Diels-alder reactions with cyclic sulfones: VII. Synthesis of 1-benzothiophene 1,1-dioxide derivatives

Article abstract of DOI:10.1023/B:RUJO.0000044549.81561.4f

5-Arylmethylene-2,2-dimethyl-1,3-dioxane-4,6-diones reacted with 5-isopropenyl-2,3-dihydrothio-phene 1,1-dioxide to give the corresponding ortho-addition products, 5-aryl-2',2',7-trimethyl-3,3a,5,6-tetra-hydro-2H- spiro[1-benzothiophene-4,5'-[1,3]dioxane]-4',6'-dione 1,1-dioxides. Their aminolysis resulted in opening of the 1,3-dioxane ring and formation of 4-carbamoyl-7-methyl-2,3,3a,4,5,6-hexahydro-1-benzo-thiophene-4-carboxylic acid 1,1-dioxide whose structure was determined by X-ray analysis. Reactions of the spiro adducts with amines and hydrazine hydrate afforded the corresponding mono- or dicarboxylic acid monoamides (hydrazide).

Full text of DOI:10.1023/B:RUJO.0000044549.81561.4f

Russian Journal of Organic Chemistry, Vol. 40, No. 6, 2004, pp. 854–865. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 6, 2004,
pp. 892–903.
Original Russian Text Copyright © 2004 by Andreev, Shul’ts, Volkov, Shakirov, Bagryanskaya, Gatilov, Tolstikov.
Dedicated to Full Member of the Russian Academy of Sciences
O.N. Chupakhin on his 70th Anniversary
Diels–Alder Reactions with Cyclic Sulfones:
VII.* Synthesis of 1-Benzothiophene 1,1-Dioxide Derivatives
G. N. Andreev, E. E. Shul’ts, A. A. Volkov, M. M. Shakirov, I. Yu. Bagryanskaya,
Yu. V. Gatilov, and G. A. Tolstikov
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: schultz@nioch.nsc.ru
Received December 29, 2003
Abstract—5-Arylmethylene-2,2-dimethyl-1,3-dioxane-4,6-diones reacted with 5-isopropenyl-2,3-dihydrothio-
phene 1,1-dioxide to give the corresponding ortho-addition products, 5-aryl-2',2',7-trimethyl-3,3a,5,6-tetra-
hydro-2H-spiro[1-benzothiophene-4,5'-[1,3]dioxane]-4',6'-dione 1,1-dioxides. Their aminolysis resulted in
opening of the 1,3-dioxane ring and formation of 4-carbamoyl-7-methyl-2,3,3a,4,5,6-hexahydro-1-benzo-
thiophene-4-carboxylic acid 1,1-dioxide whose structure was determined by X-ray analysis. Reactions of the
spiro adducts with amines and hydrazine hydrate afforded the corresponding mono- or dicarboxylic acid
monoamides (hydrazide).
Diels–Alder reactions with 2,3-dihydrothiophene
1,1-dioxide derivatives as dienophiles and dienes were
used previously to obtain various tri- and tetracyclic
compounds containing a fused tetrahydrothiophene
1,1-dioxide fragment [1–6]. Some of the prepared
compounds were found to exhibit a high antiphlogistic,
antiulcer, and psychotropic activity together with low
toxicity [7–9]. Less attention was given to the syn-
thesis of 1-benzothiophene 1,1-dioxide derivatives. We
synthesized such compounds by cycloaddition of
5-methylene-2,2-dimethyl-1,3-dioxane-4,6-dione (I)
[10] and 5-arylmethylene-2,2-dimethyl-1,3-dioxane-
4,6-diones II–VII to 5-isopropenyl-2,3-dihydrothio-
phene 1,1-dioxide (VIII) [11]. The reaction of diene
VIII with dienophile I was regioselective, and it
resulted in formation of 93% of adduct IX. The 1H and
13C NMR spectra of the product were consistent with
the assumed structure while alternative structure X was
completely ruled out.
fused at the C4 atom of the benzothiophene fragment.
The stereoselectivity depends on the substituents in the
aromatic ring of the dienophile. As a rule, mixtures of
(5R)- (compounds XI, XIII, XV, XVII, XIX, and
XXI) and (5S)-diastereoisomers (XII, XIV, XVI,
XVIII, XX, and XXII) were formed (Scheme 1).
A high stereoselectivity was observed in the addition
of 2-methoxy- and 2,3-dimethoxybenzylidene deriva-
tives III and IV: the ratio of diastereoisomeric
products XIII/XIV and XV/XVI was about 10:1. The
reaction of diene VIII with 2,3,4-trimethoxyben-
zylidene derivative V was characterized by lower
stereoselectivity. In this case, the ratio of products
XVII and XVIII was the same as in the addition of
5-benzylidene-2,2-dimethyl-1,3-dioxane-4,6-dione
(II) having no substituents in the phenyl ring (XI:XII
= 5:1). The reaction of dienophile VI with diene VIII
was not stereoselective, and almost equimolar mixture
of isomeric products XIX and XX was obtained. The
Diels–Alder reaction of VIII with 4-methoxyben-
zylidene-2,2-dimethyl-1,3-dioxane-4,6-dione (VII)
afforded adducts XXI and XXII at a ratio of ~0.22:1.
The Diels–Alder reaction of diene VIII with cyclic
arylmethylenemalonates II–VI, as well as with com-
pound VII generated in situ, was regioselective, and
the products contained the dioxodioxane moiety spiro-
Thus substituents in the aromatic ring strongly
affect the stereochemical results of the addition.
Presumably, the reaction involves two transition states
* For communication VI, see [1].
1070-4280/04/4006-0854 © 2004 MAIK “Nauka/Interperiodica”

DIELS–ALDER REACTIONS WITH CYCLIC SULFONES: VII.
855
Scheme 1.
O
CH2
O
Me
7
6
O
O
Me
Me
5
4
O
O
Me
H2C
Me
O
7a
+
O
Me
Me
3a
S
O
O
O
S
O
O
3
2
O
S
O
O
O
Me
Me
O
I
VIII
IX
X
R3
R3
Me
Me
R2
R1
R2
R1
O
O
O
O
VIII
+
R1
+
H
H
Me
Me
O
O
HC
R2
R3
O
O
O
O
O
S
S
Me
Me
O
O
O
O
O
Me
Me
II–VII
XI, XIII, XV, XVII, XIX, XXI
XII, XIV, XVI, XVIII, XX, XXII
II, XI, XII, R1 = R2 = R3 = H; III, XIII, XIV, R1 = CH3O, R2 = R3 = H; IV, XV, XVI, R1 = R2 = CH3O, R3 = H; V, XVII, XVIII,
R1 = R2 = R3 = CH3O; VI, XIX, XX, R1 = H, R2 = OH, R3 = CH3O; VII, XXI, XXII, R1 = R2 = H, R3 = CH3O.
Scheme 2.
Me
H2C
O
O
S
H2C
S
Me
O
O
R1
XI, XIII, XV,
XVII, XIX, XXI
R1
XII, XIV, XVI,
XVIII, XX, XXII
O
O
R2
R3
R2
R3
O
O
Me
Me
O
O
O
O
Me
Me
B
A
A and B (Scheme 2) in which the aromatic ring is
forced out from the methylenedioxane ring plane.
Introduction of a substituent into the ortho position
of the aromatic ring increases nonequivalence of the
transition states, and structure A becomes more favor-
able. In fact, ortho-substituted dienophiles III and IV
give rise mainly to adducts XIII and XIV. para-
Substituents in the aromatic ring stabilize transition
state B. It is also possible that in the pre-reaction
state diene and dienophile form a transition complex
stabilized by hydrogen bonding between the S=O
oxygen atoms and substituents in the aromatic ring of
the dienophile.
derivatives [12–15]. Using adducts IX and XI as
examples, we examined opening of the dioxodioxane
ring by the action of various reagents. Preliminary
deprotection by treatment with potassium hydroxide in
methanol gave monomethyl ester XXIII. The same
mode of the dioxane ring opening was observed in
the reaction of compound IX with ammonia, which
afforded amido acid XXIV (Scheme 3). The structure
of product XXIV was established by X-ray analysis.
Figure 1 shows the structure of molecule XXIV.
The bond lengths approach the corresponding standard
values [16]; they coincide within 3σ with those found
for (+)-3-benzyloxy-2,3,4,5,3a,7a-hexahydro-1-benzo-
thiophen-5-one 1,1-dioxide [17] as the closest struc-
tural analog deposited to the Cambridge Structural
Database [18]. The six-membered ring adopts a sofa
According to published data, the 1,3-dioxane ring
in isopropylidene malonates undergoes decomposition
with formation of both acetic and malonic acid
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

