Reaction of Aziridines with Trimethylsilyl Compounds
J . Org. Chem., Vol. 65, No. 5, 2000 1347
raphy using petroleum ether-AcOEt (5:1) as an eluent to give
the corresponding product.
J ) 8.06 Hz, 2H), 7.80 (d, J ) 8.21 Hz, 2H). EIMS (relative
intensity): 278 (M+, 19), 210 (100), 155 (61), 91 (96). Anal.
Calcd for C14H18N2O2S: C, 60.43; H, 6.47; N, 10.07. Found:
C, 60.55; H, 6.66; N, 9.99.
N-(2-Azid ocycloh exyl)-4-m et h ylb en zen esu lfon a m id e
(2a ).6 Colorless liquid. IR (film): 3273, 2940, 2863, 2100, 1599
cm-1 1H NMR (CDCl3/TMS) δ (ppm): 1.10-1.45 (m, 4H),
.
N-(2-Cya n ocyclop en tyl)-4-m eth ylben zen esu lfon a m id e
(4b). White solid. Mp: 107-108 °C. IR (KBr): 3252, 2933,
1.60-1.80 (m, 2H), 1.95-2.15 (m, 2H), 2.45 (s, 3H), 2.90-3.00
(m, 1H), 3.00-3.10 (m, 1H), 4.80 (bd, J ) 5.92 Hz, 1H), 7.35
(d, J ) 7.98 Hz, 2H), 7.80 (d, J ) 8.06 Hz, 2H). EIMS (relative
intensity): 295 (MH+, 1), 252 (13), 210 (73), 155 (86), 111 (70),
91 (100). HRMS: for C13H18NO2S (M - N3)+ calcd 252.1058,
found 252.1070.
1
2244, 1600 cm-1. H NMR (CDCl3/TMS) δ (ppm): 1.40-1.60
(m, 1H), 1.60-2.30 (m, 5H), 2.45 (s, 3H), 2.75-3.00 (m, 1H),
3.70-3.90 (m, 1H), 5.45 (d, J ) 6.57 Hz, 1H), 7.35 (d,
J ) 8.03 Hz, 2H), 7.85 (d, J ) 8.18 Hz, 2H). EIMS (relative
intensity): 265 (MH+, 13), 264 (M+, 25), 237 (10), 210 (55),
155 (70), 91 (100). Anal. Calcd for C13H16N2O2S: C, 59.07; H,
6.10; N, 10.60. Found: C, 58.90; H, 6.09; N, 10.39.
N-(2-Azid ocyclop en tyl)-4-m eth ylben zen esu lfon a m id e
(2b). Colorless liquid. IR (film): 3270, 2966, 2104 cm-1 1H
.
NMR (CDCl3/TMS) δ (ppm): 1.30-1.50 (m, 1H), 1.55-1.75 (m,
3H), 1.90-2.05 (m, 2H), 2.45 (s, 3H), 3.35-3.50 (m, 1H), 3.70-
3.80 (m, 1H), 4.90 (bd, J ) 6.56 Hz, 1H), 7.35 (d, J ) 8.23 Hz,
2H), 7.80 (d, J ) 8.26 Hz, 2H). EIMS (relative intensity): 371
(M+ + 91, 3), 281 (MH+, 1), 251 (11), 238 (35), 155 (57), 133
(62), 91 (100). HRMS: for C12H16NO2S (M - N3)+ calcd
238.0901, found 238.0897.
N-(2-Cya n o-1-p h en ylet h yl)-4-m et h ylb en zen esu lfon a -
m id e (4d ).8 White solid. Mp: 120-121 °C. IR (film): 3250,
2252, 1597 cm-1. 1H NMR (CDCl3/TMS) δ (ppm): 2.40 (s, 3H),
2.80-3.00 (m, 2H), 4.50-4.60 (m, 1H), 5.45 (d, J ) 6.64 Hz,
1H), 7.10-7.50 (m, 7H), 7.70 (d, J ) 8.12 Hz, 2H). EIMS
(relative intensity): 301 (MH+, 0.29), 260 (100), 155 (65), 91
(89). Anal. Calcd for C16H16N2O2S: C, 64.00; H, 5.33; N, 9.33.
