Polynuclear heterocyclic systems based on naphthalene-1,5-diol: I. Reaction of naphthalene-1,5-diol and its derivatives with β-dicarbonyl and α,β-unsaturated carbonyl compounds

Article abstract of DOI:10.1134/S1070428006100095

Reactions of naphthalene-1,5-diol and its derivatives (5-methoxynaphthalen- 1-ol, 2-bromo-5-methoxynaphthalen-1-ol, and 2,6-di-tert-butylnaphthalene-1,5- diol) with ethyl acetoacetate, acetylacetone, and p-methoxycinnamic acid under acidic conditions (HCl

Full text of DOI:10.1134/S1070428006100095

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2006, Vol. 42, No. 10, pp. 1458–1463. © Pleiades Publishing, Inc., 2006.
Original Russian Text © V.V. Mezheritskii, R.V. Tyurin, L.G. Minyaeva, A.N. Antonov, A.P. Zadorozhnaya, 2006, published in Zhurnal Organicheskoi
Khimii, 2006, Vol. 42, No. 10, pp. 1473–1478.
Polynuclear Heterocyclic Systems Based
on Naphthalene-1,5-diol: I. Reaction of Naphthalene-1,5-diol
and Its Derivatives with β-Dicarbonyl and α,β-Unsaturated
Carbonyl Compounds
V. V. Mezheritskii, R. V. Tyurin, L. G. Minyaeva, A. N. Antonov, and A. P. Zadorozhnaya
Institute of Physical and Organic Chemistry, Rostov State University, pr. Stachki 194/2, Rostov-on-Don, 344090, Russia
e-mail: mezher@ipoc.rsu.ru
Received October 6, 2005
Abstract—Reactions of naphthalene-1,5-diol and its derivatives (5-methoxynaphthalen-1-ol, 2-bromo-5-
methoxynaphthalen-1-ol, and 2,6-di-tert-butylnaphthalene-1,5-diol) with ethyl acetoacetate, acetylacetone, and
p-methoxycinnamic acid under acidic conditions (HCl, HClO4, CF3CO2H) gave substituted benzo[h]-
chromenes, naphtho[1,2-b]pyrylium salts, and 3,4-dihydrobenzo[h]chromenes, respectively. Possible mechan-
isms were proposed for the observed acid-catalyzed heterocyclizations.
DOI: 10.1134/S1070428006100095
Polynuclear ortho- and peri-fused heterocyclic
compounds possess specific properties which make
them interesting from the viewpoints of both studying
fundamental problems of organic chemistry and
searching for new luminescent, photochromic, and
other materials for data storage devices, molecular
switches, chemosensors, etc. Naphthalene-1,5-diol
may be regarded as a singular template for building up
various derivatives due to specific arrangement of the
hydroxy groups in its molecule: the para position with
respect to one hydroxy group is simultaneously the
peri position with respect to the other. As a result,
reactions of naphthalene-1,5-diol with electrophilic
reagents could give rise to ortho- or peri-fused hetero-
cyclic systems or their ortho- or peri-hydroxy-substi-
tuted carbonyl precursors. Thus, assembly of ortho-,
peri-, ortho–ortho-, peri–peri-, and mixed ortho–peri-
fused heterocyclic systems 1–5 becomes possible on
the basis of the naphthalene-1,5-diol skeleton.
derivatives with ethyl acetoacetate, acetylacetone, and
p-methoxycinnamic acid as typical representatives of
β-dicarbonyl and α,β-unsaturated carbonyl compounds.
By passing dry hydrogen chloride through a solution of
ethyl acetoacetate and naphthalene-1,5-diol (Ia) or its
monomethyl ether Ib we obtained 2H-benzo[h]-
chromen-2-ones derivatives IIa and IIb, respectively
(Scheme 1). Electron-acceptor effect of the α-pyrone
ring in molecule IIa hampers the second heterocycliza-
tion with participation of the hydroxy group in position
7; however, it is known [1] that such heterocyclization
does occur under more severe conditions.
