Synthesis of some novel bis-spiro[indole-pyrazolinyl-thiazolidine]-2, 4′-diones

Article abstract of DOI:10.1080/00397910600602560

The reaction of 1H-indol-2,3-diones with 1,6-dibromohexane has resulted in the formation of new 1H-indol-2,3-diones-1,1′-(1,6-hexanediyl)bis in quantitative yields. These compounds have been used for the synthesis of novel [3′-(2,3-dimethyl-5-oxo-1-phenyl

Full text of DOI:10.1080/00397910600602560

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Synthesis of Some Novel
bis‐Spiro[indole‐pyrazolinyl‐thiazolidine]‐2,4′‐dio
Manish Jain a , Pankaj Khanna a , Anjali Saxena a , Sunita Bhagat a , Carl E.
Olsen b & Subhash C. Jain a
a Department of Chemistry, University of Delhi, Delhi, India
b Chemistry Department, The Royal Veterinary and Agricultural University,
Copenhagen, Denmark
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To cite this article: Manish Jain, Pankaj Khanna, Anjali Saxena, Sunita Bhagat, Carl E. Olsen & Subhash
C. Jain (2006): Synthesis of Some Novel bis‐Spiro[indole‐pyrazolinyl‐thiazolidine]‐2,4′‐diones, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 36:13,
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Synthetic Communicationsw, 36: 1863–1872, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600602560
Synthesis of Some Novel bis-Spiro[indole-
pyrazolinyl-thiazolidine]-2,40-diones
Manish Jain, Pankaj Khanna, Anjali Saxena,
and Sunita Bhagat
Department of Chemistry, University of Delhi, Delhi, India
Carl E. Olsen
Chemistry Department, The Royal Veterinary and Agricultural
University, Copenhagen, Denmark
Subhash C. Jain
Department of Chemistry, University of Delhi, Delhi, India
Abstract: The reaction of 1H-indol-2,3-diones with 1,6-dibromohexane has resulted in
the formation of new 1H-indol-2,3-diones-1,10-(1,6-hexanediyl)bis in quantitative
yields. These compounds have been used for the synthesis of novel [30-(2,3-
dimethyl-5-oxo-1-phenyl-3-pyrazolin-4-yl)spiro[3H-indol-3,20-thiazolidine]-2,40-dione]-
1,10-(1,6-hexanediyl)bis via bis Schiff’s bases, [3-(2,3-dimethyl-5-oxo-1-phenyl-3-
pyrazolin-4-yl) imino-1H-indol-2-one]-1,10-(1,6-hexanediyl)bis.
Keywords: Antibacterial activity, bis indolyl compounds, bis Schiff’s bases, bis-
bases, bis-spiro[indole-pyrazolinyl-thiazolidine]-2,40-diones
The importance of heterocycles in biological systems has stimulated interest in
designing and constructing new heterocyclic systems using a molecular modifi-
cation approach. Among the various heterocyclic systems, indole holds a
prominent place because it is present as a core unit in a number of
compounds possessing a broad spectrum of biological activities.[1,2] Of these,
spiro indoles have attracted our attention because of their enhanced
Received in India December 17, 2005
Address correspondence to Subhash C. Jain, Department of Chemistry, University of
Delhi, Delhi 110 007, India. Fax: þ91-11-27667206; E-mail: jainsc48@hotmail.com
1863

1864
M. Jain et al.
activities.[3,4] In view of this, earlier we developed some new spiro hetero-
cycles[5–10] and their fluorinated analogues. Recently a literature survey has
revealed that N-alkylated isatins, because of their lypophilic character, have
been used for the synthesis of compounds that possess interesting pharma-
cological activities such as antimicrobial and antibacterial activities.[11]
Besides these, they have also been used as excitatory amino acid antagonists[12]
and ulcer inhibitors.[13] If two heterocyclic moieties are joined via a suitable
spacer of carbon chain, the resulting bis compound is expected to possess
enhanced bioactivity and can be further utilized as an intermediate for con-
structing new heterocyclic systems. A number of reports have appeared in
the literature on the bioactivity of bis heterocyclic compounds containing
.N-(CH2)n-N, linkage,[14,15] but no report, as yet, is available on bis indolyl
compounds with such linkages. Realizing the importance of these molecules,
we extended our work on spiro indoles in this direction and thought of synthesiz-
ing some novel bis spiro indoles containing a suitable spacer. The length of the
spacer was decided on the basis of molecular modeling.
