Spirocyclohexadienones: XIII.* Reactions of schiff bases with enamines derived from 3,4-Dihydroisoquinoline and with Spiro[naphthalene-1,3'- pyrrol]-4-one

Article abstract of DOI:10.1134/S1070428012040197

Addition of 1,3,3-trimethyl-3,4-dihydroisoquinolines to N-benzylideneanilines gives substituted N-[2-(3,3-dimethyl-3,4- dihydroisoquinolin-1-yl)-1-phenylethyl]anilines, whereas 2',5',5'-trimethyl-4', 5'-dihydro- 4H-spiro[naphthalene-1,3'-pyrrol]-4-one reacts with N-benzylideneanilines along two pathways involving cyclization to substituted 2,3,3a,4,10,11-hexahydrobenzo[f]pyrrolo[2,3-d]quinolin-5(1H)-ones or elimination of the aniline residue with formation of substituted 5',5'-trimethyl-2-styryl- 4',5'-dihydro-4H-spiro[naphthalene-1,3'-pyrrol]-4-ones. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012040197

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 4, pp. 575–581. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © V.A. Glushkov, G.F. Krainova, O.A. Maiorova, V.I. Karmanov, A.A. Gorbunov, P.A. Slepukhin, 2012, published in Zhurnal
Organicheskoi Khimii, 2012, Vol. 48, No. 4, pp. 577–583.
Spirocyclohexadienones: XIII.* Reactions of Schiff Bases
with Enamines Derived from 3,4-Dihydroisoquinoline
and with Spiro[naphthalene-1,3′-pyrrol]-4-one
V. A. Glushkova, G. F. Krainovaa, O. A. Maiorovaa, V. I. Karmanova,
A. A. Gorbunova, and P. A. Slepukhinb
a Institute of Technical Chemistry, Ural Division, Russian Academy of Sciences,
ul. Akademika Koroleva 3, Perm, 614013 Russia
e-mail: glusha55@gmail.com
b Postovskii Institute of Organic Synthesis, Ural Division, Russian Academy of Sciences,
ul. Akademicheskaya/S. Kovalevskoi 22/20, Yekaterinburg, 620990 Russia
Received May 24, 2011
Abstract—Addition of 1,3,3-trimethyl-3,4-dihydroisoquinolines to N-benzylideneanilines gives substituted
N-[2-(3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-1-phenylethyl]anilines, whereas 2′,5′,5′-trimethyl-4′,5′-dihy-
dro-4H-spiro[naphthalene-1,3′-pyrrol]-4-one reacts with N-benzylideneanilines along two pathways involving
cyclization to substituted 2,3,3a,4,10,11-hexahydrobenzo[f]pyrrolo[2,3-d]quinolin-5(1H)-ones or elimination of
the aniline residue with formation of substituted 5′,5′-trimethyl-2-styryl-4′,5′-dihydro-4H-spiro[naphthalene-
1,3′-pyrrol]-4-ones.
DOI: 10.1134/S1070428012040197
It is known that Schiff bases act as electrophiles. In
the presence of Lewis or Brønsted acids Schiff bases
are capable of reacting with cyclic enol ethers [2],
phenols, anisoles [3], thiophenes [4], and indoles [5]
according to Friedel–Crafts. Addition of N-benzyli-
deneaniline to electron-rich olefins, such as alkyl vinyl
ethers, alkynes, 1,2-dihydrofuran, 1,2-dihydropyran,
cyclopentadiene, indene, and N-vinylpyrrolidone is
followed by cyclization to afford 1,2,3,4-tetrahydro-
quinoline derivatives (Povarov reaction [6]). Povarov
reaction of classical enamines obtained from secondary
amines (pyrrolidine, piperidine, morpholine) was
studied in the end of the past century [7, 8], and the
reaction was shown to occur both with conservation of
the amine residue in the resulting 1,2,3,4-tetrahydro-
quinoline molecule [7] and with elimination of this
fragment [8]. There are no published data on Povarov
reaction with 3,3-dimethyl-3,4-dihydroisoquinoline
[9, 10] or spiro[naphthalene-1,3′-pyrrol]-4-one deriva-
tives [11] as enamines (it is known that 1,3,3-tri-
methyl-3,4-dihydroisoquinoline behaves as typical
enamine [12]). The goal of the present work was to
study the reactions of Schiff bases with substituted
1,3,3-dimethyl-3,4-dihydroisoquinolines and
Scheme 1.
Me
Me
MeO
MeO
Me
MeO
MeO
N
Ar
N
Me
AcOH
+
H
N
N
Me
Ar
IIIa–IIId
Ia
IIa–IId
II, III, Ar = Ph (a), 4-ClC6H4 (b), 4-BrC6H4 (c), 2-thienyl (d).
* For communication XII, see [1].
575

GLUSHKOV et al.
576
Scheme 2.
2
3
O1
4 O
Me
Me
10
8
O
O
N
Ph
Ph
5
NH
AcOH
+
9
N
6
R
Me
N
Me
R
Me
Ib
IIa, IIe
IIIe, IIIf
IIe, R = O2N; III, R = O2N (e), H (f).
2′,5′,5′-trimethyl-4′,5′-dihydro-4H-spiro[naphthalene-
1,3′-pyrrol]-4-one.
