E-1,2-diarylsulfonylethenea-Source for new class of heterocycles

Article abstract of DOI:10.1002/jhet.500

A new class of pyrazolidinediones, isoxazolidinediones, pyrimidinetriones, and thioxopyrimidinediones were synthesized by the reaction of Michael adduct, dimethyl 2-(1′,2′-diarylsulfonyl)ethylmalonate with different nucleophiles, hydrazine hydrate, hydrox

Full text of DOI:10.1002/jhet.500

January 2011
E-1,2-Diarylsulfonylethene—Source for New Class
of Heterocycles
199
Adivireddy Padmaja,* Thalari Payani, Akkarapalli Muralikrishna,
and Konda Mahesh
Department of Chemistry, Sri Venkateswara University, Tirupati 517502, India
*E-mail: adivireddyp@yahoo.co.in
Received January 29, 2010
DOI 10.1002/jhet.500
Published online 30 August 2010 in Wiley Online Library (wileyonlinelibrary.com).
A new class of pyrazolidinediones, isoxazolidinediones, pyrimidinetriones, and thioxopyrimidine-
diones were synthesized by the reaction of Michael adduct, dimethyl 2-(10,20-diarylsulfonyl)ethylmalo-
nate with different nucleophiles, hydrazine hydrate, hydroxylamine hydrochloride, and urea derivatives.
J. Heterocyclic Chem., 48, 199 (2011).
INTRODUCTION
spectra of compounds 2 displayed absorption bands in
the region 1120–1130 and 1338–1341 (SO2), 1730–1735
a,b-Unsaturated sulfur compounds have been used as
important reagents in synthetic organic chemistry [1].
For example, vinyl sulfides as carbonyl synthons [2] and
vinyl sulfonium salts as precursors of cyclopropanes [3].
Moreover, these are valuable intermediates in a variety
of synthetic transformations and useful as building
blocks in the synthesis of biologically potent hetero-
cycles [4]. The biological properties of pyrazoles, isoxa-
zoles, pyrimidines, thioxopyrimidines, and their deriva-
tives have been reviewed extensively [5–16]. In our
continued interest on the Michael addition reactions
[17–20], we have examined the reactivity of a,b-unsatu-
rated sulfones towards the synthesis of bioactive hetero-
cycles. Based on these, herein we wish to report a new
class of pyrazolidinediones, isoxazolidinediones, pyrimi-
dinetriones, and thioxopyrimidinediones from the Mi-
chael acceptor, E-1,2-diarylsulfonylethene.
1
cmꢀ1 (CO2Me) (Table 2). The H NMR spectrum of 2a
showed two double doublets at d 3.47, 3.56 (C20 AH), a
doublet at 4.05 (C2AH), and a multiplet at 4.22–4.28
(C10 AH). In addition, two singlets were observed at 3.61,
3.69 ppm due to methoxy protons of carbomethoxy
group. The downfield shift was assigned to the one pres-
ent towards arylsulfonyl moiety. This may be due to the
deshielding effect exerted by this group (Table 3). The
13C NMR spectrum of 2a exhibited signals at d 39.7 (C-
10), 52.8, 53.6 (OCH3), 60.4 (C-2), 54.9 (C-20), 168.2,
168.9 (CO2Me) (Table 3). The cyclocondensation of 2
with hydrazine hydrate and hydroxylamine hydrochlor-
ide furnished 4-(10,20-diarylsulfonylethyl)pyrazolidine-
3,5-dione (3) and 4-(10,20-diarylsulfonylethyl)isoxazoli-
dine-3,5-dione (4), respectively. Similar reaction of 2
with urea, N,N0-dimethylurea and thiourea afforded 5-
(10,20-diarylsulfonylethyl)pyrimidine-2,4,6-trione (5), 5-
(10,20-diarylsulfonylethyl)-1,3-dimethylpyrimidine-2,4,6-
trione (6), and 5-(10,20-diarylsulfonylethyl)-2-thioxopyr-
imidine-4,6-dione (7), respectively (Scheme 1 and
Table 1). The absence of a band due to ester moiety in
the IR spectra of the compounds 3–7 and the presence
of absorption bands in the regions 1655–1680 (COAN),
1115–1140 and 1330–1345 cmꢀ1 (SO2) indicated their
formation. All the compounds except 6 also displayed
RESULTS AND DISCUSSION
The Michael addition of dimethyl malonate in the
presence of anhydrous potassium carbonate in methyl
ethyl ketone to E-1,2-diarylsulfonylethene (1) produced
the Michael adduct, dimethyl 2-(10,20-diarylsulfonyl-
ethyl)malonate (2) (Scheme 1 and Table 1). The IR
C
V
2010 HeteroCorporation

200
A. Padmaja, T. Payani, A. Muralikrishna, and K. Mahesh
Vol 48
Scheme 1
an absorption band at 3306–3331 cmꢀ1 due to NH.
