New synthetic approach to peri-hydroxy-substituted carbonyl acenaphthene derivatives

Article abstract of DOI:10.1134/s107042800803007x

A new approach to the synthesis of peri-hydroxyacenaphthoyl compounds has been developed on the basis of acylation (formylation) of 5- acyloxyacenaphthenes. The reactions are accompanied by formation of the corresponding 3- and 8-acyl-substituted isomers. In some cases, the latter can be isolated and identified by ¹H NMR spectroscopy.

Full text of DOI:10.1134/s107042800803007x

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 3, pp. 353–357. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © A.N. Bezuglov, L.G. Minyaeva, V.V. Mezheritskii, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 3,
pp. 361–364.
New Synthetic Approach to peri-Hydroxy-Substituted Carbonyl
Acenaphthene Derivatives
A. N. Bezuglov, 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 July 27, 2007
Abstract—A new approach to the synthesis of peri-hydroxyacenaphthoyl compounds has been developed on
the basis of acylation (formylation) of 5-acyloxyacenaphthenes. The reactions are accompanied by formation of
the corresponding 3- and 8-acyl-substituted isomers. In some cases, the latter can be isolated and identified by
1H NMR spectroscopy.
DOI: 10.1134/S107042800803007X
peri-Hydroxyacenaphthoyl compounds attract inter-
est as potential precursors of peri-fused heterocyclic
systems having an ethylene bridge [1–3] and starting
materials for the preparation of peri-hydroxy-substi-
tued carbonyl acenaphthylene derivatives; the latter are
obtained by dehydrogenation of the ethylene unit [4].
more, we failed to obtain in this way peri-hydroxy-
acenaphthenecarbaldehyde because of side reactions of
intermediate peri-amino aldehyde, which gave rise to
an inseparable product mixture as a result of condensa-
tion of the aldehyde group with hydrazine (with forma-
tion of azines) and intermolecular self-condensation in-
volving two and more peri-amino aldehyde molecules
(with formation of cyclic and linear Schiff bases).
A traditional procedure for the synthesis of the
above acenaphthene compounds implies acylation of
acenaphthene, nitration, catalytic reduction of the nitro
group with hydrazine over Raney nickel, diazotization
of the amino group, and its replacement by hydroxy
group [2]. The main disadvantage of this procedure is
the necessity of performing the whole transformation
sequence for each of desired acenaphthene. Further-
The procedure proposed in the present work is
based on acid-catalyzed acylation (formylation) of
esters derived from 5-hydroxyacenaphthene. The use
of esters is necessary to avoid acylation at the ortho-
position with respect to the hydroxy group. The corre-
sponding methyl ketones were synthesized by acyla-
Scheme 1.
OH
OCOR
OCOR
COR'
OH
Ia, Ib
IIa–IIc
OH
COR'
OH
+
COR'
R'CO
IIIa–IIIc
IVa–IVc
V
I, R = Me (a), Ph (b); II, R = R′ = Me (a); R = R′ = Ph (b); R = Ph, R′ = Me (c); III, IV, R′ = Me (a), Ph (b), H (c); V, R′ = Ph.
353

BEZUGLOV et al.
354
tion with acetic anhydride in the presence of perchloric
acid or aluminum chloride, phenyl ketones were ob-
tained by acylation with benzoyl chloride in tetra-
chloroethane in the presence of aluminum chloride,
and AlCl3-catalyzed formylation with dichloromethyl
ethyl ether gave formyl-substituted derivatives. In the
latter case, the reactions led to the formation of mix-
tures of O-acylated ketones and aldehydes II, which
cannot be separated by chromatography. However,
after hydrolysis of the ester group, the resulting
hydroxy derivatives had different chromatographic
mobilities, and the target peri-hydroxy compounds III
were isolated from the multicomponent reaction mix-
tures. The benzoylation of 5-acetoxyacenaphthene (Ia)
in the presence of aluminum chloride was accom-
panied by partial, and the formylation, by complete
removal of the ester group (Scheme 1).
zoylation reaction (R′ = Ph); according to the 1H NMR
data, it contained about ~20% of one more isomer,
presumably 8-benzoyl-6-hydroxyacenaphthene (V).
