Vanillal esters in reaction with 2-naphthylamine and 1,3-diketones

Article abstract of DOI:10.1007/s11178-006-0011-2

Analogs of natural alkaloids of acridone series, derivatives of 4-(9-alkyl-11-oxo-7,8,9,10,1,12-hexahydro-benzo[a]acridin-12-yl) and 4-(12-oxo-12H-benzo[f]indeno[1,2-b]quinolin-13-yl)2-ethoxyphenyl carboxylates were synthesized by a three-component conden

Full text of DOI:10.1007/s11178-006-0011-2

Russian Journal of Organic Chemistry, Vol. 41, No. 11, 2005, pp. 1637-1646. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 11, 2005,
pp. 1671-1680.
Original Russian Text Copyright Ó 2005 by Kozlov, Basalaeva, Dikusar.
.
Vanillal Esters in Reaction with 2-Naphthylamine
and 1,3-Diketones
N.G. Kozlov, L.I. Basalaeva, and E.A. Dikusar
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, Minsk, 22007 Belarus
e-mail: loc@ifoch. bas-net.by
Received July 6, 2004
Abstract—Analogs of natural alkaloids of acridone series, derivatives of 4-(9-alkyl-11-oxo-7,8,9,10,1,12-hexahydro-
benzo[a]acridin-12-yl) and 4-(12-oxo-12H-benzo[f]indeno[1,2-b]quinolin-13-yl)2-ethoxyphenyl carboxylates were
synthesized by a three-component condensation of vanillal with 2-naphthylamine and 1,3-cyclohexanedione,
dimedone, phendione, or 1,3-indanedione.
Fragment of vegetable phenols is a principal pharmaco-
phore group of the naturally-occurring alkaloids of acridone
series. We formerly established [1] that an introduction
into the acridone molecule of a vanillin fragment containing
both ether and ester moieties with an alkyl substituent
C –C resulted in increased solubility of the product in
with vinillal esters II. In this study we synthesized the
presumed ketone imines A and brought into the reaction
with esters IIa–IIg. Only the initial ketone imine was
isolated from the reaction mixture. Probably the ketone
imine reacts with ester II only in statu nascendi in the
three-component reaction mixture, and formation of
4-(11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-
yl)-2-ethoxyphenyl carboxylates takes another route.
1
7
the main organic solvents and fats facilitating preparation
of preforms of drugs.
In this study we selected as an aldehyde part for
a three-component heterocyclization vanillal (4-hydroxy-
3
-ethoxybenzaldehyde), the closest structural analog of
vanillin, available natural phenol extensively used in the
preparation of fragrant substances and drugs [2–4]. The
vanillal was preliminary esterified with chlorides of
alkylcarboxilic acids C –C into esters IIa–IIg. The
condensation was carried out by boiling compounds IIa–
IIg with 2-naphthylamine (I) and 1,3-cyclohexanedione
1
4
We failed to isolate in a pure state arylidene-1,3-
diketone C in reaction of 1,3-diketone with ester II,
therefore in the scheme of the three-component con-
densation of 2-naphthylamine, 1,3-diketone, and vanillal
esters a formation of an unstable iminium intermediate B
was assumed that decomposed into arylidene-1,3-diketone
C and 2-naphthylamine (I). The latter possessing the
highest electron density on the carbon in the a-position
with respect to amino group undergoes addition to the
double bond of arylidene-1,3-diketone C furnishing
arylaminoketoenol D which via heterocyclization with
elimination of water molecule affords the final reaction
product, 4-(11-oxo-7,8,9,10,11,12-hexa-hydrobenzo[a]-
acridin-12-yl)- (Va–Vg), 4-(9,9-dimethyl-11-oxo-
7,8,9,10,11,12-hexahydrobenzo[a]-acridin-12-yl)- (VIa–
VIg), or 4-(11-oxo-9-phenyl)-7,8,9,10,11,12-hexa-
hydrobenzo[a]acridin-12-yl)-(VIIa–VIIg) -2-ethoxy-
phenyl carboxylates.
(
(
(
IIIa), 5,5-dimethyl-1,3-cyclohexanedione (dimedone)
IIIb), 5-phenyl-1,3-cyclohexanedione (phendione)
IIIc), or 1,3-indanedione (IV) in ethanol or butanol for
0
.5–4 h.
The reaction time and the yield of the ester is affected
by the sterical effect of the acyl component. The yield of
-(11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-
4
yl)-2-ethoxyphenyl isocaproate (Ve) was 52% and the
reaction time 4 h, whereas 4-(11-oxo-7,8,9,10,11,12-
hexahydrobenzo[a]acridin-12-yl)-2-ethoxyphenyl acetate
(Vb) was obtained in a 97% yield in 30 min.
Considering the mechanism of the three-component
condensation of esters II with 1,3-cyclohexanedione [1]
we assumed that from 2-naphthylamine and 1,3-diketones
formed intermediately ketone imines which further reacted
1070-4280/05/4111-1637Ó2005 Pleiades Publishing, Inc.

1638
KOZLOV et al.
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R = H (IIIa, V), Me (IIIb, VI), H, C H (IIIc, VII); R' = H (a), Me (b), C H (c), C H (d), iso-C H (e), CH CH(CH ) (f), C H (g).
6
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7
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2
3 2
6 5
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 11 2005

VANILLAL ESTERS IN REACTION WITH 2-NAPHTHYLAMINE
1639
9
It should be noted that synthesized 4-(11-oxo-9-
phenyl)-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl)-
upfield signal was assigned to the axial proton H , and
the more downfield signal was identified with the equatorial
proton H .
9
2
-ethoxyphenyl carboxylates VIIa–VIIg contained two
9
12
acymmetric atoms C and C and formed as a mixture
of diastereomers with a pseudoaxial and pseudoequatorial
In the spectra of isomer mixtures of 4-(11-oxo-9-
phenyl)-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl)-
2-ethoxyphenyl carboxylates VIIa–VIIg were detected
the singlet signals of protons at the nitrogen and C
9
position of the phenyl group at the atom C in approximate-
1
ly equal amounts as revealed by H NMR spectroscopy.
12
We found that phendione (IIIc) required higher
temperature for entering into the three-component
condensation than cyclohexanedione (IIIa) and dimedone
whose integral intensities corresponded to those of the
9
protons at the C atom. In the isomer with the axial phenyl
9
12
group linked to C the proton of the NH group and H
(
IIIb) since 4-(11-oxo-9-phenyl)-7,8,9,10,11,12-hexa-
occur in the shielding region of the benzene ring, and the
corresponding signals appear upfield with respect to those
from the isomer with the equatorial phenyl group.
hydrobenzo[a]acridin-12-yl)-2-ethoxyphenyl carboxylates
VIIa–VIIg formed from the phendione in better yield
when reaction was performed in butanol. In ethanol the
yield of the final products did not exceed 10%, and
The NMR spectra of compounds IXa–IXg possess
signals of aromatic protons whose position and multiplicity
correspond to benzoindenoquinoline structure.
4
-(11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-
yl)-2-ethoxyphenyl carboxylates Va–Vg and VIa–VIg
formed in butanol in a yield no more than 15%.
The IR spectra of benzo[a]acridines Va–Vg–VIIa–
VIIg indicate the presence of a secondary amino group
The formation of arylidene-1,3-indanediones E in the
reaction with 1,3-indanedione (IV) was proved in [5].
4
–1
(
an absorption band in the region 3276–3260 cm ) and
of a carbonyl group (an absorption band in the region
-(12,13-Dihydro-12-7H-benzo[f]-indeno[1,2-b]quinolin-
3-yl)-2-ethoxyphenyl carboxylates VIIIa–VIIIg in all
–1
1
768–1753 cm ). The carbonyl of the ester group
1
–1
appears as a strong band in the region 1608–1594 cm .
The fragments C–O–C present in the molecules give rise
to the bands in the region 1276–1242 cm . The absorption
experiments were obtained in a mixture with 4-(12-oxo-
2H-benzo[f]indeno[1,2-b]quinolin-13-yl)-2-ethoxy-
1
–1
phenyl carboxylates IXa–IXg in a ratio 1:9 according to
1
bands of the stretching vibrations of alkyl groups and
H NMR spectra. The attempt to isolate compounds
–1
cycloaliphatic CH bonds appear at 2980–2952 cm . In
VIIIa–VIIIg from the reaction mixture in an individual
state failed for the substances suffered further oxidation.