ANDREEV et al.
856
The sulfur atom has a pyramidal configuration: the
distances from the O4 and O5 atoms to the plane
including the C2, S1, and C7a atoms are –1.227 and
1.218 Å, respectively. The carboxy and carbamoyl
groups are planar, and the dihedral angle between their
planes is 79.4°. Molecules of XXIV in crystal are
linked with solvent molecules by hydrogen bonds (see
table), giving rise to layers oriented parallel to the
(001) plane (Fig. 2).
The results of reactions of compound IX with
amines depend on the amine nature and conditions.
The reaction with phenethylamine on heating to 40°C
for a short time gave the corresponding amido acid.
Methylation of the latter afforded amido ester XXV.
Opening of the dioxane ring involves intermediate
formation of phenethylammonium salt XXVI which
was isolated as the corresponding hydrochloride. Less
basic amines, such as 6-amino-4-hydroxy-2-methyl-
pyrimidine and 2-aminobenzimidazole, reacted with
compound IX in boiling DMF to give amides XXVII
and XXVIII, respectively. By heating salt XXVI in
DMF (10 h) we obtained decarboxylation product
XXIX. The reaction of IX with N-methylbenzylamine
under analogous conditions was also accompanied by
decarboxylation leading to N-benzyl-N-methylamide
XXX (Scheme 3). Treatment of spiro-dioxanediones
IX and XI with hydrazine hydrate in boiling DMF
resulted in formation of 2,3,3a,4,5,6-hexahydro-1-
benzothiophene-4-carbohydrazide 1,1-dioxides XXXI
and XXXII in high yield.
Fig. 1. Structure of the molecule of 4-carbamoyl-7-methyl-
2,3,3a,4,5,6-hexahydro-1-benzothiophene-4-carboxylic acid
1,1-dioxide (XXIV) in crystal.
The structure of the products was determined on the
basis of the spectral data. The structure of compound
IX as the ortho-addition product unambiguously
conformation [19] where five carbon atoms (C5, C6,
C7, C3a, and C7a) lie in one plane (the mean-square
deviation from the plane is 0.019 Å) while the C4 atom
deviates from that plane by 0.688 Å. The sulfur-
containing five-membered ring occurs in an envelope
conformation with the C3 atom deviating by 0.628 Å
from the plane formed by the four remaining atoms.
1
follows from its H NMR spectrum and X-ray diffrac-
tion data for aminolysis product XXIV. Four protons
at the C5 and C6 atoms give complex multiplet signals
centered at δ 2.43, 2.33, 2.28, and 2.20 ppm. The 3a-H
signal appears at δ 3.50 ppm as a multiplet due to
coupling with protons on C3. The structure of stereo-
isomeric aryl-substituted adducts XI–XXII was also
deduced from the NMR data. Their configuration was
determined by analysis of the vicinal coupling con-
stants for protons at C5 and C6. Pseudoequatorial
orientation of the aryl substituent in XII, XIV, XVI,
XVIII, XX, and XXII follows from the axial–axial
coupling constant between 5-H and 6-H (J ≈ 11 Hz).
Parameters of hydrogen bonds in the crystalline structure of
amide XXIV solvatea
DH···A D–H, Å H···A, Å D···A, Å DH···A, deg
O2H···O1R 0.97(4) 1.62(4) 2.574(3)
O1RH···O3 0.87(4) 1.87(4) 2.718(3)
N1HA···O1 0.90(3) 2.07(3) 2.954(3)
N1HB···O5 0.83(3) 2.22(3) 3.027(3)
166(4)
165(4)
166(3)
163(3)
1
The H NMR spectra of the (5S) isomers are charac-
terized by a considerably larger difference between
the chemical shifts of the methyl protons in the
isopropylidene fragment and by unusually upfield
a
O1R is the oxygen atom in the solvent molecule.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

DIELS–ALDER REACTIONS WITH CYCLIC SULFONES: VII.
857
Scheme 3.
O
O
Me
Me
6
5
OMe
OH
4
O
O
3a
S
S
NH(CH2)2Ph
R
3
2
O
H
O
O
H
O
XXV
XXIII, XXIV
IX
O
Me
Me
H
OH
· Ph(CH2)2NH3 Cl–
O
O
O
S
S
NH(CH2)2Ph
NHR
O
H
H
O
O
XXVI
XXVII–XXIX, XXXI
XXIII, R = CH3O; XXIV, R = NH2; XXVII, R = 6-hydroxy-2-methylpyrimidin-4-yl; XXVIII, R = 2-benzimidazolyl;
XXIX, R = PhCH2CH2; XXXI, R = NH2.
Me
Me
Ph
H
H
Me
IX
XI
O
O
S
S
N
NHNH2
O
H
O
H
CH2Ph
O
O
XXX
XXXII
position of one of these signals [cf. δ 0.68, 1.52 ppm
(XII) and δ 1.62, 1.65 ppm (XI)]; this pattern is likely
to arise from magnetically anisotropic effect of the
phenyl ring. The 6-H and 3a-H signals in the spectra
of the adducts with pseudoequatorial aryl substituent
at C5 are displaced downfield [cf. δ 3.62 (XII) and
3.31 ppm (XI)], and magnetic nonequivalence of the
6-H protons is stronger [cf. δ 2.60, 3.10 ppm (XII) and
δ 2.66, 2.79 ppm (XI)]. The above differences in
proton chemical shifts enabled us to estimate the ratio
of diastereoisomeric adducts from the 1H NMR spectra
of the reaction mixtures. The 13C NMR spectra of
the stereoisomers differ by the chemical shifts of the
doublet signals from C5 and C3a. The signals from
the (5R) isomers are located in a stronger field.
band is displaced to lower frequencies (ν 1628–
1633 cm–1), and vibrations of the NH–NH2 group
appear at 3430–3480 cm–1.
1
The H NMR spectrum of adduct XXVI contained
signals from protons in the hexahydro-1-benzothio-
phene fragment, 10 aromatic protons, and protons of
four methylene groups, the latter being located at δ,
ppm: 3.36 m (1H), 3.30 m (1H, CH2N), 3.00 m
(CH2N), 2.93 m (CH2Ph), 2.74 t (CH2Ph).
The trans arrangement of the substituents at C3a and
1
C4 in amides XXVII–XXX follows from the H NMR
data, specifically from the vicinal coupling constants
between 3a-H and 4-H (3J = 10.2–11.4 Hz). Mutual
orientation of the substituents on C3a, C4, and C5 in
molecule XXXII was confirmed by the NOESY
spectrum: NOE was observed for the 3a-H signal while
suppressing resonance of the 6-H proton (δ 2.33 ppm),
as well as of the ortho protons in the aryl substituent
at C5. The 4-H signal showed NOE with the downfield
6-H proton (δ 2.76 ppm).
Thus cycloaddition of 5-arylmethylene-2,2-di-
methyl-1,3-dioxane-4,6-diones to 5-isopropenyl-2,3-
dihydrothiophene 1,1-dioxide gives the corresponding
spiro adducts which react with amines and hydrazine
to afford derivatives of hexahydro-1-benzothiophene-
4-mono- and 4,4-dicarboxylic acid 1,1-dioxides.
In the IR spectra of the aminolysis products we
observed absorption bands belonging to stretching
vibrations of the amide carbonyl (ν 1628–1690 cm–1)
and N–H groups (ν 3348–3446 cm–1). Ammonium salt
XXVI showed in the IR spectrum absorption bands
from the amide (1627 and 1674 cm–1) and carboxylate
groups (1747 cm–1), bands typical of ammonium group
(ν 2059, 2599, and 2726 cm–1) [20], narrow bands
at 3300 and 3458 cm–1 [ν(NH2), ν(OH)], and bands
corresponding to stretching vibrations of the sulfonyl
group (ν 1120 and 1295 cm–1). In the IR spectra of
hydrazides XXXI and XXXII, the carbonyl absorption
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

ANDREEV et al.
858
5-Benzylidene-2,2-dimethyl-1,3-dioxane-4,6-di-
one (II) was synthesized by the procedure described
in [21]. Yield 72%, mp 84–85°C; published data [22]:
mp 85°C. UV spectrum, λmax, nm (logε): 227 (3.88),
1
264 (3.93), 321 (4.16). H NMR spectrum (CDCl3), δ,
ppm: 1.76 s (6H, 2CH3), 7.46 m (3H, Ph), 8.01 m (2H,
13
Ph), 8.38 s (1H, CH=). C NMR spectrum, δC, ppm:
27.40 q (2CH3), 104.33 s (C2), 114.75 s (C5), 128.50 d
(C2', C6'), 131.55 s (C1'), 133.36 d (C3', C4', C5'), 157.79 d
(CH=), 159.47 s and 162.98 s (C=O).
5-Isopropenyl-2,3-dihydrothiophene 1,1-dioxide
(VIII) was synthesized as described in [11], and diazo-
methane was prepared by known method [23].
5-Arylmethylene-2,2-dimethyl-1,3-dioxane-4,6-
diones (III–VI). To a solution of 2.30 g (16 mmol) of
Meldrum’s acid in 25 ml of benzene we added
24 mmol of the corresponding aldehyde, 0.10 ml of
piperidine, and 0.30 ml of acetic acid. The mixture was
heated under reflux in a flask equipped with a Dean–
Stark trap until water no longer separated (~1 h). The
solvent was distilled off under reduced pressure, and
the residue was recrystallized from ethyl acetate.
Fig. 2. Packing of molecules XXIV and solvent molecules in
crystal along the b axis (hydrogen atoms are not shown,
except for those in the NH2 and OH groups).
EXPERIMENTAL
The IR spectra were recorded on a Vector-22
spectrometer from samples prepared as KBr pellets.
The electron absorption spectra were measured on
an HP 8453 UV Vis spectrophotometer from solutions
in ethanol (c = 10–4 M). The NMR spectra were
5-(2-Methoxybenzylidene)-2,2-dimethyl-1,3-di-
oxane-4,6-dione (III). Yield 60%, mp 98–100°C;
published data [20]: mp 100°C. IR spectrum, ν, cm–1:
754, 801, 925, 1290, 1573, 1610 (C=C), 1027, 1163,
1
obtained on Bruker AC-200 (200.13 MHz for H and
1192 (C–O–C), 1728, 1765 (C=O). UV spectrum, λmax
,
50.32 MHz for 13C) and Bruker DRX-500 spec-
trometers (500.13 MHz for 1H and 125.7 MHz for 13C)
from solutions in CDCl3, CD3OD, or DMSO-d6. The
signals were assigned using various proton–proton and
carbon–proton shift correlation techniques (COSY,
nm (logε): 257 (3.94), 317 (3.85), 374 (3.83). 1H NMR
spectrum (CDCl3), δ, ppm: 1.77 s (6H, 2CH3), 3.85 s
(3H, OCH3), 6.92 m (2H, 5'-H, 6'-H), 7.45 d.t (1H,
3'-H, J = 7.8 Hz), 7.90 d.d (1H, 4'-H, J = 7.8, 8.1 Hz),
8.68 s (1H, CH=). 13C NMR spectrum, δC, ppm:
27.38 q (2CH3), 55.54 q (OCH3), 104.17 s (C2), 110.93
d (C3'), 115.44 s (C5), 120.23 d (C6'), 121.55 s (C1'),
132.26 d (C4'), 134.58 d (C5'), 152.60 d (CH=), 159.42 s
(C2'), 159.50 s (C=O), 162.85 s (C=O).
1
COLOC, CORRD) and H 2D-NOESY spectroscopy.
The mass spectra (electron impact, 70 eV) were run on
a Finnigan MAT-8200 high-resolution mass spectrom-
eter (vaporizer temperature 200–300°C). The melting
points were determined on a Koefler device.
5-(2,3-Dimethoxybenzylidene)-2,2-dimethyl-1,3-
dioxane-4,6-dione (IV). Yield 74%, yellow crystals,
mp 98–100°C. IR spectrum, ν, cm–1: 741, 797, 926,
974, 1574, 1590 (C=C), 1080 (C–O–C), 1204, 1265,
1727, 1763 (C=O). UV spectrum, λmax, nm (logε): 204
X-Ray diffraction experiment was performed on
a Bruker P4 diffractometer (MoKα-irradiation, graphite
monochromator, 2θ/θ scanning to 2θ < 50°).
The progress of reactions was monitored by TLC
on Silufol UV-254 plates. The products were isolated
from the reaction mixtures by crystallization or by
column chromatography on KSK silica gel (0–70 µm)
using chloroform and chloroform–ethanol (100:1,
100:5, or 10:1) as eluents with subsequent recrys-
tallization.
1
(4.30), 259 (3.89), 330 (3.99). H NMR spectrum
(CDCl3), δ, ppm: 1.77 s (6H, 2CH3), 3.86 s (3H,
2'-OCH3), 3.93 s (3H, 3'-OCH3), 7.07 d (2H, 4'-H,
6'-H, J = 8.1, 8.2 Hz), 7.43 t (1H, 5'-H, J = 8.1,
8.2 Hz), 8.63 s (1H, CH=). 13C NMR spectrum, δC,
ppm: 27.45 q (2CH3), 55.90 q (OCH3), 61.60 q
(OCH3), 104.34 s (C2), 116.48 s (C5), 117.08 d (C4'),
123.01 d and 123.31 d (C5', C6'), 126.26 s (C1'), 149.74 s
(C2'), 152.27 s (C3'), 152.96 d (CH=), 159.38 s (C=O),
Meldrum’s acid was synthesized by the procedure
reported in [21].
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

