Perhydrofuro[3,2-c]-, perhydropyrano[3,2-c]-, and 4-ethoxy-2-(5-R-furan-2- yl)tetrahydroquinolines. Synthesis and transformations

Article abstract of DOI:10.1134/S1070428010080142

Partly hydrogenated 2-[5-methyl(bromo, nitro)furan-2-yl]-substituted furo[3,2-c]quinolines, pyrano- [3,2-c]quinolines, and 4-ethoxyquinolines were synthesized by the imino Diels-Alder (Povarov) reaction. Cycloadditions of these compounds with maleic, citr

Full text of DOI:10.1134/S1070428010080142

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 8, pp. 1192–1206 © Pleiades Publishing, Ltd., 2010.
Original Russian Text © F.I. Zubkov, V.P. Zaitsev, A.M. Piskareva, M.N. Eliseeva, E.V. Nikitina, N.M. Mikhailova, A.V. Varlamov, 2010, published in
Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 8, pp. 1191–1204.
Perhydrofuro[3,2-c]-, Perhydropyrano[3,2-c]-,
and 4-Ethoxy-2-(5-R-furan-2-yl)tetrahydroquinolines.
Synthesis and Transformations
F. I. Zubkov, V. P. Zaitsev, A. M. Piskareva, M. N. Eliseeva, E. V. Nikitina,
N. M. Mikhailova, and A. V. Varlamov
Russian University of Peoples’Friendship, ul. Miklukho-Maklaya 6, Moscow, 117198 Russia
e-mail: fzubkov@sci.pfu.edu.ru
Received July 20, 2009
Abstract—Partly hydrogenated 2-[5-methyl(bromo, nitro)furan-2-yl]-substituted furo[3,2-c]quinolines, pyrano-
[3,2-c]quinolines, and 4-ethoxyquinolines were synthesized by the imino Diels–Alder (Povarov) reaction.
Cycloadditions of these compounds with maleic, citraconic, and dibromomaleic anhydrides, as well as with
acryloyl, methacryloyl, and cinnamoyl chlorides led to the formation of substituted epoxyisoindolo[2,1-a]-
quinolines and -quinolinecarboxylic acids. Oxidation of the double C=C bond in the adducts, esterification of
the carboxy group, and aromatization of the 7-oxabicycloheptene fragment were accomplished.
DOI: 10.1134/S1070428010080142
furyl-substituted tetrahydroquinolines [1]. In the
present work we found that increase in the electron-
acceptor power of the substituent R3 in the furan ring
favors formation of cycloaddition products II. Schiff
base Ic having a hydroxy group in the ortho-position
of the benzene ring was considerably less active in the
We previously synthesized 4-substituted 6-R-2-fur-
yltetrahydroquinolines and those fused at the C3–C4
bond and studied their [4+2]-cycloaddition reactions
with maleic anhydride and acryloyl chloride [1–3] and
the effect of electronic properties of the R substituents
in the aryl fragment on the cyclization of N-furfuryli-
deneanilines with vinyl ethers and vinyl amides to
the corresponding tetrahydroquinolines (Povarov reac-
tion) [4, 5].
The goal of the present work was to study the be-
havior of N-furfurylideneanilines with different sub-
stituents in position 5 of the furan ring in the Povarov
reaction and reveal general relations holding in the
cycloaddition of 2-furyltetrahydroquinolines thus ob-
tained with maleic, citraconic, and dibromomaleic an-
hydrides, as well as with substituted acryloyl chlorides.
N-Furfurylideneanilines I were synthesized by conden-
sation of the corresponding 5-substituted furan-2-carb-
aldehydes with ortho- and para-substituted anilines.
Compounds I were brought into cycloadditions with
dihydrofuran, dihydropyran, and ethyl vinyl ether
(Scheme 1). The reactions were carried out in diethyl
ether or benzene at 0–20°C in the presence of boron
trifluoride–diethyl ether complex (5 mol %).
1
Povarov reaction. According to the H NMR data,
5-nitrofuryl-substituted tetrahydroquinoline IIf was
formed as an equimolar mixture of two stereoisomers
differing by mutual arrangement of the 5-nitrofuryl
substituent and fused tetrahydrofuran ring. The cou-
pling constants for the cis isomer of IIf are J4,3a = 2.7,
J3a,9b = 7.4 Hz, and for the trans isomer, J4,3a = 5.4,
J
3a,9b = 10.1 Hz. Tetrahydroquinolines III and IV were
reported by us previously [1, 2].
2-Furyl-substituted tetrahydroquinolines IIa, IIc–
IIe, III, and IV readily reacted with maleic anhydride at
0–5°C, following the Diels–Alder pattern (Scheme 2),
to produce mixtures of stereoisomeric exo-tetrahydro-
furano- (Va, Vc–Ve), tetrahydropyrano- (VI), and
4-ethoxyisoindolo[2,1-a]quinolinecarboxylic acids
(VII). In the reactions with furano- and pyranoquino-
lines IIa, IId, IIe, and III, the major products were
isomers V and VI with trans orientation of the epoxy
bridge and the fused heteroring, whereas 8-hydroxy-
substituted derivative IIc gave rise to only trans iso-
mer Vc. The adduct obtained from 4-ethoxyquinoline
We previously showed that electron-withdrawing
substituents in the aniline fragment reduce the yield of
1192

PERHYDROFURO[3,2-c]-, PERHYDROPYRANO[3,2-c]-, ...
1193
Scheme 1.
R2
R2
R3
NH2
N
PhH, Δ
O
+
R3
CHO
O
R1
R1
Ia–If
2
1O
O
9
O
( )3n
, BF3 ·Et2O
R1
9a
5a
8
9b
( )n
3a
4
+
5
7
O
O
N
N
R3
NO2
6
H
H
R2
cis-IIa–cis-IIf, cis-III
trans-IIf
OEt
5
CH2=CHOEt
BF3 ·Et2O
4
3
6
2
1
N
H
7
O
8
IV
I, II, R2 = R3 =H, R1 = H (a), Ac (b); R1 = R3 = H, R2 = HO (c); R1 = R2 = H, R3 = Me (d), Br (e), O2N (f);
III, R1 = R2 = R3 = H; II, n = 1; III, n = 2.
substituted tetrahydroquinoline IIb was almost inert in
IV was represented mainly by cis isomer VII. The
cycloaddition of maleic anhydride at 110°C was
stereospecific due to reversibility of the Diels–Alder
reaction. The reactions with fused quinolines IIa, IId,
IIe, and III afforded only trans isomers Va, Vd, Ve,
and VI, while cis isomer VII was formed from
4-ethoxytetrahydroquinoline IV. Analogous results
were obtained when mixtures of isomeric adducts V–
VII were heated at 110°C. The least basic acetyl-
cycloaddition reactions.
The cycloaddition of acryloyl chloride to fused
quinolines IIa, IIc–IIe, and III in boiling benzene in
the presence of triethylamine was not stereoselective,
and mixtures of cis- and trans-isomeric epoxyisoin-
dolo[2,1-a]tetrahydroquinolines VIIIa, VIIIc–VIIIe,
and IX were formed (Scheme 2). However, 4-ethoxy-
tetrahydroquinoline IV reacted with acryloyl chloride
Scheme 2.
Y
Y
H
H
R3
OH
R3
OH
XO
XO
O
O
O
O
O
N
N
+
O
O
O
O
OX
R2
R2
Y
trans
Va, Vc–Ve, VI, VII
cis
O
Y
Y
N
R3
H
N
H
H
R3
R3
XO
XO
R2
CH2=CHC(O)Cl
Et3N, PhH
O
O
IIa, IIc–IIe, III, IV
N
+
O
O
R2
R2
trans
VIIIa, VIIIc–VIIIe, IX, X
cis
II, V, VIII, XY = (CH2)2; III, VI, IX, XY = (CH2)3; IV, VII, X, X = Et, Y = H.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010

ZUBKOV et al.
1194
Diels–Alder reactions of furyl-substituted quinolines IIa, IIc–IIe, III, and IV with maleic anhydride and acryloyl chloride at
different temperatures
Adduct with maleic anhydride
Adduct with acryloyl chloride, 80°C
Quinoline
no.
R2
R3
X
Y
comp. 0−5°C, trans/cis 110°C, isomer
comp. no. trans/cis ratio (yield, %)
no.
ratio (yield, %)
(yield, %)
IIa
IIc
IId
IIe
III
IV
H
OH
H
H
H
H
H
Me
Br
H
(CH2)2
Va [1]
Vc
Vd
Ve
VI [1]
VII [1]
71/29 (65)
trans (94)
50/50 (79)
65/35 (95)
75/25 (58)
25/75 (88)
trans (85)
VIIIa [1]
VIIIc
VIIId
VIIIe
IX [1]
X [1]
45/55 (90)
50/50 (87)
50/50 (87)
50/50 (44)
33/66 (80)
cis (53)
a
(CH2)2
(CH2)2
(CH2)2
(CH2)3
–
trans (62)
trans (75)
trans (66)
cis (99)
H
H
Et
H
a
No experiment was performed.
strictly stereoselectivity, yielding only exo-cis-adduct
X. The composition of mixtures of trans and cis iso-
mers VIIIa, VIIIc–VIIIe, and IX remained unchanged
on heating in xylene. The presence of a methyl group
or bromine atom on C5 in the furan ring of compounds
IId and IIe almost did not affect the stereoselectivity
in the cycloadditions with maleic anhydride and acryl-
oyl chloride (see table).
Citraconic anhydride turned out to be less reactive
than maleic anhydride in the cycloaddition to com-
pound IIa. The corresponding exo,trans-adduct XI was
obtained only by prolonged heating of the reactants in
boiling xylene using a large excess of citraconic an-
hydride. The methyl and carboxy groups in the adduct
are attached to the same carbon atom Scheme 3).
The structure of compound XI was determined by
measuring nuclear Overhauser effects (NOE) in the
1H NMR spectra. The NOE values η11-H{10-Me} = 4.6,
The steric structure of isomeric adducts V–VII was
determined taking into account our previous data [1]
on the chemical shifts of aromatic protons in the ortho
position with respect to the nitrogen atom (7-H or 8-H
in furano- and pyranoquinolines Va, Vd, Ve, and VI
η
12-H{10-Me} = 5.5, and η9a-H{10-Me} = 7.0 indicated
endo orientation of the methyl group relative to the
bridging oxygen atom in the oxabicycloheptene frag-
ment and cis orientation of 9a-H and 10-Me. The
absence of NOE between 9a-H and 13b-H is consistent
with their trans orientation with respect to each other.
Relatively large NOEs for the 1-HA, 13b-H, 13c-H, and
3a-H protons (η13c-H{1-HA} = 4.0, η13b-H{13c-H} = 5.2,
1
and 1-H in 4-ethoxy derivative VII). In the H NMR
spectra of these adducts, signals from the above
protons in the trans isomers are located in a stronger
field (by 0.6–0.8 ppm) relative to the corresponding
signals of the cis isomers. The ortho position with
respect to the nitrogen atom in trans-adduct Vc is
occupied by hydroxy group; therefore, its structure was
determined by comparing the chemical shifts of 3a-H
and 13b-H with those of analogous protons in isomers
Va. Stereoisomeric adducts VIIIa, VIIIc–VIIIe, IX,
and X were assigned to the cis or trans series by
analogy with compounds Va, Vc–Ve, VI, and VII.
η
3a-H{13c-H} = 6.5) allowed us to assign cis orien-
tation to 1-HA and 13c-H, as well as to 3a-H, 13c-H,
and 13b-H.
Dibromomaleic anhydride reacted with furoquino-
line IIa even at 20°C to form exo,trans-adduct XII.
The Diels–Alder reactions of compound IIa with with
methacryloyl and cinnamoyl chlorides occurred in
Scheme 3.
Me
Br
Br
2
12
1
13
O
H13a
H
N
O
O
O
O
3 O
O
11
O
O
13c
o-xylene, Δ
O
9a
O
PhH, 20°C
N8
COOH
COOH
O
Me
Br
4
Br
9
N
H
O
O
5
7
6
XI
IIa
XII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010

