Pyran derivatives peri-fused to acenaphthene and acenaphthylene

Article abstract of DOI:10.1134/S1070428011030109

peri-Acyloxyacenaphthenyl bromomethyl ketones prepared by bromination of peri-acyloxyacenaphthenyl methyl ketones reacted with sodium methoxide to give 2-acyl-3-hydroxyacenaphtho[5,6-bc]pyran derivatives, while their reaction with piperidine afforded acen

Full text of DOI:10.1134/S1070428011030109

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 3, pp. 384–391. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © I.A. Abdulaeva, L.G. Minyaeva, V.V. Mezheritskii, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 3,
pp. 393–399.
Pyran Derivatives peri-Fused to Acenaphthene
and Acenaphthylene
I. A. Abdulaeva, L. G. Minyaeva, and V. V. Mezheritskii
Research Institute of Physical and Organic Chemistry, Southern Federal University,
pr. Stachki 194/2, Rostov-on-Don, 344090, Russia
e-mail: mezher@ipoc.rsu.ru
Received August 1, 2010
Abstract—peri-Acyloxyacenaphthenyl bromomethyl ketones prepared by bromination of peri-acyloxyace-
naphthenyl methyl ketones reacted with sodium methoxide to give 2-acyl-3-hydroxyacenaphtho[5,6-bc]pyran
derivatives, while their reaction with piperidine afforded acenaphtho[5,6-bc]pyran-3-on. Heating of the latter in
acetic anhydride produced 3-acetoxyacenaphtho[5,6-bc]pyran which was subjected to dehydrogenation to
obtain a new heteroaromatic system.
DOI: 10.1134/S1070428011030109
Compounds possessing pronounced antibacterial
properties comparable with those of strong antibiotics
were found among peri-fused pyran derivatives [1, 2].
peri-Fused bis-pyran systems like 1,6- and 1,8-dioxa-
pyrenes exhibited unusual photobiological and geno-
toxic activity [3, 4], readily formed charge-transfer
complexes [5], and were used as building blocks for
the synthesis of so-called organic metals [6]. We previ-
ously synthesized 2-acylnaphtho[1,8-bc]pyran-3-ones
and coordination compounds based thereon, which
showed strong yellow–orange fluorescence and were
proposed as effective chemosensors and highly sensi-
tive analytical reagents for qualitative and quantitative
determination of heavy metals [7]. Naphtho[1,8-bc]-
pyran-3-ones were obtained by bromination of peri-
acyloxynaphthyl alkyl ketones at the side alkyl chain
Scheme 1.
OAc COCH2Br
1,4-Dioxane·Br2
Ac
OAc
Ac2O, NaOAc
VI
Ac
OH
Br
CuBr2, EtOAc–CHCl3, Δ
OH
Ac
II
IV
Ac
OBz
OBz COCH2Br
I
PhCOCl, pyridine
CuBr2, EtOAc–CHCl3, Δ
III
V
384

PYRAN DERIVATIVES peri-FUSED TO ACENAPHTHENE AND ACENAPHTHYLENE
385
Scheme 2.
Br
Br
Br–
Br Cu
Cu
O
O
O
O
BrCu
Me
O
Me
O
O
COMe
Me
Me
(1) CuBr2
(2) H2O
IV
–MeCOBr
A
B
C
with subsequent base-catalyzed heterocyclization of
α-bromoalkyl ketones thus formed [8].
frequency shifts are determined by formation of
a strong intramolecular hydrogen bond. We previously
revealed formation of a planar seven-membered
H-chelate ring (which is coplanar to the naphthalene
core) in the crystalline structure of peri-hydroxy
ketone I [10]. Presumably, analogous structure is
intrinsic to 7-bromo derivative IV. We succeeded in
synthesizing peri-acetoxy-substituted naphthenyl
bromomethyl ketone VI using 1,4-dioxane–bromine
complex as brominating agent.
In the present work we followed the same approach
to synthesize a series of pyran derivatives in which the
pyran ring is peri-fused to acenaphthene and acenaph-
thylene ring systems. As starting compound we used
1-(6-hydroxyacenaphthen-5-yl)ethanone (I) [9], which
was converted into esters II and III by conventional
methods (Scheme 1).
