A Simple, Convenient One-Pot Synthesis of Dithio-Carbamide Derivatives of Heterocyclic 1,3-Dicarbonyl Systems

Article abstract of DOI:10.1002/jhet.2754

A various new dithi-ocarbamides were synthesized from heterocyclic six-membered 1,3-dicarbonyl systems, such as 4-hydroxy-2,5-pyranopyridines, 4-hydroxy-2-pyridones, 4-Hydroxy-2-quinolones, 4-hydroxy-coumarins, and 4-hydroxy-1-methyl-2-quinolones. The dicarbonyl compounds in the presence of anhydrous potassium carbonate in dimethyformamide react with tetraalkylthiuram disulfides to yield 3-dialkylaminothiocarbonylthio derivatives through a simple, convenient one-pot reaction. The structures were confirmed by using IR, NMR, and elemental analysis.

Full text of DOI:10.1002/jhet.2754

Month 2016 A Simple, Convenient One-Pot Synthesis of Dithio-Carbamide Derivatives
of Heterocyclic 1,3-Dicarbonyl Systems
a
b
*
B. P. Nikam and Thomas Kappe
aDepartment of Chemistry, College of Engineering and Polytechnic, Sakharale, Tal. Walwa, Dist. Sangli M.S. 414 415,
Islampur, India
bInstitute of Organic Chemistry, Karl-Franzens University of Graz, Heinrichstraße 28, A-8010 Graz, Austria
*
E-mail: bpnikam@yahoo.co.in
Received May 21, 2016
DOI 10.1002/jhet.2754
Published online 00 Month 2016 in Wiley Online Library (wileyonlinelibrary.com).
A various new dithi-ocarbamides were synthesized from heterocyclic six-membered 1,3-dicarbonyl
systems, such as 4-hydroxy-2,5-pyranopyridines, 4-hydroxy-2-pyridones, 4-Hydroxy-2-quinolones,
4-hydroxy-coumarins, and 4-hydroxy-1-methyl-2-quinolones. The dicarbonyl compounds in the presence
of anhydrous potassium carbonate in dimethyformamide react with tetraalkylthiuram disulfides to yield
3-dialkylaminothiocarbonylthio derivatives through a simple, convenient one-pot reaction. The structures
were confirmed by using IR, NMR, and elemental analysis.
J. Heterocyclic Chem., 00, 00 (2016).
INTRODUCTION
relating to the sulfenylation of alicyclic 1,3-dicarbonyl
systems have been published as a lecture abstract [12].
The sulfinylation of heterocyclic 1,3-dicarbonyl systems,
such as 4-hydroxy-2-quinolones and 4-hydroxy-coumarins
[13] and 4-hydroxy-2-pyrones, 6-hydroxy-4-pyrimidones,
4-hydroxy-2-pyridones, 4-hydroxy-6-pyridazones, and
5-hydroxy-3-pyrazolones [14], was reported earlier. The
introduction of the dialkylaminothiocarbonylthio group
directly at the 5-position of barbituric acid with
tetraalkylthiuram disulfides is more effective than
reactions via the 5-chloro derivative or 5-phenyliodonium
yields [15]. The equimolar amount of the aliphatic
tetraalkylthiuram disulfides is used for the sulfinylation.
Aromatic thioethers are prepared by the reaction of
3-chloro-4-hydroxy-2-pyridones or their 3-phenyl-
iodonium yields [12,14–17]. Oxidation of the aliphatic
thioethers is not possible like the aromatic thioethers under
similar reaction conditions.
The sulfenylation of aryl compounds is an important
issue in synthetic organic chemistry [1,2]. Nonactivated
aromatic compounds can be sulfenylated by using electro-
philes of disulfides in presence of Lewis acid catalysis
(for instance SbCl5/AgSbF6) [3]. In the same way,
sulfenylchlorides (RSCl) [4] and sulfinyltosylates (RS-
SO2-p-tolyl) [5] are also used for sulfenylation. However,
the reaction with sulfenyltosylates proceeds best with phe-
nolic substrates under basic conditions [5]. The condensed
5-alkyl-6-hydoxy-4-pyrimidone and 5-arylthio-6-hydoxy-
4-pyrimidone show some anti-inflammatory activity [5].