PERHYDROFURO[3,2-c]-, PERHYDROPYRANO[3,2-c]-, ...
1195
Scheme 4.
O
O
H2C
Cl
O
H
N
H
N
O
O
Ph
Et3N, PhH
Cl
Me
Et3N, PhH
O
O
O
Ph
Me
N
H
O
O
XIII
IIa
XIV
a way similar to the reaction with actyloyl chloride. In
both cases, the cycloaddition was stereoselective, and
the corresponding exo,trans-adducts XIII and XIV
were isolated in good yields (Scheme 4). By esteri-
fication of trans-isomeric epoxyfuranoisoindoloquino-
linecarboxylic acids Va and Vd with methanol we
obtained mixtures of trans and cis isomers of esters
XVa and XVd in overall yields of 61 and 80%, respec-
tively. Presumably, the reason is retro-Diels–Alder
reaction of the initially formed trans-esters (Scheme 5)
cis-ester XVIII, cis isomer X, and trans isomers XIII
and XIV was oxidized with m-chloroperoxybenzoic
acid in methylene chloride (Scheme 6). The oxidation
products were the corresponding cis-diepoxy deriva-
tives XIX–XXII which attract interest as substrates for
further transformations [6].
The exo configuration of the oxirane ring fused to
the 7-oxabicycloheptane fragment and correspondingly
cis orientation of of the oxygen bridges with respect to
each other unambiguously followed from the coupling
constants of the 11a-H, 11-H, and 12a-H protons in
furan-fused compounds XIX and XXI and of 12a-H,
1
[1]. According to the H NMR data, the trans/cis
isomer ratios were ~7:1 for compound XVa and 2:1
for ester XVb. No retro-Diels–Alder reaction of trans-
esters XVI and XVII was observed in the esterification
of trans-isomeric carboxylic acids VI and XI.
Likewise, retro-Diels–Alder reaction did not ac-
company esterification of cis-acid VII, and the corre-
sponding cis-ester XVIII was obtained in 78% yield.
The major trans isomers of esters XVa and XVd were
isolated as individual substances by fractional crystal-
lization.
12-H, and 13a-H in pyran-fused analog XX: J11a,12a
=
J12a,13a = 3.3, J11,11a = J12,12a = 0 Hz; the corresponding
coupling constants in ethoxy-substituted diepoxides
XXII were J1a,11c = 3.2–3.4, J1a,2 = 0 Hz. The absence
of appreciable vicinal couplings (3J) for the protons in
the bridgehead positions of the oxabicyclic fragment in
XIX–XXII unambiguously indicates exo orientation of
all substituents [7, 8].
Treatment of compounds Va, VI, and VIIIa with
orthophosphoric acid at 85°C resulted in cleavage of
the epoxy bridge in the oxabicycloheptene fragment
The double bond in the oxabicycloheptene frag-
ment of trans-isomeric esters XVa, XVd, XVI, XVII,
Scheme 5.
( )n
( )n
( )n
H
N
H
H
N
R3
R3
R3
O
O
O
MeOH, H+
O
O
O
+
COOH
COOMe
COOMe
N
X
X
X
O
O
O
Va, Vd, VI, XI
trans-XVa, trans-XVd, XVI, XVII
cis-XVa, cis-XVd
EtO
EtO
5
6
H
H
4
7
MeOH, H+
8
9
3
N
N
12
O
COOH
O
2
11
1
10
O
O
COOMe
VII
cis-XVIII
XV, XVI, n = 1; XVII, n = 2; XVa, XVII, R3 = X = H; XVd, R3 = Me, X = H; XVI, R3 = H, X = Me.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010

ZUBKOV et al.
1196
Scheme 6.
O
( )n
H
N
R3
O
m-ClC6H4CO3H, CH2Cl2
O
trans-XVa, trans-XVd, XVI, XVII
COOMe
X
O
XIXa–XIXc, XX
O12
2
1
12a
11a
11
10
H
3 O
12d
m-ClC6H4CO3H, CH2Cl2
O
3a
XIII, XIV
8 N
R2
R1
4
5
9
O
7
6
XXIa, XXIb
EtO
O1
10
11
H
9
11c
11a
m-ClC6H4CO3H, CH2Cl2
1a
2
cis-X, XVIII
8
5 N
O
7
4
6
3
O
X
XXIIa, XXIIb
XIX, n = 1; XX, n = 2; XIX, R3 = H, X = H (a), Me (c); R3 = Me, X = H (b); XX, R3 = X = H; XXI, R1 = H, R2 = Ph (a);
R1 = Me, R2 = H (b); XXII, X = H (a), CO2Me (b).
and subsequent aromatization with formation of com-
pounds XXIIIa–XXIIIc in 35–89% yield (Scheme 7)
[9]. Isoindolo[2,1-a]quinolines XXIIIa and XXIIIb
were subjected to nitration with a mixture of potassium
nitrate and sulfuric acid. The reaction was regioselec-
tive, and the corresponding 5-nitro derivatives XXIVa
and XXIVb were formed in moderate yields [10].
with Fourier transform from samples prepared as KBr
1
pellets. The H NMR spectra were measured on
a Bruker WH-400 spectrometer (400 MHz) at 30°C
using the residual solvent signal as reference (CHCl3,
δ 7.26 ppm; DMSO-d5, δ 2.49 ppm). The 13C NMR
spectra were obtained on a Bruker Avance 600 instru-
ment at 150 MHz; the chemical shifts were measured
relative to the central peak of the DMSO-d6 multiplet
(δC 39.96 ppm). Signals in the NMR spectra were
assigned using two-dimensional HMQC and COSY-45
correlation techniques; NOE experiments were per-
formed according to one-dimensional procedure with-
out preliminary degassing of samples. The mass spec-
EXPERIMENTAL
Commercial reagents from Acros Organics were
used without additional purification. The IR spectra
were recorded on an Infralyum FT-801 spectrometer
Scheme 7.
( )n
( )n
H
N
H
H
N
O
O
O
H3PO4, 85°C
KNO3, H2SO4
O
N
X
X
X
O
O
O
O2N
Va, VI, VIIIa
XXIIIa–XXIIIc
XXIVa, XXIVb
XXIII, n = 1 (a, b), 2 (c); X = CO2H (a, c), H (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010

PERHYDROFURO[3,2-c]-, PERHYDROPYRANO[3,2-c]-, ...
1197
tra (electron impact, 70 eV) were recorded on
a Thermo Focus DSQ II GC–MS system (ion source
temperature 200°C, Varian FactorFour VF-5ms chro-
matographic column) or on a Thermo Trace DSQ mass
spectrometer (ion source temperature 200°C, direct
sample admission into the ion source). Thin-layer
chromatography was performed on Sorbfil plates
(spots were visualized by treatment with iodine vapor).
Neutral aluminum oxide (Fluka 507S, grain size
0.05−0.15 mm) was used for column chromatography.
Cycloaddition of Schiff bases Ia–If to dihydro-
furan (general procedure). A solution of 0.2 mol of
Schiff base I in 100 ml of anhydrous benzene (Id) or
methylene chloride (Ib, Ic, Ie, If) was cooled to 0°C,
0.63 ml (5 mmol) of boron trifluoride–diethyl ether
complex was added under stirring, and 16.6 ml
(0.22 mol) of dihydrofuran was added dropwise under
stirring. The mixture was stirred for 2 h at 0–5°C and
for 3 h at 20°C, 3–4 ml of 25% aqueous ammonia was
added until alkaline reaction, and the mixture was
concentrated under reduced pressure. The residue was
a dark viscous oily material which was purified by
column chromatography using ethyl acetate−hexane
(1:10) as eluent.
trum (CDCl3), δ, ppm: 1.85 m (1H, 3-H), 2.24 d.q (1H,
2
3-H, J2,3 = J3a,3 = 8.8, J = 12.3 Hz), 2.99 d.q (1H,
3a-H, J3a,4 = 3.0, J3a,9b = 7.9, J3a,3 = 8.7, J3a,3 = 8.8 Hz),
3.82–3.74 m (2H, 2-H), 4.69 d (1H, 4-H, J3a,4
=
3.0 Hz), 5.28 d (1H, 9b-H, J3a,9b = 7.9 Hz), 5.54 br.s
(OH, NH), 6.34 d.d (1H, 3′-H, J5′,3′ = 0.7, J4′,3′
=
3.2 Hz), 6.38 d.d (1H, 4′-H, J5′,4′ = 1.7, J4′,3′ = 3.2 Hz),
6.62 d.d (1H, 7-H, J7,9 = 0.7, J7,8 = 7.6 Hz), 6.68 d.t
(1H, 8-H, J7,8 = J8,9 = 7.6 Hz), 6.97 d.d (1H, 9-H, J7,9
=
0.7, J8,9 = 7.6 Hz), 7.40 d.d (1H, 5′-H, J5′,4′ = 1.7,
J5′,3′ = 0.7 Hz). Mass spectrum, m/z (Irel, %): 257 (100)
[M]+, 212 (61), 184 (11), 146 (30), 121 (48), 103 (42),
93 (36), 77 (55), 65 (23), 55 (31), 39 (47). Found, %:
C 70.45; H 5.58; N 5.25. C15H15NO3. Calculated, %:
C 70.02; H 5.88; N 5.44. M 257.11.
(3aS*,4S*,9bS*)-4-(5-Methylfuran-2-yl)-
2,3,3a,4,5,9b-hexahydrofuro[3,2-c]quinoline (IId).
Yield 40%. Colorless crystals, mp 79−81°C (from
hexane–ethyl acetate), Rf 0.61 (hexane–ethyl acetate,
1
8:1). IR spectrum: ν 3303 cm–1 (NH). H NMR spec-
trum (CDCl3), δ, ppm: 1.87 m (1H, 3-H), 2.22 d.d (1H,
3-H, J3a,3 = 9.1 Hz), 2.30 d (3H, Me), 2.95 d.d.q (1H,
3a-H, J3a,4 = 2.7, J3a,9b = 9.4, J3a,3 = 9.1 Hz), 3.76 d.t
2
2
(1H, 2-H, J = 8.3 Hz), 3.80 q (1H, 2-H, J = 8.3 Hz),
3.93 br.s (NH), 4.64 d (1H, 4-H, J3a,4 = 2.7 Hz), 5.23 d
1-[(3aS*,4S*,9bS*)-4-(2-Furyl)-2,3,3a,4,5,9b-
hexahydrofuro[3,2-c]quinolin-8-yl]ethanone (IIb).
Yield 37%. Colorless crystals, mp 179–181°C (from
hexane–ethyl acetate), Rf 0.26 (hexane–ethyl acetate,
2:1). IR spectrum, ν, cm–1: 3288 (NH), 1659 (C=O).
1H NMR spectrum (CDCl3), δ, ppm: 1.89 m (1H, 3-H),
(1H, 8b-H, J3a,9b = 9.4 Hz), 5.94 d.q (1H, 4′-H, J4′,3′
=
3.0 Hz), 6.15 br.d (1H, 3′-H, J4′,3′ = 3.0 Hz), 6.59 d.d
(1H, 9-H, J7,9 = 1.0, J8,9 = 7.9 Hz), 6.81 d.t (1H, 7-H,
J7,9 = 1.0, J7,8 = J6,7 = 7.6 Hz), 7.08 d.t (1H, 8-H, J7,8
J8,9 = 7.7, J6,8 = 1.5 Hz), 7.34 br.d (1H, 6-H, J6,7
=
=
7.5 Hz). Mass spectrum, m/z (Irel, %): 255 (34) [M]+,
210 (59), 167 (13), 144 (17), 130 (44), 117 (27), 95
(43), 77 (40), 65 (22), 51 (32), 43 (100), 39 (41).
Found, %: C 75.09; H 6.45; N 5.85. C16H17NO2. Cal-
culated, %: C 75.27; H 6.71; N 5.49. M 255.13.
3
2
2.14 d.q (1H, 3-H, J = 8.6, J = 12.5 Hz), 2.52 s (3H,
COMe), 2.97 d.d.q (1H, 3a-H, J3a,4 = 3.2, J3a,9b = 7.6,
2
3
J3a,3 = 8.2 Hz), 3.74 d.t (1H, 2-H, J = J = 8.6 Hz),
3.82 q (1H, 2-H, 2J = 8.4, 3J = 4.4 Hz), 4.44 br.s (NH),
4.81 d (1H, 4-H, J3a,4 = 3.2 Hz), 5.22 d (1H, 9b-H,
(3aS*,4S*,9bS*)-4-(5-Bromofuran-2-yl)-
2,3,3a,4,5,9b-hexahydrofuro[3,2-c]quinoline (IIe).
Yield 54%. Colorless crystals, mp 74−75°C (from
hexane–ethyl acetate), Rf 0.61 (hexane–ethyl acetate,
4
3
J3a,9b = 7.6 Hz), 6.30 d.d (1H, 3′-H, J = 0.8, J =
3.2 Hz), 6.38 d.d (1H, 4′-H, J5′,4′ = 1.8, J4′,3′ = 3.2 Hz),
6.59 d (1H, 6-H, J6,7 = 8.5 Hz), 7.40 d.d (1H, 5′-H,
J5′,4′ = 1.8, J5′,3′ = 0.8 Hz), 7.74 d.d (1H, 7-H, J7,9 = 2.0,
J6,7 = 8.5 Hz), 7.97 d (1H, 9-H, J7,9 = 2.0 Hz). Mass
spectrum, m/z (Irel, %): 283 (100) [M]+, 268 (22), 254
(13), 238 (90), 210 (9), 198 (6), 172 (15), 167 (5), 103
(5), 81 (6), 43 (7). Found, %: C 72.31; H 6.21; N 4.78.
C17H17NO3. Calculated, %: C 72.07; H 6.05; N 4.94.
M 283.12.
1
5:1). IR spectrum: ν 3305 cm–1 (NH). H NMR spec-
trum (CDCl3), δ, ppm: 1.86 m (1H, 3-H), 2.19 d.q (1H,
2
3-H, J2,3 = 8.5, J = 12.0, J3a,3 = 8.9 Hz), 2.95 br.d.q
(1H, 3a-H, J3a,4 = 3.0, J3a,9b = 7.9, J3a,3 = 8.9 Hz),
2
3.75 d.t (1H, 2-H, J = J2,3 = 8.5, J2,3 = 7.5 Hz), 3.80 q
2
(1H, 2-H, J = J2,3 = 8.5, J2,3 = 4.6 Hz), 3.90 br.s (NH),
4.67 d (1H, 4-H, J3a,4 = 3.0 Hz), 5.21 d (1H, 9b-H, J3a,9b
=
(3aS*,4S*,9bS*)-4-(2-Furyl)-2,3,3a,4,5,9b-hexa-
hydrofuro[3,2-c]quinolin-6-ol (IIc). Yield 14%.
Colorless crystals, mp 144−145°C (from hexane–ethyl
acetate), Rf 0.73 (hexane–ethyl acetate, 6:1). IR spec-
7.9 Hz), 5.29 d (1H, 4′-H, J4′,3′ = 3.3 Hz), 6.27 d (1H,
3′-H, J4′,3′ = 3.3 Hz), 6.61 d.d (1H, 9-H, J7,9 = 1.0,
J8,9 = 7.7 Hz), 6.83 d.t (1H, 7-H, J7,9 = 1.0, J7,8 = J6,7
7.5 Hz), 7.09 d.t (1H, 8-H, J7,8 = J8,9 = 7.7, J6,8
1.0 Hz), 7.37 br.d.d (1H, 6-H, J6,7 = 7.5, J6,8 = 1.0 Hz).
=
=
1
trum, ν, cm–1: 3386, 3216 (NH, OH). H NMR spec-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010

