CH3CH2CH2), 2.61–2.78 (2 H, t, J 7, CH2CO), 3.07 (3 H, s,
CH3SO2) and 4.08 (2 H, s, CH2SO2); δC(CDCl3) 13.77 (CH3),
21.96 (CH2), 25.01 (CH2), 41.58 (CH3SO2), 44.51 (CH2), 64.39
(CH2SO2) and 199.92 (CO).
δH (CDCl3) 1.52–1.73 (4 H, m, 2 × CH2), 2.54–2.81 (4 H, m,
PhCH2 and CH2CO), 3.04 (3 H, s, CH3SO2), 4.02 (2 H, s,
CH2SO2) and 7.14–7.36 (5 H, m, aromatic H); δC(CDCl3) 22.53,
30.44, 35.56 (3 × CH2), 41.44 (CH3SO2), 44.67 (CH2), 64.49
(CH2SO2), 125.85, 128.37 (aromatic CH), 141.86 (aromatic C)
and 199.47 (CO).
1-Methylsulfonylheptan-2-one 2. This was prepared following
the procedure described for 1 from sodium hydride (2.83 g, 60%
in mineral oil, 0.07 mol) and dimethyl sulfone (6.60 g, 0.07 mol)
in DMSO (20 ml), THF (30 ml) and ethyl hexanoate (5.01 g,
0.035 mol) in THF (10 ml). Purification by chromatography on
silica gel using gradient ethyl acetate–hexane as eluent gave 1-
methylsulfonylheptan-2-one 2 (3.36 g, 50%) as a white crystal-
line solid; mp 41–42 ЊC (lit.,10 42 ЊC, lit.,11 28–30 ЊC) (Found: C,
50.0; H, 8.2; S, 16.9. C8H16O3S requires C, 49.97; H, 8.39; S,
16.67%); νmax(KBr)/cmϪ1 1717, 1312 and 1143; δH (CDCl3) 0.83–
1.73 [9 H, m, CH3(CH2)3], 2.65–2.74 (2 H, t, J 7, CH2CO), 3.06
(3 H, s, CH3SO2) and 4.08 (2 H, s, CH2SO2); δC(CDCl3) 14.01
(CH3), 22.42, 28.46, 31.42 (3 × CH2), 41.55 (CH3SO2), 44.85
(CH2), 64.38 (CH2SO2) and 199.91 (CO).
1-Methylsulfonyloctan-2-one 3. This was prepared following
the procedure described for 1 from sodium hydride (1.60 g, 60%
in mineral oil, 0.04 mol) and dimethyl sulfone (3.78 g, 0.04 mol)
in DMSO (20 ml), THF (30 ml) and ethyl heptanoate (3.16 g,
0.02 mol) in THF (20 ml). Recrystallisation from diethyl ether
gave 1-methylsulfonyloctan-2-one 3 (2.10 g, 51%) as a white
crystalline solid; mp 46–47 ЊC (Found: C, 52.6; H, 8.9; S, 15.8.
C9H18O3S requires C, 52.40; H, 8.79; S, 15.54%); νmax(KBr)/
cmϪ1 1720, 1320 and 1140; δH (CDCl3) 0.85–0.95 (3 H, m, CH3),
1.20–1.40 [6 H, m, CH3(CH2)3], 1.52–1.70 (2 H, m,
CH2CH2CO), 2.65–2.75 (2 H, t, J 7, CH2CO), 3.10 (3 H, s,
CH3SO2) and 4.07 (2 H, s, CH2SO2); δC(CDCl3) 14.12 (CH3),
22.17, 22.72, 27.14, 29.70 (4 × CH2), 41.26 (CH3SO2), 44.62
(CH2), 64.56 (CH2SO2) and 199.81 (CO).
