PAPER
Bis(chloromethyl) Sulfone and Sulfoxide
IR (KBr): 3440 (OH), 987 (SO) cm–1.
3101
1H NMR: d = 1.29–1.49, 1.54–1.61, 1.92–2.05, 2.26, 2.49 (3 m, 2 br
s, 40 H, 16 × c-CH2, 8 × c-CH), 3.36 (s, 4 H, 2 × CH2SO2), 3.40 ( s,
4 H, 2 × CH2SO2).
13C NMR: d = 21.7, 28.2 (c-CH2), 37.2 (c-CH), 38.4, 46.1, 46.2 (c-
CH2), 46.6, 46.7 (c-CH), 65.6 (CH2SO2), 77.9 (COH).
MS: m/z (%) = 296 (M+ – H2O, 1), 229 (11), 173 (13), 164 (11), 125
(14), 124 (48), 111 (15), 110 (10), 109 (10), 108 (17), 106 (12), 96
(10), 91 (16), 83 (11), 81 (22), 80 (18), 79 (83), 67 (55), 66 (37), 55
(16).
1H NMR: d = 1.31–1.91 (m, 20 H, 10 × c-CH2), 2.84, 3.02 (2 d, J =
13.1 Hz, 4 H, 2 × CH2SO), 3.40 (br s, 2 H, 2 × OH).
13C NMR: d = 21.7, 21.9, 25.3 (3,4-c-CH2), 37.5, 38.4 (2-c-CH2),
63.5 (CH2SO), 71.5 (COH).
MS: m/z (%) = 256 (M+ – H2O, 1), 113 (26), 99 (10), 95 (100), 81
(11).
HRMS: m/z calcd for C14H26O3S [M+]: 274.1603; found: 274.1654.
HRMS: m/z [M+ – H2O] calcd for C16H24O3S: 296.1446; found:
296.1442.
Anal. Calcd for C14H26O3S: C, 61.27; H, 9.55; S, 11.68. Found: C,
61.46; H, 9.63; S, 11.68.
1,1-Dicyclopropyl-2-(2,2-dicyclopropyl-2-hydroxyethylsulfi-
nyl)-1-ethanol (4i)
White crystals; mp 77 °C; tR 16.6 min; Rf 0.4 (hexane–EtOAc, 1:1).
IR (KBr): 3402 (OH), 1025 (SO) cm–1.
1-(2-Hydroxy-3,3-dimethylbutylsulfinyl)-3,3-dimethyl-2-bu-
tanol (4a)
Diastereomeric mixture (ca. 1:1).
White crystals; mp 140 °C; tR 13.29, 13.51 min; Rf 0.2, 0.3 (EtOAc).
1H RMN: d = 0.34–0.74 (m, 16 H, 8 × c-CH2), 0.91–1.00 (m, 4 H,
4 × CH), 2.95, 3.13 (2 d, J = 13.1 Hz, 4 H, 2 × CH2SO), 3.34 (br s,
2 H, 2 × OH).
13C NMR: d = 0.0, 0.1, 0.4, 0.6 (c-CH2), 18.7, 20.8 (CH), 63.9
(CH2SO), 70.9 (COH).
MS: m/z (%) = 298 (M+, 1), 239 (13), 197 (15), 173 (35), 155 (13),
139 (10), 111 (54), 108 (29), 107 (12), 93 (23), 91 (12), 79 (26), 69
(100), 67 (9), 55 (13).
HRMS: m/z calcd for C13H21O3S [M+ – 41]: 257.1211; found:
257.1204.
IR (KBr): 3349 (OH), 980 (SO) cm–1.
1H NMR: d = 0.97 (s, 36 H, 12 × CH3), 2.82–2.91 (m, 8 H, 4 × CH2),
3.08 (2 br s, 4 H, 4 × OH), 3.91–3.98 (m, 4 H, CHOH).
13C NMR: d = 25.4, 25.5 (CH3), 35.0, 35.1, 35.3 (CMe3), 52.2, 54.2,
55.3 (CH2SO), 73.0, 73.5, 76.1, 77.2 (CHOH).
MS: m/z (%) = 250 (M+, 1), 193 (18), 175 (27), 101 (16), 84 (10),
83 (100), 57 (42), 55 (12).
MS: m/z (%) = 235 (M+ – 15, 1), 193 (16), 175 (35), 101 (17), 84
(10), 83 (100), 57 (43), 55 (12).
HRMS: m/z calcd for C12H25O2S [M+ – OH]: 233.1575; found:
233.1552.
2-(2-Hydroxybicyclo[2.2.1]hept-2-ylmethylsulfinylmethyl)bicy-
clo[2.2.1]heptan-2-ol (4k)
Diastereomeric mixture (ca. 1:1).
HRMS: m/z calcd for C12H25O2S [M+ – OH]: 233.1575; found:
233.1581.