Likewise, naphthalene-1,5-diol (Ia) and 5-meth-
oxynaphthalen-1-ol (Ib) reacted with acetylacetone in
acetic acid in the presence of perchloric acid to give
benzo[h]chromenium perchlorates IIIa and IIIb. In
this case, the electron-withdrawing effect of the cation-
ic center is so strong that closure of the second hetero-
ring with formation of the corresponding dication is
impossible even on prolonged heating of compound Ia,
In the present work we examined acid-catalyzed
reactions of 1,5-dihydroxynaphthalene and some its
X
X
X
X
X
OR
OR
X
X
X
1
2
3
4
5
1458

POLYNUCLEAR HETEROCYCLIC SYSTEMS BASED ON NAPHTHALENE-1,5-DIOL: I.
1459
Scheme 1.
O
O
O
O
O
O
Me
Me
Me
Ar
Ar
R2
OR1
O
OH
O
O
NR42
IIa–IId
V
IX
O
NR42
O
O
OH
Ar
Ar
Ar
Ar
O
OH
O
OH
R3
O
NR42
IV
VIII
R2
O
NR42
OR1
Ia–Id
O
O
OH
Ar
Ar
R2
Me
OR1
OMe
VIa, VIb
VII
O
ClO4
Me
R2
OR1
IIIa–IIIc
I, R1 = R2 = R3 = H (a); R1 = Me, R2 = R3 = H (b); R1 = H, R2 = R3 = t-Bu (c); R1 = Me, R2 = H, R3 = Br (d); II, R1 = R2 = H (a);
R1 = Me, R2 = H (b); R1 = H, R2 = t-Bu (c); R1 = Ac, R2 = H (d); III, R1 = R2 = H (a); R1 = Me, R2 = H (b); R1 = H, R2 = t-Bu (c);
VI, R1 = Me, R2 = H (a); R1 = H, R2 = t-Bu (b); Ar = 4-MeOC6H4; VII–IX, R24N = morpholino.
acetylacetone, and perchloric acid at a ratio of 1:2:2 in
boiling acetic acid.
Under analogous conditions, the reactions of 2,6-di-
tert-butylnaphthalene-1,5-diol (Ic) with ethyl aceto-
acetate and acetylacetone were accompanied by elim-
ination of one tert-butyl group, and they led to the
formation of mono-tert-butyl-substituted benzo[h]-
chromene IIc and benzo[h]chromenium perchlorate
IIIc, respectively. In the reaction of compound Ic with
2 equiv of p-methoxycinnamic acid in trifluoroacetic
acid replacement of both tert-butyl groups occurred to
produce the same product IV as that obtained from
naphthalene-1,5-diol (Ia). The reaction of equimolar
amounts of Ic and p-methoxycinnamic acid gave com-
By contrast, the reaction of naphthalene-1,5-diol
(Ia) with p-methoxycinnamic acid in trifluoroacetic
acid cannot be stopped at the first heterocyclization
stage. Regardless of the reactant ratio, the product was
chromeno[8,7-h]chromene IV. Moreover, the second
pyran ring was formed in the reaction of p-methoxy-
cinnamic acid with benzo[h]chromene IIa, despite the
presence of electron-acceptor α-pyron ring in the latter.
Methoxynaphthol Ib reacted with p-methoxycinnamic
acid to give dihydrobenzo[h]chromene VIa.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 10 2006

MEZHERITSKII et al.
1460
pound VIb as a result of elimination of only one tert-
butyl group. The bromine atom in the ortho position
with respect to the hydroxy group (compound Id)
behaved in a similar way. 2-Bromo-5-methoxynaph-
thalen-1-ol (Id) reacted with ethyl acetoacetate and
acetylacetone with formation of the same products
(IIb and IIIb, respectively) as in the reaction with
methoxynaphthol Ib, but their yields were consider-
ably lower. It is interesting that 2,6-di-tert-butylnaph-
thalene-1,5-diol (Ic) remained unchanged in blank
experiments (without carbonyl component) in HCl–
EtOH and HClO4–AcOH, while elimination of both
tert-butyl groups occurred in trifluoroacetic acid. Ob-
viously, the reason is higher nucleophilicity of tri-
fluoroacetate ion compared to Cl– and ClO4–.
(X = Cl, CF3COO) or H whose enhanced electro-
philicity ensures the process to follow intermolecular
mechanism.
