Peri-hydroxy acenaphthoyl compounds

Article abstract of DOI:10.1134/S1070428010030061

Reactions of peri-hydroxyacenaphthaldehyde and its O-methyl derivative with amines, aryl methyl ketones, and malononitrile gave the corresponding Schiff bases, chalcones, and arylidenemalononitrile. The latter underwent heterocyclization on heating in tri

Full text of DOI:10.1134/S1070428010030061

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 3, pp. 336–343. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.N. Bezuglov, L.G. Minyaeva, K.A. Lysenko, V.V. Mezheritskii, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46,
No. 3, pp. 344–351.
peri-Hydroxy Acenaphthoyl Compounds
A. N. Bezuglova, L. G. Minyaevaa, K. A. Lysenkob, and V. V. Mezheritskiia
a 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
b Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 119991 Russia
Received November 26, 2008
Abstract—Reactions of peri-hydroxyacenaphthaldehyde and its O-methyl derivative with amines, aryl methyl
ketones, and malononitrile gave the corresponding Schiff bases, chalcones, and arylidenemalononitrile. The
latter underwent heterocyclization on heating in trifluoroacetic acid to produce 2-oxoacenaphtho[5,6-bc]-
oxepine-3-carbonitrile. The condensation of 5-acetyl-6-hydroxyacenaphthene with aromatic aldehydes afford-
ed chalcones, their mixtures with heterocyclization products, or 2-arylacenaphtho[5,6-bc]oxepin-4-one, de-
pending on the substituent in the aromatic ring.
DOI: 10.1134/S1070428010030061
Naphthalene derivatives having hydroxy and car-
bonyl groups in the neighboring peri positions (1, 8)
play an important role as potential precursors of peri-
fused heterocyclic systems [1–3]. In addition, such
compounds are unique models for studying so-called
“peri effects” [4, 5] appearing due to interactions be-
tween substituents in the peri positions. The results of
our studies on the synthesis and transformations (in-
cluding heterocyclizations) of various derivatives of
peri-hydroxy-substituted naphthaldehydes, naphthyl
alkyl ketones, and naphthyl aryl ketones were partly
reviewed in [1].
dehydrogenation of peri-fused acenaphthene deriva-
tives gives new heteroaromatic systems [9–13].
In the present work we performed condensations
of peri-hydroxy-substituted acenaphthaldehyde with
amines, aryl methyl ketones, and malononitrile and
condensations of acenaphthyl methyl ketone with
aromatic aldehydes and discussed structural specificity
of some compounds thus obtained.
peri-Hydroxy-substituted Schiff bases IIa–IIe were
synthesized in good yield by heating equimolar mix-
tures of aldehydes Ia and Ib with the corresponding
primary amines in boiling alcohol (Scheme 1). Table 1
contains the chemical shifts of the OH, CHO, and
A novel line in the above field of studies appeared
due to preparation of peri-hydroxy-substituted ace-
naphthaldehyde and acenaphthyl methyl ketone [6].
The presence of an ethylene bridge in the peri posi-
tions opposite to the peri-hydroxycarbonyl moiety
strongly affects geometric parameters of the latter and
chemical transformations involving this moiety, prima-
rily heterocyclization processes. In particular, closure
of five-membered furan ring becomes difficult, but
seven-membered oxepine heteroring is readily formed
[7]. In addition, dehydrogenation of the ethylene
bridge in peri-hydroxyacenaphthoyl compounds gives
the corresponding acenaphthylene in which the hy-
droxy group may be conjugated with the carbonyl
group through the double bond system [8], whereas
1
CH=N protons in the H NMR spectra of compounds
Ia and IIa–IId, as well as of compounds Xa–Xe re-
ported previously [14, 15]. These data should reflect
the effects of the acidity of the hydroxy group, nature
of the heteroatom (oxygen or nitrogen), and molecular
geometry on some parameters of intramolecular hy-
drogen bond (seven-membered H-chelate ring) in the
above compounds.
It is believed [16] that the chemical shift of proton
involved in hydrogen bonding is sensitive to the
energy of the hydrogen bond. Hydrogen bonding usu-
ally increases the chemical shift (deshielding) which in
some cases approaches a critical range (δ >20 ppm).
Although the degree of shielding in NMR spectra does
336

peri-HYDROXY ACENAPHTHOYL COMPOUNDS
337
Scheme 1.
O
CN
CN
NR3
H
H
·
·
OR2
O
CN
·
O
R3NH2
R1 = H
CF3COOH
CH2(CN)2
R2 = H
OR2 COR1
IIa–IIe
IV
VI
COAr
Ha
CN
Hb
H
Me
H
·
·
·
·
·
O
O
CN
Ia–Id
ArCOMe
R1 = R2 = H
CH2(CN)2
R2 = Me
ArCHO
R1 = Me, R2 = H
IIIa, IIIb
V
Ar
O
Ar
O
Ha
···
H
O
O
O
O
Ar
Hb
VIIa, VIIb
VIIIb, VIIIc
IX
I, R1 = R2 = H (a), R1 = H, R2 = Me (b), R1 = Me, R2 = H (c), R1 = R2 = Me (d); II, R2 = H, R3 = Ph (a), PhCH2 (b), 4-MeOC6H4 (c),
Me2CH (d); R2 = Me, R3 = 4-MeOC6H4 (e); III, Ar = 4-MeOC6H4 (a), 3,4-(MeO)2C6H3 (b); VII, VIII, Ar = 4-MeOC6H4 (a), Ph (b),
4-ClC6H4 (c); IX, Ar = 4-O2NC6H4.
not reflect the stability (strength) of hydrogen bond
unequivocally [16], the energy of hydrogen bond in
a series of structurally related compounds may be esti-
mated at a qualitative or even semiquantitative level on
the basis of the 1H NMR chemical shifts.
the calculated H-bond energies, 9 and 13 kcal/mol,
respectively [17].
