Microwave assisted green chemical synthesis of novel spiro[indole-pyrido thiazines]: A system reluctant to be formed under thermal conditions

Article abstract of DOI:10.1016/j.tet.2004.04.018

Spiro [3H-indole-3,2′-[4H] pyrido [3,2-e]-1,3-thiazine]-2,4′ (1H) diones, a class of previously unknown compound which does not form under conventional conditions, can be prepared by treatment of 'in situ' generated 3-indolylimine derivatives with 2-mercaptonicotinic acid under microwave irradiation in absence of any solvent or solid support in 85-92% yields in 3-8 min. The facile one pot reaction is generalized for a variety of ketones and amines to give pure pyrido [3,2-e] thiazine derivatives, which do not require further purification processes.

Full text of DOI:10.1016/j.tet.2004.04.018

Tetrahedron 60 (2004) 5253–5258
Microwave assisted green chemical synthesis of novel
spiro[indole-pyrido thiazines]: a system reluctant to be formed
under thermal conditionsq
*
Anshu Dandia, Kapil Arya, Meha Sati and Sangeeta Gautam
Department of Chemistry, Lab. 215, University of Rajasthan, Jaipur 302 004, India
Received 31 July 2003; revised 15 March 2004; accepted 8 April 2004
Abstract—Spiro [3H-indole-3,20-[4H] pyrido [3,2-e]-1,3-thiazine]-2,40 (1H) diones, a class of previously unknown compound which
does not form under conventional conditions, can be prepared by treatment of ‘in situ’ generated 3-indolylimine derivatives with
2-mercaptonicotinic acid under microwave irradiation in absence of any solvent or solid support in 85–92% yields in 3–8 min. The facile
one pot reaction is generalized for a variety of ketones and amines to give pure pyrido [3,2-e] thiazine derivatives, which do not require
further purification processes.
q 2004 Elsevier Ltd. All rights reserved.
1. Introduction
the reactions of thioacids with 3-indolylimines to give
biologically active spiro compounds,26 we planned to
synthesize novel spiro[indole-pyridothiazines] 5 by reacting
3-arylimino-2H-indol-2-one (3) with 2-mercaptonicotinic
acid (4).
The spiro indole compounds are of current interest due to
their exceptional biological activity.1–4 Thiazine deriva-
tives have also been reported as well known useful
therapeutic agents.5–12 Thiazines incorporating a pyridine
nucleus have shown anticancer,13 antitumor,14 antioxi-
dant,15 and potential CNS activities.16 They have been
patented as antibacterial17 and thrombin inhibitors,18
antidiabieties,19 antiinflammatory agents,20 analgesics,21
lipogenase inhibitors in leucocyte cell.22 The presence of
an N–C–S linkage is believed to account for the
amoebicidal, anticonvulsant, fungicidal23 and antiviral24
activities.
There are a few reports on the reactions involving the
synthon mercaptonicotinic acid27 due to its low reactivity.
To the best of our knowledge its reaction with arylimines
has not been studied. Conventionally, it is reluctant to
undergo any reaction with 3-arylimino-2H-indol-2-one,
even under harsh conditions (reflux for many days) in
high boiling solvents, e.g. dry toluene with azeotropic
removal of water; or using dehydrating agents like ZnCl2þ
dioxane, strong acids tolueneþTFA/gl. AcOH, etc.
Pyridothiazine derivatives have been synthesized conven-
tionally by tedious multi-step procedures, with prolonged
refluxing using volatile and hazardous organic solvents25
and are patented as pharmacological agents, the synthetic
details of which are not available.17–22
Microwave irradiation is well known to promote the
synthesis of a variety of compounds,28,29 where chemical
reactions are accelerated because of selective absorption of
microwaves by polar molecules. Recently, the coupling of
MWI with solid supports under solvent free conditions has
received notable attention.29 A literature survey reveals
examples of specific reactions, which do not occur under
conventional heating/sonication, but could be made possible
by microwave irradiation coupled with a solid support.30
Inspite of the immense biological activities of pyrido-
thiazines and spiro indoles no report is yet available on the
synthesis of spiro [indole-pyridothiazines]. In view of these
observations, and in continuation of our earlier interest on
Hence, in continuation of our work on the synthesis of
biodynamic heterocycles under microwave irradiation,31 we
report herein for the first time a facile one-pot synthesis of
30-substituted phenyl spiro [3H-indole-3,20-[4H]pyrido
[3,2-e]-1,3-thiazine]-2,40 (1H) diones] in 88–92% yield in
3–5 min. (Scheme 1)
q Presented at the Sixth International Electronic Conference on Microwave
Chemistry (ECSOC-6), 1–30 April 2003.