We found that peri-acetoxy- and peri-benzoyloxy-
substituted acenaphthenyl methyl ketones differently
reacted with such brominating agent as copper(II)
bromide. The reaction of acetate II with CuBr2 in ethyl
acetate–chloroform involved cleavage of the ester
group and bromination at the aromatic ring (II → IV),
whereas benzoate III reacted with conservation of the
ester group, and bromination involved the side chain
(III → V). Presumably, bromination at the aromatic
ring is preceded by attack by copper(II) bromide at the
ketone carbonyl oxygen atom, and the next steps are
elimination of acetyl bromide and intramolecular rear-
rangement (A → B → C; Scheme 2). Analogous
reaction path in the case of benzoyloxy derivative III
is likely to be hindered by reduced electrophilicity of
the benzoyl group.
In the IR spectra of bromomethyl ketones V and VI
the carbonyl stretching vibration band is displaced to
higher frequencies due to negative inductive effect
of the bromine atom (1710–1715 cm–1 against 1680–
1690 cm–1 in the spectra of methyl ketones II and III).
Compounds V and VI characteristically displayed
a two-proton singlet at about δ ~4.5 ppm due to
protons in the bromomethyl group.
The reactions of bromomethyl ketones V and VI
with bases were governed by the substrate and reagent
nature (Scheme 3). Benzoyloxynaphthenyl ketone V
reacted with ammonium acetate to form a complex
mixture of products. We succeeded in isolating from
the product mixture two compounds, VII and VIII,
resulting from nucleophilic substitution of bromine by
acetoxy and hydroxy groups. Regardless of the nature
of the acyloxy group, the reaction of bromomethyl
ketones V and VI involved cleavage of the ester
moiety (V, VI → D), followed by intramolecular
nucleophilic replacement of the bromine atom with
formation of acenaphtho[5,6-bc]pyran-3-one (IX).
Treatment of benzoyloxynaphthenyl ketone V with
strong bases, e.g., potassium hydroxide, induced de-
protonation of the methylene group (V → E) with
subsequent intramolecular rearrangement (E → F) and
heterocyclization (F → X). The reaction of ketone V
with 4-methoxybenzaldehyde under analogous condi-
tions led to the formation of 2-(4-methoxybenzylidene)
derivative XI (Scheme 3).
The presence of a bromine atom in the ortho
position with respect to the hydroxy group induced
a downfield shift of the hydroxy proton signal in the
1H NMR spectrum of compound IV (δ 12.60 ppm) as
compared to hydroxy ketone I (δ 11.60 ppm) [10].
These findings suggest stronger intramolecular hydro-
gen bond in IV due to effect of bulky ortho-substituent
on the hydroxy group. The IR spectra of peri-hydroxy
ketones I and IV in the condensed phase are charac-
terized by the presence of low-frequency OH stretch-
ing vibration band at 2670 (I) and 2609 cm–1 (IV). The
carbonyl stretching vibration frequency is also reduced
to 1633 (I) and 1627 cm–1 (IV). The observed low-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011

ABDULAEVA et al.
386
Scheme 3.
H
O
O
OBz
OBz COCH2OAc
AcONH4, EtOH
R = Ph
+
RC(O)O
COCH2Br
VII
VIII
Br
O
O
OAc
O
O
O
V, VI
Piperidine
Ac2O, NaOAc
–(CH2)5NCOR
4-MeOC6H4CHO
KOH–EtOH
R = Ph
D
IX
XV
C6Cl4O2
O
C6Cl4O2
OAc
C6H4OMe-4
O
O
O
O
NaOMe
XI
XIV
XVI
O
Ph
O
O
Br
O
Ph
OH
BzO
COCH2Br
BzO
COCHBr
O
KOH–EtOH
V
E
F
X
Ph
O
BF2
O
O
XII
Ph
O
O
Cu
O
2
XIII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011

PYRAN DERIVATIVES peri-FUSED TO ACENAPHTHENE AND ACENAPHTHYLENE
387
D
The reactions of bromomethyl ketones V and VI
with ammonium acetate and piperidine were not selec-
tive, and individual compounds VII, VIII, and XII
2.0
were isolated from multicomponent reaction mixtures
in fairly poor yields (20–30%). The yield of 2-benzoyl-
acenaphthopyran X was 70%; however, this compound
turned out to be unstable. It underwent decomposition
in organic solvents and over chromatographic sorbents
(aluminum oxide, silica gel) to give products which
were not isolated and identified. Therefore, its
1H NMR spectrum cannot be regarded as informative.