In the series of Schiff bases, the downfield shift of
the OH proton (by 0.6 ppm) due to appearance of
ethylene bridge (cf. δOH for Xd and IIa) may also be
treated as strengthening of the hydrogen bond. In ad-
dition, acenaphthene Schiff bases displayed a relation
between the strength of the intramolecular hydrogen
bond and the basicity of the imino nitrogen atom:
the OH signal shifts downfield in the series IIa <
IIb < IIc < IId.
Taking the above stated into account, the difference
in the downfield shifts (δCH=N – δCHO = 2.5–3.5 ppm;
Table 1) in going from peri-hydroxy aldehydes Ia and
Xa–Xc to peri-hydroxy-substituted Schiff bases IIa–
IId, Xd, and Xe suggests appreciable strengthening of
intramolecular hydrogen bond in the seven-membered
H-chelate ring. In the series of peri-hydroxy aldehydes
we observed a downfield shift (by 1.08–1.23 ppm) of
the OH signal of Xc as compared to aldehydes Xa, Xb,
and Ia due to the presence of a nitro group in position
5 (as a result, the acidity of the OH group increases).
Despite almost coinciding chemical shifts of the OH
protons in peri-hydroxynaphthaldehyde (Xa) and its
acenaphthene analog Ia (Table 1), the latter is charac-
terized by stronger intramolecular hydrogen bond (ac-
cording to the IR data) [17]; this is also confirmed by
1
Thus analysis of the H NMR data shows that the
strength of the seven-membered H-chelate ring in the
peri-hydroxy compounds under study depends on both
acidity of the hydroxy group and basicity of the
acceptor atom X, as well as on the presence or absence
of ethylene bridge connecting the opposite peri-posi-
tions in the naphthalene ring.
Considerable increase in the acidity of the hydroxy
group, e.g., in 5,7-dinitro-8-hydroxynaphthaldehyde,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 3 2010

BEZUGLOV et al.
338
1
Table 1. Chemical shifts of some protons in the H NMR
spectra of peri-hydroxy-substituted naphthaldehydes and
Schiff bases derived therefrom
displaced toward structure A for R = H; when R = Br,
the ratio A :C is 1 :2; the compound with R = NO2
exists only as cyclic tautomer C [15].
X
OH
Scheme 2.
···
H
X
HX
H
H
O
O
R1
R2
Ia, IIa–IIe, Xa–Xe
R
R
δCH=O or
δCH=N
Comp. no. R1, R2
X
δOH
A
B
H, H
O
11.56
11.65
12.73
11.50
14.00
14.40
14.60
14.70
9.76
9.84
9.87
9.80
8.54
8.54
8.60
8.30
8.56
8.25
XH
Xa
Xb
Xc
Ia
O
Br, H
O
NO2, H
CH2–CH2
H, H
O
O
Xd
Xe
IIa
IIb
IIc
IId
NPh
NPh
R
Br, H
C
CH2–CH2 NPh
CH2–CH2 NCH2Ph
peri-Hydroxy-substituted acenaphthene aldehydes
and Schiff bases Ia and IIa–IId could not give rise to
analogous ring–chain tautomerism because of strain
appearing as a result of closure of the second five-
membered ring. The chemical shifts of the CH=X
proton within the series of aldehydes or Schiff bases
do not depend on the substituent in the naphthalene
ring and molecular geometry on the whole to an appre-
ciable extent, but the difference between the aldehyde
and Schiff base series is 1.2–1.6 ppm (Table 1).
CH2–CH2 NC6H4OMe-4 14.83
CH2–CH2 NCHMe2 15.10
could led to proton transfer from the hydroxy group to
the aldehyde carbonyl oxygen atom with simultaneous
closure of five-membered heteroring [14]. Such proto-
tropy becomes even more pronounced in going from
aldehydes (X = O) to Schiff bases (X = NAlk, NAr)
having an electron-withdrawing substituent in the para
position with respect to the hydroxy group. In this
case, increase in the acidity of the hydroxy group is
accompanied by increase in the basicity of the acceptor
atom [15]. For example, the equilibrium shown in
Scheme 2 for Schiff bases (X = NPh) is completely
The structure of peri-hydroxy aldehyde Ia and
Schiff base IIb was unambiguously determined by
X-ray analysis; some structural parameters are given in
Table 2. According to the X-ray diffraction data, the
seven-membered H-chelate ring and acenaphthene
Table 2. Selected bond angles (ω, deg) and interatomic distances (d, Å) in molecules of aldehyde Ia and Schiff base IIb
according to the X-ray diffraction data
Angle
ω, deg
Angle
ω, deg
Distance
O1– H
d, Å
Distance
d, Å
Compound Ia
O1C1C8a
124.12
C9C4C4a
109.83
1.014
O1···C11
3.168
C1C8aC8
C8aC8C11
130.01
128.26
C4C4aC5
C4AC5C10
111.11
109.19
N1···H
O1···N1
1.560
2.566
C1 ···C8
C4 ···C5
2.614
2.334
Compound IIb
O1C1C8a
C1C8aC8
C8aC8C11
123.91
130.12
127.48
C9C4C4a
C4C4aC5
C4aC5C10
109.79
111.18
109.27
O1–H
O2···H
O1···O2
0.912
1.680
2.587
O1···C11
C1 ···C8
C4 ···C5
3.142
2.610
2.333
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 3 2010

peri-HYDROXY ACENAPHTHOYL COMPOUNDS
339
tional reorganization of peri substituents, which is ac-
companied by hydrogen bonding involving the CH=N
proton and oxygen atom in the peri-methoxy group.
