Studies on Reactivity of Bisolefinic Diketo Sulfides/Sulfones. II

Article abstract of DOI:10.1081/SCC-120026310

The cycloaddition of diazomethane to bis(1-aryl-2-propen-1-one) sulfides/sulfones (1/2) and cyclocondensation of 1/2 with hydrazine hydrate has been studied.

Full text of DOI:10.1081/SCC-120026310

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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 22, pp. 3879–3889, 2003
Studies on Reactivity of Bisolefinic Diketo
Sulfides/Sulfones. II
*
V. Padmavathi, M. Rajagopala Sarma, T. V. Ramana Reddy,
and D. Bhaskar Reddy
Department of Chemistry, Sri Venkateswara University,
Tirupati, India
ABSTRACT
The cycloaddition of diazomethane to bis(1-aryl-2-propen-1-one)
sulfides/sulfones (1/2) and cyclocondensation of 1/2 with hydrazine
hydrate has been studied.
Key Words: Cyclocondensation;
Diazomethane; Hydrazine hydrate.
1,3-Dipolar
cycloaddition;
The chemistry of five membered heterocycles particularly pyrazole
and its derivatives possess a wide spectrum of biological properties.[1]
During the last one and half decades we have been actively involved
in the 1,3-dipolar cycloaddition of ylides and cyclocondensation of
*Correspondence: V. Padmavathi, Department of Chemistry, Sri Venkateswara
University, Tirupati-517 502, India; E-mail: vkpuram2001@yahoo.com.
3879
DOI: 10.1081/SCC-120026310
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3880
Padmavathi et al.
hydrazine hydrate with Michael acceptors to get 2-pyrazolines.[2] Our
recent studies on the cycloaddition of diazomethane to bifunctional
olefins, 1-aroyl-2-arylsulfonylethenes and 1,2-bis(arylsulfonyl)ethenes
under different conditions led to a variety of pyrazolines and pyrazoles.[3]
Similarly the reaction of 1-aroyl-2-arylsulfonyl-ethenes with different
ratios of hydrazine hydrate gave 2-pyrazolines, hydrazones, and dimer-
ized products.[4] Apart from these, the bifunctional bisolefins, 1-aroyl-2-
styrylsulfonylethenes have also been used as a source to obtain novel
bis pyrazolines/pyrazoles adopting similar methodology.[5] In view of
these observations and being undeterred by the results we further
examined our study on the reactivity of bisolefinic diketo
sulfides/sulfones with diazomethane and hydrazine hydrate.
The synthetic scheme involves the reaction of bis (1-aryl-2-propen-1-
one) sulfide/sulfone (1/2) with two moles of diazomethane in the presence
of triethylamine at ꢀ20 to ꢀ15ꢁC (Sch. 1, Table 1). When the progress of
the reaction was monitored at frequent intervals two spots were observed
in TLC which persisted even after 48 h. The two were separated by
column chromatography and identified as 3-aroyl-2-pyrazolinyl-20-aroyl-
ethenyl-[4,10]-sulfide/sulfone (3/4) as a major product and bis(3,30-aroyl-
2-pyrazolinyl)-[4,40]-sulfide/sulfone (5/6) as a minor one.
1
The H NMR spectra of 3/4 indicated an AMX splitting pattern for
methine and methylene protons of pyrazoline ring. Thus, three double
doublets observed in 3a at 4.70 (JAM ¼ 12.6, JAX ¼ 5.5) at 3.92
(JMX ¼ 10.0) and at 3.52 was assigned to HA, HM and HX, respectively.
However, 4a exhibited double doublets at 4.71 (JAM ¼ 12.6, JAX ¼ 5.6),
3.93 (JMX ¼ 10.1) and 3.58 which was attributed to HA, HM and HX,
respectively. The J values indicate that HA, HM and HA, HX are cis
and trans oriented while HM, HX are geminal. The olefinic proton, HC
showed a doublet at 6.60 in 3a and at 6.66 in 4a whereas HD merged with
aromatic protons and appeared as a multiplet. The coupling constant of
ethylenic protons indicated that they possess trans geometry. A broad
singlet in the region 10.12 in 3a and 10.14 in 4a was observed for N-H
proton, which disappeared on deuteration.
However, when 1/2 was treated with excess diazomethane in the
presence of triethylamine at ꢀ20ꢁC to ꢀ15ꢁC resulted only 5/6. The
latter was also obtained by the cycloaddition of one mole of diazomethane
to 3/4 under similar reaction conditions. The two pyrazoline ring protons
1
in their H NMR spectra showed AMX splitting pattern as in 3/4 and
exhibited their resonance signals almost in the same region (Table 2).
On the other hand, cyclocondensation of 1/2 with hydrazine hydrate in
ethanol afforded 3-aryl-2-pyrazolinyl-20-aroylethenyl-[5,10]-sulfide/sul-
fone (7/8) as major and bis(3,30-aryl-2-pyrazolinyl)-[5,50]-sulfide/sulfone

