Synthesis and spectral characteristics of 4-(10,10-dimethyl-8-oxo-7,8,9,10, 11,12-hexahydrobenzo[c]acridin-7-yl)-2-methoxy(ethoxy)phenyl carboxylates

Article abstract of DOI:10.1134/S1070428007100120

By reaction of vanillin and ethyl vanillin with 1-naphthylamine in ethanol previously unknown azomethines (Schiff's bases) were obtained as individual E-isomers which in heterocyclizatoion with dimedone provided in 33-77% yield individual 4-(10,10-dimethyl-8-oxo-7,8,9,10,11,12-hexahydrobenzo[c]acridin-7-yl) -2-methoxy(ethoxy)phenyl carboxylates formed as a result of recombination of the adduct of azomethine and dimedone occurring by the type of Hofmann-Martius rearrangement. The structure of compounds obtained was confirmed by elemental analyses, UV, IR, and ¹H NMR spectra.

Full text of DOI:10.1134/S1070428007100120

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 10, pp. 1481−1488. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © V.V. Skatetskii, N.G. Kozlov, E.A. Dikusar, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 10, pp. 1488−1494.
Synthesis and Spectral Characteristics of 4-(10,10-Dimethyl-8-oxo-
7,8,9,10,11,12-hexahydrobenzo[c]acridin-7-yl)-2-
methoxy(ethoxy)phenyl Carboxylates
V. V. Skatetskii, N. G. Kozlov, and E. A. Dikusar
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, Minsk, 220072 Belarus
e-mail: loc@ifoch.bas-net.by
Received November 24, 2005
Abstract—By reaction of vanillin and ethyl vanillin with 1-naphthylamine in ethanol previously unknown
azomethines (Schiff’s bases) were obtained as individual E-isomers which in heterocyclizatoion with dimedone
provided in 33–77% yield individual 4-(10,10-dimethyl -8-oxo-7,8,9,10,11,12-hexahydrobenzo[c]acridin-7-yl)-
2-methoxy(ethoxy)phenyl carboxylates formed as a result of recombination of the adduct of azomethine and
dimedone occurring by the type of Hofmann–Martius rearrangement. The structure of compounds obtained was
confirmed by elemental analyses, UV, IR, and 1H NMR spectra.
DOI: 10.1134/S1070428007100120
Introduction of fragments from the naturally occurring
substances, like esters of plant phenols, into molecules
of benzoacridines is a promising way to new bioactive
compounds. In a number of publications [1–3] an inform-
ation appeared on the synthesis based on acridines of
labaled conjugates with drugs, peptides, proteins, or
nucleic acids, of preparations with antitumor activity and
DNA-bonding properties. In [4] data are cited that
modified acridine molecules, in particular, tetrahydro
derivatives having a carbonyl group (analogs of floxacrin
alkaloid) exhibit higher antibacterial activity than the
decarbonylated compounds of this series.
group. The use of a cyclic β-diketone in this reaction
makes it possible to introduce a carbonyl group into the
structure of fused heterocycle simultaneously with the
building up of a partially hydrogenated benzo[h]quino-
line fragment As a result formed in 33–77% yield
previously unknown 4-(10,10-dimethyl-8-oxo-
7,8,9,10,11,12-hexahydrobenzo[c]-acridin-7-yl)-2-
methoxy(ethoxy)phenyl esters Va–Vo.
In the first stage 4-formyl-2-methoxy(ethoxy)-phenyl
ester Ia–Io reacted with 1-naphthylamine (II), yielding
azomethine IIIa–IIIo that in its turn added a dimedone
(IV) molecule forming 4-[(4,4-dimethyl-2,6-dioxocyclo-
hexyl)-(1-naphthylamino)methyl]-2-methoxy(ethoxy)-
phenyl ester A. Then intermediate A underwent
protonation by reaction with a solvent molecule HX
converting into cation B. In the next stage an alkoxy
anion X– formed in the previous stage attacked cation B
at the asymmetric carbon leading to the hydramine
cleavage of this structure into 1-naphthylamine (II) and
3-[(4,4-dimethyl-2,6-dioxocyclohexyl)alkoxymethyl]-2-
methoxy(ethoxy)phenyl ester C. The latter in reaction
with 1-naphthylamine (II) may add both to the amino
group and to the carbon atom possessing the highest
electron density and located in the β-position of the
naphthalene framework giving respectively 4-[(04,4-
dimethyl-2,6-dioxocyclohexyl)(1-naphthylamino)-
Unlike benzo[a]acridone derivatives obtained proceed-
ing from 2-naphthylamine compounds of this class based
on 1-naphthylamine, benzo[c]-acridones, are less known.
In this study we investigated a reaction of condensation
products of esters Ia–Io with 1-naphthylamine (II),
2-methoxy-(ethoxy)-4-(1-naphthyliminoethyl)phenyl
esters IIIa–IIIo, with 5,5-dimethyl -1,3-cyclohexanedione
(dimedone) (IV). The reaction was carried out by boiling
equimolar amounts of reagents in ethanol (in the synthesis
of compounds Va–Vd, Vf–Vo) or in the 2-propanol−
butanol mixture, 1:1 (in the synthesis of compound Ve).
Thanks to the high reactivity of the β-dicarbonyl com-
pound the reaction occurred without acid catalyst. The
absence of acid favors the retention of the labile ester
1481

SKATETSKII et al.