Some of the 3-alkylthio-4-hydroxy-2-pyrones are effective
HIV-protease inhibitors [6–9]. This and the known fungi-
cidal and antiseptic activity of thiuram (tetramethylthiuram
disulfide) [10] and disulfiram (antabuse, tetraethylthiuram
disulfide) [11] prompted us to synthesize sulfenyl deriva-
tives of 4-hydroxy-2,5-pyranopyridones, 4-hydroxy-2-
pyridones, and 4-hydroxy-coumarins. Preliminary results
As reported, the dialkylaminothiocarbonylthio deriva-
tives can be obtained by two alternative routes. The
© 2016 Wiley Periodicals, Inc.

B. P. Nikam and T. Kappe
Vol 000
1a–e were reacted with sufficiently electrophilic
alkylthiuram disulfides 2a–b in presence of anhydrous po-
tassium carbonate in dimethylformamide to yield 3-dial
kylaminothiocarbonylthio-4-hydroxy-2,5-pyranopyridones
3a–j. Here, equivalent amount of reagents 2a–b was used
to obtain aliphatic thioethers and not required to oxidize
dialkylaminodithiocarbamates as illustrated in Scheme 1.
In similar way, 4-hydroxy-2-pyridones [20] 4a–b,
4-hydroxy-2-quinolones 6a, 4-hydroxy-coumarins 6b,
and 4-hydroxy-1-methyl-2-quinolones 6c reacted with
alkylthiuram disulfides 2a–b to yield respective
3-dialkylaminothiocarbonylthio derivatives 5a–b, 7a–e as
shown in Schemes 2 and 3. The structures of the newly
obtained compounds were elucidated on the basis of IR,
NMR spectra, and elemental analysis.
Figure 1. Heterocyclic 1,3-dicarbonyl system.
starting 1,3-dicarbonyl compounds of the type 1, 4, and 6
as shown Figure 1 are converted to their 3-chloro
derivatives or their 3-phenyliodonium yields [18]. The
commercially available thiuram disulfides are used for the
sulfinylation of 1,3-dicarbonyl systems.
RESULTS AND DISCUSSION
Present article deals with the reactions of heterocyclic
1,3-dicarbonyl compounds, such as 4-hydroxy-2,5-
pyranopyridines 1a–e, 4-hydroxy-2-pyridones 4a–b,
4-hydroxy-2-quinolones 6a, 4-hydroxy-coumarins 6b,
and 4-hydroxy-1-methyl-2-quinolones 6c with aliphatic
disulfides 2a–b. 4-Hydroxy-2,5-pyranopyridones [19]
CONCLUSION
In conclusion, we have developed a simple, convenient
one-pot synthesis method to prepare dithio-carbamide de-
rivatives of heterocyclic 1,3-dicarbonyl systems, such as
Scheme 1. Synthesis of 3-dialkylaminothiocarbonylthio-4-hydroxy-2,5-pyranopyridones 3.
Scheme 2. Synthesis of 3-dialkylaminothiocarbonylthio-4-hydroxy-2-pyridone derivatives 5.
Scheme 3. Synthesis of 3-dialkyaminothiocarbonylthio-4-hydroxy-quinolin-2H-ones (7a-b), -coumarin (7c-d), and -1-methyl-quinolin-2H-one (7e).
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2016
Synthesis of Dithio-Carbamide Derivatives of Heterocyclic 1,3-Dicarbonyl Systems
4-hydroxy-2,5-pyranopyridines, 4-hydroxy-2-pyridones,
4-hydroxy-2-quinolones, 4-hydroxy-coumarins, and 4-hy-
droxy-1-methyl-2-quinolones. The present method may
be of value in organic synthesis because of operational
simplicity, as well as good availability of the starting
materials.