ZUBKOV et al.
1198
Mass spectrum, m/z (Irel, %): 319 (100) [M]+ (79Br),
274 (79), 240 (30), 212 (31), 194 (22), 170 (41), 144
(17), 130 (46), 115 (18), 77 (23), 65 (13), 39 (15).
Found, %: C 56.53; H 4.72; N 4.50. C15H14BrNO2.
Calculated, %: C 56.27; H 4.41; N 4.37. M 319.02.
off. We thus isolated trans isomers of carboxylic acids
Vd and Ve.
(3aS*,9aS*,10R*,11S*,13aR*,13bS*,13cS*)-
11,13a-Epoxy-7-hydroxy-9-oxo-1,2,9,9a,10,11,-
13b,13c-octahydro-3aH-furo[3,2-c]isoindolo[2,1-a]-
quinoline-10-carboxylic acid (Vc) (trans isomer).
Yield 94%, mp 208−210°C (from i-PrOH–DMF). IR
spectrum, ν, cm–1: 1731 (COOH), 1649 (C9=O).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.60 m (1H,
(3aS*,4S,R*,9bS*)-4-(5-Nitrofuran-2-yl)-
2,3,3a,4,5,9b-hexahydrofuro[3,2-c]quinoline (IIf)
(a mixture of cis and trans isomers, 1:1). Yield 71%.
Colorless crystals, mp 100−101°C (from hexane–ethyl
acetate), Rf 0.32, 0.42 (hexane–ethyl acetate, 2:1). IR
1-H), 2.15 m (1H, 1-H), 2.68 d (1H, 9a-H, J9a,10
9.0 Hz), 3.20 m (1H, 13c-H), 3.25 d (1H, 10-H, J9a,10
=
=
1
spectrum, ν, cm–1: 3371, 3296 (NH). H NMR spec-
9.0 Hz), 3.72 m (1H, 2-H), 3.80 m (1H, 2-H), 4.51 d
(1H, 13b-H, J13b, 13c = 3.0 Hz), 5.13 d (1H, 11-H,
J11, 12 = 1.5 Hz), 5.24 d (1H, 3a-H, J3a,13c = 8.6 Hz),
6.55 d.d (1H, 12-H, J11,12 = 1.5, J12,13 = 5.7 Hz),
6.84 d.d (1H, 4-H, J4,5 = 7.8, J4,6 = 0.9 Hz), 6.91 d
trum (CDCl3), δ, ppm: cis isomer: 1.89 m (1H, 3-H),
2.17 m (1H, 3-H), 3.04 d.q (1H, 3a-H, J3a,4 = 2.7,
J3a,9b = 7.4, J3a,3 = 8.7 Hz), 3.72 m (1H, 2-H), 3.79 q
2
(1H, 2-H, J = J2,3 = 8.1 Hz), 4.26 br.s (NH), 4.77 d
(1H, 4-H, J3a,4 = 2.7 Hz), 5.17 d (1H, 9b-H, J3a,9b
=
(1H, 13-H, J12,13 = 5.7 Hz), 6.91 br.d (1H, 6-H, J5,6
=
7.4 Hz), 6.55 d (1H, 3′-H, J4′,3′ = 3.4 Hz), 6.65 d (1H,
6-H, J6,7 = 7.7 Hz), 6.87 t (1H, 8-H, J7,8 = J8,9
7.7 Hz), 7.13 t (1H, 7-H, J6,7 = J7,8 = 7.7 Hz), 7.30 d
(1H, 4′-H, J4′,3′ = 3.4 Hz), 7.36 d (1H, 9-H, J8,9
7.7 Hz); trans isomer: 1.89 m (1H, 3-H), 2.25 m (1H,
7.8 Hz), 7.16 t (1H, 5-H, J4,5 = J5,6 = 7.8 Hz), 12.3 br.s
(COOH). Mass spectrum, m/z (Irel, %): 355 (7) [M]+,
310 (3), 256 (62), 212 (40), 196 (5), 146 (28), 131
(33), 121 (52), 99 (67), 77 (100), 65 (46), 39 (45).
Found, %: C 64.00; H 4.59; N 3.58. C19H17NO6. Cal-
culated, %: C 64.22; H 4.82; N 3.94. M 355.11.
=
=
2
3-H), 2.68 m (1H, 3a-H), 3.86 q (1H, 2-H, J = J2,3
=
8.7 Hz), 4.02 m (1H, 2-H), 4.26 br.s (NH), 4.65 d (1H,
4-H, J3a,4 5.4 Hz), 4.10 d (1H, 9b-H, J3a,9b = 0.1 Hz),
6.58 d (1H, 3′-H, J4′,3′ = 3.4 Hz), 6.67 d (1H, 6-H,
J6,7 = 7.9 Hz), 6.85 t (1H, 8-H, J7,8 = J8,9 = 7.9 Hz),
7.15 t (1H, 7-H, J6,7 = J7,8 = 7.9 Hz), 7.31 d (1H, 4′-H,
J4′,3′ = 3.4 Hz), 7.38 d (1H, 9-H, J8,9 = 7.5 Hz). Mass
spectrum, m/z (Irel, %): 286 (100) [M]+, 241 (82), 180
(14), 170 (21), 158 (12), 144 (14), 130 (29), 115 (16),
77 (14), 65 (11), 51 (15), 39 (14). Found, %: C 62.64;
H 4.77; N 9.95. C15H14N2O4. Calculated, %: C 62.93;
H 4.93; N 9.79. M 286.10.
(3aS*,9aS*,10R*,11S*,13aR*,13bS*,13cS*)-
11,13a-Epoxy-11-methyl-9-oxo-1,2,9,9a,10,11,-
13b,13c-octahydro-3aH-furo[3,2-c]isoindolo[2,1-a]-
quinoline-10-carboxylic acid (VId) (trans isomer).
Yield 62% (b), mp 178−180°C (from i-PrOH–DMF).
IR spectrum, ν, cm–1: 1724 (COOH), 1701 (C9=O).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.53 s (3H,
Me), 1.55 m (1H, 1-H), 2.10 m (1H, 1-H), 2.65 d (1H,
9a-H, J9a,10 = 8.9 Hz), 3.05 d (1H, 10-H, J9a,10
=
8.9 Hz), 3.11 m (1H, 13c-H), 3.67 m (1H, 2-H), 3.76 m
(1H, 2-H), 4.44 d (1H, 13b-H, J13b,13c = 2.8 Hz), 5.20 d
Furyl-substituted quinolines IIa, III, and IV were
reported previously [1, 2].
(1H, 3a-H, J3a,13c = 8.3 Hz), 6.37 d (1H, 12-H, J12,13
=
5.6 Hz), 6.89 d (1H, 13-H, J12, 13 = 5.6 Hz),
Cycloaddition of furoquinolines IIc–IIe to maleic
anhydride. a. A solution of 0.43 g (4.36 mmol) of
maleic anhydride in 10 ml of toluene was added to
a solution of 4.15 mmol of quinoline IIc–IIe in 10 ml
of toluene, heated to 0–5°C. The mixture was kept for
3 days at 0–5°C (TLC), and the precipitate was filtered
off and washed with diethyl ether (2×15 ml). We thus
isolated mixtures of trans and cis isomers of carbox-
ylic acids Vd and Ve or pure trans isomer Vc as
colorless crystalline substances. The isomer ratios are
given in table.
6.91 br.d.d.d (1H, 6-H, J4,6 = 1.5, J5,6 = 7.8, J6,7
8.1 Hz), 7.14 d.t (1H, 5-H, J4,5 = J5,6 = 7.7, J5,7
=
=
1.1 Hz), 7.35 d.d (1H, 4-H, J4,5 = 7.7, J4,6 = 1.5 Hz),
7.70 d.d (1H, 7-H, J5,7 = 1.1, J6,7 = 8.1 Hz). Mass spec-
trum, m/z (Irel, %): 353 (10) [M]+, 308 (18), 254 (100),
210 (99), 180 (21), 160 (34), 144 (23), 130 (29), 115
(21), 95 (28), 77 (29), 43 (64). Found, %: C 67.45;
H 5.19; N 4.21. C20H19NO5. Calculated, %: C 67.98;
H 5.42; N 3.96. M 353.13.
(3aS*,9aS*,10R*,11S*,13aR*,13bS*,13cS*)-11-
Bromo-1,13a-epoxy-9-oxo-1,2,9,9a,10,11,13b,13c-
octahydro-3aH-furo[3,2-c]isoindolo[2,1-a]quino-
line-10-carboxylic acid (VId) (trans isomer). Yield
75% (b), mp 204−206°C (from i-PrOH–DMF). IR spec-
b. A solution of 4.15 mmol of tetrahydroquinoline
IId or IIe and 0.43 g (4.36 mmol) of maleic anhydride
in 20 ml of toluene was heated for 2–10 h under reflux
(TLC). The colorless crystalline product was filtered
1
trum, ν, cm–1: 1732 (COOH), 1686 (C9=O). H NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010

