238 JOURNAL OF CHEMICAL RESEARCH 2009
6-Bromo-3-(2-(styrenesulfonyl)acetyl)-2H-chromen-2-one (3b):
7LPHꢐꢃꢋꢈꢃPLQꢂꢃSDOHꢃ\HOORZꢃVROLGꢂꢃ\LHOGꢃꢎꢋꢊꢂꢃPꢆSꢆꢃꢋꢑꢌ±ꢑꢄ°C. IR (KBr,
Jmax cm-1): 1137, 1357 (SO2), 1623 (C=C), 1689 (C=O), 1733 (C=O
of lactone), 1H NMR (CDCl3, GꢃSSPꢀꢐꢃꢍꢆꢋꢍꢃꢇVꢂꢃꢌ+ꢂꢃ±&+2), 7.24(d,
1H, SO2 H& &+ꢀꢂꢃꢑꢆꢏꢍ±ꢑꢆꢎꢑꢃꢇPꢂꢃꢎ+ꢂꢃ$U+ꢃDQGꢃ622HC=CH), 8.84 (s,
1H, C4 of coumarin proton), Anal. Calcd for C19H13 BrO5S: C, 52.67;
H, 3.02; S, 7.40. Found: C, 52.61; H, 3.00; S, 7.44%.
6, 8-Dibromo-3-(2-(styrenesulfonyl)acetyl)-2H-chromen-2-one (3c):
Time: 22 min, pale yellow solid, yield 90%, m.p. 180°C. IR (KBr,
Jmax cm-1): 1135, 1351 (SO2), 1601 (C=C), 1692 (C=O), 1740(C=O
of lactone), 1H NMR (CDCl3, GꢃSSPꢀꢐꢃꢄꢆꢎꢈꢃꢇVꢂꢃꢌ+ꢂꢃ±&+2), 6.95(d,
1H, J = 16 Hz SO2 H& &+ꢀꢂꢃꢑꢆꢌ±ꢑꢆꢉꢃꢇPꢂꢃꢈ+ꢂꢃ$U+ꢃDQGꢃ622HC=CH),
8.4 (s, 1H, C4 of coumarin proton), Anal. Calcd for C19H12 Br2O5S:
C, 44.56; H, 2.36; S, 6.26. Found: C, 44.52; H, 2.32; S, 6.30%.
6-Chloro-3-(2-(styrenesulfonyl)acetyl)-2H-chromen-2-one (3d):
Time: 19 min, pale yellow solid, yield 93%, m.p. 152°C. IR (KBr,
Jmax cm-1): 1128, 1322 (SO2), 1607 (C=C), 1692 (C=O), 1734 (C=O
of lactone), 1H NMR (CDCl3, Gꢃ SSPꢀꢐꢃ ꢄꢆꢈꢎꢃ ꢇVꢂꢃ ꢌ+ꢂꢃ ±&+2ꢀꢂꢃ ꢑꢆꢄꢎ±
7.56 (m, 6H, ArH and SO2H& &+ꢀꢂꢃ ꢑꢆꢑꢎ±ꢑꢆꢈꢏꢃ ꢇPꢂꢃ ꢌ+ꢂꢃ$U+ꢃ DQGꢃ
SO2HC=CHꢀꢂꢃꢈꢆꢅꢑ±ꢈꢆꢋꢌꢃꢇPꢂꢃꢌ+ꢂꢃ$U+ꢀꢃꢈꢆꢑꢈꢃꢇVꢂꢃꢋ+ꢂꢃ&4 of coumarin
proton.) Anal. Calcd for C19H13 ClO5S: C, 58.69; H, 3.37; S, 8.25.
Found: C, 58.64; H, 3.31; S, 8.20%.
6, 8-Dichloro-3-(2-(styrenesulfonyl)acetyl)-2H-chromen-2-one (3e):
7LPHꢐꢃ ꢌꢋꢃ PLQꢂꢃ SDOHꢃ \HOORZꢃ VROLGꢂꢃ \LHOGꢃ ꢎꢅꢊꢂꢃ PꢆSꢆꢃ ꢋꢉꢈ±ꢋꢑꢅ°C.