Inasmuch as the compounds VIIIa–VIIIg and IXa–
IXg defied the attempts at separation we subjected at
once the mixture to dehydration by boiling it in the
nitrobenzene for 3–4 h till formation of 4-(12-oxo-12H-
benzo[f]indeno[1,2-b]quinolin-13-yl)-2-ethoxyphenyl
carboxylates IXa–IXg.
the IR spectra of compounds IXa–IXg medium bands
observed at 1566–1562 cm belong to the stretching
vibrations of the carbonyl group in conjugation with the
benzene and naphthalene rings. The carbonyl of the ester
group appears as a strong band in the region 1768–
–1
–1
1
763 cm . The lack in the spectra of compounds IXa–
–1
IXg absorption bands in the region 3276–3260 cm
character-istic of amino group evidences the cyclic
structure of the tertiary amine.
The structure of compounds Va–Vg–VIIa–VIIg, and
1
IXa–IXg was confirmed by H NMR, IR, and mass
In the mass spectra of benzo[a]acridines Va–Vg–
1
spectra. In the H NMR spectra of benzo[a]-acridines
+
VIIa–VIIg the peaks of molecular ions M (I 10–
rel
Va–Vg–VIIa–VIIg the position and multiplicity of
aromatic proton signals correspond to the benzo[a]acridine
84%) are present. The most abundant peak (100%) in
the spectra of compounds Va–Vg–VIIa–VIIg was that
1
2
structure [6]. The methine proton (H ) of the dihydro-
pyridine ring gave rise to a singlet at 5.70–5.95 ppm. The
downfield shift of this signal as compared to the usual
position of the methine protons signals in the spectra of
cyclic compounds [7] is due to the anisotropic effect of
the adjacent aromatic ring.
+
of the ion [M–C H OR'COOC H ] which proved to be
2
5
6
3
stable and hardly suffered fragmentation. Besides in the
mass spectra of all compounds Va–Vg–VIIa–VIIg
a peak is present with m/z 192 (16–30%) generated by
+
elimination from the ion [M – C H OR'COOC H ] of
2
5
6
3
fragment CH CH CO for compounds Va–Vg,
2
2
1
In the H NMR spectra of compounds VIIa–VIIg
(CH ) CCH CO for dimethyl derivatives VIa–VIg, and
3 2 2
9
the signals of protons attached to C were identified as
C H CHCH CO for compounds VIIa–VIIg. The
6 5 2
two multiplets in the region 3.21–3.41 ppm. According to
the chemical shift value and the half-width the more
analysis of mass spectra of compounds IXa–IXg
revealed their stability against the electron impact.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 11 2005

1640
KOZLOV et al.
The spectra contain very strong (100%) peaks of
molecular ions M and relatively strong peaks of ions
4-Formyl-2-ethoxyphenyl ethanoate (IIb). Yield
+
87%, colorless crystalline substance, mp 33–34°C. IR
–1
with m/z 280 (39–50%) corresponding to the ions [M–
spectrum, cm : 3080, 2982, 2934, 2907, 2880, 2850, 2830,
2736, 1768, 1694, 1600, 1592, 1509, 1479, 1441, 1392,
+
OC H RCOOC H ] .
2
5
6
3
1
9
370, 1320, 1288, 1273, 1210, 1197, 1156, 1040, 1011, 973,
00, 870, 832, 800, 786, 745, 726, 667, 632, 586, 528.
EXPERIMENTAL
1
H NMR spectrum, d, ppm: 1. 41 t (3H, MeCH ), 2.32 s
2
IR spectra of compounds were recorded on a Fourier-
spectrophotometer Protege-460 (Nicolet) from thin films
[
3H, MeC(O)], 4.11 q (2H, CH ), 7.20 d, 7.45 m (3H,
2
1
C6H3), 9.92C (1H, CHO). Mass spectrum, m/z (Irel, %):
or pellets with KBr. H NMR spectra were registered
+
+
[
M] 208 (13), [M–OCMe] 166 (100), [M–
on spectrometers AC-500 (500 MHz, Bruker) or BS-
87A(100 MHz, Tesla) from 5% solutions in DMSO-d6,
chemical shifts were measured from internal reference
TMS. Mass spectra were taken on a GS-MS instrument
Chrommas GC/MS Hawlett Packard 5890/5972, column
HP-5MS (70 eV).
+
EtOC H (O)CHO] 43 (75). Found, %: C 63.72; H 5.84.
C H O . Calculated, %: C 63.46; H 5.77.
5
6
3
11 12
4
4-Formyl-2-ethoxyphenyl propanoate (IIc). Yield
84%, colorless crystalline substance, mp 45–47°C. IR
spectrum, cm : 3115, 3080, 3055, 2985, 2942, 2890, 2875,
–1
2
1
840, 2795, 2740, 1760, 1697, 1601, 1589, 1508, 1480,
465, 1435, 1401, 1380, 1353, 1324, 1288, 1264, 1206,
4
-Formyl-2-ethoxyphenyl methanoate (IIa). To
a solution of 1.66 g (0.01 mol) of vanillal and 2.06 g
0.01 mol) of dicyclohexylcarbodiimide in 500 ml of
1161, 1140, 1115, 1075, 1040, 1007, 973, 890, 872, 826,
(
1
8
2
7
00, 784, 585. H NMR spectrum, d, ppm: 1.35 m (6H,
anhydrous benzene was added 0.12 mol of 99% formic
acid. The reaction mixture was maintained with inter-
mittent shaking for 24–36 h at 20–23°C.After neutraliza-
tion with NaHCO the benzene solution was dried on
CaCl , the solvent was distilled off, and the residue was
MeCH ), 2.65 q (2H, CH C=O), 4.13 q (2H, CH O),
2
2
2
.16 q, 7.45 m (3H, C H ), 9.91 s (1H, CHO). Mass
6
3
+
+
spectrum, m/z (I , %): [M] 222 (12), [M – OCCH Me]
rel
2
3
+
166 (100), [M – EtOC H (O)CHO] 57 (78). Found, %:
6 3
2
C 65.07; H 6.44. C H O . Calculated, %: C 64.86;
H 6.31.
recrystal-lized from methanol. Yield 73%, colorless
crystalline substance, mp 47–48°C. IR spectrum, cm :
12 14
4
–
1
3
1
110, 3081, 3015, 2988, 2940, 2840, 2813, 2744, 1733,
698, 1599, 1505, 1439, 1391, 1276, 1267, 1197, 1160,
4-Formyl-2-ethoxyphenyl butanoate (IId). Yield
20
92%, colorless liquid, bp 145–146°C (0.5 mm Hg), d
2
0
1.2009, n2 1.5272. IR spectrum, cm : 3114, 3077, 3055,
0
–1
1
138, 1098, 1040, 895, 868, 851, 824, 800, 745, 618, 590.
D
1
H NMR spectrum, d, ppm: 1.46 t (3H, Me), 4.18 q (2H,
CH ), 7.22 d, 7.51 m (3H, C H ), 8.32 s [1H, OC(O)H],
2983, 2941, 2890, 2875, 2843, 2795, 2740, 1761, 1698,
1600, 1589, 1506, 1480, 1465, 1440, 1400, 1381, 1353,
1325, 1288, 1264, 1206, 1160, 1140, 1113, 1075, 1040, 1006,
2
6
3
+
9
1
.97 s (1H, CHO). Mass spectrum, m/z (I , %): [M]
rel
+
1
94 (10), [M – OCH] 166 (100). Found, %: C 62.03;
973, 890, 872, 826, 800, 784, 585. H NMR spectrum, d,
H 5.28. C H O . Calculated, %: C 61.85; H 5.19.
ppm: 1.03 t (3H, Me), 1.42 t (3H, MeCH O), 1.64 m
1
0
10
4
2
(
7
2H, CH ), 2.52 t (2H, CH ), 4.12 q (2H, MeCH O),
Vanillal esters IIb–IIg. To a solution of 3.32 g
2 2 2
.17 d, 7.44 m (3H, C H ), 9.92 s (1H, CHO). Mass
6 3
(
0.02 mol) of vanillal in 500 ml of anhydrous CH Cl was
2
2
+
+
spectrum, m/z (I , %): [M] 236 (9), [M – OC(CH ) Me]
1
C 66.34; H 7.07. C H O . Calculated, %: C 66.09;
H 6.83. M 236.3.
added 1.97 g (0.025 mol) of anhydrous pyridine and by
small portions was added while stirring by shaking the
reaction flask 0.2 mol of an appropriate alkylcarboxylic
acid chloride. The reaction mixture was heated at reflux
for 1 h, CH Cl was distilled off while heating on a water
rel
2 2
+
66 (100), [M – EtOC H (O)CHO] 71 (58). Found, %:
6 3
13 16
4
4-Formyl-2-ethoxyphenyl isobutyrate (IIe). Yield
2
2
bath, the residue was dissolved in 500 ml of benzene, the
solution was thrice washed with water, thrice with 5%
water solution of NaHCO , and dried on CaCl . The
solvent was distilled off, the residue was either distilled
in a vacuum (IId and IIf) or recrystallized from a mixture
benzene–hexane (IIb, IIc, IIe, and IIg).