(pKa 4.76). It is capable of protonating the nitrogen
atom in N-benzylideneaniline to enhance electro-
philicity of the C=N carbon atom which undergoes
nucleophilic attack by enamine. When the reaction was
carried out in acetonitrile in the presence of a catalytic
amount of CF3COOH or InCl3, we obtained cinnamo-
nitrile whose formation may be interpreted as electro-
philic attack by the Schiff base on acetonitrile mole-
cule, followed by elimination of the amine residue.
Analogous reactions where Schiff base acts as alkylat-
ing agent (aldehyde group carrier) have been reported
in the literature [14].
We initially planned to perform cyclization of
enamines with Schiff bases in a way similar to the
Povarov reaction with N-vinylpyrrolidin-2-one [13]
with a view to obtain spirocyclic compounds. How-
ever, we found that the reaction with enamines of the
6,7-dimethoxy-3,4-dihydroisoquinoline series does not
involve cyclization but stops at the stage of addition of
the Schiff base to the enamine (Scheme 1). This
1
followed from the H NMR spectrum of IIIa, which
showed no splitting of signals from protons in the two
methyl groups and from diastereotopic methylene
protons (C4H2) in the isoquinoline ring (δ ~2.5 ppm);
such splitting should be observed in the spectrum of
cyclic structure with asymmetric spiro carbon atom.
Like enamine Ia, 6,7-ethylenedioxy-1,3,4-trimeth-
yl-3,4-dihydroisoquinoline (Ib) reacted with Schiff
bases IIa and IIe to afford the corresponding
N-[2-(8,8-dimethyl-2,3,8,9-tetrahydro[1,4]dioxino-
[2,3-g]isoquinolin-6-yl)-1-phenylethyl]anilines IIIe
and IIIf (Scheme 2). Compounds IIIa–IIId and IIIf
Our preliminary experiments showed that the
optimal solvent for this reaction is glacial acetic acid
Scheme 3.
O
O
R
AcOH
+
IIa, IIc, IIe–IIg
Me
HN
N
N
Me
R'
Me
Me
IV
Me
Va–Ve
O
O
6
5
5
4
R'
6
7
4
3
2
3a
1
R
N3
9
10
11
8
Me
Me
+
5'
2'
2
N 3'
N
1
4'
Me
Me
R
VIa–VIe
VIIa–VIIc
II, R = F (f), Br (g); V, VI, R = R′ = H (a); R = H, R′ = F (b), Br (c); R = Br, R′ = H (d); R = O2N, R′ = H (e);
VII, R = H (a), Br (b), O2N (c).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

SPIROCYCLOHEXADIENONES: XIII.
are light yellow or yellow (IIIe) thick oily liquids or
577
O1
C3
amorphous substances; they are formed as racemates.
The IR spectra of these compounds contain absorption
bands due to stretching vibrations of the NH (3320–
3370 cm–1), C=C (1600–1604 cm–1), C–O–Casym
(1270 cm–1), and C–O–Csym bonds (1050–1070 cm–1).
Compounds IIIa–IIIf characteristically displayed in
C5
C6
C4
C2
C1
C9
C7
C19
1
the H NMR spectra doublets of doublets from dia-
C18
C8
C20
C21
stereotopic CH2C=N protons in the regions δ 2.7–2.8
and 3.1–3.2 ppm; the CHN proton resonated as a dou-
blet of doublets at δ 4.4–4.5 ppm (ABX spin system),
and the NH signal appeared as a broadened singlet at
δ 4.7–5.4 ppm. Treatment of IIIa–IIIf with a solution
of 2,4,6-trinitrophenol in diethyl ether resulted in the
formation of bright yellow crystalline picrates (1:1).
C13
C14
C15
C10
C17
C11
C12
C22
C16
N1
C23
2′,5′,5′-Trimethyl-4′,5′-dihydro-4H-spiro[naphtha-
lene-1,3′-pyrrol]-4-one (IV) [11] behaved differently in
the reaction under study. Initially, as in the above
cases, enamine IV adds at the electrophilic carbon atom
of the Schiff base with formation of 2′-[2-(4-aryl-
amino)-2-phenylethyl]-5′,5′-dimethyl-4′,5′-dihydro-
4H-spiro[naphthalene-1,3′-pyrrol]-4-ones Va–Ve
which cannot be isolated as individual substances; they
undergo further transformations along two independent
pathways. Intramolecular Michael adducts VIa–VIe,
hydrogenated benzo[f]pyrrolo[2,3-d]quinoline deriva-
tives, were formed in 10–40% yields, but the main
reaction pathway was elimination of aniline (or substi-
tuted aniline) from adducts Va–Ve with formation of
styrenes VIIa–VIIc in 45–76% yields (Scheme 3). We
failed to isolate analytically pure compound VIe; its
presence in the reaction mixture (~11%) was con-
firmed only by the GC–MS data (m/z 465.2 [M]+·).
Structure of the molecule of (E)-5′,5′-dimethyl-2′-styryl-
4′,5′-dihydro-4H-spiro[naphthalene-1,3′-pyrrol]-4-one (VIIa)
according to the X-ray diffraction data.
tively), and appearance of two additional doublets of
doublets due to diastereotopic methylene protons on C4
at δ 2.02 and 2.58 ppm (e.g., in the spectrum of VId)
and a multiplet signal at δ 3.54 ppm (3a-H). In the
13C NMR spectrum of VId, recorded with the use of
DEPT pulse sequence, we observed the C4′H2 signal at
δ 49.9 ppm and two signals at δ 38.71 and 39.96 ppm,
belonging to CH2 protons. These data are consistent
with the assumed structure of compounds VI. Unlike
styrenes VIIa–VIIc whose molecular ions are un-
stable, compounds VIa–VIe clearly displayed in the
mass spectra the molecular ion peaks which had the
maximal intensity (Irel 100%).