We failed to purify compound IVb from V by chroma-
tography or recrystallization. In the 1H NMR spectrum
of mixture IVb/V a singlet was present between two
triplets in the δ region 3.2–3.6 ppm belonging to the
ethylene bridge. This singlet is likely to arise from
the corresponding protons of 8-benzoyl isomer V. The
hydroxy protons in both isomers give rise to two
broadened singlets at δ 5.3–5.5 ppm. The aromatic
region of the spectrum contains a singlet and a doublet
from the 8-benzoyl isomer with an intensity of ~20%
of the intensity of the one-proton signals from 3-ben-
zoyl isomer IVb.
Among the acetylation products, we succeeded in
isolating only peri-hydroxyacetylacenaphthene IIIa as
individual substance.
In the formylation of phenyl ketone Ib, apart from
peri-hydroxy aldehyde IIIc we isolated another isomer
which was assigned the structure of 6-hydroxyace-
naphthene-3-carbaldehyde (IVc). The corresponding
3-substituted isomer IVb was also isolated in the ben-
Unlike isomers III, compounds IV lack intramolec-
ular hydrogen bond which affects the position of the
1
hydroxy proton signal in the H NMR spectra. Com-
pounds III are characterized by a downfield signal in
Scheme 2.
·
O
·
O
O
·
–HCO (–29)
–CO (–28)
F2 (196)
F4 (168)
OH
F7 (139)
–C6H6 (–78)
R = Ph
F6 (141)
H
O
·
OH
COR
O
·
–R (–15)
–CO (–28)
–CO (–28)
–C2H2 (–26)
[M1]+ (212), [M2]+ (274)
F1 (197)
F3 (169)
F5 (141)
–H2
F9(115)
R = Me
·
·
OH
Me
H
CH2
F8 (139)
–H2O (–18)
–HCO (–29)
[M1]+ (212*)
F2 (194)
F10 (165)
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NEW SYNTHETIC APPROACH TO peri-HYDROXY-SUBSTITUTED CARBONYL
355
the region δ 10–11.5 ppm, while the hydroxy proton in
isomers IV resonates at δ 5–5.5 ppm. The structure of
compounds IV as 3- rather than 8-acyl-substitued
isomers V is confirmed by the presence in their
1H NMR spectra of four one-proton doublets; com-
pounds like V should display a one-proton singlet, two
one-proton doublets, and one-proton triplet.
0.58 g (80%), colorless powder, mp 94–96°C (from
ethanol). IR spectrum, ν, cm–1: 1740 (C=O), 1590.
1H NMR spectrum, δ, ppm: 3.35–3.50 m (4H, CH2),
7.20–8.30 m (10H, Harom). Found, %: C 83.36; H 4.92.
C19H14O2. Calculated, %: C 83.19; H 5.14.
1-(6-Hydroxyacenaphthen-5-yl)ethanone (IIIa).
a. Acetic anhydride, 0.5 ml (5.3 mmol), was added to
a solution of 0.22 g (1 mmol) of compound Ia in 2 ml
of tetrachloroethane, the mixture was cooled to 0°C,
and 0.3 g (2.2 mmol) of anhydrous AlCl3 was added in
portions under stirring. The mixture was kept for 24 h
at room temperature and poured into water, the solvent
was removed by steam distillation, and the precipitate,
0.145 g, was filtered off. It was dispersed in 3 ml of
methanol, and the suspension was treated with 0.031 g
of sodium methoxide over a period of 1 h at room
temperature, acidified with dilute hydrochloric acid to
pH ~3, and diluted with water. The precipitate was
filtered off, dried, and dissolved in chloroform, and the
solution was applied to a column charged with Al2O3.