The intermolecular mechanism of formation of bis-
dihydrocoumarins IV and V in trifluoroacetic acid was
also noted by Li et al. [2]. The authors found that com-
pounds IV and V are formed from cinnamic acids and
phenols at a higher rate and with a larger yield than
from the corresponding phenyl cinnamates; moreover,
the latter were shown to decompose into initial com-
ponents (cinnamic acid and phenol) under these condi-
tions (the reaction was carried out in an NMR ampule).
An alternative version is electrocyclic [4π+2π]-
cyclization mechanism involving the C=C–C=O frag-
ment of the carbonyl compound (diene) and 1,2-double
bond in naphthol Ia–Id (dienophile). In this case, it is
easy to rationalize facile elimination of the R3 substit-
uent from the 2-position of naphthalenediol, and it
becomes clear why no naphtho[1,8-bc]oxepine deriva-
tive J or K is formed. However, the role of acid catal-
ysis and its necessity per se are difficult to understand.
Our experimental results allowed us to define
heterocyclization paths, confirm the product structure,
and propose probable mechanisms for the observed
transformations. Assuming that the reactions under
study begin with attack on the oxygen atom of
naphthol Ia–Id by O-protonated form of the carbonyl
reagent (E or G; Scheme 2), generated in acid medi-
um, cationic intermediate C or D thus formed may
undergo heterocyclization along two pathways with
closure of six-membered (B→II, IV, VI or D→III)
or seven-membered ring (B→J or D→K). However,
detailed analysis of these hypothetical mechanisms
shows that the electron-donor ortho-orienting effect of
the oxygen atom in cationic intermediate B or D is
completely eliminated; therefore, intramolecular ortho-
heterocyclization with closure of six-membered ring
seems to be hardly probable. This path becomes even
less probable if the ortho position is occupied by a sub-
stituent (R3) which creates steric hindrances to the ring
closure. The peri position seems to be more favorable
for intramolecular electrophilic attack, for it possesses
a negative π-charge due to electron-donor effect of the
hydroxy (or methoxy) group in the para position and is
not sterically shielded. As a result, naphtho[1,8-bc]-
oxepine derivative J or K would be formed; in fact,
this path is not operative.
The two mechanisms are also well suited for the
formation of coumarins from β-keto esters and methyl
phenyl ethers [3], where intermediates like A–D could
not be formed.
The structure of the newly synthesized compounds
was proved by spectral methods and (in some cases)
by chemical transformations. Thus the presence of
a hydroxy group in molecule IIa was confirmed by
O-acylation with formation of ester IId. The ortho-
fusion with closure of six-membered heteroring
(I→II, I→III) follows from the disappearance of one
tert-butyl group or bromine atom (1H NMR and mass
spectra). Treatment of dihydropyran-2-ones IV–VI
with morpholine gave amides VII–IX, indicating the
presence of a lactone moiety in molecules IV–VI.
Interestingly, in the reaction of morpholine with
heterocyclic system V containing α-pyrone and dihy-
dro-α-pyrone rings, only the latter was cleaved.
EXPERIMENTAL
Taking into account our experimental data and the
above considerations, more reasonable is intermolec-
ular heterocyclization mechanism which involves
initial attack by electrophile on the carbon atom in the
ortho position to the hydroxy group (rather than on the
oxygen atom of the hydroxy group) with formation of
a new C–C bond. Presumably, in this case the electro-
philic species is not O-protonated form of carbonyl
compound (E or G) but more reactive cation like F
The IR spectra were recorded on a Specord 71IR
spectrometer from samples dispersed in mineral oil.
The 1H NMR spectra were obtained on Bruker Avance
DPX-250 and Varian Unity-300 spectrometers from
solutions in CDCl3 and DMSO-d6 using HMDS as
internal reference. The mass spectra (electron impact,
70 eV) were run on a Kratos instrument with direct
sample admission into the ion source (control voltage
1.75 kV).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 10 2006

POLYNUCLEAR HETEROCYCLIC SYSTEMS BASED ON NAPHTHALENE-1,5-DIOL: I.
1461
Scheme 2.