Styrenes VIIa–VIIc were isolated as colorless crys-
talline substances. They were formed exclusively as
trans isomers, as followed from the large coupling
constant for the vinyl protons (J = 16.5 Hz). Three
adducts Va–Vc gave rise to the same spiro styrene
VIIa. We succeeded in obtaining a single crystal for
one enantiomer of VIIa, and its structure was deter-
mined by X-ray analysis (see figure). The spiro-fused
dihydropyrrole fragment is turned through a dihedral
angle of ~90° with respect to the naphthalene ring
plane, and the styrene fragment has trans con-
figuration.
The steric structure of tricyclic benzo[f]pyrrolo-
[2,3-d]quinolines VIa–VId containing asymmetric
carbon atoms (C2, C3a, and C9b) was not determined.
They were isolated as thick yellow oily liquids or light
yellow crystalline substances. The IR spectra of VIa–
VId contained absorption bands due to stretching vi-
brations of the C=O (1710–1720 cm–1) and C=C bonds
1
(1597–1601 cm–1). In the H NMR spectra of these
compounds diastereotopic methyl groups gave two
singlets at δ ~1.5 ppm; protons in the CH2 group of the
dihydropyrrole ring appeared as two doublets in the
region δ 2.3–2.5 ppm, J = 14.1–14.5 Hz; the 2-H
signal was a multiplet at δ 4.09–4.15 ppm. The forma-
tion of cyclization products VIa–VId follows from
disappearance of IR bands and 1H NMR signals typical
of NH group, disappearance of two doublets from
olefinic protons in spiro[naphthalene-1,3′-pyrrol]-4-
one at δ ~6.4 and 7.0 ppm (3-H and 2-H, respec-
EXPERIMENTAL
The IR spectra were recorded on a Bruker IFS 66ps
spectrometer with Fourier transform from samples
dispersed in mineral oil or thin films prepared by
evaporation of solutions in chloroform. The NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

GLUSHKOV et al.
578
spectra were recorded from solutions in CDCl3 on
a Varian Mercury Plus 300 instrument at 300 (1H) and
75 MHz (13C). The progress of reactions and the purity
of products were monitored by TLC on Sorbfil plates.
The Rf values were determined using chloroform–
acetone (10:1 by volume; compounds IIIa–IIIf) and
hexane–ethyl acetate (1:1; VIa–VIe, VIIa–VIIc) as
eluents. Spots were visualized by UV irradiation.
Column chromatography was performed on silica gel
(Lancaster, 0.035–0.07 mm); compounds IIIa–IIIf
were isolated by elution with chloroform and chloro-
form–acetone (10:1) with addition of 1 vol % of tri-
ethylamine; compounds VIa–VIe and VIIa–VIIc were
isolated by elution with petroleum ether (bp 40–
70°C)–ethyl acetate (10:1 to 5:1, by volume). The
mass spectra (electron impact, 70 eV) were obtained
on an Agilent 6890N instrument with an HP 5975B
mass-selective detector. The elemental compositions
were determined on a Leco CHNS 9321P analyzer.
The melting points were measured on an OptiMelt
MPA100 melting point apparatus (Stanford Research
Systems, USA); heating rate 1 deg/min.
spectrum, δ, ppm: 1.12 s and 1.18 s (3H each, Me),
2.50 s (2H, 4-H), 2.79 d.d (1H, CH2C=N, J = 12.5, J =
9.6 Hz), 3.17 d.d (1H, CH2C=N, J = 12.5, J = 3.6 Hz),
3.81 s and 3.82 s (3H each, OMe), 4.48 d.d (1H,
CHNH, J = 9.6, J = 3.6 Hz), 5.36 br.s (1H, NH), 6.36 d
(1H, Harom), 6.54 s (1H, 5-H), 6.95 s (1H, 8-H), 7.03–
7.49 m (9H, Harom). Found, %: C 76.81; H 7.01;
N 5.89. C27H27N3O4. Calculated, %: C 78.23; H 7.29;
N 6.76. By mixing equimolar amounts of compound
IIIa and picric acid in diethyl ether we obtained the
corresponding picrate; yellow powder, mp 96–98°C.
Found, %: C 59.88; H 4.68; N 9.87. C27H30N2O2 ·
C6H3N3O7. Calculated, %: C 61.58; H 5.17; N 10.88.
N-[1-(4-Chlorophenyl)-2-(6,7-dimethoxy-3,3-di-
methyl-3,4-dihydroisoquinolin-1-yl)ethyl]aniline
(IIIb) was synthesized from 0.93 g (4 mmol) of com-
pound Ia and 0.91 g (4 mmol) of N-(4-chlorobenzyli-
dene)aniline in 20 ml of acetic acid. Yield 0.25 g
(14%), yellow oily liquid, Rf 0.33. IR spectrum (film),
ν, cm–1: 3302 (NH), 2962, 2929, 1602, 1507, 1458,
1
1358, 1274, 1142, 1090, 828, 755. H NMR spectrum,
δ, ppm: 1.23 s (6H, Me), 2.64 s (2H, 4-H), 2.90 m (1H,
CH2C=N), 3.18 d.d (1H, CH2, J = 12.3, J = 3.6 Hz),
3.87 s and 3.92 s (3H each, OMe), 4.56 d.d (1H,
CHNH, J = 9.6, J = 3.6 Hz), 5.40 br.s (1H, NH), 6.69 s
(1H, 5-H), 7.12–7.33 m (5H, Ph), 7.37 d (2H, 2′-H,
6′-H, J = 8.7 Hz), 7.77 d (2H, 3′-H, 5′-H, J = 8.7 Hz),
8.35 s (1H, 8-H). Found, %: C 72.15; H 6.68; N 6.20.
