A new rearrangement of spiro[indane-1,3′-thiophene] and spiro[naphthalene-1,3′-thiophene] derivatives accompanied by opening of the cycloalkane ring

Article abstract of DOI:10.1007/s00706-009-0233-4

The new thioamides 2-oxoindane-1-carbothioamides and 2-oxo-1,2,3,4- tetrahydronaphthalene-1-carbothioamides underwent conjugated addition to (E)-β-nitrostyrenes followed by cyclization to give products containing 5-hydroxyimino-2-aryliminothiophene rings spiro-annulated to the 2-indanone or 2-tetralone system. On treatment with hydrochloric acid in boiling methanol the compounds underwent a new rearrangement, involving transformation of the 2-aryliminothiophene ring to a pyrrole and an opening of the alicyclic ring in the proximity of the carbonyl group, affording 2-(1,3-diaryl-2-oxo-5- thioxopyrrol-4-yl)benzeneacetic or 2-(1,3-diaryl-2-oxo-5-thioxopyrrol-4-yl) benzenepropanoic acid methyl esters. The structures of two selected pyrrole derivatives were determined by X-ray crystal analyses. The thioamides derived from 2-indanone showed unexpected reactivity towards primary alcohols and underwent conversion to 2-hydroxy-1H-indene-3-thiocarboxylic acid O-esters.

Full text of DOI:10.1007/s00706-009-0233-4

Monatsh Chem (2010) 141:63–74
DOI 10.1007/s00706-009-0233-4
ORIGINAL PAPER
A new rearrangement of spiro[indane-1,30-thiophene]
and spiro[naphthalene-1,30-thiophene] derivatives accompanied
by opening of the cycloalkane ring
•
Krystyna Bogdanowicz-Szwed Artur Budzowski
•
•
Regina Gil Paweł Serda
Received: 20 March 2009 / Accepted: 22 November 2009 / Published online: 8 January 2010
ꢀ Springer-Verlag 2009
Abstract The new thioamides 2-oxoindane-1-car-
bothioamides and 2-oxo-1,2,3,4-tetrahydronaphthalene-1-
carbothioamides underwent conjugated addition to
(E)-b-nitrostyrenes followed by cyclization to give prod-
ucts containing 5-hydroxyimino-2-aryliminothiophene
rings spiro-annulated to the 2-indanone or 2-tetralone
system. On treatment with hydrochloric acid in boiling
methanol the compounds underwent a new rearrangement,
involving transformation of the 2-aryliminothiophene ring
to a pyrrole and an opening of the alicyclic ring in the
proximity of the carbonyl group, affording 2-(1,3-diaryl-2-
oxo-5-thioxopyrrol-4-yl)benzeneacetic or 2-(1,3-diaryl-2-
oxo-5-thioxopyrrol-4-yl)benzenepropanoic acid methyl
esters. The structures of two selected pyrrole derivatives
were determined by X-ray crystal analyses. The thioamides
derived from 2-indanone showed unexpected reactivity
towards primary alcohols and underwent conversion to
2-hydroxy-1H-indene-3-thiocarboxylic acid O-esters.
Introduction
The b-ketothioamides are valuable building blocks for
the synthesis of various nitrogen and sulfur heterocyclic
compounds [1]. The versatility of nucleophilic centers of
the b-ketothioamides facilitates their reactivity towards
electrophilic reagents [2]. Acylating agents, e.g. oxalyl
chloride [3], and alkylating agents, e.g. dihaloalkanes [4,
5], attack, mainly, the nitrogen and sulfur atoms
affording thiazole or thiazine derivatives. In reactions
with electrophilic olefins, b-ketothioamides have CH-
acidic properties, e.g. reactions with a,b-unsaturated
aldehydes give 6-hydroxypiperidine-2-thiones [6]. We
have recently found that conjugate addition of b-ami-
nocycloalkenethioamides to maleimides and subsequent
domino reaction provide easy access to polycyclic mo-
nothioimides [7]. However, b-ketothioamides also react
with CH acids, e.g. malononitrile, yielding 6-aminopyr-
idine-2-thiones [8]. In acidic medium some c,d-
unsaturated b-ketothioamides undergo intramolecular
cyclization to 2,3-dihydro-4H-thiopyran-4-ones [9].
b-Ketothioamides may react with some reagents which
convert the thioamide group into five membered nitrogen
heterocycles, e.g. the reaction with DMAD leads to
pyrroles [10], and the reaction with TMS azide leads to
1,5-substituted tetrazoles [11].
Keywords Heterocycles ꢀ Michael addition ꢀ
Thioamides ꢀ Nitrostyrenes ꢀ Spiro compounds ꢀ
X-ray structure determination
Cyclic monothioimides have important biological
properties. The effect of monothioimides on tumor necrosis
factor alpha (TNF-a) production by genetically modified
B78H1 melanoma cells has been investigated [12]. It was
found that monothiophthalimide derivatives had significant
activity as enhancers of TNF-a production. Monothioi-
mides with spiro-annulated alicyclic rings have been
successfully tested for anticonvulsant activity [13, 14].
Cyclic monothioimides have recently been used for
K. Bogdanowicz-Szwed ꢀ A. Budzowski ꢀ R. Gil
Department of Organic Chemistry, Faculty of Chemistry,
´
Jagiellonian University, Krakow, Poland
K. Bogdanowicz-Szwed ꢀ A. Budzowski (&) ꢀ R. Gil
´
Andrzej Frycz Modrzewski Krakow University, Krakow, Poland
e-mail: abudzowski@afm.edu.pl
P. Serda
Regional Laboratory, Jagiellonian University, Krakow, Poland
´
123

64
K. Bogdanowicz-Szwed et al.
R2
N
O
R2
S
(CH2)n
O
(CH2)n
(CH2)n
O
or
N OH
H
Ac2O/AcOH
O
.
H
O
.
CN
.
.
S
.
H
H
H
.
N
S
S
N
S
N
N
R1
Ph
Ph
Ph
R1
n = 1 (1a), 2 (2a)
Scheme 1
Scheme 2
synthesis of protease-resistant and conformationally res-
tricted peptidomimetics [15].
forms A and B in CDCl3 solutions, A:B, ranged from 4.3:1
1
for 2c to 4.9:1 for 2b. In the H NMR spectra of 2a–2c
recorded in DMSO-d6 solutions an inverse ratio A:B has
been observed, from 1:1.2 for 2c to 1:1.7 for 2b. The
increase of amount of the keto form in more polar solvents
is typical of b-ketothioamides [21]. The presence of a
strong band at 1,711 cm-1 in the IR spectrum of 2a and a
medium band at 1,712 cm-1 in the IR spectrum of 2b show
the amount of the B form in the solid state. In the IR
spectrum of 2c the analogous C=O absorption band was not
observed.
Results and discussion
We have recently shown that N-aryl-b-ketothioamides
react readily with b-nitrostyrenes affording thiophene
derivatives with high diastereoselectivity [16–19]. Because
the thiophene skeletons contain oxime and arylimino
groups they are sensitive under acidic conditions. The
thiophenes derived from a-unsubstituted b-ketothioamides
treated with conc. HCl underwent a ring transformation to
5-thioxopyrrol-2-ones [16, 17, 19]. Thiophenes derived
from 5 and 6-membered cyclic b-ketothioamides treated
with conc. HCl underwent decomposition whereas they
reacted smoothly under the acetylation conditions Ac2O/
AcOH yielding oxime esters [18]. We have found that
thiophenes and their oxime esters spiro-annulated with a
1-tetralone skeleton underwent, under acidic conditions, an
unique rearrangement giving polycyclic systems, e.g.
6-azabicyclo[3.2.1]octane [20] (Scheme 1).
The thioamides 1a–1c and 2a–2c treated with (E)-b-
nitrostyrenes 3a–3c in the presence of a catalytic amount of
piperidine underwent a conjugated addition–cyclization to
give the products 4a–4f and 5a–5f with thiophene rings
spiro-annulated to the 2-indanone and 2-tetralone system
(Scheme 3). The matched pairs of reagents had different
aryl groups R1 and R2 (Table 1). The reactions of 1a–1c
with 3a–3c were performed in acetonitrile, because we
observed slow decomposition of the thioamides in the
presence of primary alcohols (see below). However the
desired products 4a–4f were formed in moderate or poor
yields (23–54%). The reactions of 2a–2c with 3 were
carried out in dry ethanol at boiling temperature, affording
5a–5f in moderate to good yields (33–60%). The mecha-
nism of the addition—cyclization has been reported in
detail in our previous work [16–19].
Taking into account our results on rearrangement of
compounds spiro-annulated with a 1-tetralone skeleton, in
this work we studied the synthesis and the acidic rear-
rangements of thiophenes derived from some unreported
thioamides containing 2-indanone and 2-tetralone ring
systems.
1
The H NMR spectra of 4 and 5 contained the charac-
1
teristic singlet of the oxime proton; e.g. in the H NMR
The starting thioamides 1a–1c and 2a–2c were obtained,
in moderate yields, by reaction of 2-indanone or 2-tetralone
with sodium hydride and aryl isothiocyanates. The 1H
NMR spectra of thioamides 1a–1c in CDCl3 solutions
contained singlets at d = 14.15–14.10 ppm, which indi-
cated that the compounds exist almost exclusively in the
enol form A in these solutions. The two alternative enol
forms are shown in Scheme 2 [21]. Only traces of the keto
form B were observed, e.g. the characteristic signals for the
HC-1 protons at d & 4.65 ppm. The ratio of the A and B
forms in CDCl3 solutions, based on the integration in the
1H NMR spectra, was A:B & 40:1. The IR spectra of
1a–1c in KBr pellets suggested the preference of the form
spectrum of 4b the oxime proton resonated at
1
d = 11.88 ppm and the analogous proton in the H NMR
CO2Me
R2
N
H
O
O
R2
HCl
R2
+
MeOH
H
O2N
N
R1
S
O
S
N
S
N
N
OH
R1
R1
1a-1c
3a-3c
4a-4f
6a-6f
CO2Me
R2
R2
N
H
HCl
O
R2
+
O
H
MeOH
N
1
O2N
S
O
A in the solid state also. In the H NMR spectra of the
R1
S
S
N
R1
N
R1
N
OH
thioamides 2a–2c in CDCl3 solutions two sets of signals for
the A and B forms were clearly visible. The compounds
existed predominantly in the enol form A. The ratio of
2a-2c
3a-3c
5a-5f
7a-7f
Scheme 3
123