PERHYDROFURO[3,2-c]-, PERHYDROPYRANO[3,2-c]-, ...
1199
spectrum (DMSO-d6), δ, ppm: 1.49 m (1H, 1-H),
2.11 m (1H, 1-H), 3.11 d (1H, 9a-H, J9a,10 = 8.9 Hz),
3.13 m (1H, 13c-H), 3.27 d (1H, 10-H, J9a,10 = 8.9 Hz),
3.67 m (1H, 2-H), 3.75 m (1H, 2-H), 4.55 d (1H,
J4,6 = 1.5 Hz), 9.45 s (OH); cis isomer: 1.77 d.d (1H,
2
endo-10-H, J9a,endo-10 = 9.2, J = 11.6 Hz), 1.90 m (1H,
1-H), 2.13 m (1H, 1-H), 2.17 d.d.d (1H, exo-10-H,
2
J9a,exo-10 = 3.9, Jexo-10,11 = 4.4, J = 11.6 Hz), 2.55 d.d
13b-H, J13b,13c = 2.9 Hz), 5.29 d (1H, 3a-H, J3a,13c
8.4 Hz), 6.65 d (1H, 13-H, J12,13 = 5.6 Hz), 6.91 t (1H,
6-H, J5,6 = J6,7 = 7.7 Hz), 7.07 d (1H, 12-H, J12,13
5.6 Hz), 7.28 t (1H, 5-H, J4,5 = J5,6 = 7.7 Hz), 7.36 d
(1H, 4-H, J4,5 = 7.7 Hz), 7.70 d (1H, 7-H, J6,7
=
(1H, 9a-H, J9a,exo-10 = 3.9, J9a,endo-10 = 9.2 Hz), 3.15 m
(1H, 13c-H), 3.89–4.03 m (2H, 2-H), 4.52 d (1H,
13b-H, J13b, 13c = 2.9 Hz), 5.14 d.d (1H, 11-H,
Jexo-10,11 = 4.4, J11, 12 = 1.5 Hz), 5.35 d (1H, 3a-H,
J3a,13c = 8.2 Hz), 6.53 d.d (1H, 12-H, J11,12 = 1.5,
J12,13 = 5.8 Hz), 6.58 d (1H, 13-H, J12,13 = 5.8 Hz),
7.00 d.d (1H, 6-H, J5,6 = 7.7, J4,6 = 1.5 Hz), 7.29 t (1H,
5-H, J4,5 = J5,6 = 7.7 Hz), 7.36 d.d (1H, 4-H, J4,5 = 7.7,
J4,6 = 1.5 Hz), 9.45 s (OH). Mass spectrum, m/z (Irel,
%): 311 (31) [M]+, 266 (34), 256 (27), 212 (100), 196
(17), 160 (10), 121 (47), 103 (67), 94 (60), 80 (64), 59
(66). Found, %: C 69.29; H 5.22; N 4.34. C18H17NO4.
Calculated, %: C 69.44; H 5.50; N 4.50. M 311.12.
=
=
7.7 Hz), 11.8 br.s (COOH). Mass spectrum, m/z
(Irel, %): 417 (3) [M]+ (79Br), 318 (30), 293 (100), 264
(25), 248 (43), 236 (9), 115 (5), 44 (31). Found, %:
C 54.31; H 3.65; N 3.17. C19H16BrNO5. Calculated, %:
C 54.56; H 3.86; N 3.35. M 417.02.
Isoindoloquinolines Va, VI, and VII were reported
previously [1, 2].
Cycloaddition of furoquinolines IIc–IIe, III, and
IV to acryloyl chloride. A solution of 4.15 mmol of
tetrahydroquinoline IIc–IIe, III, or IV, 1.1 ml
(12 mmol) of acryloyl chloride, and 2.4 ml
(16.7 mmol) of triethylamine in 50 ml of benzene was
heated for 2–4 h under reflux (TLC). The mixture was
cooled and poured into 50 ml of water, the organic
layer was separated, and the aqueous layer was ex-
tracted with ethyl acetate (3×40 ml). The extracts were
combined with the organic phase, dried over anhy-
drous magnesium sulfate, and evaporated, and the
residue was recrystallized from hexane–ethyl acetate to
obtain mixtures of trans- and cis-isomeric isoindolo-
quinolines VIIIc–VIIIe, IX, and X as colorless crys-
talline substances.
(3aS*,9aS,R*,11R,S*,13aR,S*,13bS*,13cS*)-
11,13a-Epoxy-11-methyl-1,2,10,11,13b,13c-hexa-
hydro-3aH-furo[3,2-c]isoindolo[2,1-a]quinolin-
9(9aH)-one (VIIId) (mixture of trans and cis isomers
at a ratio of 1:1. Yield 87%, mp 157–158°C (from hex-
ane–ethyl acetate), Rf 0.62, 0.91 (hexane–ethyl acetate,
1
1:1). IR spectrum: ν 1691 cm–1 (C=O). H NMR spec-
trum (CDCl3), δ, ppm: trans isomer: 1.69 s (3H, Me),
1.80 d.d (1H, endo-10-H, J9a,endo-10 = 9.0, 2J = 11.8 Hz),
1.86 m (1H, 1-H), 2.07 d.d (1H, exo-10-H, J9a,exo-10
=
2
3.5, J = 11.8 Hz), 2.65 m (1H, 1-H), 2.89 m (1H,
13c-H), 3.72 d.d (1H, 9a-H, J9a,exo-10 = 3.5, J9a,endo-10
=
9.0 Hz), 3.86–3.95 m (2H, 2-H), 4.42 d (1H, 13b-H,
J13b, 13c = 2.7 Hz), 5.36 d (1H, 3a-H, J3a,13c = 8.2 Hz),
6.33 d (1H, 13-H, J12,13 = 5.7 Hz), 6.54 d (1H, 12-H,
J12,13 = 5.7 Hz), 7.17 d.t (1H, 5-H, J4,5 = J5,6 = 7.7,
(3aS*,9aS,R*,11R,S*,13aR,S*,13bS*,13cS*)-
11,13a-Epoxy-7-hydroxy-1,2,10,11,13b,13c-hexa-
hydro-3aH-furo[3,2-c]isoindolo[2,1-a]quinolin-
9(9aH)-one (VIIIc) (mixture of trans and cis isomers
at a ratio of 1:1). Yield 87%, mp 181–183°C (from
hexane–ethyl acetate), Rf 0.35, 0.21 (hexane–ethyl ace-
J5,7 = 1.1 Hz), 7.32 d.d (1H, 6-H, J5,6 = 7.7, J6,7
=
8.1 Hz), 7.42 br.d (1H, 4-H, J4,5 = 7.7 Hz), 8.03 d.d
(1H, 7-H, J5,7 = 1.1, J6,7 = 8.1 Hz); cis isomer: 1.64 s
(3H, Me), 1.71 d.d (1H, endo-10-H, J9a,endo-10 = 8.7,
2J = 11.8 Hz), 1.86 m (1H, 1-H), 1.99 d.d (1H, exo-
1
2
tate, 1:2). IR spectrum: ν 1696 cm–1 (C=O). H NMR
10-H, J9a,exo-10 = 3.6, J = 11.8 Hz), 2.70 m (1H, 1-H),
spectrum (CDCl3), δ, ppm: trans isomer: 1.76 d.d (1H,
3.11 m (1H, 13c-H), 3.66 d.d (1H, 9a-H, J9a,exo-10 = 3.6,
J9a,endo-10 = 8.7 Hz), 3.84 m (2H, 2-H), 4.70 d (1H,
2
endo-10-H, J9a,endo-10 = 9.2, J = 12.1 Hz), 1.90 m (1H,
1-H), 2.05 m (1H, 1-H), 2.34 d.d.d (1H, exo-10-H,
13b-H, J13b,13c = 2.5 Hz), 5.24 d (1H, 3a-H, J3a,13c =
2
J9a,exo-10 = 3.9, Jexo-10,11 = 4.8, J = 12.1 Hz), 2.76 d.d
7.2 Hz), 6.30 d (1H, 13-H, J12,13 = 5.7 Hz), 6.44 d (1H,
(1H, 9a-H, J9a,exo-10 = 3.9, J9a,endo-10 = 9.2 Hz), 3.21 m
(1H, 13c-H), 3.89–4.03 m (2H, 2-H), 4.47 d (1H,
13b-H, J13b, 13c = 3.4 Hz), 5.17 d.d (1H, 11-H,
Jexo-10,11 = 4.8, J11, 12 = 1.5 Hz), 5.37 d (1H, 3a-H,
J3a,13c = 8.2 Hz), 6.47 d.d (1H, 12-H, J11,12 = 1.5,
J12,13 = 5.8 Hz), 6.57 d (1H, 13-H, J12,13 = 5.8 Hz),
6.98 d.d (1H, 6-H, J5,6 = 7.7, J4,6 = 1.5 Hz), 7.21 t (1H,
5-H, J4,5 = J5,6 = 7.7 Hz), 7.22 d.d (1H, 4-H, J4,5 = 7.7,
12-H, J12,13 = 5.7 Hz), 7.11 d.t (1H, 5-H, J4,5 = J5,6
7.7, J5,7 = 1.1 Hz), 7.24 d.d (1H, 6-H, J5,6 = 7.7, J6,7
=
=
8.4 Hz), 7.48 br.d (1H, 4-H, J4,5 = 7.7 Hz), 8.66 d.d
(1H, 7-H, J5,7 = 1.1, J6,7 = 8.4 Hz). Mass spectrum, m/z
(Irel, %): 309 (18) [M]+, 264 (18), 210 (100), 158 (17),
130 (11), 115 (18), 91 (17), 77 (25), 55 (73), 43 (52).
Found, %: C 73.54; H 6.00; N 4.79. C19H19NO3. Cal-
culated, %: C 73.77; H 6.19; N 4.53. M 309.14.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010

ZUBKOV et al.
(3aS*,9aS,R*,11R,S*,13aR,S*,13bS*,13cS*)-11-
1200
2-H), 4.40 d (1H, 13b-H, J13b, 13c = 2.8 Hz), 4.96 d
Bromo-11,13a-epoxy-1,2,10,11,13b,13c-hexahydro-
3aH-furo[3,2-c]isoindolo[2,1-a]quinolin-9(9aH)-one
(VIIIe) (mixture of trans and cis isomers, 1:1). Yield
44%, mp 171–173°C (from hexane–ethyl acetate),
Rf 0.62, 0.79 (hexane–ethyl acetate, 1:1). IR spectrum:
(1H, 11-H, J11, 12 = 1.7 Hz), 5.27 d (1H, 3a-H, J3a,13c
8.3 Hz), 6.58 d.d (1H, 12-H, J11,12 = 1.7, J12,13
=
=
5.7 Hz), 6.92 d (1H, 13-H, J12,13 = 5.7 Hz), 7.14 d.t
(1H, 6-H, J4,6 = 1.3, J5,6 = J6,7 = 7.6 Hz), 7.26 d.t (1H,
5-H, J4,5 = J5,6 = 7.6, J5,7 = 1.3 Hz), 7.35 d.d (1H, 4-H,
J4,5 = 7.7, J4,6 = 1.3 Hz), 7.72 d.d (1H, 7-H, J5,7 = 1.3,
J6,7 = 7.6 Hz). 13C NMR spectrum (DMSO-d6), δC,
ppm: 22.3 q (Me, J = 128.0 Hz), 24.8 t (C1, J =
131.0 Hz), 39.3 d (C13c, J = 135.5 Hz), 51.0 s (C10),
58.7 d (C13b, J = 145.0 Hz), 59.1 d (C9a, J = 137.5 Hz),
67.2 t (C2, J = 147.0 Hz), 76.0 d (C3a, J = 152.0 Hz),
84.3 d (C11, J = 166.5 Hz), 90.5 s (C13a), 120.5 d (C7,
J = 164.5 Hz), 124.8 d (C5, J = 161.0 Hz), 127.7 d (C6,
J = 161.5 Hz), 128.7 s (C3b), 130.1 d (C4, J =
159.0 Hz), 134.8 d (C13, J = 177.8 Hz), 135.1 s (C7a),
137.1 s (C12, J = 177.0 Hz), 169.5 s (C9), 174.6 s
(COOH). Mass spectrum, m/z (Irel, %): 353 (1) [M]+,
241 (21), 196 (45), 130 (22), 115 (16), 91 (24), 77
(36), 68 (42), 39 (100). Found, %: C 67.55; H 5.76;
N 4.21. C20H19NO5. Calculated, %: C 67.98; H 5.42;
N 3.96. M 353.13.
1
ν 1701 cm–1 (C=O). H NMR spectrum (CDCl3), δ,
ppm: trans isomer: 1.88 m (1H, 1-H), 2.01 m (1H,
2
1-H), 2.31 d.d (1H, endo-10-H, J9a,endo-10 = 8.6, J =
2
11.9 Hz), 2.65 d.d (1H, exo-10-H, J9a,exo-10 = 3.6, J =
11.9 Hz), 2.77 d.d (1H, 9a-H, J9a,exo-10 = 3.6, J9a,endo-10
=
8.6 Hz), 3.09 m (1H, 13c-H), 3.84 m (1H, 2-H), 3.89 m
(1H, 2-H), 4.45 d (1H, 13b-H, J13b, 13c = 2.9 Hz),
5.35 br.d (1H, 3a-H, J3a,13c = 8.3 Hz), 6.52 d (1H,
13-H, J12,13 = 5.7 Hz), 6.55 d (1H, 12-H, J12,13
5.7 Hz), 7.17 d.t (1H, 5-H, J4,5 = J5,6 = 7.7, J5,7
=
=
1.2 Hz), 7.30 br.d.d (1H, 6-H, J5,6 = 7.7, J6,7 = 7.9 Hz),
7.41 d.d (1H, 4-H, J4,5 = 7.7, J4,6 = 1.4 Hz), 8.01 d.d
(1H, 7-H, J5,7 = 1.2, J6,7 = 7.9 Hz); cis isomer: 1.80 m
(1H, 1-H), 2.19 m (1H, 1-H), 2.24 d.d (1H, endo-10-H,
2
J9a,endo-10 = 8.5, J = 12.1 Hz), 2.61 d.d (1H, exo-10-H,
2
J9a,exo-10 = 3.6, J = 12.1 Hz), 2.80 d.d (1H, 9a-H,
J9a,exo-10 = 3.6, J9a,endo-10 = 8.5 Hz), 2.89 m (1H, 13c-H),
(3aS*,9aR*,10S*,11S*,13aS*,13bS*,13cS*)-
9a,10-Dibromo-11,13a-epoxy-9-oxo-1,2,9,9a,10,11,-
13b,13c-octahydro-3aH-furo[3,2-c]isoindolo[2,1-a]-
quinoline-10-carboxylic acid (XII). A solution of
0.9 g (3.50 mmol) of dibromomaleic anhydride in
10 ml of toluene was added to a solution of 0.8 g
(3.20 mmol) of compound IIa in 10 ml of toluene, and
the mixture was stirred for 3 days at room temperature
(TLC). The precipitate was filtered off and washed
with diethyl ether (2×15 ml). Yield 32%, colorless
crystals, mp 174°C (from i-PrOH–DMF). IR spectrum,
3.66 m (1H, 2-H), 3.84 m (1H, 2-H), 4.72 d (1H,
13b-H, J13b,13c = 2.7 Hz), 5.23 br.d (1H, 3a-H, J3a,13c
=
7.1 Hz), 6.48 d (1H, 13-H, J12,13 = 5.7 Hz), 6.51 d (1H,
12-H, J12,13 = 5.7 Hz), 7.12 d.t (1H, 5-H, J4,5 = J5,6
=
7.6, J5,7 = 1.1 Hz), 7.28 br.d.d (1H, 6-H, J5,6 = 7.6,
J6,7 = 8.0 Hz), 7.48 br.d (1H, 4-H, J4,5 = 7.6 Hz),
8.61 d.d (1H, 7-H, J5,7 = 1.1, J6,7 = 8.0 Hz). Mass spec-
trum, m/z (Irel, %): 373 (25) [M]+ (79Br), 328 (14), 294
(37), 274 (100), 194 (35), 182 (33), 172 (43), 158 (81),
130 (31), 115 (26), 91 (56), 77 (43), 55 (93), 43 (70).
Found, %: C 57.92; H 4.48; N 3.98. C18H16BrNO3.
Calculated, %: C 57.77; H 4.31; N 3.74. M 373.03.
ν, cm–1: 1723 (COOH), 1702 (C9=O). H NMR spec-
1
trum (DMSO-d6), δ, ppm: 1.60 m (1H, 1-H), 1.93 m
Isoindoloquinolines VIIIa, IX, and X were re-
(1H, 1-H), 2.90 m (1H, 13c-H), 3.49 m (1H, 2-H),
ported previously [1, 2].
3.74 m (1H, 2-H), 5.04 d (1H, 13b-H, J13b, 13c
=
2.6 Hz), 5.26 d (1H, 3a-H, J3a,13c = 6.8 Hz), 5.61 d (1H,
11-H, J11, 12 = 1.8 Hz), 6.76 m (2H, 12-H, 13-H),
7.17 d.t (1H, 5-H, J4,5 = J5,6 = 7.3, J5,7 = 1.3 Hz),
7.28 d.d (1H, 6-H, J5,6 = 7.3, J6,7 = 8.3 Hz), 7.42 br.d
(1H, 4-H, J4,5 = 7.3 Hz), 8.44 d.d (1H, 7-H, J5,7 = 1.3,
J6,7 = 8.3 Hz). Mass spectrum, m/z (Irel, %): 497 (2)
[M]+ (79Br), 371 (11), 325 (26), 293 (21), 241 (67), 220
(33), 196 (92), 167(61), 143 (47), 131 (100), 115 (70),
80 (96), 59 (68). Found, %: C 45.73; H 2.88; N 2.66.
C19H15Br2NO5. Calculated, %: C 45.90; H 3.04;
N 2.82. M 494.93.
(3aS*,9aS*,10R*,11S*,13aR*,13bS*,13cS*)-
11,13a-Epoxy-10-methyl-9-oxo-1,2,9,9a,10,11,13b,-
13c-octahydro-3aH-furo[3,2-c]isoindolo[2,1-a]quin-
oline-10-carboxylic acid (XI). A solution of 1 g
(0.04 mol) of compound IIa and 16.2 ml (0.18 mol) of
citraconic anhydride in 20 ml of o-xylene was heated
for 6 h, the progress of the reaction being monitored by
TLC. The solvent was distilled off, and the precipitate
was filtered off and recrystallized from propan-2-ol–
DMF. Yield 19%, colorless crystals, mp 140°C (from
i-PrOH–DMF). IR spectrum, ν, cm–1: 1721 (COOH),
1
1659 (C9=O). H NMR spectrum (DMSO-d6), δ, ppm:
Cycloaddition of furoquinoline IIa to cinnamoyl
and methacryloyl chlorides. A solution of 1 g
(4.15 mmol) of tetrahydroquinoline IIa, 2 g (12 mmol)
1.12 s (3H, Me), 1.52 m (1H, 1-H), 2.10 m (1H, 1-H),
3.12 m (1H, 13c-H), 3.67 m (1H, 2-H), 3.75 m (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010