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Bisolefinic Diketo Sulfides/Sulfones. II
3881

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3882
Padmavathi et al.
Table 1. Physical data of compounds 1–12.
Found(calcd.) %
Compd.
no.
M.p.
(ꢁC)
Yield
(%)
Mol. formula
Mol. wt.
C
H
N
1a
1b
1c
2a
2b
2c
3a
3b
3c
4a
4b
4c
5a
5b
5c
6a
6b
6c
7a
7b
192–194
204–206
210–212
220–214
212–214
221–223
112–114
96–98
60
65
70
68
63
72
62
58
69
61
64
66
C18H14O2S
(294.38)
—
—
—
C20H18O2S
(322.43)
—
—
—
—
—
—
—
—
—
—
—
—
C18H12Cl2O2S
(363.27)
C18H14O4S
(326.37)
—
C20H18O4S
(354.43)
—
C18H12Cl2O4S
(395.26)
—
C19H16N2O2S
(336.42)
67.95
4.71
8.24
(8.33)
7.83
(67.84) (4.79)
69.07 5.44
(69.21) (5.53)
56.46 3.57
(56.31) (3.48)
61.79 4.42
(61.94) (4.38)
63.75 5.01
(63.62) (5.08)
52.31 3.14
(52.19) (3.23)
63.34 4.87
C21H20N2O2S
(364.47)
(7.69)
6.78
128–130
121–122
104–106
136–137
156–158
163–165
172–174
164–166
167–168
172–174
102–104
87–89
C19H14Cl2N2O2S
(405.31)
(6.91)
7.48
C19H16N2O4S
(368.41)
(7.60)
7.17
C21H20N2O4S
(396.47)
(7.07)
6.53
C19H14Cl2N2O4S
(437.30)
(6.41)
14.69
17
75a 62b
18
C20H18N4O2S
(378.46)
(63.47) (4.79) (14.80)
65.14 5.37 13.97
(65.00) (5.46) (13.78)
53.79 3.68 12.64
(53.70) (3.61) (12.52)
58.65 4.35 13.73
(58.53) (4.42) (13.65)
60.39 5.14 12.88
(60.26) (5.06) (12.78)
49.98 3.29 11.83
(50.11) (3.36) (11.69)
C22H22N4O2S
(406.51)
73a 64b
20
C20H16Cl2N4O2S
(447.35)
77a 68b
21
C20H18N4O4S
(410.45)
78a 60b
19
C22H22N4O4S
(438.51)
70a 61b
20
C20H16Cl2N4O4S
(479.34)
80a 66b
65
C18H16N2OS
(308.41)
70.24
(70.10) (5.23)
71.29 5.81
(71.40) (5.99)
5.16
9.20
(9.08)
8.44
60
C20H20N2OS
(336.46)
(8.33)