1482
tion of arylmethylencyclohexanedione fragment into the
β-position of the naphthalene framework analogously
to the process occurring at the transformtion of alkyl-,
dialkylanilines halides and trialkylammomium salts
known as Hofmann–Martius rearrangement [6].
methyl]-2-methoxy(ethoxy)phenyl ester A or 4-[(1-
amino-2-naphthyl)(4,4-dimethyl-2,6-dioxocyclohexyl)-
methyl]-2-methoxy(ethoxy)phenyl ester D. We guess that
the latter alternative is preferable for the benzo[c]acridi-
none derivatives Va–Vo formed in the final stage can be
obtained only by the dehydrocyclization of intermediate
D. In keeping with the data of [5] it is presumable that
the water molecules liberated during dehydrocyclization
are involved into the protonation of intermediate A
alongside the alcohol molecules.
The described mechanism is analogous to that sug-
gested for the synthesis of 7-(o- and p-R-phenyl)-10,10-
dimethyl-8,9,10,11-tetrahydrobenzo[c]acridin-8-ones [5]
and besides it is in agreement with the mechanism of
synthesis of benzo[c]acridines from 2-(naphthylamino-
methylene)cyclohexanones [7].
The formation of ester D can be regarded as a result
of a rearrangement of cation B proceeding by the migra-
Azomethines IIIa–IIIo prepared from 4-formyl-2-
methoxy(ethoxy)phenyl esters of acids Ia–Io and 1-naph-
O
NH2
N.......H.
C
O
+
+
H
RO
OCOR'
O
II
_
RO
IV
Ià Io
OCOR'
_
IIIa IIIo
O
H
O
H
+
N
N
HX
H
O
O
-
X:
RO
RO
OCOR'
OCOR'
A
B
2
3
4
1
H
11
O H2N
N
10
9
O
5
7
4'
H
8
H2N
6
_
_
X
O
O3'
5'
6'
H2O
HX
O
RO
2'
RO
1'
OCOR'
RO
OCOR'
C
OCOR'
D
_
Va Vp
R = Me, R' = Me(a), Et (b), i-Pr (c), C9H19 (d), C(Me)=CH2 (e), Bn (f), CH2CH(Me)Ph (g), Ph (h), p-MePh (i), p-ClPh (j),
p-NO2Ph (k), m-NO2Ph (l); R = Et, R’ = Me (m), Ph (n), p-MePh (o).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

SYNTHESIS AND SPECTRAL CHARACTERISTICS OF 4-(10,10-DIMETHYL-...
1483
thylamine (II) in ethanol were isolated in the form of
individual Ε-isomers [8] although this had failed before
[5]. Therefore it was possible to use the compounds in
the above discussed reaction.
Vc, and compounds Vd, Vg, and Vj are virtually non-
associated. In the IR spectra of phenyl carboxylates Va–
Vd, Vf, Vg, and Vm the strong band νC=O appears in
the region 1767–1758 cm–1. The conjugation of the
carbonyl group with multiple bond decreases the
frequency of νC=O vibration for all types of carbonyl
compounds approximately by 20 cm–1 [12]. Therefore
in the IR spectra of compounds Ve, Vh–Vl, Vn, and Vo
the strong band corresponding to the carbonyl of the ester
group is shifted to the region 1747–1732 cm–1. The
absorption band of the vinilog amide fragment is
observed at 1602–1578 cm–1. The intensity of this band
is higher than that of the ester carbonyl. These data are
in agreement with the results published in [5, 13]. The
very strong band in the region 1502–1490 cm–1 should
be assigned to the skeleton vibrations of aromatic carbon-
carbon bonds. The most strong bands in the region 1129–
1013 cm–1 should be assigned to the vibrations of the
fragment C–O–C of ether and ester groups. Out-of-plane
bending vibrations of the C–H bonds of aromatic and
heteroaromatic rings appear as one or several strong
bands at 797–694 cm–1. IR spectrum of compound Ve
contains a strong band at 939 cm–1 corresponding to out-
of-plane bending vibrations of =C–H bond of the terminal
methylene group–C(Me)=CH2. In the IR spectra of
compounds Vk and Vl a very strong band is present in
the region 1533–1529 cm–1 belonging to the antisym-
metrical stretching vibrations of the nitro group.
In the 1H NMR spectra of esters Va–Vo a singlet is
observed in the region 9.14–9.28 ppm corresponding to
the proton of the secondary amino group. The singlet at
4.94–5.30 ppm should be assigned to the methine proton
H7 of the dihydropyridine ring. The downfield shift of
this proton signal compared to the common position of
the methine proton signals in the cyclic compounds is
caused by an anisotropic effect of the contiguous aromatic
rings. The protons of methyl groups attached to C10 gave
rise to two singlets at 1.02–1.10 and 1.11–1.17 ppm. The
proton signal of the methyl group located in a pseudo-
equatorial position appeared in a weaker field. The singlet
from the protons of methoxy group in compounds Va–
Vl is seen in the region 3.70–3.78 ppm. The ethoxy group
protons in esters Vm–Vo are observed as two signals,
a triplet and broadened quartet. The triplet overlapps with
two singlets of protons from methyl groups linked to C10
and appears at 0.87–1.39 ppm, and the quartet with the
coupling constant of 5.5–6.2 Hz is located in the region
3.83–3.88 ppm. The protons of methylene groups at C9
and C11 give rise each to two broadened doublets at
A similar reaction of dimedone, 1-naphthylamine and
some aromatic aldehydes in ethanol was studied in [9].
Lielbriedis et al. presumed that the reaction products were
isomeric to hexahydrobenzo[c]acridinones hexahydro-
benzo[c]phenanthridines arising from cyclocondensation
of the product of dimedone reaction with Schiff’s bases.