Such intramolecular hydrogen bond is regarded as
a weak hydrogen bond [16].
2
O
1
···
8a
4a
···
8a
4a
H
H
N
H12
H12
1O
1O
1
8
1
8
2
3
7
6
2
3
7
6
R
R
4
5
4
5
···
H N
Me
H
N
·
·
·
H
O
9
10
9
10
O
Ia
IIb
core in molecules Ia and IIb are almost coplanar: the
torsion angles O2C11C8C8A and N1C11C8C8A are 3.0 and
3.9° for Ia and IIb, respectively. The hydrogen atom in
the H-ring is located near the straight line connecting
the O1 and O2 (N1) atoms (the O1HO2 and O1HN1
angles are 172.76° and 170.67°, respectively). Hydro-
gen bond is the strongest when the above angle is close
to 180°C [16].
IIc
IIe
R = 4-MeOC6H4.
peri-Hydroxyacenaphthaldehyde Ia reacted with
aryl methyl ketones under acid catalysis (triethyl
orthoformate–70% perchloric acid) to form chalcones
As follows from the data in Table 2, the distances
N1···H and N1···O1 in molecule IIb are shorter than
the distances O2···H and O1···O2 in aldehyde Ia mole-
cule by 0.12 and 0.021 Å, respectively. Thus the X-ray
diffraction data confirm the conclusion drawn on the
1
IIIa and IIIb. According to the H NMR data, com-
pounds IIIa and IIIb have trans configuration at the
double bond (Jab > 15 Hz). The chemical shift of Hb at
the double bond (δ ~9.3 ppm) suggests formation of
intramolecular hydrogen bond C–Hb···O (Scheme 1)
which is analogous to intramolecular hydrogen bond in
Schiff base IIe and peri-methoxyacenaphthaldehydes
1
basis of the H NMR spectra, i.e., the intramolecular
hydrogen bond in peri-hydroxy-substituted acenaph-
thene Schiff bases is stronger than in acenaphthene
aldehyde Ia.
1
[17]. The hydroxy proton resonated in the H NMR
spectra of IIIa and IIIb in CDCl3 at δ ~6.3 ppm, and
its signal was displaced downfield (to δ ~10 ppm) in
going to dimethyl sulfoxide, presumably due to forma-
Considerable difference in the bond angles formed
by naphthalene carbon atoms in the seven-membered
H-chelate ring (C1C8aC8) and five-membered carbo-
cycle (C4C4aC5) should be noted. This difference
reaches 18.94° for aldehyde Ia and 18.90° for Schiff
base IIb. Furthermore, the differences in the distances
between atoms in the peri positions (C1 ···C8 and
C4···C5 are 0.277 Å in Ia and 0.280 Å in IIb, indicat-
ing appreciable in-plane distortion of the naphthalene
fragment. Such deformation of molecules Ia and IIb
induced by contracting effect of the five-membered
ring ensures favorable conditions for closure of seven-
membered H-chelate ring and stabilizes it via neutral-
ization of repulsion between the O1 and O2 atoms in
the hydroxy and carbonyl groups or between the O1
and N1 atoms in the hydroxy and imino groups.
tion of associates like (CD3)S=O···H–O–Carom
.
peri-Hydroxyacenaphthaldehyde Ia and its methoxy
analog Ic reacted with malononitrile in the presence of
piperidine, yielding the corresponding acenaphthyli-
1
denemalononitriles IV and V. In the H NMR spectra
of these compounds the CH proton signal appeared at
δ 9.35 and 9.22 ppm, respectively. Taking into account
the color of their solutions (λmax 430 and 420 nm, re-
spectively), we presumed coplanar (or nearly coplanar)
arrangement of the naphthalene ring and HC=C(CN)2
fragment in their molecules, which is favorable for
intramolecular hydrogen bonding as in chalcones IIIa
and IIIb (Scheme 1). According to the X-ray diffrac-
tion data, the HC=C(CN)2 fragment in peri-methoxy-
naphthylidenemalononitrile is turned through an angle
of 45° with respect to the naphthalene ring plane; this
compound is light yellow (λmax 226 nm), and the CH=
The reaction of peri-methoxy-substituted acenaph-
thene aldehyde Ic with p-anisidine gave the corre-
sponding peri-methoxy-substituted Schiff base IIe.
1
1
proton signal in its H NMR spectrum is located in
a stronger field (δ 9.05 ppm) [18].