C27H29ClN2O2. Calculated, %: C 72.23; H 6.51;
N 6.24. Picrate (hydrate): yellow powder, mp 112–
115°C. Found, %: C 56.34; H 4.58; N 9.98.
C27H29ClN2O2·C6H3N3O7·H2O. Calculated, %:
C 56.94; H 5.06; N 10.06.
Schiff bases IIa–IIf were synthesized by heating
equimolar amounts of the corresponding aldehyde and
aniline in boiling ethanol over a period of 1–2 h [15]
and were purified by double recrystallization from
ethanol. Compound IId at room temperature was
an oily substance.
Compounds IIIa–IIIf, VIa–VId, and VIIa–VIIc
(general procedure). Enamine Ia [9], Ib [10], or IV
[11], 10 mmol, and Schiff base IIa–IIf, 10 mmol, were
dissolved in 50 ml of glacial acetic acid, and the
mixture was stirred for 24 h at room temperature. The
mixture was diluted with 150 ml of water, treated with
25% aqueous ammonia to pH 8, and extracted with
ethyl acetate (2×100 ml), the extract was washed with
a saturated aqueous solution of sodium chloride and
dried over MgSO4, the solvent was distilled off, and
the residue was subjected to column chromatography.
N-[1-(4-Bromophenyl)-2-(6,7-dimethoxy-3,3-di-
methyl-3,4-dihydroisoquinolin-1-yl)ethyl]aniline
(IIIc) was synthesized from 1.16 g (5 mmol) of com-
pound Ia and 1.32 g (5 mmol) of N-(4-bromobenzyli-
dene)aniline in 20 ml of acetic acid. Yield 0.31 g
(12%), yellow oily liquid, Rf 0.42. IR spectrum (film),
ν, cm–1: 3372 (NH), 1662, 1604 (C=C), 1568, 1528,
1514 (C=C), 1464, 1404, 1380, 1352, 1324, 1272
(C–O–Casym), 1232, 1210, 1174, 1144, 1096, 1072,
1052 (C–O–Csym), 1028, 1010, 984, 870, 816. 1H NMR
spectrum, δ, ppm: 1.11 s and 1.19 s (3H each, Me),
2.48 s (2H, 4-H), 2.79 d.d (1H, CH2, J = 9.0, J =
13.8 Hz), 3.11 d.d (1H, CH2, J = 4.2, J = 13.8 Hz),
3.79 s and 3.82 s (3H each, OMe), 4.47 d.d (1H,
CHNH, J = 4.2, J = 9.0 Hz), 5.39 br.s (1H, NH),
6.34 d.d (1Harom, J = 9.0, J = 1.2 Hz), 6.53 s (1H, 5-H),
6.55–6.70 m (1H, Harom), 6.82 s (1H, 8-H), 6.92–
7.17 m (3H, Harom), 7.22 d (2H, 2′-H, 6′-H, J = 9.0 Hz),
N-[2-(6,7-Dimethoxy-3,3-dimethyl-3,4-dihydro-
isoquinolin-1-yl)-1-phenylethyl]aniline (IIIa) was
synthesized from 1.28 g (5.5 mmol) of 6,7-dimethoxy-
1,3,3-trimethyl-3,4-dihydroisoquinoline (Ia) [9] and
0.99 g (5.5 mmol) of N-benzylideneaniline in 20 ml of
acetic acid. Yield 0.45 g (20%), yellow viscous oily
substance which gradually crystallized to a caramel-
like material, Rf 0.40. IR spectrum (film), ν, cm–1:
3320 (NH), 1604 (C=C), 1568, 1514 (C=C), 1464,
1404, 1380, 1352, 1322, 1272 (C–O–Casym), 1232,
1
1210, 1244, 1054 (C–O–Csym), 1028, 862. H NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

SPIROCYCLOHEXADIENONES: XIII.
579
7.35 d (2H, 3′-H, 5′-H, J = 9.0 Hz). Found, %:
C 64.19; H 5.88; N 5.20. C27H29BrN2O2. Calculated,
%: C 65.72; H 5.92; N 5.68. Picrate (hydrate): yellow
powder, mp 106–109°C. Found, %: C 53.05; H 4.62;
N 8.94. C27H29BrN2O2·C6H3N3O7·H2O. Calculated,
%: C 53.52; H 4.63; N 9.46.
13.5, J = 3.6 Hz), 4.21 s (4H, OCH2), 4.44 d.d (1H,
CHNH, J = 13.5, J = 3.6 Hz), 5.20 br.s (1H, NH),
6.35 d (2H, Harom, J = 7.8 Hz), 6.51 t (1H, Harom, J =
7.5 Hz), 6.54 s (1H, 10-H), 6.94 t (2H, Harom, J =
7.8 Hz), 7.01 s (1H, 5-H), 7.18 t (1H, Harom, J =
6.9 Hz), 7.26 t (2H, Harom, J = 6.9 Hz), 7.40 d (2H,
Harom, J = 7.5 Hz). Found, %: C 78.46; H 6.90; N 6.57.