However applying to the structure estimation the
combination of below cited spectral methods and taking
into consideration the results of previous research [5,
10, 11] at the use of combined analysis of a number 2D
NMR methods (COSY, NOESY, HSQC, and HMBC) and
X-ray diffraction study we established that the only
products of reaction between esters IIIa–IIIo and
dimedone (IV), independent of the structure of the acid
residue in the ester group were 4-(10,10-dimethyl-8-oxo-
7,8,9,10,11,12-hexahydrobenzo[c]acridin-7-yl)-2-
methoxy(ethoxy)phenyl carboxylates Va–Vo. The
structure of compounds synthesized is in agreement with
UV, IR, and 1H NMR spectra.
For the electron absorption spectra of esters Va–Vo
observed in the UV range the presence is characteristic
of absorption maxima in four regions: at 215–227, 239–
269, 279–286, and 368–378 nm. The complex spectral
pattern is due to the presence in the structure of com-
pounds synthesized of several chromophore fragments:
naphthalene framework, benzene rings, and also carbonyl
and ester groups. The substituents in the phenyl ring of
the acid residue of the ester group virtually do not affect
the position and intensity of the spectral bands, and only
electron-acceptor nitro group in the para-position to the
ester one brings about the smoothing of the vibronic
structure of the spectrum and disappearance of a band in
the region 279–286 nm.
It is known that at incomplete amines association in
the IR spectra alongside the absorption bands of the
associated amino groups appear absorption bands of the
free NH group [12]. In the spectra of compounds we
synthesized Va–Vo the absorption band of the stretching
vibrations of the free secondary amine group was
observed at 3448–3425 cm–1, and of associated, at 3342–
3283 cm–1. It is also known that the stronger the
absorption band of the associated amino group is shifted
to lower frequencies and the greater its intensity, the
higher is the association degree [12]. As to esters Va–
Vo, note that stronger associated are compounds Va and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

SKATETSKII et al.
1484
2.16–2.22 (2J 16.4–17.2 Hz) and 2.65–2.73 ppm (2J
16.2–16.9 Hz) respectively. The signal of protons H9
appears upfield with respect to proton signal from H11
due to the shielding effect of the neighboring carbonyl
group. The naphthalene protons show up as two doublets
and a multiplet. A diffuse doublet at 8.40–8.48 ppm
with a coupling constant 7.0–7.8 Hz should be assigned
to proton H1. This is consistent with data of [15]. The
multiplet in the region 7.16–7.67 ppm, and also a
broadened doublet at 7.76–7.84 ppm with a coupling
constant 7.8–8.4 Hz belongs to the other five protons
H2-6. The protons H3, H5 and H6 of vanillin and ethyl
vanillin structures appear as a singlet and two doublets
respectively (singlet of proton H3 in the region 6.90–
7.15 ppm, and doublets of protons H6 and H5, in the
region 6.57–6.73 and 6.74–6.98 ppm with a coupling
constant 7.0–7.8 Hz). A small upfield shift of H3 proton
in compounds Vm–Vo as compared with this signal in
compounds Va–Vl may originate from the influence of
a stronger +M-effect of ethoxy group than +M-effect of
methoxy group. Besides the upfield shift of signals from
protons H3, H5, and H6 may be caused by the shielding
IIIf–IIIo in 30 ml of ethanol was boiled for 3–10 h. The
resinous substance obtained after evaporation of the
solvent was recrystallized from a mixture of acetone and
1,4-dioxane, 1:1, washed with hexane, and dried. Yield
of esters Va–Vd, Vf–Vo 33–77%.
b.Asolution of 2 mmol of dimedone (IV) and 2 mmol
of azomethine IIIe in 30 ml of a mixture of 2-propanol
and 1-butanol, 1:1, was boiled for 8 h. The separated
precipitate was filtered off, recrystallized from a mixyure
of acetone with methanol, 1:1, washed with ethyl ether,
and dried. Yield of ester Ve 35%.
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-
hexahydrobenzo[C]acridin-7-yl)-2-methoxyphenyl
acetate (Va). Yield 48%, mp 276°C. UV spectrum, λmax
,
nm (log ε): 218 (4.71), 258 (4.42), 281 (4.19), 368 (4.17).
IR spectrum, cm−1: 3438 v.w [ν(Ν–Çfree)], 3289 c [ν(N–
Hbound)], 3062 m, 3044 w [ν(C–Harom)], 2961 v.s, 2934 s,
2875 m [ν(C–Haliph)], 1759 s [ν(C=Oester)], 1591 v.s
(O=C–C=C–N–H), 1496 v.s (Ar), 1420 m, 1386 v.s,
1372 s, 1344 w [δ(C–Haliph)], 1119 w, 1034 w (C–O–C),
791 w, 766 v.w, 742 w [δ(C–Harom)]. 1H NMR spectru, δ,
ppm (J, Hz): 1.08 s, 1.15 s (6H, 2Me, H10), 1.96–2.35
(2 br.d + s) (2H, H9 + 3H, OCOMe), 2.68 (2 br.d) (2H,
H11, 2J 16.9), 3.73 s (3H, OMe), 5.22 s (1H, H7), 6.64 d,
6.77 d (2H, H5, H6, 3J 7.5), 7.02 s (1H, H3), 7.19–7.62 m,
effect of the bulky R' substituent [C9H19, CH2CH(Me)Ph].
The protons of phenyl substituent R' are observed as one
or several multiplets (depending on the nature of the
substituent in question) in the region 7.06–8.67 ppm. The
broadened singlet at 8.78 ppm in the spectrum of
compound Vl should be assigned to the proton of the
substituent m-NO2Ph situated in the region of shielding
from two acceptor groups (ester and nitro groups).