Structure X shown in Scheme 3 was postulated by
analogy with more stable derivatives of the naphtha-
lene series [8]. The presence of a ketoenol fragment in
molecule X was confirmed by the ability of this com-
pound to form difluoridoboron and copper chelates
XII and XIII.
1.5
1.0
0.5
0.0
1
2
250
300
350
400
450 λ, nm
Fig. 1. Electronic absorption spectra of compounds (1) XV
and (2) XVI in acetonitrile.
tra (Fig. 1). A solution of XV in acetonitrile almost
does not absorb in the visible region; its absorbance
above ~405–410 nm is negligible, while compound
XVI in acetonitrile absorbs up to ~480 nm. In addition,
the long-wave absorption maximum of compound XVI
is located at λ 405 nm against 345 nm for pyran XV,
indicating extension of conjugated bond system in
going from acenaphthene to acenaphthylene derivative.
1
In the H NMR spectrum of 6-benzoyloxy-5-(hy-
droxyacetyl)acenaphthene (VIII) the hydroxy proton
resonated as a broadened singlet, and protons in the
neighboring methylene group gave a doublet, indicat-
ing spin–spin coupling in the HO–CH2 fragment. The
downfield position of the OH signal (δ 11.10 ppm) is
rationalized by formation of intramolecular hydrogen
bond with closure of five-membered H-chelate ring.
5-Acetoxyacetyl-6-benzoyloxyacenaphthene (VII)
peri-Fused heterocyclic compounds XV and XVI
are luminophors (Fig. 2). 3-Acetoxyacenaphtho-
[5,6-bc]pyran (XV) shows yellow–green emission at
λ 436 nm upon UV irradiation, and compound XVI is
characterized by orange luminescence at λ 518 nm.
1
displayed more complex pattern in the H NMR spec-
Comparison of the chemical shifts of the peripheral
protons (in the naphthalene ring and heteroring) in the
1H NMR spectra clearly illustrates that molecule XVI
trum, and it was difficult to identify protons of the
naphthalene core therein. This may be due to the pres-
ence of conformers (e.g., those with the peri-substit-
uents oriented at the same and opposite sides of the
naphthalene ring plane).
1
λmax 436 nm
λmax 518 nm
2
Our attempt to perform dehydrogenation of naph-
thopyranone IX to obtain fused acenaphthylene deriva-
tive XIV was unsuccessful. Heating of ketone IX with
tetrachlorobenzoquinone in boiling toluene or chloro-
benzene was accompanied by strong tarring, and we
isolated from the reaction mixture only a small amount
of the initial compound. We presumed that introduc-
tion of a double bond into the pyran ring should facili-
tate aromatization and obtained 3-acetoxy derivative
XV. In fact, dehydrogenation of XV gave expected
fused acenaphthylene XVI. However, the latter did not
undergo deacetylation upon treatment (30 min) with
sodium methoxide in methanol at ~35°C. Instead of
expected naphthopyranone XIV we isolated only
initial compound XVI.
350
450
550
λ, nm
400
500
600
Acenaphthene derivative XV is almost colorless,
whereas acenaphthylene derivative XVI is orange.
This is consistent with their electronic absorption spec-
Fig. 2. Luminescence spectra of compounds (1) XV and
(2) XVI in acetonitrile (λexcit 320 nm).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011

ABDULAEVA et al.