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Bisolefinic Diketo Sulfides/Sulfones. II
Table 1. Continued.
3883
Found(calcd.) %
Compd.
no.
M.p.
(ꢁC)
Yield
(%)
Mol. formula
(mol. wt.)
C
H
N
7c
8a
112–114
116–118
100–102
132–134
140–142
128–130
136–138
158–160
164–166
173–175
138–140
126–128
142–144
158–160
163–165
174–176
67
63
60
68
C18H14Cl2N2OS
(377.30)
57.45
3.67
7.31
(7.42)
8.11
(57.30) (3.74)
63.38 4.82
(63.51) (4.74)
65.06 5.56
(65.20) (5.47)
52.94 3.52
(52.82) (3.45)
67.19 5.54
C18H16N2O3S
(340.40)
(8.23)
7.49
8b
C20H20N2O3S
(368.46)
(7.60)
6.93
8c
C18H14Cl2N2O3S
(409.29)
(6.84)
17.26
9a
20
76a 72b
18
C18H18N4S
(322.43)
(67.05) (5.63) (17.38)
68.41 6.42 15.87
(68.54) (6.33) (15.99)
55.39 4.03 14.45
(55.25) (4.12) (14.32)
61.14 5.04 15.73
(61.00) (5.12) (15.81)
62.93 5.85 14.76
(62.81) (5.80) (14.65)
9b
C20H22N4S
(350.49)
78a 69b
21
9c
C18H16Cl2N4S
(391.33)
73a 71b
22
10a
10b
10c
11a
11b
11c
12a
12b
12c
C18H18N4O2S
(354.43)
71a 65b
19
C20H22N4O2S
382.49
76a 74b
24
C18H16Cl2N4O2S
(423.32)
51.20
51.07
65.26
3.73
(3.81) (13.23)
5.09 16.07
13.36
80a 75b
64 70a
C19H18N4OS
(350.45)
(65.12) (5.18) (15.99)
66.50 5.80 14.90
(66.64) (5.86) (14.80)
54.31 3.92 13.24
(54.42) (3.85) (13.36)
59.81 4.67 14.72
(59.67) (4.74) (14.65)
61.31 5.31 13.77
(61.45) (5.40) (13.65)
50.42 3.49 12.53
(50.56) (3.57) (12.41)
62 78a
65 76a
64 73a
68 70a
65 76a
C21H22N4OS
(378.50)
C19H16Cl2N4OS
(419.34)
C19H18N4O3S
(382.45)
C21H22N4O3S
(410.50)
C19H16 Cl2N4O3S
(451.33)
Satisfactory elemental analysis were obtained for the representative samples:
C ꢀ 0.24; H ꢀ 0.15; N ꢀ 0.22.
aFrom Method B.
bFrom Method C.

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3884
Padmavathi et al.
Table 2. 1H NMR spectral data of compounds 3–12.
Compd. no.
1H NMR ꢀ (CDCl3), ppm
3a
3.52 (dd, 1H, HX), 3.92 (dd, 1H, HM, JMX ¼ 10.0), 4.70 (dd, 1H,
HA, JAX ¼ 5.5, JAM ¼ 12.6), 6.60 (d, 1H, HC, JCD ¼ 14.2),
6.92–8.15 (m, 11H, HD and Ar-H), 10.18 (bs, 1H, NH)
2.25 (s, 6H, Ar-CH3), 3.54 (dd, 1H, HX), 3.94 (dd, 1H, HM,
JMX ¼ 10.0), 4.76 (dd, 1H, HA, JAX ¼ 5.5, JAM ¼ 12.6), 6.62
(d, 1H, HC, JCD ¼ 14.2), 6.94–8.17 (m, 9H, HD and Ar-H), 10.16
(bs, 1H, NH)
3b
4a
4c
5a
5c
6a
6b
7a
7c
8a
8c
9a
3.58 (dd, 1H, HX), 3.93 (dd, 1H, HM, JMX ¼ 10.1), 4.71 (dd, 1H,
HA, JAX ¼ 5.6, JAM ¼ 12.6), 6.66 (d, 1H, HC, JCD ¼ 14.2),
7.01–8.12 (m, 11H, HD, and Ar-H), 10.14 (bs, 1H, NH)
3.64 (dd, 1H, HX), 3.99 (dd, 1H, HM, JMX ¼ 10.2), 4.54 (dd, 1H,
HA, JAX ¼ 5.1, JAM ¼ 11.7), 6.64 (d, 1H, HC, JCD ¼ 14.2),
7.01–8.10 (m, 9H, HD and Ar-H) 10.15 (bs, 1H, NH)
3.55 (dd, 2H, HX), 3.92 (dd, 2H, HM, JMX ¼ 10.1), 4.76 (dd, 2H,
HA, JAX ¼ 5.6, JAM ¼ 12.6), 6.92–7.89 (m, 10H, Ar-H), 10.20
(bs, 2H, NH)
3.58 (dd, 2H, HX), 3.98 (dd, 2H, HM, JMX ¼ 10.5), 4.72 (dd, 2H,
HA, JAX ¼ 5.5, JAM ¼ 12.6), 7.10–7.85 (m, 8H, Ar-H), 10.24
(bs, 2H, NH)
3.60 (dd, 2H, HX), 4.10 (dd, 2H, HM, JMX ¼ 10.5), 4.78 (dd, 2H,
HA, JAX ¼ 5.6, JAM ¼ 12.6), 6.90–7.86 (m, 10H, Ar-H), 10.22
(bs, 2H, NH)
2.25 (s, 6H, Ar-CH3), 3.52 (dd, 2H, HX), 4.12 (dd, 2H, HM,
JMX ¼ 10.5), 4.76 (dd, 2H, HA, JAX ¼ 5.5, JAM ¼ 12.6), 6.92–7.86
(m, 8H, Ar-H), 10.25 (bs, 2H, NH)
2.96 (dd, 1H, HX), 3.65 (dd, 1H, HM, JMX ¼ 16.8), 5.60 (dd, 1H,
HA, JAX ¼ 5.5, JAM ¼ 11.7), 6.62 (d, 1H, HC, JCD ¼ 14.2),
7.00–8.12 (m, 11H, HD, and Ar-H), 10.08 (bs, 1H, NH)
2.98 (dd, 1H, HX), 3.68 (dd, 1H, HM, JMX ¼ 16.9), 5.62 (dd, 1H,
HA, JAX ¼ 5.5, JAM ¼ 11.7), 6.61 (d, 1H, HC, JCD ¼ 14.2),
7.12–8.14 (m, 9H, HD, and ArH), 10.10 (bs, 1H, NH)
2.96 (dd, 1H, HX), 3.78 (dd, 1H, HM, JMX ¼ 17.1), 5.70 (dd, 1H,
HA, JAX ¼ 5.55, JAM ¼ 12.0), 6.78 (d, 1H, HC, JCD ¼ 14.2),
7.10–8.16 (m, 11H, HD, and Ar-H), 10.10 (bs, 1H, NH)
3.02 (dd, 1H, HX), 3.72 (dd, 1H, HM, JMX ¼ 16.8), 5.68 (dd, 1H,
HA, JAX ¼ 5.5, JAM ¼ 11.7), 6.78 (d, 1H, HC, JCD ¼ 14.2),
7.14–8.20 (m, 9H, HD, and Ar-H), 10.12 (bs, 1H, NH)
2.99 (dd, 2H, HX), 3.72 (dd, 2H, HM, JMX ¼ 16.9), 5.65 (dd, 2H,
HA, JAX ¼ 5.6, JAM ¼ 11.8), 6.92–7.89 (m, 10H, Ar-H), 10.00
(bs, 2H, NH)