3-Dimethylaminothiocarbonylthio-4-hydroxy-6,7-diphenyl-
2H-pyrano[3,2-c]pyridine-2,5-dione (3a). IR (KBr, cmÀ1):
3150–2960, 1750, 1665, 1600, 1570, 1480, 1310.
1H-NMR (200 MHz, DMSO-d6) δ (ppm): 3.45 (s, 3H,
–CH3), 3.50 (s, 3H, –CH3), 6.95 (s, 1H, Ar–H8),
7.20–7.50 (m, 10H, Ar–H). 13C-NMR (50 MHz,
DMSO-d6) δ (ppm): 39.1, 84.5, 94.7, 110.4, 120.5,
125.3, 127.4, 128.3, 128.9, 129, 130.8, 132.4, 144.6,
154.2, 156.8, 160.5, 182.1, 198. Anal. calcd for
C23H18N2O4S2 (450.53): C 61.32, H 4.04, N 6.22%.
Found: C 61.27, H 4.11, N 6.13%.
EXPERIMENTAL
All chemical were purchased from Merck (Darmstadt,
Germany) and used without purification. The solvents were
dried over appropriate drying agents and distilled prior to
use. All reactions were monitored by TLC on pre-coated
silica gel 60 PF254 (mesh). Melting points were recorded
by using open glass capillaries on Gallenkamp MFB 595
melting point apparatus (USA) and were uncorrected.
Infrared spectra were recorded on a Perkin-Elmer 298
spectrophotometer (PerkinElmer, Inc., Waltham, MA) by
using KBr pellets. 1H-NMR and 13C-NMR spectra were re-
corded on Varian Gemini 200MHz (Agilent Technologies,
Lexington, MA) and 50 MHz, respectively, in DMSO-d6
by using TMS as an internal standard. CHN analyses were
recorded on a C,H,N-Automat Carlo Erba 1106 (CE Instru-
ments Ltd, Wigan, UK) elemental analyzer.
3-Diethylaminothiocarbonylthio-4-hydroxy-6,7-diphenyl-
2H-pyrano[3,2-c]pyridine-2,5-dione (3b).
IR (KBr,
cmÀ1): 3100–2980, 1740, 1670, 1600, 1570, 1490, 1300.
1H-NMR (200MHz, DMSO-d6) δ (ppm): 1.20 (t, J =7,
3H, –CH3), 1.35 (t, J = 7, 3H, –CH3), 3.90 (m, 4H,
2-CH2), 6.95 (s, 1H, Ar–H8), 7.20–7.40 (m, 10H, Ar–H).
13C-NMR (50 MHz, DMSO-d6) δ (ppm): 10.6, 44.5,
84.2, 94.6, 110.5, 120.4, 125.6, 127.3, 128.2, 128.8, 129,
130.9, 132.5, 144.5, 154.2, 156.7, 160.7, 182.2, 198.2.
Anal. calcd for C25H22N2O4S2 (478.58): C 62.74, H 4.63,
N 5.85%. Found: C 62.68, H 4.55, N 5.78%.
3-Dimethylaminothiocarbonylthio-8-methyl-4-hydroxy-6,7-
diphenyl-2H-pyrano[3,2-c]pyridine-2,5-dione
(3c).
IR
(KBr, cmÀ1): 3460, 2930, 1690, 1675, 1560, 1200. H-
NMR (200 MHz, DMSO-d6) δ (ppm): 1.88 (s, 3H, CH3);
3.46 (s, 3H, –CH3), 3.48 (s, 3H, –CH3), 7.15–7.35 (m,
10H, Ar–H). 13C-NMR (50 MHz, DMSO-d6) δ (ppm):
7.5, 39.2, 84.6, 104.5, 110.4, 120.4, 125.2, 127.2, 128.4,
128.6, 129.2, 130, 132.2, 134.7, 156.9, 158, 160.2, 182.8,
198. Anal. calcd for C24H20N2O4S2 (464.56): C 62.05, H
4.34, N 6.03%. Found: C 62.01, H 4.32, N 6.01%.