C27H28N2O2. Calculated, %: C 78.61; H 6.84; N 6.79.
Hydrochloride hydrate: light green powder, mp 208–
213°C (decomp., from acetone). Found, %: C 68.12;
H 5.77; N 5.48. C27H28N2O2·HCl·H2O. Calculated, %:
C 69.44; H 6.69; N 6.00.
N-[2-(6,7-Dimethoxy-3,3-dimethyl-3,4-dihydro-
isoquinolin-1-yl)-1-(2-thienyl)ethyl]aniline (IIId)
was synthesized from 0.74 g (3.2 mmol) of compound
Ia and 0.60 g (3.2 mmol) of N-(2-thienylmethylidene)-
aniline in 20 ml of acetic acid. Yield 0.30 g (22%),
yellow oily liquid, Rf 0.51. IR spectrum (mineral oil),
ν, cm–1: 3340 (NH), 1724, 1600 (C=C), 1500 (C=C),
1344, 1302, 1276 (C–O–Casym), 1156, 1070, 1064
11,11-Dimethyl-2,3-diphenyl-2,3,3a,4,10,11-hexa-
hydrobenzo[f]pyrrolo[2,3-d]quinolin-5(1H)-one
(VIa). Yield 10%, yellow oily substance, Rf 0.37. IR
spectrum (film), ν, cm–1: 3021, 2967, 1661 (C=O),
1598 (C=C), 1500, 1451, 1355, 1297, 1220, 1170, 970,
757, 699. 1H NMR spectrum, δ, ppm: 1.47 s and 1.55 s
(3H each, Me), 2.09 d and 2.29 d (1H each, 4-H, J =
13.8 Hz), 2.34 d (1H, 10-H, J = 14.1 Hz), 2.49 d (1H,
10-H, J = 14.1 Hz), 2.62–2.83 m (2H, 1-H), 3.58 m
(1H, 3a-H), 4.16 m (1H, 2-H), 6.82–7.23 m (10H, Ph),
7.44 m (1H, Harom), 7.57 m (1H, Harom), 7.64 m (1H,
Harom), 8.20 m (1H, Harom). Mass spectrum: m/z 420.3
[M]+·. Found, %: C 82.46; H 6.92; N 6.45. C29H28N2O.
Calculated, %: C 82.82; H 6.71; N 6.66. M 420.55.
1
(C–O–Csym), 1044, 946. H NMR spectrum, δ, ppm:
1.21 s (6H, Me), 2.56 s (2H, 4-H), 3.15 m (1H, CH2),
3.59 m (1H, CH2), 3.84 s and 3.88 s (3H each, OMe),
4.69 br.s (1H, NH), 5.36 m (1H, CHNH), 6.64 s (1H,
5-H), 7.05 s (1H, 8-H), 6.30–7.50 m (6H, Harom),
8.07 m (1H, Harom), 8.13 m (1H, Harom). Found, %:
C 70.96; H 6.80; N 6.53. C25H28N2O2S. Calculated, %:
C 71.40; H 6.71; N 6.66.
N-[2-(8,8-Dimethyl-2,3,8,9-tetrahydro[1,4]di-
oxino[2,3-g]isoquinolin-6-yl)-1-(4-nitrophenyl)-
ethyl]aniline (IIIe) was synthesized from 0.57 g
(3 mmol) of compound Ib and 0.68 g (3 mmol) of
N-(4-nitrobenzylidene)aniline in 15 ml of acetic acid.
Yield 0.17 g (12%), yellow powder, mp 126–130°C,
Rf 0.54. IR spectrum (film), ν, cm–1: 3386 (NH), 2931,
2876, 1605, 1566, 1516, 1341, 1180, 1067, 856, 754.
1H NMR spectrum, δ, ppm: 1.18 s (6H, Me), 2.46 s
(2H, 9-H), 2.80 m (1H, N=CCH2), 3.13 d.d (1H,
N=CCH2, J = 14.5, J = 3.6 Hz), 4.21 m (4H, OCH2),
4.61 d.d (1H, CHNH, J = 9.6, J = 3.6 Hz), 5.40 br.s
(1H, NH), 6.20–7.60 m (9H, Harom), 8.10 d (2H, 3′-H,
5-H, J = 8.1 Hz). Found, %: C 70.79; H 5.77; N 9.14.
C27H27N3O4. Calculated, %: C 70.88; H 5.95; N 9.18.
3-(4-Fluorophenyl)-11,11-dimethyl-2-phenyl-
2,3,3a,4,10,11-hexahydrobenzo[f]pyrrolo[2,3-d]-
quinolin-5(1H)-one (VIb). Yield 40%, yellow oily
1
substance, Rf 0.36. H NMR spectrum, δ, ppm: 1.46 s
and 1.53 s (3H each, Me), 2.09 d and 2.29 d (1H each,
4-H, J = 13.8 Hz), 2.35 d and 2.49 d (1H each, 10-H,
J = 14.4 Hz), 2.68 m (2H, 1-H), 3.53 m (1H, 3a-H),
4.09 m (1H, 2-H), 6.58 m (2H, Harom), 6.96 m (2H,
Harom), 7.14–7.22 m (6H, Harom), 7.44 m (1H, Harom),
7.63 m (1H, Harom), 8.15 m (1H, Harom). Mass spec-
trum: m/z 438.3 [M]+·. Found, %: C 78.66; H 5.90;
N 6.27. C29H27FN2O. Calculated, %: C 79.43; H 6.21;
N 6.39. M 438.51.
