492
D. B. Reddy et al.
PAPER
Table 1 Selected Physical and Spectroscopic Data of 3, 7 and 8
Prod-
ucta
Ar
Yield
(%)
mp or bp
IR
1H NMR (CDCl3)
δ, J (Hz)
M+
Ð
(¡C) (¡C/mm) ν (cmÐ1)
3a
3b
3c
7a
7b
7c
C6H5
68
74
71
80
85
74
122Ð125/16b
145Ð147/15
150Ð153/18
78Ð79c
1670, 1592
6.85 (d, 1 H, Hb, J = 14), 7.05Ð7.92 (m, 6 H,
Ha, 5 Harom
)
4-ClC6H4
4-NO2C6H4
C6H5
1664, 1597
6.87 (d, 1 H, Hb, J = 13.8), 7.12Ð8.02 (m, 5 201, 203 (m + 2),
H, Ha, 4 Harom 205 (m + 4)
)
1673, 1601, 6.82 (d, 1 H, Hb, J = 13.8), 7.14Ð7.98 (m, 5 211, 213 (m + 2)
1382
H, Ha, 4 Harom
)
1296, 1136
4.01 (d, 2 H, CH2, J = 6.0), 6.22 (t, 1 H,
CHCl2), 7.55Ð8.15 (m, 5 Harom
Ð
)
4-CH3C6H4
4-ClC6H4
59Ð60
1301, 1152
1304, 1126
2.02 (s, 3 H, CH3), 3.98 (d, 2 H, CH2, J = 6.1), 253, 255 (m + 2),
6.24 (t, 1 H, CHCl2), 7.49Ð8.12 (m, 4 Harom 257 (m + 4)
)
95Ð96
4.06 (d, 2 H, CH2, J = 6.0), 6.15 (t, 1 H, 273, 275 (m + 2),
CHCl2), 7.50Ð8.17 (m, 4 Harom
)
277 (m + 4), 279
(m + 6)
8a
8b
8c
C6H5
78
83
80
47Ð49d
45Ð46e
90Ð92f
1598, 1305, 6.60 (d, 1 H, Hb, J = 12), 7.45Ð8.12 (m, 6 H,
1130 Ha, 5 Harom
Ð
Ð
Ð
)
4-CH3C6H4
4-ClC6H4
1601, 1294, 2.10 (s, 3 H, CH3), 6.64 (d, 1 H, Hb, J = 12.0),
1126 7.32Ð8.10 (m, 5 H, Ha, 4 Harom
)
1605, 1302, 6.63 (d, 1 H, Hb, J = 12.2), 7.48Ð8.10 (m, 5
1135 H, Ha, 4 Harom
)
d Lit.6 mp 49Ð50¡C
e Lit.6 mp. 48¡C.
f Lit.6 mp 96Ð97¡C
a Satisfactory microanalysis obtained: C ± 0.23, H ± 0.12
b Lit.10 bp 125Ð127¡C/18 mm
c Lit.11 mp 80Ð82¡C
1-Aroyl-2-chloroethenes 3; General Procedure
1-Arylsulfonyl-2-chloroethenes 8; General Procedure
Into the solution of aroyl chloride (5 mmol) in CHCl3 (50 mL) kept
at 10Ð15¡C, anhyd AlCl3 (5 mmol) was added portionwise. The
temperature of the mixture was slowly raised to 55Ð65¡C and vinyl
chloride gas (an equimolar mixture of 1,2-dichloroethane and alc.
KOH) was passed through the mixture for 24 h. Stirring was contin-
ued for an additional period of 30 min and the contents were poured
onto crushed ice and extracted with CHCl3. The combined extracts
were washed with sat. NaHCO3 and H2O, dried (Na2SO4) and the
solvent was distilled off. The syrupy liquid obtained was distilled
under reduced pressure to get pure 1-aroyl-2-chloroethene. The
physical and spectroscopic data are given in Table 1.
Et3N (1 mmol) in benzene (20 mL) was added dropwise to an ice
cold solution of 1-arylsulfonyl-2,2-dichloroethane (1 mmol) in ben-
zene (50 mL) over 45 min and kept aside for 16Ð18 h. The precipi-
tated triethylamine hydrochloride was filtered off. The filtrate was
neutralised with 6M HCl. The organic layer was separated, dried
and solvent was removed under vacuum to get 8, which was puri-
fied by filtration through a column of silica gel (60Ð120) mesh,
BDH with hexane/EtOAc, 3:2 as eluent). The physical and spectro-
scopic data are given in Table 1.
1,2-Diarylsulfonylethenes 9; General Procedure
Method A: A solution of 1-arylsulfonyl-2-chloroethene (1.2 mmol)
in MeOH (20 mL) was added dropwise to 4 (1.2 mmol) in H2O (10
mL) and stirred at r.t. for 3 h. The crude compound separated was
filtered and recrystallized from MeOH to get 9.
1-Aroyl-2-arylsulfonylethenes 5; General Procedure
To a solution of 1-aroyl-2-chloroethene (5 mmol) in MeOH
(20 mL), 412 (5.5 mmol) in H2O (20 mL) was added dropwise with
stirring at r.t. for 5 h. The crystallized solid was filtered, washed
with H2O, dried (Na2SO4) and recrystallized from MeOH. The
physical and spectroscopic data are given in Table 2.
Method B:
A mixture of 1-arylsulfonyl-2,2-dichloroethane
(1.2 mmol) and 4 (2.4 mmol) in MeOH (20 mL) in H2O (10 mL)
was stirred at r.t. for 5 h. The solid obtained was filtered, dried and
recrystallized from MeOH to get 9. The physical and spectroscopic
data are given in Table 2.
1-Arylsulfonyl-2,2-dichloroethanes 7; General Procedure
Into a well stirred solution of arylsulfonyl chloride (5 mmol) in
CHCl3 (100 mL) kept at 10Ð15¡C was added gradually anhyd AlCl3
(5 mmol). The temperature of the mixture was slowly raised to 55Ð
65¡C and vinyl chloride gas was passed for 18 h. Stirring was con-
tinued for an additional period of 30 min and the resulting mixture
was poured onto crushed ice. The organic layer was separated,
washed with H2O, dried (Na2SO4) and the solvent was removed un-
der vacuum. The solid obtained was recrystallized from pet.ether/
EtOAc. The physical and spectroscopic data are given in Table 1.
Acknowledgement
Two of the authors (NCB and RPS) wishes to thank CSIR, New
Delhi, India for the award of Senior Research Fellowships.
Synthesis 1999, No. 3, 491–494 ISSN 0039-7881 © Thieme Stuttgart · New York