93%, colorless crystalline substance, mp 45–46°C. IR
–1
spectrum, cm : 3120, 3080, 3055, 2990, 2975, 2939, 2895,
2880, 2842, 2790, 2740, 1752, 1697, 1600, 1586, 1508,
1420, 1435, 1400, 1385, 1320, 1288, 1262, 1160, 1117, 1099,
3
2
1
1
033, 974, 916, 870, 821, 800, 785, 751, 655, 580. H NMR
spectrum, d, ppm: 1.27 d (6H, Me C), 1.38 t (3H, Me),
2
The distilled off CH Cl and benzene may be used
2.78 m (1H, CH), 4.08 q (2H, CH ), 7.10 d, 7.40 m (3H,
2
2
2
repeatedly after appropriate treatment (distillation from
P O with Vigreux column).
C H ), 9.91 s (1H, CHO). Mass spectrum, m/z (I , %):
6
3
+
rel
+
[M] 236 (16), [M – OCCHMe ] 166 (100), [M –
2
5
2
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 11 2005

VANILLAL ESTERS IN REACTION WITH 2-NAPHTHYLAMINE
1641
+
EtOC H (O)CHO] 71 (77). Found, %: C 66.29; H 7.01.
4-(11-Oxo-7,8,9,10,11,12-hexahydrobenzo[a]-
acridin-12-yl)-2-ethoxyphenyl acetate (Vb). Yield 97%,
colorless crystals, mp 292°C. IR spectrum, cm : 3264,
6
3
C H O . Calculated, %: C 66.09; H 6.83.
1
3
16
4
–
1
4
-Formyl-2-ethoxyphenyl isovalerate (IIf). Yield
2%, colorless liquid, bp 132–33°C (0.5 mm Hg), d2
1.5180. IR spectrum, cm : 3118, 3070, 3050,
020, 2963, 2936, 2874, 2834, 2785, 2737, 1764, 1699,
600, 1503, 1467, 1434, 1391, 1370, 1321, 1280, 1272,
180, 1150, 1119, 1092, 1041, 973, 915, 897, 869, 830,
86,744, 730, 650, 580. H NMR spectrum, d, ppm:
.08 d (6H, Me C), 1.40 t (3H, MeCH O), 1.40–2.85 m
2
0
3
189, 3080, 2973, 1756, 1600, 1522, 1494, 1461, 1388,
8
1
3
1
0
1
2
0
–1
1269, 1190, 1191, 1133, 1125, 1094, 979, 832. H NMR
.0954,
n
D
spectrum
, d, ppm: 1.30 t (3H, MeCH O), 3.95 q (2H,
2
MeCH O), 2.15 s (3H, OCOMe), 1.95 m (2H, CH ),
2
2
2
6
7
7
7
.30 m (2H, CH ), 2.60 m (2H, CH ), 5.90 s (1H, CH),
1
7
1
2 2
.50 d (1H, Harom, J 6.8 Hz), 6.65 d (1H, Harom, J 6.7 Hz),
.10 s (1H, Harom), 7.25 m (2H, Harom), 7.40 t (1H, Harom),
.68 d (1H, Harom, J 6.7 Hz), 7.74 d (1H, Harom, J 6.3 Hz),
1
2
2
(
3H, CH q CH ), 4.11 q (2H, MeCH O), 7.12 d, 7.42 m
2 2
.90 d (1H, Harom, J 6.8 Hz), 9.45 s (1H, NH). Mass
(
%
[
3H, C H ), 9.91 s (1H, CHO). Mass spectrum, m/z (I ,
6 3 rel
): [M] 250 (11), [M – OCCH CHMe ] 166 (100),
M – EtOC H (O)CHO] 85 (44). Found, %: C 67.49;
H 7.41. C H O . Calculated, %: C 67.18; H 7.25.
+
spectrum, m/z (I , %): [M] 427 (13), 248 (100), 192(23),
+
+
rel
2 2
1
79 (20). Found, %: C 75.86; H 5.87; N 3.25.
+
6 3
C H NO . Calculated, %: C 75.88; H 5.85; N 3.28.
2
7
25
4
1
4
18
4
4
-(11-Oxo-7,8,9,10,11,12-hexahydrobenzo[a]-
4
-Formyl-2-ethoxyphenyl benzoate (IIg). Yield
5%, colorless crystals, mp 79–80°C. IR spectrum,
cm : 3110, 3075, 2970, 2940, 2875, 2846, 2793, 1750,
698, 1600, 1592, 1410, 1400, 1382, 1320, 1284, 1157,
110, 1030, 972, 821, 800, 783, 751, 652, 580. H NMR
spectrum, d, ppm: 1.30 t (3H, MeCH O), 4.10 q (2H,
MeCH O), 7.307.60 m (6H, Harom), 8.10–8.30 m (2H,
), 9.94 s (1H, CHO). Mass spectrum, m/z (I , %):
M] 258 (16), [M – OCC H ] 153 (100), [M –
EtOC H (O)CHO] 105 (50). Found, %: C 71.15;
H 5.20. C H O . Calculated, %: C 71.11; H 5.18.
acridin-12-yl)-2-ethoxyphenyl propionate (Vc). Yield
7
–
1
9
3
1
0%, colorless crystals, mp 256°C. IR spectrum, cm :
269, 3189, 3075, 2972, 1755, 1590, 1502, 1465, 1388,
–
1
1
1
1
269, 1189, 1194, 1132, 1125, 1090, 983, 832. H NMR
1
spectrum, d, ppm: 1.30 t (3H, MeCH O), 3.93 q (2H,
2
2
MeCH O), 1.19 t (3H, OCOCH Me), 1.26 q (2H,
2
2
2
OCOCH Me), 1.95 m (2H, CH ), 2.27 m (2H, CH ),
2
2
2
H
[
arom
+
rel
2
.64 m (2H, CH ), 5.90 s (1H, CH), 6.49 d (1H, Harom,
2
+
6
5
J 6.9 Hz), 6.62 d (1H, Harom, J 7.0 Hz), 7.08 s (1H, Harom),
+
6
3
7
.27 m (2H, Harom), 7.38 t (1H, Harom), 7.68 d (1H, Harom
,
,
1
6
14
4
J 7.0 Hz), 7.71 d (1H, Harom, J 6.8 Hz), 7.90 d (1H, Harom
4
-(11-Oxo-7,8,9,10,11,12-hexahydrobenzo[a]-
J 7.2 Hz), 9.50 s (1H, NH). Mass spectrum, m/z (I , %):
rel
+
acridin-12-yl)-2-ethoxyphenyl carboxylates Va–Vg.
To a solution of 1.43 g (0.01 mol) of 2-naphthylamine (I)
in 50 ml of ethanol was added 1.12 g (0.01 mol) of
[M] 441 (12), 248 (100), 193 (16), 192 (16). Found, %:
C 76.22; H 6.12; N 3.15. C H NO . Calculated, %:
2
8
27
4
C 76.19; H 6.12; N 3.17.
1
,3-cyclohexanedione (IIIa), and 0.01 mol of ester IIa–
4
-(11-Oxo-7,8,9,10,11,12-hexahydrobenzo[a]-
IIg. The mixture was heated at reflux for 0.5–4 h
depending on the length of the acid rest in the vanillal
ester. On cooling the reaction mixture the crystalline
precipitate was separated, washed with hot methanol,
and recrystallized from benzene.
acridin-12-yl)-2-ethoxyphenyl butyrate (Vd). Yield
–1
6
3
1
7%, colorless crystals, mp 262°C. IR spectrum, cm :
263, 3187, 3070, 2976, 1753, 1598, 1502, 1465, 1388,
1
264, 1196, 1192, 1144, 1129, 1096, 983, 832. H NMR
spectrum, d, ppm: 1.28 t (3H, MeCH O), 3.95 q (2H,
2
MeCH O), 1.00 t [3H, OCO (CH ) Me], 1.70 m (2H,
4
-(11-Oxo-7,8,9,10,11,12-hexahydrobenzo[a]-
2
2 2
OCOCH2–CH Me), 2.65 m (2H,OCOCH CH Me),
acridin-12-yl)-2-ethoxyphenyl formate (Va). Yield
2
2
2
–
1
1.90 m (2H, CH2), 2.20 m (2H, CH ), 2.58 m (2H, CH ),
7
3
0%, colorless crystals, mp 287°C. IR spectrum, cm :
260, 3190, 3080, 2980, 1754, 1600, 1523, 1490, 1467,
383, 1262, 1194, 1186, 1134, 1120, 1091, 979, 823.