N-[2-(8,8-Dimethyl-2,3,8,9-tetrahydro[1,4]di-
oxino[2,3-g]isoquinolin-6-yl)-1-phenylethyl]aniline
(IIIf) was synthesized from 0.36 g (2 mmol) of
6,8,8-trimethyl-2,3,8,9-tetrahydro[1,4]dioxino[2,3-g]-
isoquinoline (Ib) [10] and 0.36 g (2 mmol) of N-(ben-
zylidene)aniline in 10 ml of glacial acetic acid. Yield
0.35 g (45%), mp 98–100°C, light yellow crystals,
Rf 0.68. IR spectrum (mineral oil), ν, cm–1: 3360 (NH),
1668, 1600 (C=C), 1572, 1516 (C=C), 1502, 1358,
1330, 1304, 1258 (C–O–Casym), 1208, 1188, 1146,
3-(4-Bromophenyl)-11,11-dimethyl-2-phenyl-
2,3,3a,4,10,11-hexahydrobenzo[f]pyrrolo[2,3-d]-
quinolin-5(1H)-one (VIc). Yield 17%, light yellow
1
oily substance, Rf 0.31. H NMR spectrum, δ, ppm:
1.46 s and 1.53 s (3H each, Me), 2.08 m and 2.29 m
(1H each, 4-H), 2.35 d and 2.49 d (1H each, 10-H, J =
14.1 Hz), 2.59–2.78 m (2H, 1-H), 3.55 m (1H, 3a-H),
4.13 m (1H, 2-H), 6.72 d (2H, 3′-H, 5′-H, J = 8.7 Hz),
6.80 m (1H, Harom), 6.98–7.17 m (6H, Harom), 7.31 m
(1H, Harom), 7.45 m (1H, Harom), 7.63 m (1H, Harom),
8.16 m (1H, Harom). Mass spectrum: m/z 498.1 [M]+·.
1
1068 (C–O–Csym), 930, 898, 880. H NMR spectrum,
δ, ppm: 1.11 s and 1.18 s (3H, Me), 2.44 s (2H, 9-H),
2.69 m (1H, CH2C=N), 3.15 d.d (1H, CH2C=N, J =
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

GLUSHKOV et al.
580
Found, %: C 68.90; H 5.63; N 5.48. C29H27BrN2O.
Calculated, %: C 69.74; H 5.45; N 5.61. M 499.44.
0.20×0.15 mm. C23H21NO. Unit cell parameters: a =
7.9620(9), b = 10.4645(18), c = 11.3743(15) Å; α =
88.084(12), β = 88.008(10), γ = 72.587(12)°; V =
903.4(2) Å3; triclinic crystal system, space group P-1;
Z = 2; dcalc = 1.204 g/cm3. Total of 6334 reflection
intensities were measured, 5164 of which were inde-
pendent (Rint = 0.0142). Completeness 98.0% for
θ < 26.0°. Absorption by the crystal was not taken into
account because of its insignificance (μ = 0.073 mm–1).
The structure was solved by the direct method and was
refined by the least squares procedure in anisotropic
(isotropic for hydrogen atoms) approximation using
SHELXTL-97 software package [16]. The positions of
hydrogen atoms were calculated on the basis of
geometry considerations according to the riding model.
The final divergence factors were wR2 = 0.1033, R1 =
0.0414 for 2926 reflections with I > 2σ(I) and wR2 =
0.1124, R1 = 0.0819 for all reflections; goodness of fit
S = 1.006. The maximal and minimal residual electron
densities were 0.194 and –0.172 e/Å3, respectively.
2-(4-Bromophenyl)-11,11-dimethyl-3-phenyl-
2,3,3a,4,10,11-hexahydrobenzo[f]pyrrolo[2,3-d]-
quinolin-5(1H)-one (VId). Yield 16%, colorless crys-
tals, mp 171–173°C (from hexane–CH2Cl2), Rf 0.25.
IR spectrum (film), ν, cm–1: 2967, 2876, 1661 (C=O),
1594 (C=C), 1485, 1453, 1394, 1301, 1218, 1170,
1072, 790, 814, 760. 1H NMR spectrum, δ, ppm: 1.44 s
and 1.51 s (3H each, Me), 2.02 m (1H, 4-Hax), 2.06 d
and 2.27 d (1H each, 4′-H, J = 13.8 Hz), 2.54–2.72 m
(3H, 4-Heq, 1-H), 3.54 m (1H, 3a-H), 4.11 d.d (1H,
2-H, J = 11.4, 3.6 Hz), 6.71 d (2H, 3′-H, 5′-H, J =
8.4 Hz), 6.82 m (1H, Harom), 6.96 m (1H, Harom), 7.05 d
(2H, 2′-H, 6′-H, J = 8.4 Hz), 7.07 m (2H, Harom),
7.26 m (1H, Harom), 7.43 d.d (1H, 7-H, J = 7.8, 1.2 Hz),
7.49 d.d (1H, 9-H, J = 7.8, 1.2 Hz), 7.62 d.d (1H, 8-H,
J = 7.8, 1.5 Hz), 8.15 d.d (1H, 6-H, J = 7.8, 1.5 Hz).
13C NMR spectrum, δC, ppm: 30.22, 32.34, 38.71,
39.95, 49.91, 61.16, 69.32, 70.40, 72.47, 120.70,
126.53, 126.77, 127.21, 127.37, 128.87, 129.41,
131.03, 131.34, 134.76, 140.85, 145.47, 147.58,
172.12, 195.26. Mass spectrum: m/z 498.1 [M]+·.