1-Methylsulfonylnonan-2-one 4. This was prepared following
the procedure described for 1 from sodium hydride (0.83 g, 60%
in mineral oil, 0.02 mol) and dimethyl sulfone (1.90 g, 0.02 mol)
in DMSO (15 ml), THF (20 ml) and ethyl octanoate (1.72 g, 0.01
mol) in THF (10 ml). Recrystallisation from diethyl ether gave
1-methylsulfonylnonan-2-one 4 (1.51 g, 69%) as a white crystal-
line solid; mp 43–45 ЊC (lit.,10 56 ЊC) (Found: C, 54.41; H,
9.37. C10H20O3S requires C, 54.51; H, 9.15%); νmax(KBr)/cmϪ1
1705, 1309 and 1139; δH (CDCl3) 0.77–0.98 (3 H, t, J 7,
CH3), 1.15–1.43 [8 H, m, CH3(CH2)4], 1.56–1.72 (2 H, m,
CH2CH2CO), 2.64–2.76 (2 H, t, J 7, CH2CO), 3.07 (3 H, s,
CH3SO2) and 4.06 (2 H, s, CH2SO2); δC(CDCl3) 14.45 (CH3),
22.97, 23.36, 29.14, 29.36, 31.99 (5 × CH2), 41.88 (CH3SO2),
45.30 (CH2), 64.87 (CH2SO2) and 200.19 (CO).
1-Methylsulfonyl-5-phenylpentan-2-one 5. This was prepared
following the procedure described for 1 from sodium hydride
(0.83 g, 60% in mineral oil, 0.02 mol) and dimethyl sulfone
(1.90 g, 0.02 mol) in DMSO (15 ml), THF (20 ml) and ethyl
4-phenylbutanoate (1.92 g, 0.01 mol) in THF (20 ml).
Recrystallisation from diethyl ether gave 1 methylsulfonyl-5-
phenylpentan-2-one 5 (1.47 g, 61%) as a white crystalline solid;
mp 45–46 ЊC (Found: C, 59.74; H, 7.03; S, 13.84. C12H16O3S
requires C, 59.98; H, 6.71; S, 13.34%); νmax(KBr)/cmϪ1 1702,
1305 and 1138; δH (CDCl3) 1.84–2.00 (2 H, m, CH2), 2.56–2.78
(4 H, m, PhCH2 and CH2CO), 3.03 (3 H, s, CH3SO2) 3.99 (2 H,
s, CH2SO2) and 7.12–7.38 (5 H, m, aromatic H); δC(CDCl3)
24.47 (CH2), 34.97 (CH2), 41.47 (CH3SO2), 44.06 (CH2), 64.49
(CH2SO2), 126.16, 128.48 (aromatic CH), 141.02 (aromatic C)
and 199.38 (CO).
Sodium borohydride reduction of â-keto sulfones
1-Methylsulfonylhexan-2-ol 7. 1-Methylsulfonylhexan-2-one
1 (0.10 g, 0.56 mmol) in ethanol (10 ml) was added dropwise
over 5 min to sodium borohydride (0.025 g, 0.66 mmol) in etha-
nol (15 ml) while stirring at 0 ЊC under nitrogen. Stirring was
continued for 20 min then water (10 ml) was added and the
reaction mixture was concentrated at reduced pressure. The
residue was partitioned between diethyl ether (40 ml) and water
(10 ml) and the layers were separated. The aqueous layer was
washed with diethyl ether (3 × 20 ml) and the combined organic
extracts were washed with brine (20 ml), dried (MgSO4), filtered
and concentrated at reduced pressure. Purification by passage
through a short column of silica gel using dichloromethane as
eluent gave 1-methylsulfonylhexan-2-ol 7 (0.092 g, 91%) as a
white crystalline solid; mp 44–46 ЊC (Found: C, 46.84; H, 9.01; S,
17.58. C7H16O3S requires C, 46.64; H, 8.95; S, 17.79%);
νmax(KBr)/cmϪ1 3420 (br), 1290 and 1124; δH (CDCl3) 0.73–0.92
(3 H, t, J 7, CH3), 1.13–1.63 [6 H, m, CH3(CH2)3], 2.12 (1 H,
s, OH), 2.91–3.19 (5 H, m, CH3SO2CH2, contains s for CH3SO2
at 2.94) and 4.13–4.30 (1 H, m, CHOH); δC(CDCl3) 13.47
(CH3), 21.92, 26.72, 36.02 (3 × CH2), 42.12 (CH3SO2), 60.32
(CH2SO2) and 66.12 (CHOH).