2 2
5
.88 C (1H, CH), 6.48 d (1H, Harom, J 7.2 Hz), 6.65 d
1H, Harom, J 7.0 Hz), 7.14 s (1H, Harom), 7.22 m (2H,
Harom), 7.40 t (1H, Harom), 7.68 d (1H, Harom, J 6.9 Hz),
(
1
1
H
NMR spectrum
, d, ppm: 1.37 t (3H, MeCH O),
.98 q (2H, MeCH O), 8.20 s (1H, OCOH), 1.98 m (2H,
2
7
9
.73 d (1H, Harom, J 7.2 Hz), 7.95 d (1H, Harom, J 7.6 Hz),
3
2
+
.48 s (1H, NH). Mass spectrum, m/z (I , %): [M] 455
CH ), 2.30 m (2H, CH ), 2.59 m (2H, CH ), 5.70 s (1H,
rel
2
2
2
(
18), 248 (100), 207(15), 192 (20). Found, %: C 76.72;
CH), 6.40 m (2H, Harom), 6.90 s (1H, Harom), 7.30 m (3H,
Harom), 7.60–7.90 m (3H, Harom), 9.50 s (1H, NH). Mass
H 6.60; N 2.96; C H NO . Calculated, %: C 76.75;
29 29
4
+
H 6.61; N 2.98.
spectrum, m/z (I , %): [M] 413 (15), 248 (100), 192(23),
rel
1
65 (10). Found, %: C 75.50; H 5.54; N 3.41. C H NO .
4-(11-Oxo-7,8,9,10,11,12-hexahydrobenzo[a]-
acridin-12-yl)-2-ethoxyphenyl isobutyrate (Ve). Yield
2
6
23
4
Calculated, %: C 75.54; H 5.56; N 3.39.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 11 2005

1642
KOZLOV et al.
–
1
6
3
1
3%, colorless crystals, mp 292°C. IR spectrum, cm :
2-naphthylamine (I) in 50 ml of ethanol was added
1.40 g (0.01 mol) of dimedone (IIIb), 0.01 mol of ester
IIa–IIg. The mixture was heated at reflux for 2–3 h
depending on the length of the acid rest in the vanillal
ester. On cooling the reaction mixture the crystalline
precipitate was separated, washed with hot methanol,
and recrystallized from benzene.
260, 3192, 3087, 2974, 1758, 1583, 1519, 1495, 1469,
385, 1264, 1192, 1180, 1137, 1096, 975, 821. H NMR
spectrum, d, ppm: 1.28 t (3H, MeCH O), 3.95 q (2H,
MeCH O), 1.20 d [6H, OCOCHMe , J 7.0 Hz], 2.70 m
1H, OCOCHMe ], 1.97 m (2H, CH ), 2.30 m (2H,
CH ), 2.63 m (2H, CH ), 5.89 s (1H, CH), 6.50 d (1H,
1
2
2
2
[
2 2
2
2
Harom, J 7.8 Hz), 6.62 d (1H, Harom, J 7.0 Hz), 7.10 s
1H, Harom), 7.27 m (1H, Harom), 7.39 t (2H, Harom),
4
-(9,9-Dimethyl-11-oxo-7,8,9,10,11,12-hexa-
(
hydrobenzo[a]acridin-12-yl)-2-ethoxyphenyl
formate (VIa). Yield 84%, colorless crystals, mp 275°C.
IR spectrum, cm : 3260, 3184, 3086, 2978, 1754, 1608,
524, 1493, 1466, 1387, 1262, 1194, 1181, 1133, 1120, 1098,
79, 820. H NMR spectrum, d, ppm: 0.90 s (3H, Me),
.20 s (3H, Me),1.30 t (3H, MeCH O), 3.92 q (2H,
MeCH O), 8.20 s (1H, OCOH), 2.02 m (2H, CH ),
2.40 m (2H, CH ), 5.70 s (1H,CH), 6.45 d (1H, Harom,
J 7.9 Hz), 6.70 s (1H, Harom), 7.25–7.40 m (3H, Harom),
7.60–7.70 m (3H, Harom), 7.94 d (1H, Harom, J 7.5 Hz),
7.68 d (1H, Harom, J 6.9 Hz), 7.74 d (1H, Harom, J 7.5 Hz),
7
.90 d (1H, Harom, J 7.6 Hz), 9.58 s (1H, NH). Mass
–1
+
spectrum, m/z (I , %): [M] 455 (18), 248 (100),
rel
1
9
1
207 (13), 192 (16). Found, %: C 76.79; H 6.65; N 3.00.
1
C H NO . Calculated, %: C 76.75; H 6.61; N 2.98.
2
9
29
4
2
4
-(11-Oxo-7,8,9,10,11,12-hexahydrobenzo[a]-
2
2
acridin-12-yl)-2-ethoxyphenyl isocaproate (Vf). Yield
2
–
1
5
3
1
2%, colorless crystals, mp 257°C. IR spectrum, cm :
267, 3180, 3076, 2980, 1763, 1594, 1523, 1472, 1395,
1
+
270, 1193, 1189, 1132, 1110, 990, 830. H NMR spectrum,
9.50 s (1H, NH). Mass spectrum, m/z (I , %): [M] 441
(15), 276(100), 192 (22), 165 (17). Found, %: C 76.17;
H 6.10; N 3.19. C H NO . Calculated, %: C 76.19;
rel
d, ppm: 1.29 t (3H, MeCH O), 3.90 q (2H, MeCH O),
2
2
1
.00 d [6H, OCOCH (CH)Me , J 7.0 Hz], 1.60 m [2H,
2 2
28 27
4
OCOCH –(CH)Me ], 2.70 m [1H, OCOCH (CH)Me ],
H 6.12; N 3.17.
-(9,9-Dimethyl-11-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[a]acridin-12-yl)-2-ethoxyphenyl acetate
2
2
2
2
1
5
.98 m (2H, CH ), 2.20 m (2H, CH ), 2.59 m (2H, CH ),
.89 s (1H, CH), 6.50 d (1H, Harom, J 7.9 Hz), 6.64 d
2 2 2
4
(
1H, Harom, J 7.8 Hz), 7.10 s (1H, Harom), 7.30 m (1H,
Harom), 7.39 t (2H, Harom), 7.68 d (1H, Harom, J 6.9 Hz),
(
VIb). Yield 93%, colorless crystals, mp 244°C. IR
spectrum, cm : 3264, 3189, 3080, 2979, 1754, 1600, 1531,
499, 1467, 1392, 1261, 1187, 1186, 1137, 1125, 1096, 976,
30. H NMR spectrum, d, ppm: 0.90 s (3H, Me), 1.22 s
3H, Me), 1.34 t (3H, MeCH O), 3.90 q (2H, MeCH O),
.15 s (3H,OCOMe), 1.90 m (2H, CH ), 2.28 m (2H,
2
–1
7
9
.75 d (1H, Harom, J 7.8 Hz), 7.90 d (1H, Harom, J 7.9 Hz),
1
8
(
2
+
.49 s (1H, NH). Mass spectrum, m/z (I , %): [M] 469
rel
1
(
15), 248 (100), 221 (10), 192 (18). Found, %: C 78.46;
2 2
H 6.73; N 3.07. C H NO . Calculated, %: C 78.43;
3
0
31
4
H 6.75; N 3.05.