In view of this and to understand the combined biological effects of both
spiro indoles along with a spacer of alkyl chain between them, we have now
developed a facile and elegant synthesis of novel bis-spiro indoles via hitherto
unknown bis Schiff’s bases, which in turn have been synthesized using
bis-indol-2,3-diones.
RESULTS AND DISCUSSION
We have synthesized fifteen novel bis indolyl compounds in all including sub-
stituted bis-indol-2,3-diones (2a–e), bis[imino-indoles] (4a–e), and bis[spiro
(indole-pyrazolinyl-thiazolidinones)] (5a–e) (Scheme 1).
The reaction of 1H-indol-2,3-dione and 1,6-dibromohexane (2:1) in the
presence of NaH/DMF at –108C has resulted in the formation of 2a. The
IR spectrum of 2a showed a characteristic broad absorption band for the
presence of a carbonyl group at 1700 cm21. Absence of absorption band in
the region 3300–3400 cm21 for .NH indicated that N-alkylation has taken
place at the indole moiety. Its 1H NMR displayed a triplet at d 3.72, integrating
for four protons, thereby showing that two indole moieties have been coupled
through nitrogen via an alkyl chain. The methylenes of the hexyl spacer
appeared as multiplets at d 1.44 and 1.73, which was further supported by
its 13C NMR spectrum, which showed methylenes carbons at d 26.4, 28.1,
and 40.3. The aromatic protons as expected for the indole moieties
appeared at d 6.87 (H-7), 7.11 (H-5), and 7.61 (H-6 and H-4). C-2 and C-3
carbonyl carbons appeared at d 175.9 and 183.8 respectively in 13C NMR.
Formation of bis product has finally been confirmed on the basis of its
EIMS, which showed the molecular ion peak at m/z 376 corresponding to
its molecular formula. On the basis of these observations, 2a has been ident-
ified as 1H-indol-2,3-diones-1,10-(1,6-hexanediyl)bis.

Novel bis-Spiro[indole-pyrazolinyl-thiazolidine]-2,40-diones
1865
Scheme 1.

1866
M. Jain et al.
The reaction of 2a with 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-
one (3) in 1:2 ratio in absolute ethanol yielded an orange-colored Schiff’s
base, 4a. It gave a molecular ion peak Mþ, at m/z 746 in FAB-MS, suggesting
the molecular formula C44H42O4N8, and indicated that the two pyrazoline
moieties have coupled with 2a with the loss of two water molecules. The
IR spectrum showed characteristic absorption band at 1646 (C55N) cm21
.
Its 1H NMR spectrum displayed two singlets at d 3.24 and 2.44, each integrat-
ing for six protons of the two N-CH3 and two 300-CH3 groups of the pyrazoline
moieties respectively. Further, multiplets at d 7.32 integrating for ten protons
are due to the presence of two phenyl groups of the pyrazoline moieties. The
peaks at d 6.81 (H-7), 7.05 (H-5), and 7.26 (H-4 and H-6) showed the presence
of aromatic protons of the indole moiety. The triplet at d 3.74 integrating for
four protons indicated the presence of two .N-CH2 linkages. The 13C NMR
spectrum of 4a displayed characteristic carbonyl signals at d 165.1 (lactam)
and 161.3 (pyrazoline), in addition to a signal at d 146.1 showing the
presence of (C55N) in the molecule. These spectral studies confirmed the
formation of the desired bis Schiff’s base, which was characterized as
[3-(2,3-dimethyl-5-oxo-1-phenyl-3-pyrazolin-4-yl) imino-1H-indol-2-one]-
1,10-(1,6-hexanediyl)bis (4a).
