ArH), 8.61–8.62 (d, 1H, J = 1.8 Hz); 13C NMR/
(CDCl3): 22.14 (CH3), 42.64 (CH2), 65.76 (CH),
123.62 (C Ar), 133.84 (C Ar), 137.26 (C Ar),
146.43 (C Ar), 149.48 (C Ar).
(+ve, CH3), 30.23 ( ve, CH2), 38.19 ( ve, CH2),
67.06 (+ve, CH), 126.03 (+ve, C Ar), 129.00 (+ve,
C Ar), 129.21 (+ve, C Ar), 136.43 (ab, C Ar).
(RS)-1-phenylthiopentan-3-ol (4g)
(RS)-1-(n-propyl)thiopropan-2ol (4d)
The procedure is same as for 4f except employing
ethyl bromide (1.09 g, 0.75 ml, 0.01 moles), magne-
sium (0.24 g, 0.01 moles) and S-benzylthio propalde-
hyde (3a) (1.5 g, 0.009 moles). Colorless liquid (68%).
IR (neat): 3540, 3020, 2980, 1580, 730 cm 1; MS
(m/z): 196 (M+), 181, 167, 137, 123, 109, 91 (100),
Yellow liquid; yield: 78%; IR (neat): 3400, 2965,
2930, 2873, 1477, 1095 cm 1; MS (m/z): 134 (M+),
1
119, 116, 105, 75, 60 (100); H NMR (CDCl3):
0.99 (t, 3H, J = 7.3 Hz, CH3), 1.25 (d, 2H, J =
6.2 Hz, CH3), 1.53–1.67 (m, 2H, CH2), 2.43 (dd,
1H, J = 9.0 and 13.6 Hz, CH2CH), 2.51 (t, 2H,
J = 7.3 Hz, SCH2), 2.62 (brs, 1H, OH), 2.73 (dd,
1H, J = 3.6 and 13.6 Hz CH2CH), 3.79–3.88
(m, 1H, CH); 13C NMR (50 MHz, CDCl3): 13.29,
21.88, 22.98, 34.26, 41.45, 65.54.
1
77; H NMR (CDCl3): 0.91 (t, 3H, CH3, J =
7.4 Hz), 1.46 (quintet, 2H, J = 7.2 Hz, CH2), 1.68–
1.80 (m, 2H, SCH2), 2.22 (brs, 1H, OH), 2.92–3.13
(m, 2H, CH2), 3.61–3.73 (m, 1H, CH), 7.12–7.36 (m,
5H, ArH); 13C NMR/DEPT (CDCl3): 9.87 (+ve,
CH3), 30.06 ( ve, CH2), 30.25 ( ve, CH2), 35.89,
( ve, CH2), 71.83 (+ve, CH), 125.73 (+ve, C Ar),
128.76 (+ve, C Ar), 129.00 (+ve, C Ar), 136.49 (ab,
C Ar).
(RS)-1-(tert-butyl)thiopropan-2-ol (4e)
Yellow liquid; yield = 78%; IR (neat): 3480, 3020,
1510, 1420 cm 1; MS (m/z): 148 (M+), 133, 103,
1
(RS)-1-phenylthiohexane-3-ol (4h)
89, 71 (100); H NMR (CDCl3, 200 MHz): 1.24
(d, 2H, J = 6.2 Hz, CH3), 1.32 (s, 9H, tert- butyl),
2.48 (brs, 1H, OH), 2.49 (dd, 1H, J = 8.57 and
12.9 Hz, CH2), 2.74 (dd, 1H, J = 3.9 and 12.9 Hz,
CH2), 3.78–3.84 (m, 1H, CH); 13C NMR (CDCl3):
21.77 (CH3), 30.41 (tert-butyl-CH3), 37.05 (CH2),
41.46 (C), 65.99 (CH).
Propyl bromide (1.23 g, 0.91 ml, 0.01 moles),
magnesium (0.24 g, 0.01 moles) and S-benzylthio
propaldehyde (3a) (1.5 g, 0.009 moles) were used for
the synthesis of 4h. Yellow liquid 64%. IR (neat):
3510, 3030, 2970, 1560, 720 cm 1; MS (m/z): 210
(M+), 195, 181, 167, 137, 123, 109, 91, 77; 1H NMR
(CDCl3): 0.92 (t, 3H, J = 6.4 Hz, CH3), 1.24–
1.47 (m, 5H, CH2CH2CH3, and OH), 1.67–1.79 (m,
2H, SCH2), 2.92–3.15 (m, 2H, CH2), 3.63–3.77 (m,
1H, CH), 7.11–7.34 (m, 5H, ArH); 13C NMR/DEPT
(CDCl3): 14.13 (+ve, CH3), 18.83 ( ve, CH2CH3),
29.89 ( ve, CH2CH2CH3), 36.41 ( ve, SCH2),
39.61 ( ve, CH2), 70.06 (+ve, CH), 125.68 (+ve,
C Ar), 128.81 (+ve, C Ar), 136.63 (ab, C Ar).
(RS)-1-phenylthiobutan-3-ol (4f)
To a stirred solution of methyl magnesium iodide
prepared from magnesium (0.24 g, 0.01 moles) and
methyl iodide (1.42 g, 0.63 ml, 0.01 moles) in an-
hydrous ether was added dropwise a solution of the
S-benzylthio propaldehyde (3a) (1.5 g, 0.009 moles)
in 5 ml of ether. The addition was done at 40 C.
The reaction mixture was stirred further for 1 h at
40 C and then for 3 h at room temperature. Fi-
nally dilute HCl was added and the mixture was
extracted with CH2Cl2. The organic extracts were
dried (Na2SO4) and evaporated to afford crude alco-
hol, which was purified with column chromatogra-
phy to yield 4f as yellow oil (72%). IR (neat): 3500,
3060, 2964, 1560, 1080, 720 cm 1; MS (m/z): 182
(RS)-1-phenylthioheptan-3-ol (4i)
For the synthesis of 4i, n-butyl bromide (1.37 g,
1.07 ml, 0.01 moles), magnesium (0.24 g, 0.01 moles)
and S-benzylthio propaldehyde (3a) (1.5 g, 0.009
moles) were employed. Yellow oil (70%); IR (neat):
3460, 3050, 2982, 1562, 742 cm 1; MS (m/z): 224
(M+), 180, 179, 123 (100), 109; 1H NMR (CDCl3):
0.91 (t, 3H, J = 7.0 Hz, CH3), 1.21–1.50 (m, 6H,
1
(M+), 138, 137, 123, 109, 91 (100), 77; H NMR
(CDCl3): 1.22 (d, 3H, CH3, J = 6.2 Hz), 1.57 (brs,
1H, OH), 1.75 (q, 2H, CH2, J = 7.0 Hz), 2.97–
3.07 (m, 2H, SCH2), 3.71–4.13 (m, 1H, CH), 7.14–
7.34 (m, 5H, ArH); 13C NMR/DEPT (CDCl3): 23.68
3
CH2), 1.65–1.80 (m, 2H, SCH2), 2.92–3.13 (m,
2H, CH2), 3.64–3.75 (m, 1H, CH), 7.12–7.35 (m,
5H, ArH); 13C NMR/DEPT (CDCl3): 14.02 (+ve,
CH3), 22.59 ( ve, CH2), 27.70 ( ve, CH2), 29.85
RESOLUTION OF HYDROXY SULFIDES
235