Synthesis, structure and antimicrobial evaluation of new 3,3a,4,5-tetrahydro-2H-benzo[g]indazol-2-yl-thiazol-4(5H)-ones

Article abstract of DOI:10.1016/j.saa.2014.06.134

The reaction of semicarbazide or thiosemicarbazide with 2-arylidene-1-tetralones under alkaline condition affords 3,3a,4,5-tetrahydro- 2H-benzo[g]indazole-2-carbo(thio)amides as a mixture of cis and trans diastereoisomers of 3-H and 3a-H. The synthesis of

Full text of DOI:10.1016/j.saa.2014.06.134

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 135 (2015) 219–226
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Synthesis, structure and antimicrobial evaluation of new
3,3a,4,5-tetrahydro-2H-benzo[g]indazol-2-yl-thiazol-4(5H)-ones
⇑
Deepika Gautam, R.P. Chaudhary
Department of Chemistry, Sant Longowal Institute of Engineering & Technology, Longowal, Sangrur, Punjab 148106, India
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Synthesis of eight new indazolyl-
thiazol-4(5H)-ones have been
accomplished.
Stereo chemical assignments were
made on the basis of spectroscopic
experiments.
X-ray diffraction of one indazolyl-
thiazol-4(5H)-one derivative has been
reported.
Results of DFT studies on
diastereoisomers are correlated with
experimental values.
R2
H
N
O
S
X
N
NH2
N
N
H
Cl (Br)
N
H
C6H4R1
R2-CH-CO H
2
C6H4R1
H
H
O
R
R
CHC6H4R1
X
NH2
X
NH2NHC-NH2
N
R
N
H
C6H4R1
H
Newly synthesised compounds
exhibit promising antimicrobial
activities.
R
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction of semicarbazide or thiosemicarbazide with 2-arylidene-1-tetralones under alkaline condi-
tion affords 3,3a,4,5-tetrahydro-2H-benzo[g]indazole-2-carbo(thio)amides as a mixture of cis and trans
diastereoisomers of 3-H and 3a-H. The synthesis of new indazolyl-thiazol-4(5H)-ones from the conden-
Received 28 April 2014
Received in revised form 22 June 2014
Accepted 25 June 2014
sation of cis isomer and
a-halo acids is reported. A DFT study along with X-ray single crystal data of a
Available online 5 July 2014
representative compound is presented. All the eight newly synthesised indazolyl-thiazol-4(5H)-ones
were screened for their antibacterial and antifungal activities and some compounds have shown prom-
ising activities.
Keywords:
2-Arylidene-1-tetralone
Indazol-2-carbothioamides
Indazolyl-thiazol-4(5H)-one
X-ray diffraction
Ó 2014 Elsevier B.V. All rights reserved.
DFT
Antimicrobial activities
Introduction
[1], anti-depressant [2], anticancer [3], antituberculosis [4], and
antimicrobial activities [5]. Tetrahydroindazole derivatives have
Pyrazoles, in general, and their benzocondensed analogues,
tetrahydroindazoles, in particular have been proved to be an effec-
tive pharmacophore in medicinal chemistry and constitutes the
key sub unit in many biologically active compounds with a broad
range of pharmacological activities including anti-inflammatory
been shown to possess antiproliferative activity against leukaemia
cells [6] and lonidamine, an indazole-3-carboxylic acid derivative
is a new nonconventional anticancer drug that inhibits the energy
metabolism of neoplastic cells and increases the cell membrane
permeability [7]. Owing to the immense importance and varied
bioactivities exhibited by tetrahydroindazole derivatives, efforts
have been made to fuse or couple tetrahydroindazole nucleus with
other bioactive scaffolds, possibly for synergic increase in their
activity profile [8].
⇑
Corresponding author. Tel.: +91 1672 253206; fax: +91 1672 280057.
E-mail address: rpchaudhary65@gmail.com (R.P. Chaudhary).
http://dx.doi.org/10.1016/j.saa.2014.06.134
1386-1425/Ó 2014 Elsevier B.V. All rights reserved.

220
D. Gautam, R.P. Chaudhary / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 135 (2015) 219–226
Also it is well documented that thiazol-4(5H)-one nucleus dis-
from X-ray structure of 3b is shown in Fig. 1. CCDC 935909 con-
tains the supplementary crystallographic data of 3b and these data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Compounds 3b–e, with X = S, on condensation with chloroacetic
play a variety of pronounced pharmacological activities such as
anticonvulsant [9], antimicrobial [10], anti-inflammatory [11], anti
cancer [12], anti-HIV [13], and antitumor [14]. Considering the
importance of tetrahydroindazole and thiazol-4(5H)-one nucleus
it was thought worthwhile to design and synthesise some new
thiazol-4(5H)-one derivatives bearing tetrahydroindazole moiety
and screen them for potential biological activities. In continuation
to our work on synthesis [15–17] and antimicrobial studies [18,19]
of new thiazol-4(5H)-ones, we report here the synthesis, X-ray dif-
fraction, DFT and antimicrobial studies of new thiazol-4(5H)-ones
bearing tetrahydroindazole moiety.
acid and
a-bromopropionic acid in presence of anhydrous sodium
acetate afford substituted 3,3a,4,5-tetrahydro-2H-benzo[g]indazol-
2-yl)thiazol-4(5H)-ones (5a–h, Scheme 2). Appearance of carbonyl
peak at 1697 cmꢁ1 in the IR spectrum of 5a indicates the cyclisation
has indeed taken place. In 1H NMR spectrum of 5a, appearance of
singlet of two protons at d 3.88 is assigned to SCH2 group of thiazo-
lidinone ring. 13C NMR of 5a displays carbonyl group at d 186.5 and
C-3a at d 49.2. The appearance of peak at m/z 348 (M+H)+ (54%) in
mass spectrum supports the cyclised structure 5a. Similarly, 1H
NMR spectrum of 5b displays a doublet at d 1.5 of CH3 group and
a quartet of one proton at d 4.15 due to SC(H)CH3 group confirm
the formation of thiazolidinone ring. 13C NMR spectrum of 5b exhib-
its C@O and C-3a at d 189.3 and d 48.8 respectively. The mass spec-
trum of 5b, displays base peak at m/z 362 (M+H)+ (100%) in support
of its cyclised structure. The structure of other derivatives (5c–h) has
been established in a similar fashion by analytical and spectral data.
