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Visible-light-mediated difunctionalization
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Cite this: Green Chem., 2015, 17,

of styrenes: an unprecedented approach
3515 to 5-aryl-2-imino-1,3-oxathiolanes†
Arvind K. Yadav and Lal Dhar S. Yadav*

Received 25th March 2015,
Accepted 21st April 2015
DOI: 10.1039/c5gc00642b
www.rsc.org/greenchem
The visible-light-induced straightforward synthesis of 5-aryl-2-imino-1,3-oxathiolanes from styrenes and
ammonium thiocyanate is reported. The protocol utilizes air (O2) and visible light as green reagents and
eosin Y as an organophotoredox catalyst. The reaction involves the formation of C–S bonds followed by
intramolecular C–O heterocyclization in a one-pot procedure at room temperature.

Introduction However, the utilization of Ru(II) and Ir(II) complexes suffers

Air, water and light are the frontiers in green chemistry,
because these are eco-sustainable, clean, cheap and unending
resources. Recently, visible-light-photoredox catalysis has
offered a new platform to synthetic organic chemists for the
construction of C–C and C–X (X = N, O, S, and P) bonds.1 In
this area, the seminal work reported by the research groups of
MacMillan et al.,2a Yoon et al.2b and Stephenson et al.3
has demonstrated that the use of photocatalysts such as
Ru(bpy)3Cl2 (bpy = 2,2′-bipyridine) and Ir(dtbbpy)3Cl2 (dtbbpy =
4,4′-di-tert butyl-2,2′-bipyridine) is capable of initiating power-
ful transformations, both for the target oriented and method
driven organic synthesis.1 Moreover, the field of visible-light-
photoredox catalysis is attractive because it has the capability
of dioxygen (air) activation. Dioxygen is not only a green
oxidant but is also an ideal oxygen source for the functionali-
zation of organic molecules. Seeking dioxygen activation by
organic molecules is an interesting and sustainable approach
for the green synthesis of fine chemicals, particularly in the
pharmaceutical industry.4 In photoredox chemistry, it has
been mostly employed as an acceptor to regenerate photocata-
lysts (PC) from their radical anion PC•−, which is formed in
the catalytic cycle via the excited state (PC*) by single electron
transfer (SET) from a donor. The PC•− completes the catalytic
cycle by the formation of the superoxide radical (O2•−).1–3 The
superoxide radical (O2•−) formed in the photoredox cycle of Ru(II),
Ir(II) complexes or eosin Y are utilized in situ for oxidation
purposes in synthetic processes.
from disadvantages such as potential toxicity, low sustainabil-
ity, high cost and problematic removal of their undesirable
traces from products, particularly in the case of drugs and
drug intermediates. Similar to the chemistry of Ru(II) and Ir(II),
eosin Y (EY), which is a long known dye, is an attractive
alternative to typical inorganic transition metal photocatalysts
and has recently been widely applied as a photoredox catalyst
in organic synthesis by several research groups5 including ours.6
The 1,3-oxathiole core is present in various pharmaceutical
products7b,e and biologically active compounds.7a–d For
example, a number of 1,3-oxathiol-2-one derivatives have been
studied for their antibacterial, tuberculostatic and antifungal
activities,7c–f whereas some oxathiolones are used as neuro-
protective agents.7b Similarly, 2-arylimino-1,3-oxathiole derivatives
have been found to exhibit potential pharmaceutical and bio-
chemical activities.7d–g Of these, compound A is a useful agro-
chemical pesticide and compound B might possess fungicidal
activity (Fig. 1).7,8
Very few methods are available in the literature for the syn-
thesis of 2-imino-1,3-oxathioles.8 Most of them have one or
more limitations such as the use of special or expensive metal
catalysts and reagents, unsatisfactory efficiencies, tedious multi-
step manipulations and narrow scopes. Compounds that
incorporate a 2-imino-1,3-oxathiolane system are associated
with potential bioactivities.7e,f Moreover, the presence of a free

Green Synthesis Lab, Department of Chemistry, University of Allahabad, Allahabad-

211002, India. E-mail: ldsyadav@hotmail.com; Fax: +91 5322460533;
Tel: +91 5322500652
† Electronic supplementary information (ESI) available: Experimental details and
copies of 1H and 13C spectra for the products. See DOI: 10.1039/c5gc00642b Fig. 1 Biologically active 2-imino-1,3-oxathiolanes.