3
7.76 br.d (5H, H2−6, J 7.9), 8.42 br.d (1H, H1, 3J 7.6),
9.14 s (1H, NH). Found, %: C 76.32; H 6.51; N 3.42.
C28H27NO4. Calculated, %: C 76.17; H 6.16; N 3.17.
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-
hexahydrobenzo[C]acridin-7-yl)-2-methoxyphenyl
propionate (Vb). Yield 43%, mp 246°C. UV spectrum,
EXPERIMENTAL
λ
max, nm (log ε): 218 (4.41), 259 (4.09), 282 (3.75), 368
(3.83). IR spectrum, cm−1: 3440 m [ν(Ν–Çfree)], 3283 s
[ν(N–Hbound)], 3062 m, 3042 w [ν(C–Harom)], 2961 s,
2933 v.s, 2872 m [ν(C–Haliph)], 1761 s [ν(C=Oester)], 1591
v.s (O=C–C=C–N–H), 1497 v.s (Ar), 1417 m, 1384 v.s,
1373 c, 1343 m [δ(C–Haliph)], 1122 C, 1032 C (C–O–
IR spectra were recorded on an IR Fourier spectro-
photometer Nicolet Protégé-460 from samples pelletized
with KBr. UV spectra were taken on a spectrophotometer
Specord UV Vis for (4–7)×10–5 M solutions in ethanol.
1H NMR spectra were registered on spectrometers Tesla
BS-567 (100 MHz) (Va–Vd, Vh–Vk, Vm–Vo) and Tesla
BS-587 (80 MHz) (Ve–Vg, and Vl) from 5% solutions
in DMSO-d6, internal reference TMS. Melting points
of compounds were measured on Koeffler heating block.
1
C), 792 C, 764 v.s, 740 C [δ(C–Harom)]. H NMR
spectrum, δ, ppm (J, Hz): 1.00–1.27 (2 s + t) (6H, 2Me,
H10 + 3H, OCOCH2Me), 2.16 (2 br.d) (2H, H9, 2J 16.5),
2.50 q (2H, OCOCH2Me, 3J 6.4), 2.68 (2 br.d) (2H, H11,
2J 16.2), 3.73 s (3H, OMe), 5.23 s (1H, H7), 6.66 d,
3
6.79 d (2H, H5, H6, J 7.4), 7.03 s (1H, H3), 7.20–
2-Methoxy(ethoxy)-4-(1-naphthyliminomethyl )-
phenyl esters IIIa, IIId–IIIo were prepared by
procedure [8].
3
7.64 m, 7.78 br.d (5H, H2−6, J 8.0), 8.45 d (1H, H1,
3J 7.4), 9.18 C (1H, NH). Found, %: C 76.74; H 6.86;
N 3.51. C29H29NO4. Calculated, %: C 76.46; H 6.42;
N 3.07.
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[c]acridin-7-yl)-2-methoxy(ethoxy)-
phenyl carboxylates Va–Vo. a. A solution of 2 mmol of
dimedone (IV) and 2 mmol of azomethine IIIa–IIId,
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[c]acridin-7-yl)-2-methoxyphenyl
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

SYNTHESIS AND SPECTRAL CHARACTERISTICS OF 4-(10,10-DIMETHYL-...
1485
2.19 (2 br.d) (2H, H9), 2.72 (2 br.d) (2H, H11), 3.75 s
(3H, OMe), 5.27 s (1H, H7), 5.80 br.s, 6.21 br.s (2H,
isobutyrate (Vc). Yield 40%, mp 253°C. UV spectrum,
max, nm (log ε): 217 (4.66), 258 (4.34), 281 (4.05), 368
λ
(4.09). IR spectrum, cm−1: 3448 v.w [ν(Ν–Çfree)],
3300 s [ν(N–Hbound)], 3058 m, 3032 v.w [ν(C–Harom)],
2957 s, 2932 v.s, 2874 m [ν(C–Haliph.)], 1764 v.s
[ν(C=Oester)], 1588 v.s (O=C–C=C–N–H), 1495 v.s (Ar),
1417 m, 1385 s, 1366 m, 1341 w [δ(C–Haliph.)], 1124 v.s,
1096 s, 1032 s (C–O–C), 797 s, 770 v.s, 751 s
3
OCOCMe=CH2), 6.69 d, 6.88 d (2H, H5, H6, J 7.2),
7.10 s (1H, H3), 7.16–7.65 m, 7.83 br.d (5H, H2−6
,
3J 8.0), 8.48 d (1H, H1, 3J 7.2), 9.22 s (1H, NH). Found,
%: C 77.32; H 6.51; N 3.40. C30H29NO4. Calculated, %:
C 77.06; H 6.25; N 3.00.
4-(10,10-Dimethyl -8-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[c]acridin-7-yl)-2-methoxyphenyl-
phenylacetate (Vf). Yield 38%, mp 272–274°C. UV
spectrum, λmax, nm (log ε): 215 (4.71), 263 (4.39), 279
(4.24), 373 (3.94). IR spectrum, cm−1: 3304 s [ν(N–
Hbound)], 3064 m, 3029 m [ν(C–Harom)], 2957 s, 2925
v.s, 2871 m [ν(C–Haliph.)], 1764 c [ν(C=Oester)], 1599 v.s
(O=C–C=C–N–H), 1490 v.s (Ar), 1418 m, 1401 v.s,
1373 v.s, 1344 C [δ(C–Haliph.)], 1121 v.s, 1031 s (C–
1
[δ(C–H arom)]. H NMR spectrum, δ, ppm (J, Hz):
1.07 s, 1.14 s (6H, 2Me, H10), 1.22 d (6H, OCOCHMe2,
3J 6.5), 2.16 (2 br.d) (2H, H9, 2J 16.4), 2.58–2.91 (m +
2 br.d) (2H, OCOCH(Me)2 + 2H, H11), 3.73 s (3H, OMe),
3
5.24 s (1H, H7), 6.64 d, 6.78 d (2H, H5, H6, J 7.1),
7.02 s (1H, H3), 7.20–7.67 m, 7.79 br.d (5H, H2−6
,
3J 8.1), 8.44 d (1H, H1, 3J 7.5), 9.17 s (1H, NH). Found,
%: C 76.90; H 7.00; N 2.68. C30H31NO4. Calculated, %:
C 76.73; H 6.65; N 2.98.