Keywords: Pyrido thiazine; Microwave irradiation.
*
Corresponding author. Tel.: þ91-98-2914-4056; fax: þ91-14-1221-4321;
e-mail address: dranshudandia@eth.net
0040–4020/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2004.04.018

5254
A. Dandia et al. / Tetrahedron 60 (2004) 5253–5258
Scheme 1.
In the present work, we studied the reaction of 3a and 4
taking different parameters of solid supports like (i)
montmorillonite KSF; (ii) neutral alumina; (iii) p-toluene
sulfonic acid (PTSA); (iv) silica gel for which promising
results were obtained.
In order to check the general applicability of the reaction for
the synthesis of pyrido [3,2-e]thiazine derivatives, we
extended the reaction of 4 with imine derivatives derived
from variety of aryl/heterocyclic amines, ketones/aldehydes
and developed facile elegant solvent free method for
exclusive synthesis of pyrido [3,2-e]thiazine derivatives
(5f–k) with an easier work up procedure.
Encouraged by the recent focus on the green chemical
theme of eliminating the use of solvents, we extended our
studies to neat reactions, since the reaction using solid
support requires an appreciable amount of solvent for
adsorption of reactants and elution of products. However, no
reaction occurred, but it could be made successful by
addition of a few drops of DMF. The role of DMF is to act as
energy transfer agent and homogenizer to increase the
reaction temperature.32 It did not lead to any side reactions
and no detectable by-product were observed. Consequently,
we extended this condition to the synthesis of compounds
(5b–e).
In order to check the possible intervention of ‘specific (non-
thermal) microwave effect’33 the best result obtained under
microwave irradiation was extrapolated to conventional
heating. In the case of compound 5a the reaction was carried
out using a preheated oil bath under the same reaction
conditions (time, temperature, pressure and vessel) for
5 min. It was found that no reaction occurred and that the
reactants remain unchanged, even on extended reaction time
(8 h), thus demonstrating that the effect of microwaves is
not simply thermal34 (Table 1).
Table 1. Comparative study for the synthesis of 5a (X¼4-CH3)
(A) Under microwave irradiation
S.No.
Solid support/energy transfer medium
MW power (W)
Time (min)
Temperaturea (8C)
Yieldb (%)
1
2
3
4
5
6
7
8
Montmorillonite KSF
Montmorillonite KSFþegl. AcOH
Montmorillonite KSFþe DMF
Neutral alumina
PTSA
SiO2
Neat (without DMF)
NeatþDMF (few drops)
640
640
640
640
275
640
640
640
12
3
6
30
20
12
12
3
112
122
132
102
125
122
95
Nil
70
86
Nil
65
72
Nil
90
140
(B) By thermal heating
S.No.
Thermal heating
Time (min)
6 days
7 days
6 days
8 days
Temperaturea (8C)
Reflux
Reflux
Reflux
Reflux
Yieldb (%)
1
2
3
4
5
6
TolueneþTFA
Nil
Nil
Nil
Nil
Nil
Nil
Dry toluene
Glacial AcOH
DioxaneþZnCl2
NeatþDMF (few drops)
3 min
480 min
140
140
NeatþDMF (few drops)
a
Final temperature is measured at the end of microwave irradiation by introducing a glass thermometer in the reaction mixture in the beaker.
Yield of the isolated products.
b

A. Dandia et al. / Tetrahedron 60 (2004) 5253–5258
5255
2. Results and discussion
stirrer, manufactured by BPL multimode Sanyo utilities
and appliances Ltd. operating at 700 W generating
2450 MHz frequency.
After analysis of the results summarized in the tables, we
found the reaction of 3-arylimino-2H-indol-2-one (3) with
2-mercaptonicotinic acid (4) afforded 5 as white needles.
The IR spectrum of 5a showed a strong absorption band at
3320–3290 cm21 (NH), two sharp bands at 1720–1710
(both CvO) and an absorption due to the CvN function-
4.1.1. General procedure for the synthesis of 3a–k. A
neat equimolar (1 mmol) mixture of indole-2,3-dione/
carbonyl compound (1a–k) and aromatic amine (2a–k)
was irradiated inside a microwave oven at 640 W untill
completion of the reaction (1–4 min). TLC, showing the
formation of a single product, determined complete
conversion. The intermediates 3 so obtained in reasonable
purity were used as such for the next step without further
purification.
ality appeared at 1625 cm21
.