PERHYDROFURO[3,2-c]-, PERHYDROPYRANO[3,2-c]-, ...
1201
of cinnamoyl chloride (in the synthesis of compound
XIII) or 1.2 ml (12 mmol) of methacryloyl chloride (in
the synthesis of XIV), and 2.4 ml (16.7 mmol) of
triethylamine in 50 ml of benzene was heated for 4 h
under reflux (TLC). The mixture was cooled and
poured into 50 ml of water, the organic layer was
separated, the aqueous layer was extracted with ethyl
acetate (3×40 ml), the extracts were combined with
the organic phase, dried over anhydrous magnesium
sulfate, and evaporated, and the residue was recrys-
tallized from hexane–ethyl acetate.
C 73.89; H 6.05; N 4.89. C19H19NO3. Calculated, %:
C 73.77; H 6.19; N 4.53. M 309.14.
Esterification of epoxyisoindoloquinolinecarbox-
ylic acids Vd, VI, VII, and XI (general procedure).
A mixture of 4.4 mmol of trans-isomeric acid Vd, VI,
or XI or cis-acid VII, 30 ml of methanol, and one drop
of sulfuric acid was heated for 2–6 h under reflux. The
solution was poured into 50 ml of water and extracted
with chloroform (3×50 ml), the extract was dried over
anhydrous magnesium sulfate and evaporated, and the
residue was recrystallized from ethyl–acetate–hexane
to isolate methyl esters XVd and XVI–XVIII as
colorless crystalline substances.
(3aS*,9aS*,10R*,11S*,13aR*,13bS*,13cS*)-
11,13a-Epoxy-10-phenyl-1,2,10,11,13b,13c-hexa-
hydro-3aH-furo[3,2-c]isoindolo[2,1-a]quinolin-
9(9aH)-one (XIII). Yield 37%, colorless crystals,
mp 174°C (from hexane–ethyl acetate), Rf 0.83
(hexane–ethyl acetate, 1:1). IR spectrum: ν 1693 cm–1
Methyl (3aS*,9aS,R*,10RS*,11SR*,13aRS*,-
13bS*,13cS*)-11,13a-Epoxy-11-methyl-9-oxo-1,2,9,-
9a,10,11,13b,13c-octahydro-3aH-furo[3,2-c]isoin-
dolo[2,1-a]quinoline-10-carboxylate (XVd) (mixture
of trans and cis isomers). Yield 80%, mp 187–189°C
(from hexane–ethyl acetate), Rf 0.47 (ethanol–ethyl
acetate, 1:8). IR spectrum, ν, cm–1: 1730 (COOMe),
1
(C=O). H NMR spectrum (CDCl3), δ, ppm: 1.96 m
(1H, 1-H), 2.18 m (1H, 1-H), 2.93 m (1H, 13c-H),
2.93 d (1H, 9a-H, J9a,10 = 4.3 Hz), 3.71 m (1H, 2-H),
3.88 m (1H, 2-H), 3.92 t (1H, 10-H, J9a,10 = J10,11
=
1
1702 (C9=O). H NMR spectrum (CDCl3), δ, ppm:
4.3 Hz), 4.81 d (1H, 13b-H, J13b,13c = 2.2 Hz), 5.29 d.d
(1H, 11-H, J11,12 = 1.6, J10,11 = 4.3 Hz), 5.30 br.s (1H,
3a-H), 6.41 d.d (1H, 12-H, J11,12 = 1.6, J12,13 = 5.6 Hz),
6.64 d (1H, 13-H, J12,13 = 5.6 Hz), 7.21–7.32 m (7H,
Harom), 7.52 d (1H, 4-H, J4,5 = 7.7 Hz), 8.69 d (1H,
7-H, J6,7 = 8.1 Hz). Mass spectrum, m/z (Irel, %): 371
(32) [M]+, 326 (15), 240 (40), 213 (14), 196 (82), 154
(16), 131 (100), 103 (67), 77 (24), 43 (64), 33 (34).
Found, %: C 77.93; H 5.98; N 3.86. C24H21NO3. Cal-
culated, %: C 77.61; H 5.70; N 3.77. M 371.15.
trans isomer: 1.68 s (3H, Me), 1.81 m (1H, 1-H),
2.05 m (1H, 1-H), 2.90 d (1H, 9a-H, J9a,10 = 8.8 Hz),
2.99 d (1H, 10-H, J9a,10 = 8.8 Hz), 3.13 m (1H, 13c-H),
3.84 s (3H, OMe), 3.86 m (1H, 2-H), 3.93 m (1H,
2-H), 4.57 d (1H, 13b-H, J13b,13c = 2.6 Hz), 5.37 d (1H,
3a-H, J3a,13c = 8.2 Hz), 6.34 d (1H, 12-H, J12,13
=
5.6 Hz), 6.69 d (1H, 13-H, J12,13 = 5.6 Hz), 7.18 br.t
(1H, 5-H, J4,5 = J5,6 = 7.5 Hz), 7.30 d.d.d (1H, 6-H,
J4,6 = 1.0, J5,6 = 7.5, J6,7 = 8.2 Hz), 7.43 br.d (1H, 4-H,
J4,5 = 7.5 Hz), 7.96 d (1H, 7-H, J6,7 = 8.2 Hz); cis iso-
mer: 1.66 s (3H, Me), 2.05 m (1H, 1-H), 2.25 m (1H,
1-H), 2.82 d (1H, 9a-H, J9a,10 = 8.8 Hz), 2.93 m (1H,
13c-H), 3.04 d (1H, 10-H, J9a,10 = 8.8 Hz), 3.77 s (3H,
(3aS*,9aS*,11R*,13aR*,13bS*,13cS*)-11,13a-
Epoxy-9a-methyl-1,2,10,11,13b,13c-hexahydro-
3aH-furo[3,2-c]isoindolo[2,1-a]quinolin-9(9aH)-one
(XIV). Yield 55%, colorless crystals, mp 148°C (from
hexane–ethyl acetate), Rf 0.50 (hexane–ethyl acetate,
OMe), 3.66 m (2H, 2-H), 4.69 d (1H, 13b-H, J13b,13c
2.3 Hz), 5.28 d (1H, 3a-H, J3a,13c = 7.2 Hz), 6.28 d (1H,
12-H, J12,13 = 5.6 Hz), 6.61 d (1H, 13-H, J12,13
5.6 Hz), 7.13 br.t (1H, 5-H, J4,5 = J5,6 = 7.5 Hz),
7.26 d.d.d (1H, 6-H, J4,6 = 0.9, J5,6 = 7.5, J6,7
=
1
2:1). IR spectrum: ν 1692 cm–1 (C=O). H NMR spec-
=
trum (CDCl3), δ, ppm: 1.06 s (3H, Me), 1.10 d (1H,
2
endo-10-H, J = 11.7 Hz), 1.84 m (1H, 1-H), 2.49 d.d
2
=
(1H, exo-10-H, Jexo-10,11 = 4.7, J = 11.7 Hz), 2.05 m
8.2 Hz), 7.48 br.d (1H, 4-H, J4,5 = 7.5 Hz), 8.65 d (1H,
7-H, J6,7 = 8.2 Hz). Mass spectrum, m/z (Irel, %): 367
(17) [M]+, 322 (16), 254 (100), 210 (37), 180 (4), 135
(6), 13 (9), 43 (6). Found, %: C 68.80; H 5.58; N 3.65.
C21H21NO5. Calculated, %: C 68.65; H 5.76; N 3.81.
M 367.14.
(1H, 1-H), 2.82 m (1H, 13c-H), 3.62 m (1H, 2-H),
3.78 m (1H, 2-H), 4.62 d (1H, 13b-H, J13b, 13c
2.7 Hz), 4.97 d.d (1H, 11-H, J11,12 = 1.6, Jexo-10,11
=
=
4.7 Hz), 5.21 d (1H, 3a-H, J3a,13c = 7.0 Hz), 6.39 d (1H,
13-H, J12,13 = 5.8 Hz), 6.48 d.d (1H, 12-H, J11,12 = 1.6,
J12,13 = 5.7 Hz), 7.06 d.t (1H, 5-H, J4,5 = J5,6 = 7.6,
J5,7 = 0.8 Hz), 7.22 d.d.d (1H, 6-H, J4,6 = 1.0, J5,6
=
Methyl (3aS*,9aS*,10R*,11S*,13aR*,13bS*,-
13cS*)-11,13a-epoxy-10-methyl-9-oxo-1,2,9,9a,-
10,11,13b,13c-octahydro-3aH-furo[3,2-c]isoindolo-
[2,1-a]quinoline-10-carboxylate (XVI) (trans iso-
mer). Yield 46%, mp 220°C (from hexane–ethyl ace-
7.6, J6,7 = 8.4 Hz), 7.43 br.d (1H, 4-H, J4,5 = 7.6 Hz),
8.61 d.d (1H, 7-H, J5,7 = 0.8, J6,7 = 8.4 Hz). Mass spec-
trum, m/z (Irel, %): 309 (7) [M]+, 264 (5), 240 (3), 180
(3), 15 (5), 91 (7), 69 (51), 41 (100). Found, %:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010