1
O–C), 748 v.s, 729 C, 694 C [δ(C–Harom)]. H, δ, ppm
(J, Hz): 1.02 C, 1.11 C (6H, 2Me, H10), 2.20 (2 br.d)
(2H, H9), 2.69 (2 br.d) (2H, H11), 3.58 C (2H,
OCOCH2Ph), 3.78 br.s (3H, OMe), 5.01 C (1H, H7),
6.62 br.d, 6.74 br.d (2H, H5, H6, 3J 7.4), 6.99 C (1H, H3),
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[c]acridin-7-yl)-2-methoxyphenyl deca-
noate (Vd). Yield 60%, mp 248–250°C. UV spectrum,
λ
max, nm (log ε): 218 (4.60), 269 (4.26), 280 (4.19), 377
(3.82). IR spectrum, cm−1: 3327 m [ν(N–Hbound)], 3056 m
[ν(C–Harom)], 2954 s, 2926 v.s, 2854 m [ν(C–Haliph)],
1762 s [ν(C=Oester)], 1600 v.s (O=C–C=C–N–H), 1495 v.s
(Ar), 1418 s, 1385 v.s, 1369 v.s, 1345 m [δ(C–H aliph.)],
3
7.15–7.56 m, 7.84 br.d (10H, H2−6, Harom, J 8.3),
8.41 br.d (1H, H1, 3J 7.2), 9.14 C (1H, NH). Found, %:
C 78.99; H 6.37; N 2.86. C34H31NO4. Calculated, %:
C 78.89; H 6.04; N 2.71.
1122 v.s, 1034 s (C–O–C), 766 v.s [δ(C–Harom)]. 1
H NMR
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[c]acridin-7-yl)-2-methoxyphenyl
3-phenylbutyrate (Vg). Yield 77%, mp 228–230°C. UV
spectrum, λmax, nm (log ε): 218 (4.47), 265 (4.05), 284
(3.87), 377(3.69). IRspectrum, cm−1:3329m[ν(N–Hbound)],
3058 m, 3027 m [ν(C–Harom)], 2957 s, 2926 s, 2867 m
[ν(C–Haliph.)], 1758 s [ν(C=Oester)], 1602 v.s (O=C–C=C–
N–H), 1494 v.s (Ar), 1417 c, 1384 v.s, 1371 v.s, 1342 m
[δ(C–Haliph.)], 1123 v.s, 1033 s (C–O–C), 764 s, 700 s
[δ(C–Harom)]. 1H NMR spectrum, δ, ppm (J, Hz): 1.04 s,
1.12 s (6H, 2Me, H10), 1.32 d (3H, OCOCH2CHMePh,
3J 6.5), 2.16 (2 br.d) (2H, H9), 2.57–2.97 m (4H,
OCOCH2CHMePh, H11), 3.07–3.95 (m + s) (1H,
OCOCH2CHMePh + 3H, OMe), 5.21 s (1H, H7),
6.57 br.d, 6.80 br.d (2H, H5, H6, 3J 7.4), 7.02 s (1H, H3),
7.06–7.67 m, 7.80 br.d (10H, H2-6, Harom, 3J 8.4), 8.44 d
(1H, H1, 3J 7.0), 9.21 s (1H, NH). Found, %: C 79.59;
H 6.92; N 3.05. C36H35NO4. Calculated, %: C 79.24;
H 6.46; N 2.57.
spectrum, δ, ppm (J, Hz): 0.92 t [3H, OCO(CH2)8Me,
3J 4.1], 1.10 s, 1.15 s (6H, 2Me, H10), 1.20–1.49 m
[12H, OCO(CH2)2(CH2)6Me], 1.64
m
[2H,
OCOCH2CH2(CH2)6Me], 2.17 (2 br.d) (2H, H9, 2J 16.6),
2.39–2.58 br.t [2H, OCOCH2(CH2)7Me], 2.65 (2 br.d)
(2H, H11, 2J 16.3), 3.70 br.s (3H, OMe), 4.95 C (1H, H7),
3
6.60 br.d, 6.75 br.d (2H, H5, H6, J 7.1), 6.92 br.s (1H,
H3), 7.22–7.64 m, 7.80 br.d (5H, H2-6, 3J 8.0), 8.40 br.d
(1H, H1, 3J 7.6), 9.28 br.s (1H, NH). Found, %: C 78.39;
H 8.27; N 2.43. C36H43NO4. Calculated, %: C 78.09;
H 7.83; N 2.53.