IR (KBr, Jmax cm-1): 1135, 1325 (SO2), 1623 (C=C), 1608 (C=O),
1734 (C=O of alctone), 1H NMR (CDCl3, G ppm): 4.69 (s, 2H,
±&+2ꢀꢂꢃꢑꢆꢄꢎ±ꢑꢆꢍꢏꢃꢇPꢂꢃꢍ+ꢂꢃ$U+ꢃDQGꢃ622H& &+ꢀꢂꢃꢑꢆꢑꢍ±ꢑꢆꢑꢎꢃꢇPꢂꢃꢌ+ꢂꢃ
ArH and SO2HC=CHꢀꢂꢃꢈꢆꢅꢈ±ꢈꢆꢋꢌꢃꢇPꢂꢃꢌ+ꢂꢃ$U+ꢀꢂꢃꢈꢆꢉꢋꢃꢇVꢂꢃꢋ+ꢂꢃ&4 of
coumarin proton). Anal. Calcd for C19H12Cl2O5S: C, 53.91; H, 2.86;
S, 7.58. Found: C, 53.86; H, 2.81; S, 7.54%.
3-(2-(Styrenesulfonyl)acetyl)-2H-benzo[h]chromen-2-one (3f): Time:
ꢌꢄꢃPLQꢂꢃ<HOORZꢃVROLGꢂꢃ\LHOGꢃꢈꢎꢊꢂꢃPꢆSꢆꢃꢌꢅꢉ±ꢌꢅꢈ°C. IR (KBr, Jmax cm-1):
1127, 1343 (SO2), 1609 (C=C), 1623 (C=O), 1716 (C=O of lactone)
1H NMR (CDCl3, GꢃSSPꢀꢐꢃꢄꢆꢑꢉꢃꢇVꢂꢃꢌ+ꢂꢃ±&+2ꢀꢂꢃꢑꢆꢉꢌ±ꢑꢆꢉꢈꢃꢇPꢂꢃꢉ+ꢂꢃ$U+ꢃ
and SO2HC=CH), 8.07 (d, 1H, J = 15 Hz, SO2HC=CHꢀꢂꢃꢈꢆꢏꢅ±ꢈꢆꢏꢏꢃꢇPꢂꢃ
6H, ArH), 8.6 (s, 1H, C4 coumarin proton). Anal. Calcd for C23H16O5S:
C, 68.30; H, 3.99; S, 7.93. Found: C, 68.24; H, 3.91; S, 7.89%.
3-(2-(p-Methylstyrenesulfonyl)acetyl)-2H-chromen-2-one
(3g):
7LPHꢐꢃꢋꢄꢃPLQꢂꢃSDOHꢃ\HOORZꢃVROLGꢂꢃ\LHOGꢃꢎꢏꢊꢂꢃPꢆSꢆꢃꢋꢏꢌ±ꢋꢄꢄ°C. IR (KBr,
Jmax cm-1): 1119, 1307 (SO2), 1606 (C=C), 1692 (C=O), 1725 (C=O
of lactone), 1H NMR (CDCl3, G ppm): 2.38 (s, 3H, CH3), 5.07 (s, 2H,
±&+2), 7.01 3 (d, 1H, J = 15 Hz, SO2 HC=CH), 7.54 (d, 1H, J = 15 Hz,
SO2HC=CHꢀꢂꢃꢑꢆꢋꢈ±ꢑꢆꢉꢈꢃꢇPꢂꢃꢈ+ꢂꢃ$U+ꢀꢂꢃꢈꢆꢍꢑꢃꢇVꢂꢃꢋ+ꢂꢃ&4 of coumarin
proton), 13C NMR (CDCl3 G ppm), 21.5, 65.0, 116.8, 118.0, 123.3,
124.3, 125.3, 128.7, 129.2, 129.8, 130.6, 135.2, 142.2, 145.3, 149.2,
155.4, 159.2, 186.2, EI-MS 367 [M-H]-.Anal. Calcd for C20H16O5S: C,
65.20; H, 4.38; S, 8.70. Found: C, 65.10; H, 4.30; S, 8.64%.