Further, the compound 4 showed a band at 1736–1748
(COAO), whereas 7 exhibited a band at 1488–1497
broad singlet was observed at d 9.11 in 3a and at 10.10
ppm in 4a due to NH which disappeared on deuteration
(Table 3). The 13C NMR spectrum of 3a displayed sig-
nals at d 51.6 (C-20), 55.4 (C-10), 63.1 (C-4), 171.6 (C-
3 and C-5), whereas 4a at 50.7 (C-20), 55.1 (C-10), 62.9
(C-4), 172.6 (C-3), 178.7 ppm (C-5) in addition to sig-
1
cmꢀ1 (C¼¼S) (Table 2). The H NMR spectra of 3a and
4a showed two double doublets at d 3.12, 3.85 and
3.14, 3.78 (C20 AH), a multiplet at 4.34–4.42, 4.31–4.38
(C10 AH), and a doublet at 4.49, 4.48 (C4AH) ppm
besides signals of aromatic protons. Apart from these, a
1
nals of aromatic carbons (Table 3). The H NMR spec-
tra of 5a, 6a and 7a also exhibited two double doublets
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Table 1
Physical and analytical data of compounds 2–7.
Analysis % Calcd./Found
H
Molecular
Formula
Compound
Mp (ꢁC)
Yield (%)
75
Ar
C
N
–
2a
105–107
C6H5
C19H20O8S2
(440.49)
51. 81
51. 90
53.83
53.88
44.80
44.75
49.99
49.94
52.28
52.32
42.78
42.72
49.87
49.93
52.16
52.20
42.69
42.75
49.53
49.51
51.71
51.77
42.78
42.86
51.71
51.76
53.64
53.71
45.03
45.00
47.77
47.82
49.98
50.05
41.46
41.49
4. 58
4. 55
5.16
5.18
3.56
3.60
3.95
3.93
4.62
4.66
2.96
2.95
3.69
3.72
4.38
4.42
2.74
2.75
3.69
3.71
4.34
4.38
2.79
2.73
4.34
4.39
4.91
4.96
3.40
3.45
3.56
3.53
4.19
4.18
2.71
2.73
2b
2c
3a
3b
3c
4a
4b
4c
5a
5b
5c
6a
6b
6c
7a
7b
7c
154–156
185–187
198–200
207–209
222–224
182–184
196–198
217–219
210-212
221–223
230–232
216–218
226–228
205–207
128–130
142–144
150–152
71
78
74
76
79
80
73
77
73
70
67
65
68
70
73
71
75
P-CH3C6H4
P-ClC6H4
C6H5
C21H24O8S2
(468.54)
–
–
C19H18Cl2O8S2
(509.38)
C17H16N2O6S2
(408.45)
6.86
6.92
6.42
6.45
5.87
5.92
3.42
3.48
3.20
3.25
2.93
2.96
6.42
6.51
6.03
6.10
5.54
5.58
6.03
6.09
5.69
5.66
5.25
5.32
6.19
6.24
5.83
5.87
5.37
5.43
P-CH3C6H4
P-ClC6H4
C6H5
C19H20N2O6S2
(436.50)
C17H14Cl2N2O6S2
(477.34)
C17H15NO7S2
(409.43)
C19H19NO7S2
(437.49)
P-CH3C6H4
P-ClC6H4
C6H5
C17H13Cl2NO7S2
(478.32)
C18H16N2O7S2
(436.46)
P-CH3C6H4
P-ClC6H4
C6H5
C20H20N2O7S2
(464.51)
C18H14Cl2N2O7S2
(505.35)
C20H20N2O7S2
(464.51)
C22H24N2O7S2
(492.57)
C20H18Cl2N2O7S2
(533.40)
C18H16N2O6S3
(452.52)
P-CH3C6H4
P-ClC6H4
C6H5
P-CH3C6H4
P-ClC6H4
C20H20N2O6S3
(480.58)
C18H14Cl2N2O6S3
(521.41)
Table 2
IR data of compounds 2–7.