Compound IIe displayed in the H NMR spectrum
an appreciable downfield shift of the CH=N signal
(δ 9.75 ppm for IIe against δ 8.56 ppm for IIc; δΔ =
1.19 ppm), presumably due to considerable conforma-
By heating peri-hydroxyacenaphthylidenemalono-
nitrile IV in trifluoroacetic acid we obtained 2-oxoace-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 3 2010

BEZUGLOV et al.
340
Table 3. Principal crystallographic data for compounds Ia
and IIb and refinement parameters
their heterocyclization products, depending on the sub-
stituent nature in the benzene ring of initial aldehyde.
Individual chalkone VIIa was obtained only from
p-methoxybenzaldehyde having an electron-donating
group in the para position. p-Chlorobenzaldehyde
(+M, –I) gave rise to a tautomeric mixture of chalcone
VII and acenaphthooxepinone VIII at a ratio of
Compound no.
Formula
Ia
IIb
C13H10O2
198.21
C20H17NO
287.35
100 (2)
Rhombic
P212121
4
Molecular weight
Temperature, K
Crystal system
Space group
Z
120
1
~80:20 (according to the H NMR data). In keeping
Monoclinic
P21/n
1
with the H NMR data, the double bond in chalcones
VII is configured trans (Jab > 15 Hz). The hydroxy
proton in VII appears at δ 10.5 ppm, indicating forma-
tion of intramolecular hydrogen bond of the same
type as in peri-hydroxyacenaphthenyl methyl ketone
(δ 11.6 ppm) [17]. The hydrogen atom in the hydroxy
group of the latter is involved in hydrogen bonding via
closure of a planar 7-membered H-chelate ring which
is coplanar to the naphthalene core (X-ray diffraction
data) [17]. In the reaction of peri-hydroxyacenaph-
thenyl methyl ketone (Ic) with p-nitrobenzaldehyde in
alkaline medium we isolated a poorly soluble amor-
phous material. It was subjected to chromatography on
aluminum oxide to obtain a small amount of acenaph-
thooxepinone IX, aromatization product of the cor-
responding acenaphthene precursor. Here, electron-
deficient p-nitrobenzaldehyde molecule is capable of
acting as dehydrogenating agent.
4
a, Å
05.5096(4)
11.4803(9)
014.3889(11)
90.00()0000
95.4841(16)
90.00()0000
905.96(12)
1.453
5.3406(5)
11.4414(11)
23.246(2)00
90
b, Å
c, Å
α, deg
β, deg
90
γ, deg
V, Å3
dcalc, g/cm3
μ, cm–1
90
1420.4 (2)
1.344
0.970
0.820
F(000)
0416
0608
2θmax, deg
0058
0<59
Total number of
9870
8978
reflection intensities
Number of independent
reflections
2421
1974
0176
2208
(Rint = 0.0293)
EXPERIMENTAL
Number of reflections
with I > 2σ(I)
2013
The IR spectra were recorded on a Specord IR-71
spectrometer from samples dispersed in mineral oil.
Number of refined
parameters
0185
1
The H and 13C NMR spectra were measured on
a Varian Unity-300 instrument using hexamethyldi-
siloxane as internal reference. The electronic absorp-
tion spectra were obtained on a Varian Cary 100 spec-
trophotometer. The elemental compositions of all
newly synthesized compounds were consistent with the
calculated values with an acceptable accuracy.
R1
0.0546
0.1131
0.0416
0.0981
wR2
Goodness of fit
Residual electron den-
0.9660
1.0320
0.399/–0.269
0.325/–0.205
sity, e×Å–3 (dmin/dmax
)
X-Ray analysis of compounds Ia and IIb was per-
formed on a Smart Apex II CCD diffractometer (MoKα
irradiation, graphite monochromator, ω-scanning) at
the Nesmeyanov Institute of Organometallic Com-
pounds, Russian Academy of Sciences. The structures
were solved by the direct method and were refined
with respect to F2hkl by the least-squares procedure
in full-matrix anisotropic approximation. Hydrogen
atoms in all structures were localized by the Fourier
difference syntheses of electron density. The principal
crystallographic and refinement parameters are given
in Table 3. All calculations were performed using
SHELXTL PLUS software package [19].
naphthooxepine-3-carbonitrile VI (Scheme 1). The CH
proton signal in the H NMR spectrum of VI is
1
appreciably displaced upfield (δ 7.60 ppm) relative to
analogous signal of its peri-hydroxy-substituted pre-
cursor IV (δ 9.35 ppm), which provides an additional
support to the existence of C–H···O attractive interac-
tion in molecule IV.
peri-Hydroxy-substituted acenaphthenyl methyl
ketone Ic reacted with aromatic aldehydes under con-
ditions of acid (triethyl orthoformate–70% perchloric
acid) or base catalysis to afford chalcones VII or
mixtures of compounds VII, VIIIb, and VIIIc with
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 3 2010

peri-HYDROXY ACENAPHTHOYL COMPOUNDS
341
Schiff bases IIa–IIe (general procedure). A solu-
tion of 6-hydroxyacenaphthene-5-carbaldehyde (Ia) or
6-methoxyacenaphthene-5-carbaldehyde (Ib) in
ethanol or propan-2-ol was heated for 15–20 min under
reflux. The mixture was cooled with ice, and the pre-
cipitate was filtered off, dried, and purified by recrys-
tallization or column chromatography on aluminum
oxide using chloroform as eluent.