R4
OH
R4
O
O
R4
O
Y
O
Y
O
Y
R3
R3
R3
R2
R2
R2
OR1
OR1
OR1
A
B
J
Ia–Id
O
R4
O
R4
X
R4
HX
Ia–Id
Ia–Id
IV–VI
R5O
Y
R5O
Y
X
Y
E
F
Me
Me
Me
Me
Me
Me
H+, AcOH
III
HO
O
HO
OH
AcO
OAc
G
H
Ia–Id
Me
O
Me
Me
Me
Me
Me
O
O
O
OH
R2
R3
R3
R3
R2
R2
OR1
OR1
OR1
C
D
K
R4 = Me, Ar; R5 = H, Et; Y = H, OH.
1
1630, 1600. H NMR spectrum (DMSO-d6–CCl4), δ,
2H-Benzo[h]chromen-2-ones IIa–IIc (general
procedure). A solution of compound Ia–Ic and ethyl
acetoacetate (molar ratio 1:2.5) in alcohol was cooled
to 5–10°C, and hydrogen chloride was passed through
the solution over a period of 5 h. The precipitate
(almost pure compound II) was filtered off, the filtrate
was diluted with water, and the precipitate was purified
by chromatography on aluminum oxide using chloro-
form as eluent to isolate an additional amount of the
product.
ppm: 2.53 s (3H, CH3), 6.35 s (1H, 3-H), 7.0 d (1H,
arom), 7.2 t (1H, Harom), 7.6 d (1H, Harom), 7.85 d (1H,
arom), 8.0 d (1H, Harom), 10.2 s (1H, OH). Found, %:
C 74.64; H 4.60. C14H10O3. Calculated, %: C 74.34;
H 4.42.
H
H
7-Methoxy-4-methyl-2H-benzo[h]chromen-2-one
(IIb). Yield 52% (from Ib), 7% (from Id), colorless
crystals, mp 188–189°C (from alcohol). IR spectrum,
ν, cm–1: 1710 (C=O), 1630, 1615. H NMR spectrum
1
(CDCl3), δ, ppm: 2.5 d (3H, CCH3, J = 1.16 Hz), 4.0 s
(3H, OCH3), 6.3 d (1H, 3-H, J = 1.16 Hz), 6.9–8.1 m
(5H, Harom). Found, %: C 75.41; H 4.83. C15H12O3.
Calculated, %: C 75.00; H 5.00.
7-Hydroxy-4-methyl-2H-benzo[h]chromen-2-one
(IIa). Yield 85%, colorless crystals, mp 298–300°C
(from acetic acid); published data [1]: mp 299–301°C.
IR spectrum, ν, cm–1: 3167 (OH), 1687, 1673 (C=O),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 10 2006

MEZHERITSKII et al.
1462
Harom), 7.85 d (1H, Harom), 8.0 s (1H, Harom), 8.3 d (1H,
Harom), 8.5 d (1H, Harom). Found, %: C 59.49; H 5.71;
Cl 9.47. C19H21ClO6. Calculated, %: C 59.92; H 5.52;
Cl 9.33.
8-tert-Butyl-7-hydroxy-4-methyl-2H-benzo[h]-
chromen-2-one (IIc). Yield 27%, colorless crystals,
mp 200–201°C (from alcohol). IR spectrum, ν, cm–1:
1
3160 (OH), 1700, 1687 (C=O), 1600. H NMR spec-
trum (CDCl3), δ, ppm: 1.5 s (9H, t-Bu), 2.5 d (3H,
4-CH3, J = 1.15 Hz), 5.6 s (1H, OH), 6.35 d (1H, 3-H,
J = 1.15 Hz), 7.5–7.6 m (2H, Harom), 7.9–8.0 d (1H,
1,7-Bis(4-methoxyphenyl)-1,2,3,7,8,9-hexa-
hydrochromeno[8,7-h]chromene-3,9-dione (IV).
