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M. Kirihara et al. / Tetrahedron 70 (2014) 2464e2471
129.93, 130.66. 19F NMR (CDCl3)
(Mþ). IR (KBr) cmꢀ1: 1406, 1214.
d
: ꢀ214.89 (1F, s). MS (m/z): 174
(16H, m), 2.08e2.01 (2H, m), 3.66 (2H, t, J¼7.8, 8.1 Hz). 13C NMR
(CDCl3) d: 14.09, 22.64, 24.26, 27.56, 28.87, 29.15, 29.19, 29.37, 31.81,
65.48. MS (m/z): 207, 140. IR (neat) cmꢀ1: 2927, 2857, 1461, 1375,
1166, 755, 735, 591, 521.
6.4.5. 4-Chlorophenylsulfonyl fluoride (3e).18 Colorless crystals,
mp 48 ꢂC (lit.18 36e37 ꢂC). 1H NMR (CDCl3)
d
: 7.61 (2H, d, J¼8.5 Hz),
: 129.89, 130.13, 131.4 (d,
: ꢀ199.90 (1F, s). MS (m/z):
7.96 (2H, d, J¼8.5 Hz). 13C NMR (CDCl3)
d
6.6. Representative experimental procedure to prepare sul-
fonyl bromide from disulfides
J¼26.5 Hz), 142.69. 19F NMR (CDCl3)
d
194 (Mþ). IR (KBr) cmꢀ1: 1412, 1213, 1089.
In a 10 mL round bottom flask, p-tolyl disulfide (1b) (246.3 mg,
1.0 mmol) was dissolved in acetonitrile (2.0 mL) and water (0.2 mL).
The round bottom flask was covered with aluminum foil to shield it
from light. N-Bromosuccinimide (1068 mg, 6.0 mmol) was added to
the mixture, and the resulting mixture was stirred at room tem-
perature for 3 h. Water (10 mL) was added and the resulting mix-
ture was extracted with ethyl acetate (20 mLꢁ3). The extract was
washed with brine, dried over anhydrous magnesium sulfate, and
evaporated. Chromatography on silica gel using n-hexane/ethyl
acetate as the eluent gave the sulfonyl bromide (5b) (371.4 mg, 79%)
as colorless crystals.
6.4.6. Cyclohexylsulfonyl fluoride (3f).20 Colorless oil. 1H NMR
(CDCl3)
d
: 1.26e1.37 (3H, m), 1.67e1.77 (3H, m), 1.94e1.97 (2H, m),
2.28e2.31 (2H, m), 3.28e3.34 (1H, m). 13C NMR (CDCl3)
d
: 14.11,
24.62, 24.67, 26.42. 19F NMR (CDCl3)
d: ꢀ225.45 (1F, s). MS (m/z):
166 (Mþ). IR (neat) cmꢀ1: 2944, 2254, 1399, 1199.
6.4.7. Decylsulfonylfluoride (3g).20 Pale yellow oil. 1H NMR (CDCl3)
d
: 0.8e0.96 (3H, m), 1.27e1.97 (16H, m), 3.35 (2H, s). 13C NMR
(CDCl3) d: 14.08, 22.63, 23.38, 27.83, 28.68, 28.773, 29.13, 29.18,
29.37, 31.80. 19F NMR (CDCl3)
d
: ꢀ213.04 (1F, s). MS (m/z): 224 (Mþ).
IR (neat) cmꢀ1: 2928, 1856, 1402, 1197.
6.6.1. p-Toluenesulfonyl bromide (5b).22 Colorless crystals, mp 95 ꢂC
(lit.22 95e96 ꢂC). 1H NMR (CDCl3)
d: 2.49 (3H, s), 7.39 (2H, d,
6.5. Representative experimental procedure to prepare sul-
fonyl chloride from disulfides
J¼8.4 Hz), 7.89 (2H, d, J¼8.4 Hz). 13C NMR (CDCl3)
d: 21.85, 126.54,
130.13, 144.61, 146.86. MS (m/z): 155, 91. IR (neat) cmꢀ1: 1361, 1296,
To a stirred solution of p-tolyl disulfide (1b) (246.3 mg,
1.0 mmol) in acetonitrile (2.0 mL) and water (0.2 mL), N-chlor-
osuccinimide (802 mg, 6.0 mmol) was added, and the resulting
mixture was stirred at room temperature for 3 h. Water (10 mL) was
added and the resulting mixture was extracted with ethyl acetate
(20 mLꢁ3). The extract was washed with brine, dried over anhy-
drous magnesium sulfate, and evaporated. Chromatography on
silica gel using n-hexane/ethyl acetate as the eluent gave the sul-
fonyl chloride (4b) (304.7 mg, 83%) as colorless crystals.
1171, 1076, 808, 647, 567, 550.
6.6.2. p-Methoxybenzenesulfonyl bromide (5c).22 Colorless oil. 1H
NMR (CDCl3)
d
: 3.93 (3H, s), 7.03 (2H, d, J¼9.1 Hz), 7.95 (2H, d,
J¼9.1 Hz). 13C NMR (CDCl3)
d: 55.99, 114.53, 129.10, 139.18, 170.26.
MS (m/z): 253 (Mþ for 81Br), 251 (Mþ for 79Br). IR (neat) cmꢀ1: 3100,
2943, 2846, 1586, 1491, 1360, 1266, 1157, 1079, 1018, 834, 655, 561.
6.6.3. 4-Chlorobenzenesulfonyl bromide (5e).23 Colorless crystals,
mp 53 ꢂC (lit.23 56 ꢂC). 1H NMR (CDCl3)
d
: 7.59 (2H, d, J¼8.4 Hz), 7.95
6.5.1. p-Toluenesulfnoyl chloride (4b).19 Mp 68 ꢂC (lit.19 65e69 ꢂC).