The analytical data of all the synthesised compounds is in accor-
dance with the assigned structures and is in good agreement with
calculated values (within range of 0.4%).
The X-ray crystal structure of compound 5a, which is reported
for the first time in this study, further confirmed the stereochem-
istry and cis orientation of H-3 and H-3a protons (Fig. 2). The crys-
tallographic data and refinement parameters of 5a are reported in
Table 1. CCDC 986834 contains the supplementary crystallographic
data and these data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Results and discussion
Chemistry
2-Arylidene-1-tetralones 2a–d were obtained by condensation
of 1-tetralones 1 and substituted aromatic aldehydes in the pres-
ence of 5% NaOH in aqueous medium [20]. 2-Arylidene-1-tetral-
ones 2a–d on condensation with nucleophilic reagents (phenyl
hydrazine, semicarbazide and thiosemicarbazide) forms isomeric
products. The isomeric composition of products was reported to
be influenced by nucleophilic reagents as well as reaction condi-
tions. Lorand et al. [21] have reported that condensation of 2 with
thiosemicarbazide afforded only cis isomer and its formation is
independent of solvent and catalyst used in the reaction. In
another communications by the same author [22,23] it has been
reported that the condensation of semicarbazide and thiosemicar-
bazide with 2-arylidene-1-tetralones 2 in acidic medium furnished
a mixture of 3-H, 3a-H cis and trans diastereoisomers in the former
case and only one cis diastereoisomer in the latter case. In contrast,
Jagtap et al. [24] have reported the formation of mixture of cis and
trans diastereoisomers during the condensation of 2-arylidene-1-
tetralones 2 with semicarbazide or thiosemicarbazide in acidic
medium. Herein, we found that condensation of 2-arylidene-1-tet-
ralones 2a–d with semicarbazide or thiosemicarbazide in presence
of alc. KOH afforded a readily separable mixture (HPLC) of cis and
trans diastereoisomers (3-H, 3a-H) 3 (i.e. 3S, 3aS-rel isomer) and
4 (i.e. 3R, 3aS-rel isomer) in 42% (X = O) and 58% (X = O) yields. In
case of carbothioamides (X = S), cis isomer 3 is the major product
(90–95%, HPLC) and isomer 4 is only a minor product (5–10%). A
mixture of 3a and 4a was separated by column chromatography
(4:1 pet. ether: ethyl acetate) and the relative configuration of
the isomers was established by 2D-COSY, 1H NMR and 13C NMR
experiments. The reaction of 2-arylidene-1-tetralones 2 with semi-
carbazide or thiosemicarbazide proceeds via hydrazone formation
resulting from 1,2-addition of semicarbazide or thiosemicarbazide
to the carbonyl group and subsequent NAH intramolecular cyclo-
addition to the double bond of 20 as depicted in Scheme 1. In 1H
NMR spectrum, the proton H-3 in 3a and 4a appeared as a doublet
at d 5.50 and d 4.79 ppm respectively, with spin–spin H-3 and H-3a
vicinal coupling constant values (3JH-3,3a) of 10.9 Hz and 11.1 Hz.
The difference in J values is too small to distinguish between cis
and trans isomers. The difference in chemical shifts of H-3 in dia-
stereoisomeric pair 3a and 4a is due to the diamagnetic anisotropy
of CA(3a)AC-4 bonds and to the orientation of the pendent phenyl
group. Firm decision on the configuration of the isomers is made
on the basis of 13C NMR spectroscopy. The C-3a chemical shifts
for the cis and trans isomers 3a and 4a are 48.1 and 55.1 ppm
respectively. The significant up field shift for C-3a in 3a proved
its cis configuration unambiguously. Finally, the structure of cis
diastereoisomer 3b (X = S) is proved by single crystal X-ray diffrac-
tion studies reported in our earlier accepted communication to
Journal of Heterocyclic Chemistry. The ortep diagram obtained
Computational studies
The molecular geometry optimisation and 1H and 13C NMR
spectra calculations were performed with the Jaguar software
package version 6.5112 by using DFT methods with B3LYP (Becke
three parameter Lee–Yang–Parr) exchange correlation functional,
which combines the hybrid exchange functional of Becke [25] with
the gradient-correlation functional of Lee et al. [26]. The 6-31G**
basis set was used for calculations in the gas phase of cis diastereo-
isomer 5a and its trans isomer 6a.
A DFT calculation was carried out to predict the geometry of the
molecules. The initial coordinates for DFT calculation were
obtained from X-ray data. The experimental and optimised bond
parameters (bond lengths and bond angles) obtained from X-ray
crystallographic study and by geometry optimisation at B3LYP/6-
31G** level of theory respectively for structure 5a is in close agree-
ment and is reported in Table 2. It may be noted here that slight
differences in bond parameters can be attributed to the fact that
the experimental results are derived from the solid phase whereas
the theoretical calculations cater to the gaseous phase. However,
the general agreements are good and therefore, the theoretical
calculations amply corroborate the solid-state structures. The opti-
mised configurations of 5a and 6a with atom numbering schemes
are shown in Figs. 3 and 4 respectively.
Shielding tensors of structure 5a and its trans isomer 6a were
evaluated by using B3LYP functional with basis set given above.
In order to express the chemical shifts in ppm, the geometry of tet-
ramethylsilane (TMS) and chloroform molecules had been opti-
mised and then their 1H and 13C NMR spectra were calculated by
the same method using same basis set as in case of the calculations
on structures 5a and its trans isomer 6a. The shielding of TMS is
32.3379 for 1H NMR and 202.8593 for 13C NMR. The calculated iso-
tropic shielding constants ri were then transformed to chemical

D. Gautam, R.P. Chaudhary / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 135 (2015) 219–226
221
Scheme 1. Synthesis of substituted-3,3a,4,5-tetrahydro-2H-benzo[g]indazol-2-carbothioamides/carboxamides.
Antimicrobial activity
All the newly synthesised indazolyl-thiazol(5H)-4-ones 5a–h
were screened for their in vitro antibacterial and antifungal activ-
ity. The microorganisms employed for antibacterial studies were
Staphylococcus aureus (MTCC 096), Escherichia coli (MTCC 443)
and Pseudomonas aeruginosa (MTCC 424). For antifungal screening,
Aspergillus niger (MTCC 282), Aspergillus fumigates (MTCC 343), and
Candida albicans (MTCC 227) strains were used. Both microbial
studies were assessed by Minimum Inhibitory Concentration
(MIC) by serial dilution method [27].