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Bisolefinic Diketo Sulfides/Sulfones. II
3885
Table 2. Continued.
1H NMR ꢀ (CDCl3), ppm
Compd. no.
9c
2.95 (dd, 2H, HX), 3.82 (dd, 2H, HM, JMX ¼ 17.0), 5.66 (dd, 2H,
HA, JAX ¼ 5.6, JAM ¼ 11.7), 6.95–7.90 (m, 8H, Ar-H), 10.20 (bs,
2H, NH)
10a
10c
11a
2.92 (dd, 2H, HX), 3.80 (dd, 2H, HM, JMX ¼ 16.9), 5.76 (dd, 2H,
HA, JAX ¼ 5.6, JAM ¼ 11.9), 6.95–7.89 (m, 10H, Ar-H), 9.96 (bs,
2H, NH)
2.97 (dd, 2H, HX), 3.81 (dd, 2H, HM, JMX ¼ 17.0), 5.78 (dd, 2H,
HA, JAX ¼ 5.6, JAM ¼ 11.7), 6.98–7.92 (m, 8H, Ar-H), 10.21 (bs,
2H, NH)
0
2.906 0 (dd, 1H, HX0), 3.42 (dd, 1H, HX), 3.74 (dd, 1H, HM
JM X ¼ 16.7), 4.10 (dd, 1H, HM JMX ¼ 10.6), 4.72 (dd, 1H, HA,
0
0 0
JAX ¼ 5.6, JAM ¼ 12.6), 5.68 (dd, 1H, HA JA X ¼ 5.6,
0
0
JA M ¼ 11.8), 6.92–8.10 (m, 10H, Ar-H), 9.92 (bs, 1H, NH),
10.20 (bs, 1H, NH)
11b
12a
12b
2.24 (s, 6H, Ar-CH3), 2.98 (dd, 1H, HX0), 3.40 (dd, 1H, HX), 3.72
(dd, 1H, HM0, JA X ¼ 17.1), 4.11 (dd, 1H, HM, JMX ¼ 10.60), 4.75
0
0
(dd, 1H, HA, JAX ¼ 5.6, JAM ¼ 12.6), 5.64 (dd, 1H, HA0, JA X ¼ 5.6,
0
0
0
0
JA M ¼ 11.8), 7.10–8.14 (m, 8H, Ar-H), 9.96 (bs, 1H, NH), 10.24
(bs, 1H, NH)
0
3.002 0 (dd, 1H, HX0), 3.40 (dd, 1H, HX), 3.74 (dd, 1H, HM
,
JM X ¼ 16.8), 4.00 (dd, 1H, HM, JMX ¼ 10.6), 4.72 (dd, 1H, HA,
0
0 0
JAX ¼ 5.6, JAM ¼ 12.6), 5.76 (dd, 1H, HA
,
JA X ¼ 5.6,
0
0
JA M ¼ 11.7), 6.90–8.14 (m, 10H, Ar-H), 10.00 (bs, 1H, NH),
10.22 (bs, 1H, NH)
2.28 (s, 6H, Ar-CH3), 3.10 (dd, 1H, HX0), 3.42 (dd, 1H, HX), 3.78
(dd, 1H, HM0, JM X ¼ 17.1), 4.12 (dd, 1H, HM, JMX ¼ 10.6), 4.76
0
0
(dd, 1H, HA, JAX ¼ 5.6, JAM ¼ 12.6), 5.78 (dd, 1H, HA0, JA X ¼ 5.6,
0
0
0
0
JA M ¼ 11.7), 6.92–7.91 (m, 8H, Ar-H), 10.00 (bs, 1H, NH), 10.24
(bs, 1H, NH)
(9/10) as minor one. The methine and methylene protons of pyrazoline
ring in 7/8 also exhibited AMX splitting pattern. Thus three double doub-
lets were observed in the spectra of 7a at 5.60 (HA), 3.65 (HM) and 2.96
(HX) with coupling constants JAM ¼ 11.7, JMX ¼ 16.8, and JAX ¼ 5.5 and
in 8a at 5.70 (HA), 3.78 (HM) and 2.96 (HX) with coupling constants
JAM ¼ 11.8, JMX ¼ 16.9 and JAX ¼ 5.5. The HC showed a doublet at
6.62 (JCD ¼ 14.2) in 7a and at 6.78 (JCD ¼ 14.2) in 8a while HD merged
with aromatic protons and appeared as a multiplet. The 7/8 on
further treatment with hydrazine hydrate gave 9/10, which was also