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-
hexahydrobenzo[c]acridin-7-yl)-2-methoxyphenyl
methacrylate (Ve). Yield 35%, mp 226–230°C. UV
spectrum, λmax, nm (log ε): 217 (4.69), 258 (4.33), 279
(4.11), 370 (4.04). IR spectrum, cm−1: 3432 m [ν(Ν–Çfree)],
3291 s [ν(N–Hbound)], 3056 m, 3041 w [ν(C–Harom)],
2957 v.s, 2929 s, 2871 m [ν(C–Haliph.)], 1739 s
[ν(C=Oester)], 1591 v.s (O=C–C=C–N–H), 1497 v.s (Ar),
1418 m, 1385 v.s, 1376 s, 1343 w, 1321 m [δ(C–Haliph.)],
1129 v.s, 1036 s (C–O–C), 939 s [δ(=CH2)], 791 s, 766 v.s,
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[c]acridin-7-yl)-2-methoxyphenyl
benzoate (Vh). Yield 49%, mp 258–262°C. UV
spectrum, λmax, nm (log ε): 223 (4.73), 258 (4.42), 281
1
737 s [δ(C–Harom)]. H NMR spectrum, δ, ppm (J, Hz):
1.09 s, 1.15 s (6H, 2Me, H10), 1.97 s (3H, OCOCMe=CH2),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

SKATETSKII et al.
1486
(4.25), 372 (4.07). IR spectrum, cm–1: 3299 s [ν(N–
%: C 74.04; H 5.68; N 3.01. C33H28ClNO4. Calculated,
%: C 73.67; H 5.24; N 2.60.
H
bound)], 3060 m, 3037 w [ν(C–Harom)], 2954 s, 2929 s,
2869 m [ν(C–Haliph)], 1741 s [ν(C=Oester)], 1589 v.s
(O=C–C=C–N–H), 1494 v.s (Ar), 1417 m, 1384 s,
1373 s, 1344 w, 1315 w [δ(C–Haliph)], 1122 s, 1079 s,
1061 s, 1024 s (C–O–C), 710 v.s [δ (C–Harom)]. 1H NMR
spectrum, δ, ppm (J, Hz): 1.08 s, 1.13 s (6H, 2Me, H10),
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[c]acridin-7-yl)-2-methoxyphenyl
p-nitrobenzoate (Vk). Yield 34%, mp 264–266°C. UV
spectrum, λmax, nm (log ε): 217 (4.26), 260 (4.27), 370
(3.80). IR spectrum, cm−1: 3431 m [ν(Ν–Çfree)], 3324 s
[ν(N–Hbound)], 3053 m [ν(C–Harom)], 2962 s, 2922 v.s,
2866 m [ν(C–Haliph)], 1732 s [ν(C=Oester)], 1596 v.s
(O=C–C=C–N–H), 1529 v.s [ν(NO2)], 1502 v.s (Ar),
1419 m, 1408 s, 1390 v.s, 1385 v.s [δ(C–Haliph)],
1121 v.s, 1074 s, 1035 s, 1014 s (C–O–C), 714 v.s
[δ(C–Harom)]. 1H NMR spectrum, δ, ppm (J, Hz): 1.05 s,
1.14 s (6H, 2Me, H10), 2.18 (2 br.d) (2H, H9, 2J 16.8),
2
2.19 (2 br.d) (2H, H9, J 17.1), 2.70 (2 br.d) (2H, H11,
2J 16.8), 3.72 s (3H, OMe), 5.28 s (1H, H7), 6.73 br.d,
6.82 br.d (2H, H5, H6, 3J 7.0), 7.10 br.s (1H, H3), 7.23–
7.71 m, 7.80 br.d, 7.95–8.21 m (10H, H2-6, Harom, 3J 7.8),
3
8.46 d (1H, H1, J 7.4), 9.21 s (1H, NH). Found, %:
C 78.92; H 6.22; N 2.48. C33H29NO4. Calculated, %:
C 78.71; H 5.80; N 2.78.
2
2.68 (2 br.d) (2H, H11, J 16.5), 3.73 s (3H, OMe),
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[c]acridin-7-yl)-2-methoxyphenyl
p-methyl benzoate (Vi). Yield 42%, mp 140–146°C. UV
spectrum, λmax, nm (log ε): 218 (4.48), 242 (4.49), 281
(4.13), 369(3.92). IRspectrum, cm−1: 3329 s [ν(N–Hbound)],
3060 m, 3037 w [ν(C–Harom)], 2953 s, 2924 v.s, 2867 m
[ν(C–Haliph.)], 1742 s [ν(C=Oester)], 1589 v.s (O=C–C=C–
N–H), 1502 v.s (Ar), 1418 m, 1391 s, 1384 s, 1340 w,
1319 w [δ(C–Haliph)], 1123 s, 1066 s, 1018 s (C–O–C),
748 v.s [δ(C–Harom)]. 1H NMR spectrum, δ, ppm (J, Hz):
1.06 s, 1.12 s (6H, 2Me, H10), 2.17 (2 br.d) (2H, H9,
2J 16.9), 2.42 s [3H, OCO(p-Me)Ph], 2.69 (2 br.d) (2H,
H11, 2J 16.6), 3.71 s (3H, OMe), 5.24 s (1H, H7), 6.70 d,
3
5.26 s (1H, H7), 6.72 d, 6.96 d (2H, H5, H6, J 7.7),
7.12 s (1H, H3), 7.20–7.60 m, 7.77 br.d (5H, H2−6
,
3J 8.0), 8.19–8.53 m (5H, Harom, H1), 9.21 s (1H, NH).
Found, %: C 72.48; H 5.56; N 5.45. C33H28N2O6.
Calculated, %: C 72.25; H 5.14; N 5.11.