6-Bromo-3-(2-(p-methylstyrenesulfonyl)acetyl)-2H-chromen-2-
one (3h):ꢃ 7LPHꢐꢃ ꢋꢈꢃ PLQꢂꢃ SDOHꢃ \HOORZꢃ VROLGꢂꢃ \LHOGꢃ ꢎꢌꢊꢂꢃ PꢆSꢆꢃ ꢋꢑꢉ±
178°C. IR (KBr, Jmax cm-1): 1137, 1357 (SO2), 1606 (C=C), 1683
(C=O), 1736 (C=O of lactone), 1H NMR (CDCl3, G ppm): 2.9(s, 3H,
CH3ꢀꢂꢃꢍꢆꢋꢍꢃꢇVꢂꢃꢌ+ꢂꢃ±&+2), 7.25 (d, 1H, J = 15 Hz, SO2 HC=CH),
ꢑꢆꢏꢅ±ꢑꢆꢈꢅꢃꢇPꢂꢃꢈ+ꢂꢃ$U+ꢃDQGꢃ622HC=CH), 8.79 (s, 1H, C4 of coumarin
proton), Anal. Calcd for C20H15BrO5S: C, 53.70; H, 3.38; S, 7.17.
Found: C, 53.78; H, 3.32; S, 7.10%.
6, 8-Dibromo 3-(2-(p-methylstyrenesulfonyl)acetyl)-2H-chromen-
2-one (3i):ꢃ7LPHꢐꢃꢌꢄꢃPLQꢂꢃSDOHꢃ\HOORZꢃVROLGꢂꢃ\LHOGꢃꢎꢅꢊꢂꢃPꢆSꢆꢃꢋꢉꢈ±
170°C. IR (KBr, Jmax cm-1): 1127, 1317 (SO2), 1603 (C=C), 1691
(C=O), 1740 (C=O of lactone), 1H NMR (CDCl3, G ppm): 2.4 (s,
3H, CH3ꢀꢂꢃꢄꢆꢎꢃꢇVꢂꢃꢌ+ꢂꢃ±&+2), 7.15 (d, 1H, J = 15 Hz, SO2 HC=CH),
ꢑꢆꢏ±ꢑꢆꢍꢇPꢂꢃꢑ+ꢂꢃ$U+ꢃDQGꢃ622HC=CH), 8.4 (s, 1H, C4 of coumarin
proton), Anal. Calcd for C20H14Br2O5S: C, 45.65; H, 2.68; S, 6.09.
Found: C, 45.60; H, 2.72; S, 6.12%.
6-Chloro-3-(2-(p-methylstyrenesulfonyl)acetyl)-2H-chromen-
2-one (3j):ꢃ7LPHꢐꢃꢋꢑꢃPLQꢂꢃSDOHꢃ\HOORZꢃVROLGꢂꢃ\LHOGꢃꢎꢌꢊꢂꢃPꢆSꢆꢃꢋꢍꢉ±
157°C. IR (KBr, Jmax cm-1): 1128, 1315 (SO2), 1609 (C=C), 1690
(C=O), 1735 (C=O of lactone), 1H NMR (CDCl3, G ppm): 2.4 (s, 3H,
CH3ꢀꢂꢃꢍꢆꢅꢃꢇVꢂꢃꢌ+ꢂꢃ±&+2), 6.95(d, 1H, J = 15 Hz, SO2 H& &+ꢀꢃꢑꢆꢌ±ꢑꢆꢑꢃ
(m, 8H, ArH and SO2HC=CH), 8.4 (s, 1H, C4 of coumarin proton),
Anal. Calcd for C20H15ClO5S: C, 59.63; H, 3.75; S, 7.96. Found: C,
59.72; H, 3.79; S, 7.93%.
