; N 4.15. C23H19NO3. Calculated, %:
C 77.31; H 5.32; N 3.92.
2-(3,4-Dimethoxyphenyl)-1-methyl-1,2,3,4,7,8-
hexahydroacenaphtho[5,6-bc]azepin-4-one (Vb) was
prepared in the same way as compound Va from 450 mg
(1.25 mmol) of compound IIb [1], 426 mg (3 mmol) of
potassium carbonate, 0.4 ml (3.48 mmol) of methyl
iodide by boiling in 10 ml of acetonitrile for 15 h. Yield
430 mg (92%), yellow crystals, mp 167–168°C. IR
1
spectrum, ν, cm–1: 1673 (C=O), 1600. H NMR spectrum
2-(3,4-Dimethoxyphenyl)-1,4-dihydroacenaphtho-
[5,6-bc]azepin-4-one (IVb). To a solution of 244 mg
(0.68 mmol) of compound IIIb in 4 ml of THF was added
at stirring a solution of 334 mg (1.36 mmol) of chloranil
in 6 ml of THF, the mixture was kept for 3 h at room
temperature, the solvent was removed in air, the dry
residue was dissolved in chloroform and subjected to
column chromatography on aluminum oxide (eluent
chloroform), collecting the first fraction (Rf 0.35). Yield
(CDCl3), δ, ppm: 2.75 s (3H, CH3N), 2.95 q (1H, HαCHβ,
J1 5.68, J2 6.64 Hz), 3.32–3.47 m (5H, HαCHβ, CH2CH2),
3.75 s (3H, CH3O), 3.85 s (3H, CH3O), 4.81 q (1H,ArCH,
J1 5.37, J2 6.00 Hz), 6.75–6.87 m (3H, H10, 2HAr),
6.94 d (1H, H6, J6,5 7.58 Hz), 7.27 br.d (2H, H9, HAr,
J 7.58 Hz), 7.78 d (1H, H5, J5,6 7.58 Hz). Found, %:
C 77.56; H 6.32; N 3.48. C24H23NO3. Calculated, %:
C 77.21; H 6.17; N 3.75.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

ANTONOV et al.
1070
5.05 Hz), 7.37 d (1H, H8, J8,7 5.05 Hz), 7.48 d (1H, H10,
1-Methyl-2-(4-methoxyphenyl)-1,2,3,4-tetra-
10,9 7.75 Hz), 7.53 d (2HAr, J 8.53 Hz), 7.90 d (1H, H9,
9,10 7.76 Hz), 8.05 d (1H, H6, J6,5 7.45 Hz), 8.78 d (1H,
hydroacenaphtho[5,6-bc]azepin-4-one (VIa).
A solution of 46 mg (0.134 mmol) of compound Va and
33 mg (0.134 mmol) of chloranil in 1 ml of o-dichloro-
benzene was boiled for 5 min. The solvent was evaporat-
ed in air, the dry residue was dissolved in chloroform
and subjected to column chromatography on aluminum
oxide (eluent chloroform), collecting the first fraction
(Rf 0.9). Yield 20 mg (44%), violet powder, mp 94–95°C.
IR spectrum, ν, cm–1: 1660 (C=O), 1590. 1H NMR spec-
trum (CDCl3), δ, ppm: 2.90 s (3H, NCH3), 3.30 d.d (1H,
J
J
H5, J5,6 7.44 Hz). Found, %: C 81.57; H 5.13; N 4.24.
C23H17NO2. Calculated, %: C 81.42; H 5.01; N 4.13.
1-Methyl-2-(3,4-dimethoxyphenyl)-1,4-dihydro-
acenaphtho[5,6-bc]azepin-4-one (VIIb) was obtained
similarly to compound VIIa from 100 mg (0.268 mmol)
of compound Vb and 132 mg (0.536 mmol) of chloranil.
Yield 46 mg (47%), red substance, mp 166–167°C. UV
spectrum, λmax, nm (ε × 10–4): 550 (0.096), 468 (0.41),
420 (0.50), 395 (0.44), 361 (0.61), 311 (1.32), 288 (1.49),
1
2
HαCHβ, J 4.42, J 9.16 Hz), 3.50 d.d (1H, HαCHβ,
2J 10.11, J 3.48 Hz), 3.75 s (3H, CH3O), 4.80 d.d
(1H, ArCH, J1 4.58, J2 5.68 Hz), 6.70 d (1H, H10,
3
1
256 (1.51). IR spectrum, ν, cm–1: 1600, 1580. H NMR
spectrum (CDCl3), δ, ppm: 3.50 s (3H, NCH3), 3.96 br.s
(6H, 2CH3O), 6.17 s (1H, H3), 6.93 d (1H, H10,
J 8.06 Hz), 7.06 d (1HAr, J 2.21 Hz), 7.14 d.d (1HAr,
1J 8.05, 2J 2.21 Hz), 7.23 d (1H, H7, J7,8 5.25 Hz), 7.38 d
(1H, H8, J8,7 5.25 Hz), 7.47 d (1HAr, J 8.05 Hz), 7.90 d
(1H, H9, J9,10 8.08 Hz), 8.04 d (1H, H6, J6,5 7.45 Hz),
8.77 d (1H, H5, J5,6 7.44 Hz). Found, %: C 78.37;
H 5.33; N 4.02. C24H19NO3. Calculated, %: C 78.05;
H 5.15; N 3.79.
