F. Martinelli, A. Palmieri, M. Petrini
FULL PAPER
with a Perkin–Elmer Paragon 500 FTIR. All chemical used were
commercial. α-Amido sulfones 1 were prepared as described pre-
viously.[17]
Ethyl N-Benzoylcarbamate (3f): Yield: 0.131 g (68%). White solid.
M.p. 110–112 °C. IR (nujol): ν = 804, 1026, 1077, 1206, 1242, 1366,
˜
1469, 1600, 1677, 1710, 3068, 3289 cm–1. 1H NMR (400 MHz,
3
3
CDCl3): δ = 1.33 (t, JH,H = 7.3 Hz, 3 H, CH3), 4.30 (q, JH,H
=
General Procedure for the Synthesis of Imides 3a–m: To a stirred
solution of α-amido sulfone 1 (1 mmol) in CH2Cl2 (10 mL) was
added m-chloroperoxybenzoic acid (77% pure, 4 mmol) at room
temperature. TMG (1.1 mmol) was added dropwise, and the mix-
ture was stirred for the appropriate amount of time (see Table 2) at
the same temperature. The mixture was diluted with CH2Cl2
(30 mL) and then washed with aqueous sodium hydrogensulfite
(2.5%, 2ϫ10 mL) and saturated NaHCO3 (2ϫ 10 mL). The or-
ganic phase was dried with MgSO4 and after evaporation of the
solvent under reduced pressure, the crude product was purified by
column chromatography (hexanes/ethyl acetate, 6:4).
7.3 Hz, 2 H, CH2), 7.44–7.51 (m, 2 H, ArH), 7.54–7.61 (m, 1 H,
ArH), 7.79–7.85 (m, 2 H, ArH), 8.22 (br. s, 1 H, NH) ppm. 13C
NMR (100 MHz, CDCl3): δ = 14.4, 62.6, 127.8, 129.1, 133.2, 133.3,
151.3, 165.1 ppm. MS (EI): m/z (%) = 177 (29), 149 (18), 122 (27),
105 (100), 77 (55), 51 (18). C10H11NO3 (193.20): calcd. C 62.17, H
5.74, N 7.25; found C 62.01, H 5.65, N 7.33.
tert-Butyl N-Benzoylcarbamate (3g): Yield: 0.155 g (70%). White
solid. M.p. 149–151 °C. IR (nujol): ν = 936, 1128, 1217, 1480, 1501,
˜
1677, 1747, 3074, 3252 cm–1. 1H NMR (400 MHz, CDCl3): δ =
1.52 (s, 9 H, tBu), 7.41–7.48 (m, 2 H, ArH), 7.51–7.58 (m, 1 H,
ArH), 7.77–7.83 (m, 2 H, ArH), 8.08 (br. s, 1 H, NH) ppm. 13C
NMR (100 MHz, CDCl3): δ = 28.2, 82.9, 127.7, 128.9, 132.9, 133.5,
149.9, 165.5 ppm. MS (EI): m/z (%) = 147 (55), 105 (100), 77 (80),
51 (27), 50 (17). C12H15NO3 (221.25): calcd. C 65.14, H 6.83, N
6.33; found C 65.25, H 6.72, N 6.36.
N-Acetylbenzamide (3a): Yield: 0.137 g (84%). White solid. M.p.
115–117 °C. IR (nujol): ν = 679, 1204, 1481, 1499, 1600, 1678,
˜
1
1735, 3064, 3273 cm–1. H NMR (400 MHz, CDCl3): δ = 2.60 (s,
3 H, CH3), 7.45–7.53 (m, 2 H, ArH), 7.56–7.63 (m, 1 H, ArH),
7.85–7.91 (m, 2 H, ArH), 9.06 (br. s, 1 H, NH) ppm. 13C NMR
(100 MHz, CDCl3): δ = 25.9, 128.0, 129.2, 132.9, 133.5, 166.1,
173.9 ppm. MS (EI): m/z (%) = 163 (25) [M]+, 162 (21), 105 (100),
77 (42), 51 (13), 43 (18). C9H9NO2 (163.17): calcd. C 66.25, H 5.56,
N 8.58; found C 66.34, H 5.48, N 8.66.