6, 8-Dichloro-3-(2-(p-methylstyrenesulfonyl)acetyl)-2H-chromen-
2-one (3k):ꢃ7LPHꢐꢃꢌꢌꢃPLQꢂꢃSDOHꢃ\HOORZꢃVROLGꢂꢃ\LHOGꢃꢎꢅꢊꢂꢃPꢆSꢆꢃꢋꢉꢌ±
164°C. IR (KBr, Jmax cm-1): 1127, 1317 (SO2), 1609 (C=C), 1685
(C=O), 1738 (C=O of lactone) 1H NMR (CDCl3, G ppm): 2.38 (s,
3H, CH3ꢀꢂꢃꢄꢆꢈꢍꢃꢇVꢂꢃꢌ+ꢂꢃ±&+2ꢀꢂꢃꢑꢆꢌꢅ±ꢑꢆꢄꢃꢇPꢂꢃꢈ+ꢂꢃ$U+ꢃDQGꢃHWK\OHQHꢃ
protons), 8.2 (s, 1H, C4 of coumarin proton), Anal. Calcd for
C20H14Cl2O5S: C, 54.93; H, 3.23; S, 7.33. Found: C, 54.90; H, 3.29;
S, 7.38%.
Table 1 Optimisation of reaction for the formation of 3a under
a range of condition
Entry Solvent
Time/h
Isolated
yield/%a
3-(2-(p-Methylstyrenesulfonyl)acetyl)-2H-benzo[h]chromen-2-one
(3l): Time: 27 min, yellow solid, yield 88%, m.p. 214°C. IR (KBr,
Jmax cm-1): 1130, 1313 (SO2), 1620 (C=C), 1673 (C=O), 1721 (C=O
of lactone), 1H NMR (CDCl3, G ppm): 2.40 (s, 3H, CH3), 4.9 (s, 2H,
±&+2), 7.17 (d, 1H, J = 15 Hz, SO2 H& &+ꢀꢂꢃ ꢑꢆꢌꢍ±ꢑꢆꢑꢃ ꢇPꢂꢃ ꢋꢋ+ꢂꢃ$U+ꢃ
and SO2HC=CH), 8.4 (s, 1H, C4 of coumarin proton), Anal. Calcd for
C24H18O5S: C, 68.88; H, 4.34; S, 7.66. Found: C, 68.82; H, 4.30; S, 7.61%.
1
2
3
4
5
6
7
Absolute ethanol
8
42
58
Aqueous ethanol
DMF
8
8
8
0.15
0.15
0.12
66
Aqueous DMF
70
Solid state (few drops of DMF)
Solid state (1 equiv of K2CO3)
PEG-400
86b
70b
94c
This work was supported by grants from CSIR, New Delhi
for the sanction of the project (No.01 (2062) 06/EMR-II) is
gratefully acknowledged.
aReagents and conditions: D-halo ketone (1 mmol) sodium
E-styrenesulfinate (1.25 mmol), reflux temperature in given
solvent.
Received 7 December 2008; accepted 2 February 2009
Published online: 21 April 2009
bReaction was carried out at solid state.
cReaction was carried out at room temperture.
R1
R1
R2
O
O
O
O
O
O
R2
PEG-400
rt
O
S
O
+
R
Br
R
SO2Na
1
2
3
(g) R= R1=H, R2=CH3
(h) R=Br, R 1=H,R2=CH3
(i) R=R 1=Br, R2=CH3
(j) R=Cl, R 1=R2=CH3
(k) R=R 1=Cl, R2=CH3
(l) 7,8 benzo, R 2=CH3
(a) R= R 1= R2= H
(b) R=Br, R 1
=R2=H
(c) R=R 1=Br, R2=H
(d) R=Cl, R 1
=R2=H
(e) R=R 1=Cl, R2=H
(f) 7,8 benzo, R 2=H
Scheme 1