DIELS–ALDER REACTIONS WITH CYCLIC SULFONES: VII.
859
162.62 (C=O). Mass spectrum, m/z (Irel, %): 292 (23),
234 (100), 203 (80), 162 (55). Found: [M]+ 292.09445.
C15H16O6. Calculated: M 292.09468.
acetate. Yield 2.92 g (93%), mp 193–195°C (from
ethyl acetate). IR spectrum, ν, cm–1: 750, 1640 (C=C),
1131, 1292, 1312 (CO2), 1681, 1732, 1772 (C=O). UV
spectrum, λmax, nm (logε): 207 (3.99). H NMR spec-
1
2,2-Dimethyl-5-(2,3,4-trimethoxybenzylidene)-
1,3-dioxane-4,6-dione (V). Yield 82%, yellow crys-
tals, mp 123–124°C. IR spectrum, ν, cm–1: 796, 894,
957, 1586, 1615 (C=C), 1007, 1097 (C–O–C), 1199,
trum (CDCl3), δ, ppm: 1.70 s (3H, CH3), 1.73 s (3H,
CH3), 1.81 m (1H, 3-H), 2.10 d (3H, CH3, J = 2.1 Hz),
2.15 m (1H, 3-H), 2.20 m (1H, 6-H), 2.28 m (1H, 6-H),
2.33 m (1H, 5-H), 2.43 m (1H, 5-H), 2.93 m (1H, 2-H),
3.13 m (1H, 2-H), 3.50 m (1H, 3a-H). 13C NMR
spectrum, δC, ppm: 17.85 q (4-CH3), 22.16 t (C3),
28.84 q (CH3), 29.14 q (CH3), 29.80 t (C5), 30.94 t
(C6), 42.96 d (C3a), 50.18 t (C2), 50.67 s (C4), 105.27 s
(C2'), 130.92 s (C7a), 140.83 s (C7), 164.15 s (C=O),
169.22 s (C=O). Mass spectrum, m/z (Irel, %): 314 (5),
256 (25), 228 (41), 212 (36), 184 (33), 120 (94), 105
(45), 921 (44), 91 (100). Found: [M]+ 314.08187.
C14H18O6S. Calculated: M 314.08240.
1286, 1724, 1760 (C=O). UV spectrum, λmax, nm
1
(logε): 205 (4.32), 256 (3.98), 375 (4.15). H NMR
spectrum (CDCl3), δ, ppm: 1.77 s (6H, 2CH3), 3.83 s
(3H, 3'-OCH3), 3.93 s and 3.98 s (3H each, 2'-OCH3,
4'-OCH3), 6.71 d (1H, 5'-H, J = 7.9 Hz), 8.16 d (1H,
13
6'-H, J = 7.9 Hz), 8.72 s (1H, CH=). C NMR spec-
trum, δC, ppm: 27.43 q (2CH3), 56.14 q (OCH3),
60.82 q (OCH3), 61.99 q (OCH3), 104.00 s (C2),
106.85 d (C5'), 112.28 s (C1'), 119.00 s (C5), 129.08 d
(C6'), 141.40 s (C2'), 152.43 d (CH=), 155.91 s (C3'),
159.11 s (C4'), 160.39 s (C=O), 163.53 s (C=O). Mass
spectrum, m/z (Irel, %): 322 (18), 264 (51), 232 (100).
Found: [M]+ 322.10520. C16H18O7. Calculated:
M 322.10524.
5-Aryl-2',2',7-trimethyl-2,3,3a,4,5,6-hexahydro-
spiro[1-benzothiophene-4,5'-[1,3]dioxane]-4',6'-di-
one 1,1-dioxides XI–XX (general procedure). A mix-
ture of 9 mmol of 5-arylmethylene-2,2-dimethyl-1,3-
dioxane-4,6-dione II–VI, 1.42 g (9 mmol) of diene
VIII, and 0.09 g of L-proline in aqueous benzene
(10 ml + 1 ml) was heated for 24–40 h under reflux
(TLC). The mixture was cooled, and the precipitate
was filtered off and recrystallized from ethyl acetate to
isolate compounds XI, XIII, XV, XVII, and XIX. The
mother liquor was evaporated, and the residue was
subjected to column chromatography. In the order of
elution, we isolated unreacted dienophile II–VI, diene
VIII, (5R) isomers XI, XIII, XV, XVII, and XIX, and
(5S) isomers XII, XIV, XVI, XVIII, and XX. Com-
5-(3-Hydroxy-4-methoxybenzylidene)-2,2-di-
methyl-1,3-dioxane-4,6-dione (VI). Yield 75%, yellow
crystals, mp 130–131°C. IR spectrum, ν, cm–1: 798,
811, 928, 959, 974, 1507, 1574 (C=C); 1017, 1114
(C–O–C); 1160, 1283, 1718, 1750 (C=O), 3116 (OH).
UV spectrum, λmax, nm (logε): 204 (4.33), 261 (3.99),
1
380 (3.95), 391.0 (4.26). H NMR spectrum (CDCl3),
δ, ppm: 1.75 s (6H, 2CH3), 3.96 s (3H, OCH3),
5.86 br.s (1H, OH), 6.90 d (1H, 6'-H, J = 7.5 Hz),
7.67 d.d (1H, 5'-H, J = 7.5, 1.8 Hz), 7.89 d (1H, 2-H,
J = 1.8 Hz), 8.27 s (1H, CH=). 13C NMR spectrum, δC,
ppm: 27.34 q (2CH3), 56.06 q (OCH3), 104.06 s (C2),
110.19 d (C2'), 111.56 d (C6'), 119.50 s (C5), 125.36 s
(C1'), 129.98 d (C5'), 145.33 s (C3'), 151.79 s (C4'),
157.86 d (CH=), 160.08 s (C=O), 163.80 s (C=O).
Mass spectrum, m/z (Irel, %): 278 (30), 220 (76), 175
(100), 161 (78). Found: [M]+ 278.07927. C14H14O6.
Calculated: M 278.07903.
1
pounds XIV (yield 5%, according to the H NMR
spectrum of a mixture of diastereoisomers) and XVI
1
(yield 5%, according to the H NMR spectrum of
a mixture of diastereoisomers XV and XVI) were not
1
isolated as individual products. The H NMR data for
compound XVI were obtained from the spectrum of
diastereoisomer mixture XV/XVI.
2',2',7-Trimethyl-2,3,3a,4,5,6-hexahydrospiro-
[1-benzothiophene-4,5'-[1,3]dioxane]-4',6'-dione
1,1-dioxide (IX). To a solution of 1.44 g (15 mmol)
of Meldrum’s acid in 20 ml of acetonitrile we added
0.01 g of L-proline and 20 ml of a 40% formaldehyde
solution. The mixture was stirred for 5 min, and 1.58 g
(10 mmol) of diene VIII was added in portions over
a period of 20 min. The mixture was stirred for 2 h at
room temperature and was poured into 20 ml of ice
water. The precipitate was filtered off, washed with
water, dried in air, and recrystallized from ethyl
(5'R)-2',2',7-Trimethyl-5-phenyl-2,3,3a,4,5,6-
hexahydrospiro[1-benzothiophene-4,5'-[1,3]di-
oxane]-4',6'-dione 1,1-dioxide (XI). Yield 60%,
mp 165–168°C (from ethyl acetate). IR spectrum, ν,
cm–1: 702, 736, 1497 (Ph), 1125, 1294 (SO2), 1678,
1725, 1746, 1780 (C=O). UV spectrum, λmax, nm
1
(logε): 258 (3.41). H NMR spectrum (CDCl3), δ,
ppm: 1.62 s (3H, CH3), 1.65 s (3H, CH3), 2.09 m (2H,
3-H), 2.23 d (3H, CH3, J = 2.9 Hz), 2.66 d.d.d (1H,
6-H, J = 18.0, 6.2, 4.4 Hz), 2.79 d.d.d (1H, 6-H, J =
18.0, 6.1, 1.8 Hz), 3.00 m (1H, 2-H), 3.23 m (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