Compound 4a was then subjected to the cyclocondensation reaction with
mercaptoacetic acid under refluxing conditions using a Dean–Stark apparatus.
The new compound 5a gave a molecular ion peak at m/z 894, corresponding
to the molecular formula C48H46O6N8S2 as indicated by its FAB-MS. The
IR spectrum showed the presence of characteristic absorption peaks at 1720
(thiazolidinone carbonyl), 1700 (lactam carbonyl), and 1684 (pyrazolinyl
carbonyl) cm21, indicating that cycloaddition has occurred. This was
1
1
further confirmed by its H and 13C NMR data. H NMR spectrum of 5a
showed, as expected, the aromatic protons of indole nucleus as multiplets at
d 6.72 (H-7) and 7.13 (H-4, H-5, and H-6) integrating for eight protons.
Two doublets, which integrated for four protons of the two methylenes of
the thiazolidinone rings, appeared at d 3.79 and 4.32 (J ¼ 15.0 Hz each).
The four methyl groups appeared at d 2.99 (2 ꢀ N-CH3) and 2.21 (2 ꢀ 300-
CH3). The protons of the two phenyl groups of pyrazoline moieties
appeared as multiplets at d 7.30. Methylenes of the hexyl linker appeared at
d 3.63, 1.69 and 1.40. 13C NMR spectra also showed all expected character-
istic peaks at d 177.1 (thiazolidine carbonyl), 173.1 (lactam carbonyl),
161.0 (pyrazoline carbonyl), and 108.6–134.5 (aromatic carbons). Besides
these, methyl carbons at d 35.4 (-NCH3) and d 12.1 (300-CH3) of pyrazoline
moiety and methylene carbons of the carbon chain at d 40.7 (C-10), 30.0
(C-20) and d 27.3 (C-30) and of thiazolidine moiety at d 35.6 (S-CH2) were
also displayed in 13C NMR. The signals for N-CH3 and S-CH2 have been dis-
tinguished on the basis of the DEPT-135 experiment.
On the basis of these spectral studies, 5a was characterized as [30-(2,3-
dimethyl-5-oxo-1-phenyl-3-pyrazolin-4-yl)spiro[3H-indol-3,20-thiazolidine]-
2,40-dione]-1,10-(1,6-hexanediyl)bis. Using these steps and taking different

Novel bis-Spiro[indole-pyrazolinyl-thiazolidine]-2,40-diones
1867
substituted indol-2,3-diones, we have synthesized four other new bis-spiro
compounds, 5b–e.
Some of the synthetic samples have been evaluated for antibacterial
activity against E. coli cultures and showed promising results.
EXPERIMENTAL
Melting points were determined in a capillary tube in sulphuric acid bath and
are uncorrected. IR spectra were recorded on Shimadzu model IR-435 spectro-
1
photometer using KBr discs. H NMR spectra were recorded on Bruker AC
(300 MHz) in CDCl3. 13C NMR were recorded on Bruker AC (75.47 MHz)
in CDCl3. Mass spectra were recorded on Jeol-JMS-DX 303 mass spec-
trometer. Substituted indol-2,3-diones (1b–e) were prepared by literature pro-
cedures[8] starting from the corresponding aniline.
1H-Indol-2,3-dione-1,10-(1,6-hexanediyl)bis
A solution of 1H-indol-2,3-dione (0.01 mol) in DMF (5 ml) was added dropwise
to a stirred soultion of NaH (0.02 mol) in 10 ml of dry DMF during 20 min
at 2108C under an inert atmosphere. A deep purple-colored suspension was
formed. 1,6-Dibromohexane (0.005 mol) was then added dropwise to the
reaction mixture during 30 min at 2108C. The contents were allowed to stir
at room temperature for 20h and then quenched with ice water. A red-
colored solid 2a was purified by column chromatography using silica gel as
an adsorbent. Compounds 2b–e were also synthesized using this procedure.