Chemical shifts (δ, ppm) of protons in the naphthalene ring and heteroring in the 1H NMR spectra of compounds XV–XIX
388
a
a
a
a
a
OAc
OAc
b
b
b
O
O
O
O
O
b
b
f
c
f
c
f
c
f
c
f
c
e
d
e
d
e
d
e
d
e
d
b
b
O
O
a
a
XVII
XV
XVI
XVIII
XIX
Proton
XVII
XV
XVI
XVIII
XIX
a
6.71
5.91
6.77
–
7.73
–
6.14
5.40
6.16
6.08
6.16
6.08
6.17
5.35
6.01
6.01
6.18
6.18
b
c
6.67
6.62
7.00
6.93
6.44
7.42
d
7.19
8.04
e
7.24
8.10
f
6.72
7.30
Range
5.91–7.24
6.44–7.00
7.30–8.10
5.40–6.16
5.35–6.18
becomes aromatic as the amount of π-electrons in the
peripheral contour attains 14: signals of these protons
shift downfield relative to those observed for nonaro-
matic heterocyclic systems XV and XVII [11] having
an odd number of π-electrons (13) at the periphery. By
contrast, the existence of an 18π-electron peripheral
contour makes structures XVIII and XIX [3, 11] anti-
aromatic, and signals from all peripheral protons in
EXPERIMENTAL
1
The H NMR spectra were recorded on Bruker
DPX-250 and Varian Unity-300 spectrometers at 250
and 300 MHz, respectively, using tetramethylsilane as
internal reference. The IR spectra (attenuated total
reflectance) were measured on a Varian Excalibur
3100 FT-IR spectrometer. The electronic absorption
spectra were obtained from solutions in acetonitrile on
a Varian Cary 100 Scan UV-Vis spectrophotometer,
and the luminescence spectra (acetonitrile) were meas-
ured on a Hitachi 6010 spectrofluorimeter.
1
their molecules are located in the H NMR spectra in
a stronger field relative to those of both aromatic
(XVI) and nonaromatic systems (XV, XVII).
These data clearly confirm the assumption [12–16]
that just peripheral electrons determine aromatic, non-
aromatic, or antiaromatic character of carbo- and het-
erocyclic systems. Comparison of the data for acetoxy
derivatives XV and XVI with those of compounds
XVII–XIX which lack acetoxy substituent may be
regarded as appropriate, taking into account weak ef-
fect of acetoxy group on their spectral parameters. It is
sufficient to consider the chemical shifts of protons in
positions a, c, and f (that are distant from the ethylene
bridge) of XV and XVII and their electronic absorp-
tion spectra (see Fig. 1 and the data of [17, 18]).
6-Acetylacenaphthen-5-yl acetate (II). A small
amount (on a tip of spatula) of anhydrous sodium
acetate was added to a solution of 0.67 g (3 mmol) of
1-(6-hydroxyacenaphthen-5-yl)ethanone (I) in 6 ml of
acetic anhydride, and the mixture was heated for
30 min under reflux. The mixture was cooled and
poured into 20 ml of cold water. When hydrolysis of
acetic anhydride was complete, the precipitate was
filtered off and dried in air. Yield 0.6 g (75%), dark
brown crystals, mp ~60°C. Chromatographic purifica-
tion (aluminum oxide, chloroform) followed by recrys-
tallization from light petroleum ether with addition of
a few drops of benzene gave light yellow crystals with
mp 79–80°C. IR spectrum, ν, cm–1: 1767 (C=O, ester),
1
In the H NMR spectra of all acenaphthene deriva-
tives obtained in the present work signals from protons
in the naphthalene ring in the ortho positions with
respect to the ethylene bridge are broadened due to
long-range spin–spin couplings. Therefore, all aro-
matic protons can be identified unambiguously.
1
1693 (C=O, ketone), 1588. H NMR spectrum
(CDCl3), δ, ppm: 2.30 s (3H, COCH3), 2.60 s (3H,
OCOCH3), 3.40 m (4H, CH2CH2), 7.24 d (1H, 4-H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011

PYRAN DERIVATIVES peri-FUSED TO ACENAPHTHENE AND ACENAPHTHYLENE
389
J3,4 = 8.19 Hz), 7.30 br.d (1H, 8-H, J7,8 = 7.85 Hz),
7.33 br.d (1H, 3-H, J3,4 = 8.19 Hz), 7.47 d (1H, 7-H,
J7,8 = 7.85 Hz). Found, %: C 75.25; H 5.70. C16H14O3.