The 1H NMR spectrum of 5a revealed characteristic signals
for methyl protons at 2.15 (s, 3H, CH3) along with aromatic
protons at d 6.83–7.52 (m, Ar-H, 8H), d 7.62–8.73 (m, 3H,
pyridyl-H,) and NH proton at d 9.01(s, 1H, NH, exchanged
with deuterium). Formation of the 5a was further confirmed
on the basis of 13C NMR spectroscopy and Mass
spectrometry. In the 13C NMR spectrum of 5a, sharp
signals were observed at 21.08 (CH3), 82.17(spiro carbon),
120.8–147.86 (aromatic ring carbons), 161.4 (S–CvN),
163.7,168.2 (two CvO). The mass spectrum of 5a showed
molecular ion peak m/z at 373 [Mþ] (32.4%) along
with peaks at 345 (Mþ2CO, 9.4%) and base peak at 264
(Mþ-C5H3NS, 100%), 194 (13.2), 186 (31.1), 163 (28.5),
129 (63.7), 76 (50.4), 55 (19.2).
The structure of the compounds were confirmed by IR and
1H NMR spectroscopy and by comparison with authentic
samples (3a–k) prepared according to literature
methods.26d,35a–f
4.2. Investigation of the reaction of 3 and
mercaptonicotinic acid (4)
4.2.1. Under conventional condition.
(a) An equimolar (1 mmol) mixture of 3 and mercapto-
nicotinic acid was refluxed 6–8 days in dry toluene
(25 ml) with azeotropic removal of water/toluene
(25 ml)þTFA (5 drops)/dioxane (25 ml)þZnCl2/
glacial AcOH (25 ml). TLC indicated the unchanged
reactants and no product formation.
On the basis of spectral data, the products (5a–k) have been
identified as cyclocondensed product 5 instead of addition
product 6.
(b) An equimolar (1 mmol) mixture of 3 and mercapto-
nicotinic acid (4) was heated on pre heated oil bath
under identical conditions of time, temperature, pres-
sure, vessel and medium as under microwaves. TLC
indicated the unchanged reactants. Even extended
heating for 8–24 h not lead to formation of any product.
3. Conclusion
In conclusion, we have developed an economical, safe and
environmentally benign-solvent free synthesis, for spiro and
other pyrido [3,2-e] thiazine derivatives. The use of
microwave conditions is absolutely essential for this
transformation, as conventional heating fails.
4.2.2. Under microwave irradiation (one pot synthesis).
In all cases, a comparison of the reactions using
either thermal or microwave heating under the same
(a) Using different solid supports such as montmorillonite
KSF, neutral alumina, silica gel, p-toluene sulfonic
acid (PTSA). Equimolar quantities of ‘in situ’ syn-
thesized 3a (1 mmol, 236 mg) and 4 (1 mmol, 155 mg)
were introduced into a beaker and dissolved in
methanol (15 ml). Solid support (1 g) (montmorillonite
KSF/neutral alumina/p-toluene sulfonic acid (PTSA)/
silica gel) was then added and swirled for a while
followed by removal of the solvent under gentle
vacuum. The dry free flowing powder obtained was
placed into a pyrex-glass opened vessel and irradiated
in the microwave oven at a power output of 90%
(640 W), for the specifies time and at the final
temperature as indicated in the Table 2. When
irradiation was stopped, the final temperature was
measured by introducing a glass thermometer into the
reaction mixture and homogenizing it, in order to
obtain a temperature value representative of the whole
mass. After completion of the reaction (monitored by
TLC) the recyclable solid support was separated by
filtration after eluting the product with methanol and
excess solvent was evaporated on a rotary evaporator
to give solid, which was recrystallized from methanol
to give desired product.
conditions shows clearly
microwave effect.
a specific (non-thermal)
4. Experimental
4.1. Equipment
Melting points were determined in open glass capillaries
and are uncorrected. IR spectra were recorded on a
Perkin–Elmer (Model 577) infra cord spectrophotometer
using KBr pellets 1H NMR spectra were recorded on
model Jeol-FX-90Q, Bruker-DRX-300/DRX-200 using
CDCl3 as solvent at 89.95, 300.13 and 200.13 MHz and
13C NMR spectra were recorded on model Bruker-DRX-
300 using CDCl3 as solvent at 300.13 MHz. TMS was
used as internal reference for 1H NMR and 13C NMR
spectra. Mass spectra of the representative compounds
were recorded on Kratos-30 spectrometer. All compounds
were homogenous on TLC in various solvent systems.