The spectral data of compounds 2a–e are recorded in Table 1.
[3-(2,3-Dimethyl-5-oxo-1-phenyl-3-pyrazolin-4-yl)imino-1H-indol-
2-one]-1,10-(1,6-hexanediyl)bis
A mixture of 2a (0.01 mol) and 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-
5-one (0.02 mol) in absolute ethanol (30 ml) was refluxed at 808C for about
6 h. An orange-colored solid that separated was filtered, dried, and crystallized
from ethanol to give Schiff’s base 4a.
Compounds 4b–e were also synthesized in a similar manner. The spectral
data of compounds 4a–e are included in Table 2.
[30-(2,3-Dimethyl-5-oxo-1-phenyl-3-pyrazolin-4-yl)spiro[3H-indol-
3,20-thiazolidine]-2,40-dione]-1,10-(1,6-hexanediyl)bis
A mixture of 4a (0.01 mol) and mercaptoacetic acid (0.022 mol) was refluxed
in dry toluene for 8 h with simultaneous removal of water azeotropically,

Table 1. Spectral data of compound 2
Compound Yield (%)
Mp (8C)
EIMS, m/z
1H NMR (d, CDCl3)
13C NMR (d, CDCl3)
2a
80
205
376, 244, 202, 174, 160, 1.44 (m, 4H, 2 ꢀ H-30), 1.73 (m, 4H,
26.4 (C-30), 28.1 (C-20), 40.3 (C-10),
110.4, 124.0, 125.1, 138.0, 151.2,
158.0, 175.9 (C-2), 183.8 (C-3)
146, 132, 118, 90
2 ꢀ H-20), 3.72 (t, 4H, J ¼ 6.3 Hz,
2 ꢀ H-10), 6.87 (d, 2H, J ¼ 9.0 Hz,
2 ꢀ H-7), 7.11 (t, 2H, J ¼ 9.3 Hz,
2 ꢀ H-5), 7.61 [m, 4H, 2 ꢀ (H-4 &
H-6)]
2b
76
190
412, 327, 234, 206, 192, 1.36 (m, 4H, 2 ꢀ H-30), 1.69 (m, 4H,
28.2 (C-30), 30.3 (C-20), 41.5 (C-10),
111.2, 127.0, 133.0, 139.9, 150.2,
159.5, 174.8 (C-2), 181.4 (C-3)
178, 164, 150, 136,
118, 90
2 ꢀ H-20), 3.71 (t, 4H, J ¼ 7.1 Hz,
2 ꢀ H-10), 6.86 (d, 2H, J ¼ 9.1 Hz,
2 ꢀ H-7), 7.30 [m, 4H, 2 ꢀ (H-4 &
H-6)]
2c
75
73
185
220
412, 234, 206, 178, 164, 1.42 (m, 4H, 2 ꢀ H-30), 1.68 (m, 4H,
27.1 (C-30), 28.2 (C-20), 40.1 (C-10),
110.4, 126.2, 132.9, 139.1, 149.2,
158.0, 174.7 (C-2), 182.2 (C-3)
136, 118
2 ꢀ H-20), 3.68 (t, 4H, J ¼ 6.5 Hz,
2 ꢀ H-10), 6.77 [m, 4H, 2 ꢀ (H-4 &
H-7)], 7.39 (m, 2H, 2 ꢀ H-5)
2d
