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M. G. Cabiddu et al. / Tetrahedron 58 "2002) 4529±4533
137.68, 139.06, 196.64 'CO). EI-MS m/z: 228 '51%,
M1), 213 '100%), 151 '26%), 123 '3%), 105 '19%), 77
'48%), 51 '21%), 45 '26%). Anal calcd for C14H12OS: C,
73.65; H, 5.30; S, 14.04%. Found: C, 73.57; H, 5.35; S,
13.87.
'M1, 21.1), 213 '100.0%), 184 '36.0%), 176 '8.0%), 165
'10.9%), 153 '1.7%), 152 '7.8%), 139 '3.9%), 82 '4.3%), 76
'10.2%), 63 '9.6%), 51 '9.6%). Anal calcd for C14H10O2S:
C, 69.40; H, 4.16; S, 13.23%. Found: C, 69.32; H, 4.21; S,
13.11.
1.1.6. 2-[-&Methylsulfonyl)phenyl]&phenyl)methanone &10).
To a vigorously stirred solution of 9 '2.3 g, 10mmol) in
dichloromethane '75 mL) 3-chloroperbenzoic acid '4.3 g,
25 mmol)) was gradually added at 5±108C. After the
addition was complete, the reaction mixture was worked
up in the same manner described for 5. The product was
¯ash-chromatographed on silica gel '2/1 petroleum ether/
diethyl ether). Yield 78%, crystallized from 1/1 aqueous
EtOH as white crystals; mp 128±1308C. IR 'nujol, cm21):
1.1.9. 1-[2-&Methylthio)phenyl]-1-ethanone &13). To a
vigorously stirred solution of 8 '2 g, 9.8 mmol) in anhy-
drous diethyl ether '20mL) a 1.2 M solution of butyllithium
in hexane '7.3 mL, 9.8 mmol) was added dropwise under
argon at 2258C and stirring was continued at the same
temperature for 0.5 h. The mixture was then cooled to
2808C and
a solution of methyl acetate '0.72 g,
9.8 mmol) in anhydrous diethyl ether '10mL) was gradu-
ally added under argon. After the addition was complete,
stirring was continued at the same temperature '2808C) for
2 h. The mixture was then allowed to warm to room
temperature with stirring, and then poured into water
'50mL). The pH was adjusted to 4±5 by addition of 10%
aqueous hydrochloric acid. The organic layer was separated,
and the aqueous layer extracted with diethyl ether '2£
20mL). The organic phases were combined and dried
'Na2SO4). Evaporation of the solvent was followed by
¯ash-chromatography on silica gel '2/1 petroleum ether/
diethyl ether). Yield 73%; crystallized from 2/1 aqueous
EtOH as pale yellow crystals, mp 46±488C. IR 'nujol,
cm21): 1762 'CO). 1H NMR 'CDCl3) d: 2.31 's, 3H,
SCH3), 2.51 's, 3H, COCH3), 7.41 'm, 4H, Ar±H). 13C
NMR 'CDCl3) d: 16.51 'SCH3), 28.82 'COCH3), 124.02,
125.48, 131.81, 133.00, 134.77, 143.34, 199.58 'CO).
EI-MS m/z: 166 '27%, M1), 151 '100%), 136 '2%), 123
'8%), 108 '7%), 91 '4%), 77 '10%), 69 '7%), 45 '52%),
43 '22%), 39 '4.5%). Anal calcd for C9H10OS: C, 65.02; H,
6.06; S, 19.29%. Found: C, 64.94; H, 5.97; S, 19.16.
1
1660'C vO), 1365 and 1155 'SO2). H NMR 'CDCl3) d:
3.28 's, 3H, SCH3), 7.71 'm, 9H, Ar-H). 13C NMR 'CDCl3)
d: 46.19 'SCH3), 128.32, 128.53, 129.90, 130.13, 130.45,
132.91, 133.94, 136.27, 139.41, 140.18, 196.28 'CO).
EI-MS m/z: 260'8%, M 1,), 213 '4%), 183 '22%), 181
'21%), 152 '10%), 105 '100%), 77 '46%), 51 '15%). Anal
calcd for C14H12O3S: C, 64.60; H, 4.65; S, 12.32%. Found:
C, 64.48; H, 4.59; S, 12.15.
