New heteroaromatic bis-peri-fused azoxonium cation

Full text of DOI:10.1134/S1070428012050223

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 5, pp. 747−749. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © V.V. Mezheritskii, N.I. Omelichkin, L.G. Minyaeva, O.M. Golyanskaya, A.A. Milov, 2012, published in Zhurnal Organicheskoi Khimii,
2012, Vol. 48, No. 5, pp. 746−748.
SHORT
COMMUNICATIONS
New Heteroaromatic Bis-peri-fused Azoxonium Cation
V. V. Mezheritskiia, N. I. Omelichkina, L. G. Minyaevaa, O. M. Golyanskayaa, and A. A. Milovb
aResearch Institute of Physical and Organic Chemistry at the Southern Federal University
Rostov-on-Don, 344090 Russia
e-mail: mezher@ipoc.rsu.ru
bSouthern Scientific Center, Russian Academy of Sciences, Rostov-on-Don, Russia
Received November 16, 2011
DOI: 10.1134/S1070428012050223
In continuation of the research on the chemistry of
peri-fused heterocycles [1–3] we report here on the
synthesis of a new bis-peri-fused heteroaromatic cation
isolated as salt with perchlorate anion as the counter-ion.
The target product was obtained in several stages.
The bis-acylation of 1,5-dimethoxynaphthalene (I) af-
forded compound II whose demethylation proceeded
through intermediate A giving compound III with
a methylenequinone structure which at heating both with
1 mol of ethylhydrazine and its double excess furnished
monoheterocycle IV, whereas the 5-hydroxy-6-carbonyl
peri-moiety was not affected in this process. This result
seems rather unusual since the short heating in alcohol of
peri-hydroxycarbonyl compounds with hydrazines is the
easiest way of the preparation of peri-fused 1,2-diazines
[4–6]. The short heating of diazine IV with perchloric
acid in the acetic acid solution resulted in the dehydration
of the peri-hydroxycarbonyl moiety with the closure of
a five-membered ring and the formation of perchlorate V.
The closure of the five-membered furylium ring and the
formation of cation V is confirmed by the disappearance
of the bands of carbonyl and hydroxy groups in the IR
C6H4Me-п
1
2
OH
COC6H4Me-п
1
OMe
OMe COC6H4Me-п
O
8
1
8
2
(CHCl2)2
AlCl3
7
6
2
3
п-MeC6H4CO2Cl
8
7
7
6
3
4
_H2O
3
AlCl3
5
4
5
4
6
5
CO
п-MeC6H4
OH
OMe
CO OMe
п-MeC6H4
CO
O
п-MeC6H4
I
II
III
А
3'
Me
Me
4'
2'
1'
2
2
N
Et
N
C6H4Me-п
1
N
Et
N
N
+
5'
1
N
Et
6'
3
3
6
+
4
9
8
4
NH2NHEt
HClO4
9
8
_
5
H2O
5
7
_
_
ClO4
O
ClO4
7
O
п-MeC6H4CO OH
6
IV
Me
Va
Vb
Me
747

MEZHERITSKII et al.
748
spectra, by the appearance of intensive yellow-orange
fluorescence with λmax 538 nm (quantum yield μ 0.65) at
the irradiation with light of λmax 320 nm, and also by the
considerable downfield shift of all proton signals in its
1H NMR spectrum compared to the spectra of precur-
sor IV due to the formation of the 14π-electron hetero-
aromatic circuit on the periphery of the bis-peri-fused
framework in cation V.
ethyl acetate, the precipitate was filtered off. Yield 5.85 g
(98%), yellow substance, mp 252–254°C (from benzene).
1
IR spectrum, ν, cm–1: 1655, 1605, 1591, 1551. H NMR
spectrum (CDCl3), δ, ppm: 2.35 s [6H, (CH3)2], 3.50 s
[6H, (OCH3)2], 6.80 d (2H, H3,7, J 8.0 Hz), 7.15 d (4H,
Htoluyl, J 7.9 Hz), 7.33 d (2H, H2,6, J 8.0 Hz), 7.55 d (4H,
Htoluyl, J 7.9 Hz). Found, %: C 79.44; H 5.91. C28H24O4.
Calculated, %: C 79.23; H 5.70.
The quantum-chemical calculations by the method
of functional density theory B3LYP/6-31G** [7] show
that system V is stable and corresponds to the minimum
on PES. The calculation shows that the central bis-peri-
fused frame of molecule V is flat. Therewith the analysis
of the electron density distribution demonstrated suffi-
ciently weak delocalization of the positive charge along
the π-system and its prevailing localization around the
oxygen center of the molecule Va. The calculation data
are shown on the figure.
6-(4-Methylbenzoyl)-2-(4-methylphenyl)-5H-
naphtho[1,8-bc]furan-5-one (III). Into a slurry of
2.07 g (5 mmol) of compound II in 48 ml of tetrachloro-
ethane heated to 30–35°C was added by portions 3.25 g
(25 mmol) of anhydrous aluminum chloride, and the
reaction mixture was heated for 5 h on a boiling water
bath. On cooling the mixture was poured on ice with
added 2–3 ml of hydrochloric acid, the organic layer was
separated, the solvent was removed by steam distillation
to obtain 1.7 g of yellow substance, mp 160–170°C.
On crystallization from benzene we obtained 1.47 g
(83%) of chromatographically pure compound III, mp
214–216°C. IR spectrum, ν, cm–1: 1665, 1637, 1605,
1,5-Di(4-methylbenzoyl)4,8-dimethoxynaphtha-
lene (II). To a slurry of 2.66 g (14 mmol) of 1,5-dime-
thoxynaphthalene (I) in 10 ml of 1,2-dichloroethane was
added 4 g (30 mmol) of anhydrous aluminum chloride,
the mixture was cooled to 0°C and thereto was added by
small portions while stirring 4 ml (30 mmol) of p-toluic
acid chloride. The mixture was stirred for 12 h at room
temperature, then it was poured on ice with added 2–3 ml
of hydrochloric acid, and it was left under hood till total
evaporation of dichloroethane. The separated precipitate
was filtered off, dried at 40–50°C, boiled for 4–5 min in
1
1576, 1556. H NMR spectrum (CDCl3), δ, ppm: 2.35 s
(3H, 2-C6H4CH3), 2.45 s (3H, 6-COC6H4CH3), 6.60 d
(1H, H8, J 9.4 Hz), 7.18 d (2H, 2-C6H4CH3, J 7.8 Hz),
7.38 d (2H, 6-COC6H4CH3, J 8.1 Hz), 7.45 d (1H, H4,
J 8.1 Hz), 7.68 d (2H, 2-C6H4CH3, J 7.8 Hz), 7.74 d (1H,
H3, J 8.1 Hz), 7.90–8.00 M (3H, 6-COC6H4CH3, H7).
Found, %: C 82.44; H 4.91. C26H18O3. Calculated, %:
C 82.52; H 4.79.
Results of calculation of cation V by the method B3LYP/6-31G**. Bond lengths are given in Å.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 5 2012