Calculated, %: C 75.58; H 5.55.
6-(Bromoacetyl)acenaphthen-5-yl acetate (VI).
1,4-Dioxane–bromine complex, 0.379 g (1.5 mmol),
was added in portions under continuous stirring to
a solution of 0.382 g (1.5 mmol) of compound II in
dioxane. The solution was evaporated, and the residue
was dried in air and subjected to chromatography on
aluminum oxide using chloroform as eluent; a fraction
with Rf 0.8 was collected. Yield 0.35 g (70%), orange
powder, mp 124–125°C (from alcohol). IR spectrum,
ν, cm–1: 1758 (C=O, ester), 1715, 1693 (C=O, ketone),
6-Acetylacenaphthen-5-yl benzoate (III). Freshly
distilled benzoyl chloride, 0.6 ml (4 mmol), was added
to a solution of 0.67 g (3 mmol) of 1-(6-hydroxyace-
naphthen-5-yl)ethanone (I) in 3 ml of anhydrous pyri-
dine, and the mixture was kept for 2 h at 0°C. The
mixture was then poured into ice water acidified with
hydrochloric acid; after 2 h, the precipitate was filtered
off and dried in air. Yield 0.8 g (85%), mp 98–99°C
(from ethanol). IR spectrum, ν, cm–1: 1736 (C=O,
1
1590. H NMR spectrum (CDCl3), δ, ppm: 2.35 s
(3H, CH3), 3.40 m (4H, CH2CH2), 4.50 s (2H, CH2),
7.25–7.45 m (4H, Harom). Found, %: C 57.34; H 3.67;
Br 23.49. C16H13BrO3. Calculated, %: C 57.68; H 3.93;
Br 23.98.
1
ester), 1683 (C=O, ketone), 1599. H NMR spectrum
(CDCl3), δ, ppm: 2.30 s (3H, COCH3), 3.20 m (4H,
CH2CH2), 7.10–8.15 m (9H, Harom). Found, %: C 79.50;
H 5.37. C21H16O3. Calculated, %: C 79.73; H 5.10.
6-(Acetoxyacetyl)acenaphthen-5-yl benzoate
(VII) and 6-(hydroxyacetyl)acenaphthen-5-yl ben-
zoate (VIII). Ammonium acetate, 0.12 g (1.6 mmol),
was added to a solution of 0.2 g (0.5 mmol) of com-
pound V in 3 ml of ethanol. The mixture was heated
for 30 min under reflux, and the red oily material was
separated and subjected to chromatography on alumi-
num oxide using chloroform as eluent. The first frac-
tion (Rf 0.9) contained compound VII. Yield 35 mg
(18%), light yellow powder, mp 111–112°C. IR spec-
trum, ν, cm–1: 1740 (C=O, ester), 1721 (PhC=O), 1697
1-(7-Bromo-6-hydroxyacenaphthen-5-yl)etha-
none (IV). A solution of 0.32 g (1.26 mmol) of com-
pound III in a small amount of chloroform was added
to a suspension of 0.47 g (2.1 mmol) of copper(II)
bromide in 5 ml of ethyl acetate. The mixture was
heated for 3 h under reflux with continuous stirring
and filtered, the filtrate was evaporated, and the dry
residue was purified by chromatography on aluminum
oxide using benzene as eluent. Yield 0.27 g (72%),
orange powder, mp 161–162°C (from ethanol). IR
1
(C=O, ketone). H NMR spectrum (CDCl3), δ, ppm:
1.85 s (3H, CH3), 3.46 m (4H, CH2CH2), 5.03 s (2H,
CH2), 7.30–7.42 m (3H, Harom), 7.48–7.58 m (3H, Ph)
7.62–7.70 m (1H, Harom), 8.18–8.24 m (2H, Ph).
Found, %: C 73.36; H 4.63. C23H18O5. Calculated, %:
C 73.79; H 4.85. The second fraction (Rf 0.6) con-
tained compound VIII. Yield 22 mg (13%), yellow
powder, mp 131–132°C. IR spectrum, ν, cm–1: 3430
(OH), 1738 (C=O, ester), 1659, 1637 (C=O, ketone).