This journal is © The Royal Society of Chemistry 2015 Green Chem., 2015, 17, 3515–3520 | 3515
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Paper Green Chemistry

Table 1 Optimisation of reaction conditionsa

Time Yieldb
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Entry Catalyst (mol%) Solvent (h) (%)

1 Eosin Y (2) CH3CN 12 92

2 Rose bengal (2) CH3CN 12 72
3 Eosin Y (2) EtOH 12 63
4 Eosin Y (2) DMF 12 78
5 Eosin Y (2) DMSO 12 86
6 Eosin Y (1) CH3CN 12 67
7 Eosin Y (3) CH3CN 12 92
8 Eosin Y (2) CH3CN 24 Tracesc
Scheme 1 Synthesis of 5-aryl-2-imino-1,3-oxathiolanes. 9 Eosin Y (2) CH3CN 24 Tracesd
10 — CH3CN 24 n.d.e
11 Eosin Y (2) CH3CN 24 Traces f
12 Eosin Y (2) CH3CN 24 58g
13 Eosin Y (2) CH3CN 24 62h
imino (vNH) group would allow several synthetically impor- 14 Eosin Y (2) CH3CN 12 92i
tant functional group manipulations in 2-imino-1,3-oxathiol- 15 Eosin Y (2) CH3CN 12 89 j
anes. To the best of our knowledge, the literature records only a
Reaction conditions: 1a (1.0 mmol), NH4SCN (1.0 mmol), catalyst
one method for the synthesis of 2-imino-1,3-oxathiolanes (mol%), in 3 mL solvent irradiated using Luxeon Rebel high power
green LEDs [2.50 W, λ = 535 nm] under atmosphere at rt for 12–24 h.
bearing a free imino (vNH) group, which involves the conver- b
Isolated yield of the pure product 2a. c Reaction was performed under
sion of phenacyl bromides into phenacyl thiocyanates followed nitrogen. d Reaction was performed in the dark. e Reaction was carried
by their reduction with NaBH4 and subsequent cyclization out without a catalyst. f Reaction was quenched with 2,2,6,6-
tetramethylpiperidyl-1-oxyl (TEMPO (1.0 mmol). g 18 W CFL (compact
(Scheme 1a).8a However, the most serious drawbacks of this
fluorescent lamp, Philips) was used. h KSCN was used instead of
method are the utilization of hazardous (highly lachrymator NH4SCN. i O2 balloon was used. j The reaction was not quenched with
and toxic) phenacyl bromides as the starting material and the DABCO (1.0 mmol).
need for a reduction step, which reduces cost effectiveness and
produces additional waste.
Thus, the development of a convenient and eco-sustainable
method for the synthesis of 2-imino-1,3-oxathiolanes will be a tion, because in the absence of any of the reagents/reaction
valuable contribution to this class of heterocycles. In view of parameters either the product was not detected (n.d.) or was
the abovementioned points and our recent research, which is formed in trace amounts (Table 1, entry 1 versus 8–10). The
focused on the functionalization of alkenes6c,9a–d and alky- optimum amount of eosin Y required for the reaction was
nes,9e,f we report herein the novel synthesis of 2-imino-1,3- 2 mol%. On decreasing the amount of eosin Y from 2 mol% to
oxathiolanes from styrenes and NH4SCN. The method is con- 1 mol%, the yield was considerably reduced (Table 1, entry 6),
siderably more advantageous in terms of green and sustain- whereas the yield was not enhanced even with the use of
able chemistry than the available method8a because it (i) uses 3 mol% of eosin Y (Table 1, entry 7). The use of another organic
styrenes as the substrate instead of highly lachrymator and photocatalyst such as rose bengal (2 mol%) was not as
toxic phenacyl bromides, (ii) has better atom- and pot- effective as eosin Y (2 mol%) (Table 1, entry 1 versus 2).
economy and (iii) utilizes the most inexpensive regents, which Green LEDs [2.50 W, λ = 535 nm] were more effective than
are visible light and atmospheric oxygen (Scheme 1b). fluorescent light (Table 1, entry 12), which shows the higher
photocatalytic activity of eosin Y in presence of high intensity
green light. The presence of O2 (air) is also essential for the
Results and discussion reaction because only a trace amount of product was detected
under a nitrogen atmosphere (Table 1, entry 8). Notably, the
In order to realise our idea and optimise the reaction con- same result was obtained on using O2 (balloon) instead in
ditions, the key reaction of styrene (1a) with NH4SCN was per- atmosphere (Table 1, entry 14). Moreover, the reaction was
formed using a catalytic amount of eosin Y in a solvent under quenched with 2,2,6,6-tetramethylpiperidyl-1-oxyl (TEMPO)
irradiation with green LEDs [2.50 W, λ = 535 nm] in open air (1.0 mmol) in its standard state, which shows that there may
(Table 1). We were delighted to get the desired product, 5-aryl- be radical intermediates involved in the reaction (Table 1,
2-imino-1,3-oxathiolanes (2a), in 92% yield (Table 1, entry 1). entry 11). Furthermore, the reaction was not quenched in the
Then, the control experiments were carried out, which show presence of DABCO (1.0 mmol) (Table 1, entry 15), which indi-
that eosin Y, air (O2) and visible light are essential for the reac- cates the involvement of triplet oxygen in the reaction.10