Various concentrations (6.25, 12.5, 25, 50, 100, 200, 500 and
1000 lg/ml) of each compound were prepared by serially diluted
DMSO from the stock solution. For MIC, a standard drop of the
microbial culture, prepared for the assay, was added to the differ-
ent dilution of compounds in Muller Hilton (MH) broth for bacteria
and Sabouraud Dextrose (SD) broth for fungi. Test solutions were
then incubated for 16–18 h for bacteria and 28–30 h for fungi at
37 °C. MIC is the minimum concentration of the compound, which
inhibits the visible growth of bacteria or fungi. To determine zone
of inhibition, inoculated MH agar for bacteria and SD agar for fungi
were separately poured into the sterilized petri dishes. The poured
material was allowed to set and thereafter the ‘‘CUPS’’ (08 mm
diameter) were made by punching into the agar surface with a
sterile cork borer and scooping out the punched part of the agar.
The test compound solution was added into these cups with the
help of a sterile syringe. The plates were incubated at 37 °C for
16–18 h for bacteria and 28–30 h for fungi. Clinically antimicrobial
drugs Ciprofloxacin and Miconazole were used as the positive
Fig. 1. ORTEP drawing (drawn at 50% probability level) indicating molecular
structure and atomic labelling of (3S, 3aS)-3-phenyl-3,3a,4,5-tetrahydro-2H-
benzo[g]indazole-2-carbothioamide (3b).
shifts relative to TMS by the equation di = rTMS
ꢁ
ri. A comparison
between experimental and calculated 1H and 13C NMR chemical
shifts (ppm) of compound 5a and its trans isomer 6a have been
reported in Table 3. The correlation values of proton chemical
shifts are found to be 0.9561 for structure 5a and 0.8158 for its
trans isomer 6a (Fig. 5). The correlation values of carbon chemical
shifts of 5a and its trans isomer 6a are found to be 0.9898 and
0.9827 respectively (Fig. 6). It may be noted that there is large
deviation in correlation values of trans isomer 6a. Based upon com-
parison of experimental and theoretical NMR studies, 1H and 13C
data show good correlations for the proposed cis structure 5a.
5
R
R1
R2
a
b
H
H
c
H
d
H
e
f
g
h
H
H
H
OMe OMe OMe OMe
H
H
4-Cl 4-Cl
CH3
H
CH3
4-Cl 4-Cl
CH3
CH3
H
H
Scheme 2. Synthesis of Indazolyl-thiazol-4(5H)-ones from substituted-3,3a,4,5-tetrahydro-2H-benzo[g]indazol-2-carbothioamides.

222
D. Gautam, R.P. Chaudhary / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 135 (2015) 219–226
Table 2
Selected bond parameters of cis isomer 5a and trans isomer 6a.
Parameters
Compound 5a
Isomer 6a
Experimental Calculated Parameters
Calculated
Bond lengths (Å)
S(1)AC(3)
S(1)AC(1)
N(2)AC(3)
N(2)AC(4)
O(1)AC(2)
N(1)AC(3)
N(1)AC(2)
N(3)AC(6)
N(3)AN(2)
C(6)AC(7)
C(6)AC(5)
1.752(4)
1.807(4)
1.335(5)
1.493(4)
1.219(4)
1.324(5)
1.357(5)
1.291(4)
1.403(4)
1.468 (5)
1.511 (5)
1.7838
1.8028
1.3352
1.4707
1.1880
1.2777
1.3757
1.2594
1.3870
1.4679
1.5058
S(1)AC(7)
1.7731
1.8061
1.3354
1.4738
1.1878
1.2794
1.3790
1.2587
1.3827
1.4680
1.5014
S(1)AC(17)
N(3)AC(7)
N(3)AC(10)
O(4)AC(12)
N(5)AC(7)
N(5)AC(12)
N(13)AC(10)
N(3)AN(2)
C(6)AC(8)
C(6)AC(13)
Bond angles (°)
C(3)AS(1)AC(1)
88.17(18)
88.8699
107.7592
119.9252
127.6440
112.1809
112.9312
124.6650
114.5100
124.2106
118.1553
117.6207
99.6568
C(7)AS(1)AC(17)
C(6)AN(2)AN(3)
C(7)AN(3)AN(2)
C(7)AN(3)AC(10)
N(2)AN(3)AC(10)
C(7)AN(5)AC(12)
N(2)AC(6)AC(8)
N(2)AC(6)AC(13)
N(5)AC(7)AN(3)
N(5)AC(7)AS(1)
N(3)AC(7)AS(1)
88.3798
108.3699
119.1699
123.7635
113.1863
112.5095
125.3921
114.7116
122.0472
119.0050
118.9412
C(6)AN(3)AN(2) 106.2 (3)
C(3)AN(2)AN(3) 120.8 (3)
C(3)AN(2)AC(4) 125.3 (3)
N(3)AN(2)AC(4) 113.9(3)
C(3)AN(1)AC(2) 110.9 (3)
N(3)AC(6)AC(7) 124.6 (3)
N(3)AC(6)AC(5) 114.9 (3)
N(1)AC(3)AN(2) 121.7 (3)
Fig. 2. An ORTEP diagram of 2-((3S, 3aS)-3-phenyl-3,3a,4,5-tetrahydro-2H-
benzo[g]indazol-2-yl)thiazol-4(5H)-one 5a with nonhydrogen ellipsoids drawn at
50% probability level.
Table 1
Crystal data and structure refinement parameters of compound 5a.
N(1)AC(3)AS(1)
N(2)AC(3)AS(1)
N(2)AC(4)AC(5)
119.4 (3)
118.9 (3)
99.4 (3)
CCDC no.