A new rearrangement of spiro[indane-1,30-thiophene] and spiro[naphthalene-1,30-thiophene]
65
Table 1 Results from synthesis
Thioamide
Nitroalkene
R1
R2
Yield
(%)
Yield
(%)
of the thiophene derivatives
4a–4f and 5a–5f and subsequent
reactions with HCl in methanol
(Scheme 3)
1a
1a
1b
1b
1c
1c
2a
2a
2b
2b
2c
2c
3b
3c
3a
3c
3a
3b
3b
3c
3a
3c
3a
3b
C6H5
4-CH3–C6H4
4-Cl–C6H4
C6H5
4a
4b
4c
4d
4e
4f
36
54
46
56
24
23
46
48
47
33
49
60
6a
6b
6c
6d
6e
6f
26
23
11
20
27
29
41
38
32
22
77
54
C6H5
4-CH3–C6H4
4-CH3–C6H4
4-Cl–C6H4
4-Cl–C6H4
C6H5
4-Cl–C6H4
C6H5
4-CH3–C6H4
4-CH3–C6H4
4-Cl–C6H4
C6H5
5a
5b
5c
5d
5e
5f
7a
7b
7c
7d
7e
7f
C6H5
4-CH3–C6H4
4-CH3–C6H4
4-Cl–C6H4
4-Cl–C6H4
4-Cl–C6H4
C6H5
4-CH3–C6H4
spectrum of 5b resonated at d = 11.62 ppm. The proton
attached to C-40 of the spiro[indane-1,30-thiophene] system
of 4b resonated at d = 5.00 (s) ppm, and the protons
attached to C-3 appeared as two doublets at d = 3.77 and
3.63 ppm. The proton attached to C-40 of the spiro[naph-
thalene-1,30-thiophene] system of 5b resonated at d = 4.95
(s) ppm, and the protons attached to C-3 and C-4 appeared
as four signals coupled together (d 9 d 9 d) at d = 2.77,
2.62, 2.11, and 1.92 ppm.
The reactivity of the thiophene derivatives 4a–4f and
5a–5f, which contain two exocyclic C=N bonds, towards
acidic reagents has been investigated. The compounds were
stable in acetic acid and acetic anhydride. When treated
with hydrochloric acid in methanol solutions, however,
4a–4f and 5a–5f underwent a rearrangement involving
transformation of the thiophene ring and breaking of the
alicyclic ring in the proximity of the carbonyl group. The
reaction mixture after work up afforded the products 6a–6f
in moderate to poor yields (11–29%) and 7a–7f in mod-
erate to good yields (22–77%). The IR spectra of the
products contained the characteristic bands indicating ester
functionality, e.g. broad bands at 1,733 cm-1 (C=O) and at
Fig. 1 A perspective view of the molecule of 6d with the crystal-
lographic atom numbering scheme
Two crystalline compounds 6d and 7a were chosen and
submitted to X-ray crystal analysis. Perspective views of
the molecules of 6d and 7a with the crystallographic atom
numbering are shown in Figs. 1 and 2, respectively.
Despite the similar structures, there is one rather significant
difference. The terminal COOCH3 group has one more
single bond separating it from the phenyl ring and thus
more rotational freedom. This manifests itself in the dis-
order of this substituent in 7a, whereas the same moiety
does not show any disorder in 6d. This could be modeled in
part by splitting the atom O17 in 7a, with both positions
rotated by about 37 degrees. Also, the atomic displacement
parameters of the remaining atoms in this moiety are
somewhat high. As a result there is a residual electron
1
1,150 cm-1 (C–O) in the IR spectrum of 6b. In the H
NMR spectrum of 6b the ester methyl group appeared as
singlet at d = 3.45 ppm, overlapping the two doublets of
the AB system of the methylene fragment adjacent to the
ester group. The HSQC spectrum revealed correlations of
the protons with two carbon atoms: the methyl carbon at
d = 52.0 and the methylene carbon at d = 39.6 ppm. The
13C NMR spectrum of 6b also revealed the thiocarbonyl
group at d = 199.3 ppm. Other signals, especially those of
the aromatic and alkene fragments appear very close to
each other and cannot be assigned. Therefore, the structure
of compounds 6 and 7 was unequivocally determined on
the basis of crystallographic measurements.
-3
˚
density peak of 0.63 eA in the final Fourier map of 7a.
The conformations of the molecules of both 6d and 7a are
stabilized by an intramolecular close contact C25-
123

66
K. Bogdanowicz-Szwed et al.
+
O
R OH
OH
H
S
N
S
OR
Ph
1a
16a, 16b
R = CH3 (16a), C2H5 (16b)
Scheme 5
MeOH affording the methyl ester. Nucleophilic attack of
the thioamide nitrogen on the carbon of the aldoxime group
leads to the closure of a pyrrole ring. Subsequent elimi-
nation of a water molecule from 14 followed by a
spontaneous hydrolysis of the imine 15 provides the
products 7a–7f.
Fig. 2 A perspective view of the molecule of 7a with the crystal-
lographic atom numbering scheme. The oxygen atom O17 has two
disordered positions, of which only one is presented in the figure for
clarity
We observed unusual reactivity of the thioamides
derived from 2-indanone 1a–1c towards primary alcohols.
For example, the thioamide 1a reacted with boiling meth-
anol or ethanol affording appropriate thiocarboxylic acid
O-esters 16a or 16b in good yields of 43 and 61%
(Scheme 5). The direction of these reactions is opposite to
the typically observed synthesis of amides from esters [22,
23]. The new reactions seem to be the only method of
transformation of thioamides into O-thioesters, because the
reactions of thioamides with alkylating agents, e.g. alkyl
iodides or dimethyl sulfate, give S-thioesters [24, 25]. In
the 13C NMR spectrum of 16b in CDCl3 solution the
thiocarbonyl carbon atom appeared at d = 204.6 ppm. The
1H NMR spectrum of 16b contained a triplet at
d = 1.64 ppm (CH3) and quartet at d = 4.74 ppm (CH2)
for the ethyl group, which clearly indicate the presence of
the O-ester group. The singlet at d = 13.84 ppm assigned
to the OH proton shows that the product 16b exists almost
exclusively in enol form in CDCl3 solution.
H+
5a-5f
O
O
O
H
R1
H
R1
N
R2
N
R2
N
R2
H
R1
H
S
S
S
H
N
O
OH
N OH
N
OH
8
9
10
O
CH3
CO2Me
R2
MeOH
O
H
R2
-H+
S
R2
S
S
R1
N
N
H
N
H
R1
R1
H
H
N
OH
N
OH
N
OH
H H
11
12
13
CO2Me
R2
CO2Me
R2
-H2O
CO2Me
R2
H3O+
-NH3
H
N
S
S
NH
S
O
N
R1
N
R1
N
R1
OH
H
In conclusion, we have developed new applications of
tandem conjugate addition–cyclization reactions for syn-
thesis of functionalized thiophenes and pyrroles. This study
revealed a unique rearrangement of spiro-annulated thio-
phene derivatives under acidic conditions involving
breakage of a C-C single bond and ring transformations of
iminothiophenes to pyrroles. The results presented provide
easy access to new heterocycles with potential biological
properties.
14
15
7a-7f
Scheme 4
H25…O5 (in both cases). Neither crystal structure shows
typical intermolecular hydrogen bonds.
The reaction of 4a–4f and 5a–5f with HCl and MeOH
leading to the formation of 6a–6f and 7a–7f might be
explained by a mechanism shown in Scheme 4 for 5a–5f.
Initial protonation of the arylimino group leads to opening
of the thiophene ring and formation of hydroxyiminium ion
9. The key step of rearrangement is the conversion of the
ion 9 to the carbocation 10 by a 1,2-hydrogen shift. The
tertiary carbocation 10, which is also stabilized by the aryl
group R2, undergoes subsequent rearrangement involving
the formation of a C=C double bond and the opening of the
tetralone ring at a position adjacent to the carbonyl group.
The newly formed acylium ion 11 reacts with the solvent
Experimental
Melting points were determined on a Boetius hot-stage
apparatus and are corrected. IR spectra were run in KBr
pellets on a Bruker IFS 48 spectrometer. Mass spectra were
obtained on a Finnigan Mat 95 (EI) or a Bruker Esquire
3000 (ESI) mass spectrometer. NMR spectra were recorded
123