J
J
10,9 7.59 Hz), 6.81 d (2HAr, J 8.84 Hz), 6.82 d (1H, H7,
7,8 5.06 Hz), 7.08 d (1H, H8, J8,7 5.05 Hz), 7.10 d (2HAr,
J 8.84 Hz), 7.55 d (1H, H9, J9,10 7.58 Hz), 7.63 d (1H,
H6, J6,5 7.15 Hz), 7.90 d (1H, H5, J5,6 7.15 Hz). Found,
%: C 80.73; H 5.68; N 3.93. C23H19NO2. Calculated, %:
C 80.94; H 5.57; N 4.10.
1-Methyl-2-(3,4-dimethoxyphenyl)-1,2,3,4-tetra-
hydroacenaphtho[5,6-bc]azepin-4-one (VIb) was
obtained similarly to compound VIa from 50 mg
(0.134 mmol) of compound Vb and 33 mg (0.134 mmol)
of chloranil. Yield 23 mg (46%), violet substance, mp
135–136°C. IR spectrum, ν, cm–1: 1660 (C=O), 1590.
1H NMR spectrum (CDCl3), δ, ppm: 2.95 s (3H, CH3N),
3.30 d.d (1H, HαCHβ, 3J 4.18, 2J 9.11 Hz), 3.52 d.d (1H,
HαCHβ, 2J 10.51, 3J 2.82 Hz), 3.72 s (3H, CH3O), 3.83 s
(3H, CH3O), 4.77 d.d (1H, ArCH, J1 4.39, J2 5.65 Hz),
6.66 s (1HAr), 6.73 d (1H, H10, J10,9 7.65 Hz), 6.75 br.s
(2HAr), 6.82 d (1H, H7, J7,8 5.20 Hz), 7.08 d (1H, H8,
9-Acetyl-2,7-di(4-methoxyphenyl)-1,2,3,4,12,13-
hexahydroazepino[2',3',4':5,6]acenaphtho[1,2-
c]indeno[1,7-gh]quinolin-4-one (IXa). To a solution of
438 mg (1.331 mmol) of compound IIa in 20 ml of ethyl
ether was added at stirring a solution of 327.5 mg (1.331
mmol) of chloranil in 10 ml of ether, the mixture was
kept for 1 h at room temperature, and again a solution
of 327.5 mg (1.331 mmol) of chloranil in 10 ml of ether
was added. The solution obtained was stirred for 2 h.
The solvent was evaporated in air, the dry residue was
dissolved in chloroform and subjected to column
chromatography on aluminum oxide (eluent chloroform),
collecting the fraction of Rf 0.25. On removing the solvent
yield 26 mg (3%), brown powder, mp > 300°C. IR spec-
trum, ν, cm–1: 3350, 1660, 1650, 1610. 1H NMR spectrum
(CDCl3), δ, ppm: 2.50 s (3H, COCH3), 3.15 d (1H,
HαCHβ, J 15.18 Hz), 3.40–3.60 m (5H, HαCHβ,
CH2CH2), 3.80 s (3H, CH3O), 3.95 s (3H, CH3O), 4.70 d
(1H,ArCH, J 11.69 Hz), 5.23 br.s (1H, NH), 6.78 d (1HAr,
J 7.89 Hz), 6.95 d (2HAr, J 8.22 Hz), 7.13 d (2HAr, J 8.85
Hz), 7.25 d (2HAr, J 9.79 Hz), 7.27 d (1HAr, J 7.30 Hz),
7.50 d (1HAr, J 7.28 Hz), 7.85 d (1HAr, J 8.53 Hz), 7.88 s
(1HAr), 7.92 d (1HAr, J 6.63 Hz), 8.13–8.25 m (3HAr).
Found, %: C 81.27; H 5.23; N 4.12. C44H32N2O4.
Calculated, %: C 80.96; H 4.94; N 4.29.
J
8,7 5.20 Hz), 7.54 d (1H, H9, J9,10 7.67 Hz), 7.63 d (1H,
H6, J6,5 7.12 Hz), 7.90 d (1H, H5, J5,6 7.12 Hz). Found,
%: C 77.45; H 5.96; N 3.54. C24H21NO3. Calculated, %:
C 77.63; H 6.17; N 3.77.
1-Methyl-2-(4-methoxyphenyl)-1,4-dihydroace-
naphtho[5,6-bc]azepin-4-one (VIIa). A solution of
46 mg (0.134 mmol) of compound Va and 66 mg
(0.268 mmol) of chloranil in 1 ml of o-dichlorobenzene
was boiled for 30 min. The solvent was evaporated in
air, the dry residue was dissolved in chloroform and
subjected to column chromatography on aluminum oxide
(eluent chloroform), collecting the first fraction (Rf 0.5).
Yield 22 mg (49%), red powder, mp 177–178°C. IR spec-
trum, ν, cm–1: 1607, 1600. 1H NMR spectrum (CDCl3),
δ, ppm: 3.50 s (3H, NCH3), 3.90 s (3H, CH3O), 6.15 s
(1H, H3), 6.97 d (2HAr, J 8.53 Hz), 7.25 d (1H, H7, J7,8
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OXIDATIVE TRANSFORMATINS OF 2-ARYL-1,2,3,4,7,8-HEXAHYDRO-...
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Antonov, A.N., Zh. Org. Khim., 2006, vol. 42, p. 293.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008