The Journal of Organic Chemistry
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stirred for 8 h. After completion, the solvent was evaporated
HRMS (ESIꢀFTꢀICR) calcd. for C16H16BrClNO2S [M+H]+:
399.9774, found: 399.9766.
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under the reduced pressure and the residue was purified by
silica gel column chromatography (hexanes/EtOAc as elute
solvent) to afford the corresponding products 5.
(E)-N-(1-bromo-2-(4-chlorophenyl)vinyl)-N,4-
dimethylbenzenesulfonamide (5g). Purified by flash column
chromatography (ethyl acetate / hexanes = 1:20), yellow solid,
62.8 mg, 79% yield. Mp 142–143°C. 1H NMR (400 MHz,
Chloroformꢀd) δ 7.76 (d, J = 8.3 Hz, 2H), 7.52 (d, J = 8.6 Hz,
2H), 7.33 – 7.27 (m, 4H), 6.59 (s, 1H), 3.02 (s, 3H), 2.44 (s,
3H).13C{1H} NMR (100 MHz, ) δ 144.6, 134.5, 134.1, 131.6,
131.1, 129.9, 129.5, 128.9, 128.7, 35.7, 21.6. HRMS (ESIꢀFTꢀ
ICR) calcd. for C16H16BrClNO2S [M+H]+: 399.9774, found:
399.9764.
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(E)-N-benzyl-N-(1-bromo-2-phenylvinyl)-4-
methylbenzenesulfonamide (5a),1 Purified by flash column
chromatography (ethyl acetate / hexanes = 1:20), white solid,
1
72.4 mg, 82% yield. Mp 142–143°C. H NMR (400 MHz,
Chloroformꢀd) δ 7.86 (d, J = 8.1 Hz, 2H), 7.34 (d, J = 8.1 Hz,
2H), 7.33 – 7.27 (m, 2H), 7.24 (dd, J = 6.2, 1.9 Hz, 2H), 7.23
– 7.04 (m, 6H), 6.81 (s, 1H), 4.83 (d, J = 13.1 Hz, 1H), 3.94 (d,
J = 13.1 Hz, 1H), 2.46 (s, 3H). 13C{1H} NMR (100 MHz, ) δ
144.7, 139.7, 134.3, 133.6, 133.2, 129.9, 129.6, 129.2, 128.7,
128.6, 128.3, 128.1, 128.0, 119.6, 53.3, 21.7.
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(E)-N-(1-bromo-2-(4-fluorophenyl)vinyl)-N,4-
dimethylbenzenesulfonamide (5h). Purified by flash column
chromatography (ethyl acetate / hexanes = 1:20), white solid,
62.6 mg, 82% yield. Mp 86ꢀ88°C. 1H NMR (400 MHz, Chloꢀ
roformꢀd) δ 7.77 (d, J = 7.7 Hz, 2H), 7.67 – 7.51 (m, 2H), 7.30
(d, J = 7.9 Hz, 2H), 7.03 (t, J = 8.3 Hz, 2H), 6.81 (s, 1H), 2.97
(s, 3H), 2.43 (s, 3H).19F NMR (376 MHz, Chloroformꢀd) δ ꢀ
111.2 (dq, J = 9.0, 5.0, 4.3 Hz). 13C{1H} NMR (100 MHz,
Chloroformꢀd) δ 162.7 (d, J = 250.0 Hz), 144.7, 135.8, 133.5,
130.7, 130.6, 129.5, 129.0, 121.1, 115.7 (d, J = 21.7 Hz), 36.6,
21.6. HRMS (ESIꢀFTꢀICR) calcd. for C16H16BrFNO2S
[M+H]+: 384.0069, found: 384.0061.