A new rearrangement of spiro[indane-1,30-thiophene] and spiro[naphthalene-1,30-thiophene]
67
on a Bruker AMX 500 spectrometer (1H, 500.14 MHz;
13C, 125.76 MHz) or Bruker Avance II 300 MHz in CDCl3
or DMSO-d6 using TMS as internal standard. Microanal-
yses (C, H, N) of the crystalline compounds were
performed with a Euro EA 3000 Elemental Analyzer; the
results agreed satisfactorily ( 0.3%) with calculated val-
ues. Diffraction data were collected using a Nonius Kappa
CCD diffractometer with graphite monochromated Mo–Ka
radiation.
2,3-Dihydro-N-(4-methylphenyl)-2-oxo-1H-indene-1-
carbothioamide (1b, C17H15NOS)
Dark orange crystals (9.89 g, 70%); m.p.: 121–122 ꢁC;
Rf = 0.42 (CHCl3); H NMR (300 MHz, CDCl3): 97% of
1
enol A ? 3% of ketone B, d = 14.15 (s, 1H, OH A), 9.21
(bs, 1H, NH B), 8.87 (bs, 1H, NH A), 7.53 (d, 2H,
3J = 8.4 Hz, CH arom B), 7.46-7.36 (m, 4CH arom
A ? 2CH arom B), 7.34-7.22 (m, 3CH arom A ? 3CH
arom B), 7.16 (ddd, 3J & 7.5, 7.5, 4J = 0.9 Hz, 1CH arom
A ? 1CH arom B), 4.65 (s, 1H, HC-1 B), 3.66 (s, 2H
A ? 2H B, H2C-3 A ? B), 2.39 (s, 3H, CH3 A), 2.34 (s,
3H, CH3 B) ppm; 13C NMR (75 MHz, CDCl3): d = 188.8,
181.8, 140.2, 137.3, 134.6, 132.7, 129.7, 127.3, 125.1,
124.7, 124.1, 117.6, 111.3, 39.1, 21.2 ppm; IR (KBr):
General procedure for synthesis of thioamides 1a–1c,
2a–2c
To a vigorously stirred suspension of sodium hydride
(50 mmol) in 90 cm3 dry DMF at -10 ꢁC, 2-indanone (for
1a–1c; 6.60 g, 50 mmol) or 2-tetralone (for 2a–2c; 7.30 g,
50 mmol) was added slowly, over a period of 1 h, so the
temperature did not exceed 0 ꢁC. After the gas was
evolved, a solution of the appropriate aryl isothiocyanate
(50 mmol) in 10 cm3 dry DMF was added dropwise. The
mixture was stirred for 3 h at -10 ꢁC, left in a fridge
overnight, then added slowly to 50 cm3 1 M HCl, and
acidified with 2 M HCl. After 3 h most of the water–DMF
solution was decanted. The oily residue was dissolved in
CH2Cl2, washed twice with 1 M HCl and water, then
evaporated and purified by flash chromatography on silica
gel using CH2Cl2 as eluent. The crude 2a–2c was treated
with Et2O, cooled in a fridge, and collected by filtration.
The crude 1a–1c was dissolved in MeCN at 50 ꢁC and
treated with 50 cm3 2 M HCl for hydrolysis of imine side-
products. After evaporation of the solvent the product was
purified again by flash chromatography on silica gel, using
CH2Cl2 as eluent, and crystallized from Et2O.
ꢀ
m = 3,365, 3,314, 3,079–3,018, 2,951, 1,562, 1,512, 1,488,
1,457, 1,401, 1,377, 1,299, 1,212, 1,142, 906 cm-1; MS
(70 eV): m/z (%) = 281.1 (31) [M]?, 247.1 (18), 174.0
(29), 146.0 (36), 145.0 (19), 132.1 (10), 107.1 (100), 106.1
(64), 102.1 (22), 77.0 (12).
N-(4-Chlorophenyl)-2,3-dihydro-2-oxo-1H-indene-1-
carbothioamide (1c, C16H12ClNOS)
Orange crystals (9.516 g, 63%); m.p.: 151–153 ꢁC;
Rf = 0.44 (CHCl3); 1H NMR (300 MHz, CDCl3): 97%
of enol A ? 3% of ketone B, d = 14.10 (s, 1H, OH A),
9.31 (bs, 1H, NH B), 8.83 (bs, 1H, NH A), 7.66 (d, 2H,
3J = 8.7 Hz, CH arom B), 7.51 (d, 2H, J = 8.7 Hz, CH
3
arom A), 7.44–7.37 (m, 4CH arom A ? 4CH arom B),
7.36-7.28 (dd, 3J & 7.4, 7.4 Hz, 1CH arom A ? 1CH
arom B), 7.18 (ddd, 3J & 7.4, 7.4, 4J = 1.1 Hz, 1CH arom
A ? 1CH arom B), 4.64 (s, 1H, HC-1 B), 3.67 (s, 2H,
H2C-3 A ? B) ppm; 13C NMR (75 MHz, CDCl3):
d = 188.9, 182.5, 140.0, 135.7, 132.7, 132.6, 129.3,
127.3, 126.4, 124.8, 124.3, 117.6, 111.4, 39.2 ppm; IR
ꢀ
(KBr): m = 3,369, 3,090–3,021, 2,925–2,851, 1,548, 1,502,
1,465, 1,430, 1,392, 1,378, 1,273, 1,138, 1,103, 1,090,
901 cm-1; MS (70 eV): m/z (%) = 303.0 (8) [M ? 2]?,
301.1 (51) [M]?, 204.1 (12), 174.0 (41), 146.0 (51), 145.0
(24), 132.1 (10), 129.0 (31), 127.0 (100), 102.1 (26), 65.1
(11).
2,3-Dihydro-2-oxo-N-phenyl-1H-indene-1-
carbothioamide (1a, C16H13NOS)
Orange crystals (7.41 g, 56%); Rf = 0.41 (CHCl3); m.p.:
1
127–128 ꢁC; H NMR (300 MHz, CDCl3): 97% of enol
A ? 3% of ketone B, d = 14.15 (s, 1H, OH A), 9.29 (bs,
1H, NH B), 8.87 (bs, 1H, NH A), 7.53 (d, 2H, 3J = 8.0 Hz,
CH arom B), 7.57 (d, 2H, 3J = 8.0 Hz, CH arom A), 7.50-
7.27 (m, 6CH arom A ? 6CH arom B), 7.17 (ddd,
3J & 7.4, 7.4, 4J = 1.0 Hz, 1CH arom A ? 1CH arom
B), 4.66 (s, 1H, HC-1 B), 3.67 (s, 2H A ? 2H B, H2C-3
A ? B) ppm; 13C NMR (75 MHz, CDCl3): d = 188.8,
182.1, 140.2, 137.2, 132.7, 129.1, 127.30, 127.27, 125.1,
1,2,3,4-Tetrahydro-2-oxo-N-phenylnaphthalene-1-
carbothioamide (2a, C17H15 NOS)
Yellow crystals (12.65 g, 90%); m.p.: 129–131 ꢁC;
Rf = 0.39 (CHCl3); 1H NMR (500 MHz, CDCl3): 83%
of enol A ? 17% of ketone B, d = 14.01 (bs, 1H, OH A),
9.29 (bs, 1H, NH B), 8.87 (bs, 1H, NH A), 7.67 (d, 2H,
3J = 7.7 Hz, CH arom B), 7.56–7.08 (m, 9CH arom
A ? 7CH arom B), 4.79 (s, 1H, C-1 B), 3.34 (ddd,
ꢀ
124.8, 124.2, 117.7, 111.4, 39.2 ppm; IR (KBr): m = 3,333,
3,041, 3,003, 2,923, 1,549, 1,515, 1,494, 1,472, 1,457,
1,417, 1,359, 1,314, 1,291, 1,227, 1,139, 913 cm-1; MS
(70 eV): m/z (%) = 267.1 (51) [M]?, 233.1 (18), 204.1
(20), 174.0 (25), 146.0 (35), 132.1 (17), 131.1 (18), 102.0
(20), 93.0 (100), 77.0 (17).
2
3
1H, J = 15.7 Hz, J = 9.7, 5.8 Hz, HC-3 B), 3.01 (ddd,
1H, 2J = 15.7 Hz, 3J & 6, 5.5 Hz, HC-3 B), 2.91 (dt, 1H,
2J = 17.5 Hz, 3J & 5.5 Hz, HC-4 B), 2.82 (t, 2H,
3
3J & 7 Hz, H2C-3 A), 2.63–2.52 (m, J & 7 Hz, H2C-4
123

68
K. Bogdanowicz-Szwed et al.
A, HC-4 B) ppm; 13C NMR (125 MHz, CDCl3):
d = 206.7, 190.9, 174.0, 165.7, 138.4, 137.6, 135.7,
133.7, 132.8, 129.4, 129.0, 128.9, 128.5, 128.2, 127.4,
127.11, 127.07, 126.98, 125.7, 124.9, 124.8, 123.4, 109.7,
3J & 7 Hz, H2C-3 A ? m, 1H B, HC-4 B), 2.63–2.52
3
(m, 2H A, J & 7 Hz, H2C-4 A, ? 1H B, HC-4 B) ppm;
1H NMR (300 MHz, DMSO-d6): 45% of enol A ? 55% of
ketone B, d = 12.15 (bs, 1H, NH B), 11.62 (bs, 1H, OH
A), 10.18 (bs, 1H, NH A), 7.94 (bd, 2H, CH arom A), 7.85
ꢀ
69.5, 37.2, 31.1, 27.9, 27.7 ppm; IR (KBr): m = 3,291 (N–
3
3
H), 3,129, 3,060, 3,034, 2,968–2,850, 1,711 (C=O), 1,596,
1,541, 1,493, 1,412, 1,231, 1,205, 1,158, 1,117 cm-1; MS
(70 eV): m/z (%) = 281.1 (96) [M]?, 248.1 (27), 188 (49),
160.0 (23), 115.0 (41), 93 (100), 77.0 (25).
(d, 2H, J = 8.8 Hz, CH arom B), 7.48 (m, J = 8.8 Hz,
2CH arom B ? 2CH arom A), 7.32–7.20 (m, 4CH arom
B), 7.15–6.94 (m, 4CH arom A), 5.04 (s, 1H, HC-1 B), 3.44
2
3
(ddd, 1H, J = 15.5 Hz, J = 9.3, 5.4 Hz, HC-3 B), 3.00
(dt, 1H, 2J = 15.5 Hz, 3J & 6 Hz, HC-3 B), 2.89-2.71 (m,
1,2,3,4-Tetrahydro-N-(4-methylphenyl)-2-oxonaphthalene-
1-carbothioamide (2b, C18H17NOS)
3
2H A, H2C-3 A ? 1H B, 2J = 16.3 Hz, J & 6 Hz, HC-4
2
3
B,), 2.62 (ddd, 1H, J = 16.3 Hz, J = 9.3, 5.9 Hz, HC-4
B), 2.48–2.40 (m, 2H, H2C-4 A) ppm; 13C NMR (75 MHz,
DMSO-d6): d = 207.2, 200.1, 156.3, 139.7, 139.0, 137.9,
136.9, 135.9, 132.9, 131.3, 130.7, 129.7, 129.5, 129.3,
129.0, 128.2, 128.1, 127.8, 127.4, 126.1, 125.2, 124.1,
Yellow crystals (11.59 g, 79%); m.p.: 113–115 ꢁC;
Rf = 0.40 (CHCl3); 1H NMR (300 MHz, CDCl3): 82%
of enol A ? 18% of ketone B, d = 13.99 (bs, 1H, OH A),
9.22 (bs, 1H, NH B), 8.83 (bs, 1H, NH A), 7.50 (d, 2H,
3J = 8.4 Hz, CH arom B), 7.44–7.06 (m, 8CH arom
A ? 6CH arom B), 4.77 (s, 1H, C-1 B), 3.34 (ddd, 1H,
ꢀ
68.2, 39.3, 29.3, 28.6, 28.5 ppm; IR (KBr): m = 3,309,
3,089–3,026, 2,942–2,817, 1,584, 1,561, 1,508, 1,483,
1,413, 1,393, 1,311, 1,285, 1,210, 1,194, 1,139,
1,091 cm-1; ESI–MS: m/z (%) = 318.2 (44), 316.3 (100)
[M ? H]?.
3
2J = 15.5 Hz, J = 9.4, 5.8 Hz, HC-3 B), 3.04–2.86 (m,
3
2H, HC-3 B, HC-4 B), 2.81 (t, 2H, J & 7 Hz, H2C-3 A),
3
2.64–2.50 (m, 2H A ? 1H B, J & 7 Hz, H2C-4 A, HC-4
B), 2.36 (s, 3H, CH3 A), 2.33 (s, 3H, CH3 B) ppm; H
1
NMR (300 MHz, DMSO-d6): 37% of enol A ? 63% of
ketone B, d = 12.01 (bs, 1H, NH B), 11.43 (bs, 1H, OH
General procedure for synthesis of spiro[indane-1,
30-thiophenes] 4a–4f
3
A), 10.32 (bs, 1H, NH A), 7.73 (bd, 2H, J & 7.4 Hz, CH
arom A), 7.65 (d, 2H, 3J = 8.5 Hz, CH arom B), 7.33–6.90
(m, 6CH arom A ? 6CH arom B), 5.02 (s, 1H, HC-1 B),
To a solution of the appropriate thioanilide 1a–1c
(5 mmol) in 20 cm3 MeCN (for 1c 60 cm3) two drops of
piperidine were added at 50 ꢁC. The appropriate (E)-b-
nitrostyrene 3a–3c (5.5 mmol) was then added slowly over
a period of 0.5 h. The mixture was stirred for 0.5 h at
50 ꢁC, then concentrated in vacuo to half of the initial
volume, and cooled in a fridge. The product was isolated
by filtration and recrystallized from EtOAc.
2
3.47 (ddd, 1H, J = 15.6 Hz, J = 9.4, 5.6 Hz, HC-3 B),
3
2
3
2.99 (dt, 1H, J = 15.6 Hz, J & 6 Hz, HC-3 B), 2.88–
2
3
2.72 (m, J = 16.3 Hz, J & 6 Hz, HC-4 B, H2C-3 A),
2
3
2.61 (ddd, 1H, J = 16.3 Hz, J = 9.4, 5.8 Hz, HC-4 B),
2.48-2.40 (m, 2H, H2C-4 A), 2.31 (s, 3H A ? 3H B, CH3
A ? B) ppm; 13C NMR (75 MHz, DMSO-d6): d = 206.2,
198.1, 194.0, 155.8, 137.0, 136.7, 136.4, 135.8, 135.7,
134.8, 131.9, 128.9, 128.7, 128.1, 127.7, 126.9, 126.8,
126.5, 126.2, 124.0, 123.4, 123.2, 123.0, 114.4, 66.7, 38.1,
2,3,40,50-Tetrahydro-50-(hydroxyimino)-40-(4-methyl-
phenyl)-20-(phenylimino)spiro[1H-indene-1,30(20H)-
thiophene]-2-one (4a, C25H20N2O2S)
ꢀ
28.2, 27.4, 27.3, 20.6 ppm; IR (KBr): m = 3,322, 3,211,
3,059, 3,032, 2,956–2,832, 1,712 (C=O), 1,597, 1,560,
1,513, 1,483, 1,431, 1,412, 1,312, 1,292, 1,202, 1,188,
Pale yellow crystals (734 mg, 36%); m.p.: 226–228 ꢁC;
1H NMR (300 MHz, DMSO-d6): d = 11.66 (s, 1H,
NOH), 7.81 (d, 1H, 3J = 7.5 Hz, CH arom), 7.49–7.29
(m, 4H, CH arom), 7.22-7.13 (m, 2H, CH arom), 6.97
1,142, 921 cm-1
;
ESI–MS: m/z (%) = 318.0 (31)
[M ? Na]?, 296.1 (100) [M ? H]?.
3
(d, 2H, J = 8.0 Hz, CH arom), 6.88–6.77 (m, 4H, CH
2
arom), 5.02 (s, 1H, HC-40), 3.56 (d, 1H, J = 23.1 Hz,
N-(4-Chlorophenyl)-1,2,3,4-tetrahydro-2-oxonaphthalene-
1-carbothioamide (2c, C17H14ClNOS)
HC-3), 2.67 (d, 1H, 2J = 23.1 Hz, HC-3), 2.19 (s, 3H,
CH3) ppm; 13C NMR (75 MHz, DMSO-d6): d = 210.8,
167.1, 151.7, 150.3, 139.6, 137.3, 136.8, 130.0, 129.8,
129.3, 128.5, 128.3, 127.7, 125.9, 125.0, 124.1, 119.0,
Yellow crystals (13.87 g, 88%); m.p.: 99–102 ꢁC;
Rf = 0.42 (CHCl3); 1H NMR (300 MHz, CDCl3): 81%
of enol A ? 19% of ketone B, d = 13.98 (bs, 1H, OH A),
9.34 (bs, 1H, NH B), 8.81 (bs, 1H, NH A), 7.65 (d, 2H,
ꢀ
73.8, 56.9, 42.4, 20.5 ppm; IR (KBr): m = 3,250, 3,094–
3
3J = 8.8 Hz, CH arom B), 7.47 (d, 2H, J = 8.8 Hz, CH
3,011, 2,920–2,858, 1,751, 1,655, 1,633, 1,592, 1,485,
1,428, 1,134, 1,118, 1,071, 964 cm-1; MS (70 eV): m/z
(%) = 411.8 (100) [M]?, 277.1 (13), 248.1 (14), 234.1
(22), 233.0 (38), 232.0 (16), 205.1 (16), 204.1 (32), 77.2
(11).
arom A), 7.40–7.08 (m, 6CH arom A ? 6CH arom B),
4.78 (s, 1H, HC-1 B), 3.32 (ddd, 1H, 2J = 15.6 Hz,
2
3J = 9.7, 6.0 Hz, HC-3 B), 3.01 (ddd, 1H, J = 15.6 Hz,
3J & 6.0, 5.2 Hz, HC-3 B), 2.91–2.75 (t, 2H A,
123