1-Methylsulfonylheptan-2-ol 8. Reduction was conducted as
described for 1 using 1-methylsulfonylheptan-2-one 2 (0.10 g,
0.52 mmol) in ethanol (10 ml) and sodium borohydride (0.02 g,
0.53 mmol) in ethanol (15 ml) to give 1-methylsulfonylheptan-
2-ol 8 (0.093 g, 92%) as a white crystalline solid; mp 52–54 ЊC
(Found: C, 49.6; H, 9.4; S, 16.4. C8H18O3S requires C, 49.46; H,
9.34; S, 16.50%); νmax(KBr)/cmϪ1 3430 (br), 1305 and 1140;
δH (CDCl3) 0.76–0.89 (3 H, t, J 7, CH3), 1.17–1.64 [8 H, m,
CH3(CH2)4], 2.81–2.89 (1 H, d, J 10, OH), 2.94–3.19 (5 H, m,
CH3SO2CH2, contains s for CH3SO2 at 2.96) and 4.14–4.28 (1
H, m, CHOH); δC(CDCl3) 13.96 (CH3), 22.51, 24.74, 31.46,
36.82 (4 × CH2), 42.62 (CH3SO2), 60.84 (CH2SO2) and 66.59
(CHOH).
1-Methylsulfonyloctan-2-ol 9. Reduction was conducted as
described for 1 using 1-methylsulfonyloctan-2-one 3 (0.10 g,
0.48 mmol) in ethanol (10 ml) and sodium borohydride (0.02 g,
0.53 mmol) in ethanol (15 ml) to give 1-methylsulfonylheptan-2-
ol 9 (0.088 g, 88%) as a white crystalline solid; mp 57–60 ЊC
(Found: C, 52.26; H, 9.36; S, 15.83. C9H20O3S requires C, 51.89;
H, 9.68; S, 15.39%); νmax(KBr)/cmϪ1 3500 (br), 1291 and 1130;
δH (CDCl3) 0.80–0.97 (3 H, t, J 7, CH3), 1.20–1.71 [10 H, m,
CH3(CH2)5], 2.80–2.91 (1 H, br s, OH), 2.97–3.26 (5 H, m,
CH3SO2CH2, contains s for CH3SO2 at 3.04) and 4.23–4.40 (1
H, m, CHOH); δC(CDCl3) 14.01 (CH3), 22.54, 25.05, 28.99,
31.61, 36.89 (5 × CH2), 42.65 (CH3SO2), 60.98 (CH2SO2) and
66.67 (CHOH).
1-Methylsulfonylnonan-2-ol 10. Reduction was conducted as
described for 1 using 1-methylsulfonylnonan-2-one 4 (0.10 g,
0.45 mmol) in ethanol (10 ml) and sodium borohydride (0.023
g, 0.60 mmol) in ethanol (15 ml) to give 1-methyl-
sulfonylheptan-2-ol 10 (0.095 g, 95%) as a white crystalline solid;
mp 62–64 ЊC (Found: C, 54.36; H, 9.81; S, 14.36. C10H22O3S
requires C, 54.02; H, 9.97; S, 14.42%); νmax(KBr)/cmϪ1 3480
(br), 1290 and 1126; δH (CDCl3) 0.76–0.83 (3 H, t, J 7, CH3),
1.10–1.62 [12 H, m, CH3(CH2)6], 2.63–2.74 (1 H, br d, J 5, OH),
2.94–3.16 (5 H, m, CH3SO2CH2, contains s for CH3SO2 at 3.02)
and 4.12–4.30 (1 H, m, CHOH); δC(CDCl3) 14.04 (CH3), 22.61,
25.08, 29.14, 29.30, 31.74, 36.91 (6 × CH2), 42.65 (CH3SO2),
60.97 (CH2SO2) and 66.65 (CHOH).
1-Methylsulfonyl-6-phenylhexan-2-one 6. This was prepared
following the procedure described for 1 from sodium hydride
(0.83 g, 60% in mineral oil, 0.02 mol) and dimethyl sulfone (1.90
g, 0.02 mol) in DMSO (15 ml), THF (20 ml) and ethyl 4-
phenylpentanoate (2.06 g, 0.01 mol) in THF (20 ml). Recrystal-
lisation from diethyl ether gave 1-methylsulfonyl-6-phenyl-
hexan-2-one 6 (1.38 g, 54%) as a white crystalline solid; mp 48–
50 ЊC (Found: C, 61.16; H, 7.19; S, 12.74. C13H18O3S requires C,
61.39; H, 7.13; S, 12.60%); νmax(KBr)/cmϪ1 1703, 1301 and 1141;
1-Methylsulfonyl-5-phenylpentan-2-ol 11. Reduction was
conducted as described for
1 using 1-methylsulfonyl-5-
J. Chem. Soc., Perkin Trans. 1, 1997
237