IR (KBr) cmꢀ1
Compound
SO2
C¼S
NAC¼O
CO2Me
OACO
NH
2a
2b
2c
3a
3b
3c
4a
4b
4c
5a
5b
5c
6a
6b
6c
7a
7b
7c
1126
1130
1121
1119
1122
1126
1136
1129
1130
1134
1131
1128
1125
1126
1131
1135
1129
1127
1341
1338
1339
1340
1330
1332
1336
1337
1331
1333
1339
1336
1334
1341
1339
1336
1332
1335
–
–
–
–
1733
1735
–
–
–
–
–
–
–
1731
–
–
–
–
1676
1668
1672
1678
1664
1655
1661
1667
1671
1674
1668
1662
1673
1679
1670
3327
3325
3319
3327
3319
3322
3306
3310
3312
–
–
–
–
–
–
–
–
–
1736
–
–
–
–
1742
1748
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
1488
1492
1497
3327
3331
3324
–
–

202
A. Padmaja, T. Payani, A. Muralikrishna, and K. Mahesh
Vol 48
Table 3
1H and 13C NMR data of compounds 2–7.
Compound
1H NMR (CDCl3/DMSO-d6) d, (ppm)
13C NMR (CDCl3/DMSO-d6) d, (ppm)
39.7 (C-10), 52.8 and 53.6 (OCH3), 54.9 (C-20), 60.4
(C-2), 168.2 and 168.9 (CO2Me), 128.2, 129.2,
130.4, 132.6, 133.2, 133.8, 135.4 (aromatic
carbons)
22.5 (Ar-CH3), 39.2 (C-10), 53.2 and 53.9 (OCH3),
54.8 (C-20), 60.7 (C-2), 167.9 and 168.7 (CO2Me),
127.8, 129.6, 130.1, 131.5, 133.7, 134.2, 135.9,
136.1 (aromatic carbons)
2a
3.47 (dd, 1H, C0AH, J ¼ 9.0, 14.6 Hz), 3.56 (dd, 1H,
2
C0AH, J ¼ 4.4, 14.8 Hz), 3.61 (s, 3H, OCH3), 3.69 (s,
2
3H, OCH3), 4.05 (d, 1H, C2AH, J ¼ 8.4 Hz), 4.22–
4.28 (m, 1H, C0AH), 7.18–7.59 (m, 10H, Ar-H)
1
2b
2.36 (s, 6H, Ar-CH3), 3.46 (dd, 1H, C0AH, J ¼ 8.8, 14.2
2
Hz), 3.58 (dd, 1H, C0AH, J ¼ 4.4, 14.4 Hz), 3.64 (s,
2
3H, OCH3), 3.66 (s, 3H, OCH3), 4.09 (d, 1H, C2AH, J
¼ 8.6 Hz), 4.26–4.32 (m, 1H, C0AH), 7.23–7.76 (m,
1
8H, Ar-H)
2c
3a
3b
3c
4a
4b
4c
5a
5b
5c
6a
6b
6c
3.49 (dd, 1H, C0AH, J ¼ 9.1, 14.7 Hz), 3.58 (dd, 1H,
39.6 (C-10), 53.0 and 53.1 (OCH3), 54.9 (C-20), 59.7
(C-2), 166.5 and 167.1 (CO2Me), 125.2, 128.7,
129.4, 131.6, 133.8, 134.9, 136.0, 138.5 (aromatic
carbons)
51.6 (C-20), 55.4 (C-10), 63.1 (C-4), 171.6 (C-3 and C-
5), 129.6, 130.5, 131.1, 132.0, 133.3, 133.7, 135.3,
136.8 (aromatic carbons)
2
C0AH, J ¼ 4.6, 14.9 Hz), 3.65 (s, 3H, OCH3), 3.72 (s,
2