ANDREEV et al.
860
2-H), 3.32 m (1H, 3a-H), 3.54 d.d (1H, 5-H, J = 6.1,
4.4 Hz), 7.10 m (2H, Ph), 7.30 m (3H, Ph). C NMR
6.83 d.d (1H, 3''-H, J = 8.0, 1.5 Hz), 6.97 d.t (1H,
4''-H, J = 8.0, 1.8 Hz), 7.12 d.d (1H, 6''-H, J = 7.5,
1.8 Hz), 7.29 d.t (1H, 5''-H, J = 7.5, 1.5 Hz). 13C NMR
spectrum, δC, ppm: 17.96 q (4-CH3), 21.66 t (C3),
28.40 q (CH3), 29.84 q (CH3), 37.69 t (C6), 37.74 d
(C3a), 39.00 d (C5), 50.27 t (C2), 54.63 q (OCH3),
54.98 s (C4), 105.35 s (C2'), 110.22 d (C3''), 121.45 d
(C5''), 126.45 s (C1''), 127.23 d and 129.45 d (C4'', C5''),
131.64 s (C7a), 140.57 s (C7), 156.69 s (C2''), 164.71 s
(C=O), 165.20 (C=O). Mass spectrum, m/z (Irel, %):
420 (4), 289 (22), 148 (38), 108 (100). Found: [M]+
420.12191. C21H24O7S. Calculated: M 420.12426.
13
spectrum, δ, ppm: 18.37 q (4-CH3); 22.60 t (C3);
27.86 q (CH3); 30.33 q (CH3); 36.22 t (C6); 37.70 d
(C3a); 46.52 d (C5); 50.65 t (C2); 57.40 s (C4); 105.87 s
(C2'); 132.04 s (C7a); 137.48 s (C1'); 128.97 d, 128.50 d,
127.97 d (C2'', C3'', C4'', C5'', C6''); 140.53 s (C7), 164.94 s
(C=O), 166.36 s (C=O). Mass spectrum, m/z (Irel, %):
390 (5), 332 (29), 314 (35), 304 (50), 287 (22), 250
(53), 235 (32), 225 (25), 222 (49), 196 (93), 195
(89), 181 (58), 118 (85), 91 (84), 31 (100). Found:
[M]+ 390.11290. C20H22O6S. Calculated: M 390.11370.
(5S)-2',2',7-Trimethyl-5-phenyl-2,3,3a,4,5,6-
hexahydrospiro[1-benzothiophene-4,5'-[1,3]di-
oxane]-4',6'-dione 1,1-dioxide (XII). Yield 12%,
mp 194–195°C (from ethyl acetate). IR spectrum, ν,
cm–1: 707, 896, 1498, 1602 (C=Carom), 1133, 1291
(5R)-5-(2,3-Dimethoxyphenyl)-2',2',7-trimethyl-
2,3,3a,4,5,6-hexahydrospiro[1-benzothiophene-4,5'-
[1,3]dioxane]-4',6'-dione 1,1-dioxide (XV). Yield
60%, mp 219–220°C (from ethyl acetate). IR spec-
trum, ν, cm–1: 721, 759, 1482, 1584 (C=Carom), 1133,
(SO2), 1680, 1726, 1759 (C=O). UV spectrum, λmax
,
1289, 1310 (SO2), 1737, 1774 (C=O). UV spectrum,
1
1
nm (logε): 206 (4.56), 280 (2.60). H NMR spectrum
(CDCl3), δ, ppm: 0.68 s (3H, CH3), 1.52 (3H, CH3),
1.85 m (1H, 3-H), 2.10 m (1H, 3-H), 2.21 d (3H, CH3,
J = 2.2 Hz), 2.60 d.d.d (1H, 6-H, J = 19.0, 6.0, 1.5 Hz),
2.98 m (1H, 2-H), 3.10 m (1H, 6-H, J = 19.0, 11.8 Hz),
3.20 m (1H, 2-H), 3.64 m (1H, 3a-H), 3.70 d.d (1H,
5-H, J = 11.8, 6.0 Hz), 7.20 m (2H, Ph), 7.30 (3H, Ph).
13C NMR spectrum, δC, ppm: 18.00 q (4-CH3); 22.78 t
(C3); 28.36 q (CH3); 29.58 q (CH3); 36.89 t (C6);
46.16 d (C5); 46.36 d (C3a); 50.71 t (C2); 56.88 s (C4);
106.04 s (C2'); 127.99 d, 128.68 d, 129.00 d, 129.06 d
(C2'', C3'', C4'', C5'', C6''); 130.11 s (C7a); 137.07 s (C1');
142.42 s (C7); 163.15 s (C=O); 168.46 s (C=O). Mass
spectrum, m/z (Irel, %): 390 (15), 332 (60), 314 (62),
304 (33), 288 (47), 259 (34), 250 (92), 235 (42), 222
(43), 195 (65), 181 (46), 174 (46), 167 (47), 165
(64), 118 (92), 102 (56), 91 (80), 77 (40), 43 (100).
Found: [M]+ 390.113977. C20H22O6S. Calculated:
M 390.11370.
λ
max, nm (logε): 203 (4.57), 281 (3.24). H NMR
spectrum (CDCl3), δ, ppm: 1.70 s (3H, CH3), 1.86 m
(1H, 3-H), 1.94 s (3H, CH3), 2.05 m (1H, 3-H), 2.23 d
(3H, CH3, J = 2.9 Hz), 2.46 d.d (1H, 6-H, J = 18.4, 2.9,
2
2.0 Hz), 2.87 m (1H, 6-H, J = 18.4 Hz), 2.93 m (1H,
2-H), 3.16 m (1H, 2-H), 3.40 m (1H, 3a-H), 3.81 s
(3H, OCH3), 3.82 s (3H, OCH3), 4.02 d.d (1H, 5-H,
J = 6.0, 2.9 Hz), 6.76 d.d (1H, 4''-H, J = 8.0, 2.0 Hz),
6.88 d.d (1H, 6''-H, J = 8.0, 2.0 Hz), 7.03 t (1H, 5''-H,
J = 8.0). 13C NMR spectrum, δC, ppm: 17.97 q
(4-CH3), 21.55 t (C3), 28.39 q (CH3), 29.74 q (CH3),
37.48 d (C3a), 37.59 t (C6), 39.96 d (C5), 50.16 t (C2),
54.96 s (C4), 55.61 q (OCH3), 60.19 q (OCH3),
105.34 s (C2'), 112.48 d (C4''), 118.78 d (C5''), 124.37 d
(C6'), 131.51 s (C7a), 132.04 s (C1'), 140.59 s (C7),
146.79 s (C2''), 151.82 s (C3''), 164.64 s (C=O),
165.16 s (C=O). Mass spectrum, m/z (Irel, %): 450 (2),
364 (4), 319 (16), 138 (100). Found: M+ 450.13479.
C22H26O8S. Calculated; M 450.13483.
(5S)-5-(2,3-Dimethoxyphenyl)-2',2',7-trimethyl-
2,3,3a,4,5,6-hexahydrospiro[1-benzothiophene-4,5'-
[1,3]dioxane]-4',6'-dione 1,1-dioxide (XVI). Yield 5%.
1H NMR spectrum (CDCl3), δ, ppm: 1.09 s (3H, CH3),
1.56 s (3H, CH3), 1.75 m (1H, 3-H), 1.98 m (1H, 3-H),
(5R)-5-(2-Methoxyphenyl)-2',2',7-trimethyl-
2,3,3a,4,5,6-hexahydrospiro[1-benzothiophene-4,5'-
[1,3]dioxane]-4',6'-dione 1,1-dioxide (XIII). Yield
50.5%, mp 217–218°C (from ethyl acetate). IR spec-
trum, ν, cm–1: 738, 756, 1491, 1600 (C=Carom), 1117,
1132, 1298 (SO2), 1738, 1774 (C=O). UV spectrum,
2
2.16 d (3H, CH3, J = 2.9 Hz), 2.50 m (1H, 6-H, J =
19.0 Hz), 2.88 m (1H, 2-H), 3.12 m (1H, 6-H), 3.20 m
(1H, 2-H), 3.67 m (1H, 3a-H), 3.70 m (1H, 5-H, J =
11.5, 6.0 Hz), 3.85 s (3H, OCH3), 3.87 s (3H, OCH3),
6.78 d.d (1H, 4''-H, J = 7.8, 1.8 Hz), 6.90 d.d (1H,
6''-H, J = 7.8, 1.8 Hz), 7.05 t (1H, 5''-H, J = 7.8 Hz).
λ
max, nm (logε): 220 (2.51), 276 (2.55), 283 (2.51).
1H NMR spectrum (CDCl3), δ, ppm: 1.72 s (3H, CH3),
1.97 m (1H, 3-H), 1.98 s (3H, CH3), 2.02 m (1H, 3-H),
2.24 d (3H, CH3, J = 2.8 Hz), 2.48 d.d.d (1H, 6-H, J =
2
19.0, 2.8, 2.0 Hz), 2.84 m (1H, 6-H, J = 19.0 Hz),
2.9 m (1H, 2-H), 3.15 m (1H, 2-H), 3.31 m (1H, 3a-H),
(5R)-2',2',7-Trimethyl-5-(2,3,4-trimethoxy-
3.74 s (3H, OCH3), 4.10 d.d (1H, 5-H, J = 6.2, 2.8 Hz),
phenyl)-2,3,3a,4,5,6-hexahydrospiro[1-benzothio-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

