1004
P. Phukan, A. Sudalai / Tetrahedron: Asymmetry 9 (1998) 1001–1005
product. Yield: 92 mg (35%). Chiral analysis was performed using 96% ethanol–water with a flow rate
of 0.4 mL/min. The detector wavelength was fixed at 210 nm; retention times: 20.60 (minor) and 23.00
(major).
3
.1.1. 2-(N-(p-Tolylsulfonyl)amino)cyclohexanone
−1
Yield: 35%; mp: 139–140°C; IR (CHCl , cm ): 3290, 1695, 1585, 1350, 1310, 1265, 1160, 1090,
3
1
815, 740, 670; H NMR (300 MHz, CDCl ): δ 1.5 (m, 3H, ring CH), 1.8 (m, 1H, ring CH), 2.0 (m, 1H,
3
ring CH), 2.2 (dt, 1H, ring CH) 2.35 (s, 3H, Ar-CH ), 2.5 (m, 2H, ring CH), 3.7 (m, 1H, CHN), 5.75
3
(d, J=6.2 Hz, NH), 7.25 (d, J=9.4 Hz, 2H, Ar-H) 7.7 (d, J=9.4 Hz, 2H, Ar-H); MS: m/z (% rel intensity)
2
8
1
39 (68), 211 (20), 155 (83), 154 (41), 139 (23), 133 (12), 111 (17), 97 (12), 91 (100), 90 (63), 84 (42),
3 (33), 73 (7). [α] =−10 (c 0.5, CHCl ). Anal.: C H NO S requires C, 58.43; H, 6.37; N, 5.24; S,
D
3
13 17
3
1.985%. Found: C, 58.44; H, 6.3; N, 5.3; S, 11.91%.
3
.1.2. 2-(N-(p-Tolylsulfonyl)amino)-4-methylcyclohexanone
−1
Yield: 38%; mp: 99–100°C; IR (CHCl , cm ): 3280, 1695, 1590, 1400, 1320, 1220, 1160, 1090,
3
1
920, 810, 740, 660; H NMR (200 MHz, CDCl ): δ 1.0 (d, J=8.1 Hz, 3H, ring-CH ), 1.15–1.35 (m, 2H,
3
3
ring CH), 1.6–1.7 (bs, 1H, ring CH), 1.9–2.0 (m, 1H, ring CH), 2.25–2.35 (m, 1H, ring CH), 2.4 (s, 3H,
Ar-CH ), 2.4–2.5 (m, 2H, ring CH), 3.75 (m, 1H, CHN), 5.75 (d, J=5.4 Hz, 1H, NH), 7.3 (d, J=9.2 Hz,
3
+
2
H, Ar-H), 7.7 (d, J=9.2 Hz, 2H, Ar-H); MS: m/z (% rel. intensity) 281 (M , 6), 237 (8), 224 (51), 216
(
0
51), 155 (88), 133 (9), 126 (26), 98 (81), 91 (100), 81 (29), 70 (14), 65 (37), 55 (15); [α] =−8.3 (c
D
.5, CHCl using (DHQD) –CLB); −14.8 (c 0.5, CHCl using (DHQD) –PYR). Anal.: C H NO S
3
2
3
2
14 19
3
requires C, 59.79; H, 6.76; N, 4.98; S, 11.39%. Found: C, 59.77; H, 6.78; N, 4.95; S, 11.36%.
3
.1.3. 2-(N-(p-Tolylsulfonyl)amino)-4-tert-butylcyclohexanone
−1
Yield: 34%; mp: 120–121°C; IR (CHCl , cm ): 3290, 1700, 1600, 1340, 1290, 1160, 1090, 980, 920,
3
1
8
10, 760, 670; H NMR (200 MHz, CDCl ): δ 0.9 (s, 9H, tBu), 1.25–1.5 (m, 2H, ring-CH), 1.55–1.7
3
(
(
(
m, 1H, ring CH), 2.05–2.15 (m, 1H, ring CH) 2.2–2.35 (m, 1H, ring CH), 2.4 (s, 3H, Ar-CH ), 2.45–2.6
3
m, 2H, ring CH), 3.75 (m, 1H, CHN), 5.75 (bd, J=5.4 Hz, 1H, NH), 7.25 (d, J=9.2 Hz, 2H, Ar-H), 7.75
d, J=9.2 Hz, 2H, Ar-H). 13C NMR (CDCl , 50.3 MHz): δ 21.7, 27.8, 28.6, 32.6, 38.3, 39.9, 46.0, 60.4,
3
+
127.3, 129.9, 143.8, 206.4; MS: m/z (% rel. intensity) 323 (M , 3), 266 (54), 238 (22), 210 (25), 172 (9),
1
55 (49), 140 (17), 123 (24), 110 (17), 91 (100), 82 (20), 77 (7), 65 (36), 57 (70), 55 (49). [α] =−11.4
D
(c 0.5, CHCl ). Anal.: C H NO S requires C, 63.16: H, 7.74; N, 4.33; S, 9.91%. Found: C, 63.13; H,
3
l7 25
3
7.74; N, 4.34; S, 6.02%.
3
.1.4. 2-(N-(p-Tolylsulfonyl)amino)propiophenone
−1
Yield: 41%; mp: 115–116°C; IR (CHCl , cm ): 3280, 1670, 1590, 1400, 1345, 1220, 1160, 1090,
3
1
9
60, 860, 750, 700, 660; H NMR (200 MHz, CDCl ): δ 1.4 (d, J=8.1 Hz, 3H, CH ) 2.3 (s, 3H, Ar-CH ),
3
3
3
4.95 (m, 1H, CHCH ), 5.8 (d, J=8.1 Hz, 1H, NH), 7.15 (d, J=8.1 Hz, 2H, ArH), 7.45 (t, J=8.1 Hz, 2H,
3
13
ArH), 7.55 (t, J=8.1 Hz, 1H, ArH), 7.7 (d, J=8.1 Hz, 2H, ArH), 7.8 (d, J=8.1 Hz, ArH); C NMR (50.3
MHz, CDCl ): δ 21.0, 21.5, 53.5, 127.2, 128.6. 128.8, 129.0, 129.8, 133.6, 134.2, 137.3, 143.6, 198.4;
3
+
MS: m/z (% rel. intensity) 303 (M , 1) 199 (10), 198 (100), 155 (70), 105 (33), 91 (26), 90 (16), 77
(
9); [α] =−17 (c 1, CHCl , using (DHQD) –CLB); −20.7 (c 1, CHCl , using (DHQD) –PYR). Anal.:
D
3
2
3
2
C H NO S requires C, 63.36; H, 5.61; N, 4.62; S, 10.561%. Found: C, 63.35; H, 5.60; N, 4.64; S,
16
17
3
10.57%.