3H, OCH3), 4.08 (d, 1H, C2AH, J ¼ 8.6 Hz), 4.30–
4.38 (m, 1H, C0AH), 7.32–7.56 (m, 8H, Ar-H)
1
3.12 (dd, 1H, C0AH, J ¼ 3.2, 15.0 Hz), 3.85 (dd, 1H,
2
C0AH, J ¼ 9.7, 14.9 Hz), 4.34–4.42 (m, 1H, C0AH),
2
1
4.49 (d, 1H, C4AH, J ¼ 13.9 Hz), 7.12–7.75 (m, 10H,
Ar-H), 9.11 (bs, 2H, NH)
2.32 (s, 6H, Ar-CH3), 3.14 (dd, 1H, C0AH, J ¼ 3.1, 14.8
21.9 (Ar-CH3), 51.2 (C-20), 55.8 (C-10), 62.7 (C-4),
172.3 (C-3 and C-5), 128.4, 129.9, 130.7, 131.6,
132.9, 133.2, 134.9, 135.7, 136.4 (aromatic
carbons)
51.8 (C-20), 56.2 (C-10), 59.6 (C-4), 171.0 (C-3 and C-
5) 125.7 128.9, 129.2, 131.9, 133.6, 134.3, 135.8,
137.5, (aromatic carbons)
2
Hz), 3.82 (dd, 1H, C0AH, J ¼ 9.2, 14.6 Hz), 4.32–4.38
2
(m, 1H, C0AH), 4.46 (d, 1H, C4AH, J ¼ 13.7 Hz),
1
7.21–7.81 (m, 8H, Ar-H), 9.08 (bs, 2H, NH)
3.16 (dd, 1H, C0AH, J ¼ 6.3, 16.2 Hz), 3.80 (dd, 1H,
2
C0AH, J ¼ 8.4, 16.0 Hz), 4.35–4.41 (m, 1H, C0AH),
2
1
4.45 (d, 1H, C4AH, J ¼ 13.9 Hz), 7.16–7.39 (m, 8H,
Ar-H), 9.14 (bs, 2H, NH)
3.14 (dd, 1H, C0AH, J ¼ 3.5, 15.1 Hz), 3.78 (dd, 1H,
50.7 (C-20), 55.1 (C-10), 62.9 (C-4), 172.6 (C-3),
178.7 (C-5), 129.6, 130.2, 131.5, 132.4, 132.9,
134.6, 136.1, 137.4 (aromatic carbons)
2
C0AH, J ¼ 9.7, 14.9 Hz), 4.31–4.38 (m, 1H, C0AH),
2
1
4.48 (d, 1H, C4AH, J ¼ 13.9 Hz), 7.07–7.84 (m, 10H,
Ar-H), 10.10 (bs, 1H, NH)
2.38 (s, 6H, Ar-CH3), 3.16 (dd, 1H, C0AH, J ¼ 3.4, 15.0
22.6 (Ar-CH3), 51.2 (C-20), 55.9 (C-10), 63.5 (C-4),
173.4 (C-3), 179.2 (C-5), 129.2, 130.7, 131.3,
132.9, 133.5, 134.9, 135.7, 136.8 (aromatic
carbons)
50.9 (C-20), 56.2 (C-10), 63.1 (C-4), 172.9 (C-3),
178.6 (C-5), 129.7, 130.4, 131.9, 132.6, 133.7,
134.2, 136.7, 138.9 (aromatic carbons)
2
Hz), 3.87 (dd, 1H, C0AH, J ¼ 9.5, 14.8 Hz), 4.36–4.42
2
(m, 1H, C0AH), 4.50 (d, 1H, C4AH, J ¼ 13.7 Hz),
1
7.10–7.98 (m, 8H, Ar-H), 10.19 (bs, 1H, NH)
3.05 (dd, 1H, C0AH, J ¼ 3.3, 14.9 Hz), 3.70 (dd, 1H,
2
C0AH, J ¼ 9.3, 14.7 Hz), 4.33–4.39 (m, 1H, C0AH),
2
1
4.46 (d, 1H, C4AH, J ¼ 13.8 Hz), 7.16–7.36 (m, 8H,
Ar-H), 9.08 (bs, 1H, NH)