3516 | Green Chem., 2015, 17, 3515–3520 This journal is © The Royal Society of Chemistry 2015
 View Article Online

Green Chemistry Paper

Next, the reaction was optimized for an effective solvent

system and source of SCN ion. It was found that CH3CN was
the best among the tested solvents (EtOH, DMF, DMSO and
CH3CN), and hence it was used throughout the present study
(Table 1, entry 1 versus 3–5). With regards to the thiocyanate
ion sources, NH4SCN was better than KSCN (Table 1, entry 1
versus 13) in terms of yield and time.
Under the established reaction conditions, we surveyed the
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generality and scope of the present protocol across a range of

styrenes that incorporate various substituents such as Me,
MeO, NO2, Cl, Br, F and Me2N. The reaction worked well in all
the cases and afforded product 2 in good to excellent yields
(74–96%). However, styrene 1 with an electron-donating group
on the aromatic ring appears to react faster and afford margin-
ally higher yields in comparison to those bearing an electron-
Scheme 2 Plausible mechanism for the formation of 5-aryl-2-imino-
withdrawing group (Table 2, products 2b, 2c, 2j versus 2d–2i). 1,3-oxathiolanes 2.

The reaction did not work to produce 5-alkyl-2-imino-1,3-

Table 2 Substrate scopea
oxathiolanes in the case of aliphatic alkenes such as 1-hexene
and 1-heptene. This is probably because of the lower stability
of the alkyl free radicals formed after the attack of the thio-
cyanate radical on the aliphatic alkenes as compared to the
benzyl free radicals formed in the case of styrenes.
On the basis of our observations and the literature,6c,8a,11 a
plausible mechanistic pathway is depicted in Scheme 2. Eosin
Y (EY) upon absorption of light goes to its excited state (EY*).
Single electron transfer between SCN− and EY* affords •SCN
and EY•−.11a The photoredox cycle of eosin Y is completed by
the aerobic oxidation of EY•− to its ground state (EY). The
in situ generated thiocyanate radical attacks styrene 1 to form
intermediate A,6c which combines with O2 to form the peroxy
radical B,11b which reacts with A to give radical C.6c,11c The
alkoxy radical C is either reduced and protonated with O2•−/
NH4+ or abstracts hydrogen to form β-hydroxythiocyanate D.11e
Extremely fast cyclization of D affords the desired product 2.8a

Conclusion
In conclusion, we have disclosed a novel, one-pot procedure for
the synthesis of 5-aryl-2-imino-1,3-oxathiolanes from styrenes
and ammonium thiocyanate. The protocol utilizes atmospheric
oxygen and visible light as cheapest and eco-sustainable
reagents and eosin Y as an organophotoredox catalyst at room
temperature. Thus, it is a superior alternative to the existing
method with respect to green and sustainable chemistry (better
atom- and step-economy) for the synthesis of 5-aryl-2-imino-1,3-
oxathiolanes bearing a free imino (vNH) group.

a
Experimental section
Reaction conditions: 1 (1.0 mmol), NH4SCN (1.0 mmol), eosin Y
(2 mol%) in CH3CN (3 mL) irradiated using Luxeon Rebel high power green General information
LEDs [2.50 W, λ = 535 nm] in open air at rt for 12–18 h. b Isolated yield of
product 2. c For the general procedure and characterization of All commercially available reagents were used without further
compounds, see Experimental section and ESI. purification unless otherwise specified by a reference. Solvents

This journal is © The Royal Society of Chemistry 2015 Green Chem., 2015, 17, 3515–3520 | 3517