Found: C, 64.02; H, 5.35; N, 9.45.
N-(2-Azid o-1-p h en ylet h yl)-4-m et h ylb en zen esu lfon a -
m id e (2d ).6 Colorless liquid. IR (film): 3279, 2105, 1599 cm-1
.
N-(2-Cya n oh exyl)-4-m eth ylben zen esu lfon a m id e (4e).8
1H NMR (CDCl3/TMS) δ (ppm): 2.40 (s, 3H), 3.55 (d, J ) 5.89
Hz, 2H), 4.42-4.52 (dd, J ) 12.89, 5.95, 5.91 Hz, 1H), 5.20 (d,
J ) 7.13 Hz, 1H), 7.10-7.40 (m, 7H), 7.65 (d, J ) 8.31 Hz,
2H). EIMS (relative intensity): 274 ((M - N3)+, 1.91), 260 (25),
184 (35), 155 (74), 91 (100). HRMS: for C15H16NO2S (M - N3)+
calcd 274.0952, found 274.0927.
White solid. Mp: 73-74 °C. IR (film): 3262, 2248, 1599 cm-1
.
1H NMR (CDCl3/TMS) δ (ppm): 0.77 (t, J ) 7.22, 6.78 Hz,
3H), 1.00-1.30 (m, 4H), 1.40-1.60 (m, 2H), 2.40 (s, 3H), 2.50-
2.60 (m, 2H), 3.40-3.50 (m, 1H), 4.80 (d, J ) 7.72 Hz, 1H),
7.30 (d, J ) 7.95 Hz, 2H), 7.80 (d, J ) 8.29 Hz, 2H). EIMS
(relative intensity): 281 (MH+, 8), 240 (83), 155 (100), 91 (88).
Anal. Calcd for C14H20N2O2S: C, 60.00; H, 7.14; N, 10.00.
Found: C, 60.04; H, 7.30; N, 9.84.
N-(2-Azid o-2-p h en ylet h yl)-4-m et h ylb en zen esu lfon a -
m id e (3d ).6 Colorless liquid. IR (film): 3279, 2105, 1599 cm-1
.
1H NMR (CDCl3/TMS) δ (ppm): 2.45 (s, 3H), 3.05-3.15 (m,
1H), 3.18-3.30 (m, 1H), 4.55-4.65 (dd, J ) 8.84, 5.12, 5.11
Hz, 1H), 4.75-4.90 (m, 1H), 7.10-7.40 (m, 7H), 7.80 (d, J )
8.31, 2H). EIMS (relative intensity): 274 ((M-N3)+, 1.91), 260
(25), 184 (35), 155 (74), 91 (100). HRMS: for C15H16NO2S
(M - N3)+ calcd 274.0952, found 274.0927.
N-(2-Cyan ooctyl)-4-m eth ylben zen esu lfon am ide (4f). Col-
orless liquid. IR (film): 3277, 2931, 2251, 1599 cm-1. 1H NMR
(CDCl3/TMS) δ (ppm): 0.85 (t, J ) 7.24, 6.65 Hz, 3H), 1.00-
1.30 (m, 7H), 1.40-1.75 (m, 3H), 2.40 (s, 3H), 2.50-2.70 (m,
2H), 3.30-3.50 (m, 1H), 4.60 (d, J ) 7.87 Hz, 1H), 7.30 (d,
J ) 7.98 Hz, 2H), 7.80 (d, J ) 8.31 Hz, 2H). EIMS (relative
intensity): 309 (MH+, 23), 268 (100), 223 (7), 155 (84), 91 (65).
HRMS: for C16H24N2O2S (M+) calcd 308.1558, found 308.1543.