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3886
Padmavathi et al.
obtained directly from 1/2 with excess hydrazine hydrate. The two
pyrazoline ring protons in 9/10 showed similar type of splitting pattern
as in 7/8 in their 1H NMR spectra (Table 2). On the other hand 3/4 with
hydrazine hydrate furnished 3-aroyl-30-aryl-bis-(2-pyrazolinyl)-[4,50]-
sulfide/sulfone (11/12), which has two different pyrazoline rings as
1
evidenced by their H NMR. The latter were also obtained by the treat-
ment of 7/8 with diazomethane. Interestingly enough in 11/12, the protons
HA, HM, and HX of ring A exhibited resonance signals almost in the same
region as in 3–6 while ring B protons as in 7–10. The authenticity of bis
1
pyrazolines obtained by different routes was confirmed by H NMR and
m.mp. The IR spectra of 3–12 showed absorption bands in the regions
1565–1575 (C ¼ N), 3330–3350 (NH). Apart from these 4, 6, 8, 10, and 12
displayed bands around 1325–1350, 1130–1150 (SO2), 3, 4, 7, 8 in the
region 1610–1620 (C ¼ C) and 3–8, 11, 12 around 1660–1685 (C ¼ O).
In conclusion, a novel type of bis pyrazolines have been developed
from bis(1-aryl-2-propen-1-one) sulfide/sulfone by either 2 þ 3 and/or
3 þ 2 cyclization of diazomethane and hydrazine hydrate.
EXPERIMENTAL
Melting points were determined on Tempo Mel-Temp apparatus and
were uncorrected. The IR spectra were recorded on a Perkin-Elmer grating
Infrared spectrophotometer model 337 as KBr pellets and the wave
1
numbers were in cmꢀ1. The H NMR spectra were recorded on Bruker
spectrospin 300 MHz spectrometer in CDCl3 with TMS as an internal
standard and the chemical shifts were measured in ppm. The purity of
the compounds was checked by TLC using silica gel ‘G’ (BDH) and
hexane-ethyl acetate as eluents. Microanalyses were performed by the
Regional Sophisticated Instrumentation Centre, Punjab University,
Chandigarh, India.
bis(1-Aryl-2-propen-1-one)-3,30-sulfide (1)
General Procedure
To a solution of 10 mmol of Na2S in 20 mL of methanol, 20 mmol of
1-aroyl-2-chloroethane in 20 mL of methanol was added dropwise with
stirring at room temperature for half an hour. The separated solid was
filtered, washed with water and recrystallized from methanol to get 1.