The column was eluted with chloroform to isolate
0.04 g (33%) of compound IIIa as an orange powder
with mp 98–99°C; published data [1]: mp 96°C. IR
The structure of IIIa and IIIb was also confirmed
by mass spectrometry. Probable fragmentation path-
ways of their molecules under electron impact are
shown in Scheme 2. The main fragmentation pathway
of molecular ions [M1]+ and [M2]+ derived from com-
pounds IIIa and IIIb, respectively, includes initial
elimination of methyl or phenyl radical with formation
of stable fragment ion F1 (Irel = 70, 98%) which under-
goes further decomposition to give stable (Irel ≥ 50%)
ions F5, F6, F8, and F9 (except for F3, Irel = 3, 15%).
Some alternative decomposition pathways are also
possible.
EXPERIMENTAL
The IR spectra were recorded on a Specord 71IR
spectrophotometer from samples dispersed in mineral
1
spectrum, ν, cm–1: 2670, 1635 (C=O), 1590. H NMR
1
oil. The H NMR spectra were measured on a Varian
spectrum, δ, ppm: 2.80 s (3H, CH3), 3.35 m (2H, 1-H),
3.43 m (2H, 2-H), 7.14 d (1H, 7-H, J7,8 = 7.65 Hz),
7.24 br.d (1H, 3-H, J3,4 = 7.47 Hz), 7.32 br.d (1H, 8-H,
J8,7 = 7.62 Hz), 8.20 d (1H, 4-H, J4,3 = 7.55 Hz),
11.60 s (1H, OH). Mass spectrum, m/z (Irel, %): 212
(100) [M]+, 197 (98) F1, 194 (18) F2*, 169 (15) F3, 165
(22) F4*, 141 (75) F5 or F6, 139 (55) F8, 115 (60) F9, 43
(35) [MeCO]+. Found, %: C 78.89; H 5.47. C14H12O2.
Calculated, %: C 79.23; H 5.70.
Unity-300 instrument in CDCl3 using hexamethyldi-
siloxane as internal reference. The mass spectra (elec-
tron impact, 70 eV) were obtained on a Varian MAT-44
instrument.
Acenaphthen-5-yl acetate (Ia). A solution of
0.63 g (3.7 mmol) of acenaphthen-5-ol in 3 ml of
acetic anhydride containing a catalytic amount of
sodium acetate was heated under reflux for 30 min.
The mixture was cooled and poured into water, and the
precipitate was filtered off and washed with water.
Yield 0.73 g (92%), colorless powder, mp 90–91°C
(from ethanol). IR spectrum, ν, cm–1: 1767 (C=O),
b. Two drops of 72% perchloric acid were added to
a solution of 0.22 g (1 mmol) of compound Ia in 2 ml
of acetic anhydride, and the mixture was kept for 3 h at
room temperature and poured into water. An oily
material separated and was extracted into chloroform,
and the extract was concentrated and subjected to
column chromatography on Al2O3 using chloroform as
eluent. A fraction with Rf 0.6 was collected. The eluate
was evaporated, the oily residue was dissolved in 3 ml
of methanol, 0.03 g of sodium methoxide was added,
and the mixture was kept for 30 min at room tem-
perature, acidified with dilute hydrochloric acid to
pH ~3, and diluted with water. Yield 0.05 g (23%),
orange powder, mp 98–99°C (from ethanol).
1
1607. H NMR spectrum, δ, ppm: 2.4 s (3H, CH3),
3.30–3.45 m (4H, CH2), 7.16 d (1H, 4-H, J4, 3
=
7.50 Hz), 7.24 d (1H, 3-H, J3,4 = 7.50 Hz), 7.30 br.d
(1H, 8-H, J8,7 = 5.05 Hz), 7.43–7.51 m (2H, 6-H, 7-H).
Found, %: C 79.52; H 5.51. C14H12O2. Calculated, %:
C 79.23; H 5.70.