N-(2-Cya n oeth yl)-4-m eth ylben zen esu lfon a m id e (4g).16
White solid. Mp: 80-81 °C (lit.16mp >250 °C). IR (film): 3260,
2250, 1595 cm-1. 1H NMR (CDCl3/TMS) δ (ppm): 2.40 (s, 3H),
2.60 (t, J ) 6.68, 6.59 Hz, 2H), 3.25 (q, J ) 13.16, 6.59, 6.58
Hz, 2H), 5.15 (br, 1H), 7.35 (d, J ) 8.04 Hz, 2H), 7.75 (d, J )
8.29 Hz, 2H). EIMS (relative intensity): 224 (M+, 4), 184 (37),
155 (71), 91 (100). Anal. Calcd for C10H12N2O2S: C, 53.57; H,
5.36; N, 12.50. Found: C, 53.75; H, 5.31; N, 12.44.
N-(2-Azid oh exyl)-4-m eth ylben zen esu lfon a m id e (2e).6
Colorless liquid. IR (film): 3279, 2104, 1599 cm-1 1H NMR
.
(CDCl3 /TMS) δ (ppm): 0.80 (t, J ) 7.03, 4.01 Hz, 3H), 1.00-
1.30 (m, 4H), 1.35-1.55 (m, 2H), 2.40 (s, 3H), 3.25-3.40 (m,
3H), 4.75 (d, J ) 7.68 Hz, 1H), 7.35 (d, J ) 8.60 Hz, 2H), 7.80
(d, J ) 8.51 Hz, 2H). EIMS (relative intensity): 240 ((M-
CH2N3)+, 33), 155 (57), 91 (100). HRMS: for C12H18NO2S
(M - CH2N3)+ calcd 240.1114, found 240.1086.
N-(2-Azidooctyl)-4-m eth ylben zen esu lfon am ide (2f). Col-
orless liquid. IR (film): 3279, 2930, 2860, 2104, 1599 cm-1
.
1H NMR (CDCl3/TMS) δ (ppm): 0.85 (t, J ) 7.17, 6.72 Hz,
3H), 1.00-1.35 (m, 7H), 1.35-1.60 (m, 3H), 2.45 (s, 3H), 3.20-
3.40 (m, 3H), 4.55 (d, J ) 7.70 Hz, 1H), 7.35 (d, J ) 7.99 Hz,
2H), 7.80 (d, J ) 8.31 Hz, 2H). EIMS (relative intensity): 325
(MH+, 6.26), 282 (12), 268 (100), 254 (13), 155 (39), 91 (45).
HRMS: for C15H25N4O2S (MH+) calcd 325.1698, found 325.1717.
N-(2-Azid oet h yl)-4-m et h ylb en zen esu lfon a m id e (2g).
White solid. Mp: 37-38 °C. IR (film): 3305, 3268, 2928, 2104,
N-(2-Cya n o-1-m eth ylcycloh exyl)-4-m eth ylben zen esu l-
fon a m id e (4h ). White solid. Mp: 138-140 °C. IR (film): 3293,
1
2940, 2239, 1598 cm-1. H NMR (CDCl3/TMS) δ (ppm): 1.30
(s, 3H), 1.40-1.80 (m, 7H), 1.90-2.10 (m, 1H), 2.40 (s, 3H),
3.25-3.35 (dd, J ) 4.09, 4.04 Hz, 1H), 4.90 (br, 1H), 7.30 (d,
J ) 8.15 Hz, 2H), 7.80 (d, J ) 8.27 Hz, 2H). EIMS (relative
intensity): 293 (MH+, 4), 292 (M+, 10), 224 (61), 210 (23), 155
(64), 91 (100). Anal. Calcd for C15H20N2O2S: C, 61.62; H, 6.90;
N, 9.59. Found: C, 61.57; H, 6.98; N, 9.56.
1
1598 cm-1. H NMR (CDCl3/TMS) δ (ppm): 2.40 (s, 3H), 3.10
(q, J ) 11.92, 6.13, 5.77 Hz, 2H), 3.40 (t, J ) 5.99, 5.53 Hz,
2H), 5.10 (br, 1H), 7.35 (d, J ) 7.91 Hz, 2H), 7.75 (d, J ) 8.31
Hz, 2H). EIMS (relative intensity): 241 (MH+, 31), 225 (2),
184 (52), 155 (94), 91 (100). Anal. Calcd for C9H12N4O2S: C,
44.99; H, 5.03; N, 23.32. Found: C, 44.90; H, 5.00; N, 23.44.