Found, %: C 69.46; H 5.53; N 5.47. C29H27BrN2O.
Calculated, %: C 69.74; H 5.45; N 5.61. M 499.44.
(E)-2′-(4-Bromostyryl)-5′,5′-dimethyl-4′,5′-di-
hydro-4H-spiro[naphthalene-1,3′-pyrrol]-4-one
(VIIb). Yield 32%, colorless crystals, mp 169.4°C,
Rf 0.45. IR spectrum (film), ν, cm–1: 2966, 2823, 1685
(C=O), 1596 (C=C), 1488, 1349, 1290, 1221, 1070,
1010, 824, 757, 701. 1H NMR spectrum, δ, ppm: 1.50 s
and 1.60 s (3H each, Me), 2.35 d and 2.49 d (1H each,
4′-H, J = 13.8 Hz), 6.32 d (1H, trans-CH=, J =
16.5 Hz), 6.52 d (1H, 3-H, J = 10.5 Hz), 6.78 d (1H,
trans-CH=, J = 16.5 Hz), 7.00 m (3H, 2-H, 3′-H, 5′-H),
7.22 d (1H, 8-H, J = 7.5 Hz), 7.31 d (2H, 2′-H, 6′-H,
(E)-5′,5′-Dimethyl-2′-styryl-4′,5′-dihydro-4H-
spiro[naphthalene-1,3′-pyrrol]-4-one (VIIa). Yield
76 (from VIa), 60 (from VIb), 45% (from VIc).
Colorless crystals, mp 150.9°C, Rf 0.46. IR spectrum,
ν, cm–1: 1658 (C=O), 1631 (C=N), 1597, 1588, 1450,
1305, 1271, 1174, 1073, 969, 772, 753. 1H NMR spec-
trum, δ, ppm: 1.51 s and 1.60 s (3H each, Me), 2.35 d
and 2.49 d (1H each, 4′-H, J = 14.4 Hz), 6.36 d (1H,
trans-CH=, J = 16.5 Hz), 6.52 d (1H, 3-H, J = 9.9 Hz),
6.82 d (1H, trans-CH=, J = 16.5 Hz), 7.01 d (1H, 2-H,
J = 9.9 Hz), 7.14–7.25 m (6H, Harom), 7.42 d.d and
3
J = 8.4 Hz), 7.42 d.d (pseudotriplet, 1H, 6-H, J =
7.8 Hz), 7.57 d.d (pseudotriplet, 1H, 7-H, 3J = 7.8 Hz),
3
13
8.22 d (1H, 5-H, J = 8.4 Hz). C NMR spectrum, δC,
ppm: 30.82, 31.16, 54.04, 61.51, 72.96, 120.88, 123.12,
126.65, 127.37, 127.54, 127.65, 128.46, 131.04, 131.67,
133.44, 134.10, 137.46, 145.75, 150.69, 166.57, 184.08.
Mass spectrum: m/z 405 [M]+·. Found, %: C 67.92;
H 5.07; N 3.38. C23H20BrNO. Calculated, %: C 67.99;
H 4.96; N 3.45. M 408.33.
3
4
7.56 d.d (1H each, Harom, pseudotriplet, J = 7.5, J =
3
4
1.5 Hz), 8.23 d.d (1H, 6-H, J = 7.8, J = 1.2 Hz).
13C NMR spectrum, δC, ppm: 30.92, 31.27, 54.22,
61.62, 72.90, 120.39, 126.69, 127.13, 127.33, 127.64,
127.65, 128.57, 129.14, 131.12, 133.48, 135.25,
138.98, 146.04, 151.00, 166.90, 184.26. Mass spec-
trum: m/z 327 [M]+·. Found, %: C 84.51; H 6.43;
N 4.15. C23H21NO. Calculated, %: C 84.37; H 6.46;
N 4.28. M 329.43.
(E)-5′,5′-Dimethyl-2′-(4-nitrostyryl)-4′,5′-di-
hydro-4H-spiro[naphthalene-1,3′-pyrrol]-4-one
(VIIc). Yield 15%, light yellow crystals, mp 170.3°C,
Rf 0.20. IR spectrum(film), ν, cm–1: 3069, 2971, 1656
(C=O), 1592 (C=N), 1522, 1451, 1348, 1285, 1218,
1
1172, 1056, 838, 758. H NMR spectrum, δ, ppm:
The X-ray diffraction data for compound VIIa were
acquired on an Xcalibur 3 automatic diffractometer at
295(2) K (MoKα irradiation, graphite monochromator,
ω/2θ-scanning in the range θ < 30.51°) from a frag-
ment of a colorless prismatic single crystal, 0.25×
1.53 s and 1.63 s (3H, Me), 2.39 d and 2.53 d (1H,
4′-H, J = 14.4 Hz), 6.45 d (1H, trans-CH=, J =
16.5 Hz), 6.55 d (1H, 3-H, J = 9.9 Hz), 6.91 d (1H,
trans-CH=, J = 16.5 Hz), 7.00 m (1H, 2-H, J =
9.9 Hz), 7.23 d (1H, 8-H, J = 7.8 Hz), 7.31 d (2H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

SPIROCYCLOHEXADIENONES: XIII.