The microwave induced reactions were carried out in an
open borosil glass vessel under atmospheric pressure in
BMO-700T domestic oven, equipped with magnetic

5256
A. Dandia et al. / Tetrahedron 60 (2004) 5253–5258
Table 2. Cyclocondensation of arylimines with 2-mercaptonicotinic acid under microwave irradiation
Entry
Product No.
Carbonyl compounds
Amines
Temperaturea
(8C)
MW
D
Mp
(8C)
Timeb
(min.)
Yieldc
(%)
Timed
(hrs.)
Yield
(%)
1
2
3
4
5
6
5a
5b
5c
5d
5e
5f
Indole-2,3-dione
Indole-2,3-dione
Indole-2,3-dione
Indole-2,3-dione
Indole-2,3-dione
Cyclopentanone
4-Methyl aniline
140
138
138
140
142
138
0.5þ3
2þ4
90
92
89
90
92
87
8
7
7
6
8
14
Nil
Nil
Nil
Nil
Nil
Nil
138
172
205
220
192
175
2-Trifluoromethyl aniline
4-Methoxy aniline
4-Chloro aniline
1þ2.5
0.5þ3
1þ3
4-Fluoro aniline
4þ8
7
8
9
10
11
5g
5h
5i
5j
5k
Cyclohexanone
Benzaldehyde
Benzaldehyde
Acetophenone
Acetophenone
4-Chloro aniline
2-Amino 6-methyl pyridine
4-Methyl aniline
2-Amino 6-methyl pyridine
4-Methyl aniline
140
132
142
145
138
3þ7
4þ6
3þ7
5þ7
3þ8
85
87
85
89
86
24
22
26
22
23
Nil
Nil
Nil
Nil
Nil
248
202
172
215
245
a
Final temperature is measured at the end of microwave irradiation by introducing a glass thermometer in the reaction mixture in the beaker.
b
Compounds 5a–k were synthesiszed in one pot and time is indicated for the condensation of ‘in situ’ generated arylimines in microwave oven e.g. 5a 0.5þ3
indicates first irradiation for 0.5 min give intermadiate 3a (100% conversion, TLC) and then further irradiation after adding 2-mercaptonicotinic acid for
3 min.
Isolated yield of purified compounds that exhibited physical and spectral properties in accordance with the assigned structure.
Extended reaction time for reaction of thermally presynthesized arylimines under identical reaction conditions and temperature used under microwaves.
c
d
(b) Neat reaction with few drops of DMF. An equimolar
(1 mmol) mixture of 3 and 4 with few drops of DMF, in
an open tall beaker was irradiated inside microwave
oven for an appropriate time (monitored by TLC). The
solid mass obtained poured in to water to give
crystalline product with no need of further purification
(TLC) in most cases (5f–k), while in cases (5a–e) the
solid was recrystallized by methanol to give pure
product.
4.2.6. Compound 5d. Mp 220 8C; [Found: C, 61.2; H, 3.1;
N, 10.7; S, 8.1. C20H12ClN3O2S requires C, 61.06; H, 3.05;
N, 10.68; S, 8.11%]; nmax (KBr) 3340–3310 (br), 1720,
1710, 1625, 770 cm21; dH (90 MHz, CDCl3) 9.04 (1H, br,
NH, D2O exchangeable), 8.46–7.14 (11H, m, Ar-H and
pyridine H); dC (300 MHz, CDCl3) 168.3, 163.8, 161.8,
140.5–119.2, 81.8; m/z 393(15, MHþ), 365 (25), 256 (100),
196 (22), 186 (15), 156 (19%).
4.2.7. Compound 5e. Mp 192 8C; [Found: C, 63.4; H, 3.1;
N, 11.0; S, 8.5. C20H12FN3O2S requires C, 63.65; H, 3.18;
N, 11.13; S, 8.48%]; nmax (KBr) 3330–3290 (br), 1715,
1705, 1620, 720; dH (90 MHz, CDCl3) 9.04 (1H, br, NH,
D2O exchangeable), 8.56–7.10 (11H,, m, Ar-H and pyridine
H); dC (300 MHz, CDCl3) 167.2, 164.7, 161.5, 147.8–
121.0, 117.2, 82.1; m/z 377(14, MHþ), 349 (14), 240 (100),
192 (43), 74 (51%).