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-
hexahydrobenzo[c]acridin-7-yl)-2-methoxyphenyl m-
nitrobenzoate (Vl). Yield 48%, mp 280–284°C. UV
spectrum, λmax, nm (log å): 219 (4.62), 258 (4.26), 283
(3.95), 373 (3.74). IR spectrum, cm−1: 3425 m [ν(Ν–
Ç
H
free)], 3301 s [ν(N–H bound)], 3067 m, 3040 w [ν(C–
arom)], 2956 v.s, 2929 c, 2868 m [ν(C–Haliph)], 1746 s
3
6.87 d (2H, H5, H6, J 7.8), 7.07 br.s (1H, H3), 7.20–
[ν(C=Oester)], 1589 v.s (O=C–C=C–N–H), 1533 v.s
[ν(NO2)], 1497 v.s (Ar), 1419 m, 1391 s, 1385 s [δ(C–
−
7.65 m, 7.70–8.06 m (9H, H2 6, Harom), 8.44 br.d (1H,
H1, 3J 7.1), 9.17 s (1H, NH). Found, %: C 78.93; H 6.49;
N 3.20. C34H31NO4. Calculated, %: C 78.89; H 6.04;
N 2.71.
H
aliph)], 1125 s, 1060 s, 1032 s (C–O–C), 753 s, 718 v.s
[δ(C–Harom)]. 1H NMR spectrum, δ, ppm (J, Hz): 1.10 s,
1.17 s (6H, 2Me, H10), 2.22 (2 br.d) (2H, H9), 2.73
(2 br.d) (2H, H11), 3.76 br.s (3H, OMe), 5.30 s (1H, H7),
6.73 d, 6.98 d (2H, H5, H6, 3J 7.0), 7.15 s (1H, H3), 7.29–
7.62 m, 7.70–8.03 m (6H, H2–6, Harom), 8.31–8.67 m (3H,
H1, Harom), 8.78 br.s (1H, Harom), 9.20 s (1H, NH). Found,
%: C 72.33; H 5.45; N 4.98. C33H28N2O6. Calculated,
%: C 72.25; H 5.14; N 5.11.
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[c]acridin-7-yl)-2-methoxyphenyl
p-chlorobenzoate (Vj). Yield 74%, mp 194–198°C. UV
spectrum, λmax, nm (log ε): 219 (4.49), 242 (4.52), 283
(3.92), 372 (3.73). IR spectrum, cm−1: 3427 m [ν(Ν–Çfree)],
3342 m [ν(N–H bound)], 3066 m [ν(C–Harom)], 2955 s,
2925 v.s, 2868 m [ν(C–Haliph)], 1747 s [ν(C=Oester)],
1590 v.s (O=C–C=C–N–H), 1495 v.s (Ar), 1418 m,
1398 s, 1384 s, 1376 s, 1344 w, 1310 w [δ(C–Haliph)],
1123 s, 1091 s, 1067 s, 1013 s (C–O–C), 753 v.s
[δ(C–Harom)]. 1H NMR spectrum, δ, ppm (J, Hz): 1.08 s,
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[c]acridin-7-yl)-2-ethoxyphenyl acetate
(Vm). Yield 37%, mp 292–296°C. UV spectrum, λmax
,
nm (log ε): 223 (4.34), 264 (4.12), 282 (3.92), 378 (3.74).
IR spectrum, cm−1: 3311 s [ν(N–Hbound)], 3073 m,
3038 v.w [ν(C–H arom)], 2956 s, 2928 v.s, 2872 m [ν(C–
2
1.13 s (6H, 2Me, H10), 2.17 (2 br.d) (2H, H9, J 17.1),
2.70 (2 br.d) (2H, H11, 2J 16.8), 3.72 s (3H, OMe), 5.25 s
(1H, H7), 6.70 d, 6.91 d (2H, H5, H6, 3J 7.8), 7.09 s (1H,
H
aliph.)], 1767 s [ν(C=Oester)], 1578 v.s (O=C–C=C–N–
H), 1493 v.s (Ar), 1423 m, 1386 v.s, 1371 v.s, 1346 m
H3), 7.21–7.67 m, 7.78 br.d, 7.93–8.16 m (9H, H2-6, Harom
3J 8.5), 8.43 br.d (1H, H1, 3J 7.1), 9.18 s (1H, NH). Found,
,
[δ(C–Haliph)], 1120 s, 1041 s (C–O–C), 755 s [δ(C–
1
H
arom)]. H NMR spectrum, δ, ppm (J, Hz): 0.92–
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SYNTHESIS AND SPECTRAL CHARACTERISTICS OF 4-(10,10-DIMETHYL-...
1487
3
1.39 (2 s + t) (6H, 2Me, H10 + 3H, OCH2Me), 2.18
2J 16.7), 3.88 br.q (2H, OCH2Me, J 5.5), 5.02 s (1H,
(2 br.d) (2H, H9, 2J 17.2), 2.24 s (3H, OCOMe), 2.70
H7), 6.72 br.d, 6.87 br.d (2H, H5, H6, J 7.8), 6.98 br.s
3
(2 br.d) (2H, H11, J 16.9), 3.83 br.q (2H, OCH2Me,
(1H, H3), 7.20–7.59 m, 7.76–8.08 m (9H, H2–6, Harom),
8.42 br.d (1H, H1, 3J 7.6), 9.17 s (1H, NH). Found, %:
C 79.20; H 6.51; N 2.25. C35H33NO4. Calculated, %:
C 79.07; H 6.26; N 2.63.
2
3J 5.8), 4.94 s (1H, H7), 6.57 br.d, 6.75 br.d (2H, H5, H6,
3J 7.7), 6.90 br.s (1H, H3), 7.19–7.62 m, 7.83 br.d (5H,
H2-6, 3J 8.1), 8.40 br.d (1H, H1, 3J 7.7), 9.16 s (1H, NH).
Found, %: C 76.77; H 6.90; N 3.51. C29H29NO4.
Calculated, %: C 76.46; H 6.42; N 3.07.