Acenaphthen-5-yl benzoate (Ib). Benzoyl chlo-
ride, 0.9 ml (7.81 mmol), was added at 0°C to a solu-
tion of 0.45 g (2.6 mmol) of acenaphthen-5-ol in 2 ml
of anhydrous pyridine, the mixture was kept for 1 h at
room temperature, acidified with dilute hydrochloric
acid to pH ~3, and diluted with water, and an oily
material separated and was ground with ethanol. Yield
(6-Hydroxyacenaphthen-5-yl)phenylmethanone
(IIIb) and (6-hydroxyacenaphthen-3-yl)phenyl-
methanone (IVb). a. Benzoyl chloride, 0.4 ml
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 3 2008

BEZUGLOV et al.
356
(3.47 mmol), was added to a solution of 0.5 g
(1.8 mmol) of compound Ib in 4.5 ml of tetrachloro-
ethane, the mixture was cooled to 0°C, and 0.62 g
(4.6 mmol) of anhydrous AlCl3 was added in portions
under stirring. The mixture was kept for 4.5 h at room
temperature, poured into water, and subjected to steam
distillation. The solid residue, 0.32 g was subjected to
chromatography on aluminum oxide using chloroform
as eluent to isolate 0.22 g of a mixture of isomeric
benzoates IIb. The isomer mixture was dispersed in
3 ml of methanol, 0.031 g of sodium methoxide was
added, and the mixture was kept for 30 min at room
temperature, acidified with dilute hydrochloric acid to
pH ~3, and diluted with water. The precipitate was
filtered off, dried, and dissolved in chloroform, and the
solution was subjected to column chromatography on
Al2O3 using chloroform as eluent to isolate compound
IIIb (Rf 0.75) and a mixture of compounds IVb and
V (Rf 0.25).
acidified with dilute hydrochloric acid to pH ~3 and
diluted with water. The precipitate was filtered off,
dried, and dissolved in chloroform, and the solution
was subjected to column chromatography on Al2O3
using chloroform as eluent to isolate 0.025 g (19%) of
compound IIIb as orange powder with mp 115°C,
Rf 0.75. Overall yield of IIIb 0.055 g.
6-Hydroxyacenaphthene-5-carbaldehyde (IIIc)
and 6-hydroxyacenaphthene-3-carbaldehyde (IVc).
a. Compound Ib, 0.27 g (1 mmol), was dissolved in
3 ml of tetrachloroethane, 0.3 ml of dichloromethyl
ethyl ether was added, the mixture was cooled to 0°C,
and 0.2 g (1.5 mmol) of anhydrous AlCl3 was added in
portions under stirring. The mixture was left to stand
overnight at room temperature, poured into water, and
subjected to steam distillation. The residue was dis-
solved in chloroform, and the solution was subjected to
column chromatography on Al2O3 using chloroform as
eluent to isolate 0.17 g of an aldehyde mixture which
was dispersed in 3 ml of methanol. Sodium methoxide,
0.03 g, was added to the suspension, and the mixture
was kept for 30 min at room temperature, acidified
with dilute hydrochloric acid to pH ~3, and diluted
with water. The precipitate was filtered off, dried, and
dissolved in chloroform, and the solution was sub-
jected to column chromatography on Al2O3 using
chloroform as eluent to isolate compounds IIIc (Rf 0.7)
and IVc (Rf 0.2).
(6-Hydroxyacenaphthen-5-yl)phenylmethanone
(IIIb). Yield 0.04 g (25%), red plates, mp 117–118°C;
published data [1]: mp 115°C. IR spectrum, ν, cm–1:
1
1633 (C=O), 1590. H NMR spectrum, δ, ppm: 3.4 m
(4H, CH2), 7.2–7.9 m (9H, Harom), 9.6 s (1H, OH).
Mass spectrum, m/z (Irel, %): 274 (80) [M]+, 197 (70)
F1, 196 (85) F2, 169 (3) F3, 168 (27) F4, 141 (52) F5 or
F6, 139 (25) F7, 139 (63) F8, 115 (55) F9, 105 (45)
[PhCO]+, 77 (100) [Ph]+. Found, %: C 83.47; H 4.93.