A mixture of 0.5 g (3.125 mmol) of naphthalene-1,5-
diol (Ia) and 1.113 g (6.25 mmol) of 4-methoxy-
cinnamic acid in 5 ml of trifluoroacetic acid was
heated for 5 h under reflux. The mixture was cooled
and diluted with water, and the precipitate was filtered
off, dried, and purified by chromatography on alumi-
num oxide using chloroform as eluent. Yield 1.3 g
(87%), colorless crystals, mp 255–257°C. IR spectrum,
H
arom), 8.05–8.1 d (1H, Harom). Found, %: C 76.28;
H 6.53. C18H18O3. Calculated, %: C 76.60; H 6.38.
4-Methyl-2-oxo-2H-benzo[h]chromen-7-yl
acetate (IId). Compound IIa, 0.226 g (1 mmol), was
dispersed in 1 ml of acetic acid, the suspension was
cooled to 0°C, 5 drops of 72% perchloric acid were
added, and the mixture was kept for 5 min. The precip-
itate was filtered off and washed with ethanol. Yield
67%, colorless crystals, mp 159–160°C (from alcohol).
IR spectrum, ν, cm–1: 1747 (C=O), 1727 (C=O), 1607.
1H NMR spectrum (DMSO-d6–CCl4), δ, ppm: 2.4 s
(3H, COCH3), 2.55 d (3H, 4-CH3, J = 1.15 Hz), 6.4 d
(1H, 3-H, J = 1.15 Hz), 7.4 d (1H, Harom), 7.6–7.8 m
(3H, Harom), 8.4 d (1H, Harom). Found, %: C 71.68;
H 4.53. C16H12O4. Calculated, %: C 71.64; H 4.48.
1
ν, cm–1: 1767 (C=O). H NMR spectrum (CDCl3), δ,
ppm: 3.05–3.25 d.d (4H, CH2CH, J = 6.5 Hz), 3.75 s
(6H, OMe), 4.45 t (2H, CH2CH, J = 6.5 Hz), 6.85 d
(4H, C6H4), 7.05 d (4H, C6H4), 7.15 d (2H, naphtha-
lene), 8.0 d (2H, naphthalene). Found, %: C 74.85;
H 4.7. C30H24O6. Calculated, %: C 75.0; H 5.0.
1-(4-Methoxyphenyl)-7-methyl-1,2,3,9-tetra-
hydrochromeno[8,7-h]chromene-3,9-dione (V).
A mixture of 0.2 g (0.885 mmol) of compound IIa and
0.157 g (0.885 mmol) of 4-methoxycinnamic acid in
5 ml of trifluoroacetic acid was heated for 48 h under
reflux. The mixture was cooled and diluted with water,
and the precipitate was filtered off, dried, and purified
by chromatography on aluminum oxide using chloro-
form as eluent. Yield 0.27 g (79%), colorless crystals,
mp 129–130°C. IR spectrum, ν, cm–1: 1770 (C=O),
7-Hydroxy-2,4-dimethylbenzo[h]chromenium
perchlorate (IIIa). Five drops of 72% perchloric acid
were added to a solution of 0.2 g (1.25 mmol) of
naphthalene-1,5-diol (Ia) and 0.25 ml of acetylacetone
in 4 ml of acetic acid, and the mixture was heated for
10 min under reflux. The solution was cooled, and the
precipitate was filtered off. Yield 0.223 g (55%),
orange crystals, mp 281–282°C (from nitromethane).
IR spectrum, ν, cm–1: 3247 (OH), 1630 (C=O), 1100
(ClO4–). Mass spectrum, m/z (Irel, %): 324 (100)
[M – 1]+, 209 (5), 181 (12), 165 (15), 152 (20), 139
(10), 15 (9), 89 (9), 75 (10), 63 (17), 51 (19), 39 (23).
Found, %: C 55.24; H 3.95; Cl 11.21. C15H13ClO6.
Calculated, %: C 55.47; N 4.01; Sl 10.94.
1
1715 (C=O). H NMR spectrum (CDCl3), δ, ppm:
2.55 d (3H, 7-CH3, J = 1.16 Hz), 3.05–3.25 d.d (2H,
2-H, J = 6.95 Hz), 3.75 s (3H, OMe), 4.45 t (1H, 1-H,
J = 6.95 Hz), 6.4 d (1H, 8-H, J = 1.16 Hz), 6.85 d (2H,
C6H4), 7.05 d (2H, C6H4), 7.24 d (1H, naphthalene),
7.7 d (1H, naphthalene), 8.15 d (1H, naphthalene),
8.25 d (1H, naphthalene). Found, %: C 74.41; H 4.71.
