Job/Unit: O42177
/KAP1
Date: 28-05-14 12:04:27
Pages: 20
H.-J. Knölker et al.
m.p. 111 °C. UV (MeOH): λ = 264, 270, 275, 286 nm. IR (ATR):
FULL PAPER
0.370 mmol) in THF (10 mL), and the mixture was stirred at room
temperature for 16 h. Water (50 mL) was added, and the reaction
mixture was extracted with diethyl ether (3ϫ 50 mL). The com-
bined organic layers were dried with magnesium sulfate, and the
solvent was evaporated. Purification of the residue by chromatog-
raphy on a silica gel column (petroleum ether/diethyl ether, 3:1)
provided 15a (121 mg, 99 % yield) as yellow crystals; m.p. 120–
ν = 3278, 3245, 2946, 1595, 1569, 1493, 1466, 1421, 1331, 1305,
˜
1283, 1265, 1240, 1217, 1186, 1157, 1120, 1092, 1072, 1018, 998,
943, 916, 885, 866, 844, 816, 766, 726, 704, 665 cm–1. 1H NMR
(500 MHz, CDCl3): δ = 2.01 (t, J = 2.6 Hz, 1 H), 2.37 (s, 3 H),
2.54 (ddd, JAB = 17.0 Hz, J = 6.0, 2.6 Hz, 1 H), 2.61 (ddd, JAB
=
17.0 Hz, J = 6.4, 2.6 Hz, 1 H), 3.87 (s, 3 H), 4.73 (m, 1 H), 5.32
(d, J = 8.0 Hz, 1 H), 6.91 (d, J = 2.5 Hz, 1 H), 7.175 (d, J = 2.6 Hz,
1 H), 7.177 (d, J = 8.1 Hz, 2 H), 7.58 (d, J = 8.2 Hz, 2 H) ppm.
13C NMR and DEPT (125 MHz, CDCl3): δ = 21.47 (CH3), 26.54
(CH2), 51.23 (CH), 61.29 (CH3), 72.78 (CH), 78.28 (C), 126.98 (2
CH), 128.23 (C), 129.26 (C), 129.46 (3 CH), 129.60 (CH), 135.23
121 °C. UV (MeOH): λ = 222, 272 nm. IR (ATR): ν = 3285, 3250,
˜
2922, 2841, 1960, 1923, 1599, 1494, 1454, 1439, 1421, 1338, 1320,
1305, 1292, 1247, 1216, 1188, 1154, 1118, 1091, 1065, 1026, 941,
862, 839, 815, 781, 750, 706, 667 cm–1 1H NMR (500 MHz,
.
CDCl3): δ = 1.88 (t, J = 2.6 Hz, 1 H), 2.31 (s, 3 H), 2.68 (dd, J =
2.5, 1.6 Hz, 1 H), 2.69 (d, J = 2.6 Hz, 1 H), 3.73 (s, 3 H), 4.61 (dt, (C), 136.78 (C), 143.76 (C), 151.73 (C) ppm. MS (EI): m/z (%) =
J = 9.6, 6.8 Hz, 1 H), 5.65 (d, J = 9.6 Hz, 1 H), 6.67 (d, J = 8.1 Hz,
362 (10), 360 (50), 358 (73) [M – C3H3]+, 155 (67), 91 (100), 65
1 H), 6.75 (dt, J = 0.8, 7.4 Hz, 1 H), 6.98 (dd, J = 7.5, 1.6 Hz, 1 (16). C18H17Cl2NO3S (398.30): calcd. C 54.28, H 4.30, N 3.52, S
H), 7.07 (d, J = 8.1 Hz, 2 H), 7.13 (m, 1 H), 7.54 (d, J = 8.3 Hz, 2
H) ppm. 13C NMR and DEPT (125 MHz, CDCl3): δ = 21.38
(CH3), 25.78 (CH2), 54.58 (CH), 55.11 (CH3), 71.07 (CH), 80.03
(C), 110.41 (CH), 120.31 (CH), 126.42 (C), 126.90 (2 CH), 128.87
(CH), 129.10 (3 CH), 137.37 (C), 142.89 (C), 156.02 (C) ppm. MS
(EI): m/z (%) = 329 (0.1) [M]+, 290 (100), 155 (21), 91 (35). HRMS
(EI): calcd. for C15H16NO3S+ [M – C3H3]+ 290.0851; found
290.0833. C18H19NO3S (329.41): calcd. C 65.63, H 5.81, N 4.25, S
9.73; found C 65.86, H 5.93, N 4.20, S 9.43.