NEW HETEROAROMATIC BIS-peri-FUSED AZOXONIUM CATION
749
C 66.74; H 5.91; Cl 7.09; N 5.54. C28H27ClN2O5. Calcu-
lated, %: C 66.33; H 5.57; Cl 6.99; N 5.53.
[1-Ethyl-6-hydroxy-3-(4-methylphenyl)-1H-
benzo[de]cinnolin-7-yl](4-methylphenyl)methanone
(IV). To a solution of 280 mg (0.7 mmol) of peri-oxo-
ketone III in a mixture of 3 ml of ethanol and 2 ml of
chloroform was added 55 mg (0.9 mmol) of ethylhydra-
zine, and the mixture was heated at reflux on a boiling
water bath for 60–70 min. Then the reflux condenser was
removed, and the solvent was partially evaporated till
the precipitate started to separate. On cooling the solu-
tion 210 mg (75%) of dark-red precipitate was filtered
off. After crystallization from acetic acid the precipitate
was heated for 4 h at 40–50°C in the drying cabinet to
obtain a substance of mp 234–236°C. IR spectrum, ν,
cm–1: 3052, 3025, 1607, 1585, 1546. UV spectrum, λ,
nm (ε), in acetonitrile: 266 (13048), 363 (3929), 494
(9667). 1H NMR spectrum (CD2Cl2), δ, ppm: 1.39 t (3H,
CH2CH3, J 7.5 Hz), 2.42 s (3H, C6H4CH3), 2.43 s (3H,
C6H4CH3), 4.04 (2H, CH2CH3, J 7.5 Hz), 6.07 d (1H, H9,
J 9.1 Hz), 7.16 d (1H, H5 , J 8.3 Hz), 7.25–7.35 M (5H,
3-C6H4CH3, 7-COC6H4CH3, H4), 7.48 d (2H, 3-C6H4CH3,
J 8.0 Hz), 7.62 d (2H, 7-COC6H4CH3, J 8.0 Hz), 7.75 d
(1H, H9, J 9.1 Hz), 10.55 s (1H, OH). Found, %: C 79.64;
H 5.91; N 6.34. C28H24N2O2. Calculated, %: C 79.98;
H 5.75; N 6.66.
1H NMR spectra were registered on a spectrometer
Bruker DPX-250 (250 MHz), internal reference TMS.
IR spectra were obtained on a spectrophotometer Varian
Excalibur 3100 FT-IR by the method of distorted com-
plete internal reflection. Electronic spectra in acetonitrile
were recorded on a spectrophotometer (Uv-Vis) Varian
Cary 100 Scan, luminescence spectra (in acetonitrile), on
a spectrofluorimeter Hitachi 6010.
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1-Ethyl-3,7-bis(4-methylphenyl)-1H-[1]-
benzofuro[5,4,3-def]cinnolin-6-ium (V). In 6 ml of acetic
acid was heated to complete dissolution 82 mg (0.2 mmol)
of diazine IV, and 4 drops of 70% perchloric acid was
added. On cooling the separated precipitate was filtered
off, dried at 50°C to complete removal of acetic acid
(monitoring by IR spectrum) to obtain 92 mg (93%) of
dark-red perchlorate, mp 253–255°C. IR spectrum, ν,
cm–1: 1610, 1549, 1431, 1092 (ClO4 ). UV spectrum, λ,
−
nm (ε), in acetonitrile: 224 (28277), 287 (26278), 497
(45778). 1H NMR spectrum (CDCl3), δ, ppm: 1.82 t
(3H, CH2CH3, J 7.1 Hz), 2.51 s (3H, C6H4CH3), 2.53 s
(3H, C6H4CH3), 5.11 (2H, CH2CH3, J 7.4 Hz), 7.52 d
(4H, 3-C6H4CH3, J 8.1 Hz), 7.88 d (2H, 7-COC6H4CH3
, J 8.1 Hz), 8.14 d (1H, H9, J 9.1 Hz), 8.29 d (2H, 7-CO-
C6H4CH3 , J 8.1 Hz), 8.47 d (1H, H5, J 8.8 Hz), 8.61 d
(1H, H4, J 8.8 Hz), 9.02 d (1H, H8, J 9.1 Hz). Found, %:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 5 2012