Sulfonamide Synthesis via Oxyma-O-Sulfonates
procedure for the synthesis of sulfonate esters. Rf = 0.58 (EtOAc/
N-Benzyl-2,4-dinitrobenzenesulfonamide: This compound (Table 2,
Entry 5) was prepared by using the general procedure for the syn-
thesis of sulfonamides from sulfonate esters of Oxyma. Rf = 0.21
hexane 1:4). Yield 246 mg, 75%, colorless crystalline solid, m.p.
1
113 °C. IR (KBr): ν = 3103, 2988, 1748, 1544, 928, 742 cm–1. H
˜
NMR (400 MHz, CDCl3): δ = 8.27–8.25 (d, J = 8.0 Hz, 1 H, 1ϫ
(EtOAc/hexane, 1:6). Yield 298 mg, 83%, white solid, m.p. 151 °C.
1
ArH), 7.95–7.85 (m, 3 H, 3ϫ ArH), 4.47–4.42 (q, 2 H, CH2), 1.40– IR (KBr): ν = 3379, 3096, 2346, 1532, 1336, 1159 cm–1. H NMR
˜
1.37 (t, 3 H, CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 155.6, (400 MHz, CDCl3): δ = 9.16–9.15 (s, J = 2.4 Hz, 1 H, 1ϫ ArH),
1
2
148.0, 137.1, 133.4, 132.8, 126.3, 125.5, 105.9, 65.1, 13.9 ppm.
8.91 (s, 1 H, 1ϫ ArH), 8.24–8.21 (dd, J = 2.4, J = 2.8 Hz, 1 H,
HRMS (ESI): calcd. for C11H10N3O7S [M + H]+ 328.0239; found 1ϫ ArH), 7.43–7.26 (m, 5 H, 5ϫ ArH), 6.92–6.90 (d, J = 5.2 Hz,
328.0237.
1 H, 1ϫ ArH), 4.66–4.64 (d, 1J = 5.6 Hz, 2 H, CH2) ppm. 13C
NMR (100 MHz, CDCl3): δ = 148.3, 136.2, 135.7, 130.6, 130.2,
129.2, 128.2, 127.1, 124.0, 114.6, 47.4 ppm. MS (ESI): m/z = 338.04
[M]+.
(E)-Ethyl
2-Cyano-2-(2,4-dinitrophenylsulfonyloxyimino)acetate:
This compound (Table 1, Entry 5) was prepared by using the gene-
ral procedure for the synthesis of sulfonate esters. Rf = 0.39
(EtOAc/hexane 1:4). Yield 201 mg, 54%, yellow crystalline solid,
4-Methyl-N-(1-phenylethyl)benzenesulfonamide: This compound
(Table 2, Entry 6) was prepared by using the general procedure for
the synthesis of sulfonamides from sulfonate esters of Oxyma. Rf
= 0.46 (EtOAc/hexane 1:4). Yield 168 mg, 61%, white solid, m.p.
m.p. 109 °C. IR (KBr): ν = 3121, 2989, 1752, 1602, 985, 767 cm–1.
˜
1H NMR (400 MHz, CDCl3): δ = 8.91–8.90 (d, J = 2.4 Hz, 1 H,
1ϫ ArH), 8.54–8.50 (m, 1 H, 1ϫ ArH), 7.95–7.92 (d, J = 9.2 Hz,
1 H, 1ϫ ArH), 4.51–4.46 (q, 2 H, 2ϫ CH2), 1.40–1.37 (t, 3 H,
CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 156.1, 154.2, 144.0,
137.5, 131.7, 129.6, 118.8, 106.6, 64.9, 14.0 ppm. HRMS (ESI):
calcd. for C11H9N4O9S [M + H]+ 373.0090; found 373.0098.
78 °C. IR (KBr): ν = 3307, 2931, 2854, 1926, 1597, 1494, 1427,
˜
1
1159, 1092, 925 cm–1. H NMR (400 MHz, CDCl3): δ = 7.55–7.53
(d, J = 8 Hz, 2 H, 2ϫ ArH), 7.09–7.07 (d, J = 8 Hz, 5 H, 5ϫ
ArH), 7.02–7.01 (m, 2 H, 2ϫ ArH), 5.22–5.21 (d, J = 3.6 Hz, 1 H,
NH), 4.38–4.35 (t, J = 12 Hz, 1 H, CHAr), 2.29 (s, 3 H, ArCH3),
1.33–1.32 (d, J = 6.8 Hz, 3 H, CHCH3) ppm. MS (ESI): m/z =
276.10 [M + H]+.