A new rearrangement of spiro[indane-1,30-thiophene] and spiro[naphthalene-1,30-thiophene]
69
40-(4-Chlorophenyl)-2,3,40,50-tetrahydro-50-(hydroxyimi-
no)-20-(phenylimino)spiro[1H-indene-1,30(20H)-
thiophene]-2-one (4b, C24H17ClN2O2S)
130.0, 129.8, 129.3, 128.5, 128.3, 127.7, 125.9, 125.0,
124.1, 119.0, 73.8, 56.9, 42.4, 20.5 ppm; IR (KBr):
ꢀ
m = 3,260, 3,100–3,036, 2,961, 2,916, 1,753, 1,592,
Pale yellow crystals (1.164 g, 54%); m.p.: 185–187 ꢁC; 1H
NMR (300 MHz, DMSO-d6): d = 11.88 (s, 1H, NOH),
7.44–7.15 (m, 8H, CH arom), 7.07 (d, 2H, J = 8.5 Hz,
1,557, 1,517, 1,491, 1,418, 1,377, 1,183, 1,131, 1,091,
1,063 cm-1; MS (70 eV): m/z (%) = 446.1 (2) [M]?,
420.1 (36), 419.1 (37), 418.1 (93), 417.1 (32), 281.1 (36),
280.1 (22), 269.1 (28), 268.1 (22), 265.1 (27), 254.1 (13),
250.1 (13), 249.1 (19), 248.1 (100), 247.1 (37), 236.1 (17),
219.1 (22), 218.1 (22), 205.1 (19), 204.1 (32), 203.1 (14),
150.0 (28), 146.0 (17), 138.0 (22), 132.1 (14), 125.0 (24),
107.1 (31), 65.1 (26), 63.0 (21).
3
3
CH arom), 6.88 (d, 1H, J = 7.6 Hz, CH arom), 6.79 (d,
3
2H, J = 7.3 Hz, CH arom), 5.00 (s, 1H, HC-40), 3.77 (d,
1H, 2J = 23.1 Hz, HC-3), 3.63 (d, 1H, 2J = 23.1 Hz,
HC-3) ppm; 13C NMR (75 MHz, DMSO-d6): d = 210.7,
167.3, 151.4, 149.9, 137.9, 137.0, 134.0, 132.3, 131.0,
129.4, 128.7, 128.0, 127.0, 125.5, 125.3, 124.9, 119.2,
20-[(4-Chlorophenyl)imino]-2,3,40,50-tetrahydro-50-
(hydroxyimino)-40-phenylspiro[1H-indene-1,30(20H)-
thiophene]-2-one (4e, C24H17ClN2O2S)
ꢀ
72.8, 53.6, 42.1 ppm; IR (KBr): m = 3,271, 3,054, 2,956–
2,853, 1,754, 1,593, 1,556, 1,513, 1,494, 1,440, 1,418,
1,375, 1,183, 1,130, 1,094, 1,061, 955 cm-1; MS (70 eV):
m/z (%) = 432.0 (6) [M]?, 429.3 (36), 428.3 (100), 427.2
(28), 413.1 (46), 406.2 (28), 405.2 (30), 404.2 (79), 335.0
(21), 267.1 (46), 234.1 (76), 233.1 (56), 205.1 (39), 204.1
(61), 169.0 (27), 146.0 (24), 136.0 (35), 102.0 (33), 93.0
(41), 77.0 (23).
Pale yellow crystals (522 mg, 24%); m.p.: 211–214 ꢁC; 1H
NMR (300 MHz, DMSO-d6): d = 11.84 (s, 1H, NOH),
7.44 (d, 2H, J = 8.7 Hz, CH arom), 7.32–7.10 (m, 6H,
3
CH arom), 7.09–7.02 (m, 2H, CH arom), 6.83 (d, 2H,
3J = 8.7 Hz, CH arom), 6.76 (d, 1H, 3J = 7.7 Hz, CH
arom), 4.93 (s, 1H, HC-40), 3.80–3.59 (m, 2H,
2J = 23.0 Hz, H2C-3) ppm; 13C NMR (75 MHz, DMSO-
d6): d = 210.5, 168.8, 151.6, 148.8, 138.0, 137.0, 135.1,
129.41, 129.37, 129.1, 128.5, 128.0, 127.7, 126.8, 125.7,
2,3,40,50-Tetrahydro-50-(hydroxyimino)-20-[(4-methyl-
phenyl)imino]-40-phenylspiro[1H-indene-1,30(20H)-
thiophene]-2-one (4c, C25H20N2O2S)
ꢀ
124.7, 121.1, 73.0, 54.5, 42.0 ppm; IR (KBr): m = 3,205,
Pale yellow crystals (941 mg, 46%); m.p.: 199–201 ꢁC; 1H
NMR (300 MHz, DMSO-d6): d = 11.76 (s, 1H, NOH),
7.34–7.12 (m, 8H, CH arom), 7.09–7.02 (m, 2H, CH arom),
6.82 (d, 1H, 3J = 7.6 Hz, CH arom), 6.70 (d, 2H,
3J = 8.3 Hz, CH arom), 4.90 (s, 1H, HC-40), 3.75 (d, 1H,
3,067, 3,037, 2,921–2,830, 1,756, 1,647, 1,616, 1,484,
1,457, 1,422, 1,390, 1,209, 1,146, 1,123, 965 cm-1; MS
(70 eV): m/z (%) = 434.1 (40) [M ? 2]?, 432.1 (100)
[M]?, 387.1 (11), 267.1 (14), 263.1 (16), 246.1 (11), 234.1
(11), 233.1 (15), 220.1 (19), 219.1 (12), 218.1 (15), 217.1
(12), 215.1 (13), 205.1 (16), 204.1 (24), 191.1 (20).
2
2J = 23.0 Hz, HC-3), 3.59 (d, 1H, J = 23.0 Hz, HC-3),
2.29 (s, 3H, CH3) ppm; 13C NMR (75 MHz, DMSO-d6):
d = 210.8, 167.0, 152.0, 147.5, 138.2, 137.0, 135.0, 134.5,
129.8, 129.2, 128.4, 127.9, 127.6, 126.8, 125.6, 124.7,
20-[(4-Chlorophenyl)imino]-2,3,40,50-tetrahydro-50-
(hydroxyimino)-40-(4-methylphenyl)spiro[1H-indene-
1,30(20H)-thiophene]-2-one (4f, C25H19ClN2O2S)
ꢀ
119.2, 72.9, 54.4, 42.1, 20.4 ppm; IR (KBr): m = 3,284,
Pale yellow crystals (527 mg, 23%); m.p.: 191–193 ꢁC; 1H
NMR (300 MHz, DMSO-d6): d = 11.81 (s, 1H, NOH),
7.43 (d, 2H, J = 8.7 Hz, CH arom), 7.33–7.24 (m, 2H,
3,065–3,002, 2,951, 2,951, 1,757, 1,554, 1,514, 1,416,
1,380, 1,308, 1,286, 1,185, 1,133, 1,061 cm-1; MS
(70 eV): m/z (%) = 412.1 (100) [M]?, 281.1 (10), 263.1
(14), 247.1 (35), 246.1 (16), 234.1 (12), 233.1 (14), 220.1
(17), 218.1 (27), 205.1 (15), 204.1 (16), 191.1 (18), 174.0
(11), 146.1 (16), 107.1 (48), 106.1 (28), 102.0 (18), 91.0
(19), 77.0 (13).
3
3
4
CH arom), 7.17 (dd, J & 7.4, J = 1.9 Hz, CH arom),
6.99 (d, 2H, 3J = 8.2 Hz, CH arom), 6.92 (d, 2H,
3J = 8.2 Hz, CH arom), 6.87–6.78 (m, 3H, CH arom),
4.88 (s, 1H, HC-40), 3.79–3.55 (m, 2H, 2J = 23.1 Hz, H2C-
3), 2.20 (s, 3H, CH3) ppm; 13C NMR (75 MHz, DMSO-
d6): d = 210.6, 168.9, 151.6, 148.7, 138.1, 137.0, 136.8,
131.8, 129.40, 129.36, 129.0, 128.5, 126.9, 125.6, 124.8,
40-(4-Chlorophenyl)-2,3,40,50-tetrahydro-50-(hydroxyimi-
no)-20-[(4-methylphenyl)imino]spiro[1H-indene-1,30(20H)-
thiophene]-2-one (4d, C25H19ClN2O2S)
ꢀ
121.1, 73.1, 54.3, 42.1, 20.5 ppm; IR (KBr): m = 3,267,
Pale yellow crystals (1.256 g, 56%); m.p.: 184–186 ꢁC; 1H
NMR (300 MHz, DMSO-d6): d = 11.84 (s, 1H, NOH),
7.34–7.16 (m, 7H, CH arom), 7.07 (d, 2H, J = 8.5 Hz,
3,095–3,021, 2,961, 2,920, 1,754, 1,555, 1,513, 1,417,
1,379, 1,283, 1,186, 1,131, 1,091, 1,065, 1,015 cm-1; MS
(70 eV): m/z (%) = 446.1 (3) [M]?, 420.1 (35), 419.1 (35),
418.1 (84), 417.1 (34), 301.0 (17), 270.1 (38), 269.1 (27),
268.1 (100), 267.1 (30), 265.1 (56), 248.1 (28), 236.1 (23),
205.1 (26), 204.1 (37), 174.0 (35), 169.0 (22), 146.0 (42),
129.0 (26), 127.0 (65), 118.1 (41), 117.1 (22), 115.1 (36),
105.1 (36), 102.1 (32), 91.0 (24).
3
3
CH arom), 6.90 (d, 1H, J = 7.5 Hz, CH arom), 6.70 (d,
3
2H, J = 8.2 Hz, CH arom), 4.97 (s, 1H, HC-40), 3.76 (d,
1H, 2J = 23.1 Hz, HC-3), 3.61 (d, 1H, 2J = 23.1 Hz, HC-
3), 2.28 (s, 3H, CH3) ppm; 13C NMR (75 MHz, DMSO-
d6): d = 210.8, 167.1, 151.7, 150.3, 139.6, 137.3, 136.8,
123