N-Benzoyl-p-toluenesulfonamide (3h): Yield: 0.179 g (65%). White
solid. M.p. 93–95 °C. IR (nujol): ν = 661, 775, 1164, 1344, 1456,
˜
1593 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.49 (s, 3 H, ArCH3),
5.45 (s, 1 H, NH), 7.37–7.50 (m, 7 H, ArH), 7.93 (d, 3JH,H = 8.5 Hz,
2 H, ArH) ppm. 13C NMR (100 MHz, CDCl3): δ = 22.0, 128.4,
128.9, 129.6, 130.2, 130.8, 131.6, 131.7, 146.6 ppm. MS (EI): m/z
(%) = 259 (19), 195 (8), 155 (66), 104 (14), 91 (100), 77 (17), 65
(23), 51 (11). C14H13NO3S (275.32): calcd. C 61.07, H 4.76, N 5.09;
found C 60.91, H 4.82, N 4.96.
N-Benzoylbenzamide (3b): Yield: 0.112 g (50%). White solid. M.p.
146–148 °C. IR (nujol): ν = 706, 1221, 1470, 1675, 1702, 3030,
˜
3242 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.42–7.50 (m, 4 H,
ArH), 7.53–7.60 (m, 2 H, ArH), 7.83–7.89 (m, 4 H, ArH), 9.49 (br.
s, 1 H, NH) ppm. 13C NMR (100 MHz, CDCl3): δ = 128.3, 128.9,
133.2, 133.7, 167.1 ppm. MS (EI): m/z (%) = 225 (24) [M]+, 197
(9), 122 (6), 105 (100), 77 (55), 51 (17). C14H11NO2 (225.24): calcd.
C 74.65, H 4.92, N 6.22; found C 74.83, H 5.03, N 6.13.
N-Butyryl-(4-trifluoromethyl)benzamide (3i): Yield: 0.190 g (73%).
White solid. M.p. 135–138 °C. IR (nujol): ν = 693, 764, 867, 1066,
˜
1670, 1683, 1713, 3277 cm–1. 1H NMR (400 MHz, CDCl3): δ =
3
N-Propanoylbenzamide (3c): Yield: 0.098 g (55%). White solid.
1.03 (t, JH,H = 7.3 Hz, 3 H, CH3), 1.70–1.81 (m, 2 H, CH2), 2.98
3
3
M.p. 97–99 °C. IR (nujol): ν = 804, 1079, 1208, 1243, 1366, 1470,
˜
(t, JH,H = 7.3 Hz, 2 H, CH2), 7.77 (d, JH,H = 8.5 Hz, 2 H, ArH),
1600, 1678, 1711, 3068, 3285 cm–1. 1H NMR (400 MHz, CDCl3):
7.98 (d, 3JH,H = 8.1 Hz, 2 H, ArH), 8.85 (br. s, 1 H, NH) ppm. 13
C
3
3
δ = 1.20 (t, JH,H = 7.3 Hz, 3 H, CH3), 3.02 (q, JH,H = 7.3 Hz, 2
H, CH2), 7.45–7.52 (m, 2 H, ArH), 7.55–7.62 (m, 1 H, ArH), 7.86–
7.93 (m, 2 H, ArH), 9.13 (br. s, 1 H, NH) ppm. 13C NMR
(100 MHz, CDCl3): δ = 8.4, 31.4, 128.0, 129.1, 133.1, 133.4, 166.0,
177.7 ppm. MS (EI): m/z (%) = 177 (30) [M]+, 149 (19), 122 (28),
105 (100), 77 (54), 51 (18). C10H11NO2 (177.20): calcd. C 67.78, H
6.26, N 7.90; found C 67.63, H 6.19, N 7.99.
NMR (100 MHz, CDCl3): δ = 13.9, 17.7, 39.8, 126.1, 126.2, 126.3,
126.4, 128.4, 136.4, 164.7, 176.2, 176.3 ppm. MS (EI): m/z (%) =
259 (9) [M]+, 244 (10), 231 (22), 190 (58), 173 (100), 145 (68), 125
(9), 95 (12), 71 (25), 55 (16), 43 (37). C12H12F3NO2 (259.22): calcd.
C 55.60, H 4.67, N 5.40; found C 55.72, H 4.73, N 5.50.
Ethyl N-(4-Fluorobenzoyl)carbamate (3j): Yield: 0.180 g (85%).
White solid. M.p. 91–93 °C. IR (nujol): ν = 777, 1161, 1231, 1505,
˜
N-Octanoylbenzamide (3d): Yield: 0.171 g (69%). White solid. M.p.