C24H18O5. Calculated, %: C 74.61; H 4.66.
Compounds IIIb and IIIc were synthesized in
a similar way.
7-Methoxy-4-(4-methoxyphenyl)-3,4-dihydro-
2H-benzo[h]chromen-2-one (VIa). A mixture of
0.32 g (1.84 mmol) of 5-methoxynaphthol Ib and
0.327 g (1.84 mmol) of 4-methoxycinnamic acid in
5 ml of trifluoroacetic acid was kept for 48 h at room
temperature. It was then cooled and diluted with water,
and the precipitate was filtered off, dried, and sub-
jected to chromatography on aluminum oxide using
chloroform as eluent, the first fraction being collected.
Yield 0.59 g (96%), colorless solid, mp 114–115°C. IR
7-Methoxy-2,4-dimethylbenzo[h]chromenium
perchlorate (IIIb). Orange crystals. Yield 45% (from
Ib), 10% (from Id), mp 197–199°C (from acetic acid).
IR spectrum, ν, cm–1: 1630 (C=O), 1100 (ClO4–).
Found, %: C 56.42; H 4.95; Cl 10.01. C16H15ClO6.
Calculated, %: C 56.72; H 4.43; Cl 10.49.
8-tert-Butyl-7-hydroxy-2,4-dimethylbenzo[h]-
chromenium perchlorate (IIIc). Yield 15%, orange
crystals, mp 260–261°C (from acetic acid). IR spec-
–
1
1
trum, ν, cm–1: 1630 (C=O), 1100 (ClO4 ). H NMR
spectrum (CDCl3), δ, ppm: 1.6 s (9H, t-Bu), 3.0 s (3H,
Me), 3.2 s (3H, Me), 7.0 br.s (1H, OH), 7.75 d (1H,
spectrum, ν, cm–1: 1770 (C=O). H NMR spectrum
(CDCl3), δ, ppm: 2.9–3.2 d.d (2H, 3-H, J = 6.5 Hz),
3.75 s (3H, OMe), 4.0 s (3H, OMe), 4.4 t (1H, 4-H, J =
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 10 2006

POLYNUCLEAR HETEROCYCLIC SYSTEMS BASED ON NAPHTHALENE-1,5-DIOL: I.
1463
6.5 Hz), 6.8–6.9 m (3H, Harom), 7.0–7.1 m (3H, Harom),
7.4–7.5 t (1H, Harom), 7.8–7.85 d (1H, Harom), 7.95–8.0 d
(1H, Harom). Found, %: C 75.85; H 5.35. C21H18O4.
Calculated, %: C 75.45; H 5.39.
Compounds VII and VIII were synthesized in
a similar way.
3-(1-Hydroxy-5-methoxynaphthalen-2-yl)-3-(4-
methoxyphenyl)-1-morpholinopropan-1-one (VII)
was obtained from 0.11 g (0.33 mmol) of compound
VIa. Yield 0.13 g (93.5%), colorless solid, mp 65–
69°C. IR spectrum, ν, cm–1: 1600–1620 d (C=O),
8-tert-Butyl-7-hydroxy-4-(4-methoxyphenyl)-3,4-
dihydro-2H-benzo[h]chromen-2-one (VIb). A mix-
ture of 0.272 g (1 mmol) of compound Ic and 0.178 g
(1 mmol) of 4-methoxycinnamic acid in 5 ml of tri-
fluoroacetic acid was heated for 5 h under reflux. The
mixture was cooled and diluted with water, and the
precipitate was filtered off and dried. Fractional crys-
tallization from isooctane gave 0.057 g (15%) of com-
pound VIb as a colorless solid with mp 117–120°C. IR
1
3000–3200 sh (OH). H NMR spectrum (CDCl3),
δ, ppm: 3.2 m (2H, CH2CO), 3.4–3.6 m (8H,
NCH2CH2O), 3.8 s (3H, OMe), 3.95 s (3H, OMe),
5.15 d.t (1H, 2-CH), 6.75–6.95 m (4H, Harom), 7.2 d
(2H, C6H4), 7.4 t (1H, naphthalene), 7.6 d (1H, naph-
thalene), 8.0 d (1H, naphthalene), 9.6 br.s (1H, OH).