3.09 (dd, 1H, C0AH, J ¼ 3.6, 15.0 Hz), 3.75 (dd, 1H,
50.1 (C-20), 57.3 (C-10), 62.7 (C-5), 158.1 (C-2),
165.3 (C-4 and C-6), 127.3, 129.2, 130.7, 132.1,
132.8, 133.7, 134.6, 135.8 (aromatic carbons)
2
C0AH, J ¼ 9.7, 14.8 Hz), 4.34–4.41 (m, 1H, C0AH),
2
1
4.49 (d, 1H, C5AH, J ¼ 13.6 Hz), 6.99–7.39 (m, 10H,
Ar-H), 9.91 (bs, 2H, NH)
2.34 (s, 6H, Ar-CH3), 3.04 (dd, 1H, C0AH, J ¼ 3.5, 14.9
21.7 (Ar-CH3), 50.4 (C-20), 57.6 (C-10), 62.3 (C-5),
157.8 (C-2), 166.1 (C-4 and C-6), 128.5, 129.6,
130.3, 131.8, 132.3, 133.4, 135.7, 136.6 (aromatic
carbons)
50.3 (C-20), 60.1 (C-10), 64.1 (C-5), 158.3 (C-2),
166.5 (C-4 and C-6), 125.8 128.4, 129.0, 129.8,
132.3, 133.3, 133.9, 135.1, (aromatic carbons)
2
Hz), 3.71 (dd, 1H, C0AH, J ¼ 9.5, 14.7 Hz), 4.37–4.44
2
(m, 1H, C0AH), 4.51 (d, 1H, C5AH, J ¼ 13.5 Hz),
1
7.19–7.69 (m, 8H, Ar-H), 9.99 (bs, 2H, NH)
3.07 (dd, 1H, C0AH, J ¼ 3.7, 15.0 Hz), 3.74 (dd, 1H,
2
C0AH, J ¼ 9.7, 14.9 Hz), 4.25–4.36 (m, 1H, C0AH),
2
1
4.62 (d, 1H, C5AH, J ¼ 13.6 Hz), 7.18–7.59 (m, 8H,
Ar-H), 9.89 (bs, 2H, NH)
2.78 (s, 6H, NACH3), 3.09 (dd, 1H, C0AH, J ¼ 3.8, 14.9
27.5 (NACH3), 52.7 (C-20), 57.9 (C-10), 64.4 (C-5),
157.1 (C-2), 167.9 (C-4 and C-6), 129.3, 130.6,
131.2, 132.4, 132.8, 133.6, 134.5, 135.2 (aromatic
carbons)
22.3 (Ar-CH3), 27.9 (NACH3), 51.9 (C-20), 58.2 (C-
10), 63.9 (C-5), 156.7 (C-2), 168.7 (C-4 and C-6),
128.8, 130.3, 131.9, 132.6, 132.9, 133.0, 133.7,
134.9 (aromatic carbons)
27.4 (NACH3), 51.2 (C-20), 58.9 (C-10), 63.3 (C-5),
157.3 (C-2), 167.7 (C-4 and C-6), 129.2, 130.9,
131.4, 132.2, 132.7, 133.4, 134.9, 136.2 (aromatic
carbons)
2
Hz), 3.72 (dd, 1H, C0AH, J ¼ 9.5, 14.7 Hz), 4.31–4.36
2
(m, 1H, C0AH), 4.47 (d, 1H, C5AH, J ¼ 13.9 Hz),
1
7.09–7.81 (m, 10H, Ar-H)
2.25 (s, 6H, ArACH3), 2.71 (s, 6H, NACH3), 3.03 (dd,
1H, C0AH, J ¼ 3.6, 14.8 Hz), 3.70 (dd, 1H, C0AH, J
2
2
¼ 9.3, 14.6 Hz), 4.29–4.35 (m, 1H, C0AH), 4.43 (d,
1
1H, C5AH, J ¼ 13.6 Hz), 7.11–7.74 (m, 8H, Ar-H)
2.75 (s, 6H, NACH3), 3.06 (dd, 1H, C0AH, J ¼ 3.7, 14.9
2