4.2.3. Compound 5a. Mp 138 8C; [Found: C, 67.7; H, 4.0;
N, 11.0. C21H15N3O2S requires C, 67.54; H, 4.02; N,
11.25%]; nmax (KBr) 3320–3290 (br), 1720, 1710,
1625 cm21; dH (300 MHz, CDCl3) 9.26 (1H, br, NH, D2O
exchangeable), 7.93–7.20 (11H, m, Ar-H and pyridine H),
2.37 (3H, s, CH3); dC (300 MHz, CDCl3) 168.1, 161.4,
159.8, 142.1–109.4, 77.4, 22.4; m/z 373 (32, MHþ), 345
(10), 264 (100), 194 (13), 186 (31), 163 (29), 129 (64), 76
(50), 55 (19%).
4.2.8. Compound 5f. Mp 175 8C; [Found: C, 62.2; H, 4.6;
N, 11.5; S, 17.4. C19H17N3O2S2 requires C, 62.11; H, 4.63;
N, 11.44; S, 17.43%]; nmax (KBr) 3030–3010, 2920–2850,
1720, 1620 cm21; dH (200 MHz, CDCl3) 7.41–7.03 (6H, m,
Ar-H and pyridine H), 2.72 (4H, m, CH2–CH2), 2.29 (3H, s,
CH3), 1.47 (4H, m, CH2–CH2); dC (300 MHz, CDCl3)
172.5, 162.7, 145.2–120.0, 72.1, 36.3, 20.9, 17.5; m/z 367
(40, MHþ), 339 (24), 258 (100), 217 (45), 205 (20), 181
(20), 138 (60), 125 (14%).
4.2.4. Compound 5b. Mp 172 8C; [Found: C, 58.8; H, 2.7;
N, 9.7; S, 7.43. C21H12F3N3O2S requires C, 59.01; H, 2.81;
N, 9.83; S, 7.49%]; nmax (KBr) 3330–3290 (br), 1715, 1705,
1620 cm21; dH (90 MHz, CDCl3) 9.08 (1H, br, NH, D2O
exchangeable), 8.75–7.01 (11H, m, Ar-H and pyridine H);
dC (22.4 MHz, CDCl3) 168.2, 163.5, 162.4, 140.86–119.2,
82.12, 64.13; m/z 427 (20, MHþ), 399 (16), 290 (100), 196
(33), 184 (12), 165 (19), 128 (44), 74 (41%).
4.2.9. Compound 5g. Mp 248 8C; [Found: C, 62.7; H,
4.78; N, 8.0; S, 9.2. C18H17 ClN2OS requires C, 62.59;
H, 4.92; N, 8.11; S, 9.27%]; nmax (KBr) 2930–2840,
1720, 1610, 770 cm21; dH (90 MHz, CDCl3) 8.46–7.15
(7H, m, Ar-H and pyridine H), 1.87 (4H, m, CH2–CH2),
1.29 (6H, m, (CH2)3; m/z 347 (4, MHþþ2), 345 (12.0),
317 (100), 208 (45), 178 (35), 149 (7), 135 (60), 121
(14%).
4.2.5. Compound 5c. Mp 205 8C; [Found: C, 64.8; H, 3.8;
N, 10.8; S, 8.2. C21H15N3O3S requires C, 64.77; H, 3.85; N,
10.79; S, 8.22%]; nmax (KBr) 3330–3300 (br), 1730, 1720,
1620, 1110–1050 cm21; dH (200 MHz, CDCl3) 9.4 (1H, br,
NH, D2O exchangeable) 7.40–7.03 (11H, m, Ar-H and
pyridine H), 3.84 (3H, s, OCH3); dC (300 MHz,
CDCl3)170.2, 164.5, 161.4, 157.6, 145.8–122.0, 81.1,
56.2; m/z 389(11, MHþ), 361 (12), 252 (100), 178 (22),
126 (53), 72 (41%).
4.2.10. Compound 5h. Mp 202 8C; [Found: C, 68.2; H, 4.5;
N, 12.5; S, 9.6. C19H15N3OS requires C, 68.45; H, 4.50; N,

A. Dandia et al. / Tetrahedron 60 (2004) 5253–5258
5257
11. Doi, N. Ten kan-Kenkyu 1990, 8, 167. Chem. Abstr. 1991, 114,
114947s.
12.60; S, 9.60%]; nmax (KBr) 2840–2810, 1710,
1620 cm21; dH (90 MHz, CDCl3) 8.35–7.10 (11H, m, Ar-
H and pyridine H), 5.64 (1H, s, CH), 2.28 (3H, m, CH3); dC
(22.4 MHz, CDCl3) 163.6, 159.2, 140.8–118.5, 70.5, 21.3;
m/z 333 (14, MHþ), 305 (36), 224 (100), 165 (13%).