Paper
were purified by the usual methods and stored over molecular
sieves. All reactions were performed using oven-dried glass-
ware. Organic solutions were concentrated using a Buchi
rotary evaporator. Column chromatography was carried out
over silica gel (Merck 100–200 mesh) and TLC was performed
using silica gel GF254 (Merck) plates. IR spectra in KBr were
recorded using a Perkin-Elmer 993 IR spectrophotometer and
1
H (400 MHz), 13C (100 MHz) NMR spectra were recorded
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using a Bruker AVII spectrometer in CDCl3 using TMS as the
internal reference. All chemical shifts are reported in δ ( ppm)
and coupling constants ( J) in hertz (Hz). MS (EI) spectra were
recorded using a double focusing mass spectrometer. Green
LEDs (2.50 W, λ = 535 nm, Rebel LED), mounted on a 25 mm
cool base was purchased from commercial supplier Luxeon
Star LEDs Quadica Developments Inc. 47 6th Concession Rd.
Brantford, Ontario N 32 5L7 Canada.
General procedure for the synthesis of 5-aryl-2-imino-1,3-
oxathiolanes (Table 2)
A round bottom flask was charged with styrene 1 (1.0 mmol),
eosin Y (2 mol%), NH4SCN (1.0 mmol) and CH3CN (3 mL),
and the contents were stirred in open air under irradiation
with Luxeon Rebel high power green LEDs [2.50 W, λ =
535 nm] at room temperature for 12–18 h. After the completion
of reaction (as indicated by TLC), it was quenched with water
(5 mL) and extracted with ethyl acetate (3 × 5 mL). The organic
phase was dried over anhydrous magnesium sulfate and con-
centrated under reduced pressure to yield the crude product,
which was purified by silica gel column chromatography using
a mixture of EtOAc-Hexane to give the pure product 2 in high
yields (Table 2).
The structure of the products was confirmed by the com-
parison of IR, 1H, 13C NMR and MS spectral data with those
reported in the literature.8a
Characterization data of compound 2 are summarised
below with the relevant references:
Compound 2a.8a IR (KBr): 3165, 1693, 1642, 1585, 1490,
1284 cm−1; 1H NMR (CDCl3, 400 MHz): δ = 7.37–7.31 (m, 3H),
7.29 (d, 2H |3JHH| 9 Hz), 5.35 (s, 1H (vNH), 4.65 (dd, 1H
|3JHH| 9 Hz, |3JHH| 6 Hz), 3.60 (dd, 1H |2JHH| 11 Hz, |3JHH|
6 Hz), 3.42 (dd, 1H |2JHH| 11 Hz, |3JHH| 9 Hz); 13C NMR
(CDCl3, 100 MHz): δ = 168.7, 136.5, 128.7, 128.3, 125.2, 84.0,
39.3. HRMS (EI) calcd for C9H9NOS: 179.0405, found 179.0403.
Compound 2b. IR (KBr): 3153, 2922, 1687, 1637, 1570, 1387,
857, 672 cm−1; 1H NMR (CDCl3, 400 MHz): δ = 7.35 (d, 2H
|3JHH| 9 Hz), 7.20 (d, 2H |3JHH| 9 Hz), 5.60 (s, 1H (vNH), 5.56
(dd, 1H |3JHH| 9 Hz, |3JHH| 6 Hz), 3.60 (dd, 1H |2JHH| 11 Hz,
|3JHH| 6 Hz), 3.43 (dd, 1H |2JHH| 11 Hz, |3JHH| 9 Hz), 2.30
(s, 3H); 13C NMR (CDCl3, 100 MHz): δ = 168.9, 136.8, 136.3,
128.6, 125.5, 84.1, 39.2, 21.1. HRMS (EI): calcd for C10H11NOS
193.0561, found 193.0559.
Compound 2c. IR (KBr): 3146, 2920, 1683, 1639, 1509, 1463,
1259, 1173, 1025, 830 cm−1; 1H NMR (CDCl3, 400 MHz): δ =
7.30 (d, 2H |3JHH| 9 Hz), 6.98 (d, 2H |3JHH| 9 Hz), 5.64 (s, 1H
(vNH), 5.56 (dd, 1H |3JHH| 9 Hz, |3JHH| 6 Hz), 3.79 (s, 3H),
3.61 (dd, 1H |2JHH| 11 Hz, |3JHH| 6 Hz), 3.43 (dd, 1H |2JHH|
3518 | Green Chem., 2015, 17, 3515–3520
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11 Hz, |3JHH| 9 Hz); 13C NMR (CDCl3, 100 MHz): δ = 168.7,