DIELS–ALDER REACTIONS WITH CYCLIC SULFONES: VII.
861
m/z (Irel, %): 480 (24), 422 (51), 208 (35), 195 (68),
192 (24), 168 (100), 59 (26), 43 (36). Found: [M]+:
480.14571. C23H28O9S. Calculated: M 480.14539.
phene-4,5'-[1,3]dioxane]-4',6'-dione 1,1-dioxide
(XVII). Yield 58%, mp 202–204°C (from ethyl
acetate). IR spectrum, ν, cm–1: 720, 748, 1498, 1600
(C=Carom), 1098, 1119, 1290 (SO2), 1736, 1774 (C=O).
UV spectrum, λmax, nm (logε): 205 (4.60), 270 (3.20),
285 (3.42). 1H NMR spectrum (CDCl3), δ, ppm: 1.71 s
(3H, CH3), 1.87 m (1H, 3-H), 1.94 s (3H, CH3), 2.04 m
(1H, 3-H), 2.22 d (3H, CH3, J = 2.2 Hz), 2.43 d.d.d
(1H, 6-H, J = 18.8, 2.8, 1.6 Hz), 2.85 m (1H, 6-H, 2J =
18.8 Hz), 2.92 m (1H, 2-H), 3.16 (1H, 2-H), 3.34 m
(1H, 3a-H), 3.78 s (3H, OCH3), 3.83 s (3H, OCH3),
3.88 s (3H, OCH3), 3.94 d.d (1H, 5-H, J = 6.2, 2.8 Hz),
6.63 d (1H, 5''-H, J 7.2 Hz), 6.82 d (1H, 6''-H, J =
7.2 Hz). 13C NMR spectrum, δC, ppm: 17.85 q
(4-CH3); 21.39 t (C3); 28.27 q (CH3); 29.75 q (CH3);
37.67 d (C5); 37.70 t (C6); 38.73 d (C3a); 50.14 t (C2);
55.20 s (C4); 55.65 q (OCH3); 60.23 q and 60.48 q
(OCH3); 105.21 s (C2'); 106.95 d (C5''); 121.52 d (C6'');
123.14 s (C1''); 132.03 s (C7a); 140.43 s (C7); 151.44 s
and 153.68 s (C2'', C3'', C4''); 164.56 s (C=O); 165.27 s
(C=O). Mass spectrum, m/z (Irel, %): 480 (15), 337
(28), 195 (24), 168 (100). Found: [M]+ 480.14680.
C23H28O9S. Calculated: M 480.14539.
(5R)-5-(3-Hydroxy-4-methoxyphenyl)-2',2',7-
trimethyl-2,3,3a,4,5,6-hexahydrospiro[1-benzothio-
phene-4,5'-[1,3]dioxane]-4',6'-dione 1,1-dioxide
(XIX). Yield 30%, mp 186–188°C (from ethyl
acetate). IR spectrum, ν, cm–1: 736, 767, 1512, 1590
(C=Carom), 1120, 1297 (SO2), 1743, 1774 (C=O), 3456
(OH). UV spectrum, λmax, nm (logε): 206 (4.39), 283
1
(3.54). H NMR spectrum (CDCl3), δ, ppm: 1.65 s
(3H, CH3), 1.67 s (3H, CH3), 2.07 m (2H, 3-H), 2.21 d
(3H, CH3, J = 2.9 Hz), 2.69 m (1H, 6-H, 2J = 18.8 Hz),
2.98 d.d.d (1H, 6-H, J = 18.8, 6.2, 2.6 Hz), 3.04 m
(1H, 2-H), 3.21 m (1H, 2-H), 3.35 m (1H, 3a-H),
5.46 d.d (1H, 5-H, J = 6.2, 4.2 Hz), 3.85 s (3H, OCH3),
5.60 s (1H, OH), 6.61 d.d (1H, 6''-H, J = 7.8, 2.0 Hz),
6.68 d.d. (1H, 2''-H, J = 2.0 Hz), 6.77 d (1H, 5''-H, J =
7.6 Hz). 13C NMR spectrum, δC, ppm: 18.37 q
(4-CH3), 22.54 t (C3), 28.04 q (CH3), 30.42 q (CH3),
36.70 t (C6), 37.65 d (C3a), 46.25 d (C5), 50.74 t (C2),
56.00 q (OCH3), 57.75 s (C4), 105.90 s (C2'), 110.91 d
(C5''), 114.41 d (C2''), 119.64 d (C6'') 130.71 s (C7a),
132.11 s (C1'), 140.38 s (C7), 145.83 s, 146.65 s (C3'',
C4''), 165.06 s (C=O), 166.37 s (C=O). Mass spectrum,
m/z (Irel, %): 436 (3), 350 (14), 149 (16), 86 (76), 84
(100). Found: [M]+ 436.11909. C21H24O8S. Calculated:
M 436.11918.
(5S)-2',2',7-Trimethyl-5-(2,3,4-trimethoxy-
phenyl)-2,3,3a,4,5,6-hexahydrospiro[1-benzothio-
phene-4,5'-[1,3]dioxane]-4',6'-dione 1,1-dioxide
(XVIII). Yield 13%, mp 169–170°C (from ethyl
acetate). IR spectrum, ν, cm–1: 727, 770, 1516, 1611
(C=Carom), 1133, 1280, 1288, 1300, 1331 (SO2), 1730,
1763 (C=O). UV spectrum, λmax, nm (logε): 279
(5S)-5-(3-Hydroxy-4-methoxyphenyl)-2',2',7-tri-
methyl-2,3,3a,4,5,6-hexahydrospiro[1-benzothio-
phene-4,5'-[1,3]dioxane]-4',6'-dione 1,1-dioxide
(XX). Yield 30%, mp 207–209°C (from ethyl acetate).
1H NMR spectrum (CDCl3), δ, ppm: 0.83 s (3H, CH3),
1.56 s (3H, CH3), 1.83 m (1H, 3-H), 2.16 m (1H, 3-H),
2.21 d.d (3H, CH3, J = 2.8 Hz), 2.52 d.d.d (1H, 6-H,
J = 18.6, 5.8, 2.0 Hz), 2.98 m (1H, 2-H), 3.02 d.d.d
(1H, 6-H, J = 18.6, 11.8, 3.8 Hz), 3.20 m (1H, 2-H),
3.61 d.d (1H, 5-H, J = 11.8, 5.8 Hz), 3.63 m (1H,
3a-H), 3.85 s (3H, OCH3), 6.68 d.d (1H, 4''-H, J = 8.0,
2.0 Hz), 6.75 d (1H, 5''-H, J = 8.0 Hz), 6.78 d (1H,
2''-H, J = 2.0 Hz), 5.6 br.s (1H, OH, halfwidth 8.0 Hz).
13C NMR spectrum, δC, ppm: 18.05 q (4-CH3), 22.82 t
(C3), 28.75 q (CH3), 29.55 q (CH3), 37.34 t (C6),
45.74 d (C3a), 46.51 d (C5), 50.76 t (C2), 55.89 q
(OCH3), 56.98 s (C4), 105.88 (C2'), 110.68 d (C5''),
114.89 d (C2''), 120.82 d (C6''), 130.15 s and 130.36 s
(C7a, C1''), 142.47 (C7), 145.99 s and 146.58 s (C2'',
C3''), 163.13 s (C=O), 168.49 s (C=O). Mass spectrum,
m/z (Irel, %): 436 (57), 378 (72), 350 (38), 334
(25), 333 (31), 322 (22). Found: [M]+ 436.11916.
C21H24O8S. Calculated: M 436.11918.
1
(3.31). H NMR spectrum, δ, ppm: in CDCl3: 1.57 s
(3H, CH3), 1.84 s (3H, CH3), 1.87 m (1H, 3-H), 2.16 d
(3H, CH3, J = 2.5 Hz), 2.19 m (1H, 3-H), 2.42 d.d.d
(1H, 6-H, J = 18.6, 3.2, 2.0 Hz), 2.8 m (1H, 2-H),
3.02 m (1H, 6-H), 3.22 m (1H, 2-H), 3.76 m (1H,
3a-H), 3.86 m (1H, 5-H), 3.78 s (3H, OCH3), 3.80 s
(3H, OCH3), 3.87 s (3H, OCH3), 6.58 d (1H, 5''-H),
6.83 d (1H, 6''-H); in DMSO-d6: 1.12 s (3H, CH3),
1.59 s (3H, CH3), 1.65 m (1H, 3-H), 2.05 d (3H, CH3,
J = 2.5 Hz), 2.21 m (1H, 3-H), 2.49 m (1H, 6-H),
2.52 m (1H, 2-H), 2.70 m (1H, 2-H), 3.20 m (1H, 6-H),
3.70 m (1H, 3a-H), 3.73 s (3H, OCH3), 3.78 s (3H,
OCH3), 3.79 (3H, OCH3), 4.03 d.d. (1H, 5-H, J = 11.6,
13
6.1 Hz), 6.68 s (2H, 5''-H, 6''-H). C NMR spectrum,
δC, ppm: 17.95 q (4-CH3), 22.72 t (C3); 28.32 q (CH3);
30.39 q (CH3); 38.20 t (C6); 45.26 d (C5); 45.34 d
(C3a); 50.81 t (C2); 55.78 s (C4); 55.90 q (OCH3);
60.54 q (OCH3); 61.37 q (OCH3); 105.76 s (C2');
106.75 d (C5''); 122.00 d (C6''); 130.46 s (C7a, C1'');
130.49 s, 152.21 s, 153.75 s (C2'', C3'', C4''); 141.92 s
(C7); 163.90 s (C=O); 167.95 s (C=O). Mass spectrum,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