ZUBKOV et al.
1202
tate), Rf 0.50 (hexane–ethyl acetate, 2:1). IR spectrum,
ν, cm–1: 1721 (COOMe), 1687 (C9=O). 1H NMR spec-
trum (CDCl3), δ, ppm: 1.33 s (3H, Me), 1.78 m (1H,
1-H), 2.04 m (1H, 1-H), 3.13 m (1H, 13c-H), 3.82–
10-H, J120a,endo-10 = 9.2 Hz), 3.70 d.q and 3.59 (1H each,
3
OCH2, J = 9.0, J = 6.9 Hz), 3.81 s (3H, OMe),
4.54 d.d (1H, 6a-H, J6a,6-ax = 12.5, J6a,6-eq = 2.6 Hz),
4.83 d.d (1H, 5-H, J5,6-ax = 11.5, J5,6-eq = 5.9 Hz),
5.26 d (1H, 9-H, J8,9 = 1.3 Hz), 6.56 m (2H, 7-H, 8-H),
7.12 d.t (1H, 3-H, J2,3 = J3,4 = 7.7, J1,3 = 0.8 Hz),
3.92 m (2H, 2-H), 4.48 d (1H, 13b-H, J13b, 13c
=
3.1 Hz), 5.05 d (1H, 11-H, J11, 12 = 1.9 Hz), 5.36 d (1H,
3a-H, J3a,13c = 8.1 Hz), 6.58 d.d (1H, 12-H, J11,12 = 1.9,
J12,13 = 5.6 Hz), 6.70 d (1H, 13-H, J12,13 = 5.6 Hz),
7.26 d.d.d (1H, 2-H, J1,2 = 8.4, J2,3 = 7.7, J2,4
=
0.8 Hz), 7.58 d (1H, 4-H, J3,4 = 7.7 Hz), 8.63 d.d (1H,
1-H, J1,2 = 8.4, J1,3 = 0.8 Hz). Mass spectrum, m/z
(Irel, %): 355 (24) [M]+, 242 (43), 196 (100), 168 (7),
130 (12), 113 (17), 77 (6), 65 (5). Found, %: C 67.72;
H 5.88; N 3.76. C20H21NO5. Calculated, %: C 67.59;
H 5.96; N 3.94. M 355.38.
7.30 d.d.d (1H, 6-H, J4,6 = 1.2, J5,6 = 7.5, J6,7
8.1 Hz), 7.17 d.t (1H, 5-H, J4,5 = J5,6 = 7.5, J5,7
=
=
1.2 Hz), 7.42 br.d (1H, 4-H, J4,5 = 7.5, J4,6 = 1.2 Hz),
7.97 d.d (1H, 7-H, J5,7 = 1.2, J6,7 = 8.1 Hz). Mass spec-
trum, m/z (Irel, %): 367 (9) [M]+, 322 (7), 240 (100),
196 (43), 127 (52), 101 (26), 83 (14), 59 (23), 43 (47).
Found, %: C 68.92; H 5.53; N 3.56. C21H21NO5. Cal-
culated, %: C 68.65; H 5.76; N 3.81. M 367.14.
trans- and cis-Isomeric methyl esters XVa were
reported previously [1, 2].
Epoxidation of compounds X, XIII, XIV, trans-
XVa, trans-XVd, trans-XVI, trans-XVII, and cis-
XVIII (general procedure). A solution of 5 mmol of
isoindoloquinoline X, XIII, XIV, trans-XVa, trans-
XVd, trans-XVI, trans-XVII, or cis-XVIII and 2.19 g
(12.7 mmol) of m-chloroperoxybenzoic acid in 50 ml
of methylene chloride was stirred for 2 h, the progress
of the reaction being monitored by TLC. The mixture
was then poured into 50 ml of water and made weakly
alkaline by adding a saturated solution of sodium car-
bonate. The organic layer was separated, the aqueous
phase was extracted with methylene chloride (3×
50 ml), the extracts were combined with the organic
phase, dried over anhydrous magnesium sulfate, and
filtered. The solvent was distilled off, and the residue
was recrystallized from ethyl acetate–hexane.
Methyl (4aS*,10aS*,11R*,12S*,14aR*,14bS*,-
14cS*)-12,14a-Epoxy-10-oxo-2,3,10,10a,11,12,-
14b,14c-octahydro-1H,4aH-pyrano[3,2-c]isoindolo-
[2,1-a]quinoline-11-carboxylate (XVII) (trans iso-
mer). Yield 93%, mp 256°C (from hexane–ethyl ace-
tate), Rf 0.50 (hexane–ethyl acetate, 1:4). IR spectrum,
ν, cm–1: 1690 (C10=O), 1736 (COOMe). 1H NMR spec-
trum (CDCl3), δ, ppm: 1.45 m (1H, 1-H), 1.53 m (1H,
1-H), 1.64 m (1H, 2-H), 1.81 m (1H, 2-H), 2.60 m (1H,
14c-H), 2.83 d (1H, 11-H, J10a,11 = 9.1 Hz), 2.85 d (1H,
10a-H, J10a,11 = 9.1 Hz), 3.31 m (1H, 3-H), 3.65 m
(1H, 3-H), 3.81 s (3H, OCH3), 4.37 br.d (1H, 14b-H,
J14b,14c = 1.9 Hz), 5.15 br.d (1H, 4a-H, J4a,14c = 5.9 Hz),
5.18 d (1H, 12-H, J12,13 = 1.7 Hz), 6.53 d.d (1H, 13-H,
J13,14 = 5.7, J12,13 = 1.7 Hz), 6.66 d (1H, 14-H, J13,14
=
5.7 Hz), 7.17 br.d.t (1H, 6-H, J6,7 = 7.5, J5,6 = 7.7,
Methyl (3aS*,9aS*,10R*,11R*,11aR*,12aR*,-
12bR*,12cS*,12dS*)-11,12b-epoxy-9-oxo-1,2,9,9a,-
10,11,11a,12a,12c,12d-decahydro-3aH-furo[3,2-c]-
oxirano[6,7]isoindolo[2,1-a]quinoline-10-carbox-
ylate (XIXa). Yield 53%, colorless crystals, mp 192°C
(from hexane–ethyl acetate), Rf 0.20 (hexane–ethyl
acetate, 1:1). IR spectrum, ν, cm–1: 1725 (COOMe),
J6,8 = 1.1 Hz), 7.28 d.d.d (1H, 7-H, J7,8 = 8.1, J6,7
7.5, J5,7 = 0.9 Hz), 7.54 d.d (1H, 5-H, J5,6 = 7.7, J5,7
=
=
0.9 Hz), 8.10 d.d (1H, 8-H, J7,8 = 8.1, J6,8 = 1.1 Hz).
Mass spectrum, m/z (Irel, %): 367 (33) [M]+, 308 (11),
254 (100), 210 (11), 196 (37), 167 (6), 113 (15), 77
(6), 59 (5). Found, %: C 68.99; H 5.91; N 3.66.
C21H11NO5. Calculated, %: C 68.65; H 5.76; N 3.81.
M 367.40.
1
1696 (C9=O). H NMR spectrum (CDCl3), δ, ppm:
1.76 m (1H, 1-H), 2.10 m (1H, 1-H), 3.04 d (1H, 10-H,
Methyl (5S*,6aS*,6bS*,9R*,10S*,10aR*)-6b,9-
Epoxy-5-ethoxy-11-oxo-6,6a,9,10,10a,11-hexahydro-
5H-isoindolo[2,1-a]quinoline-10-carboxylate
(XVIII) (cis isomer). Yield 78%, mp 154−156°C
(from hexane–ethyl acetate), Rf 0.65 (hexane–ethyl
acetate, 6:1). IR spectrum, ν, cm–1: 1691 (C11=O),
J9a,10 = 9.4 Hz), 3.14 d (1H, 9a-H, J9a,10 = 9.4 Hz),
3.14 m (1H, 12d-H), 3.49 d (1H, 11a-H, J11a,12a
=
3.3 Hz), 3.56 d (1H, 12a-H, J11a,12a = 3.3 Hz), 3.80 s
(3H, OMe), 3.81 m (1H, 2-H), 3.93 m (1H, 2-H),
4.52 d (1H, 12c-H, J12c, 12d = 2.5 Hz), 4.79 s (1H,
11-H), 5.36 d (1H, 3a-H, J3a,12d = 8.1 Hz), 7.17 d.d.d
(1H, 6-H, J4,6 = 0.9, J5,6 = 7.7, J6,7 = 8.3 Hz), 7.27 d.t
(1H, 5-H, J5,7 = 0.9, J4,5 = J5,6 = 7.7 Hz), 7.42 br.d (1H,
4-H, J4,5 = 7.7 Hz), 7.94 br.d (1H, 7-H, J6,7 = 8.3 Hz).
Mass spectrum, m/z (Irel, %): 369 (100) [M]+, 338 (6),
280 (3), 174 (7), 156 (3), 143 (4), 130 (5), 113 (5), 77
1
1739 (COOMe). H NMR spectrum (CDCl3), δ, ppm:
3
1.30 t (3H, CH2CH3, J = 6.9 Hz), 2.27 d.t (1H, 6-Hax,
2
J5,6-ax = 11.5, J6a,6-ax = J = 12.5 Hz), 2.47 d.d.d (1H,
2
6-Heq, J5,6-eq = 5.9, J6a,6-eq = 2.6, J = 12.5 Hz), 2.82 d
(1H, 10a-H, J10a,endo-10 = 9.2 Hz), 3.03 d (1H, endo-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010