1H NMR spectrum (CDCl3), δ, ppm: 3.40 m (4H,
1
spectrum, ν, cm–1: 2609 (OH), 1627 (C=O). H NMR
spectrum (CDCl3), δ, ppm: 2.80 s (3H, CH3), 3.38 m
(4H, CH2CH2), 7.26 br.d (1H, 3-H, J3,4 = 7.55 Hz),
7.57 br.s (1H, 8-H), 8.22 d (1H, 4-H, J3,4 = 7.55 Hz),
12.60 s (1H, OH). Found, %: C 57.57; H 3.90;
Br 27.31. C14H11BrO2. Calculated, %: C 57.76; H 3.81;
Br 27.44.
6-(Bromoacetyl)acenaphthen-5-yl benzoate (V).
A solution of 0.6 g (1.9 mmol) of compound III in
a small amount of chloroform was added to a suspen-
sion of 0.8 g (3.6 mmol) of copper(II) bromide in
10 ml of ethyl acetate. The mixture was heated for 3 h
under reflux with continuous stirring and filtered, the
filtrate was evaporated, and the dry residue was
purified by chromatography on aluminum oxide using
chloroform as eluent. Yield 0.65 g (87%), yellow
powder, mp 120–121°C. IR spectrum, ν, cm–1: 1735
(C=O, ester), 1711, 1678 (C=O, ketone), 1599.
1H NMR spectrum (CDCl3), δ, ppm: 3.45 m (4H,
CH2CH2), 4.35 s (2H, CH2), 7.30–7.70 m (7H, Harom),
8.22 d (2H, Harom). Found, %: C 63.54; H 3.70;
Br 20.41. C21H15BrO3. Calculated, %: C 63.82; H 3.83;
Br 20.22.
3
CH2CH2), 5.20 d (2H, HOCH2, J = 4.32 Hz), 7.18 d
(1H, 4-H, J3, 4 = 7.6 Hz), 7.31 d (1H, 8-H, J7, 8
7.5 Hz), 7.35 d (1H, 3-H, J3,4 = 7.6 Hz) 7.46–7.58 m
(3H, Ph), 7.88–7.95 (2H, Ph), 8.33 d (1H, 7-H, J7,8
=
=
7.5 Hz), 11.10 br.s (1H, OH). Found, %: C 75.45;
H 4.57. C21H16O4. Calculated, %: C 75.89; H 4.85.
6,7-Dihydroindeno[6,7,1-def]chromen-3(2H)-one
(IX). a. Piperidine, 0.3 ml, was added dropwise to
a hot solution of 0.456 g (1.4 mmol) of compound VI
in a mixture of 27 ml of hexane and 9 ml of benzene.
The mixture was heated for 1 h under reflux and
cooled, the precipitate of piperidinium bromide was
filtered off, the filtrate was evaporated, and the residue
was purified by chromatography on aluminum oxide
using chloroform as eluent; a fraction with Rf 0.8 was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011

ABDULAEVA et al.
390
collected. Yield 0.104 g (36%), yellow–green powder,
taneously separated, and the mixture turned violet. The
mixture was diluted with petroleum ether, and the pre-
cipitate was filtered off. Yield 0.029 g (80%), dark red
(almost black) powder, mp 259°C (decomp.). 1H NMR
spectrum (DMSO-d6), δ, ppm: 3.45 m (4H, CH2CH2),
mp 155–156°C. IR spectrum, ν, cm–1: 1677 (C=O),
1
1613, 1502. H NMR spectrum (CDCl3), δ, ppm:
3.45 m (4H, CH2CH2), 4.95 s (2H, CH2), 7.03 d (1H,
9-H, J9,8 = 7.5 Hz), 7.25 d (1H, 8-H, J8,9 = 7.5 Hz),
7.40 d (1H, 5-H, J5,4 = 7.4 Hz), 8.05 d (1H, 4-H, J4,5
=
7.02 d (1H, 9-H, J9,8 = 7.8 Hz), 7.25 d (1H, 8-H, J8,9 =
7.4 Hz). Found, %: C 80.38; H 4.56. C14H10O2. Cal-
culated, %: C 79.98; H 4.79.