White crystals; mp 136 °C; tR 19.1 min; Rf 0.27 (EtOAc).
3-(2-Ethyl-2-hydroxybutylsulfinylmethyl)-3-pentanol (4e)
White crystals; mp 87 °C; tR 13.8 min; Rf 0.27 (EtOAc).
IR (KBr): 3317 (OH), 979 (SO) cm–1.
1H NMR: d = 0.93, 0.94 (2 t, J = 7.5 Hz, 12 H, 4 × CH3), 1.65, 1.77,
1.80 (3 q, J = 7.5 Hz, 8 H, 4 × CH2CH3), 2.82, 3.03 (2 d, J = 13.3
Hz, 4 H, 2 × CH2SO), 3.32 (br s, 2 H, 2 × OH).
13C NMR: d = 7.6, 8.1 (CH3), 31.5, 31.7 (CH2CH3), 60.8 (CH2SO),
74.8 (COH).
IR (KBr): 3376 (OH), 994 (SO) cm–1.
1H NMR: d = 1.27–1.49, 1.54–1.63, 1.73–1.80, 2.00–2.18, 2.25–
2.31, 2.49–2.54 (6 m, 40 H, 16 × c-CH2, 8 × c-CH), 2.82–2.91, (2
m, d at 2.89, J = 13.1 Hz, 4 H, 2 × CH2SO), 3.11–3.19 (m, d at 3.15,
J = 13.1 Hz, 4 H, 2 × CH2SO).
13C NMR: d = 21.1, 21.8, 28.0, 28.4 (c-CH2), 37.0, 37.5 (c-CH),
38.1, 38.8, 45.3, 46.2 (c-CH2), 46.3, 47.3, 48.0 (c-CH), 61.7, 61.9
(CH2SO), 78.6, 79.2 (COH).
MS: m/z (%) = 250 (M+, 1), 221 (10), 203 (10), 132 (19), 121 (18),
101 (14), 87 (14), 84 (10), 83 (100), 59 (17), 57 (17), 55 (30).
HRMS: m/z calcd for C12H26O3S [M+]: 250.1603; found: 250.1598.
MS: m/z (%) = 298 (M+, 1), 281 (12), 221 (12), 170 (16), 156 (15),
154 (14), 139 (26), 125 (54), 124 (19), 111 (100), 108 (18), 107
(58), 95 (13), 93 (19), 91 (18), 83 (17), 81 (26), 79 (68), 77 (15), 67
(49), 66 (23), 62 (10), 55 (18).
4-(2-Hydroxy-2-propylpentylsulfinylmethyl)-4-heptanol (4f)
White crystals; mp 68 °C; tR 15.5 min; Rf 0.31 (hexane–EtOAc,
1:1).
IR (KOH): 3365 (OH), 978 (SO) cm–1.
HRMS: m/z calcd for C16H26O3S [M+ – H2O]: 298.1603; found:
298.1622.
Anal. Calcd for C16H26O3S: C, 64.39; H, 8.78; S, 10.74. Found: C,
64.83; H, 8.88; S, 9.14.
1H NMR: d = 0.95, 0.96 (2 t, J = 7.2 Hz, 12 H, 4 × CH3), 1.30–1.46,
1.58–1.74 (2 m, 16 H, 4 × CH2CH2CH3), 2.78, 3.02 (2 d, J = 13.3
Hz, 4 H, 2 × CH2SO), 3.29 (br s, 2 H, 2 × OH).
13C NMR: d = 14.4, 14.5 (CH3), 16.6, 17.0 (CH2CH3), 41.8, 42.0
(CH2CH2CH3), 61.7 (CH2SO), 74.5 (COH).
X-ray Crystal Structure Analysis
Diffraction data were taken on a Bruker Smart CCD SMART
APEX diffractometer at the University of Alicante. Crystal data are
summarized in Table 2 and have been deposited at the Cambridge
Crystallographic Data Centre: 2e (CCDC 262934), 2h (CCDC
262935), 4e (CCDC 262936), 4h (CCDC 262937).
MS: m/z (%) = 279 (M+ – 43, 1), 261 (10), 111 (100), 71 (16), 69
(41), 55 (15).
HRMS: m/z calcd for C16H34O3S [M+ – H2O]: 306.2229; found:
306.2157.
Acknowledgment
This work was generously supported by the current Spanish Mini-
sterio de Educación y Ciencia (MEC; grant no. BQU2001-0538)
and the Generalitat Valenciana (project no. GRUPOS03/135).
B. M. thanks the MEC for a predoctoral fellowship.
1-(1-Hydroxycyclohexylmethylsulfinylmethyl)-1-cyclohexanol
(4h)
White crystals; mp 136 °C; tR 17.9 min; Rf 0.2 (EtOAc).
Synthesis 2005, No. 18, 3095–3102 © Thieme Stuttgart · New York