1600, 1704, 1768, 3031, 3333 cm–1. 1H NMR (400 MHz, CDCl3):
64–66 °C. IR (nujol): ν = 773, 1185, 1237, 1465, 1508, 1676, 1707,
˜
3
3
δ = 1.34 (t, JH,H = 7.3 Hz, 3 H, CH3), 4.30 (q, JH,H = 7.3 Hz, 2
H, CH2), 7.12–7.19 (m, 2 H, ArH), 7.82–7.89 (m, 2 H, ArH), 8.08
(br. s, 1 H, NH) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.5,
62.8, 116.1, 116.4, 130.4, 130.5, 164.5, 167.0 ppm. MS (EI): m/z
(%) = 165 (8), 139 (51), 123 (100), 95 (76), 75 (27), 50 (10), 44 (10).
C10H10FNO3 (211.19): calcd. C 56.87, H 4.77, N 6.63; found C
56.71, H 4.80, N 6.70.
1
3
3064, 3320 cm–1. H NMR (400 MHz, CDCl3): δ = 0.88 (t, JH,H
= 6.8 Hz, 3 H, CH3), 1.22–1.45 (m, 8 H, 4 CH2), 1.66–1.76 (m, 2
3
H, CH2), 2.99 (t, JH,H = 7.3 Hz, 2 H, CH2CO), 7.46–7.53 (m, 2
H, ArH), 7.57–7.63 (m, 1 H, ArH), 7.85 (d, J = 7.7 Hz, 2 H, ArH),
8.66 (br. s, 1 H, NH) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.3,
22.9, 24.4, 29.3, 29.4, 31.9, 37.8, 127.8, 129.2, 133.1, 133.4, 165.7,
176.5 ppm. MS (EI): m/z (%) = 247 (2) [M]+, 176 (40), 163 (47),
122 (50), 105 (100), 77 (51), 57 (13), 41 (16). C15H21NO2 (247.33):
calcd. C 72.84, H 8.56, N 5.66; found C 73.02, H 8.65, N 5.58.
Ethyl N-(4-Trifluoromethylbenzoyl)carbamate (3k): Yield: 0.208 g
(80%). White solid. M.p. 119–122 °C. IR (nujol): ν = 777, 1032,
˜
1113, 1192, 1326, 1498, 1692, 1754, 3066, 3303 cm–1. 1H NMR
N-2-Fluoroacetylbenzamide (3e): Yield: 0.096 g (53%). White solid.
3
(400 MHz, CDCl3): δ = 1.30 (t, JH,H = 7.3 Hz, 3 H, CH3), 4.19–
M.p. 119–122 °C. IR (nujol): ν = 801, 912, 1049, 1240, 1401, 1602,
˜
3
4.30 (m, 2 H, CH2), 7.69 (d, JH,H = 7.7 Hz, 2 H, ArH), 7.94 (d,
1683, 1712, 3075, 3300 cm–1. 1H NMR (400 MHz, CDCl3): δ =
3JH,H = 8.1 Hz, 2 H, ArH), 8.21 (br. s, 1 H, NH) ppm. 13C NMR
(100 MHz, CDCl3): δ = 14.4, 62.9, 125.9, 126.0, 126.1, 126.2,
128.4 ppm. MS (EI): m/z (%) = 215 (26), 196 (10), 173 (100), 145
(89), 125 (9), 95 (13), 75 (16), 50 (9), 31 (9). C11H10F3NO3 (261.20):
calcd. C 50.58, H 3.86, N 5.36; found C 50.38, H 3.95, N 5.47.
2
5.43 (d, JH,H = 47.9 Hz, 2 H, CH2F), 7.48–7.54 (m, 2 H, ArH),
7.59–7.65 (m, 1 H, ArH), 7.89–7.94 (m, 2 H, ArH), 9.52 (br. s, 1
H, NH) ppm. 13C NMR (100 MHz, CDCl3): δ = 80.4, 82.2, 128.1,
129.3, 131.4, 134.0, 166.1, 171.2, 172.4 ppm. MS (EI): m/z (%) =
181 (17) [M]+, 161 (14), 105 (100), 103 (31), 77 (57), 81 (18).
C9H8FNO2 (181.16): calcd. C 59.67, H 4.45, N 7.73; found C 59.49, Ethyl N-(2-Chlorobenzoyl)carbamate (3l): Yield: 0.091 g (40%).
H 4.37, N 7.79. White solid. M.p. 76–78 °C. IR (nujol): ν = 775, 1163, 1215, 1501,
˜
5088
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Eur. J. Org. Chem. 2010, 5085–5089