PERHYDROFURO[3,2-c]-, PERHYDROPYRANO[3,2-c]-, ...
1203
(2). Found, %: C 65.13; H 5.08; N 3.99. C20H19NO6.
mp 278−280°C (from hexane–ethyl acetate), Rf 0.65
(hexane–ethyl acetate, 1:4). IR spectrum, ν, cm–1:
Calculated, %: C 64.99; H 5.21; N 3.76. M 369.12.
1
1691 (C10=O), 1734 (COOMe). H NMR spectrum
Methyl (3aS*,9aS*,10R*,11R*,11aR*,12aR*,-
12bR*,12cS*,12dS*)-11,12b-epoxy-11-methyl-9-oxo-
1,2,9,9a,10,11,11a,12a,12c,12d-decahydro-3aH-furo-
[3,2-c]oxirano[6,7]isoindolo[2,1-a]quinoline-10-car-
boxylate (XIXb). Yield 58%, colorless crystals,
mp 225−227°C (from hexane–ethyl acetate), Rf 0.55
(ethyl acetate). IR spectrum, ν, cm–1: 1740 (COOMe),
(CDCl3), δ, ppm: 1.44 m (1H, 1-H), 1.55 m (1H, 1-H),
1.67 m (1H, 2-H), 1.82 m (1H, 2-H), 2.63 m (1H,
13d-H), 3.01 d (1H, 11-H, J10a,11 = 9.4 Hz), 3.05 d (1H,
10a-H, J10a,11 = 9.4 Hz), 3.28 m (1H, 3-H), 3.46 d (1H,
12a-H, J11a,12a = 3.2 Hz), 3.60 d (1H, 13a-H, J12a,13a
=
3.2 Hz), 3.63 m (1H, 3-H), 3.78 s (3H, OCH3), 4.33 d
(1H, 13c-H, J13c,13d = 1.9 Hz), 4.76 s (1H, 12-H),
5.13 d (1H, 4a-H, J4a,13d = 5.9 Hz), 7.18 d.t (1H, 6-H,
J5,6 = J6,7 = 7.7, J6,8 = 1.0 Hz), 7.28 d.d.d (1H, 7-H,
J7,8 = 8.2, J6,7 = 7.7, J5,7 = 0.8 Hz), 7.54 br.d (1H, 5-H,
1
1701 (C9=O). H NMR spectrum (CDCl3), δ, ppm:
1.55 s (3H, Me), 1.72 m (1H, 1-H), 2.08 m (1H, 1-H),
2.99 d (1H, 10-H, J9a,10 = 9.4 Hz), 3.07 d (1H, 9a-H,
J9a,10 = 9.4 Hz), 3.12 m (1H, 12d-H), 3.32 d (1H,
J5,6 = 7.7 Hz), 8.06 d.d (1H, 8-H, J7,8 = 8.2, J6,8
=
11a-H, J11a,12a = 3.3 Hz), 3.59 d (1H, 12a-H, J11a,12a
=
1.0 Hz). Mass spectrum, m/z (Irel, %): 383 (93) [M]+,
324 (11), 294 (11), 280 (14), 254 (17), 238 (17), 224
(16), 210 (19), 196 (63), 186 (64), 170 (46), 156 (65),
144 (47), 130 (64), 113 (41), 101 (86), 91 (48), 80
(87), 71 (78), 59 (100), 43 (57). Found, %: C 65.97;
H 5.67; N 3.44. C21H21NO6. Calculated, %: C 65.79;
H 5.52; N 3.65. M 383.39.
3.3 Hz), 3.78 s (3H, OMe), 3.78 m (1H, 2-H), 3.92 m
(1H, 2-H), 4.50 d (1H, 12c-H, J12c,12d = 2.7 Hz), 5.34 d
(1H, 3a-H, J3a,12d = 8.0 Hz), 7.16 d.t (1H, 5-H, J5,7
1.2, J4,5 = J5,6 = 7.7 Hz), 7.27 d.d.d (1H, 6-H, J4,6
1.3, J5,6 = 7.7, J6,7 = 8.3 Hz), 7.41 d.d (1H, 4-H, J4,6
1.3, J4,5 = 7.7 Hz), 7.92 d.d (1H, 7-H, J5,7 = 1.2, J6,7
=
=
=
=
8.3 Hz). Mass spectrum, m/z (Irel, %): 383 (100) [M]+,
308 (19), 280 (66), 254 (39), 222 (32), 172 (44), 130
(46), 13 (44), 101 (55), 76 (61), 59 (89), 43 (75).
Found, %: C 65.67; H 5.39; N 3.82. C21H21NO6. Cal-
culated, %: C 65.79; H 5.52; N 3.65. M 383.14.
(3aS*,9aS*,10R*,11R*,11aR*,12aR*,12bR*,-
12cS*,12dS*)-11,12b-Epoxy-10-phenyl-1,2,10,11,-
11a,12a,12c,12d-octahydro-3aH-furo[3,2-c]oxirano-
[6,7]isoindolo[2,1-a]quinolin-9(9aH)-one (XXIa).
Yield 57%, colorless crystals, mp 200°C (from hex-
ane–ethyl acetate), Rf 0.73 (hexane–ethyl acetate, 1:1).
Methyl (3aS*,9aS*,10R*,11R*,11aR*,12aR*,-
12bR*,12cS*,12dS*)-11,12b-epoxy-10-methyl-9-
oxo-1,2,9,9a,10,11,11a,12a,12c,12d-decahydro-3aH-
furo[3,2-c]oxirano[6,7]isoindolo[2,1-a]quinoline-
10-carboxylate (XIXc). Yield 54%, colorless crystals,
mp 223°C (from hexane–ethyl acetate), Rf 0.25 (hex-
ane–ethyl acetate, 1:2). IR spectrum, ν, cm–1: 1724
1
IR spectrum: ν 1702 cm–1 (C=O). H NMR spectrum
(CDCl3), δ, ppm: 1.92 m (1H, 1-H), 2.23 m (1H, 1-H),
2.95 m (1H, 12d-H), 3.11 d (1H, 9a-H, J9a,10 = 5.0 Hz),
3.39 d (1H, 11a-H, J11a,12a = 3.3 Hz), 3.55 d (1H,
12a-H, J11a,12a = 3.3 Hz), 3.68 m (1H, 2-H), 3.86 m
(1H, 2-H), 3.97 t (1H, 10-H, J9a,10 = J10,11 = 5.0 Hz),
4.69 d (1H, 12c-H, J12c,12d = 2.8 Hz), 4.84 d (1H, 11-H,
J10,11 = 5.0 Hz), 5.23 d (1H, 3a-H, J3a,12d = 7.2 Hz),
7.11 br.t (1H, 5-H, J4,5 = J5,6 = 7.7 Hz), 7.25–7.35 m
(6H, Harom), 7.49 d (1H, 4-H, J4,5 = 7.7 Hz), 8.60 d
(1H, 7-H, J6,7 = 8.8 Hz). Found, %: C 74.15; H 5.68;
N 3.82. C24H21NO4. Calculated, %: C 74.40; H 5.46;
N 3.62. M 387.15.
1
(COOMe), 1690 (C9=O). H NMR spectrum (CDCl3),
δ, ppm: 1.47 s (3H, Me), 1.67 m (1H, 1-H), 2.06 m
(1H, 1-H), 2.54 s (1H, 9a-H), 3.09 m (1H, 12d-H),
3.56 d (1H, 11a-H, J11a,12a = 3.3 Hz), 3.58 d (1H,
12a-H, J11a,12a = 3.3 Hz), 3.74 s (3H, OMe), 3.74 m
(1H, 2-H), 3.87 m (1H, 2-H), 4.41 d (1H, 12c-H,
J12c,12d = 2.8 Hz), 4.52 s (1H, 11-H), 5.30 d (1H, 3a-H,
J3a,12d = 7.7 Hz), 7.13 d.t (1H, 5-H, J5,7 = 1.5, J4,5
J5,6 = 7.7 Hz), 7.24 d.d.d (1H, 6-H, J4,6 = 1.7, J5,6
7.7, J6,7 = 8.2 Hz), 7.37 d.d (1H, 4-H, J4,6 = 1.7, J4,5
=
=
=
(3aS*,9aS*,11R*,11aR*,12aR*,12bR*,12cS*,-
12dS*)-11,12b-Epoxy-9a-methyl-1,2,10,11,11a,12a,-
12c,12d-octahydro-3aH-furo[3,2-c]oxirano[6,7]iso-
indolo[2,1-a]quinolin-9(9aH)-one (XXIb). Yield
48%, colorless crystals, mp 190°C (from hexane–ethyl
acetate), Rf 0.33 (hexane–ethyl acetate, 1:1). IR spec-
trum: ν 1697 cm–1 (C=O). 1H NMR spectrum (CDCl3),
7.7 Hz), 7.87 d.d (1H, 7-H, J5,7 = 1.5, J6,7 = 8.2 Hz).
Found, %: C 65.55; H 5.33; N 3.81. C21H21NO6. Cal-
culated, %: C 65.79; H 5.52; N 3.65.
Methyl (4aS*,10aS*,11R*,12R*,12aR*,13aR*,-
13bR*,13cS*,13dS*)-12,13b-epoxy-10-oxo-2,3,10,-
10a,11,12,12a,13a,13c,13d-decahydro-1H,4aH-
pyrano[3,2-c]oxirano[6,7]isoindolo[2,1-a]quinoline-
11-carboxylate (XX). Yield 87%, colorless crystals,
2
δ, ppm: 1.32 s (3H, Me), 1.42 d (1H, endo-10-H, J =
12.7 Hz), 1.88 m (1H, 1-H), 2.16 m (1H, 1-H),
2
2.49 d.d (1H, exo-10-H, J = 12.7, Jexo-10,11 = 5.3 Hz),
2.94 m (1H, 12d-H), 3.47 d (1H, 11a-H, J11a,12a
=
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010

ZUBKOV et al.
1204
3
3.3 Hz), 3.52 d (1H, 12a-H, J11a,12a = 3.3 Hz), 3.66 m
3.3 Hz), 3.74 m and 3.59 m (1H each, OCH2, J =
(1H, 2-H), 3.85 m (1H, 2-H), 4.53 d (1H, 11-H,
6.9 Hz), 3.77 s (3H, OMe), 4.41 d.d (1H, 11a-H,
J11a,11-ax = 12.5, J11a,11-eq = 2.3 Hz), 4.78 d.d (1H, 10-H,
J10,11-ax = 11.2, J10,11-eq = 5.9 Hz), 4.84 s (1H, 2-H),
7.13 t (1H, 8-H, J7,8 = J8,9 = 7.7 Hz), 7.25 d.d (1H,
Jexo-10,11 = 5.3 Hz), 4.58 d (1H, 12c-H, J12c,12d
=
2.8 Hz), 5.24 d (1H, 3a-H, J3a,12d = 7.1 Hz), 7.11 d.t
(1H, 5-H, J5,7 = 1.1, J4,5 = J5,6 = 7.6 Hz), 7.24 m (1H,
6-H), 7.48 br.d (1H, 4-H, J4,5 = 7.6 Hz), 8.59 d.d (1H,
7-H, J5,7 = 1.1, J6,7 = 8.5 Hz). Mass spectrum, m/z
(Irel, %): 325 (97) [M]+, 309 (8), 280 (100), 240 (12),
200 (12), 156 (25), 139 (34), 128 (36), 101 (52), 83
(27), 69 (37), 55 (54), 43 (62). Found, %: C 70.37;
H 6.02; N 4.17. C19H19NO4. Calculated, %: C 70.14;
H 5.89; N 4.31. M 325.13.
7-H, J6,7 = 8.2, J7,8 = 7.7 Hz), 7.58 d (1H, 9-H, J8,9
=
7.7 Hz), 8.56 d (1H, 6-H, J6,7 = 8.2 Hz). Mass spec-
trum, m/z (Irel, %): 371 (81) [M]+, 326 (17), 295 (32),
267 (26), 238 (52), 196 (46), 182 (24), 167 (21), 130
(39), 113 (24), 101 (36), 76 (100), 55 (87), 43 (77).
Found, %: C 64.87; H 5.17; N 3.32. C20H21NO6. Cal-
culated, %: C 64.68; H 5.70; N 3.77. M 371.38.
Aromatization of carboxylic acids Va and VI
(general procedure). A solution of ~1 g (~2.8 mmol) of
carboxylic acid Va or VI in 15 ml of phosphoric acid
was stirred for 30 min at 85°C. The mixture was
cooled to 20°C and poured into 50 ml of water, and the
precipitate was filtered off and recrystallized from
propan-2-ol–DMF.
(1aS*,2S*,3aR*,10S*,11aS*,11bS*,11cS*)-2,11b-
Epoxy-10-ethoxy-1a,3,3a,11,11a,11c-hexahydro-
10H-oxirano[6,7]isoindolo[2,1-a]quinolin-4(2H)-one
(XXIIa). Yield 48%, colorless crystals, mp 149−150°C
(from hexane–ethyl acetate), Rf 0.29 (hexane–ethyl
acetate, 1:1). IR spectrum: ν 1691 cm–1 (C=O).
1H NMR spectrum (CDCl3), δ, ppm: 1.27 t (3H,
3
CH2CH3, J = 7.0 Hz), 1.86 d.d (1H, endo-3-H,
(3aS*,13bS*,13cS*)-9-Oxo-1,2,3a,9,13b,13c-
hexahydrofuro[3,2-c]isoindolo[2,1-a]quinoline-10-
carboxylic acid (XXIIIa). Yield 89%, colorless crys-
tals, mp 236–238°C (i-PrOH–DMF). IR spectrum, ν,
2
J3a,endo-3 = 9.1, J = 12.7 Hz), 2.10 br.q (1H, 11-Hax,
2
J10, 11-ax = 11.0, J11a,11-ax = 12.1, J = 12.7 Hz),
2.25 d.d.d (1H, exo-3-H, J2,exo-3 = 5.1, J3a,exo-3 = 3.8,
2J = 12.7 Hz), 2.54 d.d.d (1H, 11-Heq, J10,11-eq = 5.7,
1
cm–1: 1705 (COOH), 1620 (C9=O). H NMR spectrum
2
2
J11a,11-eq = 1.5, J = 12.7 Hz), 2.80 d.d (1H, 3a-H,
(DMSO-d6), δ, ppm: 0.99 d.d.d.d (1H, 1-H, J = 12.2,
J3a,exo-3 = 3.8, J3a,endo-3 = 9.1 Hz), 3.43 d (1H, 11c-H,
J1a,11c = 3.2 Hz), 3.47 d (1H, 1a-H, J1a,11c = 3.2 Hz),
J2,1 = 9.4, J2,1 = 7.4, J1,13c = 10.2 Hz), 1.45 d.d.d (1H,
2
1-H, J1,1 = 12.2, J2,1 = 7.2, J1,2 = 3.9 Hz), 3.51 br.d.t
3
2
3.72 m and 3.57 m (1H each, OCH2, J = 7.0 Hz),
(1H, 2-H, J = 8.6, J2, 1 = 3.9, J2, 1 = 7.4 Hz),
4.40 d.d (1H, 11a-H, J11a,11-ax = 12.1, J11a,11-eq
=
3.58 d.d.d.d (1H, 13c-H, J13c,13b = 8.0, J13c,3a = 3.8,
2
1.5 Hz), 4.62 d (1H, 2-H, J2,exo-3 = 5.1 Hz), 4.72 d.d
(1H, 10-H, J10,11-ax = 11.0, J10,11-eq = 5.7 Hz), 7.09 br.t
J13c,1 = 8.7, J13c,1 = 10.2 Hz), 3.66 br.q (1H, 1-H, J =
8.6, J2,1 = 7.2, J2,1 = 9.4 Hz), 5.35 d (1H, 13b-H,
J13b,13c = 8.0 Hz), 5.50 d (1H, 3a-H, J3a,13c = 3.8 Hz),
7.28 d.t (1H, 5-H, J4,5 = J5,6 = 7.5, J5,7 = 1.0 Hz),
7.42 d.t (1H, 6-H, J6,5 = J6,7 = 7.7, J4,6 = 1.3 Hz),
7.50 d.d (1H, 4-H, J4,5 = 7.5, J4,6 = 1.3 Hz), 7.88 t (1H,
12-H, J11,12 = J12,13 = 7.5 Hz), 8.01 d (1H, 13-H,
J12,13 = 7.5 Hz), 8.06 d (1H, 11-H, J11,12 = 7.5 Hz),
8.22 d.d (1H, 7-H, J6,7 = 7.7, J5,7 = 1.0 Hz). Mass spec-
trum, m/z (Irel, %): 321 (70) [M]+, 277 (100), 247 (14),
232 (22), 204 (15), 178 (5), 115 (13), 89 (6), 77 (12),
63 (6), 39 (10). Found, %: C 70.93; H 4.52; N 4.71.
C19H15NO4. Calculated, %: C 71.02; H 4.71; N 4.36.
M 321.33.
(1H, 8-H, J7,8 = J8,9 = 7.6 Hz), 7.23 d.d (1H, 7-H, J6,7
=
8.3, J7,8 = 7.6 Hz), 7.55 d (1H, 9-H, J8,9 = 7.6 Hz),
8.61 d (1H, 6-H, J6,7 = 8.3 Hz). Mass spectrum, m/z
(Irel, %): 313 (100) [M]+, 284 (22), 268 (46), 266 (15),
196 (12), 180 (13), 130 (30), 77 (11). Found, %:
C 68.77; H 6.07; N 4.32. C18H19NO4. Calculated, %:
C 68.99; H 6.11; N 4.47. M 313.35.
Methyl (1aS*,2S*,3S*,3aR*,10S*,11aS*,11bS*,-
11cS*)-2,11b-epoxy-10-ethoxy-4-oxo-1a,2,3,3a,4,11,-
11a,11c-octahydro-10H-oxirano[6,7]isoindolo[2,1-a]-
quinoline-3-carboxylate (XXIIb). Yield 49%, color-
less crystals, mp 189−190°C (from hexane–ethyl
acetate), Rf 0.61 (ethyl acetate). IR spectrum, ν, cm–1:
(4aS*,14bS*,14cS*)-10-Oxo-2,3,4a,10,14b,14c-
Hexahydro-1H-isoindolo[2,1-a]pyrano[3,2-c]quino-
line-11-carboxylic acid (XXIIIc). Yield 77%, color-
less crystals, mp 260°C (i-PrOH–DMF). IR spectrum,
1
1736 (COOMe), 1701 (C4=O). H NMR spectrum
3
(CDCl3) δ, ppm: 1.31 t (3H, CH2CH3, J = 6.9 Hz),
2.26 br.q (1H, 11-Hax, J10,11-ax = 11.2, J11a,11-ax = 12.5,
2J = 12.8 Hz), 2.56 d.d.d (1H, 11-Heq, J10,11-eq = 5.9,
1
ν, cm–1: 1706 (COOH), 1623 (C10=O). H NMR spec-
2
J11a,11-eq = 2.3, J = 12.8 Hz), 2.99 d (1H, 3a-H, J3a,3
=
trum (DMSO-d6), δ, ppm: 0.63 d.q (1H, 1-H, J1,2 = 3.7,
J1,3 = 12.5 Hz), 0.83 m (1H, 1-H), 1.33 m (1H, 2-H),
1.53 m (1H, 2-H), 3.01 m (1H, 14c-H), 3.08 m (1H,
9.5 Hz), 3.22 d (1H, 3-H, J3a,3 = 9.5 Hz), 3.47 d (1H,
11c-H, J1a,11c = 3.3 Hz), 3.55 d (1H, 1a-H, J1a,11c
=
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010