404, 278, 198, 174, 160, 1.42 (m, 4H, 2 ꢀ H-30), 1.68 (m, 4H,
20.9 (5-CH3), 26.7 (C-30), 27.4 (C-
20), 40.3 (C-10), 110.4, 126.1,
133.8, 139.0, 149.1, 158.0, 175.2
(C-2), 182.2 (C-3)
146, 132, 118, 104
2 ꢀ H-20), 2.33 (s, 6H, 2 ꢀ 5-CH3),
3.68 (t, 4H, J ¼ 6.1 Hz, 2 ꢀ H-10),
6.78 (d, 2H, J ¼ 9.0 Hz, 2 ꢀ H-7),
7.41 [m, 4H, 2 ꢀ (H-4 & H-6)]
1.32 (m, 4H, 2 ꢀ H-30), 1.66 (m, 4H,
2 ꢀ H-20), 3.78 (t, 4H, J ¼ 6.8 Hz,
2 ꢀ H-10), 6.89 [m, 6H, 2 ꢀ (H-5 &
H-7)], 7.23 (m, 2H, 2 ꢀ H-6)
2e
70
185
512, 242, 228, 214, 172
25.8 (C-30), 27.7 (C-20), 41.7 (C-10),
110.4, 115.4 (4-CF3), 125.3, 133.1,
140.0, 152.1, 159.8, 174.8 (C-2),
185.1 (C-3)

Table 2. Spectral data of compound 4
Compound Yield (%) Mp (8C) FAB-MS, m/z
1H NMR (d, CDCl3)
13C NMR (d, CDCl3)
4a
4b
4c
4d
4e
90
85
80
76
75
214
198
190
215
190
746
782
782
774
882
1.44 (m, 4H, 2 ꢀ H-30), 1.70 (m, 4H, 2 ꢀ H-20), 2.44
(s, 6H, 2 ꢀ 300-CH3), 3.24 (s, 6H, 2 ꢀ N-CH3), 3.74
(t, 4H, J ¼ 6.1 Hz, 2 ꢀ H-10), 6.81 (d, 2H, J ¼ 9.1 Hz,
2 ꢀ H-7), 7.05 (t, 2H, J ¼ 9.1 Hz, 2 ꢀ H-5), 7.26
[m, 4H, 2 ꢀ (H-4, & H-6)], 7.32 (m, 10H, 2 ꢀ N-C6H5)
12.8 (300-CH3), 27.0 (C-30), 27.7
(C-20), 36.3 (N-CH3), 40.2 (C-10),
108.9-138.7 (aromatic carbons),
146.1 (C-3), 161.3 (C-500), 165.1
(C-2)
1.36 (m, 4H, 2 ꢀ H-30), 1.68 (m, 4H, 2 ꢀ H-20), 2.47
(s, 6H, 2 ꢀ 300-CH3), 3.29 (s, 6H, 2 ꢀ N-CH3), 3.74
(t, 4H, J ¼ 7.3 Hz, 2 ꢀ H-10), 6.74 (d, 2H, J ¼ 9.0 Hz,
2 ꢀ H-7), 7.05 [m, 4H, 2 ꢀ (H-4 & H-6)], 7.43
(m, 10H, 2 ꢀ N-C6H5)
14.7 (300-CH3), 25.6 (C-30), 30.4
(C-20), 32.4 (N-CH3), 43.4 (C-10),
110.2-138.4 (aromatic carbons),
141.0 (C-3), 161.3 (C-500), 167.1
(C-2)
1.26 (m, 4H, 2 ꢀ H-30), 1.65 (m, 4H, 2 ꢀ H-20), 2.46
(s, 6H, 2 ꢀ 300-CH3), 3.28 (s, 6H, 2 ꢀ N-CH3), 3.75
(t, 4H, J ¼ 7.3 Hz, 2 ꢀ H-10), 6.74 [m, 4H, 2 ꢀ (H-4
& H-7)], 7.31 (m, 2H, 2 ꢀ H-5), 7.43 (m, 10H,
2 ꢀ N-C6H5)
13.3 (300-CH3), 28.5 (C-30), 29.2
(C-20), 32.1 (N-CH3), 44.0 (C-10),
110.0-134.3 (aromatic carbons),