(E)-N-(1-bromo-2-phenylvinyl)-N-heptyl-4-
methylbenzenesulfonamide (5b). Purified by flash column
chromatography (ethyl acetate / hexanes = 1:25), pale yellow
oil, 85 mg, 86% yield. 1H NMR (400 MHz, Chloroformꢀd) δ
7.82 (d, J = 8.2 Hz, 2H), 7.76 – 7.61 (m, 2H), 7.66 – 7.23 (m,
5H), 6.98 (s, 1H), 3.62 – 3.59 (m, 1H), 2.89 – 2.87 (m, 1H),
2.44 (s, 3H), 1.77 – 1.35 (m, 2H), 1.35 – 0.93 (m, 8H), 0.82 (t,
J = 7.0 Hz, 3H). 13C{1H} NMR (100 MHz, ) δ 144.6, 139.0,
134.0, 133.8, 129.4, 129.2, 129.0, 120.2, 49.7, 31.6, 28.8, 27.4,
26.9, 22.5, 21.7, 14.0. HRMS (ESIꢀFTꢀICR) calcd. for
C22H29BrNO2S [M+H]+: 450.1102, found: 450.1099.
(E)-N-(1-bromo-2-(4-bromophenyl)vinyl)-N-
(E)-N-(1-bromo-2-phenylvinyl)-N-methylmethanesulfonamide
(5c).10 Purified by flash column chromatography (ethyl acetate
/ hexanes = 1:20), pale yellow solid, 49 mg, 85% yield. Mp
phenylmethanesulfonamide (5i). Purified by flash column
chromatography (ethyl acetate / hexanes = 1:20), white solid,
69 mg, 81% yield. Mp 121–122°C. 1H NMR (400 MHz,
Chloroformꢀd) δ 7.53 (d, J = 8.1 Hz, 2H), 7.44 (q, J = 8.4 Hz,
4H), 7.35 (t, J = 7.6 Hz, 2H), 7.29 (d, J = 6.6 Hz, 2H), 6.99 (s,
1H), 3.14 (s, 3H).13C{1H} NMR (100 MHz, ) δ 138.7, 137.3,
132.2, 131.9, 130.1, 129.6, 127.6, 123.6, 123.3, 118.6, 39.0.
HRMS (ESIꢀFTꢀICR) calcd. for C15H14Br2NO2S [M+H]+:
429.9107, found: 429.9100.
1
90–92°C. H NMR (400 MHz, Chloroformꢀd) δ 7.8 – 7.4 (m,
2H), 7.36 – 7.31 (m, 3H), 6.9 (s, 1H), 3.1 (s, 3H), 3.0 (s, 3H).
13C{1H} NMR (100 MHz, ) δ 137.3, 133.4, 129.2, 128.8,
128.6, 120.5, 37.4, 36.5.HRMS (ESIꢀFTꢀICR) calcd. for
C10H13BrNO2S [M+H]+: 289.9850, found: 289.9842.
(E)-N-(1-bromo-2-phenylvinyl)-N-phenylmethanesulfonamide
(5d).10 White solid, 58 mg, 83% yield. Mp 136–137°C. 1H
NMR (400 MHz, Chloroformꢀd) δ 8.03 – 7.36 (m, 4H), 7.54 –
7.14 (m, 6H), 7.06 (s, 1H), 3.14 (s, 3H). 13C{1H} NMR (100
MHz, ) δ 138.9, 138.5, 133.3, 128.7, 128.6, 127.4, 123.7,
117.9, 39.0. HRMS (ESIꢀFTꢀICR) calcd. for C15H15BrNO2S
[M+H]+: 352.0007, found: 352.0001.