ANDREEV et al.
862
oxide (XXIII). Adduct IX, 0.63 g (2 mmol), was
(5'R)- and (5S)-5-(4-Methoxyphenyl)-2',2',7-tri-
added under stirring to a solution of 0.011 g
(0.2 mmol) of potassium hydroxide in 20 ml of
methanol. The mixture was stirred for 7 h at 20°C and
evaporated, 0.1 ml of dilute (1:1) hydrochloric acid
and 5 ml of methanol were added to the residue, and
the precipitate was filtered off and recrystallized from
methanol. Yield 0.51 g (52%), mp 160–163°C. UV
spectrum, λmax, nm (logε): 209 (4.01), 275 (2.28), 288
(2.30). IR spectrum, ν, cm–1: 1128, 1287 (SO2); 1715,
methyl-2,3,3a,4,5,6-hexahydrospiro[1-benzothio-
phene-4,5'-[1,3]dioxane]-4',6'-dione 1,1-dioxides
XXI and XXII. Cetyltrimethylammonium bromide,
0.54 g, and L-proline, 0.15 g, were added to a solution
of 2.04 g (15 mmol) of 4-methoxybenzaldehyde,
0.87 g (6 mmol) of Meldrum’s acid, and 0.95 g
(6 mmol) of diene VIII in 30 ml of distilled water. The
mixture was stirred for 24 h at 20°C, heated for 36 h
under reflux, and extracted with chloroform. The
extract was dried over MgSO4 and evaporated, and
the residue was subjected to column chromatography
to isolate (in the order of elution) 1.70 g of 4-methoxy-
benzaldehyde, 0.66 g of dienophile VII [23], 0.06 g of
diene VIII, 0.37 g (14.7%) of adduct XXI, and 1.27 g
(50.04%) of adduct XXII. The ratio XXI:XXII was
0.22:1.0. Compound XXI was not isolated in the pure
1
1732 (CO); 3200, 3480 (OH). H NMR spectrum
(CDCl3), δ, ppm: 1.88 m (1H, 3-H), 2.06 d (3H, CH3,
J = 2.8), 2.40 m (4H, 3-H, 5-H, 6-H), 2.95 m (1H,
2-H), 3.20 m (3H, 2-H, 3a-H, 6-H), 3.78 s (3H, OCH3),
8.1 br.s (1H, OH). 13C NMR spectrum, δC, ppm:
17.81 q (CH3), 22.51 t (C3), 28.95 t and 29.96 t (C5,
C6), 41.29 d (C3a), 50.68 t (C2), 52.91 q (CH3), 55.33 s
(C4), 131.72 s (C7a), 141.47 s (C7), 170.60 s (CO),
171.31 s (CO). Mass spectrum, m/z (Irel, %): 288 (1),
242 (6), 184 (16), 119 (17), 91 (20), 84 (100). Found:
[M]+ 288.06713. C12H16O6S. Calculated: M 288.06675.
1
state. H NMR spectrum of XXI (CDCl3), δ, ppm
(from the spectrum of a mixture with XXII): 1.65 s
(6H, 2CH3), 2.10 m (2H, 3-H), 2.23 d (3H, CH3, J =
2.8 Hz), 2.58 d.d (1H, 6-H, J = 19.0, 6.2 Hz), 2.70 m
(1H, 6-H), 3.0 m (1H, 2-H), 3.22 m (2H, 2-H, 3a-H),
3.52 d.d (1H, 5-H, J = 6.2, 4.3 Hz), 3.75 s (3H, OCH3),
6.81 d (2H, 3''-H, 5''-H, J = 8.0 Hz), 7.18 d (2H, 2''-H,
6''-H, J = 8.0 Hz).
4-Carbamoyl-7-methyl-2,3,3a,4,5,6-hexahydro-
1-benzothiophene-4-carboxylic acid 1,1-dioxide
(XXIV). Aqueous ammonia, 15 ml, was added drop-
wise over a period of 10 min to a solution of 0.63 g
(2 mmol) of adduct IX in 13 ml of dioxane. The
mixture was stirred for 7 h at 20°C, the solvent was
removed under reduced pressure, 5 ml of water was
added to the residue, and the solution was acidified
with 6 N hydrochloric acid to pH ≈ 2. The precipitate
was filtered off to obtain 0.04 g of compound XXIV.
The filtrate was evaporated, and the residue was dried
by azeotropic distillation with isopropyl alcohol and
dissolved in ethanol. The precipitate was filtered off.
Yield 0.45 g (83%), mp 198–201°C. IR spectrum, ν,
cm–1: 1118, 1122, 1275, 1292 (SO2); 1639, 1673, 1718
(5S)-5-(4-Methoxyphenyl)-2',2',7-trimethyl-
2,3,3a,4,5,6-hexahydrospiro[1-benzothiophene-4,5'-
[1,3]dioxane]-4',6'-dione 1,1-dioxide (XXII).
mp 240–241°C (from ethyl acetate). IR spectrum, ν,
cm–1: 727, 770, 1516, 1611 (C=Carom), 1133, 1280,
1288, 1300, 1331 (SO2), 1730, 1763 (C=O). UV spec-
trum, λmax, nm (logε): 224 (4.12), 277 (3.22), 282
1
(3.35). H NMR spectrum (CDCl3), δ, ppm: 0.76 s
(3H, CH3), 1.54 s (3H, CH3), 1.82 m (1H, 3-H), 2.16 m
(1H, 3-H), 2.20 d (3H, CH3, J = 2.8 Hz), 2.52 d.d.d
(1H, 6-H, J = 18.8, 6.2, 1.8 Hz), 3.0 m (2H, 2-H, 6-H),
3.20 m (1H, 2-H), 3.63 m (1H, 3a-H), 3.66 d.d (1H,
5-H, J = 11.8, 6.2 Hz), 3,74 s (3H, OCH3), 6.81 d
(2H, 3''-H, 5''-H, J = 7.8 Hz), 7.12 d (2H, 2''-H, 6''-H,
J = 7.8 Hz). 13C NMR spectrum, δC, ppm: 17.93 q
(4-CH3), 22.81 t (C3), 28.56 q (CH3), 29.55 q (CH3),
37.22 t (C6), 45.71 d (C3a), 46.17 d (C5), 50.76 t (C2),
55.21 q (OCH3), 57.15 s (C4), 105.97 s (C2'), 114.33 d
(C3'', C5''), 129.08 s (C1''), 130.03 s (C2'', C6''), 130.17 s
(C7a), 142.44 s (C7), 159.72 c (C4''), 168.59 s (C=O),
163.26 s (C=O). Mass spectrum, m/z (Irel, %): 420
(12), 362 (100), 277 (28), 226 (64), 148 (69), 135
(38). Found: [M]+ 420.12399. C21H24O7S. Calculated:
M 420.12426.
1
(C=O); 2970, 3147, 3446 (NH2, OH). H NMR spec-
trum (CDCl3), δ, ppm: 2.03 m (1H, 5-H), 2.05 d (3H,
CH3, J = 2.2 Hz), 2.40 m (3H, 3-H, 6-H), 2.52 m
(2H, 3a-H, 6-H), 2.95 m (1H, 2-H), 3.19 s (1H, 2-H),
3.35 m (1H, 5-H), 6.06 br.s and 6.82 br.s (NH, OH).
13C NMR spectrum, δC, ppm: 17.86 q (CH3), 21.91 t
(C3), 30.61 t (C5), 32.14 t (C6), 41.13 d (C3a), 50.65 t
(C2), 55.77 s (C4), 132.46 s (C7a), 140.16 s (C7),
171.91 s (C=O), 172.61 s (C=O). Mass spectrum, m/z
(Irel, %): 257 [M – 16]+ (2), 229 (23), 184 (100), 119
(36), 105 (49), 91 (48).
Methyl 7-methyl-4-phenethylcarbamoyl-2,3,3a,-
4,5,6-hexahydro-1-benzothiophene-4-carboxylate
1,1-dioxide (XXV). Adduct IX, 0.31 g (1 mmol), was
dissolved in 1 ml of phenethylamine, and the solution
4-Methoxycarbonyl-7-methyl-2,3,3a,4,5,6-hexa-
hydro-1-benzothiophene-4-carboxylic acid 1,1-di-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