(2H, d, J¼8.4 Hz). 13C NMR (CDCl3)
d: 127.91, 129.91, 142.06, 145.33.
1H NMR (CDCl3)
d
: 2.49 (3H, s), 7.41 (2H, d, J¼8.4 Hz), 7.93 (2H, d,
MS (m/z): 144, 109. IR (neat) cmꢀ1: 1570, 1470, 1365, 1282, 1161,
J¼8.4 Hz). 13C NMR (CDCl3)
d: 21.83, 127.06, 130.23, 141.71, 146.79.
1089, 1012, 826, 749, 691, 590, 463.
MS (m/z): 190 (Mþ for 35Cl). IR (neat): 1591, 1375, 1299, 1172, 1079,
810, 653, 567, 525.
6.6.4. Cyclohexanesulfonyl bromide (5f). Pale yellow oil. 1H NMR
(CDCl3)
d: 1.45e1.21 (3H, m), 1.75e1.66 (3H,m), 1.99 (2H, d,
6.5.2. p-Methoxybenzenesulfonyl chloride (4c).19 Colorless crystals,
J¼13.7 Hz), 2.42 (2H, d, J¼12.9 Hz), 3.49 (1H, tt, J¼11.8, 3.4 Hz). 13
C
mp 38 ꢂC (lit.19 39e42 ꢂC). 1H NMR (CDCl3)
d: 3.93 (3H, s), 7.05 (2H,
NMR (CDCl3) d
: 24.80, 24.99, 27.55, 78.84. IR (neat) cmꢀ1: 2940,
d, J¼9.0 Hz), 7.98 (2H, d, J¼9.0 Hz). 13C NMR (CDCl3)
d: 55.96, 114.69,
2861, 1451, 1357, 1270, 1151, 995, 893, 742, 572, 525, 474. MS (ESI)
(m/z): 251 [(MþNa)þ for 81Br], 249 [(MþNa)þ for 79Br]. HRMS (ESI)
calcd for C6H1179BrO2SNa [(MþNa)þ], 248.9555, found: 248.9549.
129.54, 136.07, 164.85. MS (m/z): 206 (Mþ for 35Cl). IR (neat) cmꢀ1
:
3101, 2945, 2846, 1589, 1493, 1371, 1268, 1163, 1083, 1022, 832, 659,
566.
6.6.5. Decanesulfonyl bromide (5g). Pale yellow oil. 1H NMR (CDCl3)
6.5.3. Benzylsulfonyl chloride (4d).19 Colorless oil. 1H NMR (CDCl3)
d
129.21, 130.28,131.38. MS (m/z): 190 (Mþ for 35Cl), 192 (Mþ for 37Cl).
IR (neat) cmꢀ1: 2989, 2918, 1494, 1455, 1367, 1257, 1162, 908, 772,
696, 515.
: 4.87 (2H, s), 7.43e7.51 (5H, m). 13C NMR (CDCl3)
d: 70.90, 126.10,
d
: 0.89 (3H, t, J¼7.0 Hz), 1.52e1.27 (16H, m), 2.04 (2H, m), 3.66 (2H,
t, J¼8.0 Hz). 13C NMR (CDCl3)
d: 14.09, 22.64, 24.58, 27.28, 28.90,
29.16, 29.20, 29.37, 31.81, 69.66. IR (neat) cmꢀ1: 2939, 2860, 1451,
1354, 1212, 1154, 955, 848, 742, 571, 529. MS (ESI) (m/z): 309
[(MþNa)þ for 81Br], 307 [(MþNa)þ for 79Br]. HRMS (ESI) calcd for
10H2179BrO2SNa [(MþNa)þ], 307.0338, found: 307.0331.
6.5.4. 4-Chlorobenzenesulfonyl chloride (4e).19 Colorless crystals,
C
mp 53 ꢂC (lit.19 50e52 ꢂC). 1H NMR (CDCl3)
d
: 7.61 (2H, d, J¼8.8 Hz),
7.99 (2H, d, J¼8.8 Hz). 13C NMR (CDCl3)
d: 128.43, 130.04, 142.21,
Acknowledgements
142.59. MS (m/z): 211 (Mþ for 35Cl). IR (neat) cmꢀ1: 1577, 1474, 1377,
1280, 1174, 1091, 1011, 826, 753, 603, 565, 468.
This study was supported in part by the grant from the Strategic
Research Foundation Grant-aided Project for Private Universities
from Ministry of Education, Culture, Sport, Science and Technology,
Japan (MEXT), 2010e2014 (S1001032).
6.5.5. Cyclohexanesulfonyl chloride (4f).19 Colorless oil. 1H NMR
(CDCl3)
d: 1.43e1.20 (3H, m), 1.78e1.68 (3H, m), 2.00 (2H, d,
J¼13.4 Hz), 2.43 (2H, d, J¼12.4 Hz), 3.51 (1H, tt, J¼12.4, 3.4 Hz). 13
C
NMR (CDCl3) d: 24.73, 25.07, 27.23, 74.93. MS (m/z): 99, 83. IR (neat)
References and notes
cmꢀ1: 2941, 2863, 1452, 1366, 1272, 1160, 994, 750, 589, 539, 483.
6.5.6. Decanesulfonyl chloride (4g).21 Colorless crystals, mp 30 ꢂC
(lit.21 34 ꢂC). 1H NMR (CDCl3)
d
: 0.89 (3H, t, J¼6.3, 7.1 Hz), 1.52e1.27