C19H14O2. Calculated, %: C 83.19; H 5.14.
6-Hydroxyacenaphthene-5-carbaldehyde (IIIc).
Yield 0.04 g (36%), orange plates, mp 128–130°C. IR
(6-Hydroxyacenaphthen-3-yl)phenylmethanone
(IVb) and (5-hydroxyacenaphthen-3-yl)phenyl-
methanone (V) (isomer mixture). Yield 0.04 g (25%),
yellow powder, mp 183–186°C. IR spectrum, ν, cm–1:
3394 (OH), 1650 (C=O). Found, %: C 82.82; H 5.33.
C19H14O2. Calculated, %: C 83.19; H 5.14.
1
spectrum, ν, cm–1: 1660 (C=O), 1607. H NMR spec-
trum, δ, ppm: 3.31–3.38 m (2H, 1-H), 3.38–345 m
(2H, 2-H), 7.13 d (1H, 7-H, J7,8 = 7.69 Hz), 7.32 d
(1H, 3-H, J3,4 = 7.04 Hz), 7.34 d (1H, 8-H, J8,7
=
7.62 Hz), 7.93 d (1H, 4-H, J4,3 = 7.09 Hz), 9.8 s (1H,
CHO), 11.5 s (1H, OH). Found, %: C 78.52; H 5.40.
C13H10O2. Calculated, %: C 78.77; H 5.09.
b. Benzoyl chloride, 0.4 ml (3.47 mmol), was added
to a solution of 0.32 g (1.5 mmol) of compound Ia in
4 ml of tetrachloroethane, the mixture was cooled to
0°C, and 0.62 g (4.6 mmol) of anhydrous AlCl3 was
added in portions under stirring. The mixture was kept
for 4.5 h at room temperature, poured into water, and
subjected to steam distillation. The oily residue was
dissolved in chloroform, and the solution was sub-
jected to column chromatography on silica gel using
hexane as eluent to isolate 0.03 g of compound IIIb
(orange product, mp 115°C, Rf 0.75) and 0.15 g of
a mixture of ketones IIIb and IVb (Rf 0.4). Isomer
mixture IIIb/IVb was treated with 0.03 g of sodium
methoxide in 3 ml of methanol, and the mixture was
6-Hydroxyacenaphthene-3-carbaldehyde (IVc).
Yield 0.015 g (14%), yellow powder, mp 168–170°C.
IR spectrum, ν, cm–1: 3300, 1660 (C=O), 1590.
1H NMR spectrum, δ, ppm: 3.41 t (2H, 1-H, J1 = 4.55,
J2 = 5.86 Hz), 3.77 t (2H, 2-H, J1 = 6.01, J2 = 5.72 Hz),
5.21 s (1H, OH), 6.98 d (1H, 7-H, J7,8 = 7.47 Hz),
7.22 d (1H, 8-H, J8,7 = 7.40 Hz), 7.84 d (1H, 5-H, J5,4
=
8.65 Hz), 7.87 d (1H, 4-H, J4,5 = 8.60 Hz), 10.3 s (1H,
CHO). Found, %: C 78.51; H 4.83. C13H10O2. Calcu-
lated, %: C 78.77; H 5.09.
b. Dichloromethyl ethyl ether, 0.3 ml, was added to
a solution of 0.22 g (1 mmol) of acetate Ia in 2 ml of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 3 2008

NEW SYNTHETIC APPROACH TO peri-HYDROXY-SUBSTITUTED CARBONYL
tetrachloroethane, the mixture was cooled to 0°C, and REFERENCES
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0.3 g (2.2 mmol) of anhydrous AlCl3 was added in
portions under stirring. The mixture was left to stand
overnight at room temperature and poured into water,
and the solvent was removed by steam distillation. The
product was extracted into chloroform, and the extract
was washed with water, dried, and subjected to column
chromatography on Al2O3 using chloroform as eluent.
Yield of compound IIIc 0.07 g (29%), orange plates,
mp 125–126°C.
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