70
K. Bogdanowicz-Szwed et al.
General procedure for synthesis of spiro[naphthalene-
1,30-thiophenes] 5a–5f
3,4,40,50-Tetrahydro-50-(hydroxyimino)-20-[(4-methyl-
phenyl)imino]-40-phenylspiro[naphthalene-1(2H),-
30(20H)-thiophene]-2-one (5c, C26H22N2O2S)
1
To a solution of the appropriate thioanilide 2a–2c
(5 mmol) and (E)-b-nitrostyrene 3a–3c (5 mmol) in
50 cm3 dry EtOH, two drops of piperidine were added. The
mixture was gently heated under reflux for 3 h then the
solvent was removed by evaporation. The residue was
chromatographed on silica gel using CHCl3 or CHCl3–
acetone 100:1 as eluent, and crystallized from MeOH.
Colorless crystals (1.003 g, 47%); m.p.: 238-240 ꢁC; H
NMR (500 MHz, DMSO-d6): d = 11.55 (s, 1H, NOH),
7.66 (d, 1H, 3J = 7.9 Hz, CH arom), 7.42 (t, 1H,
3J = 7.4 Hz, CH arom), 7.31–7.16 (m, 6H, CH arom),
7.12 (d, 1H, 3J = 7.4 Hz, CH arom), 6.83 (d, 2H,
3J = 7.3 Hz, CH arom), 6.73 (d, 2H, 3J = 8.2 Hz, CH
arom), 4.86 (s, 1H, HC-40), 2.69 (dt, 1H, 2J = 15.7,
3J & 5.5 Hz, CH2), 2.54 (ddd, 1H, J = 15.0, J = 11.2,
2
3
3,4,40,50-Tetrahydro-50-(hydroxyimino)-40-(4-methyl-
phenyl)-20-(phenylimino)spiro[naphthalene-1(2H),-
30(20H)-thiophene]-2-one (5a, C26H22N2O2S)
2
5.8 Hz, CH2), 2.29 (s, 3H, CH3), 2.01 (dt, 1H, J = 15.0,
3J & 5 Hz, CH2), 1.82 (ddd, 1H, 2J = 15.7, J = 11.2,
3
4.6 Hz, CH2) ppm; 13C NMR (125 MHz, DMSO-d6):
d = 206.6 (C=O), 169.5, 152.1, 148.0, 137.7, 137.4, 134.2,
133.0, 130.2, 129.7, 129.6, 127.7, 127.6, 127.4, 127.2,
127.0, 118.8, 71.0, 61.1, 38.8, 25.9, 20.4 ppm; IR (KBr):
Pale yellow crystals (979 mg, 46%); m.p.: 242–243 ꢁC; 1H
NMR (500 MHz, DMSO-d6): d = 11.53 (s, 1H, NOH),
7.67 (d, 1H, J = 7.8 Hz, CH arom), 7.44–7.37 (m, 3H,
3
3
CH arom), 7.29 (t, 1H, J = 7.3 Hz, CH arom), 7.19–7.12
3
ꢀ
m = 3,205 (OH), 3,064, 3,027, 2,960–2,843 (C–H), 1,716
(m, 2H, CH arom), 7.00 (d, 2H, J = 8.0 Hz, CH arom),
(C=O), 1,598, 1,504, 1,449, 1,391, 1,229, 1,209, 1,124,
1,069, 957 cm-1; MS (70 eV): m/z (%) = 426 (100) [M]?,
277 (62), 261 (44), 260 (39), 248 (15), 232 (36), 218 (13),
217 (13), 116 (30), 115 (35), 91 (32).
6.82 (d, 2H, 3J = 7.3 Hz, CH arom), 6.73 (d, 2H,
3J = 8.0 Hz, CH arom), 4.84 (s, 1H, HC-40), 2.71 (dt,
1H, 2J = 15.7, 3J & 5.5 Hz, CH2), 2.54 (ddd, 1H,
2J = 15.0, 3J = 11.0, 5.8 Hz, CH2), 2.23 (s, 3H, CH3),
2
3
2.02 (dt, 1H, J = 15.0, J & 5 Hz, CH2), 1.88 (ddd, 1H,
2J = 15.7, 3J = 11.0, 4.6 Hz, CH2) ppm; 13C NMR
(125 MHz, DMSO-d6): d = 206.6 (C=O), 170.1, 152.1,
150.5, 137.7, 137.4, 137.0, 130.0, 129.9, 129.6, 129.3,
128.2, 127.4, 127.2, 127.0, 124.9, 118.8, 71.0, 60.9, 38.8,
40-(4-Chlorophenyl)-3,4,40,50-tetrahydro-50-
(hydroxyimino)-20-[(4-methylphenyl)imino]spiro-
[naphthalene-1(2H),30(20H)-thiophene]-2-one
(5d, C26H21ClN2O2S)
Crystallized from CHCl3. Colorless crystals of 5dꢀCHCl3
1
ꢀ
25.9, 20.5 ppm; IR (KBr): m = 3,183 (OH), 3,064, 3,023,
(949 mg, 33%); m.p.: 222–224 ꢁC; H NMR (300 MHz,
2,960–2,856 (C–H), 1,712 (C=O), 1,610, 1,591, 1,512,
1,488, 1,447, 1,380, 1,210, 1,121, 959 cm-1; MS (70 eV):
m/z (%) = 426 (100) [M]?, 276.7 (56), 260.7 (42), 259.8
(37), 231.9 (34), 115.2 (36), 91 (32).
DMSO-d6): d = 11.59 (s, 1H, NOH), 8.31 (s, CHCl3) 7.66
3
3
(d, 1H, J = 7.8 Hz, CH arom), 7.42 (dt, 1H, J = 7.3,
4J = 1.3 Hz, CH arom), 7.33–7.25 (m, 3H, CH arom),
3
7.22–7.13 (m, 3H, CH arom), 6.85 (d, 2H, J = 8.6 Hz,
3
CH arom), 6.73 (d, 2H, J = 8.2 Hz, CH arom), 4.93 (s,
40-(4-Chlorophenyl)-3,4,40,50-tetrahydro-50-(hydroxyimi-
no)-20-(phenylimino)spiro[naphthalene-1(2H),30(20H)-thio-
phene]-2-one (5b, C25H19ClN2O2S)
2
3
1H, HC-40), 2.76 (ddd, 1H, J = 15.7, J & 5.7, 5.0 Hz,
CH2), 2.61 (ddd, 1H, J = 14.9, J = 11.4, 5.7 Hz, CH2),
2
3
2
3
2.29 (s, 3H, CH3), 2.10 (dt, 1H, J = 14.9, J & 5 Hz,
Pale yellow crystals (1.071 g, 48%); m.p.: 241–243 ꢁC; 1H
NMR (500 MHz, DMSO-d6): d = 11.62 (s, 1H, NOH), 7.69
(d, 1H, J = 8.0 Hz, CH arom), 7.45–7.37 (m, 3H, CH
2
3
CH2), 1.91 (ddd, 1H, J = 15.7, J = 11.4, 4.6 Hz, CH2)
ppm; 13C NMR (75 MHz, DMSO-d6): d = 206.3, 168.9,
151.8, 147.9, 137.7, 137.1, 134.2, 132.5, 132.1, 132.0,
129.7, 127.7, 127.5, 127.3, 127.1, 118.8, 79.1 (CHCl3),
3
arom), 7.33–7.27 (m, 3H, CH arom), 7.17 (dd, 2H, 3J & 7,
7 Hz, CH arom), 6.87–6.81 (m, 4H, CH arom), 4.95 (s, 1H,
2
ꢀ
71.0, 59.9, 38.7, 26.0, 20.4 ppm; IR (KBr): m = 3,192,
3,062, 3,021, 2,917, 2,854, 1,713, 1,605, 1,493, 1,414,
3
HC-40), 2.77 (dt, 1H, J = 15.8, J & 5.5 Hz, CH2), 2.62
2
3
(ddd, 1H, J = 14.9, J = 11.3, 5 Hz, CH2), 2.11 (dt, 1H,
2J = 14.9, 3J & 5 Hz, CH2), 1.92 (ddd, 1H, 2J = 15.8,
3J = 11.3, 4.4 Hz, CH2) ppm; 13C NMR (125 MHz, DMSO-
d6): d = 206.3, 169.4, 151.7, 150.4, 137.7, 137.0, 132.5,
132.1, 132.0, 129.7, 129.3, 127.7, 127.5, 127.3, 127.1, 125.0,
1,398, 1,228, 1,216, 1,129, 1,091, 1,017, 997, 960 cm-1
;
ESI–MS: m/z (%) = 462.9 (39), 461.2 (100) [M ? H]?,
376.5 (20).
20-[(4-Chlorophenyl)imino]-3,4,40,50-tetrahydro-50-
(hydroxyimino)-40-phenylspiro[naphthalene-1(2H),-
30(20H)-thiophene]-2-one (5e, C25H19ClN2O2S)
ꢀ
118.8, 71.0, 59.9, 38.7, 26.0 ppm; IR (KBr): m = 3,201
(OH), 3,026, 2,959–2,854 (C–H), 1,711 (C=O), 1,609, 1,592,
1,490, 1,383, 1,127, 1,088, 960 cm-1; MS (70 eV): m/z
(%) = 448 (38) [M ? 2]?, 446 (100) [M]?, 313 (17), 311
(56), 282 (13), 266 (15), 247 (42), 246 (28), 218 (12), 116.1
(12), 115.1 (17).
Pale yellow crystals (1.092 g, 49%); m.p.: 240–242 ꢁC; 1H
NMR (500 MHz, DMSO-d6): d = 11.62 (s, 1H, NOH),
7.69 (d, 1H, J = 8.0 Hz, CH arom), 7.47–7.39 (m, 3H,
3
3
4
CH arom), 7.30 (ddd, 1H, J = 7.5, 7.5, J = 1.1 Hz, CH
123