986834
C20H17N3OS
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
N(3)AC(10)AC(13) 100.5836
347.43
293 (2)
0.71073 Å
Triclinic
Pꢁ1
Unit cell dimensions
a (Å)
b (Å)
c (Å)
7.9857 (9)
10.5056 (13)
10.8119 (14)
98.293 (11)
101.310 (11)
104.388 (11)
843.58 (18)
2
a
(ꢀ)
b (ꢀ)
c
(ꢀ)
Volume (Å3)
Z
Density (calculated) (Mg/m3)
Absorption coefficient (mmꢁ1
Crystal size
1.368 Mg/m3
0.205 mmꢁ1
0.31 ꢂ 0.26 ꢂ 0.22 mm3
2.89–29.05
)
Theta range for data collection
Reflections collected
6408
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
1958
3791/0/226
1.026
Final R indices [I > 2
R indices (all data)
r
(I) = 2591 data]
R1 = 0.0823, wR2 = 0.1730
R1 = 0.1524, wR2 = 0.2196
ꢁ0.269, 0.349
Largest diff. Peak and hole (e Åꢁ3
)
control and DMSO was used for blank. The experiments were
repeated three times, and the average values are presented in
Table 4. Compounds 5d and 5h (MIC 12.5
activity against S. aureus, E. coli and A. Niger. Compounds 5f and
5b with MIC 6.25 g/ml displayed excellent antibacterial activity
lg/mL) showed good
Fig. 3. Optimised structure of 5a.
l
against S. aureus and E. coli respectively. Compounds 5a and 5c
exerted wide range of antibacterial and antifungal activities
against the entire tested stains. 5b and 5e (MIC, 12.5 lg/mL)
displayed very good antifungal activities against C. albicans and
NMR were recorded in CDCl3 and DMSO-d6 on a BRUKER ADVANCE
II 400 NMR spectrometer using tetramethylsilane (TMS) as an
internal standard (chemical shift in d, ppm). Mass spectra were
recorded on a WATERS, Q-TOF MICROMASS (LC-MS) instrument.
The elemental analyses of the compounds were performed on Euro
EA 3000 Elemental Analyzer. X-ray diffraction was performed on X
Calibur EOS OXFORD Diffractometer. The percentage composition
of the mixture of diastereoisomers 3a and b and 4a and b was
determined by Breeze HPLC system and reported as Fig. S1 of the
Supplementary material. The structures were optimised by molec-
ular mechanics using PM3 method based on Hyperchem with ver-
sion 7.5 packages. 1-Tetralone and 6-methoxy-1-tetralone were
procured from Sigma and were used without purification.
A. fumigates.
Experimental
Melting points were determined in sulphuric acid bath and are
reported uncorrected. TLC was performed on silica gel G plates
using petroleum ether-ethyl acetate (4:1) as eluent and iodine
vapours as visualising agent. IR spectra were recorded on ABB FTIR
spectrometer and the results are reported in cmꢁ1. 1H NMR and 13
C

D. Gautam, R.P. Chaudhary / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 135 (2015) 219–226
223
to half and kept overnight. The solid obtained was filtered and
washed with ice cold ethanol. Recrystallization from 95% ethanol
furnished a pure mixture of two diastereoisomers.
(3S, 3aS)-3-Phenyl-3,3a,4,5-tetrahydro-2H-benzo[g]indazole-2-
carboxamide (3a)
White solid; yield 55%; mp: 238–40 °C; IR (cmꢁ1): 3483, 3276,
3215 (NH), 1684 (C@O), 1571 (C@N); 1H NMR (400 MHz, DMSO-
d6): d 0.81–0.85 (m, 1H, CH2), 1.72–1.76 (m, 1H, CH2), 2.87–2.92
(m, 1H, CH2), 3.15–3.19 (m, 1H, CH2), 3.72–3.75 (m, 1H, H-3a),
5.50–5.43 (d, 1H, H-3, J = 10.9 Hz), 6.48 (br, 2H, NH2), 7.0–7.2 (d,
2H, C6H5, J = 7.16 Hz), 7.17–7.33 (m, 6H, C6H5), 7.98–8.0 (m, 1H,
C6H5); 13C NMR (100 MHz, DMSO-d6): d 154.6, 151.6, 139.1,
138.3, 129.8, 128.2, 127.3, 126.4, 125.7, 124.2, 62.8, 61.2, 60.6,
48.1, 28.5, 23.5, 15.3; MS m/z 292.2 (M+H+) 80%. Anal. Calc. for
C18H17N3O: C, 74.20; H, 5.88; N, 14.42; Found: C, 74.36; H, 5.97;
N, 14.68%.
(3S, 3aS)-3-Phenyl-3,3a,4,5-tetrahydro-2H-benzo[g]indazole-2-
carbothioamide (3b)
Light yellow crystals; yield 65%; mp: 208–210 °C; IR (cmꢁ1):
3443, 3263, 3144 (NH), 1590 (C@N), 1347(C@S); 1H NMR
(400 MHz, DMSO-d6): d 0.8–0.91 (m, 1H, CH2), 1.78–1.82 (m, 1H,
CH2), 2.78–2.94 (m, 2H, CH2), 3.73–3.80 (m, 1H, H-3a), 6.05–6.08
(d, 1H, H-3, J = 10.6 Hz), 7.01–7.03 (d, 2H, C6H5, J = 7.28 Hz),
7.16–7.35 (m, 6H, C6H5), 7.49 (br, 1H, NH2), 7.81 (br, 1H, NH2),
8.06–8.08 (d, 1H, C6H5, J = 7.68 Hz); 13C NMR (100 MHz, DMSO-
d6): d 178.4, 175.4, 156.1, 155.1, 143.4, 139.8, 137.4, 130.6, 128.9,
126.9, 125.9, 124.8, 69.6, 48.2, 28.6, 27.5, 23.7, 18.3; MS m/z
308.1 (M+H+) 40%. Anal. Calc. for C18H17N3S: C, 70.33; H, 5.57; N,
13.67; S, 10.43; Found: C, 70.58; H, 5.77; N, 13.87; S, 10.67%.
Fig. 4. Optimised structure of 6a.
General procedure for synthesis of 2
Compound 2 is prepared by refluxing a mixture of 1-tetralone
and aromatic aldehyde in aq. NaOH by the reported [20] procedure.
(E)-2-benzylidene-3,4-dihydronaphthalen-1(2H)-one (2a)
Greyish white solid; yield 82%; mp 103–05 °C; (Lit. [20] mp
105 °C); IR (cmꢁ1): 1705 (C@O); 1H NMR (400 MHz, DMSO-d6): d
2.93–2.97 (t, 2H, CH2, J = 6.08 Hz), 3.12–3.16 (t, 2H, CH2,
J = 6.88 Hz), 7.24–7.26 (m, 1H, ArAH), 7.33–7.51 (m, 8H, ArAH),
7.87 (s, 1H, @CH). MS m/z 235 (M+H+) 100%.