REFERENCES
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[c]acridin-7-yl)-2-ethoxyphenyl benzoate
1.Delfourne, E., Roubin, C., and Bastide, J., J. Org. Chem.,
2000, vol. 65, p. 5476.
2.Antonini, J., Polucci, P., Magnano, A., and Martelli, S.,
J. Med. Chem., 2001, vol. 44, p. 3329.
3.Ferlin, M.G., Marzano, C., Chiarelotto, G., Baccichetti, F.,
and Bordin, F., Eur. J. Med. Chem., 2000, vol. 35, p. 827.
4.Blache, Y., Benezech, V., Chezal, J.-M., Boule, P.,
Viols, H., Chavignon, O., Teulade, J.-C., and Chapat, J.-P.,
Heterocycles, 2000, vol. 53, p. 905.
5.Cortés, E., Martínez, R., Avila, J.G., and Toscano, R.A.,
J. Heterocycl. Chem., 1988, vol. 25, p. 895.
6.Gauptman, Z., Grefe, Yu., and Remane, Kh., Organiche-
skaya khimiya (Organic Chemistry), Moscow: Khimiya,
1979, p. 487.
7.Hall, G.E. and Walker, J., J. Chem. Soc. C, 1986, p. 2237.
8.Dikusar, E.A. and Kozlov, N.G., Zh. Org. Khim., 2006,
vol. 42, p. 383.
9.Lielbriedis, I., Trusov, S.R., and Gudriniece, E., Latv. P.S.R,
Zinat. Akad. Vestis, Kim. Ser., 1971, p. 39.
10. Kozlov, N.G., Basalaeva, L.I., Firgang, S.I., and Shash-
kov, A.S., Zh. Org. Khim., 2004, vol. 40, p. 549.
11. Kozlov, N.G., Gusak, K.N., Tereshko, A.B., Firgang, S.I.,
and Shashkov,A.S., Zh. Org. Khim., 2004, vol. 40, p. 1228.
12. Kazitsyna, L.A. and Kupletskaya, N.B., Primenenie UF-,
IK-, YaMR- i mass-spektroskopii v organicheskoi khimii
(Application of UV, IR, NMR and Mass Spectroscopy in
Organic Chemistry), Moscow: Izd. Moskov. Gos. Univ.,
1979, p. 77.
13. Greenhill, J.V., Chem. Soc. Rev., 1977, vol. 6, p. 277.
14. Dyer, J.R., Applications of Absorption Spectroscopy of
Organic Compounds, Englewood Cliffs: Prentice Hall,
1965.
(Vn). Yield 33%, mp 302–306°C. UV spectrum, λmax
,
nm (log ε): 227 (4.66), 265 (4.36), 286 (4.15), 376 (3.94).
IR spectrum, cm−1: 3426 m [ν(Ν–Hfree)], 3297 s [ν(N–
Hbound)], 3070 m, 3037 w [ν(C–Harom)], 2955 s,
2929 v.s, 2871 m [ν(C–Haliph)], 1740 s [ν(C=Oester)], 1581
v.s (O=C–C=C–N–H), 1495 v.s (Ar), 1422 w, 1401 s,
1373 v.s, 1344 m, 1313 m [δ(C–Haliph)], 1120 s, 1079 s,
1061 s, 1024 s (C–O–C), 706 v.s [δ(C–Harom)]. 1H NMR
spectrum, δ, ppm (J, Hz): 0.90–1.32 (2 s + t) (6H, 2Me,
2
H10 + 3H, OCH2Me), 2.17 (2 br.d) (2H, H9, J 16.9),
2.72 (2 br.d) (2H, H11, 2J 16.6), 3.88 br.q (2H, OCH2Me,
3J 6.2), 5.01 s (1H, H7), 6.67 d, 6.79 d (2H, H5, H6,
3J 7.1), 6.97 br.s (1H, H3), 7.30–7.73 m, 7.84 br.d, 7.94–
3
8.18 m (10H, H2−6, Harom, J 7.7), 8.42 d (1H, H1,
3J 7.8), 9.19 s (1H, NH). Found, %: C 79.25; H 6.44;
N 3.19. C34H31NO4. Calculated, %: C 78.89; H 6.04;
N 2.71.
4-(10,10-Dimethyl-8-oxo-7,8,9,10,11,12-hexa-
hydrobenzo[C]acridin-7-yl)-2-ethoxyphenyl
p-methylbenzoate (Vo). Yield 40%, mp 294–296°C.
UV spectrum, λmax, nm (log å): 221 (4.62), 239 (4.68),
283 (4.22), 378 (3.87). IR spectrum, cm−1: 3307 s [ν(N–
Hbound)], 3068 m, 3038 w [ν(C–Harom)], 2955 s, 2927 v.s,
2871 m [ν(C–Haliph)], 1739 s [ν(C=Oester)], 1579 v.s
(O=C–C=C–N–H), 1495 v.s (Ar), 1425 w, 1401 s, 1385 s,
1373 v.s, 1345 m, 1314 m [δ(C–Haliph.)], 1122 s 1069 s,
1
1019 s (C–O–C), 747 v.s [δ(C–Harom)]. H NMR
spectrum, δ, ppm (J, Hz): 0.87–1.32 (2 s + t) (6H, 2Me,
2
H10 + 3H, OCH2Me), 2.17 (2 br.d) (2H, H9, J 17.0),
15. Doncket, E.V., Martin, R.H., and Geerts-Evrard, F.,
Tetrahedron, 1964, vol. 20, p. 1495.
2.45 s [3H, OCO(p-Me)Ph], 2.71 (2 br.d) (2H, H11,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007