N-Butyl-4-methylbenzenesulfonamide: This compound (Table 2, En-
try 1) was prepared by using the general procedure for the synthesis
of sulfonamides from sulfonate esters of Oxyma. Rf = 0.52 (EtOAc/
hexane 1:4). Yield 275 mg, 84%, white solid, m.p. 44 °C. IR (KBr):
N-(Benzo-1,3-dioxol-5-ylmethyl)-4-methylbenzenesulfonamide: This
compound (Table 2, Entry 7) was prepared by using the general
procedure for the synthesis of sulfonamides from sulfonate esters
of Oxyma. Rf = 0.59 (EtOAc/hexane 2:3). Yield 211 mg, 69%,
ν = 3470, 3090, 1652, 1358, 1163 cm–1. 1H NMR (400 MHz,
˜
CDCl3): δ = 7.77–7.75 (d, J = 8 Hz, 2 H, 2ϫ ArH), 7.31–7.29 (d,
J = 8 Hz, 2 H, 2ϫ ArH), 5.12 (br. s, 1 H, NH), 2.91 (t, J = 6.8 Hz,
2
H, NHCH2), 2.42 (s, 3 H, CH3), 1.45–1.41 (m, 2 H,
white solid, m.p. 139 °C (lit. 134–137 °C). IR (KBr): ν = 3268,
˜
1
1586, 1337, 1263, 1089, 926 cm–1. H NMR (400 MHz, CDCl3): δ
NHCH2CH2), 1.30–1.25 (m, 2 H, CH2CH3), 0.85–0.83 (t, J =
5.6 Hz, 3 H, CH2CH3) ppm. MS (ESI): m/z = 228.10 [M + H]+
= 7.64–7.62 (d, J = 8.4 Hz, 2 H, 2ϫ ArH), 7.33–7.31 (d, J = 8.4 Hz,
2 H, 2ϫ ArH), 6.58–6.65 (m, 3 H, 2ϫ ArH), 5.9 (s, 2 H, CH2),
4.92 (t, J = 6.4 Hz, NH), 4.20 (d, J = 6.4 Hz, 2 H, CH2), 2.43 (s,
3 H, CH3) ppm. MS (ESI): m/z = 306.08 [M + H]+.
N-Butyl-2,4-dinitrobenzenesulfonamide: This compound (Table 2,
Entry 2) was prepared by using the general procedure for the syn-
thesis of sulfonamides from sulfonate esters of Oxyma. Rf = 0.21
(EtOAc/hexane 1:6). Yield 261 mg, 86%, pale yellow solid, m.p.
N-Benzyloxy-4-methylbenzenesulfonamide:
This
compound
151 °C. IR (KBr): ν = 3262, 2943, 1729, 1532, 1350, 1336, 1236,
˜
(Table 2, Entry 8) was prepared by using the general procedure for
the synthesis of sulfonamides from sulfonate esters of Oxyma. Rf
= 0.46 (EtOAc/hexane 1:6). Yield 202 mg, 73%, white solid, m.p.
1159, 830, 736 cm–1. H NMR (400 MHz, CDCl3): δ = 9.14–9.13
1
(d, J = 2.4 Hz, 1 H, 1ϫ ArH), 8.56 (s, 1 H), 8.28–8.28 (d, 1J = 2.4,
2.8 Hz, 1 H, 1ϫ ArH), 6.94–6.91 (d, 1 H, 1ϫ ArH), 3.44–3.40 (m,
2 H, CH2CH2), 1.81–1.74 (m, 2 H, CH2CH2CH2), 1.54–1.48 (m, 2
H, CH2CH2CH2), 1.03–0.98 (m, 3 H, CH3) ppm. 13C NMR
(100 MHz, CDCl3): δ = 148.3, 135.5, 130.1, 129.9, 123.9, 114.1,
43.2, 30.6, 20.0, 13.5 ppm. MS (ESI): m/z = 304.06 [M + H]+.
74 °C (lit. 72 °C). IR (KBr): ν = 3268, 1586, 1337, 1263, 1089, 926
˜
1
cm–1. H NMR (400 MHz, CDCl3): δ = 7.82–7.80 (d, J = 8.0 Hz,
2 H, 2ϫ ArH), 7.37–7.26 (m, 7 H, 2ϫ ArH), 4.97 (s, 2 H, CH2),
2.43 (s, 3 H, CH3) ppm. MS (ESI): m/z = 278.08 [M + H]+.