-(11-Oxo-7,8,9,10,11,12-hexahydrobenzo[a]-
acridin-12-yl)-2-ethoxyphenyl benzoate (Vg). Yield
CH ), 5.94 s (1H, CH), 6.55 d (1H, Harom, J 7.2 Hz),
2
4
6.60 d (1H, Harom, J 7.0 Hz), 7.12 C (1H, Harom), 7.28 m
(2H, Harom), 7.40 t (1H, Harom), 7.70 d (1H, Harom
J 6.9 Hz), 7.76 d (1H, Harom, J 6.8 Hz), 7.90 d (1H, Harom,
,
–
1
7
3
1
4%, colorless crystals, mp 286°C. IR spectrum, cm :
275, 3180, 3084, 2992, 1768, 1608, 1534, 1476, 1398,
J 6.8 Hz), 9.45 s (1H, NH). Mass spectrum, m/z (I , %):
rel
1
+
276, 1198, 1196, 1137, 1117, 998, 833. H NMR
[M] 455 (19), 276 (100), 192 (20), 179 (28). Found, %:
spectrum, d, ppm: 1.25 t (3H, MeCH O), 4.00 q (2H,
C 76.46; H 6.39; N 3.07. C H NO . Calculated, %:
2
29 29
4
MeCH O), 2.00 m (2H, CH ), 2.28 m (2H, CH ), 2.67 m
C 76.48; H 6.37; N 3.08.
2
2
2
(
2H, CH ), 5.90 s (1H, CH), 6.59 d (1H, Harom, J 7.3 Hz),
.80 d (1H, Harom, J 7.8 Hz), 7.19 s (1H, Harom), 7.25,
.40, 7.50 m (5H, Harom), 7.60, 7.70, 7.74 m (3H, Harom),
2
4-(9,9-Dimethyl-11-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[a]acridin-12-yl)-2-ethoxyphenyl
6
7
7
(
2
propionate (VIc). Yield 90%, colorless crystals, mp
.93 d (1H, Harom, J 6.9 Hz), 8.09 m (2H, Harom), 9.49 s
–1
270°C.
IR spectrum, cm : 3260, 3190, 3075, 2975, 1756,
+
1H, NH). Mass spectrum, m/z (I , %): [M] 489 (20),
rel
1603, 1534, 1497, 1460, 1387, 1254, 1181, 1134, 1122, 1091,
48 (100), 241(7), 192 (18). Found, %: C 78.50; H 5.54;
1
9
74, 832. H NMR spectrum, d, ppm: 0.95 s (3H, Me),
N 2.87; C H NO . Calculated, %: C 78.53; H 5.52;
N 2.86.
3
2
27
4
1.20 s (3H, Me), 1.30 t (3H, MeCH O), 3.96 q (2H,
2
MeCH O), 1.17 t (3H,OCOCH Me), 1.29 q (2H,
2
2
4
-(9,9-Dimethyl-11-oxo-7,8,9,10,11,12-hexa-
OCOCH Me), 1.95 m (2H, CH ), 2.29 m (2H, CH ),
2 2 2
hydrobenzo[a]acridin-12-yl)-2-ethoxyphenyl carb-
oxylates VIa–VIg. To a solution of 1.43 g (0.01 mol) of
5.90 s (1H, CH), 6.47 d (1H, Harom, J 7.4 Hz), 6.56 d
(1H, Harom, J 7.0 Hz), 7.10 s (1H, Harom), 7.30 m (2H,
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 11 2005

VANILLAL ESTERS IN REACTION WITH 2-NAPHTHYLAMINE
Harom), 7.40 t (1H, Harom), 7.68 d (1H, Harom, J 7.0 Hz),
1643
OCOCH (CH)Me ], 1.97 m (2H, CH ), 2.20 m (2H,
2
2
2
7
9
.75 d (1H, Harom, J 6.4 Hz), 7.90 d (1H, Harom, J 7.2 Hz),
CH ), 5.87 s (1H, CH), 6.50 d (1H, Harom, J 7.9 Hz),
6.67 d (1H, Harom, J 7.8 Hz), 7.15 s (1H, Harom), 7.28 m
2
+
.50 s (1H, NH). Mass spectrum, m/z (I , %): [M] 469
rel
(
22), 276 (100), 192 (22), 193(25). Found, %: C 76.75;
(1H, Harom), 7.39 t (2H, Harom), 7.64 d (1H, Harom
,
H 6.60; N 2.99. C H NO . Calculated, %: C 76.76;
J 6.9 Hz), 7.73 d (1H, Harom, J 7.8 Hz), 7.90 d (1H,
3
0
31
4
H 6.61; N 2.98.
Harom
,
J 7.9 Hz), 9.53 s (1H, NH). Mass spectrum, m/z
+
(Irel, %): [M] 497 (21), 276 (100), 221 (19), 192 (23).
4
-(9,9-Dimethyl-11-oxo-7,8,9,10,11,12-hexa-
Found, %: C 77.26; H 7.03; N 2.85. C H NO .
Calculated, %: C 77.26; H 7.04; N 2.82.
hydrobenzo[a]acridin-12-yl)-2-ethoxyphenyl
butyrate (VId). Yield 72%, colorless crystals, mp 230°C.
IR spectrum, cm : 3264, 3187, 3075, 2975, 1756, 1607,
32 35
4
–
1
4-(9,9-Dimethyl-11-oxo-7,8,9,10,11,12-hexa-
1
8
538, 1489, 1463, 1388, 1256, 1178, 1133, 1127, 1095, 970,
37. H NMR spectrum, d, ppm: 0.93 s (3H, Me), 1.18 s
hydrobenzo[a]acridin-12-yl)-2-ethoxyphenyl
benzoate (VIg). Yield 85%, colorless crystals, mp 282°C.
IR spectrum, cm–1: 3262, 3184, 3063, 2977, 1754, 1610,
1532, 1501, 1470, 1394, 1268, 1176, 1132, 1122, 1091, 972,
830. 1H NMR spectrum, d, ppm: 0.90 s (3H, Me), 1.10 s
1
(
3H, Me), 1.28 t (3H, MeCH O), 3.98 q (2H, MeCH O),
2 2
1
.00 t [3H, OCO (CH ) Me], 1.65 m (2H,
2
2
OCOCH CH Me), 2.67 m (2H, OCOCH CH Me), 2.10
m (2H, CH ), 2.40 m (2H, CH ), 5.88 s (1H, CH), 6.50 d
2
2
2
2
2
2
(3H, Me), 1.28 t (3H, MeCH O), 4.00 q (2H, MeCH O),
2
2
(
1H, Harom, J 7.4 Hz), 6.65 d (1H, Harom, J 7.0 Hz), 7.16 s
2.15 m (2H, CH ), 2.60 m (2H, CH ), 5.90 s (1H, CH),
2 2
(
(
7
1H, Harom), 7.27 m (2H, Harom), 7.38 t (1H, Harom), 7.68 d
6.60 d (1H, Harom, J 7.6 Hz), 6.80 d (1H, Harom, J 7.5 Hz),
7.15 s (1H, Harom), 7.30, 7.40, 7.50 m (5H, Harom), 7.65 m
(1H, Harom), 7.75 m (2H, Harom), 7.90 d (1H, Harom,
1H, Harom
,
J 6.9 Hz), 7.77 d (1H, Harom, J 7.6 Hz),
.95 d (1H, Harom, J 7.6 Hz), 9.45 s (1H, NH). Mass
+
spectrum, m/z (I , %): [M] 483 (19), 276 (100),
2
C H NO . Calculated, %: C 77.01; H 6.83; N 2.90.
J 7.9 Hz), 8.10 m (2H, H ), 9.40 s (1H, NH). Mass
rel
arom
07 (23), 192 (24). Found, %: C 77.03; H 6.81; N 2.94.
spectrum, m/z (I , %): [M]+ 517 (22), 248 (100),
rel
3
1
33
4
241 (17), 192 (23). Found, %: C 78.95; H 5.98; N 2.69.
4
-(9,9-Dimethyl-11-oxo-7,8,9,10,11,12-hexa-
C34H31NO4. Calculated, %: C 78.92; H 6.00; N 2.71.
hydrobenzo[a]acridin-12-yl)-2-ethoxyphenyl
isobutyrate (VIe). Yield 65%, colorless crystals, mp
4-(11-Oxo-9-phenyl-7,8,9,10,11,12-hexahydro-
benzo[a]acridin-12-yl)-2-ethoxyphenyl carboxylates
VIIa–VIIg. To a solution of 1.43 g (0.01 mol) of
2-naphthylamine (I) in 50 ml of butanol was added
1.88 g (0.01 mol) of 5-phenyl-1,3-cyclohexanedione
(IIIc), and 0.01 mol of ester IIa–IIg, and the mixture
was heated at reflux for 1–3 h depending on the length
of the acid rest in the vanillal ester. On cooling the reaction
mixture the crystalline precipitate was separated, washed
with ether, and recrystallized from a mixture alcohol-
benzene, 1:3.