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Bisolefinic Diketo Sulfides/Sulfones. II
bis(1-Aryl-2-propen-1-one)-3,30-sulfone (2)
General Procedure
3887
To a solution of 10 mmoles of 1 in 20 mL of glacial acetic acid, 35 mL
of 30% hydrogen peroxide was added in portions and refluxed for 1–2 h.
The contents were cooled and poured onto crushed ice. The solid
obtained was filtered, washed with water and dried. The crude compound
was recrystallized from 2-propanol.
3-Aroyl-2-pyrazolinyl-20-aroylethenyl-[4,10]-sulfide/sulfone
(3/4) and bis(3,30-Aroyl-2-pyrazolinyl)-[4,40]-
sulfide/sulfone (5/6)
General Procedure
Method A. A solution of 10 mmoles of 1/2 in 20 mL of dichloro-
methane was cooled at an ice-salt bath temperature. To this 80 mL of
4 M ethereal solution of diazomethane and a catalytic amount of triethy-
lamine was added. The reaction mixture was kept at ꢀ20ꢁC to ꢀ15ꢁC for
48 h. The solvent was removed under reduced pressure. The resultant
product indicated a mixture in TLC which were separated by column
chromatography using ethyl acetate–hexane (1:3) as eluents and
identified as 3/4 and 5/6.
Method B. The compounds 5/6 were also obtained when a solution of
10 mmoles of 3/4 was treated with 40 mL of 4 M ethereal diazomethane
and triethylamine. The work-up procedure was same as above.
Method C. The compounds 5/6 were also prepared by the treatment
of 10 mmoles of 1/2 with 120 mL of 4 M ethereal diazomethane under
similar conditions.
3-Aryl-2-pyrazolinyl-20-aroylethenyl-[5,10]-sulfide/sulfone
(7/8) and bis(3,30-Aryl-2-pyrazolinyl)-[5,50]-
sulfide/sulfone (9/10)
General Procedure
Method A. A mixture of 10 mmoles of 1/2, 25 mmoles of 80% hydra-
zine hydrate in 20 mL of ethanol was refluxed for 2–3 h. The reaction
mixture was cooled and poured onto crushed ice. The solid obtained was

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3888
Padmavathi et al.
filtered and dried. The crude compound indicated two spots in TLC
which were separated by column chromatography and identified as 7/8
and 9/10.
Method B. The 9/10 were also obtained by the treatment of
10 mmoles of 7/8 with 15 mmoles of 80% hydrazine hydrate. The
resultant solid was purified by recrystallization from ethanol.
Method C. The compounds 1/2 with 30 mmoles of 80% hydrazine
hydrate under above conditions afforded only 9/10 which was purified by
recrystallization from ethanol.
3-Aroyl-30-aryl-bis-(2-pyrazolinyl)-[4,50]-sulfide/sulfone (11/12)
Method A. To a solution of 10 mmoles of 7/8 in 20 mL of dichloro-
methane 40 mL of ethereal diazomethane and a catalytic amount of
triethylamine was added. The reaction mixture was kept at ꢀ20ꢁC to
ꢀ15ꢁC for 48 h. This on work up afforded a product, 11/12, which was
recrystallized from ethanol.
Method B. The 11/12 was also obtained by refluxing 10 mmoles of
3/4 and 15 mmoles of 80% hydrazine hydrate in 20 mL of ethanol for
2–3 h. The solid separated was filtered and recrystallized from ethanol.
ACKNOWLEDGMENTS
One of us (MRGS) wishes to thank CSIR New Delhi, India for the
award of Senior Research Fellowship.
REFERENCES
1. (a) Joseph, J.P.; Dusza, J.P.; Bernstein. US Patent 4374251 1982;
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Bisolefinic Diketo Sulfides/Sulfones. II
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Received in India June 13, 2003

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