NMe2, J = 6.28 Hz), 3.30 m (4H, CH2CH2), 4.83 q
(1H, NCHMe2, J = 6.28 Hz), 6.95 d (1H, 4-H, J3,4
=
7.53 Hz), 7.10 br.d (1H, 8-H, J7,8 = 6.92 Hz), 7.20 br.d
(1H, 3-H, J3,4 = 7.54 Hz), 7.43 d (1H, 7-H, J7,8
=
6.91 Hz), 8.25 s (1H, HC=N), 15.10 br.s (1H, OH).
N-(6-Methoxyacenaphth-5-ylmethylidene)-4-me-
thoxyaniline (IIe) was synthesized from 0.05 g
(0.24 mmol) of 6-methoxyacenaphthene-5-carbalde-
hyde and 0.03 g (0.24 mmol) of p-anisidine in 2 ml of
ethanol. Yield 0.03 g (40%), red–brown powder,
mp 139–140°C. IR spectrum, ν, cm–1: 1640 (C=N),
6-(Phenyliminomethyl)acenaphthen-5-ol (IIa)
was synthesized from 50 mg (0.18 mmol) of 6-hy-
droxyacenaphthene-5-carbaldehyde and 0.02 ml
(0.2 mmol) of aniline in 2 ml of propan-2-ol. Yield
45 mg (65%), mp 120°C (from propan-2-ol). IR spec-
trum, ν, cm–1: 1620 (C=N), 1600, 1580. 1H NMR spec-
trum (CDCl3), δ, ppm: 3.30 m (4H, CH2CH2), 7.06 d
1
1607, 1570. H NMR spectrum (CDCl3), δ, ppm:
3.37 m (4H, CH2CH2), 3.85 s (3H, 6-CH3O), 3.95 s
(3H, p-CH33O), 6.88 d (1H, 7-H, J7,8 = 7.59 Hz), 6.94 d
4
(2H, m-H, J = 8.85, J = 2.21 Hz), 7.18 d (1H, 8-H,
3
4
J8, 7 = 7.58 Hz), 7.29 d (2H, o-H, J = 8.85, J =
2.21 Hz), 7.34 d (1H, 3-H, J3,4 = 7.59 Hz), 8.35 d (1H,
4-H, J4,3 = 7.58 Hz), 9.75 s (1H, HC=N).
(1H, 4-H, J3,4 = 7.62 Hz), 7.22 br.d (1H, 8-H, J7,8
=
7.15 Hz), 7.25–7.50 m (6H, C6H5, 3-H), 7.66 d (1H,
7-H, J7,8 = 7.15 Hz), 8.60 s (1H, HC=N), 14.60 br.s
(1H, OH).
3-(6-Hydroxyacenaphthen-5-yl)-1-(4-methoxy-
phenyl)prop-2-en-1-one (IIIa). 6-Hydroxyacenaph-
thene-5-carbaldehyde, 0.1 g (0.5 mmol), and p-methox-
yacetophenone, 0.075 g (0.5 mmol), were dispersed in
2 ml of triethyl orthoformate, 3 drops of 72% per-
chloric acid were added, the suspension became a dark
blue solution, and the latter was kept for 1 h at room
temperature. The dark precipitate (perchlorate, black
powder, mp >300°C) was filtered off and dispersed in
10 ml of acetone, 20 drops of water was added, and the
resulting red solution was heated for 30 min under
reflux, cooled, and diluted with water. The fine precip-
itate was extracted into chloroform, and the solution
was passed through a small layer of aluminum oxide
using chloroform as eluent. Yield 0.12 g (74%), red
powder, mp 195–197°C. IR spectrum, ν, cm–1: 3287
6-(Benzyliminomethyl)acenaphthen-5-ol (IIb)
was synthesized from 0.08 g (0.4 mmol) of 6-hy-
droxyacenaphthene-5-carbaldehyde and 0.04 ml
(0.4 mmol) of benzylamine in 2 ml of ethanol. Yield
0.08 g (69%), orange powder, mp 129–130°C (from
ethanol). IR spectrum, ν, cm–1: 1630 (C=N), 1590,
1
1580. H NMR spectrum (CDCl3), δ, ppm: 3.30 m
(4H, CH2CH2), 4.83 s (2H, NCH2), 6.06 d (1H, 4-H,
J3,4 = 7.53 Hz), 7.14 br.d (1H, 8-H, J7,8 = 7.22 Hz),
7.22 br.d (1H, 3-H, J3,4 = 7.54 Hz), 7.24–7.37 m (5H,
C6H5), 7.48 d (1H, 7-H, J7,8 = 7.22 Hz), 8.30 s (1H,
HC=N), 14.70 br.s (1H, OH).