PERHYDROFURO[3,2-c]-, PERHYDROPYRANO[3,2-c]-, ...
1205
3-H), 3.57 d.d (1H, 3-H, J2,3 = 4.5, J1,3 = 12.5 Hz),
5.31 d.d (1H, 14b-H, J14a,14b = 0.7, J14b,14c = 5.6 Hz),
5.38 d (1H, 4a-H, J4a,5 = 2.8 Hz), 7.32 d.t (1H, 6-H,
off, washed with water until neutral washings, dried in
air, and recrystallized from i-PrOH–DMF. Yield 0.32 g
(57%), light yellow crystals, mp 282–284°C. IR spec-
1
trum, ν, cm–1: 1720 (COOH), 1631 (C9=O). H NMR
J5,6 = 1.1, J6,7 = 7.6 Hz), 7.43 d.d.d (1H, 7-H, J7,8
0.8, J6,7 = 7.6, J5,7 = 8.1 Hz), 7.58 d.d (1H, 5-H, J5,6
=
=
spectrum (DMSO-d6), δ, ppm: 1.02 m (1H, 1-H),
1.50 m (1H, 1-H), 3.55 m (1H, 2-H), 3.62 m (1H,
1.1, J5,7 = 7.7 Hz), 7.88 br.t (1H, 13-H, J12,13 = 7.8,
J13,14 = 7.6 Hz), 7.99 d.d (1H, 14-H, J13,14 = 7.6,
J14,14a = 0.8 Hz), 8.04 br.d (1H, 12-H, J12,13 = 7.8 Hz),
8.41 d.d (1H, 8-H, J7,8 = 1.0, J6,8 = 8.3 Hz). Mass spec-
trum, m/z (Irel, %): 335 (20) [M]+, 291 (44), 232 (31),
204 (53), 127 (29), 115 (37), 102 (48), 88 (32), 77
(100), 63 (54), 55 (27), 51 (72), 39 (69). Found, %:
C 71.52; H 5.36; N 4.33. C20H17NO4. Calculated, %:
C 71.63; H 5.11; N 4.18. M 335.35.
13c-H), 3.72 m (1H, 2-H), 5.45 d (1H, 13b-H, J13b,13c
=
8.1 Hz), 5.54 d (1H, 3a-H, J3a,13c = 3.4 Hz), 7.87 m
(2H, 11-H, 13-H), 7.66 m (1H, 12-H), 8.27 d.d (1H,
6-H, J4,6 = 2.8, J6,7 = 9.0 Hz), 8.30 d (1H, 4-H, J4,6
=
2.8 Hz), 8.52 d (1H, 7-H, J6,7 = 9.0 Hz). Mass spec-
trum, m/z (Irel, %): 366 (18) [M]+, 322 (100), 304 (21),
277 (17), 231 (11), 217 (15), 189 (10), 151 (6), 115
(9), 89 (6), 75 (5), 63 (5). Found, %: C 62.05; H 3.61;
N 7.86. C19H14N2O6. Calculated, %: C 62.30; H 3.85;
N 7.65. M 366.32.
(3aS*,13bS*,13cS*)-1,2,13b,13c-Tetrahydrofuro-
[3,2-c]isoindolo[2,1-a]quinolin-9(3aH)-one (XXIIIb).
A solution of 1 g (3.39 mmol) of compound VIIIa in
15 ml of phosphoric acid was stirred for 1 h at 85°C.
The mixture was cooled, poured into 50 ml of water,
and extracted with ethyl acetate (3×50 ml). The extract
was dried over anhydrous magnesium sulfate, the sol-
vent was distilled off, and the residue was recrystal-
lized from hexane– ethyl acetate. Yield 0.33 g (35%),
colorless crystals, mp 118–120°C (from hexane–ethyl
acetate), Rf 0.65 (hexane–ethyl acetate, 1:1). IR spec-
(3aS*,13bS*,13cS*)-5-Nitro-1,2,13b,13c-tetra-
hydrofuro[3,2-c]isoindolo[2,1-a]quinolin-9(3aH)-
one (XXIVb). A solution of 0.50 g (1.8 mmol) of
compound XXIIIb in 8 ml of concentrated sulfuric
acid was cooled with ice, 0.18 g (1.82 mmol) of potas-
sium nitrate was added in portions under stirring, and
the mixture was stirred for 1 h at –5 to 0°C, and poured
into 50 ml of water. The precipitate was filtered off,
washed with water and a solution of sodium carbonate,
dried in air, and recrystallized from i-PrOH–DMF.
Yield 0.22 g (38%), yellow crystals, mp 210–212°C.
trum: ν 1699 cm–1 (C=O). 1H NMR spectrum (CDCl3),
2
δ, ppm: 1.27 d.t (1H, 1-H, J = 12.4, J1,13c = J1,2
=
=
1
IR spectrum: ν 1710 cm–1 (C=O). H NMR spectrum
9.0 Hz), 1.57 d.d.t (1H, 1-H, J1,2 = 4.5, J1,2 = J1,13c
2
7.9, J = 12.4 Hz), 3.38 d.q (1H, 13c-H, J13b,13c = 3.4,
J = 9.3 Hz), 3.67 d.t (1H, 2-H, J1,2 = 4.5, J = 8.7 Hz),
(DMSO-d6), δ, ppm: 0.96 m (1H, 1-H), 1.47 m (1H,
1-H), 3.55 m (2H, 2-H, 13c-H), 3.71 q (1H, 2-H, J =
7.8 Hz), 5.43 d (1H, 13b-H, J13b,13c = 7.7 Hz), 5.47 d
(1H, 3a-H, J3a, 13c = 3.2 Hz), 7.61 br.t (1H, 11-H,
2
3.80 br.q (1H, 2-H, J = J1,2 = 7.9 Hz), 5.14 d (1H,
13b-H, J13b,13c = 3.4 Hz), 5.41 d (1H, 3a-H, J3a,13c
=
7.9 Hz), 7.22 t (1H, 5-H, J4,5 = J5,6 = 7.5 Hz), 7.40 d.d
(1H, 6-H, J6,7 = 8.2, J5,6 = 7.5 Hz), 7.54 d (2H, 4-H,
13-H, J4,5 = 7.5, J12,13 = 7.5 Hz), 7.56 t (1H, 11-H,
J10,11 = J11,12 = 7.6 Hz), 7.77 br.t (1H, 12-H, J11,12
=
J12,13 = 7.6 Hz), 7.80 br.d (1H, 13-H, J12,13 = 7.6 Hz),
7.87 d (1H, 10-H, J10,11 = 7.6 Hz), 8.26 d.d (1H, 6-H,
J10,11 = J11,12 = 7.5 Hz), 7.65 t (1H, 12-H, J11,12 = J12,13
=
J4,6 = 2.4, J6,7 = 8.6 Hz), 8.27 d (1H, 4-H, J4,6
=
7.5 Hz), 7.98 d (1H, 10-H, J10,11 = 7.5 Hz), 8.43 d (1H,
7-H, J6,7 = 8.2 Hz). Mass spectrum, m/z (Irel, %): 277
(91) [M]+, 248 (86), 232 (100), 218 (59), 204 (42), 165
(22), 128 (32), 115 (97), 105 (41), 89 (78), 76 (76), 59
(74), 51 (36), 43 (49). Found, %: C 78.11; H 5.23;
N 5.37. C18H15NO2. Calculated, %: C 77.96; H 5.45;
N 5.05. M 277.32.
2.4 Hz), 8.56 br.d (1H, 7-H, J6,7 = 8.6 Hz). Mass spec-
trum, m/z (Irel, %): 322 (100) [M]+, 306 (7), 292 (36),
277 (21), 265 (6), 247 (8), 231 (8), 218 (10), 205 (4),
76 (14), 59 (19), 43 (18). Found, %: C 66.88; H 4.51;
N 8.86. C18H14N2O4. Calculated, %: C 67.07; H 4.38;
N 8.69. M 322.31.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 07-03-00083a).
(3aS*,13bS*,13cS*)-5-Nitro-9-oxo-1,2,3a,9,13b,-
13c-hexahydrofuro[3,2-c]isoindolo[2,1-a]quinoline-
10-carboxylic acid (XXIVa). Compound XXIIIa,
0.49 g (1.53 mmol), was dissolved in 9 ml of concen-
trated sulfuric acid, 0.18 g (1.8 mmol) of potassium
nitrate was added in portions under stirring, and the
mixture was stirred for 90 min at 45–50°C, cooled, and
poured into 40 ml of water. The precipitate was filtered
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