1
Preparation of 3-dialkyaminocarbonylthio-4-hydroxy-6-
phenyl-2H-pyrano[3,2-c]pyridine-2,5-diones (3a–j). General
procedure.
The appropriate 4-hydroxy-6,7-diphenyl-
6H-pyrano-[3,2-c]-pyridine-2,5-dione 1 [19] (10 mmol),
tetraalkylthiuramdisulphide 2 (11 mmol), and anhydrous
potassium
carbonate
(30 mmol)
in
75mL
dimethylformamide was refluxed at 90°C for 5 to 6 h.
The solution was cooled, and dimethylformamide was
removed on rotary evaporator. The concentrate obtained
was added to 150mL ice-water and filtered. The filtrate
was precipitated by acidification with conc. hydrochloric
acid, filtered by suction, dried, and recrystallized from
acetic acid to give the corresponding derivative 3.
Physical data and yields are listed in Table 1.
3-Diethylaminothiocarbonylthio-8-methyl-4-hydroxy-6,7-
diphenyl-2H-pyrano[3,2-c]pyridine-2,5-dione (3d).
IR
(KBr, cmÀ1): 2980–2940, 1750, 1670, 1550, 1490, 1300,
1270, 1200. 1H-NMR (200 MHz, DMSO-d6) δ (ppm):
1.22 (t, J = 7, 3H, –CH3), 1.37 (t, J = 7, 3H, –CH3), 1.92
(s, 3H, –CH3), 3.95 (m, 4H, 2-CH2), 7.20–7.40 (m, 10H,
Ar–H). 13C-NMR (50 MHz, DMSO-d6) δ (ppm): 7.4,
Table 1
Preparation of 3-dialkyaminocarbonylthio-4-hydroxy-6-phenyl-2H-pyrano[3,2-c]pyridine-2,5-diones 3.
R
R1
R2
Compound no.
mp (°C)
Yield (%)
Ph
Ph
Ph
Ph
Ph
Ph
i-Propyl
i-Propyl
t-Butyl
t-Butyl
H
H
Me
Et
Me
Et
Me
Et
Me
Et
3a
3b
3c
3d
3e
3f
3g
3h
3i
269–270
205–207
266–267
264–265
250–252
235–236
243–244
249–250
249–250
231–232
50
61
60
82
60
57
87
77
58
93
Me
Me
Et
Et
H
H
H
H
Me
Et
3j
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

B. P. Nikam and T. Kappe
Vol 000
10.4, 44.4, 84.6, 104.4, 110.2, 120.5, 125.4, 127, 128.2,
128.4, 129, 130.7, 132.4, 134.6, 156.8, 158.2, 160.4, 182,
198.2. Anal. calcd for C26H24N2O4S2 (492.61): C 63.39,
H 4.91, N 5.69%. Found: C 63.36, H 4.93, N 5.63%.
3-Dimethylaminothiocarbonylthio-8-ethyl-4-hydroxy-6,7-
3H, –CH3 t-butyl), 3.45 (s, 3H, –CH3), 3.48 (s, 3H,
–CH3), 6.90 (s, 1H, Ar–H8), 7.55 (s, 5H, Ar–H), 13.85 (s,
1H, OH). 13C-NMR (50 MHz, DMSO-d6) δ (ppm): 28,
36.5, 39.2, 84.5, 88.4, 110.6, 120.5, 125, 128.6, 132,
155.6, 158.2, 158.6, 160, 182.5, 198.2. Anal. calcd for
C21H22N2O4S2 (430.54): C 58.58, H 5.15, N 6.51%.
Found: C, 58.49; H 5.20, N 6.45%.
diphenyl-2H-pyrano[3,2-c]pyridine-2,5-dione (3e).