6-(4-Methoxyphenyliminomethyl)acenaphthen-
5-ol (IIc) was synthesized from 0.1 g (0.5 mmol) of
6-hydroxyacenaphthene-5-carbaldehyde and 0.062 g
(0.5 mmol) of p-anisidine in 5 ml of ethanol. Yield
0.096 g (64%), red powder, mp 127–128°C. IR spec-
trum, ν, cm–1: 1620 (C=N), 1590, 1580. 1H NMR spec-
trum (CDCl3), δ, ppm: 3.30 m (4H, CH2CH2), 3.90 s
(3H, CH3O), 6.96 d (2H, m-H, 3J = 8.94, 4J = 2.19 Hz),
7.05 d (1H, 4-H, J3,4 = 7.62 Hz), 7.22 d (1H, 8-H,
J7,8 = 7.18 Hz), 7.28 d (1H, 3-H, J3,4 = 7.62 Hz), 7.36 d
1
(OH), 1640 (C=O), 1590, 1580. H NMR spectrum
(DMSO-d6), δ, ppm: 3.35 m (4H, CH2CH2), 3.85 s
(3H, OCH3), 6.85 d (1H, 7-H, J7,8 = 7.36 Hz), 7.04 d
(2H, m-H, J = 8.54 Hz), 7.10 d (1H, 8-H, J = 7.36 Hz),
7.27 d (1H, 3-H, J3,4 = 7.36 Hz), 7.65 d (1H, Ha, Jab =
15.35 Hz), 8.05 d (1H, 4-H, J4,3 = 7.36 Hz), 8.11 d
(2H, o-H, J = 8.64 Hz), 9.20 d (1H, Hb, Jba
=
15.35 Hz), 10.05 s (1H, OH).
3
4
(2H, o-H, J = 8.94, J = 2.19 Hz), 7.64 d (1H, 7-H,
J7,8 = 7.19 Hz), 8.56 s (1H, C=N), 14.83 s (1H, OH).
1-(3,4-Dimethoxyphenyl)-3-(6-hydroxyacenaph-
then-5-yl)prop-2-en-1-one (IIIb) was synthesized in
a similar way. Yield 53%, red–orange powder, mp 238–
240°C. IR spectrum, ν, cm–1: 3354 (OH), 1640 (C=O),
6-(4-Isopropyliminomethyl)acenaphthen-5-ol
(IId) was synthesized from 0.08 g (0.4 mmol) of
6-hydroxyacenaphthene-5-carbaldehyde and 0.04 ml
(0.4 mmol) of isopropylamine in 2 ml of ethanol. Yield
0.048 g (50%), yellow–orange powder, mp 67–68°C.
IR spectrum, ν, cm–1: 1630 (C=N), 1590, 1580.
1H NMR spectrum (CDCl3), δ, ppm: 1.30 d (6H,
1
1590. H NMR spectrum (CDCl3), δ, ppm: 3.35 m
(4H, CH2CH2), 3.95 s (6H, OCH3), 6.30 br.s (1H, OH),
6.90 d (1H, 7-H, J7,8 = 7.36 Hz), 6.93 d (1H, 5′-H, 3J =
8.20 Hz), 7.10 br.d (1H, 3-H, J3,4 = 7.01 Hz), 7.25 d
(1H, 4-H, J4, 3 = 7.01 Hz), 7.40 d (1H, Ha, Jab
=
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BEZUGLOV et al.
342
4
15.43 Hz), 7.67 d (1H, 2′-H, J = 2.10 Hz), 7.75 d.d
and diluted with water. The precipitate was filtered off,
dried, and purified by column chromatography on
silica gel using chloroform as eluent. Yield 0.18 g
(58%), dark red powder, mp 144°C (from ethanol).
IR spectrum, ν, cm–1: 3200 (OH), 1640 (C=O), 1590,
3
4
(1H, 6′-H, J = 8.20, J = 2.10 Hz), 7.81 d (1H, 8-H,
J8,7 = 7.36 Hz), 9.30 d (1H, Hb, Jba = 15.43 Hz).
[(6-Hydroxyacenaphthen-5-yl)methylidene]-
malononitrile (IV). One drop of piperidine was added
to a solution of 0.2 g (1 mmol) of 6-hydroxyacenaph-
thene-5-carbaldehyde and 0.066 g (1 mmol) of malo-
nonitrile in 2 ml of acetonitrile. The solution instan-
taneously turned dark and was left to stand for 30 min
at room temperature, and the precipitate was filtered
off. Yield 0.09 g (36%), red powder, mp 229–230°C.
UV spectrum, λmax, nm (ε×10–4): in toluene: 350 (0.24),
428 (1.00); in acetonitrile: 350 (0.24), 430 (0.96). IR
spectrum, ν, cm–1: 3367, 3340 (OH), 2215, 2210 (CN),
1
1580. H NMR spectrum (CDCl3), δ, ppm: 3.37 m
(4H, CH2CH2), 3.85 s (3H, CH3O), 6.94 d.d (2H, m-H,
4
3J = 8.79, J = 1.88 Hz), 7.13 d (1H, 7-H, J7,8
=
7.70 Hz), 7.25 d (1H, 3-H, J3,4 = 7.37 Hz), 7.29 d (1H,
8-H, J8,7 = 7.70 Hz), 7.53 d (1H, Ha, Jab = 15.70 Hz),
3
4
7.60 d.d (2H, o-H, J = 8.79, J = 1.88 Hz), 7.86 d
(1H, Hb, Jba = 15.70 Hz), 8.16 d (1H, 4-H, J4,3
=
7.37 Hz), 10.55 s (1H, OH).
b. 4-Methoxybenzaldehyde, 0.12 ml (1 mmol), and
30% aqueous sodium hydroxide, 0.6 ml, were added to
a suspension of 0.2 g (1 mmol) of compound Id in
5 ml of ethanol. The mixture was stirred for 2 h at
room temperature, diluted with water, and acidified
with dilute (1:1) hydrochloric acid to a weakly acidic
reaction. The precipitate was filtered off, dried, and
purified by column chromatography on aluminum
oxide using chloroform as eluent. Yield 0.22 g (71%),
dark red powder, mp 144–146°C (from ethanol).