7.8 Hz), 7.38 br.d (1H, 5-H, J5,4 = 7.3 Hz), 7.50–
7.70 m (3H, Ph), 8.01 d (1H, 4-H, J4,5 = 7.3 Hz), 8.36–
8.43 (2H, Ph). Found, %: C 69.25; H 3.88; F 10.60.
C21H13BF2O3. Calculated, %: C 69.65; H 3.62; F 10.49.
b. Compound IX was synthesized in a similar way
from 0.452 g (1.1 mmol) of bromomethyl ketone V.
Yield 0.038 g (16%), yellow powder, mp 156–157°C
(from ethanol).
3-Hydroxy-6,7-dihydro[6,7,1-def]chromen-2-yl-
(phenyl)methanone copper complex (XIII). A satu-
rated aqueous solution of copper(II) acetate was added
to an approximately equal volume of a saturated solu-
tion of 0.04 g (0.13 mmol) of compound X in diethyl
ether. The mixture was shaken for ~30 min, and the
dark red precipitate was filtered off and dried. Yield
0.074 g (84%), red powder, mp 210°C (decomp.). IR
spectrum, ν, cm–1: 1624, 1585, 1546, 1503, 1477,
1447, 1411, 1375. Found, %: C 73.69; H 4.07.
C42H26CuO6. Calculated, %: C 73.13; H 4.28.
3-Hydroxy-6,7-dihydro[6,7,1-def]chromen-2-yl-
(phenyl)methanone (X). A solution of 0.2 g
(0.5 mmol) of compound V in 10 ml of ethanol was
cooled with an ice bath, 2 ml of 5% potassium hydrox-
ide was added, and a dark red solid separated. After
25–30 min, the mixture was acidified with dilute (1:1)
hydrochloric acid, and the precipitate turned bright red.
It was filtered off, washed with water, and dried in air.
Yield 0.1 g (70%), red powder, mp 156–157°C. Found,
%: C 80.65; H 4.17. C21H14O3. Calculated, %: C 80.24;
H 4.49.
6,7-Dihydroindeno[6,7,1-def]chromen-3-yl
acetate (XV). A solution of 0.114 g (0.5 mmol) of
compound IX in 3 ml of acetic anhydride containing
a catalytic amount of sodium acetate was heated for
30 min under reflux. The mixture was cooled and
poured into water, and the precipitate was filtered off,
washed with water, and subjected to chromatography
on Silokhrom using chloroform as eluent. Yield
0.075 g (55%), bright yellow powder, mp 85–86°C.
IR spectrum, ν, cm–1: 1757 (C=O), 1696, 1651, 1604,
1586. UV spectrum, λmax (logε), nm: 202 (4.21), 221
(4.32), 233 (4.31), 341 (3.96), 374 (3.58). Lumines-
2-(4-Methoxybenzylidene)-6,7-dihydroindeno-
[6,7,1-def]chromene-3(2H)-one (XI). A suspension of
0.2 g (0.5 mmol) of compound V in 7 ml of methanol
was added to a solution of 0.06 ml (0.5 mmol) of
4-methoxybenzaldehyde and 0.03 g (0.6 mmol) of
sodium methoxide in 3 ml of methanol. The mixture
turned orange, and it was heated until the initial
bromomethyl ketone dissolved completely (the solu-
tion turned red). The mixture was cooled, acidified
with dilute (1:1) hydrochloric acid to weakly acidic
reaction, and diluted with water, and the red precipitate
was filtered off, washed with water, dried, and purified
by chromatography on aluminum oxide using chloro-
form as eluent. Yield 0.08 g (48%), red powder,
mp 204–205°C. IR spectrum, ν, cm–1: 1670 (C=O),
1585, 1563, 1505. 1H NMR spectrum (CDCl3), δ, ppm:
3.45 m (4H, CH2CH2), 3.88 s (3H, OCH3), 6.99 d (2H,
C6H4, J = 9.0 Hz), 7.15 s (1H, CH), 7.22 d (1H, 9-H,
J9,8 = 7.6 Hz), 7.28 d (1H, 8-H, J9,8 = 7.6 Hz), 7.45 d
(1H, 5-H, J5,4 = 7.3 Hz), 7.90 d (2H, C6H4, J = 9.0 Hz),
8.20 d (1H, 4-H, J4,5 = 7.3 Hz). Found, %: C 80.68;
H 4.67. C22H16O3. Calculated, %: C 80.47; H 4.91.