8.05; found C 54.30, H 4.26, N 3.52, S 7.86.
N-[1-(3,5-Dibromo-2-methoxyphenyl)-but-3-ynyl]-4-methylbenzene-
sulfonamide (15d): TBAF (1.0 m solution in THF, 1.24 mL,
1.24 mmol) was added at room temperature to a solution of 11d
(634 mg, 1.13 mmol) in THF (25 mL), and the mixture was stirred
at room temperature for 15 h. Water (100 mL) was added, and the
reaction mixture was extracted with diethyl ether (3ϫ 100 mL).
The combined organic layers were dried with magnesium sulfate,
and the solvent was evaporated. Purification of the residue by
chromatography on a silica gel column (petroleum ether/diethyl
N-[1-(3,5-Difluoro-2-methoxyphenyl)-but-3-ynyl]-4-methylbenzene-
sulfonamide (15b): TBAF (1.0 m solution in THF, 2.60 mL, ether, 2:1) provided 15d (533 mg, 97% yield) as yellow crystals; m.p.
2.60 mmol) was added at room temperature to a solution of 11b
147–148 °C. UV (MeOH): λ = 226 nm. IR (ATR): ν = 3311, 3246,
˜
(1.03 g, 2.35 mmol) in THF (50 mL), and the mixture was stirred
3073, 2923, 2853, 1730, 1599, 1558, 1493, 1461, 1420, 1325, 1310,
at room temperature for 15 h. Water (100 mL) was added, and the 1299, 1261, 1228, 1182, 1156, 1093, 1080, 1017, 991, 954, 938, 886,
reaction mixture was extracted with diethyl ether (3ϫ 100 mL).
The combined organic layers were dried with magnesium sulfate,
and the solvent was evaporated. Purification of the residue by
chromatography on a silica gel column (petroleum ether/diethyl
ether, 3:1) provided 15b (814 mg, 95% yield) as light orange crys-
864, 842, 830, 811, 764, 710, 699, 675, 651, 637 cm–1. 1H NMR
(500 MHz, CDCl3): δ = 2.01 (t, J = 2.6 Hz, 1 H), 2.38 (s, 3 H),
2.53 (ddd, JAB = 17.0 Hz, J = 6.0, 2.6 Hz, 1 H), 2.62 (ddd, JAB
=
17.0 Hz, J = 6.3, 2.6 Hz, 1 H), 3.86 (s, 3 H), 4.76 (m, 1 H), 5.36
(d, J = 7.9 Hz, 1 H), 7.09 (d, J = 2.3 Hz, 1 H), 7.18 (d, J = 8.0 Hz,
tals; m.p. 128 °C. UV (MeOH): λ = 230, 270 nm. IR (ATR): ν = 2 H), 7.48 (d, J = 2.3 Hz, 1 H), 7.57 (d, J = 8.3 Hz, 2 H) ppm. 13C
˜
3289, 3245, 3013, 2984, 2951, 2925, 2841, 1597, 1491, 1461, 1442,
1422, 1328, 1319, 1306, 1289, 1264, 1224, 1189, 1156, 1120, 1084,
1048, 1019, 998, 971, 941, 862, 845, 815, 779, 740, 703, 666,
NMR and DEPT (125 MHz, CDCl3): δ = 21.51 (CH3), 26.60
(CH2), 51.05 (CH), 61.37 (CH3), 72.84 (CH), 78.22 (C), 117.08 (C),
117.63 (C), 126.93 (2 CH), 129.48 (2 CH), 130.49 (CH), 135.18
(CH), 135.74 (C), 136.73 (C), 143.75 (C), 153.27 (C) ppm. MS (EI):
m/z (%) = 450 (31), 448 (58), 446 (29) [M – C3H3]+, 155 (68), 91
(100), 65 (15). C18H17Br2NO3S (487.21): calcd. C 44.37, H 3.52, N
2.87, S 6.58; found C 44.51, H 3.50, N 2.91, S 6.48.