–
1
2
1
9
1
60°C. IR spectrum, cm : 3267, 3181, 3072, 2970, 1756,
602, 1534, 1492, 1470, 1388, 1255, 1174, 1138, 1122, 1093,
72, 836. H NMR spectrum, d, ppm: 0.98 s (3H, Me),
1
.10 s (3H, Me), 1.30 t (3H, MeCH O), 3.90 q (2H,
2
MeCH O), 1.20 d (6H, OCOCHMe , J 7.0 Hz), 2.70 m
2
2
(
1H, OCOCHMe2), 1.99 m (2H, CH ), 2.30 m (2H,
2
CH ), 5.85 s (1H, CH), 6.50 d (1H, Harom, J 7.8 Hz), 6.65
2
d (1H, Harom, J 7.0 Hz ), 7.09 s (1H, Harom), 7.28 m (2H,
.
Harom), 7.40 m (2H, Harom), 7.69 d (1H, Harom, J 7.2 Hz),
7
9
.74 d (1H, Harom, J 7.5 Hz), 7.95 d (1H, Harom, J 7.8 Hz),
4-(11-Oxo-9-phenyl-7,8,9,10,11,12-hexahydro-
benzo[a]acridin-12-yl)-2-ethoxyphenyl formate
+
.40 s (1H, NH). Mass spectrum, m/z (I , %): [M] 483
rel
(
20), 276 (100), 207 (19), 192 (17). Found, %: C 77.00;
(
VIIa). Yield 63%, colorless crystals, mp 242°C. IR
H 6.80; N 2.95. C H NO . Calculated, %: C 77.01;
H 6.83; N 2.90.
–1
3
1
33
4
spectrum, cm : 3270, 3190, 2957, 1757, 1600, 1584, 1520,
1
497, 1469, 1425, 1400, 1386, 1261, 1242, 1184, 1153,
1
4
-(9,9-Dimethyl-11-oxo-7,8,9,10,11,12-hexa-
1119, 1098, 819, 744. H NMR spectrum, d, ppm: 8.10 s
8
10
hydrobenzo[a]acridin-12-yl)-2-ethoxyphenyl
isovalerate (VIf). Yield 60%, colorless crystals, mp
2
(1H, COCOH), 2.58 m (2H, C H ), 2.90 m (2H, C H ),
2 2
6.03 m (1H, Harom), 6.15 m (1H, Harom), 7.10–7.20, 7.25–
7.35, 7.37–7.43 m (9H, Harom), 7.45 d (1H, Harom
J 7.4 Hz), 7.78–7.85 m (2H, H ). Mass spectrum, m/z
–
1
56°C. IR spectrum, cm : 3264, 3179, 3067, 2979, 1752,
,
1604, 1538, 1497, 1476, 1391, 1261, 1172, 1132, 1126, 1087,
arom
1
+
9
9
1
76, 832. H NMR spectrum, d, ppm: 0.99 s (3H, Me),
(I , %): [M] 489 (70), 324 (100), 192 (10). Isomer C -
rel
.06 s (3H, Me), 1.28 t (3H, MeCH O), 3.75 q (2H,
Ph , d, ppm: 1.28 t (3H, MeCH O), 3.96 q (2H,
2
a
2
9
12
MeCH O), 1.05 d [6H, OCOCH (CH)Me , J 7.4 Hz],
1
MeCH O), 3.39 m (1H, H ), 5.84 s (1H, H ), 9.40 s
2 e
(1H, NH). Isomer C -Ph , d, ppm: 1.24 t (3H,
2
2
2
9
.65 m [2H, OCOCH (CH)(Me) ], 2.73 m [1H,
2
2
e
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 11 2005

1644
KOZLOV et al.
9
MeCH O), 3.90 q (2H, MeCH O), 3.28 m (1H, H ),
5
Harom), 7.06–7.12, 7.25–7.35, 7.37–7.45 m (9H, Harom),
7.48 d (1H, Harom, J 7.0 Hz) 7.79–7.85 m (2H, Harom).
2
2
a
1
2
.92 s (1H, H ), 9.52 s (1H, NH). Found, %: C 78.51;
H 5.54; N 2.83. C H NO . Calculated, %: C 78.53;
H 5.52; N 2.86.
-(11-Oxo-9-phenyl-7,8,9,10,11,12-hexahydro-
benzo[a]acridin-12-yl)-2-ethoxyphenyl acetate
VII b). Yield 70%, colorless crystals, mp 257°C. IR
spectrum, cm : 3273, 3189, 2952, 1754, 1603, 1586, 1520,
493, 1467, 1421, 1405, 1386, 1261, 1244, 1188, 1153,
123, 1098, 821, 745. H NMR spectrum, d, ppm: 2.19 s
+
Mass spectrum, m/z (I , %): [M] 531 (24), 324 (80),
3
2
27
4
rel
9
192 (18), 76 (100). Isomer C -Ph , d, ppm: 1.30 t (3H,
a'
9
MeCH O), 4.00 q (2H, MeCH O), 3.45 m (1H, H ), 5.90
s (1H, H ), 9.45 s (1H, NH). Isomer C -Ph , d, ppm:
4
2
2
a'
1
2
9
e'
1
.26 t (3H, MeCH O), 3.90 q (2H, MeCH O), 3.30 m
(
2 2
9
12
–1
(1H, H ), 5.95 s (1H, H ), 9.55 s (1H, NH). Found, %:
a'
C 79.10; H 6.25; N 2.61. C H NO . Calculated, %:
1
1
35 33
4
1
C 79.09; H 6.21; N 2.63.
8
10
(
3H, OCOMe), 2.64 m (2H, C H ), 2.89 m (2H, C H ),
4-(11-Oxo-9-phenyl-7,8,9,10,11,12-hexahydro-
benzo[a]acridin-12-yl)-2-ethoxyphenyl isobutyrate
(VIIe). Yield 58%, colorless crystals, mp 253°C. IR
2
2
6
(
.60 m (1H, Harom), 6.80 m (1H, Harom), 7.10–7.28 m
2H, Harom), 7.30–7.50 m (7H, Harom), 7.80 m (2H, Harom),
.00 d (1H, Harom, J 7.6 Hz). Mass spectrum, m/z (Irel,
): [M] 503 (18), 324 (85), 192 (27), 78 (25), 43 (100).
Isomer C -Ph , d, ppm: 1.26 t (3H, MeCH O), 4.00 q
2H, MeCH O), 3.35 m (1H, H ), 5.83 s (1H, H ), 9.80
–1
8
%
spectrum, cm : 3275, 3183, 2956, 1752, 1600, 1582, 1522,
1492, 1469, 1420, 1417, 1388, 1291, 1242, 1185, 1150,
+
9
1
1119, 1091, 819, 744. H NMR spectrum, d, ppm: 1.16 d
a
2
9
12
(
[6H, OCOCHMe , J 7.0 Hz], 2.67 m [1H, OCOCHMe ],
2
e'
2
2
9
8
10
s (1H, NH). Isomer C -Ph , d, ppm: 1.23 t (3H,
2.64 m (2H, C H ), 2.80 m (2H, C H ), 6.02 m (1H,
e
2 2
9
MeCH O), 3.90 q (2H, MeCH O), 3.28 m (1H, H ),
Harom), 6.15 m (1H, Harom), 7.02–7.10, 7.25–7.35, 7.35–
2
2
a'
1
2
5
.90 s (1H, H ), 9.90 s (1H, NH). Found, %: C 78.70;
H 5.77; N 2.79. C H NO . Calculated, %: C 78.72;
7.48 m (9H, Harom), 7.50 d (1H, Harom J 7.2 Hz), 7.73–
+
7.76 m (2H, Harom). Mass spectrum, m/z (I , %): [M]
531 (14), 324 (100), 192 (16), 76 (77). Isomer C -Ph
3
3
29
4
rel
9
H 5.76; N 2.78.
-(11-Oxo-9-phenyl-7,8,9,10,11,12-hexahydro-
benzo[a]acridin-12-yl)-2-ethoxyphenyl propionate
VIIc). Yield 65%, colorless crystals, mp 262°C. IR
spectrum, cm : 3276, 3185, 2952, 1755, 1600, 1584, 1518,
495, 1468, 1418, 1411, 1386, 1254,1242, 1183, 1151, 1127,
a'
d, ppm: 1.29 t (3H, MeCH O), 3.97 q (2H, MeCH O),
4
2
2
9
12
3
.34 m (1H, H ), 5.90 s (1H, H ), 9.48 s (1H, NH).