A new rearrangement of spiro[indane-1,30-thiophene] and spiro[naphthalene-1,30-thiophene]
3
71
arom), 7.25 (t, 1H, J = 7.4 Hz, CH arom), 7.19 (dd, 2H,
3J & 7.4, 7.4 Hz, CH arom), 7.12 (d, 1H, 3J = 7.5 Hz, CH
arom), 6.88–6.81 (m, 4H, CH arom), 4.90 (s, 1H, HC-40),
2.70 (dt, 1H, 2J = 15.6, 3J & 5.5 Hz, CH2), 2.55 (ddd, 1H,
2J = 15.2, 3J = 11.1, 5.5 Hz, CH2), 2.00 (dt, 1H,
2J = 15.2, 3J & 5 Hz, CH2), 1.83 (ddd, 1H, 2J = 15.6,
3J = 11.1, 4.6 Hz, CH2) ppm; 13C NMR (125 MHz,
DMSO-d6): d = 206.4 (C=O), 171.2, 151.6, 149.3, 137.7,
137.0, 132.9, 130.1, 129.6, 129.3, 129.1, 127.7, 127.6,
127.4, 127.3, 127.0, 120.7, 71.1, 61.1, 38.8, 25.9 ppm; IR
chromatography on silica gel using CHCl3 as eluent. The
products 6d, 6f, 7a, 7d, and 7f crystallized from MeOH
solution in a fridge.
2-[2,5-Dihydro-4-(4-methylphenyl)-5-oxo-1-phenyl-2-
thioxo-1H-pyrrol-3-yl]benzeneacetic acid methyl ester
(6a, C26H21NO3S)
Brown thick oil (55 mg, 26%); 1H NMR (300 MHz,
CDCl3): d = 7.56–7.33 (m, 10H, CH arom), 7.28–7.24 (m,
1H, CH arom), 7.09 (d, 2H, 3J = 8.1 Hz, CH arom), 3.54–
3.37 (2 9 d, AB system, 2H, 2J = 16.1 Hz, CH2, ? s, 3H,
OCH3), 2.30 (s, 3H, CH3) ppm; 13C NMR (75 MHz,
CDCl3): d = 199.8, 172.2, 171.0, 140.6, 140.0, 133.9,
133.0, 131.6, 131.55, 131.0, 130.9, 130.0, 129.55, 129.4,
129.1, 128.7, 128.4, 127.3, 125.8, 51.9, 39.6, 21.5 ppm; IR
ꢀ
(KBr): m = 3,233 (OH), 3,065, 3,031, 2,963–2,844 (C–H),
1,718 (C=O), 1,607, 1,484, 1,451, 1,398, 1,230, 1,211,
1,125, 1,008, 959 cm-1; MS (70 eV): m/z (%) = 448 (38)
[M ? 2]?, 446 (100) [M]?, 282 (13), 281 (33), 280 (15),
277 (66), 260 (13), 248 (15), 246 (12), 232 (28), 218 (17),
217 (17), 116 (23), 115 (29).
ꢀ
(KBr): m = 3,439, 3,030, 2,948, 2,923, 2,854, 1,732, 1,710,
1,597, 1,499, 1,434, 1,380, 1,294, 1,222, 1,148,
1,016 cm-1; ESI–MS: m/z (%) = 450.1 (42) [M ? Na]?,
428.5 (70) [M ? H]?, 412.5 (71), 396.6 (27).
20-[(4-Chlorophenyl)imino]-3,4,40,50-tetrahydro-50-
(hydroxyimino)-40-(4-methylphenyl)spiro[naphthalene-
1(2H),30(20H)-thiophene]-2-one (5f, C26H21ClN2O2S)
1
Colorless crystals (1.377 g, 60%); m.p.: 216–218 ꢁC; H
2-[4-(4-Chlorophenyl)-2,5-dihydro-5-oxo-1-phenyl-2-
thioxo-1H-pyrrol-3-yl]benzeneacetic acid methyl ester
(6b, C25H18ClNO3S)
NMR (300 MHz, DMSO-d6): d = 11.60 (s, 1H, NOH),
7.67 (d, 1H, J = 7.9 Hz, CH arom), 7.48–7.38 (m, 3H,
3
CH arom), 7.29 (dd, 1H, 3J & 7.4, 7.4 Hz, CH arom), 7.13
(d, 1H, J = 7.4 Hz, CH arom), 6.99 (d, 2H, J = 8.0 Hz,
1
Dark green, thick oil (51 mg, 23%); H NMR (300 MHz,
3
3
CDCl3): d = 7.57–7.43 (m, 6H, CH arom), 7.42–7.35 (m,
4H, CH arom), 7.30–7.21 (m, 3H, CH arom), 3.51–3.37
(2 9 d, AB system, 2H, 2J = 15.6 Hz, CH2, ? s, 3H,
OCH3) ppm; 13C NMR (75 MHz, CDCl3): d = 199.3,
171.9, 170.9, 140.9, 136.5, 133.8, 133.0, 131.3, 131.2,
131.0, 130.7, 130.5, 129.9, 129.2, 129.0, 128.9, 128.4,
127.5, 127.1, 52.0 (OCH3), 39.6 (CH2) ppm; IR (KBr):
3
CH arom), 6.86 (d, 2H, J = 8.6 Hz, CH arom), 6.72 (d,
3
2H, J = 8.0 Hz, CH arom), 4.85 (s, 1H, HC-40), 2.69
2
3
(ddd, 1H, J = 15.5, J & 5.7, 5.3 Hz, CH2), 2.55 (ddd,
1H, 2J = 14.9, 3J = 10.8, 5.7 Hz, CH2), 2.23 (s, 3H, CH3),
2
3
2.01 (dt, 1H, J = 14.9, J & 5 Hz, CH2), 1.88 (ddd, 1H,
2J = 15.5, 3J = 10.8, 4.7 Hz, CH2) ppm; 13C NMR
(75 MHz, DMSO-d6): d = 207.1, 171.9, 152.4, 149.9,
138.3, 137.8, 137.6, 130.6, 130.4, 130.2, 129.9, 129.7,
128.9, 128.1, 127.9, 127.7, 121.4, 71.7, 61.5, 26.6,
ꢀ
m = 3,441, 3,063, 2,948, 2,852, 1,733, 1,592, 1,496, 1,379,
1,293, 1,223, 1,150, 1,092, 1,013 cm-1; MS (70 eV): m/z
(%) = 449.1 (40) [M ? 2]?, 447.1 (100) [M]?, 418.1 (19),
416.1 (14), 414.1 (21), 390.1 (24), 389.1 (23), 388.1 (65),
376.1 (22), 374.0 (56), 346.1 (15), 221.0 (17), 189.2 (25).
ꢀ
21.1 ppm; IR (KBr): m = 3,200, 3,054, 3,027, 2,912,
2,848, 1,719, 1,608, 1,513, 1,483, 1,444, 1,229, 1,161,
1,136, 1,091, 999, 965 cm-1; ESI–MS: m/z (%) = 483.1
(11) [M ? Na]?, 463.1 (39), 461.4 (100) [M ? H]?.
2-[2,5-Dihydro-1-(4-methylphenyl)-5-oxo-4-phenyl-2-
thioxo-1H-pyrrol-3-yl]benzeneacetic acid methyl ester
(6c, C26H21NO3S)
General procedure for synthesis of 6a–6f and 7a–7f
Brown thick oil (23 mg, 11%); 1H NMR (300 MHz,
CDCl3): d = 7.56 (dd, 2H, 3J = 8.3, 4J = 1.7 Hz, CH
arom), 7.48–7.25 (m, 11H, CH arom), 3.54–3.36 (2 9 d,
To a solution of the appropriate iminothiophene 4a–4f or
5a–5f (0.5 mmol) in MeOH (for 4a–4f: 80 cm3; for 5a–
5f: 120–160 cm3) at reflux temperature 1 cm3 conc. HCl
was added in one portion. For 5a–5f, the mixture was
gently heated under reflux for 0.5 h, then 1 cm3 conc.
HCl was added again. All the mixtures were stirred at
reflux temperature for 3 h then concentrated to a volume
of ca. 40 cm3. Then 40 cm3 water was added, the mix-
ture was left overnight, then most of the solution was
decanted. The oily residue was dissolved in CHCl3,
washed with plenty of water, and the organic layer was
dried with MgSO4, concentrated, and purified by column
2
AB system, 2H, J & 16 Hz, CH2, ? s, 3H, OCH3), 2.42
(s, 3H, CH3) ppm; 13C NMR (75 MHz, CDCl3):
d = 199.8, 172.1, 170.9, 140.7, 138.9, 133.0, 131.53,
131.37, 131.25, 131.0, 130.9, 130.0, 129.9, 129.6, 128.7,
128.6, 128.1, 127.3, 51.9, 39.6, 21.3 ppm; IR (KBr):
ꢀ
m = 3,453, 3,059, 2,948, 2,922, 2,853, 1,731, 1,710, 1,514,
1,444, 1,434, 1,382, 1,293, 1,148, 1,019 cm-1; MS
(70 eV): m/z (%) = 427.1 (100) [M]?, 398.1 (19), 394.1
(19), 369.1 (18), 368.1 (62), 367.1 (25), 355.1 (16), 354.1
(57), 326.1 (15), 221.0 (14), 191.1 (12), 189.1 (21).
123