DIELS–ALDER REACTIONS WITH CYCLIC SULFONES: VII.
863
was heated for 3 h at 40°C and was then diluted with
0.5 ml of cold 10% hydrochloric acid. The aqueous
phase was extracted with chloroform, the extract was
dried over MgSO4 and evaporated, and the oily residue
was treated with a saturated solution of diazomethane
in diethyl ether. When the reaction was complete
(nitrogen no longer evolved), the mixture was
evaporated, and the residue was purified by column
chromatography on silica gel. Yield 0.20 g (50%).
IR spectrum, ν, cm–1: 702, 752, 1498, 1600 (C=Carom);
1127, 1291 (SO2); 1532, 1657, 1740 (C=O); 3375,
(CH2); 30.19 t (CH2); 32.97 t (C6); 34.85 t (CH2);
40.60 t (CH2); 41.26 d (C3a); 50.61 t (C2); 55.74 s (C4);
126.11 d, 126.76 d (C4''); 128.31 d, 128.66 d, 128.68 d,
128.72 d, 128.73 d, 128.74 d, 128.78 d, 128.79 d (C2',
C3', C5', C6'); 133.27 s (C7); 137.45 s (C3); 138.94 s,
139.39 s (C1, C7a); 169.73 s (C=O); 171.04 s (C=O).
Found, %: C 59.9; H 6.7; Cl 6.6; N 4.5; S 7.4.
C25H33N2O5S·HCl. Calculated, %: C 58.9; H 6.7;
Cl 6.9; N 5.5; S 6.3.
N-(6-Hydroxy-2-methylpyrimidin-4-yl)-7-
methyl-2,3,3a,4,5,6-hexahydro-1-benzothiophene-4-
carboxamide 1,1-dioxide (XXVII). A solution of
0.94 g (3 mmol) of adduct IX and 0.41 g (3.6 mmol) of
4-amino-6-hydroxy-2-methylpyrimidine in 10 ml of
DMF was heated for 14 h at 130°C (TLC). The
mixture was cooled, and the precipitate, 0.70 g, was
filtered off. The filtrate was evaporated, the residue
was dissolved in ethyl acetate, the solution was cooled,
and an additional portion of amide XXVII, 0.22 g,
was filtered off. Overall yield 91%, mp 152–154°C.
IR spectrum, ν, cm–1: 806, 1457, 1500, 1610, 1629
(C=C); 1125, 1285 (SO2); 1629, 3167, 3349, 3505
(C–N, OH); 1680 (CO). UV spectrum, λmax, nm (logε):
211 (4.33), 259 (3.80). 1H NMR spectrum (DMSO-d6),
δ, ppm: 1.72 m (2H, 3-H, 5-H), 2.10 s (3H, CH3),
2.15 m (1H, 4-H, J = 2.0, 10.2 Hz), 2.31 m (3H, 3-H,
1
3500 (NH). H NMR spectrum (CDCl3), δ, ppm:
1.88 m (1H, 6-H), 1.93 d (3H, CH3, J = 2.1 Hz),
2.15 m (4H, 3-H, 6-H, 3a-H), 2.30 m (1H, 5-H), 2.74 t
(2H, CH2, J = 7.2 Hz), 2.79 m (1H, 2-H), 3.05 m
(1H, 2-H), 3.14 m (1H, 5-H), 3.46 m (2H, CH2), 3.57 s
(3H, OCH3), 6.59 t (1H, NH), 7.09 m (2H, Ph), 7.13 m
(1H, Ph), 7.21 m (2H, Ph). 13C NMR spectrum, δC,
ppm: 17.42 q (CH3), 21.67 t (C3), 30.23 t (CH2), 31.14 t
(C6), 34.74 (C5), 40.57 t (CH2), 41.14 d (C3a), 50.34
(C2), 52.34 q (OCH3), 55.89 s (C4), 126.17 d (C4'),
128.18 d and 128.34 d (C2', C3', C5', C6'), 132.44 (C7a),
138.04 s (C1'), 139.29 (C7), 168.44 s (C=O), 170.74 s
(C=O). Mass spectrum, m/z (Irel, %): 391 (100), 332
(89), 243 (30), 211 (74), 105 (52), 91 (44). Found: [M]+
391.14547. C20H25NO5. Calculated: M 391.14533.
Phenethylammonium hydrochloride–7-methyl-
4-phenethylcarbamoyl-2,3,3a,4,5,6-hexahydro-1-
benzothiophene-4-carboxylic acid 1,1-dioxide
(XXVI). A mixture of 1.13 g (3.6 mmol) of adduct IX
and 4 ml of phenethylamine was heated for 3 h at
40°C, 0.5 ml of cold 10% hydrochloric acid was
added, and the aqueous phase was extracted with
chloroform. The combined extracts were dried over
MgSO4 and evaporated, the residue was treated with
a saturated solution of hydrogen chloride in ether, and
the precipitate was filtered off. Yield 1.23 g (83%),
mp 142–144°C (from ethyl acetate). IR spectrum, ν,
cm–1: 745, 940, 1498, 1602 (C=Carom); 1120, 1295
5-H, 6-H), 2.51 m (1H, 6-H), 2.87 m (1H, 3a-H, J3a,4
=
10.2 Hz), 2.99 m (1H, 2-H), 3.20 m (1H, 2-H), 6.12 s
(1H, 5'-H), 7.4 br.s and 9.6 br.s (2H, OH, NH).
13C NMR spectrum, δC, ppm: 17.82 q (CH3), 20.86 q
(CH3), 26.15 t and 26.16 t (C3, C5), 31.86 t (C6),
43.67 d and 46.99 d (C3a, C4), 50.94 t (C2), 82.87 d
(C5'), 135.42 s (C7a), 140.00 s (C7), 156.13 s and
158.76 s (C2', C6'), 163.34 s and 168.20 s (C4', C=O).
Mass spectrum, m/z (Irel, %): 184 [M – 153]+ (53), 125
(100), 105 (32), 97 (46), 68 (49), 42 (64).
N-(2-Benzimidazolyl)-7-methyl-2,3,3a,4,5,6-
hexahydro-1-benzothiophene-4-carboxamide 1,1-di-
oxide (XXVIII). A solution of 0.94 g (3 mmol) of
adduct IX and 0.48 g (3.6 mmol) of 2-aminobenz-
imidazole in 10 ml of DMF was heated for 14 h at
130°C (TLC). The mixture was cooled, and 0.12 g of
compound XXVIII was filtered off. The filtrate was
evaporated, the residue was dissolved in ethyl acetate,
the solution was cooled, and an additional portion of
amide XXVIII, 0.81 g, was filtered off. Overall yield
89%. IR spectrum, ν, cm–1: 699, 719, 779, 1500, 1552
(C=C, C=N); 1651, 1667 (C=O, C=N); 2366, 2604,
2734, 3449, 3500 (NH). UV spectrum, λmax, nm (logε):
206 (4.21), 251 (2.50), 257 (2.59), 262 (2.50), 268
+
(SO2); 1674, 1747 (C=O); 2059 (NH3 ); 1627, 2525,
2599, 2726, 3300, 3458 (NH2). UV spectrum, λmax, nm
(logε): 207 (3.29), 252 (2.08), 258 (2.08), 264 (2.04).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.83 m (1H,
6-H), 1.89 d (3H, CH3, J = 2.4 Hz), 2.03 m (1H, 3-H),
2.17 m (1H, 6-H), 2.21 m (2H, 6-H, 5-H), 2.32 m (1H,
3a-H), 2.73 t (2H, CH2, J = 7.2 Hz), 2.87 m (1H, 2-H),
2.92 m (1H, 5-H), 2.93 m (2H, CH2), 3.00 m (2H,
CH2), 3.12 m (1H, 2-H), 3.30 m, 3.37 m (2H, CH2),
7.16 m (3H, Ph), 7.26 m (5H, Ph), 7.30 m (2H, Ph),
7.88 br.s and 8.22 br.s (NH, NH2, OH). 13C NMR
spectrum, δC, ppm: 17.50 q (CH3); 22.17 t (C3); 29.45 t
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

ANDREEV et al.
864
(2.44). 1H NMR spectrum (DMSO-d6), δ, ppm: 1.68 m
(1H, 3-H), 1.86 m (2H, 5-H, 6-H), 1.97 d (3H, CH3,
J = 2.9 Hz), 2.0–2.6 m (5H, 3a-H, 3-H, 4-H, 5-H, 6-H),
3.0–3.5 m (2H, 2-H), 5.8 br.s (2H, NH), 7.02–7.12 m
(2H, 4'-H, 7'-H), 7.36–7.46 m (2H, 5'-H, 6-H).
13C NMR spectrum, δC, ppm: 17.62 q (CH3), 25.30 t
(C3), 25.98 t (C5), 28.17 t (C6), 36.28 d, 45.88 d (C3a,
C4), 50.76 t (C2), 121.17 d (C5', C6'), 124.88 s and
126.61 s (C3a', C7a'), 128.54 d and 129.66 d (C4', C7'),
134.64 s (C7a), 140.28 s (C7), 146.34 s (C2'), 173.29 s
(C=O). Mass spectrum, m/z (Irel, %): 345 (7), 184 (28),
160 (27), 134 (24), 133 (100), 105 (41), 91 (43), 77
(30). Found: [M]+ 345.11701. C17H19N3O3S. Calcu-
lated: M 345.11470.
J3a,4 = 11.5 Hz), 2.95 (1H, 2-H), 3.12 m (1H, 2-H),
3.92 s (2H, CH2), 7.31 (3H, Ph), 7.43 m (2H, Ph).
13C NMR spectrum, δC, ppm: 17.84 q (CH3), 26.19 t
(C3, C5), 31.91 t (C6), 32.84 q (NCH3), 40.01 d (C3a),
47.35 d (C4), 50.95 t (C2), 52.28 t (CH2), 128.09 d
(C4'), 128.49 d and 129.34 d (C2', C3', C5', C6'), 134.97 s
and 135.50 s (C1', C7a), 139.93 s (C7), 176.92 s (C=O).
Mass spectrum, m/z (Irel, %): 333 (0.5), 230 (12), 184
(100), 120 (36), 93 (59), 105 (46). Found: [M]+
333.13920. C18H23NO3S. Calculated: M 333.13985.
7-Methyl-2,3,3a,4,5,6-hexahydro-1-benzothio-
phene-4-carbohydrazide 1,1-dioxide (XXXI). Hy-
drazine hydrate, 1.5 ml, was added to a solution of
0.63 g (2 mmol) of compound IX in 5 ml of DMF, and
the mixture was heated for 12 h under reflux. The
solvent was distilled off under reduced pressure, and
the residue was recrystallized from ethanol. Yield
0.42 g (86%), mp 260–261°C. IR spectrum, ν, cm–1:
702, 733, 1500, 1580 (C=C); 1119, 1120, 1287 (SO2);
1554, 3438, 3486 (NHNH2); 1660, 1670 (C=O).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.50 m (2H,
3-H, 5-H), 1.93 d (3H, CH3, J = 3.0 Hz), 1.99 m (1H,
4-H), 2.20 m (2H, 5-H, 6-H), 2.35 m (2H, 3-H, 6-H),
2.70 m (1H, 3a-H, J3a,4 = 11.2 Hz), 2.90 m (1H, 2-H),
3.05 m (1H, 2-H). 13C NMR spectrum, δC, ppm:
17.72 q (CH3), 23.47 t (C3, C5), 31.91 t (C6), 39.79 d
(C3a),46.99 d (C4), 50.92 t (C2), 135.37 s (C7a), 139.70
s (C7), 176.09 s (C=O). Mass spectrum, m/z (Irel, %):
229 [M – 15]+ (7), 184 (100), 105 (73), 93 (56), 92
(45), 91 (63), 79 (36).
N-Phenethyl-7-methyl-2,3,3a,4,5,6-hexahydro-1-
benzothiophene-4-carboxamide 1,1-dioxide (XXIX).
A mixture of 0.59 g (1.2 mmol) of hydrochloride
XXVI and 5 ml of DMF was heated for 12 h at 160°C.
The solvent was distilled off under reduced pressure,
and the residue was subjected to column chromatog-
raphy to isolate 0.18 g (53%) of compound XXIX,
mp 144–146°C (from diethyl ether). IR spectrum, ν,
cm–1: 720, 725, 753 (Ph); 1126, 1298 (SO2); 1549,
1658, 1666 (CONH); 3312, 3352, 3385 (NH). UV
spectrum, λmax, nm (logε): 253 (2.20), 259 (2.30).
1H NMR spectrum (CDCl3), δ, ppm: 1.52 m (1H, 3-H),
1.80 m (3H, 3-H, 5-H), 2.05 d (3H, CH3), 2.20 m (2H,
4-H, 6-H), 2.83 m (3H, CH2, 6-H), 2.92 m (1H, 2-H),
3.06 m (1H, 2-H), 3.55 m (3H, CH2, 3a-H), 7.20 m
13
(5H, Ph). C NMR spectrum, δC, ppm: 18.08 q (CH3);
25.04 t (C3); 25.51 t (CH2); 31.95 t (C6); 35.45 t (C5);
39.54 d (C3a); 40.30 t (CH2); 47.34 s (C4); 50.92 t (C2);
126.47 d, 128.52 d, 128.57 d (C2', C3', C5', C6'); 134.57
s (C7a); 138.46 s (C4'); 140.86 s (C7); 172.68 s (C=O).
Mass spectrum, m/z (Irel, %): 333 (43), 185 (32), 119
(26), 105 (100), 93 (25), 79 (38), 77 (39), 55 (32).
Found: [M]+ 333.13920. C18H23NO3S. Calculated:
M 333.13985.
7-Methyl-5-phenyl-2,3,3a,4,5,6-hexahydro-1-ben-
zothiophene-4-carbohydrazide 1,1-dioxide (XXXII)
was synthesized as described above using compound
XI. Yield 81%, mp 156–158°C (from ethanol).
UV spectrum, λmax, nm (logε): 252 (2.39), 258 (2.41),
265 (2.33). IR spectrum, ν, cm–1: 702, 733, 1500, 1580
(C=C); 1119, 1120, 1287 (SO2); 1554, 3438, 3486
1
(NHNH2); 1660, 1670 (C=O). H NMR spectrum
N-Benzyl-7,N-dimethyl-2,3,3a,4,5,6-hexahydro-
1-benzothiophene-4-carboxamide 1,1-dioxide
(XXX). A mixture of 0.63 g (2 mmol) of adduct IX
and 1.8 ml of N-methylbenzylamine was heated for 9 h
at 100°C. The mixture was cooled, 5 ml of diethyl
ether was added, and the precipitate was filtered off
and recrystallized from ethyl acetate. Yield 0.51 g
(76%), mp 153–155°C. IR spectrum, ν, cm–1: 726, 749,
1517 (Ar); 1126, 1138, 1287 (SO2); 1577, 1634, 1691
(DMSO-d6), δ, ppm: 1.42 m (1H, 3-H), 2.08 d (3H,
CH3, J = 2.4, 1.2 Hz), 2.25 d.d (1H, 4-H, J = 3.8 Hz,
11.0), 2.36 d.d (1H, 6-H, J = 19.2, 2.5 Hz), 2.40 m
(1H, 3a-H, J3a,4 = 11.0 Hz), 2.51 m (1H, 3-H),
2.77 d.d.d.d (1H, 6-H, J = 19.2, 7.0, 4.4, 1.2 Hz),
2.93 m (1H, 2-H), 3.11 m (1H, 2-H), 3.60 d.d (1H,
5-H, J = 7.0, 3.8 Hz), 7.03 m (2H, o-H), 7.16 m (1H,
o-H), 7.20 m (2H, m-H). 13C NMR spectrum, δC, ppm:
17.86 q (7-CH3), 26.36 t (C3), 34.36 d (C3a), 38.60 t
(C6), 40.00 d (C5), 50.91 t (C2), 51.53 d (C4), 126.28 d
(C4'), 127.73 d and 127.87 d (C2', C3', C5', C6'), 136.23 s
(C7a), 139.75 s (C1'), 142.79 s (C7), 174.76 s (C=O).
1
(CO). H NMR spectrum (DMSO-d6), δ, ppm: 1.47 m
(2H, 3-H, 5-H), 1.90 m (1H, 4-H), 1.93 d (3H, CH3,
J = 2.9 Hz), 1.95 m (1H, 5-H), 2.18 m (2H, 6-H),
2.33 m (1H, 3-H), 2.40 s (3H, CH3), 2.66 m (1H, 3a-H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