Isomer C -Ph , d, ppm: 1.25 t (3H, MeCH O), 3.92 q
e'
9
(
e
'
2
9
12
–1
(2H, MeCH O), 3.28 m (1H, H ), 5.95 s (1H, H ), 9.53 s
2 a'
(
1H, NH). Found, %: C 79.07; H 6.20; N 2.64.
1
1
1
C H NO . Calculated, %: C 79.09; H 6.21; N 2.63.
092, 820, 743. H NMR spectrum, d, ppm: 1.17 t (3H,
35 33
4
OCOCH Me), 1.25 q (2H, OCOCH Me), 2.59 m (2H,
4-(11-Oxo-9-phenyl-7,8,9,10,11,12-hexahydro-
benzo[a]acridin-12-yl)-2-ethoxyphenyl isovalerate
(VIIf). Yield 46%, colorless crystals, mp 259°C. IR
2
2
8
10
C H ), 2.90 m (2H, C H ), 6.04 m (1H, Harom), 6.10 m
2
2
(
1H, Harom), 7.10–7.15, 7.20–7.30, 7.35–7.44 m (9H,
–1
Harom), 7.48 d (1H, Harom, J 7.0 Hz) 7.76–7.82 m (2H,
spectrum, cm : 3271, 3186, 2952, 1754, 1600, 1581, 1514,
1489, 1471, 1426, 1422, 1389, 1253, 1242, 1187, 1153,
+
Harom). Mass spectrum, m/z (I , %): [M] 517 (20), 324
rel
9
1
(
(
70), 192 (30), 62 (100). Isomer C -Ph , d, ppm: 1.28 t
3H, MeCH O), 3.92 q (2H, MeCH O), 3.38 m (1H, H ),
.90 s (1H, H ), 9.45 s (1H, NH). Isomer C -Ph , d,
1131, 1094, 822, 743. H NMR spectrum, d, ppm: 0.98 d
a'
9
[6H, OCOCH (CH)Me , J 7.8 Hz], 2.30 m [2H,
2
2
e'
2
2
1
2
9
5
OCOCH (CH)–Me ], 2.58 m [1H, OCO CH (CH)Me ],
2 2 2 2
e'
8
10
ppm: 1.25 t (3H, Me–CH O), 3.88 q (2H, MeCH O),
2.76 m (2H, C H ), 2.94 m (2H, C H ), 6.54 m (1H,
2
2
2 2
9
9
12
3
.28 m (1H, C H ), 5.94 s (1H, H ), 9.50 s (1H, NH).
Harom), 6.13 m (1H, Harom), 7.00–7.13, 7.24–7.30, 7.33–
7.49 m (9H, Harom), 7.81–7.84 m (2H, Harom), 8.00 (1H,
a'
Found, %: C 78.94; H 5.96; N 2.70. C H NO .
3
4
31
4
+
Calculated, %: C 78.92; H 5.99; N 2.71.
-(11-Oxo-9-phenyl-7,8,9,10,11,12-hexahydro-
benzo[a]acridin-12-yl)-2-ethoxyphenyl butyrate
VII d). Yield 62%, colorless crystals, mp 260°C. IR
Harom, J 7.2 Hz). Mass spectrum, m/z (I , %): [M] 545
rel
9
(
9), 324 (100), 122 (11), 78 (80). Isomer C -Ph , d, ppm:
4
a'
1
.24 t (3H, MeCH O), 3.90 q (2H, MeCH O), 3.31 m
2 2
9
12
(
1H, H ), 5.89 s (1H, H ), 9.80 s (1H, NH). Isomer
(
e'
9
–1
C -Ph , d, ppm: 1.18 t (3H, MeCH O), 3.80 q (2H,
MeCH O), 3.26 m (1H, H ), 5.92 s (1H, H ), 9.84 s
spectrum, cm : 3275, 3183, 2956, 1757, 1603, 1582, 1511,
e'
2
9
12
1
499, 1471, 1420, 1414, 1381, 1252, 1244, 1183, 1152,
2
a'
1
(1H, NH). Found, %: C 79.29; H 6.44; N 2.55.
C H NO . Calculated, %: C 79.27; H 6.42; N 2.57.
1126, 1090, 824, 747. H NMR spectrum, d, ppm: 1.00 t
[
2
2
3H, OCO (CH ) Me], 1.62 m (2H, OCOCH CH Me),
36 35
4
2
2
2
2
8
.69 m (2H, OCOCH –CH Me), 2.60 m (2H, C H ),
4-(11-Oxo-9-phenyl-7,8,9,10,11,12-hexahydro-
benzo[a]acridin-12-yl)-2-ethoxyphenyl benzoate
2
2
2
1
0
.80 m (2H, C H ), 6.04 m (1H, Harom), 6.15 m (1H,
2
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 11 2005

VANILLAL ESTERS IN REACTION WITH 2-NAPHTHYLAMINE
VIIg). Yield 45%, colorless crystals, mp 267°C. IR
1645
(
%: C 78.46; H 4.54; N 3.00. C H NO . Calculated, %:
30 21 4
–1
spectrum, cm : 3274, 3182, 2952, 1754, 1600, 1585, 1511,
C 78.43; H 4.58; N 3.05.
-(12-Oxo-12H-benzo[f]indeno[1,2-b]quinolin-
3-yl)-2-ethoxyphenyl propionate (IXc). Yield 60%,
1
489, 1478, 1422, 1420, 1381, 1258, 1241, 1186, 1150,
4
1
1134, 1092, 827, 746. H NMR spectrum, d, ppm: 6.65 m
1
(
1H, Harom), 6.90 m (1H, Harom), 7.10–7.45, 7.58, 7.70,
–1
yellow crystals, mp 250°C. IR spectrum, cm : 3050,
2970, 1765, 1710, 1566, 1502, 1331, 1245, 1149, 1119, 1033,
7
.86 m (14H, Harom), 8.05 m (3H, Harom). Mass spectrum,
+
m/z (I , %): [M] 565 (84), 324 (68), 192 (23), 105 (100),
7
4
H ), 9.80 s (1H, NH). Isomer C -Ph , d, ppm: 1.28 t
3H, MeCH O), 3.97 q (2H, MeCH O), 3.26 m (1H, H ),
1
rel
842, 702. H NMR spectrum, d, ppm: 1.30 t (3H,
9
7 (55). Isomer C -Ph d, ppm: 1.30 t (3H, MeCH O),
.08 q (2H, MeCH O), 3.31 m (1H, H ), 5.89 s (1H,
a'
2
MeCH O), 3.90 q (2H, MeCH O), 1.20 t (3H, OCH Me),
2
2
2
9
2
e'
1.26 q (2H, OCH2Me), 6.85 d (1H, Harom, J 7.9 Hz),
7.10 s (1H, Harom), 7.25 m (2H, Harom), 7.55, 7.68, 7.79 m
(5H, Harom), 7.98 d (1H, Harom, J 7.2 Hz), 8.08–8.20 m
1
2
9
e’
9
(
2
2
a
'
1
2
+
5
.93 s (1H, H ), 9.90 s (1H, NH). Found, %: C 83.64;
(3H, Harom). Mass spectrum, m/z (I , %): [M] 473 (100),
rel
H 5.51; N 2.47. C H NO . Calculated, %: C 83.67;
280 (39), 193 (25). Found, %: C 78.63; H 4.89; N 3.00.
C H NO . Calculated, %: C 78.65; H 4.87; N 2.95.
3
8
31
4
H 5.49; N 2.48.
-(12-Oxo-12H-benzo[f]indeno[1,2-b]-quinolin-
3-yl)-2-ethoxyphenyl carboxylates IXa–IXg. To
a solution of 1.46 g (0.01 mol) of 1,3-indanedione (IV) in
0 ml of alcohol was added a solution of 1.43 g
0.01 mol) of 2-naphthylamine (I) in 10 ml of alcohol and
a solution of 0.01 mol of an appropriate ester IIa–IIg in
0 ml of alcohol. The reaction mixture was heated at
3
1
23
4
4
4-(12-Oxo-12H-benzo[f]indeno[1,2-b]quinolin-
13-yl)-2-ethoxyphenyl butyrate (IXd). Yield 55%,
1
–
1
yellow crystals, mp 242°C. IR spectrum, cm : 3045,
2970, 1763, 1716, 1608, 1566, 1504, 1473, 1382, 1331,
1
(
1
284, 1241, 1174, 1152, 1119, 1038, 842, 746, 702.