72
K. Bogdanowicz-Szwed et al.
2-[4-(4-Chlorophenyl)-2,5-dihydro-1-(4-methylphenyl)-5-
oxo-2-thioxo-1H-pyrrol-3-yl]benzeneacetic
2-[2,5-Dihydro-4-(4-methylphenyl)-5-oxo-1-phenyl-2-
thioxo-1H-pyrrol-3-yl]benzenepropanoic acid methyl
ester (7a, C27H23NO3S)
acid methyl ester (6d, C26H20ClNO3S)
Dark green crystals (46 mg, 20%); m.p.: 135 ꢁC; 1H NMR
(300 MHz, CDCl3): d = 7.53 (d, 2H, 3J = 8.9 Hz, CH
arom), 7.49–7.20 (m, 10H, CH arom), 3.50–3.37 (2 9 d,
AB system, 2H, 2J = 15.5 Hz, CH2, ? s, 3H, OCH3), 2.42
(s, 3H, CH3) ppm; 13C NMR (75 MHz, CDCl3):
d = 199.4, 172.0, 170.9, 140.8, 139.0, 136.4, 133.0,
131.32, 131.17, 131.10, 130.7, 130.5, 129.9, 129.8, 128.9,
128.1, 127.4, 127.2, 51.9, 39.6, 21.3 ppm; IR (KBr):
Brown crystals (91 mg, 41%); m.p.: 136–137 ꢁC; 1H NMR
3
(500 MHz, CDCl3): d = 7.52 (dd, 2H, J = 7.6, 7.6 Hz,
CH arom), 7.48–7.39 (m, 6H, CH arom), 7.34–7.28 (m, 2H,
3
CH arom), 7.22 (d, 1H, J = 7.5 Hz, CH arom), 7.09 (d,
3
2H, J = 8.5 Hz, CH arom), 3.60 (s, 3H, OCH3), 2.80–
2.66 (2 9 ddd, 2H, 2J = 14.6, 3J = 9.7, 9.5, 6.3 Hz, CH2),
2
3
2.42 (ddd, 1H, J = 16.0, J = 9.5, 6.3 Hz, CH2), 2.36–
2.27 (m, 4H, 3J = 9.7, 6.5 Hz, H–CH ? s, CH3) ppm; 13
C
ꢀ
m = 3,433, 3,067, 2,950, 2,921, 2,853, 1,725, 1,587, 1,513,
NMR (125 MHz, CDCl3): d = 200.3 (C=S), 173.0, 172.2,
140.6, 140.5, 139.0, 134.0, 131.3, 131.1, 130.8, 129.8,
129.5, 129.4, 129.1, 129.0, 128.7, 128.4, 126.4, 126.0, 51.6
(OCH3), 34.4 (C-3), 28.5 (C-2), 21.5 (CH3) ppm; IR
1,481, 1,382, 1,308, 1,291, 1,263, 1,223, 1,148, 1,090,
1,013 cm-1; ESI–MS: m/z (%) = 484.3 (81) [M ? Na]?,
464.3 (40), 462.4 (100) [M ? H]?.
(nujol): m = 1,727 (C=O), 1,591, 1,278, 1,143 cm-1; MS
ꢀ
(70 eV): m/z (%) = 441.0 (100) [M]?, 412.0 (13), 408.1
(52), 368 (32), 367.0 (30), 354.0 (51), 348.1 (41), 326.0
(18), 320.1 (18), 203.0 (15), 202.0 (20).
2-[1-(4-Chlorophenyl)-2,5-dihydro-5-oxo-4-phenyl-2-
thioxo-1H-pyrrol-3-yl]benzeneacetic acid methyl ester
(6e, C25H18ClNO3S)
1
Dark green solid (61 mg, 27%); m.p.: 77–79 ꢁC; H NMR
2-[4-(4-Chlorophenyl)-2,5-dihydro-5-oxo-1-phenyl-2-
thioxo-1H-pyrrol-3-yl]benzenepropanoic acid methyl
ester (7b, C26H20ClNO3S)
(300 MHz, CDCl3): d = 7.57–7.23 (m, 13H, CH arom),
3.47–3.35 (2 9 d, AB system, 2H, 2J = 15.5 Hz,
CH2, ? s, 3H, OCH3) ppm; 13C NMR (75 MHz, CDCl3):
d = 199.4, 171.9, 170.9, 141.0, 134.8, 133.0, 132.3, 131.7,
131.2, 130.9, 130.3, 130.1, 129.81, 129.77, 129.5, 128.7,
Brown thick oil (87 mg, 38%); 1H NMR (500 MHz,
CDCl3): d = 7.56–7.40 (m, 8H, CH arom), 7.35–7.29 (m,
3
2H, CH arom), 7.26 (d, 2H, J = 8.7 Hz, CH arom), 7.21
ꢀ
128.5, 127.4, 52.0, 39.6 ppm; IR (KBr): m = 3,448, 3,063–
(d, 1H, 3J = 7.4 Hz, CH arom), 3.60 (s, 3H, OCH3), 2.79–
2.64 (2 9 ddd, 2H, 2J = 14.7, 3J = 9.5, 9.1, 6.6 Hz, CH2),
2.46 (ddd, 1H, 2J = 16.3, 3J = 9.1, 6.4 Hz, CH2), 2.36
(ddd, 1H, 2J = 16.3, 3J = 9.5, 6.6 Hz, CH2) ppm; 13C
NMR (125 MHz, CDCl3): d = 199.8 (C=S), 172.9, 171.9,
141.5, 138.9, 136.4, 133.8, 131.1, 130.6, 130.1, 129.7,
129.1, 129.05, 128.9, 128.8, 128.4, 127.3, 126.5, 51.6
2,996, 2,948, 2,945, 1,736, 1,493, 1,434, 1,383, 1,305,
1,289, 1,270, 1,211, 1,159, 1,089, 1,018 cm-1; MS
(70 eV): m/z (%) = 449.1 (41) [M ? 2]?, 447.1 (100)
[M]?, 418.1 (23), 416.1 (14), 414.1 (22), 390.1 (31), 389.0
(31), 388.1 (86), 387.1 (29), 376.1 (24), 374.0 (63), 355.1
(12), 311.1 (13), 310.1 (18), 221.1 (20), 191.1 (15), 189.1
(28), 165.1 (13).
ꢀ
(OCH3), 34.4 (C-3), 28.4 (C-2) ppm; IR (nujol): m = 1,733
(C=O), 1,558, 1,492, 1,296, 1,166, 1,150, 1,090 cm-1; MS
(70 eV): m/z (%) = 463.1 (40) [M ? 2]?, 461 (100) [M]?,
430.1 (21), 428.1 (35), 388.0 (31), 376.0 (23), 374.0 (59),
372.1 (21), 368.1 (30), 340.1 (15), 202.1 (29), 93.0 (16),
77.0 (17).
2-[1-(4-Chlorophenyl)-2,5-dihydro-4-(4-methylphenyl)-5-
oxo-2-thioxo-1H-pyrrol-3-yl]benzeneacetic acid
methyl ester (6f, C26H20ClNO3S)
Brown crystals (68 mg, 29%); m.p.: 109–110 ꢁC; 1H NMR
(300 MHz, CDCl3): d = 7.52–7.33 (m, 9H, CH arom),
7.27–7.22 (m, 1H, CH arom), 7.10 (d, 2H, J = 8.1 Hz, CH
2-[2,5-Dihydro-1-(4-methylphenyl)-5-oxo-4-phenyl-2-
thioxo-1H-pyrrol-3-yl]benzenepropanoic acid methyl
ester (7c, C27H23NO3S)
2
arom), 3.48–3.35 (2 9 d, AB system, 2H, J = 15.5 Hz,
CH2, ? s, 3H, OCH3), 2.31 (s, 3H, CH3) ppm; 13C NMR
(75 MHz, CDCl3): d = 199.5, 171.9, 170.9, 140.8, 140.2,
134.6, 133.0, 132.3, 131.6, 131.4, 131.1, 130.9, 130.0,
129.74, 129.65, 129.45, 129.37, 127.3, 125.7, 51.9, 39.6,
Brown thick oil (70 mg, 32%); 1H NMR (500 MHz,
CDCl3): d = 7.53 (d, 2H, 3J = 8.6 Hz, CH arom), 7.42 (dt,
1H, J = 7.6, J = 1.4 Hz, CH arom), 7.35–7.25 (m, 9H,
3
4
3
ꢀ
21.5 ppm; IR (KBr): m = 3,445, 3,095-2,994, 2,948, 2,923,
CH arom), 7.22 (d, 1H, J = 7.5 Hz, CH arom), 3.59 (s,
2
3H, OCH3), 2.75 (ddd, 1H, J = 14.6, J = 9.8, 6.2 Hz,
3
1,734, 1,612, 1,493, 1,386, 1,305, 1,289, 1,270, 1,211,
1,160, 1,089, 1,016 cm-1; MS (70 eV): m/z (%) = 463.1
(43) [M ? 2]?, 461.1 (100) [M]?, 432.1 (17), 430.0 (16),
428.1 (28), 404.1 (23), 403.0 (25), 402.1 (59), 401.0 (27),
390.0 (18), 388.0 (44), 291.1 (21).
2
3
CH2), 2.67 (ddd, 1H, J = 14.6, J = 9.5, 6.4 Hz, CH2),
2.46–2.39 (m, 4H, 2J = 16.1, 3J = 9.5, 6.2 Hz, H–
CH ? s, CH3), 2.27 (ddd, 1H, 2J = 16.1, 3J = 9.8,
6.4 Hz, CH2) ppm; 13C NMR (125 MHz, CDCl3):
123