1
1640 (C=C), 1590, 1580. H NMR spectrum (CDCl3),
δ, ppm: 3.40 m (4H, CH2CH2), 5.73 br.s (1H, OH),
6.90 d (1H, 7-H, J7,8 = 7.41 Hz), 7.20 d (1H, 3-H,
J3,4 = 7.43 Hz), 7.38 d (1H, 8-H, J8,7 = 7.41 Hz), 8.20 d
(1H, 4-H, J4,3 = 7.43 Hz), 9.35 s (1H, HC=C).
[(6-Methoxyacenaphthen-5-yl)methylidene]-
malononitrile (V) was synthesized in a similar way.
Yield 0.054 g (89%), red powder, mp 157–158°C. UV
spectrum (acetonitrile), λmax, nm (ε×10–4): 337 (0.18),
420 (0.68). IR spectrum, ν, cm–1: 2200 (CN), 1590,
Compounds VIIb and VIIc were synthesized as
described above in b.
1
1580. H NMR spectrum (CDCl3), δ, ppm: 3.38 m
(4H, CH2CH2), 3.95 s (3H, CH3O), 6.94 d (1H, 7-H,
J7,8 = 7.89 Hz), 7.25 d (1H, 8-H, J8,7 = 7.90 Hz), 7.35 d
(2E)-1-(6-Hydroxyacenaphthen-5-yl)-3-phenyl-
prop-2-en-1-one (VIIb) was synthesized from 0.2 g
(1 mmol) of 5-acetyl-6-hydroxyacenaphthene and
0.1 ml (1 mmol) of benzaldehyde in 3 ml of ethanol
using 0.6 ml of 30% aqueous sodium hydroxide. Yield
0.158 g (56%), red–brown powder, mp 157–159°C.
IR spectrum, ν, cm–1: 3200 (OH), 1640 (C=O), 1600,
(1H, 3-H, J3,4 = 7.43 Hz), 8.05 d (1H, 4-H, J4,3
=
7.43 Hz), 9.22 s (1H, HC=C).
2-Oxoacenaphtho[5,6-bc]oxepine-3-carbonitrile
(VI). A suspension of 0.024 g (0.1 mmol) of com-
pound IV in 3 ml of trifluoroacetic acid was heated for
1 h on a water bath (70–80°C). The mixture was
cooled and diluted with water, and the precipitate was
filtered off and dried. Yield 0.02 g (82%), orange
powder, mp 237–239°C (from acetonitrile). IR spec-
trum, ν, cm–1: 2210 (CN), 1700 (C=O), 1590, 1580.
1H NMR spectrum, δ, ppm: in CDCl3: 3.38 m (4H,
CH2CH2), 7.20 m (2H, 6-H, 10-H), 7.30 d (1H, 9-H,
1
1580. H NMR spectrum of tautomer mixture
VIIb/VIIIb (CDCl3), δ, ppm: 3.43 m (4H, CH2CH2),
3.52 d.d (0.4H, VIIIb, O=CCH2, J = 11.35, 16.53 Hz),
5.45 d.d (0.2H, VIIIb, PhCH, J = 2.44, 10.98 Hz),
7.1–8.35 m (~10H, Harom, Ha, Hb), 7.14 d (0.8H, VIIb,
7-H, J7,8 = 7.56 Hz), 7.30 d (0.8H, VIIb, 8-H, J8,7
=
7.57 Hz), 7.64 d (0.8H, VIIb, Ha, Jab = 15.40 Hz),
7.86 d (0.8H, VIIb, Hb, Jba = 15.40 Hz), 8.16 d (0.8H,
VIIb, 4-H, J4,3 = 7.40 Hz), 8.31 d (0.2H, VIIIb, 5-H,
3
3J = 7.54 Hz), 7.40 d (1H, 5-H, J = 7.22 Hz), 7.60 s
(1H, 4-H); in DMSO-d6: 3.35 m (4H, CH2CH2), 7.19 d
3
(1H, 10-H, J = 7.54 Hz), 7.35 m (2H, 6-H, 9-H),
J5,6 = 7.30 Hz), 10.55 s (0.8H, VIIb, OH).
7.75 d (1H, 5-H, 3J = 7.22 Hz), 8.19 s (1H, 4-H).