1
650 cm–1. H NMR (500 MHz, CDCl3): δ = 1.96 (t, J = 2.6 Hz, 1
H), 2.36 (s, 3 H), 2.59 (m, 2 H), 3.88 (d, 5JH,F = 2.1 Hz, 3 H), 4.69
(dt, J = 8.5, 6.4 Hz, 1 H), 5.41 (d, J = 8.6 Hz, 1 H), 6.58 (m, 1 H),
3
4
6.67 (ddd, JH,F = 11.4, 8.2 Hz, JH,H = 3.1 Hz, 1 H), 7.18 (d, J =
8.1 Hz, 2 H), 7.61 (d, J = 8.3 Hz, 2 H) ppm. 13C NMR and DEPT
(125 MHz, CDCl3): δ = 21.42 (CH3), 26.33 (CH2), 51.92 (CH),
2-(2-Methoxyphenyl)-1-(p-tolylsulfonyl)-2,3-dihydro-1H-pyrrole
(13a): Silver acetate (177 mg, 1.06 mmol) was added at room tem-
perature to a solution of 15a (3.50 g, 10.6 mmol) in acetone
(150 mL), and the mixture was heated at reflux for 72 h. The sol-
vent was evaporated, and the residue was purified by chromatog-
raphy on a silica gel column (pentane/ethyl acetate, 3:1) to provide
13a (3.39 g, 97% yield) as light yellow crystals; m.p. 142–145 °C.
4
61.40 (d, JC,F = 7.1 Hz, CH3), 72.30 (CH), 78.59 (C), 104.44 (dd,
2
4
2JC,F = 26.6, 23.3 Hz, CH), 110.40 (dd, JC,F = 23.6 Hz, JC,F
=
2.9 Hz, CH), 127.02 (2 CH), 129.41 (2 CH), 134.08 (m, C), 136.95
2
4
(C), 140.76 (dd, JC,F = 10.9 Hz, JC,F = 3.5 Hz, C), 143.60 (C),
154.63 (dd, 1JC,F = 249.8 Hz, 3JC,F = 12.3 Hz, C), 157.12 (dd, 1JC,F
= 244.8 Hz, 3JC,F = 11.8 Hz, C) ppm. MS (EI): m/z (%) = 326 (100)
[M – C3H3]+, 155 (51), 91 (73). C18H17F2NO3S (365.39): calcd. C
59.17, H 4.69, N 3.83, S 8.78; found C 59.45, H 4.99, N 3.88, S
8.71.
UV (MeOH): λ = 220, 264, 270, 277 nm. IR (ATR): ν = 3099,
˜
2924, 2839, 1923, 1731, 1620, 1593, 1491, 1466, 1438, 1398, 1359,
1342, 1287, 1262, 1243, 1194, 1156, 1115, 1096, 1053, 1028, 987,
962, 931, 895, 873, 840, 815, 804, 782, 752, 720, 664 cm–1. 1H NMR
(500 MHz, CD2Cl2): δ = 2.22–2.26 (m, 1 H), 2.45 (s, 3 H), 2.87
N-[1-(3,5-Dichloro-2-methoxyphenyl)-but-3-ynyl]-4-methylbenzene-
sulfonamide (15c): TBAF (1.0 m solution in THF, 2.20 mL, (ddt, J = 16.8, 10.9, 2.4 Hz, 1 H), 3.82 (s, 3 H), 5.04 (dd, J = 10.9,
2.20 mmol) was added at room temperature to a solution of 11c
(945 mg, 2.01 mmol) in THF (25 mL), and the mixture was stirred
at room temperature for 15 h. Water (100 mL) was added, and the
reaction mixture was extracted with diethyl ether (3ϫ 100 mL).
The combined organic layers were dried with magnesium sulfate,
and the solvent was evaporated. Purification of the residue by
chromatography on a silica gel column (petroleum ether/diethyl
ether, 3:1) provided 15c (779 mg, 97% yield) as colorless crystals;
6.1 Hz, 1 H), 5.10 (dt, J = 4.4, 2.4 Hz, 1 H), 6.49 (m, 1 H), 6.90
(d, J = 8.2 Hz, 1 H), 6.98 (dt, J = 0.7, 7.5 Hz, 1 H), 7.27 (dt, J =
1.7, 7.8 Hz, 1 H), 7.36 (d, J = 8.0 Hz, 2 H), 7.47 (dd, J = 7.6,
1.6 Hz, 1 H), 7.67 (d, J = 8.3 Hz, 2 H) ppm. 13C NMR and DEPT
(125 MHz, CD2Cl2): δ = 21.67 (CH3), 40.09 (CH2), 55.66 (CH3),
57.90 (CH), 110.69 (CH), 111.58 (CH), 120.80 (CH), 127.17 (CH),
128.04 (2 CH), 128.62 (CH), 129.93 (2 CH), 130.80 (CH), 131.76
(C), 133.93 (C), 144.32 (C), 156.28 (C) ppm. MS (EI): m/z (%) =
12
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