159.2, 132.7, 127.4, 125.3, 84.2, 55.7, 39.4. HRMS (EI) calcd for
C10H11NO2S: 209.0510, found 209.0513.
Compound 2d.8a IR (KBr): 3204, 1637, 1057, 832, 670 cm−1;
1
H NMR (CDCl3, 400 MHz): δ = 7.40 (d, 2H |3JHH| 9 Hz), 7.33
(d, 2H |3JHH| 9 Hz), 5.65 (s, 1H (vNH), 5.57 (dd, 1H |3JHH| 9
Hz, |3JHH| 6 Hz), 3.62 (dd, 1H |2JHH| 11 Hz, |3JHH| 6 Hz), 3.40
(dd, 1H |2JHH| 11 Hz, |3JHH| 9 Hz); 13C NMR (CDCl3, 100 MHz):
δ = 168.7, 135.3, 134.7, 129.2, 127.1, 83.3, 39.7. HRMS (EI)
calcd for C9H8ClNOS: 213.0015, found 213.0017.
Compound 2e.8a IR (KBr): 3334, 1636, 1563, 1032, 837,
676 cm−1; 1H NMR (CDCl3, 400 MHz): δ = 7.50 (d, 1H |4JHH|
2 Hz), 7.48 (d, 1H |3JHH| 8 Hz), 7.26 (dd, 1H, |3JHH| 8 Hz,
|4JHHJHH| 2 Hz), 5.65 (s, 1H (vNH), 5.54 (dd, 1H |3JHH| 9 Hz,
|3JHH| 6 Hz), 3.68 (dd, 1H |2JHH| 11 Hz, |3JHH| 6 Hz), 3.42 (dd,
1H |2JHH| 11 Hz, |3JHH| 9 Hz); 13C NMR (CDCl3, 100 MHz): δ =
168.5, 137.0, 133.2, 132.0, 130.8, 127.7, 124.6, 82.3, 39.4.
HRMS (EI) calcd for C9H7Cl2NOS: 246.9625, found 246.9628.
Compound 2f.8a IR (KBr): 3340, 1664, 1595, 1541, 1405,
1337, 1081, 781 cm−1; 1H NMR (CDCl3, 400 MHz): δ = 8.22 (d,
2H |3JHH| 9 Hz), 7.57 (d, 2H |3JHH| 9 Hz), 5.71 (s, 1H (vNH),
5.69 (dd, 1H |3JHH| 9 Hz, |3JHH| 6 Hz), 3.74 (dd, 1H |2JHH|
11 Hz, |3JHH| 6 Hz), 3.41 (dd, 1H |2JHH| 11 Hz, |3JHH| 9 Hz);
13
C NMR (CDCl3, 100 MHz): δ = 168.6, 148.2, 144.0, 126.3,
124.0, 82.4, 39.2. HRMS (EI): calcd for C9H8N2O3S 224.0256,
found 224.0253.
Compound 2g.8a IR (KBr): 3417, 1633, 1526, 1434, 1307,
1087, 785 cm−1; 1H NMR (CDCl3, 400 MHz): δ = 8.26 (d, 1H
|4JHH| 2 Hz), 8.23 (dd, 1H |3JHH| 8 Hz, |4JHH| 2 Hz), 7.76 (d, 1H
|3JHH| 8 Hz), 7.60 (t, 1H |3JHH| 8 Hz), 5.73 (s, 1H (vNH), 5.68
(dd, 1H, |3JHH| 9 Hz, |3JHH| 6 Hz), 3.75 (dd, 1H |2JHH| 11 Hz,
|3JHH| 6 Hz), 3.47 (dd, 1H |2JHH| 11 Hz, |3JHH| 9 Hz); 13C NMR
(CDCl3, 100 MHz): δ = 168.8, 148.2, 139.2, 131.5, 130.3, 123.5,
120.6, 82.5, 39.7. HRMS (EI): calcd for C9H8N2O3S 224.0254,
found 224.0250.
Compound 2h. IR (KBr): 3207, 1634, 1449, 1257, 1040, 831,
671 cm−1; 1H NMR (CDCl3, 400 MHz): δ = 7.45 (d, 2H, |3JHH|
9 Hz), 7.32 (d, 2H |3JHH| 9 Hz), 5.59 (s, 1H (vNH), 5.57 (dd,
1H |3JHH| 9 Hz, |3JHH| 6 Hz), 3.60 (dd, 1H |2JHH| 11 Hz, |3JHH|
6 Hz), 3.41 (dd, 1H |2JHH| 11 Hz, |3JHH| 9 Hz); 13C NMR
(CDCl3, 100 MHz): δ = 168.6, 135.5, 134.7, 129.0, 127.0, 83.4,
39.5. HRMS (EI): calcd for C9H8BrNOS 256.9510, found
256.9513.
Compound 2i. IR (KBr): 3203, 1632, 1057, 825, 750, cm−1;
1
H NMR (CDCl3, 400 MHz): δ = 7.42–7.36 (m, 2H), 7.24–7.19
(m, 2H), 5.64 (s, 1H (vNH), 5.58 (dd, 1H |3JHH| 9 Hz, |3JHH|
6 Hz), 3.63 (dd, 1H |2JHH| 11 Hz, |3JHH| 6 Hz), 3.41 (dd, 1H
|2JHH| 11 Hz, |3JHH| 9 Hz); 13C NMR (CDCl3, 100 MHz): δ =
168.7, 160.3, 134.9, 127.0, 115.4, 83.2, 39.5. HRMS (EI) calcd
for C9H8FNOS: 197.0311, found 197.0310.
Compound 2j. IR (KBr): 3421, 3141, 2952, 1639, 1354, 1059,
853, 776 cm−1; 1H NMR (CDCl3, 400 MHz): δ = 7.24 (d, 2H
|3JHH| 9 Hz), 6.76 (d, 2H |3JHH| 9 Hz), 5.63 (s, 1H (vNH), 5.57
(dd, 1H |3JHH| 9 Hz, |3JHH| 6 Hz), 3.60 (dd, 1H |2JHH| 11 Hz,
|3JHH| 6 Hz), 3.43 (dd, 1H |2JHH| 11 Hz, |3JHH| 9 Hz), 3.06
(s, 6H); 13C NMR (CDCl3, 100 MHz): δ = 168.1, 149.3, 134.9,
This journal is © The Royal Society of Chemistry 2015