N-Benzyloxy-4-nitrobenzenesulfonamide: This compound (Table 2,
Entry 9) was prepared by using the general procedure for the syn-
thesis of sulfonamides from sulfonate esters of Oxyma. Rf = 0.42
(EtOAc/hexane 1:4). Yield 234 mg, 76%, white solid, m.p. 91–
N-Cyclohexyl-4-methylbenzenesulfonamide:
This
compound
(Table 2, Entry 3) was prepared by using the general procedure for
the synthesis of sulfonamides from sulfonate esters of Oxyma. Rf
= 0.61 (EtOAc/hexane 1:4). Yield 226 mg, 89%, white solid, m.p.
93 °C. IR (KBr): ν = 2946, 1739, 1446, 1337, 1263 cm–1. 1H NMR
˜
87–89 °C. IR (KBr): ν = 3328, 2937, 1755, 1684 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 9.02 (d, 1 H, 1ϫ ArH), 8.71–8.69 (dd, J
= 2.8 Hz, 1 H, 1ϫ ArH), 8.41–8.38 (dd, J = 2.6 Hz, 1 H, 1ϫ ArH),
8.18–8.04 (m, 2 H, 2ϫ ArH), 8.76–7.26 (m, 4 H, 4ϫ ArH), 5.06
(s, 2 H, CH2) ppm. MS (ESI): m/z = 309.05 [M + H]+.
(400 MHz, CDCl3): δ = 7.79–7.77 (d, J = 8.4 Hz, 2 H, 2ϫ ArH),
7.32–7.28 (d, J = 8.4 Hz, 2 H, 2ϫ ArH), 4.97 (br. s, 1 H, NH),
3.11–3.09 (m, 1 H, NHCH), 2.42 (s, 3 H, CH3), 1.74–1.72 (m, 4 H,
2ϫ NHCHCH2), 1.63–1.60 (m, 4 H, 2ϫ NHCHCH2CH2), 1.27–
1.07 (m, 2 H, NHCHCH2CH2CH2) ppm. MS (ESI): m/z = 254.12
[M + H]+.
1-Tosylpiperidine: This compound (Table 2, Entry 10) was prepared
by using the general procedure for the synthesis of sulfonamides
from sulfonate esters of Oxyma. Rf = 0.42 (EtOAc/hexane 1:4).
N-Benzyl-4-methylbenzenesulfonamide: This compound (Table 2,
Entry 4) was prepared by using the general procedure for the syn-
thesis of sulfonamides from sulfonate esters of Oxyma. Rf = 0.58
(EtOAc/hexane 1:4). Yield 206 mg, 79%, white solid, m.p. 87–
Yield 216 mg, 90%, white solid, m.p. 82 °C. IR (KBr): ν = 2946,
˜
1739, 1446, 1337, 1263 cm–1. 1H NMR (400 MHz, CDCl3): δ =
7.64–7.62 (d, J = 8.4 Hz, 2 H, 2ϫ ArH), 7.33–7.31 (d, J = 8.4 Hz,
2 H, 2ϫ ArH), 2.97 (t, J = 5.6 Hz, 4 H, 2ϫ CH2), 2.43 (s, 3 H,
CH3), 1.66–1.61 (m, 4 H, 2ϫ CH2), 1.42–1.39 (m, 2 H, CH2) ppm.
MS (ESI): m/z = 240.10 [M + H]+.
89 °C. IR (KBr): ν = 3262, 3027, 1594, 1492, 1450, 1320, 1156
˜
1
cm–1. H NMR (400 MHz, CDCl3): δ = 7.77–7.75 (d, J = 8.4 Hz,
2 H, 2ϫ ArH), 7.31–7.26 (m, 5 H, 5ϫ ArH), 7.20–7.18 (d, J =
8.8 Hz, 2 H, 2ϫ ArH), 4.74 (br. s, 1 H, NH), 4.11 (s, 2 H, CH2), 1-(Phenylsulfonyl)piperidine: This compound (Table 2, Entry 11)
2.43 (s, 3 H, CH3) ppm. MS (ESI): m/z = 261.02 [M]+.
was prepared by using the general procedure for the synthesis of
Eur. J. Org. Chem. 2013, 2627–2633
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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