IR
(KBr, cmÀ1): 1740, 1670, 1550, 1390, 1300, 1170. H-
NMR (200 MHz, DMSO-d6) δ (ppm): 1.00 (t, J = 8, 3H,
–CH3), 1.30 (q, J = 7.5, 2H, –CH2), 3.46 (s, 3H, N–CH3),
3.49 (s, 3H, N–CH3), 7.21–7.30 (m, 10H, Ar–H), 14.45
(s, 1H, OH). 13C-NMR (200 MHz, DMSO-d6) δ (ppm):
10.4, 12.5, 39.4, 84.2, 108.8, 110.3, 120.4, 125.4, 127.2,
128.4, 128.8, 129, 130, 132.4, 134, 156.4, 158.7, 160,
182.4, 198. Anal. calcd for C25H22N2O4S2 (478.58): C
62.74, H 4.63, N 5.85%. Found: C 62.69, H 4.66, N 5.82%.
3-Diethylaminothiocarbonylthio-8-ethyl-4-hydroxy-6,7-
1
3-Diethylaminothiocarbonylthio-4-hydroxy-7-t-butyl-6-phe-
nyl-2H-pyrano[3,2-c]pyridine-2,5-dione (3j).
IR (KBr,
cmÀ1): 3110–2980, 1750, 1670, 1580, 1470, 1210.
1H-NMR (200MHz, DMSO-d6) δ (ppm): 1.16 (s, 9H
3–CH3 t-butyl), 1.20 (t, J = 7, 3H, –CH3), 1.34 (t, J =7,
3H, –CH3), 3.90 (m, 4H, 2-CH2), 6.92 (s, 1H, Ar–H8),
7.56 (s, 5H, Ar–H), 13.85 (s, 1H, OH). 13C-NMR
(50 MHz, DMSO-d6) δ (ppm): 10.4, 26.5, 36.6, 44.2,
84.8, 88, 110.5, 120.6, 125, 128.7, 132.4, 155.6, 158.1,
158.6, 160.4, 180.8, 198. Anal. calcd for C23H26N2O4S2
(258.59): C 60.24, H 5.72, N 6.11%. Found: C 60.16, H
5.75, N 6.05%.
diphenyl-2H-pyrano[3,2-c]pyridine-2,5-dione (3f).
IR
(KBr, cmÀ1): 3460, 2980, 1740, 1670, 1550, 1470, 1300,
1
1210. H-NMR (200 MHz, DMSO-d6) δ (ppm): 1.00 (t,
J =8, 3H, –CH3), 1.19 (t, J = 7, 3H, –CH3), 1.34 (t, J= 7,
3H, –CH3), 2.25 (q, J= 7.5, 2H, –CH2), 3.89 (m, 4H,
2 N–CH2), 7.20–7.40 (m, 10H, Ar–H), 14.43 (s, 1H, OH).
13C-NMR (50 MHz, DMSO-d6) δ (ppm): 10.5, 12.6, 44.2,
84.6, 108.4, 110.2, 120.6, 125, 127.5, 128.1, 128.6,
129.4, 130, 132.4, 134.2, 155.6, 158, 160.6, 182, 198.2.
Anal. calcd for C27H26N2O4S2 (506.64): C 64.01, H 5.17,
N 5.53%. Found: C 64.10, H 5.19; N 5.48%.
Preparation of 3-dialkyaminocarbonylthio-4-hydroxy-1-
phenypyridin-2H-ones (5a–b). General procedure.
The
appropriate 4-hydroxy-1,6-diphenylpyridin-2(1H)-one 4
(10 mmol), tetraalkylthiuramdisulphides (11mmol),
2
and anhydrous carbonate (30 mmol) in 50mL
dimethylformamide were refluxed at 90°C for 5 h. The
solution was cooled, and dimethylformamide was
removed on rotary evaporator. The concentrate obtained
was added to 150mL ice-water and filtered. The filtrate
obtained was precipitated by acidification with conc.
hydrochloric acid, filtered by suction, dried, and
recrystallized from acetic acid to give 5a. Physical data
and yields are listed in Table 2.
3-Dimethylaminothiocarbonylthio-4-hydroxy-1,6-diphenylpyridin-
2H-one (5a). IR (KBr, cmÀ1): 2930, 2690, 2600, 1650,
1625, 1600, 1580, 1490, 1390. 1H-NMR (200MHz,
DMSO-d6) δ (ppm): 3.45 (s, 3H, –CH3), 3.48 (s, 3H,
3-Dimethylaminothiocarbonylthio-4-hydroxy-7-i-propyl-
6-phenyl-2H-pyrano[3,2-c]pyridine-2,5-dione (3g).