Hz), 3.73 (dd, 1H, C0AH, J ¼ 9.4, 14.7 Hz), 4.32–4.38
2
(m, 1H, C0AH), 4.46 (d, 1H, C5AH, J ¼ 13.7 Hz),
1
7.12–7.40 (m, 8H, Ar-H)
(continued)
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

January 2011
E-1,2-Diarylsulfonylethene—Source for New Class of Heterocycles
203
Table 3
(Continued)
Compound
1H NMR (CDCl3/DMSO-d6) d, (ppm)
13C NMR (CDCl3/DMSO-d6) d, (ppm)
52.9 (C-20), 59.4 (C-10), 64.2 (C-5), 167.4 (C-4 and C-
7a
3.10 (dd, 1H, C0AH, J ¼ 3.9, 15.1 Hz), 3.78 (dd, 1H,
2
C0AH, J ¼ 9.6, 15.0 Hz), 4.33–4.37 (m, 1H, C0AH),
6), 171.3 (C-2), 128.2, 129.2, 130.6, 131.4, 132.0,
133.2, 134.5, 135.7 (aromatic carbons)
2
1
4.49 (d, 1H, C5AH, J ¼ 13.9 Hz), 7.12–7.78 (m, 10H,
Ar-H), 9.38 (bs, 2H, NH)
7b
7c
2.27 (s, 6H, Ar-CH3), 3.08 (dd, 1H, C0AH, J ¼ 3.8, 15.0
22.7 (Ar-CH3), 51.7 (C-20), 58.8 (C-10), 64.9 (C-5),
166.9 (C-4 and C-6), 172.5 (C-2), 128.9, 129.4,
131.3, 132.9, 133.4, 134.6, 135.0, 135.8 (aromatic
carbons)
51.1 (C-20), 58.2 (C-10), 64.4 (C-5), 167.3 (C-4 and C-
6), 171.9 (C-2), 129.6, 130.4, 131.7, 132.4, 133.7,
134.9, 135.6, 136.6 (aromatic carbons)
2
Hz), 3.75 (dd, 1H, C0AH, J ¼ 9.5, 14.9 Hz), 4.31–4.35
2
(m, 1H, C0AH), 4.46 (d, 1H, C5AH, J ¼ 13.6 Hz),
1
7.17–7.82 (m, 8H, Ar-H), 9.31 (bs, 2H, NH)
3.11 (dd, 1H, C0AH, J ¼ 3.9, 15.1 Hz), 3.79 (dd, 1H,
2
C0AH, J ¼ 9.7, 15.0 Hz), 4.29–4.36 (m, 1H, C0AH),
2
1
4.47 (d, 1H, C5AH, J ¼ 13.8 Hz), 7.14–7.93 (m, 8H,
Ar-H), 9.36 (bs, 2H, NH)
washed with water, brine and dried (anhyd. Na2SO4). The sol-
vent was removed in vacuo. The resultant solid was recrystal-
lized from 2-propanol.
at d 3.09, 3.75; 3.09, 3.72; 3.10, 3.78, a multiplet at
4.34–4.41, 4.31–4.36, 4.33–4.37, and a doublet at 4.49,
4.47, 4.49 which were accounted for C20 AH, C10 AH,
C5AH. The compounds 5a and 7a displayed a broad
singlet at d 9.91, 9.38 ppm for NH which disappeared
on deuteration. Besides, compound 6a showed a singlet
at 2.78 ppm for N-Me group. The structures of the
compounds 5–7 were further confirmed by 13C NMR
spectra (Table 3).