(3S,3aS)-3-(4-Chlorophenyl)-3,3a,4,5-tetrahydro-2H-
benzo[g]indazole-2-carbothioamide (3c)
Yellow solid; yield 62%; mp: 178–80 °C; IR (cmꢁ1): 3435, 3212,
3119 (NH), 1598 (C@N), 1246 (C@S); 1H NMR (400 MHz, DMSO-
d6): d 0.81–0.85 (m, 1H, CH2), 1.77–1.81 (m, 1H, CH2), 2.82–2.93
(m, 2H, CH2), 3.76–3.83 (m, 1H, H-3a), 6.03–6.06 (d, 1H, H-3,
J = 10.7 Hz), 7.01–7.03 (d, 2H, C6H5, J = 7.76 Hz), 7.17–7.66 (m,
4H, C6H5), 7.94 (br, 1H, NH2), 8.03 (br, 1H, NH2), 8.06–8.08 (d,
2H, C6H5, J = 7.68 Hz); 13C NMR (100 MHz, DMSO-d6): d 175.4,
156.0, 155.0, 142.3, 139.8, 136.5, 131.8, 130.6, 128.9, 127.5,
126.5, 124.8, 69.0, 65.7, 48.1, 28.6, 27.3, 23.8; MS m/z 342.1
(M+1) 100%, 344 (M+3) (32%). Anal. Calc. for C18H16ClN3S: C,
63.24; H, 4.72; N, 12.29; S, 9.38; Found: C, 63.46; H, 4.82; N,
12.54; S, 9.49%.
(E)-2-(4-chlorobenzylidene)-3,4-dihydronaphthalen-1(2H)-one (2b)
White solid; yield 86%; mp 128–32 °C; (Lit. [20] mp 134 °C); IR
(cmꢁ1): 1702 (C@O); 1H NMR (400 MHz, DMSO-d6): d 2.92–2.94 (t,
2H, CH2, J = 6.86 Hz), 3.12–3.14 (t, 2H, CH2, J = 6.74 Hz), 7.01–7.03
(d, 2H, C6H5, J = 7.76 Hz), 7.34–7.42 (m, 5H, ArAH), 7.92 (s, 1H,
@CH), 8.11–8.13 (d, 1H, ArAH, J = 7.34 Hz).
(E)-2-benzylidene-6-methoxy-3,4-dihydronaphthalen-1(2H)-one (2c)
Light brown solid; yield 88%; mp 100–02 °C; IR (cmꢁ1): 1712
(C@O); 1H NMR (400 MHz, CDCl3): d 2.90–2.93 (t, 2H, CH2,
J = 6.76 Hz), 3.09–3.11 (t, 2H, CH2, J = 6.8 Hz), 3.87(s, 3H, OCH3),
6.70–6.71(d, 1H, ArAH, J = 2.44 Hz), 6.86–6.89 (m, 1H, ArAH),
7.34–7.42 (m, 5H, ArAH), 7.83 (s, 1H, @CH), 8.11–8.13 (d, 1H,
ArAH, J = 8.7 Hz).
(3S,3aS)-7-Methoxy-3-phenyl-3,3a,4,5-tetrahydro-2H-
benzo[g]indazole-2-carbothioamide (3d)
Light brown solid; yield 72%; mp: 160–62 °C; IR (cmꢁ1): 3470,
3204, 3146 (NH), 1590 (C@N), 1250 (C@S); 1H NMR (400 MHz,
DMSO-d6): d 0.81–0.86 (m, 1H, CH2), 1.77–1.80 (m, 1H, CH2),
2.54–2.56 (m, 2H, CH2), 3.69–3.75 (m, 1H, H-3a), 3.79 (s, 3H,
OCH3), 6.02–6.04 (d, 1H, H-3, J = 10.5 Hz), 6.69 (d, 1H, C6H5,
J = 2.32 Hz), 6.79–6.90 (m, 1H, C6H5), 7.01–7.03 (d, 2H, C6H5,
J = 7.28 Hz), 7.19–7.29 (m, 3H, C6H5), 7.44 (br, 1H, NH2), 7.70 (br,
1H, NH2), 7.98–7.99 (d, 1H, C6H5, J = 2.96 Hz); 13C NMR (DMSO-
d6): d 178.3, 161.2, 156.2, 147.8, 142.0, 137.5, 128.2, 126.8, 125.7,
124.4, 119.1, 113.4, 69.4, 66.1, 55, 48.3, 29.2, 25.6, 21.3; MS m/z
338.1 (M+H+) 100%. Anal. Calc. for C19H19N3OS: C, 67.63; H, 5.68;
N, 12.45; S, 9.50; Found: C, 67.91; H, 5.79; N, 12.68; S, 9.63%.
(E)-2-(4-chlorobenzylidene)-6-methoxy-3,4-dihydronaphthalen-
1(2H)-one (2d)
White solid; yield 90%; mp 125–27 °C; IR (cmꢁ1): 1715 (C@O);
1H NMR (400 MHz, DMSO-d6): d 2.95–2.98 (t, 2H, CH2, J = 6.84 Hz),
3.10–3.12 (t, 2H, CH2, J = 6.92 Hz), 3.9 (s, 3H, OCH3), 6.88–6.9
(m, 1H, ArAH), 7.38–7.44 (m, 5H, ArAH), 7.86 (s, 1H, @CH),
8.14–8.16 (d, 1H, ArAH, J = 7.86 Hz).
General procedure for synthesis of (3a–e)
To a solution of 2-benzylidene-3,4-dihydronaphthalen-1(2H)-
ones
2
(1.0 mol) and semicarbazide or thiosemicarbazide
(1.0 mol) in absolute ethanol (20 mL), 1.0 g of KOH was added
and the reaction mixture was heated at 70–80 °C for 3–4 h. The
progress of the reaction was monitored by TLC. After completion
of the reaction, the volume of the reaction mixture was reduced
(3S,3aS)-3-(4-Chlorophenyl)-7-methoxy-3,3a,4,5-tetrahydro-2H-
benzo[g]indazole-2-carbothioamide (3e)
White solid; yield 68%; mp: 182–84 °C; IR (cmꢁ1): 3441,
3215, 3125 (NH), 1602 (C@N), 1276 (C@S); 1H NMR (400 MHz,

224
D. Gautam, R.P. Chaudhary / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 135 (2015) 219–226
Table 3
Experimental and calculated 1H NMR and 13C NMR chemical shifts (ppm) of 5a and 6a.