142.0 (C-3), 162.2 (C-500), 166.3
(C-2)
1.42 (m, 4H, 2 ꢀ H-30), 1.67 (m, 4H, 2 ꢀ H-20), 2.14
(s, 6H, 2 ꢀ 300-CH3), 2.32 (s, 6H, 2 ꢀ 5-CH3), 3.24
(s, 6H, 2ꢀ N-CH3), 3.71 (t, 4H, J ¼ 6.8 Hz, 2 ꢀ H-10),
6.69 (m, 2H, 2 ꢀ H-7), 7.14 [m, 2H, 2 ꢀ (H-4 & H-6)],
7.35 (m, 10H, 2 ꢀ N-C6H5)
13.5 (300-CH3), 22.5 (5-CH3), 26.6
(C-30), 29.9 (C-20), 30.6 (N-CH3),
41.2 (C-10), 111.0-140.2 (aromatic
carbons), 141.1 (C-3), 161.4 (C-
500), 165.4 (C-2)
1.43 (m, 4H, 2 ꢀ H-30), 1.66 (m, 4H, 2 ꢀ H-20), 2.45
(s, 6H, 2 ꢀ 300-CH3), 3.25 (s, 6H, 2 ꢀ N-CH3), 3.74
(t, 4H, J ¼ 6.9 Hz, H-10), 6.78 [m, 6H, 2 ꢀ (H-5, H-6
& H-7)], 7.41 (m, 10H, 2 ꢀ N-C6H5)
13.3 (300-CH3), 28.5 (C-30), 29.2
(C-20), 32.8 (N-CH3), 41.8 (C-10),
110.0-142.2 (aromatic carbons),
143.0 (C-3), 160.9 (C-500), 167.2
(C-2)

Table 3. Spectral data of compound 5
Compound
Yield (%)
65
Mp (8C)
FAB-MS, m/z
1H NMR (d, CDCl3)
13C NMR (d, CDCl3)
5a
95
894
1.40 (m, 4H, 2 ꢀ H-30), 1.69 (m, 4H, 2 ꢀ H-20), 2.21 (s, 6H,
2 ꢀ 300-CH3), 2.99 (s, 6H, 2 ꢀ N-CH3), 3.63 (t, 4H,
12.1 (300-CH3), 27.3 (C-30), 30.0
(C-20), 35.4 (N-CH3), 35.6
(S-CH2), 40.7 (C-10), 108.6-
134.5 (aromatic carbons), 161.0
(C-500),173.1 (C-2), 177.1 (C-4000)
J ¼ 6.0 Hz, 2 ꢀ H-10), 3.79 & 4.32 (dd, 4H, J ¼ 15.0 Hz
each, 2 ꢀ S-CH2), 6.72 (d, 2H, J ¼ 9.0 Hz, 2 ꢀ H-7), 7.13
[m, 6H, 2 ꢀ (H-4, H-5 & H-6)], 7.30 (m, 10H, 2 ꢀ N-C6H5)
5b
5c
5d
63
65
55
80
85
930
930
922
1.30 (m, 4H, 2 ꢀ H-30), 1.65 (m, 4H, 2 ꢀ H-20), 2.35 (s, 6H,
2 ꢀ 300-CH3), 3.02 (s, 6H, 2 ꢀ N-CH3), 3.70 (t, 4H,
J ¼ 7.5 Hz, 2 ꢀ H-10), 3.78 & 4.27 (dd, 4H, J ¼ 15.0 Hz
each, 2 ꢀ S-CH2), 6.70 (s, 2H, 2 ꢀ H-7), 7.15 [m, 4H,
2 ꢀ (H-4 & H-6)], 7.26 (m, 10H, 2 ꢀ N-C6H5)
1.38 (m, 4H, 2 ꢀ H-30), 1.64 (m, 4H, 2 ꢀ H-20), 2.24 (s, 6H,
2 ꢀ 300-CH3), 3.02 (s, 6H, 2 ꢀ N-CH3), 3.64 (t, 4H,
J ¼ 7.1 Hz, 2 ꢀ H-10), 3.81 & 4.30 (dd, 4H, J ¼ 15.0 Hz
each, 2 ꢀ S-CH2), 6.67 [d, 4H, J ¼ 9.1 Hz, 2 ꢀ (H-4 &
H-7)], 7.34 (m, 2H, 2 ꢀ H-5), 7.48 (m, 10H, 2 ꢀ N-C6H5)