N-(2-Azid o-1-m eth ylcycloh exyl)-4-m eth ylben zen esu l-
fon a m id e (2h ). White solid. Mp: 148-149 °C. IR (film): 3270,
2933, 2092, 1599 cm-1. 1H NMR (CDCl3/TMS) δ (ppm): 1.20-
1.40 (m, 6H), 1.40-1.70 (m, 4H), 1.80-1.90 (m, 1H), 2.40 (s,
3H), 3.05-3.15 (m, 1H), 4.60 (bd, J ) 7.98 Hz, 1H), 7.30 (d,
J ) 8.14 Hz, 2H), 7.80 (d, J ) 8.29 Hz, 2H). EIMS (relative
intensity): 398 (((M - 1) + 91)+, 0.2), 307 ((M - 1)+, 1), 266
(95), 210 (27), 155 (28), 125 (100), 91 (70). Anal. Calcd for
N-(2-Ch lor ocycloh exyl)-4-m eth ylben zen esu lfon a m id e
(6a ).17 White solid. Mp: 100-102 °C. IR (film): 3255, 2947,
2869, 1922, 1596 cm-1. 1H NMR (CDCl3/TMS) δ (ppm): 1.20-
1.40 (m, 3H), 1.55-1.75 (m, 3H), 2.10-2.30 (m, 2H), 2.40 (s,
3H), 3.10-3.20 (m, 1H), 3.60-3.70 (m, 1H), 4.85 (br, 1H), 7.30
(d, J ) 8.04 Hz, 2H), 7.80 (d, J ) 8.25 Hz, 2H). EIMS (relative
intensity): 289 (M+, 37Cl, 8), 287 (M+, 35Cl, 22), 252 (18), 210
(100), 155 (89), 91 (65). Anal. Calcd for C13H18ClNO2S: C,
54.26; H, 6.26; N, 4.87. Found: C, 54.55; H, 6.26; N, 4.71.
N-(2-Ch lor ocyclopen tyl)-4-m eth ylben zen esu lfon a m id e
(6b).17 White solid. Mp: 86-87 °C. IR (film): 3266, 2976, 2879,
1
1908, 1598 cm-1. H NMR (CDCl3/TMS) δ (ppm): 1.30-1.50
(m, 1H), 1.60-2.00 (m, 3H), 2.10-2.25 (m, 2H), 2.40 (s, 3H),
3.50-3.60 (m, 1H), 4.05-4.15 (m, 1H), 4.80 (bd, J ) 5.24 Hz,
1H), 7.35 (d, J ) 8.28 Hz, 2H), 7.80 (d, J ) 8.30 Hz, 2H). EIMS
C
14H20N4O2S: C, 54.52; H, 6.54; N, 18.17. Found: C, 54.18;
H, 6.58; N, 18.45.
N-(2-Cya n ocycloh exyl)-4-m eth ylben zen esu lfon a m id e
(4a ).8 White solid. Mp: 113-114 °C. IR (film): 3279, 2245,
1600 cm-1. 1H NMR (CDCl3/TMS) δ (ppm): 1.20-1.50 (m, 3H),
1.50-1.80 (m, 3H), 1.85-2.20 (m, 2H), 2.40 (s, 3H), 2.60-2.90
(m, 1H), 3.30-3.50 (m, 1H), 5.25 (d, J ) 7.92 Hz, 1H), 7.35 (d,
(16) Bailly, C.; Houssin, R.; Bernier, J . L.; Henichart, J . P. Tetra-
hedron 1988, 44, 5833.
(17) Chem. Abstr. 1990, 112, 157798v. Tanimoto, S.; Reddy, C. P.;
Okamoto, T. Bull. Inst. Chem. Res., Kyoto University 1989, 66, 615.