Entry
CH2
CH2
H-3a
H-3
SCH2
ArAH
R2
1H NMR
Expt. (5a)
Calcd. (5a)
Calcd. (6a)
0.91
2.80
3.96
2.88
2.54
5.93
5.15
4.29
3.88
7.54
0.97a
1.67a
2.45a
2.55a
3.07a
3.04a
7.37a
7.43a
0.9561
0.8158
C@N
SC@N
C-3
C@O
C-3a
–
R2
13C NMR
Expt. (5a)
Calcd. (5a)
Calcd. (6a)
177.19
166.34
164.89
186.55
189.55
191.80
66.83
61.87
64.88
180.75
185.86
186.18
49.28
46.09
54.55
–
–
–
0.9898
0.9827
a
Average value.
161.3, 156.1, 142.0, 136.5, 131.8, 128.1, 127.5, 126.6, 119.0,
113.5, 112.7, 65.5, 48.2, 28.9, 23.8; MS m/z 372.1 (M+1) 100%,
374 (M+3) (38%). Anal. Calc. for C19H18ClN3OS: C, 61.36; H, 4.88;
N, 11.30; S, 8.62; Found: C, 61.68; H, 4.98; N, 11.58; S, 8.76%.
Structure 5a
Structure 6a
B3LYP/6-31G**
R2 (Structure 5a) = 0.95613
R2 (Structure 6a) = 0.81587
8
7
6
5
4
3
2
1
0
(3R,3aS)-3-Phenyl-3,3a,4,5-tetrahydro-2H-benzo[g]indazole-2-
carboxamide (4a)
White solid; Yield 46%; mp: >250 °C; IR (cmꢁ1): 3476, 3248,
3205 (NH), 1668 (C@O), 1580(C@N); 1H NMR (400 MHz, DMSO-
d6): 1.89–1.93 (m, 1H, CH2), 2.13–2.16 (m, 1H, CH2), 2.87–2.92
(m, 2H, CH2), 3.12–3.19 (m, 1H, H-3a), 4.79–4.82 (d, 1H, H-3,
J = 11.1 Hz), 6.51 (br, 2H, NH2), 7.23–7.37 (m, 8H, C6H5), 7.90–
7.92 (m, 1H, C6H5); 13C NMR (100 MHz, DMSO-d6): d 162.1,
156.9, 152.1, 143.0, 139.3, 129.1, 128.3, 127.1, 125.8, 124.2, 99.5,
67.8, 61.1, 55.1, 15.0; MS m/z 292.2 (M+H+) 80%. Anal. Calc. for
C18H17N3O: C, 74.20; H, 5.88; N, 14.42; Found: C, 74.36; H, 5.92;
N, 14.68%.
0
1
2
3
4
5
6
7
8
1
Experimental H NMR shifts (ppm)
General procedure for the synthesis of 5(a–h)
Fig. 5. Plot of the calculated vs. experimental 1H NMR chemical shifts (ppm) of 5a
and its trans isomer 6a.
An equimolar mixture of 3b–e (0.001 mol), chloroacetic acid or
2-bromopropionic acid (0.001 mol) and anhydrous sodium acetate
(0.16 g, 0.002 mol) in ethanol (10 mL) was heated under reflux for
4–5 h. The progress of the reaction was monitored by TLC. After
completion of the reaction volume of the reaction mixture was
reduced to half under vacuum and kept overnight. The solid, thus
obtained was filtered, dried and recrystallized from ethanol-DMF
mixture (3:1).
Structure 5a
Structure 6a
B3LYP/6-31G**
R2 (Structure 5a) = 0.98985
R2 (Structure 6a) = 0.98276
200
180
160
140
120
100
80
2-[(3S,3aS)-3-phenyl-3,3a,4,5-tetrahydro-2H-benzo[g]indazol-2-
yl]thiazol-4(5H)-one (5a)
Yellow crystalline solid; yield: 64%; mp: 258–60 °C; IR (cmꢁ1):
1697 (C@O), 1589 (C@N); 1H NMR (400 MHz, DMSO-d6): d 0.90–
0.94 (m,1H, CH2), 1.80–1.84 (m, 1H, CH2), 2.79–3.01 (m, 2H, CH2),
3.88 (s, 2H, SCH2), 3.95–4.02 (m, 1H, H-3a), 5.92–5.95 (d, 1H, H-
3, J = 10.5 Hz), 7.06–7.08 (d, 2H, C6H5, J = 7.12 Hz), 7.25–7.43 (m,
6H, C6H5), 8.02–8.04 (dd, 1H, C6H5, J = 6.68 Hz, J = 1.08 Hz); 13C
NMR (100 MHz, DMSO-d6): d 186.5 (C@N), 180.7 (C@O), 177.1
(C@N), 161.1, 140.3, 135.3, 135.1, 131.5, 129.0, 128.5, 127.7,
126.6, 125.7, 125.1, 66.8, 49.2, 28.5, 23.7; MS m/z 348 (M+H)+
(54%). Anal. Calc. for C20H17N3SO: C, 69.14; H, 4.93; N, 12.09; S,
9.23; Found: C, 69.04; H, 4.89; N, 11.98; S, 9.12.
60
40
40
60
80
100
120
140
160
180
200
Experimental 13C NMR Shifts (ppm)
Fig. 6. Plot of the calculated vs. experimental 13C NMR chemical shifts (ppm) of 5a
and its trans isomer 6a.