4-(10,20-Diarylsulfonylethyl)pyrazolidine-3,5-dione (3): Gen-
eral procedure. The compound 2 (1 mmol), hydrazine hydrate
(1.5 mmol), MeOH (20 mL), and NaOMe (5 mL) were
refluxed for 3–5 h. The solution was cooled and poured onto
crushed ice containing conc. HCl. The solid obtained was fil-
tered, dried, and recrystallized from methanol.
4-(10,20-Diarylsulfonylethyl)isoxazolidine-3,5-dione
(4):
General procedure. To a solution of 2 (1 mmol) in MeOH
(10 mL), hydroxylamine hydrochloride (1 mmol) and NaOMe
(5 mL) were added and refluxed for 4–6 h. The reaction mix-
ture was cooled and poured into ice-cold water containing
conc. HCl. The solid separated was filtered, dried, and recrys-
tallized from methanol.
CONCLUSIONS
A new class of pyrazolidinedione, isoxazolidinedione,
pyrimidinetrione, and thioxopyrimidinedione were
developed from the synthetic intermediate E-1,2-diary-
lsulfonylethene adopting facile, simple, and well-versed
synthetic methodologies.
5-(10,20-Diarylsulfonylethyl)pyrimidine-2,4,6-trione
(5)/5-
(10,20-diarylsulfonylethyl)-1,3-dimethylpyrimidine-2,4,6-trione
(6): General procedure. A mixture of compound 2 (1 mmol),
urea/N,N0-dimethylurea (1 mmol), MeOH (5 mL), and NaOMe
(5 mL) was refluxed for 8–10 h. The contents were cooled and
poured into ice-cold water containing conc. HCl. The sepa-
rated solid was filtered, dried, and recrystallized from
methanol.
EXPERIMENTAL
General. Melting points were determined in open capillaries
on a Mel-Temp apparatus and are uncorrected. The purity of
the compounds was checked by TLC (silica gel H, BDH, ethyl
acetate/hexane, 1:3). The IR spectra were recorded on a
Thermo Nicolet IR 200 FTIR spectrometer as KBr pellets and
5-(10,20-Diarylsulfonylethyl)-2-thioxopyrimidine-4,6-dione
(7): General procedure. To an equimolar mixture (1 mmol)
of 2 and thiourea, MeOH (10 mL) and NaOMe (2 mL) were
added and refluxed for 6–8 h. It was cooled and poured into
ice-cold water containing conc. HCl. The solid separated was
filtered, dried, and purified by recrystallization from methanol.
the wave numbers were given in cmꢀ1. The H NMR spectra
1
were recorded in CDCl3/DMSO-d6 on a Varian EM-360 spec-
trometer (300 MHz). The 13C NMR spectra were recorded in
CDCl3/DMSO-d6 on a Varian VXR spectrometer operating at
75.5 MHz. All chemical shifts are reported in d (ppm) using
TMS as an internal standard. The microanalyses were per-
formed on a Perkin-Elmer 240C elemental analyzer. The start-
ing compound 1,2-diarylsulfonylethene (1) was prepared as per
the literature procedure [20].
Dimethyl 2-(10,20-diarylsulfonylethyl)malonate (2): General
procedure. A mixture of dimethyl malonate (15 mmol),
methyl ethyl ketone (5 mL), and anhydrous potassium carbon-
ate (10 mmol) was cooled to 5–10ꢁC. To this, compound 1
(10 mmol) was added and stirred for 2–4 h maintaining the
same temperature. The contents of the flask were diluted with
water and extracted with chloroform. The organic layer was
Acknowledgment. The authors are thankful to UGC, New Delhi
for financial assistance under minor research project.
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