DIELS–ALDER REACTIONS WITH CYCLIC SULFONES: VII.
865
Mass spectrum, m/z (Irel, %): 306 [M – 15]+ (7), 260
(95), 181 (41), 168 (28), 104 (41), 91 (38), 44 (100).
7. Tolstikov, G.A., Shul’ts, E.E., Vafina, G.F., Tolstiko-
va, T.G., Davydova, V.A., Ismagilova, A.F., Spiri-
khin, L.V., Zarudii, F.A., and Lazareva, D.N., Khim.-
Farm. Zh., 1991, no. 11, p. 39.
X-Ray diffraction study of compound (XXIV).
A 0.80×0.40×0.16-mm single crystal was selected.
Triclinic system with the following unit cell param-
eters: a = 8.6915(7), b = 10.058(1), c = 10.346(1) Å;
α = 103.998(7), β = 111.127(7), γ = 103.748(8)°; V =
764.05(14) Å3; space group P-1; Z = 2; C11H15NO5S1 +
C2H5OH; dcalc = 1.388 g/cm3; µ = 0.238 mm–1. Intens-
ities of 2597 independent reflections were measured.
A correction for absorption was introduced empirically
by psi-curves (transmission 0.79–0.84). The structure
was solved by the direct method using SHELXS-97
program. Hydrogen atoms in molecule XXIV and in
the hydroxy group of the solvent molecule were
localized by the difference synthesis of electron
density. The positions of hydrogen atoms attached to
carbon atoms of the solvent were calculated at each
refinement cycle from coordinates of the respective
carbon atoms, and they were not refined. The final
refinement of the structure parameters was performed
by the least-squares procedure in full-matrix aniso-
tropic approximation (isotropic for hydrogen atoms)
using SHELXL-97 program with respect to all F2 to
wR2 = 0.1188, S = 1.030; 260 parameters were refined
(R = 0.0431 for 2340 F > 4σ).
8. Tolstikova, T.G., Shul’ts, E.E., Popov, V.G., Lazare-
va, D.N., Davydova, V.A., and Tolstikov, G.A., Dokl.
Akad. Nauk SSSR, 1991, vol. 320, p. 242.
9. Tolstikov, G.A., Tolstikova, T.G., Shul’ts, E.E., Mukha-
metyanova, T.Sh., Popov, V.G., Davydova, V.A., Lazare-
va, D.N., and Zarudii, F.S., Khim.-Farm. Zh., 1992,
no. 11, p. 20.
10. Bazinkai, J.F., Hrubowchak, D.M., and Smith, F.X.,
Tetrahedron Lett., 1985, vol. 26, p. 3195.
11. Argyle, C.S., Mason, K.G., Smith, M.A., and
Stern, E.S., J. Chem. Soc. C, 1967, p. 2176.
12. Chen, B.-C., Heterocycles, 1991, vol. 32, p. 929.
13. McLab, H., Chem. Soc. Rev., 1978, vol. 7, p. 345.
14. Kunz, F.J. and Polansky, O.E., Monatsh. Chem., 1969,
vol. 100, p. 920; Kraus, C.A. and Krolski, M.E., J. Org.
Chem., 1986, vol. 51, p. 3347; Strozhev, M.F., Liel-
briedis, I.E., and Neiland, O.Ya., Khim. Geterotsikl.
Soedin., 1991, p. 579.
15. Zitsine, D.R., Ravinya, I.T., Riikurs, I.A., Tetere, Z.F.,
Gudrinietse, E.Yu., and Kalei, U.O., Russ. J. Org.
Chem., 1999, vol. 35, p. 1457.
16. Allen, F.H., Kenard, O., Watson, D.G., Bramer, L.,
Orpen, A.G., and Taylor, R., J. Chem. Soc., Perkin
Trans. 2, 1987, p. S1.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 03-03-33093).
17. Lynch, V.M., Daniel, D., Martin, S.F., and Davis, B.E.,
Acta Crystallogr., Sect. C, 1991, vol. 47, p. 1340.
18. Allen, F.H. and Kenard, O., Chem. Design Autom.
News, 1993, vol. 8, p. 31.
REFERENCES
19. Molecular Mechanics, Burkert, U. and Allinger, N.L.,
Eds., Washington, DC: Am. Chem. Soc., 1982. Tran-
slated under the title Molekulyarnaya mekhanika,
Moscow: Mir, 1986, p. 110.
1. Tolstikov, G.A., Shul’ts, E.E., Vafina, G.F., and Spiri-
khin, L.V., Zh. Org. Khim., 1992, vol. 28, p. 192.
2. Tolstikov, G.A., Kazakov, V.P., Shul’ts, E.E., Bulga-
kov, R.G., and Kantyukova, R.G., Zh. Org. Khim., 1984,
vol. 20, p. 303.
3. Tolstikov, G.A., Shul’ts, E.E., Struchkov, Yu.T.,
Yufit, D.S., and Lindeman, S.V., Zh. Org. Khim., 1986,
vol. 22, p. 121.
20. Nakanishi, K., Infrared Absorption Spectroscopy. Prac-
tical, San Francisco: Holden-Day, 1962. Translated
under the title Infrakrasnye spektry i stroenie organi-
cheskikh soedinenii, Moscow: Mir, 1965, p. 188.
21. Davidson, D. and Bernhard, S.A., J. Am. Chem. Soc.,
4. Tolstikov, G.A., Shults, E.E., and Spirikhin, L.V., Tetra-
hedron, 1986, vol. 42, p. 591.
1948, vol. 70, p. 3426.
22. Schuster, P., Polansky, O.E., and Wessely, F., Monatsh.
Chem., 1964, vol. 95, p. 53.
5. Tolstikov, G.A., Shul’ts, E.E., Vafina, G.F., Spiri-
khin, L.V., and Panasenko, A.A., Zh. Org. Khim., 1989,
vol. 25, p. 1231.
23. Obshchii praktikum po organicheskoi khimii (General
Practicum on Organic Chemistry), Kost, A.N., Ed.,
Moscow: Mir, 1965, p. 532.
6. Shul’ts, E.E., Vafina, G.F., Spirikhin, L.V., and Tolsti-
kov, G.A., Zh. Org. Khim., 1990, vol. 26, p. 1139.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004