5-Methyl-2-[(3S,3aS)-3-phenyl-3,3a,4,5-tetrahydro-2H-
benzo[g]indazol-2-yl]thiazol-4(5H)-one (5b)
DMSO-d6): d 0.77–0.86 (m, 1H, CH2), 1.76–1.79 (m, 1H, CH2), 2.75–
2.91 (m, 2H, CH2), 3.70–3.78 (m, 1H, H-3a), 3.80 (s, 3H, OCH3),
6.00–6.03 (d, 1H, H-3, J = 10.6 Hz), 6.71–6.76 (m, 1H, C6H5), 6.83–
6.86 (m, 1H, C6H5), 7.00–7.02 (d, 2H, C6H4, J = 7.88 Hz), 7.24–7.33
(m, 2H, C6H5), 7.54 (br, 1H, NH2), 7.91 (br, 1H, NH2), 7.98–7.99
(d, 1H, C6H4, J = 3.72 Hz); 13C NMR (100 MHz, DMSO-d6): d 175.0,
White solid; yield: 62%; mp: 218–20 °C; IR (cmꢁ1): 1705 (C@O),
1594 (C@N); 1H NMR (400 MHz, DMSO-d6): d 0.82–0.88 (m,1H,
CH2), 1.48–1.53 (d, 3H, CH3, J = 7.28 Hz), 1.77–1.81 (m, 1H, CH2),
2.82–2.91 (m, 2H, CH2), 3.97–4.05 (m, 1H, H-3a), 4.12–4.17 (q,
1H, SCHCH3, J = 7.12 Hz), 5.93–5.95 (d, 1H, H-3, J = 10.8 Hz), 7.06–
7.08 (d, 2H, C6H5, J = 7.4 Hz), 7.24–7.45 (m, 6H, C6H5), 7.98–8.0

D. Gautam, R.P. Chaudhary / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 135 (2015) 219–226
225
Table 4
Antibacterial and antifungal activities of compounds 5(a–h).
2-[(3S,3aS)-7-methoxy-3-phenyl-3,3a,4,5-tetrahydro-2H-
benzo[g]indazol-2-yl]thiazol-4(5H)-one (5e)
Light yellow solid; yield: 84%; mp: 208–10 °C; IR (cmꢁ1): 1705
(C@O), 1594 (C@N); 1H NMR (400 MHz, DMSO-d6): d 0.86–0.91 (m,
1H, CH2), 1.79–1.83 (m, 1H, CH2), 2.76–2.98 (m, 2H, CH2), 3.77 (s,
3H, OCH3), 3.82 (s, 2H, SCH2), 3.89–3.96 (m, 1H, H-3a), 5.88–5.91
(d, 1H, H-3, J = 10.4 Hz), 6.76 (s, 1H, C6H5), 6.88–6.91 (m, 1H,
C6H5), 7.06–7.07 (m, 2H, C6H5), 7.27–7.34 (m, 4H, C6H5); 13C
NMR (100 MHz, DMSO-d6): d 186.4 (C@O), 176.5, 161.9 (C@N),
142.6, 135.3, 128.9, 127.6, 125.7, 118.3, 113.8, 112.8, 66.6, 55.1,
49.3, 35.8, 30.7, 28.9, 23.6; MS m/z 378 (M+H)+ (100%). Anal. Calc.
for C21H19N3O2S: C, 66.82; H, 5.07; N, 11.13; S, 8.49. Found: C,
66.74; H, 4.99; N, 11.01; S, 8.32
2-[(3S,3aS)-7-methoxy-3-phenyl-3,3a,4,5-tetrahydro-2H-
benzo[g]indazol-2-yl]-5-methylthiazol-4(5H)-one (5f)
Orange crystalline solid; yield: 80%; mp: 218–20 °C; IR (cmꢁ1):
1697 (C@O), 1602 (C@N); 1H NMR (400 MHz, DMSO-d6): d 0.79–
0.81 (m,1H, CH2), 1.49–1.50 (d, 3H, CH3, J = 7.28 Hz), 1.78–1.82
(m, 1H, CH2), 2.88–2.94 (m, 2H, CH2), 3.80 (s, 3H, OCH3), 3.91–
3.98 (m, 1H, H-3a), 4.08–4.13 (q, 1H, SCHCH3, J = 7.24 Hz), 5.89–
5.91 (d, 1H, H-3, J = 10.4 Hz), 6.77–6.78 (m, 1H, C6H5), 6.89–6.91
(m, 1H, C6H5), 7.05–7.07 (m, 2H, C6H5), 7.25–7.35(m, 3H, C6H5),
7.95–7.95(m, 1H, C6H5); 13C NMR (100 MHz, DMSO-d6): d 189.2
(C@O), 175.0, 162.0 (C@N), 135.5, 128.5, 127.6, 125.8, 118.3,
113.8, 112.9, 66.4, 55.2, 49.2, 48.8, 35.8, 30.7, 28.9, 23.7, 18.8; MS
m/z 392 (M+H)+ (100%). Anal. Calc. for C22H21N3O2S: C, 67.50; H,
5.41; N, 10.73; S, 8.19. Found: C, 67.48; H, 5.28; N, 10.71; S, 8.08.
Antimicrobial activity (MIC in
l
g/mL)
E. coli P.
aeruginosa
Entry
S.
A.
niger
C.
A.
aureus
albicans
fumigates
5a
50
50
25
25
25
12.5
25
12.5
12.5
25
6.25
–
25
25
12.5
25
12.5
12.5
50
50
50
–
6.25
25
12.5
50
25
12.5
50
50
50
–
6.25
5b
5c
25
25
6.25
25
12.5
12.5
12.5
25
12.5
12.5
12.5
–
5d
5e
12.5
25
12.5
25
5f
5g
6.25
25
25
25
5h
Cipro
Miconazole
12.5
6.25
–
12.5
6.25
–
6.25
2-[(3S,3aS)-3-(4-chlorophenyl)-7-methoxy-3,3a,4,5-tetrahydro-2H-
benzo[g]indazol-2-yl]thiazol-4(5H)-one (5g)
(d, 1H, C6H5, J = 7.08 Hz); 13C NMR (100 MHz, DMSO-d6): d 189.3
(C@O), 175.4, 160.9 (C@N), 140.5, 135.5, 131.6, 129.1, 128.6,
127.7, 126.7, 125.8, 125.7, 125.0, 66.7, 49.2, 48.8, 28.5, 23.7, 18.8;
MS m/z 362 (M+H)+ (100%). Anal. Calc. for C21H19N3SO: C, 69.78;
H, 5.30; N, 11.63; S, 8.87; Found: C, 69.88; H, 5.39; N, 11.78; S, 8.98.