Found, %: C 70.97; H 6.54; N 3.19. C25H27NO5. Cal-
culated, %: C 71.26; H 6.42; N 3.33.
1
spectrum, ν, cm–1: 1767 (C=O). H NMR spectrum
(CDCl3), δ, ppm: 1.3 s (9H, t-Bu), 3.0–3.2 d.d (2H,
3-H, J = 6.4 Hz), 3.6 s (3H, OMe), 4.65 s (1H, OH),
4.4–4.5 t (1H, 4-H, J = 6.4 Hz), 6.6–6.8 m (3H, Harom),
7.0–7.1 d (2H, Harom), 7.15–7.23 d (1H, Harom), 7.25–
7.34 d (1H, Harom), 8.0 d (1H, Harom). Found, %:
C 76.85; H 6.45. C24H24O4. Calculated, %: C 76.6;
H 6.38.
3-{1,5-Dihydroxy-6-[1-(4-methoxyphenyl)-3-
morpholino-3-oxopropyl]naphthalen-2-yl}-3-(4-
methoxyphenyl)-1-morpholinopropan-1-one (VIII)
was obtained from 0.224 g (0.5 mmol) of compound
IV. Yield 0.3 g (92%), colorless solid, mp 165–170°C.
IR spectrum, ν, cm–1: 1600 (C=O), 3100 sh (OH).
1H NMR spectrum (CDCl3), δ, ppm: 3.2 d (4H,
CH2CO), 3.4–3.6 m (16H, NCH2CH2O), 3.75 s (6H,
OMe), 5.1 t (2H, 2-CH), 6.7–6.8 d (4H, C6H4), 6.9 d
(2H, naphthalene), 7.15 d (4H, C6H4), 7.8 d (2H,
naphthalene), 9.45 s (2H, OH). Found, %: C 69.7;
H 6.54; N 4.09. C38H42N2O8. Calculated, %: C 69.73;
H 6.42; N 4.28.
3-(7-Hydroxy-4-methyl-2-oxo-2H-benzo[h]-
chromen-8-yl)-3-(4-methoxyphenyl)-1-morpholino-
propan-1-one (IX). A solution of 0.386 g (1 mmol) of
compound V in 2 ml of morpholine was heated for
5 min under reflux. The mixture was cooled and
diluted with water, and the precipitate was filtered off,
dried, and purified by chromatography on aluminum
oxide using chloroform as eluent, the first fraction
being collected. Yield 0.4 g (84.5%), colorless solid,
mp 153–155°C. IR spectrum, ν, cm–1: 1720 (C=O),
REFERENCES
1
3500 (OH). H NMR spectrum (CDCl3), δ, ppm: 2.5 s
(3H, 4-CH3, J = 1.16 Hz), 3.2 d (2H, CH2CO, J =
6.5 Hz), 3.5–3.7 m (8H, NCH2CH2O), 3.8 s (3H,
OMe), 5.2 t (1H, 8-CH, J = 6.5 Hz), 6.3 d (1H, 3-H,
J 1.16 Hz), 6.85 d (2H, C6H4), 7.1 d (1H, naphthalene),
7.2 d (2H, C6H4), 7.6 d (1H, naphthalene), 7.95 d (1H,
naphthalene), 8.25 d (1H, naphthalene), 10.05 s (1H,
OH). Found, %: C 71.25; H 5.55; N 3.0. C28H27NO6.
Calculated, %: C 71.04; H 5.71; N 2.96.
1. Robinson, R. and Weygand, F., J. Chem. Soc., 1941,
p. 387.
2. Li, K., Foresee, L.N., and Tunge, J.A., J. Org. Chem.,
2005, vol. 70, p. 2881.
3. Sethna, S. and Phadke, R., Organic Reactions,
Adams, R., Ed., New York: Wiley, 1953, vol. 7. Trans-
lated under the title Organicheskie reaktsii, Moscow:
Inostrannaya Literatura, 1956, vol. 7, p. 7.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 10 2006