1.37 (m, 4H, 2 ꢀ H-30), 1.63 (m, 4H, 2 ꢀ H-20), 2.24 (s, 6H,
2 ꢀ 5-CH3), 2.35 (s, 6H, 2 ꢀ 300-CH3), 3.11 (s, 6H, 2 ꢀ N-
CH3), 3.66 (t, 4H, J ¼ 7.0 Hz, 2 ꢀ H-10), 3.80 & 4.21 (dd,
4H, J ¼ 15.1 Hz each, 2 ꢀ S-CH2), 6.62 (s, 2H, 2 ꢀ H-7),
7.15 [m, 4H, 2 ꢀ (H-4 & H-6)], 7. 36 (m, 10H, 2 ꢀ N-
C6H5)
14.3 (300- CH3), 27.1 (C-30), 31.1
(C-20), 33.2 (N-CH3), 35.5 (S-
CH2), 43.8 (C-10), 113.0-134.9
(aromatic carbons), 162.4 (C-500),
171.2 (C-2), 178.0 (C-4000)
14.1 (300-CH3), 24.2 (C-30), 30.1
(C-20), 33.2 (N-CH3), 34.6 (S-
CH2), 43.8 (C-10), 110.0-140.2
(aromatic carbons), 161.1 (C-500),
172.2 (C-2), 177.9 (C-4000)
105
14.1 (300-CH3), 22.5 (5-CH3), 29.6
(C-30), 30.3 (C-20), 35.1 (N-
CH3), 35.2(S-CH2), 43.7 (C-10),
110.0-142.3 (aromatic carbons),
160.9 (C-500), 171.1 (C-2), 177.5
(C-4000)
5e
52
101
1030
1.39 (m, 4H, 2 ꢀ H-30), 1.65 (m, 4H, 2 ꢀ H-20), 2.10 (s, 6H,
2 ꢀ 300-CH3), 2.99 (s, 6H, 2 ꢀ N-CH3), 3.67 (t, 4H,
J ¼ 7.2 Hz, 2 ꢀ H-10), 3.81 & 4.23 (dd, 4H, J ¼ 15.1 Hz
each, 2 ꢀ S-CH2), 6.72 (m, 2H, 2 ꢀ H-7), 7.25 [m, 4H,
2 ꢀ (H-5 & H-6)], 7.34 (m, 10H, 2 ꢀ N-C6H5)
11.2 (300-CH3), 27.2 (C-30), 29.7
(C-20), 35.5 (S-CH2), 36.2 (N-
CH3), 43.3 (C-10), 108.6-141.3
(aromatic carbons), 161.2 (C-500),
170.1 (C-2), 177.8 (C-4000)

Novel bis-Spiro[indole-pyrazolinyl-thiazolidine]-2,40-diones
1871
using a Dean–Stark apparatus. Solution turned light yellow, and a sticky solid
was formed. The solvent was removed under reduced pressure, and the residue
was treated with a saturated solution of sodium bicarbonate to remove the
unreacted acid, if any. The solid left was filtered, dried, and crystallized
from a methanol–chloroform mixture to give 5a.
Compounds 5b–e were also synthesized following this procedure, and
their spectral data are included in Table 3.
ACKNOWLEDGMENTS
Authors thank CSIR, UGC, DST (New Delhi) and DANIDA (Denmark) for
financial assistance.
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