1
cence spectrum: λexcit/λmax 320/436 nm. H NMR spec-
trum (CDCl3), δ, ppm: 2.30 s (3H, CH3), 3.25 m
(4H, CH2CH2), 6.44 d (1H, 9-H, J9,8 = 7.0 Hz), 6.62 d
(1H, 4-H, J4,5 = 7.6 Hz), 6.77 s (1H, 2-H), 6.93 d (1H,
8-H, J8,9 = 7.0 Hz), 7.00 d (1H, 5-H, J = 7.6 Hz).
Found, %: C 76.47; H 4.91. C16H12O3. Calculated, %:
C 76.18; H 4.79.
Indeno[6,7,1-def]chromen-3-yl acetate (XVI).
2,3,5,6-Tetrachloro-1,4-benzoquinone, 0.068 g
(0.28 mmol), was added to a solution of 0.07 g
(0.28 mmol) of compound XIV in 2 ml of o-dichloro-
benzene. The solution turned green and was heated for
40 min under reflux. After cooling, the colorless pre-
cipitate was filtered off, the filtrate was cooled and
evaporated, and the residue was subjected to chroma-
tography on silica gel using chloroform as eluent.
Yield 0.035 g (50%), orange powder, mp 113–114°C.
IR spectrum, ν, cm–1: 1762 (C=O), 1639, 1595. UV
3-Hydroxy-6,7-dihydro[6,7,1-def]chromen-2-yl-
(phenyl)methanone complex with BF3 (XII). Boron
trifluoride–diethyl ether complex, 4–5 drops (~0.1 ml),
was added to a solution of 0.032 g (0.1 mmol) of
compound X in 2 ml of benzene, a violet solid instan-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011

PYRAN DERIVATIVES peri-FUSED TO ACENAPHTHENE AND ACENAPHTHYLENE
391
7. Tsukanov, A.V., Dubonosov, A.D., Golyanskaya, O.M.,
Mezheritskii, V.V., Revinskii, Yu.V., Bren’, V.A., and
Minkin, V.I., Russ. J. Gen. Chem., 2006, vol. 76, p. 841.
spectrum, λmax (logε), nm: 202 (4.13), 215 (4.23), 252
(4.44), 313 (3.32), 328 (3.30), 402 (3.89). Lumines-
1
cence spectrum: λexcit/λmax 320/518 nm. H NMR
8. Mezheritskii, V.V., Minyaeva, L.G., and Golyan-
spectrum (CDCl3), δ, ppm: 2.43 s (3H, CH3), 7.30 d
skaya, O.M., Zh. Org. Khim., 1992, vol. 28, p. 1187.
(1H, 9-H, J9, 8 = 7.3 Hz), 7.41 d (1H, 7-H, J7, 6
=
4.9 Hz), 7.42 d (1H, 4-H, J4,5 = 7.8 Hz), 7.49 d (1H,
6-H, J6, 7 = 4.90 Hz), 7.73 s (1H, 2-H), 8.04 d (1H,
5-H, J5,4 = 7.80 Hz), 8.10 d (1H, 8-H, J8,9 = 7.3 Hz).
Found, %: C 76.41; H 4.24. C16H10O3. Calculated, %:
C 76.79; H 4.03.
9. Mezheritskii, V.V., Pikus, A.L., and Tregub, N.G.,
Zh. Org. Khim., 1991, vol. 27, p. 2198.
10. Mezheritskii, V.V., Minyaeva, L.G., Bezuglov, A.N.,
Lysenko, K.A., Revinskii, Yu.V., and Milov, A.A., Russ.
J. Org. Chem., 2010, vol. 46, p. 98.
11. Platzer, N., Buisson, J.P., and Demerseman, P.,
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