IR
(KBr, cmÀ1): 3070–2940, 1750, 1670, 1380, 1150. H-
NMR (200 MHz, DMSO-d6) δ (ppm): 1.15 (d, J = 7, 6H,
2–CH3 i-propyl), 2.45 (m, 1H, –CH), 3.45 (s, 3H, –CH3),
3.50 (s, 3H, –CH3), 6.95 (s, 1H, Ar–H8), 7.50–7.70 (m,
5H, Ar–H). 13C-NMR (50 MHz, DMSO-d6) δ (ppm): 18,
28.4, 38.9, 84.2, 90, 110.4, 120.5, 125.6, 128.8, 132,
150.2, 155.8, 158, 160.4, 182.4, 198. Anal. calcd for
C20H20N2O4S2 (416.51): C 57.67, H 4.84, N 6.73%.
Found: C 57.74, H 4.88, N 6.65%.
1
–CH3), 6.10 (s, 1H, Ar–H ), 7.00–7.40 (m, 10H, Ar–H).
5
13C-NMR (50MHz, DMSO-d6) δ (ppm): 40.2, 88.2, 94.4,
120.4, 123.7, 125.6, 128, 128.8, 130, 131.4, 135, 144.4,
156.8, 182.5, 194.3. Anal. calcd for C20H18N2O2S2 (382.5):
C 62.80, H 4.74, N 7.32%. Found: C 62.81, H, 4.79, N,
7.25%.
3-Diethylaminothiocarbonylthio-4-hydroxy-7-i-propyl-6-phe-
nyl-2H-pyrano[3,2-c]pyridine-2,5-dione (3h).
IR (KBr,
cmÀ1): 3080–2940, 1740, 1670, 1570, 1480, 1280, 1200.
1H-NMR (200 MHz, DMSO-d6) δ (ppm): 1.15 (d, J =7,
6H, 2-CH3 i-propyl), 1.20 (t, J= 7, 3H, –CH3), 1.34 (t,
J =7, 3H, –CH3), 3.95 (m, 4H, 2-CH2), 6.91 (s, 1H,
Ar–H8), 7.50–7.70 (m, 5H, Ar–H). 13C-NMR (50 MHz,
DMSO-d6) δ (ppm): 10.4, 18.2, 28, 44.4, 84.4, 90.2,
110.4, 120.4, 125.2, 128.6, 132.2, 150.4, 155.4, 158,
160.4, 182, 198.4. Anal. calcd for C22H24N2O4S2
(444.57): C 59.44, H 5.44, N 6.30%. Found: C 59.49, H
5.41, N 6.25%.
3-Diethylaminothiocarbonylthio-4-hydroxy-1,6-diphenylpyridin-
2H-one (5b). IR (KBr, cmÀ1): 3200–2980, 1625, 1600,
1
1550, 1500, 1420, 1200. H-NMR (200MHz, DMSO-d6)
Table 2
Preparation of 3-dialkyaminocarbonylthio-4-hydroxy-1-phenypyridin-
2H-ones 5.
R
R1
R2
Compound no.
mp (°C)
Yield (%)
3-Dimethylaminothiocarbonylthio-4-hydroxy-7-t-butyl-6-
phenyl-2H-pyrano[3,2-c]pyridine-2,5-dione (3i). IR (KBr,
cmÀ1): 3060–2930, 1745, 1670, 1590, 1530, 1460, 1290,
Ph
Ph
H
H
Me
Et
5a
5b
205–206
188–190
76
76
1
1250. H-NMR (200 MHz, DMSO-d6) δ (ppm): 1.15 (s, 9
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2016
Synthesis of Dithio-Carbamide Derivatives of Heterocyclic 1,3-Dicarbonyl Systems
δ (ppm): 1.20 (t, J=7, 3H, –CH3), 1.35 (t, J=7, 3H,
–CH3), 3.90 (m, 4H, 2-CH2), 6.10 (s, 1H, Ar–H 5),
7.00–7.40 (m, 10H, Ar–H), 11.25 (s, 1H, OH). 13C-NMR
(50MHz, DMSO-d6) δ (ppm): 10.6, 44.6, 88, 94.6, 120.2,
123, 125.7, 128.2, 129, 129.6, 131.5, 135.4, 144, 156.4,
180.9, 194.2. Anal. calcd for C22H22N2O2S2 (410.55): C
64.39, H 5.37, N 6.83%. Found: C 64.45, H 5.43, N
6.76%.