12. Surrey, A. R.; Webb, W. G.; Gesler, R. M. J. Am. Chem. Soc.
1958, 80, 3469.
13. Temple, C.; Wheeler, G. P.; Comber, R. N.; Elliot, R. D.;
Montgomery, J. A. J. Med. Chem. 1983, 26(11), 1641.
14. El-Subbagh, H. I.; Abadi, A.; Al-Khawad, I. E.; Al-Pashood,
K. A. Arch. Pharm. 1999, 332(1), 19.
4.2.11. Compound 5i. Mp 172 8C; [Found: C, 72.1; H, 4.7;
N, 8.3; S, 9.5. C20H16N2OS requires C, 72.26; H, 4.81; N,
8.43; S, 9.63%]; nmax (KBr) 2860–2820, 1715, 1615 cm21
;
15. Malinka, W.; Kaczmarz, M.; Filipek, B.; Sepa, J.; Gold, B.
Farmco 2002, 57(9), 737.
dH (300 MHz, CDCl3) 8.10–7.26 (12H, m, Ar-H and
pyridine H), 5.91 (1H, s, CH), 2.73 (3H, s, CH3); dC
(300 MHz, CDCl3) 164.2, 158.5, 140.5–118.2, 71.2, 20.5;
m/z (%) 332 (25, MHþ), 304 (100), 195 (45), 181(14), 139
(60), 118 (14), 98 (32%).
16. Malinka, W.; Pyng, S.; Sicklucka-Dziuba, M.; Rajtar, G.;
Glowniak, A.; Kleinrok, Z. Farmco 1994, 49, 783.
17. Maeda, T.; Koide, T.; Nakai, H.; Yozota, M.; Araki, T.;
Murakai, T.; Nohare, C. Jpn Kokai Tokkyo Koho JP 07, 17,
1995, 980; Chem. Abstr. 1995, 122, 265167d.
18. Sandersan, P. E.; Cutrona, K. PCT Int. Appl. WO 18, 1998,
762; Chem. Abstr. 1999, 132, 251163u.
4.2.12. Compound 5j. Mp 215 8C; [Found: C, 69.3; H, 4.9;
N, 12.1; S, 9.2. C20H17N3OS requires C, 69.14; H, 4.89; N,
12.09; S, 9.21%]; vmax (KBr) 2840–2820, 1720, 1620 cm21
;
19. Tomaji, N.; Yoshiyuki, M.; Ishikawa, H. PCT Int. Appl WO
00 94, 22, 1996, 875; Chem. Abstr. 1995, 122, 214086u.
20. Malinka, W.; Zawisza, T.; Gieldenowski, J. Pol. PT PL 139,
1987, 585, Appl. 253, 057, 1985; Chem Abstr. 1991, 114,
102026n.
dH (90 MHz, CDCl3) 8.52–7.18 (12H, m, Ar-H and pyridine
H), 2.32(3H, s, CH3), 1.87(3H, s, CH3); dC (300 MHz, CDCl3)
164.5, 162.4, 148.2–118.2, 68.2, 27.5, 20.9; m/z (%) 347 (15,
MHþ), 319 (14), 234 (100), 184 (20%).
21. Malinka, W.; Zawisza, T.; Millimowski, M. Pol. PT PL 143,
1988, 077, Appl. 257, 400, 1986; Chem. Abstr. 1989, 111,
78013n.
4.2.13. Compound 5k. Mp 245 8C; [Found: C, 72.6; H, 5.1;
N, 8.1; S, 9.2. C21H18N2OS requires C, 72.73; H, 5.19; N,
8.08; S, 9.23%]; nmax (KBr) 2850–2820, 1720, 1620 cm21
;
22. Klausener, A.; Fengler, G.; Buysch, H. J.; Pelster, B. Ger.
Offen DE 3, 1987, 545; Chem. Abstr. 1987, 107, 154346n.
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(300 MHz, CDCl3) 168.9, 164.6, 145.6–117.8, 66.2, 28.2,
21.5; m/z (%) 346 (12, MHþ), 318 (10), 237 (100), 183 (50%).
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Acknowledgements
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Financial assistance from CSIR 01 (1907)/03 is gratefully
acknowledged. We are also thankful to RSIC, CDRI,
Lucknow, for the spectral analyses.
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