581
6. Povarov, L.S., Usp. Khim., 1967, vol. 36, p. 1533;
Glushkov, V.A. and Tolstikov, A.G., Usp. Khim., 2008,
vol. 77, p. 138; Kouznetsov, V.V., Tetrahedron, 2009,
vol. 65, p. 2721; Bello, D., Ramon, R., and Lavilla, R.,
Curr. Org. Chem., 2010, vol. 14, p. 332.
7. Tomoda, S., Takeuchi, Y., and Nomura, Y., Tetrahedron
Lett., 1969, p. 3549.
8. Nomura, Y., Kimura, M., Takeuchi, Y., and Tomoda, S.,
Chem. Lett., 1978, vol. 7, p. 267.
9. Glushkov, V.A. and Shklyaev, Y.V., Mendeleev Com-
mun., 1998, p. 17.
10. Glushkov, V.A., Rozhkova, Yu.S., Vakhrin, M.I., and
Shklyaev, Yu.V., Khim. Geterotsikl. Soedin., 2005,
p. 1198.
2′-H, 6′-H, J = 8.7 Hz), 7.46 d.d (pseudotriplet, 1H,
6-H, J = 7.8 Hz), 7.60 d.d.d (pseudotriplet, 1H, 7-H,
3
J = 7.8, 7.8, 1.5 Hz), 8.07 d (2H, 3′-H, 5′-H, J =
8.7 Hz), 8.25 d.d (1H, 5-H, J = 7.8, 1.5 Hz). 13C NMR
spectrum, δC, ppm: 30.81, 31.16, 54.01, 61.52, 73.36,
123.89, 124.46, 126.85, 127.57, 127.68, 127.71,
127.93, 131.12, 133.64, 136.12, 141.45, 145.43,
147.64, 150.30, 166.27, 184.06. Mass spectrum:
m/z 372.1 [M]+·. Found, %: C 74.15; H 5.36; N 7.55.
C23H20N2O3. Calculated, %: C 74.18; H 5.41; N 7.52.
M 372.42
The authors thank research worker E.V. Baigacheva
(Institute of Technical Chemistry, Ural Division, Rus-
sian Academy of Sciences) for performing elemental
analysis. This study was performed under financial
support by the Presidium of the Russian Academy of
Sciences (program no. 09-P-3-2001).
11. Nifontov, Yu.V., Glushkov, V.A., and Shklyaev, Yu.V.,
Izv. Ross. Akad. Nauk, Ser. Khim., 2003, p. 418.
12. Shklyaev, V.S., Aleksandrov, B.B., Legotkina, G.I.,
Vakhrin, M.I., Gavrilov, M.S., and Mikhailovskii, A.G.,
Khim. Geterotsikl. Soedin., 1983, p. 1560.
REFERENCES
13. Kouznetsov, V.V., Bohurquez, A.R.R., Saavedra, L.A.,
and Medina, R.F., Mol. Diversity, 2006, vol. 10, p. 29;
Kouznetsov, V.V., Cruz, U.M., Zubkov, F.I., and Nikiti-
na, E.V., Synthesis, 2007, p. 375; Zhou, Y., Jia, X.,
Li, R., Liu, Z., Liu, Z., and Wu, L., Tetrahedron Lett.,
2005, vol. 46, p. 8937; Zhang, W., Guo, Y., Liu, Z.,
Jin, X., Yang, L., and Liu, Z.-L., Tetrahedron, 2005,
vol. 61, p. 1325; Han, B., Jia, X.-D., Jin, X.-L.,
Zhou, Y.-L., Yang, L., Liu, Z.-L., and Yu, W., Tetra-
hedron Lett., 2006, vol. 47, p. 3545; Jia, X., Han, B.,
Zhang, W., Jin, X., Yang, L., and Liu, Z.-L., Synthesis,
2006, p. 2831; Savitha, G. and Perumal, P.T., Tetra-
hedron Lett., 2006, p. 3589.
1. Glushkov, V.A., Rotermel’, E.V., Odegova, T.F., and
Shklyaev, Yu.V., Russ. J. Org. Chem., 2011, vol. 47,
p. 1318.
2. Jiménez, O., de la Rosa, G., and Lavilla, R., Angew.
Chem., Int. Ed., 2005, vol. 44, p. 6521.
3. Liu, C.-R., Li, M.-B., Yang, C.-F., and Tian, S.-K., Chem.
Commun., 2008, p. 1249; Liu, G., Zhang, S., Li, H.,
Zhang, T., and Wang, W., Org. Lett., 2011, vol. 13,
p. 828.
4. Huang, Z., Zhang, J., and Wang, N.-X., Tetrahedron,
2011, vol. 67, p. 1788.
14. Rong, L., Li, X., Wang, H., Shi, D., Tu, S., and
Zhuang, Q., Synth. Commun., 2006, vol. 36, p. 2345.
15. Roe, A. and Montgomeri, J.A., J. Am. Chem. Soc., 1953,
5. Desimoni, G., Faita, G., Mella, M., Toscanini, M., and
Boiocchi, M., Eur. J. Org. Chem., 2009, p. 2627; Das, B.,
Kumar, J.N., Kumar, A.S., and Damodar, K., Synthesis,
2010, p. 914; Husmann, R., Sugiono, E., Mersmann, S.,
Raabe, G., and Rueping, M., Org. Lett., 2011, vol. 13,
p. 1044.
vol. 75, p. 910.
16. Sheldrick, G.M., Acta Crystallogr., Sect. A, 2008,
vol. 64, p. 112.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012