(2E)-3-(4-Chlorophenyl)-1-(6-hydroxyacenaph-
(2E)-1-(6-Hydroxyacenaphthen-5-yl)-3-(4-me-
thoxyphenyl)prop-2-en-1-one (VIIa). a. 4-Methoxy-
benzaldehyde, 0.12 ml (1 mmol), was added to a sus-
pension of 0.2 g (1 mmol) of 5-acetyl-6-hydroxyace-
naphthene in 2 ml of freshly distilled triethyl ortho-
formate, 4 drops of 72% perchloric acid were added,
and the mixture was kept for 3 h at room temperature
then-5-yl)prop-2-en-1-one (VIIc) was synthesized
from 0.106 g (0.5 mmol) of 5-acetyl-6-hydroxyace-
naphthene and 0.07 g (0.5 mmol) of 4-chlorobenzalde-
hyde in 3 ml of ethanol using 0.3 ml of 30% aqueous
sodium hydroxide. Yield 0.15 g (89%), red–brown
powder, mp 162°C. IR spectrum, ν, cm–1: 3200 (OH),
1
1650 (C=O), 1600, 1590. H NMR spectrum of tauto-
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peri-HYDROXY ACENAPHTHOYL COMPOUNDS
343
5. Pozharskii, A.F., Usp. Khim., 2003, vol. 72, p. 498.
6. Bezuglov, A.N., Minyaeva, L.G., and Mezheritskii, V.V.,
Russ. J. Org. Chem., 2008, vol. 44, p. 353.
7. Mezheritskii, V.V., Pikus, A.L., and Tregub, N.G.,
mer mixture VIIc/VIIIc, δ, ppm: 3.40 m (4H,
CH2CH2), 3.60 d.d (0.4H, VIIIc, O=CCH2, J = 11.38,
16.75 Hz), 5.42 d.d (0.2H, VIIIc, PhCH, J = 2.53,
11.05 Hz), 7.1–8.40 m (~9H, Harom, Ha, Hb), 7.17 d
(0.8H, VIIc, 7-H, J7,8 = 7.62 Hz), 7.34 d (0.8H, VIIc,
Zh. Org. Khim., 1991, vol. 27, p. 2198.
8. Bezuglov, A.N., Minyaeva, L.G., Tyurin, R.V., and
Mezheritskii, V.V., Russ. J. Org. Chem., 2007, vol. 43,
p. 1256.
8-H, J8,7 = 7.59 Hz), 7.64 d (0.8H, VIIc, Ha, Jab
=
15.57 Hz), 7.84 d (0.8H, VIIc, Hb, Jba = 15.56 Hz),
8.18 d (0.8H, VIIc, 4-H, J4,3 = 7.47 Hz), 8.34 d (0.2H,
VIIIc, 5-H, J5,6 = 7.47 Hz), 10.50 s (0.8H, VIIc, OH).
9. Pozharskii, A.F., Vinokurova, T.I., and Zaletov, V.G.,
Khim. Geterotsikl. Soedin., 1976, p. 539.
2-(4-Nitrophenyl)acenaphtho[5,6-bc]oxepin-4-
one (IX). 4-Nitrobenzaldehyde, 0.15 g (1 mmol), and
30% aqueous sodium hydroxide, 0.6 ml, were added to
a suspension of 0.2 g (1 mmol) of 5-acetyl-6-hydroxy-
acenaphthene in 3 ml of ethanol. The mixture was
stirred for 2 h at room temperature, diluted with water,
and acidified with dilute (1:1) hydrochloric acid to
a weakly acidic reaction. The precipitate, 0.32 g, was
filtered off, dried, and purified by column chromatog-
raphy on aluminum oxide using chloroform as eluent.
Yield 0.02 g (1.2%), brown powder, mp 150–152°C.
IR spectrum, ν, cm–1: 1670 (C=O), 1620, 1580.
1H NMR spectrum (CDCl3), δ, ppm: 3.5 m (4H,
10. Vinokurova, T.I. and Pozharskii, A.F., Khim. Getero-
tsikl. Soedin., 1976, p. 545.
11. Kashparov, I.S. and Pozharskii, A.F., Khim. Geterotsikl.
Soedin., 1985, p. 372.
12. Mezheritskii, V.V., Minyaeva, L.G., Golyanskaya, O.M.,
Tyurin, R.V., Borbulevich, O.Ya., Borodkin, G.S., and
Antonov, A.N., Russ. J. Org. Chem., 2006, vol. 42,
p. 278.
13. Tyurin, R.V., Milov, A.A., Bezuglov, A.N., Anto-
nov, A.N., Minyaeva, L.G., and Mezheritskii V.V., Russ.
J. Org. Chem., 2007, vol. 43, p. 1466.
14. Chunaev, Yu.M., Przhiyalgovskaya, N.M., Kurkov-
skaya, L.N., and Gal’bershtam, M.A., Izv. Vyssh.
Uchebn. Zaved., Ser. Khim. Khim. Tekhnol., 1982,
vol. 25, p. 278.
15. Chunaev, Yu.M., Przhiyalgovskaya, N.M., and Kurkov-
skaya, L.N., Izv. Vyssh. Uchebn. Zaved., Ser. Khim.
Khim. Tekhnol., 1985, vol. 28, p. 28.
CH2CH2), 7.16 s (1H, 3-H), 7.31 d (1H, 6-H, J6,5
=
7.70 Hz), 7.35 d (1H, 10-H, J10,9 = 7.35 Hz), 7.51 d
3
(1H, 9-H, J9,10 = 7.35 Hz), 8.10 d.d (2H, o-H, J =
8.80, 4J = 1.73 Hz), 8.26 d.d (2H, m-H, 3J = 8.80, 4J =
1.73 Hz), 8.28 d (1H, 5-H, J5,6 = 7.70 Hz).
16. Sobczyk, L., Grabowski, S.J., and Krygowski, T.M.,
Chem. Rev., 2005, vol. 105, p. 3513.
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