A new rearrangement of spiro[indane-1,30-thiophene] and spiro[naphthalene-1,30-thiophene]
73
d = 200.3 (C=S), 173.0, 172.1, 141.3, 138.9, 138.8, 131.2,
130.86, 130.82, 129.94, 129.86, 129.8, 129.5, 128.95,
128.88, 128.5, 128.1, 126.3, 51.6 (OCH3), 34.4 (C-3), 28.4
(C-2), 21.3 (CH3) ppm; IR (nujol): ꢀm = 1,733 (C=O),
1,558, 1,492, 1,296, 1,166,1,150, 1,090 cm-1; MS (70 eV):
m/z (%) = 441 (100) [M]?, 412.1 (14), 408.1 (42), 368.1
(33), 367.0 (23), 354.1 (55), 348.1 (39), 320.1 (16), 355.0
(32), 203.1 (17), 202.1 (16), 159.8 (34), 127.9 (49), 63.9
(49).
140.78, 139.0, 134.6, 132.4, 131.4, 131.0, 130.8, 129.9,
129.8, 129.6, 129.5, 129.3, 129.1, 126.4, 125.9, 51.7, 34.4,
ꢀ
28.4, 21.5 ppm; IR (KBr): m = 3,441, 3,090–2,985, 2,946,
2,917, 1,728, 1,608, 1,494, 1,385, 1,304, 1,290, 1,192,
1,150, 1,090, 1,017 cm-1; ESI–MS: m/z (%) = 514.2
(100), 498.2 (38) [M ? Na]?, 476.4 (76) [M ? H]?,
460.4 (63), 444.5 (63), 442.5 (83).
General procedure for synthesis of 2-hydroxy-
1H-indene-3-thiocarboxylic acid O-esters 16a, 16b
2-[4-(4-Chlorophenyl)-2,5-dihydro-1-(4-methylphenyl)-5-
oxo-2-thioxo-1H-pyrrol-3-yl]benzenepropanoic
acid methyl ester (7d, C27H22ClNO3S)
A solution of 1a (1 mmol) in 30 cm3 dry MeOH (for 16a)
or EtOH (for 16b) was heated under reflux until the starting
material was consumed (TLC; 9 h for 16a, 36 h for 16b).
The solvent was evaporated, and the residue was chro-
matographed on silica gel using CHCl3 as eluent then
crystallized from Et2O.
1
Green crystals (52 mg, 22%); m.p.: 80–86 ꢁC; H NMR
(300 MHz, CDCl3): d = 7.50 (d, 2H, 3J = 8.8 Hz, CH
arom), 7.42 (ddd, 1H, 3J & 7.5, 7.5, 4J = 1.5 Hz, CH
arom), 7.36–7.17 (m, 9H, CH arom), 3.60 (s, 3H, OCH3),
2.81–2.62 (m, 2H, CH2), 2.52–2.29 (m, 5H, CH2, CH3)
ppm; 13C NMR (75 MHz, CDCl3): d = 200.0, 173.0,
172.0, 141.4, 139.0, 138.9, 136.3, 131.13, 131.07, 130.65,
130.61, 130.1, 129.9, 129.8, 129.1, 128.9, 128.1, 127.4,
2-Hydroxy-1H-indene-3-thiocarboxylic acid
O-methyl ester (16a, C11H10O2S)
Reddish brown crystals (89 mg, 43%); m.p.: 108–109 ꢁC;
ꢀ
126.5, 51.7, 34.4, 28.4, 21.3 ppm; IR (KBr): m = 3,434,
1H NMR (300 MHz, CDCl3): d = 13.75 (s, 1H, OH), 7.78
(d, 1H, J = 7.8 Hz, CH arom), 7.32–7.23 (m, 2H, CH
3,062, 2,921, 2,852, 1,726, 1,588, 1,514, 1,387, 1,293,
1,149, 1,092, 1,011 cm-1; ESI–MS: m/z (%) = 492.2
(100), 476.4 (25) [M ? H]?, 460.4 (42), 444.5 (72),
442.5 (48).
3
3
4
arom), 7.13 (ddd, J & 7.5, 7.5, J = 1.2 Hz, CH arom),
4.26 (s, 3H, OCH3), 3.68 (s, 2H, H2C-3) ppm; 13C NMR
(75 MHz, CDCl3): d = 205.4, 185.4, 140.3, 131.4, 127.1,
124.4, 123.5, 121.8, 114.6, 56.5, 39.3 ppm; IR (KBr):
2-[1-(4-Chlorophenyl)-2,5-dihydro-5-oxo-4-phenyl-2-
thioxo-1H-pyrrol-3-yl]benzenepropanoic acid methyl ester
(7e, C26H20ClNO3S)
ꢀ
m = 3,043, 3,001, 2,941, 2,919, 1,544, 1,483, 1,460, 1,440,
1,385, 1,304, 249, 1,234, 1,214, 1,183, 1,038, 944 cm-1
;
Brown thick oil (177 mg, 77%); 1H NMR (300 MHz,
MS (70 eV): m/z (%) = 206.0 (37) [M]?, 174.0 (57), 146.0
(100), 145.0 (23), 134.0 (20), 102.0 (41).
CDCl3): d = 7.55–7.46 (m, 4H, CH arom), 7.44–7.25 (m,
3
4
8H, CH arom), 7.21 (dd, 1H, J = 7.6 Hz, J = 1.4 Hz,
CH arom), 3.59 (s, 3H, OCH3), 2.80–2.60 (2 9 ddd, 2H,
2J = 14.5, 3J = 9.7, 9.2, 6.5 Hz, CH2), 2.42 (ddd, 1H,
2J = 16.1, 3J = 9.2, 6.5 Hz, CH2), 2.26 (ddd, 1H,
2J = 16.1, 3J = 9.7, 6.5 Hz, CH2) ppm; 13C NMR
(75 MHz, CDCl3): d = 199.8, 173.0, 171.8, 141.6, 138.9,
134.7, 132.3, 131.4, 130.8, 130.6, 130.2, 129.9, 129.73,
129.68, 129.4, 129.0, 128.69, 128.63, 126.4, 51.7, 34.4,
2-Hydroxy-1H-indene-3-thiocarboxylic acid
O-ethyl ester (16b, C12H12O2S)
1
Yellow crystals (135 mg, 61%); m.p.: 90–92 ꢁC; H NMR
(300 MHz, CDCl3): d = 13.84 (s, 1H, OH), 7.80 (d, 1H,
3J = 7.8 Hz, CH arom), 7.33–7.23 (m, 2H, CH arom), 7.13
3
4
(ddd, J & 7.4, 7.4, J = 1.1 Hz, CH arom), 4.74 (q, 2H,
3J = 7.1 Hz, OCH2), 3.72 (s, 2H, H2C-3), 1.64 (t, 3H,
3J = 7.1 Hz, CH3) ppm; 13C NMR (75 MHz, CDCl3):
d = 204.6, 185.4, 140.4, 131.4, 127.1, 124.3, 123.5, 121.7,
ꢀ
28.4 ppm; IR (KBr): m = 3,441, 3,059–2,994, 2,948, 2,850,
1,733, 1,493, 1,441, 1,377, 1,304, 1,285, 1,149, 1,089,
1,017 cm-1; ESI–MS: m/z (%) = 478.2 (100), 462.3 (40)
[M ? H]?, 446.3 (51), 430.4 (63), 428.4 (63).
ꢀ
114.4, 66.1, 39.2, 13.9 ppm; IR (KBr): m = 3,041, 2,988,
2,975, 2,892, 2,672, 2,629, 1,533, 1,483, 1,458, 1,366,
1,324, 1,300, 1,253, 1,211, 1,172, 1,150, 1,036, 1,022,
918 cm-1; MS (70 eV): m/z (%) = 220.1 (71) [M]?, 174.0
(100), 146.0 (80), 102.0 (25).
2-[1-(4-Chlorophenyl)-2,5-dihydro-4-(4-methylphenyl)-5-
oxo-2-thioxo-1H-pyrrol-3-yl]benzenepropanoic
acid methyl ester (7f, C27H22ClNO3S)
1
X-ray structure analysis
Brown crystals (128 mg, 54%); m.p.: 88–91 ꢁC; H NMR
(300 MHz, CDCl3): d = 7.51–7.25 (m, 9H, CH arom),
3
4
Compound 6d, formula C26H20ClNO3S, crystallizes in the
triclinic system, space group P-1, with unit cell parameters
7.20 (dd, 1H, J = 7.7 Hz, J = 1.4 Hz, CH arom), 7.09
(d, 2H, 3J = 8.0 Hz, CH arom), 3.58 (s, 3H, OCH3), 2.80–
2.62 (m, 2H, CH2), 2.51–2.24 (m, 5H, CH2, CH3) ppm; 13
C
˚
a = 8.3419(2), b = 11.3337(2), c = 13.8126(4) A, a =
66.627(1), b = 74.298(1), c = 88.138(1) 8, V = 1,149.86
NMR (75 MHz, CDCl3): d = 200.0, 173.1, 172.0, 140.81,
123

74
K. Bogdanowicz-Szwed et al.
3
˚
2. Britsun VN, Lozinskii MO (2007) Chem Heterocycl Comp
43:1083
3. Britsun VN, Borisevich AN, Samoylenko LS, Chernega AN,
Lozynskii MO (2005) Russ Chem Bull 54:770
4. Bogdanowicz-Szwed K, Kozicka M (1987) Z Naturforsch B
42:1174
(3) A , Z = 2. A total of 4,478 independent reflections
(Rint = 0.0204) were collected from a sample (size
0.35 9 0.2 9 0.15 mm) using a Kappa CCD diffractometer
and Mo–Ka radiation. The structure was solved by direct
methods with SHELXS97 [26] and refined by the full-matrix
least-squares method on F2 using SHELXL97 [27] software.
Final discrepancy indices for I [ 2r(I) were: R1 = 0.0476,
wR2 = 0.1048, and R1 = 0.0656, wR2 = 0.1411 for all
data. The final difference Fourier map of electron density
was featureless with the largest peak and hole of 0.18 and
5. Bogdanowicz-Szwed K, Kozicka M, Lipowska M (1989) J Prakt
Chem 331:231
´
´
6. Jagodzinski TS, Sosnicki JG, Wesołowska A (2003) Tetrahedron
59:4183
7. Budzowski A, Pitak M, Stadnicka K (2007) Monatsh Chem
138:1257
8. Abdel-Zaher AE (2004) Indian J Chem Sect B 43:1314
´
9. Gros L, Westerlich S, Wesołowska A, Jagodzinski TS (2006)
Chem Heterocycl Comp 42:176
10. Nakano H, Ishibashi T, Sawada T (2003) Tetrahedron Lett
44:4175
11. Lehnhoff S, Ugi I (1995) Heterocycles 40:801
-0.23 eA-3, respectively. All calculations and molecular
˚
graphics were done using the WinGX package [28].
Compound 7a, formula C27H23NO3S, crystallizes in the
monoclinic system, space group P21/c, with unit cell
parameters a = 9.7300(1), b = 10.3974(2), c = 23.0241
3
(4) A, b = 95.731(1) 8, V = 2317.63(6) A , Z = 4. A total
of 4,046 independent reflections (Rint = 0.0246) were
´
´
12. Orzeszko A, Lasek W, Switaj T, Stoksik M, Kaminska B (2003)
Il Farmaco 58:371
˚
˚
13. Obniska J, Zejc A (2003) Acta Polon Pharm-Drug Res 60:383
14. Obniska J (2004) Acta Polon Pharm-Drug Res 61:467
15. Hammond MC, Harris BZ, Lim WA, Bartlett PA (2006) Chem
Biol 13:1247
16. Bogdanowicz-Szwed K, Grochowski J, Pałasz A, Rys B, Serda P,
Soja D (1996) Liebigs Ann 1457
17. Bogdanowicz-Szwed K, Czarny A (2003) J Chem Res (S) 51
18. Bogdanowicz-Szwed K, Gil R (2004) Monatsh Chem 135:1415
19. Bogdanowicz-Szwed K, Gil R, Serda P (2006) Monatsh Chem
137:219
20. Bogdanowicz-Szwed K, Grochowski J, Obara A, Rys B, Serda P
(2001) J Org Chem 66:7205
´
21. Hansen PE, Duus F, Bolvig S, Jagodzinski TS (1996) J Mol
Struct 378:45
22. Hennen WJ, Hinshaw BC, Riley TA, Wood SG, Robins RK
(1985) J Org Chem 50:1741
23. Elmore DT, Guthrie DJS, Kay G, Williams CH (1988) J Chem
Soc Perkin Trans 1:1051
24. Harrowven DC, Lucas MC, Howes PD (1999) Tetrahedron
55:1187
collected from
a sample (size 0.35 9 0.25 9 0.15
mm) using a Kappa CCD diffractometer and Mo–Ka radia-
tion. The structure was solved by direct methods using
SHELXS97 [26] and refined by the full-matrix least-squares
method on F2 using SHELXL97 [27] software. Final dis-
crepancy indices for I [ 2r(I) were: R1 = 0.0526,
wR2 = 0.1413, and R1 = 0.0616, wR2 = 0.1500 for all
data. The final difference Fourier map of electron density had
-3
˚
the largest peak and hole of 0.63 and -0.408 eA
,
respectively. All calculations and molecular graphics were
done using the WinGX package [28].
The structural data for compounds 6d and 7a have been
deposited with Cambridge Crystallographic Data Centre as
Supplementary Publications CCDC-720640 (6d) and
CCDC-720639 (7a). Copies of these data can be obtained
free of charge via www.ccdc.cam.ac.uk/conts/retrieving.
html or from the CCDC, 12 Union Road, Cambridge CB2
1EZ, UK; Fax: (internat.) ?44-1223-336033; E-mail:
deposit@ccdc.cam.ac.uk.
25. Darabi HR, Aghapoor K, Tabar-Heidar K (2004) Monatsh Chem
135:79
26. Sheldrick GM (1997) SHELXS97, Program for crystal structure
¨
solution. University of Gottingen, Germany
27. Sheldrick GM (1997) SHELXL97, Program for crystal structure
¨
refinement. University of Gottingen, Germany
28. Farrugia LJ (1997) J Appl Cryst 32:837
References
´
1. Jagodzinski TS (2003) Chem Rev 103:197
123