1.1.7. 3-Hydroxy-3-phenyl-2,3-dihydro-1H-1-benzothio-
phene-1,1-dioxide &11). A solution of 10 '2 g, 7.7 mmol)
in anhydrous terahydrofuran '10mL) was added dropwise
at 2808C into a solution of LDA '7.8 mmol) in anhydrous
tetrahydrofuran '10mL). After the addition was complete,
stirring was continued overnight at the same temperature
'2808C). The mixture was then allowed to warm to room
temperature with stirring, and then poured into water
'50mL). The pH was adjusted to 4±5 by addition of 10%
aqueous hydrochloric acid. The organic layer was separated,
and the aqueous layer extracted with diethyl ether
'2£20mL). The organic phases were combined and dried
'Na2SO4). Evaporation of the solvent was followed by ¯ash-
chromatography on silica gel '2/1 petroleum ether/diethyl
ether). The crude product was crystallized from 1/1 aqueous
EtOH as white crystals. Yield 73%; mp 114±1168C 'Lit.15).
1.1.10. 1-[2-&Methylsulfonyl)phenyl]-1-ethanone &14). To
a vigorously stirred solution of 13 '1.7 g, 10mmol) in
dichloromethane '75 mL) 3-chloroperbenzoic acid '4.3 g,
25 mmol)) was gradually added at 5±108C. After the
addition was complete, the reaction mixture was worked
up in the same manner as described for 12. The product
was ¯ash-chromatographed on silica gel '2/1 petroleum
ether/diethyl ether). Yield 76%, crystallized from 1/1
aqueous EtOH as white crystals, mp 97±998C. IR 'nujol,
cm21): 1687 'CvO), 1320and 1155 'SO 2). 1H NMR
'CDCl3) d: 2.65 's, 3H, COCH3), 3.25 's, 3H, SO2CH3),
7.68 'm, 4H, Ar-H). 13C NMR 'CDCl3) d: 31.01
'COCH3), 46.01 'SO2CH3), 126.29, 129.82, 130.12,
133.48, 137.79, 142.26, 203.35 'CO). EI-MS m/z: 198
'2%, M1), 183 '100%), 152 '5%), 141 '3%), 121 '4%),
109 '6.5%), 91 '12%), 77 '15%), 50 '11%), 43 '33%).
Anal calcd for C9H10O3S: C, 54.53; H, 5.08; S, 16.18%.
Found: C, 54.61; H, 4.97; S, 16.07.
1
IR 'nujol, cm21): 3450'OH), 130and 1155 'SO 2). H
NMR 'CDCl3) d: 3.36 's. 1H, OH, D2O exchangeable),
3.84 's, 2H, CH2), 7.51 'm, 9H, Ar-H). 13C NMR
'acetone-d6) d: 66.55 'CH2), 77.30' C±OH) 120.50,
125.74, 126.74, 128.52, 128.94, 130.65, 134.23, 139.60,
144.31, 145.00. EI-MS m/z: 260'2%, M 1), 242 '31%),
225 '20.5%), 213 '100%), 195 '23%), 194 '25%), 181
'20.5%), 165 '18%), 152 '20.5%), 105 '36%), 91 '32%),
77 '45%), 51 '18%). Anal calcd for C14H12O3S: C, 64.60;
H, 4.65; S, 12.32%. Found: C, 64.52; H, 4.57; S, 12.20.
1.1.8. 3-Phenyl-1-benzothiophene-1,1-dioxide &12). A
solution of 11 '1 g, 3.8 mmol) and p-toluenesulfonic
'0.1 g) in anhydrous benzene '10 mL) was heated at re¯ux
temperature with stirring for 30min, then poured into water
'50mL). This mixture was extracted with ether '2 £20mL),
washed with water '3£10mL), dried 'Na 2SO4), and concen-
trated. Yield 97%; crystallized from EtOH as white crystals;
mp 159±1608C 'Lit.17 mp 158±1608C). IR 'nujol, cm21):
1.1.11. 3-Hydroxy-3-methyl-2,3-dihydro-1H-1-benzothio-
phene-1,1-dioxide &15). A solution of 14 '2 g, 10.1 mmol)
in anhydrous tetrahydrofuran '10mL) was added dropwise
into a solution of LDA '10.2 mmol) in anhydrous tetra-
hydrofuran '10mL). After the addition was complete the
mixture was worked up in the same manner as described
for 11. The crude product was ¯ash-chromatographed using
diethyl ether as eluent. Yield 68%; crystallized as white
crystals from 5/1 hexane/acetone, mp 102±1048C 'Lit.15
1
1318 and 1155 'SO2). H NMR 'CDCl3) d: 6.91 's, 1H,
SO2CH), 7.54 'm, 9H, Ar-H). 13C NMR 'CDCl3) d:
121.65, 124.15, 125.78, 128.01, 129.21, 130.62, 131.14,
131.97, 133.28, 138.24, 144.15. EI-MS m/z: '%): 242