Preparation of 3-dialkyaminocarbonylthio-4-hydroxy-
quinolin-2H-one (7a–b), 4-hydroxy-coumarin (7c–d)-one,
and 4-hydroxy-1-methyl-quinolin-2H-one (7e). General
procedure. The appropriate 4-hydroxy-quinolin-2H-one
1H, Ar–H), 7.63 (t, J = 7, 1H, Ar–H), 7.95 (dd, J = 7, 1.5,
1H, Ar–H), 11.00 (s, 1H, -NH), 11.50 (s, 1H, OH).
13C-NMR (50 MHz, DMSO-d6) δ (ppm): 10.4, 44.2, 84,
114.6, 120.4, 125, 126.4, 128.7, 135.6, 159, 180.4,
192.6. Anal. calcd for C14H16N2O2S2 (308.42): C 54.52,
H 5.23, N 9.08%. Found: C 54.60, H 5.21, N 9.12%.
3-Dimethylaminothiocarbonylthio-4-hydroxy-coumarin (7c).
Yield: 5.2 g (93%). mp 180–181° (acetic acid). IR (KBr,
cmÀ1): 3180, 1680, 1620, 1550, 1495, 1400, 1380, 1290.
1H-NMR (200MHz, DMSO-d6) δ (ppm): 3.50 (s, 3H,
–CH3), 3.55 (s, 3H, –CH3), 7.40–7.50 (m, 2H, Ar–H),
7.75 (t, J = 7, 1H, Ar–H), 8.00 (dd, J= 7, 1.5, 1H, Ar–H).
13C-NMR (50 MHz, DMSO-d6) δ (ppm): 40.4, 80.6,
116.4, 120.4, 126, 127.2, 128.8, 148.9, 160.7, 184.4,
196.6. Anal. calcd for C12H11NO3S2(281.35): C 51.23, H
3.94, N 4.98%. Found: C 51.18, H 3.89, N 4.91%.
or
quinolin-2H-one
tetraalkylthiuramdisulphides 2 (22 mmol) and anhydrous
potassium carbonate (60 mmol) in 100mL
4-hydroxy-coumarin
or
4-hydroxy-1-methyl-
6
(20 mmol),
corresponding
dimethylformamide, was refluxed at 90°C for 5h. The
solution was cooled, and dimethylformamide was
removed on rotary evaporator. The concentrate obtained
was added to 200mL ice-water and filtered. The filtrate
obtained was precipitated by acidification with conc.
hydrochloric acid, filtered by suction, dried at reduced
pressure, and recrystallized from acetic acid to give 7.
Physical data and yields are listed in Table 3.
3-Dimethylaminothiocarbonylthio-4-hydroxy-quinolin-2H-
one (7a). Yield: 4.18g (75%). mp 315° dec. (acetic acid).
IR (KBr, cmÀ1): 3360–2900, 1640, 1600, 1500, 1410,
1375, 1200. 1H-NMR (200 MHz, DMSO-d6) δ (ppm):
3.45 (s, 3H, –CH3), 3.55(s, 3H, –CH3), 7.22 (t, J =7, 1H,
Ar–H), 7.32 (d, J = 8, 1H, Ar–H), 7.61 (t, J = 7, 1H,
Ar–H), 7.92 (d, J = 7, 1H, Ar–H), 11.02 (s, 1H -NH),
11.55 (s, 1H, OH). 13C-NMR (50 MHz, DMSO-d6) δ
(ppm): 10.5, 44, 84.6, 114.5, 120.6, 125.4, 126, 128.8,
135.4, 159.7, 180.8, 192.4. Anal. calcd for C12H12N2O2S2
(280.37): C 51.41, H 4.31, N 9.99%. Found: C 51.37; H,
4.29; N, 9.92%.