1
H NMR spectrum, d, ppm: 1.28 t (3H, MeCH O), 3.95 q
2
(
2H, MeCH O), 1.00 t [3H, OCO(CH ) Me], 1.70 m
1
2 2 2
(
2H, OCOCH CH Me), 2.65 m (2H, OCOCH CH Me),
reflux for 30–60 min. On cooling the formed precipitate
was separated, 15 ml of nitrobenzene was added, and
the solution was boiled for 3–4 h. The solvent was
evaporated, the solid residue was washed with ether and
crystallized from a mixture ethanol-benzene, 1: 3.
2 2 2 2
6
.88 d (1H, Harom
, J 8.0 Hz), 7.10 s (1H, Harom), 7.28 m
(
2H, Harom), 7.50, 7.68, 7.75 m (5H, Harom), 7.90 d (1H,
Harom, J 7.2 Hz), 8.11–8.22 m (3H, Harom). Mass spectrum,
+
m/z (I , %): [M] 487 (100), 280 (42), 207 (30). Found,
rel
%
: C 78.86; H 5.16; N 2.90. C H NO . Calculated, %:
32 25 4
4
-(12-Oxo-12H-benzo[f]indeno[1,2-b]quinolin-
C 78.85; H 5.13; N 2.87.
1
3-yl)-2-ethoxyphenyl formate (IXa). Yield 52%,
4
-(12-Oxo-12H-benzo[f]indeno[1,2-b]quinolin-
–
1
yellow crystals, mp 263°C. IR spectrum, cm : 3052,
1
3-yl)-2-ethoxyphenyl isobutyrate (IXe). Yield 46%,
2
1
975, 1762, 1700, 1563, 1506, 1334, 1245, 1143, 1112,
039, 843, 704. H NMR spectrum, d, ppm: 1.30 t (3H,
–
1
yellow crystals, mp 286°C. IR spectrum, cm : 3055,
1
2
1
7
971, 2936, 2834, 1765, 1602, 1567, 1468, 1404, 1331,
MeCH O), 3.95 q (2H, MeCH O), 8.15 s (1H, OCOH),
2
2
285, 1246, 1200, 1171, 1145, 1117, 1072, 1034, 933, 842,
6
.90 d (1H, Harom
,
J 7.6 Hz), 7.05 s (1H, Harom), 7.20 m
1
45, 702. H NMR spectrum, d, ppm: 1.30 t (3H,
(
2H, Harom), 7.50, 7.65, 7.70 m (5H, Harom), 7.90 d (1H,
MeCH O), 4.00 q (2H, MeCH O), 1.40 d (6H,
2
2
Harom, J 7.8 Hz), 8.00–8.15 m (3H, Harom). Mass spectrum,
OCOCHMe , J 8.0 Hz), 2.85 m(1H, OCOCHMe ),
2
2
+
m/z (I , %): [M] 445 (100), 280 (40), 165 (24). Found,
rel
6
.90 d (1H, Harom, J 7.6 Hz), 7.05 s (1H, Harom), 7.15 m
%
: C 78.19; H 4.25; N 3.17. C H NO . Calculated,%:
29 19 4
(
2H, Harom), 7.50, 7.65, 7.69 m (5H, Harom), 7.93 d (1H,
C 78.20; H 4.27; N 3.16.
Harom, J 7.7 Hz), 8.00–8.15 m (3H, Harom). Mass spectrum,
4
-(12-Oxo-12H-benzo[f]indeno[1,2-b]quinolin-
+
m/z (I , %): [M] 487 (100), 280 (42), 207 (22). Found,
rel
1
3-yl)-2-ethoxyphenyl acetate (IXb). Yield 63%,
%: C 78.88; H 5.12; N 2.84. C H NO . Calculated,
3
2
25
4
–
1
yellow crystals, mp 263°C. IR spectrum, cm : 3058,
%
: C 78.85; H 5.13; N 2.87.
-(12-Oxo-12H-benzo[f]indeno[1,2-b]quinolin-
3-yl)-2-ethoxyphenyl isovalerate (IXf). Yield 40%,
2
1
971, 1768, 1700, 1566, 1508, 1335, 1240, 1147, 1110,
4
1
042, 847, 706. H NMR spectrum
,
d, ppm: 1.35 t (3H,
1
MeCH O), 4.00 q (2H, MeCH O), 2.35 s (3H, OCOMe),
–1
2
2
yellow crystals, mp 260°C. IR spectrum, cm : 3053,
2968, 2931, 2833, 1763, 1600, 1562, 1466, 1401, 1331,
1285, 1244, 1202, 1176, 1147, 1112, 1073, 1032, 935, 840,
748, 707. 1H NMR spectrum, d, ppm: 1.29 t (3H,
MeCH O), 3.90 q (2H, MeCH O), 1.30 d [6H,
6
.90 d (1H, Harom, J 7.6 Hz), 7.10 s (1H, Harom), 7.22 m
(
2H, Harom), 7.50, 7.62, 7.75 m (5H, Harom), 7.90 d (1H,
Harom, J 7.6 Hz), 8.03–8.10 m (3H, Harom). Mass spectrum,
+
m/z (I , %): [M] 459 (100), 280 (43), 179 (20). Found,
rel
2
2
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 11 2005

1646
KOZLOV et al.
OCOCH (CH)Me , J 7.0 Hz], 1.60 m [2H,
REFERENCES
2
2
OCOCH (CH)Me ], 2.70 m [1H, OCOCH (CH)Me2],
2
2
2
1
2
. Kozlov, N.G., Basalaeva, L.I., and Dikusar, E.A., Khim.
Polimer. Soedin., 2004, vol. 40, p. 79.
6
.90 d (1H, Harom J 7.6 Hz), 7.10 s (1H, Harom), 7.21 m
(
2H, Harom), 7.55, 7.68, 7.74 m (5H, Harom), 7.89 d (1H,
. Shulov, L.M. and Kheifits, L.A., Dushistye veshchestva i
poluprodukty parfyumerno-kocmeticheskogo proizvod-
stva: Spravochnik (Fragrant Chemicals and Internediates
of Perfumery Cosmetical Industry: Handbook), Moscow:
Agropromizdat, 1990, 208 p.
. Shaikh, Y., Specialty Aroma Chemicals in Flavors and
Fragrance, Illinois:Allured Publishing, 2002, 165 p.
. Voitkevich, S.A. and Kheifits, L.A., Ot drevnikh blagovonii
k sovremennym parfyumerii i kocmetike (From Ancient
Incenses to Modern Perfumary and Cosmetics), Moscow:
Pishch. Prom., 1997, 218 p.
Harom, J 7.7 Hz), 8.05–8.20 m (3H, Harom). Mass spectrum,
+
m/z (I , %): [M] 501 (100), 280 (50), 221 (27). Found,
rel
%
: C 79.00; H 5.40; N 2.80. C H NO . Calculated, %:
33 27 4
C 79.04; H 5.38; N 2.79.
4
-(12-Oxo-12H-benzo[f]indeno[1,2-b]quinolin-
3
4
1
3-yl)-2-ethoxyphenyl benzoate (IXg). Yield 35%,
–
1
yellow crystals, mp 260°C. IR spectrum, cm : 3055,
2
968, 2837, 1766, 1602, 1506, 1407, 1334, 1281, 1246,
1
1177, 1145, 1112, 1073, 1038, 934, 841, 748, 703. H NMR
spectrum, d, ppm: 1.29 t (3H, MeCH O), 3.90 q (2H,
2
MeCH O), 6.87 d (1H, Harom, J 7.6 Hz), 7.15 s (1H, Harom),
2
7
.26 m (2H, Harom), 7.50, 7.66, 7.78 m (8H, Harom), 7.88 d
5. Kozlov, N.G. and Gusak, K.N., Zh. Org. Khim. 1999, vol. 35,
p. 426.
6. Martinez, R., Cortes, E., and Toscano, R.A., J. Heterocycl.
Chem. 1990, vol. 27, p. 363.
(1H, Harom
,
J
7.7 Hz), 8.10–8.25 m (5H, Harom). Mass
+
spectrum, m/z (I , %): [M] 521 (100), 280 (48), 241
rel
(
30). Found, %: C 80.63; H 4.40; N 2.71. C H NO .
35 23 4
Calculated, %: C 80.61; H 4.41; N 2.69.
7
. Daier, D.R., Prilozhenie absorbtsionnoi spektroskopii
organicheskikh soedinenii (Application of Absorbtion
Spectroscopy of Organic Compounds), Moscow: Khimiya,
1970, p. 100.
The study was carried out under financial support of
the Foundation for Basic Research of the National
Academy of Sciences of Belarus’ (grant no. X03–79).
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 11 2005