(E)-N-(1-bromo-2-(4-cyanophenyl)vinyl)-N,4-
dimethylbenzenesulfonamide (5j). Purified by flash column
chromatography (ethyl acetate / hexanes = 1:15), colorless oil,
64 mg, 82% yield. Mp 131ꢀ134°C. 1H NMR (400 MHz, Chloꢀ
roformꢀd) δ δ 7.75 (d, J = 7.7 Hz, 2H), 7.68 (d, J = 8.0 Hz,
2H), 7.62 (d, J = 7.9 Hz, 2H), 7.31 (d, J = 7.8 Hz, 2H), 6.87 (s,
1H), 2.98 (s, 3H), 2.44 (s, 3H). 13C{1H} NMR (100 MHz, ) δ
145.1, 138.2, 135.1, 133.1, 132.4, 129.6, 129.1, 129.0, 124.9,
118.6, 112.0, 36.8, 21.7. HRMS (ESIꢀFTꢀICR) calcd. for
C17H16BrN2O2S [M+H]+: 391.0116, found: 391.0106.
(E)-N-(1-bromo-2-(2-chlorophenyl)vinyl)-N,4-
dimethylbenzenesulfonamide (5e). Purified by flash column
chromatography (ethyl acetate / hexanes = 1:20), yellow solid,
62 mg,78% yield. Mp 82ꢀ83°C. 1H NMR (400 MHz, Chloroꢀ
formꢀd) δ 7.80 (dd, J = 6.7, 2.8 Hz, 1H), 7.71 (dd, J = 8.4, 1.6
Hz, 2H), 7.43 – 7.29 (m, 1H), 7.26 (dd, J = 7.2, 3.4 Hz, 4H),
7.17 (s, 1H), 2.95 (s, 3H), 2.42 (s, 3H). 13C{1H} NMR (100
Methyl (E)-3-(2-bromo-2-(N-phenylmethylsulfonamido)vinyl)
benzoate (5k). Purified by flash column chromatography
(ethyl acetate / hexanes = 1:15), colorless oil, 52.4 mg, 64%
yield. 1H NMR (400 MHz, Chloroformꢀd) δ 8.15 (s, 1H), 7.97
(d, J = 6.8 Hz, 1H), 7.85 (d, J = 8.1 Hz, 1H), 7.57 (d, J = 8.1
Hz, 2H), 7.43 (t, J = 7.8 Hz, 1H), 7.34 (t, J = 7.6 Hz, 2H), 7.28
(d, J = 7.1 Hz, 1H), 7.08 (s, 1H), 3.90 (s, 3H), 3.13 (s, 3H).
13C{1H} NMR (100 MHz, ) δ 166.5, 138.9, 137.2, 133.6,
132.5, 130.5, 130.0, 129.9, 129.6, 128.9, 127.7, 124.0, 119.3,
52.2, 39.0. HRMS (ESIꢀFTꢀICR) calcd. for C17H17BrNO4S
[M+H]+: 410.0062, found: 410.0054.
MHz, ) δ 144.6, 133.5, 133.4, 133.3, 132.3, 129.6, 129.5,
+
126.9, 123.5, 36.9, 21.6. HRMS (ESI
) calcd. for
C16H16BrClNO2S[M+H]+: 399.9774, found: 399.9770.
(E)-N-(1-bromo-2-(3-chlorophenyl)vinyl)-N,4-
dimethylbenzenesulfonamide (5f). Purified by flash column
chromatography (ethyl acetate / hexanes = 1:20), white solid,
65.2 mg, 82% yield. Mp 113ꢀ114°C. 1H NMR (400 MHz,
Chloroformꢀd) δ 7.83 – 7.67 (m, 2H), 7.50 (s, 1H), 7.46 (s,
1H), 7.28 (t, J = 6.5 Hz, 4H), 6.79 (d, J = 2.0 Hz, 1H), 2.98 (s,
3H), 2.43 (s, 3H). 13C{1H} NMR (100 MHz, ) δ 144.6, 133.5,
133.4, 133.5, 132.3, 129.6, 129.5, 126.9, 123.5, 36.9, 21.6.
6. Hydrochlorination of ynamides 4
To a solution of ynamides 4 (0.2 mmol) in DCM (0.5 mL) was
o
added DMPU/HCl (43 wt/wt%) (34 mg, 0.4 mmol) at 0 C,
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