Yellow solid; yield: 68%; mp: 210–12 °C; IR (cmꢁ1): 1702
(C@O), 1610 (C@N); 1H NMR (400 MHz, DMSO-d6): d 0.86–0.94
(m, 1H, CH2), 1.79–1.83 (m, 1H, CH2), 2.75–2.97 (m, 2H, CH2),
3.82 (s, 3H, OCH3), 3.86 (s, 2H, SCH2), 3.91–3.99 (m, 1H, H-3a),
5.90–5.93 (d, 1H, H-3, J = 10.5 Hz), 6.81–6.82 (m, 1H, C6H5), 6.88–
6.91 (m, 1H, C6H5), 7.07–7.10 (m, 1H, C6H5), 7.33–7.40 (m, 2H,
C6H5), 7.93–7.95 (m, 2H, C6H5); 13C NMR (100 MHz, DMSO-d6): d
186.3 (C@O), 162.0, 160.6 (C@N), 142.6, 134.4, 132.6, 128.5,
127.6, 118.2, 113.8, 112.9, 65.9, 55.2, 49.2, 35.8, 30.7, 28.9, 23.7;
MS m/z 412 (M+1) (100%), 414 (M+3) (38%). Anal. Calc. for C21H18-
ClN3O2S: C, 61.23; H, 4.40; N, 10.20; S, 7.78. Found: C, 67.38; H,
5.18; N, 10.68; S, 7.98.
2-[(3S,3aS)-3-(4-chlorophenyl)-3,3a,4,5-tetrahydro-2H-
benzo[g]indazol-2-yl]thiazol-4(5H)-one (5c)
Greyish solid; yield: 78%; mp: 238–40 °C; IR (cmꢁ1): 1707
(C@O), 1605 (C@N); 1H NMR (400 MHz, DMSO-d6): d 0.89–0.92
(m, 1H, CH2), 1.79–1.82 (m, 1H, CH2), 2.51–2.53 (m, 2H, CH2),
3.85 (s, 2H, SCH2), 3.98–4.05 (m, 1H, H-3a), 5.94–5.97 (d, 1H, H-
3, J = 10.6 Hz), 7.09–7.11 (d, 2H, C6H5, J = 8.12 Hz), 7.24–7.45 (m,
5H, C6H5), 7.99–8.01 (d, 1H, C6H5, J = 6.72 Hz); 13C NMR
(100 MHz, DMSO-d6): d 186.4 (C@O), 177.1, 160.8 (C@N), 140.4,
134.4, 132.6, 131.6, 129.1, 128.6, 127.7, 126.7, 125.6, 66.1, 49.2,
28.5, 23.7; MS m/z 382 (M + 1) (100%), 384 (M + 3) (28%). Anal.
Calc. for C20H16ClN3OS: C, 62.90; H, 4.22; N, 11.00; S, 8.40. Found:
C, 62.84; H, 4.19; N, 10.98; S, 8.32.
2-[(3S,3aS)-3-(4-chlorophenyl)-7-methoxy-3,3a,4,5-tetrahydro-2H-
benzo[g]indazol-2-yl]-5-methylthiazol-4(5H)-one (5h)
Orange solid; yield: 80%; mp: 162–64 °C. IR (cmꢁ1): 1705
(C@O), 1598 (C@N); 1H NMR (400 MHz, DMSO-d6): d 0.84–0.89
(m,1H, CH2), 1.48–1.49 (d, 3H, CH3, J = 7.3 Hz), 1.77–1.85 (m, 1H,
CH2), 2.75–2.91 (m, 2H, CH2), 3.81 (s, 3H, OCH3), 3.91–3.98 (m,
1H, H-3a), 4.05–4.11 (q, 1H, SCHCH3, J = 7.22 Hz), 5.90–5.93 (d,
1H, H-3, J = 10.4 Hz), 6.71–6.72 (m, 1H, C6H5), 6.77–6.80 (m, 1H,
C6H5), 6.89–6.92(m, 1H, C6H5), 7.07–7.09 (d, 1H, C6H5,
J = 8.08 Hz), 7.35–7.38 (m, 1H, C6H5), 7.89–7.92 (d, 1H, C6H5,
J = 8.72 Hz), 8.02–8.04 (d, 1H, C6H5, J = 8.8 Hz); 13C NMR
(100 MHz, DMSO-d6): d 189.2 (C@O), 176.5, 160.7 (C@N), 142.7,
132.6, 128.6, 126.9, 124.9, 118.2, 112.9, 55.2, 41.6, 29.5, 26.8,
21.8, 18.9; MS m/z 426 (M+1) (100%), 428 (M+3) 32%. Anal. Calc.
for C22H20ClN3O2S: C, 62.04; H, 4.73; N, 9.87; S, 7.53. Found: C,
62.08; H, 4.68; N, 9.78; S, 7.48.
2-[(3S,3aS)-3-(4-chlorophenyl)-3,3a,4,5-tetrahydro-2H-
benzo[g]indazol-2-yl]-5-methylthiazol-4(5H)-one (5d)
Greyish solid; yield: 72%; mp: 218–20 °C; IR (cmꢁ1): 1695
(C@O), 1595 (C@N); 1H NMR (400 MHz, DMSO-d6): d 0.86–0.95
(m,1H, CH2), 1.49–1.51 (d, 3H, CH3, J = 7.24 Hz), 1.79–1.83 (m,
1H, CH2), 2.76–3.00 (m, 2H, CH2), 3.97–4.05 (m, 1H, H-3a), 4.11–
4.18 (q, 1H, SCHCH3, J = 7.68 Hz, J = 7.32 Hz), 5.93–5.97 (d, 1H, H-
3, J = 10.6 Hz), 7.08–7.10 (d, 2H, C6H5, J = 8.0 Hz), 7.24–7.44 (m,
5H, C6H5), 7.98–8.0 (d, 1H, C6H5, J = 7.48 Hz); 13C NMR (100 MHz,
DMSO-d6): d 189.3 (C@O), 175.5, 160.8 (C@N), 140.4, 139.4,
132.6, 131.6, 129.1, 128.6, 127.7, 126.6, 125.6, 65.9, 49.1, 48.9,
28.5, 23.7, 18.7; MS m/z 396 (M+H)+ (100%). Anal. Calc. for C21H18-
ClN3OS: C, 63.71; H, 4.58; N, 10.61; S, 8.10. Found: C, 63.74; H,
4.49; N, 10.58; S, 8.02.
Conclusion
All the newly synthesised indazolyl-thiazol-4(5H)-ones have
been characterised by 1H NMR, 13C NMR, mass and IR studies.

226
D. Gautam, R.P. Chaudhary / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 135 (2015) 219–226
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It is evidenced that some compounds have emerged as potent anti-
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Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.saa.2014.06.134.
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