3-Diethylaminothiocarbonylthio-4-hydroxy-coumarin (7d).
Yield: 4.66g (75%). mp 170–172° (acetic acid). IR (KBr,
cmÀ1): 3200–2900, 1695, 1610, 1600, 1550, 1540, 1440,
1
1270. H-NMR (200MHz, DMSO-d6) δ (ppm): 1.20 (t,
J = 7, 3H, –CH3), 1.40 (t, J= 7, 3H, –CH3), 3.80–4.50 (m,
4H, 2-CH2), 7.40–7.50 (m, 2H, Ar–H), 7.70–7.80 (m,
1H, Ar–H), 8.00 (dd, J= 7, 1.5, 1H, Ar–H), 11.50 (s, 1H,
OH). 13C-NMR (50 MHz, DMSO-d6) δ (ppm): 10.8,
42.6, 83.4, 116.8, 120.5, 126, 126.9, 127.4, 148.5, 160.8,
180.4, 196.7. Anal. calcd for C14H15NO3S2(309.4): C
54.35, H 4.89, N 4.53%. Found: C 54.27, H 4.84, N
4.53%.
3-Dimethylaminthioocarbonylthio-4-hydroxy-1-methyl-
quinolin-2H-one (7e).
Yield: 4.26 g (73%). mp 300°
(acetic acid). IR (KBr, cmÀ1): 3100, 1620, 1585, 1550,
1370, 1310, 1210. 1H-NMR (200 MHz, DMSO-d6) δ
(ppm): 3.45 (s, 3H, –CH3), 3.50 (s, 3H, –CH3), 3.60 (s,
3H, N–CH3), 7.35 (t, J = 7, 1H, Ar–H), 7.55 (dd, J = 8,
1H, Ar–H), 7.75 (t, J = 7, 1H, Ar–H), 8.05 (dd, J = 8, 1H,
Ar–H). 13C-NMR (50 MHz, DMSO-d6) δ (ppm): 30.2,
40.8, 84.6, 114.4, 120.6, 125.5, 127, 128.6, 134.9, 158.4,
183.6, 192.6. Anal. calcd for C13H14N2O2S2(294.39): C
53.04, H 4.79, N 9.52%. Found: C 52.98, H 4.72, N
9.45%.
3-Diethylaminothiocarbonylthio-4-hydroxy-quinolin-2H-one
(7b). Yield: 4.6 g (74%). mp 198–200° (acetic acid). IR
(KBr, cmÀ1): 3250–2980, 1700, 1600, 1500, 1420, 1270,
1210, 1150. 1H-NMR (200 MHz, DMSO-d6) δ (ppm):
1.20 (t, J = 7, 3H, –CH3), 1.40 (t, J =7, 3H, –CH3), 3.95
(m, 4H, 2-CH2), 7.20 (t, J = 7, 1H, Ar–H), 7.35 (d, J =8,
Acknowledgment. Dr. B.P. Nikam thanks Austrian Academic
Exchange Service, Austria for granting the Post Doctorate
Fellowship.
Table 3
Preparation of 3-dialkyaminocarbonylthio-4-hydroxy-quinolin-2H-ones
(7a–b), 4-hydroxy-coumarin-one (7c–d), and 4-hydroxy-1-methyl-
quinolin-2H-one (7e).
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X
R2
Compound no.
mp (°C)
Yield (%)
NH
NH
O
O
NMe
Me
Et
Me
Et
7a
7b
7c
7d
7e
315 dec
198–200
180–181
170–172
300
75
74
93
75
73
Me
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

B. P. Nikam and T. Kappe
Vol 000
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Journal of Heterocyclic Chemistry
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