Green Chemistry
129.2, 127.0, 83.3, 40.2, 38.6. HRMS (EI) calcd for C11H14N2OS:
222.0827, found 222.0825.
Compound 2k. IR (KBr): 3146, 1674, 1043, 910, 874,
776 cm−1; 1H NMR (CDCl3, 400 MHz): δ = 8.01–7.92 (m, 2H),
7.68–7.50 (m, 2H), 7.47 (s, 1H), 7.33–7.27 (m, 2H), 5.52 (s, 1H
(vNH), 5.47 (dd, 1H |3JHH| 9 Hz, |3JHH| 6 Hz), 3.65 (dd, 1H
|2JHH| 11 Hz, |3JHH| 6 Hz), 3.43 (dd, 1H |2JHH| 11 Hz, |3JHH|
9 Hz); 13C NMR (CDCl3, 100 MHz): δ = 168.3, 135.4, 134.9,
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129.0, 128.3, 127.6, 127.2, 126.7, 126.3, 125.6, 123.8, 83.4, 39.2.
HRMS (EI) calcd for C13H11NOS: 229.0561, found 229.0564.
Compound 2l. IR (KBr): 3203, 3040, 1642, 1053, 828, 728,
700 cm−1; 1H NMR (CDCl3, 400 MHz): δ = 8.30 (s, 1H),
7.73–7.68 (m, 1H), 7.46–7.40 (m, 2H), 5.42 (s, 1H (vNH), 5.35
(dd, 1H |3JHH| 9 Hz, |3JHH| 6 Hz), 3.61 (dd, 1H |2JHH| 11 Hz,
|3JHH| 6 Hz), 3.40 (dd, 1H |2JHH| 11 Hz, |3JHH| 9 Hz); 13C NMR
(CDCl3, 100 MHz): δ = 168.4, 145.3, 142.7, 138.3, 132.1, 123.0,
83.5, 39.6. HRMS (EI) calcd for C8H8N2OS: 180.0357, found
180.0354.
Acknowledgements
We sincerely thank the SAIF, Punjab University, Chandigarh,
for providing spectra. One of us (A.K.Y.) is grateful to the CSIR,
New Delhi, for the award of a Senior Research Fellowship.
Notes and references
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